Organophosphorus Chemistry (Volume 18) Specialist Periodical Report

Organophosphorus Chemistry Volume 18 A Specialist Periodical Report Organophosphorus Chemistry Volume 18 ~~ ~ A Re...

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Organophosphorus Chemistry Volume 18

A Specialist Periodical Report

Organophosphorus Chemistry Volume 18 ~~

~

A Review of the Literature published between July 1985 and June 1986 Senior Reporter

B. J. Walker, Department of Chemistry, David Keir Building, The Queen's University of Belfast Reporters

C. W. Allen, University of Vermont, U.S.A. D. W. Allen, Sheffield City Polytechnic

0. Dahl, University of Copenhagen, Denmark

R. S. Edmundson, formerly of University of Bradford C. D. Hall, King's College, London

J. B. Hobbs, The City University, London J. C. Tebby, North Staffordshire Polytechnic, Stoke-on- Trent

SOCIETY OF HEMISTRY

ISBN 0-85186-166-0 ISSN 0306-0713 Copyright 0 1987 The Royal Society of Chemistry

All Rights Reserved No part of this book may be reproduced or transmitted in any form or by any means-graphic, electronic, including photocopying, recording, taping, or information storage and retrieval systems- without written permksion from the Royal Society of Chemistry

Published by The Royal Society of Chemistry Burlington House, London, W1V OBN Printed in Great Britain by Staples Printers Rochester Limited, Love Lane, Rochester, Kent.

Introduction Professor Stewart Trippett is an initiator and has led the development of modern organophosphorus chemistry. He is also a founder and the original Senior Reporter of this Report and we were all concerned to hear 0.f his recent illness. colleagues wish him well.

A l l his friends and

It is appropriate and significant that

the areas where he has contributed so much, those of the Wittig reaction and hypervalent intermediates, are still among the most actively investigated topics. The increased availability of "user friendly" MO programmes is reflected in the proliferation of papers concerned with theoretical aspects. In view of this Professor John Tebby has agreed to add to his chapter on Physical Methods a new section significally covering this area. The continuing revelations of enzyme-like activity of certain RNA molecules offer new opportunities and challenges for both

chemists and biochemists. This must result in an increased demand for oligoribonucleotides of defined sequence and significant e f f o r t s have been made to improve methods of synthesis with the ultimate aim to render it as easy and reliable as present-day oligodeoxyribonucleotide synthesis. While this latter process is still being refined, the ready accessibility of oligodeoxyribonucleotides of defined sequence prepared on automated synthesizers using phosphoramidite chemistry is permitting chemists, biochemists and molecular biologists to address problems previously beyond reach. Oligodeoxyribonucleotide analogues containing methylphosphonate linkages offer exciting prospects for the control of gene expression in living systems, as also do sequence-specific DNA cleavage agents. The interest in pT-bonded phosphorus, as measured by the number of publications, continues to increase (the fairly small number of phospnaalkynes known has been significantly increased and all show very high field 31P chemical shifts). However, there are some signs that we are approaching a point where consolidation, rather than exciting new results, will dominate the subject area.

Introduction

vi

There has been c o n t r o v e r s y o v e r t h e mechanism o f h y d r o l y s i s o f e t h y l e n e methyl p h o s p h a t e and i n v e s t i g a t i o n s i n t o t h e n a t u r e o f metaphosphate and i t s r o l e i n t h E h y d r o l y s i s o f p h o s p h o r u s e s t e r s have c o n t i n u e d .

Elegant experiments r e l a t i n g t o each of these

problems have been r e p o r t e d . I n v e s t i g a t i o n s o f h y p e r v a l e n t p h o s p h o r u s compounds have t e n d e d t o c o n c e n t r a t e on t h e more s t a b l e b i c y c l i c s y s t e m s .

Elegant s t u d i e s

of s p i r o p h o s p h o r a n e s and a t h o r o u g h i n v e s t i g a t i o n o f p e r m u t a t i o n a l i s o m e r i s a t i o n s w i t h i n amidinium f l u o r p h o s p h a t e s a r e w o r t h n o t i n g . The n o t a b l e i n c r e a s e s i n t h e o r e t i c a l s t u d i e s o f y l i d e s and t h e i r r e a c t i o n s r e f l e c t s s i m i l a r developments t h r o u g h o u t o r g a n i c chemistry.

The renewed i n t e r e s t i n t h e mechanism o f t h e W i t t i g

r e a c t i o n have c o n t i n u e d , b u t i n s p i t e of s e v e r a l y e a r s o f c o n s i d e r a b l e e f f o r t from a number o f r e s p e c t e d r e s e a r c h g r o u p s a f u l l y s a t i s f a c t o r y e x p l a n a t i o n i s s t i l l some way o f f . Work on phosphazene h i g h polymers c o n t i n u e s t o a t t r a c t increased interest.

Advances i n t h e s t u d y o f t h e r i n g - o p e n i n g

p o l y m e r i z a t i o n , and p h y s i c a l c h a r a c t e r i z a t i o n i n t h e s o l i d s t a t e , o f t h e m a t e r i a l s produced by t h e s e r e a c t i o n s have been r e p o r t e d . A number o f a b i n i t i o m o l e c u l a r o r b i t a l c a l c u l a t i o n s have b e e n

p e r f o r m e d on a c y c l i c and c y c l i c p h o s p h a z e n e s .

These c a l c u l a t i o n s

p o i n t t o a p h o s p h o r u s - n i t r o g e n bond w i t h a l a r g e d e g r e e o f c h a r g e s e p a r a t i o n and a small b u t e s s e n t i a l c o n t r i b u t i o n from p h o s p h o r u s d-orbitals. I n t h e a r e a o f t h e o r y and p h y s i c a l methods t h e r e h a s b e e n a s u g g e s t i o n t h a t five-membered r i n g s may p s e u d o r o t a t e v i a t o p s t r u c t u r e s p o s s e s s i n g a d i r a d i c a l five-membered

ring.

The i n t r o d -

u c t i o n o f o r t h o and p a r a s u b s t i t u e n t s t o a l l t h e p h e n y l r i n g s o f triphenylphosphine dramatically increases t h e b a s i c i t y , t h e r e s u l t i n g compounds b e i n g more b a s i c t h a n p i p e r i d i n e . F i n a l l y , I am v e r y p l e a s e d t o r e p o r t t h a t Dr. John Hobbs h a s a g r e e d t o become j o i n t S e n i o r R e p o r t e r from Volume 1 9 onwards.

B. J

.

Walker

Contents CHAPTER 1

Phosphines and Phosphonium Salts

D.M.

By

1

Allen

1

Phosphines

I. 1

1.1.1

From H a l o g e n o p h o s p h i n e s a n d O r g a n o metallic Reagents From M e t a l l a t e d P h o s p h i n e s By A d d i t i o n o f P - H t o U n s a t u r a t e d Compounds By R e d u c t i o n Miscellaneous Methods

1.1.2 1.1.3 1.1.4 1.1.5 1.2

3

Nucleophilic Attack a t Carbon Nucleophilic Attack a t Halogen N u c l e o p h i l i c A t t a c k a t O t h e r Atoms Miscellaneous Reactions

6 8 8

11 11 13 14

Halogenophosphines

17

2.1 2.2

17 19

Preparation Reactions

Phosphonium S a l t s

22

3.1 3.2

22

Preparation Reactions

4

p

5

Phosphirenes,

-Bonded

24

P h o s p h o r u s Compounds Phospholes,

and Phosphorins

References

CHAPTER 2

1 3

11

Reactions 1.2.1 1.2.2 1.2.3 1.2.4

2

1

Preparation

27 38

41

Pentaco-ordinated and Hexaco-ordinated Compounds By C.D.

Hall

1

Introduction

52

2

Structure,

52

3

Acyclic P h o s p h o r a n e s

55

4

Ring Containing Phosphoranes

58

4.1 4.2

58 65

5

Bonding and Ligand Reorganization

Monocyclic B i c y c l i c and T r i c y c l i c

Hexaco-ordinated References

P h o s p h o r u s Compounds

77

81

OrganophosphorusChemistry

viii CHAPTER 3

Phosphine Oxides and Related Compounds By B . J .

Walker

1

Introduction

83

2

P r e p a r a t i o n of Acyclic Phosphine Oxides

83

3

P r e p a r a t i o n of C y c l i c P h o s p h i n e O x i d e s

83

4

S t r u c t u r e and P h y s i c a l Aspects

85

5

Reactions a t Phosphorus

88

6

Reactions a t t h e Side-chain

90

7

Phosphine Oxide Complexes and E x t r a c t a n t s

99

References

CHAPTER 4

102

Tervalent Phosphorus Acids By 0 . Dahl

1

Introduction

104

2

Nucleophilic Reactions

104

2.1 2.2 2.3

104 107 107

3

A t t a c k on S a t u r a t e d Carbon Attack on Unsaturated Carbon Attack on Nitrogen, Chalcogen, o r Halogen

Electrophilic Reactions

110

3.1 3.2 3.3 3.4

110 116 119 126

Preparation Mechanistic Studies Use f o r N u c l e o t i d e S y n t h e s i s Miscellaneous

Reactions i n v o l v i n g Two-co-ordinate

5

Miscellaneous Reactions

129

References

129

CHAPTER 5

Quinquevalent Phosphorus Acids By R . S .

1

Edmundson

Phosphoric Acids and t h e i r D e r i v a t i v e s

134

1.1

134 135

1.2

2

Phosphorus

126

4

Synthesis Reactions and P r o p e r t i e s

P h o s p h o n i c a n d P h o s p h i n i c A c i d s a n d t h e i r D e r i v a t i v e s 151 2.1 2.2

Synthesis Reactions and P r o p e r t i e s

References

151 167 182

ix

Contents CHAPTER 6

Nucleotides and Nucleic Acids B y J.B.

Hobbs

1

Intrcauction

187

2

Mononucleotides

187

2.1 2.2

187 201

Chemical Synthesis Cyclic Nucleotides

3

Nucleoside

4

Oligo-

4.1 4.2 5

6

CHAPTER 7

Polyphosphates

and Poly-nucleotides

Chemical Synthesis Enzymatic Synthesis

203 216 216 238

Other Studies

245

5.1 5.2 5.3 5.4 5.5

245 248 254 263 278

Affinity Separation Affinity Labelling Post-synthetic Modification Sequencing and Cleavage Studies Metal C o m p l e x e s

A n a l y t i c a l Techniques and P h y s i c a l Methods

280

References

285

Ylides and Related Compounds B y B.J.

Walker

298

1

Introduction

2

Methylenephosphoranes

298

2.1 2.2

298

PreparatZon Reactions

2.2.1 2.2.2 2.2.3

and Structure

Alaehydes Ketones Miscellaneous Reactions

302

30 2 309 312

3

R e a c t i o n s of P h o s p h o n a t e A n i o n s

322

4

Selected Applications i n Synthesis

331

4.1 4.2 4.3 4.4 4.5 4.6

331 334 338 34 1 345 345

C a r o t e n o i d s , R e t i n o i d s a n d R e l a t e d Compounds a-Lactams L e u k o t r i e n e s a n d R e l a t e d Compounds M a c r o l i d e s a n d R e l a t e d Compounds Pheromones Miscellaneous Reactions

References

CHAPTER 8

356

Phosphazenes By C.W.

Allen

1

Introduction

364

2

Acyclic Phosphazenes

364

Organophosphorus Chemistry

X

3

Cyclophosphazenes

371

4 5

Cyclophospha(thia)zenes Miscellaneous Phosphazene-containing Ring Systems

377 378

6 7

Poly(ph0sphazenes)

380

Molecular Structures of Phosphazenes

385

References

387

CHAPTER 9

Physical Methods By J.C.

l'ebby

1

Theoretical Studies

394

2

Nuclear Magnetic Resonance Spectroscopy 2.1 Biological and Analytical Applications

397 397

2.2.1

2.5.1 J(PP) 2.5.2 J(P0) and J(PN) 2.5.3 J(PC) 2.5.4 J(PH) 2.6 Anisotropy, Magnetisation Transfer, Relaxation and CIDNP 2.7 Nuclear Quadrupole Resonance Electron Spin Resonance Vibrational Spectroscopy

40 1 402 402 402

4.1 4.2 4.3

405 405

2.5

4

5

Assignments Bonding Stereochemistry

Electronic Spectroscopy 5.1 5.2 5.3 5.4

6

397 397 397 398 399 399 399

2.3 2.4

3

Phosphorus-31

6 p of n1 and n2 compounds d p of n3 compounds 6p of n4 compounds 6p of n5 and n6 compounds 2.2.2 Carbon-13 Shift Reagents and Liquid Crystals Valence Isomerism, Restricted Rotation and Permutational Isomerism Spin-Spin Couplings

Absorption Spectroscopy Fluorescence Circular Dichroism Photoelectron and X-ray Spectroscopy

401 401

403 403 405 405

406 406 406 407 407 407

Diffraction

409

6.1

X-ray Diffraction

409

6.1.1

409 409 409 412 412

6.2

n 2 Compounds 6.1.2 n3 Compounds 6.1.3 n4 Compounds 6.1.4 n5 Compounds Electron Diffraction

xi

Contents 7

D i p o l e M o m e n t s , Kerr E f f e c t s , P o l a r o g r a p h y and Conductance

412

7.1 7.2

412 412

D i p o l e M o m e n t s a n d Kerr E f f e c t Polarography and Conductance

8

Mass S p e c t r o s c o p y

413

9

A c i d i t i e s , B a s i c i t i e s and Thermochemistry

413

10

11

Chromatography

415

10.1 10.2 10.3

415 416

Gas L i q u i d c h r o m a t o g r a p h y Thin Layer Chromatography Liquid Chromatography

416

Kinetics

416

References

417

AUTHOR INDEX

425

Abbreviations * AIBN CIDNP CNDO CP DAD DBN DBU DCC DIOP DMF DMSO DMTr EDTA E.H.T. ENU FID g.1.c.-m.s HMPT h.p.1.c. i.r. L.F.E.R. MIND0 MMT r MO MS-C1 MS-nt MS-tet WBS n.q.r. p.e. PPA SCF TBDMS TDAP TFAA Tf 20 THF Thf ThP TIPS t.1.c. TPS-C 1 TPS-nt TPS-te t TsOH U.V.

bisazoisobutyronitrile Chemically Induced Dynamic Nuclear Polarization Complete Neglect of Differential Overlap cyclopentadienyl diethy: azodicarboxylate 1,5-diazabicycl0[4.3.C]non-5-ene 1,5-diazabicyclo[ 5 . 4 .O jundec-5-ene dicyclohexylcarbodi-imide

[(L,?-dimethyl-1,3-dioxolan-4,5-diyl)bis-(methylene)] bisidiphenylphosphine) dimethylformamide dimethyl sulphoxide 4,4‘-dimethoxytrityl e t h y l e n e d i a m i n e t e t r a - a c e t i c acid Extended HKckel Treatment N-ethyl-N-nitrosourea Free Induction Decay gas-liquid chromatography-mass spectrometry hexamethylphosphortriamide

high-performance liquid chromatography infrared Linear Free-Energy Relationship Modified Intermediate Neglect of Differential Overlap 4-monomethoxytrityl Molecular Orbital mesitylenesulphonly chloride mesitylenesulphonly-3-nitro-l,2,4-triazole mesitylenesulphonyltetrazole

A!-bromosuccinimide nuclear quadrupole resonance photoelectron polyphosphoric acid Self-consistent Field t-butyldimethylsilyl tris(diethy1amino)phosphine

trifluoroacetic acid t r i f l u o r e m e t h a n e s u l p h o n i c anhydride

tetrahydrofuran 2-tetrahydrofuranyl 2-tetrahydropyranyl tetraisopropyldisiloxanyl

thin-layer chromatography chloride tri-isopropylbenzenesulphonyl-3-nitro-l,Z,4-triazole tri-isopropylbenzenesulphonyl

tri-isopropylbenzenesulphonyltetrazole

toluene-p-sulphonic acid ultraviolet

“Abbreviations used in Chapter 6 are detailed in Biochem. J.,1970,120,449 and 1978,171,i

Phosphines and Phosphonium Salts BY D. W. ALLEN

1 Phosohines

1.1 P r e p a r a t i o n

1.1.1 From Halogenophosphines and O r g a n o m e t a l l i c R e a g e n t s . g r e a t l y improved r o u t e t o t r i s - t - b u t y l p h o s p h i n e

A

i s a f f o r d e d by

t h e a d d i t i o n of a benzene s o l u t i o n of p h o s p h o r u s t r i c h l o r i d e t o a pentane s o l u t i o n of t - b u t y l l i t h i u m .

D i r e c t m e t a l l a t i o n of

benzenechromiumtricarbonyl w i t h b u t y l l i t h i u m a t - 3 O o C , f o l l o w e d by t r e a t m e n t w i t h c h l o r o d i p h e n y l p h o s p h i n e , p r o v i d e s a more d i r e c t r o u t e t o d i p h e n y l b e n c h r o t e n y l p h o s p h i n e ( 1). 2 The r e a c t i o n s o f p e n t a d i e n y l l i t h i u m w i t h h a l o g e n o p h o s p h i n e s have g i v e n a s e r i e s of pentadienylphosphines, e.g.

(2),

i s o l a t e d as t h e corresponding

o x i d e s a f t e r t r e a t m e n t w i t h hydrogen p e r o x i d e . 3

L i t h i a t i o n of

o-bromophenyldimethylarsine w i t h b u t y l l i t h i u m , f o l l o w e d by t r e a t m e n t w i t h p h o s p h o r u s t r i c h l o r i d e , g i v e s t h e new p o l y d e n t a t e l i g a n d ( 3 ) , b u t i n o n l y 15% y i e l d . 4

The r e a c t i o n of t h e

a - d i a z o m e t h y l l i t h i u m r e a g e n t ( 4 ) w i t h chlorodi(isopropy1amino)p h o s p h i n e l e a d s t o t h e f i r s t a - d i a z o m e t h y l p h o s p h i n e , ( 5 1 , which is s t a b l e t o d i s t i l l a t i o n . P h o t o l y s i s of ( 5 ) g e n e r a t e s t h e p h o s p h i n o c a r b e n e ( 6 1 , which is found t o b e more s t a b l e t h a n might have b e e n e x p e c t e d , b e h a v i n g e i t h e r a s a p h o s p h o r u s v i n y l y l i d e o r a s a X 5 - p h o s p h a - a c e t y l e n e . ' 6 The h e t e r o c y c l i c s y s t e m s ( 7 a r e formed i n t h e r e a c t i o n s o f t r i p h e n y l s i l y l l i t h i u m w i t h t h e corresponding h e t e r o c y c l i c c h l o r o p h o s p h i n e s .

7

C o n v e n t i o n a l a r y l G r i g n a r d p r o c e d u r e s have b e e n u s e d i n t h e s y n t h e s i s of t h e new p h o s p h i n e s ( 8 ) , 8

(9)

9

and

The

r e a c t i o n s of chlorodiphenylphosphine with Grignard r e a g e n t s d e r i v e d from c h l o r o m e t h y l s i l a n e s have g i v e n a r a n g e of p h o s p h i n e s b e a r i n g a s i l i c o n - c o n t a i n i n g s u b s t i t u e n t o r back-bone, ( l l ) . l l The t r i d e n t a t e p h o s p h i n e l i g a n d ( 1 2 ; R =

e .g. Me) i s formed o n

t r e a t m e n t of t h e p r e c u r s o r h a l o g e n o p h o s p h i n e ( 1 2 ; R = C l ) w i t h a n e x c e s s o f methylmagnesium c h l o r i d e . l 2 The r e a c t i o n s of t h e u n s a t u r a t e d dichloro(amino)phosphine

(13) with a range of a l k y l

G r i g n a r d r e a g e n t s g i v e r i s e t o a m i x t u r e of t h e r e a r r a n g e d 1

2


Me3Si-C-Li

(Pr'2N12P-C

II

II

-Si Me,

(Pri2Nl2P-t-SiMe3

N2

N2

(4)

(7) R'=BuS, But, PhCH2 or Ph 2 R = H or Me n = O or 1

( 5 )

(6)

( 8 )

(9)

,CH,PR, RP

Ph,PC H2Si Me,CH=C H

But

MeCH=CHN

0

'

PCL,

(13)

Me ' c R2P0

=N Bu+

HcH

\

CH2PR2

Me >C=CHNHR R2P

1: Phosphines and Phosphonium Salts phosphines 1.1.2

(

14) and

(

3

1 5 ) . l3

P r e p a r a t i o n o f P h o s p h i n e s from M e t a l l a t e d P h o s p h i n e s . -

It

h a s b e e n shown t h a t p h o s p h i d e a n i o n s may be g e n e r a t e d from p r i m a r y and s e c o n d a r y p h o s p h i n e s u n d e r a q u e o u s c o n d i t i o n s u s i n g concent r a t e d a q u e o u s a l k a l i i n DMSO o r o t h e r d i p o l a r a p r o t i c s o l v e n t s . A l k y l a t i o n o f t h e r e s u l t i n g a n i o n s h a s g i v e n a r a n g e of s e c o n d a r y 14

and t e r t i a r y p h o s p h i n e s .

The g e n e r a t i o n of t h e b i s m e t a l l o p h o s p h i d e r e a g e n t s ( 1 6 1 by l i t h i u m - i n d u c e d c l e a v a g e of p h e n y l g r o u p s from a,w-bis(dipheny1phosphino)alkanes i s g r e a t l y f a c i l i t a t e d by i r r a d i a t i o n w i t h u l t r a s o u n d . l 5 The d i r e c t i o n of t h e l i t h i u m i n d u c e d c l e a v a g e of t h e h e t e r o c y c l i c d i p h o s p h i n e ( 1 7 ) d e p e n d s on t h e n a t u r e of t h e non-phosphorus s u b s t i t u e n t s . When R = P h , P-P t c l e a v a g e t a k e s p l a c e , w h e r e a s when R = Bu , c l e a v a g e o f a n exoc y c l i c p h e n y l g r o u p o c c u r s , r e s u l t i n g i n t h e f o r m a t i o n of t h e c y c l i c a n i o n ( 1 8 ) , which u n d e r g o e s t h e e x p e c t e d p r o t o n a t i o n a n d a l k y l a t i o n r e a c t i o n s a t p h o s p h o r u s on s u b s e q u e n t t r e a t m e n t w i t h e l e c t r o p h i l i c r e a g e n t s . l 6 T r e a t m e n t of 2 , 4 - b i s ( c h l o r o m e t h y l ) pyrazolium s a l t s with l i t h i u m diphenylphosphide a f f o r d s t h e p y r a z o l y l d i p h o s p h i n e ( 1 9 ) , which i s f o u n d t o b e v e r y e a s i l y o x i d i s e d by a i r a n d i s t h e r e f o r e s t o r e d i n t h e form of a n i c k e l complex from which it c a n b e f r e e d by c y a n i d e i o n . " The r e a c t i o n of t h e d i l i t h i o d i p h o s p h i d e ( 2 0 ) w i t h w h i t e p h o s p h o r u s g e n e r a t e s t h e l i t h i o p h o s p h i d e (21) d e r i v e d from t h e 2,3-dihydro-lHb e n z o t r i p h o s p h o l e s y s t e m . l8

The [ 2 + 1 1 c y c l o c o n d e n s a t i o n o f 1,2-dichloropropane with d i l i t h i u m t-butylphosphide y i e l d s t h e 19 s u r p r i s i n g l y s t a b l e p h o s p h i r a n e ( 2 2 1. Baudler's group h as co n ti n u ed t o i n v e s t i g a t e t h e u s e s o f i n o r g a n i c p o l y p h o s p h i d e s , e . g . L i 3 P 7 and L i 2 P 1 6 , i n t h e s y n t h e s i s 20,21

of p o l y c y c l i c o r g a n o p h o s p h i n e s o f e v e r - i n c r e a s i n g c o m p l e x i t y .

I n r e l a t e d work, t h e f i r s t bicyclo[3,2,0]heptaphosphine, P7But5, ( 2 3 ) , h a s been i s o l a t e d from t h e r e a c t i o n of b u t y l d i chlorophosphine , phosphorus t r i c h l o r i d e

, and

magnesium. 2 2

The

r e a c t i o n s of various l i t h i u m phosphides with dichlorodiorganos i l a n e s have g i v e n a r a n g e of c y c l i c s i l y l p h o s p h i n e s . 23-26 four-membered

The

r i n g s y s t e m ( 2 4 ) , i s o l a t e d i n 76% y i e l d i n t h e

r e a c t i o n of m o n o l i t h i u m p h o s p h i d e w i t h di-t-butyldichlorosilane, h a s been u s e d f o r t h e s y n t h e s i s of o t h e r , more complex, s i l y l phosphines bearing t h i s s t r u c t u r a l u n i t , e.g.

(25).

24

23

4


RT_1R PhPLi(CH&,PLi (16) n = 2

Ph

-6

PhP(17 1

PPh

Bu*

But

I 7

PhP-P-

R = But or Ph

(18)

Ph

CH2PPh, W

Ph2PCH20N

P P Li

H

Ph (21 1

(201

(19 1

But

But

I P - - P- P But I .I ButP 'p' P - P But

(23)

(22)

Ph,P

Ph,P

I

Me,N -CH

I

n NH NH

W

(27)

fH=c

n

HN

2c

CHzSMe (28)

(241

(26)

(25)

CH,PPh,

But,Si-PH I I HP-si e u t 2

(29)

Nup (30)

5

I : Phosphines and Phosphonium Salts Sodium a n d p o t a s s i u m o r g a n o p h o s p h i d e r e a g e n t s c o n t i n u e t o b e employed i n t h e s y n t h e s i s of new p h o s p h i n e s .

The t e t r a d e n t a t e

s y s t e m ( 2 6 ) i s formed i n t h e r e a c t i o n s of sodium d i o r g a n o p h o s p h i d e A series r e a g e n t s w i t h N , N ’ -bis(2-chloroethyl)ethylenediamine.27 o f phosphino-functionalised m a c r o c y c l i c s y s t e m s , e . g . ( 2 7 1 , h a s b e e n p r e p a r e d by t h e r e a c t i o n s o f t h e r e l a t e d 2 - c h l o r o e t h y l a m i n o d e r i v a t i v e s w i t h p o t a s s i u m d i p h e n y l p h o s p h i d e . 2 8 The r e a c t i o n between p o t a s s i u m d i p h e n y l p h o s p h i d e and c h l o r o f o r m h a s been explored as a p o s s i b l e r o u t e t o tris(diphenylphosphino)methane, but without success. isolated in

ca

However, bis(dipheny1phosphino)methane

is

40% y i e l d from t h e above r e a c t i o n c o n d u c t e d i n

l i q u i d ammonia.2g

New c h i r a l p h o s p h i n e s , e . g .

( 2 8 1 , d e r i v e d from

L - c y s t e i n e , L-methionine,

and D-penicillamine,

have been p r e p a r e d

by t h e m e s y l a t e - p o t a s s i u m

o r g a n o p h o s p h i d e r o u t e . 30

The r e a c t i o n

of monopotassium p h o s p h i d e w i t h allyl(2-chloroethy1)amine

gives

t h e p r i m a r y p h o s p h i n e ( 2 9 ) which, on t r e a t m e n t w i t h formaldehyde i n e t h a n o l , is c o n verted i n t o t h e b i c y c l i c system ( 3 0 ) .

Curiously,

w h i l e t h i s compound reacts n o r m a l l y w i t h s u l p h u r t o p r o d u c e t h e

r e l a t e d p h o s p h i n e s u l p h i d e , t h e r e a c t i o n w i t h iodomethane r e s u l t s i n q u a t e r n i z a t i o n a t n i t r o g e n . 31

Baudler’ s group h a s r e p o r t e d a

number of s t u d i e s o f t h e c l e a v a g e r e a c t i o n s undergone by t h r e e membered p h o s p h o r u s h e t e r o c y c l e s on t r e a t m e n t w i t h p o t a s s i u m , and o f t h e s y n t h e t i c u t i l i t y of t h e r e s u l t i n g p h o s p h i d e a n i o n s . e.g.,

the cyclotriphosphine (31; X

=

Thus,

But) undergoes cleavage t o

form t h e p h o s p h i d e ( 3 1 ; X = K ) , 3 2 h y d r o l y s i s o f which y i e l d s t ( 3 1 ; X = HI which i s t h e r m a l l y s t a b l e , 3 3 u n l i k e ( 3 1 ; X = Bu 1. The r e a c t i o n of ( 3 1 ; X = K ) w i t h c h l o r o t r i m e t h y l s t a n n a n e y i e l d s t h e s t a n n y l p h o s p h i n e ( 3 1 ; X = SnMe,), which on s u b s e q u e n t t r e a t ment w i t h dichloro(methyl)phosphine, is c o n v e r t e d i n t o t h e

bis(cyc1otriphosphino)phosphine ( 3 2 ) . 34 I n r e l a t e d work, i t h a s been shown t h a t p o t a s s i u m - i n d u c e d c l e a v a g e o f ( 3 3 ; X = BNPri, 01” CMe,) p r o c e e d s w i t h r i n g - o p e n i n g c l e a v a g e of t h e phosphorusp h o s p h o r u s bond, w h e r e a s t h e c o r r e s p o n d i n g r e a c t i o n of ( 3 3 ; X = NPrl) proceeds w i t h c l e a v a g e of t h e phosphorus-nitrogen bond.35y36 I n t e r e s t c o n t i n u e s i n t h e a p p l i c a t i o n of r e a g e n t s d e r i v e d from p h o s p h i n e s by l i t h i a t i o n a t c a r b o n of one of t h e p h o s p h o r u s substituents.

The p r o p y n y l p h o s p h i n e ( 3 4 ) is m e t a l l a t e d o n t r e a t -

ment w i t h b u t y l l i t h i u m t o g i v e ( 3 5 ) , which g i v e s r i s e t o t h e t e t r a p h o s p h a a l l e n e ( 3 6 ) on s u b s e q u e n t r e a c t i o n w i t h c h l o r o d i p h e n y l p h o s p h i n e . 37

The B-hydroxyethylphosphines

(37

and ( 3 8 ) are


6

formed i n t h e r e a c t i o n s o f lithiomethyldiphenylphosphine w i t h hexaf l u o r o a ~ e t o n eand ~ ~ di-t-butylketone

39 r e s p e c t i v e l y

.

T r e a t m e n t of t h e d i a l k y l a m i n o p h o s p h i n e s ( 3 9 ) w i t h b u t y l l i t h i u m and N,N'-tetramethylethylenediamine r e s u l t s i n predominant l i t h i a t i o n at carbon;

however, d i r e c t d i s p l a c e m e n t o f a d i m e t h y l -

amino g r o u p from p h o s p h o r u s is a c o m p e t i n g p r o c e s s . 4 0

Further

examples have been g i v e n of t h e p r e p a r a t i o n of p h o s p h i n o m e t h y l d e r i v a t i v e s o f metals

e . g. t i t a n i u m , 4 1 z i r c o n i u m , 4 1 , 4 2 h a f n i u m , 42

and a l u m i n i u m , 4 3 from t h e r e a c t i o n s o f l i t h i o m e t h y l d i o r g a n o p h o s p h i n e s w i t h a p p r o p r i a t e metal h a l i d e s .

The r e a g e n t l i t h i u m

trisCdimethy1phosphino)methanide h a s been found t o b e v e r y u s e f u l for t h e p r e p a r a t i o n o f c o o r d i n a t i o n complexes of t h e main g r o u p e l e m e n t s , e . g . aluminium44 a n d t i n , 4 5 i n which a l l l i g a t e d atoms are p h o s p h o r u s . M e t a l l a t i o n r e a c t i o n s a t c a r b o n of c o o r d i n a t e d p h o s p h i n e s have been r e v i e w e d .

46

1 . 1 . 3 P r e p a r a t i o n o f P h o s p h i n e s by Addit i o n of P-H t o U n s a t u r a t e d Compounds.-

The a d d i t i o n r e a c t i o n s of P-H compounds t o C=O a n d

C=N s y s t e m s have been r e v i e w e d . 4 7

A modified procedure f o r t h e

b a s e - c a t a l y s e d a d d i t i o n of d i p h e n y l p h o s p h i n e t o a c r y l o n i t r i l e h a s b e e n d e v e l o p e d , and s u b s e q u e n t l y u s e d i n t h e s y n t h e s i s o f

.

2 - ~ y a n o p r o p y l d i p h e n y l p h o s p h i n e , (40 ) 48

The a d d i t i o n o f

b i s ( p h o s p h i n 0 ) m e t h a n e t o d i e t h y l ( v i n y 1 ) p h o s p h i n e y i e l d s t h e new l i g a n d (41), c a p a b l e of b r i d g i n g t w o m e t a l c e n t r e s . 4 9 A study of t h e r a d i c a l - i n i t i a t e d a d d i t i o n of s e c o n d a r y p h o s p h i n e s t o a series o f d i ( a l l y 1 ) o r g a n o p h o s p h i Q e s h a s r e v e a l e d t h a t t h e r e a c t i o n is i n h i b i t e d by t h e p r e s e n c e o f b u l k y s u b s t i t u e n t s i n t h e s e c o n d a r y phosphine. I n c o n t r a s t , dimethylphosphine r e a d i l y a d d s t o t h e t e r m i n a l d o u b l e bonds o f w - a l k e n y l p h o s p h i n e s t o form new p o l y d e n t a t e p h o s p h i n e s , e . g . ( 4 2 ) . 5 0 A series o f n o v e l 1,4-diphosphac y c l o h e x a n e s e . g . ( 4 3 ) , i n which t h e bonds from p h o s p h o r u s t o t h e e x o c y c l i c s u b s t i t u e n t s a r e o f o p p o s i t e p o l a r i t y , is a c c e s s i b l e from t h e r a d i c a l - i n i t i a t e d a d d i t i o n o f t r i m e t h y l s i l y l p h o s p h i n e t o d i e t hy l a m i n o d i ( viny1)phosphine. 51

Formation of a h e t e r o c y c l i c

p h o s p h i n e is a l s o o b s e r v e d i n t h e a d d i t i o n of p h e n y l p h o s p h i n e t o t h e amino-enone

(441, which r e s u l t s i n t h e b i c y c l i c s y s t e m (45),

together with other products.

52

7

I : Phosphines and Phosphonium Salts

(32I

(311

(331

Ph,P Ph2PC=CMe

n Bu Li

---+

Ph2PCH C ( C F3l2 0 H

(37)

(

Ph2PCH2CH(MelCN

(401

(43l

e3

)But2

38 I

[(Et2PCH,CH,)2P],CH2 (41 1

n

pw ps

Ph,PCH,C(OH

\

/c=c=c \

Ph2P

(351

(34)

Et2

P h 2 P C G CCH,Li

Ph2PCI

PPh,

ZCH2P( NMe,),

(39)Z=Ph or Me3Si

P[(CH,),PMe2]3

(421

8

Organophosphorus Chemistry 1.1.4 P r e p a r a t i o n of P h o s p h i n e s by R e d u c t i o n . -

A procedure f o r

t h e r e d u c t i o n of p h o s p h i n e o x i d e s u s i n g t r i c h l o r o s i l a n e i n i n e r t

h a l o g e n a t e d hydrocarbon s o l v e n t s h a s been d e s c r i b e d i n a p a t e n t . 5 3

T r i c h l o r o s i l a n e h a s a l s o been u s e d for t h e s t e r e o s p e c i f i c r e d u c t i o n of a series of p r e v i o u s l y r e s o l v e d c h i r a l phosphine o x i d e s t o y i e l d b o t h (R) and ( S )

forms of t h e c h i r a l b i n a p h t h y l

d i p h o s p h i n e s ( 4 6 ) , 5 4 and a l s o i n t h e f i n a l s t e p o f t h e s y n t h e s i s o f t h e p h o s p h a j u l o l i d i n e s y s t e m ( 4 7 ) by r e d u c t i o n of t h e corresponding phosphine oxide.

An _X-ray s t u d y o f ( 4 7 ) h a s shown t h a t

t h e geometry a t p h o s p h o r u s i s p y r a m i d a l , i n s p i t e o f t h e c o n s t r a i n t s imposed by t h e r i n g s y s t e m . 5 5

P r o c e d u r e s for t h e

r e d u c t i o n o f phosphine oxides u s i n g combinations o f a t r i a l k y l aluminium a n d a b o r o n t r i h a l i d e o r e s t e r a t 200-400" d e v e l o p e d . 56 ' 5 7

have b e e n

Combination of l i t h i u m aluminium h y d r i d e w i t h

c e r i u m ( I I 1 ) c h l o r i d e g i v e s a r e a g e n t which r e d u c e s p h o s p h i n e o x i d e s i n good y i e l d u n d e r m i l d c o n d i t i o n s , b u t which i s u n f o r t u n a t e l y n o t s t e r e o s p e c i f i c . 58

I n c o r p o r a t i o n o f sodium

b o r o h y d r i d e i n t o t h e above s y s t e m r e s u l t s i n t h e i s o l a t i o n o f phosphine-borane

a d d u c t s ( 4 8 ) which are u s e f u l r e a g e n t s f o r t h e

s y n t h e s i s o f new p h o s p h i n e s .

Thus, e . g . ,

metallation of t h e

adduct (49) with sec-butyllithium r e s u l t s i n t h e lithiomethyl d e r i v a t i v e (50), which, on t r e a t m e n t w i t h c o p p e r ( I1 ) c h l o r i d e , g i v e s t h e d i p h o s p h i n o e t h a n e d e r i v a t i v e (51). The b o r a n e p r o t e c t i n g 59

g r o u p i s e a s i l y removed o n t r e a t m e n t w i t h d i e t h y l a m i n e . Reduction of phosphine o x i d e s under mild conditions is also a f f o r d e d by sodium aluminium h y d r i d e i n c o m b i n a t i o n w i t h aluminium c h l o r i d e o r a mixed sodium-aluminium c h l o r i d e r e a g e n t . 6 0 9 6 1 L i t h i u m aluminium h y d r i d e h a s been u s e d t o c l e a v e a f u r f u r y l g r o u p from a r a n g e o f f u r f u r y l p h o s p h o n i u m s a l t s , which are e a s i l y a c c e s s i b l e by t h e r e a c t i o n s o f trimethylsilylphosphines w i t h f u r f u r y l bromide.

Thus, e . g . ,

t h e r e a c t i o n of d i p h e n y l t r i m e t h y l -

s i l y l p h o s p h i n e y i e l d s t h e s a l t (52) which, o n t r e a t m e n t w i t h l i t h i u m aluminium h y d r i d e , is c o n v e r t e d i n t o t h e p h o s p h i n e ( 5 3 ) .

62

L i t h i u m aluminium h y d r i d e h a s a l s o been u s e d f o r t h e p r e p a r a t i o n o f p r i m a r y and s e c o n d a r y p h o s p h i n e s which b e a r b u l k y d i a l k y l a m i n o 63,64 s u b s t i t u e n t s , e.g. (54). 1 . 1 . 5 M i s c e l l a n e o u s Methods o f P r e p a r i n g P h o s p h i n e s . -

Methods f o r

t h e p r e p a r a t i o n o f c h i r a l p h o s p h i n e s have been r e v i e w e d . 6 5

A new

r o u t e t o c h i r a l p h o s p h i n e s i s a f f o r d e d by t h e r e a c t i o n s o f b u l k y o r g a n o l i t h i u m r e a g e n t s w i t h o p t i c a l l y a c t i v e menthyl o r b o r n y l

esters ( 5 5 ) o f phenylphosphonous a c i d which p r o c e e d w i t h a h i g h

I: Phosphines and Phosphonium Salts

(46)A r = P h , p-tolyl

9

(471

(48)

or p - 6 d ~ ~ t - 1 ~

Ph,PCH,

i

%

Ph,PCH,Li

Ph2PCH2CH2PPh2

I

BH,

BH3

Ph,PCH (52)

2o

R’*N P H R ~ 1

(53)

c

BH3

(54)R.H, Pr’

, But

or

Me3S i 2 R = H IBut, or NPrZi

,OR’ PhP

/

PhP

‘OR’

\

R2

O*O

OR’

H--)L~H Ph2P

1

( 5 5 ) R = bornyl or menthyl

( 56

1

PPh2

(57)


10

degree of asymmetric induction to give differing amounts of the diastereoisomeric phosphinous acid esters (56). Subsequent reactions of these with a second organolithium reagent yield chiral phosphines 66 Chiral polymer -bound phosphines based on the well-established DIOP system have been prepared by copolymerisation of the chiral, unsaturated phosphine (571, which is accessible from DIOP by acid-catalysed ring-opening of the ketal unit, followed by formation of the acetal with 2-vinylbenzaldehyde.67 The reaction of white phosphorus with a mixture of 2,4,6tri(t-buty1)bromobenzene and 2,4,6-tri-(t-butyl)phenyllithium leads to the predominant formation of the bicyclotetraphosphine Three diastereoisomeric forms of the macrocyclic ( 5 8 ) .68 tetraphosphine (59) have been isolated in the fprm of palladium complexes from the palladium(I1) template-assisted cyclocondensation of 1,2-bis(methylphosphino)ethane with 1,2-bis(ch10romethyl)benzene.~~ A range of new hybrid P,N-donor ligands, e.g. (601, has been prepared utilising conventional functional group transformations of 2-aminophenyldiphenylphosphine (and its oxide), 2-diphenylphosphinobenzaldehyde, and 2-diphenylphosphinobenzoic acid.70 The reactions of the mixture of isomeric secondary phosphines formed on addition of phosphine to 1,5-cyclooctadiene with alkyl halides, followed by treatment of the intermediate phosphonium salts with sodium hydride, lead to new bicyclic terxiary phosphines, e.g. (61). The corresponding reactions with perfluoroalkyl halides lead to mixtures of isomeric PP-diphosphines and not to the expected p e r f l u o r o a l k y l p h o s p h i n e s . 71 Various 72 routes to 1,3,2,4-diazaphosphaboretidines (62) have been studied. Haloacylphosphines, e.g. (63), have been prepared by the reactions of trimethylsilylphosphines with haloacyl halides. In general, these compounds are found to be thermally unstable, but can be 73-75 studied in the form of the related transition metal complexes. Studies of the effect of various catalysts on the formation of tris(hydroxymethy1)phosphine from formaldehyde and phosphine have been reported.76 ’77 The reaction between dimethylaluminium hydride and methylphenylphosphine leads to the elimination of hydrogen with the formation of the aluminophosphine Me,AlPMePh, 78 which is reported t o exist as a trimer in benzene solution.

.

1: Phosphines and Phosphonium Salts

11

1 . 2 R e a c t i o n s of P h o s p h i n e s

1 . 2 . 1 N u c l e o p h i l i c A t t a c k a t C a r b o n . - The r e a c t i o n s o f s i l y l a m i n o p h o s p h i n e s w i t h c a r b o n d i s u l p h i d e r e s u l t i n t h e f o r m a t i o n of t h e b e t a i n e s ( 6 4 ) , no c l e a v a g e o f , o r i n s e r t i o n i n t o , P-N o r Si-N b o n d s b e i n g ~ b s e r v e d . ~ ’The s t a b i l i s e d y l i d e ( 6 5 ) i s f o r m e d i n t h e r e a c t i o n of t r i b u t y l p h o s p h i n e w i t h c a r b o n d i s e l e n i d e .

80

F u r t h e r e x a m p l e s o f e n a n t i o s e l e c t i v e n u c l e o p h i l i c a d d i t i o n of p h o s p h i n e s t o c o o r d i n a t e d d i e n e s h a v e b e e n d e s c r i b e d . 81

Treat-

ment o f t h e 1:l a d d u c t of t r i b u t y l p h o s p h i n e w i t h e t h o x y a c e t y l e n e w i t h a s e c o n d mole o f t h e a c e t y l e n e g i v e s a 1 : 2 a d d u c t of u n c e r t a i n s t r u c t u r e , which, on r e a c t i o n w i t h bromoethane, i s 82 c o n v e r t e d i n t o t h e phosphonium s a l t ( 6 6 ) . 1.2.2 N u c l e o p h i l i c Attack a t Halogen.-

F u r t h e r a p p l i c a t i o n s of

t e r t i a r y phosphine-tetrahalogenomethane have been d e s c r i b e d .

and r e l a t e d “ r e a g e n t s ”

The r e a c t i o n s o f p r i m a r y a n d s e c o n d a r y

a l c o h o l s w i t h p o t a s s i u m c a r b o x y l a t e s i n t h e p r e s e n c e of t h e

triphenylphosphine-tetrachloromethane r e a g e n t l e a d t o t h e f o r m a t i o n of e s t e r s i n good y i e l d . However, a p p l i c a t i o n of t h i s p r o c e d u r e t o t h e e s t e r i f i c a t i o n of ( - ) - 2 - o c t a n o l w i t h p o t a s s i u m b e n z o a t e w a s f o u n d t o p r o c e e d w i t h b o t h i n v e r s i o n and r a c e m i s a t i o n a t t h e c h i r a l c a r b o n atoms.83 formed

via

I t h a s now b e e n shown t h a t 6-hydroxyamides

t h e c o n d e n s a t i o n o f c a r b o x y l i c a c i d s and a m i n o a l c o h o l s ,

i n t h e p r e s e n c e of triphenylphosphine-tetrachloromethane,undergo c y c l i s a t i o n t o o x a z o l i n e s w i t h complete i n v e r s i o n o f t h e c a r b i n o l centre.84 The y l i d e (6’7) i s r e p o r t e d t o be f o r m e d i n the r e a c t i o n cf p-nitrophenylsulphenamide

with t h e triphenylphosphine-

t e t r a c h l o r o m e t h a n e c o m b i n a t i o n . 85

Polymer-bound d i h a l o m e t h y l e n e y l i d e s a r e formed i n t h e r e a c t i o n s o f polymer-bound t r i a r y l -

p h o s p h i n e s w i t h t e t r a h a l o g e n o m e t h a n e s . 86 Polymer-bound p h o s p h i n e h a l o g e n r e a g e n t s h a v e b e e n shown t o b e c o n v e n i e n t r e a g e n t s f o r t h e c o n v e r s i o n of e p o x i d e s t o h a l o h y d r i n s u n d e r m i l d a n d n o n - a c i d i c c o n d i t i o n s , t h e procedure r e q u i r i n g only a f i l t r a t i o n and e v a p o r a t i o n s t a g e f o r p r o d u c t i s o l a t i o n . 87

The t r i b u t y l p h o s p h i n e t e t r a c h l o r o m e t h a n e c o m b i n a t i o n h a s b e e n shown t o p r o m o t e t h e

c o n v e r s i o n of (€I)-(+)-a-phenylneopentyl

a l c o h o l i n t o ( S ) - ( ->-a-

p h e n y l n e o p e n t y l c h l o r i d e w i t h t h e greatest d e g r e e of stereos p e c i f i c i t y y e t r e c o r d e d . 88

Dichlorophosphoranes are formed i n

t h e r e a c t i o n s of t e r t i a r y p h o s p h i n e s w i t h n i t r o g e n t r i c h l o r i d e . 89 The r e a c t i o n o f t r i p h e n y l p h o s p h i n e w i t h t h e g e m i n a l d i c h l o r o

Cl) i n t h e p r e s e n c e o f water l e a d s t o t h e f o r m a t i o n o f ( 6 8 ; R = H). However, i n t h e a b s e n c e o f water, t h e

compound ( 6 8 ; R

=


12

(59)

(60)

RpG R’N-BR,

I

I

CCI,COPR,

MeP-NR’

(61)

( 6 2 1 R’= Me or But 2 R = F,CI, Br,Me,

(63 1 R = C6H,,

E t or Ph Me

OE t

I+ Me3SiNR P - CS, I

+I 6u3PC=CH-C =C H E t

I

OEt

Me

( 6 4 ) R = Me3Si or Me

(651

Br-

(661

(69 1

(67)

+ R3P-

BH,CN

(70)

Ph,PC H,PP h,

4

BH3

(71)

-

I

I : Phosphines and Phosphoniurn Salts

13

a l k e n e ( 6 9 ) i s formed, p o s s i b l y i m p l y i n g t h e involvement of a carbene intermediate.

90

1 . 2 . 3 N u c l e o p h i l i c A t t a c k a t O t h e r Atoms.-

The r e a c t i o n o f t e r t i a r y

p h o s p h i n e s w i t h sodium b o r o h y d r i d e and i o d i n e i n THF p r o v i d e s a new r o u t e t o p h o s p h i n e - b o r a n e a d d u c t s . 91

The cyanoborane a d d u c t s ( 7 0 ) are s i m i l a r l y formed i n t h e r e l a t e d r e a c t i o n s w i t h sodium

.

cyanoborohydride 92

The react i o n of b i s ( d i p h e n y l p h o s p h i n o )methane

w i t h sodium b o r o h y d r i d e and i o d i n e p r o v i d e s t h e monoborane a d d u c t

( 7 1 ) , whereas t h e corresponding r e a c t i o n with iodoborane r e s u l t s i n t h e formation of t h e c y c l i c salt ( 7 2 ; g

salts (72;

J-I

= 2-4)

=

l ) . 9 3 The r e l a t e d

have been p r e p a r e d by t h e r e a c t i o n s o f

a ,w-bis ( d i p h e n y l p h o s p h i n o ) a l k a n e s w i t h t h e dimet h y l s u l p h i d e - b o r a n e

a d d u c t i n t h e p r e s e n c e of i o d i n e .

94

Diethoxytriphenylphosphorane ( t h e p r o d u c t o f i n s e r t i o n o f triphenylphosphine i n t o diethyl peroxide) f i n d s use as a mild, n e u t r a l r e a g e n t which i n i t i a t e s c y c l o d e h y d r a t i o n o f N- and Cs u b s t i t u t e d 6 - a m i n o a l c o h o l s t o form a z i r i d i n e s i n e x c e l l e n t y i e l d , w i t h t h e e x p e c t e d c o m p l e t e r e t e n t i o n o f c o n f i g u r a t i o n a t t h e amino carbon. 95

The r e l a t e d phosphorane d e r i v e d f rom a polymer-bound

t r i a r y l p h o s p h i n e a c t s a s an e f f i c i e n t c y c l o d e h y d r a t i o n r e a g e n t 96 f o r t h e c y c l i s a t i o n of s i m p l e a , L O - d i o l s t o c y c l i c e t h e r s . Second o r d e r k i n e t i c s have been o b s e r v e d f o r oxygen t r a n s f e r from a r s e n i c t o p h o s p h o r u s i n t h e r e a c t i o n between t r i p h e n y l a r s i n e o x i d e and t r i p h e n y l p h o s p h i n e i n t h e m o l t e n s t a t e . 9 7

A second

o r d e r r a t e l a w h a s a l s o been o b s e r v e d i n t h e o x i d a t i o n of t r i p h e n y l p h o s p h i n e ( a n d a l s o t r i p h e n y l a r s i n e and t r i p h e n y l s t i b i n e ) by p o t a s s i u m p e r o x o d i p h o s p h a t e , and a mechanism i n v o l v i n g n u c l e o p h i l i c a t t a c k a t oxygen s u g g e ~ t e d . ’ ~A d e t a i l e d s t u d y of t h e

r a t e s o f r e a c t i o n o f t r i a r y l p h o s p h i n e s (and o t h e r t r i v a l e n t p h o s p h o r u s compounds) w i t h e l e m e n t a l s u l p h u r i n t o l u e n e i s c o n s i s t e n t w i t h b i p h i l i c i n s e r t i o n i n t o t h e sulphur-sulphur bond, i n v o l v i n g a p o l a r t r a n s i t i o n s t a t e i n which p h o s p h o r u s a c q u i r e s a p a r t i a l p o s i t i v e c h a r g e . 99

Tris(dimethy1amino)phosphine h a s been

u s e d f o r t h e c o n v e r s i o n o f d i s u l p h i d e s t o t h i o e t h e r s . l o o The r e a c t i o n s of t r i s - ( t - b u t y 1 ) p h o s p h i n e

w i t h e l e m e n t a l s e l e n i u m and

t e l l u r i u m have g i v e n t h e r e s p e c t i v e s e l e n i d e and t e l l u r i d e , t h e

l a t t e r undergoing r a p i d t e l l u r i u m t r a n s f e r t o o t h e r phosphide A l k y l t e l l u r o p h o s p h i n o u s esters have been

m o l e c u l e s i n s o l u t i o n . lo’

p r e p a r e d by t h e exchange r e a c t i o n s o f t e t r a - a l k y l d i p h o s p h i n e s and 102 dialkylditellurides.

14

Organophosphorus Chemistry N u c l e o p h i l i c a t t a c k a t n i t r o g e n a p p e a r s t o be i n v o l v e d i n t h e 103

r e a c t i o n s of t r i p h e n y l p h o s p h i n e w i t h b i c y c l i c t h i a z y l s y s t e m s . F u r t h e r examples of t h e f o r m a t i o n o f X'-phosphazenes

in the

r e a c t i o n s o f p h o s p h i n e s w i t h a z i d o compounds have b e e n described.1049105

The r e a c t i o n s of a z i d e s w i t h one mole e q u i -

v a l e n t of t r i p h e n y l p h o s p h i n e , i n

t h e presence of a s l i g h t excess

Of

w a t e r , i n THF r e s u l t i n t h e c h e m o s e l e c t i v e f o r m a t i o n o f p r i m a r y amines. lo6 A g e n e r a l r o u t e t o f i v e - ,

six-,

and seven-membered

c y c l i c i m i n e s i s o f f e r e d by t h e r e a c t i o n s i n a n h y d r o u s media of t r i p h e n y l p h o s p h i n e w i t h w - a z i d o k e t o n e s . l o 7 The t r i p h e n y l p h o s p h i n e d i e t h y l a z o d i c a r b o x y l a t e s y s t e m h a s now been u s e d t o p r e p a r e a c i d a n h y d r i d e s from c a r b o x y l i c a c i d s . l o * Under h i g h - d i l u t i o n c o n d i t i o n s , s i x - and seven-membered c y c l i c d i o x y t r i p h e n y l p h o s p h o r a n e s are formed i n t h e r e a c t i o n s of p r o p a n e - 1 , 3 - d i o l butane-1,4-diol, di-isopropyl

and

r e s p e c t i v e l y , w i t h t r i p h e n y l p h o s p h i n e and

azodicarboxylate.

A t higher concentrations, t h e s e 109

phosphoranes appear t o oligomerise.

1 . 2 . 4 M i s c e l l a n e o u s R e a c t i o n s of P h o s p h i n e s . -

The r o l e o f c h i r a l

p h o s p h i n e s a s l i g a n d s i n t h e c a t a l y s i s of r e a c t i o n s l e a d i n g t o t h e f o r m a t i o n o f c h i r a l p r o d u c t s h a s b e e n r e v i e w e d . 'lo A p r o c e d u r e f o r t h e d e t e r m i n a t i o n of t h e e n a n t i o m e r i c e x c e s s i n c h i r a l p h o s p h i n e s h a s been d e v e l o p e d , b a s e d on '!C n.m.r. s t u d i e s of t h e d i a s t e r e o i s o m e r i c complexes formed by p h o s p h i n e s w i t h t h e c h i r a l p i n e n y l n i c k e l bromide complex. '11 Studies of t h e sulphonation o f t r i p h e n y l p h o s p h i n e and o f c h i r a l a r y l p h o s p h i n e s have been r e p o r t e d i n a t t e m p t s t o p r e p a r e water s o l u b l e l i g a n d s which a i d p r o d u c t i s o l a t i o n and c a t a l y s t - r e c o v e r y from homogeneouslyc a t a l y s e d r e a c t i o n s . '12-'14 t h e p r o m o t i o n of Michael-type

F u r t h e r examples have a p p e a r e d o f a d d i t i o n s t o t h e d o u b l e bond o f

1,l-bis(dipheny1phosphino)ethene

a s a r e s u l t of c o o r d i n a t i o n of

t h e p h o s p h o r u s atoms t o t r a n s i t i o n metal a c c e p t o r s . 115-117 E v i d e n c e of phosphorus-carbon

c l e a v a g e r e a c t i o n s undergone by

t e r t i a r y p h o s p h i n e s a s components o f homogenous c a t a l y s t s y s t e m s c o n t i n u e s t o accumulate.

In hydroformylation systems involving

c o b a l t - p h o s p h i n e complexes, it h a s been shown t h a t e l e c t r o n w i t h d r a w i n g a r y l g r o u p s enhance t h e r a t e o f p h o s p h i n e d e g r a d a t i o n , 118,119 whereas electron-donating s u b s t i t u e n t s reduce t h e rate. Phenyl-phosphorus c l e a v a g e h a s a l s o been o b s e r v e d i n a dimolybdenum-triphenylphosphine complex, 120 and c l e a v a g e of t h e p h o s p h o r u s - c a r b o n backbone of diphosphinomethane-di-iron complexes h a s b e e n r e p o r t e d . 12' ,122 An u n p r e c e d e n t e d c l e a v a g e of a m e t h y l


15

group from p h o s p h o r u s o c c u r s i n t h e r e a c t i o n of a d i m e t h y l -

(pheny1)phosphine-tantalum(II1) b a s e s . 123

bromide complex w i t h s t r o n g

C o n s t a n t c u r r e n t e l e c t r o l y s i s of t r i p h e n y l p h o s p h i n e i n d i c h l o r o m e t h a n e i n t h e p r e s e n c e of amides and N , N ' - d i s u b s t i t u t e d u r e a s l e a d s t o t h e f o r m a t i o n o f n i t r i l e s and c a r b o d i m i d e s ,

.

r e s p e c t i v e l y 124 A triphenylphosphine-dibutylt i n d i c h l o r i d e complex h a s found u s e a s a c a t a l y s t f o r t h e r e g i o s e l e c t i v e r i n g o p e n i n g o f o x i r a n e s . 125

P h e n y l p h o s p h i n e h a s been found t o r e d u c e

a r o m a t i c k e t o n e s t o t h e c o r r e s p o n d i n g d i a r y l m e t h a n e s . 12'

The

r e a c t i o n of 2 - q u i n o n e monoimides w i t h t r i p h e n y l p h o s p h i n e g i v e s 127 r i s e t o benzoxazoles. Valence i s o m e r i s m of t h e 7,8-bis(phosphino)cycloocta-l,3,5t r i e n e s (73) h a s been s t u d i e d i n a r a n g e of compounds, and t h e p r o d u c t s a r i s i n g from c o n r o t a t o r y (74) and d i s r o t a t o r y (75) r i n g o p e n i n g i d e n t i f i e d . 12'

Both +-and

t r a n s - i s o m e r s of t h e

p h o s p h i r a n e s (76) u n d e r g o t h e r m a l r e a r r a n g e m e n t a t 150' t h e p h o s p h o l e n e (77 1. 12'

t o form

The r e a c t i o n s of a l k y l b i s ( t r i m e t h y 1 -

sily1)phosphines with phenylisocyanate give rise t o t h e adducts

(78) which on t r e a t m e n t w i t h sodium h y d r i d e form hexamethyld i s i l o x a n e and o l i g o m e r i c ( p h e n y l i m i n o ) m e t h y l i d i n e p h o s p h i n e s .

130

The m e t a l l o p h o s p h i n e s (79) r e a c t n o r m a l l y w i t h s u l p h u r , b u t on treatment with

iodomethane o r f l u o r o t r i c h l o r o m e t h a n e undergo c l e a v a g e o f t h e metal-phosphorus bond. 3 1 The i m i n o b i s ( p h o s p h i n e s ) ( 8 0 ) undergo a l k y l a t i o n a t p h o s p h o r u s t o form t h e phosphoranimine-

phosphonium s a l t s (811, t h e r e b y p r o v i d i n g t h e f i r s t examples of p r o t o t r o p i s m i n t h i s c l a s s of compound which are i n d u c e d by P - a l k y l a t i o n . 132

T r e a t m e n t of t h e s u l p h u r d i i m i d e s y s t e m (82)

w i t h p o t a s s a m i d e g e n e r a t e s t h e s a l t (83) which, w i t h d i - t - b u t y l ( c h l o r o ) a r s i n e , g i v e s t h e p h o s p h i n o - a r s i n e s y s t e m (84). 133

The

r e a c t i o n of t r i m e t h y l p h o s p h i n e w i t h p e r f l u o r o p r o p e n e g i v e s t h e phosphorane (85) i n h i g h y i e l d , w h e r e a s t h e c o r r e s p o n d i n g 134 r e a c t i o n o f d i m e t h y l p h o s p h i n e g i v e s t h e p h o s p h i n e (86 1. T e t r a m e t h y l d i p h o s p h i n e and t e t r a m e t h y l d i a r s i n e u n d e r g o r a p i d exchange r e a c t i o n s i n s o l u t i o n i n benzene a t 25OC t o g i v e a n e q u i l i b r i u m m i x t u r e which c o n t a i n s t h e p h o s p h i n o a r s i n e (87).

In

c o n t r a s t , no e v i d e n c e of exchange r e a c t i o n s between t e t r a m e t h y l d i p h o s p h i n e and t h e r e l a t e d d i s t i b i n e s o r d i b i s m u t h i n e s h a s been

.

o b t a i n e d 135

P r e v i o u s l y unknown d i p h o s p h i n e c a t i o n r a d i c a l s have

been o b s e r v e d by e . s . r . t e c h n i q u e s on e l e c t r o c h e m i c a l o x i d a t i o n 136 of a series of s t e r i c a l l y crowded t e t r a a r y l d i p h o s p h i n e s .


16

(73)

Me Si

/-

3

-7 7 P

A But

B Ut

(76 1

(77)

Ph2PR2P-M(CO),

(

N

H

- PR1

80) R 1 =Butor Ph

\

;

,SiMe3

N-C-P\

Ph’

R

( 7 8 ) R = PhCH, or E t

+

Ph2P=N-PRiR2 H ( 81 1 R1=But or Ph

2

( 7 9 ) M=Cr,Mo or W R=CF3 or CN

R = M e or Ph,C

N A N

I

I

But2P

PBu‘,

(82)

Me3P(F)CF=CFCF3

(85)

(83)

=C FCF3

Me2PCF

(86)

Me2P-AsMe2

(87)

PF;

17

I : Phosphines and Phosphonium Salts The e f f e c t s o f g a m m a - i r r a d i a t i o n o n 1,2-bis(diphenylphosphino)e t h a n e have been studied.137

The a c t i o n o f d r y a i r o n p o l y c y c l i c

o r g a n o p o l y p h o s p h i n e s h a s g i v e n t h e f i r s t monoxides o f t h e s e s y s t e m s a s t h e i n i t i a l p r o d u c t s . 13'

Studies of t h e r e a c t i o n s of

t r i f l u o r o m e t h y l p h o s p h i n e s w i t h v a r i o u s n i t r o s o compounds h a v e b e e n 139,140 reported

.

2 H a l o g en o p h o s p h i n es 2.1 Preparation. -

P a t e n t s h a v e a p p e a r e d which claim improved

p r o c e d u r e s f o r t h e s y n t h e s i s of a r y l d i c h l o r o p h o s p h i n e s and d i a r y l c h l o r o p h o s p h i n e s from a r o m a t i c hydrocarbons, phosphorus t r i c h l o r i d e , and a l u m i n i u m c h l o r i d e , t h e i n t e r m e d i a t e c o m p l e x e s b e i n g decomposed by tris(2-chloroethyl)phosphite1*1f 142 o r

bis(2-chloroethyl)vinylphosphonate. 143 High t e m p e r a t u r e e x c h a n g e r e a c t i o n s between t r i o c t y l p h o s p h i n e a n d p h o s p h o r u s t r i b r o m i d e h a v e y i e l d e d o c t y l d i b r o m o p h o s p h i ne a n d d i o c t ylbromop h o s p h i n e

.144

P h e n y l p h o s p h o n i c d i c h l o r i d e i s r e d u c e d by t r i o c t y l p h o s p h i n e a t 50-100°C t o g i v e p h e n y l d i c h l o r o p h o s p h i n e a n d t r i o c t y l p h o s p h i n e o x i d e i n good y i e l d . 145

The d i b e n z o x a s i l i n ( 8 8 ; X = H) is

c o n v e r t e d i n t o t h e c o r r e s p o n d i n g d i c h l o r o p h o s p h i n e ( 8 8 ; X = PC1,) on h e a t i n g w i t h p h o s p h o r u s t r i c h l o r i d e a n d a l u m i n i u m c h l o r i d e a t 65-75OC. 14'

B o t h ( 8 9 ) and ( 9 0 ) are f o r m e d i n t h e r e a c t i o n s of

2,6-di-t-butylphenol

with phosphorus t r i h a l i d e s , t h e latter

.

p r o d u c t p r e d o m i n a t i n g 14'

The s u b s t i t u t e d - v i n y l d i h a l o g e n o -

p h o s p h i n e s ( 9 1 ) are formed i n t h e r e a c t i o n s o f s u b s t i t u t e d - v i n y l e t h e r s w i t h p h o s p h o r u s t r i h a l i d e s i n t h e p r e s e n c e of triethylamine. 14' 14'

The r e a c t i o n o f b e n z a l d i m i n e s w i t h p h o s p h o r u s

t r i c h l o r i d e i n a c e t o n e , i n t h e p r e s e n c e of p y r i d i n e , is c l a i m e d t o proceed with s u b s t i t u t i o n at t h e S c h i f f ' s base carbon t o give t h e d i c h l o r o p h o s p h i n e s ( 9 2 1. 150 P h o t o l y s i s of d i m e t h y l d i a c e t y l e n e i n t h e presence o f phosphorus tribromide y i e l d s t h e u n s a t u r a t e d 151

dibromophosphine ( 9 3 ) .

The p r e p a r a t i o n o f i n t e r m e d i a t e d i a l k y l a m i n o p h o s p h i n e s from t h e c o n t r o l l e d react i o n s of dialkylaminochlorophosphines w i t h o r g a n o m e t a l l i c r e a g e n t s , and t h e subsequent r e a c t i o n of t h e s e i n t e r m e d i a t e s w i t h h y d r o g e n c h l o r i d e , c o n t i n u e s t o b e u s e d as a r o u t e t o less a c c e s s i b l e h a l o g e n o p h o s p h i n e s .

Among compounds

r e c e n t l y p r e p a r e d b y t h i s r o u t e are ( 9 4 ) 1 5 2 a n d ( 9 5 ) . 153 o f new silylaminohalogenophosphines, e . g .

A series

(96), h a s b e e n p r e p a r e d

b y t h e r e a c t i o n s o f bis(trimethylsily1)methyldichlorophosphine w i t h v a r i o u s l i t h i u m s i l y l a m i d e s . 154

The r e a c t i o n of


18

0-SiCl,

&=J

H:bPX2

X

(88)

X, PC(R' I =c HOR

But (89)X:Cl or Br

C12PC( Ph )=NC,H,R

(90) X = C l or Br

Me(Br)C=C-CC=CMe

I

PBr,

(91) R'= a l k y l or Br 2

( 9 2 ) R = H,Cl or NO2

(93)

R = M e , E t or Bu X = C I or B r

L

(97)

(95)

(96 1

(98) R = B u t or M e s

(99)

X' X2PC(C F3),OS iM e3

(100)

(101 X ' = C I or 6 r 2

X = H or halogen

X P"Jf \

f

(1021X=CI or 6 r

Z=0,S ,NMe or NPX2


19

1,2 - b i s ( p h o s p h i n o ) b e n z e n e w i t h s i x moles o f p h o s g e n e i n d i c h l o r o m e t h a n e s o l u t i o n a t -78OC r e s u l t s i n t h e f o r m a t i o n o f t h e r e l a t e d b i s ( d i c h 1 o r o ) p h o s p h i n e ( 9 7 ) i n 45-55% y i e l d .

Using bulky Grignard o r o r g a n o z i n c r e a g e n t s , t h i s may be p a r t i a l l y s u b s t i t u t e d t o g i v e

( 9 8 1 , which may t h e n b e s u b j e c t e d t o f u r t h e r a l k y l a t i o n r e a c t i o n s . 155 A s i m i l a r s e q u e n t i a l s u b s t i t u t i o n a p p r o a c h h a s b e e n employed i n t h e s y n t h e s i s o f v a r i o u s o p t i c a l l y a c t i v e m e n t h y l 156 halogenop hosph i n e s

.

The r e a c t i o n s of t r i m e t h y l s i l y l h a l i d e s w i t h t r i s ( d i m e t h y l a m i n 0 ) p h o s p h i n e o f f e r a c o n v e n i e n t r o u t e t o bis(dimethy1amino)halogenop h o s p h i n e s . 157

S t e r i c a l l y crowded h a l o g e n o p h o s p h i n e s , e . g .

(99),

h a v e b e e n p r e p a r e d by t h e r e a c t i o n s o f tris(trimethylsily1)silylc h l o r i d e w i t h dialkylarninodichlorophosphines d e r i v e d from bulky s e c o n d a r y a m i n e s . 15'

Treatment of t h e primary phosphine ( 100)

( e a s i l y a c c e s s i b l e from t h e r e a c t i o n of phosphine w i t h hexafluoro-

a c e t o n e , f o l l o w e d by 0 - s i l y l a t i o n ) w i t h N-chlorosuccinimide y i e l d s t h e halogenophosphines

o r N-bromo-

( 1 0 1 ) , which c a n b e

c o n v e r t e d t o t h e c o r r e s p o n d i n g f l u o r o p h o s p h i n e s o n react i o n w i t h a n t i m o n y t r i f l u o r i d e . 15'

V a r i o u s compounds o f t h e g e n e r a l t y p e

( 1 0 2 ) have been p r e p a r e d by t h e r e a c t i o n s o f 2 - d i f u n c t i o n a l

aromatic compounds w i t h p h o s p h o r u s t r i h a l i d e s . 160-164

A mixture

o f (difluoromethy1)iodophosphines i s f o r m e d i n t h e s e a l e d - t u b e r e a c t i o n o f w h i t e p h o s p h o r u s w i t h d i f l u o r o i o d o m e t h a n e a t 190OC.

