Organosphophorus Chemistry (Specialist Periodical Reports) (v. 4)

A Specialist Periodical Report

Organophosphorus C hem istry Volume 4

A Review of the Literature Published between July 1971 and June 1972

Senior Reporter

S. Trippett, Department of Chemisfry, The Universify, Leicester Reporters R. S. Davidson, The Universify, Leicesfer

N. K. Hamer, Cambridge University D. W. Hutchinson, University of Warwick R. Keat, Glasgow Universify

J. A. Miller, University of Dundee

D. J. H. Smith, The Universify, Leicesfer J. C. Tebby, North Sfaffordshire Polyfechnic B. J. Walker, Queen's Universify of Belfast

@ Copyright 1973

The Chemical Society Burlington House, London, W I V OBN

ISBN: 0 85186 036 2 Library of Congress Catalog Card No. 73-268317

Organic formulae composed by Wright’s Symbolset method

PRINTED IN GREAT BRITAIN BY JOHN WRIGHT AND SONS LTD., AT THE STONEBRIDGE PRESS, BRISTOL BS4 5NU

Foreword

The period covered by this Report has, in most areas of organophosphorus chemistry, been one of consolidation with few new exciting advances. Notable exceptions have been in the study of stable quinquecovalent phosphoranes and of their pseudorotation phenomena, and in the application of molecular orbital calculations to studies of bonding in phosphorus compounds. These together promise a new understanding of the factors which affect stability and reactivity in organophosphorus chemistry and this is bound to provide a powerful stimulus to future progress. The volume of publication continues to increase and, in order to keep the Report to its present size, Reporters have had to be more selective. However, we hope that all significant publications have been covered.

S. T.

Contents ~-

Chapter 1 Phosphines and Phosphonium Salts By D. J. H. Smith

I Phosphines 1 Preparation From Halogenophosphine and Organometallic Reagent From Metallated Phosphines By Reduction Miscellaneous 2 Reactions Nucleophilic Attack on Carbon Activated Olefins Activated Acetylenes Carbonyls Nucleophilic Attack at Halogen Nucleophilic Attack at Other Atoms Miscellaneous

1

1 2 3 4 5 5

5 6 7 8 11 13

I I Phosphonium Salts 1 Preparation 2 Reactions Alkaline Hydrolysis Additions to Vinylphosphonium Salts Miscellaneous

15 18 18 21 22

I II Phosphorins and Phospholes 1 Phosphorins Preparation React ions 2 Phospholes

23 23 25 27

Chapter 2 Qu i nq uecovalent Phosphorus Corn po unds By S. Trippett 1 Introduction 2 Ligand Reorganization and Structure

29 29

vi

Contents 3 Acyclic Systems

31

4 Four-membered Rings

33

5 Five-membered Rings 1,3,2-Dioxaphospholans 1,3,2-Dioxaphospholens 1,2-Oxaphospholans 1,2-Oxaphospholens 1,3,2-Oxazaphospholans 1,3,5-Oxazaphospholens Miscellaneous 6 Six-co-ordinate Species

37 37 39 41 42 43 44 46 49

Chapter 3 Halogenophosphines and Related Compounds By J. A. Miller 1 Halogenophosphines Physical Aspects Reactions Nucleophilic Attack by Phosphorus Electrophilic Attack by Phosphorus Biphilic Reactions with Dienes and with Unsaturated Carbonyl Compounds Miscellaneous

51 51 52 52 53

2 Halogenophosphoranes Preparation and Structure Reactions

62 62 65

3 Phosphines containing a P-X Bond (X = Si, Ge, or Sn)

71

Chapter 4 Phosphine Oxides and Sulphides By J. A, Miller 1 Physical Aspects 2 Preparation From Secondary Phosphine Oxides and Sulphides By Arbusov and Related Reactions By Oxidation of Phosphines By Miscellaneous Routes

60 60

73

74 74 77 77 79

Contents

vii

3 Reactions At the P=O or P=S Group Additions to Unsaturated Phosphine Oxides Miscellaneous Reactions

Chapter 5 Tervalent Phosphorus Acids By B. J. Walker 1 Introduction

79 79 81 82

87

2 Phosphorous Acid and its Derivatives Nucleophilic Reactions Attack on Saturated Carbon Attack on Unsaturated Carbon Attack on Nitrogen Attack on Oxygen Attack on Halogen Electrophilic Reactions Rearrangements Cyclic Esters of Phosphorous Acid Miscellaneous Reactions

87 87 87 89 103 104 107 109 112 113 114

3 Phosphonous and Phosphinous Acids and their Derivatives

115

Chapter 6 Quinquevalent Phosphorus Acids By N. K. Hamer 1 Phosphoric Acid and its Derivatives Synthetic Methods Solvolyses of Phosphoric Acid Derivatives Reactions

117 117 121 126

2 Phosphonic and Phosphinic Acids and Derivatives Synthetic Methods Solvolyses of Phosphonic and Phosphinic Esters Reactions of Phosphonic and Phosphinic Acid Derivatives

129 129 133

3 Miscellaneous

141

137

...

Contents

Vlll

Chapter 7 Phosphates and Phosphonates of Biochemical Interest By D. W. Hutchinson 1 Introduction

143

2 Mono-, Oligo-, and Poly-nucleotides Mononucleotides Nucleoside Polyphosphates Oligo- and Poly-nucleotides Analytical Techniques and Physical Methods

143 143 151 153 158

3 Coenzymes and Cofactors Nucleoside Diphosphate Sugars Vitamin B, and Related Compounds Other Cofactors

158 158 160 161

4 Naturally Occurring Phosphonates

165

5 Oxidative Phosphorylation

166

6 Sugar Phosphates

167

7 Phospholipids

169

8 Enzymology

171

9 Other Compounds of Biochemical Interest

1 74

Chapter 8 Ylides and Related Compounds By S. Trippett 1 Methylenephosphoranes Preparation React ions Halides Car bonyls Miscellaneous

176 176 177 177 178 183

2 Phosphoranes of Special Interest

187

3 Selected Applications of Ylides in Synthesis Natural Products Macrocyclic Compounds Carbohydrates

192 192 195 199

4 Selected Applications of Phosphonate Carbanions

ix 199

5 Ylide Aspects of Iminophosphoranes

203

Contents

Chapter 9 Phosphazenes By R. Keaf 1 Introduction

205

2 Synthesis of Acyclic Phosphazenes From Amides and Phosphorus(v) Halides From Cyano-compounds and Phosphorus(v) Halides From Azides and Phosphorus(I1r) Compounds Other Methods

205 205

3 Properties of Acyclic Phosphazenes Halogeno-derivatives Alkyl and Aryl Derivatives

212 212 216

4 Synthesis of Cyclic Phosphazenes

219

5 Properties of Cyclic Phosphazenes General Halogeno-derivatives Amino-derivatives Alkoxy- and Aryloxy-derivatives Aryl and Alkynyl Derivatives

223 223 224 225 228 23 1

6 Polymeric Phosphazenes

233

7 Molecular Structures of Phosphazenes Determined by Diffraction Methods

234

207 209 210

Chapter 10 Radical, Photochemical, and Deoxygenation Reactions By R. S. Davidson 1 Radical and Photochemical Reactions

236

2 Deoxygenation and Desulphurization Reactions

245

Contents

X

Chapter 11 Physical Methods By J. C. Tebby 1 Nuclear Magnetic Resonance Spectroscopy Chemical Shifts and Shielding Effects 8P

PIx1Compounds

PIv Compounds Pv Compounds Isotopes effects 6C

8H

Studies of Equilibria, Reactions, and Solvent Effects Pseudorotation Restricted Rotation Inversion, Non-equivalence, and Configuration Spin-Spin Coupling JPP and JPM JPC

'JPH JPC*H

JPXH and JPXC,H Relaxation Times, Paramagnetic Effects, and N.Q.R. Studies

250 250 250 252 254 254 255 255 256 257 259 26 1 263 264 264 266 268 268 270 27 1