165

The r e a c t i o n s o f w h i t e p h o s p h o r u s w i t h t e t r a a l k y l a m m o n i u m c y a n i d e s i n t h e p r e s e n c e of a crown e t h e r i n a c e t o n i t r i l e g i v e r i s e t o t h e d i c y a n o p h o s p h i d e i o n , w h i c h is f o u n d t o react w i t h a v a r i e t y of

a n i o n i c phosphorus n u c l e o p h i l e s w i t h displacement of cyanide i o n

t o g e n e r a t e new P-P b o n d e d compounds. 166 2.2 R e a c t i o n s o f Ha1ogenophosphines.-

'

The t r i c y c l i c s y s t e m ( 1 0 3 )

h a s b e e n p r e p a r e d f r o m p h e n y l d i c h l o r o p h o s p h i n e b y t h e McCormack react i o n . 16' The b i c y c l i c s y s t e m ( 1 0 4 ) i s f o r m e d i n t h e r e a c t i o n of a 1,6-diene

or -diketone w i t h methyldichlorophosphine i n t h e a c e t i c a c i d , f o l l o w e d by t r e a t m e n t w i t h water. The presence of b r i d g e d d i c h l o r o t e t r a p h o s p h i n e ( 1 0 5 ) h a s b e e n o b t a i n e d by t h e 170 c a t h o d i c r e d u c t i o n of 1,2-bis(dichlorophosphino)benzene (97). T r e a t m e n t of b u t y l b i s ( t r i m e t h y l s t a n n y l ) amine w i t h p h o s p h o r u s t r i c h l o r i d e l e a d s t o t h e f o r m a t i o n of t h e c h l o r o p h o s p h i n e ( 1 0 6 ) w h i c h decomposes r a p i d l y a t room t e m p e r a t u r e t o g i v e t h e zwitterionic system (107). 1 7 1 N o t s u r p r i s i n g l y , t h e v a s t m a j o r i t y o f r e a c t i o n s of h a l o g e n o phosphines reported over t h e past year involve nucleophilic a t t a c k


20

a t p h o s p h o r u s w i t h d i s p l a c e m e n t of h a l i d e i o n .

The c h l o r o -

p h o s p h i n e ( 1 0 8 1 , formed i n t h e r e a c t i o n of a p e n t a m e t h y l c y c l o p e n t a d i e n y l i r o n d i c a r b o n y l a n i o n w i t h t -but y l d i c h l o r o p h o s p h i n e n o r m a l l y i n s u b s e q u e n t react i o n s a t p h o s p h o r u s . 172

, behaves

A s t u d y of t h e

r e a c t i o n s o f h a l o g e n o p h o s p h i n e s d e r i v e d from t h e anti-7-phosphanorbornene system (109) w i t h Grignard r e a g e n t s has proved t o be s u r p r i s i n g l y complex.

The d e s i r e d d i s p l a c e m e n t o f c h l o r i n e w i t h

r e t e n t i o n o f c o n f i g u r a t i o n w a s o b s e r v e d i n o n l y one case, t h e g e n e r a l s i t u a t i o n b e i n g c o m p l i c a t e d by l o s s of t h e b r i d g i n g g r o u p a n d h a l o g e n exchange w i t h t h e G r i g n a r d r e a g e n t . 173

A r a n g e o f new ( 1 1 0 ) 1 7 4 h a s been p r e p a r e d by t h e 174-176 r e a c t i o n s o f NH compounds w i t h c h l o r o d i p h e n y l p h o s p h i n e .

c h i r a l aminophosphines e . g .

V a r i o u s p h o s p h i n a t e d c l a y s have been p r e p a r e d by t h e r e a c t i o n s o f chlorodiphenylphosphine with c l a y s under b a s i c c o n d i t i o n s .

Such

m a t e r i a l s have p o t e n t i a l a s l i g a n d s for t h e p r e p a r a t i o n of n o v e l h e t e r o g e n e o u s c a t a l y s t s y s t e m s . 177 The f i r s t d i t e l l u r o p h o s p h i n e ( 1 l l ) h a s been p r e p a r e d b y t h e a c t i o n o f t h e t r i s ( t r i m e t h y l s i l y 1 ) d i t e l l u r i d e a n i o n on di-t-butylchlorophosphine. 178 The r e a c t i o n s of t h e bis(ch1orophosphino)methanes ( 1 1 2 ) w i t h p r i m a r y amines h a v e y i e l d e d t h e bis(aminophosphino)methanes ( 1 1 3 ) , which on t r e a t m e n t w i t h an amine h y d r o c h l o r i d e undergo c y c l i s a t i o n t o form t h e 1,2,4-azadiphosphetidines (114). 17' The e a s i l y a c c e s s i b l e and c r y s t a l l i n e bis(diisopropy1amino)chlorophosphine h a s found u s e i n n u c l e o t i d e s y n t h e s i s . 180 H y d r o l y s i s of c h l o r o p h o s p h i n e s c o o r d i n a t e d t o p a l l a d i u m or p l a t i n u m h a s been s t u d i e d . 18' The r e a c t i o n s o f isobutenyldichlorophosphine w i t h n u c l e o p h i l e s h a v e b e e n e x p l o r e d . 182 Chlorophosphine-borane a d d u c t s u n d e r g o t h e u s u a l n u c l e o p h i l i c d i s p l a c e m e n t react i o n s a t p h o s p h o r u s w i t h o u t d i s r u p t i o n o f t h e phosphorus-boron l i n k . 183 The p h o s p h i n o p h o s p h a z e n e s ( 1 1 5 ) are t h e i n i t i a l p r o d u c t s i n t h e r e a c t i o n s o f N-metallated

aminophosphines w i t h chlorodialkylphosphines.

In the

p r e s e n c e o f v a r i o u s c a t a l y s t s , t h e s e compounds r e a r r a n g e t o form

bi~(dialky1phosphino)amines.~~ H~e t e r o c y c l i c s y s t e m s , e.g. ( 1 1 6 1 , are formed i n t h e r e a c t i o n s of bis(dich1orophosphino)methane w i t h 185,186 N,N' - d i s i l y l u r e a s . Treatment of dichlorophosphines w i t h s i l v e r t h i o c y a n a t e i n d i c h l o r o m e t h a n e s o l u t i o n l e a d s t o t h e f o r m a t i o n of t h e c o r r e s p o n d i n g di(isothiocyanato)phosphines, which are f o u n d t o be thermally unstable.

I socyanatodiorganophosphines u n d e r g o

c y c l i s a t i o n on t r e a t m e n t w i t h a l d e h y d e s t o form o x a z a p h o s p h o l i n e s , e.g. (11.7). 188

1: Phosphines and Phosphoniurn Salts

21

CI

Cl (1031

CIP+N 2 8 1 a n d ( 1 7 3 ) . 282

The b i s p h o s p h a -

a l k e n e ( 1 7 4 ) i s formed i n t h e r e a c t i o n of a s i l y l a t e d 1,2diphosphinobenzene w i t h diphenylcarbodiimide. Phospha-alkenes b e a r i n g a t r a n s i t i o n metal complex fragment a s a s u b s t i t u e n t a t

e it h e r p h o s p h o r u s 284-289 o r c a r b o n 290-291 have a l s o b e e n d e s c r i b e d . (175) h a s b e e n c h a r a c t e r i s e d i n s o l u t i o n as a complex i n v o l v i n g .rr-donation from t h e d o u b l e bond t o a t u n g s t e n c a r b o n y l a c c e p t o r . T h i s complex r e a c t s w i t h 1,3d i e n e s t o g i v e a d d u c t s e . g . ( 1 7 6 ) , i n which t h e p h o s p h o r u s atom

The u n h i n d e r e d phospha-alkene


/o

0

Me3Si

31

0,

(163 1 A r = 2,4 ,6- But3C6H2

MeNP*CH

\

.-0

H-

(164)

(165)

2

( 1 6 8 ) R = H ,Meor Ph

(166)

(167)

F3CP(H )CF2 X

F3CP( X )CF2H

(169) X=OH,OR,NR,

or PMe2

But-

P=C

/SR

\

( 1 7 0 ) X = C I , B r , SMe, SeMe or AsMe,

@-p=c(

\

X

( 17 1 1X= OR, N R2 or PMe2

X

( 1 7 3 ) X - C L or Br

PCI

(175)

F,CP=C

SR

(172) R = M e or Bus

CH2=

H

( 17 4 )

Me3Si

(176)

-

P=C

(177)

/Osi Me3

\

But

32


is now a - c o o r d i n a t e d t o t h e m e t a l . 2 9 2 A d d i t i o n s t o t h e d o u b l e bond o f p h o s p h a - a l k e n e s c o n t i n u e t o b e explored.

The r e a c t i o n s o f ( 1 7 7 ) w i t h a l i p h a t i c d i a z o compounds

a n d w i t h n i t r i l e o x i d e s have g i v e n 1 , 2 , 4 - d i a z a p h o s p h o l e s and -oxazaphospholes, phospha-alkene

r e s p e c t i v e l y . 293

The a l k y n y l - s u b s t i t u t e d

( 1 7 8 ) u n d e r g o e s a wide r a n g e o f a d d i t i o n r e a c t i o n s

e x c l u s i v e l y a t t h e P=C c e n t r e , g i v i n g , e . g . ( 1 7 9 1 , o n t r e a t m e n t w i t h s u l p h u r , s e l e n i u m or diphenyldiazornethane. 2 9 4 V a r i o u s a d d i t i o n s t o t h e silylaminophospha-alkene ( 180

have been

r e p o r t e d , i n c l u d i n g a [2+21 c y c l o a d d i t i o n w i t h a r e a c t i v e s i l a a l k e n e t o g i v e t h e four-membered r i n g s y s t e m ( 1 8 1 ) . 295,296 R e a c t i o n s l e a d i n g t o s u b s t i t u t i o n a t t h e p h o s p h o r u s atom o f p h o s p h a - a l k e n e s have a l s o r e c e i v e d f u r t h e r s t u d y . phospha-alkene

The c h l o r o -

( 1 8 2 ; X = C 1 ) u n d e r g o e s halogen-exchange o n

t r e a t m e n t w i t h s i l v e r f l u o r i d e o r t r i r n e t h y l s i l y l bromide o r i o d i d e t o g i v e ( 1 8 2 ; X = F , Br o r I ) , r e s p e c t i v e l y . 2 9 7 The r e a c t i o n o f (182; X = C l ) w i t h sterically-crowded

lithiophosphide reagents has

g i v e n t h e phosphinophospha-alkene s y s t e m ( 1 8 3 ) which is r e p o r t e d t o i s o m e r i s e t o form t h e diphosphene ( 1 8 4 ) . 2 9 8 The a r y l phosphaa l k e n e ( 1 8 5 ) i s formed i n t h e r e a c t i o n of t h e c o r r e s p o n d i n g

-

chlorophospha-alkene w i t h t h e p-(t-buty1)phenyl Grignard r e a g e n t . D i e l s - A l d e r a d d u c t s o f b o t h g- and Z-isomers of ( 1 8 5 ) have b e e n i s o l a t e d from t h e i r r e a c t i o n s w i t h c y c l o p e n t a d i e n e . 2 9 9

The

e l e c t r o n - r i c h s i l y l - s u b s t i t u t e d phospha-alkenes (186; X

=

SiR,)

u n d e r g o exchange r e a c t i o n s a t p h o s p h o r u s w i t h o t h e r s i l y l h a l i d e s , a n d a l s o w i t h t r i p h e n y l g e r m y l - and t r i p h e n y l s t a n n y l h a l i d e s t o g i v e e . g . ( 1 8 6 ; X = SnPh,). 300 With t r i e t h y l s i l a n o l , ( 1 8 6 ; X = H )

is formed,301 a n d t h e r e l a t e d r e a c t i o n w i t h c h l o r o d i - t - b u t y l p h o s p h i n e g i v e s t h e phosphinophospha-alkene ( 1 8 6 ; X = PButz 1. 302 I t h a s a l s o b e e n shown t h a t e l e c t r o n - r i c h phospha-alkenes ( 1 8 6 ; X = Ph) ( a n d r e l a t e d p h o s p h a - a l l y 1

e.g.

c a t i o n s ) t a k e up two

e q u i v a l e n t s o f oxygen a t p h o s p h o r u s when t r e a t e d w i t h ozone a t room t e m p e r a t u r e t o g i v e z w i t t e r i o n i c s y s t e m s , e . g . ( 187 1. 303 The r e a c t i o n of t h e phospha-ally1

c a t i o n ( 1 8 8 ) w i t h iodomethane r e s u l t s

i n t h e f o r m a t i o n o f t h e p h o s p h i n e ( 1 8 9 ) which b e a r s two c a t i o n i c substituents.

An X-ray s t u d y of ( 1 8 9 ) h a s shown t h a t t h e geometry

a b o u t p h o s p h o r u s is p y r a m i d a l . 304

Two r o u t e s f o r t h e s y n t h e s i s of

t h e de l o c a l i s e d 2 -p hosp hon io-sub st it u t ed- 1-p ho s p h a - a l k e n e s y s t e m (190) have b e e n r e p o r t e d . 305 A number o f n o v e l c o o r d i n a t i o n complexes o f p h o s p h a - a l k e n e s have b e e n c h a r a c t e r i s e d by A p p e l ' s 3 0 6-308

group.


33

Me3SiC-CP

Me Si CECP=C(Si MeJ2 3

/x\

-C(Si

Me,)

( 1 7 9 ) X = S , Se or Ph2C

( 1 78)

(Me3SiI2NP-CHSi

I

(Me3Si),NP=CHSiMe3

I

8utCH2CH-Si

(180)

Me3 ( Me3SiI2C =PX

Me,

(182)

(181)

-@

P= P

, Ph

S ‘

Ph ( R, N

I

I

( 1 88)

=PX

i Mej

I

o=p-c

/

I

NMe2

0- \;Me2 ( 1 8 6 ) R = M e or Et

(185)

NMe2 NMe,

-cr61me312

(187)

NMe2 NMe2 I

(1 89)

(190)

34

Organophosphorus Chemistry Two a p p r o a c h e s f o r t h e s y n t h e s i s o f d i p h o s p h a d i e n e s y s t e m s

have been d e s c r i b e d .

The r e a c t i o n o f t h e p h o s p h a k e t e n e ( 1 9 1 )

w i t h t h e phospha-alkene lY3-diphosphabutadiene

( 1 9 2 ) has given t h e f i r s t s t a b l e a c y c l i c ( 193 1.

309

Nucleophilic displacement o f

c h l o r i n e from t h e chlorophosphino-substituted phospha-alkene

( 194)

by a n i o n i c metal c a r b o n y l complexes r e s u l t s i n t h e f o r m a t i o n o f t h e 4-metalla-1,3-diphosphadiene

s y s t e m ( 1 9 5 ) . 310

The complex

( 1 9 6 ) h a s b e e n i s o l a t e d from t h e r e a c t i o n o f t h e p h o s p h a k e t e n e ( 1 9 1 ) w i t h Fe,(CO)q. 311 and d i p h o s p h a - a l l e n e s

The f i r s t complexes o f 1 - p h o s p h a - a l l e n e s 312,313

have b e e n c h a r a c t e r i s e d .

The c h e m i s t r y of t h r e e c o o r d i n a t e p e n t a c o v a l e n t p h o s p h o r u s systems c o n t i n u e s t o develop.

Various r o u t e s t o t h e t h r e e

c o o r d i n a t e p h o s p h o r a n e s ( 1 9 7 ) have been d e s c r i b e d .

A s a result of

s e v e r e s t e r i c crowding, t h e s e m o l e c u l e s a d o p t a c h i r a l , nonp l a n a r s t r u c t u r e . 314-316

The f i r s t example of a t r i ( m e t h y 1 e n e ) -

p h o s p h a t e i o n (1981, i n which t h e c e n t r a l PC, u n i t is almost p l a n a r , h a s been p r e p a r e d by t h e a c t i o n o f f l u o r e n y l l i t h i u m on ( 1 9 7 ; R = C l ) . 317

The dialkylaminothiophosphoranes ( 199 1 u n d e r g o

c y c l o a d d i t i o n r e a c t i o n s i n v o l v i n g t h e P=C bond on t r e a t m e n t w i t h d i a z o a l k a n e s t o form A s - d i a z a p h o s p h o l e s . 318

The X5a3-phospha-

a l k y n e (200) is r e p o r t e d t o d i m e r i s e , w i t h a p h o s p h o r u s t o oxygen 319 r e a r r a n g e m e n t , t o form t h e X5-diphosphete s y s t e m ( 2 0 1 ) . The p r e p a r a t i o n , s t r u c t u r e and p r o p e r t i e s of p h o s p h a - a l k y n e s have been r e v i e w e d . 320 A g e n e r a l r o u t e t o phospha-alkynes a p p e a r s t o be offered i n the reactions of acid chlorides with tris(trimethylsily1)phosphine. phospha-alkenes

I n some c a s e s , t h i s l e a d s i n i t i a l l y t o t h e

( 2 0 2 1 which u n d e r g o b a s e - i n d u c e d

elimination of

h e x a m e t h y l d i s i l o x a n e u n d e r r e d u c e d p r e s s u r e t o form t h e phosphaa l k v n e s (. 2 0. 3 1 . ~ ~ I ~n 9o t ~h e~r ~cases. t h e l a t t e r are i s o l a t e d d i r e c t l y from t h e i n i t i a l r e a c t i o n . 3 2 i y324 Using t h i s a p p r o a c h , t h e f i r s t s t a b l e c r y s t a l l i n e phospha-alkynes

(203;

R = 1-

a d a m a n t ~ lor~ ~9 -~t r i p t y c y l 323) have b e e n i s o l a t e d . The phosphaa l k y n e s r e a d i l y undergo c y c l o a d d i t i o n r e a c t i o n s w i t h d i a z o m e t h a n e , a z i d e s and n i t r i l e o x i d e s t o form d i a z a - ,

t r i a z a - and oxazaphos-

A similar a p p r o a c h h a s b e e n u s e d i n t h e s y n t h e s i s of t h e f i r s t a r s a - a l k y n e (204), i s o l a t e d as a p a l e y e l l o w c r y s t a l l i n e s o l i d . 325 The c y c l o a d d i t i o n r e a c t i o n s of

pholes,

p h o s p h a - a l k y n e s w i t h s t e r i c a l l y crowded c y c l o b u t a d i e n e s l e a d t o t h e f i r s t D e w a r phosphabenzenes e . g . ( 2 0 5 ) , which are f o u n d t o b e s u r p r i s i n g l y s t a b l e t o h e a t a n d t o d i o x y g e n . 26 Not s u r p r i s i n g l y , t h e c o o r d i n a t i o n c h e m i s t r y o f phospha-alkynes

continues t o attract


+

P=C=O

35

,OSiMz

@

Me3Si-P=C

,OSiMe,

P=C,

,0SiMe3 P=c

‘But

\

But

( 194) R

(195) M = Mo or W

= 2 4 6- BUt3C6H2

-

-

L

( 197) R: alkyl ,a r y I

(196)

(1 98 1

,

CI, NMe2 or SPh 0

0

S

1

I/

R2N - P

‘;ti

, II

1 1 2 3

R2P-CPR

R

R

II

(200)R’=Ph or NPr’2 R2= Ph R’= Ph or OMc

Me3Si-P=C

/ OSi Me3

0 (201 1

RCEP

R‘

(202)

(203)

(204)

36

OrganophosphorusChemistry interest. 327y328

The phospha-alkyne

t ( 2 0 3 ; R = Bu ) u n d e r g o e s

c y c l o d i m e r i s a t i o n i n t h e c o o r d i n a t i o n s p h e r e of c e r t a i n t r a n s i t i o n

metal complexes t o form t h e 1,3-diphosphacyclobutadiene s y s t e m ( 2 0 6 1 , i s o l a t e d as a metal complex. 3 2 9 Raman s p e c t r o s c o p i c d a t a f o r t h e s i m p l e s t phospha-alkyne t h e m o l e c u l e e x h i b i t i n g v(C-H) 3 30 respectively.

(203;

R

=

H) h a v e b e e n r e c o r d e d ,

and v(C5P) a t 3218 a n d 1 2 7 7 cm’l,

The c h e m i s t r y of compounds i n v o l v i n g two c o o r d i n a t e p h o s p h o r u s i n N-P=N s y s t e m s a l s o c o n t i n u e s t o be e ~ p l o r e d , ~ ~ and l - f ~u r~t h~e r p r o g r e s s h a s b e e n r e p o r t e d i n t h e area of t h r e e c o o r d i n a t e p e n t a c o v a l e n t phosphorus-nitrogen unknown b o r a p h o s p h e n e s , R-B=P-R,

s y s t e m s . 337 y 3 3 8 The a s y e t may b e i n v o l v e d a s t r a n s i e n t

i n t e r m e d i a t e s i n t h e r e a c t i o n s o f s t e r i c a l l y crowded d i a l k y l a m i n o d i c h l o r o b o r a n e s w i t h a m i x t u r e of mono- and d i - l i t h i a t e d m e s i t y l p h o s p h i d e s , which l e a d t o t h e d i m e r i c s y s t e m ( 2 0 7 ) . 339 The t w o c o o r d i n a t e t h i o p h o s p h e n o u s a c i d d e r i v a t i v e s , X-P=S (X = RO o r

R, N)

, have

b e e n c h a r a c t e r i s e d i n t r a p p i n g e x p e r i m e n t s , 340 and t h e

c h e m i s t r y of t h e t h r e e c o o r d i n a t e a r y l d i t h i o p h o s p h o r a n e ( 2 0 8 ) h a s b e e n reviewed.341

C o n s i d e r a b l e i n t e r e s t h a s been shown i n t h e

c h e m i s t r y of t e r m i n a l p h o s p h i n i d e n e -complexes which i n v o l v e t h e R-P=MLn s k e l e t o n , where MLn r e p r e s e n t s a complexed t r a n s i t i o n 342-349 a n d t h e g e n e r a l area h a s been metal Tragment , r e v i e w e d . 350’351 M a t h e y ’ s g r o u p h a s c o n t i n u e d t o s t u d y t h e g e n e r a t i o n o f s u c h complexes by t h e t h e r m a l d e c o m p o s i t i o n of

7-phosphanorbornadiene s y s t e m s ,342-344 and o f p a r t i c u l a r i n t e r e s t i s t h e i r o b s e r v a t i o n t h a t t h e 1-pentenylphosphinidene-tungsten

p e n t a c a r b o n y l complex u n d e r g o e s an i n t r a m o l e c u l a r s e l f - i n s e r t i o n p r o c e s s t o form t h e complexed b i c y c l i c p h o s p h i r a n e ( 2 0 9 ) . 344 The f i r s t s t a b l e s t a n n a p h o s p h e n e ( 2 1 0 ) h a s been i s o l a t e d as a r e d , c r y s t a l l i n e s o l i d , from t h e r e a c t i o n o f a fluorosilyl(ary1)phosphine w i t h t - b u t y l l i t h i u m . T h i s compound is

air-sensitive,

r e p o r t e d t o b e s t a b l e a t room t e m p e r a t u r e f o r a b o u t o n e week, and r e a d i l y u n d e r g o e s a d d i t i o n s t o t h e d o u b l e bond, t h e d i r e c t i o n o f which i n d i c a t e s t h a t , as e x p e c t e d , t h e t i n atom i s t h e more 352 positive partner. The c h e m i s t r y of phosphenium i o n s , R,P+, ( c a t i o n i c s y s t e m s which i n v o l v e two c o o r d i n a t e p h o s p h o r u s ) a l s o c o n t i n u e s t o d e v e l o p , a n d h a s b e e n t h e s u b j e c t o f a major r e v i e w . 353 Full d e t a i l s of t h e r e a c t i o n s o f phosphenium i o n s w i t h d i e n e s have now a p p e a r e d . 354

I n a n e x t e n s i o n of t h i s s t u d y , it h a s been shown

t h a t t h e 9 - p h o s p h a b a r b a r a l a n e d e r i v a t i v e ( 2 1 1 ) i s formed i n t h e


37

P-CBut

tll

Bu c-P (205) R = 1-adamantyl

II

MesP-

B N R,

F$NB-

PMes

I

(206)

I

(207)

L?

W(CO),

(208)

(209)

[ R3P--P-PR31+AlCI~

( 2 1 0 1 Ar = 2,4,6-B~*~%H,

[ R13&

PTPR,] + l 2AlC1, R

(211 1

R2vR3 P.

R' ( 21 4)

( 2 1 5 ) R ' = M e , B u t o r Ph R 2 , R 3 = E t or Ph

(216)

\ / P h l C0l5 P-P

( R3P)zM

(217) R'=Ph R 2 = E t or Ph M = Cr or Mo

P -LW ( Ph

( 2 1 8 ) M = Pd or Pt

P R

(219)

38


r e a c t i o n of a phosphenium i o n w i t h c y c l o o c t a t e t r a e n e .

An X-ray

s t u d y of ( 2 1 1 ) r e v e a l s t h a t i t s geometry i n t h e s o l i d s t a t e c l o s e l y a p p r o a c h e s t h a t o f t h e t r a n s i t i o n s t a t e f o r a Cope r e a r r a n g e m e n t , which o c c u r s i n s o l u t i o r a c c o r d i n g t o n.m.r. d a t a . 355

The r e a c t i o n s of t r i p h o s p h e n i u m s a l t s ( 2 1 2 ) have a l s o

a t t r a c t e d some a t t e n t i o n . -3 Selecti v e intramolecular exchange r e a c t i o n s i n v o l v i n g t h e o u t e r p h o s p h o r u s l i g a n d s have been o b s e r v e d , s u c h r e a c t i o n s i n v o l v i n g t h e u s e of c h e l a t i n g diphosphines having given a range of h e t e r o c y c l i c triphosphenium

s a l t s . 357

T r e a t m e n t of t r i p h o s p h e n i u m s a l t s w i t h a l k y l - o r a r y l -

h a l i d e s i n t h e p r e s e n c e of aluminium c h l o r i d e r e s u l t s i n t h e d i c a t i o n i c t r i p h o s p h o r u s s y s t e m ( 2 1 3 ) which is e f f e c t i v e l y a t e r t i a r y p h o s p h i n e b e a r i n g two c a t i o n i c s u b s t i t u e n t s .

Consistent

w i t h t h i s view, t h e e x p e c t e d p y r a m i d a l geometry a t t h e c e n t r a l 358 p h o s p h o r u s is o b s e r v e d . 5 P h o s p h i r e n e s , P h o s p h o l e s and P h o s p h o r i n s

The c h e m i s t r y of t h e p h o s p h i r e n e s y s t e m is a t t r a c t i n g i n c r e a s i n g a t t e n t i o n , w i t h t h e e v e n t u a l g o a l of p r e p a r i n g t h e p o t e n t i a l l y a r o m a t i c Huckel s y s t e m ( 2 1 4 ) .

A s i m p l e p r e p a r a t i o n of t e r v a l e n t

p h o s p h i r e n e s ( 2 1 5 ) i s a f f o r d e d by t h e r e a c t i o n s o f d i c h l o r o p h o s p h i n e s w i t h a l k y n e s i n t h e presence of aluminium c h l o r i d e , f o l l o w e d by r e d u c t i o n o f t h e i n t e r m e d i a t e c h l o r o p h o s p h i r e n i u m

s a l t s w i t h t r i b u t y l p h ~ s p h i n e . ~A ~new ~ r o u t e t o t h e complexed c h l o r o p h o s p h i r e n e ( 2 1 6 ) h a s been d e s c r i b e d . 360 M a t h e y ' s g r o u p h a s a l s o d e v e l o p e d a new one-pot c o n v e r s i o n of complexed p h o s p h o l e s t o t h e r e l a t e d complexed p h o s p h i r e n e s , which i n v o l v e s t h e r e a c t i o n of t h e p h o s p h o l e complex w i t h d i m e t h y l a c e t y l e n e d i c a r b o x y l a t e and a second d i s u b s t i t u t e d a l k y n e . 361 Upon t r e a t m e n t w i t h aluminium c h l o r i d e , l-B-chloroethylphosphirene-tungsten p e n t a c a r b o n y l complexes l o s e e t h y l e n e t o y i e l d t h e c o r r e s p o n d i n g complex o f t h e l-chlorophosphirene. 362

T e r v a l e n t p h o s p h i r e n e s seem t o behave

normally i n t h e i r r e a c t i o n s w i t h e l e c t r o p h i l i c r e a g e n t s , undergoing t h e u s u a l r e a c t i o n s a t phosphorus.

However, n u c l e o p h i l i c r e a g e n t s

a t t a c k complexed p h o s p h i r e n e s a t e i t h e r phosphorus d e p e n d i n g on t h e n a t u r e o f t h e r e a g e n t .

or

carbon,

The f r e e p h o s p h i r e n e s c a n

r e a d i l y b e l i b e r z t e d from t h e i r metal complexes o n t r e a t m e n t w i t h i o d i n e i n t h e p r e s e n c e of N-methylimidazole.

Complexed

p h o s p h i r e n e s undergo i n s e r t i o n r e a c t i o n s on h e a t i n g w i t h c a r b o n monoxide u n d e r p r e s s u r e t o g i v e complexes of p h o s p h o r u s a n a l o g u e s

of u n s a t u r a t e d B-lactams ( 2 1 7 ) . 363

A r e l a t e d i n s e r t i o n of zero-

39

1: Phosphines and Phosphonium Salts v a l e n t metal-phosphine

f r a g m e n t s h a s a l s o been r e p o r t e d , g i v i n g

( 2 1 8 1 %364 The t r i p h o s p h i r e n e s y s t e m ( 2 1 9 ) h a s been c h a r a c t e r i s e d 365 i n t h e form of a metal complex. The r e a c t i o n s o f p h o s p h o l e s w i t h a c i d s l e a d t o a v a r i e t y of r e a r r a n g e m e n t and d i m e r i s a t i o n p r o c e s s e s . Thus, e . g . , t r e a t m e n t o f l-phenyl-3-methylphosphole a t - 9 O O C w i t h hydrogen c h l o r i d e r e s u l t s i n i t i a l l y i.n p r o t o n a t i o n a t p h o s p h o r u s , b u t , o n r a i s i n g t h e t e m p e r a t u r e , t h e la-phospholium c h l o r i d e r e a r r a n g e s r a p i d l y t o g i v e t h e l-chloro-2,5-dihydrophospholium

salt (220).

r e a c t i o n of l-phenyl-3,4-dimethylphosphole

P a l l a d i u m ( 11) complexes o f

r e s u l t s i n thedimeric system ( 2 2 1 ) . 366

l-phenyl-3,4-dimethylphosphole

In contrast, the

w i t h hydrogen c h l o r i d e

r e a d i l y undergo D i e l s - A l d e r

a d d i t i o n s w i t h palladium(I1)-complexed

v i n y l p h o s p h i n e s t o form

complexes o f t h e u n s y m m e t r i c a l d i p h o s p h i n e s ( 2 2 2 1 , from which t h e 367 f r e e l i g a n d s c a n be o b t a i n e d by t r e a t m e n t w i t h c y a n i d e i o n . T r e a t m e n t of t h e B - c h l o r o e t h y l p h o s p h o l e

complex ( 2 2 3 ) w i t h

aluminium c h l o r i d e i n d i c h l o r o m e t h a n e s o l u t i o n l e a d s t o t h e 6,7-dihydrophosphepin

complex ( 2 2 4 ) which e x h i b i t s t h e e x p e c t e d The t h e r m a l

h a l o g e n o p h o s p h o r u s r e a c t i v i t y t o w a r d s n u c l e o p h i l e s . 368 d e g r a d a t i o n of phosphole dimers, e . g .

(225) in toluene solution

h a s been shown t o b e v e r y dependent o n c o n c e n t r a t i o n .

At

c o n c e n t r a t i o n s lower t h a n 0.04 M , i n t h e t e m p e r a t u r e r a n g e

--

120-130°, t h e p a r e n t p h o s p h o l e s a r e p r o d u c e d , w h e r e a s a t concentrations g r e a t e r than 1 . 0 M,

intermolecular reactions

p r e d o m i n a t e , l e a d i n g t o l o s s of t h e b r i d g i n g p h o s p h o r u s from t h e 7-phosphanorbornene m o i e t y t o g i v e d i h y d r o p h o s p h i n d o l e s , e . g . ( 2 2 6 ) . 369

P h o s p h o l e dimers h a v i n g

or anti-configuration at

t h e b r i d g i n g p h o s p h o r u s have been shown t o react w i t h Fe,(CO)S w i t h complete r e t e n t i o n of c o n f i g u r a t i o n at each phosphorus.

Both

isomers of t h e 9-phenylbicyclo[4,2, llnonatriene system ( 2 2 7 ) a l s o u n d e r g o c o m p l e x a t i o n w i t h c o m p l e t e r e t e n t i o n of c o n f i g u r a t i o n , 370 r a t h e r t h a n w i t h r e a r r a n g e m e n t a s h a s been s u g g e s t e d by o t h e r w o r k e r s . 371

F u l l d e t a i l s have now been r e p o r t e d o f t h e m e t a l -

c a t a l y s e d t h e r m a l d i m e r i s a t i o n of p h o s p h o l e s t o complexed 2 , 2 ' biphospholenes. 372

-

A n e w r o u t e t o monophosphaferrocenes ( 2 2 8 ) h a s

been d e v e l o p e d , which i n v o l v e s t h e r e a c t i o n o f a p h o s p h o l i d e a n i o n w i t h a f e r r i c i n i u m s a l t . 373

E l e c t r o c h e m i c a l s t u d i e s o f phospha374

f e r r o c e n e s have a l s o been r e p o r t e d .

F u l l d e t a i l s o f t h e s y n t h e s i s of b e n z o x a-p h o s-p h o l e s ( 2 2 9 ) have now a p p e a r e d . 375 The r e a c t i v i t y of t h e 1 , 2 - t h i a p h o s p h o l e - 2 s u l p h i d e ( 2 3 0 ) t o w a r d s n u c l e o p h i l e s h a s been e x p l o r e d . 376

The

Organ0rororororororororororororororororo osphoms Chemistry

40

Ph

CI >&=&DMe

Ph

2 CI-

Ph'

PR2 Me

Me

(222)

(221 1

(220 1

Ph ALCL 3

b

*

'P

l

4 P Ph

CICH2CH2

(224)

( 223)

225)

(

& Ph

Ph

a

.

(228)

(227)

(226)

R

ArqR

S=P,

S

(2301

( 2 2 9 ) R = a l k y l or aryl

Rc3C02Me

R p ' Ph'

Me0 ( 2 3 2 ) X = C0,Me or COPh

C02Me

'Ph

(233)

e

41

1: Phosphines and Phosphonium Salts p r e v i o u s l y unknown 1 H - 1 , 2 - a z a p h o s p h o l e s

( 2 3 1 ) a r e a c c e s s i b l e by

t h e regioselective addition of various acetylenes t o 1,3,2-

diazaphosphole-4-carbonitriles, a n d are f o u n d t o be r e m a r k a b l y i n s e n s i t i v e t o water a n d t o o x i d a t i o n . 3 7 7

I n t e r e s t i n t h e synthe-

sis a n d r e a c t i v i t y of o t h e r a z a p h o s p h o l e s y s t e m s h a s

c o n t i n ~ e d . ~ ~ ~ - ~ ~ ~ A s t r u c t u r a l s t u d y o f a molybdenum c a r b o n y l complex o f p h o s p h a b e n z e n e h a s shown t h a t t h e p h o s p h o r u s i s o-bonded t o t h e

m e t a l , a n d t h a t t h e g e o m e t r y of t h e l i g a n d c l o s e l y resembles t h a t o f t h e f r e e s y s t e m . 384 A d d i t i o n react i o n s of v a r i o u s p h o s p h a z e n e s w i t h a c e t y l e n e s have l e d t o 1,2X5-azaphosphorins 1,4X5-azaphosphorins

(233) y386 r e s p e c t i v e l y .

s u b s t i t u t e d As-phosphatriazines

(232>385 and

The p e r f l u o r o a l k y l -

(234) have been p r e p a r e d from t h e

r e a c t i o n s o f an imidoylamidine w i t h e i t h e r phosphorus p e n t a 387 c h l o r i d e o r phenyltetrachlorophosphorane. References

1 2 3 4 5

6 7 8 9 10 11

12 13 14 15

16 17

18 19 20 21 22

23 24

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42 25

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35 36 37 38

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39

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86.

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41,

399.

24, -

3680.

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40

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41

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42

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24,

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402.

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2344.

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50 51 52 53

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26, -

143.

M.L.J.Hackney and A.D.Norman, J.Chem. Soc., Chem. Commun., 1986, 850. G.M. Isaeva B.M.Butin, and K.B.Erzhanov, Izv. Akad. Nauk Kaz. SSR, Ser. Khim. , 1985, 43 (Chem. Abstr. , 1986, 104,168 560). J.Y.Lee and D.P.Bauer, U.S. P. 4 514 575 (Chem. Abstr. , 1985, 103, 37 620).

54 55 56

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57

J.Y.Lee and F.W.Frey, U.S. P. 4 507 504 (Chem. Abstr., 1985,

37 614).

37 6 1 5 ) .

58 59

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60 61 62 63

103, 107,

G.E.Nelson, U . S . P. 4 507 501 (Chem. Abstr. , 1985, 103,37 6 1 6 ) . G.E.Nelson, U.S. P. 4 507 502 (Chem. Abstr. , 1985, 103,37 6 1 7 ) . E-Lindner and C. Scheytt, Z.Naturforsch. , B: Anorg. Chem. , Org. Chem. , 1986, 41, 10. R.B.King and N.D.Sadanani, Inorg. Chem. , 1985, 24, 3169.

43

I : Phosphines and Phosphonium Salts 64 65 66 67 68 69

70 71 72 73 74 75 76 77 78 79 80 81 82 83 84 85

86 87 88 89 90 91 92 93 94 95 96 97 98 99 100 101 102

103 104 105 106 107

E.Niecke, R.Rk~er,and W.G&h, Z.Naturforsch. , B: Anorg. Chem, Org. Chem., 1985, 40, 1049. D.Valentine Jr. , Asymmetric Synth., 1984, 4,263. J.Neuffer and W.J.Richter, J.Organomet. Chem. , 1986, 301,289. R.Deschenaux and J.K.Stille, J.Org. Chem. , 1985, 50, 2299. R.Riede1, H. -D.Hausen, and E.Fluck, Angew. Chem. , Int. Ed. Engl. , 1985 , 24, 1056. D.J.Brauer, F.Gol, S-Hietkamp,H.Peters, H.Sommer, O.Stelzer, and WSSheldrick, Chem. Ber. , 1986, 119,349. D-Hedden and D.M.Roundhil1, Inorg. Chem., 1985, 24, 4152. T.V.Harris and W.R.Pretzer, 1norg.Chem. , 1985, 24, 4437. W.Jacksties, H.N%h,and W.Storch, Chem. Ber. , 1985, 118,2030. E.Lindner and R.D.Merkle, Z.Naturforsch., B: Anorg. Chem. , Org. Chem. , 1985, 40, 1580. E.Lindner, R.D.Merkle, and H.A.Mayer, Chem. Ber., 1986, 119,645. E.Lindner, R.D.Merkle, W.Hiller, and R.Fawzi, Chem. Ber. , 1986, 119, 659. A.P.Khardin, O.I.Tuzhikov, L.I.Grekov, R.K.Valetdinov, V.I.Pankov, E.V.Matveeva, G.V.Nazarova, B.N.Popov, and D.D.Chuvashov, USSR P. 1 145 022 (Chem. Abstr., 1985, 103,71510). R.K.Valetdinov, A.Ya.Dorfman, A.A.Kutuev, and I.T.Shaikhutdinova, Khim. Tekhnol. Elementoorg. Soedin. Polim., 1984, 22 (Chem. Abstr., 1985, 102, 132 147). 0.T.Beachley Jr. and L.Victorianio, Inorg. Chem., 1986, 25, 1948. 315. D.W.Morton and R.H.Neilson, Phosphorus Sulfur, 1985, 5, H.P.Fritz, G.M;ller, G . R e b e r m w . Chem. , Int. Ed. Engl. , 1985, 24, 1058. J.A.S.Howel1 and M.J.Thomas, Organometallics, 1985, 4, 1054. G.G.Minasyan, A.M.Torgomyan, M. Zh.Ovakimyan, and M.G. Indzhikyan, Arm. Khim. Zh. , 1985, 38, 204 (Chem. Abstr. , 1986, 104,19 636). M.Ramaiah, J.Org. Chem., 1985, 50, 4991. A.I.Meyers and D.Hoyer, Tetrahedron Lett., 1985, 2, 4687. I.N.Zhmurova, V.G.Yurchenko, and A.M.Pinchuk, Zh. Obshch. Khim. , 1985, 55, 321 (Chem. Abstr. , 1985, 103,87 977). P. Hodge and E.Khoshde1, React. Polym. , Ion Exch. , Sorbents, 1985, 2, 143. R.Caputo, C.Ferreri, S.Noviello, and G.Palumbo, Synthesis, 1986 , 499. H.E.Zieger, D.A.Bright, and H.Haubenstock, J.Org. Chem. , 1986, 51, 1180. R.M.Kren and H.H.Sisler, Inorg. Chim. Acta, 1986, 111,31. D.J.Brauer, H.Bkger, and G.Pawelke, J-FluorineChem. , 1985, 27, 347. M.K.Das and S.Roy, Syn. React. Inorg. Met.-Org. Chem., 1986, 16,67. M.K.Das and S.Roy, S y n . React. Inorg. Met.-Qrg. Chem., 1986, 15,53. R.P.Martin, C.M.Merke1, and J.P.Ruiz, Inorg. Chim. Acta, 1986, 115,L29. D.R.Martin, C.M.Merke1, J.P.Ruiz,and J.U.Monda1, Inorg. Chim. Acta, 1985, 100, 293. J.W.Kelly, N.L.Anderson, and S.A.Evans, J.Org. Chem., 1986, 51, 95. J.W.Kelly, P.L.Robinson, and S.A.Evans Jr., J.Org. Chem., 1985, 50, 5007. S.S.Sandhu, T.S.Lobana, and S.S.Deo1, J.Indian Chem. SOC., 1985, 62, 160. C.Srinivasin and K.Pitchumani, Can.J.Chem. , 1985 , 63, 2285. J.R.Lloyd, N.Lowther , G. Zsabo, and C.D.Hal1, J.Chem. SOC., Perkin Trans.I1 , 1985, 1813. R.K.Olsen, G.D.Kini, and W.J.Hennen, J.Org. Chem. , 1985, 50, 4332. W.-W.du Mont, Z.Naturforsch. , B:Anorg. Chem. , Org. Chem. , 1985, 1453. W.-W.du Mont, S.Kubiniok, and T. Severengiz, Z-Anorg. Allg. Chem. , 1985, 531, 21. R.T.Boer6, A.W.Cordes, S.L.Craig, J.B.Graham, R.T.Oakley, and J.A. J.Privett, J.Chem. SOC., Chem. Commun. , 1986, 807. J.Kovacs, I.Pinter, A.Messrner, and G.Toth, Carbohydr. R e s . , 1985, 141,57. D.Schomburg, U.Wermuth, and R.Schmutzler, Phosphorus Sulfur, 1986, 26, 193. N.Knouzi, M.Vaultier, and R.Carri6, Bull. SOC. Chim. Fr., 1985, 8 1 5 7 M-Vaultier, P.H.Lambert, and R.Carri6, Bull. SOC. Chim. Fr., 1986, 83. ~

-


44

108 E.Grochowski, H.Stepowska, and C.J.Michejda, Bull. Pol. Acad. Sci. Chem., 1984, 32, 129 (Chem. Abstr., 1985, 103,5970). 109 M.mn Itzstein and I.D.Jenkins, J.Chem. SOC. , Perkin Trans. 1, 1986, 437. 110 H.B.Kagan, Asymmetric Synth. , 1985, g , 1. 111 R.Mynott , W. J.Richter , and G.Wilke , Z. Naturforsch. , B: Anorg. Chem. , Org. Chem., 1986, 41, 85. 112 J.Jenck and D.More1, Eur. Pat. Appl. 133 410 (Chem. Abstr., 1985, 103, 6511). 113 T.P.Dang, J.Jenck, and D.More1, Eur. Pat. Appl. 133 127 (Chem. Abstr., 1985, 103,6509). 114 F.Alario, Y.Amrani, Y.Colleuille, T.P.Dang, J.Jenck, D.Morel,and D. Sinou, J.Chem. SOC., Chem. Comun. , 1986, 202. 115 H.Schmidbaur, R.Herr, G.MP-OPh

+

.o

09

2: Pentaco-ordinated and Hexaco-ordinated Compounds m e c h a n i s m h a s i m p l i c a t i o n s f o r t h e m e c h a n i s m o f h y d r o l y s i s of a c y c l i c p h o s p h o n i u m s a l t s w h i c h , i t is a r g u e d , i n v o l v e s r a t e l i m i t i n g f o r m a t i o n cf a h y d r o x y p h o s p h o r a n e i n t e r m e d i a t e " .

A

q u a n t i t a t i v e st,udy o f t h e e q u i l i b r i u m c o n s t a n t s and rate c o n s t a n t s f o r t h e t r a n s f o r m a t i o n s o f a s p i r o c y c l i c hydroxyphosphorane (52) i n a q u e o u s s o l u t i o n h a s a l s o b e e n a ~ c o m p l i s h e d ~ ~ T. h e p h o s p h o r a n e e q u i l i b r a t e s w i t h t h e isomeric p h o s p h i n a t e ( 5 3 ) a n d i n b a s e f o r m s

is e s t i m a t e d t c l i e i n

t h e p h o s p h o r a n o x i d e i o n ( 5 4 ) f o r w h i c h pK

-2

A s t u d y of t h e k i n e t i c s a n d m e c h a n i s m of t h e

t h e r a n g e 9-10,

h y d r o l y s i s o f ( 5 4 ) is a l s o r e p o r t e d i n t h i s p a p e r . The tetraoxahydrospirophosphorane ( 5 7 ) h a s b e e n i s o l a t e d i n

66% y i e l d f r o m t h e r e a c t i o n of ( 5 5 ) w i t h t r i e t h y l a r n m o n i u m p e r f l u o r opinacolate (56).

H e x a f l u o r o a c e t o n e i n s e r t s i n t o t h e P-H b o n d of

( 5 7 ) t o f o r m ( 5 8 ) w h i c h may a l s o b e o b t a i n e d f r o m ( 5 9 ) as s h o w n ' l . T h e 'H a n d "F

n.1n.r.

s p e c t r a of t h e p h o s p h o r a n e s r e v e a l r a p i d

pseudorotati.ona1 processes and a time-averaged f l a t t e n e d c h a i r f o r t h e six-membered

conformation o f a

rings.

In a r e l a t e d paper, r e a c t i o n of(60a) with (56) gave t h e h y d r o s p i r o p h o s p h o r a n e ( 6 1 ) w hi c h upon ~ 1 . v . i r r a d i a t i o n i n t h e p r e s e n c e o f d i m e t h y l d i s u l p h i d e gave t h e m e t h y l t h i o d e r i v a t i v e ( 6 2 ) which w a s also prepared b y t h e r e a c t i o n of(60b) with hexafluoroI n c o n t r a s t , t h e reaction of (63) w i t h h e x a f l u o r o a c e t o n e f u r n i s h e d a i : l m i x t u r e of t h e 1,,3,2-l5- and 1,3.4-A5dioxapllospholanes (64) and ( 6 5 ) . F u r t h e r i n v e s t i g a t i o n s f o r t h e r a d i c a l i s o m e r i s a t i o n of hydros p i r o p h o s p h o r a n e s h a v e shown t h a t o n h e a t i n g w i t h d i - t - b u t y l p e r o x i d e i n benzene, phosphoranes ( 6 6 ) and ( 6 7 ) are t r a n s f o r m e d The p r o p o s e d mechanism, as

i n t o (68) and (69) respectively".

w r i t t e n for ( 6 7 ) , p r o c e e d s t h r o u g h t h e phospho ra n y l r a d i c a l ( 7 0 ) which r e a r r a n g e s t o (71) which i n t u r n reacts w i t h ( 6 7 ) t o form

(69) and ( 7 0 ; i n t h e propagation s t e p . T h e f i r s t p h o s p h o r a n e (74) w i t h a ; , " - p h o s p h o r u s - s i l i c o n h a s been prepared ( a l b e i t

bond

i n l o w , 2 0 ' R o , y i e l d ) by t h e r e a c t i o n o f

( 7 2 ) w i t h bis(trimethylsily1)magnesium

(73)44.

I t h a s a n un-

u s u a l l y h i g h p h o s p h o r u s c h e m i c a l s h i f t b u t n o &-ray

d a t a a r e , as

yet, available. An e x t e n s i v e p a p e r by B u r g a d a

5 g.

reports the reactions

of c y c l i c p h o s p h i t e s ( 7 5 a b ) a n d c y c l i c p h o s p h o r a m i d i t e s ( 7 6 a b ) w i t h trans-1,2-dibenzoylethene, m e t h y l f u m a r a t e , b e n z a l a c e t o n e (PhCH=CH C O M e ) , methyl-4-keto-pent-2-enoate (MeCO.CH=CH.CO2Mej a n d b e n z a l a c e t o p h e n o n e (PhCH=CHCOPh)L5. ylids

( s7. 7)

or spirophosphoranes

These r e a c t i o n s l e a d t o

(e.g. 78

a b ) a n d i n some

70


(83)

P-OMe

(85)X=Me,Ph

+

Me

(86)

- xyxx Y

(85) X=Me, Ph

Me0

Me

O

(84)Y=H,Me

x

(87)

R

( 8 9 a-d 1

( 88a- d 1

a ) R = PrjO ; R‘=Pri b ) R = Pr’O ; R’= But c ) R =Pr’NH,R‘= P r ’

d ) R = Bu‘NH ,R‘= But

(Et0)2PNHC,H,X

(X=pNO,, H , p -Me)

(90)

+

(92) 6”PJX=pNO2= + 3 . 8 , - 2 9 . 8

71

2: Pentaco-ordinated and Hexaco-ordinatedCompounds

(92)

(93)

6 31 P, X = H ,+ 137. 2 , - 27.9 b3'P, X=pMe,+135.0,-32.0

Et,N

PhCH=NSiMe3

+

- NCH,Ph

(91) 31

( 94)

(9616 P=-25.9

NzCHPh

( 9 5 ) 631P,- 24.7,-28.6


72

(97)

CL

I

tx2

( 106)

tx2

R = CH F2C F2C H

[

( R0)2P-N=C=0

]

P=N,

I

c-0

I

CN

,c=o

]

2: Pentaco-ordinatedand Hexaco-ordinated Compounds

73

cases t h e s p i r o p h o s p h o r a n e s u n d e r g o r i n g e x p a n s i o n t o g e n e r a t e spirophosphoranes of type (79).

-

S e v e r a l new s p i r o p h o s p h o r a n e s ( e . g . 82) h a v e b e e n d e r i v e d f r o m a f u r t h e r s t u d y o f t h e r e a c t i o n s o f p h o s p h i t e s ( e . g . 80) w i t h i s a t i n (81)46. The compounds were c h a r a c t e r i s e d by a n a l y s i s , i . r . and 31P n . m . r . s p e c t r a and t h e c o u r s e and rates o f r e a c t i o n depend s u b s t a n t i a l l y o n t h e s t e r i c a n d e l e c t r o n i c e f f e c t s of t h e s u b s t i t u e n t s on phosphorus. Two s e r i e s of p h o s p h o r a n e s ( 8 6 o r 8 7 ) c o n t a i n i n g a d i o x a p h o s pholene r i n g and a 2-phospholene s y n t h e s i s e d from t r i c o - o r d i n a t e 1,2-dicarbonyl by a n a l y s i s ,

or 3-phospholene

r i n g have been

p h o s p h o l e n e s (83) o r (84) a n d

compounds ( 8 5 ) 4 7 . The compounds were c h a r a c t e r i s e d a n d , i n c o n t r a s t t o e a r l i e r work$8

IH and j l P n . m . r .

were f o u n d t o b e s t a b l e t o w a r d s t h e r e t r o d i e n e f r a g m e n t a t i o n . The r e a c t i o n of o n e e q u i v a l e n t o f d i a c e t y l w i t h t h e a z a d i p h o s p h e t i d i n e s (88 a-d) gave t h e corresponding spirophosphoranes (89 a - d ) 4 9 . With t w o e q u i v a l e n t s o f b i a c e t y l , p o l y m e r i c p r o d u c t s were f o r m e d a n d i t w a s n o t e d t h a t (89 a , b ) h a d j l P n . m . r . s i g n a l s a t -24 a n d -32 p . p . m . r e s p e c t i v e l y , w h e r e a s ( 8 9 c , d ) h a d j l P n . m . r . s i g n a l s a t about + 20 p.p.m. The r e a c t i o n of p h o s p h o r a m i d i t e s ( 9 0 ) w i t h t h e c h l o r o p h o s p h o r a n e s ( 9 1 ) p r o d u c e d t h e n o v e l i m i d o p h o s p h a t e s (92) c o n t a i n i n g b o t h t e t r a c o - o r d i n a t e and p e n t a c o - o r d i n a t e

p h o s p h o r ~ s ~ ~ P. h o s -

p h o r o t r o p i c m i g r a t i o n t o f o r m (93) o c c u r s f o r X

=

H o r Me.

The s y n a n d a n t i f o r m s of b e n z y l i d e n e a m i n o p h o s p h o r a n e s (95) h a v e b e e n p r e p a r e d b y r e a c t i o n of N-trimethylsilylbenzaldimines ( 9 4 ) w i t h ( 9 1 ) a n d r e a c t i o n of (95) w i t h d i e t h y l a m i n e g a v e ( 9 6 ) 5 1 . T h e same r e a c t i o n w i t h t h e t r i c h l o r o p h o s p h o r a n e ( 9 7 ) h o w e v e r , g a v e t h e d i a z a d i p h o s p h e t i d i n e (100) v i a ( 9 8 ) a n d ( 9 9 ) . D i a z a d i p h o s p h e t i d i n e s ( 1 0 6 ) o r ( 1 0 7 ) are a l s o p r o d u c e d b y t h e r e a c t i o n o f bis(2,2,3,3-tetrafluoropropyl)phosphoroisocyanatidite (101) w i t h e i t h e r b e n z o y l c y a n i d e (102) o r c h l o r a l ( 1 0 3 ) r e s p e c t i v e -

lp2.

The mechanism, as shown f o r t h e f o r m a t i o n o f ( 1 0 6 ) , p r e s -

umably i n v o l v e s t h e u n s t a b l e b e t a i n e ( 1 0 4 ) a n d t h e c y c l i c i m i n o y l i d (105). An i n t e r e s t i n g r e a c t i o n b e t w e e n 2,4,6-tri-t-butylphenylphosphine (108) and d i e t h y l a z o d i c a r b o x y l a t e (109) r e s u l t s i n t h e formation of t h e di-imidophosphorane

(l12)53.

The a u t h o r s p r o p o s e

(110) a n d ( 1 1 1 ) a s i n t e r m e d i a t e s i n t h i s r e a c t i o n a n d r e p o r t t h a t thermal decomposition of (112) l e a d s f i r s t t o t h e diazadiphospheti d i n e ( 1 1 3 ) a n d t h e n , a f t e r s e v e r a l h o u r s a t IlOOC, t o (114).


74

(98)

+

____,

CI3CCHO

(103)

ArPH,

+

6NC0, E t Ar , P NC0,Et

EtO2CN=NCO2Et

Ar=

-)-@

,NCO,Et

(1091

ArP,

(110)

I

NC02Et (111)

CO,

Et

2 (112)

/

(114) Z= C02Et

C02Et I

CO2Et (113)

63’P,+57.2, + 4 2 . 6

2: Pentaco-ordinatedand Hexaco-ordinatedCompounds

75

0 MeN'NMe \ /

MeN,

Ph3P

/ P-N3 \

N2

+

MeNKNMe 0

,NMe P- N=PPh,

/ \

MeNHNMe 0

(115)

(116)

0

0

K

K

MeN

NMe MeN, ,NMe

p \-' / \ MeNKNMe

MeN

i

\

NMe / P-Cl

/ \

0-P MeNyNMe /\

0

0

+

MeN\ /NMe P-OSi Me3 / \

MeNKNMe 0 MeNKNMe 0 (117)

(118)

0 ( 120)

R2

1

*P-N

R3

R = H , P h , pMeOC,H,, 2 R = H , Ph 3 R = H , Me


76

( 1 2 2 ) R = H , Me

-P-N

/\

\'

(126) A = BH,, BF,

+ + , CH, ,H

(123) R = H , M e

77

2: Pentaco-ordinated and Hexaco-ordinated Compounds The s p i r o p h o s p h o r a n e ( 1 1 5 ) h a s b e e n f o u n d t o react w i t h triphenylphosphine by a conventional Staudinger r e a c t i o n t o p r o d u c e ( 1 1 6 ) w i t h t h e n o v e l i 5 P-N-;4P

g r o u p i n g ; X-ray

d a t a are

available for t h e latterT4. I n a r e l a t e d s t u d y , t h e r e a c t i o n of (117) w i t h (118) f a i l e d

t o g i v e t h e expected bis-spirophosphorane (119) b u t i n s t e a d gave a n isomer ( 1 2 0 ) w i t h t w o N , N 1 - d i m e t h y l u r e a b r i d g e s a c r o s s a A 5 P-0-

5P bond s y s t e m .

crystal s-ray

T h e p r o d u c t was c h a r a c t e r i s e d b y m . s . ,

and its s t r u c t u r e w a s d e t e r m i n e d by a s i n g l e

i . r . and n.m.r.

diffraction studyc5.

T h e 1 3 C a n d P-C

coupling c o n s t a n t s o f a range of b i c y c l i c -

p h o s p h o r a n e s of t y p e ( 1 2 1 ) - some w i t h c h i r a l p h o s p h o r u s a t o m s , B i c y c l i c p h o s p h o r a n e s of t y p e

have been described i n (122) with R

=

H h a v e b e e n shown t o r e a c t w i t h G r o u p

171

a n d Group

V l l l metal c o m p l e x e s w i t h f o r m a t i o n o f a d d u c t s o f t h e g e n e r i c ligand (123)57.

T h u s r e a c t i o n o f bis(2-methylallylchloro-

p a l l a d i u m ) - ( 1 2 4 ) w i t h t w o e q u i v a l e n t s of ( 1 2 2 , R m o n o n u c l e a r complex ( 1 2 5 ) .

=

Me) g a v e t h e

C a t i o n i c s p e c i e s derived from t h e s e

complexes c a t a l y s e t h e o l i g o m e r i s a t i o n o f b u t a d i e n e t o a f f o r d m a i n l y t r i m e r s a n d tetramers. phosphorus-nitrogen

The c o o r d i n a t i o n c h e m i s t r y o f t h e

e n t i t y is d i s c u s s e d i n a p a p e r b y Riess5* which

p o i n t s o u t t h a t n i t r o g e n atoms a p i c a l l y b o n d e d t o f i v e - c o o r d i n a t e d , formally pentavalent phosphorus atoms, d i s p l a y d e f i n i t e b a s i c i t y . S t r u c t u r e s o f t y p e (126) and (127) are i n c l u d e d i n t h e d i s c u s s i o n . Finally i n t h i s section,

a s e r i e s o f n e u t r a l a n d c a t i o n i c 10-

P-5 s p e c i e s ( 1 2 9 - 1 3 1 ) h a v e b e e n o b t a i n e d f r o m t h e r e a c t i o n of ( 1 2 8 ) BF3 a n d E t 3 S i + ) 5 q . w i t h L e w i s a c i d s (3.

5.

H e x a c o - o r d i n a t e d P h o s p h o r u s Compounds. - T h e r e a c t i o n of PCL5

w i t h alkylammonium f l u o r i d e s i n t h e p r e s e n c e o f s e c o n d a r y a m i n e s g i v e s PF5-amine

adducts (132)6G.

The a d d i t i o n a l p r e s e n c e o f

a l c o h o l s o r phenols l e a d s t o t h e formation of alkoxy- or aroxypentaf l u o r o p h o s p h a t e s , ROPF5-.

T h e PF5-amine

a d d u c t s may a l s o b e

c o n v e r t e d i n t o ROPF5- b y t r e a t m e n t w i t h a l c o h o l s o r i n t o ArNHPF5by treatment with primary arylamines.

An n . m . r . s t u d y of t h e p e r m u t a t i o n a l i s o m e r i s a t i o n s w i t h i n a series of a m i d i u m f l u o r o p h o s p h a t e s ( 1 3 3 ) h a s r e v e a l e d a n i r r e g u l a r m e c h a n i s m w i t h d i s s o c i a t i o n of t h e P-N a n d a l s o t h e P-0 b o n d s o f t h e b i d e n t a t e l i g a n d s a n d t h e f o r m a t i o n of f i v e - c o o r d i n a t e i n t e r mediates (134)61.

Reversible i n t r a m o l e c u l a r m i g r a t i o n s o f pentaco-

o r d i n a t e p h o s p h o r u s i n t h e N-C-N

-

t r i a d of amidines ( e . g .

135,

136,

1 3 7 ) were s t u d i e d f o r t h e f i r s t t i m e i n t h e s e s y s t e m s .

In a r e l a t e d p a p e r , t h e permutational i s om e r is a tio n s of N,N-

78


(129) O3'P, -18.1

0

?SiEt3

II

(128)

(130)

63'P, -18.7

631P,-6.6

E t,S
P-NEt2

>P-NEt2*H2NEt: k-1

+

>P-NEt;H2NEt:

MeOH

-% k

+ MeCOOH

>P-NEt2

+ Et2NH 4-

>P-OMe

Et2NH:

>P-OCOMe

+

>P-OMe+

MeCOOH

Et2NH

k-1

I- MeOH

>P-OCOMe

-%

Scheme 1

+

R~P? I

2 R N :

R2=Mc E t ,Bu

R1: Me E t

DMTou DMToPB 1

0.

0,

'P-N-CH2-@

I

MeO'

MeO'

Et

+

I

vN

HX

+

(RIS),PX

R2,NH

X=OR,SR

(133)

+

,NZN

(132)

(131)

(R1S),PNR2,

EtSP(NEt2I2

P-N

\o/

ZnC12

-+

Et-bP(NEt,),

I 1

EtSCH2C?OP(NEt,),

C H2CH20-

(134)

(135)

(136)

RS02CH2CH20- P

NC'

PhS02CH2CH20-P

.0

NMc2

" i 0

W

(137) R=Me Pri I But PhCH,, L-O,NC,H,CH, j Ph

c1 ,

" " ' O V

( 1381

O\ P-NR22

R' SO,CH,C

3 0 '

( 139)

4: Tervalent Phosphorus Acids

119

The reactions were catalysed by acids (amine hydrochlorides or LiC1). The “mechanisms” propoacetic acid) but not by anions (3. sed are given in Scheme 1 . The function of the acidic catalyst in alcoholysis reactions of phosphoramidites has not been elucidated yet, but low reactivity of a series of alkylphosphinylenebis(trialky1ammonium) iodides (130) towards water and alcohols 69 points against protonation at nitrogen as the way of activation. Tetrazole has been shown not to act solely as a proton donor when used as a catalyst for nucleoside phosphoramidite couplings.7 0 This follows from experiments with polyrnersupported nucleoside phosphoramidites (1311, from which compounds fully activated for reaction with nucleosides are liberated upon treatment of (131) with a solution of tetrazole in acetonitrile. Whether the active compounds are nucleoside phosphortetrazolides (132) or subsequent products was not clarified. Dithiophosphoramidites (133) react with alcohols, phenol, or R2N is a alkanethiols by displacement of the amino group,7 1 better leaving group than RS in these systems. Similar compounds, 3. (1341, react with ethylene oxide, catalysed by zinc chloride, (136), to give (135). 7 2 The reaction probably proceeds R2S+ is a better leaving group than R 2 N .

e.

e.

3.3 Use for Nucleotide Synthesis.- Several new tervalent phosphorus reagents have been proposed to introduce phosphorus at 3’- or 5’-OH groups in nucleosides These ipclude the 2-sulphonylethyl phosphoramidochloridites ( 1 37) 73 and ( 1 38) ,7 4 which gave deoxyribonucleoside-3’ phosphoramidites (139) containing O-alkyl groups easily removable after DNA synthesis by B-elimination; di(2,2,2-trifluoroethyl) trimethylsilyl phosphite ( 140) , which gave high yields of deoxyribonucleoside-3’ phosphates (141); and dialkyl diisopropylphosphoramidites (142), 7 6 which were used as the last cycle reagents in automated DNA synthesis to give 5’-phosphorylated oligonucleotides. Diisopropylphosphorodichloridite (143) has been applied for the preparation of several deoxyribonucleotide-3’ phosphoramidites (144), including N and S analogues.7 7 In a similar approach, tetraisopropylphosphorodiamidochloridite (145) was used to obtain deoxyribonucleoside-3’ phosphoramidites ( 1 4 6 ) 7 8 To prepare deoxyribonucleoside-3 hydrogenphosphonates (1471, which are promising alternatives to phosphoramidites for DNA synthesis,79 the reagents (148) and (149) ,80 or (150),81 may be profitably used. A new reagent, ( 1 5 1 1 , has been used to prepare deoxyribonucleoside-3’phosphoramidites ( 146 , R = CM2CH2CN) in situ;82 the solutions of

.

’’

.

120


DMTopB

(CF3Ct$O),P-OSiMc,

i)(l&o)/Py

ii) peracid iii)Et3N / H20

(140)

OH

R'O

0, CF~CH~O'

,

40

P

'0 -

(141 1

,P-NPrI2 RO (I4 21

R' = ~ ec H , ~ H,C C N

c H,CH,

No2

R'= CH~CH'CN CH,CH~--@~,

+ Pr',NPCl,

+

D M T O ~ T D M T O ~ T

B

~ ~

D M T DMTO-,@

I

(143)

O

~

~

I

OH

cl/PO\

Rxy

DMTov

NPrip

,O

P-NR'2 RX' I1441 R X Z MeO, NCCH,CH,O ,CCl3CH20 CC13CMc20,PhCH20, 2-Cl-C,HLOJ P h S , PhNH

(Pr',N),PCI (145)

+

Et N

.

I

0 -PIN Pr ;),

OH

p 2 0 r o l e

DMToPB

+

,0 ,PNPr', RO (146) R =CH2CH2CN CH?CH=CHZ CH2-C6HL- 2 NO2

-

OCOPh

4: TervalentPhosphorus Acids

121

0- P(NEt,),

NCCH2CH20P(NPrip)2 I

ar4

I

\

\ 1311

,O

I

Oib Oib

OR

NCCH,C%O-P,

(153) i b =PriCO

NPr',

(152) R

C H T CHCH2OP( NMe, 1,

0

, ButMezSi

MMTold bSi ButMe2 (155)

B = T , AbZ


122

(146) were applied successfully on an automated DNA synthesizer. The same reagent was used to prepare ribonucleoside-3’phosphoramidites’ (152, R = 2-tetrahydropyranyl) 83 for RNA synthesis on silica supports, and (152, R = t-butyldimethylsilyl) and (153) for assemblage of a branched tetraribonucleotide 84 Another alkyl phosphorodiamidits (154) has been introduced to prepare dinucleoside allyl phosphates (155);85 the allyl group is easily removed by catalytic amounts of Pd(Ph3PI4 and a nucleophile, e.g. butylamine. An elegant route to synthesise RNA oligomers on solid supports, which obliviates the need to protect and deprotect the 5‘-OH groups of the ribonucleoside monomers, has been briefly described.83 The procedure is outlined in Scheme 2. Ribonucleoside-3’phosphoramidites (156) have been prepared from methyl phosphoramidochloridites (157) and used for automated synthesis of oligoribonucleotides on a controlled pore glass support.86 The phosphoramidites (156, R = Pri) gave coupling efficiencies of up to 98%. The chloridite (157, R = Pri) has also been used to prepare (158) and (159) which were applied in the first synthesis of branched triribonucleotides.87 Polystyrene-supported deoxyribonucleoside-3’ phosphoramidites (160), or analogous compounds bound to the support via a piperazine linkage, have been used in a three-phase synthesis of oligonucleotides. 7 0 An activated nucleoside derivative, presumably (1 61 ) , is liberated upon treatment of (160) with tetrazole in acetonitrile, giving high coupling yields in standard polymer-supported DNA synthesis. Several groups have used dinucleoside-3’ phosphoramidites as building blocks for synthesis of oligodeoxyribonucleotides.88-90 In one case the dimer used contained l80 on the phosphate in a known configuration,89 in another case the use of dimers allowed synthesis of a 101-mer in a 15% overall yield (DMT efficiency).9 0 A triribonucleoside 2-5A core analogue has been synthesised using 2,2,2-trichloroethyl phosphorodichloridite. Modifications of guanine bases by nucleoside phosphoramidites are shown to occur during solid phase synthesis of oligonucleotides.92 This is claimed to cause very low yields of oligonucleotides if they contain a large number of guanine bases. In a study of the relative yields of the components in synthesis of mixed sequence oligonucleotides it was observed that deoxyribonucleoside-3’ phosphoramidites containing 2-cyanoethyl groups were more stable in solution than their methyl protected counterparts.93

.

123


cat.

" - O V ' OH OR

O ,

OR

.

MeO-P,

N Pr '2

@wold' . .

1 2 / H20 f

"-"V' Me0

-

O,

OR

p'oYiB2

OH OR

OH

OR

Scheme 2 MeO,

"".OV O,

MeO-

R;NAp-oYl

OSiButMe2

P,

NR2

.

(156) NR,= NPr',, N

W0 M M1

Pr ;N

-Po, ,

P - N Pr I2 OMC MtO'

"""VB McO' (160 1

0,

DMTo

I

Et

(161)


124

+ ( COD 1 P t I

/

/Pt

\

I I

@*

(162)

+ (163)

ii'

-C -Si Me3

( PriN 12P

hv

[( Pr ;N

),Pr C -Sib&,++(

Pr LN),l%-Si

,I

Me

(165) 6, -41

(164)

Xb0

CL

'

I

( Pr;N ),P=C(

Si Me,),

(166)

OPPh,

(168) R = H , M e

I

R3

I

\Ph

(169) R ' = H , Me R2, R 3 = H , PPh,

PPh, (170)

\Ph

125


H

2 , [ph-P=S]

ROH

+

I

Ph-PP=S

I OR

(173)

H

5 [Ph-P=Se]

MeOH

+

A

[x-P=S]

0

(179) X = OCHZCCI,,

%Me

\ NM e 2 (177)

I R' (180)

I

OMe

(174)

-

I

Ph-PZSe


126

3.4 Miscellaneous.- The planar 10-P-3 compound (162) forms a platinum complex (163) in which the ligand is bent (has the normal 8-P-3 structure) 94 A distillable diamino (diazomethyl)phosphine ( 164) upon uv irradiation gave a very unstable intermediate, presumably (165), trimethylsilyl chloride to give which could be trapped with g . (166). 9 5 New tervalent phosphorus ligands for use in asymmetric catalysis reactions are (167) 96 and (168)-(170). 97

.