2 Electron Spin Resonance Spectroscopy

272

3 Vibrational Spectroscopy Band Assignment and Stnict ural Elucidation Stereochemical Aspects Studies of Bonding

274 274 276 277

4 Microwave Spectroscopy

278

5 Electronic Spectroscopy

279

6 Rotation and Refraction

28 1

7 Diffraction

282

8 Dipole Moments, Conductance, and Polarography

286

9 Mass Spectrometry

287

xi

Contents 10 pK and Thermochemical Studies

290

11 Surface Properties

291

12 Radiochemical Studies

292

Author I ndex

293

Abbreviations

AIBN DBU DCC DMF DMSO g.1.c. HMPT NBS n.q.r. PPi TCNE

THF t.1.c.

bisazoisobutyronitrile 1,5-diazabicyclo[5,4,O]undec-5-ene dicyclohexylcarbodi-imide NN-dimethylformamide dimethyl sulphoxide gas-liquid chromatography hexamethylphosphorictriamide N-bromosuccinimide nuclear quadrupole resonance inorganic pyrophosphate tetracyanoethylene tetrahydrofuran thin-layer chromatography

1

Phosphines and Phosphonium Salts BY D. J. H. SMITH

PART I: Phosphines 1 Preparation From Halogenophosphine and Organometallic Reagent.-Unsymmetrical tertiary phosphines (1) have been obtained by the stepwise addition of organometallic reagents of different reactivity to dich1orophenylphosphine.l Dia1kylphenylphosphines and dia1kylst yrylphosphines have been prepared by the reduction of tetrachlorophenylphosphoranewith Grignard reagents.2 The reaction of dichlorophenylphosphine with a large excess of toluene in the presence of aluminium chloride in an autoclave at 210 "Cgave ditolylphenylphosphine.3 The ligand o-diphenylphosphinobenzyldimethy 1silane (2) has been prepared from chlorodiphenylphosphineand the corresponding Grignard reagent.* PhPCl, +ArlZnC1

PhAr'PCI

Ar2Li

Ar'Ar2PhP Arl = .-C,,H, (l' Ar2 = PhC,H,

_I_,

Ph,PCI Mg

a

G. Wittig, H. Braun, and H . 4 . Cristau, Annalen, 1971, 751,17. B. V. Timokhin, E. F. Grechkin, N. A. Tran'kova, and 0. A. Yakutina, J. Gen. Chem.

(U.S.S.R.), 1971, 41, 99. H. Nohira, Y. Hirayama, and T. Hattaha, Yuki Gosei Kagaku kyokai Shi, 1971, 29, 424 (Chem. Abs., 1972,76, 14 649). H. G. Ang and P. T. Lau, J. Organometallic Chem., 1972, 37, C4.

1

2

Organophosphorus Chemistry

A variety of phosphinoacetylenes has been prepared by reaction of an acetylene and a chloroyhosphine in the presence of butyl-lithium.6 The synthesis of several quadridentate ligands containing both phosphorus and arsenic donor atoms, e.g (3), from a chlorophosphine and the appropriate lithio-derivative has been described.6

(Mp-c' +

I

(3)

From Metallated Phosphines.-The polymeric ligand (4) has been formed from chloromethylated styrene-divinylbenzene copolymer and lithium diphenylphosphide.' Trimethylsilylation of potassium phenylphosphide gave the phosphine ( 5 ) , which on treatment with bromine gave phenylphosp horus. (Trimethylstanny1)phosphine (6) has been prepared in high yield from trimethyltin chloride and lithium tetraphosphinoaluminate.B

PhPHK

+ Me,SiCI

Rr2

--+ PhPHSiMe, -+

Me,SiBr

+

HBr

+

+(PhP),

(5)

Na,P

+ ClC0,Et

--+ P(CO,Et), ( 7 ) 2'>'>r,

A. J. Corty, N. K. Hota, T. W. Hg, H. A. Patel, andT. J. O'Connor, Canad. J. Chem., 1971, 49,2706.

' *

J. W. Dawson and L. M. Venanzi, J. Chem. SOC.( A ) 1971, 2897. M. Capka, P. Suoboda, M. Cerny, and J. Hetflejs, Tetrahedron Letters, 1971, 4787. M. Baudler and A. Zarkadas, Chem. Ber., 1971, 104, 3519. A. D. Norman, J. Organometallic Chem., 1971, 28, 81.

3 The elusive tricarbethoxyphosphine (7) has been obtained from the reaction of trisodium phosphide and ethyl chloroformate.1° Ethylphosphorus reacts with various amounts of phenyl-lithium to give the lithium phosphides (8), which are more reactive than ethylphosphorus towards phenyl-lithium and can react further to give complex mixtures of other lithium phosphides.ll Unsaturated phosphines (9) have been prepared with high stereospecificity by the addition of di-t-butylphosphine to

Phosphines and Phosphonium Salts

(EtP), But,PH PhPHK

+

+ PhLi * EtLiP-P(Et),-P(Et)Ph

+ HCECX

PhC=CH

-

(8)

d

(9) X

11 =

0-3

(But),PCH=CHX = CN(cis) or CO,Me(/rcm)

(PhCH=CH),PPh

+

PhCH=CHPPhK

(10)

H201

PhCH=CHPHPh (1 1)

( I 2) 73%

activated acetylenes in ether.12 Treatment of phenylacetylene with potassium phenylphosphide gave a mixture of the phosphines (10) and (ll).l3 The unusual phosphorus heterocycle (12) can be prepared in high yield by the reaction of pentaphenylcyclopentaphosphane with potassium followed by the addition of an equimolar amount of dichloromethane.14 By Reduction.-Cyclopolyphosphines

can be reduced electrochemically to primary phosphines.15 For example, phenylphosphorus when electrolysed in 8% methanol with platinum and mercury electrodes gave phenylphosphine. A two-stage reduction of o-nitrophenylphosphonate to (o-aminopheny1)phosphine has been described.16 l1

A. W. Frank and G . L. Drake, J. Org. Chem., 1971,36,3461. 0 . Glemser, 2. anorg. Chem., 1971, 385, 47.

la

R. G. Kostyanovskii, Y. I. El'natanov, and V. G. Plakhanov, Bull. Acad. Sci. U.S.S.R.,

l*

K. Issleib, H. Boehne, and C. Rockstroh, J. prakt. Chem., 1970,312, 571 (Chem. Abs.,

l4

M. Baulder, J. Vesper, P. Junkes, and H. Sandmann, Angew. Chem. Internat. Edn.,

1971, 20, 2244,

l6

l6

1971, 74, 112 133).

1971, 10, 940. A. Tzschach, H. Matschiner, and E. Reiss, Ger. (East) P. 79 728 (Chem. Abs., 1972,76, 14 714). K. Issleib, H. U. Bruenner, and H. Oehme, Orgunometullic Chem. Synthesis, 1971,1,161 (Chem. Abs., 1971, 74, 112 130).

4

Organophosphorus Chemistry Miscellaneous.-Polytertiary phosphines and phosphinoarsines have been prepared by the base-catalysed addition of phosphorus-hydrogen or arsenic-hydrogen bonds to vinylphosphines or ethyny1pho~phines.l~The same type of reaction was utilized to prepare the diphosphine (1 3). Radical addition of primary phosphines to vinylphosphines has also been

H2C=CHSiX3

+

Me,PH

I1 v

> Me,PCH,CHzSiX3 (15) X = F o r CI

shown ID to give diphosphines (14). Similarly photochemical addition of dimethylphosphine to vinylhalogenosilane gave (dimethy1phosphino)ethylsilanes (15) in high yield.20 Tertiary phosphines have been partially resolved 21 by complexation with the asymmetric palladium(I1) complex (16). Treatment of this complex with racemic phosphine gave (17), phosphine of low rotation being recovered from the mother liquor. The enantiomeric phosphine can be

AS1ArzAAr3p Rso:3~i IICHO >

[ A r ' A r z A r 3 ~ C t l , 0 H ] RS0,(+)

(18) CH2-

+ As'Ar2Ar3P (-1

R-Q" l7 l8

l9 2o

a1

R. B. King and P. N . Kapoor, J. Amer. Chem. Soc., 1971,93, 4158. R. B. King and P. N. Kapoor, Angew. Chem. Internat. Edn., 1971, 10, 734. K. Issleib and H. Weichmann, 2. Chem., 1971, 11, 188 (Chem. Abs., 1971, 75, 63 899) J. Grobe and U. Moller, J. Organometallic Chem. 1971, 31, 157. S. Otsuka, A. Nakamura, T. Kano, K. Tani, J. Amer. Chem. Soc., 1971, 93,4301.