4 Reactions involving Two-co-ordinate Phosphorus Pyrolysis of ally1 phosphorodichloridite (171) at 1150 K gave phosphoryl chloride (172) which was characterized by mass and matrix infrared spectroscopy.98 Phenylthioxophosphine ( 173) and phenylselenoxyphosphine (174) are probable intermediates in thermolysis of (175) and photolysis of ( 1 76) , resp.9 9 Similar tricyclic compounds (1 77) gave (178) on thermolysis in the presence of 2,3-dimethylbutadieneI probably via the thiophosphenous acid derivatives (179).100 1 review has appeared on cycloaddition reactions of tervalent P=C, P=N, and P=P compounds. Like a-diketones, a-diimines with 1 ,2,4 ,3The aminoiminophostriazaphospholes ( 180) gave phosphoranes ( 18 1 ) phine (182) is alkylated at the three-co-ordinated phosphorus atom by methyl iodide, but at the two-co-ordinated phosphorus atom by more bulky alkyl halides. O2 Aminoiminophosphines have carbene or alkene character depending on the substituents. Thus (183) with hexafluoroacetone gave (1841, but (185) gave (186).'Io3 The results were correlated with the n and 71 ionisation potentials. The first representatives of a 1 ,2-azaphosphole, (1 87), O 4 and a 1 ,2 ,4-thiadiphosphole , ( 1 88) , have been prepared. Phosphenium ion synthesis and reactions have been reviewed. A full paper has appeared on the reactions of phosphenium ions with 1 ,3- and 1,4-dienes. The reactions with 1,3-dienes are stereo(189) with transItrans-2,4-hexadiene gave only (190), specific, the product expected from a [2+4]cheletropic cycloaddition reaction. With l,$-dienes, 1,5-additionoccursto give, %. ( 1 9 1 ) . Cyclo-octatetraene and the phosphenium ion (192) gave a 9-phosphabarbaralene (193),which undergoesfast Cope rearrangements at room temperature; an 5-ray crystal structure determination shows a nearly symmetrical structure. O7 The stannazene (1 94) with phosphorus trichloride surprisingly gave the dipolar phosphenium stannate (195).108 Two diphosphenes (1 96) , O 9 two phosphaarsenes (197) and a phospha-

.

%.

127

4: Tervalent PhosphorusAcids

+

R~N-PP=N-R' 1

(CF,),CO

f 181)

(183) R'= R2= Me3Si

(185) R'= P r ' , R2= But

Pr;N

- P-NBut

I I 0- C(CF3l2

Me3SiS,

I

R' ( 1 87 1

I

Me (190)

(189) Me N

2 \ +

P

(191)

+

CI'

(192) But

But

I

I PCI,

-t 2 ButN(SnMe3I2 (19L)

C I - P /N-

\

SnMe3

N-SnMe3

I But

*

+

N ,SnMe,CI

/ \ -

P,

N

I

B"+ (195)


128

J

-LO

(196)E=P, R2N=(Me3SiI2N, (197) E=As,R=Me3Si 6ufMe2Si (1 98) E = S b R = But Me2Si

C;

P-NEt,

Et,N

-P

OC


129

stibene 11981 have been prepared by thermal elimination of trimethylsilyl chloride as shown. Even the phosphastibene (198) i s stable "for a long time" at room temperature. The trans-diphosphene (199) reacts with diazomethane to give a thermally stable diphosphirane (200);'I1 diazomethane did not react with the isomeric cisdiphosphene at -78 OC. 5 Miscellaneous Reactions

Polymerisation of 2-diethy1amino-lr3,2-dioxaphosphorinanes (201) and ( 2 0 2 ) t o high molecular weight polyphosphoramidites are initiated by potassium t-butoxide; after hydrolysis and oxidation polyphosphordi112 esters of potential for biological applications are obtained. References

1 A. H. Cowley and R. A. Kemp, Chem. Rev., 1985, 25, 567. Dianova, Phosphorus Sulfur, 1986,

2 B. A . Arbuzov and E. M .

26, 203.

3 J . G. Riess, Phosphours Sulfur, 1986, 27, 93. 4 Chemica Scripta, 1986, 26, pp.1-251. 5 B. Corbel, L. Medinger, J. P. Haelters, and G. Sturtz, Synthesis, 1985, 1048. 6 J . R. H . Wilson, J. Chem. SOC., Perkin Trans. 1, 1986, 1065. 7 W . J . Stec, G. Zon, W. Egan, R. A. Byrd, L. R. Phillips, and K. A. Gallo, J. Org. Chem., 1985, 50, 3908. 8 H. R . Hudson, L. Powroznyk, and A. R. Qureshi, Phosphorus Sulfur, 1985, 25, . , 289. 9 A.-M. Caminade, E. Ocando, J.-P. Majoral, M. Cristante, and G. Bertrand, Inorg. Chem., 1986, 25, 712. 10 P. A. Gurevich, T. V. Komina and G . Yu. Klimentova, J. Gen. Chem. USSR, 1984, 54, 2510. 1 1 M. V. Livantsov, A. A. Prishchenko, and I. F. Lutsenko, J. Gen. Chem. USSR, 1985, 2,2195. 12 R. Meuwly and A. Vasella, Helv. Chim. Acta, 1986, 2,25. 13 K . Issleib, A. Balszuweit, J. Kotz, S. Richter, and R. Leutloff, 2 . Anorg. Allg. Chem., 1985, 529, 151. 14 F . Effenberger and H. Kottmann, Tetrahedron, 1985, 41, 4171. 15 D. El Manouni, Y. Leroux, and R. Burgada, Phosphorus Sulfur, 1985, 25, 319. 16 D . E l Manouni, Y. Leroux, and R. Burgada, Tetrahedron, 1986, 42, 2435. 1 7 K. Issleib, W. M8gelin, and A. Balszuweit, 2 . Chem., 1985, 370.

18 Yu. G . Shermolovich, A. V. Solov'ev, E. A. Danchenko, and L. N. Markovskii, J. Gen. Chem. USSR, 1985, 55, 254. 1 9 2 . S . Novikova, M. M. Kabachnik, N. V. Mashchenko, and I. F. Lutsenko, J. Gen. Chem. USSR, 1985, 2, 404.


130

2 0 D. W. Morton and R. H. Neilson, Phosphorus Sulfur, 1 9 8 5 , 25,, 3 1 5 . 2 1 T. Kobayashi and M. Nitta, Chem. Lett., 1 9 8 5 ,

1459.

2 2 L. WoZniak, J. Kowalski, and J. Chojnowski, Tetrahedron Lett., 1 9 8 5 , 26, 4 9 6 5 . 2 3 D. V. Griffiths, H. A. R. Jamali, and J. C. Tebby, Phosphorus Sulfur, 1 9 8 5 , 25, 1 7 3 . 2 4 D. V. Griffiths and J. C. Tebby, J. Chem. SOC., 1986, 871.

Chem. Commun.,

2 5 I. L. Odinets, 2. S. Novikova, and I. F. Lutsenko, J. Gen. Chem. USSR, 1 9 8 5 , 55, 5 5 3 . 2 6 J. R. Lloyd, N. Lowther, G. Zsabo, and C. D. Hall, J. Chem. SOC., Perkin Trans. 2, 1 9 8 5 , 1 8 1 3 . 2 7 G. A. Krafft and T. L. Siddall, Tetrahedron Lett., 1 9 8 5 , 2 8 A. Plopusifiski and A. Haas, Chem. Ber., 1 9 8 5 ,

26,

4867

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535,

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4 9 V.

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J. 7 3 C. R. 7 4 N.

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3, 1 0 2 3 ;

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27,

27,

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9 3 G.


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25,

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2,1 5 3 .

5

Quinquevalent Phosphorus Acids BY

R. S. EDMUNDSON

Aspects of the chemistry of carbohydrate phosphates,' and of phosphonomycin ( cis-3-methy 1-2- oxirany lbhosphonic acid have been reviewed.

1. Phosphoric Acids and their Derivatives 1.1 Synthesis of Phosphoric Acids and their Derivatives.- A detailed study of the kinetics of formation of alkyl phosphorodichloridates and dialkyl phosphorochloridates from P0Cl3 and alcohols has been described in a series of papers.3 Monoalkyl dihydrogen phosphates have been prepared in quite high yield in the apparently facile interaction of alcohols and a reagent prepared from P4Ol0 and he~amethyldisiloxane.~Several cyclic hydrogen phosphates ( 1 ; K = Me, MeO, EtO, C1, or C12) have been synthesized and resolved; the 2-chlorophenyl compound is an effective resolving agent, and its absolute configuration has been deter~nined.~ The cyclic acid (2) and its trimethylsilyl ester have been obtained during a study of the chemistry of 2,2,2-triethoxy-2,2-dihydro-tetrakis~trifluoromethyl~-ly3y2-

dioxaphospholane.6 Enol phosphate esters of types ( 4 ) and ( 5 ) have been prepared by reaction between trialkyl phosphites and (3; R = H or Me). Shikimic acid has been converted into the 5-enol-3-phosphate (6; R = CH2Ph), and thence to the free acid (6;R = OH) by the use of tetrabenzyl pyrophosphate.8 During the course of an examination of the substrate specificity of glycerol kinase, several 3-substituted-propane-ly2-diol1-phosphates were ~ r e p a r e d . ~A general method for the synthesis of glycerophospholipids (Scheme 1 ) employs compounds of tervalent phosphorus in the initial stages;lOthe choice of reagent (v or vi, vii or vi) depends on the protecting group in R2 derived from choline tosylate, N-tritylethanolamine, or 1,2-isopropylide-eglycerol. A second prccedure designed for 134

5: Quinquevalent Phosphorus Acids

135

related compounds (Scheme 2) is based on a condensation achieved by the use of 2,4,6-triisopropylbenzenesulphonyl chloride (TPS-C1) .I1 Methylation of (7; R-H) was employed as a means of purification of the acid since the methyl ester (7;R=Me) could be demethylated readily by NaI. Solution and solid phase techniques have each been used in the synthesis of appropriately N-protected g-phosphoseryl 12 peptides. Trialkyl phosphorotetrathioates are convertible to the phosphorodibromidodi thioates ( 8 1 by the use of PSBr3.l 3 A study of the 1,5-dihydro-7,8-dimethyl-2,4,3-benzodithiaphosphepin derivatives (9 has centred on spectroscopic and X-ray techniques .I4 Bis(trifluoromethy1) disulphide has been shown to react with the phosphite ( 1 0 ) ( and also its phosphorus epimer) in an essentially stereospecific manner giving the thiophosphates (11; a and b) in the ratio 8 9 ~ 1 1 .However, methanolysis of the latter compounds is much less stereospecific; from lla, for example, the yields of (12) and (13) are in the ratio 69:31, and the compounds ( 1 4 ) and ( 1 5 ) are also formed in the ratio73:27.15 The thermally-induced cyclization of (2-haloethyl)phosphoramidothioic esters (16) to give the 1,3,2-thiazaphospholclosely related idines ( 1 7 ) has been reported in fu1l;''some syntheses were reported several years a g o but only in preliminary form. The example illustrated in Scheme 3 is, perhaps, a little more surprising.17 In a new approach to the synthesis of phosphoramidates by the Todd-Atherton reaction, those from the more weakly basic amines, more particularly aromatic amines, have been obtained by reaction between dialkyl hydrogen phosphonates and the N-formyl or N-chloroacetylarylamine in a two-phase system.1 8

1.2. Reactions and Properties of Phosphoric Acids and their Derivatives.-The use of isotope labels, in particular l 8 O , at appropriate sites, as a means of differentiating between alternative mechanisms in phosphorus chemistry, continues to expand. The Appel reaction (between dialkyl hydrogen phosphate and arnine in the presence of Ph3P/CC14) exemplifies such application. The known final products could arise either directly by interaction of a nucleophile and the proposed intermediate


136

&;, \

Me

R

5

R

(3)

0

a II

0 P(OR21, I

R'

0

\

R'o R'O

slL

vd o r vi

0IIO ,R ,OP,

. S

OP, i , Pr$(MeO)FCi

, Et3N;

2

Scheme 1

'''1 .

:,OR2 OP O 'H

-

R'O7 OR ,2;

OR2

OP\

OMe

i i , R 2OH, tetrazole;

i v y S8 ; v , PhSH ( o r EtSH) , Me3N

R'o

OMe

v i i or V I.

,I Reagents:

OMe

OH

i i i , Me3COOH ;

; v i , MeCOOH ; v i i ,

Me3 N


137

R'O

I

Me0

I

OR3

OH (71 2

1

R = palmitoyl or oleoyl ; R = palmitoyl ReagenTs: i , T E - C l

;

ii, CH2N2

Scheme

2

i

RSPBr, S

( 8 )

A

X

(12) X = OMe ; Y = = O (13) X - = O ; Y =OMe

OAr

(14) A = = O (15)P.z F

;

B=F

i B:=O

138


(18;Scheme 4) or indirectly by initial expulsion of k'h3k'0 and subsequent involvement of a phosphoryl chloride. The model compounds examined were based on the 4-methyl-1,3,2-dioxaphosphorinane system. The =-and trans-2-hydroxy 2-18U-oxides ( 1 91 were separately converted into the diastereoisomeric anilides (2U). No evidence was forthcoming to suggest the participation of an initially-formed phosphorochloridate, and evidently the axial oxygen undergoes preponderant reaction (by a factor of 6 6 1 , the reaction proceeding with inversion of configuration through an intermediate probably of type (18).19 Another brief but interesting communication2' outlines a reexamination, based on 180-induced changes in phosphorus chemical shifts, of the reaction between a methyl phosphate ester and a phosphorylchloride to give a pyrophosphate, and which employed models based on the 5,5-dimethyl-1,3,2-dioxaphosphorinane system. Far from being the simple process of phosphoryl attack on phosphorus a s originally envisaged, the complete scrambling of the oxygen label was attributed primarily to the participation of a tricyclic dioxadiphosphetane intermediate ( 2 1 1 , but the presence of: free cyclic phosphoric acid introduced further complications. The kinetics of hydrolysis of 4-nitr0phenyL~~ and 2,4-dinitrophenyl dihydrogen phosphates22 (see also ref. 3 0 1 have been determined. In the hydrolysis of diphenyl 4-nitrophenyl phosphate,replacement of R=H in the tetraco-ordinate zinc complex (22) by R=C16H33 results in the enhancement of the catalytic effect of the complex.2 3 Expulsion of dinitrophenate and formation of monodentate N-bound phosphoramidate in almost quantitative yield is observed when coordinated 2,4-dinitrophenyl pentaaminecobalt( I 1 1 1 is treated with aqueous base. 24 A further test of the stereoelectronic theory ot reactivity of phosphate esters has been attempted using measurements ot the rates of displacement of: 4-nitrophenate from the esters ( 2 3 ) and (241, their phosphorus epimers, and also (251, in aqueous methanol; the introduction of the 4a-Me group into the system would, it was hoped, reduce the the flexibility of the bicyclic structures and so possibly eliminate the participation of twist-boat conformations. The presence of the 4a-Me group has no effect of: the rate of displacement of the axial ArO group


139

(16)

X = C I or

(17) 2

1

Br ; R = a l k y l ; R = alkyl or CH,CH,X

; Z =alkyl ,alkoxy, or aryloxy

0

II

(Et2N),P-NCH2CH,Br

I

heat

+

-EtBr

Et Scheme 3

(18)

\

- Ph3P0

'

Reagents: i , Ph,P Cclq ; ii, bhki

Scheme 4

i; (19)

(20)

.=

18

0

0

\p4 a'


140

CI

(211

0

II

R

(23)R = H ( 2 4 ) R = Me 0

(26)

11

R'-

Re (27)

kR+

c p

,.OMe

0-P0

oI'-

-0

- cp/.0-P.

Ib o -

0 Me

ROCH CH OP-0

*

(29)

* I

(30)

Scheme 5

0-


141

whereas for the (pseudo)equatorial aryloxy groups, the added methyl group reduces the rate of displacement. Each equatorial epimer hydrolyses faster than the corresponding axial compound, and compound (25) hydrolyses at a rate intermediate between those of the equatorial isomers on the one hand, and the axial isomers on the other. Such relative rates of hydrolysis were thought to be consistent with the idea that axial isomers react via chair conformations, whilst the equatorial isomers react via twist-boat conformations with the aryloxy group in the pseudoaxial position. 2 5 The factors involved and mechanistic pathways in the hydrolysis of phosphate esters, particularly those of a cyclic nature, continue to be the source of much speculation. A further study of the simplest cyclic triester, ethylene methyl phosphate, seems only to have served to consolidate already polarized views. The original experiments of Westheimer's group employed H nmr spectroscopy and demonstrated that ethylene methyl gc and ' phosphate (26) hydrolyses under alkaline conditions by processes which include exocyclic bond fission. More recent work by Gorenstein et al. using 31P nmr spectroscopy apparently showed that, consistent with the stereoelectronic theory of phosphate ester reactivity, there was complete endocyclic bond cleavage for solutions of (26) in 5M aqueous alkali. A re-examination of the hydroLysis of ester (261, using both ' H and 31P nmr techniques, now confi-rms that exocyclic cleavage to give MeOH and ethylene hydrogen phosphate does indeed occur, and that che extent of that process increases with higher concentrations of base (Scheme 5: R=H, O=O=160). In addition, the - methyl 2-hydroxyethyl product of initial ring opening,viz hydrogen phosphate, hydrolyses too slowly to account for the amount of methanol liberated in the early stages of the hydrolysis of (26).26 The mechanism outlined in the Scheme requires that direct ring opening of the initial pentaco-ordinate intermediate ('27328) competes with proton ( R - H ) removal (27--)29) prior to pseudorotation. The minimal amount of exocyclic cleavage product produced in dilute base indicates that ring opening is faster than pseudorotation. As the concentration of base is increased, the rate of proton removal increases relative to that of ring opening.

142


The results of additional experiments using D20 containing D2I80 are also conveniently incorporated into Scheme 5 (R=D; O= 160, 0= 18O).27 Using conditions as close as possible to those employed by Goren scein et al., Kluger et al-showed that only one equivalent of base DO- was incorporated during exocyclic cleavage; in spite of kinetics indicating second order dependence on base, the lack of incorporation of a second equivalent of base suggests that it is probably used simply for proton removal in the stage (27+29). Since 2-hydroxyethyl dihydrogen phosphate (30) triply labelled with isotopic oxygen is also not formed, it seems unlikely that hexaco-ordinate intermediates are not involved in the hydrolysis of (261, a point over which chere does appear to be agreement. Many mechanistic aspects of the hydrolysis of phosphate esters in protic media remain uncertain. In spite of predictions that racemization at phosphorus should be the final outcome if indeed the (hypothetical)metaphosphate intermediate is involved in the solvolysis of monoesters, Che results of several studies on the methanolysis of appropriately 0-isotopically labelled compounds are consistent with reactions proceeding with inversion o f configuration, as observed for all enzymic and non-enzymic systems so far examined; this has resulted in the suggestion that if metaphosphate is actually formed, then it must be in a 'masked' form. In the quest for 'free' metaphosphate, racemization has been observed for phosphoryl transfer from phenyl dihydrogen ( E l - [ 160,170,180]-phosphate to tert-butyl alcohol in MeCN. 28 The solvolysis of isotopically-chiral (S)-adenosine-5'-diphosphate (31) by inter alia tert-butyl alcohol a l s o proceeds with racemization.29 However,the preassociation of metaphosphate with solvent molecules and multiple transfers with other solvent molecules before entrapment by the alcohol has been advanced as an alternative explanation for the racemization observed. Moreover, Ramirez et al. found that the liberation of 2,4-dinitrophenoxide from its monophosphate dianion in aqueous solution is accelerated by pressure, a result not possible to reconcile with the intermediacy of 'free' metaphosphate.30 Other workers have concluded that, for the solvolysis of phosphate monoesters, the bonding between nucleophile and mecaphosphate is not far developed in the transition state and


143

that the very large rate accelerations observed in enzymecatalysed transfers must depend particularly on the microenvironment:large rate enhancements were found for dipolar aprotic solvents specific for the dianion substrate.31 Compound (32) phosphorylates hindered alcohols in the presence of EtOH consistent with a dissociative mechanism involving a metaphosphate-like intermediate,since it proceeds with considerable racemization at phosphorus(Scheme 6 ) . The extent of phosphoryl transfer which proceeds with retention of configuration is ca. 35% ( i L . ca. 70% racemization); the excess of (SIP configuration would arise from transfer with configurational inversion, and might indicate a relatively 'free' metaphosphate but is also consistent with the preassociative mechanism discussed above. 32 33 The involvement of monomeric metaphosphate in the phosphoryl transfer from phosphate monoesters, and of pentaco-ordinate intermediates from phosphotriesters represent two extremes in the mechanistics of the phosphoryl transfer process. Between the extremes are the ( S N 2 ) p processes involving transition states having various bond orders, but no true intermediates. The conclusion reached from a study of the hydrolysis of j180]-glucose-6-phosphate was that the total bond order izo phosphorus is not conserved in the transition state.34,35 Evidence has appeared suggesting the participation of pentaco-ordinate intermediates in the reaction between phosphorothioic acids (Scheme 7 : RL=Et or Ph) and carbohydrate epoxides. The reactions were followed by 31P nmr spectroscopy and signals were observed corresponding to the 2-alkyl esters (33), the isomeric 9-alkyl esters ( 3 4 ) and also stereoisomeric forms of the 1,3,2-oxathiaphospholane (35), the formation of which was favoured for R1=Ph presumably because of the better leaving character of PhO-, but the equilibrium can be shifted towards (35) by removal of EtOH. Since (35) cannot be the intermediate between (33) and (34), there must be another, and this is purportedly the pentaco-ordinate species which undergoes pseudorotation. 36 In the reaction between nucleotide cyclic 0,0-3',5'-phosphorothioic acids with styrene oxide, oxidation is accompanied by extensive rearrangement of the six-membered ring to the Fsomeric cyclic 2',3'-phosphate.37 An interesting communication concerns an attempt to quantify bond orders in thiophosphoric acids using 34s and 36s-


144

( 31

S-

0-

I

EtOP-0-P-0

II

0

(32)

I

0 . ~ ~ 0e ,= o 17

, o =18o

-

II 0

yo

MeS

/ \ -

0

EtO

0

0 It

S P(OR’),,

2

0

Scheme 6 R2

0

\

R’O-P-S

I

I\

R’O OH

2

R2CP,0R1 o-p\

I

0R’

OH

11

(33)

R‘

(35)

R2=

F0Y0

1””

(34)

0

O+Me Me

Scheme 7

145


induced perturbations of "P chemical shifts for the model compounds ( 3 6 ) and (37).38The results have suggested chat che negative charge in the anion of the hvdrolysis product (38) is located on sulphur with the phosphorus-sulphur bond of order 1. This is in agreement with earlier measurements of l 8 O perturbations of 31P chemical shifts in 0-alkyl and O,O-dialkyl phosphorothioates. An X-ray analysis has confirmed the structure of the product ( 3 9 ) formed when 2-aminobenzamiae is heated with P4Sl0 in pyridine (there is no reaction in toluene,. In the presence of alkali, dimethyl sulphate converts ( 3 9 1 into (40; R=SMe) which, in turn, yields ( 4 0 ; R=C H N or PhNH) by reaction with pyrrolidine or aniline. 34 In the synthesis of butenolides substituted in a position adjacent to the carbonyl, the bis(dimethy1amino)phosphinyloxy group has been employed for the direction of an incoming electrophile (Scheme 8).40 Azines have been prepared by initial condensation of diethoxyphosphinylhydrazine anions with aldehydes or ketones (Scheme 9 ) . Phosphoryl azides undergo 1,3-dipolar cycloaddition to 2-tetralone enamines to give triazolines, possibly en rouce to amidines.42 A full paper on the addition of diethyl dibromophosphoramidate to alkenes(1eading to the synthesis of 2-bromoalkylamines) has appeared.4 3

'+'

The phosphorylation of alcohols by CEP-imidazole" (41;X=N)with CEP-ring retention is already well-established. Following from the observation that CEP-pyrrole (41;X=CH) phosphorylates alcohols with CEP-ring opening, an explanation has been advanced based upon the differences in apicophilicities of the pyrrole and imidazole moieties in pentaco-ordinate intermediates (Scheme 10).44 A scale of relative reactivities based upon the reactions in the equations + Azole' , k CEP-Azole2 + Azole 1 CEP-Azole' .t*

-1.

CEP-Azole + TMGH"" 7 --l CEP-TMG + Azole was drawn up for a series of azoles and also for N , N , N I N 1 tetramethylguanidine and its derivative (45).Increased replacement of N by CH leads to decreased reactivity towards both TMGH and other azoles. CEP-pyrrole cannot be prepared from

CEP

.,-.to

cyclic enediol phosphoryl ;

I\

I\

TMGH

=

tetramethylguanidine


146

(36) X = S , Y = O (37) X = O , Y = S

(38)

H NH

S

R

(39)

(40)

Reagents:

i, BuLi ;

ii, E+

; iii, HCOOH

Scheme 8

Reagents:

i, R1R2C0

; ii, NaH ; iii, R3R4C0

Scheme 9

147


OR

Scheme 10

'PN

11

Me

\

Scheme 11

NMe,

148

Organophosphorus Chernistry

other CEP-azoles by reaction with pyrrole because the latter is insufficiently nucleophilic, but zhe nucleophilicity of TMGH allows the preparation of CEP-TMG from CEP-azoles; both CEP-pyrrole and CEP-imidazole react with TMGH with complete CEP-ring retention. Such a contrast to the behaviour of CEP-pyrrole and CEP-TMG towards alcohols is explicable assuming that the pyrrole moiety i s apicophobic. In Scheme 11, therefore, for X=CH, (421-4431 and, because the strong basicity of TMGH prevents protonation of ( 4 4 ) the ring-opening reaction cannot be driven to completion. However, the conversion of (44) into (43) with expulsion of TMGH, and hence ultimately into (451, are possible. The lack of reactivity of (45) and CEP-pyrrole towards alcohols is attributed, at least partly, to the double bond character of the phosphorus-nitrogen bond as evidenced by the crystallographically determined abnormally short P-N bond lengths. A problem of a related nature concerns the reactivity of the cyclic diamides (46):marked differences are to be observed in methanolysis between, on the one hand, (46; R=Ph or OPh) and (46;R=MeNH)on the other. In all cases ring opening occurs to some extent although in different ways (Scheme 1 2 ) . 45 F o r (46;R=OPh)ring retention is also observed. The lower reactivity of (46;R=MeNH)is possibly linked to the smaller endocyclic NPN angle (demonstrated by X-ray analysis) and a high degree of coplanarity of the phospholidine ring with possible resonance interactions between endocyclic nitrogens and carbonyl and phosphoryl groups. Both ring opening and ring retention are observed in the interaction of (46;R=PhO)and anisidine, and here reaction occurs at both the phosphoryl and the carbonyl (giving (47)1 groups, whereas with a sterically hindered amine reaction occurs only at a carbonyl group. With a more reactive primary amine, e.g. benzylamine, the initially-formed (48) cyclizes spontaneously to (49). Continuing their studies on analogues and derivatives of cyclophosphamide as agents for cancer therapy, Luaeman et al.have synchesized the phosphoramidates (50 a,b,c; R=Me or Ph) by established methods and have studied their r e a ~ t i v i t y .By ~~ contrast L O aldophosphamide (50a; R = H ) whicn unaergoes tautorrieric cyclization to (51a ; R=H), '4-phenylketophosphamide'. (50a; R-Ph) and to a lesser extent the methyl analogue, are resistent t o t h e change. In aqueous solution the phenyl compound(50a; R=Ph) is converted into the diamide (52) faster


I49

Me

(47) Me

(46)

(MeO),P(O)NHMe Reagent :

+

( CONHMeI,

i , MeOH

S c h e m e 12

(48)

(49)

R '3

'

H2°2

OPNHR'

I

N R2R3

R'CH=CR

2 ~ ~CH,3 = (53)

+

C I C HR' C R L CR 3CH2P(0)CI

150


H;)

bH

0 (57)

(56)

(58)

COOR

0 ( R’

II

R2

0

II

I

o i2p-c H - P z

( Me3SiO),P(X)COOR

(60)

0

(61)

0

I

(EtO),!-CHGR’

It

(R0I2P
I l l

'

R'+CI NNHCOOMe

Reagents :

R1+P=":

N N HCOOMe i , R;POR4

;

ii . Me2C0

0 ;

iii , H30'

11

0

(79)

S c h e m e 14

0

0

+ (80)

0

II

(R'O),PCH,COR~

(81)

R

156


U

0

0

II

II

-

( R~ oi2 PCH~CHCR'

I

OTs

Reagents:

i,

'

\"

Os04, H202 ;

0

II

CN I

I R'O),PCH,CHCR~

II

0

+

(R'O),PCH,

+

(R~O)~PCH=CCR~

0 0

0

ii, TsCl, pyr. ;

0

0

II

II

I

iii, H2-Pd ; iv; BU4NtCN-

v, Eiu4X!+N3S c h e m e 15

OEt

R

R

0

R

OEt

R


157

Migration of phosphorus €rom oxygen to aromatic carbon is induced by Lithium diisopropylamide and provides a convenient route to esters of (2-hydroxyary1)phosphonic acids (90) and bis ( 2-hydroxyaryl Iphosphinic acids (911 . Interaction of chlorides of tervalent phosphorus and phenols, particularly those in which the hydroxyl group is sterically hindered, leads to 5-phosphorylation, and the products may be oxidized to esters or (4-hydroxyphenyl1phosphonic acids; (&hydroxy-3,5-di-tert-butylphenyl )phosphonic acid was thus prepared.82 ihe reaction between sterically hindered phosphorous chlorides (92; n=O or 1 ) and benzyL alcohol affords the phosphonates ( 9 3 1 .83 The bisphosphonic acid 1 9 4 ) has been prepared and its chelating properties investigated.84 Methylenebisphosphinic acid (95 has been described and its crystal and molecular structure determined. 85 Pd(PPh3j2Ll2 catalyses the internal alkylatjon of the phosphonate esters ( 9 6 ) and the formation of the 3-methyLene-lo x a - 2 - p h o s p h a c y c l o a l k a n e 2-oxides (971, phosphorus-containing analogues of a-methylenelactones ." Further examples of the lY3,2-dioxaphosphorin system (991 have been prepared as indicated with the esters (98) as isolable intermediates.87 The related compounds (100;R-Et or Pri) are obtained by a rearrangement process at room temperature.8 8 Studies described in earlier Reports have shown that the diketone (101; _n=3) reacts with dichloromethylphosphine/acetic acid to give the bicyclic anhydride (102). but such a reaction does not occur with MePC12/A1C13. A new paper now describes reactions of the diketone (101; n = 4 ) with MePC12/CH3COOH. These reagents yield (103). Evidently the acidity of unpurified chloroform is 'sufficient to transform 11031 into the phosphinic acid (104);other reactions are illustrated in Scheme 16. Using the unsaturated ketones (105) and (106!, the bicyclic 1,2-oxaphosphole derivatives (107) and (108',respectively, were obtained; the structure of the latter was confirmed by X-ray analysis. The tautomeric nature of (1081 is evidenced by its reaction with diazomethane to g i v e the methyl ester of the phosphinic acid (109).8 9 The preparation of the 1,3,2,4-dithiadiphosphetane 2,4-disulphides (110; R=Me, Et, Pri, or Ph) has been described. 90 Some new sulphur-containing compounds including the oximino esters (111; isolable as their methyl esters) and the dihydro-


158

.CI i Me3C

Me3C

R

O

Me

159


Br 0

(105)

0

Ph

Ph

(103) Reagents:

i , Mepc12, MeCOOH ; ii, k120

iii, Br2

;

iv, E30+

S c h e m e 16

,

0

160


1,3,2-thiazaphospholes (112) have been obtained from oximes by reaction with 2 , 4 - b i s ( 4 - m e t h o x y p h e n y l ) - 1 , 3 , 2 , 4 - d i t h i a d i p h o s p h etane 2,4-disulphide (Lawesson's reagent;LR). Depending on the nature of R in (1131, it is also possible to prepare the 91 dihydro-1,3,5,2-oxathiazaphospholes (114). Details have appeared of reactions which occur between 2,4,6-tris-tert-butylphenyldithiaphosphorane (115) and MeOH, to give ( 1 1 6 ) , and 2,3-dimethyl-1,3-butadiene, when (117) is formed.92 Scheme (17) illustrates the synthesis of the diphenyl ester (118) of (1-amino-2-propeny1)phosphonic acid (1191, an acid which is a strong inhibitor of the alanine racemases from P-aeruginosa and &faecilis.93 Other aminophosphonic acids prepared by a variety of methods include the compounds (120-1281 94-97 The Arbuzov reaction was employed in the preparation of the"-(phosphonoacety1)-1-aminoalkyl]phosphonic acids (Scheme 18) and the same publication describes the acids (129-131). N-(Phosphonoacety1)-L-aspartic acid is of particular interest since it is a tumour inhibitor active against several transplantable tumours;lung carcinomas and melanomas are very sensitive to this compound, but leukemias and bladder cancers are unaffected.98 A convenient synthesis of (aminomethyl)phosphonic acid proceeds through its N-benzoyl derivative.99 A successful synthesis (Scheme 19) of the phosphonic acid analogues of S a n d L-penicillamine commences with the cyclic phosphorochloridite (132). Other attempts using (132; R=Me or COOEt 1 failed.loo 2-Amino-4-phosphonobutanoic acid , the phosphonic acid analogue of glutamic acid, has been obtained in resolved forms by the action of papain, followed by aniline, on 2-benzoylamino-4-(diethoxyphosphinyl)butanoic acid when anilide occurs preferentially for the L- compound. Enantiomers of 4-amino-4-phosphonobutanoic acid were obtained by resolution of the N-benzyloxycarbonyl diethyl ester derivative with 1-phenylethylamine.101 Bromination of the (acylarninomethy1)phosphonic esters (133) and subsequent dehydrobromination, leads to the (acyliminornethyllphosphonate esters ( 1 3 4 ) , precursors to a variety of phosphonate types (Scheme 20). Treatment of (134) with Grignard reagents ( R 2=vinyl, phenylethynyl, or 1-naphthyl) affords the a-substituted esters (135). The bisphosphonic acid derivatives (136; R 2 =Me or Et) are obtained through Arbuzov reactions. A two-stage process provides the alkylated derivatives

161


S

\\

2, / S R

1 2

R R C=NOH

RS

LR

S

(11 0)

LR

(116)

But (115)

II

R’R~C=NOP-SH


162

0 ( P hO l,P(

II

PhS-

01

P(OPh),

NH2

Ph

It

s-fp(o NH2

0

0 II

0

0 II

v

__* q / P ( OIIH ) 2

~ P ( O P h ) zv i

~

Ph I2

NH2

NH 2

(118)

(119)

i, MeCOOH ; ii, F'hSCK2CH2CH0 ; iii, PnCF!;,9XJM12

Reagents:

; v, heat

iv, H202, MeCOOH

Scheme

\

R

; vi, H30+

17

N HCH2CO0E t

COOH

(mg5

( 1 2 0 1 ~ '=~H (121 l9'R = CH,COOH

I123 1''

,

@c H, NH CH co o H HOO,T")@ N 95

1127Ig6R= H or Me

( 125 Ig5

(121) n = 0,l R HOCH,CH,NCH

(126)96 @CR~NHCH,C%OH

( n C 0 O H !Hz@

H

R 2C HC HN , CH,CH ,OH

I

OH

@

(l28Ig7R = CH2@ or CMe2@ 0

= P(0)(OH12

0

I1

( R' 0 l2 P CR2 R N H CO C H2C I

\L

II

II

( HO),PCR2R3N HCOCH,P(

0

It

0

( R'O),PCR2

Reagents:

0

II

/ l l

R3NHC0CH,P(OEt),

i , (Et0)3P

;

ii, MeCixIH, HBr.

Scheme 18

0 H,)


163

@ CH,CON H C H R’ I

CHR~

I

( 1 2 9 )= ~ COOH (130)R’= @ (131) R’=COOH

I I

R~=COOH

@

R2=COOH

, R2=

i

@

= P(O)(OH),

(1321

Ill

R = CMe,(OMel

HNXS

H N X s

Me

Me

‘Ho12p+Me SH H NH,

Reagents:

i , Me3COH ;

“x’ Scheme 19

ii, BF -Et20 ; iv, H30+ 3

164


(137; R1=4-chlorophenyl).102 Scheme 21 summarizes further reactions leading to phosphonic acid analogues of amino acids. Treatment of the nitrone (138; R1=Me or Pri) with a dialicyl hydrogen phosphonate (best as the Li derivative which shows greater diastereoselectivity than the Na or K salts), and subsequent steps involving acidolysis of the oximino compound (139) lead to the free (a-aminoalky1)phosphonic acids (140)(phosphonoalanine, phosphonovaline). As an alternative process, the nitrone (138; R 1 =CH20CH2Ph) yields a mixture of diastereoisomeric (benzyloxymethy1)phosphonic derivatives of which (141) is the main component;acidolysis and hydrogenolytic debenzylation lead to phosphoserine (1431, the (S) chirality of which was demonstrated by X-ray analysis of the derivative (144). In a further variation, the di-tert-butyl ester analogue of (142) was employed, the ester groups being removed by acidolysis.103 Several acyl derivatives of (aminomethyl)-and (1-aminoethy1)-phosphonic acids, in the latter case including [L-1-([L-alanyl]amino)ethyljphosphonic acid (alafosfalin), have been prepared in their various diastereoisomeric forms and the relationship between structure and biological reactivity discussed.104 (2-Aminoethy1)phosphonic acid occurs in many aquatic and terrestrial animals as well as microorganisms, and their lipid fractions arethe most abundant source of the glycerophosphonolipids based upon that acid. Examples of such phosphonolipds have been prepared by a condensation between the glycerol esters (145;R=C15H31C0 or C18H37CO) and the phosphonic derivatives (146;R=H or CH2Ph; n=2 or 3) in the presence of TPS-C1; the phosphonolipids are obtained by a final hydrogenolysis; the same products (147) can also be obtained through the use of the phthalimide derivatives (148) the protecting group being removed with hydrazine. 105 Spontaneous dimerization of the benzylideneamido phosphites (149) yields dihydrodiazadiphosph(v)orines (150;R=Et, or (RO) -ethylenedioxy or phenylenedioxy) lo' whilst similar 2starting materials are stated to give the diazaphospholidines (151; R 1 ,R3=alkyl; R2=alkyl o r Ph) . I o 7 The 1 3-diaza-4,6-diphosphorine derivative (152) i - s obtainable from methylenebisphosphonic dichloride.lo8 The reaction between the d i a m i n o d i a z a d i p h o s p h e t i d i n e (153; R=cyclohexyl) and aromatic aldehydes with the formation of

165


0

(133 1

Reagents:

(135)

i , NBS, CC14; V,

(p20)3p

ii, E t 3 N

; i i i , R k X i n THF

vii, Et2E

; vi,

Scheme

20

; iv, H301

CMe

;

166


A

I

Me Me

R’

Ho+ !

R’ ( 139)

J’ii,

H

(138 1

O ‘ NN(

iv

P(01 0 C H,Ph l2 OCHZPh

OH

(1411

Reagents: i, (EtO)$OLi,

CH2C12,

-70’

; ii, H C 1 - k O H

iv, H30+

Scheme 21

; iii, H2-Pd

;


167

the 1,3,4-oxazaphospholidines (154;R=cyclohexyl), structures confirmed by X-ray analysis, have been discussed in terms of a 109 tricyclic biphosphorane intermediate. 2.2.Reactions and Properties of Phosphonic and Phosphinic Acids and their Derivatives.-A free radical mechanism has been proposed to

acccunt for the cleavage of the phosphorus-carbon bond in the alkylphosphonic acids (155) by E.coli to give a mixture of alkane (methane only, from methylphosphonic acid) and terminal alkene. A much higher ratio of unsaturated:saturated hydrocarbons is observed than in the case of cleavage with lead tetraacetate. 110 Hexamethyldisiloxane converts the chloride (156;R=Cli directly into the anhydride of the acid( 156;R=OH).'I1 The rates of disproportionation of mixed anhydrides from protected 0 a-aminoacids and phosphorus acids are insignificant at 0 C,from a preparative viewpoint, compared with the rates of aminolysis. On balance, diphenylphosphinic and tetramethylenephosphinic chlorides are the best chlorides for u s e in peptide synthesis .'I2 Phosphinic acids in the 3-phospholene series are converted into their diethylamides by direct reaction with TDAP. Alkylphosphonic dichlorides (and even PC13) have been suggested as reagents for the determination of enantiomeric excesses in chiral alcohols and thiols using 31P chemical shifts. Best results are achieved with the smaller alkyl group in the acid chloride and the larger in the alcohol. Derivatives of phosphonoacetic acid and related acids have been acylated (for example to give ( 1 5 7 ) and nitrosated (to give, for example, (158))?16 The latter compound forms blue solutions thought to contain dimeric species. Somewhat unexpectedly. monodemethylation of the esters (159;R=Me) proved impossible using several standard techniques. Deallylation of mono and diallyl ester analogues of ( 1 5 9 1 , and of diallyl and ally1 methyl [ (1-acety1oxy)alkylJphosphonates was however acheived using palladium-containing catalysts, suggesting a potential wider applicability of the diallyloxv117 phosphinyl group in synthesis. Carbanions from tetraethyl methylenediphosphonates have been studied using several spectroscopic techniques The monohalogen esters !160;X=H,Y=Cl or B r ' l have been alkylated via their thallium salts,'l9 and sulphenation of their Li or Na derivatives with CC1nF3-nSC1 has been shown to be a complex

168


+

0

0 OH

II/

II

PhCH20CNH(CH21,P,

OH

OR

(145)

i TPS-CI

RO Ro{

b0

!'

1 0 CI 2 n 'OH

0

0 PhNKNPh

CL-P-

1

1

II

0

P-CI

II0

(152)

0

0

II

(RO)2PCHCONEt2

I

C H2C0N Et (1 5 7

II t OP (CH2),,NH3 i

(146) @N(CH

0

II

Me

I

( Et0I2P-CCOOMe

1

NO (158)


169

0:

P h C HO , C0N H

o

I1

x

(Pr'O),P-C-

0

P(OR1,

I

I

0

0

II

I1

P(OPr' I2

( RO),PCFXCOYH

Y

(160)

( 1 59)

(161)

0

0

II

( Et0I2PCF,Li

cs2 Me I

~

II

( E t O),P CF2 C SS M e

0

II

(Pr'01,PCHFLi

0

It

c-52 Mel ( Pr

(1 6 4 )

pXsMe

O I2

F

NuH

SMe

" F

Br

/RO'

Ph Reagents:

i , NBA

Scheme 2 2

CONu

H

170


process and, depending on the individual sulphenyl chloride, unexpected reactions include the replacement of F by C1, and sometimes loss of sulphur.120 The dihalogen esters (160;X=Y=Cl or Br) are monodehalogenated using KF in MeCN containing a 18-crown6-ether.121 (Fluoromethyljphosphonate ester anions react with C02 or COS to yield esters of the type (161;Y=O or S ) which may be dealkylated to the free acid through the use of bromotrimethylsilane, but the course of the reaction with CS2 depends on the individual ester; thus, (162) yields (163), but (1651 is formed from (164).Iz2 Esters of [1-(diethoxyphosphinyloxy)perfluoro-1-alkenelphosphonic acid appear to be effective reagents for the synthesis of perfluoro-a,B-unsaturated carboxylic acids and their derivatives;presumably an initially-generated perfluoroketene (166) is acted upon by a nucleophile (NuH=RNH2, R2NH, or ROH). The

(E)/(Z-) ratio of the product components increases with increasing length of Rf. 1 2 3 In contrast with the behaviour of typical vinylphosphonic acid derivatives, the carbon-carbon double bond in the 1,2-oxaphospholene ( 1 6 7 ) is remarkably unreactive towards a broad spectrum of reagents including electrophiles, most epoxidizing and organometallic reagents, as well as to dipolar addition reactants. Exceptional reagents are, however, N-bromoacetamide (NBA), ozone, dimethyllithiumcuprate, and sodium-naphthalene. The reaction between (167) and NBA is set out in Scheme 2 2 . In aqueous solution, the reaction proceeds cleanly; ‘H nmr spectroscopic analysis indicates the formation of only one diastereoisomer of the acid (168;R=H);Chis acid was too labile for isolation but was isolated as a 1:l mixture of the esters (168;R=Me) enantiomeric at phosphorus. Ozone reacted slowly with & (169); (167) in chloroform To give phenylphosphonous acid y 124 the last was characterized as (170). The addition of g,g-diethyl hydrogen dithiophosphate to diethyl (3-rnethyl-1,Z-butadiene)phosphonate (171; R = H ) occurs at the 1,2-double bond, but on introduction of a vinyl group (171; R=CH=CH2) addition occurs across the latter to give 125 (172) after rearrangement. Addition of chiral sulphenylchlorides to cyclohexene affords diastereoisomeric mixtures of 2-chlorocyclohexylthio


171

COOH

Ph

Me

’

M eO “/O ’

‘ 0

(169)

x C I I M e

(170)

0

0

II

( E t O ),PCR=C=CMe,

0

II

(Et0I2PCCH=CMe2

II

(

II

R’0 ),PC

H=C

=C R2R

CHCH,SP(S)(OEt), (171 1

(172)

0

II

( R’ 0 l2 P C H

RLS\e

=CC H R 5CI

I

R2fip:lR, R

SeR

(173)

Ph N H C H, P h

OPr‘

Me

(174)

R10\ /

0

II

-

MeNHNH2

PCH=C=CR2R3

CI

/ \

H2NN Me

( 177)

i

PhNHNH2

(178)

(1 79)

172


esters Further observations on the addition of sulphenyl chlorides to (1,2-diene)phosphonic acid derivatives ( 1 7 3 ) have been reported.127 For the unsubstituted phosphonates, (173;R2=R3=HI) addition occurs at the terminal double bond to give (174;R5= H )

mainly in the (2) form for R4=Ph, but a mixture of (E) and ( Z ) forms for R4 =Me. For monosubstituted compounds,e.g. (173;R2=Pr; R 3 = H I the formation of acyclic addition product (174; R5=Pr) is accompanied by a small amount of 1,2-oxaphospholene (175; R2gPr; R3=H). Finally, t e r m i n a l l y - d i s u b s t i t u t e d compounds yield 1,2-oxaphospholenes (175) exclusively. The 1,2-oxaphospholene 1176) is formed by the BF3catalysed addition of benzylideneaniline to diisopropyl (3-methyl-l,2-butadiene)phosphonate.128 The course of the reaction between allenephosphonic monochloride monoesters and hydrazines depends on the individual hydrazine and is explicable in terms of the relative nucleophilicity of the nitrogen atoms in each. Thus (177; R1=Me,Et, Ph,PhCH2, or 1-naphthyl; R2 =H or Me; R3=H) reacts with methylhydrazine at the more nucleophilic nitrogen atom, .&i that carrying the methyl group, to give initially the hydrazide (178) which cyclizes t o (179). With phenylhydrazine, the more nucleophilic nitrogen atom is that in the NH2 group, and the reaction course is then (177)+(180)+1181). Depending on the manner of work-up, only one of (180) or (181) is is01able.l~~ Isolable pyrazolines (183) are obtained from the (1,3-butadiene)phosphonic acid esters 1182; X=S02Me, COOalkyl; R 1=H or Me; R2=Me or Ph) (products from (182;X=CN)are thermolabile) and diazomethane. Pyrolysis of the phosphorylated pyrazolines affords phosphonopentadienes rather than phosphonocyclopropanes (contrast (184)) and with NaH give pyrazoles or pyrazolephosphonic acid esters.130 Interaction of ( 173;R2=R3=Me1 and chromyl chloride affords the (cyc1opentenone)phosphonic esters (185). I 3 ' (a-Hydroxyalky1)phosphinic acid esters (186; R1,R2= H, or alkyl) are deoxygenated when treated with P214 yielding the compounds (187).132 The ester (188) rearranges to (189) in dry alcoholic(ROHI-HC1.133 In a useful communication, the cd and absolute configurations of the (a-hydroxybenzylphosphonic esters (190) have been reported. Normally obtained in small (10% for R1=R 2=Me; X = C 1 ) to medium (20% for R1=R 2=Pri; X=C1) enantiomeric

173


(193) X = OSO,CF, (194) X = OCH,P(O)(OEt), ( 1 9 5 ) X . NR, or OAr

174


excess, this can easily be raised by crystallization. The dextrorotatory compound (190;K1 =R 2=Me; X=C1) was shown crystallographically to have the (2)configuration.134 The decomposition of n i t r i l o t r i m e t h y l e n e t r i p h o s p h o n i c acid in acid solution has been studied. At 125-175O and pH 1.5, carbon-phosphorus bond cleavage occurs, but in 3M HC1 aq. carbon-nitrogen fission becomes important.135 A spectroscopic study of the esters (191) and (192) (R=H,C1,Br,N02,Me0,Me2N) has shown that the C=C, P=O, and C=O bonds are coplanar with, in (1Y2), a trans arrangement between the benzene ring and the ethoxycarbonyl group. It then becomes easy to explain the dephosphorylation which occurs when such esters are treated with aqueous alkali by postulating attack by HO- on the B-carbon of the carbon-carbon double bond.136 ' h e successful synthesis of diethyl phosphonomethyl at higher temperatures triflate ( 1 9 3 ) is possible only at (-15%; formation of the ether (1Y4) becomes important and exemplifies the further reaction with nucleophiles, including R2NH and ArO-, from which the esters (195) are obtained.137 in acetic acid, or aqueous acetone with subsequent treatment with acetic anhydride, the esters (196; R=4-MeO or 4-MeS) give rise to the expected esters(l97) or (198). For the 4-chlorophenyl derivative, a mixture of the unexpected products (199, 200; Ar=4-chlorophenyl) was obtained. The unsubstituted compound (196;R=H) gave only (1Y9) in aqueous acetone, but ( 2 0 0 ) in acetic acid. The postulated mechanism tor such a rearrangement centres around pseudophosphonium and-or phosphorane intermediates. The ester (201) also yields a mixture of rearranged and non-rearranged products. 138 Several communications have described uses for Lawesson's reagent and related compounds. Carboxylic acids have been the use of the reagent converted into their dithio analogue;13' as a peptide coupling agent proceeds with low racemization. 140 The products from the reagent and alcohols depend on the nature of the alcohol. Primary alcohols yield the esters (202) from which several derivatives have been obtained. When the -p-toluidine salts of (202) are heated in xylene, the phosphonamidodithioates (203) and the phosphonodiamidothioate (204) are formed. Tert-butyl alcohol presumably yields (202;R=CMe3) initially but at the reaction temperature butene is evolved

175


r

1

OMS

OR

(197) R = H (198) R = Ac

(1 9 6 )

1

\

s

/’

C H 3CHP ( 0Et l2

Ar CH-P(OEt),

I

I

OMS ( 201 1

(i:;R=H

(200)R = Ac

Ms = 2 , 4 , 6 - t r i m e t h y l benzenesulphonyl

0 2CNH SR

Me 0

(202)

(204)

Me

(203)

S

s”’

‘Ar

II ArPI

RO

S

0-

II

PAr

I

OR

(205)

Ar = I - MeOC6HL

Ar t I

- Me OC6 HL

176


and (205) is formed; in the presence of -p-toluidine (204) is once again produced, together with, for a reaction using 1-phenylethanol as substrate, (203; R=CHMePh) and (206; R 1=R 2=CHMePh). In the presence of pyridine, 1-phenylethanol gives the trithiophosphonate (206) as the sole product. 2-Butanol and cyclohexanol yield 141 0,O-diesters of type (207); phenol behaves similarly. Lawesson's reagent converts pyrrolidone derivatives into thioxopyrrolidones and peptides into thioxopeptides.143 N,N-Diacylhydrazines have been shown to yield 2,5-disubstituted1,3,4-thiadiazolesand 5 - p h e n y l - 1 , 3 , 4 - t h i a d i a z o l e - 2 ( 3 H ) - t h i o n e s ; in the case of N-acetyl-N'-ethoxycarbonylhydrazine, the thiadiazaphosphole ( 2 0 8 ) has been characterized by spectroscopic means.144 Other reactions which have already been discussed are those with oximes. The oxidative desulphurization of mono and dithio phosphonic and phosphinic acid esters may be carried out using hypochlorite.145 The stereochemistries of the reactions between g-aryl 0-methyl p h o s p h o n o c h l o r i d o t h i o a t e s and nucleophiles have been studied in relation to the synthesis of 1,3,2-oxazaphospholidines. No displacement of chlorine takes p l a c e on treatment of 2-methyl 0-4-nitrophenyl p h o s p h o n o c h l o r i d o t h i o a t e with 2-methoxyethanol, and in the presence of 1-phenylethylamine, it is only the latter which reacts. In addition, when the same phosphonochloridothioate is treated with sodium ethoxide, it is the 4-nitrophenoxy group, rather than chlorine, which is displaced. Both displacements were shown to occur with inversion of configuration at phosphorus. The use of such an acid chloride as a two-step 'cyclophosphorylating' agent of 2-aminoalcohols to give 1,3,2-oxazaphospholidines ( 2 0 9 1 , is illustrated.146 Differences in chirality of substrate, and nature of solvent, have no effect on the competitive nature of the displacement of 2-alkyl and S-methyl groups in the reactions between (+I-pinacolyl alkoxide and 0-ethyl (and methyl) S-methyl methylphosphonothioates (Scheme For the ( E l - ( + 1 esters , e.g. (2101, the displacements are highly stereoselective and occur with configurational inversion,but the enantiomeric esters do not display such stereoselectivity. (-)-Menthol might be considered a mirror image of (S)-pinacol, and similar reactions with the sodium salt of (-)-menthol occur highly stereoselectively

177


S

OH

OMe

(2081

(209) 0

II

I

P

1

( Pin0I2P(O)Me

MeS’“ \Me OPin

Iii

II

P / ’ I \ Me Me 0

SMe

MeO’

1

” p\

Pin = pinacolyl

OPin

Me

Reagents:

i,

;

Scheme 2 3

ii, M ~ O -

178


with the (?)-(-I esters but not with the enantiomers. Methoxide displaces the 5-alkyl group only. The effects of leaving group, solvent, and nucleophile, on the kinetics of aminolysis of a series of substituted aryl diphenylphosphinates and their mono and dithio analogues have been investigated.148 For the dithiophosphoric acid esters (211; R 1=R 2=alkylO) earlier work has already shown that methyl isocyanate (212; R 3 =Me) reacts with (211) under mild conditions to give the corresponding (2141, stable at room temperature, presumably y & the rearrangement of ( 2 1 3 ) (route b). At higher temperatures the products are the corresponding (215) and (216)(route a). A similar behaviour has now149 been shown for (212; R 3 =Et) but for isopropyl isocyanate, only route b is involved. The S + N rearrangement is inhibited in the case of the phenylphosphonate esters (211; R 1=alkylO; R 2=Ph) and diphenylphosphinic esters. The analogous behaviour of ?,2-2,3-butylene 2-trimethylsilyl phosphorodithioate suggested the possible intermediacy of the four-membered-ring phosphoranes as depicted in Scheme 24. A reaction between the bicyclic thiaphospholes (217) and alcohols occurs only in the presence of triethylamine. T h e products are ( 2 2 0 1 , probably formed by the dimerization of (2191, and the 2-alkoxy-1,2-thiaphosphole derivatives (218). Analogues of the latter are obtained with -p-toluenethiol and dialkylamines. The compound (217; R=Ph) is more reactive than (217; R=CMe3) and will react with aniline on addition of triethylamine even at room temperature, from which the formation of (221) was observed by spectroscopic characterization. Even more reactive is cyclohexylamine which furnishes an analogue of (221) without addition of strong base. 1 5 0 The phenylphosphonic diamides (222; X=O or S 1 15' and (223)152 are new condensing agents for the preparation of amides and esters of carboxylic acids. Interaction of allylphosphonic bis(dimethylamides1 and Schiff's bases ( 2 2 4 ) at low to moderate temperatures leads to both a and y adducts, but the rates of formation of these depend on reaction conditions and on steric effects of substituents in the base. For (224; Arl=Ph; Ar2=2-chloroor 2,4-dichlorophenyl) only the y adducts are formed. l-Aryl-1,3-butadienes are produced when the initial adduct anions are heated. 1 5 3

179


.

-

R' Rt.

I

R'

Me3SiS'A,!o 'P-NR3

S

II

'POSiMe3

2/

-4-

R3NCS

R

-I

S S R''P-N,COSiMe3 II II

2'

R

(214)

Scheme 24 Ar

R

-[

(218)

( 2 1 91

Ar

Ar

PhN=P$Ph \

s-s

(2211

I \ X

K0

yh

1 Kx 0

N-P-N

nN-P-NYh n KS ys S

S

180


Molecular geometrical differences between the amides (225) and (2261, the latter having the more pyramidal arrangement around nitrogen, have been correlated with the known differences in their solvolytic behaviour.154 Treatment of the sulphonate esters of N-phosphinylhydroxylamines with a strong base such as methoxide often results in a Lossen-like rearrangement. Thus with methoxide in methanol, the N-(arylphenylphosphiny1)hydroxylamine 2-methanesulphonates (227; R 1=Ph; K 2=Ar; R 3=Me) rearrange with competitive migration of Ph and Ar groups. For the -p-substituents,MeO, Me, C 1 , and NO2, the relative rates for ArIPh migrations are 30-35, s . 3 , 0.7, and 0.06; thus electron release into the aromatic ring encourages migration of that ring.155 Such a migration could conceivably (but is very unlikely to) occur through a phosphinylnitrene (235). Sulphides are known to be effective trapping reagents for nitrenes but attempts to employ them to attempt to demonstrate the intermediacy of such species are complicated by the fact that compounds (227) react readily with dialkyl sulphides,with displacement of sulphonate anion to give protonated N-phosphinylated sulphilimines and thence the sulphilimine (234). The reaction between (227; R1=R2=Ph; K3=Me) and dimethyl sulphide in the presence of tert-butylamine yields 90% of (231; R 1=R 2=Ph), and, 10% of (234); the latter, together with (233; R1=R2=Ph; R4=Me), is also produced when the nucleophile is m e t h 0 ~ i d e . l ~ In~ contrast to the behaviour of the phosphonic and phosphinic acid derivatives of type (2271, the phosphoric acid derivatives (227; R 1=R 2=ArO; R 3=Me or 4-nitrophenyl) in the presence of tert-butylamine do not rearrange but instead afford the amides (236) and the hydrazides (237). Some liberation of phenol may occur from (227;R1=ArO; K2=Ar) and thiswould arise either by attack by MeO- at phosphorus, or by elimination from the conjugate base (228) resulting in the formation of (232; R 3=Me) and (233; R4.=H) in approximately equal proportions, presumably by way of (229) and the formation therefrom of a mixed anhydride. Replacement of R 3=Me by R 3=4-nitrophenyl in (227) should result in increased formation of ( 2 3 1 ) at the expense of (2301, a 157 feature observed experimentally. The course of the alkylation of several potentially tautomeric phosphorus thio amides has been investigated. That of the diphosphazane (238) in the presence of' triethylamine


181

l

Ar’CH=NAr2

(224)

+

(Me

N) PC=XH-CH2

II

( Me,N),PCH=CH

o

CH2CHAr’NHAr2

+

( Me2N),PCH CH-CH,

I

0

CHAr’ NHAr

Ph2P(0)NMe2

Ph2P(0)N3

/

o SO,R~

(227)

(228)

(230)

1

I I

+ I

0 R2’

0

0 / \ B ~ N H NHR~

‘N-SMe2

( 2 3 4I

-

+

(231) R
C H PP h

‘P-CH, Ph2

(110)

/CH2-AU-CH\2, PR2

R2 p,

CH2-Au-CH2

CHCN

CHCOEt

HCOOMe

K+

(112)

COOR’

COORL

I

H2C=CH(CH2),,CH

P(OR3),

II

0 (115)

+

R4CH0 R4 COOR‘

7: Ylides and Related Compounds

325

the ester alkyl group was much less marked and the (E)-product predominated in all cases except for one involving the ester ( 1 1 5 , The alkylidenediphosphonate anions (117) can be

R3=CF,CH,).

generated directly through phosphonylation of the alkylphosphonates (116) using two molar equivalents of LDA as base.75

The anions

(117) react readily with aldehydes to give good yields of (E)-vinylphosphonates ( 1 1 8 ) , often stereospecifically (Scheme 6). Unsymmetrical diphosphonate anions

(e.g. 119) eliminate the most

electrophilic group; (EtO)2P(0) in the case o f (119).

The

previously reported76 olef ination reaction of arylmethylphosphon~ ~ used to diamide anions (120) has been further i n ~ e s t i g a t e dand prepare a variety of substituted (Z)-stilbenes.

The high

stereoselectivity observed in most cases under conditions of thermodynamic control is explained on the basis of the erythro adduct ( 1 2 1 ) being thermodynamically most stable. Improvements are still required in Wittig-type methods for the preparation of tetrasubstituted alkenes since even phosphonate reactions often give low yields.78 of added salts" appeared.

A

further report7'

of the effect

on the phosphonate olef ination reaction has

The addition of stoichiometric amounts of lithium o r

magnesium salts allows the use of triethylamine as the base in reactions o f triethyl phosphonoacetate with aldehydes (ketones do not react). critical.

The nature of the solvent is important but not A

comparison of the use of triethyl phosphonoacetate

anion with the Reformatsky and Peterson olefination reactions of ketones shows that the phosphorus route is preferred or equivalent except in the case of highly hindered ketones.81 The DIBAL reduction of esters to aldehydes in the presence of phosphonate anions appears to solve problems of overreduction to alcohol and provides a good general method of 2-carbon homologation (Scheme 7).8 2

The phosphonate (122), prepared by alkylation of


326

R’

0

R’ (118) 0 Reagents : i

II

2 L D A , - 7 8 O C , THF; ii ( E t 0 1 2 P C l ; ii i

R2CH0

Scheme 6

R’

0

Ar 2

LI

(1201

(1191

(121 1

I

R’COR~

A

COOEt

H

Reagents

: i , D l B A L (Et0)2P(01CHCOOEt

,

- 7 8 O C ,THF

Li+

Scheme 7

321

7: Ylides and Related Compounds triethyl phosphonoacetate, has been reacted with formalin in the

presence of potassium carbonate to provide a synthesis of the alkene (123). 83

The carbanions generated by treatment of cyclopropyl-

phosphonates with LDA react with aldehydes to give 1-(hydroxymethy1)cyclopropylphosphonates

(124). 84

In most cases the

reaction is highly stereoselective and treatment of the adducts (124) with sodium hydride in the presence of catalytic amounts o f crown ether leads to elimination and formation of the expected alkene (Scheme 8). followed in one case by ring cleavage.

Vinyl

derivatives (126) of phenanthroiine and (127) of bipyridine have been synthesized by reaction of the appropriate diphosphonates with formaldehyde in methanol-methoxide. 8 5

The reaction involves initial

formation of the vinylphosphonate (125) (a similar reaction has been reported for phosphonium salts)86 followed by addition of methoxide and olefination (Scheme 9).

Wittig-type reactions of the

phosphonate-sulphone anion (129) with carbohydrates (128) give the tetrahydropyrans (130) as isomeric mixtures which can be isomerised to the pure 6-isomers by base.87

1.4-Diaryl-1.3-dienes and, in one

case, a tetraene have been synthesized in moderate yield in a one-pot reaction.88

The diphosphonate anion (131), generated from

the appropriate vinylphosphonate and diethylphosphonate anion, was reacted sequentially with aromatic aldehyde (Scheme 10).

2-Keto-

phosphonates (132) and (133). containing an oxygen function at the 5- o r 6-positions, are conveniently prepared by reaction of diethyl

alkylphosphonate anions with, respectively, y- and 6-lactones.89'90

Compounds (132) and (133) can be used directly in

synthesis and also, through oxidation and cyclization, provide a route to cyclopentanones or cyclohexanones (Scheme 11). 89

Moderate

to good yields of cycloalkenols (135) and (136) have been obtained through the reactions of phosphonates (134) with glutaraldehyde and succinaldehyde, respectively, in aqueous potassium carbonate


328

0

II

30'/0 F o r m a l i n

( E t O ),PCHCOOEt

r

ZC03

Reagents : i , L D A

, -78

"C

I

T H F ; ii

R3CH0 ; iii

N a H , 18-Crown- 6

Scheme 8

0

II

RCH-

RCH,P(OE+),

CH,O-

___)

I

(EtO)

P\

' 0

Rr

eJ OMe

(126)

R

(127)

R =

Me0

CJ

Me0 Reagents : i

HCHO

...

Ill

t---

MeO-; ii

MeOH ; i i i

HCHO

Scheme 9

, MeO-

I

THF


329

+ *

0

II-

( Et0I2PCHSO2Ph

O "OMe H

T

0Me

\

(128)

Z = CN,CI

OMe

0 0

0

II -

It

II

+ I

( EtO ),PCXCH,P(OEt)z

Li+

H'

(131 1

X = SO,Ar

Reagents :

I,

ArCHO ;

Ar

or

,

COOEt

LDA ;

III

, ArCHO

Scheme 10

CH,P(OE t 1

X

\

II , 1 1 1

(

(

330


H0

0

+

CH R 2P( 0 )( O E t )2

I LiCHR P ( O E t ) , + 21

(132) n = 2 n=3

(133)

0

0

It

II

C OCHR2P ( 0 Et )2

/

/

Reagents : i , DMSO

, COC12,

CH2C12, -60 “C

C O C H R 2 P ( O E t),

Et3N ; ii , NaH THF, r . t.

Scheme 11

0

II

(EtO12PCH2X

+

(136) X = C O O E t ,

,

C HO

(CH2)n \

CHO

-

0

II

K2C03 ’L

( E t O )2PCHXCH(OH)(CH2)nCH0

C N ,COMe

OH

(135)n=2 (136)n = 3

33 1


solution.91

The first synthesis of a phospho-statine derivative

(138) has been achieved by the stereoselective reaction o f dimethyl methylphosphonate anion with N-trityl-L-phenylalinal (137). 92 3-Phosphonomethyl-A2-isoxazolines

(139), prepared by

cycloaddition reactions of 1-(diethy1phosphono)acetonitrile oxide, provide routes to a variety of A2-isoxazoline derivatives through olefination and alkylation followed by oxidation (Scheme 12). 93 1.3.5-Trienes (142) are obtained in good to excellent yields by olefination with the phosphonate (141). which is available from thermolysis o f the A’-pyrazoline

(140) (Scheme 13). 94

An

alternative approach to the ether ( 1 4 5 ) . involving generation o f an alkylidene carbene and in situ trapping, is provided by the reaction of 4-methyl-3-cyclohexenone with the phosphonate (144) in the presence of alcohol (143) and base.95

A footnote in the paper

suggests that the original routeg6 via a Wittig reaction of (146) is not repeatable.

However, the authors also claim that their product

(145) has a similar ’H n.m.r. spectrum to the product of this Wittig reaction!

The use of LDA as a base in the preparation of

0x0-2-alkylphosphonates from the acylation of alkylphosphonate carbanions leads to increased yields and allows the use of stoichiometric amounts o f phosphonate rather than the excess usually employed . 97

Tr iha logenome thyl thiome thy 1ene bisphosphona tes

( 148 )

have been prepared by the reaction o f methylenebisphosphonate anions (147) with trihalogenomethanesulphenyl chlorides.

’*

Moderate yields

of a-arylakanenitriles (149) have been obtained from the copper(1) catalyzed reaction of dialkyl cyanomethanephosphonate anions with aryl iodides under vigorous conditions. 9 9

4 4.1

Selected Applications in Synthesis

Carotenoids, Retinoids and Related Combounds.- Methods of


332

I

PhCH2

(137 1

(138)

R Reagents: i , BuLi

ii

, R 1 R 2CO ;

1

iii, R X ; i v I O 2

Scheme 12

0

II

4(EtO)ZPCHXCH=CHCH=CR1R2 (141)

1

i i , iii

R 3CH=CX C H= CHC H =C R' R 2

4 142) Reagents : i

, 100 "C

; ii L D A , THF ; iii

, R3CH0

Scheme 13

333


b

CH,OH I

n

+ \I

t 2(R012PCHN2

5 0

II-

( R~OI~PCHCN

cu I 2 00 "c Ar I

+

KOBut*

I

ckO

GHO --+

[ CNi

ArCHP(OR'Iz

3

(145)

R'

I

ArCHCN (149)


334

synthesis of retenoids have been reviewed. loo In studies directed towards the synthesis of specifically deuterated retinals the reactions of triethyl phosphonoacetate and methoxycarbonylmethylene ylide with hexadeuterioacetone have been investigated.lo'

The ylide

route is preferred since use of the phosphonate leads to deuterium scrambling, presumably due to initial deuterium exchange between acetone and phosphonate anion.

The method has been applied to the

synthesis of [8,10,12,14,19,19,19,Z0,Z0,20-Dlo]retinals using the reaction of the ylide (150) with the perdeuterio aldehyde (151) as a key step.

Cyano-stabilized phosphonates, followed by Dibal

reduction of the nitrile function, can be used to synthesize the 8-, 9-, 12-, and 1 3 - m 0 n o - ~ ~ C - r e t i n a l s . Intramolecular ~~~ olef ination of

the phosphonate (152) (Scheme 14) has been used to prepare (153). a key intermediate in the first reported synthesis of all-trans-18,18.18-trif luororetinal (154).lo3 Standard methods have been used to prepare a variety of 13-modified retinalslo4 and modified retinals bearing non-conjugated positive charges along the polyene chain for use in studies of spectroscopic properties of visual constituents. lo5 The Wittig reaction has been used extensively in syntheses of all-(E)-citreomontanin

iso-citreoviral

(155), I o 6 (+)-citreoviral (156), and

(157). lo7

In an effort to develop

an efficient

polyene (hexaene and heptaene) synthesis a comparison of several potential methods has been carried out.lo8

The approaches used

involving phosphorus-based methods were found to be unsatisfactory due to either side-reactions or low yields.

However, the

dodecapentaenephosphonate (158) has been used to synthesize the hexaene fragment (159) of the aglycone of amphotericin B.lo9 4.2 B-Lactams.-

The now standard intramolecular Wittig

cyclization procedure has been used1l0'll1 to prepare a number of bicyclic trans-substituted B-lactams related to olivanic acids

335

7: Ylidesand Related Compounds

+ DCO D

(150)

I

Reagents : i L i H

THF, H M P A ; ii

(151)

, D I B A L , hexane; iii M n 0 2 CH2CLZ

Scheme 14


336

OMe

I

Rk 1

(156) R =OH R3=Me , R2=RL=H (157) R ’ = R 3 = H R 2 = O H , RL=Me 0

II

( RO ),P

Et,Sig I

COOEt

L

9 S i Me2Buf

CHO

I

I

MeCH

H H NHAc

0 COOH (160)


337

COOR’

COO R’

(1611

(162)

COOR’

Reagents : i O 3 ; i i

MeZS ; iii

,

DBU

Scheme 15

0

OHC*SCH200Me

Reagents : i J P h P=CH3

OHC

’ CHO

; i;

I, ,

S CH2C0 OMc

hv

S c h e m e 16 OH

SCH2Ph


338

(9. 160).

Of more interest is the use of the

cyclohexa-1.4-diene-derived azetidine-2-one (161) to obtain the

thermodynamically unstable &-substituted 162),110

@-lactams (9.

Following the failure of attempts to synthesize the

appropriate phosphonium ylide intermediates, 6-aza-l-carba-2-cepham-3-carboxylates

(163) have been prepared for

the first time using a phosphonate-mediated cyclization step (Scheme 15) .I1’ 4.3

Leukotrienes and Related Compounds.-

The reaction of

3-formylpropenylidene ylide with aldehyde (164). followed by light-catalyzed iodine isomerisation, has been used to synthesize (165) in almost quantitative yield (Scheme 16).113

Further use of

the Wittig reaction converts (165) into the thialeukotriene A4 (166).

The Wittig reaction has been used to synthesize a variety of

other leukotrienes, e g .

leukotriene B4 (169) from the aldehyde

(167) and the ylide (168),ll4 the acetylenic analogues of leukotrienes A and D,

leukotrienes and lipoxygenase inhibitors

(170) and (171)116 and the compound (172) which displays leukotriene-like activity.’l7

Both Wittig and phosphonate methods

have been used in a total synthesis of lipoxin A.118

Reaction of

the ylide (173) with the aldehyde (175) gives a 1:l mixture of isomeric alkenes (176). while reaction with the corresponding phosphonate anion (174) gives a 3:l preponderance of the required (El-alkene, both reactions give an excellent yield.

However, the

stereochemistry is not important since isomerization with iodine to (11:l)

(E:z) is

easily achieved.

The Wittig reaction has also been used extensively in the synthesis of hydroxyeicosatetraenoic acids (HETEls).

Examples

include the total synthesis of 12-HETE (177), ’19’ lZo 12,20-di HETE (1781,I2O dihydroxy- and epoxyeicosatrienoic acids’”

and 19-hydroxy metabolites of 12(S)-HETE.122

and the 20-

20-Hydroxy (179) and

339

7: YIides and Related Compounds

COOH X

uywc5H11 - (170 1 X = C H Z , Y = S (171) X = S , Y = C H 2

\\\

\

CH( S(CH213COOHI 2

(172)

340

+, Me3Si

-


-

x

+ OHC

ICH*),COOR

+

(173) X = P h 3 P

II (17L) X = (Me0I2P

H

I

OR I

+OR H

1

( CH2),COOR

OH 11 77)


341

20-carboxyleukotriene B4 (180) (metabolites of LB4) have been synthesized using the phosphonate ( ~ 1 ) ~to' introduce ~ the C1-Cll side chain.

4.4 Macrolides and Related Compounds.- Phosphorus-based methods have been widely used in macrocyclic ~ynthesis.~' The C-11 to C-25 northern hemisphere fragment (184) of the milbemycins has been prepared using a Wittig reaction of (182) with aldehyde (183) followed by cyclization (Scheme

17)

.Iz4

Cyclization of complex

phosphonates provides a route to various macrocylces, -..the of (185) to prepare (+)-rosaramicin aglycone.

use

The first total

synthesis of (+)-latrunculin B (187) has been achieved through use of a Wittig reaction of the ylide (186) (Scheme 18).lz6

In studies

related to the synthesis of the antibiotic elaiophylin, the preparation of the diene (189) has been achieved by a Wittig reaction of the aldehyde (188). lZ7

Attempts to use phosphonate

olefination gave only low yields of (189). apparently due to an elimination reaction caused by the greater basicity of the phosphonate anion than the ylide.

The applicability of

intramolecular phosphonate-based olefination to the cyclization step in the synthesis of polyene macrolides has been investigated by degradation of amphetericin B followed by conversion to the phosphonate (190) and cyclization to give (191) .Iz8

This approach

allows assessment o f the cyclization method on a model with appropriate stereochemistry and indicates that intramolecular phosphonate-based olefination, which has proved s o useful in the synthesis o f 16-membered ring macrolide antibiotics, will also prove important in the synthesis of the larger ring polyene macrolides. Phosphonate-based cyclization has been increasingly used in macrocyclic terpene synthesis.

In a synthesis of the marine

cembranoid (+)-desepoxyasperidiol the cyclization of the phosphonate (192) was attempted under a variety of conditions without success,


342

0 ( Me0 I2P II

(CH,),COOH

w

(1791 R = CH,OH (180) R = C O O H

I

H

OR' &(CH21,COOMe

(181 1

+ i- i v _____)

OSiButPh2 OCH2Ph

Reagents : i

BuLi

-78OC ; i i ,

; i i i , MeOH , MeO-; i v , HCL, H 2 0

""'3c. AcO

(183)

Scheme 17

%

y

CHO O ( Me0 1,P

M

e0

343


R=HN

I

I

R’ (187 1

R e a g e n t s : i, 5.8 K N ( S i M e 3 I 2

, THF,

O°C ;

; I. .I .I , c y c l i z a t i o n ii

k’ S c h e m e 18


344

OTBDMS MOM0

0si B ut Me,

But Me,S i

I

Oq,(CH BufMe2Si0

,OS i Me, 6 ut

B u Me,S i 0

R

‘Me Me,

0

345

7: Ylides and Related Compounds probably due to the steric consequences of a reaction of the However, the Masamune-Roush conditions

a-branched aldehyde. lZ9

(large excess of DBU and lithium chloride in acetonitrile) provided the required 14-membered cyclic alkene in 30% yield as a mixture of isomers.

The methyl ester of the 14-membered ring sesterterpene

(194) has been synthesized by cyclization of the phosphonate (193). 130

Difficulties were experienced in synthesizing (193) by

alkylation of triethyl phosphonacetate.

These were overcome by

using a two-step procedure, alkylation of dimethyl methylphosphonate anion followed by further reaction with chloroformate to introduce the methoxycarbonyl group.

Phosphonate-based cyclization of (195)

has been used as a key step in the first total synthesis of (-)-bertyadional (196). 13 1 4.5

Pheromones.- Pheromone syntheses involving the Wittig reaction

include those o f (197) (a component of the olive fly pheromonecomplex) ,13’ (198) and ( 1 9 9 ) (which act as self-defensive substances against rice-blast disease)133 and (ZOO) (the pheromone of Drosophila meianogaster) ‘H8 ]octadec-(92)-enoate

Methyl [8,8,ll,11,16,16,17,17(203) has been prepared by the Wittig

reaction of the specifically labelled ylide (201) with the aldehyde (202).135

The reaction o f Grignard reagents with

ketenylidenetriphenylphosphorane (204) has been used to prepare the key phosphonium ylides (e.g. - 205) in syntheses of the sex pheromone components ( L g . 206) and

(%.

207) of the Douglas fir tussock moth

and the peach fruit moth, ~ e s p e c t i v e 1 y . l ~A~s reported previously this reaction provides a convenient method of chain lengthening v i a the potentially difunctional (204). 4.6

Miscellaneous Reactions.-

The Schlosser-Wittig reaction of

ylide (209) with aldehyde (208) and treatment of the intermediate 8-oxido ylide with perchloryl fluoride has been used to construct the 13-fluoro unit (210) in a total synthesis of (+)-13-fluoroprosta-


346

-

COOEt

COO Et

33 x L i C l ,25'C, MeCN

McOOC

x

fi

COOMe

(193)

( Et0I2P=O

(196) (195)


341

I

I

OH

D

Ph3P=C=C=0 (201)

D

D

D D - D

m(cH )/C0wPPh3

CH3( C H 2 4

23

(206)

CH3(C H2),C 0 ( CH,

1CH, ),C H


348

glandin F2 (Scheme 19).137

Other uses of the Wittig reaction in

prostaglandin synthesis include the preparation of o x a p r ~ s t a g l a n d i n s l and ~ ~ a new route to prostaglandin D2.139 The (9E)- and (9Z)-trisporic acids A (212) and B (213) have been synthesized y&i

Wittig reactions of the lactol (211) with

appropriate phosphonium ylides. 1 4 0

A

key step in a total synthesis

of (2)-tirandamycin A (214) is the attachment of the 3-acyl tetramic acid fragment &y (215).141

olefination with the phosphonate dianion

Reactions of the ylide (216; R = H ) with D-ribose and of

the analogous ylide (216; R=Ph3C) with 2.3-0-isopropylidene-D-ribose gave, respectively, (217) and (218)

The stereochemistry of

these products is important since it determines the stereochemistry of ring-closure which, followed by further modification provides a synthesis of showdomycin (219).

These results repute previous

claims143 that reactions of ylides with unprotected D-ribose and D-glucose do not offer routes to alkenes.

The reaction of ylide

(220) with D-ribofuranose derivatives has been used to synthesize a

variety of novel C-nucleosides. 144 Dictyopterene B (221) and its e n a n t i ~ m e r land ~~

R-(-)-dictyopterene

C (223)146 have been prepared.

In the latter

case the synthesis involves reductive olefination of the lactone (222) followed by oxidation, methylenation and cyclization (Scheme

20).

A

Wittig reaction of cyclobutylideneacetaldehyde with cyclo-

butylidenetriphenylphosphorane has been used to prepare dicyclobutylideneethane (224) after the silicon-based method, used previously to prepare the cyclopropyl analogue, failed. 147 Methano-bridged bisdehydroannulenes (225) have been prepared by the Wittig reaction of cyclohepta-1,3,5-triene-l,6-dialdehyde

o r its

vinylogues with 3-methylpenten-2-yn-4-ylidenetriphenylphosphorane followed by intramolecular oxidative c 0 u p 1 i n g . l ~ ~ 1,6-Bis(2-


349

OR I

A

CHO

ph3p2z

+

0

0

U

(2081

? 2 4 JHc ( 3Hc

Reagents :

I ,

Toluene

,

-78OC ;

0

ii,

0

B U L I ; i i i , FC103

Scheme

-35OC

19

*, 0 II

C H ( C H 2 1,COC H3

COO H

I2131

350


-o-%NR

(2151

HO OH ( 2 19)

(220)


35 I

... III

0

0

,i v

(222)

Reagents : i

I

DIBAH

, - 7 8 “C;

ii, Ph3P=CH(CH2I3Me , “ S a l t

c h l o r o c h r o m a t e ; i v , Ph3P=CH2 ; v

I

- Free”

; iii , pyridinium

75OC 5 h .

Scheme 2 0

+ CHO 4pph3

-

(226)


352

formylvinyl)cyclohepta-l~,3,5-triene ( 2 2 6 ) . which can be converted to

the corresponding bis methano[24lannulene

by reductive coupling, has

been synthesized by a double Wittig reaction of cycloheptatriene 1,6-dial.dehyde.’49

The sterol (g,E,E)-triene (227) has been

prepared together with the (g,&E)-isomer ( E ) - c j. nnamy 1t r ip heny 1p ho s p ho r ane

.

by a Wittig reaction using

The p r evi ous 1y r e p o r ted

reaction of ethoxycarbonylmethylenetri-n-butylphosphorane with cyclic epoxides, which leads to ring-contraction, has been applied to 2,3-steroidal epoxides (e.9. - 228) .15’ are ring-contracted alkenes (229).

As

expected the products

However, in some cases the

aldehyde (230) could be isolated and the authors suggest that the mechanism of all these reactions involves initial attack of epoxide oxygen at phosphorus and not attack of ylide carbanion at epoxide carbon as previously proposed. Wittig reactions of the thermally unstable ylide (231). generated in situ by the reaction of 2.2-dichlorohexafluoropropane with triphenylphosphine, have been used to prepare novel ].,I.-bis(trifluoromethy1)alkenes

(232).

A

en route to pyrethroid analogues

number o f naturally occuring polyhydroxystilbenes have

been synthesized using the Wittig reaction. 153

The selectivity of

the Wittig reaction is illustrated by the use of

methylenetriphenylphosphorane to convert chlorophyll 3-vinyl-3-desmethyl chlorophyll

to

without modification of any other

functional group or disruption of magnesium coordination. 154 The total synthesis of the novel, potent antiulcer agent U-68,215 (239) has been achieved using a modified intramolecular

phosphonate olefination as a key step.155

The method involves

reaction of the phosphonate anion (234) with the enol lactone (233) to give initially (235).

However, the authors suggest that (235)

rapidly ring-opens to give (237) which is depKOtOnated by any phosphonate anion (234) still present to give the dianion (236).

353


1

Cu(II 1acetate

n = 0,l m =O,l,2

(226)

Organophosphoms Chemistry

354

Bu3P=C HCO 0 R

ROOC

OHC

[Ph3P=C(CF (

1

3 21

231 1

&'

&

RCHO

R\

c=c,

c,

F3

0 H

F3


8

+

355

0

II L i (MeO),P C H R (234)

0

CHRP(OMe1,

II

0

(233) (235) R=ICH 1 C

’Hr ‘**OTHP RJ

R

OL i

0 ( Me0l2P=O

0 4p(OM (236) X= H ( 2 3 7 ) X = Li

1238)

1

8

0

(239)

XSR x+PPh, (240)

H (241)


356

This last compound cannot cyclize to the product (239) unless it reacts with a sufficiently acidic proton source to give (238) and thus any sequence starting with only one equivalent of phosphonate anion would have a maximum yield of 5

0

%

~Support ~ ~ ~for this was

obtained by carrying out a reaction with two equivalents of anion (234) followed by addition of 1 equivalent of glacial acetic acid, a procedure which gave a 70% yield of (239).

Full details of the use

of the vinylphosphonium salts (240) in the synthesis of highly functionalised bicyclo[3.3 .O]octanes (241) have appeared.157 Reaction of the aldehyde (242) with the phosphonate (243) is the key Step in a highly convergent synthesis of the HMG CoA reductase inhibitor (+)-compactin. 15*

The phosphonate (243) was prepared by

alkylation of dimethyl methylphosphonate anion; it is important to use the alkylating agent without a silyl protecting group in this reaction since in the presence of such a group only a low yield of (243) is obtained.

A

variety of stereoisomeric long-chain

1.2.3.4-tetrols (3. 244) have been prepared by the reaction of 1.2.3-protected pentodialdo-1.4-furanoses with pentadecyl- or tridecyltriphenylphosphorane followed by hydrogenation, hydrolysis and reduction,15’

Trans-selective Wittig reactions of long-chain

alkylidene ylides have been used to prepare a number of D-erythrospingosines (245). I 6 O

In a new route to (+)-pilocarpine a key

intermediate (246) has been prepared by olefination using the cyanoalkylphosphonate anion (247) since the corresponding alkoxycarbonylalkylphosphonate failed to give the appropriate alkene on reaction with the aldehyde (248). 16’

The potentially membrane-active

tropan-3-01s (250) have been prepared by Wittig reactions of the 162 tropane-1-carbaldehyde (249). REFERENCES -.-1.

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7: Yiides and Related Compounds

357

+

R

O

OR’

0

O

C

0

1

L ( 0 Me l2

1

L I C I , DBU , CH3CN

CH,( CH2 ),5( CH OH I3C H, O H (244.) y

2

OH

( 2 4 5 ) n=12,14

COOBut (246)

OHC (247)

Me


358

H H

CHO

MeN*oAc 1249)

I

MeFo (250)

R = n - Pr, CH2C=CH

359


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361

7: Ylides and Related Compounds 75. E.E. Aboujaoude, S. Lietje, N. Collignon, M.P. Teulade, and Ph. Savignac, Tetrahedron Lett., 1985, 26, 4435. 76. J. Petrova, S. Momchilova, and M. Kirilov, Phosphorus Sulfur, 1983, __ 17, 29. 77. J . Petrova, S. Momchilova, and M. Kirilov, Phosphorus Sulfur, 1985, 24, 243. 78. TTJ. Erickson, J. Org. Chem., 1986, 2 , 934. 79. M.W. Rathke and M. Nowak, J. Org. Chem., 1985, LO_,2624. 8 0 . M.A. Blanchette, W. Choy, J.T. Davis, A.P. Essenfeld, S. Masamune. W.P. Roush, and T. Sakai, Tetrahedron Lett., 1984, 25, 2183. 81. R.S. Budhram, V.A. Palaniswamy, and E.J. Eisenbraun, J. Org. Chem., 1986, 51, 1402. 82. J.M. Takacs, M.A. Helle, and F.L. Seely, Tetrahedron Lett., 1986, 27, 1257. Chem., 83, V.T.R. Kumar, S. Swaminathan, and K. Rajagopalan, J.Org. 1985, 50, 5867. 84. T. Hirao, T. Nakamura, M. Hagihara, and T. Agawa, J . Org. Chem., 5860. 1985, 85. G.R. Newkome, G.E. Kiefer, N. Matsumura, and W.E. Puckett, J. Or%. Chem., 1985, 50, 3807. 86. S. Trippett, in 'Organophosphorus Chemistry', Ed. S. Trippett (Specialist Periodical Reports), The Chemical Society, London, 1970, Vol.1, p.34. 87. N . J . Barnes, A.H. Davidson, L.R. Hughes, and G. Proctor, J . Chem. Soc., Chem. Commun., 1985, 1292. 88 . T. Minami, S. Tokumasu, and I. Hirao, Bull. Chem. SOC. Japan, 1985, _-58, 2139. 89. H.-J. Altenbach, W. Holzapfel, G. Smerat, and S.H. Finkler, Tetrahedron Lett.., 1981, 26, 6329. 90. K. Ditrich and R.W. Hoffmann, Tetrahedron Lett., 1985, 26, 6325. 91. M. Graff, A.A. Dilaimi, P. Seguineau, M . Rambaud, and J. Villieras, Tetrahedron Lett., 1986, 2 7 , 1577. 92. J.F. Dellaria. Jr. and R.G. Maki, Tetrahedron Lett., 1986, 27, 2337. 93. 0 . Tsuge, S. Kanemasa, and H. Suga, Chem. Letts., 1986, 183. 94. T. Minami, S. Tokumasu, R. Mimasu, and I. Hirao, Chem. Lett., 1985, 1099. 95. J.C. Gilbert and B.E. Wiechman, J . Org. Chem., 1986, 258. 96. M. Suda, Tetrahedron Lett., 1982, 23, 427. 97. E.E. Aboujaoude, N. Collignon. M.-P. Teulade, and P. Savignac, Phosphorus Sulfur, 1985, 2 5 , 5 7 . 98. G.M. Blackburn and T.W. Maciej, J. Chem. Soc., Perkin Trans.1, 1985, 1935. 99. H. Suzuki, K. Watanabe, and Q. Yi, Chem. Letts., 1985, 1779. 100 M.B. Sporn, A.B. Roberts, and D.S. Goodman (Eds.), 'The Retinoids', Vol.1, Academic Press, 1984. 101 H.J. Bestmann and P. Ermann, Liebigs Ann. Chem., 1985, 2061. 102. T.A. Pardoen, P.P.J. Miller, E.M.M. Van den Berg, and J. Lugtenburg, ~Can. J . Chem., 1985, 63, 1431. 103. T. Taguchi, A. Hosoda, and Y. Koboyashi, Tetrahedron Lett., 1985, 26, 6209. 104. H.J. Bestmann, P. Ermann, H. Ruppel, and W. Sperling, Liebigs Ann, Chem., 1986, 479. 105. G a a s o v and M. Sheves, J. Am. Chem. Soc., 1985, 107, 7524. 106. P. Patel and G . Pattenden, Tetrahedron Lett., 1985, 26, 4789. 107. M.C. Bowden, P. Patel, and G. Pattenden, Tetrahedron Lett., 1985, 26, 4793; 4797. 108. J.M. Williams and G.J. McGarvey, Tetrahedron Lett., 1985, 26, 4891. 109. D. Boschelli, T. Takemasa, Y. Nishitani, and S. Masamune, Tetrahedron Lett., 1985, 26, 5239.

so,

z,

I


3 62

110. J.H. Bateson, A.M. Quinn, T.C. Smale, and R. Southgate, J. Chem. Soc., Perkin Trans.1, 1985, 2219. 111. T.C. Smale and R. Southgate, J. Chem. S o c . , Perkin Trans.1, 1985, 2235, 112. E.C. Taylor and H.M.L. Davies, J. Org. Chem., 1986, 5 l , 1537. 113. G.A. Tolstikov, M.S. Miftakhov, and A.G. Tolstikov, Tetrahedron Lea., 1985, 2 6 , 3867. 114. C.-Q. Han, D. Di Tullio, Y.-F. Wang, and C.-J. Sih, J. Org. Chem.. 1986, 51, 1253. 115, R.N. Young, E . Champion, J.Y. Gauthier, T.R. Jones, S. Leger, and R. Zamboni, Tetrahedron Lett., 1986, 2 7 , 539. 116. E.J. Corey, M. d'Alarcao, and K.S. Kyler, Tetrahedron Lett., 1985, -26, 3919. 117. A.K. Saksena, M.J. Green, P. Mangiaracina, J.K. Wong, W. Kreutner, and A.R. Gulbenkian, Tetrahedron Lett., 1985, 2 6 , 6427. 118. K.C. Nicolaou, C.A. Veale, S.E. Webber, and H. Katerinopoulos, JAm. Chem. S o c . , 1985, 107, 7515. 119. B.P. Gunn and D.W. Brooks, J. O m . Chem., 1985, 8 0 , 4418. 120 Y. Leblanc, B.J. Fitzsimmons, J. Adams, F. Perez, and J. Rokach, JOrg. Chem., 1986, 51, 789. 121 C.A. Moustakis, J. Viala, J. Capdevila, and J.R. Falck, J. Am. Chem. 1985, 107, 5283. ,.cK 122 * S. Manna, J. Viala, P. Yadagiri, and J.R. Falck, Tetrahedron Lett., 1986, 27, 2679. 123. K.C. Nicolaou, Y.S. Chung, P,E. Hernandez, I.M. Taffer, and R.E. Zipkin, Tetrahedron Lett., 1986, 2 l , 1881. 124. D. Culshaw, P. Grice, S.V. Ley, and G.A. Strange, Tetrahedron Lett., 1985, 26, 5837. 125. R.H. Schlessinger, M.A. Poss, and S. Richardson, J. Am. Chem. SOC., 1986, 108, 3112. 126. R. Zibuck, N.J. Liverton, and A . B . Smith, 111, J. Am. Chem. SOC., 1986, 108, 2451. 127 R.F.W. Jackson, M.A. Sutter,and D. Seebach, Liebigs Ann. Chem., 1985, 2313. 128 K.C. Nicolaou, T.K. Chakraborty, R.A. Dianes, and N.S. Simpkins, JChem. SOC., Chem. Commun., 1986, 413. 129. M.A. Tius and A.H. Fauq, J. Am. Chem. SOC., 1986, 108,1035. 130. M. Kodama, Y. Shiobara, H. Sumitomo, K. Fukuzumi, H. Minami, and Y. Miyamoto, Tetrahedron Lett., 1986, 2 7 , 2157. 131. A.B. Smith, 111, B.D. Dorsey, M. Visnick, T. Maeda, and M.S. Malamas, J. Am. Chem. S o c . , 1986, 108,3110. 132. H.J. Bestmann and M. Schmidt, Tetrahedron Lett., 1986, 27, 1999. 133. A.V.R. Rao and E . R . Reddy, Tetrahedron Lett., 1986, 27, 2279. 134. N.V. Bac, Y. Fall, and Y. Langlois, Tetrahedron Lett., 1986, 27, 841. 135. L. Crombie and S.J. Holloway, J. Chem. SOC., Perkin Trans.1, 1985, 2425. 136. H.J. Bestmann and H. Schmidt, Tetrahedron Lett., 1985, 26, 6171. 137. P.A. Grieco, T. Takigawa, and T.R. Vedananda, J. O m . Chem., 1985, 50, 3111. 138. J. Thiem and H. Luders, Liebigs Ann. Chem., 1985, 2151. 139. Y. Ogawa, M. Nunomoto, and M. Shibasaki, J. Org. Chem., 1986, 5 l , 1625. 140. J.D. White, K. Takabe, and M.P. Prisbylla, J. Org. Chem., 1985, S O , 5233. 141. P. Deshong, S. Ramesh, V. Elango, and J.J. Perez, J. Am. Chem. SOC., 1985, 107, 5219. 142. A.G.M. Barrett, H.B. Broughton, S.V. Attwood, and A.A.L. Gimatilaka, J. Org. Chem., 1986, S l , 495. 143. R.E. Harmon, G. Wellman, and S.K. Gupta, Carbohydr Res., 1910, . 4 l, t

a

I

I

-

-

-1

ILJ.


144. T.L. Cupps, D.S. Wise, Jr., and L.B. Townsend, J. Org. Chem., 1986, 51, 1058. 145. D. Doren, E. Kunz, and G. Helmchen, Tetrahedron Lett., 1985, 26, 3319, 146. T. Schotten, W. Boland, and L. Jaenicke, Tetrahedron Lett., 1986, 27, 2349. 147. G. Wickham, G.J. Wells, L. Waykole, and L.A. Paquette, J. O r p ; . 1985, 3485. 148. J. Ojima, E. Ejiri, T. Kato, S. Kuroda, S. Hirooka, and M. Shibutani, Tetrahedron Lett., 1986, 2 7 , 2467. 149. K. Yamamoto, M . Shibutani, S. Kuroda, E . Ejiri, and J. Ojima, Tetrahedron Lett., 1986, 27, 975. 150. J. Drew, G. Gowda, P. Morand, P. Prouex, A.G. Szabo,and D. Williamson, J. Chem. SOC.. Chem. Comun., 1985, 901. 151. M.L. Forcellese, S. Calvitti, E . Camerini, I. Martucci, and E . Mincione, J. Or%. Chem., 1985, 5 0 , 2191. 152. H. Mack and M. Hanack, Angew. Chem., Int. Ed. Engl., 1986, 25, 184. 153. L. Cardona, I. Fernandez, B. Garcia, and J.R. Pedro, Tetrahedron, 1986, 42, 2725. 154. T.J. Michalski, J.E. Hunt, J.C. Hindman, and J.J. Katz, Tetrahedron E., 1985, 26, 4875. 155. P.A. Aristoff, P.D. Johnson, and A.W. Harrison, J. Am. Chem. SOC., 1985, 107, 7967. 156. B.J. Walker, in 'Organophosphorus Chemistry', Ed. D.W. Hutchinson and B.J. Walker (Specialist Periodical Reports), The Royal Society of Chemistry, London 1986, Vo1.17, p . 3 4 2 . 157. A.T. Hewson and D.T. MacPherson, J. Chem. SOC., Perkin Trans.1, 1985, 2625. 158. T. Rosen and C.H. Heathcock, J. Am. Chem. SOC., 1985, 107,3731. 159. A. Kjaer, D. Kjaer, and T. Skrydstrup, Tetrahedron, 1986, 42, 1439. 160. R.R. Schmidt and P. Zimmermann, Tetrahedron Lett., 1986, 27, 481. 161. R.S. Compagnone and H. Rapoport, J. Org. Chem., 1986, 2 , 1713. 162. R. Dharanipragada and G. Fodor, J. Chem. SOC., Perkin Trans.1, 1986, 545. I

m.,

so.

3 63

Phosphazenes BY C.W. ALLEN

1

Introduction This chapter covers the literatures of phosph(v)azenes. The general pattern of development in this area is similar to that observed in previous yearly reviews with additional interest being shown in polyphosphazenes and in a variety of molecular orbital calculations of both linear and cyclic phosphazenes. Reviews are all limited to highly focused accounts and will be quoted in the appropriate sections below. 2 Acyclic Phosphazenes Acyclic phosphazenes (phosphazo derivatives, phosphine imines, phosphoranimines) continue to attract interest. A review of the three coordinate materials, RN=PR'=X has appeared. Several molecular orbital calculations have been reported. An ab initio treatment of the H2PN energy surface suggests that this species is best regarded as having a dative phosphorus-nitrogen double bond rather than a triple bond and the phosphonitrene, once formed, does not rearrange to the thermodynamically more stable isomer because of the high barrier to a 1,2 hydrogen shift.2 Extended basis set SCF calculations (including correlation effects) on (H2N)2PN give good agreement with the observed geometry and again the isomer resulting from the 1,2 hydrogen shift, (NH)2PNH2, is more stable. The (NH ) PN moiety has a highly reactive double bond 2 2 since it is an unprotected nitrene. All isomers are best considered as having a positively charged phosphorus atom with the (NH2)2PN species containing a 4 electron-3 center molecular orbital which is The possialternatively described by the canonical forms la-b. bility of coordination of the phosphonitrene, H2PN, to transition metal fragments has been explored by the use of extended Huckel calculations with behavior similar to that of aminonitrenes being ~ u g g e s t e d . ~An ab initio study of the bonding in the tricoordinate orbital contribution with 71 species HP(=NH)2 indicates a small ~b initio calculations polarization paralleling u polarization.

a

on the iminophosphorane H 3P=NH indicates a situation reminiscent of 3 64

8: Phosphazenes

-

RN=P

+

-NR,

IR

-

365

RN-LNR,

II

EljR

"

b

a

12)

Me

(.)

S

Me3SiCH-

PN=PPh,

P ''

N 2 Me

Me3SiN4

'N(SiMe3)2 ( 5 )

(4)

NEt,

I

MejSiN=P-CH2Si

(Me3Si1,N-P-

R'

I Me3SiN=P-CH(SiMe3)2

I CI

I

Me3

CH2Si Me3


366

the phosphorus-carbon bond in ylides with a polar P + N bond counterbalanced, in part, by a .rN + P(dT) bond yet retaining significant dipolar (P, +0.73; N, -1.02) character.6 Semiempirical m.0. calculation (PRDDO) on the triphenylphosphazo derivatives, Ph3P=NC H -m,p-R (R=N02,CN,CF3,C1,F,H,CH3,0CH3, NMe2) suggest that *6 4 the uPN orbital is able to compete with fi orbitals in TT bond formation. Extensive spectroscopic data are also available for this series of compounds. Chemical shifts (31P, 15N, 13C) and 'JPc can be correlated with u- substituent constants and 3Jpc with uR-constants. The 13C nmr data indicates that the Ph3PN unit is a poorer donor to the aryl function than is the NH2 group. The oxidation potentials (obtained from cyclic voltammetry) can be correlated with u+ constants and the ionization potentials derived from the m.0. The 31P nmr parameters and structures of several short chain linear phosphazenes have been com8 pared to the corresponding polyphosphazenes (see section 6). The kinetics of the reactions of tributyl- and triphenylphosphines with alkyl azides show that steric hinderance is not a significant factor in the Staudinger reaction.' The reaction of PhNHN=C(N 3 ) C O 2Me with triphenylphosphine leads to the expected triphenylphosphazo derivative which may be cyclized with aldehydes to give triazoles.lo Straightforward applications of the Staudinger reaction lead to the preparation of unprotected sugar phosphinimines," 2-furylethylene (2) derivatives,12 1,3,4,2-oxadiazaphospholine imides (3),l3 bis (triphenylphosphazocarbonyl)amine, HN (CON=PPh3)2,14 and a novel iminophosphorane ( 4 ) with nitrogen atoms in all five positions15 Reactions of ionic phosphorus compounds with azides continue to appear including the first reported Staudinger reaction on an anionic phosphorus (111) species, PhP (CN)2C1-, which provides RN=P (Ph)(CN)2C1-. l6 Further details of the reactions of chlorophosphenium ions, R2NPCl'AlCl4-, with phenyl and trimethylsilyl azide leading to iminophosphonium The reaction of aminoand bis phosphocations have appeared. 17'18 (dialkoxyphosphiny1)diazoacetate with triphenylphosphine provides The reaction of ethyl diazoacetate C (=N-N=PPh3)C02Et. (EtO)2P (0) with the coordinated diphosphine in trans-[W(N2)(Ph2PCH2CH2PPh2)] leads to the dihydrazino derviative Ph2P(=N-N=CHC02Et)CH2CH2PPh2(=N-N=CHC02Et) 2 o The reactions of phosphines with diphenyl 21 diazomethane provides the hydrazinophosphoranes, R3P=N-N=CPh2.

calculation^.^

''

.

367

8: Phosphazenes

The 2+1 cycloaddition of (Me3Si)2NP(S)=CHSiMe3 with trimethylsilylazide leads to a novel three membered ring with a phosphazo substituent (5). The same product is formed by the cycloaddition of sulfur to the corresponding iminomethylene phosphorane.22 The 2+1 cycloaddition of hexafluoroacetone to the appropriate iminophosphine provides 6 . 23 The reaction of the A3-iminophosphine, (Me3Si)2NP=NP(CMe3)2, with bulky alkyl iodides occurs at the less basic, but more accessible, phosphorus atom giving RPN(SiMe3I2N=PI (CMe3)2. 2 4 The reaction of the methylene phosphine, (Me3Si)2NP=CHSiMe3, with diethylamine provides the aminophosphine Me SiNH3 PNEt2(CH2SiMe3) which in turn adds a second mole of dimethylamine to give the novel phosphorus (111)-phosphorus (v) derivative 7 . The aforementioned aminophosphine reacts with carbon tetrachloride to give Me3SiN=P(C1)(NET2)CH2SiMe3 while deprotonation gives the expected anion which may be quenched with Ph2PC1 to give Me3SiN= P (PPh2)(NET2)CH2SiMe3 or with (Me3Si)2NP (C1)CH2SiMe3 as an alternate route to 7.25 The reactions of carbon tetrachloride with aminophosphines of the type (Me3Si)3NP (R)CH (SiMe3) to give the iminophosphoranes ( 8 ) vary with the nature of R. The following pattern of functions in the aminophosphine (R) to those in the iminophosphorane (R') was observed : R=R'=Ph; R=Me, R'=CH and 3 CH2SiMf; R= CH2SiMe3, R'=CH(SiMe3)2; R= CH=CH2, R'=Me SiC=CH2 and 3 Me3SiCHCH2CC13. Upon heating, 8 [R'=CH(SiMe3)21 rearranges to Me3SiN=PCH (SiMe3 ) 2 (=CHSiMe3) 26 The reactions of other halofunctional compounds lead to linear phosphazenes e.g. R2PN(M)R' 11 (M=Li,Na) with dialkylchlorophosphines, R2 PC1, give tetraalkyldiphosphine imines, R2P(=NR')PR2 which rearrange to the isomeric diphosphazanes R2PNR'PR2'I.27 Also, the combination of amidophosphites, (EtO)2PNHC6H 4X with bis(catecho1)chlorophosphorane leads to the imino phosphoranes, 9, which undergo a 1,2 migration to the amides, 10. 2 8 The amidophosphites react with benzimidoyl chlorides to give (EtO)2~ ( = N c ~ H ~cx(=NR) ) Ph. 29 Prototropic rearrangements in aminodiphosphines can be induced by phosphorus alkylation reactions. Thus, the reaction of (Ph2PI2NH with triphenylcarbenium hexafluorophosphate produces Ph2P (HI=N-PPh2 (CPh3)+ and the corresponding ion with a methyl group in place of the CPh3 moiety is formed when methyl trifluoromethylsulfonate is the alkylating agent. In the mixed diphosphine, (CMe3I2PNHPPh2, the identity of the phosphorus atom undergoing attack depends on the nature of the

.

II

368


alkyl (aryl)ating agent. 30 A variety of reactions with strong bases lead to linear phosphazenes e.g. the treatment of tetrakis(dialkylamino)phosphonium bromides with bases (OH-,NH2-) yields the iminophosphoranes, (R2N)3P=NR.31 The treatment of the aziridino derivatives, (C2H4N),(Et2N)3-nPNH2+ with sodium in liquid ammonia gives the iminophosphoranes (C H N) (Et2N)3-nP=NH ( ~ = 1 - 3 ) ? ~ 2 4 n A particularly noteworthy observation is that the bis(tripheny1reacts with sodium methoxide phosphine)nitrogen (+1) cation (PPN') to give Ph2P(0)N=PPh3. Thus, PPN' cannot always be considered to be a non-participating counter ion.33 Aziridine ring opening occurs upon direct halogenation of the dialkylamino aziridinophosphines, (R N) PNC2H4 to yield the iminophosphoranes, (R2N)2P(X) = 2 2 NCH2CH2X (X=Br, I) which spontaneously cyclize to diazaphospholidinium dihalides. 34 The aminolysis of hexachlorocyclodiphosphazanes, (C13PNC5H4N)2, leads to the 1,3-diaryl-2-oxo-imino-2,4diaminocyclodiphosphazanes, 11. 35 The thermolysis of bis (dimethylamino)phosphoranes leads to the cyclic dications [ (Me2N)2PNMe I 2+ which upon hydrolysis gives (Me2N)2P (0) N (Me)P (NMe2) = NMe. 362 Triphenylphosphine imine, Ph3P=NH, is obtained from the reaction of the thiazylchloride, (NSC1)3 , with triphenylphosphine.37 The thermolysis of dithiomethoxycarbonyl phosphonium iodide [Me3Si) NPMe2C(S)SMe]I gives the iminophosphorane Me3SiN=PMe2C(S)SMe. 3 g 2 The anions derived from deprotonation of R2P(X)NHR' (X=O,S) react I1 with non-metal halides Rn MX (M=Si, Ge, P) to provide either the n expected R2P(X)NR'MRn or the phosphazenes R2P(=NR')SMR - depending on the nature of-the substituents.39 '40 Numerous reactions, involving either transformation or conservation of the phosphazene unit, have been reported. The oxidation of the indanone phosphazene, 12, with singlet oxygen yields the corresponding ketone and triphenylphosphine oxide presumably via a 2+4 cycloaddition of oxygen to the -N=N-N=PPh3 unit which, following nitrogen elimination, forms the dioxetane, 13. 41,42 Reactions of phosphoramidic bromides, (R2N)2P (Br)=NR with aprotic nucleophiles occur at the phosphazene bond e.g. the addition of hexamethylphosphoramide gives (phosphiny1amino)phosphonium bromides, (R2N)2P (0)N (R)P (NMe2)3+Br-, while ethylene oxide gives The corresponding reaction with N-substi(R2N),P(0)N(R)CH2CH2Br. tuted aziridines gives diazaphospholidium bromides which upon reaction with sodium amide give N-vinyl iminophosphoranes, (R2Nl2II

369

8: Phosphazenes

i6h&x P-

P- N - P(0Et

P(0Et

(9)

12

(10)

(121

N= PPh,

0

CMe

'NHMc

Mc3C $C 'R *0 ;

CO, R

CMe3

CMc,

(14)

Me

T

F

e

( 1 5)

h

8

Ni

0

do, R R = SiMe,

(16) R2N

R N

R

(17)

370


P (=NR)N (R)CH=CH2.4 3 The reactions of trichlorophosphazene-N-phosphoryl dichloride with the sodium salt of trifluoroethanol provide the series, (CF3CH20)3-n C1 P=NP(0)C12 (n_=1,2) and (CF CH 0) n 3 2 3P=NP (0)(OCH2CF3)2. Upon heating , (CF CH 0)C12P=NP (0) C12 is transformed into [C12P ( 0 )I 2NCH2CF3.443 Tie reactions of a-lithiated derivatives of RCH2PPh2=NPh with alkyl halides give the expected RR1CHPPh2=NPh entities while the reaction with benzonitriles gives p-R1C6H4C(NH2)=CRPPh2=NPh.4 5 The quaternization of [ (Me2N)3P=N)I 3P0 with methyliodide gives (Me2N)3P=N]3POMefI-. 4 6 Addition of organolithium compounds to the phosphazene bond in (Me3Si)(R)NP (=NR) followed by treatment with a proton donor gives (Me3Si)(R)NPR' (=NR)NRH.47 The desulfurization of 14 leads to without decomposition of the phosphazene unit. The reactions of a triphenylphosphazo uracil derivative with dialkyl acetylene dicarboxylates in aprotic solvents yields the pyridinedionates, 15, which undergo heterocyclization in protic solvents to give 16.49The presence of the phosphazo group greatly facilitates assignment of the I3C nmr spectra of 15 and 16. The trans-silylation of RR'R"P=NSiMe with hydro3 silanes leads to the replacement of the trimethylsilyl group with the SiMe2C1 and SiC13 functions.50 The reactions of Ph3P=NSiMe3 51 with tungsten hexafluoride provides WF6-n(N=PPh ) (n_=1,2) 3n_ while the analogous reactions with selenium tetrachloride give The reaction of (Ph3P=N)*SeC12 with (Ph3P=N) SeC14-n (g=l,2 ) n antimony pentachloride gives [(Ph3P=N)2SeCll+SbC+-. 52 The reaction of the phosph(II1)azene R2NP=NR (R=SiMe3) with bi(cyclooctadieny1) nickel(0) followed by treatment with bipyridine gives a nickel azadiphosphetine, 17. 5 3 Reaction R2NP (=NR) (R=SiMe3) with methyl lithium followed by treatment with zirconium tetrachloride leads 54 to the zirconacycle, 18. A few applications of acyclic phosphazenes have been mentioned. Derivatives of the type PhCH2PRR1=NR"(R"=H, Me, SiMe3) have been prepared and studied as perfumes. 5 5 The preparation paryl (N,Nbis(f3-chloroethyl)amino)-guanidinophosphates, (C1CH2CH2)2N=P(0)(OC6H4R)N=C(NH2)2, has been reported and it has been found that they exhibit lower toxicity and higher antitumor activity than do the corresponding diarylamidophosphates 56 Poly (methylsiloxanes) are stabilized by C13P=NPC12=NPC13+PC16-.57 The synthesis and use as lubricating agents of perfluoroalkyl monophosphazenes, (RO),-

2,4,6-(Me3C)3C6H21??NC6H2(CMe3)2Me

.

.

8: Phosphazenes

37 1

(Z=O, S; R=perfluoroalkyl; 5 = 1-3; y = 1,2) C13-xP=NP(Z)(OR) C 1 _y ggY havebeen patented. 3 Cyclophosphazenes A review of the applications of HUckel molecular orbital theory to various aspects of phosphazene chemistry, including geometric and electronic structure, reactivity and stability, has appeared. 5 9 More highly focused reviews on natural polyamino phosphazene derivatives6' and the use of the mass spectrometer to probe cyclophosphazene ring-opening polymerization6' are also available. There is renewed interest in theoretical calculations on cyclophosphazenes. The first non-empirical m.0. calculations (STO-3G * and STO-3G ) have been performed on cyclophosphazenes and it was determined that the phosphorus-nitrogen bond lengths can only be adequately reproduced with a basis set which includes phosphorus d functions.62 The recent report of the synthesis of a cyclodiphosphazene (see SPR 17) has generated interest in the electronic structure of these materials. Extended basis set SCF calculations suggest that the dimer, [(NH2I2PNl2, is best considered as having zwitterionic form with an additional tetravalent P+ in a P'Nnitrogen lone pair to phosphorus 3d orbital intera~tion.~The importance of the zwitterionic structure is also indicated in @ initio calculations using pseudopotentials on (H2 PN)-23' A large nitrogen P population and a strong interaction of phosphorus _dxy orbitals (thus favoring the Dewar island model) have been found. No evidence for transannular phosphorus-phosphorus bonding could be uncovered. 6 3 D e l Re calculations for nine cyclophosphazene derivatives have been reported and the total atomic charges are in agreement with 31P nmr chemical shifts, basicity data and first ionization potentials. 64 A theoretical model for exocyclic spirodelocalization, vi;5d?l-Ellbonds, to the phosphorus-nitrogen ring has been proposed. The electrochemical reductions of the spiro(phena1ene) derivatives (19, R=NMr, X=OCH2CF3; 20) have been reported. The fact that the esr spectra of the reduced species shows that at least half, and probably all, of the ring nuclei 65 are esr active lends support to the spirodelocalization model. The exo-endocyclic phosphorus-phosphorus coupling constants, J PP have been reported €or nineteen phosphazenylcyclophosphazenes. These measurements allow for extensions of previous correlations


372

of solid state structures and solution conformations.66 The infrared spectra of the NH group in polyamines linked to cyclophosphazenes show evidence for some hydrogen bonding, allow for determination of NH acidity and correlations to biological activity have been proposed.67 Interest in the mass spectrometry of cyclophosphazenes continues. Loss of the amino substituent dominates the fragmentation of various dimethylamino derivatives of (NPX2)4(X=C1,F) while bromine atom loss is most significant in the fragmentation of N4P4F8-11XE (X=C1,Br; ;=2,4) 6 8 Gas phase ionmolecule reactions between various ammonium ions or radical cations and (NPC1 ) lead to the appropriate monosubstituted phosphazene derivativ;~?~’ Several investigations of the gas phase polymerization of cyclophosphazenes by mass spectrometry have been reported. The behavior of (NPCl2I4 is complex, including oligomerization up to (NPC12)12 and formation of N4P4;l7+ which is formulated as a cyclotriphosphazene with a NPC12 side chain. Evidence is presented to show that (NPCl2I3 and (NPC12)4 exhibit different gas phase polymerization processes. 70 The oligomerization of [NP(OPh) 3 in the ion source of a mass spectrometer has been examined.712 iimilar investigations on hexaminocyclotriphosphazenes show variable behavior, h. the hexa(ani1ino) derivative only undergoes fragmentation while the piperdino and morpholino derivatives undergo polymerization. As in the case of the hexaphenoxy and hexachloro derivatives, the oligomerization to the hexameric species is v i a the pentasubstituted cyclotriphosphazenium cation.72 The gas phase polymerization of tris (o-phenylenedioxy)cyclotriphosphazene in the mass spectrometer follows a different mechanism wherein a monomer adds to linear phosphazene radical cations.73 Scanning electron microscopy and x-ray crystallography (see section 7 ) studies have shown that the clathration of the tri(o-phenylenedioxy) derivative proceeds via a solid state monoclinic to hexagonal transition which provides improved opportunities for van der Waals attraction as the guest molecules enter 74 the lattice. Scattered reports of the synthesis of the cyclophosphazene ring system from the aminolysis of halophosphoranes continue to appear. The most interesting of these is the synthesis of the first spirocyclic organophosphazenes, [ (CH2)4PNl 3 , 4 , from (CH2)4PC13 and ammonium ~hloride.’~ The use of ammonium carbamate in

.

8: Phosphazenes

373

place of ammonium chloride in the synthesis of (NPC1 ) (n_=3-10) 211 has been reported.76 Measurement of HC1 absorption curves in the reaction of ammonium chloride and phosphorus(v) chloride show three distinct stages of the reaction and allow for kinetic measurements.77 A non-catalytic , two stage , process for the preparation of chlorophosphazene oligomers has been described.78 A s in previous years, most reports concern nucleophilic substition reactions of halocyclophosphazenes. The fluorination of &2,4-N P C1 (NEt2)2 (as monitored by I 9 F nmr and glc) with antimony 3 3 4 trifluoride gives the cis non-geminal difluoride while the use of potassium fluorosulfate gives the geminal difluoride. The tetrafluoro derivative, cis-2,4-N3P3F4(NEt2)2 can be obtained from treatment of the non-geminal difluoride with potassium fluorosulfate or the geminal difluoride with antimony trifl~oride.~’ A detailed study of the reactions of N3P3C15N=PPh3 with aziridine leading to the series N3P3 (NPPh3)C15,n (NC2H4)_n (n_=1-5) has appeared.80 The trans non-geminal derivative is favored (but not exclusively) at the mono stage of substitution. The non-geminal preference continues until the tris stage of substitution where only the geminal derivative is obtained. The fluoro derivative, N 3 P 3 F 5N=PPh3, is unreactive towards aziridine even under drastic conditions. The enzyme (reverse transcriptase) inhibiting activity of N3P3(NPPh3) (NC2H4)5 is much higher than that of N3P3(NC2H4)6.80 A study of isomer dependent cytostatic activity of a broad range of aziridinylcyclophosphazenes has shown that nongeminal bis derivatives of (NPC12)3,4 are potent tumor inhibitors in contrast to the geminal and mono substituted derivatives.81 DNA damage by trans-2,4-N3P3 (NC2H4) (NHMe) occurs V J crosslinking while with trans-2,6-N4P4(NC H ) (NHMeI6 both single strand breaking and cross-linking occurs.8 2 2 ilthough cumulative bone marrow toxicity induced by 2,2-N3P3(NC2H 41 4 (Pyr)2 (Pyr=pyrrolidinyl) leads to death in mice, the corresponding effect was absent when trans-2,4-N3P3 (NC2 H4 ) 2 (NHMe) was administered.83 The prepar14 ation of the C-14 labeled aziridinyl derivative, [NP(N C2H4l2I2NP (NC2H4)NC4H8C, has been noted.84 The reactions of (NPC12) with amine substituted polymers85 or carboxylic acid terminated polymers and diamines86 can be used to incorporate the cyclophosphazene into polymeric systems. The residual chlorine atoms in tris(hydroxyphenoxy)chlorocyclotriphosphazene have been allowed to


374

6 #+

N

E

(E=O,NMe; X = CI ,0CH2CF,)

R = OCH,CF, (20)

(19)

R = OCH2CF3 (21)

-N-

N

II

FP-

CP M

CP

F2

ll N

'Ru

I =PF

' c p\

N

(M = Ru ,Fe 1

(22)

8: Phosphazenes

375

react with propyleneimine to give a material which is converted to a cross-linked polymer on heating.87 Interest in the reactions of phosphazenes with bifunctional reagents continues. The two ring assembly, N3P3C15NH(CH ) NHN3P3C15 ( g = 5 - 1 0 ) is obtained from 2n Mixed the reaction of N P C 1 with the appropriate diamines. 3 3 6 dispirocyclotriphosphazenes,N3P3C12 [NH (CH ) NH] [NH(CH ) NH] 2m_ 211 ~ # I J= 2,3,4) , have been prepared from the monospiro derivative and the diamine.*’ The reactions (NPC12) with the difunctional reagents NH2 (CH2lBNH2 (n=2,3), HO (CH ) OH (n=2,3 ) and MeNH (CH2)20H 2 n lead to the monospiro derivatives, N P C1 [X(CH ) XI (X=O,NH,NMe), 2 n 4 4 6 which can be then converted to the dimethylamino or methoxy derivatives. The compounds with two methylene units in the spirocyclic unit are particularly unstable. The reaction of (NPC12) with 2-bis(hydroxymethy1)carborane leads to the novel monospiro The reactions of 1 ,9-disubstituted phenalenes derivative 2 2 . with (NPCl2I3 lead to the spiro derivatives 19 (X=Cl). Only the amino derivative (19. E=NMe) can be derivatized with the trifluoroethoxide ion; the corresponding reaction with 19 (E=O) leads to disruption of the spirocyclic unit to form the monosubstituted derivative 20. Alkylation of 19 (E=NMe) gives the cationic species There has been an increase in the number of reports of the reactions of oxygen bases with cyclophosphazenes. A complete report of the reactions of N 3 P 3 X 5 N=PPh3 (X=F,Cl) with sodium methoxide to yield the series N3P3 (NPPh3)(OMe)nX5-Q (X=F,Cl; n=1-5) has appeared. Replacement of the chlorine-atoms gives isomers in unequal proportions, the &-2,4 derivative being the major product for “1 while the geminal isomer is formed when ~ = 3 . The corresponding reactions of the fluoro derivatives give geometrical isomers in roughly equal proportions. Although the chlorine atom at the ZPClNPPh3 center is fairly reactive, the corresponding displacement of a fluorine atom does not occur until all other fluorine atoms are displaced.9 2 The reaction of N3P3C15NPPh3 with excess methoxide ion gives, in addition to the expected pentamethoxy derivative, two hydroxy derivatives, N3P3(NPPh3)(OMe)5-n (OH) ( ~ = ,l2) which exist in the oxophosphazadiene form. Similar reactions of N3P3(NPPh3) (NMe2)C14 give a tetramethoxy derivative and N3P3 (NPPh3)“Me2) (OMe)30H. In both cases the monohydroxy derivatives are present as & and trans isomers.93 The conditions for the preparation of N 3 P3 C15OAr (Ar=C6H5, _p-BrC6H4, -p-MeC6H4) have been optimi~ed.’~The synthesis of the hexakis-

**

d5


376

(methylacryloylethoxy)cyclotriphosphazene, N3P3(OCH2CH20C(0)C(Me)= CH2)695 and its use as a dental resing6 have been described. The reaction of (NPCl2I3 with octafluoropentoxytrimethylsilane is reported to give octafluoropentoxy derivatives. A series of mixed trifluoroethoxy-phenoxy derivatives of (NPC1,I3 have been Phase-transfer prepared and studied as fire resistant fluids. catalysis has been used in the preparation of (NP(OPh)2)3.99 The synthesis of the salt [N3P3(0NC H ) 16+(C1-)6 from (NPC12)3 and pyridine N-oxide has been reported.‘0° The pentakis allyloxy derivative, N3P3(OCH2CH=CH2)5(OCH2CHBrCH2Br) , has been prepared and grafted to cellulose by treatment with Ce(1V) .lol The reaction of sodium silicate with 2,4-N3P3C12(NMe is proposed to give siloxy-bridged cyclophosphazene polymers. f02 The interaction of N3P3(0Ph) C1 with the hydroxyphosphazenes, N3P3(0Ph)50H gives 5 POP-bridged cyclophosphazenes. The POP bridge in [N3P3(OPh)5 1 2O can be cleaved by nucleophiles to give N3P3(0Ph)5X(X=C1,F,0H,0Ph, OMe) l o 3 Patents on the preparation of condensed poly (alkoxyphosphazenes), low molecular weight oligomers, have been granted.lo4-lo6 Fewer papers than in previous years are available on organometallic reactions of cyclophosphazenes. The preparation of (NPMe2)6-12 from (NPF2)6-12 and methylmagnesium bromide and the characterization of (NPMe2)9-12 by X-ray crystallography (see section 7 ) makes this the largest known series of cyclic compounds with full structural characterization.lo7 Full details of the reactions of (NPC12)3 with methyl or t-butyl lithium and excess propan-2-1 have been reported. Mixtures of cylcic derivatives of various types, Q. alkylated, bicyclics and alkoxy hydrido derivatives are obtained in 80 to 90% yield.l o 8 The reaction of the transannular organometallic derivative 2,6-N4P4F6[(C5H4)2Ru] with a mixture of mono and dilithiated ruthenocene gives 23 (M=Ru) and the bis transannular derivative ( 2 4 ) . The fluorine atoms in 24 cannot be replaced by reaction with the methoxide ion. The reaction 2,6-N4P4F6[(C H ) Rul with (LiC H ) Fe only gives the iron 5 4 2 5 4 2 analog of 23 (M=Fe). I o 9 Reactions at the exocyclic position of cyclophosphazene derivatives represent a means f o r widely expanding the range of available phosphazenes. The synthesis of covalently bound cyclophosphazene heme complexes starts with N3P3(0Ph)5C1 which is converted to N3P3(OPh),NMeCH2CH2CN. Following reduction of the

’’ ’*

.

8: Phosphazenes

377

cyano function to the amine, coupling with porphyrins (a modified picket fence hemin and a protohemin chloride 3-(l-imidazolyl) propylamide) containing a carboxylic acid substituent leads to N 3P3 (OPh)5NMe (CH2)3NHC (0) R (R=(CH)2C ( 0 )NHC6H4 porphyrin, (CH2) porphyrin) 'lo The reduction of N3P3 (OPh)50C6H4CH0 followed by coupling with 4-nitro-2-dicyanobenzene leads to N3P3(0Ph)5OC6 H 4 CH,0C6H3(CN)2 which on treatment with cuprous bromide and substituted phthalonitriles give the copper phthalocyanine derivatives ( 2 5 ) which are non-aggregated in solution.11' The copolymerization of N3P3F5C(OEt)=CH2 with styrene or methyl methacrylate gives fire resistant copolymers with the cyclophosphazene as a substituent on the carbon-chain backbone. Reactivity ratio data and the derived Alfrey-Price parameters indicate that the major perturbation of the olefinic center is through the u electron withdrawThe hexallylamino derivative, ing effect of the phosphazene. '12 N P (NHCH2CH=CH2) undergoes photo reactions with polythiols.'13 3 3 The acylation of g-nitroaniline can be effected by a (NPC12)3 pyridine-N-oxide mixture in acetic acid. The reaction is first The reactions of N3P3 (OCH2CF3)50Na with order in phosphazene. sulfonyl chlorides lead to the sulfonates N3P3(0CH2CF3)50S02R which in turn react with organic acid chlorides to give phosphaPhoszene esters, N3P3 (OCH2CF3)50C (O)R, of varying stability.'15 phazene esters can also be prepared by the reaction of N3P3(0Me)5OH with acid chlorides and in turn may be converted to amides V I reaction with primary amines. The conversion of N 3P3C14 (NH2)2 to N 3P3C15NPPh3 by reaction with Ph3PC12 has been optimized. The monophosphazo derivative can also be prepared by the reaction of the diamine with triphenylphosphine in carbon tetrachloride or via a Staudinger reaction of triphenylphosphine with N3P3C15N3. The coordination of TaF5 to N3P3(OPhI6 in the 1:l addition compound is in a monodentate fashion through the nitrogen atom."* The few remaining miscellaneous patents include the use of

.

amidophosphazenes as soil urease inhibitors1lg the treatment of fibers with alkoxy, aryloxy or thioalkoxy phosphazenes to produce low friction and antistatic properties12* and the preparation of vinyloxyphosphazenes and their potential as comonomers in addition 121 polymerization. 4 Cyclophospha (thia)zenes Calculations at the MNDO and Hartree-Fock-Slater levels suggest


378

that the five membered N2S2P ring, 26, is a stable, 6 a electron system. The reaction of 27 (X=Cl) with triphenylantimony leads to the radical (NPPh2)2(NS): The esr spectrum of this radical was obtained and ab initio calculations indicate that although the II system is highly polarized towards the NSN fragment, orbitals on the phosphorus atoms allow for delocalization of spin density from sulfur to phosphorus centers.123 The low temperature electronic absorption and preresonance Raman spectra of 28 and 29 have been observed. Details of the electronic spectra of 28 and 29 have been calculated from the Raman data. 124 The 6,6-spirocycleI 30, is obtained from the solid state thermolysis of 27 [X=C1,Br,I,N3 or NR (R=Me2, Et2, C5Hlo)I, 31, 32 or 33. In the case of the amino derivatives of 27, 34 is isolated and shown to be an intermediate from 27 to 30. The reaction of 27 (X=C1) with sodium azide yields 30, 32 and the new phospha(thia)zene, 35.125 Phospha(thia)zenes with four coordinate sulfur atoms continue to exhibit interesting chemical and biological properties. The reactions of NPC12(NSOX)2 (X=Ph,Cl,F) with the aliphatic difunctional reagents NH2 (CH2)2, 3YH (Y=NH, 0) give the spirocyclic derivatives NP [NH (CH2)2, 3Y1 (NSOX)2. The 31P nmr chemical shifts of these materials undergo a large change when included in the spiro ring. 126 The Friedel-Crafts reaction of (NPC12)2NSOC1 with monosubstituted benzenes, C6H5R (R=Me, OMe, Et, i-Pr, C1, Br, I) provide a route to (NPC12)2NSOC6H4R. For R=Me, OMe ortho-and paraisomers of the aryl ring were obtained while only the para-isomer was obtained for the remaining derivatives. In the Friedel-Crafts reaction of cis-(NPC12)(NSOC1)2 with chlorobenzene, five of the six possible NPC12 (NSOC6H4C1) isomers were isolated.127 The biological activity of the aziridino derivative [NP(NC2H4)2]2NSO(NC2H4) (SOAz) continues to be of interest. Although no detectable evidence for single strand breaks or DNA cross-linking was observed,82 significant bone marrow toxicity in mice has been noted.83 5 Miscellaneous Phosphazene-containing Ring Systems The reactions of phosphorus(II1) isocyanates, R2PNC0, with Measurements aldehydes lead to oxazaphospholines (36.128 12' of dipole moments and Kerr effects show that the orientation of the aryl groups in the aryl phosphatriazenes 37 (R,R'=Ar) is not coplanar with triazene ring. 130 The reactions of imidoylamines, RfC(=NH)N=CRfNH with PC15 give the chloro monophospha-s-triazenes 37 (R=C7F15, C3F70CF (CF3)CF20CF (CF3) ; R'=Cl) Similar syntheses

.

8: Phosphazenes

379

R

R

s-s X (26)

(27)

(28)

(29)

3 80


can be effected using C6H5PC15 to give the monophenyl derivatives. The fragmentation patterns observed in the mass spectrometry of these materials have been presented.131 The reaction of (RO)2P ( 0 ) C (CH=CH2)=C=CMe2 with Et2NC (Ph)=NP (OEt) gives the complex heterocycle 3 8 . 132 The preparation of the borato phosphazenes 39 (X=F, Cl,Br,I) appears in a patent. 133 The dimerization of PhCH=NP (OR) leads to the diazadiphosphorine 4 0 . 134 The reactions of perfluoro amidines, RfC(=NH)NH2 with PhPC13-N=PPhC12 give the diphospha-2triazenes 41 (M=CRf; X=Cl) which undergo reaction with the azide ion and triphenylphosphine to give 41 (M=CRf; X=NPPh3). The mass spectrometry of the new compounds is discussed in The reactions of 41 (M=CRf; X=Cl) and 37 (R=Rf' R'=Cl,Ph) with phenyl thiol have been studied with the aim of preparation of anticorrosive and antioxidative fluids.136 The first cyclophosphazene with an endocyclic metal atom ( 4 1 , M=WC13) is obtained from the reaction of tungsten hexachloride with [H2NPPh2NPPh NH21 C1. 137 2 The nucleophilic degradation of white phosphorus with lithium bis(dipheny1phosphino)amide gives the fascinating phosphorus rich 138 cyclophosphazenes 4 2 . 6 Poly (phosphazenes) This section is devoted to polymers containing open-chain phosphazenes. Cyclolinear and cyclomatrix phosphazene polymers are covered in section 3. Reviews are limited to a discussion of the fluoralkoxy and aryloxy phosphazene polymers produced by the Ethyl corporation139 along with two brief reviews in Japanese covering current inorganic polymer research in Japan14' and structure, phase transition and applications of poly (phosphazenes) 14' Fundamental work on the ring-opening polymerization of cyclophosphazenes has appeared. The use of mass spectrometry to probe gas-phase polymerization of cyclophosphazenes was discussed in section 3 . The application Raman spectroscopy and laser light scattering to the study of both melt142 and solution143 polymerization of (NPC12)3 has been described. On line monitoring of the

.

~

-

melt polymerization gives data including gP and \ in situ for this process. 142 These techniques show that in the solution polymerization the molecular weight of (NPC1 1 remains relatively 211. constant during polymerization and that rates can be measured directly.143 The application of these and other methodologies has been applied to the boron trichloride catalyzed solution polymerization of (NPC12)3. The boron trichloride does not require water

38 1

8: Phosp hazenes

X

( 35)

(36)

X

I


382

as a cocatalyst, is inhibited by arylphosphates and can be involved in initiation, catalysis and inhibition steps depending on concentration. A high yield of uncross-linked polymer with moderate molecular weight and wide polydispersity is obtained.144 Various patents on the formation of (NPC1 ) continue to appear. 2; The borato phosphazene, 3 8 , acts as a catalyst for this process. 133 A two step polymerization involving formation of oligomeric phosphazenes and their subsequent treatment with ammonium chloride has been noted. 145 The elimination of P0Cl3 from C12P (0)NPCl3 appears to be a good route to linear phosphazene polymers. 146 Treatment of the oligomeric materials Cl(PC1 N) POCl with linear PN salts147 2 1 1 or with PC15 followed by ammonium chloride348 also gives poly(phosphazenes). The interest in preparation of other poly(phosphazene) derivatives continues. The direct reaction of elemental phosphorus, ammonia and ammonium chloride in carbon tetrachloride leads to [(NH2)2PN]n which is claimed to be of value in chemotherapy. The meit polymerization of 22 and subsequent treatment with trifluoroethanol leads to a stable poly (phosphazene) The reaction of (NPC1 ) with diallylamine followed by treatment 2 n with alkoxy, aryloxy, amino or mercapto functions gives rubbery polymers.150 Mixed aryloxy/alkoxy phosphazenes, which have low Tg values and good smoke values in burning tests, can be prepared. 151 Patents describing improvements in the preparation of alkoxy or aryloxy poly(phosphazenes) include the sodium dispersion for the alcoholate preparation,152 solvent extraction to removal of metal halides153 and the use of solvents in which the metal chlorides are insoluble. 154 There is increasing interest in chemistry occurring at side chain positions of poly(phosphazenes). A series of polymers with etheric substituents, [NP(OR)2l and [NP(OR) (OR' 1 (R=OCH2CF3, Y 9 0(CH2)20Me, 0(CH2CH20)2CH3, 0(CH2CH20)12CH3), h a 6 been prepared. These materials are of potential biomedical interest and their salts are excellent solid state electrolytes.155 The lithium salts are good electrolytes for thin film batteries showing high ionic conductivity and high lithium transport numbers. 156 Other etheric phosphazenes where the phosphorus-nitrogen chains are cross-linked by oligo(oxyethy1enes) function as pseudo crown ethers and are active catalysts for nucleophilic substitution reactions.157 Alumina particles coated with [NP (OPh) 1 undergo 2 2 reactions at the phenoxy site. The aminophenoxy unit, which is

.

-

383

8: Phosphazenes

prepared by a nitration, reduction sequence, is activated by reaction with cyanogen bromide, nitrous acid or glutaric dialdehyde. Treatment with enzymes gives immobilized glucose-6-phosphate or trypsin. The bound enzyme retains activity and remains linked to the phosphazene through several catalytic cycles. lS8 Poly (phosphazenes) with covalently bound heme units have been prepared by routes identical to those used for preparation of the cyclotrimeric model systems (see section 3 ) . The electrochemical reduction of these species has been studied and the oxygen carrier ability has been probed by electronic spectroscopy and iron-57 Mossbauer specPoly (phosphazenes) with copper phthalocyanine side troscopy chains have also been prepared by the routes used to prepare the cyclotrimeric analogs (see section 3 ) . The oxidation potentials of these species are equivalent to those of the free copper phthalocyanine. Due to the fact that there is no significant interphthalocyanine contact, the electrical conductivity is in the semiconA full report of the hydroformylation behavior ductor range. of cobalt phosphines bound to poly(phosphazenes) has appeared. The reaction of dicobalt octacarbonyl with [NP(OPh)l.7(0C H P6 4 Ph2)o.3]G gives three different phosphine bound cobalt carbonyls. The initial hydroformylation activity of the heterogeneous catalyst is equal to that of homogeneous catalysts but deactivation occurs Poly (allylaminophosphavia carbon-phosphorus bond cleavage. (R=allyl, diallyl; R'=n-C H9 , piperidino) zenes) , [NP(NHR)( N H R ' ) ] are photocurable upon treatment with polythiols-I1' The use of 3aminopropyltriethoxysilane as a curing agent for poly(aminophos160 phazenes) has been mentioned. The solid state conformations of macromolecular phosphazene chains can be successfully modeled using short chain oligomers. In both cases, intramolecular non-bonded contacts are important in solid state stacking of chains.* Nmr relaxation studies of poly[bis(trifluoroethoxy)phosphazenel, PBFP, show that sample prehistory effects phase composition and phase dynamics. Poly alkoxy and aryloxyphosphazenes have been discussed as examples of condis (conformationally disordered) crystals which are a newly Two crystalline phases of polyrecognized type of mesophase. [di(4-isopropylphenoxy)phosphazenel have been identified by X-ray fiber diffraction. In each case, the side group location is the major structural determinant. The observation that the melting point, enthalpy of melting and crystallinity of melt crystallized

.'''

.


384

PBFP increases as the temperature of prior annealing above the melting point increases has been taken to indicate that crystallization occurs in the mesophase region. Solution cast films of poly[bis(p-f1uorophenoxy)-phosphazenel show a thermally reversible transformation between a crystalline (hexagonally packed chains) and a mesophase. Cooling of the mesophase gives another The spherulitic form of crystalline form (planar &/trans) PBFP has been studied by electron scanning microscopy showing a morphology consisting of cospherical aggregates which change on heating. 166 Extensive structural and optical studies on PBFP show three polymorphic forms and a mesoform. The thermotropic transitions in these materials have been correlated to chain extension and folding.167 The kinetics of the transformation from two dimensional to a three dimensional structure in poly[bis(pmethylphenoxy)phosphazenel on passing through the mesophase has been studied by wide angle and small angle X-ray scattering.168 Low angle polarized light scattering and Z-ray studies on poly(phosphazenes) show that with alkyl groups in the side chain, chain crystallization occurs with long chain alkyl groups while with aryl groups both side chain and main chain effects are The thermal analysis of poly (diorganophosphazenes) important.16' show that Tg increases as the symmetry of the side group decreases and that the melt transition and crystallinity vanish if the backbone symmetry is removed. All of the organophosphazenes decompose in the range of 3 5 0 to 400° with (NPMe ) being the most 211 stable material.170 It has been found that poly[bis(4-benzoylphenoxy)phosphazene] is an efficient, reversible, triplet state energy donor thus inducing photoreactions in suitable acceptors.171 The photochemical iodine doping of.poly[bis(p-toly1amino)phosphazene] produces stable samples with specific conductivities which are two orders of magnitude greater than the undoped polymers 172 The addition of trinitrofluorenone to poly [bis(2naphthoxy)phosphazene] transforms the polymer to a strong photoconductor with high sensitivity.173 The thromboresistance of PBFB (in dogs) is higher than polyfethylene)or poly(tetraf1uoroethylene) 174 Solutions of PBFP with 0.16 mole percent residual chlorine atoms in blood serum show a viscosity decrease over a three month period, presumably due to hydrolysis, but no detrimental effect on the biological properties of the medium were 175 observed.