Phosphines and Phosphonium Salts

5

generated by addition of bis(dipheny1phosphino)ethane to (17). The reaction of triarylphosphines with paraformaldehyde and one half of an equivalent of (+)-camphor-10-sulphonicacid gave a crystalline sulphonate (1 8). Optically active phosphine was isolated from the mother liquor. A review of the preparation of phosphines and other organophosphorus compounds and the stereochemistry of their reactions has appeared.22 2 Reactions Nucleophilic Attack on Carbon.-Activated OleJins. Triarylphosphines react with 7,7,8,8-tetracyanoquinodimethane(19) in the presence of water and a trace of hydrochloric acid to give a quantitative Ar,P

+ (CN),C O

C K N ) ,

H,O-HC

Ar,PO Ph,P

+

+

(CN)*CHO C H ( C N 1,

I

XC,H,CH=C(CN)z HtO-H

-

+

-

P h t3 $ C H (C6H, X )* C H (CN ) CON H (20) X = H, p-Me0, p - M e , or /I-NO, Ph

‘h

0

0

PI1

Ph,P’

‘$,

‘b

Ptl

PI1 H

Ptl

PI1

C02R H-0

R

=

Me or Pti

H za

CO-

H. Christol and H. J. Cristau, Ann. Chim.(France), 1971, 179 (Chem. Abs., 1972, 76, 13 277).

6

Organophosphorus Chemistry

yield of 1,4-bis(di~yanomethyl)benzene.~~ The authors propose that the reaction proceeds via a phosphinium radical cation. The reaction of triphenylphosphine with a series of benzylidenemalononitrilesin chloroform in the presence of hydrochloric acid 24 gave the corresponding monoamides (20), presumably by way of nucleophilic addition followed by acid-catalysed hydrolysis. An interesting compound, formulated as (21), is formed from The the reaction of triphenylphosphine with diphenylcycl~propenone.~~ reactions of (21) with methanol and trans-a-phenylcinnamic acid occur by nucleophilic attack on the keten rather than the ylide group. Activated Acetylenes. The unstable 1 : 2 adduct formed from the reaction of triphenylphosphine and dimethyl acetylenedicarboxylate at - 50 “C is now thought 26 to have the cyclopropene structure (22); the PhP X

X IF

>c-c,c-x

&J ?.--.

(22) X

=

CO,Me

(22) X

=

C0,hIe Me0 X

Ph,P a3

25

M. P. Naan, R. L. Powell, and C. D. Hall, J. Chem. SOC.(B), 1971, 1683. R. L. Powell and C . D. Hall, J. Chem. SOC.(C), 1971, 2336. A. Homada and T. Takizawa, Tetrahedron Letters, 1972, 1849. N. E. Waite, D. W. Allen, and J. C. Tebby, Phosphorus, 1971, 1, 139.

7

Phosphines and Phosphoniiim Salts

adduct reacts with triphenylphosphine in methanol or chloroform to give the 1,4-diphosphorane (23). The stable products (24) and (25) are thought to be formed from rearrangement of (22) as shown. The product from the reaction of tri-p-tolylphosphine and excess of dimethyl acetylenedicarboxylate has been shown 27 by X-ray crystallography to be (26). Carbonyls. The reaction of diphenylphosphine with methyl pyruvate gave (27), isolated as the oxide,2Ewhereas reaction of tributylphosphine OH PhzPH

I

+ MeCOC0,Me

Ph2P-C-CO,Me

I

Me

(27)

Bu3P

0I +

+ MeCOC0,Me

+

MeC-PBu,

Me-E-O-PBu3 I C02Me

I

C02Me

J

Me02C(Me)C=C( Me)C02Me

(28)

with methyl pyruvate is reported 29 to lead to a mixture of cis- and transalkenes (28). 1,3-Oxaphospholans (29) are obtained from secondary phosphines and aldehydes or ketones.so Similarly, condensation of (o-aminopheny1)phosphine with carbonyl compounds l6 gave substituted lY3-benzazaphosPhP(H)CH,CH,OH

4-

R2, R'

,C=O

--+

ph-p

n

(29) R1 = H or Ph R2 = Me or Ph R', R2 = (CHJ,

aPH2 + R$o

NHZ

27 28

30

H

2 R ; f @

R2

(30):2

-

R'

HorMe H, Et, or Ph

0. Kennard, W. D. S. Motherwell, and J. C. Coppola, J. Chem. SOC.(C), 1971, 2461. A. N. Pudovik, I. V. Gur'yanova, G. V. Romanov, and A. A. Lapin, J, Gen. Chem.

(U.S.S.R.),1971, 41, 710. A. N. Pudovik, I. V. Gur'yanova, V. P. Kakurina, and N. P. Anoshina, J. Gen. Chem. (U.S.S.R.), 1971, 41, 1237. H. Oehme, K. Issleib, and E. Leissing, Tetrahedon, 1972, 28, 2587.

Organophosphorus Chemistry

8

pholines (30). A full report has appeared on the reaction of secondary phosphines with ethanolic carbon disulphide in the presence of base31 to give the thioformates (3 1) or (32), depending upon the phosphine used. The position of equilibrium in solution depends primarily on the inductive effects of the substituent on phosphorus. Lithium diphenylphosphide in THF reacts with epoxides stereospecifically. Quaternization of the phosphorus of the product generally led directly to the alkene with inversion of stereochemistry relative to the starting epoxide :32

Nucleophilic Attack at Halogen.-Allylic alcohols have been converted into the chloride without rearrangement by the use of the triphenylphosphine-carbon tetrachloride reagent.33 Use of the same system as a chlorinating agent has been extended to the reaction with enolizable ketones.34 Six-membered-ring ketones gave predominantly enyl halides whereas smaller-ring ketones gave predominantly exocyclic dichloromethylene compounds. The reaction of triphenylphosphine-carbon tetrahalide with cis-2-phenyl-1,3-dioxan-5-01 (33) gave a mixture 35 of the diastereomeric 1,3-dioxolans (34).

(33)

(34)

Further reports of the reaction of tris(dimethy1amino)phosphine and carbon tetrachloride with aldehydes 36 and esters or amides of trichloroacetic acid3' have appeared. Addition of tertiary phosphines to the imide (35) gave (36) after h y d r ~ l y s i s . ~ ~ 31

32

33 34 35

36

37

s8

0. Dahl, Acta Chem. Scand., 1971, 25, 3163. E. Vedejs and P. L. Fuchs, J. Amer. Chem. Soc., 1971, 93,4070. E. I. Snyder, J . Org. Chem., 1972, 37, 1466. N. S. Isaacs and D. Kirkpatrick, J. C. S. Chem. Comm., 1972, 443. R. Aneja and A. P. Davies, J. C. S. Chem. Comm., 1972, 722. G. Lavielle, J.-C. Combert, and J. Villieras, Bull. Suc. chim. France, 1971, 2047. G. Lavielle, J.-C. Combret, and J. Villieras, Compt. rend., 1971, 272, C, 2175. M.-F. Chasle and A. Foucaud, Bull. Soc. chim. France, 1972, 1535.

9

Phosphines and Phosphonium Salts

I

(35)

H,O

Dehydration reactions using the tertiary phosphine-carbon tetrachloride adduct have appeared quite regularly in the literature again this year. Among those reported have been the dehydrations of oximes to nitriles,ss carboxylic acids to anhydride^,^^ and the amides (37) to the cumulenes (38).40 Further reaction of the dehydration product from treatment of the RINHC( R2)=C(C0,Et)CONHR3 R1 = Ar (37) R2 = Me

I

R3 = Bu' PhaP-CCI,

RIN= C ( R2) C (C0,Et ) =C=N R3

(38)

Ar$~r~Hz

Ph P-CCI

wAr2 r

Ar'

2

CN

N

(39)

Ar'-C=C I

..