.

-

.

.

385

8: Phosphazenes

Applications of poly(ph0sphazenes) continue to be announced, particularly in the patent literature. The flame retardant properties of aryloxyphosphazene elastomers,176 poly (phenylphosphazene isothiocyanate)ethylenimine,177 along with the effects of a broad range of phosphazene polymers on the combustibility and smoke formation in epoxy resins17' have been pointed out. Processes for poly(ary1oxy or alkoxyphosphazene) foam production are available. 1 7 9 f 1 8 0 Increased interest has been shown in poly(phosphazene) membranes for the separation of gases181-184 and

.

fluids 185 The use of the commercial poly(phosphazene) fluoroelastomer, PNF, as a permanent soft liner for removable dentures has been proposed. 186 The use of naphthalenic derivatized plasticizers €or poly (phosphazenes)187 and the use of poly (phosphazenes) for the low-temperature vulcanization of chloroprene rubbers188 have been noted. Bis (perfluoromethyl)phosphazenes, [ (CF3)2PN] (;=3-100) give good heat resistance and flexibility to epoxy resins.189 7 Molecular Structures of Phosphazenes The following structures have been determined by X-ray diffraction. All distances are in picometers and angles in degrees. Compound C13P=NC( CF3) [O(CH2CH,)2N]3P=N

4

Reference

Comments PN 150.5(3);

190

L P N C 142.9(3)

P=N 159.1( I ) ; PN 164.2( 1)-1.66.3(

1)

P=N 158.9(2) ; L PNPexo148.3(2)

191 15

no PN data reported

49

16 (R=C2H5)

no PN data reported

49

WF4(N=PPh ) 3 2

PN 159.4(6); &s-0

51

15 (R=C2Hs)

Ph3P=NSeC1 3 (Ph P=N) 2SeC12 3 Ph3PNPPh20N( 10)

h

PN 160.0(4);

L SeNP

137.1(3)

52

PN 160.6(4);

LSeNP 124.5(3)

52

Average PN 158.2;

33

PNP 138

54

18

PN endocyclic 160.5(9); exocyclic 164.1(9)

17

P=N 155.6(2); PN endocyclic 170.0(3) 177.2(3), exocyclic 173.8(3), 175.9(3)

OP( C12)NPC13 OP ( C12)NP (C1 NPC13

161.9(9)

PN 158.0(8) , 151.9(8) PN 154.6(9), 154.3(9), 153.7(9),

53

8 158.9(9)

8


386

Compound

Comments

Reference 8

[ C13PNP(C12)NP ( C12)NPC13]+PC16-

PN 149.8(5), 152.7(3)

157.2(5),

OP (OPh)2NP(0Ph)

PN 159.6(4),

152.5(4)

OP (NHPh)2NP (NHPh)

PN 161.0(2), 157.7(2) PNH 162.9 (2)-165.5 ( 3 )

8

PN 158('1), 157(1), 161(1) 156(1); PMI 162(1)-167(1)

8

21

8

PN 159.3(6); LNPN 116.7(22); L PNP 136.1(43)

107

PN 159.2(6); NPN 116.4(22); LPNP 138.2(52)

107

PN 159.6(5); 1: NPN 116.6(21); L PNP 134.8(45)

107

PN 159.6(5); NPN 116.3(22); L PNP 132.8(40)

107

PN endocyclic 156.7(4)-158.5(3); exocyclic 166.7(3), 167.1(3), planar N3P3 PN 152(1)-159(2)

65

PN 155.5(8),

158.1(8)

74

PN endocyclic 157.6(4)-161.0(4); PNPPh , 158.9(1), 155.7(5); PN exocyzlic (NC H ) 168.0(4)172.4(7) ; New2dPh3 conformation

80

74

24

PN 155.9-157.2(3); Average L PNP 109 134.2; boat conformation

30

PN(PNP fragment) 158.4(4)159.5 ( 4 ) PN(PNS fragment) 159.2(4)160.8(4) Planar P SN rings 2 3 PN (PNP fragment) 156.9 (6)158.7 (6) PN(PNS fragment) 160.8(5)162.2 (5) P2S2N4 rings puckered

125

PN endocyclic 160.8(5) ,161.3(6)

126

PN 157.3; Skew boat; cis-phenyl groups

192

33

125

3 87

8: Phosphazenes

Comments

Compound

Reference

[NP(n-C3H5) (i-C3H7)] (NSOPh)2

PN 1 6 1 . 0 ( 4 ) , 160.6(4); t w i s t boat; trans-phenyl groups

193

[NPI(i-C3H7) ] (NSOPh)

PN 1 6 1 . 0 ( 6 ) , 1 6 0 . 8 ( 6 ) ; t w i s t b o a t ; trans-phenyl groups

194

PN 1 5 6 . 8 ( 6 ) , 157.9(4) t r a n s - C6H4C1

127

PN e n d o c y c l i c 1 5 7 . 6 ( 1 2 ) , 1 5 9 . 8 ( 7 ) ; e x o c y c l i c 160.9(9) ; e x o c y c l i c N pyramidal

195

2

-

PN e n d o c y c l i c 1 5 8 . 9 ( 9 ) , 161.7(10);195 e x o c y c l i c 167.0 (10) ; e x o c y c l i c N pyramidal

PN 1 6 4 . 0 ( 7 ) , 1 6 6 . 3 ( 7 ) , 159.6(6); Planar r i n g

158.7(7),

f i b e r d i f f r a c t i o n s t u d y , two phases

137 163

References

26,

1 H. Germa and J. Navech, Phosphorus S u l f u r , 1986, 327. 2 M.T. Nguyen, M.A. McGinn,and A.F..Hegarty, J . Am. Chem. SOC., 1985, 107, 8029. 6494. 3 R . A h r i c h s and H . S c h i f f e r , J. Am. Chem. S O C . , 1985, 4 G. T r i n q u i e r and G . B e r t r a n s , I n o r & . Chem., 1985, 24, 3842. 5 W.W. S c h o e l l e r and C . L e r c h , I n o r g . Chem., 1986, 576. Can. J. 6 D. Gonbeau, G . P f i s t e r - G u i l l o u z o , M.-R. M a r i e r e s , a n d M. Sanchez, -Chem., 1985, 63, 3242. Chou, L . Throckmorton, 7 M. Pomerantz, D.S. Marynick, K . Rajeshwar, W.-N. E.W. T s a i , P.C.Y. Chen,and T . Cain, J . Org. Chem., 1986, 51, 1223. 8 H.R. A l l c o c k , N.M. T o l l e f s o n , R.A. Arcus,and R.R. W h i t t l e , J. Am. Chem. SOC., 1985, 107,5166. 9 M.P. Ponomarchuk, L . S . Sologub, L.F. Kasukhin,and V.P. Kukhar, J. Gen. Chem. USSR (Engl. T r a n s l . ) , 1985, 55, 1532. --10 L . Bruche, L. G e r a n t i , a n d G . Z e c c h i , S y n t h e s i s , 1985, 304. 1985, = , 5 7 . 11 J. Kovacs, I . P i n t e r , A. Messmer,and G . Toth, Carbohydr. 12 D. Vegh, M. K r i z , J . Kovac, A. F u l i e r o v a , a n d R. Kada, C o l l e c t . Czech. Chem. Commun., 1985, 50, 1415. 1 3 A. Razhabov a n d 3 . M . Yusopov, J. Gen. Chem. USSR (Engl. T r a n s l . ) , 1985, 55, 667. 14 M.N. G e r t s y u k and L . I . Sarnarai, J. Org. Chem. USSR (Engl. T r a n s l . ) , 1985, 21, 1436. 15 D. Schomburg, U . Wermuth,and R . S c h m u l t z l e r , Phosphorus S u l f u r , 1986, 26, 193. 16 A. B a c e i r e d o , G . B e r t r a n d , J . P . Majora1,and K.B. D i l l o n J . Chem. SOC., Chem. Commun., 1985, 562. 17 M.R. Marre-Mazieres, M. Sanchez, R . Wolf,and J . B e l l a n , E .J. Chim., 1985, 3 , 605. 18 M.R. M a z i e r e s , M. Sanchez, J . B e l l a n , a n d R . Wolf, Phosphorus S u l f u r , 1986, 26, 97. -

107,

25,

=,

388

19 20 21

22 23 24

25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51


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117,

301,

118,

1,

5,

54,

3,

55,

5,

55,

26,

107,

109,

.

~~

104,

3 89

8: Phosphazenes

H.W. Roesky, K.L. Weber, U . Seseke, W. P i n k e r t , M. Noltemeyer, W . Clegg

52

and G . M . S h e l d r i c k , J . Chem. SOC., D a l t o n T r a n s . , 1985, 565. S h e r e r , R . W a l t e r , a n d W.S. S h e l d r i c k , Angew. Chem. I n t . Ed. E n g l . , 1985, 525. L.N. Markovskii, V . D . Romanenkov, V.F. S h u l ' g i n , A.V. Ruban, A.N. Chernega, M.Yu A n t i p i n , a n d Yu. T . Struchkov, 3 . Gen. Chem. USSR (Engl. T r a n s l . ) , 1985, 55, 1555. R . Muenstedt and U. Wannagat, ~Monatsh. Chem., 1985, 7. 1.1. Kuzmenko, -Farm. Zh. (K i e v ) , 1985, 7 1 (Chem. A b s t . , 1985, 103, 2 1 5 4 0 8 ~ ) . M. R i e d e r e r , U.S. US4564693 (Chem. A b s t . , 1986, 150215d). A . Q u a s s i n i and R . DeJaeger, F r . Demande FR 2548188 A 1 (Chem. - _ _Abst., 1985, 103, 8 8 0 8 4 j ) . N.L. Paddock, -___-I n t . Rev. Phys. Chem., 1986, 2, 161. J.-F. L a b a r r e , __-Top, C u r r . Chem., 1985, 173. P . T r a l d i , M . G l e r i a , G . A u d i s t o , S . Daolio,and E. Vecchi, --Comm. Eur. Commu n i t i e s , [ R e p . ] EUR, EUR 9421, Mass Spectrom. Large Mol., 1985, 303 (Chem. Abst., 1 9 8 r E 7 7 8 m a r R . C . Haddon, Chem. Phys. L e t t . , 1985, A 2 i , 372. G . T r i n q u i e r , J . Am. Chem. S O C . , 1986, 108, 568. C . M i h a r t , S . Raduly and Z . Simon, Rev. G m . __ Chim., 1983, 857 (Chem. A b s t . , 1984, 23595). R . C . Haddon, S.L. Mayo, S . V . C h i c h e s t e r , a n d J.H. M a r s h a l l , J . Am. Chem. S O C . , 1985, 107, 7585. M. B i d d l e s t o n e , R . K e a t , H . G . P a r k e s , H . Rose, D . S . R y c r o f t , a n d R.A. Shaw, Phosphorus S u l f u r , 1985, 25, 25. R. M a t h i s , M. W i l l s o n , F . M a t h i s , J.-F. L a b a r r e , G . Guerch, R . Lahana, A . Mahmoun,and F. S o u r n i e s , Spectrochim. Acta, P a r t A, 1985, G , 573. T . T . Bamgboye and O.A. Bamgboye, Org. Mass. Spectrom., 1985, 487. M. Gleria, S . D a o l i o , A.M. Maccioni, E. Vecchi,and P . T r a l d i , Org. Mass. Spectrom., 1985, 2, 686. M. G l e r i a , G . A u d i s i o , S . D a o l i o , E . Vecchi, P. T r a l d i , a n d S . S . Krishnamurthy, J . Chem. S O C . , D a l t o n T r a n s . , 1986, 905. M. G l e r i a , G . A u d i s i o , S. D a o l i o , P . T r a l d i , a n d E . Vecchi, J . Chem. SOC., 1547. D a l t o n_T r a n_ s . , 1985, ~ _ M. Gleria, G . A u d i s i o , S . D a o l i o , E . Vecchi,and P . T r a l d i , Org. Mass. Spectrom., 1985, 498. S. D a o l i o , P . T r a l d i , E . Vecchi,and M. G l e r i a , Org. _ _Mass Spectrom., 1985, 20, 492. H.R. A l l c o c k , M.L. Levin,and R.R. W h i t t l e , I n o r g . Chem., 1986, 41. R.C. O l i v a r e s and Y.L. Cantu, Revue Roamaine d e Chemie, 1985, 525. J . R e t u e n t and F . M a r t i n e z , Chem. I n d . (London), 1985, 597. E . Devadoss, J . Polym. Mater., 1984, 1, 170. H.M.Li, U . S . U S m 5 m e m . Abst:, 1986, 34464k). T . T . Bamgboye and O.A. Bamgboye, Spectrochim. Acta, P a r t A, 1985, G, 981. K.C.K. Swamy, M.D. Poojany, S.S. Krishnamurthy,and H. Manohar, -J . Chem. S_ O ~_. D ,_a l-t o n Trans., 1985, 1881. A.A. v a n d e r Huizen, T. W i l t i n g , J . C . van d e Grampel, P. L e l i e v e l d , A. van d e r Meer-Kalverkamp, H.B. Lamberts,and N.H. Mulder, J . Med. Chem., 1986, 1341. J . G . Z i j l s t r a , S . d e Jong, J . C . van de Grampel, E.G.E. d e V r i e s , a n d N . H . Mulder, Cancer R e s e a r c h , 1986, 46, 2726. N.H. Mulder, E . G . E . d e V r i e s , H. Timmer-Bosscher,and J . C . van d e Grampel, Eur. _ J. Cancer l i n ._O n_ col_ . , 1986, 195. _ _ C_ ~ G . V . Bornovalova, L.F. L i n b e r g , E.G. Tikhonova,and T . S . Safonova, Khim. 109782~). -Farm. 1985, 19, 583 (Chem. A b s t . , 1986, _ _ _ _Zh., _ R.E. Meyers, U.S. US 45351478 (Chem. A b s t . , 1985, 103, 143227k). R.E. Meyers, U.S. US 45337268 (Chem. A b s t . , 1985, 103, 1 4 2 9 6 6 ~ ) . E . Devadoss and C.P.R. Nair, Polymer, 1985, 6, 1895. ~~

53 54

55 56 57 58 59 60 61

O.J.

24,

116, 104,

129,

~

62 63 64 65

101,

28,

~

~

66 67 68 69 70

20,

~~

71 72 73 74 75 76 77 78 79 80 81

82 83 84 85 86 87

0,

5, 30,

104,

3,

22,

104,


390

88 89 90 91

92 93 94 95 96 97 98 99 100 101 102 103

104 105 106 107

108 109 110

111 112 113 114 115 116 117 118

P. C a s t e r a , J . P . Faucher, G. Guerch, R. Lahana, A. Mahmoun, F. S o u r n i e s , 29. and J.F. Labarre, Inorg. Chim. Acta, 1985, M. Willson, L . L a F a i l l e , G . Comenges,and J.F. Labarre, Phosphorus S u l f u r , 1985, 25, 273. V . C h a z r a s e k h a r , S. Karthikeyan, S. S, Krishnamurthy, and M. Woods, I n d i a n J . Chem., S e c t . A, 1985, 379. -V.V. Korshak, N . I . Bekasova, M.P. P r i g o z h i n a , E.G. Bulycheva,and S.V. Vinogradova, Vysokomol. Soedin. S e r . B y 1985, 847 (Chem. Abst., 1986, 104, 168963f). E . K . Swamy and S.S. Krishnamurthy, Inorg. Chem., 1986, 920.

108,

3,

2,

2,

K.C.K. Swamy and S.S. Krishnamurthy, J . Chem. SOC., Dalton Trans., 1985, 1431. M. Poetzsch, G . I . Mitropol'skaya,and V.V. Korshak, J. Gen. Chem. USSR (Engl. T r a n s l . ) , 1985, 55, 1158. M. Anzai and M. Dhashi, Shika Zairyo K i k a i , 1984, 2, 401 (Chem. Abst., 1985, 102, 1 9 1 1 0 9 ~ ) . M. A n z z a n d M. Ohashi, J . Nihon Univ. Sch. Dent., 1984, 26, 23 (Chem. Abst. 1985, 102 137742n)T ---S.G. Fedorov, G.S. Gol'din, G.S. N i k i t i n a , a n d V.A. Rusakov, Zh. P r i k l . Khim. (Leningrad) , 1985, 58, 1357 (Chem. Abst., 1986, 104, 1990611). R.E S i n g l e r , A . J . Deome, D.A. Dunn,and M . J . B i e b e r i c h , Ind. Eng. Chem. Prod R e s . Dev. , 1986, 25, 46. L . J . Carr and G.M. Nichols, Eur. P a t . Appl. EP 145002 A2 (Chem Abst., 1985, 178459q). A . E . Shumeiko, G.D. T i t s k i i , L.M. Litvinenko, L.P. Kurchenko,and V.V. Vapirov, J . Gen. Chem. USSR (Engl. T r a n s l . ) , 1985, 55, 697. H.S. Pyo, H.J. Chae, H.S. Lyu,and S.W.K., Han'guk Somyu Konghakhocchi, 106514f). 1985, 22, 74 (Chem. Abst., 1985, M. Kajiwara and N. Yamamoto, Angew. Makromol. Chem., 1986, 140, 33. K.V. K a t t i , S.S. Krishnamurthy,and M. Woods, Phosphorus S u l f u r , 1985, 25, 167. Otsuka Chemical Co., L t d . , Jpn. Kokai Tokkyo Koho JP 60/18527 A2 (Chem. Abst., 1985, 103, 7 2 0 3 ~ ) . Otsuka Pharmaceutical Co., Ltd, Jpn Kokai Tokkyo Koho JP 60/40132 A2 (Chem. Abst., 1985, 103, 37901r). Otsuka Chemical Co., Ltd. Jpn. Kokai Tokkyo Koho JP 60/13815 A2 (Chem. Abst., 1985, 103, 3 7 9 3 7 ~ ) . R.T. Oakley, S . J . R e t t i g , N.L. Paddock,and J . T r o t t e r , J . Am. Chem. SOC., 6923. 1985, H. Winter and J . C . van d e Grampel, J . Chem. SOC., Dalton Trans., 1986, 1269. K.D. Lavin, G.H. Riding, M.Parvez,and H.R. Allcock, J. Chem. SOC., Chem. Comm., 1986, 117. H.R. A l l c o c k , T.X. Neenan,and B. BOSO, Inorg. Chem., 1985, 24, 2656. H.R. Allcock and T.X. Neenan, 1986, 5, 1495. C.W. A l l e n and R.P. B r i g h t , Macromolecules, 1986, 19,571. K.D. Ahn, U.Y. Kim,and C.H. K i m , J . Macromol. S c i . , Chem., 1986, A23, 169. A.E. Shumeiko. C.D. T i t s k i i , L.M. Litvinenko, L.P. Kurchenko,and V.V. Vapirov, J. Gen. Chem. USSR (Engl. T r a n s l . ) , 1985, 55, 746. S. Lanoux and R.H. Mas, Phosphorus S u l f u r , 1986, 26, 139. K.V. K a t t i and S.S. Krishnamurthy, I n d i a n J. Chem., S e c t . A, 1985, 24A, 384. K.C.K. Swamy, P. Ramabrahmam,and S.S. Krishnamurthy, Synth. React. Inorg. Metal-Org. Chem., 1985, 15, 1023. M.E. Ignatov, B.V. Levin, Z.G. Rumyantseva,and E.G. I l ' i n , Russ. J . I n o r g . Chem. (Engl. T r a n s l . ) , 1986, 373.

.

103,

103,

107,

Macromolecules.

31,

391

8: Phosphazenes

119 120 121

122 123 124 125 126

127 128 129

R . Medina and J . M . S u l l i v a n , D e f . P u b l . , U . S . P a t . O f f . T US 105605H (Chem. A b s t . , 1985, 103, 177559k). I . Noda, Jpn. Kokai Tokkyo Koho J P 60/173168 A2 (Chem. Abst., 1986, 104, 13141bd). C.W. A l l e n , K . Ramachandran, R . Bright,and J . C . Shaw, US 605317 A0 (Chem. Abst., 1985, 103, 7 1 9 6 ~ ) . 0. Treu J r . and M. T r s i c , J . Mol. S t r u c t . , 1985, 133, 1 . R.T. Oakley, J . Chem. S OC . , Chem. Commun.,1986, 596. Y . Y . Yang and J . I . Zink, I n o r g . Chem.?, 1985, 4012. T . Chivers, M . N . S . Rao,and J.F. Richardson, Inorg. Chem., 1985, 24, 2237. V . Hoeve, K.S. Dhathathreyan, J . C . van de Grampe1,and F. Van Bolhuis, 293. Phosphorus S u l f u r , 1986, F . J . Viersen, E. Bosma, B. d e R u i t e r , K.S. Dhathathreyan, J . C . van de Grampe1,and F. van Bolhuis, Phosphorus S u l f u r , 1986, 26, 285. R . I . Tarasova, T.A. Dvoinishnikova,and M . V . Alparova, J . Gen. Chem. USSR (Engl. T r a n s l . ) , 1985, 55, 739. R . I . Tarasova, T.A. Dvoinishnikova, N . I . S i n i t s y n a , L.A. Vasyakina and V.V. Moskva, I z v . Vyssh. Ucheben. Zaved., --Khim. Khim. Teknol., 1985, 28, 39 (Chem. Abst., 1986, 8 8 6 8 4 a r S.B. Bulgarevich, N.A. Ivanova, P.P. Kornuta, N.V. K o l o t i l o , T . A . Yusman, D.Ya. Movshovish, V.A. Kogan,and O.A. Osipov, J . Gen. Chem. USSR (Engl. T r a n s l . ) , 1985, 55, 142. K . J . L . Paciorek, J . H . Nakahara, M.E. Smythe, D.H. H a r r i s , a n d R.H. K r a t z e r , J. F lu o r i n e Chem., 1985, 28, 441. Z.A. Bredkhina, N . G . Khusainova, Yu.Ya. Efremov, R.L. Korshunov,and A.N. Pudovik, J . Gen. Chem. USSR (Engl. T r a n s l . ) , 1985, 55, 1710. D.F. Graves, U.S. US 45240526 (Chem. Abst., 1985, 71827f). L . I . Nesterova and A.D. S i n i t s a , J . Gen. Chem. USSR (Engl. T r a n s l . ) , 1985, 55, 1064. K.J.L. P a c i o r e k , D.H. H a r r i s , M.E. Smythe, J . H . Nakahara,and R.H. K r a t z e r , J . F l u o r i n e Chem., 1985, 28, 387. K . J . L . Paciorek, D.H. H a r r i s , J.H. Nakahara, M.E. Smythe,and R.H. K r a t z e r , J. _ F l_ u o_ r i n_ e Chem., 1985, 28, 399. _ H.W. Roesky, K.V. K a t t i , U . Seseke, M. W i t t , E. E g e r t , R . Herbst,and G.M. S h e l d r i c k , Angew. Chem. I n t . Ed. Engl. 1986, 25, 477. A. Schmidpeter and G. Burget, Angew. Chem. I n t . Ed. Engl., 1985, 580. H.R. Penton, Kautsch. Gummi, K u n s t s t . , 1986, 39, 301 (Chem. Abst., 1986, --104, 2 2 6 1 3 1 ~ ) . K. Murakami, Kino Zairyo, 1985, 5, 5 (Chem. Abst., 1985, 1239405). T. Masuko, Kob u n s h i , 1985, 932 (Chem. Abst., 1986, 51295~). D.-C. Lee, J . R . Ford, G . F y t a s , B . Chu,and G.L. Hagnauer, Macromolecules, 1986, 19, 1586. B. Chu and D.-C Lee, Macromolecules, 1986, 1592. M.S. S e n n e t t , G . L . Hagnauer, R.E. S i n g l e r , a n d G . Davies, Macromolecules, 959. 1986, H.M.Li, U . S . US4551317A (Chem. Abst., 1986, 187113~). R. DeJaeger, M. H e l i o u i , a n d E. P u s k a r i c , U.S. US 45445368 (Chem. Abst., 34521b). 1986, G.S. Lum, H.M. L i , F.A. P e l t i g r e w , U.S. US 4522798A (Chem. Abst., 1985, 103, 88376f). F.A. P e t t i g r e w , H.M.Li,and G.S. Lum, U.S. US 4522797A (Chem. Abst., 1985, 103, 3 7 8 9 7 ~ ) . H.A. Lehmann, H. Schadow, B. Thomas, W. Topelmann, K . D o s t a l , L . Meznik, E . Herrmann,and S . Albrecht, Ger. (East) DD 226291 A 1 (Chem. Abst., 1986, 104, 1 4 7 6 6 9 ~ ) . W.L. Hergenrother and A.F. Halasa, U.S. US 4558103A (Chem. Abst., 1986, 104, 8 9 2 4 7 ~ ) .

24,

26,

3,

130

131 132 133 134 135 136

137 138 139 140 14 1 142 143 144 145 146 147 148 149

150

103,

24,

103, 104,

34,

2,

19,

104,

104,

392


151 F.A. Peltigrew and H.R. Penton, U.S. US 4567229 A (Chem. Abst., 1986, 104, 187469r). 152 G.M. Sulzer, R.W. Riley, Jr.,and D.H. Thomas, Em. Pat. Appl. EP 159020 A2 (Chem. Abst., 1986, 104, 69351~). 153 M.K. Juneau, U.S. US 4576806 A (Chem. Abst. , 1986, 104, 209498d). 154 H.R. Penton, U.S. US 4514550 A (Chem. Abst., 1985, 103, 6898r). 155 H.R. Allcock, P.E. Austin, T.X. Neenan, J.T. Sisko, P.M. Blonsky,and D.F. Shriver, Macromolecules, 1986, 19, 1508. 156 P.M. Blonsky, D.F. Shriver, P. Austin,and H.R. Allcock, Polym. Mater. Sci. Eng., 1985, 2, 118. 157 V. Janout, P. Cefelin, D.R. Tur,and S.V. Vinogradova, Polym. Bull., 1986, 15, 311. 158 K R . Allcock and S. Kwon, Macromolecules, 1986, 2, 1502. 159 R.A. Dubois, P.E. Garrou, K.D. Lavin and H.R. Allcock, Organometallics, 1986, Iy460. 160 V.A. Kovyazin, G.I. Mitropol'skaya, V.M. Kopylov and M.A. Dolgikh, U.S.S.R. SU 1164241 A1 (Chem. Abst., 1985, 103, 142555d). 161 V.M. Litvinov, V.S. Papkov,and D.R. Tur, Vysokomol. Soedin., Ser. A, 1986, 28, 289 (Chem. Abst., 1986, 104, 187159q). 162 B. Wunderlich and J. Grebowicz, Polym. Sci. Technol. (Plenum),1985, 28, 145. 163 S.V. Meille, W. Porzio, G. Allegra, G. Audisio,and M. Gleria, Makromol. Chem., Rapid Commun., 1986, 7, 217. 164 V.S. Papkov, V.M. Litvinov, 1.1. Dubovik, G.L. Slinimskii, D.R. Tur,and S.V. Vinogradov, Dokl. Akad. Nauk SSSR [Phys. Chem.], 1985, 284, 1423. 165 S. Matsuzawa, K. Yamaura, T. Tanigami,and M. Higuchi, Colloid polvm. a, 1985, 263, 888. 166 M. Kojima and J.H. Magill, Sen'i Gakkaishi, 1986, 42, 111 (Chem. Abst., 1986, 104, 187231g). 167 M. Kojima and J.H. Magill, Polymer, 1985, 26, 1971. 168 J.H. Magill and C. Kiekel, Makromol. Chem., Rapid Commun., 1986, 1, 287. and V.P. Shibaev, 169 I.B. Sokol'skaya, Ya.S. Freidzon, V.V=hervinskii Vysokomol. Soedin., Ser. A, 1986, 28, 300 (Chem. Abst., 1986, 104, 207994~). 170 J.J. Meister, P. Wisian-Neilson,and R. Neilson, Polym. Mater. Sci. Eng., 1985, 52, 528. 171 M. Gleria, F. Minto, S. Lora, L. Busulini,and P. Bortolus, Macromolecules, 1986, 19, 574. 172 G. Beggiato, G. Casalbore-Miceli, G. Giro,and S. Lora, Eur. Polym. J., 1986, 22, 245. 173 P. DiMarco, G. Giro, M. Gleria,and S. Lora, Thin Solid Films, 1986, 135, 157. 174 D.R. Tury V.V. Korshak, S.V. Vinogradova, N.B. Dobrova, S.P. Novikova, M.B. Il'ina and E.S. Sidorenko, hcta Polym., 1985, 36, 627. Slonimskii, M.N. Il'ina, 175 D.R. Tur, V.V. Korshak, S.V. Vined-.L. 1.1. Dubovik, N . I . Provotorova, N.B. Dobrova,and E.V. Smurova, Acts Polym., 1986, 37, 203. Chem. Abst., 1986, 104,70080r. 176 -SU 1154293 A1 177 S.I. Golina, G.I. Mitropol'skaya,and S . N . Glushakov, U.S.S.R. (Chem. Abst. , 1985, 103, 142942~). 178 -Chem. Abst., 1986, 104,89673h. 179 W.B. Mueller, U.S. US 4536520 A (Chem. Abst., 1986, 104, 6680j). 106109~). 180 W.B. Mueller, U . S . US 4535095 A (Chem.Abst., 1985,-=, 181 M.A. Kraus and M.K. Murphy, Eur. Pat. Appl. EP 149988 A2 (Chem. Abst., 1985, 103, 1615802). 182 M. K a j s r a , PCT Int. Appl. WO 85/1669 A1 (Chem. Abst., 1985, 103, 161482~). 183 M.K. Murphy, Eur. Pat. Appl. EP 150699 A2 (Chem. Abst., 1985, 103, 216563d). ~2 184 F. Fujita and M. Hirakawa, Jpn. Kokai T o k k y ~ 0 ~ 6 0 / 1 6 6 0 0(Chem. Abst., 1986, 104,90039n).

393

8: Phosphazenes

185 M.A. Kraus and M.K. Murphy, Eur. Pat. Appl. EP 150700 A2 (Chem. Abst., 1985, 103, 179417m). 186 L. Gettleman and L.M. Ross, Polym. Mater. Sci. Eng., 1985, 53, 770. 187 A.E. Oberster and J.C. Vicic, U.S. US 4567211 A (Chem. Abst., 1986, 104, 150221~).

Chem. Abst., 1985, 103, 7575v. 188 -189 Hitachi, Ltd., Jpn.Kokai Tokkyo Koho JP 60/60128 A2 (Chem. Abst., 1985, 103, 161480s). 190 M.Yu. Antipin, Yu. Struchkov,and E . S . Kozlov, J. Struct. Chem. (Engl. Transl.), 1985, 26, 5 7 5 . 19 1 G.O. Nevstad, C. R#mming,and J. Songstad, Acta Chem. Stand., Ser. A, 1985, A39, 691. 192 A. Meetsma, A.L. Spek, H. Winter, C. Cnossen-Voswijk, J.C. van de Grampel, and J.L. DeBoer, Acts Crystallogr., Sect.C: Cryst. Struct. Commun., 1986, C42, 365. 193 A. Meetsma, A.L. Spek, H. Winter, J.C. van de Grampe1,and J.L. DeBoer, 368. Acta Crystallogr., Sect. C: Cryst. Struct. Commun., 1986, 194 A. Meetsma, A.L. Spek, R. Olthof-Hazekamp, H. Winter, J.C. van de Grampel, and J.L. DeBoer, Acts Crystallogr., Sect. C: Cryst. Struct. Commun., 1985, C41, 1801. 195 T.S. Cameron, J . F . Labarre, F. Sournies, J.C. van de Grampe1,and A.A. van de Huizen, J . Chim. Phys. Phys.-Chim. Biol., 1985, 82, 941.

s,

Physical Methods BY J. C. TEBBY

T h e a b b r e v i a t i o n s n 2 , n', n 4 , n', a n d n6 r e f e r t o t h e c o - o r d i n a t i o n number of phosphorus a s opposed t o t h e commonly used valency term, A , w h i c h d o e s not d i s t i n g u i s h b e t w e e n p h o s p h o n i u m s a l t s , p h o s p h i n e o x i d e s etc. a n d p e n t a - c o v a l e n t p h o s p h o r a n e s . C o m p o u n d s i n e a c h subsection a r e usually dealt with in t h e a b o v e order. I n t h e formulae, the letter R represents hydrogen, alkyl or aryl, X represents a n electronegative substituent, Ch represents chalcogenide (usually oxygen a n d sulphur), and Y and Z a r e used t o r e p r e s e n t g r o u p s o f a m o r e v a r i e d n a t u r e . A s in p r e v i o u s v o l u m e s t h e terminology apical and radial has been retained f o r the s t e r e o c h e m i c a l d e s c r i p t i o n o f s u b s t i t u e n t s o n 'n a t o m s t h a t p o s s e s s t r i g o n a l b i p y r a m i d a l g e o m e t r y , so t h a t t h e t e r m s a x i a l a n d equatorial can be reserved to describe the conformational p r e f e r e n c e s o f s u b s t i t u e n t s o n n4 a t o m s o f a n y e l e m e n t in s i x membered and related rings. T h e non-IUPAC nomenclature "phosphane" is u s e d f o r n3 p h o s p h o r u s c o m p o u n d s i n g e n e r a l , r e s e r v i n g t h e t e r m "phosphine" for phosphanes which possess three carbon o r hydrogen substituents and the term "phosphite" f o r phosphanes which possess three alkoxy o r aryloxy substituents. T h e number of theoretical studies involving phosphorus compounds and their reactions has grown sufficiently to warrant a separate section this year. T h i s now f o r m s section 1 of t h i s chapter. Theoretical studies relating t o specific physical m e t h o d s will be f o u n d i n t h e a p p r o p i a t e s e c t i o n a s usual. In addition, studies of the kinetics of equilibria and reactions involving organophosphorus compounds have been reviewed and this a p p e a r s in section 1 1 at t h e end of t h i s chapter.

1

Theoretical Studies

A b i n i t i o NO c a l c u l a t i o n s o n t h e b o n d i n g o f t h e d i p h o s p h e n e (1, X = HI i n d i c a t e d t h a t t h e PP n - b o n d is s i g n i f i c a n t l y s t r o n g e r t h a n t h a t f o r SiSi a n d is s u f f i c i e n t t o p r o d u c e a p l a n a r m o l e c u l e w h i c h

Y =

394

9: Physical Methods

395

e v e n p e r s i s t s in t h e a n i o n r a d i c a l w h e r e t h e b o n d o r d e r 15 o n l y 1.5. T h e PP b o n d r o t a t i o n a l b a r r i e r is e s t i m a t e d t o b e 63.5 kcal m c l - ' A t h e o r e t i c a l s t u d y of w h i c h is v e r y s i m i l a r t o d i i m i n e (HN=NH).' the cycloaddition reactions of dienes with two coordinate molecules ( l ) , ( 2 ' ) a n d ( 3 ) s h o w e d that t h e a m i n o s u b s t i t u t e d c o m p o u n d s ( 1 - 3 , X = NR2) are electron-donating towards the dienes, whereas others had e l e c t r o n - a c c e p t i n g properties.' The energies and properties of d i p h o s p h i n e ( 1 , X = Y = H) a n d c y c l o p o l y p h o s p h i n e s (PHj3-6 h a k e b e e n e s t i m a t e d by a b i n i t i o m e t h o d s t 3 T h e s t r u c t u r e o f i m i n o p h o s p h i n e sulphides and their desulphurisation have been studied using similar methods.' Ab initio calculations have been applied to a number o f p h o s p h i n e s . T h e b o n d i n g in t h e p h o s p h i r e n e (4) a p p e a r s t o i n v o l v e whereas the s i g m a d e l o c a l i s a t i o n a n d a E-II A-n interaction,' inversion barriers o f primary and secondary phosphanes ( 5 ) increase T h e barriers to w i t h r i s e i n e l e c t r o n e g a t i v i t y o f X a n d Y.6 n i t r o g e n i n v e r s i o n in d i f l u o r o a m i n o p h o s p h i n e h a v e a l s o b e e n studied.' Studies of hyperconjugation and the molecular orbitals of phospholane indicated increased electrophilicity of the antibonding o r b i t a l s o n t h e e n d o c y c l i c b o n d s t o phosphorus." The conformations of teraalkyldiphosphines and di-t-butylphosphines have b e e n s t u d i e d u s i n g e x t e n d e d H u c k e l calculations' a n d m o l e c u l a r mechanics," r e s p e c t i v e l y . T h e a n o m e r i c e f f e c t i n v o l v i n g t h e PH2 g r o u p is g r e a t l y a t t e n u a t e d r e l a t i v e t o nitrogen. T h i s is attributed to the poorer r-donation properties a n d lower MNDO c a l c u l a t i o n s a r e e l e c t r o n e g a t i v i t y o f s e c o n d r o w elements." a l s o reported on the circumbulatory rearrangement o f cyclopentadienephosphines ( 6 ) . The sigmatropic arrangement with r e t e n t i o n is f a v o u r e d f o r t h e f l u o r i d e (6, Y = F ) but i n v e r s i o n o c c u r s w h e n Y is trirnethylsilyl.'' Two s t u d i e s o f a3 A 5 m o l e c u l e s h a v e b e e n r e p o r t e d . One c o n c e r n e d t h e d i i m i n o p h o s p h a n e ( 7 ) a n d its dimers,'= t h e o t h e r c o n c e r n e d t h e r e a c t i o n o f m e t a p h o s p h a t e w i t h p r o t o n donors.'' T h e r e h a v e b e e n a b i n i t i o s t u d i e s of t h e b o n d i n g f o r a s e r i e s o f i m i n o a n d a m i n o p h o s p h o r u s molecules," and for the phosphonium y l i d e s (8).16 T h e a n i o n c h a r a c t e r of t h e y l i d i c c a r b o n is intermediate between that of olefinic and substituted carbanions. Polarisation o f the HJP group has a stabilising effect. T h e i n f l u e n c e of t h e s u b s t i t u e n t X o n t h e i n v e r s i o n o f t h e c a r b a n i o n a n d a l s o the tendency o f the molecule t o dissociate to carbene and CNDO/S MO c a l c u l a t i o n s o n t h e p h o s p h i n e is a l s o discussed."

396


x\

P= P Y '

x\

x\

P=cYz

P=N

\Y

Ph

PR

Ph

\/ RCEP

Ph2P' NC-C,

It

-P= P 'C-CN

II

,PPh2 P= P

//

(9)

Ph

(11)

Ph

CO, R (BU'S)~C=P /

But But

(12)

(13) t

BU - P

Et -Me /p Ph (151

w

Et

P

\

(16)

Ph (17)

9: Physical Methods

397

conformational preferences of 1,3,2- and 1 , 3 , 5 - d i o x a p h o s p h o r i n a n e s includes a n estimate of coupling effects." T h e role o f d-orbitals and the phosphoryl electron pair in the stabilisation of ethyl phosphonate free radicals has been studied.'' A theoretical study of model pentacoordinate phosphoranes H4PX was directed at estimates of geometries, electron densities and apicophilicities of X . T h e order for ligand apicophilicities is as fOllOWS.'~ C1 > C N > F > CZCH > CH3 > OH > 0- > S- > NHz > BHz

2

Nuclear Magnetic Resonance Spectroscopy

- Phosphorus-31 n.m.r. continues to expand its application in the medical and biological fields2" and is now being applied to soil a n a l y ~ i s . ' ~ T h e problems involved in the use of FT " P n.m.r. for quantitative determinations have been discussed.22 Samples of phosphinic carboxylic acids were cooled to -40°C for quantitative estimations."

2.1 Biological and Analytical Applications.

2.2 Chemical Shifts and Shielding Effects. 2.2.1

Phosphorus-31. Positive shifts a r e downfield of the reference

85% phosphoric a c i d , and are usually given without the appellation

p+p.m. of n' and n' compounds. Phosphaalkyne chemistry has taken a large step forward. Five new compounds ( 9 , R = P h , T m s , 1-adamantyl, iso-propyl, neo-pentyl) have been characterised and found to possess a range of chemical shifts between -51.4 and -66.0." The so-called hydrobromide derivatives have shifts much further downfield ( 0 - 512' and thus there must be some doubt now on the validity of their proposed structures. Many new types of phosphalkenes have been prepared. Their chemical shifts vary from -141.5 for the cyclic polyphosphine to -62.6 for the diamino compound (11, Y = H ) 2 7 , to -10.7 for the phosphinophosphaalkene (11, Y = PBu",'' moving downfield to 287.7 for the dithio compound ( 1 2 ) , " and to 312 for the Dewar analogue (13, R = Pr'),30 and at lowest field, 350 to 367 for the halides (14, Hal = F , B r , I ) . 3 1 6~ of n3 compounds. A number of three membered phosphorus heterocycles have been described.32 All resonate well upfield e 3 . -171.8 6p

398


f o r t h e C i s - p h o s p h i r a n e ( 1 5 1 , -181.5 f o r t h e t r a n s - i ~ o m e r ~ a~ n,d -188.1 f o r t h e p h o s p h i r e n e (16>.34 V a r i o u s t r i f l u o r o m e t h y l t e r t i a r y p h o s p h i n e s h a v e b e e n p r e p a r e d by D i e l s - A l d e r r e a c t i o n s . T h e y h a v e c h e m i c a l s h i f t s in t h e r a n g e -20 t o +40.35 W h i l s t a r e c o r d d o w n f i e l d s h i f t (152.5) w a s o b s e r v e d f o r t h e b i c y c l i c p h o s p h i n e (17),3h the underlying reasons f o r the very large deshielding effect o b s e r v e d f o r t h i s t y p e o f c o m p o u n d h a v e yet t o b e d e t e r m i n e d . A n u m b e r o f A 5 n3 c o m p o u n d s (18) h a v e c h e m i c a l s h i f t s i n t h e r a n g e 127 t o 178.37 A t h e o r e t i c a l s t u d y s u p p o r t s t h e s u g g e s t i o n m a d e in t h e last v o l u m e t h a t t h e s e c o m p o u n d s a r e r e p r e s e n t e d a s phosphonium ylides with the negative charge distributed between the t w o sp' c a r b o n a t o m s b o u n d t o t h e p h o s p h o r u s atom.38 6 p o f n4 c o m p o u n d s . Transmission of substituent effects in a r y l d i m e t h y l p h o s p h i n e b o r a n e s h a v e b e e n s t u d i e d by n.m.r.39 A detailed investigation of the 3 1 P chemical shift t r e n d s o f phosphoryl compounds showed that inductive and resonance effects of s u b s t i t u e n t s h a v e a d i r e c t e f f e c t w i t h -I a n d +R e f f e c t s c a u s i n g shielding according t o t h e relationship below. T h e chemical shift

w a s a l s o l i n e a r l y r e l a t e d t o t h e c h a r g e o n p h o s p h o r u s a s m e a s u r e d by t h e PK. l i n e i n t h e X-ray e m i s s i o n The relationship b e t w e e n t h e PO s t r e t c h i n g f r e q u e n c y a n d p h o s p h o r u s c h e m i c a l s h i f t f o r a series of diphenvlphosphoazolides and diphenylphosphoryl ammonium cations has also been ~ t u d i e d . ~ ' Equilibria involving ring o p e n i n g o f c y c l i c p h o s p h o n a t e s ( 1 9 ) t o g i v e t h e a c i d s (20) h a s t h r o w n s o m e d o u b t o n t h e e x i s t e n c e 0.f t h e t a u t o m e r s (21).42 T h e anomeric contribution to the conformational preferences o f the diphenylphosphinoyl group in cyclohexane compounds h a s been e s t i m a t e d t o b e 3 kcal m o 1 - 1 . 4 3 A t h e o r e t i c a l NO s t u d y o f p h o s p h o n i u m s a l t s s h o w e d t h a t t h e paramagnetic component of the magnetic screening constant is dependent on the electronegativity of the phosphorus substituents. The multiplicity of the phosphorus bonds and the resonance integrals of the u components was also disc~ssed.~' Whereas ylides generally give signals upfield of the corresponding salts, the phosphonate a n i o n s , eg (22) w h i c h h a s 6 p 40, r e s o n a t e d o w n f i e l d o f t h e b i s ( d i e t h o x y p . h o s p h o n y l ) m e t h a n e w h i c h h a s SP 1 9 . 4 5 It is p o s s i b l e t h a t f o r these molecules, a larger inbalance o f substituent e l e c t r o n e g a t i v i t i e s is c a u s i n g a n e n h a n c e m e n t o f t h e p a r a m a g n e t i c contribution.

9:Physical Methods

399

Isotope effects on phosphorus n.m.r. signals a r e proving invaluable f o r the study of mechanisms, stereochemistry and assignments. A deuteriomethyl isotope effect of 0.25 was utilised for the study o f a reverse Menschutkin reaction.4b Oxygen-18 isotopic shifts have been used to study the mechanism of phosphinate esterification,” the formation of ~ ~ r o p h o s ~ h aand t e ~the ~ stereochemistry of some phosphoranilidate r e a c t i o n s a 4 ? Substitution of sulphur-34 and suphur-36 in phosphorothioate ( 2 3 ) induced upfield shifts which were used to show that the P-S bond order is about o n e s 5 ’ Oxygen isotope shifts have also been used in the study o f adenosine phosphates and the configurational analysis of nucleosides and nucleotides.” 6~ of n5 and nb compounds. - T h e products o f the reaction of a phosphoranide with aryl azides ( 6 p = -91.5) have been assigned the novel five coordinate structure (24).52 The structure can also be represented a s the amide (25) with a neutral phosphorus atom. T h e large temperature dependence o f the shifts of the bicyclic a m i n o t e t r a o x y p h o s p h o r a n e ( 2 6 ) has been attributed to a n equilibrium with a n* s ~ e c i e s . ’ ~ Similar equilibria, involving chlorotropy, have been proposed for some chlorophosphorates.54 T h e oxygen-18 isotopic shift in oxyphosphoranes is greater for the radial oxygen than for the longer apical bond. This was used to follow the An permutational isomerism by variable temperature 3 t P n.m.r.’5 interesting correlation between the chemical shifts of a wide range o f related phosphonium cations, n5 phosphoranes and nb anions has been reported and may be of use to predict the chemical shifts of new compounds.’b 2.2.2

Carbon-13. T h e molecular structure o f phosphinothioformamides (27) and their chalcogenides have been studied in the solid and liquid states.” The I 3 C n.m.r. spectra of solid methylphenyl phosphonium salts have been studied using high power decoupling cross-polarisation and slow magic angle rotation. Dipolar coupling and shielding anisotropy cause unequal intensity of spinning side bands. The scalar coupling enabled magic angle rotation to distinguish two sets o f sub-spectra.58 2.3 Shift Reagents and Liquid Crystals. - T h e chiral shift reagent ( 2 8 ) allows the enantiomeric excess of phosphine oxides to be measured. F o r example the methyl signal of ethylmethylphenylphosphine oxide in the presence of one equivalent of reagent gives


C(TmsI2

+/ R-

pK Y

/c-Tms

Me

Me

OH

I cooTp*CH/

CO,R

(EtO)

//O

P

'CH ( EtO l2 P

Ph

(20)

(19)

(18)

/

(21)

(22)

CI

CI

I

123)

q-, N/R -Me

0-P-0

cN3=N-Ar CI

CI (25)

(26) Y

I

S

NO2

(27)

(28

OTms

9: Physical Methods t w o doublets separated by 5.5 H z . ~ S~ e e also S e c t i o n T h e use of Europium shift reagent in combination with t o study chelation to phospholipids.60 N.m.r. s t u d i e s of liquid crystal media showed that sulphonate counter ions induced abrupt changes in the coupling of methylphosphonate."

401 2.4 below.

EDTA w a s used phenyl dipolar

2.4 Valence I s o m e r i s m , Restricted Rotation and Permutational Isomerism. - T h e variable temperature spectra of bicyclic tetraphosphines ( 2 9 ) has been analysed in terms of valence isomerism involving the corresponding tuo coordinate open-chain isomers.b2 A report on a b initio NO calculations of the inversion barriers for a series of methyl phosphines includes a discussion of the electronic consequences of steric e f f e c t s e h 3 Inversion barriers of 1,2diphosphinobenzenes are in the range 100 - 110 k J mo1-'.b4 T h e ring inversion barrier for a dibenzophosphorin h a s a l s o been measured.b' Restricted rotation in a series of ditert-butylphosphines (30; R = H, A l k , P h etc) has been studied using molecular mechanics calculations." Rotation about the P-N bond in phosphonyl acetamides has a barrier of dG' 16.3 hcal mol-' 3 1 P N.m.r. spectroscopy with the aid of a chiral shift r e a g e n t , s h o w e d that pseudorotation of oxyphosphoranes (31) involves a t.b.p. intermediate with a diradial five-membered ring.67 T h e t-butyloxyphosphoranes (32, R = t-Bu) had significant barriers to pseudorotation compared with the trifluoroethyl a n a l o g u e s (32, R = CH2CF3).'" S o m e tricyclic diazatrioxyphosphoranes have been shown t o have barriers of 11 - 12 kcal m o l - 1 . b 9 A study of pseudorotation in solid h e x a c h l o r o c y c l o d i p h o s p h a z a n e w a s performed by a multipulse spin-locking technique.70 Permutational isomerism o f six-coordinate t r i f l u o r o d i a m i n o p h o s p h o r a t e s and d i a m i n o t e t r a o x y p h o s p h o r a n e s have been shown to occur by a dissociation mechanism involving a n' intermediate." 2.5 Spin-Spin Couplings. -

3 1 P Relayed and double quantum filtered correlation spectroscopy has n o w been used for the assignments o f the n.m.r. s i g n a l s o f a short DNA

lH-'H

2.5.1 J(PP).

T h e characteristic very low values of the direct PP couptings for 1 , 2 - d i p h o ~ p h e t e n e s ~h~a s been attributed t o compensating effects of ' J P P . " Inner projection o f the polarisation projector (IPPP) has been used to study through-space

402


(proximate) and through-bond contributions t o ? J P p in ( b i s d i f l u o r o p h o s p h i n o ) a m i n e 7 ' a n d c&-1,2-diphosphinoethylene176 is concluded that overlap of t h e lone pair of electrons of both phosphorus a t o m s constitute a very efficient pathway for transmitting spin information associated with the Fermi contact term.

It

2.5.2

J(P0) a n d J(PN)). T r e n d s in ' J ( P i 7 0 ) h a v e b e e n u s e d t o s t u d y t h e protonation of phosphoryl tribromide, phosphoryl trifluoride a n d difluorophosphoric acid. Nitric acid had a greater protonation power than Hammett acidity functions This coupling has been t h e subject of a semiempirical s u m over s t a t e s theoretical S ~ U ~ Y * "

T r e n d s i n 'J(P"N) a n d 6'" for a series of triphenylphospha(h')azenes (33) w e r e u s e d w i t h 1 3 C a n d " P n.m.r. d a t a , c y c l i c v o l t a m e t r y a n d MO c a l c u l a t i o n s t o e v a l u a t e t h e n a t u r e o f t h e b o n d i n g t o ~ h o s p h o r u s . ' ~ D i p h o s p h o r y l a m i d e s (34)80 a n d a d i a z a p h o s p h o r i n dithione"' w a s a l s o s t u d i e d by "N n.m.r* spectroscopy. 2.5.3 J(PC). V a l u e s o f 'J(PC) f o r a s e r i e s o f 40 h a l o m e t h y l d i h a l o p h o s p h i n e s (35) a n d t h e i r d e r i v a t i v e s w e r e i n t h e r a n g e 17 t o 78 Ht f o r t h e n3 c o m p o u n d s a n d 97 t o 1 4 1 Hz f o r t h e n' c o m p o u n d s r 8 2 T h i s c o u p l i n g v a r i e d f r o m 151 t o 224 f o r a s e r i e s o f p h o s p h o r y l a t e d o x i m e s (361, b e i n g h i g h e s t f o r t h e E isomer^.'^ I t a l s o c o r r e l a t e d w e l l w i t h 6 t i 3 C > f o r a d a m a n t y l p h o s p h o r y l derivatives." T h e very l a r g e c o u p l i n g s ( 1 9 5 t o 236 H z ) f o r p h o s p h o n a t e c a r b a n i o n s h a v e b e e n studied using INDO-SCPT calculations. T h e results indicated that t h e c o u p l i n g s a r e p o s i t i v e f r o m a p o s i t i v e c o n t a c t t e r m but t h a t a n e g a t i v e o r b i t a l t e r m a l s o p l a y s a n i m p o r t a n t part."' Two-and threebond couplings continue t o play a n important role in t h e s t e r e o c h e m i c a l a s s i g n m e n t s o f c y c l i c compounds," and a l k e n y l p h o s p h o n a t e s e a 7 A '3C n.m.r. s t u d y o f t h e e l e c t r o n i c a n d s t e r i c effects in arylalkylthiophosphates included a n a n a l y s i s o f J ( P 0 C ) trends.''

2.5.4 J(PH). T h e c h a n g e s i n 'J(PH) o f h y p o p h o s p h o r o u s a c i d w h e n i t is e n g a g e d i n c h e l a t i o n , h a s b e e n studied.'* The high value for 'J(PH) f o r t h e r a d i a l h y d r o g e n o f 'n c o m p o u n d s r e l a t i v e t o t h e apical hydrogens has been used t o estimate apicophilicities. The r e s u l t s i n d i c a t e d t h e a p i c o p h i l i c i t y t r e n d R O > H > RNH.*'

9: Physical Methods

403

T h e geminal c o u p l i n g o f s o m e a z o l o o x a p h o s p h o l e n e s is r e p o r t e d t o correlate with Vicinal c o u p l i n g s h a v e b e e n u s e d in t h e c o n f o r m a t i o n a l a n a l y s i s o f a v a r i e t y o f c o m p o u n d s s u c h as d i o x a p h o s p h o r i n a n e ~ . ~p~h o s p h o r i n a n e s ( i n c o m b i n a t i o n w i t h C N D 0 / 2 calculation^),^^ a n d b r o m o p h o s p h o r i n a n e s cin c o m b i n a t i o n w i t h d i p o l e m o m e n t measurements).94 T h e v a r i o u s c o u p l i n g s f o r 1,l-vinylidened i p h o s p h o n i c a c i d a n d its s a l t s h a v e a l s o b e e n measured."

2.6 A n i s o t r o p y , M a g n e t i s a t i o n Transf,er, R e l a x a t i o n a n d C I D N P . - S i x p h o s p h o n i c a c i d s h a v e c h e m i c a l s h i f t a n i s o t r o p i e s o f 149 - 182 a n d a s y m m e t r y p a r a m e t e r s o f 0 . 1 - 0.5.96 T h e r a t e s o f c e r t a i n e x c h a n g e p r o c e s s e s a r e s u i t a b l e f o r s t u d y by t h e m a g n e t i s a t i o n t r a n s f e r technique. A DANTE pulse sequence w a s used to selectively invert a n a r r o w signal f o r t h e s t u d y o f p h o s p h o l i p i d e x c h a n g e in r e v e r 5 e m i c e l l e s c o n t a i n i n g p r a e s o d y n i u m s h i f t r e a g e n t in t h e a q u e o u s core.97 Relaxation times of aminophosphonic acid diastereomers are very similar.98 Longitudinal and transverse relaxation rates were used t o s t u d y c o m p l e x a t i o n d u r i n g t h e d e c o m p o s i t i o n o f acetylphosphate." T h e v a l u e o f TI f o r l i t h i u m a r y l p h o s p h i d e s s u p p o r t e d t h e d i m e r i c s t r u c t u r e w i t h a P--Li--P link.6k M e t h y l e n e b i s p h o s p h o n i c a c i d h a s a Tl v a l u e o f 3 . 5 5 . l o o A general m e t h o d f o r s e p a r a t i n g intra- a n d inter-molecular t e r m s o f d i p o l e r e l a x a t i o n u p o n s e l e c t i v e d e u t e r i a t i o n u t i l i z e d t h e G i e r e r W i r t z f o r m u l a , It was s h o w n that i n t h e a b s e n c e o f a PH bond t h e internal t e r m predominate5.'O1 Weak CIDNP effects were observed for the thermolysis o f the azophosphate ( 3 7 ) ' 0 2 - A variety of dichlorophosphanes h a v e n.q.r. 3 5 C l r e s o n a n c e s w h o s e a v e r a g e f o r e a c h c o m p o u n d c o r r e l a t e l i n e a r l y w i t h t h e total T a f t c o n s t a n t s . l o 3 T h e s p e c t r a o f a number of polyfluoroaryl hexach orophosphazenes have been A r1.q.r. s t u d y o f p e n t a f l u o r o p h e n y l studied.lO' t e t r a c h l o r o p h o s p h o r a n e s i n d i c a t e d that t h e o r g a n i c g r o u p p r e f e r s t h e a p i c a l p o s i t i o n o f t h e t . b + ~ . ' ~ T~ h e e f f e c t o f p r e s s u r e o n c y c l o t r i p h o s p h a z e n e s a n d c y c l o t e t r a p h o s p h a z e n e s h a s b e e n s t u d i e d by n.q.r. s ~ e c t r o s c o p y . ~ ~ ~ 2.8 N u c l e a r Q u a d r u p o l a r R e s o n a n c e


404

XYP,

'0 O L p 'ORL g

Ph3P=N

0

0

II

0 (E t 0I2P-N "

Y2P-C=NOH

Hal2 P-CXYz

I R (36)

(35)

+oMe

(37)

(Et 0) PO*

PR2

(39)

(411

(40)

QI H

(42)

(431

9: Physical Methods 3

405

Electron Spin Resonance

Electrochemical reduction of a diphosphene gave the first three e l e c t r o n P-P a-bond a n d a n e.s.r. s p e c t r u m , ap = 43.5 G , e x h i b i t i n g v e r y d i f f e r e n t l i n e widths."' Pyramidal inversion and methyl r o t a t i o n o f t h e t-butyl r a d i c a l h a s b e e n s t u d i e d by a b i n i t i o calculation^.'^^ T h e e.s.r. s p e c t r u m o f t r i m e s i t y l p h o s p h i n e r a d i c a l c a t i o n p e r c h l o r a t e , g e n e r a t e d by e l e c t r o c h e m i c a l o x i d a t i o n w a s c l o s e t o t h o s e p r e v i o u s l y reported.'09 Electrochemical oxidation o f t e t r a a r y l d i p h o s p h i n e s g a v e r a d i c a l c a t i o n s w i t h a p = 170 - 175 G."OThe s p e c t r a o f r a d i c a l c a t i o n s o b t a i n e d by t h e g a m m a r a d i a t i o n of tertiary phosphines and trialkyl phosphites were studied with the The molecular and a i d o f s e m i e m p i r i c a l MNDO SCF calculations."' e l e c t r o n i c s t r u c t u r e s o f t h e d i m e r i c s p e c i e s M e b P 2 + . a n d Me, P 2 - * h a v e a l s o b e e n t h e s u b j e c t o f a t h e o r e t i c a l 5tudy.'" T h e e.s.r. spectrum of the diethoxy phosphoryl radical ( 3 8 ) w a s a strongly p o l a r i s e d d o u b l e t w i t h ap = 696 G . % l 3 E.s.r. s h o w e d that )(-ray irradiation o f tetraalkyldiphosphine d i p h o s p h i d e s g a v e p h o s p h o r a n y l r a d i c a l s w i t h t.b.p. s t r u c t u r e s (39)."' A structure has been assigned to rhosphinylhydrazyls (40). T h e d i m e t h y l a m i n o r a d i c a l w a s p a r t i c u l a r l y persistent."' The e.s.r. p a r a m e t e r s o f t h e e l e c t r o g e n e r a t e d p y r a z i n e r a d i c a l c a t i o n s ( 4 1 ) h a v e b e e n recorded."' The spectra of a stable furanyl p h o s p h a t e r a d i c a l adduct"' and a phenalene radical anion which involves injection o f spin density into half a n attached c y c l o p h o s p h a z e n e ring,'l8 a r e r e p o r t e d .

4

Vibrational Spectroscopy

T h e m e t h o d of e l i m i n a t i n g t h e i n f l u e n c e o f a t o m i c a b s o r p t i o n in FT infra-red s p e c t r o s c o p y h a s b e e n d e s c r i b e d u h i c h i n v o l v e s a n a t t e n u a t i o n technique."' 4 . 1 Assignments. - Electric modulation of vibrational rotational

Ringb a n d s o f p o l a r m o l e c u l e s i n c l u d e d a s t u d y o f phosphine.'20 bending (puckering) transition frequencies have been measured for T h e PO t h e p h o s p h o l e n e ( 4 2 ) f o r t h e g r o u n d a n d e x c i t e d states.I2' d e f o r m a t i o n b a n d f o r t h e s u l p h i d e (43) h a s b e e n a s s i g n e d . 1 2 2


406

- An infra-red spectroscopic study of triphenylinteraction a s the cause phosphonium difluoride indicated a P'---Fof splitting and weakening of the HFz- band at 1208 cm-'.1z3 T h e carbonyl band o f carboxylic acids is split by the addition o f hexamethylphosphoramide. T h i s has been attributed to the formation of &-and trans-associates.'24 Hydrogen bonding between phenol and various phosphites, such as (44; Y = O E t , NEt2) have been studied.12' I n addition there have been several studies of phosphoryl compounds. Basicity scales have been plotted using V O and ~ aCo for methanol in phosphoryl and thiophosphoryl The P=O stretching frequency of phosphorylamides have been correlated with inductive effects. This included a study of n.m.r. methods of measuring basicity.'27 The phosphoryl group of 2-phosphaadamantane was found to have above normal basicity towards phenols.128 A c a r b a m o y l m e t h y l p h o s p h i n i c acid w a s studied in some detail by i.r. S P ~ C ~ ~ O S C O ~ Y . ' ~ ' 4.2 Bonding.

4.3 Stereochemistry. - There has been a far infra-red spectroscopic study o f ethylphosphine,I3" and in combination with z-ray fluorescence, further work completed on the conformational analysis of d i a l k y l p h e n y l p h o s p h i n e s . 1 3 i T h e influence o f water on the conformational equilibria of trimethyl phosphate has received attention.I3' There has been a low temperature solid state a n d matrix isolation study of methyl p h o s p h o r o d i c h l o r i d a t e , i 3 3 and a conformational study of polymorphic modifications of diphenylphosphinyl acetic acid h ~ d r a 2 i d e . l ~ ~ T w o heterocyclic systems have been investigated - the 1,3,2-dioxaphosphepene (45) and its oxide,13' 1,3,2-dioxaphosphorinanes and their oxides, sulphides and selenides (46).i369'37Three ring vibrations were involved in the conformational study of the amides (46,Y = N R 2 ) . 1 3 7

5

Electronic Spectroscopy

5.1 Absorption Spectroscopy. - T h e u + v . spectra of triarylphosphines

indicate that the phosphino group has a strong +M effect on a 4-nitrophenyl ring but that the phosphorus atom a c t s as barrier t o conjugation between aryl rings bound to phosphorus.'38 An additional band appearing in s o m e spectra is attributed to a charge

9: Physical Methods

407

t r a n s f e r e x c i t a t i o n b e t w e e n d o n o r a n d a c c e p t o r a r y l rings.'" U.V., i.r. a n d n . m + r + s p e c t r a o f t h e d i p h o s p h o n a t e s (47) h a v e b e e n r e ~ 0 r t e d . l ~ T~h e i n t e n s i t y o f t h e s e c o n d a r y b e n z e n o i d b a n d at s. 262 n m f o r t h e 1 , 3 , 2 - d i o x y p h o s p h o r i n a n e s ( 4 6 ; Y = OPh) was u s e d to a s s e s s t h e e x t e n t o f p-T c o n j u g a t i o n a n d t h u s t h e c o n f o r m a t i o n a l preference of the phenoxy groups.t36 I

5.2 F l u o r e s c e n c e . - A f u r t h e r r e p o r t o n t h e u s e o f n a p h t h a l e n e phosphorus compounds for fluorescence derivatization concerns the d e p e n d e n c e o f f l u o r e s c e n c e on t h e t y p e a n d p o s i t i o n o f s u b s t i t u e n t s o n t h e n a p h t h a l e n e rings.'" It h a s b e e n f o u n d t h a t t h e diphenylphosphinyl group enhances the fluorescence properties of b i p h e n y l s ( 4 8 ) but r e d u c e s t h e f l u o r e s c e n c e p r o p e r t i e s o f naphthalenes.t42 The fluorescence and photoisomerisation o f d i p h e n y l p h o s p h i n y l s t i l b e n e s has also been studied.*43 5.3 C i r c u l a r D i c h r o i s m . - T h e a b s o l u t e c o n f i g u r a t i o n o f t h e m - h y d r o x y p h o s p h o n a t e ( 4 9 ) w a s e s t a b l i s h e d t h r o u g h its n e g a t i v e C o t t o n e f f e c t a t 2 1 5 nm.'44

5.4 P h o t o e l e c t r o n a n d X-ray S p e c t r o s c o p y . - T h e p h o t o e l e c t r o n s p e c t r u m o f t h e n' p h o s p h a a l k e n e (50) w a s s i m i l a r t o t h a t o f t h e c o r r e s p o n d i n g i m i n e . Its f i r s t i o n i s a t i o n p o t e n t i a l was a t 9 . 6 9 e v e i 4 ' P r e d i c t i o n s o f t h e r e a c t i v e b e h a v i o r o f i m i n o p h o s p h a n e s (51) a n d t h e c o r r e s p o n d i n g m e t h y l e n e a n a l o g u e 5 c a n b e m a d e on t h e b a s i s o f t h e l i n e a r r e l a t i o n s h i p b e t w e e n t h e i r optical t r a n s i t i o n s a n d ionisation P h o t o e l e c t r o n s p e c t r o s c o p y a n d MO c a l c u l a t i o n s o f p h o s p h i r a n e s i n d i c a t e l o w s y m m e t r y a n d small e n e r g y s e p a r a t i o n b e t w e e n b a s i c orbital e n e r g i e s o f t h e P-C, P-S a n d P-N u bands o n one side and the lone pair of electrons o n phosphorus or h e t e r o a t o m o n t h e o t h e r . T h e r e is a s t r o n g m i x i n g f o r m o s t m o l e c u l a r o r b i t a l s a n d t h e r e f o r e l o c a l i s a t i o n p r o p e r t i e s o f HOMO w a v e f u n c t i o n s d e p e n d o n t h e substituents.'47 T h e p.e. s p e c t r a o f d i m e t h y l p h e n y l p h o s p h i n e i n d i c a t e s that t h e m o s t f a v o u r e d A study o f the c o n f o r m a t i o n d o e s not a l l o w P-n conjugation.'4a p h o s p h a n e (52: A r = C a F 5 , Y = O M e ) a n d o t h e r p e n t a f l u o r o p h e n y l compounds has been -X-ray f l u o r e s c e n c e s p e c t r a o f t e r t i a r y p h o s p h i n e s (52: A r = P h , Y = a l k y l ) i n d i c a t e d t h a t w h e n t h e PY2 g r o u p is in t h e best g e o m e t r y f o r p-T c o n j u g a t i o n t h e i n t e r a c t i o n is still o n l y 25% o f t h a t o f t h e dimethylamino groupbt3'


408

(47)

Me-P=CH2 (50)

(481

RZN-P=Y

/R Z‘

Ar-PY2

(51)

(52)

Ph ‘C=PfUY Tms’

(53)

(54)

(55)

Z-N,

f7 ,N-Z

P

(59)

I

NEtZ

(60)

(61)

9: Physical Methods

6

409

Diffraction

6.1 X-ray Diffraction. - T h e crystal structures of a number o f

cyclic organophosphorus compounds have been reviewed'"' 6.1.1

n2 Compounds. T n e molecular structure o f a number of twocoordinate P = C compounds have been described. The group at B o n n have examined three methylene phosphaalkenes ( 5 3 ; Y = P h , iPrlN, tBu2P). T h e P=C bond length in the phenyl compound w a s 165 pm.'" and (13),30together with a T w o cyclic compounds ( 5 4 ) ' " phosphaallyl cation (55),'53 complete t h i s group. T h e structure of two P=P compounds have been determined. O n e w a s the diphosphaalkene ( I ; X = Y = CTmsJ)ti'4 the other w a s the diphosphoniaphosphide (56) "

.*

6.1.2

n3 Compounds. T h e phosphorus a t o m in the bicyclic tertiary phosphine ( 5 7 ) has been shown t o have a pronounced pyramidal arrangement,lS6 similar to the diphosphinine ( 5 8 ) . 1 ' 7 The the structures of the ten-membered cyclic 1,2-diphosphine ( 5 9 1 , ' ' ' and a lithio dibenzotriphosphole,l6' have been mono-oxide ( 6 0 ) , " ' determined. Reports on a dichlorophosphane derivative of a b i p h e n y l , l b l a benzotriphosphazane (61, Z = PS(NEt2 ) z ) , ' " 1 , 3 , 2 - d i a z a p h o s ~ h i n a n e , ~and ~ ~ a d i a z a d i ~ h o s p h e t i d i n e ' ~have ~ also appeared., T h e first trimethylenephosphate (62) has a planar PC3 group with three very similar C P C bond ang1es.16' S t u d i e s o f the charge distribution will be interesting.

6.1.3 n4 Compounds. A number a quaternary phosphonium salts have been studied. They include a diethylphospholanium iodide,lb6 a diphenylphosphorinanium bromide,I6' a 1,4-diphosphac y c l ~ h e x a d i e n e , ' ~a ~ 2,2-diphosphonia ethyl ether,'69 1 - ( t r i p h e n y 1 p h o s p h o n i a ) e t h y l a m m o n i u m bromide,"' a s well a s methyl The a n d i o d o m e t h y l t r i p h e n y l p h o s p h o n i u m trinitromethanide.17' molecular structures o f the stabilised ylide (63)172a n d the s p i r o ylide (64)'73 have a l s o been determined. S t u d i e s o f nk c o m p o u n d s possessing three P-C bonds a r e presented below. I n a d d i t i o n to a diazaphosphole oxide,"' the internal molecular motions of triphenylphosphine oxide h a v e been analysed,l7' and the anomeric interaction o f a d i p h e n y l P h o s p h i n o y l - l , 3 - d i t h i a n e T h e structures o f t w o sulphides h a v e been e x a m i n e d ,


410

a n ethylene 1 , l - b i s ( d i p h e n y 1 p h o s p h i n e s u l ~ h i d e ) ' ~and ~ the phosphorinanone (65).178 Other compounds in this group which have been studied include a m i n o t r i p h e n y l p h o s p h o n i u m chloride,"' two triphenylphosphazenes,"' a bis(triphenylphosphonia)imide,'al the bis salt (66),la2 and a germyl phosphonium ylide."' A variety o f compounds have been examined which a r e in the phosphinic acid class. They include a phenyl cyclopentyl ester,Ia4 a phosphinothioic anhydride,I8' a d i p h e n y l p h o s p h i n a m i d e , I a 6 a red b i s ( d i - t - b u t y l t h i o p h o s p h i n a m i d e ) and its selenide analogue,"' the anisylphosphorinane (67),Iaathe thioamide (68),18' and the phospholenium amide (69, Y = i-Pr2N).*'O Phosphonic acid derivatives a r e also well represented. Phosphonic acid analogues of aspartic a c i d , glutamicacid C-benzy1g1ycine,191 and the phosphorinane (70)'92 have been studied, a l s o the oxime (71)19' a phosphonopiperidinol - with a very distorted chair structure,Iq4 the phosphonate (72),19' a pyrazole,Lq6 a t h i o c a r b a m o y l p h o s p h o n a t e , 1 q 7 and two iminobis(methylphosphonic acids).'" Additionally there have been studies o f the new bicyclic sulphur heterocycle (73),199 the oxazaphospholidine (74)200and a triaminophosphetanium aluminium betainea2' X-ray crystallographic studies of phosphoric compounds abound. Some concern phosphates such a s naphthyl and quinolyl phosphates,202 a n d alkylammonium phosphate betaine,*" a 1,3,2-dioxaphosphorinane resolving agent (75),204a glycosyl phosphatet2" and a fructofuranose 1 , 6 - d i p h o s ~ h a t e . ~ ~Three ~ thiophosphates have been examined, one containing a germyl group,zo7 another a chelated arsenic group,2oa the other a dithiaphosphepin, which has a pseudo chair conformation+z0' Many amides have also been investigated. They include a guanidine derivative of 1 , 3 , 2 - d i o ~ a p h o s p h o l e n e , ~ ~ ~ three sulphoximides (76),2'' a 2 - a m i n o - l , 3 , 2 , - d i o x a ~ h o s p h o r i n a n e ~ ' ~ a related sydnonimine,2'3 the fluoride (77),2'4 a ribitol thiophosphorylamide,21' and two 2 , 1 , 3 - b e n z o p h o s ~ h a d i a z i n e s . ~ ~ ~ There have been several studies o f cyclophosphazenes and closely related compounds. T h e first cyclodiphosphazene to be reported h a s all four P-N bonds equal in length,217 other studies include three cyclo- triphosphazenes,2'a - one o f which contains a cyclotetrasiloxane three large ring phosphazenes (NPMe2 2220 and two unusual spirocycl e s (PhPNI4 S3N4 and (Ph2PN)eSNz T h e structure o f the t r i s - m o r p h o l i n o p h o s p h i n i m i n e (78) has a l s o been d e t e r m i n e d r Z Z 2 e Z 2 '

9: Physical Methods

41 1

SePh

Li+

Ph,P =C

/ \

COPh C0,Me

(64)

(63)

(62)

Ph P + 3 \

PH

/

Ph3P+

Tms

Me

Me

M

/

(67)

(66)

(65)

(/ O N Lj pP o0 i3 H 2

P+

H

y2

(70)

(69)

(68)

Ph --‘C -C H=NOH

I

OMe

(72)

(71) RNH

0

0

\//

P-N

(73)

II

/R

MeSN-

0, ’0

(74)

po,

P(OR I2

II

0

‘OH

(75)

(76)


412

n' Compounds. T h e number of five co-ordinate structures that have been reported over the past year has diminished even further. A trigonal bipyramidal structure was found for the bicyclic trioxamidophosphorane ( 7 9 ) . 2 2 3 6.1.4

6 . 2 Electron Diffraction. - Three gas-phase molecular structures

have been determined by electron diffraction. They a r e the hypophosphite (80)224trifluorophosphine sulphide,225 and dichlorotrifluorophosphorane.22*

7 Dipole Moments, Herr Effects, Polarosraphv and Conductance

7.1 Dipole Moments and Kerr Effect. - T h e structures of two conformers of ethyldifluorophosphane have been determined using a combination of dipole moments and microwave spectroscopy.227 Dipole moments have been used to study the different twist angles of allenic phosphonates (81),22'and also to deduce the stereochemistry of 1 , 3 , 2 , 5 - d i o x a b o r a p h o s ~ h o r i n a n e ~ ~ ~ ~ Combined dipole moment and Herr effect studies a r e regularly used by Russian workers for the conformational analysis of phosphorus heterocyclesr'35*230 In a study of the interaction o f phenol with phosphoryl groups the Kerr effect was used to evaluate not only the extent of hydrogen bonding but also the influence o f changes in polarity and polarisation upon stability constants.*" I n a similar study the orientation of the aryl groups of 1,3,5-triazaphosphorines (82) were shown to be less coplanar than biphenyl in the gas phase.'32 7 . 2 Polarosraphy and Conductance. - A polarographic study of

trialkyl phosphites, thiophosphites, and related compounds showed that only the P-S bond is reductively cleaved at a dropping mercury electrode to give alkyl sulphide and ~ h o s p h i d e . ~Conductometric ~~ titrations of trialkylphosphines with bromine, iodine and iodine bromide showed the formation o f highly conducting 1:2, 1 : l and 2:l adducts. T h e latter two were isolated.234 Redox reactions o f b i s ( m e t h y 1 e n e ) p h o s p h o r a n e s ( 1 8 ) are irreversible and cyclicvoltametry oxidation peaks a r e independent o f s u b ~ t i t u t i o n . ~ '

413

9:Physical Methods

8

Mass Spectroscopy

T h e doubly charged mass spectra of eleven organophosphorus compounds w e r e o b t a i n e d u s i n g m e t h a n e as a t a r g e t gas. MO c a l c u l a t i o n s w e r e used t o e s t i m a t e s t r u c t u r a l p a r a m e t e r s a n d e n e r g i e s o f p r o m i n e n t i o n s s u c h as ( 8 3 ) . A p p e a r a n c e e n e r g i e s r a n g e d f r o m 23 t o 38 eV.23' There has been a mass spectrographic study o f trifluoromethyl( d i f l u o r o m e t h y 1 e n e ) ~ h o s p h i n e ~ ~a'n d a c o m p a r a t i v e s t u d y o f t r i m e t h y l phosphite and dimethyl methylphosphonate. T h e molecular ion of the l a t t e r w a s s h o w n t o u n d e r g o i s o m e r i s a t i o n t o t h e r a d i c a l c a t i o n (84) prior to dissociatione2" D i e t h y l t h i o p h o s p h i n i c e s t e r s (85) a n d ( 8 6 ) c a n be d i s t i n g u i s h e d by m a s s s p e c t r o m e t r y , t h e l a t t e r g i v i n g m o r e a b u n d a n t m o l e c u l a r i o n s a n d a l o w a b u n d a n c e o f t h e i o n (87). T h e p o t a s s i u m salts o f t h e p y r o p h o s p h o n i c a c i d s g a v e FAB s p e c t r a f r e e f r o m m a t r i x interferance.238 Chemical ionisation induced c o m p e t i n g a n d c o n s e c u t i v e h e t e r u l y t i c r i n g c l e a v a g e in t h e m a s s s p e c t r a o f t h e o x i d e s (88).239T h e b a s e p e a k s o f i m p h o s a n d c y c l o p h a n e w e r e q u i t e d i f f e r e n t a n d b a s e p e a k s a p p e a r e d at m/z 131 a n d 21 r e s p e c t i v e l y . 2 4 0 T h e m a s s s p e c t r a of p h e n y l p h o s p h o n a t e s a n d p h o s p h a t e s s u c h as (89) h a v e b e e n reviewed.24'

9

Acidities. Basicities and Thermochemistry

T h e r e h a s b e e n a MO s t u d y o f t h e s t e r e o e l e c t r o n i c e f f e c t s in m e t h y l p h o s p h i n e s ( 9 0 ) . S t e r i c e f f e c t s w e r e f o u n d t o c o n c e n t r a t e in t h e HOMO a n d a c c o u n t e d f o r h a l f t h e s u b s t i t u e n t e f f e c t s o n t h e pK, v a l u e s , w h i l s t e l e c t r o n i c e f f e c t s o n t h e HOMO w a s The relative basicities o f p o l y m e t h o x y t r i a r y l p h o s p h i n e s have been i n e considerably m e a s u r e d . T r i s ( 2 , 4 , 6 - t r i m e t h o x ~ ~ h e n ~ l ) ~ h o s ~ hwas m o r e b a s i c t h a n p i p e r i d i n e . 2 4 3 T h e b a s i c i t i e s o f P-N c o m p o u n d s h a v e b e e n r e v i e w e d a n d t h e i r c o r r e l a t i o n w i t h P-N b o n d l e n g t h s in~estigated.'~~ A method for determining the basicities of phosphoryl compounds h a s b e e n d e c r i b e d w h i c h is b a s e d o n " P n.m.r. c h e m i c a l s h i f t measurement and a two phase system consisting of a n organic solvent T h e gas-phase protonation of aliphatic a n d 12M s u l p h u r i c acid."' p h o s p h i n e o x i d e s h a v e b e e n d e t e r m i n e d by c y c l o t r o n r e s o n a n c e . T h e r e was a g o o d c o r r e l a t i o n o f pK. w i t h K a b a c h n i k c o n s t a n t s a n d MO


414

( TmsO),

PH

But N=C=CH

*r(ril*r

L

'P(OR1,

N$p"

0

0

(82)

(81)

(80)

OH I 12+ POCH, 6~~P+ (OM ( 8 3)

R2

0

II

0

EtzP-SR

?I

Et 2P-OR (86)

( 85)

(84) R

I

Et2PHS+

(87)

(88)

(89)

9: Physical Methods

415

c a l c u l a t i o n s i n d i c a t e d that f o r a m i d a t e s o x y g e n p r o t o n a t i o n is f a v o u r e d o v e r n i t r o g e n p r o t o n a t i o n by a b o u t 100 k c a l . m o l - ’ . 2 4 6 The pK, v a l u e s o f d i m e t h y l t h i o p h o s p h i n a t e s h a v e b e e n d e t e r m i n e d . 2 4 7 Protonation of a t e t r a a m i n o m e t h y l e n e p h o s p h o n i c acid was studied u s i n g p ~ t e n t i o r n e t r y . ~ ~ ’T h e a c i d i t y o f t h e P-H b o n d o f d i e t h y l . 2 4 9 The carbon p h o s p h o n a t e c o r r e s p o n d e d t o a PK, o f 2.5 a c i d i t i e s of m e t h y l e n e g r o u p s a c t i v a t e d by p h o s p h o r y l g r o u p s a n d phosphonium groups have been studied. Modified o c - constants have The b e e n d e r i v e d f r o m t h e u q c o r r e l a t i o n o f PK, v a l u e s e 2 ” acidifying effect o f phosphonium groups and the enhancement caused by m i c e l l a t i o n h a s b e e n i n v e s t i g a t e d . 2 5 1 I t h a s b e e n s h o w n that t h e h y d r o x y p h o s p h o r a n e ( 9 1 ) h a s a pK. o f 9 - 10 a n d is in r a p i d e q u i l i b r i u m w i t h its c o n j u g a t e a n i o n a n d t h e ring opened alcohol . 2 3 2 The heats o f ionisation and neutralisation of amino and hydroxylic bis and tris phosphonic a c i d s have been investigated.253 C a l o r i m e t r y in c o m b i n a t i o n w i t h U.V. a n d n.m.r+ s p e c t r o s c o p y w a s used to study the adducts of fluoroalkyl carboxylic acids with diethyl phosphonate.25‘ The heats of formation of the t - b u t o x y t r i p h e n y l p h o s p h o r a n y l radical was consistent with the p h o s p h o n i u m s t r u c t u r e (92).2’5 T h e r e h a s b e e n a thermal a n a l y s i s o f t h e adducts of phosphonic and phosphoric acids with semicarbazide,256 and the heats o f solution and heats o f reaction in t h e methylation o f triphenylphosphine have been studied with regard t o ’ solvent effects, transfer thermodynamic quantities and various extended Bronsted treatments.257

10

Chromatography

10.1 Gas L i q u i d C h r o m a t o g r a p h y . - T h e t h e r m o d y n a m i c s o f t h e m o l e c u l a r a s s o c i a t i o n o f tri-n-octylphosphine o x i d e a n d h a l o a l k a n e s h a v e b e e n s t u d i e d e 2 ’ * T h e r e h a s b e e n a g.1.c. a n a l y t i c a l s t u d y o f t h e d e g r a d a t i o n p r o d u c t s o f tri-n-butyl phosphate,2’9 t h e p y r o l y s i s products of quaternary phosphonium salts,260 and bifunctional amines after derivatisation with methyldichlorophosphane and sulphur.261 Cyclophosphamide a n d related compounds have been the subject o f several studies262 including g.c.mrsb263 Plant extracts containing ethyl p h o s p h o n a t e a n d p h o s p h a t e s h a v e b e e n a n a l y s e d by g.1.c. a n d h.p.1 .c.264

Organoph osphoms Chemistry

416

10.2 Thin Layer Chromatography. - The technique has been applied to the determination o f tricresvl phosphate in edible oils,263 and insecticides in tobacco leaves.266

10.3 Liquid Chromatography. - Diasteriomeric phosphonodipeptides have been separated by ion exchange column chromatography.267 H.p.1.c. has been used for the analysis of a variety of biologically active phosphorus compounds1 such as aminoacid phosphate esters,2b8 phosphinothrycinlZ6’ inositol t r i p h o s ~ h a t e , ~ ”fructose diphosphate,27’ pyridoxal and A T P . 2 7 J

11

Kinetics

T h e kinetics of deuterium isotope exchange between diphenylphosphine and t-butylthiol have been studied by ‘ H n*m.r. ~ p e c t r o s c o p y . ~A~ ~ negative temperature coefficient w a s observed for the reaction o f a perfluoroalkyl phosphite with a fluorinated aldehyde.27’ The kinetics for the reaction of alcohols with phosphoryl trichloride bore strong similarities t o those of carboxylic acid derivatives.276 An interesting report desribed the solvolysis of arylhydroxymethylphosphonates. It was shown that a phosphoryl group does not prevent carbocation formation on a n immediately adjacent carbon atom.277 There have been a number of hydrolysis studies. T h e mechanism o f alkaline hydrolysis of phenyl dimethylthiophosphinate has been compared to that of phenyl acetate.278 Evidence for the formation o f five coordinate oxyphosphorane intermediates in the alkaline hydrolysis of aryl d i p h e n y l t h i o p h o s p h i n a t e s is based on the lack o f development o f negative charge on the leaving group in the transition

9: Physical Methods

417

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H . S c h m i d t a n d S. M. Gordon, I n o r g . Chem., 1986, 3 %248. W. S c h o e l l e r r J . Chem. Soc.,Chem. Commun.~ 1985, 334. Y O S h i f U j i r N. I n a m o t o , K . I o t o t a n d S. Nagase, Chem. L e t t . , 1985, 437. Y o s h i f u j i , K . Shibayama,and K. T o y o t a , Chem. L e t t . , 1985, 237. Gonbeau and G. P f l s t e r - G u i l l o u z o g Nouv. J. Chim.9 19851 91 71. Y a b u s h i t a and H. S. Gordanr Chem. Phys. L e t t . , 1985, 117,321. E. Boggs and Z . N i n , J. Comput. Chem.9 19858 46. N. T s v e t k o v and A . A . K o r k i n , T e o r . Eksp. Khim., 1985, 21159. A . M. A 1 1 1 B. D. E l - I s s a , a n d N. I . Swiedan, P h o s p h o r u s S u l f u r , 1985, 2 ,

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Author Index I n t h i s i n d e x t h e number g i v e n i n p a r e n t h e s i s i s t h e C h a p t e r number of t h e c i t a t i o n and t h i s is f o l l o w e d by t h e r e f e r e n c e number o r numbers of t h e r e l e v a n t c i t a t i o n s within t h a t Chapter

Aaron, H.S. ( 4 ) 30 Aba-Ella, E.M. ( 8 ) 35 A b d e l - G a l i l , F. ( 1 ) 1 9 3 , 240 Abdel-Halim, F.M. ( 1 ) 220, 221 Abdou, W.M. ( 2 ) 3 5 ; ( 9 )

68 Abdul-Masih, M.T. ( 6 ) 216 Abdulwajid, A.W. ( 6 ) 6 8 Abed, O.H. (1) 2 2 2 ; ( 7 ) 24 A b e l l , K.W.Y. ( 5 ) 31 A b e l s o n , J . ( 6 ) 280, 341 A b i c h t , H.-P. (1) 2 9 , 46 Abiyuov, B.D. ( 9 ) 194 Aboujaoude, E.E. ( 5 ) 55, 5 9 ; ( 7 ) 75: 97 A b o u l - e l a , F. ( 6 ) 147 Abraham, S . J . ( 1 ) 2 3 0 , 2 3 1 ; ( 9 ) 260 Abramov, I . A . ( 1 ) 1 4 1 , 142 Abramova, T.V. ( 6 ) 283 Abu-Orabi, S. ( 1 ) 384 Acevedo, O.L. ( 6 ) 189 Acheson, R.M. ( 5 ) 3 9 ; ( 9 ) 216 Acost F l o r e s , M. ( 9 ) 259 Adam, S. ( 6 ) 381 Adamiak, R.W. ( 6 ) 2 7 3 , 380 Adams, J. ( 7 ) 120 Ades, C. ( 1 ) 266 A d r i a n , F.J. ( 9 ) 113 Aganov, A.V. ( 9 ) 9 2 , 1 3 6 Agarwal, K. ( 6 ) 1 7 3 Agashkin, O.V. ( 9 ) 1 7 8 Agawa, T. ( 5 ) 5 0 ; ( 7 ) 8 4 Agbossou, S. ( 2 ) 57 Agrawal, S. ( 6 ) 115 A g u i l a r , M.A. ( 3 ) 13

A h l e r s , H. (3) 25 Ahmad, M.M. (1) 213; ( 9 ) 181 Ahn, K.D. ( 8 ) 1 1 3 Ahrichs, R. (8) 3 Aitken, R.A. ( 7 ) 62 Akasaka, T . ( 7 ) 5 9 ; ( 8 ) 4 1 , 42 A k e l a h , A . ( 1 ) 1 9 3 , 240 A k h l e b i n i n , A . K . ( 9 ) 213 Akhmedzade, D.A. ( 1 ) 161, 162; ( 4 ) 56, 57, 59, 6 0 Akhmetkhanova, F.M. ( 2 ) 43 Akpan, C.A. (1) 313 Aksenova, T.B. ( 4 ) 6 8 Akutagawa, S . (1) 54 A l a r i o , F. ( 1 ) 114 A l b e r n e s e , J.A. ( 9 ) 39 A l b e r t , K . ( 9 ) 57 Albrecht, S. ( 4 ) 31; ( 8 ) 149 A l c o c k , N.W. ( 1 ) 367 A l d e r , L. ( 9 ) 1 4 3 Alderfer, J.L. (6) 191, 260, 377 Aldwegg, M. ( 6 ) 308 A l e i n i k o v , S.F. ( 9 ) 254; ( 9 ) 275 A l e k s a n d r o v a , N . A . ( 4 ) 37 Alemagna, A. ( 7 ) 5 3 , 5 4 Alewood, P.F. ( 5 ) 1 2 A l e x a n d e r , C.A. ( 1 ) 4 8 A l ' f o n s o v , V.A. ( 4 ) 4 9 , 50; ( 9 ) 233 A l i , A.A.M. (9) 9 A l i , R. (1) 187 A l i g , B. (1) 128 Allcock, H.R. (1) 118; ( 8 ) 8, 7 4 , 109-111, 155, 156, 158, 159; (9) 218

425

A l l e g r a , G . (8) 1 6 3 A l l e n , C.W. ( 8 ) 1 1 2 , 1 2 1 A l l e n , L. ( 6 ) 348 A l l s p a c h , T. ( 1 ) 3 2 1 , 3 2 2 ; ( 9 ) 24 A l o n i , Y. ( 6 ) 1 6 3 Alparova, M.V. ( 8 ) 127, 128; ( 9 ) 134 Al-Rawi, J . M . A . ( 2 ) 5 6 ; (9) 86 A l r i c h s , R . ( 9 ) 13 A l t , H.G. ( 1 ) 8 Altenbach, H.-J. ( 7 ) 89 A l t e r m a t t , R. ( 6 ) 139 Altman, S. ( 6 ) 3 4 7 , 348 Alvarado-Urbina, G. ( 6 ) 154 A l y e a , E.C. (1) 11 Amann, P. ( 1 ) 26 Ambrose, B . J . B . ( 6 ) 298 Aminova, R.M. ( 9 ) 9 3 Amrani, Y. (1) 114 Anders, E. ( 7 ) 4 6 Anderson, D . J . ( 6 ) 1 4 3 Anderson, N.L. (1) 9 5 Anderson, P.M. ( 6 ) 81 Anderson, T.P. (5) 1 4 0 , 142 Ando, T. (5) 1 2 3 Ando, W. ( 7 ) 5 9 ; ( 8 ) 4 1 , 42 Andra, K. (1) 160; ( 4 ) 55 Andrew, S.S. (5) 1 3 7 Andriamizaka, J . D . ( 1 ) 352 A n d r i a n a r i s o n , M. ( 9 ) 154 Ang, H.G. (1) 9 , 1 3 9 , 140 A n g e l e t t i , E. ( 1 ) 242 Angelov, Kh.M. (5) 1 2 7 ; (9) 87 A n g e r e r , W. (1) 1 7 2


426 Antberg, M. ( 1 ) 50 Antczak, K. ( 5 ) 101 Anthony, D.D., ( 6 ) 229 Antipin, M.Yu. ( 1 ) 331; ( 4 ) 102; ( 8 ) 24, 54, 190; ( 9 ) 150, 159, 166, 201, 203, 212 Anzai, M. ( 8 ) 9 5 , 96 Apal'kova, G.M. ( 1 ) 146; ( 9 ) 161 Appel, R . ( 1 ) 271, 273, 282, 294, 299, 306-309, 312, 314-317; ( 4 ) 105; ( 7 ) 6 ; ( 9 ) 33, 37, 62, 151, 158, 165 Appelt, A. ( 1 ) 43-45 Appling, J . R . ( 9 ) 235 Arai, M. ( 6 ) 40 Arbuzov,'B.A. ( 1 ) 245, 380-382; ( 2 ) 47; ( 4 ) 2; ( 9 ) 9 2 , 9 4 , 135, 136, 174, 215, 229, 230 Arcus, R.A. (8) 8 Arduengo, A.J. ( 4 ) 94 Arenz, T. ( 7 ) 12 Argyropoulos, N.G. ( 7 ) 44 A r i f , A.M. (1) 287, 288, 339, 347, 348, 355; ( 4 ) 107 A r i f i e n , A.E. ( 8 ) 35 Aripov, E.A. ( 9 ) 240, 263 Arison, B. ( 6 ) 16 A r i s t o f f , P.A. ( 7 ) 155 Armour, M.-A. ( 5 ) 66 Arnold, J.R.P. ( 6 ) 76, 80 Arshinova, R.P. ( 9 ) 1 7 , 135-137, 229, 230 Arzoumanian, H. ( 7 ) 65 Asaka, M. ( 6 ) 121 Ashbrook, C. ( 6 ) 193 Ashe, A . J . ( 1 ) 135, 384 Ashinadze, L.D. ( 9 ) 125 Ashley, G.W. ( 6 ) 94 Ashton, W.T. ( 6 ) 16 Asirvatham, E. (7) 32, 33 Askham, F.R. ( 1 ) 49 Asknes, G . ( 3 ) 11 A s s e l i n e , U. ( 6 ) 161 Atherton, F.R. ( 5 ) 104 Atherton, J.I. ( 7 ) 62 Atmadja, J. ( 6 ) 292 Atoh, M. ( 1 ) 27 Ator, M.A. ( 6 ) 9 2 , 9 3 Atrash, B. ( 5 ) 112; ( 9 ) 23 A t t w e l l , D. ( 6 ) 5 Attwood, S.V. (7) 142 Audisio, G. ( 8 ) 6 1 , 7072, 163 A u r e l i a n , L. ( 6 ) 180 A u s t i n , P.E. ( 8 ) 155, 156 Ayad, M. ( 5 ) 129

Ayed, N. ( 2 ) 56; ( 9 ) 86

B a r t l e t t , P.A. ( 5 ) 8 Barton, D.H.R. ( 1 ) 227; (2) 9 Barton, J . K . ( 6 ) 366-368 Baas, P.D. ( 6 ) 354 B a r t s c h , R. ( 1 ) 328 Baasov, J . (7) 105 Baryanoff, B.E. ( 5 ) 51 Baba, A. ( 1 ) 125; ( 3 ) 45 Baryeva, E.S. ( 4 ) 71 Bac, N.V. ( 7 ) 134 Basil, J . D . ( 7 ) 70 Baccar, B. ( 5 ) 129 Basso-Bert, M. ( 1 ) 41 Baceiredo, A. ( 1 ) 5 , 6 , B a t a i l , P. (1) 214; ( 9 ) 337; ( 4 ) 95; ( 7 ) 16; ( 8 ) 16; ( 9 ) 52, 217 168 Bach, S.A. ( 6 ) 169 Bateson, J . H . ( 7 ) 110 B a c h e l l e r i e , J.-P. ( 6 ) Batyeva, E.S. ( 4 ) 3 6 , 4 9 , 50, 72; ( 9 ) 233 305 Badanyan, Sh.0. (5) 131 Baudler, M. ( 1 ) 19-22, 32-36, 138; ( 3 ) 10; ( 9 ) Badrudin, B. ( 9 ) 115 32, 147 B a i l e y , J . M . ( 6 ) 227, 228 Bauer, D.P. ( 1 ) 53 Baindur, S.R. (6) 278 Baker, B.F. ( 6 ) 333 Baumgartner, R. ( 1 ) 8 Bausk, E.V. ( 6 ) 151 Baker, J . C . ( 6 ) 100 Balcom, B.J. ( 9 ) 97 Bax, A. ( 6 ) 370 Baldy, A. ( 7 ) 65 Baxter, S.G. (1) 355; ( 4 ) 107 Balgobin, N . ( 4 ) 74; ( 6 ) 107 Bayard, B. ( 6 ) 187 B a l i t s k a y a , O.V. ( 9 ) 53 Bayev, A.A. ( 6 ) 317 Balszuweit, A. ( 4 ) 1 3 , Baylor, D.A. ( 6 ) 54 17, 34; ( 5 ) 52, 60 Bays, J.P. ( 9 ) 18 B a l t h a z e r , T.M.' ( 5 ) 99 Bazbouz, A. ( 1 ) 216 B a l z a r i n i , J. ( 6 ) 44, 45 Bazin, H. ( 6 ) 129 Bamgboye, O.A. ( 8 ) 6 8 , 79 Beachley, O.T. ( 1 ) 78 Bamgboye, T.T. ( 8 ) 6 8 , 79 Beardsley, G.P. ( 6 ) 264 B a n f a l v i , G. (6) 225 Beaucage, S.L. ( 6 ) 3 4 , Bankmann, M. ( 1 ) 276; ( 7 ) 123 Beaver, B.D. (7) 20, 21 3; ( 9 ) 145 Bannwarth, W. ( 4 ) 88; (6) Becher, R. ( 1 ) 21 104 Beck, D . J . ( 6 ) 364 B a r a i , V.N. ( 6 ) 185 Becker, C.R. ( 6 ) 153 Bararn, G . I . ( 6 ) 249 Becker, G. ( 1 ) 130, 322; Baranetskaya, N . K . ( 1 ) 2 ( 9 ) 24 Baraniak, J. ( 5 ) 19; ( 6 ) Becker, W. ( 1 ) 322; ( 9 ) 24 57 B a r a n s k i i , V.A. ( 9 ) 278 Been, M.D. ( 6 ) 345 Barclay, L. ( 9 ) 97 Beggiato, G. ( 8 ) 172 Barendt, J . M . ( 4 ) 58; ( 9 ) Behe, M.J. ( 6 ) 199 162 Behnam, G.Q. ( 9 ) 86 B e j e r , B. ( 6 ) 110 Barget, G. ( 9 ) 26 Barker, M.F. ( 6 ) 14 Bekasova, N . I . ( 8 ) 91 Barluenga, J. ( 1 ) 386; Bekker, A.R. ( 4 ) 68; ( 5 ) ( 3 ) 42; ( 8 ) 45 65; (9) 195 Barnes, N . J . ( 7 ) 87; ( 9 ) Belakhov, V.V. ( 5 ) 2 133 B e l e t s k i i , I.P. ( 9 ) 1 4 Barone, A.D. ( 4 ) 83 B e l l a n , J. ( 1 ) 265, 332, Barr, R.G. ( 6 ) 358 333; ( 4 ) 111; ( 8 ) 1 7 , Barrans, J. ( 1 ) 378; ( 4 ) 18, 21 101 B e l l e a u , B. ( 5 ) 143 Barreau, M. ( 7 ) 48 Belmont, S.E. (1) 366 Barrett, A.G.M. ( 7 ) 142 B e l ' s k i i , F.I. (5) 84 Barry, C.N. ( 2 ) 20 B e l t r a n , A.M. ( 5 ) 21 Barstow, L.E. ( 6 ) 150 Benage, B. ( 9 ) 18 Barsukov, A.V. (5) 96, Benight, A.S. ( 6 ) 208 Benkovic, S.J. ( 6 ) 201 97; ( 9 ) 253 B a r t h , V. ( 1 ) 271; ( 9 ) 62 Bennamara, A. ( 1 ) 225;

427

Author Index (7) 14 B e n s e l e r , F. (6) 127 B e n t r u d e , W.G. ( 2 ) 4 2 ; ( 6 ) 4 4 , 45 Benziman, M . ( 6 ) 1 6 3 B e r c h a d s k y , Y . ( 9 ) 115 B e r d n i k o v , E.A. ( 5 ) 1 2 5 ; ( 9 ) 95 Beremzhanov, B.A. ( 9 ) 256 Beres, J. ( 6 ) 44, 45 Bergmann, P. ( 1 ) 283 B e r l i n , K . D . (5) 14; ( 9 ) 209 B e r n h a r d t , F.C. ( 9 ) 36 B e r r a d a , M . ( 5 ) 42 B e r r y , D.E. ( 1 ) 181 B e r s e n e v a , L.S. ( 1 ) 1 4 4 ; ( 5 ) 13 B e r t h e l o t , M . ( 9 ) 126 B e r t r a n d , G. ( 1 ) 5 , 6 , 132, 337; (4) 9 , 95; ( 7 ) 16; ( 8 ) 4 , 16, 30; ( 9 ) 5 2 , 217 B e s s e n b a c h e r , C. (9) 116 Bessmann, M.J. ( 6 ) 216 Best-Belpomme, M. ( 6 ) 9 9 Bestmann, H.J. ( 7 ) 1 , 1 2 , 2 9 , 3 0 , 56-58, 1 0 1 , 1 0 4 , 1 3 2 , 136; ( 9 ) 1 6 B e t s c h , D.F. ( 6 ) 401 B e t t e r m a n n , G . ( 1 ) 212 B e t z , A . ( 9 ) 187 B e v e r i d g e , K . A . ( 1 ) 181 Beynon, J.H. ( 6 ) 4 3 Bhatnagar, N.Y. ( 2 ) 9 B h a t t a c h a r y a , S. ( 6 ) 225 B i , Y. ( 9 ) 88 B i a l a , E. ( 6 ) 124 B i a s t o c h , R . ( 1 ) 23-25 B i d d l e s t o n e , M. ( 8 ) 6 6 B i e b e r i c h , M.J. ( 8 ) 9 8 Biernat, J. (4) 90 B i l d s t e i n , B. ( 1 ) 1 7 8 B i n d e r , D. (1) 261 B i n n e w i e s , M. ( 1 ) 279; ( 4 ) 9 8 ; ( 9 ) 236 B i r y k o v , I . P . ( 9 ) 103 B i s b a l , C. ( 6 ) 187 B i s c h o f f , R . ( 6 ) 387 B l a c h e r , R.W. ( 6 ) 206 B l a c k b u r n , G.M. ( 5 ) 80, 120, 122; (7) 98 B l a i r , P. ( 9 ) 225 B l a k e , K.R. ( 6 ) 174-176 B l a k e l y , W . f . ( 6 ) 266 B l a n c h e t t e , M.A. ( 7 ) 80 B l a n q u e t , S. ( 6 ) 9 9 , 233 B l e c h s c h m i t t , K . ( 7 ) 67 B l o c k e r , H. ( 6 ) 3 0 3 , 318 Blonsky, P.M. ( 8 ) 1 5 5 , 156 Bloom, J . D . ( 3 ) 36

Blumenkopf, T.A. ( 5 ) 67 B o b s t , A.M. ( 6 ) 194 Bock, H . ( 1 ) 276; ( 7 ) 3 ; ( 9 ) 145 Bodner, M . ( 6 ) 392 B o h s h a r , M . ( 3 ) 26 Boekemeier, W . ( 6 ) 339 Boer;, R.T. (1) 3 8 , 103 B o e s e , K . ( 7 ) 69 B o e s e , R . ( I ) 284, 285, 290 Boske, J . ( 1 ) 318; ( 8 ) 22; ( 9 ) 189 Boggs, J . E . ( 9 ) 7 B o h l e , D.S. ( 1 ) 289 Bohlen, R . ( 2 ) 1 0 , 4 1 , 42; (5) h Roisdon, M.T. ( I ) 378: ( 4 ) 100 B o l a n d , W . ( 7 ) 146 B o l d e s k u l , I.E. ( 1 ) 331; ( 4 ) 102; ( 8 ) 24; ( 9 ) 1 5 9 , 1 6 6 , 201, 212 B o l e s , T.C. ( 6 ) 310 B o l i k a l , D . (1) 223, 236, 237; ( 9 ) 251 Bollinger, J.C. (3) 17; ( 9 ) 1 2 7 , 246 Bornpeix, G . ( 9 ) 264 Bond, D . R . ( 9 ) 202, 211 Bondarenko, N . A . ( 1 ) 1 4 Bone, R. ( 6 ) 98 Bone, S.A. ( 2 ) 1 5 B o n n e t , M.C. ( 2 ) 57 Bord;, J. ( 2 ) 11 Borisenko, A . A . ( 1 ) 7 , 179; ( 4 ) 3 9 , 5 1 , 5 2 , 54; ( 9 ) 1 6 3 B o r i s o v , E.V. ( 4 ) 6 8 ; ( 9 ) 213 Borisov, G. (3) 4 Borm, J . ( 1 ) 262, 269, 270 B o r n o v a l o v a , G.V. ( 8 ) 8 4 B o r t o l u s , P. ( 8 ) 1 7 1 Bosch, M.P. ( 3 ) 39 B o s c h e l l i , D. ( 7 ) 1 0 9 Bosma, E. (8) 126 B o s n i c h , B. ( 1 ) 1 7 BOSO, B. (8) 110 Bostedor, R . ( 6 ) 16 Bosyakov, Yu.G. ( 9 ) 178 B o t s t e i n , D. ( 6 ) 203 B o t t i n - S t r z a l k o , T. ( 5 ) 118; ( 7 ) 72; (9) 42, 45, 85 B o u c h e r , H. ( 1 ) 17 Boudin, A. (2) 6 , 7 B o u l a y , F. ( 6 ) 243 B o u l o s , L.S. ( 5 ) 7 Bourson, J . ( 3 ) 1 4 ; ( 9 ) 142

Bowden, M.C. ( 7 ) 107 Bowen, S.M. ( 5 ) 1 1 5 Boyd, V.L. ( 5 ) 46 Brauer, D.J. ( 1 ) 12, 69, 90, 121; ( 4 ) 43 B r a u n s t e i n , P. (1) 374 B r e c h t , A . ( 7 ) 5 0 , 51 B r e d k h i n a , Z.A. ( 8 ) 132 Brennan, C . A . ( 6 ) 211 B r e s l o w , R . ( 5 ) 23; ( 6 ) 35 1 B r e u e r , E. ( 7 ) 72 B r e v e t , A . ( 6 ) 99 B r i g h t , D.A. ( 1 ) 88 B r i g h t , R . ( 8 ) 1 1 2 , 121 Brimacombe, R. ( 6 ) 292 Brook, C.P. ( 3 ) 1 6 ; ( 9 ) 175 B r o o k s , D.W. ( 7 ) 1 1 9 Broughton, H.B. ( 7 ) 142 B r o v a r e t s , V.S. ( 1 ) 203 Brown, D. ( 5 ) 122 Brown, L. ( 7 ) 38 Brown, N.C. ( 6 ) 6 6 Brown, R.S. ( 6 ) 353 Brown, T. ( 6 ) 375 Broyde, S. ( 6 ) 288 Bruch, R.C. ( 6 ) 6 B r u c h e , L. (8) 10 Bruck, B. ( 9 ) 158 Brune, H . A . ( 1 ) 8 B r u n n e r , H. ( 1 ) 1 7 4 , 1 7 5 ; ( 4 ) 97 B r u n s , A . ( 9 ) 57 B r u z i k , K.S. ( 4 ) 6 6 ; ( 5 ) 10 B r y c e , M.R. ( 1 ) 2 1 3 ; ( 5 ) 3 9 ; ( 9 ) 216 Buck, H.M. ( 2 ) 1 6 ; ( 6 ) 371, 3 7 2 ; ( 9 ) 6 7 , 114 B u d e s i n s k y , M. ( 6 ) 24 Budhram, R.S. ( 7 ) 81 Buhlmeyer, W . ( 1 ) 133 B u r g e r , H. (1) 9 0 B u r k l i n , M. ( 1 ) 1 7 1 Bugerenko, E.F. ( 1 ) 1 4 6 ; ( 9 ) 161 Bukachuk, O.M. (1) 200, 20 1 B u l a r g i n a , T.V. ( 6 ) 232 Bulgakov, R . ( 6 ) 57 B u l g a r e v i c h , S.B. (8) 130; ( 9 ) 232 B u l o t , J.J. ( 5 ) 55 Bulycheva, E.g. (8) 9 1 Buneva, V . N . ( 6 ) 249 Bunton, C.A. ( 5 ) 22 B u r d i c k , G.W. ( 9 ) 235 Burg, A . B . (1) 1 6 5 Burgada, R. ( 2 ) 28-30, 45; (4) 1 5 , 16; (7) 17, 18, 60


428 Burger, R.M. ( 6 ) 328 Burget, G. (1) 1 8 , 166, 167; ( 8 ) 138; ( 9 ) 160 Burik, A. ( 1 ) 180; ( 4 ) 78; ( 6 ) 26 Burilov, A . R . ( 4 ) 48 Burkey, T.J. ( 9 ) 113, 255 Burklin, M. ( 4 ) 108 Burnaeva, L.A. ( 2 ) 52 Burski, J. ( 2 ) 31 Buryanov, Ya.1. ( 6 ) 317 Bushnell, G.W. ( 1 ) 181 Bushweller, C.H. ( 9 ) 10 Buss, A.D. ( 3 ) 28 Busulini, L. ( 8 ) 171 Butin, B.M. (1) 52 Butler, W. (1) 384 Bychkov, N . N . ( 9 ) 65 Byrd, R . A . ( 4 ) 7 , 93; ( 6 ) 146, 171, 376 Cable, M.B. ( 6 ) 247 Cabral, J. ( 9 ) 89 Cadet, J . ( 6 ) 269 Cai, W. ( 1 ) 229 Cain, T. ( 8 ) 7 ; ( 9 ) 79 Cairns, S.M. ( 2 ) 26; ( 7 ) 22 Callahan, L. ( 6 ) 173 Calvitti, S. ( 7 ) 151 Camerini, E. ( 7 ) 151 Cameron, T.S. ( 8 ) 195 Caminade, A,-M. ( 1 ) 132, 266; ( 4 ) 9 ; ( 8 ) 30 Campana, J.E. ( 9 ) 237 Campbell, J . A . ( 9 ) 167 Camps, F. ( 3 ) 39 Canning, L.F. ( 6 ) 16 Cantor, C.R. ( 6 ) 393 Cantu, Y.L. ( 8 ) 75 Capdevila, J. ( 7 ) 121 Caputo, R . ( 1 ) 87 Cardona, L. ( 7 ) 153 Caretta, A . ( 6 ) 47 Carle, G.F. ( 6 ) 394 Carlquist, M. ( 6 ) 241 Carmichael, D. ( 1 ) 364 Carmichael, I. ( 9 ) 108 Carniato, D. ( 5 ) 93 Carpenter, L.E. ( 2 ) 59 Carr, L . J . ( 8 ) 99 Carrie', R. (1) 106, 107, 379 Carroy, A. ( 1 ) 28 Caruthers, M.H. ( 4 ) 8 3 , 8 4 ; ( 6 ) 123, 150, 166 Casalbore-Miceli, G. ( 8 ) 172 Casser, C. (1) 282, 294, 306, 307; (9) 33 Cassir Chury, M. ( 9 ) 259

Castagnino, E. ( 5 ) 133 Castedo, L. ( 3 ) 40 Caster, K.C. (1) 369 Castera, P. ( 8 ) 88 Castro, M.M. ( 6 ) 147 Cavaggioni, A. ( 6 ) 47 Cech, D. ( 6 ) 317 Cech, T.R. ( 6 ) 342, 343, 345, 346 Cefelin, P. ( 8 ) 157 Cernia, E. (1) 176 Cerrini, S. ( 9 ) 206 Cerveau, G. ( 2 ) 6 , 7 Cesar Castells, R. ( 9 ) 258 Chadha, R . K . ( 9 ) 207 Chae, H . J . ( 8 ) 101 Chakraborty, T.K. ( 7 ) 128 Champion, D.H. ( 1 ) 311 Champion, E. ( 7 ) 115 Chan, G.L. ( 6 ) 262 Chandrasekaran, S. ( 6 ) 383

Chandrasekhar, V. ( 8 ) 90 Chang, C.-W. ( 6 ) 254 Chang, D.-K. ( 6 ) 144 Chang, L.-H., ( 6 ) 324 Charrier, C. ( 1 ) 342, 366; ( 9 ) 73, 74 Chattopadhyaya, J. ( 4 ) 74, 1 5 , 107, 118, 129 Chavez, F. ( 6 ) 212 Chawla, R.R. ( 6 ) 12 Chen, C. ( 6 ) 132 Chen, C.B. ( 6 ) 188 Chen, C.H. ( 1 ) 55; ( 3 ) 9 ; ( 9 ) 156 Chen, H . - J . ( 4 ) 53; ( 9 ) 164 Chen, J.-K. ( 6 ) 275, 276 Chen, P.C.Y. ( 8 ) 7 ; ( 9 ) 79 Cheng, H.-L. ( 6 ) 341 Cheng, M.S. ( 6 ) 76 Cheng, S.-C. ( 6 ) 98, 341 Cherkasov, R . A . ( 2 ) 1 ; ( 5 ) 125, 149, 158 Chermykh, T.E. ( 4 ) 45 Chernega, A . N . (1) 331; ( 4 ) 102; ( 8 ) 24, 54; ( 9 ) 150, 159, 166, 194, 201, 203, 212 Chernov, A.N. ( 1 ) 182, 380; ( 9 ) 90, 174 Chernov, P.P. ( 9 ) 95 Chernykh, T.E. ( 1 ) 184; ( 8 ) 27 Chernyshev, E.A. ( 1 ) 146; ( 9 ) 161 Chernyuk, I . N . ( 1 ) 219 Chiarello, R.H. ( 6 ) 154 Chiche, L. (1) 225, 226

Chichester, S.V. ( 8 ) 65; ( 9 ) 118 Chichkanova, T.V. (1) 191 Chimishkyan, A.L. ( 5 ) 77; ( 8 ) 19 Chinsky, L. ( 6 ) 395 Chivers, T. ( 8 ) 124; ( 9 ) 221 Choder, M. ( 6 ) 392 Choffat, Y. ( 6 ) 308 Chojnowski, J . ( 1 ) 157; ( 3 ) 1 ; ( 4 ) 22 Chong, C. ( 9 ) 46 Chou, T. ( 1 ) 15 Chou, W.-N. ( 8 ) 7; ( 9 ) 79 Choudary, B.M. ( 1 ) 177 Chouinard, P.M. ( 5 ) 8 Choukroun, R. (1) 41 Chovnikova, N . G . ( 1 ) 202 Choy, W. ( 7 ) 80 Christau, H . - J . ( 1 ) 215, 216, 218, 226 Christodoulou, C. ( 6 ) 115 Christol, H. (1) 215, 218, 225 Chu, B. ( 8 ) 142, 143 Chuit, C. ( 2 ) 6 , 7 Chung, Y.S. ( 7 ) 123 Church, J.S. ( 9 ) 227 Churilino, N.V. ( 5 ) 135 Chuvashov, D.D. ( 1 ) 76; ( 9 ) 148 Cicero, S.E. ( 6 ) 387 Ciesiolka, J . ( 6 ) 277 Claesen, C . A . A . ( 4 ) 73; ( 6 ) 32, 107, 125, 160 Clark, J . H . ( 9 ) 123 Clark, J . M . ( 6 ) 264 Clark, T. ( 7 ) 46 Clarke, J. ( 6 ) 224 Claude, C. ( 1 ) 16 Cleary, D.G. ( 7 ) 74 Clegg, W. ( 8 ) 52 Cleland, W.C. ( 5 ) 34, 35 Cleve, C. ( 9 ) 152 Cnossen-Voswijk, C. ( 8 ) 192 Cocito, C. ( 6 ) 390 Coene, M. ( 6 ) 390 Cohen, S. ( 9 ) 197 Coiro, V.M. ( 9 ) 206 Colanduoni, J . A . ( 6 ) 238 Colburn, J.C. (1) 384 Coll, J. ( 3 ) 39 Colleuille, Y. ( 1 ) 114 Collignon, N. ( 5 ) 55, 59; ( 7 ) 75, 97 Collins, M.L. ( 6 ) 204 Colman, R.F. ( 6 ) 227, 228 Comasseto, J . V . ( 9 ) 172 Commenges, G. ( 8 ) 8 9 Cornpagnone, R.S. ( 7 ) 161

429

A uthor Index Condron, L.M. ( 9 ) 21 Conley, M.P. ( 6 ) 257 Connell, C.R. ( 6 ) 299 Connelly, C.J. ( 6 ) 289 Connolly, B.A. ( 6 ) 374; ( 9 ) 51

Constantinides, I. ( 5 ) 124

Contreras, R . H .

( 9 ) 75,

76

Cook, B. ( 5 ) 58 Cook, R.D. ( 5 ) 148; ( 6 )

32; ( 6 ) 7 4 , 76, 272; ( 9 ) 48, 51 Culshaw, D. (7) 124 Cummings, A. ( 6 ) 269 Cummins, J.H. ( 6 ) 20; ( 9 ) 51 Cupps, T.L. (7) 144 Cusack, N.J. ( 6 ) 8 5 , 60 Cypryk, M. ( 1 ) 157 Czech, T.R. ( 6 ) 1 Czerwiuski, E . W . ( 9 ) 170

90; ( 9 ) 247, 279

Cooke, M.P. ( 7 ) 49 Cooney, J.V. ( 7 ) 20 Coons, D.E. ( 4 ) 53; (9) 164

Corbel, B. ( 4 ) 5; ( 5 ) 73 Corbin, J.D. ( 6 ) 55, 56 Cordes, A.W. ( 1 ) 103 Cordiero, M.L. ( 5 ) 110 Corey, E.J. ( 7 ) 28, 116 Corgano, S . ( 5 ) 133 Cornish, C.A. ( 3 ) 29 Corriu, R.J.P. ( 2 ) 5-7 Corset, J . ( 5 ) 118; ( 9 ) 45

Cosstick, R. ( 6 ) 167, 312 Costisella, B. ( 2 ) 37 Cotter, R.J. ( 6 ) 63 Coull, J.M. ( 6 ) 401 Couret, C. (1) 256, 267, 352; ( 9 ) 107, 154 Cowley, A.H. (1) 172, 287, 288, 311, 339, 347, 348, 351, 353-355; ( 4 ) 1, 106, 107, ( 9 ) 190 Cradock, S. ( 9 ) 225 Craig, S.L. (1) 103 Cramm, D.A. ( 2 ) 40; ( 9 ) 252 Crans, D.C. ( 5 ) 9 Crea, R. ( 6 ) 154 Creary, X . ( 5 ) 138; ( 9 ) 1 8 , 277 Cremer, S.E. ( 9 ) 167 Criddle, W.J. ( 1 ) 230, 231; ( 9 ) 260 Cristante, M. ( 1 ) 132; ( 4 ) 9 ; ( 8 ) 30 Cristau, H . J . ( 7 ) 14 Crombie, L. ( 7 ) 135 Cross, R.L. ( 6 ) 234 Crothers, D.M. ( 6 ) 391 Crowther, J.B. ( 6 ) 385 Crumbliss, A.L. ( 1 ) 370 Crysler, C.S. ( 6 ) 82 Cubellis, M.V. ( 6 ) 388 Culcasi, M. ( 1 ) 136, 267; ( 9 ) 107, 110 Cullis, P.M. ( 5 ) 20, 29,

Dabkowski, W. ( 4 ) 64 Daemen, C.J.M. ( 6 ) 3 2 , 160

Dahl, 0. (4: 40, 82 Dahlenburg, L. ( 1 ) 50 Dai, <J. ( 1 ) 229 Daigle, K. ( 6 ) 320 d'Alarcao, M. ( 7 ) 116 Dalbon, P. ( 6 ) 243 Dalley, N.K. ( 6 ) 11 D'Ambrosio, S.M. ( 6 251 Damha, M.J. ( 4 ) 8 7 , 92 : ( 6 ) 122, 164

Dana, V. ( 2 ) 11 Danchenko, E.A. ( 4 ) 1 8 Dang, T.P. ( 1 ) 1 1 3 , 114 Dangyan, Yu.M. ( 5 ) 31 Daniel, H, ( 7 ) 41 Danilova, 0.1. ( 9 ) 229, 230

Daolio, S. (8) 6 1 , 69-73 Daouk, W.A. ( 5 ) 148 Darakis, G. ( 9 ) 264 Darensbourg, D.J. ( 8 ) 33 Dartmann, M . (1) 287, 318; ( 8 ) 22; ( 9 ) 189

Das, M.K. ( 1 ) 9 1 , 92 Datema, R. ( 6 ) 15 Dauter, Z. ( 5 ) 39; ( 9 ) 216

Davidowitz, B. (5) 154; ( 9 ) 186

Davidson, A.H. ( 7 ) 87 Davidson, F. ( 4 ) 94 Davies, D.B. ( 6 ) 369 Davies, G. ( 8 ) 144 Davies, H.M.L. ( 7 ) 112 Davies, R.w. ( 6 ) 344 Davis, J.T. ( 7 ) 80 Davy, H. (5) 139 Dawson, J.M. ( 6 ) 90 Day, H. ( 5 ) 90 Day, R.O. ( 1 ) 303, 304; ( 9 ) 153

DeBoer, J.L. ( 8 ) 192-194 De Bruijn, E.A. ( 9 ) 262 de Clercq, E. ( 6 ) 4 4 , 45 Degener, H.J. ( 1 ) 1 8 5 , 186; ( 5 ) 108

Degl'Innocenti, A. ( 7 ) 58 Dehnicke, K. ( 9 ) 171 DeJaeger, R. ( 8 ) 4 4 , 5 8 , 146

de Jong, S. ( 8 ) 82 Del Buttero, P. ( 7 ) 5 3 , 54

Delius, H. ( 6 ) 224 Dellaria, J.F. ( 7 ) 92 Dellinger, D. ( 4 ) 8 3 Delmas, M. ( 7 ) 25 Delord, T.J. ( 7 ) 70 Delort, A.M. ( 6 ) 140, 141 Dembech, P. ( 7 ) 58 de Murcia, G . ( 6 ) 291 Dencheva, N. ( 3 ) 4 Denney, D.B. (2) 1 9 ; ( 9 ) 6 8 , 69

Denney, D.Z. ( 2 ) 1 9 ; ( 9 ) 6 8 , 69

Dennis, D. ( 6 ) 162 Denny, W.A. ( 6 ) 376; ( 9 ) 72

Deol, S.S. (1) 97 Deome, A.J. ( 8 ) 9 8 de Riese-Meyer, L. ( 1 ) 34 deRuiter, B. ( 8 ) 126 Dervan, P.B. ( 6 ) 331-334 Desai, M.C. ( 7 ) 28 De Sarlo, F. ( 1 ) 379 Deschamps, B. ( 1 ) 292, 362, 368, 374

Deschenaux, R. ( 1 ) 67 Deshong, P. ( 7 ) 141 Dessen, P. ( 6 ) 233 Dettoff, B.S. ( 7 ) 74 Devadoss, E. ( 8 ) 77, 87 De Villiers, L.S. ( 9 ) 272 de Vries, E.G.E. ( 8 ) 8 2 , 83

de Vroorn, E. ( 6 ) 172 Dewan, J.C. ( 6 ) 353 Dharanipragada, R. ( 7 ) 162

Dhathathreyan, K.S. (8) 125, 126

Diallo, 0. (1) 378; ( 4 ) 101

Dianes, R.A. ( 7 ) 128 Dianova, E.N. ( 1 ) 245, 380-382;

( 4 ) 2 ; ( 9 ) 174

Diekmann, S. (6) 391 Diel, P.J. ( 5 ) 95 Diemert, K. ( 1 ) 152 Dilaimi, A.A. ( 7 ) 91 Dillon, K.B. ( 1 ) 187, 239; ( 8 ) 1 6 ; ( 9 ) 5 2 , 56, 105 DiMarco, P. (8) 173 Ding, W . ( 1 ) 229 Dingwall, J.G. ( 5 ) 58 Disdaroglu, M. ( 6 ) 270


430

Ditrich, K. (7) 90 Di Tullio, D. (7) 114 Dixon, K.R. (1) 181 Diz, A.C. (9) 76 Dizdaroglu, M. (6) 266 Dmitriev, V.I. (9) 131 Dobberstein, B. (6) 177 Dobrova, N.B. (8) 174, 175 Dodd, C. (6) 299 Doel, G.R. (1) 120 Doetsch, P.W. (6) 259, 262 Dogadina, A.V. (5) 48; (9) 228 Doherty, N.M. (1) 122 Doi, T. (6) 210 Dolenko, G.N. (9) 40, 131 Dolgikh, M.A. (8) 160 Dolle, R.E. (3) 38 Dombroski, B.A. (6) 338 Doney, J.J. (1) 55; (3) 9; (9) 156 Doren, D. (7) 145 Dorfman, A.Ya. (1) 77 Dorsey, B.D. (7) 131 Dose, K . (6) 245 Doskeland, S.O. (6) 55, 56 Dostal, K. (8) 149 Douglas, K.T. (6) 278 Dove, M.F.A. (2) 3 Downes, J.M. (1) 17 Drach, B.S. (1) 203 Drahovsky, D. (6) 196 Drake, A.F. (6) 252 Drake, J.E. (9) 207 Draper, D.E. (6) 336 Dreef, C.E. (6) 172 Dresler, S.L. (6) 291 Drew, J. (7) 150 Driler, H. (6) 137 Driska, S.P. (6) 247 Dubendorff, J.W. (4) 83 Dubois, R.A. (1) 118, 119; (8) 159 Dubovik, 1.1. (8) 164, 175 Dubuc, G. (6) 207 DUC, G. (7) 14 Duchamp, D. (6) 173 Duchange, N . (6) 148 Dudchenko, T.N. (2) 50; (8) 28, 29 Duddeck, H. (5) 49; (9) 84 Dudis, D. (7) 70 Dudycz, L.W. (6) 66 Duke, A.E. (6) 14 Dumont, J.E. (6) 52 du Mont, W.-W. (1) 101, 102

Dunach, E. (9) 59 Dunitz, J.D. (3) 16; (9) 175 Dunker, K.-H. (1) 314, 315; (7) 6; (9) 37 Dunn, D.A. (8) 98 Dupont, Y. ( 6 ) 72 du Preez, J.G.H. (3) 46 Durig, J.R. (9) 130, 133, 227 Durmis, J. (9) 86 DUS, D. (5) 98 Dvoinishnikova, T.A. (1) 188; (8) 127-129 Dyatlova, N.M. (5) 96, 97; (9) 248,, 253 Dykema, K.J. (1) 248; (7)

221 Elgamal, M.H.A. (5) 49 Eliseeva, G.D. (9) 278 El-Issa, B.D. (9) 9 El-Khatib, F. (1) 266 El Khoshnieh, Y.O. (2) 28, 29 Elliot, J. (3) 34 El Manouni, D. (2) 30, 45; (4) 15, 16; ( 7 ) 17, 18 Elov, A.A. (6) 158 El-Yazigi, A. (9) 262 Empfield, J.R. (1) 127 Engelhardt, L.M. (1) 39 Engelhardt, M. (5) 126 Engelke, U. (6) 39 Engels, J. (4) 76; (6) 5 Dzhiembaev, B.Zh. (9) 194 157 Eppstein, D.A. (6) 186 Dziegielewski, J . O . (1) 137 Epshtein, L.M. (9) 125 Erastov, O.A. (9) 94 Erhenfeld, G.M. (6) 324 Erickson, T.J. (7) 78 Eadie, J.S. (6) 169 Ericson, A.C. (6) 15 Eads, C.D. (6) 238 Eastman, A. (6) 363 Eriksson, S. (6) 241 Echsler, K.-J. (3) 25 Erkasov, R.Sh. (9) 256 Ermann, P. (7) 101, 104 Eckl, E. (1) 128 Eckstein, F. (6) 50, 54, Ermolaeva, L.V. (9) 17 88, 167, 202, 312, 374; Erneux, C. (6) 52 Ernst, L. (1) 212 (9) 51 Eddy, D.B. (5) 14 Ernst, R.R. (6) 376 Edery, I . ( 6 ) 350 Erzhanov, K.B. (1) 52 Edmonds, M. (4) 84; (6) Escalier, J. (6) 361 166 Escudig, J. (1) 256, 267, Efcavitch, J.W. (6) 153 352; (9) 107, 154 Effenberger, F. ( 4 ) 14; Espenbetov, A.A. (9) 194 Essenfeld, A.P. (7) 80 (5) 56 Efremov, Yu.Ya. (1) 382; Estekhina, M.N. (1) 2 (8) 132 Etemad-Moghadam, G. (1) Egamberdyev, Sh. ( 5 ) 109; 265; (4) 111 (9) 200 Eto, M. (5) 146 Egan, W. (4) 7; (6) 171 Evans, S.A. (1) 95, 96; Egert, E. (5) 100; (8) (2) 20-22 137 Everett, G.W. (6) 84 Ehrenreich, W. (1) 133; Evseev, A.M. (9) 248 Evtyagin, G.A. (9) 233 (9) 187 Ehresmann, B. (6) 305 Ehresmann, C. (6) 305 Ehrlich, K.C. (6) 320 Fackler, J.P. (7) 70 Ehrlich, M. (6) 320 Fahrney, D.E. (6) 42 Eisenbraun, E.J. (7) 81 Falck, J.R. (7) 121, 122 Ejchart, E. (9) 101 Fall, Y. (7) 134 Ejiri, E. (7) 148, 149 Fanni, T. (2) 34 Farag, R.S. (8) 35 Ekanger, R. (6) 55 Ekeland, R. (9) 167 Farnham, W.B. (2) 4 El-Anba, F. (1) 337 Farquhar, D. (6) 17 Elango, V. (7) 141 Faucher, J.P. (8) 88 El-Badawi, M. (5) 74 Fauq, A.H. (7) 129 El-Barbary, A.A. (5) 91, Fawzi, R. (1) 75 Fazakerley, G.V. (6) 377, 141; (9) 188 El-Batouti, M. (1) 220, 382

Author Index F a z i o , S.D. ( 6 ) 387 Feasey, N.D. (1) 120 Fedorov, S.G. ( 8 ) 97 Fedorova, O.S. ( 6 ) 283 Fehlhammer, W.P. ( 1 ) 206; (7) 13 Fenske, D. (1) 260, 261 F e r i n g a , B.L. ( 5 ) 114 Fernandez, I. ( 7 ) 153 F e r r e n t t i , L. ( 6 ) 155 F e r r e r i , C . ( 1 ) 87 Feshchenko, N.G. (1) 243; ( 4 ) 69; ( 9 ) 166 F i e l d , A . K . ( 6 ) 16 F i e l d e r , H.P. ( 9 ) 269 Fincham, J.K. ( 9 ) 218 Finet, J.P. (2) 9 Fi nk, J. (1) 326; ( 9 ) 30 F i n k l e r , S.H. ( 7 ) 89 F i o r e n z a , M. ( 7 ) 58 F i o r i n i , M. (1) 176 F i s c h e r , J. (1) 342, 363, 372; ( 3 ) 7 Fitzsimmons, B . J . ( 7 ) 120 Fl anagan, J.M. ( 6 ) 386 F l e m i n g , H.W. ( 9 ) 141 F l e t c h e r , P. ( 6 ) 71 F l i e s s , A. ( 6 ) 318, 319 F l i t s c h , W . (1) 199; ( 7 ) 35, 45 F loyd, T.R. ( 6 ) 385, 387 Fl uck, E. (1) 68, 211; ( 2 ) 1 8 ; ( 7 ) 15; ( 9 ) 199 Fodor, G. ( 7 ) 162 Fodor, S.P.A. ( 6 ) 396 F o l l i n g , P. ( 1 ) 309 F o e r s t e r , H. ( 9 ) 57 F ontai ne, X.L.R. (1) 116 F o r c e l l e s e , M.L. ( 7 ) 151 Ford, J.R. ( 8 ) 142 F or d, R . R . ( 1 ) 154, 295; ( 8 ) 26 F o r r e s t , . B . J . ( 9 ) 97 For s t ova, J . ( 6 ) 103 FOSS, V.L. ( 1 ) 184; ( 4 ) 45; ( 5 ) 159, 160; (8) 27, 39, 40 Fout s, C.S. ( 6 ) 376 Fox, J . L . (1) 55; ( 3 ) 9 ; ( 9 ) 156 Fox, K . R . ( 6 ) 314 Fraenkel-Conrat, H . ( 6 ) 213 Fr ancke, R. (5) 6 F r a nczek, F.R. ( 5 ) 8 5 Frank, A . ( 6 ) 318 Fr ank, M. ( 6 ) 394 Frank, R. ( 6 ) 177, 303 Franke, E. ( 1 ) 335 Franke, L.A. ( 6 ) 276 F r a n k l i n , W . A . ( 6 ) 259 FrazZo, C.M.F. (1) 189;

43 1 ( 6 ) 35 (7) 9 G a r r e t t , G . ( 5 ) 124 F r e b e l , M. (1) 285, 286 Garrou, P.E. (1) 1 1 8 , F r e e d , J.J. ( 6 ) 12 119; ( 8 ) 159 Freeman, A. ( 9 ) 115 G a s e t , A. ( 7 ) 25 F r e i d z o n , Ya.S. ( 8 ) 169 Gasparro, F.P. ( 6 ) 258 F r e i s t , W. ( 6 ) 65 G a s s n e r , T. (7) 46 French, R . J . ( 9 ) 226 G a u t h i e r , J.Y. ( 7 ) 115 F r e n k e l , K . ( 6 ) 269 G a v a r i n i , H.O. ( 9 ) 7 5 , 76 F r e sc o , J . R . ( 6 ) 258 Gaydoul, K.-R. ( 1 ) 3; ( 3 ) Frey, F.W. ( 1 ) 5 6 , 57 F r e y , M.H. ( 6 ) 376; ( 9 ) 2, 3 Gayen, A . K . ( 7 ) 39 72 Gazizova, L.Kh. ( 9 ) 9 5 F r e y , P.A. ( 5 ) 38; ( 9 ) 50 Gee, Y.G. ( 6 ) 105 Friedman, J . M . ( 5 ) 28 G e f e l , E . I . (9) 82 F r i j n s , J . H . G . ( 3 ) 43 Gehrke, C.W. ( 6 ) 320 F r i t z , G. ( 1 ) 23-26 Gellman, S.H. ( 5 ) 23 F r i t z , H . (9) 81 Gensheimer, H.-P. ( 6 ) 53 F r i t z , H.-J. ( 6 ) 321 F r i t z , H.P. (1) 8 0 ; ( 7 ) 7 G e n tn e r , N.E. ( 6 ) 261 George, R.D. ( 6 ) 11 F r o e h l e r , B.C. ( 4 ) 79; G e r a n t i , L. ( 8 ) 10 ( 6 ) 28 Gereke, R . ( 4 ) 9 8 F r o l o v a , S.B. ( 6 ) 250 Gerhard, J . ( 5 ) 145 Froment, F. ( 5 ) 1 1 8 ; ( 9 ) Germa, H. (1) 247; ( 8 ) 1 45 Germeshausen, J . (1) 1 9 ; Fronczek, F. ( 9 ) 100 ( 6 ) 16; ( 9 ) 32 F r o s t , J.W. ( 5 ) 110 G e r ts y u k , M.N. ( 8 ) 14 F r y , S.E. (1) 241 G e r v a is , D. (1) 41 Fuchs, P.L. (1) 192 F u c i a r e l l i , A . F . ( 6 ) 271 Gettleman, L. ( 8 ) 186 G h a t t a s , A.B.A.G. ( 5 ) 91; F u j i i , M. ( 6 ) 29 ( 9 ) 188 Fujimura, R . K . ( 6 ) 386 Gibbs, D.E. (5) 6 9 , 70 F u j i t a , F. ( 8 ) 184 Gibbs, E.J. ( 6 ) 238 F u j i t a , J . (1) 27 G ie r e n , A. ( 1 ) 186; ( 9 ) F u j i wa r a , M. ( 3 ) 45 187 F u j i wa r a , T. ( 6 ) 25 G ig a n tin o , J.J. (2) 19 Fukui, T. ( 6 ) 235, 236 G i l b e r t , J . C . ( 7 ) 95 Fukuzumi, K . ( 7 ) 130 Gilbert, W. (6) 3 F u l i e r o v a , A . (8) 1 2 G i l e s , J.W. ( 6 ) 150 F u r i n , G.G. ( 2 ) 1 7 ; ( 9 ) Gilheany, D.G. ( 9 ) 173 104, 149 G im a tila k a , A.A.L. ( 7 ) F u r l o n g , J . C . ( 6 ) 306 142 F y t a s , G. ( 8 ) 142 Gimautdinova, 0.1. ( 6 ) 250 Ginsburg, A . ( 6 ) 69 Gaffney, B.L. ( 6 ) 1 2 6 , Giongo, G.M. ( 1 ) 176 135 G ir o , G . ( 8 ) 1 7 2 , 173 G a i t , M . J . ( 6 ) 115 G a i t z s c h , E. ( 1 ) 314, G l a s s , R.S. ( 3 ) 12; (9) 43 315, 317; ( 7 ) 6 ; ( 9 ) Glave, S.A. ( 6 ) 175 37, 165 G a i t z s c h , T. (1) 314, 316 Gleiter, R . ( 9 ) 147 G l e r i a , M. ( 8 ) 6 1 , 69-73, Galat, A. ( 6 ) 380 163, 171, 173 Galazka, G . ( 6 ) 267 G lid e w e ll, C. ( 9 ) 1 1 1 , Galeeva, I . Z . (1) 380; 112 ( 9 ) 174 Gloede, J. (1) 160; ( 2 ) G a l l o , K.A. ( 4 ) 7 , 93; 37; ( 4 ) 55 ( 5 ) 46; ( 6 ) 146, 171 Glowiak, T. ( 9 ) 191 Gao, X. ( 6 ) 126 Gloyna, D. ( 9 ) 143 Ga r b a r i n o , J . E . ( 6 ) 230 Gluber, N.S. ( 9 ) 124 Garbauskas, M.F. (1) 127 Glushakov, S.N. ( 8 ) 177 G a r c i a , B. ( 7 ) 153 Gnewuch, T. ( 6 ) 195 Garegg, P.J. ( 4 ) 7 9 , 8 1 ;


432 Gnuchev, N.V. ( 6 ) 97 Godovikov, N.N. ( 9 ) 184 Godovikova, T.S. ( 6 ) 249 Goldner, W. ( 1 ) 20 Goghova, M. ( 9 ) 86 Gogte, V.N. ( 9 ) 239 Goh, K.M. ( 9 ) 21 Gol, F. ( 1 ) 69 Goldberg, I . ( 1 ) 169; (5) 89 Goldberg, J . M . ( 6 ) 366 Gol'dfarb, E.I. ( 9 ) 102 Gol'dfarb, E.L. ( 5 ) 158 Gol'din, G.S. ( 8 ) 97 Golina, S . I . ( 8 ) 177 Goljer, I. ( 9 ) 86 Golobish, T.D. ( 1 ) 127 Gololobov, Yu.G. ( 9 ) 203 Gomelya, N.D. ( 9 ) 166 Gonbeau, D. ( 8 ) 6; ( 9 ) 5 , 15 Goodman, D.S. (7) 100 Goody, R.S. ( 6 ) 87 Gordan, M.S. ( 9 ) 6 Gordillo, B. ( 3 ) 41 Gordon, M.S. ( 1 ) 248, 249; ( 7 ) 5 ; ( 9 ) 1 Gorenstein, D.G. ( 2 ) 34; (5) 25 Gorn, V.V. ( 6 ) 151, 156 Gornicki, P. ( 6 ) 273, 274, 277 Gorshunov, I.Yu. ( 4 ) 36 Gottikh, M.B. ( 6 ) 159 Gowda, G. ( 7 ) 150 Gozman, I . P . (9) 102 Grabowski, G. ( 9 ) 126 Grachev, M.A. ( 4 ) 68; ( 6 ) 237 Gradov, V.A. ( 1 ) 141, 142 Graff, M. ( 7 ) 91 Graham, J.B. ( 1 ) 103 Gralla, J . D . ( 6 ) 309 Gramstad, T. ( 3 ) 15 Graves, D.F. ( 8 ) 133 Grebowicz, J. ( 8 ) 162 Green, M . J . ( 7 ) 117 Gregoli, S. ( 6 ) 272 Grekov, L . I . ( 1 ) 76 Grens, E. ( 6 ) 209 Greuer, B. ( 6 ) 292 Grice, P. ( 7 ) 124 Grieco, P.A. ( 7 ) 137 Griffin, J.H. ( 1 ) 30 Griffiths, D.V. ( 4 ) 23, 24; ( 7 ) 19 Griller, D. ( 9 ) 255 Grimley, E. ( 1 ) 4 Grobe, G. ( 9 ) 35 Grobe, J. ( 1 ) 131, 268, 278-280; ( 9 ) 236 Grochowski, E. ( 1 ) 108

Grotzinger, L. ( 1 ) 175 Groginsky, C.M. ( 6 ) 150 Gromov, A.V. (9) 82 Gromova, E.S. ( 6 ) 316, 317 Gronchi, G. ( 1 ) 136, 267; ( 9 ) 107, 110 Groner, P. ( 9 ) 130, 227 Gross, E. ( 1 ) 350 Gross, H. ( 2 ) 37; (5) 84 Gross, M. ( 1 ) 374 Gross, R. ( 9 ) 116 Grosse, F. ( 6 ) 303 Grossmann, G. ( 9 ) 78, 80 Gruner, M. ( 9 ) 78 Gruszeoka, E. ( 9 ) 191 Gruys, K.J. ( 6 ) 86 Gudat, D. ( 1 ) 250, 287, 288; ( 4 ) 103; ( 8 ) 23; ( 9 ) 146 Guengerich, F.P. ( 6 ) 256 Guerch, G. ( 8 ) 6 7 , 88 Guerrier-Takada, C. ( 6 ) 347, 348 Guerro, A. ( 3 ) 39 Guth, W. ( 1 ) 64; ( 4 ) 33 Guga, P. (5) 37; ( 6 ) 51; ( 9 ) 49 Gulbenkian, A.R. ( 7 ) 117 Guldner, K. ( 1 ) 133 Gumport, R . I . ( 6 ) 211 Gunn, B.P. ( 7 ) 119 Gupta, K.C. ( 4 ) 70; ( 6 ) 149; ( 9 ) 226 Gupta, R.K. ( 9 ) 208 Gupta, S.K. ( 7 ) 143 Gurevich, P.A. ( 1 ) 224; ( 4 ) 10, 47 Gurov, M.V. (5) 159, 160; ( 8 ) 39, 40 Guschlbauer, W. ( 6 ) 382 Guseinova, M.M. ( 4 ) 59, 60 Gusev, A . I . ( 1 ) 146; ( 9 ) 161 Gutsche, C.D. ( 9 ) 99 Guy, A. 6 ) 141 Gwara, J (5) 126 Gzewczyk J. ( 5 ) 101 Haake, P ( 9 ) 89 Haas, A. ( 4 ) 28; ( 5 ) 15 Haase. M (1) 158 Habib; M. (lj 48 Hacklin, H. ( 2 ) 41 Hackney, M.L.J. (1) 51; ( 4 ) 46 Hadden, S. ( 6 ) 126 Haddon, R.C. ( 8 ) 62, 65; ( 9 ) 118 Hagele, G. ( 1 ) 156; ( 5 )

126; ( 9 ) 185 Haelters, J.P. ( 4 ) 5 ; ( 5 ) 73 Haeuptle, M.-T. ( 6 ) 177 Hagan, M.P. ( 6 ) 266 Hagerman, P.J. ( 6 ) 391 Hagihara, M. ( 5 ) 50; ( 7 ) 84 Hagnauer, G.L. ( 8 ) 142, 144 Hahn, J. (1) 22, 138; ( 3 ) 10 Hai, T.T. ( 6 ) 62-64 Hajj, A.N. ( 5 ) 148 Hakeem, N.A. ( 6 ) 43 Halasa, A.F. ( 8 ) 150 Halet, J.F. (1) 214; ( 9 ) 168 Haley, B.E. ( 6 ) 71 Hall, C.D. ( 1 ) 99; ( 2 ) 23, 48; ( 4 ) 26 Hall, C.R. ( 5 ) 147 Haltiwanger, R.C. ( 4 ) 41, 53, 58; ( 9 ) 162, 164 Hamblin, M.R. (6) 253 Hamill, R.L. ( 6 ) 11 Hammond, P . J . ( 2 ) 48 Hampton, A. ( 6 ) 1 2 , 62-64 Han, C.-Q. ( 7 ) 114 Han, F.-S. ( 6 ) 173 Hanack, M. ( 7 ) 152 Hanafusa, T. ( 9 ) 46 Hanawalt, E.M. ( 1 ) 228; ( 7 ) 55 Hanaya, T. ( 5 ) 66 Hanecker, E. ( 1 ) 171; ( 4 ) 108 Hanna, A . G . (5) 49; ( 9 ) 84 Hanna, M.M. ( 6 ) 91 Hanna, M.T. ( 1 ) 220, 221 Hansen, D.E. ( 6 ) 79 Hansen, H.F. ( 5 ) 140 Hanski, E. ( 6 ) 6 Harada, F. ( 6 ) 311 Harger, M.J.P. ( 5 ) 155157 Haris, G.S. ( 9 ) 234 Harmon, R.E. ( 7 ) 143 Harnett, S.P. ( 6 ) 77, 78 Harris, D.H. ( 1 ) 387; ( 8 ) 131, 135, 136 Harris, G. ( 6 ) 94 Harris, R.K. ( 9 ) 58 Harris, T.M. ( 6 ) 256 Harris, T.V. ( 1 ) 71 Harrison, A.W. ( 7 ) 155 Harrowfield, J . M . ( 1 ) 39 Harshman, K.D. ( 6 ) 334 Hartley, J . A . ( 6 ) 255 Hartmann, B. (6) 395 Hartmann, G.R. ( 6 ) 237

433

Author Index Hartwick, R . A . ( 6 ) 385, 387

Haseltine, W . A .