:N _ .

,CN 'AT'

kh3P

Ar'-C=C, I

,CN

Ar2

N, PPh,

(40) 40

41

R. Appel, R. Kleinstiick, and K.-D. Ziehn, Chem. Ber., 1971, 104, 2025. J. Coerdeler and C. Lindner, Tetrahedron Letters, 1972, 1519. B. Castro and J.-R. Dormoy, Buff. SOC.chim.France, 1971, 3034.

10

Organophosphorus Chemistry

azirine derivative (39) with triphenylphosphine gave the triphenyliminophosphorane (40),possibly via a nitrene intermediate.4a The formation of a peptide bond using tertiary phosphines and a halogenomethane has been studied in more detai1.43~44Trisaminophosphines and carbon tetrachloride are the reagents of choice. Tripeptides are formed in high yield and with high optical purity. The simultaneous action of triphenylphosphine and carbon tetrachloride 45 on the sulphonyl compounds (41), followed by triethylamine, gave iminophosphoranes (42). Ph3P

+ CCl4 + H,NSO,R jEhN

Ph,P=Pu'-SOzR

(42) R

=

(41)

+ + CHCl, + Et3NHCl-

Ph, NH,, or NMe,

Several debrominations using triphenylphosphine have been reported. Stilbene dibromides and other vicinal dibromides are debrominated stereospecifically in an anti-eliminati~n.~~ 9,9-Dibromofluorene and dibromodiphenylmethane (43) have been converted into the corresponding ethylene,*' and the compounds (44)gave moderate yields of aroyl cyanides when fused with triphenylpho~phine.~~ Ph,CBr,

Ph,P benzene

> PhzC-Br

*Ph2C-CPh2 I

(43)

I

~

+ PhZC=CPhz

Br Br

ArCOC(Br)=NOH

(44)

+ Ph,P

---+

ArCOCN

The vinyl ether (45) and triphenylphosphine gave the phosphonium salt (46). The reaction is thought to proceed by initial attack at halogen followed by quaternization of the phosphine by the intermediate formed.49 Hydrolysis of (46) gave (1-formylethyl)triphenylphosphoniumbromide (47). When triphenylphosphine is heated with the bromoesters (48) quaterniza42 43

44

45 46

47

49

T. Nishiwaki, J . C . S. Chem. Comm., 1972, 565. S. Yamada and Y. Takeuchi, Tetrahedron Letters, 1971, 3595. T. Wreland and A. Seeliger, Chem. Ber., 1971, 104, 3992. R. Appel, R. Kleinstiick, and K.-D. Ziehn, Chem. Ber., 1971, 104, 2250. I. J. Borowitz, D. Weiss, and R. K. Crouch, J. Org. Chem., 1971, 36, 2377. I. J. Borowitz, P. E. Rusek, and P. D . Readio, Phosphorus, 1971, 1, 147. M. I. Shevchuk, S. T. Shpak, and A. V. Dombrovskii, Zhur. org. Khirn, 1971, 7, 1004 (Chem. Abs., 1971,75, 63 350). L. Reichel and H.-J. Jahns, Annalen, 1971, 751, 69.

11

Phosphines and Phosphonium Salts Br I Me-C=CHOEt

‘ I I

+ Ph3P - - - - - - - - - + MeC =CHOEt

(45)

Br-

‘PPh,

H,O

MeCHCHO I Br+PPh3

Ph3P

+

Br3:i --+-

OEt

(48)

RL = CO,Et R2

=

PI

Ph3PEt

LL5

+ C02 +

R1R2C=CH, (49)

C0,Et or H

tion occurs;6othis is followed by a cyclic elimination to give ap-unsaturated carbonyls (49). Nucleophilic Attack at Other Atoms.-The formation of iminophosphoranes from tetrazolopolyazines (50) and triphenylphosphine has been studied kinetically.61 Evidence was produced which indicated that the reaction occurred by nucleophilic attack of the phosphine on the tetrazolo-ring. An iminophosphorane was also formed 5 2 when the diazocompound (51) was added to molten triphenylphosphine at 140 “C.

Ph& N2 Ph 1 Ph (51) Ph3P

6o

+

Ph3P

-6 -

+ PhN=NPh + HC104

Ph Ph..--

N-N=P Ph,

Ph

Ph-N-NHPh I ClO, +PPh3

D. Orth, Tetrahedron Letters, 1972, 825. T. Sasaki, K. Kanematsu, and M. Murata, Tetrahedron, 1972, 28, 2383. D. Lloyd and M. I. C. Singer, J. Chem. SOC.,(Ch. 1971 2941

12

Organophosphorus Chemistry

Azobenzene reacts readily with triphenylphosphine 53 in aqueous ethanol containing perchloric acid to yield a phosphonium salt (52). The complex formed between diethyl azodicarboxylate and triphenylphosphine is a very useful reagent for condensation reactions. The reaction of alcohols with phthalimides, in the presence of diethyl azodicarboxylate and triphenylphosphine, resulted in the formation of the corresponding N-alkylphthalimide in good yield.54 The reaction proceeds stereospecifically with complete inversion, as shown by conversion of (S)-(+)-2-octanol to (R)-(-)-2-octylamine, isolated by treatment of the initially formed phthalimide with hydrazine hydrate. Condensation between alcohols and other active-hydrogen compounds using the same reagents has also been described (Scheme l).65 Phosphorylation of alcohols by initial activation

.x

RCHXY

+

Et02CNHNHC0,Et

+

Ph,PO

Scheme 1

X Y

= =

CN or MeCO CN or C0,Et

of the alcohol by the diethyl azodicarboxylate-triphenylphosphine complex (Scheme 2) has been Ph3P

+ EtO,CN=NCO,Et

I(

EtO2CN-NTC-OEt P h 3 b -\\I0

1-

EtO,C N H- N- CO,E t RO),P0,'fh3 EtOH

J

EtO-P(OR),

II

0 53 54 55 B6

+

[ Ph,~-OEtl(RO),P02-

+

Et 0,CN HNHC0,Et

Ph3P0

Scheme 2

R. E. Humphrey and E.E . Hueske, J . Org. Chem., 1971,36, 3994. 0. Mitsunobu, M. Wada, and T. Sano, J . Amer. Chem. SOC.,1972, 94, 679. M. Wada and 0. Mitsunobu, Tetrahedron Letetrs, 1972, 1279. 0. Mitsunobu and M. Eguchi, Bull. Chem. SOC.Japan, 1971, 44, 3427.

13

Phosphines and Phosphonium Salts

Tetracyclones react with phenylphosphine to yield trans-dihydrotetracyclones (53). The reaction is thought to proceed via initial attack at oxygen.67

ph&O Ph ..-

3- PhPHz

Ph

Ph

(53)

For the reaction of triarylphosphines with radicals and related reactions see Chapter 10, Section 1. The reaction of several phosphines with diethylperoxide is described in Chapter 2. Miscellaneous.-Mislow has now found an example of a phosphine which does not obey the electronegativity rule for correlating energy barriers with pyramidal inversion in p h o s p h i n e ~ . ~ The ~ inversion barrier of the trimethoxysilylphosphine (54) is found to be 2 kcal mol-l lower than the Ph P r P Si (0 Me) (54)

analogous trimethylsilylphosphine, an effect which is ascribed to negative hyperconjugation. The reduction of hydroperoxides by triphenylphosphine in ethanol is second order. Unsuccessful attempts to inhibit the reaction by the use of free-radical traps suggest a non-radical mechanism.69 The reaction is catalysed by strong acids.60 Soluble salts of molybdenum or vanadium are lo4-lo5 times more effective catalysts than H+. The autoxidation of triphenylphosphine and phosphorus esters has been studied kinetically.61 After a short induction period the reaction gave the corresponding quinquecovalent phosphorus compounds. The intermediate (55) is probably formed by the addition of oxygen to perfluoroacyldiarylphosphines.sa Subsequent decomposition afforded diarylphosphinates (56). The oxadiazine (57) has been prepared from the reaction of carbon dioxide and ally1 isocyanate in the presence of trib~tylphosphine.~~ Dibromoketen can be generated from the reaction of trimethylsilyl tribromoacetate and triphenylph~sphine.~~ The isolated product (58) is derived from reaction with the cyclopentadiene solvent. 5' 58