( 6 ) 259,

262, 329

Hashimoto, H. ( 7 ) 37 Hashimoto, Y. ( 6 ) 49 Hassall, C.H. ( 5 ) 104 Hassan, F.S.M. ( 1 ) 116 Hassan, M.E. ( 6 ) 19 Hassanein, M. (1) 193, 240

Hasung, 0. ( 9 ) 81 Hata, T. ( 6 ) 29, 95, 1 1113, 128, 165

Hattori, K . ( 6 ) 58 Haubenstock, H. ( 1 ) 88 Haubold, R. ( 1 ) 131 Hausen. H.-D. (1) 68 Hayakawa, Y . ( 4 ) ' 8 5 ; ( 6 ) 108

Hayashi, H. ( 6 ) 397 Hayashi, Y. ( 6 ) 49 Hayatsu, H. ( 6 ) 214, 215, 297

Haydock, K. ( 6 ) 348 Hayes, J . E . ( 1 ) 228; ( 7 ) 55 Hayes, R.C. ( 6 ) 265 Heathcock, C.H. ( 7 ) 158 Heberhold, M. (1) 133 Hecht, S.M. ( 6 ) 323, 324, 335

Hedberg, K. ( 9 ) 226 Hedden, D. ( 1 ) 70 Hegarty, A . F . ,(1) 251255; ( 8 ) 2

Heikkila, J. ( 6 ) 129 Heine, H.W. ( 1 ) 127 Heine, .J. ( 2 ) 41, 42; ( 5 ) 6 Heiner, C.R. ( 6 ) 153, 299 Heinicke, J. (1) 375 He'lzne, C . ( 6 ) 161, 178 Helioui, M. ( 8 ) 146 Helle, M . A . ( 7 ) 82 Helmchen, G. ( 7 ) 145 Hendry, P. ( 5 ) 24 Hennen, W . J . (1) 100; ( 4 ) 29

Henner, W.D. ( 6 ) 329 Henrie, R.N. ( 6 ) 201 Herberhold, M. ( 9 ) 187 Herbst, R. ( 8 ) 137 Herdering, W. ( 4 ) 89; ( 6 ) 37

Hergenrother, W.L. ( 8 ) 150 Herman, T. ( 6 ) 223 Hernandez, P.E. ( 7 ) 123 Herr, R. ( 1 ) 115, 198; ( 9 ) 169

Herr; W. (6) 307

Herring, A.M. ( 1 ) 117 Herrmann, E. ( 4 ) 31; ( 8 ) 149; ( 9 ) 8 0

Herrmann, R. ( 8 ) 20 Herrndorf, M. ( 1 ) 257 Hertzberg, R.P. ( 6 ) 335 Hess, H. ( 9 ) 199 Heubach, G. ( 1 ) 190 Heubel, J . ( 8 ) 44 Hewson, A.T. ( 7 ) 157 Heydt, H. ( 3 ) 24. 26; ( 4 ) 99

Hibbert, R . C . ( 9 ) 77 Hibino, S. ( 5 ) 152 Hietkamp, S. ( 1 ) 1 2 , 6 9 , 121; ( 4 ) 4 3

Higashizaki, S. ( 9 ) 243 Higgins, S.J. ( 1 ) 116,

209

Holt, M.S. (1) 367 Holtzclaw, J . R . ( 9 ) 237 Holwitt, E. ( 6 ) 266 Holy, A . ( 6 ) 23, 24 Holzapfel, W. ( 7 ) 8 9 Honjo, M . ( 6 ) 25 Honnens, J. ( 4 ) 40 Honrath, U. ( 1 ) 153 Hood, L.E. ( 6 ) 299, 300 Hopkins-Davis, T. ( 6 ) 221 Hoppe, I . ( 5 ) 100 Hoppe, J . ( 6 ) 65 Hopton, D. ( 5 ) 112; ( 9 ) 23

Horn, T. ( 6 ) 105, 152 Horner, L. ( 5 ) 145; ( 9 ) 141

117

Horvath, S . J . ( 6 ) 280 Horwitz, S.B. ( 6 ) 328 Higuchi, M. ( 8 ) 165 Hoskins, B.F. ( 9 ) 208 Higuchi, S. ( 6 ) 112 Higuchi, T. (1) 263, 274, Hosoda, A. ( 7 ) 103 275 Hosseini, H.E. (1) 277 Hostomsky, 2. (6) 103 Hill, T.G. ( 4 ) 4 1 , 53; Hotoda, H. ( 6 ) 112 ( 9 ) 164 Hiller, W. (1) 75; ( 9 ) 57 Houkom, E. ( 6 ) 223 Hountondji, C. ( 6 ) 233 Himes, R . H . ( 6 ) 8 4 , 240 Hindman, J . C . ( 7 ) 154 Houriet, R. ( 3 ) 1 7 ; ( 9 ) 246 Hingerty, B.E. ( 6 ) 288 Hinke, A. (1) 264 Hovnanian, N. ( 1 ) 123 Hinke, A.M. ( 1 ) 264 Howard, F.B. ( 6 ) 192 Hirakawa, M. ( 8 ) 184 Howell, J.A.S. ( 1 ) 81 Hiraksuka, 1. ( 5 ) 151 Hoyer, D. (1) 8 4 Hirao, I. ( 1 ) 205; ( 5 ) Hoyer, P.B. ( 6 ) 71 Hsu, A . ( 6 ) 220 130; ( 7 ) 8 8 , 94 Hirao, T. ( 5 ) 50; ( 7 ) 84 Hsu, C.Y.J. (6) 162 Hiremath, S.P. ( 6 ) 61 HSU, S.-H. ( 6 ) 387 Hirooka, S. ( 7 ) 148 Huang, Y . ( 7 ) 27 Hirotsu, K . ( 1 ) 263, 274, Huber, B. ( 1 ) 310, 356 275 Huber, R. ( 5 ) 103; ( 9 ) 9 8 Hitchcock, P.B. ( 1 ) 329, Hubert-Pfalzgraf, L.G. 364

Hixson, S.S. ( 6 ) 275, 276 Hnilica, L.S. ( 6 ) 296 Hobbs, J . B . ( 6 ) 106 Hockensmith, J.W. ( 6 ) 293 Hodge, P. (1) 86 Hodgson, M. (1) 239 Hock, N. ( 1 ) 50 Honle, W. ( 1 ) 25, 264 Hoeve, V . ( 8 ) 125 Hoffmann, R.W. ( 7 ) 90 Hofmann, F. ( 6 ) 53 Hofmockel, U. ( 1 ) 287 Hogan, M.E. ( 6 ) 310 Hogarth, G. ( 1 ) 122 Holloway, S.J. ( 7 ) 135 Holmes, J.M. ( 1 ) 303, 304; ( 9 ) 153 Holmes, R . R . ( 1 ) 303, 304: ( 9 ) 153 Holt,'E..M: ( 5 ) 1 4 ; ( 9 )

( 1 ) 123

Hubner, T. ( 1 ) 186; ( 9 ) 187

Hudson, H.R. ( 4 ) 8 Hughes, L.R. ( 7 ) 87 Hughes, P. ( 6 ) 299 Hullin, R. ( 6 ) 53 Humayun, M.Z. ( 6 ) 257 Hundhammer, B. (1) 244 Hunerbein, J . ( 9 ) 158 Hung, S.C. (1) 1 5 Hunsaker, W.R. (6) 204 Hunt, J.E. (7) 154 Hunting, D.J. ( 6 ) 29 Huque, T. ( 6 ) 6 Hurley, L.H. ( 6 ) 335 Hurst, R.R. ( 9 ) 72 Hursthouse, M.B. ( 8 ) 37 ; ( 9 ) 1 7 9 , 218

Husebye, S. ( 3 ) 1 5 ; 172

9)

434 228 Ionkin, A.S. ( 9 ) 94 I o t o , K. ( 9 ) 3 I s a a c s , N.S. ( 1 ) 222; ( 7 ) 24 I s a e v a , G.M. (1) 52 I s a g u l y a n t s , M.G. ( 6 ) 315 Isenbeg, G. ( 6 ) 239 I s h i d a , M. ( 1 ) 238 I s h i h a r a , T. ( 5 ) 123 I s h i i , K . ( 5 ) 46 Ishmaeva, E.A. (1) 320 Ismaev, I.E. ( 9 ) 8 3 I s s l e i b , K. ( 1 ) 29, 31, Ibrahim, E.H.M. ( 8 ) 35 40, 283; ( 4 ) 13, 1 7 , 34, 42; ( 5 ) 52, 60; ( 9 ) I d e , H. ( 6 ) 263 I g l o i , G.L. ( 6 ) 226 64 I t a i , A. ( 9 ) 183 I g n a t ' e v , N.V. ( 2 ) 17 I t o , T. ( 4 ) 75; ( 6 ) 33, I g n a t ' e v , Yu.A. ( 9 ) 109 I g n a t o v , M.E. ( 8 ) 118; 119 Ivanov, B.E. ( 1 ) 191 ( 9 ) 245 Ivanova, E.M. ( 6 ) 170; I g o l e n , J. ( 6 ) 148, 381 I i o , H. ( 7 ) 36 ( 9 ) 41 Ivanova, N.A. (8) 130; Ikeda, S. ( 6 ) 219 I k e h a r a , M. ( 4 ) 77 ( 9 ) 232 I k e h a r a , M. ( 6 ) 30, 36, Ivanova, N.L. ( 4 ) 68 120, 133, 134, 210 Ivanovskaya, M.G. ( 6 ) 159, 315 Iksanova, S.V. ( 4 ) 109 I v e s , D.H. ( 6 ) 219 I l ' i c h e v , S.A. ( 9 ) 192 I v i n , B.A. (5) 136; ( 9 ) I l ' i n , E.G. ( 8 ) 118; ( 9 ) 245 140 I l ' i n a , M.B. ( 8 ) 174, 175 Iwai, S. ( 6 ) 121 I w a m i , H . ( 6 ) 40 I l ' y a s o v , A.V. ( 1 ) 380; Iwata, T. (1) 238 ( 9 ) 83, 90, 109, 174 I m a i , J. ( 4 ) 91; ( 6 ) 182, I z a n t , J . G . ( 6 ) 179 184 Imai, K. ( 4 ) 75; ( 5 ) 70; Jackson, R.F.W. ( 7 ) 127 ( 6 ) 33 J a c k s t i e s , W. ( 1 ) 72 Imai, S. ( 9 ) 20 Jacob, K. ( 9 ) 261 Imamoto, T . (1) 58, 59; Jacobsen, G.B. ( 1 ) 116, ( 3 ) 18, 19 117 Imbach, J.-L. ( 6 ) 144, Jacobsen, J . S . ( 6 ) 257 145 Jacobson, K.B. ( 6 ) 386 Immenkeppel, M. ( 1 ) 282 Jacobson, M.K. ( 6 ) 100 Imura, A. ( 6 ) 142 J a e g e r , D.A. ( 1 ) 223, I n a g a k i , K. ( 6 ) 365 Inamoto, N. (1) 263, 274, 236, 237; ( 9 ) 251 J a e n i c k e , L. ( 7 ) 146 275, 313; ( 5 ) 76; ( 7 ) Jagendorf, A.T. ( 6 ) 230 71; ( 8 ) 48; ( 9 ) 3 J a i n , V.K. ( 9 ) 208 I n c h , T.D. ( 5 ) 147 Jakubowski, H. ( 6 ) 101 Indzhikyan, M.G. ( 1 ) 82 Jamali, H.A.R. ( 4 ) 23 I n g o l d , K.U. ( 9 ) 113 Jarnil, Z. ( 1 ) 177 Inoguchi, Y. ( 9 ) 183 J a n i c e k , M.F. ( 6 ) 329 Inokawa, S. ( 4 ) 96; (5) J a n o u t , V. ( 8 ) 157 66, 132 J a n s e n , W. ( 5 ) 111 Inoue, H. ( 6 ) 121, 142 Inoue, T. ( 6 ) 188 J a n s s e n , R.A.J. (9) 114 Inoue, Y. ( 7 ) 37 J a n s z , H.S. ( 6 ) 354 Inouye, Y. ( 5 ) 152 J a r o r i , G.K. ( 6 ) 356 Inskeep, P.B. ( 6 ) 256 J a r r e l l , K.A. ( 6 ) 341 J a s i n s k i , J. (5) 14; ( 9 ) I o n i n , B . I . ( 1 ) 151; ( 2 ) 209 46; ( 5 ) 2 , 48, 75; ( 9 )

Hussong, R . ( 3 ) 24; ( 4 ) 99 Hutchins, R.O. ( 3 ) 12; ( 9 ) 43 Hutchinson, D.W. ( 5 ) 119, 121; ( 9 ) 238; ( 6 ) 102 H u t t n e r , G. ( 1 ) 262, 269, 270, 345, 346 Hutton, A.T. ( 5 ) 45 Huynh-Dinh, T. ( 6 ) 148, 381 Hyver, K . J . ( 6 ) 6 3

Organophosphorus Chemistry J a s t o r f f , B. ( 6 ) 52, 53, 56, 57, 400 Jaw, J.Y. ( 7 ) 49 J e a n n i n , Y . ( 1 ) 16; ( 9 ) 73 Jemmis, E.D. ( 9 ) 11 J e n c k , J. ( 1 ) 112-114 J e n k i n s , B.G. ( 6 ) 377 J e n k i n s , I . D . ( 1 ) 109; ( 2 ) 36 J e r n s t e d t , K.K. (5) 11 J i b r i l , I. ( 1 ) 345 J i n g , X. ( 9 ) 119 J i n g l i n , Z. ( 1 ) 383 Jb'rg, K . ( 1 ) 310, 349, 350 Joergensen, P. ( 5 ) 142 John, A. ( 9 ) 80 Johns, R.B. ( 5 ) 12 Johnson, D.L. ( 6 ) 286 Johnson, K.A. ( 6 ) 201 Johnson, L.D. ( 6 ) 261 Johnson, N.P. ( 6 ) 361 Johnson, P.D. ( 7 ) 155; ( 9 ) 130 J o n e s , P.G. ( 8 ) 51 J o n e s , R.A. ( 1 ) 259; ( 6 ) 126, 135, 162, 383 J o n e s , T.R. ( 7 ) 115 J o v i n , T.M. ( 6 ) 196 J u a r i s t i , E. ( 3 ) 1 2 , 13, 41; ( 9 ) 43, 176 Judek, M. ( 6 ) 274 Juneau, M.K. ( 8 ) 153 Juodka, B.A. ( 6 ) 41 J u s t , G. ( 5 ) 117 Kabachnik, M . I . ( 5 ) 8 4 , 135; (9) 184, 250 Kabachnik, M.M. (1) 1 3 , 1 4 , 179; ( 2 ) 49; ( 4 ) 1 9 , 51, 52; ( 5 ) 107 Kabbani, A. ( 5 ) 148 Kachkovskaya, L.S. ( 1 ) 297; ( 9 ) 31 Kada, R. ( 8 ) 12 Kadyrov, R.A. ( 9 ) 135, 136 K a f a r s k i , P. ( 5 ) 98; ( 9 ) 267 Kaga, K. (1) 238 Kagan, H.B. ( 1 ) 110; ( 9 ) 59 Kagawa, Y. ( 6 ) 245 Kaim, W. ( 9 ) 116 Kaiser, K. ( 6 ) 138 Kaiser, M. ( 5 ) 49 Kaiser, N.F. ( 6 ) 153 Kaiser, R . J . ( 6 ) 299 Kajiwara, M. ( 8 ) 102, 182 Kakadii, L . I . ( 5 ) 116

435

Author Index Kakiuchi , H . ( 1 ) 194 Kakuchi, J . ( 6 ) 311 Kalasinsky, V.F. ( 1 ) 330 Kalbitzer, H . R . ( 6 ) 373 Kal'chenko, V.I. ( 2 ) 61, 62; ( 9 ) 53, 54, 6 6 , 71 Kalinichenko, E.N. (6) 185 Kalisch, B.W. ( 6 ) 196 Kallmerten, J . ( 3 ) 33 Kalman, A . ( 6 ) 44 Kamber, M . ( 5 ) 117 Kamimura, ' 7 . ( 6 ) 95 Kamishiro, J . ( 6 ) 40 Kanemasa, S. ( 7 ) 93 Kanjolia, R.K. ( 1 ) 208 Kant, M. ( 2 ) 60 Kao, S.-C. ( 6 ) 194 Kapetanovic, E. ( 6 ) 228 Kaplan, B.E. ( 6 ) 150 Kappler, F. ( 6 ) 12, 62-64 Kapur, O.P. ( 9 ) 265 Karaghiosoff, K. ( 1 ) 358, 377; ( 4 ) 104; ( 9 ) 152, 182 Karas, M. ( 9 ) 86 Kardinov, N . A . ( 9 ) 184 Karelov, A . A . ( 4 ) 71 Kargin, Yu.M. ( 9 ) 109, 233 Karkas, J.D. (6) 16 Karnik, S.S. ( 6 ) 155 Karpova, G . G . ( 6 ) 250 Karpova, R . D . ( 1 ) 143 Karsch, H.H. ( 1 ) 43-45, 305, 310; ( 7 ) 11 Karthikeyan, S. ( 8 ) 90 Karuppiah, N . ( 6 ) 48 Kashemirov, B.A. ( 5 ) 77, 116; ( 8 ) 19 Kashiwabara, K. (1) 27 Kashman, Y. (1) 169; (5) 89 Kaslina, N . A . ( 5 ) 96, 9 7 , 135; ( 9 ) 253 Kasukhin, L.F. ( 8 ) 9 Katahira, M. (6) 397 Katerinopoulos, H. ( 7 ) 118 Kato, H . ( 4 ) 8 5 ; (6) 108 Kato, M. (1) 168; ( 3 ) 8 Kato, S. ( 1 ) 238 Kato, T. ( 7 ) 148 Katti, K.V. ( 8 ) 103, 116, 137 Katz, J . J . ( 7 ) 154 Kaub, J . (1) 335 Kauffmann, T. ( 1 ) 3 ; ( 3 ) 2 , 3 , 25 Kawakami, N . ( 6 ) 40 Kawamoto, H . ( 5 ) 66 Kawanobe, W . ( 4 ) 67

Kawashima, T. (5) 76; ( 7 ) 71 Kay, P.B. ( 2 ) 14; ( 5 ) 20; ( 9 ) 4 7 , 4 8 , 55 Kazankova, M . A . ( 1 ) 148, 149 Kazimierzcuk, 2. ( 6 ) 46 Kean, J.M. ( 6 ) 336 Keana, J.F.W. ( 5 ) 1 1 Keat, R . ( 8 ) 66 Keglevich, G. ( 1 ) 173 Kehne, A . ( 4 ) 8 9 ; ( 6 ) 38, 136 Keitel, 1. (5) 84 Kelbanskii, E.O. ( 1 ) 331 Keller, H. ( 1 ) 319; ( 3 ) 21 Keller, K. ( 7 ) 8 Kellogg, R . M . ( 1 ) 3 0 ; ( 5 ) 114 Kelly, J.W. (1) 9 5 , 9 6 ; ( 2 ) 20-22; ( 6 ) 366 Kelly, T..J. ( 6 ) 222 Kemp, R . A . ( 1 ) 353, 354; ( 4 ) 1 , 106; ( 9 ) 190 Kennedy, D . A . ( 9 ) 173 Kent, D.E. ( 5 ) 80 Kent, J . R . (6) 343 Kent, S.B.H. ( 6 ) 299 Kerby, M.C. (1) 155 Kern, C.W. ( 3 ) 17; ( 9 ) 246 Kernan, P . A . (6) 11 Kesbeke, E. (6) 57 Kessenikh, A.V. ( 5 ) 9 6 , 9 7 , 135; ( 9 ) 253 Kezdy, F . J . ( 6 ) 173 Khafizova, G.S. ( 2 ) 52 Khailova, N . A . ( 1 ) 182 Khairullin, V.K. ( 1 ) 182 Khalil, F.Y. ( 1 ) 220, 221 Khammatova, Z.M. ( 9 ) 8 3 Khan, N.N. ( 6 ) 66 Khardin, A.P. ( 1 ) 76 Kharitonov, V.G. (1) 204 Kharitonov, Yu.Yu. ( 9 ) 122 Khbeis, S.G. ( 9 ) 196 Khokhlov, P.S. ( 1 ) 144; ( 5 ) 1 3 , 77, 116; (8) 19 Khorana, H.G. (6) 155 Khropov, Yu.V. (6: 232 Khusainova, N . G . ( 5 ) 125; ( 8 ) 132 Khusnutdinova, E.K. ( 2 ) 52 Kibardina, L.K. ( 4 ) 56 Kibrik, G.E. ( 9 ) 7r3 Kidani, Y . ( 6 ) 365 Kiefer, G.E. ( 7 ) 8 5 Kiekel. C. (. 8,) 168 Kierzek, R. ( 4 ) 8 3 . 8 4 ;

( 6 ) 123, 124, 130, 166 Kilkurkie, R.E. ( 6 ) 323, 324 Kim, C.H. ( 8 ) 113 Kim, D.Y. (5) 61 Kim, T.V. ( 9 ) 203, 212 Kim, U.Y. ( 8 ) 113 King, C. 5 ) 85; ( 9 ) 100 King, C.M ( 6 ) 286 King, R . B (1) 6 3 ; ( 4 ) 32 Kingston, E.E. (6) 43 Kini, G.D (1) 100; ( 4 ) 29 Kinochita M. ( 5 ) 105 Kirby, A . . ( 5 ) 31 Kireyev, V.V. ( 9 ) 219 Kirfel, A . ( 8 ) 49; ( 9 ) 180 Kirilov, M. (7) 76, 77 Kirzow, K.H. ( 1 ) 303 Kischkel, H . (1) 159; ( 2 ) 27 Kise, H. ( 7 ) 6 3 Kiseleva, E.I. ( 9 ) 203, 212 Kishi, Y. (7) 73 Kisilenko, A . A . ( 4 ) 69 Kitane, S. (5) 42 Kiuchel, P.W. ( 6 ) 384 Kjaer, A . ( 7 ) 159 Kjaer, D. ( 7 ) 159 Klaebe, A. ( 5 ) 21 Klebanskii, E.O. ( 4 ) 1 0 2 , 109, 110; ( 8 ) 24 Klehr, H. ( 1 ) 377; ( 4 ) 104 Kleiner, H . J . ( 1 ) 145 Klirnentova, G.Yu. ( 1 ) 224; ( 4 ) 1 0 , 47 Klingebiel, U. ( 1 ) 158 Klochkov, V.V. ( 9 ) 9 2 , 136 Klose, G. (9) 9 6 Kaosin'ski, P. ( 4 ) 1 1 2 Klug, A . ( 6 ) 353 Kluger, R . ( 2 ) 3 2 , 3 3 ; ( 5 ) 26, 27 Klysik, J. (6) 267 Knachel, H. ( 7 ) 70 Kneip, H.-G. ( 1 ) 199; ( 7 ) 35 Knierzinger, A. (5) 103; ( 9 ) 98 Knight, W.B. ( 5 ) 3 4 , 35 Knoch, F. (1) 271, 273, 299, 306-309, 312, 315317; ( 7 ) 6 ; ( 9 ) 6 2 , 151, 1 5 8 , 165 Knorre, D.G. ( 6 ) 114, 131, 249, 282, 283 Knouzi. N. ( 1 ) 106 Knowles, J . R . ( 5 ) 28; ( 6 ) 1

,


436 79 Knox, S.A.R. ( 1 ) 120, 122 Kobayashi, H. ( 1 ) 168; (3) 8; ( 6 ) 109 Kobayashi, M. ( 4 ) 96 Kobayashi, T. ( 1 ) 385; ( 4 ) 21 Kobayashi, Y. ( 6 ) 134; ( 7 ) 103 Kobayshi, K. ( 7 ) 52 Kober, R. ( 5 ) 102 Kobori, J . A . ( 6 ) 300 Koch, E.M. ( 6 ) 313 Kochergina, L.A. ( 5 ) 135; ( 9 ) 253 K ochervi nski i , V.V. (8) 169 Kockkanyan, R.O. ( 9 ) 91 Kodama, M. ( 7 ) 130 Koenig, M. ( 1 ) 265, 266; ( 4 ) 111 K oes sel , H. ( 6 ) 226 Kotz, J . ( 4 ) 13; ( 5 ) 52 Koga, N. ( 6 ) 256 Kogan, V.A. (8) 130; ( 9 ) 232 Kogoh, K. ( 9 ) 271 Koh, J.J. (1) 42 Kohn, K.W. ( 6 ) 255 Koidan, G.N. ( 1 ) 209, 232; ( 8 ) 31, 32, 46 Kojima, M. ( 8 ) 166, 167 Koketsu, J. ( 1 ) 126 K o l a t a , G.B. ( 6 ) 4 K o l l e r , B. ( 6 ) 224 Kolodyazhnyi, 0.1. ( 1 ) 281; ( 9 ) 29, 159 K o l o t i l o , N . V . ( 1 ) 301; (8) 130; ( 9 ) 27, 232 Komarov, E.V. ( 5 ) 2 Komarov, V.Ya. ( 9 ) 228 Komarova, N . I . ( 6 ) 250 Komina, T.V. ( 1 ) 224; ( 4 ) 10, 47 Konareva, I.E. ( 9 ) 65 Konarska, M.M. ( 6 ) 340 Kondo, M. ( 9 ) 60 Kondo, S. ( 4 ) 75; ( 6 ) 33 Kondo, Y. ( 9 ) 257 Konovalova, I . V . ( 2 ) 52 KOO, H.-S. ( 6 ) 391 Koole, L.H. ( 2 ) 16; ( 6 ) 371, 372; ( 9 ) 67 Kopola, N. ( 5 ) 40 Kopp, D.W. ( 4 ) 84; ( 6 ) 166 Kopylov, V.M. (8) 160; ( 9 ) 219 Koreeda, M. ( 7 ) 38 Korkin, A.A. (9) 8 Kormachev, V.V. ( 1 ) 141143

Kornilov, M.U. (9) 5 3 Kornuta, P.P. (8) 130; ( 9 ) 232 Ko r o b e i n i c h e r a , I . K . ( 9 ) 41 Koroleva, T . I . ( 9 ) 6 5 Korsakov, M.V. ( 5 ) 136; ( 9 ) 140 Korshak, V.V. (8) 9 1 , 9 4 , 1 7 4 , 175 Korshin, E.E. ( 4 ) 6 1 , 62; (5) 88 Korshunov, R.L. ( 1 ) 382; (8) 132 Kos, A . J . ( 7 ) 1; ( 9 ) 1 6 Kosacheva, E.M. ( 1 ) 191 Koshdel, E. ( 1 ) 8 6 Koslov, I . A . ( 6 ) 244 Ko st e r , H. ( 4 ) 9 0 K o s t i n , V.P. ( 4 ) 71, 72 Kosykh, V.G. ( 6 ) 317 Kottmann, H. ( 4 ) 1 4 ; ( 5 ) 56 Ko t t wi t z , B. ( 1 ) 152 Kovacs, J. ( 1 ) 104; (8) 1 1 , 12 Kovenya, V.A. ( 8 ) 36 Kovyazin, V.A. (8) 160; ( 9 ) 219 Kow, Y.K. ( 6 ) 263 Kowalski, J. ( 3 ) 1; ( 4 ) 22; ( 9 ) 191 Koyano, K . ( 1 ) 54 Kozarich, J . W . ( 6 ) 325, 326 Ko z i a r a , A . ( 5 ) 41 Kozlov, E.S. ( 8 ) 190 Kozlowski, S.A. ( 6 ) 135 Kraemer, R. ( 1 ) 341; ( 3 ) 22; ( 5 ) 92; ( 9 ) 8 6 K r a f f t , G.A. (1) 234; ( 4 ) 27 Krannich, L.K. ( 1 ) 208 K r a s i l ' n i k o v a , E.A. (5) 53 Krasnova, T.L. ( 1 ) 146; ( 9 ) 161 Kraszewski, A . ( 6 ) 140 K r a t z e r , R.H. ( 1 ) 387; (8) 1 3 1 , 135, 136 Kraus, M.A. (8) 181, 185 Krause, D. ( 6 ) 184 Krauss, G. ( 6 ) 303 Krauss, J . H . ( 6 ) 275 Krawczyk, E. ( 2 ) 31 Krebs, B. ( 1 ) 287, 318; ( 8 ) 22; ( 9 ) 189 Krech, F. (1) 31 K r e i d e r , D.G. ( 9 ) 39 K r e i s z , S. ( 7 ) 50 Kren, R.M. ( 1 ) 8 9 Kr e u t n e r , W. ( 7 ) 117

K r is c h , H.M. ( 6 ) 178 Krishnamurthy, M.N. ( 9 ) 265 Krishnamurthy, S.S. (8) 7 0 , 80, 9 0 , 9 2 , 9 3 , 103, 116, 117 Krishnan, V. ( 9 ) 106 K r i z , M. ( 8 ) 12 Krokhina, S.S. ( 1 ) 191 Kroto, H.W. (1) 277 Krueger, W.E. ( 9 ) 193 Kruger, C. ( 1 ) 1 2 ; ( 4 ) 4 3 Krugh, T.R. ( 6 ) 285 Krupnov, V.K. ( 2 ) 47 Krupoder, S.A. ( 9 ) 40 K r u tik o v , V . I . ( 9 ) 254, 275 Krynetskaya, N.F. ( 6 ) 158 Krzyzosiak, W . J . ( 6 ) 274 Ku, L . ( 6 ) 105 Kubareva, E.A. ( 6 ) 316 Kubasek, W.L. ( 6 ) 293 Kubiniok, S. ( 1 ) 102 K u b li, E. ( 6 ) 308 Kuchen, W. (1) 152, 264 Kudelska, W. ( 5 ) 36 Kudryavtsev, A.A. ( 5 ) 1 7 ; ( 8 ) 43 Kiickelhaus, W. (1) 156; ( 9 ) 185 Kuehne, U. ( 1 ) 31 Kuendgen, U. ( 9 ) 151 Kuge, 0. ( 6 ) 297 Kuhn, N. ( 1 ) 207; ( 3 ) 2 7 , 44 Kuhn, W. ( 2 ) 42; ( 6 ) 373 Kukhar, V.P. (1) 281; (8) 9 ; ( 9 ) 2 9 , 128, 159 Kukhareva, T.S. (1) 147; ( 5 ) 82 Kulak, T.I. ( 6 ) 185 K u lie v , A.A. ( 4 ) 5 6 , 5 7 , 59, 60 K u lie v , A . K . ( 1 ) 161, 162 K u lk a r n i, P.S. ( 9 ) 239 Kumar, C.V. ( 6 ) 366 Kumar, K.R. ( 1 ) 177 Kumar, V.T.R. ( 7 ) 83 Kume, A. ( 6 ) 29 Kumobayashi, H. (1) 54 Kunz, E. (7). 145 Kunz, H. ( 1 ) 235 Kunze, U. ( 9 ) 57 Kupprat, G. (1) 3 5 , 36 Kurchenko, L.P. (8) 100, 114 Kurku, A . ( 5 ) 148 Kurochkin, V.V. ( 4 ) 5 4 Kuroda, S. ( 7 ) 148, 149 Kusabayashi, S. ( 9 ) 257 Kusmierek, J.I. ( 6 ) 213 Kusumoto, T. (1) 58, 5 9 ;

A ut hor Index (3) 1 8 , 19 K u t i a v i n , I . V . ( 6 ) 284 K u t u e v , A . A . (1) 77 K u t y r e v , G.A. ( 5 ) 1 4 9 K u t z k e , U. ( 6 ) 50 K u y l - Y e h e s k i e l y , E. ( 4 ) 80; ( 6 ) 2 7 , 4 1 Kuzmenko, 1.1. ( 8 ) 56 K u z n e t s o v , A . V . ( 6 ) 231 Kvasyuk, E . I . ( 6 ) 185 Kwiatkowski, M. ( 6 ) 118 Kwon, S . ( 8 ) 1 5 8 Kyba, E.P. (1) 1 5 5 K y l e r , K.S. ( 7 ) 116 Kyogoku, Y. ( 6 ) 1 3 4 K y u n t s e l , I . A . ( 9 ) 70 L a a k s o n e n , M. ( 6 ) 290 Laane, J. ( 9 ) 121 L a b a r r e , J.-F. ( 8 ) 6 0 , 6 7 , 88, 8 9 , 195 L a b a u d i n i e r e , L. ( 7 ) 60 L a b e l l e , M. ( 6 ) 351 L a c o s t e , A.-Marie ( 5 ) 93 L a F a i l l e , L. ( 8 ) 89 L a f e r , E.M. ( 6 ) 220 L a h a n a , R . (8) 6 7 , 88 L a i , K . (5) 2 5 L a i , R . ( 7 ) 65 L a i g l e , A. ( 6 ) 395 L a i n g , E.M. ( 6 ) 18 L a j o i e , G. ( 5 ) 1 4 3 Lamba, D. ( 9 ) 206 L a m b e r t , P.H. (1) 1 0 7 L a m b e r t , R.W. ( 5 ) 1 0 4 L a m b e r t s , H.B. ( 8 ) 81 L a n c e t , D. ( 6 ) 6 L a n d g r a f , W. ( 6 ) 53 L a n e , D . J . ( 6 ) 301 Lang, H. ( 1 ) 3 4 5 , 346 L a n g e r , W. ( 7 ) 4 5 L a n g e r b e i n s , K. (1) 33 L a n g l o i s , Y. ( 7 ) 1 3 4 L a n g r i c k , C.R. ( 1 ) 10, 2 8 Lanoux, S . ( 8 ) 115 t a p i e n i s , G. ( 4 ) 112 L a p p e r t , M.F. ( 1 ) 39 L a r i n , Z. ( 6 ) 322 L a r s e n , C. ( 5 ) 69 L a r s e n , R. ( 9 ) 1 6 7 L a r s s o n , A . ( 6 ) 15 L a s c h , J.G. (1) 3 5 4 ; ( 4 ) 1 0 6 ; ( 9 ) 190 L a s k o r i n , B.I. ( 9 ) 245 L a s s o t a , P. ( 6 ) 4 6 L a t s c h a , H.P. (1) 1 7 0 ; (2) 8 L a t y p o v a , V.Z. ( 9 ) 2 3 3 L a u , P.T. ( 1 ) 9 Laude, B. ( 5 ) 42 L a u r e n c e , C. ( 9 ) 1 2 6

437 L a v i n , K.D. (1) 118; ( 8 ) 109, 159 L a v r e n t ' e v , A . N . ( 9 ) 254 , 275 Lawessf.n, S.-0. ( 5 ) 91, 140-142, 1 4 4 ; ( 9 ) 188 L a z i u s , A . G . ( 6 ) 339 Lebedev, A . V . ( 6 ) 1 5 1 , 283 Lebedev, N . N . (5) 3 ; ( 9 ) 276 Le B i g o t , Y . (7) 2 5 L e b l a n c , Y. ( 7 ) 1 2 0 L e b l e u , B. ( 6 ) 1 8 7 L e C l e r c , .J.E. ( 6 ) 265 L e c l e r c q , P.A. ( 9 ) 262 Le C o r r e , M. ( 7 ) 4 1 L e d e r e r , F. ( 6 ) 2 3 3 L e e , B.L. ( 6 ) 1 3 4 L e e , C.S. ( 6 ) 83 L e e , D.-C. ( 8 ) 1 4 2 , 1 4 3 L e e , J.Y. ( 1 ) 5 3 , 5 6 , 57 L e e , M.H. ( 6 ) 8 7 L e e , M.-S. ( 6 ) 286 L e e , M.Y.W.T. ( 6 ) 6 7 L e e , Y.M. ( 6 ) 242 L e f e u v r e , M. ( 7 ) 4 7 Le F l o c ' h , Y . ( 7 ) 47 L e g e r , S. ( 7 ) 1 1 5 l e G o f f i c , F. (5) 93 Lehmann, H.A. ( 1 ) 2 3 3 ; ( 8 ) 149 ( 1 ) '28 Lehn, J.-M. L e i b f r i t z , D. ( 6 ) 400 L e i c h t l i n g , B.H. ( 6 ) 4 2 L e i s s r i n g , E . (9) 6 4 L e j c z a k , B. ( 5 ) 9 8 ; ( 9 ) 267 L e k s u n k i n , V . A . ( 5 ) 159, 1 6 0 ; ( 8 ) 39, 4 0 L e l i e v e l d , P. ( 8 ) 81 Lemarchand, A . ( 6 ) 1 4 8 Lemoine, P. ( 1 ) 3 7 4 L e m p e r e u r , L. ( 6 ) 305 Leng, M. ( 6 ) 3 7 8 , 395 l e N o b l e , W . ( 5 ) 30 L e n z , G. ( 1 ) 316 L e o n a r d , N . J . ( 6 ) 61 Leonov, A.A. ( 9 ) 2 2 8 Lequan, M. ( 1 ) 2 1 4 ; (9) 168 Lequan, R.M. ( 1 ) 2 1 4 ; ( 9 ) 168 L e r c h , C. (8) 5 L e r n e r , L. ( 6 ) 3 7 0 L e r o u x , Y. ( 2 ) 28-30, 4 5 ; ( 4 ) 15, 16; 7) 1 7 , 18 Leserman, L.D. ( 6 ) 1 8 7 L e s i a k , K. ( 4 ) 9 1 ; ( 6 ) 182-184 L e t s i n g e r , R.L ( 6 ) 1 6 9 Leupin, W. (6) 376; ( 9 )

72 L e u t l o f f , R. ( 4 ) 1 3 ; (5) 52 Le Van, D. (1) 2 6 8 , 2782 8 0 ; ( 9 ) 35, 2 3 6 L e v i n , B.V. ( 8 ) 118 L e v i n , D. (3) 30 L e v i n , M.L. (8) 7 4 ; ( 9 ) 218 L e v i n , Ya.A. ( 9 ) 95, 102 L e v i n a , A.S. ( 6 ) 1 7 0 Lewin, R . ( 6 ) 3 4 0 L e w i s , E.S. ( 9 ) 249 Lewy, M . ( 5 ) 4 4 ; ( 9 ) 210 Ley, S.V. ( 7 ) 3 4 , 1 2 4 Leykam, J . F . ( 9 ) 2 6 8 L i , B.-L. ( 1 ) 295, 296 L i , H.M. ( 8 ) 78, 145, 147, 148 L i , L.B. ( 8 ) 2 5 L i , W. ( 4 ) 9 7 L i , Y.S. ( 9 ) 227 L i , Z. ( 5 ) 5 4 , 86 L i c a n d r o , E. ( 7 ) 53, 5 4 L i e t j e , S . ( 5 ) 59; ( 7 ) 7 5 L i l l e y , D . M . J . ( 6 ) 306,

39 1 Limn, W. ( 6 ) 1 9 2 L i n , R.-J. ( 6 ) 341 L i n , Y . ( 7 ) 61 L i n b e r g , L.F. ( 8 ) 8 4 L i n c o l n , J. ( 9 ) 105 L i n d h a r d t , P. ( 5 ) 1 4 2 L i n d n e r , E. ( 1 ) 6 2 , 73-75 L i n e s , C.T. ( 5 ) 3 9 ; ( 9 ) 216 L i o r b e r , B.G. ( 9 ) 83 L i o u , R . (6) 16 Lipman, R. ( 6 ) 330 Lippard, S.J. (6) 362 L i s t v a n , V . N . ( 1 ) 196, 197 L i t i n a s , K.E. ( 7 ) 4 4 L i t t l e , T.S. ( 9 ) 133 L i t v i n e n k o , L.M. ( 8 ) 100, 114 L i t v i n o v , I . A . (1) 380; ( 9 ) 150, 1 7 4 , 2 1 5 , 224 L i t v i n o v , V.M. ( 8 ) 1 6 1 , 164 L i u , S. ( 1 ) 153 L i u , X. ( 6 ) 1 3 2 L i u , Z. ( 3 ) 2 3 L i v a n t s o v , M.V. ( 4 ) 11, 35; ( 5 ) 6 2 Liverton, N.J. (7) 126 L l o y d , J . R . (1) 9 9 ; ( 2 ) 4 8 ; ( 4 ) 2 6 ; ( 5 ) 113 Lobana, T.S. (1) 9 7 Lobanov, O.P. (1) 2 0 3 L o c h s c h m i d t , S. ( 1 ) 2 1 0 , 356-359; (9) 1 5 5 , 1 8 2


438 Logan, N. ( 9 ) 77 Logunov, A.P. ( 9 ) 178 Loomis, R.E. ( 6 ) 191 Lopez, F. ( 1 ) 386; ( 3 ) 42; ( 8 ) 45

Lopez, L. ( 1 ) 378; ( 4 ) 101

Lbpez-NGzez, N.A.

( 3 ) 12;

( 9 ) $3

Lopusinski, A. ( 4 ) 28; ( 5 ) 15

Lora, S. ( 8 ) 171-173 Loreau, N . ( 6 ) 178 Losilkina, V . I . (1) 2 Lough, J. ( 6 ) 223 Lowe, G. ( 5 ) 33; ( 6 ) 7578, 80; ( 9 ) 51

Lown, J.W. ( 6 ) 144 Lowther, N. ( 1 ) 99; ( 2 ) 23; ( 4 ) 26

Lu, S.-B. ( 7 ) 32 Ludeman, S.M. ( 5 ) 46 Luders, H. ( 7 ) 138 Ludwig, E.G. ( 1 ) 135 Lugtenburg, J. ( 7 ) 102 Lukanov, L.K. ( 5 ) 18 Lukanyuk, S.S. ( 9 ) 91 Lum, G.S. ( 8 ) 147, 148 Luss, H.R. ( 1 ) 55; ( 3 ) 9 ; ( 9 ) 156

Lusztyk, J. ( 9 ) 113 Lutke, H. ( 7 ) 57 Lutsenko, A . I . ( 2 ) 49 Lutsenko, I.F. (1) 1 3 , 148, 149, 179, 184; ( 2 ) 49; ( 4 ) 11, 19, 25, 35, 45; ( 5 ) 62, 107; ( 8 ) 27 Lygin, A.V. ( 5 ) 149 Lygo, B. ( 7 ) 34 Lyu, H.S. ( 8 ) 101

Maartmann-Moe, K. ( 3 ) 15; ( 7 ) 10

Maas, G. (1) 319; ( 3 ) 21; ( 7 ) 8 ; ( 9 ) 196 McBride, L.J. ( 6 ) 123 McCabe, D.J. ( 5 ) 115 Maccioni, A.M. ( 8 ) 69 McClelland, R.A. ( 2 ) 3840; ( 9 ) 252 McConnell, D.J. ( 6 ) 366 McCourt, D.W. ( 9 ) 268 McDowell, R.S. ( 2 ) 12; ( 9 ) 19 McElroy, A.B. ( 3 ) 31 McEwan, W.E. ( 2 ) 26; ( 7 ) 20-22 McGall, G.H. ( 2 ) 38-40; ( 9 ) 252 McGarvey, G.J. ( 7 ) 108 McGee, D.P.C. (6) 1 4

McGinn, M.A. ( 1 ) 251, 253, 254; ( 8 ) 2 Maciej, T.W. (5) 120; ( 7 ) 98 McIntosh, L.P. ( 6 ) 196 Mack, H. ( 7 ) 152 McKechnie, J.S. ( 9 ) 234 Mackenzie, P.B. ( 1 ) 17 MacKinnon, I . A . (1) 39 McLaughlin, L.W. ( 6 ) 127, 387 Macomber, R.S. ( 5 ) 124 McPherson, D.T. ( 7 ) 157 Macpherson, K . A . ( 1 ) 122 Macquet, J.P. ( 6 ) 361 Maeda, T. ( 7 ) 131 Markl, G. (1) 128, 323325; ( 9 ) 157 Maerkl, R. (1) 272 Magdeeva, R.K. ( 5 ) 64, 65; ( 9 ) 195 Magdesieva, N.N. (1) 202 Magill, J.H. ( 8 ) 166-168 Magnusson, E. ( 9 ) 63, 242 Mahh, M.J. (1) 329 Mahoun, A. ( 8 ) 67, 88 Mahran, M.R. ( 2 ) 35 Maier, L. (5) 95 Maigrot, N. ( 1 ) 16; ( 9 ) 74 Maiorana, S. ( 7 ) 54 Majewski, M. ( 9 ) 255 Majewski, P. ( 3 ) 11 Majoral, J.-P. (1) 132, 337; ( 4 ) 9 ; ( 8 ) 1 6 , 30; ( 9 ) 52, 217 Makaranets, B.I. ( 9 ) 192 Makhmudov, M.K. ( 5 ) 109; ( 9 ) 200 Maki, R.G. ( 7 ) 92 Makovetskii, Yu.P. ( 1 ) 243 Makowka, B. (1) 32, 33 Malakhova, I.G. ( 1 ) 14 Malamas, M.S. ( 7 ) 131 Malarova, M.A. ( 9 ) 215 Malavaud, C. ( 1 ) 378; ( 4 ) 110 Malecha, M. ( 6 ) 154 Malenko, D.M. ( 4 ) 63; ( 5 ) 71, 87 Malik, L. ( 9 ) 86 Malisch, W. ( 1 ) 172, 287, 310, 349, 350 Malkovskaya, T.H. ( 9 ) 253 Malone, J.F. ( 9 ) 173 Malovik, V.V. (1) 142 Mal'tseva, T.V. ( 9 ) 41 Mamzurin, B.V. ( 5 ) 3; ( 9 ) 276 Manaev, S.V. ( 6 ) 284 Manami, H. ( 7 ) 130

Mangiaracina, P. ( 7 ) 117 Maniatis, T. ( 6 ) 322 Manna, S. ( 7 ) 122 Manninen, P.A. ( 9 ) 241 Manohar, H. ( 8 ) 80 Manolson, M.F. ( 6 ) 248 Manuel, G. ( 1 ) 337 Marchenko, A.P. (1) 209, 232; ( 5 ) 17; ( 8 ) 31, 32, 34, 36, 43, 46 Marecek, J.F. ( 5 ) 30; ( 9 ) 210 Marinetti, A. ( 1 ) 342, 344, 361, 363; ( 3 ) 6 , 7; ( 9 ) 34 Marino, G. ( 6 ) 388 Markiewicz, W.T. ( 6 ) 124 Markova, L. ( 9 ) 87 Markovskaya, T.A. ( 5 ) 9 6 , 97 Markovskii, L.N. (1) 297, 298, 300-302, 331, 334; ( 2 ) 61, 62; ( 4 ) 18, 38, 102, 109, 110; ( 8 ) 24, 47, 54; ( 9 ) 27, 28, 31, 53, 54, 6 6 , 71, 201 Marler, D.O. ( 7 ) 70 Marlier, J.F. ( 6 ) 201 Marmetova, G.R. ( 9 ) 263 Marques, E.C. (1) 49 Marre-Mazieres, M.R. ( 8 ) 6 , 1 7 , 18, 21; ( 9 ) 15 Marsh, T.L. ( 6 ) 349 Marsh, Y.V. ( 6 ) 186 Marshall, J.H. ( 7 ) 74; ( 8 ) 65; ( 9 ) 118 Martin, C.R. ( 9 ) 262 Martin, D.R. ( 1 ) 94 Martin, F.H. ( 6 ) 147 Martin, J.C. ( 2 ) 4 ; ( 6 ) 14 Martin, M.R. ( 9 ) 181 Martin, R. (5) 7 8 Martin, R.P. (1) 93 Martin, S.J. ( 5 ) 122 Martinez, F. (8) 76 Martucci, I. ( 7 ) 151 Marugg, J.E. (1) 180; ( 4 ) 40, 65, 78, 80, 82; ( 6 ) 26, 27, 172 Maruthamuthu, P. ( 9 ) 117 Maruyama, T. ( 6 ) 25 Marx, J.L. ( 6 ) 379 Maryanoff, B.E. ( 2 ) 24, 25; ( 7 ) 23 Marynick, D.S. ( 8 ) 7 ; (9) 79 Marzilli, L.G. ( 6 ) 360, 376 Mas, R.H. ( 8 ) 115 Masafumi, Y. ( 6 ) 245 Masamune, S. ( 7 ) 80, 109

439

Author Index MascareEas, J.L. ( 3 ) 40 Mashchenko, N . V . ( 1 ) 1 3 ; ( 4 ) 19; ( 5 ) 107 Mashima, K. ( 1 ) 54

Maslennikova, V.I. ( 5 ) 64, 65; ( 9 ) 195

Masojidkova, M. ( 6 ) 24 Masse, G. (5) 68 Massoud, S . S . ( 6 ) 359 Mastalerz, P. ( 5 ) 94, 9 8 ; ( 9 ) 267

Mastryukova, T.A. ( 9 ) 250 Masuda, N . ( 6 ) 128 Masui, M. ( 1 ) 124 Masuko, T. ( 8 ) 141 Mateev, I . S . ( 9 ) 25 Mathey, F. ( 1 ) 16, 292, 342-344, 359-364, 366, 368, 372, 374; ( 3 ) 6 , 7 ; ( 9 ) 34, 73, 74 Mathieu, S . ( 1 ) 341; ( 3 ) 22 Mathis, F. ( 5 ) 129; ( 8 ) 67 Mathis, R. ( 5 ) 129; ( 8 ) 67 Matkovskaya, T.A. ( 9 ) 248 Matsuda, H. ( 1 ) 125; ( 3 ) 45 Matsugi, J. ( 6 ) 120, 210 Matsumura, N . ( 7 ) 85 Matsuura, T. ( 6 ) 294 Matsuzaki, J.-i. ( 6 ) 111, 112 Matsuzawa, S. ( 8 ) 165 Mattes, W.3. ( 6 ) 255 Matteucci, M.D. ( 4 ) 79 ; ( 6 ) 2 8 , 281 Matthes, K.E. (1) 28 Matthews, T.R. ( 6 ) 14 Matus, B. ( 6 ) 48 Matveeva, E.V. (1) 76 Matveicheva, G.P. ( 1 ) 146; ( 9 ) 161 Mauer, K.H. ( 6 ) 400 Maurizi, M.R. ( 6 ) 69 Mavarez, E.O. ( 9 ) 217 Maximova, T.G. ( 6 ) 237 Mayer, H.A. (1) 74 Mayer, R . ( 6 ) 163 Mayers, A.I. ( 1 ) 84 Mayo, S.L. ( 8 ) 65; ( 9 ) 118 Mayol, L. ( 6 ) 388 Mazalov, L.N. ( 9 ) 149 Mazany, A.M. ( 7 ) 70 Mazard, A.M. ( 6 ) 361 Mazhar, M. ( 2 ) 5 Mazieres, M.R. (1) 332, 333 Meares; C.F. ( 6 ) 327 Mecklenburg, K.L. ( 6 ) 341

Medina, R. ( 8 ) 119 Medinger, L . ( 4 ) 5; ( 5 ) 73

Medved, T.Ya. (5) 84 Meek, D.W. ( 1 ) 4 Meek, J.L. ( 9 ) 270 Meetsma, A . ( 8 ) 192-194 Mehrotra, R.C. ( 9 ) 208 Mehrsheikh-Mohammadi, M.E. ( 5 ) 138; ( 9 ) 18 Mei, G. ( 9 ) 99 Meidine, M.F. ( 1 ) 313, 327

Meier, I.K. ( 7 ) 64 Meille, S.V. ( 8 ) 163 Meine, G. ( 1 ) 291 Meinwald, J. ( 3 ) 39 Meir, C . J . (1) 327 Meister, J.J. ( 8 ) 170 Mejillano, M.R. ( 6 ) 8 4 Melchior, F. ( 1 ) 122 Mel'nichuk, E.A. ( 4 ) 69 Mel'nikov, B.V. ( 9 ) 233 Mendz, G.L. ( 6 ) 384 Menzel, J. ( 1 ) 273, 299; ( 9 ) 151

Mercier, F. (1) 360, 372 Merecek, J.F. (5) 44 Merkel, C.M. (1) 9 3 , 94 Merkle, R.D. ( 1 ) '73-75 Merrick, W.C. ( 6 ) 229 Mertes, K.B. ( 6 ) 59 Mertes, M.P. ( 6 ) 59 Merzweiler, K . ( 1 ) 260 Meshcheryakov, N.M. ( 9 ) 245

Messmer, A . ( 1 ) 104; ( 8 ) 11

Metelev, V.G. ( 6 ) 317 Metni, M. ( 9 ) 247 Metzgar, J. ( 7 ) 65 Metzner, P. ( 5 ) 139 Meuwly, R. ( 4 ) 12; ( 9 ) 205

Meyer, A. ( 1 ) 349, 350 Meyers, E.A. ( 9 ) 172 Meyers, R.E. ( 8 ) 8 5 , 8 6 Meznik, L. ( 1 ) 233; (8) 149

Michaeli, D. ( 6 ) 163 Michalska, M. ( 5 ) 36 Michalski, J . ( 1 ) 157; ( 4 ) 64

Michalski, T.J. ( 7 ) 154 Michejda, C . J . ( 1 ) 108 Michels, M. (1) 22, 138;

Mikailov, V.V. ( 9 ) 240, 263

Mikhailopulo, I .A . ( 6 ) 185

Mikhailov, G.Yu. (1) 148, 149

Mikhailov, Yu.B. ( 1 ) 163, 164; ( 4 ) 56

Mikityuk, A.D. ( 5 ) 77; ( 8 ) 19

Milavetz, B. ( 6 ) 221 Milburn, R.M. ( 6 ) 359 Miles, H.T. ( 6 ) 192 Milgrom, Ya.M. ( 6 ) 244 Miller, E .J . ( 9 ) 193 Miller, J.P. ( 6 ) 5 5 , 56 Miller, P.P.J. ( 7 ) 102 Miller, P.S. ( 6 ) 174-176, 180

Milliaresi, E.E. ( 9 ) 125 Milne, C . R . C . ( 1 ) 17 Mimasu, R. ( 7 ) 94 Minami, T . ( 1 ) 205; ( 5 ) 130; ( 7 ) 8 8 , 94 Minasu, R. (5) 130 Minasyan, G.G. (1) 8 2 Mincione, E. ( 7 ) 151 Minore, J . ( 5 ) 30 Minter, S.J. ( 6 ) 344 Minto, F. ( 8 ) 171 Mirilov, M. ( 5 ) 153 Miroschichenko, V.V. ( 8 ) 34, 4 3 ; ( 5 ) 17

Misiura, K . ( 9 ) 214 Misumi, S. ( 9 ) 46 Mitomo, S. ( 7 ) 6 3 Mitrolol'skaya, G.I. (8) 9 4 , 160, 177 Mitrosov, Yu.N. ( 5 ) 47 Mitsunobu, 0. ( 6 ) 40 Miura, K . ( 6 ) 311 Miwa, T. ( 1 ) 168; ( 3 ) 8 Miyama, Y. ( 8 ) 41 Miyamoto, Y. ( 7 ) 130 Miyashiro. H . ( 6 ) 133 Mizrahi, V . ( 6 ) 201 Mizuki, Y. (1) 124 Mizusawa, S. ( 6 ) 302 Mochida, K . ( 9 ) 183 Mochizuki, A . ( 5 ) 151 Modak, A.S. ( 9 ) 239 Modro, T.A. ( 5 ) 45, 154; ( 9 ) 186, 202, 211

Magelin, W. ( 4 ) 1 7 , 3 4 ; ( 5 ) 60

Moeps, A . ( 9 ) 96 Mohammad, A.T. ( 1 ) 217 ( 3 ) 10 Michniewicz, J.J. (6) 207 Mokeeva, V.A. ( 9 ) 70 Miftakov, M.S. ( 7 ) 113 Molineux, I.J. ( 6 ) 335 Miguel Nardillo, A . ( 9 ) Molko, D. ( 6 ) 141 258 Mollow. N.M. ( 5 ) 1 8 Mihart, C. ( 8 ) 64 Momchilova, S.' ( 7 ) 7 6 , 77


440 Mondal, J.U. (1) 94 Mondeshka, D.M. (9) 87 Monin, E.A. (1) 179; (2) 49; (4) 51, 52 Monius, T. (7) 56, 57 Monkiewicz, J. (7) 26 Montgomery, C.D. (1) 38 Moore, J.M. (6) 355 Moore, M.F. (6) 34 Moors, R. (4) 105 Mootz, D. (9) 185 Moran, T.F. (9) 235 Morand, P. (1) 215, 216, 218; (7) 150 Morel, D. (1) 112-114 Morioka, H. (6) 120, 210 Mormachov, V.V. (5) 47 Morr, M. (6) 57 Morris, P.G. (6) 102 Morschheuser, 0.S. (2) 8 Morton, D.W. (1) 79; (4) 20; ( 8 ) 38 Morton, S. (1) 327 Morvan, F. (6) 144 Moskva, V.V. (1) 161, 162, 188; (4) 56, 57, 59, 60; (8) 129; (9) 134 Moskvin, A.V. (5) 136; (9) 140 Motherwell, W.B. (2) 9 Motoki, S. (1) 376; (5) 150; (7) 52 Mouriiio, A. (3) 40 Moustakis, C.A. (7) 121 Movshovish, D.Ya. (8) 130; (9) 232 Mowbray, J. (6) 102 Moyse, C.D. (6) 43 Miiller, G. (1) 12, 43, 45, 80, 115, 183, 189, 198, 305, 310, 356; (9) 177 Miiller, U. (1) 217 Mueller, W. (6) 388, 389 Mueller, W.B. (8) 179, 180 Muenstedt, R. (8) 55 Mujasaka, T. (5) 152 Mukaiyama, T. (6) 49 Mukhacheva, O.A. (9) 129 Mukhametov, F.S. (4) 61, 62; (5) 88 Mukherjee, S. (6) 242 Mukhtarov, R.L. (9) 120 Mukmenev, E.T. (9) 215 Mukroyannidis, J.A. (3) 20

Mulder, N.H. (8) 81-83 Mullenbach, G.T. (6) 206 Muller, A.J. (4) 30 Muller, E.P. (9) 223

Muller, G . (4) 43; (7) 7, 9, 11; (9) 169 Murakami, A. (6) 174-176 Murakami, K. (8) 140 Murataliev, M.B. (6) 244 Murphy, M.K. (8) 181, 183, 185 Murray, H.H. (7) 70 Murugesan, N. (6) 324 Musin, R.Z. (1) 382 Mustaev, A.A. (6) 237 Myasnikova, L.G.(5) 2 Myers, R.M. (6) 322 Mynott, R. (1) 111 Nader, F.W. (7) 50, 51 Naesman, J.H. (5) 40 Nafikova, A.A. (9) 90 Nagai, N. (1) 124 Nagaoka, H. (7) 73 Nagarajan, K . (9) 81 Nagase, S. (1) 275; (8) 48; (9) 3 Nagase, T. (5) 76; (7) 71 Nair, C.P.R. (8) 87 Nakahama, S. (4) 67 Nakahara, J.H. (1) 387; (8) 131, 135, 136 Nakamura, S. (5) 152 Nakamura, T. (7) 84 Nakane, M. (7) 52 Nakanishi, K. ( 6 ) 330 Nakano, K. (6) 236 Nakashima, T.T. (5) 66 Nakazawa, M. (9) 20 Narain, R.P. (1) 150 Narang, S.A. (6) 207 Narmetova, G.R. (9) 240 Nassal, M. (6) 155 Nassimbeni, L.R. (9) 202, 211 Nath, J.P. (6) 240 Natiello, M.A. (9) 75, 76 Naumov, V.A. (9) 224 Navech, H. (9) 86 Navech, J. (1) 247, 338, 341; (2) 53; (3) 22; (5) 92; (8) 1 Nazarova, G.V. (I) 76 Kedecheva, G . (3) 4 Neenan, T.X. (8) 110, 111, 155 Negareche, M. (9) 115 Negishi. K . (6) 214, 215, 297 Negrebetskii, V.V. (2) 61, 62; (9) 53, 54, 65, 66, 71 Neidlein, R. (1) 185, 186; ( 5 ) 108 Neilson. R.H. (1) 79.