6n 8o

e2 63 64

Y. Kashman and H. Ronen, Tetrahedron Letters, 1971, 3973. R. D. Baechler and K. Mislow, J . C. S. Chem. Comm., 1972, 185. R. Hiatt, R. J. Smythe, and C. McColeman, Cunad. J. Chern., 1971, 49, 1707. R. Hiatt and C. McColeman, Canad. J . Chem. 1971,49, 1712. Y. Ogata and M. Yamashita, J . C.S. Perkin I l , 1972, 730. E. Lindner, H.-D. Ebert, K. Geibeland, and A. Haag, Chem. Ber., 1971, 104, 3121. A. Etienne, B. Bonte, and B. Druet, Bull. SOC.chim. France, 1972, 242. T. Okada and R. Okawara, Tetrahedron Letters, 1971, 2801.

14 RCOPAr, -I- 0, + H,O

-

Organophosphorus Chemistry

0-0 (55) I

+

CO, -t- RH

j. O H 0 II I II Ar,P-C-OPAr,

I

R (56) R = CF,, CzF5,or C,H, Ar = Ph or MeC,H,

0

RN=C=O

Me,SiOCOCBr,

RCH=SO,

+ CO,

o//c'o/c"o (57) R

-

+ Ph,P

+ Ph,P

Bu,,P

Me,SiBr

---+

(59)

R = H or Ph X = CI or (NO,),C,H,O

I1 R,N/C,N/R I I

RCH-SO,

\P/

Ph 3

+

=

Ally1

Ph,PO -I- [Br,C=C=Ol

- so,

1

> RCH=PPh3 E&H

,

X-

RC H, P P ti X -

Phosphines and Phosphonium Salts

15

Sulphenes (59), generated from the reaction of sulphonate esters or sulphonyl chlorides with triethylamine, react with triphenylphosphine to form phosphonium saltsB5 The degree of correlation with the Hammett equation for the protonation of triarylphosphines depends on the solvent used.6s The presence of an o-anisyl group causes a small acceleration in the reaction of triarylphosphines with benzyl ~hloride.~' PART 11: Phosphonium Salts 1 Preparation The quaternization of (S)-( - )-benzylmethylphenylphosphine with aryl bromides, by the complex salt method using nickel bromide, proceeds with predominant retention of configuration at phosphorus.6s Optically active phosphonium salts are also obtained by quaternization of optically active triarylphosphines with b e n z y n e ~ . ~ ~ Allyltriphenylphosphonium chloride prepared from triphenylphosphine in excess refluxing ally1 chloride is far superior to the material synthesized from equimolar amounts of the reagents in boiling benzene because of the tendency of the product to rearrange to propenyltriphenylphosphonium chloride at the higher temperature. Allyltriphenylphosphonium bromide is stable in refluxing benzene.'O Triphenylphosphine can be quaternized by the vinyl bromide (60) to yield a phosphonium salt which on treatment with methyl-lithium followed by water gave the hydroxyphosphonium salt (61) stere~specifically.'~A

Ph,P

+

Br/Me H C0,Et

-

CH2

+

II

Ph,PCH,CCO,Et Br-

+I

i, MeLi ii, H,O

Ph,P

MMeBr-

H

,CMe, HO

(61) 65 66

6'

J. F. King, E. G. Lewars, and L. J. Danks, Canad. J. Chem., 1972, 50, 866. G. P. Schiemenz, Terrahedron, 1971, 27, 3231. W. E. McEwen, V. L. Kyllingstad, D. N. Schulz, and Y . I. Yeh, Phosphorus, 1971, 1, 145.

70

R. Luckenbach, Phosphorus, 1971, 1, 77. G. Wittig and H. Braun, Annalen, 1971, 751, 27. 0.Buchi and H. Wuest, Helu. Chem. Acta, 1971, 54, 1767. C. F. Garbers, J. S. Malherbe, and D. F. Scheider, Tetrahedron Letters, 1972, 1421.

16 Organophosphorus Chemistry convenient preparation of vinylphosphonium salts by treatment of the corresponding chloroethyl derivatives with triethylamine in dichloromethane has been described.72 The phosphinolium salt (62) has been synthesized by intramolecular quaternization of the phosphine (63) using hydrogen bromide followed by sodium arbo on ate.^^ Partial resolution of the salt was achieved by the use of silver hydrogen dibenzoyltartrate. Ph

Ph

Et-I'

Et-PH

\+

\

Br-

P 11

H

The spirophosphonium salt (64) is formed, together with some secondary phosphine oxide (65), when phosphorus trichloride is mixed with diphenylamine at 210 "C and the reaction mixture treated with water.74 Cyclic phosphonium salts (66) have been prepared by the reaction of substituted vinylphosphines with nitrilimine~.~~ Cyclization of the intermediate betaine with triethylammonium chloride is prevented by the presence of strong electron-accepting groups on the a carbon, in which case stable azo-ylides (67) are isolated. 72

73 74 76

J. M. Swan and S. H. B. Wright, Austral. J. Chem., 1971, 24, 777. C. H. Chen and K. D. Berlin, J. Org. Chem., 1971, 36, 2791. R. N. Jenkins, L. D. Freedman, and J. Bordner, Chem. Comm., 1971, 1213. V.V. Kosovtsev, V . N . Chistokletov, and A. A. Petrov, J. Gen. Chem. (U.S.S.R.), 1971, 41, 2676.

Phosphines and Phosphonium Salts PhZPCH=CHPh

+

+ R-C=N-N-Ph

-

17

CH-CHPh / Ph2P 'C-N=NPh I R (67)

I'

Et,NH C1-

CH,CHPh

+/

Ph,P

/

\

NPh

C=N R

/

C1-

The action of hydrogen chloride gas on a solution of (cu-acetylphenacy1idene)triphenylphosphorane (68) in benzene produced the phosphonium salt (69), a fairly strong acid, which exists entirely in a trans-enol form.76 The alkoxyphosphonium chlorides (70) have been obtained from the Ph,P=CCoPh I COMe (68)

(Me,N),P

+ CCI,

benLenc

+ ,COMe Ph,PCH, COPh

c1-

(69)

+ (Me,N),PCI

ROH

+

(Me,N),POR

cc1,-

c1-

+ CHCI,

(70) R = PhCH,, CoHln,or C,HII

+

Br CH,CH,CH2PPh,

NaOH --+[RrCH,CH,CH=PPh,l

Br(71)

CH,, + I ,CH-PPh, CH, Br-

PhzPCl

+ CaCz BrBr

'13

(72)

T. A. Mastryukova, V. Rubashevskaya, I. M. Aladzheva, and M. I. Kabachnik, J. Gen. Chem. (U.S.S.R.), 1971, 41, 2358.

18

Organophosphorus Chemistry

reaction of tris(dimethy1amino)phosphine and carbon tetrachloride with primary Dichloroamines have been used to quaternize triphenylphosphine to give N-chloro-N-alkylaminotriphenylphosphonium chlorides in good yield.78 Cyclopropyltriphenylphosphonium bromide was isolated in high yield79from the addition of one equivalent of sodium hydroxide to the phosphonium salt (71). 2,2-Diphenylisophosphindoliumsalts (72) can be formed directly by the addition of o-xylylene dibromide to a mixture of chlorodiphenylphosphine and calcium carbide.80

2 Reactions Alkaline Hydrolysis.-The steric course of the alkaline cleavage of a variety of benzylphosphonium salts (73) has been investigated.*' The reaction proceeds with various amounts of inversion depending upon the nature of the R group. However, the alkaline hydrolysis of the phosphonium salts (74) has been shown to occur with partial retention Me