154, 295, 296; (4) 20; (8) 25, 26, 38, 170 Nelson, G.E. (1) 60, 61 Nelson, J.H. (1) 367, 372, 374 Nerstad, G.O. (9) 222 Nesmeyanov, N.A. (1) 204 Nesterov, L.V. (4) 37 Nesterova, L.I. (2) 51; (5) 106; ( 8 ) 134 Neubert, W.J. (6) 313 Neuffer, J. (1) 66; (4) 44 Neumann, J.-M. (6) 381 Neuzil, E. (5) 93 Nevskii, N.N. (1) 7; (4) 39; (5) 65; (9) 163, 195, 213 Nevstad, G.O. (7) 10; (8) 191 Nevzorova, O.L. (5) 53 Newkome, G.R. (7) 85 Newman, A.J. (6) 341 Newman, R.H. (9) 21 Newton, B.H. (1) 39 Newton, R.P. (6) 43 Nguyen, M.T. (1) 251-255; (8) 2 Nichols, G.M. (8) 99 Nicolaides, D.N. (7) 44 Nicolaou, K.C. (3) 38; (7) 118, 123, 128 Nicoletti, F, (9) 270 Nicoloso, M. (6) 305 Niecke, E. (1) 64, 250, 287, 288, 318; (4) 33, 103; (8) 22, 23; (9) 189 Nieger, M. (5) 100 Nieke, E. (9) 146 Nielsen, J. (4) 40, 82 Nielson, P. (9) 138, 139 Niemann, J. (7) 4; (9) 38 Nientiedt, J. (1) 280 Niewiarowski, W. (6) 21, 22 Nifant'ev, E.E. (1) 7, 147; (4) 39, 54, 68; (5) 64, 65, 81 Nifant'ev, E.E. (9) 125, 163, 195 Nikitin, E.V. (9) 109 Nikitina, G.S. (8) 97 Nikitina, T.T. (6) 209 Nikloaeva, L.S. (9) 248 Nikonov, G.N. (9) 94 Nin, 2. (9) 7 Nishimura, S. (6) 302 Nishimura, Y. (6) 112, 397 Nishitani, Y. (7) 109 Nishivama. S. (6) 95

Author Index Ogreid, D. ( 6 ) 5 5 , 56 Ogura, Y. ( 9 ) 60 Oh, D . Y . ( 5 ) 61 Ohashi, M. ( 8 ) 9 5 , 96 Ohashi, 0. ( 1 ) 277 Ohler, E. ( 5 ) 74; ( 7 ) 42 Ohmori, H . ( 1 ) 124 Ohtsuka, E. ( 6 ) 36, 120, 121, 142, 210 Ohuigin, C. ( 6 ) 366 Oikawa, H . ( 5 ) 151 Oishi, H . ( 6 ) 25 Ojima, J. ( 7 ) 148, 149 Okamoto, Y. ( 5 ) 4 Okazaki, H . ( 9 ) 210 Okotrub, A.V. ( 9 ) 149 Okruszek, A . ( 5 ) '37; ( 6 ) 51, 312 Okui, S. ( 9 ) 183 Oleski, P. ( 9 ) 101 Olivares, R.C. ( 8 ) 75 Oliveros, L. (3) 14; ( 9 ) 142 Olsen, C.J. ( 6 ) 301 Olsen, R . K . ( 1 ) 100; ( 4 ) 29 Olson, M . V . ( 6 ) 394 Olthof-Hazekamp, R . (8) 25, 51, 52; ( 5 ) Nowak, M. ( 7 ) 79 194 O'Neill, R.E. ( 6 ) 229 Nowak, S. ( 5 ) 84 Oprian, D.D. ( 6 ) 155 Nowak, T. ( 6 ) 87 Orahovats, A.S. ( 5 ) 128 Noyori, R . ( 1 ) 54 ( 4 85; ( 6 ) 108 Orama, 0. ( I ) 270, 346 Nunomoto, M. ( 7 ) Organ, H.M. ( 7 ) 34 256 Orgel, L.E. ( 6 ) 188, 189 Nurakhmetov, N.N. 37 Orleva, T.D. ( 5 ) 135; ( 9 ) Nuretdinov, I . A . 253 Nuretdinova, O.W. 229, 230 Orpen, A . G . ( 1 ) 122, 348 Osaki, Y. ( 6 ) 95 Oshikawa, T. ( 4 ) 96; ( 5 ) 132 Oakley, R.T. (1) 103; 107, 123; ( 9 ) 220 Osipov, O.A. ( 8 ) 130; ( 9 ) 232 Obendorf, D. (1) 178 Oberster, A . E . ( 8 ) 187 Osipova, T . I . ( 6 ) 96 Obrecht, J.P. ( 5 ) 103; Osman, F.H. ( 2 ) 56 Osowska-Paciewicka, K . ( 9 ) 98 Ocando, E. (1) 132; ( 4 ) ( 5 ) 43 Osswald, M. ( 6 ) 292 9 ; ( 8 ) 30 Ostroukhova, O . K . ( 9 ) 266 O'Connor, D. ( 6 ) 287 O'Sullivan, W.J. ( 6 ) 83 Odinets, I . L . ( 4 ) 25 Odoriso, P.A. ( 5 ) 8 3 Ott, J. ( 6 ) 202, 374; ( 9 ) 51 Oeberg, B. ( 6 ) 15 Oefner, C. (6) 352 Ouahab, L. (1) 214; ( 9 ) Oertel, U. (1) 244 168 Otvos, L. ( 6 ) 45, 200 Ouyang, T. ( 9 ) 119 Ovakimyan, M.Zh. ( 1 ) 82 Ofengand, J. ( 6 ) 277 Offermann, W. ( 2 ) 41, 42 Ovchinnikov, Yu.E. ( 9 ) 219 Ogawa, K . ( 6 ) 25 Ovodova, O.V. ( 9 ) 229, Ogawa, Y. ( 7 ) 139 230 Ogden, R.C. ( 6 ) 280 Ogilvie, K . K . ( 4 ) 8 6 , 8 7 , Ozakaki, H. ( 5 ) 44 92; ( 6 ) 31, 122, 164 Ozaki, K . ( 6 ) 29

Nishizawa, M. ( 6 ) 214 Nitta, M. ( 1 ) 385; ( 4 ) 21; ( 6 ) 297 Niven, M.L. ( 5 ) 45, 154; ( 9 ) 186 Nixon, J.F. (1) 277, 313, 327-329, 364 Noda, I . ( 8 ) 120 Nijtfi,H. ( I ) 72, 171; ( 4 ) 108 Noltemeyer, M. ( 8 ) 51, 52 Nomura, S. ( 1 ) 168; ( 3 ) 8 Noorda, S. ( 5 ) 134; ( 9 ) 144 Nordheim, A . ( 6 ) 306, 378 Norman, A.D. (1) 51; ( 4 ) 41, 46, 53 58; ( 9 ) 164 Norman, N.C. (1) 172, 348, 354; 4 ) 106; ( 9 ) 190 Normanly, J . ( 6 ) 280 Norman, A . D ( 9 ) 162 Nortay, S.O. ( 5 ) 51 Noviello, S. ( 1 ) 87 Novikova, S.P. (8) 174 Novikova, Z.S. ( 1 ) 1 3 ,

441 Pace, B. ( 6 ) 301 Pace, N.R. ( 6 ) 42, 301, 349 Pace, U. ( 6 ) 6 Paciorek, K.J.L. (1) 387; ( 8 ) 131, 135, 136 Packer, K . J . ( 9 ) 58 Paddock, N.L. ( 8 ) 5 9 , 107; ( 9 ) 220 Padgett, R . A . ( 6 ) 340 Padiou, J. (1) 214; ( 9 ) 168 Paillous, N. ( 1 ) 266 Paine, R.T. ( 5 ) 115 Pakulski, M. (1) 339, 347, 348; ( 2 ) 31 Pala, M. ( 8 ) 33 Palacios, F. (1) 386; ( 3 ) 42; ( 8 ) 45 Palaniswamy, V . A . ( 7 ) 8 1 Palecek, E. ( 6 ) 267 Paleologue, A. ( 6 ) 293 Palumbo, G . ( 1 ) 87 Panczek, S. ( 4 ) 112 Paneth, P. ( 5 ) 3 8 ; (9) 50 Pankov, V.I. ( 1 ) 76 Panosyan, G . A . ( 5 ) 131 Panov, A.M. ( 9 ) 131, 148 Papagni, A . ( 7 ) 53, 54 Papkov, V.S. ( 8 ) 161, 164 Paquette, L . A . ( 7 ) 147 Parakin, O.V. (9) 109 Paramonov, V . I . (1) 142 Paranawithana, S.R. ( 6 ) 368 Pardoen, T.A. ( 7 ) 102 Pariza, R . J . ( 1 ) 192 Parkanyi, L. ( 6 ) 44 Parker, D. ( 1 ) 1 0 , 28, 239 Parkes, H.G. ( 8 ) 6 6 ; ( 9 ) 218 Parrott, M.J. (5) 112 Parvez, M. ( 8 ) 109 Pastor, S.D. ( 5 ) 8 3 ; ( 9 ) 6 8 , 69 Pastushenko, E.V. ( 2 ) 4 3 Patel, D . J . ( 6 ) 135 Patel, G. ( 2 ) 39 Patel, P. ( 7 ) 38, 106, 107 Paterson, M.C. ( 6 ) 252, 26 1 Patoprsty, V. ( 9 ) 8 6 Patsanovskii, 1.1. ( 1 ) 320 Pattenden, G. ( 7 ) 106, 107 Paulen, W. ( 1 ) 271; ( 9 ) 62 Pavlov, V.A. ( 9 ) 8 3 Pawelke, G. ( 1 ) 9 0


442 Payard, M. (1) 265; ( 4 ) 111 Payne, C. ( 6 ) 221 Payne, N.C. ( 1 ) 38 Pearson, J . D . ( 6 ) 8 5 P e c h s i r i , S. ( 1 ) 330 Pedersen, U. ( 5 ) 140, 144 Pedro, J . R . ( 7 ) 153 P e e b l e s , C.L. ( 6 ) 341 Peh, M.-L.N. ( 7 ) 65 P e i s a c h , J . ( 6 ) 328 P e l k a , H. ( 6 ) 279 P e l t i g r e w , F.A. ( 8 ) 147, 148, 151 P e n s a r , G. ( 5 ) 40 Penton, H.R. ( 8 ) 139, 151, 154 Penz, G. ( 5 ) 79 P e r e z , F. ( 7 ) 120 P e r e z , J.J. ( 7 ) 141 P e r i c h , J . W . ( 5 ) 12 P e r i e , J.J. ( 5 ) 21 P e r i n g e r , P. ( 9 ) 223 Perlman, P.S. ( 6 ) 341 P e r r e t , D. ( 3 ) 1 7 ; ( 9 ) 246 P e r r o t t , M . J . ( 9 ) 23 P e r u z z i n i , M. ( 1 ) 365 P e t e r s , G.H. ( 9 ) 133 P e t e r s , H. ( 1 ) 69 P e t e r s , K . ( 1 ) 257 P e t e r s , T . J . ( 6 ) 90 P e t e s , W. (5) 126 P e t r a g i n i , N. ( 9 ) 172 P e t r e d i s , G. ( 6 ) 57 P e t r i e , C.R. ( 6 ) 11 P e t r i l l o , M.L. ( 6 ) 341 P e t r o s y a n , E.R. ( 9 ) 120 P e t r o v , A . A . ( 5 ) 48; ( 9 ) 228 P e t r o v a , I. ( 5 ) 153 P e t r o v a , J. ( 7 ) 76, 77 P e t r o v a , T.M. ( 9 ) 266 P e t r o v s k i i , P.V. ( 1 ) 204 P e t s o n , A. ( 3 ) 1 2 ; ( 9 ) 43 P e t t e r , R. ( 5 ) 23 P e t t e r , W. ( 9 ) 223 P f e i f e r , G.P. ( 6 ) 196 P f e u t z n e r , E. ( 9 ) 80 P f i s t e r - G u i l l o n z o , G. ( 8 ) 6 ; ( 9 ) 5 , 15 P f l e i d e r e r , W. ( 6 ) 13 P h i l l i o n , D.P. ( 5 ) 137 P h i l l i p s , L.R. ( 4 ) 7; ( 6 ) 171 P i a n c a t e l l i , G. ( 5 ) 133 P i c c i a l l i , G. ( 6 ) 388 Pichko, N.P. ( 6 ) 283 Pidcock, A. ( 1 ) 364 Pidwer, M . J . ( 5 ) 99 P i e n t a , N.J. (1) 241 P i e r o t h , M. ( 1 ) 22, 138;

( 3 ) 1 0 ; ( 7 ) 65 P i e t r u s i e w i c z , K.M. ( 7 ) 26 Pinchuk, A.M. ( 1 ) 85, 209, 232; ( 5 ) 17; ( 8 ) 31, 32, 34, 36, 43, 46 Pingoud, A. ( 6 ) 318, 319 P i n k e r t , W. ( 8 ) 52 Pinnavaia, T.J. ( 6 ) 358 P i n t e r , I. (1) 104; ( 8 ) 11 P i n t o , A.L. ( 6 ) 362 P i s t o r i u s , A.M.A. ( 6 ) 125 Pitchumani, K . ( 1 ) 9 8 P l a g a , A. ( 9 ) 269 P l a t e a u , P. ( 6 ) 99 PlGnat, F. ( 1 ) 225, 226; ( 7 ) 14 P l e s s , R.C. ( 6 ) 298 Plyamovatyi, A.Kh. ( 9 ) 137 Pochet, S. ( 6 ) 381 Pochlauer, P. (9) 223 Podkopaeva, T.L. ( 6 ) 185 Podyminogin, M.A. ( 6 ) 284 Poetzsch, M. ( 8 ) 94 P o i r i e r , M. ( 2 ) 5 Polenov, E.A. ( 5 ) 116 Poleshchuk, O.Kh. ( 9 ) 104 P o l e t a e v , A . I . ( 6 ) 97 Polezhaeva, M.A. ( 2 ) 1 Polk, M. ( 1 ) 284, 285, 290 P o l l o k , T. ( 1 ) 37, 198; ( 3 ) 5 ; ( 9 ) 169 Polyachenko, L.K. ( 1 ) 298 Polyak, M.S. ( 5 ) 2 Polyakov, A.Yu. ( 9 ) 70 Polyakova, I . A . ( 5 ) 9 6 , 9 7 , 135; ( 9 ) 253 Polyanchuk, G.V. ( 9 ) 198 Polynova, T.N. ( 9 ) 192 Pomberio, A.J.L. ( 8 ) 20 Pomerantz, M. ( 8 ) 7; ( 9 ) 79 Pompliano, D.L. ( 5 ) 110 Pon, R.T. ( 4 ) 8 6 , 8 7 , 92; ( 6 ) 31, 122, 164 Ponomarchuk, M.P. ( 8 ) 9 P o n s i n e t , G. ( 7 ) 48 Poojany, M.D. ( 8 ) 80 Poole, R . J . ( 6 ) 248 Popoff, S. (6) 364 Popov, B.N. ( 1 ) 76 Popov, I . L . ( 6 ) 185 Popova, I . A . ( 9 ) 122 Porai-Koshits, M.A. (9) 192 P o r z e l , A. ( 9 ) 22 P o r z i o , W. ( 8 ) 163 Posner, G.H. ( 7 ) 32, 33 Poss, M.A. ( 7 ) 125

Potapov, V.K. ( 6 ) 315, 316 P o t t a g e , C. ( 5 ) 147 P o t t e r , B.V.L. ( 6 ) 20, 253; ( 9 ) 51 Pouet, M.-J. ( 5 ) 118; ( 7 ) 72; ( 9 ) 42, 45 Pougeois, R. ( 6 ) 72 Povolotskii, M . I . (1) 297, 300, 302; ( 9 ) 28, 31, 54 Power, J . M . ( 1 ) 339 Powroznyk, L. ( 4 ) 8 P r e i s s , J. ( 6 ) 242 P r e n g l , C. (1) 50 P r e t z e r , W.R. ( 1 ) 71 Prezhdo, V.V. ( 9 ) 231 Prigozhina, M.P. ( 8 ) 91 P r i s b e , E.J. ( 6 ) 14 P r i s b y l l a , M.P. ( 7 ) 140 Prishchenko, A.A. ( 4 ) 11, 35; ( 5 ) 62; ( 9 ) 82 P r i v e t t , J.A.J. ( 1 ) 103 P r o c t o r , G. ( 7 ) 87 Prokof'ev, M.A. ( 6 ) 158 Proskurnina, M.V. ( 2 ) 43; ( 5 ) 62 P r o s s e r , K. ( 4 ) 83 Prouex, P. ( 7 ) 150 Provotorova, N . I . ( 8 ) 175 Pu, J. ( 1 ) 229 P u c k e t t , W.E. . ( 7 ) 85 Pudovik, A.N. ( 1 ) 163, 164, 182; ( 2 ) 52; ( 4 ) 36, 48-50, 56, 71, 72; ( 5 ) 125, 149, 158; ( 8 ) 132; ( 9 ) 90, 109, 233 Pudovik, M.A. ( 1 ) 161164; ( 4 ) 48-50, 5 6 , 57; ( 9 ) 90 P u j o l , L. (1) 267; ( 9 ) 107 Pushkareva, G. ( 9 ) 124 P u s k a r i c , E. ( 8 ) 146 Pyo, H.S. ( 8 ) 101 Quan, C. ( 5 ) 22 Quashie, S. ( 1 ) 287, 288 Q u a s s i n i , A. ( 8 ) 4 4 , 58 Quin, L.D. ( 1 ) 173, 340, 366, 369, 370; ( 4 ) 100; ( 5 ) 113; ( 9 ) 33, 36 Quinn, A.M. ( 7 ) 110 Q u r e s h i , A.R. ( 4 ) 8 Rabinowitz, J.C. ( 6 ) 84 Radeglin, R. (9) 78 Rademacher, P. ( 1 ) 250; ( 4 ) 103; ( 8 ) 23 Raduly, S. ( 8 ) 64

Author Index 117 R a d z i k o w s k i , C. ( 5 ) 98 Reeve, R . N . ( 9 ) 56 R a e v s k i i , O.A. ( 9 ) 132 R e f o l o , L.M. ( 6 ) 257 R a g l i o n e , T.V. ( 6 ) 387 Regan, J . B . ( 5 ) 4 6 R a h a r i n i r i n a , A . ( 1 ) 352 R a h h a l - A r a b i , L. ( 9 ) 279 Regberg, T. ( 4 ) 7 9 , 8 1 ; R a i , A . K . ( 9 ) 208 ( 6 ) 35 R e g i t z , M . ( 1 ) 293, 3 1 9 , R a j a g o p a l a n , K . ( 7 ) 83 3 2 1 , 3 2 2 , 326; ( 3 ) 2 1 , R a j a l a k s h m i , S. ( 9 ) 265 2 4 , 26; ( 4 ) 9 9 ; ( 5 ) 7 8 ; Rajeshwar, K. ( 8 ) 7 ; ( 9 ) ( 7 ) 8 ; ( 9 ) 2 4 , 196 79 Rakhmankulov, D.L. (2) 4 3 R e i c h , W. (1) 349 R e i d , D.G. ( 6 ) 375 Rakov, R . D . ( 6 ) 234 R e i d , T.M. ( 6 ) 286 R a l e i g h , J.A. ( 6 ) 271 R e i l y , M.D. ( 6 ) 360 Ramabrahmam, P. ( 8 ) 117 R e i m s c h u s s e l , W. ( 5 ) 38; Ramachandran, K . (8) 1 2 1 Ramage, R . ( 5 ) 112; ( 9 ) (9) 50 R e i s a c h e r , H.-U. ( 1 ) 3 0 5 , 23 310; ( 7 ) 11 Ramaiah, M. (1) 83 Ramakrishna, J . ( 9 ) 106 R e i s c h e r , R.J. ( 6 ) 1 4 3 Rambaud, M. ( 7 ) 9 1 R e i t z , A . B . (2) 2 4 , 2 5 ; (5) 51; ( 7 ) 23 Ramesh, S. ( 7 ) 1 4 1 R e i z i g , K . ( 1 ) 2 5 8 , 284Ramirez, F. ( 5 ) 3 0 , 4 4 ; 286, 290, 291 ( 9 ) 210 Remizov, A.B. ( 9 ) 134 R a n a i v o n j a t o v o , H . (1) 256; ( 9 ) 154 Remizova, A . A . ( 9 ) 219 Rankin, D.W.H. ( 9 ) 225 Renhof, R . ( 6 ) 209 Ransom, S.C. ( 6 ) 238 R e p i n a , L.A. ( 4 ) 6 3 ; ( 5 ) Rao, A . V . R . ( 7 ) 1 3 3 71, 87 Rao, B.D.N. ( 6 ) 356 R e t t i g , S.J. ( 8 ) 1 0 7 ; ( 9 ) Rao, C . V . N . ( 5 ) 1 4 ; ( 9 ) 220 R e t u e n t , J. ( 8 ) 76 209 R e t u e r t , P . J . ( 9 ) 199 Rao, M.N.S. ( 8 ) 124; ( 9 ) 3 3 , 221 Reuther, W. (1) 195 Rao, V.S. ( 5 ) 1 4 3 Reutov, O.A. (1) 204 R a p h a e l , A.L. ( 6 ) 367 Revankar, G . R . ( 6 ) 11 R a p o p o r t , H. ( 7 ) 1 6 1 R e v e l , M. (1) 338, 3 4 1 ; Rasmussen, P.B. ( 5 ) 1 4 2 , ( 2 ) 53; ( 3 ) 2 2 ; ( 5 ) 92 144 Reye, C. ( 2 ) 6 , 7 R a s t o n , C.L. ( 1 ) 39 Reynolds, C.D. ( 5 ) 39; R a t h g e b e r , G. ( 6 ) 245 ( 9 ) 216 R a t h k e , M . W . ( 7 ) 79 R e y n o l d s , V.L. ( 6 ) 335 Ratovskii, G.V. ( 9 ) 131, Rezumov, A . I . ( 9 ) 134 148 Rezvukhin, A . I . ( 9 ) 40 Ray, B.D. ( 6 ) 356 Rheingold, A . L . ( 8 ) 33; R a y f o r d , R . ( 6 ) 229 (9) 193 R a y n e r , B. ( 6 ) 1 4 4 , 145 R i c c i , A. ( 7 ) 5 8 Razhabov, A . ( 8 ) 13 Ricci, J.S. ( 5 ) 44; ( 9 ) Razumov, A . I . ( 4 ) 4 7 ; ( 9 ) 210 129 R i c h , A. ( 6 ) 220, 378 Rea, P.A. (6) 248 R i c h a r d s o n , J . F . (8) 1 2 4 ; R e b e r , G. (1) 80; ( 7 ) 7 ( 9 ) 221 ( 6 ) 293 Reboud, A.-M. R i c h a r d s o n , S. ( 7 ) 125 Reboud, J . - P . ( 6 ) 293 R i c h t e r , S. ( 4 ) 13; ( 5 ) R e b r o v a , O.A. (1) 204 52 Reckmann, B. ( 6 ) 303 R i c h t e r , W.J. (1) 6 6 , Reddy, C.D. ( 5 ) 1 4 ; ( 9 ) 111, 1 2 9 , 371; ( 4 ) 4 4 ; 209 ( 9 ) 81 Reddy, D.B. ( 9 ) 209 R i c k a r d , C.E.F. ( 1 ) 289 Reddy, E.R. ( 7 ) 133 R i c k e n b e r g , H.V. ( 6 ) 42 Reddy, M.P. ( 6 ) 1 7 5 , 180 R i d e r , P. ( 6 ) 110 Reed, G.H. ( 6 ) 355 R i d i n g , G.H. ( 8 ) 109 R e e s e , C.B. ( 6 ) 1 1 4 , 1 1 6 , R i e d e , J. ( 1 ) 1 1 5 , 1 9 8 ;

443 ( 9 ) 169 R i e d e l , R . (1) 6 8 R i e d e r e r , M. (8) 57 R i e g e r , P.H. ( 1 ) 42 R i e h l , N. ( 6 ) 305 Riemer, M . ( 9 ) 6 4 R i e s e l , L. ( 2 ) 6 0 R i e s n e r , D. ( 6 ) 321 R i e s s , J.G. ( 2 ) 5 8 ; ( 4 ) 3; ( 9 ) 244 R i f f e l , H. ( 1 ) 1 3 0 ; ( 9 ) 199 R i l e y , R.W., ( 8 ) 152 R i n e s , S.P. ( 1 ) 155 R i s e n , W.M. ( 1 ) 42 R i s s a l u , Kh.1. ( 2 ) 46 R i t h n e r , C.D. ( 9 ) 10 R o b e r t , F. (1) 1 6 ; ( 9 ) 7 3 R o b e r t s , A.B. ( 7 ) 100 R o b e r t s , D.M. ( 6 ) 154 R o b e r t s , R.M.G. (1) 3 7 3 R o b e r t s , T.G. ( 3 ) 3 5 R o b i n s , R . K . ( 6 ) 11 R o b i n s o n , G. (6) 384 R o b i n s o n , P.L. ( 1 ) 9 6 ; ( 2 ) 20-22 R o d r i g u e z , L.O. ( 6 ) 324 Roemming, C. ( 9 ) 1 8 8 , 222 Roesch, L. ( 2 ) 44 Rosch, W. (1) 2 9 3 , 3 2 1 , 3 2 6 ; ( 9 ) 2 4 , 30 R o s c h e n t h a l e r , G.-V. (1) 134, 159; ( 2 ) 10, 27, 41, 42; (5) 6 Roesky, H.W. (8) 5 1 , 5 2 , 137 R o g o z i n a , I . N . ( 9 ) 275 Rokach, J. ( 7 ) 120 R o l ' n i k , L.Z. ( 2 ) 4 3 Romakhin, A.S. ( 9 ) 109 Romanenko, V.D. (1) 2 9 7 , 298, 300-302, 3 3 1 , 334; ( 4 ) 38, 1 0 2 , 109, 1 1 0 ; ( 8 ) 24, 47, 54; ( 9 ) 27, 2 8 , 3 1 , 201 Romano, L . J . ( 6 ) 286 Romanov, G . V . ( 9 ) 1 0 9 , 224 Romao, M.J. (1) 1 2 ; ( 4 ) 43 R@mming, C. ( 7 ) 10; (8) 191 R o n j a t , M. ( 6 ) 72 Roobeek, C.F. (3) 4 3 R o p e r , W.R. (1) 289 Rose, H. ( 8 ) 6 6 Roseman, B. ( 6 ) 223 Rosen, B. ( 6 ) 220 Rosen, T. ( 7 ) 1 5 8 R o s e n b e r g , I . ( 6 ) 2 3 , 24 R o s e n d a h l , M. ( 4 ) 83 R o s e n f e l d , P . J . ( 6 ) 222


444

Rosenthal, A. (6) 103, 317, 318 Ross, C. (9) 97 Ross, L.M. (8) 186 Ross, P. (6) 163 Roundhill, D.M. (1) 70; (5) 85; (9) 100 ROUS, A . J . (5) 29, 32; (6) 74; (9) 51 Roush, W.P. (7) 80 Roy, S. (1) 91, 92 Royo, G. (2) 5 Ruban, A.V. (1) 298; (8) 54 Rudemacher, P. (9) 146 Rudi, A. (1) 169; (5) 89 Rudley, K . (9) 61 Rudolf, H. (9) 177 Rudomino, M.V. (5) 135; (9) 253 Rudyi, R.B. ( 2 ) 61, 62; (9) 54, 66, 71 Riiger, R. (1) 64; (4) 33 Ruelle, P. (1) 254 Ruiz, J.P. (I) 93, 94 Ruland, A. (1) 195 Rumyantseva, Z.G. (8) 118 Rupp, W.D. (6) 364 Ruppel, H. (7) 104 Rusakov, V.A. (8) 97 Rushkina, N.G. (9) 125 Russkamp, P. ( 7 ) 45 Rycroft, D.S. (8) 66 Rycyna, R.e. (6) 260 Ryder, J . M . (9) 273 Sachse, B. (1) 190 Sadanani, N.D. (1) 63; (4) 32 Safonova, T.S. (8) 84 SGgi, J. (6) 200 Sahasrabudhe, S.D. (9) 239 Saindrenan, P. (9) 264 Saito, I. (6) 294 Saito, T. (1) 376; (5) 150; (7) 52 Sakai, K. (1) 124 Sakai, T. (7) 80 Sakhnovskaya, E.B. (1) 161, 162; (4) 57, 59, 60 Saks, V.A. (6) 231 Saksena, A . K . (7) 117 Sakurai, T. (7) 52 Salamanczyk, G. (4) 66; (5) 10 Salbeck, G. (5) 7 2 Salih, S.G. (6) 43 Salisbury, S.A. (6) 375 Salomon, Y. (6) 6

Samaha, M. (5) 148 Samakaev, R.Kh. (9) 248 Samarai, L . I . (8) 14 Sambamurti, K . (6) 257 Samitov, Yu.Yu. (9) 92, 93, 229, 230 Samples, M.S. (9) 39 Samson, C . J . (4) 93; (6) 146 Sancar, A. (6) 364 Sanchez, M. (1) 332, 333; (8) 6, 17, 18, 21; (9) 15 Sanders, J.Z. (6) 299 Sandhu, S.S. (1) 97 Sandstroem, A. (6) 118 Sanford, D.G. (6) 285 Sannia, G. (6) 388 Sargeson, A.M. (5) 24 Sarina, T.V. (9) 27, 28 Sarina-Pidvarko, T.V. (1) 300-302 Sarjudeen, N . (1) 328 Sarkar, A.B. (9) 207 Sarkar, N . (6) 225 Sarukhanov, M.A. (9) 122 Satg;, J. (1) 256, 352; (9) 154 Sato, K . (1) 59; ( 3 ) 19 Sato, R. (7) 59; (8) 41, 42 Sato, Y. ( 6 ) 25 Saundes, J . K . ( 6 ) 252 Sauve, G. ( 5 ) 143 Savel'yanov, V.P. (5) 3; (9) 276 Savenkov, N.F. (1) 144; ( 5 ) 13 Savignac, P. (1) 367; (5) 16, 55, 59; (7) 75, 97 Sawada, M. (9) 46 Sawai, H. (6) 182, 184 Sawaki, H . (4) 91 Sawka-Dobrowolska, W. (9) 191 Sazonova, G . V . (9) 184 Scaillet, S. (5) 45 Schade, G. (7) 56, 57 Schadour, H. (1) 233 Schadow, H. (8) 149 Schafer, A. (1) 257 Schafer, H. (1) 261 Schaefer, H . - J . (6) 245 Schaefer, W. (9) 147 Schaeffer, C.D. (9) 39 Schaeffner, A.R. (6) 237 Schaumloffel, G. (1) 235 Schellenberg, K.A. (6) 268 Scheller, K.H. (6) 357 Schenck, T.G. (1) 1 7 Scherer, O . J . (1) 246,

335, 336 Scherfise, K.D. (9) 171 Scheytt, C. (1) 62 Schiebel, H.M. (6) 399, 400 Schier, A. (1) 189, 198; (7) 9; (9) 169 Schiffer, H. (8) 3; (9) 13

Schipperus, 0. (6) 181 Schleich, T. (6) 193 Schleicher, M. (6) 239 Schlessinger, R.H. (7) 125 Schleyer, P.von R. (7) 1; (9) 11, 16 Schmeusser, M. (1) 350 Schmid, G. (7) 56 Schmidbauer, H. (1) 37, 115, 183, 189, 198; (3) 5; (7) 9; (9) 169, 177 Schmidpeter, A. (1) 18, 166, 167, 210, 303, 304, 356-359, 377; (4) 104; (5) 39; (8) 138; ( 9 ) 26, 152, 153, 155, 160, 182, 216 Schmidt, B.F. (6) 193 Schmidt, H. (1) 40, 283; (4) 42; (7) 132, 136 Schmidt, M.C. (6) 91 Schmidt, M.W. (1) 249 Schmidt, R.R. (7) 160 Schmidt, W. (6) 312 Schmidt, W.M. (9) 1 Schmidt, W.N. (6) 296 Schmiemenz, G.P. (9) 138, 139 Schmoburg, D. (1) 212 Schmutzler, R. (1) 105, 212; (2) 44, 54, 55; (4) 98; (5) 6; (8) 15 Schnabl, G. (9) 261 Schnockel, H. (4) 98 Schobert, R. (7) 29, 30 Schoeller, W.W. (1) 250; (4) 103; (7) 4; (8) 5 , 23; (9) 2, 12, 38, 146 Schoellkopf, U. (5) 100 Schoffstall, A.M. (6) 18 Scholten, P.M. (6) 306 Schomburg, D. (1) 105; (2) 10, 54, 55; (8) 15; (9) 152 Schott, H. (6) 385 Schotten, T. (7) 146 Schouten, J.P. (6) 293, 295 Schow, S.R. (3) 36 Schrader, R. (5) 102 Schram, K.H. (6) 398 Schreiber, G. (6) 313

445

Author Index S c h r y v e r , B.B. (6) 1 8 6 S c h u b e r t , U. ( 1 ) 349 Schuhn, W . ( 1 ) 309 Schulman, L.H. ( 6 ) 279 S c h u l t e n , H.R. ( 6 ) 399 S c h u l t z e , P. ( 6 ) 400 S c h u l z , B.S. ( 6 ) 13 S c h u l z , H. ( 3 ) 2 5 Schumann, H . ( 1 ) 2 0 7 ; (3) 2 7 , 44 Schupp, W. ( 8 ) 4 9 ; ( 9 ) 180 S c h u s t e r , R . ( 9 ) 269 S c h u s t e r , S.M. ( 6 ) 8 6 , 8 9 S c h w a r t z , B.D. ( 9 ) 268 S c h w a r t z , J. ( 7 ) 6 4 S c h w e i z e r , E.E. ( 1 ) 228; ( 7 ) 55 S c h w e i z e r , W.B. ( 3 ) 1 6 ; ( 9 ) 175 S c h w e l l n u s , K . ( 6 ) 318 S c k o l ' n i k o v a , L.M. ( 9 ) 198 S c o t t , T.L. ( 6 ) 73 S e c o n i , G . ( 7 ) 58 S e e b a c h , D. ( 7 ) 127 S e e b e r g e r , M.H. ( 1 ) 259 S e e g a , J. ( 1 ) 156 S e e l a , F. ( 4 ) 8 9 ; ( 6 ) 373 9 , 5 7 , 136-138, 302 S e e l y , F.L. ( 7 ) 8 2 S e e l y , R.J. ( 6 ) 42 S e g e r s , R.P.A.M. ( 4 ) 7 3 ; ( 6 ) 107 S e g u i n e a u , P. ( 7 ) 9 1 S e j p k a , H. (1) 272, 323325

( 9 ) 188 S h a b a r o v a , Z.A. ( 6 ) 1 5 8 , 1 5 9 , 315-317 S h a e f f e r , J. ( 6 ) 268 Shagidullin, R.A. (1) 182; ( 9 ) 135-137 S h a g v a l e e v , F.Sh. ( 4 ) 6 0 S h a i d u l i n , S.A. ( 9 ) 224 Shaikhutdinova, I.T. (1) 77 S h a k i r o v , T.Kh. ( 9 ) 137 Shakya, R.P. (1) 11 Shalamov, E.A. ( 9 ) 178 Shao, K.-L. ( 4 ) 9 3 ; ( 6 ) 146 Shao Yong Wu ( 5 ) 146 S h a p i r o , L. ( 6 ) 1 3 5 S h a p i r o , R . ( 6 ) 288 Sharapov, V . A . ( 1 ) 146; ( 9 ) 161 S h a r i k o v , I.Kh. ( 9 ) 1 3 5 , 136 Sharrna, A . S . ( 7 ) 3 9 S h a r p , P . A . ( 6 ) 340 Shaw, B.L. (1) 1 1 6 , 117 Shaw, J . C . ( 8 ) 121 Shaw, L.S. ( 9 ) 218 Shaw, R.A. ( 8 ) 6 6 ; ( 9 ) 218 Shayban, F. 5 ) 146 Shchelkunova M.A. 9) 129 S h c h u k i n a , L I . ( 2 ) 47 Shebana, R . 5 ) 9 1 Shechenko, I v. ( 9 ) 159 S h e l d r i c k , G M. ( 8 ) 51 , 137

S h e l d r i c k , W s. ( 1 ) 1 8 , S e k i , H. ( 6 ) 40 6 9 , 1 6 6 , 3 3 6 , 358; ( 8 ) S e k i n e , M. ( 6 ) 2 9 , 9 5 , 52, 53; ( 9 ) 155, 160, 111-113, 1 2 8 , 1 6 5 S e l i g e r , H. ( 4 ) 7 0 ; ( 6 ) 182 S h e l n e s s , G.S. ( 6 ) 304 149 S h e n , W. ( 1 ) 229 S e m e n i i , V.Ya. ( 2 ) 1 7 Shen, Y. ( 7 ) 61 Semple, G. ( 5 ) 1 1 9 , 1 2 1 ; Shenoy, S. ( 6 ) 3 2 0 ; ( 9 ) ( 9 ) 238 81 S e n d y u r e v , M.V. ( 1 ) 151 Sherer, O.J. (8) 53 S e n n e t t , M.S. ( 8 ) 144 S h e r m o l o v i c h , Yu.G. ( 4 ) Seno, M. ( 7 ) 6 3 18 Senocq, F. (1) 4 1 Shevchenko, I . V . ( 1 ) 281; Sentemov, V . V . ( 5 ) 5 3 S e r a f i n o w s k a , H.T. ( 6 ) ( 9 ) 29 Shevchuk, M . I . ( 1 ) 200, 117 S e r f o n t e i n , W.J. ( 9 ) 272 201, 219 S h e v e s , M. ( 7 ) 105 S e r i n a , L. ( 6 ) 209 S h i , L. ( 7 ) 27 S e s e k e , U. ( 8 ) 5 1 , 5 2 , S h i b a e v , V.P. (8) 1 6 9 137 S h i b a s a k i , M. ( 7 ) 1 3 9 S e t k i n a , V.N. ( 1 ) 2 S h i b a t a , I . ( 1 ) 125; ( 3 ) S e v e r e n g i z , T. ( 1 ) 102 45 S e v e r i n , E.s. ( 6 ) 232 Seyden-Penne, J. ( 5 ) 118; Shibayarna, K . ( 8 ) 48; ( 9 ) 4 (7) 72; ( 9 ) 42, 45, 8 5 S h a b a n a , R. ( 5 ) 9 1 , 1 4 1 ; S h i b u t a n i , M. ( 7 ) 1 4 8 ,

149 S h i i k i , S. ( 1 ) 194 S h i l o v , S.A. ( 1 ) 1 5 1 Shim, I . W . (1) 42 S h i m i z u , M. ( 5 ) 11 S h i o b a r a , Y. ( 7 ) 130 S h i r a i s h i , M. ( 6 ) 36 S h k l o v e r , V.E. (9) 219 S h o m s h t e i n , Z.A. ( 6 ) 209 S h o r t l e , D. ( 6 ) 203 S h r e e v e , J . M . ( 9 ) 226 S h r i v e r , D.F. ( 8 ) 1 5 5 , 156 S h u g a r , D. ( 6 ) 4 6 S h u l ' g i n , V.F. (1) 3 3 4 ; ( 4 ) 38; ( 8 ) 47, 54; ( 9 ) 201 Shum, F.Y. ( 6 ) 271 Shumeiko, A.E. ( 8 ) 100, 114 Shumyantseva, V . V . ( 6 ) 97 Shvedova, Yu.1. ( 5 ) 48 S i a e o k i , Z. ( 9 ) 191 S i c a r d , G. ( 1 ) 5; ( 4 ) 9 5 ; (7) 16 S i d d a l l , T.L. (1) 234; ( 4 ) 27 S i d d i q u i , M.Z. ( 1 ) 150 S i d k y , M.M. ( 5 ) 7 S i d o r e n k o , E.S. ( 8 ) 174 S i e b e r , H . ( 6 ) 237 S i g e l , H. ( 6 ) 357 Sigman, D.S. ( 6 ) 337 S i h , C.-J. ( 7 ) 114 S i l v e r m a n , R . H . ( 6 ) 184 S i l v e r t o n , J.V. ( 9 ) 214 Simon, Z. ( 8 ) 6 4 Simonnin, M.-P. ( 5 ) 118; ( 7 ) 72; (9) 42, 45, 8 5 Sirnpkins, N.S. ( 7 ) 1 2 8 S i n g e r , B. ( 6 ) 212, 213 S i n g l e r , R.E. ( 8 ) 9 8 , 144 S i n i t s a , A . D . ( 2 ) 50, 5 1 ; ( 4 ) 63; (5) 71, 87, 106; ( 8 ) 28, 29, 134; ( 9 ) 212 S i n i t s y n a , N . I . ( 1 ) 188; (8) 1 2 9 S i n o u , D. ( 1 ) 114 S i n y a s h i n , O.G. ( 4 ) 3 6 , 7 1 , 72 S i p p e l ' , I.Ya. ( 5 ) 1 2 5 S i r o t k i n , K . ( 6 ) 205 S i s k o , J.T. (8) 155 S i s l e r , H. (1) 89 S i u , G. ( 6 ) 300 S j o b e r g , B.-M. ( 6 ) 241 S k a l s k i , B. (6) 380 S k e l t o n , B.W. (1) 3 9 Skone, P.A. ( 6 ) 116 Skopenko, V . V . ( 1 ) 3 3 4 ; ( 4 ) 38; (8) 47; ( 9 ) 201

446 Skowronska, A. (2) 31; ( 5 ) 126 Skrydstrup, T. (7) 159 Skrzypczynski, 2. (4) 64 Skurat, A.V. (6) 232 Sladky, F. (1) 178 Slinimskii, G.L. (8) 164,

Organophosphorus Chemistry Spassky, A. (6) 337 Spassov, S.L. (9) 87 Spears, L.G. (9) 249 Spector, T. (6) 93 Spek, A.L. (8) 192-194 Spengler, S.J. (6) 212,

213

Sperling, W. (7) io4 Slowikowski, D.L. (6) 398 Spiro, T . G . (6) 396 Smaardijk, A.A. (5) 114, Spitz, F.R. (9) 89 Spitz, S . A . (6) 175 134; (9) 144 Smale, T.C. (7) 110, 111 Spitznagel, G.W. (9) 11 Spitzner, D. (7) 43 Smee, D.F. (6) 14 Spivach, J . D . (5) 83 Smegal, J . A . (7) 64 Sporn, M.B. (7) 100 Smerat, G. (7) 89 Sprivzl, M. (6) 196 Smirnova, E . I . (4) 54 Sproat, B.S. (6) 110 Smith, A. (5) 155-157 Sridharan, K.R. (9) 106 Smith, A.B. (3) 36, 37; Srinivasin. C. (1) 98 (7) 126, 131 Srivastava, R.C. (1) 1 Smith, C.C. (6) 180 Srivastava, S. (5) 30; Smith, C . L . (6) 393 Smith, L.M. (6) 299 (6) 247 Stahl, D.A. (6) 301 Smith, R. (6) 17 Stanley, G.C. (1) 49 Smith, S.J. (6) 70 Starke, U. (2) 44 Smorygo, N.A. (5) 136; Starr, P.A. (6) 396 (9) 140 Starzewski, K.A.O. (7) 66 Smrt, J. (6) 103 Stasyuk, A.P. (1) 196, Smurova, E.V. (8) 175 Smythe, M.E. (1) 387; (8) 197 Stawirkki, J. (4) 79, 81; 131, 135, 136 So, K . K . (1) 139, 140 (6) 35 Sobolev, V.G. (5) 75 Stec, W . J . (4) 7, 66; (5) Soderlund, H. (6) 290 10, 19, 37; (6) 22, 51, Sogin, M.L. (6) 301 57, 168, 171; (9) 49, 214 Soifer, G.B. (9) 70 Steger, G. (6) 321 Sokol, O.G. (5) 116 Steglich, W. (5) 102 Sokolov, M.P. (9) 83 Sokol'skaya, I . B . (8) 169 Steiger, T. (9) 78 Solaiman, D. (6) 68 Steinberg, J.J. (6) 269 Solnick, D. (6) 340 Steiner, K . S . (6) 206 Stelten, J. (2) 42 Sologub, L . S . (8) 9 Stelzer, 0. (1) 12, 69, Solomon, J. (6) 269 121; (4) 43 Solov'ev, A.V. (4) 18 Sommer, H. (1) 12, 69, Stepanov, B . I . (9) 65 Stepanov, V.A. (2) 17 121; (4) 43 Stepanova, T.Ya. (9) 224 Sonenberg, N. (6) 350 Songstad, J. (7) 10; (8) Stephen, S . J . (9) 123 Stepowska, H. (1) 108 21, 191; (9) 222 Sonnemans, M.H.W. (9) 114 Stercho, J . P . (3) 12; (9) 43 Sontheimer, G.M. (6) 373 Stevenson, W.H. (2) 4 Sorbi, R.T. (6) 47 Stewart, C.A. (1) 354; Sorenson, O.W. (6) 376;

175

(9) 72

(4) 94, 106; (9) 190

Sorokina, S.F. (1) 7; (4) Stiege, W. (6) 292 Stille, J.K. (1) 67 39; (9) 163 Stoehrer, G. (6) 287 Sosnovsky, D. (6) 195 Sournies, F. (8) 67, 88, Stohrer, W.D. (6) 400 Stollberg, D. (1) 160; 195 Sousa, R. (6) 220 (4) 55 Southgate, R. (7) 110, Stoppioni, P. (1) 365 111 Storch, W. (1) 72, 171; (4) 108 Sowerby, D.B. (2) 3

Storhoff, B.N. (1) 48 Strange, G.A. (7) 124 Strauss, E.C. (6) 300 Streitweiser, A. (2) 12;

(9) 19 Strepikheev, Yu.A. (5)

77; (8) 19 Strijtveen, B. (5) 114 Stritt, H.P. (1) 170 Stromberg, R. (4) 79,

81; (6) 35 Struchkov, Yu.T. (1) 331,

380; (4) 102; (8) 24, 54, 190; (9) 150, 159, 166, 174, 178, 194, 201, 203, 212, 215 Stryer, L. (6) 54, 88 Stubbe, J. (6) 92-94, 325, 326 Sturm, P. (6) 55 Sturtz, G. (4) 5 (5) 68, 73 Stuv;, L. (6) 193 Styruchkov, Yu.T. (9) 219 Subotkowski, W. (5) 94 Subramanian, R. (6) 327 Suck, D. (6) 352 Suda, M. (7) 96 Suga, H. (7) 93 Suggs, J.W. (6) 197, 198 Sugiura, M. (4) 96; (5) 132 Sugiyama, H. (6) 323, 324 Sullivan, J.M. (8) 119 Sulzer, G.M. (8) 152 Sumitomo, H. (7) 130 Summers, M.F. ( 4 ) 93; (6) 146, 376 Suter, B. (6) 308 Sutoh, K. (6) 246 Sutter, M.A. (7) 127 Suva, R.H. (6) 55, 56 Suzuki, H. (5) 57; (7) 99 Suzuki, N. (1) 59; (3) 19 Svara, J. (1) 211, 343, 344; (2) 18; (7) 15 Swaminathan, S. (7) 83 Swamy, K.C.K. (8) 80,92, 93, 117 Swiedan, N . I . (9) 9 Swoboda, H. (7) 43 Symons, M.C.R. (6) 272 Syrneva, L.P. (9) 134 Syvunen, A.-C. (6) 290 Szabo, A.G. (7) 150 Szabolcs, A. (6) 200 Szemzo, A. (6) 200 Szewczyk, J. (1) 340; (4) 100; (5) 113; (9) 33 Taagaard, M. (4) 40, 82

447

Author Index Tabata, S. 5 ) 105 Taber, A.M. ( 1 ) 151 Tabor, J.H. ( 6 ) 341 Taboury, J. ( 6 ) 381 Tabrizi, A . ( 6 ) 206 Tafesse, F. ( 6 ) 359 Taffer, I.M. ( 7 ) 123 Tagaya, M . ( 6 ) 235, 236 Taguchi, T. ( 7 ) 103 Taillandier, E. ( 6 ) 381 Taira, K . ( 2 ) 34; ( 5 ) 25 Takabe, K . ( 7 ) 140 Takacs, J.M. ( 7 ) 82 Takahashi. K. ( 6 ) 58 Takahashi, M. ( 6 ) 40, 214, 215 Takai, Y. ( 9 ) 46 Takaku, H. ( 4 ) 75; ( 5 ) 70; ( 6 ) 33, 109, 119 Takaya, H. ( 1 ) 54 Takemasa, T. ( 7 ) 109 Taketomi, T. (1) 54 Takeyama, T. ( 1 ) 58; ( 3 ) 18 Takigawa, T. ( 7 ) 137 Tamano, M. ( 1 ) 126 Tamas, J . ( 6 ) 402 Tamatsukuri, S. ( 4 ) 77; ( 6 ) 30 Tamm, C. (6) 139 Tamer, T. ( 1 ) 190 Tamura, J.K. ( 6 ) 234 Tanaka, H . ( 1 ) 376; ( 5 ) 150 Tanaka, T. ( 4 ) 77; ( 6 ) 30 Tancheva, Ch. ( 5 ) 127; ( 9 ) 87 Tanielian, O.V. ( 5 ) 148 Tanigami, T. (8) 165 Tanimura, H. ( 6 ) 113 Tanner, N.K. ( 6 ) 342 Tansley, G. ( 6 ) 77, 78 Tarasevich, A.S. ( 9 ) 44 Tarasova, R . I . ( 1 ) 188; (8) 127-129, 134 Tarusova, N.B. ( 6 ) 96 Tashenov, A. ( 9 ) 256 Tashkhodzhaev, B. ( 5 ) 109; ( 9 ) 200 Tashma, 2 . ( 9 ) 197 Tatsuoka, T. ( 3 ) 39 Tautchenko, I. ( 2 ) 57 Taylor, A.J. ( 6 ) 143 Taylor, D.A. ( 6 ) 197, 198 Taylor, E.C. ( 7 ) 112 Taylor, J.W. ( 6 ) 202, 312 Tebby, J . C . ( 4 ) 23, 24; ( 7 ) 19 Teebor, G.W. ( 6 ) 269 ten Hoeve, W. ( 5 ) 5; ( 9 ) 204

Teoule, R . ( 6 ) 140, 141

Terent'eva, S.A. ( 9 ) 90 Tesser, G.I. ( 4 ) 73; ( 6 ) 32, 107, 125, 160 Teulade, M.-P. ( 5 ) 16; ( 7 ) 75, 97 Thatcher, G.R.J. ( 2 ) 32, 33; ( 5 ) 26, 27 Thayer, A.M. ( 9 ) 58 Thiem, J. (7) 138 Thoma, R.J. ( 1 ) 295 Thomas, B. ( 1 ) 233; (8) 149; ( 9 ) 22, 80 Thomas, D.H. ( 8 ) 152 Thomas, M.J. (1) 81 Thompson, A.S. ( 3 ) 36 37 Thompson, M.D. ( 5 ) 14 ( 9 ) 209 Thompson, M.L. ( 4 ) 53 ( 9 ) 164 Thomsen, I. (5) 142, 44 Thornton-Pett, M. ( 1 ) 116 Thorson, M. ( 5 ) 140 Throckmorton, L. (8) 7 ; ( 9 ) 79 Thuong, N.T. ( 6 ) 161, 178, 395 Thyagarajan, G. ( 1 ) 177 Tiekink, E.R.T. ( 9 ) 208 Tikhonova, E.G. ( 8 ) 84 Tilak, B.D. ( 9 ) 239 Tilhard, H.-J. ( 3 ) 25 Tirnmer-Bosscher, H. ( 8 ) 83

Tirnokhin, B.V. ( 2 ) 2 Timpe, H.-J. ( 1 ) 244 Tinoco, I . ( 6 ) 147 Tirakyan, M.R. (5) 131 Titskii, C.D. ( 8 ) 100, 114 Tius, M.A. ( 7 ) 129 Tjaden, U.R. ( 9 ) 262 Tkachev, V . V . ( 9 ) 184 Tocher, J. ( 7 ) 70 Topelmann, W. ( 1 ) 233 Togo, H. (1) 227 Tokoroyamo, T. ( 7 ) 36 Tokumasu, S. (5) 130; ( 7 ) 88, 94 Tollefson, N.M. ( 8 ) 8 Tolman, R.L. ( 6 ) 16 Tolstikov, A.G. ( 7 ) 113 Tolstikov, G.A. ( 7 ) 113 Tomasz, J . ( 6 ) 402 Tomasz, M. (6) 330 Tomaszek, T.A. ( 6 ) 89 Tomita, K. ( 6 ) 25, 133 Tomoi, M. (1) 194 Toomey, N.L. ( 6 ) 67 Topelmann, W. ( 8 ) 149 Topping, R . J . ( 1 ) 370 Tordo. P. ( 1 ) 136, 267: ( 9 ) ' 1 0 7 , -110, 115

Toren, P.C. (6) 401 Torgomyan, A.M. (1) 82 Tornvall, H. ( 6 ) 241 Torreilles, E. ( 1 ) 215, 216, 218 Torrence, P.F. ( 4 ) 9 1 ; ( 6 ) 182-184 Tosing, G. ( 1 ) 156; ( 9 ) 185 Tossi, A . B . ( 6 ) 366 Toth, G . ( 1 ) 104; ( 8 ) 11 Toulade, M.P. (5) 59 Toulmg, J.J. ( 6 ) 178 Toupet, L. ( 1 ) 379 Towner, P. (6) 344 Townsend, L.B. ( 7 ) 144 Toyofuku, M. ( 7 ) 37 Toyota, K . ( 1 ) 274, 275, 313; ( 8 ) 48; ( 9 ) 4 Trahms, L. ( 9 ) 96 Traldi, P. ( 8 ) 61, 69-73 Tran-Dinh, S. ( 6 ) 381 Trifonov, E.N. ( 6 ) 392 Trifonov, L.S. ( 5 ) 128 Trinquier, G . ( 8 ) 4 , 6 3 Trippett, S. ( 2 ) 13-15; ( 5 ) 20; ( 7 ) 8 6 ; ( 9 ) 47, 48, 55 Tromp, M. ( 1 ) 180; ( 4 ) 78, 80; ( 6 ) 26, 27, 172, 181 Trostyanskaya, I.G. ( 1 ) 148, 149 Trotta, F. ( 1 ) 242 Trotter, J . ( 8 ) 107; ( 9 ) 220 Trsic, M. (8) 1 2 2 True, 0. ( 8 ) 122 Trujillo, H. ( 1 ) 48 Truong, T.N. ( 1 ) 248; ( 7 ) 5

Trzcinska-Bancroft,B. ( 7 ) 70 Tsai, E.W. ( 8 ) 7; ( 9 ) 79 Tsao, C.-H., ( 1 ) 1 5 Ts'o, P.O.P. (6) 175, 180 Tsuboi, A . ( 9 ) 243 Tsuboi, M. ( 6 ) 112, 397 Tsuchiya, H. ( 5 ) 70; ( 6 ) . 109 Tsuchiya, S. ( 7 ) 6 3 Tsuda, S. ( 6 ) 311 Tsuge, 0. ( 7 ) 9 3 Tsukamoto, M. ( 7 ) 36 Tsunekawa, K. ( 4 ) 96; ( 5 ) 132 Tsvetkov, E.N. ( 1 ) 1 4 ; (9) 8 Tuck, S.P. ( 5 ) 33; ( 6 ) 75; ( 9 ) 51 Tufano. M.D. ( 7 ) 40 Tullius, T.D. ' ( 6 ) 338


448 Tundo, P. (1) 242 Tupchienko, S.K. (2) 50; (8) 28, 29

Tur, D.R. (8) 157, 161, 164,. 174, 175 Turpin, P.Y. (6) 395 Turro, N.J. (6) 366 Turski, K. (5) 41 Tuzhikov, 0.1. (1) 76 Tyka, R. (5) 94 Tzschach, A. (1) 375

Ubbink, J.B. (9) 272 Uchiyama, M. (4) 85; (6) 108

Van den Berg, E.M.M. (7) 102

van der Hofstad, W.J.M. (2) 16; (9) 67

van der Huizen, A.A. (8) 81

van der Klein, P.A.M. (6) 41

van der Marel, G.A.. (1) 180; (4) 65, 78, 80; (6) 26, 27, 41, 172, 323

van der Meer-Kalverkamp, A. (8) 81 Van der Veken, B.J. (9) 133

van de Sande, J.H. (6) Ueda, M. (5) 151 Ueda, S. (6) 109; (6) 119 196 van Genderen, M.H.P. (6) Ueda, T. (6) 311 372 Uesugi, S. (6) 133, 134 van Haastert, P.J.M. (6) Uhl, W. (1) 130 57 Uhlmann, E. (4) 76; (6) van Heerikhuizen, H. (6) 157 224 Ulanovsky, L. (6) 392 van Kooyk, R.J.L. (6) Ulses, R. (5) 111 371, 372 Underiner, T.L. (9) 277 Van Leeuwen, P.W.N.M. (3) Underwood, G.R. (6) 288 43 Une, F. (5) 105 van Mansfeld, A.D.M. (6) Urbanke, C. (6) 303 354 Urbauer, J.L. (6) 86 Urdea, M . S . (6) 105, 152 Van Sande, J. (6) 52 Usman, N. (4) 86; (6) 31 van Teeffelen, H.A.A.M. Usmanova, L.N. (4) 48 (6) 354 van Westrenen, J. (6) 181 Uznanski, B. (6) 21, 22, Vapirov, V.V. (8) 100, 168 114

Vakulenko, O.V. (2) 47 Valeeva, T.G. (9) 102 Valentin, A. (2) 11 Valentin, L.H. (2) 11 Valentine, D. (1) 65 Valentini, C. (1) 176 Valenzuela, B.A. (3) 13; (9) 176

Valerio, R.M. (5) 12 Valetdinov, R.K. (1) 76, 77

Valle, L. (3) 13, 41; (9) 176

van Bolhuis, F. (5) 134; (8) 125, 126; (9) 144

van Boom, J.H. (1) 180; (4) 40, 65, 78, 80, 82; (6) 26, 27, 41, 172, 181, 323 van Brunt, J. (6) 150 van de Grampel, J.C. (8) 81-83, 108, 125, 126, 192-195 van de Huizen, A.A. (8) 195

Varbanov, S. (3) 4 Vasella, A. (4) 12; (5) 103; ( 9 ) 98, 205

Vasil'ev, V.P. (2) 46; (5) 135; (9) 253

Vasil'eva, T.V (1) 141143

Vasseur , J.-J. (6) 145 Vasyakina, L.A (1) 188; 29 Vaultier, M. (1) 106, 107 Vdovenko, S.I. ( 9 ) 128 Veale, C.A. ( 7 ) 118 Vebrel, J. (5) 42 Vecchi, E. (8) 61, 69-73 Vecerkova, H. (6) 103 Vedananda, T.R. (7) 137 Veeneman, G.H. (4) 65 Vegh, D. (8) 12 Veiko, V.P. (6) 317 Veits, Yu.A. (1) 184; (4) 45; (5) 159, 160; (8) 27, 39, 40 Venkov, A.P. (5) 18 Venturello, P . (1) 242 Ven'yaminova, A.G. (6) (4) 68; (8)

114

Verdine, G.L. (6) 330 Verheyden, J.P.H. (6) 14 Verjovsky-Almeida, S. (6) 72

Verkade, J.G. (2) 59 Verrier, M. (1) 266 Viala, J. ( 7 ) 121, 122 Vicic, J.C. (8) 187 Victorianio, L. (1) 78 Viersen, F.J. (8) 126 Vignais, P.V. (6) 243 Villafranca, J.J. (6) 81, 82, 238; (9) 51

Villieras, J. ( 7 ) 91 Vinogradov, S.V. (8) 164 Vinogradova, M.N. (6) 317 Vinogradova, S.V. (8) 91, 157, 174, 175

Viscidi, R.P. (6) 289 Visnick, M. (7) 131 Visser, G.M. (6) 41, 181 Vizel', A.O. (2) 47 Vlasov, V.V. (6) 282, 284 Vogel, S. (6) 65 Vogelbacher, U. (9) 24 Vogelbacher, V.-J. (1) 321, 326

Vogt, W. (9) 261 Volkov, V.N. (9) 240 Volter, A. (4) 90 Volz, P. (1) 273 von Allwoerden, U. (1) 134

von der Saal, W. (6) 81, 82; (9) 51

von Hippel, P.H. (6) 293 von Itzstein, M. (1) 109; (2) 36

von Schnering, H.G. (1) 25, 257

Vo-Quang, L. ( 5 ) 93 Vorachek, W.R. (6) 293 Vorob'eva, L.A. (1) 7; (4) 39; (9) 163

Voronkov, M.G. (9) 278 Voropai, L.M. (9) 125 Vougloukas, A.E. (1) 11 Vulfson, E.N. (6) 244 Wada, M. (9) 243 Wakabayashi, T. (6) 246 Walker, B.J. (7) 2, 31, 156; (9) 173

Walker, N.P. (8) 37; (9) 179

Wallace, P. (3) 32 Wallace, S.S. (6) 263 Walter, R. (1) 336; (8) 53

Wamhoff, H. (8) 49; ( 9 )

Author Index 180

Wan, J.K.S. ( 9 ) 113 Wang, A . H . ( 6 ) 378 Wang, Q. ( 6 ) 132 Wang, Y. ( 6 ) 132 Wang, Y.-F. ( 7 ) 114 Wang, Z. ( 9 ) 88 Wani, A.A. ( 6 ) 251 Wannagat, U. ( 8 ) 55 Waring, R.B. ( 6 ) 344 Warner, B.D. ( 6 ) 105 Warren, S. ( 3 ) 28-32, 34 Warrens, C.P. ( 8 ) 37; ( 9 ) 179 Wartell, R.M. ( 6 ) 377 Wassow, H.G. ( 9 ) 185 Watanabe, K . ( 5 ) 57; ( 7 ) 99 Watanabe, T. ( 7 ) 52 Watkins, C.L. ( 1 ) 208 Watt, W. ( 6 ) 173 Watterson, D.M. ( 6 ) 154 Wawer, A. ( 9 ) 274 Wawer, I. ( 9 ) 274 Waykole, L. ( 7 ) 147 Webb, G.A. ( 9 ) 85 Webb, T.R. ( 6 ) 281 Webber, S.E. ( 7 ) 118 Weber, G. (1) 186 Weber, H. (3) 174, 175; ( 4 ) 97 Weber, J . ( 3 ) 17; ( 9 ) 246 Weber, K.L. ( 8 ) 52 Weber, L. (1) 258, 284286, 290, 291; ( 7 ) 6 8 , 69 Weber, W. ( 9 ) 157 Webster, J . (1) 120 Wechter, W.J. ( 6 ) 143 Wedrychowski, A. ( 6 ) 296 Wegener, W. ( 9 ) 143 Weidenbruch, M. (1) 257 Weinberger-Ohana, P. ( 6 ) 163 Weinfeld, M. ( 6 ) 252, 261 Weinhouse, H. ( 6 ) 163 Weintraub, H . ( 6 ) 179 Weis, M. (1) 80; ( 7 ) 7 Weiss, E. (1) 183 Weiss, P.M. ( 5 ) 34, 35 Weiss, W. ( 9 ) 157 Weissman, S.A. ( 1 ) 355; ( 4 ) 107 Weith, H.L. ( 6 ) 401 Welch, C . J . (6) 15, 129 Weller, F. ( 9 ) 171 Wellman, G. ( 7 ) 143 Wells, A.S. (1) 373 Wells, G . J . ( 7 ) 147 Wells, R.D. ( 6 ) 267 Werner, D.E. ( 6 ) 208 Wendisch, D. ( 5 ) 126

449 Wendland, M.F. ( 6 ) 84 Wermuth, U. (1) 105; ( 2 ) 54, 55; ( 8 ) 15 Werntges, H. ( 6 ) 321 Wesseley, H.-J. (1) 130 Westerduin, P. ( 4 ) 65 Westheimer, F.H. ( 6 ) 2 Wewers, D. ( 7 ) 68, 69 Whelan, J. (1) 17 White, A . H . (1) 39 White, H.D. ( 6 ) 70 White, J. ( 7 ) 6 6 , 140 White, S.A. ( 6 ) 336 Whitesides, G.M. ( 5 ) 9 ; ( 6 ) 190 Whitham, G. ( 3 ) 35 Whittle, P . J . ( 2 ) 15 Whittle, R . R . ( 8 ) 8 , 74 Whittlesey, B.R. (1) 259, 354; ( 4 ) 106; ( 9 ) 190 Wickham, G . ( 7 ) 147 Wiechman, B.E. ( 7 ) 95 Wieczorkowski, J . ( 9 ) 211 Wife, R.L. ( 3 ) 43 Wilk, A. ( 9 ) 49 Wilke, G. (1) 111 Will, G. ( 8 ) 49; ( 9 ) 180 Willhalm, A. ( 1 ) 303, 304; ( 9 ) 153 Williams, D.G. ( 6 ) 375 Williams, D.L. ( 6 ) 304 Williams, E.A. (1) 127 Williams, J.M. ( 7 ) 108 Williams, N.E. ( 5 ) 147 Williams, N . R . ( 5 ) 1 Williamson, D. ( 7 ) 150 Willis, C . J . ( 1 ) 38 Willson, M. ( 8 ) 6 7 , 8 9 Wilson, J . R . H . ( 4 ) 6 ; ( 5 ) 63 Wilson, S. (2) 4 Wilson, W.D. ( 6 ) 383 Wilt, J.W. ( 7 ) 40 Wilting, T. ( 8 ) 81 Winkle, S.A. ( 6 ) 387 Winter, H. ( 8 ) 108, 192194 Winzenberg, K . N . ( 3 ) 36 Wirkner, Ch. (1) 40; ( 4 ) 42 Wise, D.S. ( 7 ) 144 Wisian-Neilson, P. ( 8 ) 170 Witke, W. ( 6 ) 239 Witt, M. ( 8 ) 137 Wittman, M.D. ( 3 ) 33 Witzgal, K . ( 7 ) 1, 58 Woerz, H.-J. (1) 170 Woisard, A . ( 6 ) 377, 382 Wolanski, A. ( 6 ) 274 Wolf, R. (1) 332, 333; (8) 17, 18

Wolfenden, R. ( 6 ) 98 Wolfes, H. ( 6 ) 318, 319 Wolfsberger, W. ( 1 ) 47; ( 8 ) 50 Wolmershauser, G. ( 3 ) 44 Wong, C.-H. ( 6 ) 190 Wong, J . K . ( 7 ) 117 Wonnacott, A. ( 7 ) 34 Woods, M. ( 8 ) 90, 103 Woollins, J . D . ( 8 ) 37; ( 9 ) 179 Wozniak, L. ( 3 ) 1; ( 4 ) 22 Wren, B.W. ( 6 ) 272 Wright, G.E. ( 6 ) 6 6 , 67 Wright, T.C. (1) 354; ( 4 ) 106; ( 9 ) 190 Wroblewski, K. ( 9 ) 101 WU, F.Y.-H. ( 6 ) 68 WU, H.-M. ( 6 ) 391 WU, H.-y. ( 6 ) 199 Wu, J . C . ( 6 ) 325, 326 Wuethrich, K . ( 6 ) 376; ( 9 ) 72 Wunderlich, B. (8) 162 Wyatt, J . R . ( 9 ) 237 Wynberg, H. ( 5 ) 5 , 114, 134; ( 9 ) 144, 204 Xin, Y. ( 7 ) 61 Xu, C. ( 6 ) 324 XU, J.-F. ( 6 ) 132 Xu, Y . ( 5 ) 8 6 ; ( 6 ) 132 Yabushita, S. ( 9 ) 6 Yadagiri, P. ( 7 ) 122 Yafina, A . A . ( 9 ) 109 Yagi, M. (1) 54 Yagodin, V.G. ( 9 ) 245 Yagodinets, P . I . (1) 219 Yagupol'skii, L.M. ( 2 ) 17 Yakobi, L.V. ( 6 ) 159 Yakobson, G.G. ( 9 ) 104 Yakout, E.M. ( 5 ) 7 Yakovleva, E.P. ( 5 ) 2 Yakovleva, O.G. ( 9 ) 233 Yakovson, G.G. ( 9 ) 149 Yamaguchi, K . ( 4 ) 67 Yamamoto, H. ( 4 ) 96; (5) 66 Yamamoto, K . (6) 246; ( 7 ) 149 Yamamoto, N. (8) 102 Yamanaka, G. ( 6 ) 54, 88 Yamane, A. (6) 120 Yamasaki, Y. ( 5 ) 123 Yamashita, M. ( 4 ) 96; ( 5 ) 66, 132 Yamashita, Y. ( 6 ) 214 Yamauchi, K . ( 5 ) 105 Yamaura, K. (8) 165


450 Yamazaki, N. (4) 67 Yang, J. (7) 27 Yang, N.C. (6) 254 Yang, S. (9) 88 Yang, Y. (9) 88 Yang, Y.Y. (8) 123 Yang, Z. (6) 132 Yanovskii, A . I . (9) 178 Yao, F.L. (6) 207 Yaouane, J.J. (5) 68 Yarkov, A . v . (9) 132 Yaroshenko, G.F. (5) 96, 97; (9) 253

Yashina, N.S. (9) 82 Yashkin, V.V. (9) 245 Yasumoto, F. (6) 40 Yatsimirskii, K . B . (9) 14 Yde, B. (5) 140, 144 Yen Vo-Quang (5) 93 Yeung Lam KO, Y.Y.C. (1) 379

Yi, Q. (5) 57; (7) 99 Yoder, C.H. (9) 39 Yohannes, P.G. (6) 59 Yokoi, M. (1) 238 Yolken, R.H. (6) 289 Yolov, A.A. (6) 316, 317 Yoshifuji, M. (1) 263, 274, 275, 313; (8) 48; ( 9 ) 3, 4 Young, R.N. (7) 115 Youngquist, R.S. (6) 332 Yousif, N . M . (5) 141 Yuanyao Xu (5) 54 Yudelevich, V . I . (5) 2 Yui, S. (6) 297 Yurchenko, V.G. (1) 85 Yurkova, M . S . (6) 232 Yusman, T.A. (8) 130; (9) 232

(8) 13; (5) 109; (9) 200 Yvernault, G. (9) 127 Yvernault, T. (3) 17; (9) 127, 246

Yusopov, M.M.

Zabirov, N.G. (5) 158 Zabotina, E.Ya. (1) 381, 382

Zahn, T. (7) 67 Zajicek, J. (6) 24 Zakim, M.M. (6) 148 Zal'tsman, I.S. (1) 209; (8) 32

Zamaletdinova, G.U. (9) 233

Zamboni, R. (7) 115 Zanka, A. (9) 257 Zan-Kowalczewska, M. (6) 46

Zappia, G. (6) 117 Zard, S.Z. (1) 227 Zarytova, V.F. (6) 131, 156, 249, 284 (6) 1, 343, 346 Zavalishina, A . I . (4) 54 Zavgorodnii, C.G. (6) 96 Zawadzka, H. (6) 288 Zayakina, G.V. (6) 158 Zaychikov, E . f . (6) 237 Zbiral, E. (5) 74, 79; (7) 42 Zdravkova, Z. (5) 153 Zecchi, G. (8) 10 Zeelie, B. (3) 46 Zeiger, H.E. (1) 88 Zemlyyanoi, V.N. (9) 128 Zhadanov, B.V. (5) 96,

Zaug, A . J .

97, 135; (9) 253

Zhang, M. (9) 119 Zhdankovich, E.L. (9) 278 Zhenodarova, S.M. (6) 114 Zhisong, C . (1) 383 Zhmurova, I . N . (1) 85 Zhuzhi, Z. ( 9 ) 103 Zibuck, R. ( 7 ) 126 Ziegler, M . L . (7) 67 Zielinski, W.S. (6) 196 Zijlstra, J . G . (8) 82 Zimmerman, A.L. (6) 54 Zimmermann, P. ( 7 ) 160 Zimmermann, R.A. (6) 275, 276

Zinchenko, A . I . (6) 185 Zingaro, R.A. (9) 172 Zink, J.I. (8) 123 Zinner, G. (1) 206; (7) 13

Zinzyuk, T.A. (1) 200 Zipkin, R.E. (7) 123 Zlot'skii, S.S. (2) 43 Zobowa, M. (6) 292 Zon, G. (4) 7, 93; (5) 46; (6) 146, 168, 171, 376 Zsabo, G. (1) 99; (4) 26 Zschunke, A. (9) 64 Zsohai, L. (1) 262, 269 Zuev, M.B. (9) 93 Zurmuhlen, F. (1) 293 Zwaschka, F. (1) 166 Zwierzak, A. (5) 41, 43 Zyablikova, T . A . (2) 47; (9) 83, 93 Zyk, N.V. (5) 65; (9) 195 Zykova, T.V. (4) 47, 60 Zyryanova, L . I . (2) 47

Organophosphorus Chemistry (Volume 18) Specialist Periodical Report

Organometallic Chemistry, Volume 36 (Specialist Periodical Reports)

Organometallic Chemistry, Volume 31 (Specialist Periodical Reports)

Catalysis: v. 18 (Specialist Periodical Reports)

Organophosphorus Chemistry (Volume 21)

Organosphophorus Chemistry (Specialist Periodical Reports) (v. 4)

Heterocyclic Chemistry: v.4 (Specialist Periodical Reports)

Organophosphorus Chemistry - Volume 22 (SPR Organophosphorus Chemistry (RSC))

Organophosphorus Chemistry - Volume 15 (SPR Organophosphorus Chemistry (RSC))