\+

Ph---P-CHoPh / R Br-

(73) Ar

=

Me.:+ Pr-P -Ar /

Ph

Br-

hle. ..+ Pr-P-C,H,, /

Ph

Br-

(75) (74) cr-ClnHi,/3-C,,Hi, or p-PhC,H,

of configuration with loss of the aryl group, whereas when only one aromatic group is present [e.g. (75) ] loss of that group with a small amount of inversion occurs on treatment with base.82 These results would seem to indicate that the phenyl group prefers the apical position in the first-formed intermediate phosphoranes, but as the amount of stereochemical control is very small, the energy differences between the various intermediates possible must also be very small, and no conclusions about the relative apicophilicities of the various aromatic and alkyl groups can be drawn. Inversion of configuration at phosphorus is found when the phosphonium salt (76) is treated with hydroxide ion, whereas the reaction of the phosphonium salt (77) with cyanide ion gave the corresponding phosphine with retention of c~nfiguration.~~ It has been shown that the cyclic cisand trans-phosphonium salts (78) are hydrolysed with complete inversion of ~onfiguration.~~ Presumably the larger ring size permits the ring to be accommodated in relatively strain free diequatorial positions in the intermediate phosphoranes. 77 7B

82 88 84

B. Castro and C. Selve, Bull. SOC.chim, France, 1971, 2296 R. M. Kren and H. H. Sisler, Inorg. Chem., 1971, 10, 2630. H. J. Bestmann and E. Kranz, Chem. Ber., 1972, 105, 2098. T. E. Snider and K. D. Berlin, Phosphorus, 1971, 1, 59. R. Luckenbach, Phosphorus, 1972,1,223. R. Luckenbach, Phosphorus, 1972, 1,229. L. Horner and R. Luckenbach, Phosphorus, 1971, 1,73. K. L. Marsi, J . Amer. Chem. SOC., 1971, 93, 6341.

19

Phosphines and Phosphoniuin Salts M':.+ Pr -P--CH2CH==CE-I, /

Ph

OH-

Br(76)

Me-,+ Ph-P-CH&H=CH? /

PhCH, Br-

CN-

Me + O=P-Pr \ Ph

Me., > Ph-'P /

+

Me I CH,=CCN

PhCH,

(77)

Me

Ph CH,Ph

Me

/ \

Ph 0

The kinetics of the alkaline hydrolysis of a series of (heteroarylmethy1)triphenylphosphonium salts have been investigated.86The rates of reaction decrease in the predicted order. The phosphorus-furan bond is broken as expected when the heteroarylphosphonium salts (79) are treated with aqueous alkali.86

The basic hydrolysis of the bisphosphonium salt (80) gave a phosphonium salt (81) and a phosphine oxide (82) in a ratio which depended upon the acidity of the solvent used. The reaction is presumed to proceed via a carbanion from which the phosphonium salt arises by protonation by the solvent and the phosphine oxide by phenyl migration from p h o s p h o r ~ s . ~ ~ The mechanism of the unexpected formation of 2-methyl-2H-benzopyran from the phosphonium salt (83), under normal Wittig conditions, has been discussed in some detail.EE The basic hydrolysis of phosphonium salts of the type (84) has been described.8BUsually the R group is lost; only in one case (85), in which 86

86

88

8B

D. W. Allen and B. G. Huntley, J. C. S. Perkin ZZ, 1972, 67. D. W. Allen, B. G. Huntley, and M. J. J. Mellor, J . C. S. Perkin ZZ, 1972, 63. E. E. Schweizer and C. S. Kim, J. Org. Chem., 1971, 36,4041. E. E. Schweizer, T. Minami, and D. M. Crouse, J. Org. Chem., 1971, 36, 4028. M. Simalty and M. H. Mebazaa, Tetrahedron, 1972, 28, 3343.

20

Organophosphorus Chemistry

-

4,

N&

I

Ph,PO

P'Ph,

CH,CH,PPh, +

n

+d )

P'-+ ,

CH,C H,P Ph Br-

2Br-

(80)

ocHoa '

Br-

base

~

0(CH,) 6 Ph

CH3

R1 = Ph, C=CPh, or CECMe

R2,R3,R4 = H, Me. or Ph (84)

P h O P h / \

NCCH,CH, Ph SbC1,(86)

I Ph

+ CH,=CHCN

21

Phosphines and Phosphonium Salts

the ring contained a phenyl group in the 2-position, was the heterocyclic ring broken. The increased rate of reaction of the phosphonium salt (86) over that of the saturated analogue (87) has been attributed to the stability of the phosphole

Additions to Vinylphosphonium Salts.-The addition of triphenylvinylphosphonium bromide to a number of active methylene compounds has been s t ~ d i e d . ~A l correlation was observed between the acidity of the active rnethylene species and the ease of formation of 2 : 1 adducts. Pyrazolinyltriphenylphosphonium salts (88) can be prepared by 1,3-dipolar addition of excess diazomethane to triphenylvinylphosphonium Thermolysis of (88) gave phosphonium salts (89) by elimination

+

CH,=CHPPh, Br-

+

R1R2CN,

-

+ J f 1R H'

N '

PPh, Br-

(88)

H (90) R2

=

H or Me

of nitrogen or pyrazole hydrobromides (90) by loss of triphenylphosphine. l-Hydroxypyrroles are formed from the reaction of the oximes (91) with triphenylvinylphosphonium bromide in the presence of base,Q3as outlined in Scheme 3. B1 g2

W. B. Farnham and K. Mislow, J. C. S. Chem. Comm., 1972, 469. E. E. Schweizer and C. M. Kopay, J. Org. Chem., 1971,36, 1489. E. E. Schwiezer and C. S. Kim, J. Org. Chem., 1971, 36,4033. E. E. Schweizer and C. M. Kopay, J. Org. Chem., 1972,37, 1561.

2

22

Organophosphorus Chemistry HO \N

II

Ph-C-C

NaH

4

-0 \N II // Ph-C-C

~

Ph,PCH=CH,

\

\

\

Ph,P=CHCH,O \ O N II 4 Ph-C-C

H

H

H

(91)

0 phlp

Ph

-Ph,PO

Ph

I

I

OH

N=&

0-

Scheme 3

Purines, pyrimidines, and nucleosides, for example cytidine, condense with the vinylphosphonium salt (92) to yield (93), which on treatment with alkali eliminate triphenylpho~phine.~~

+

Ph,PCH=CHCOMe Br(92)

+

NT

+

P h3PCH2- C =C,- M e

____,

Br- O NY - Y

O J h

H

+

or

Ph,P CH,-C=C ---Me

Br-

Me-F=C-Me \

Miscellaneous.-The carbanions (94), formed from the reaction of the corresponding phosphonium salt with sodium ethoxide and the sodium salt of t-butyl hydroperoxide, decompose in a number of ways. Migration of a phenyl group to oxygen yields the phosphine oxide (95) and formation of the alkyl ethyl ethers may be due to the intermediacy of a carbene, which is trapped by E. Zbiral and E. Hugl, Tetrahedron Letters, 1972, 439. K. Yamada, K. Akiba, and N. Inamoto, Bull. Chem. SOC.Japan, 1971, 44,2437.

Phosphines and Phosphonium Salts Ph3P-cR1R2

I

Ph2PCKLR2 L+ II

__I,

Ph2PCHK'R2 II 0

0

O-OBut

I

23

(94)

(95)

R1R2C:

+ Ph,PO + ButO-

+ R1R2COEt + ButOH

EtoH

Cyclopropyl ketones (96) have been formed in moderate yield from the esters of 3-hydroxypropylphosphonium salts by treatment with potassium t-b~toxide.~ The ~ acidity and enolization of several /3-ketophosphonium salts have been investigated and discussed in detail.Q7~Q8 0

II R1C-O-CR2R3CH2CH,h3

RlCCH-CR2R3

+ Ph,PO

R1 = Me or Ph

Br-

(96) R2 = H or Ph R3 = H or PhCO

(Cyanomethy1)triphenylphosphonium chloride readily reacts with malonaldehyde acetals gg in pyridine to form phosphorus polymethine dyes (97). Ph3kH2CN

c1-

+

I

(EtO),CHCH( R)CH(OEt),

pyridine NaCIO,

+

Ph3P-C=CHC( R)=CHC=PPh, I I CN CN (97)

The dependence of the 31Pchemical shift of various phosphonium salts on the amount of d,,-pa bonding has been discussed loo(see Chapter 11). PART HI: Phosphorins and Phospholes 1 Phosphorins Preparation.-Undoubtedly the greatest advance in this area of chemistry in the past year has been the discovery of a simple one-step E. E. Schweizer and W. S. Creasy, J. Org. Chem., 1971,36, 2379. T. A. Mastryukova, Kh. A. Suerbaev, P. V. Petrovskii, E. I. Matrosov, and M. I. Kabachnik, Doklady Chem., 1972,202,354. T . A. Mastryukova, I. M. Aladzheva, Kh. A. Suerbaev, E. I. Matrosov, and P. V. Petrovskii, Phosphorus, 1971, 1, 159. A. V. Kazymov and E. B. Sumskaya, J. Gen. Chem. (U.S.S.R.),1971, 41,938. l o o H. Goetz, H. Juds, and F. Marschner, Phosphorus, 1972,1,217. 97

24

Organophosphorus Chemistry

synthesis of phosphabenzene, reported by Ashe.lol The addition of phosphorus tribromide to 1,4-dihydro-1,l-dibutylstannabenzene (98) gave the hydrobromide of phosphabenzene. The free phosphine, a colourless volatile liquid, could be obtained by addition of DBU. Arsabenzene was formed directly in the same way using arsenic trichloride.

Tris(hydroxymethy1)phosphine converted the naphtho[b]pyrylium salt (99) to the corresponding 4-phosphaphenanthrene (100) in the usual way.lo2 Treatment of diphenyl ether with butyl-lithium followed by dichlorophenylphosphine gave 1 O-phenylphenoxaphosphine(101) in low yield.lo3 P11

Ph

Ph (101) 17%

1,l-Disubstituted phosphabenzenes (102) have been prepared by treating pyrylium salts with primary phosphines in pyridine, followed by alcohols or thioalcohols. The yields could be improved by using bis(hydroxymethy1)phosphine instead of the primary phosphine.lo4

p h o p h

BF,-

lol lo2

lo3

lo4

6

aP h \ + R1PH2

I R'

Ph

P 11 R2xH

'P

h 0 . i / /

R2X R'

X = OorS (102) R' = Ph or PhCH, R2 = Ph, Me, or PhCH,

A. J. Ashe, J . Amer. Chem. SOC.,1971, 93, 3293. K. Dimroth and H. Odenwalder, Chem. Ber., 1971, 104,2984. I. Granoth, J. B. Levy, and C. Symmes, J . C. S. Perkin 11, 1972, 697. G. Markl, A. Merz, and H. Rausch, Tetrahedron Letters, 1971, 2989.

Phosphines and Phosphonium Salts

25

Reactions.-The phosphorins (103) were obtained by oxidation of 2,4,6-triphenylphosphorinwith mercuric acetate and an equivalent of alcohol in benzene. If water was added (1 equivalent) and 1.5 equivalents of alcohol used, the compounds (104) were formed.los Deacylation of

/ \

RO 0-

l-acetoxy-l-alkoxy-2,4,6-triphenylphosphorins(103) occurred with base.lo6 Thermal rearrangement of (103) in refluxing dioxan gave (105), an equilibrium reaction which is thought to occur via an intramolecular fourmembered cyclic intermediate. The reaction of the 1,l -bis(dimethylamino)phosphorin (106) with excess methanol in the presence of trifluoroacetic acid produced the methoxyderivative (107) by nucleophilic attack of methanol on the intermediate cation.lo7 105 lo6

lo'

A. Hettche and K. Dimroth, Tetrahedron Letters, 1972, 829. A. Hettche and K. Dimroth, Tetrahedron Letters, 1972, 1045. K. Dimroth, A. Hettche, H. Kanter, and W. Stade, Tetrahedron Letters, 1972, 835.

26

Ph

6 Ph

\

Organophosphorus Chemistry

MeOH

CF,CO,H,

Ph

Me,N

fi

Ph H

Ph H

Ph /p\ Me,N 1 OMe NMe,

/-\

NMe,

Phosphorinylcarboniumtetrafluoroborates were obtained by hydride-ion abstraction from (1 08) with triphenylcarbonium tetrafluoroborate.lo8 The ambidentate character of the carbonium ions was shown by their reactions

i/

Pli

6 Ph

\

0 OMe (110) X = C1, Br, or I -t

'Ph:; NaBH,BF,-,

P hO \

P

h

f---j

/ /

/ /

Me0

CH,

CH,

OMc

Me0

P h O P h / \

M e 0 OMe

OMc

(108)

/ \

(111) lo8

Me0 (109) Y

=

OMe

C N or SCN

K. Dimroth, W. Schafer, and H. H. Pohl, Tetrahedron Letters, 1972, 839.

27

Phosphines and Phosphonium Salts

with n ~ c l e o p h i l e s . Sodium ~~~ borohydride reduction gave the original starting material (108). Cyanide and thiocyanate ions similarly added to give (log), but reaction with halide ions gave the methylene derivatives (110). However, addition of aqueous sodium bicarbonate led to bisphosphorinylmethanes (111). The sequence of the highest-occupied molecular orbitals for phosphorins has been calculated from the photoelectron spectrum of 2,4,6-tri-tbutylphosphorin.l1° The reaction of phosphorins with singlet oxygen has been studied ll1 (see Chapter 10, Section 1).

2 Phospholes A general method of synthesis of phosphole derivatives is illustrated by the preparation of l-phenoxy-3,4-diphenylphospholel-oxide (1 12) by a bromination-debrominationsequence as shown.l12 Br

Further reports on the preparation of phospholes, e.g. (113), by the addition of phosphines to diacetylenes have appeared.ll3#114 Braye and coworkers 113 found that the reaction was best catalysed by concentrated potassium hydroxide or by means of cuprous or mercury salts. Contrary to previous reports the free radical reaction, catalysed by AIBN, also gave good yields. A full account 11*has now been produced of the low inversion barrier of phospholes (114). The energy barriers to inversion of phosphindoles (115) and dibenzophospholes (116) are significantly higher, results interpreted in terms of disruption of stabilization due to phosphole aromaticity in the planar transition state. The site of protonation of 109

l11

11*

114

W. Schafer and K. Dimroth, Tetrahedron Letters, 1972, 843. H. Oehling, W. Schafer, and Armin Schweig, Angew. Chem. Internat. Edn., 1971, 10, 656.

K. Dimroth, A. Chatzidakis, and 0. Schaffer, Angew. Chem. Internat. Edn., 1972, 11, 506.

F. B. Clarke and F. H. Westheimer, J. Amer. Chem. SOC.,1971, 93, 4541. E. H. Braye, I. Caplier, and R. Saussez, Tetrahedron, 1971, 27, 5523. W. Egon, R. Tang, G. Zon, and K. Mislow, J. Amer. Chem. SOC.,1971,93,6205.

Organophosphorus Chemistry

28

1,2,5-triphenylphospholeis the phosphorus atom.115 Some phospholium salts (1 17) are remarkably stable. The anions (118) are formed by the addition of alkali metals to 1 -phenylphospholes. Protonation of the anions gave phosphorusunsubstituted phospholes, reaction with alkyl halides afforded the phospholes (1 19), and subsequently the phosphonium salts (120).

(118) R1 = H or Ph

R'

R'

P h g P h P

I R2

( 1 19)

R: R'X

R'

'

xi\ R2 R 2 ( 120)

The formation of radical-anion intermediates from the reaction of phospholes with alkali metals has been demonstrated by e.s.r. 11' 116

116 117

R. Churchman, D. G . Holah, A. N. Hughes, and B. C. Hin, J . Heterocyclic Chem., 1971, 8, 877. C. Thomson and D. Kilcast, Chem. Comm., 1971, 782. D. Kilcast and C. Thomson, Tetrahedron, 1971, 27, 5705.

2

Quinquecovalent Phosphorus Compounds BY S. TRIPPETT

1 Introduction Interest in stable quinquecovalent phosphorus compounds has shown remarkable growth in the year under review, published work having quadrupled. This is undoubtedly due to a general realization that a knowledge of the factors which affect the stability of such compounds and control the processes of ligand reorganization within them is essential to a proper understanding of the mechanism of substitutions at phosphorus. Variable-temperature n.m.r. studies on stable phosphoranes are giving an increasing amount of data on the relative apicophilicities of groups and on the preference of small-membered rings for the apical-equatorial position, and it should soon be possible to discuss this area of organophosphorus chemistry on a firm semi-quantitative basis.

2 Ligand Reorganization and Structure Several accounts have appeared of the turnstile rotation (TR) process for the reorganization of the ligands of a trigonal bipyramid. As an alternative to the Berry pseudorotation process (BPR), TR offers the prospect of multiple-TR routes which avoid the high-energy trigonal bipyramids which of necessity must be traversed in comparable BPR routes. However, the experimental evidence for TR is still limited to the adamantoid oxyphosphoranes derived from hexafluoroacetone,2and it may be that the possibility of irregular isomerizations has not been entirely eliminated in these cases.3 Until more compelling evidence is forthcoming most workers are using BPR for discussion of their results. Non-empirical * and semi-empirical lo, MO calculations have appeared on the electronic structure and bonding in simple phosphoranes and on the (a) F. Ramirez, S. Pfohl, E. A. Tsolis, J. F. Pilot, C. P. Smith, I. Ugi, D. Marquarding,

P. Gillespie, and P. Hoffmann, Phosphorus, 1971, 1, 1; (b) I. Ugi, D. Marquarding, H. Klusacek, P. Gillespie, and F. Ramirez, Accounts Chem. Res., 1971, 4, 288; (c) P. Gillespie, P. Hoffmann, H. Klusacek, D. Marquarding, S. Pfohl, F. Ramirez, E. A. Tsolis, and I. Ugi, Angew. Chem. Internat. Edn., 1971,10,687; ( d )I. Ugi and F. Ramirez, Chem. in Britain, 1972, 8, 198. ‘Organophosphorus Chemistry’, ed. S. Trippett (Specialist Periodical Reports), The Chemical Society, London, 1972, vol. 3, pp. 39 and 255. See reference l(c) p. 712 for a discussion of this point. A. Rauk, L. C. Allen, and K. Mislow, J. Amer. Chem. Soc., 1972, 94, 3035. (a) J. B. Florey and L. C. Cusachs, J . Amer. Chem. SOC.,1972,94,3040; (6) R. Hoffman, J. M. Howell, and E. L. Muetterties, J. Amer. Chem. Soc., 1972, 94, 3047.

29

30

0rganophospho r us Chemistry

barriers to BPR. They agree with all previous approaches in confirming that the more electronegative substituents will prefer to occupy the apical positions in a trigonal bipyramid. However, other predictions are novel and promise to be of fundamental significance. They can be summarized as follows : ( a ) Electronegative substituents will prefer to occupy the basal positions in a square ~ y r a m i d5 ,b ~as~ will 7r-acceptors 5 b ; n-donors, on the other hand, favour apical These preferences will affect the energy barriers to Berry pseudorotations. (b) In a trigonal bipyramid, orbital overlap from 7r-donors is substantially greater lc,5 b from equatorial than from apical positions. Conversely, orbital overlap is greater for n-acceptors in the apical positions. The overall apicophilicity of a group is therefore a balance between electronegativity and rr-donor or 7r-acceptor proper tie^.^^ This concept has been used independently to explain experimentally derived relative apicophilicities (see below). (c) An equatorial substituent with a single donor orbital will prefer to have that orbital in the equatorial plane.5b Consequently there will be a barrier to rotation round the equatorial bond. This is probably the origin of the slow rotations observed round these bonds in amino- and alkylthiofluorophosphoranes;8 if so the energy barriers found, ranging from 5 to 12 kcal mol-l, reflect the importance of this effect. (d)An overall stabilization of a trigonal bipyramid occurs when all the equatorial or both of the apical positions are occupied by the same type of substituent, lC Computer simulationDof the line broadening of the methyl resonances in the n.m.r. spectra of the phosphoranes (1; R = Me or Ph) down to - 184 "C gave a value for the free energy of activation for pseudorotation between the equivalent structures (la) and (lb) of 4.9-5.1 kcal mol-l. A

knowledge of the barrier to pseudorotation between trigonal bipyramids of identical energies is important in interpreting the barriers observed between non-identical trigonal bipyramids.

'

R. K. Oram and S. Trippett, J. C. S. Chem. Comm., 1972, 554. M. J. C. Hewson, S. C. Peake, and R. Schmutzler, Chem. Comm., 1971, 1454. S . C. Peake and R. Schmutzler, J . Chem. SOC.( A ) , 1970, 1049. C. H. Bushweller, H. S. Bilofsky, E. W. Turnblom, and T. J. Katz, Tetrahedron Letters, 1972, 2401.

Quinquecoualent Phosphorus Compounds

31

Orbital symmetry considerations5 b show that the concerted reactions are symmetry forbidden for apical-equatorial loss or addition, but allowed for apical-apical or equatorial-equatorial. Further kinetic investigations lo of the reactions of phosphites with a-diketones are held to support the previously suggested mechanism in which the first and slow step involves nucleophilic attack of phosphorus on carbonyl carbon. The relative rates of reaction of a series of phosphines with diethyl peroxide to give diethoxyphosphoranes are in the reverse order of those for reaction with ethyl i0dide.l' The differences involved are small but are consistent with a concerted biphilic addition to the peroxide. A group theoretical description of isomerization processes in a trigonal bipyramid has been given.12 3 Acyclic Systems Aminotetrafluorophosphorane has been prepared l3 by amination of the corresponding chloro-compound in the vapour state. Rotation round the PN bond is slow on the n.m.r. timescale at 30°C and analysis of the lH and 19Fn.m.r. spectra of the 16Nisomer shows that in the ground state the hydrogens and apical fluorines are coplanar, as in (2), with strong intramolecular hydrogen-bonding.

Full details have appeared l4 of the preparation of aryloxyfluorophosphoranes (3) according to the general equation

Ar = CeHS or C6F5 R = Me or Ph n = 0, 1, or 2

The lQFn.m.r. spectrum of PhOPPhzFzdid not change down to - 80 "C, lo l1

la

l3

l4

Y. Ogata and M. Yamashita, J. C . S. Perkin ZI, 1972, 493; J. Org. Chem., 1971, 36, 2584; Tetrahedron, 1971, 27, 2725. D. B. Denney, D. Z. Denney, C. D. Hall, and K. L. Marsi, J. Amer. Chem. SOC.,1972, 94, 245.

J. Brocas and M. Gielen, Bull. SOC.chim. belges, 1971, 80, 207. A. H. Cowley and J. R. Schweiger, J . C . S. Chem. Comm., 1972, 560. S. C. Peake, M. Fild, M. J. C. Hewson, and R. Schmutzler, Znorg. Chem., 1971,10,2723.

32

Organophosphorus Chemistry

-

suggesting that rotation round the PO bond is still rapid at this temperature. R,P=CH,

+ HF

-70" C

R,MePF (4)

The fluorophosphoranes (4;R = Me, Bu, or Ph) were obtained15 from the corresponding methylenephosphoranes as shown. Although showing unit molecular weights in non-polar solvents, their i.r. and Raman spectra suggest that they are largely ionic, while the lack of H F and PF coupling in their n.m.r. spectra shows that rapid intermolecular fluorine exchange is occurring. The methoxyphosphorane (5; R = Me) is in rapid equilibrium with the ylide and methanol in non-polar solvents at room temperature, but with the phenoxyphosphorane (5; R = Ph) this equilibration is slow on the n.m.r. timescale under the same conditions.16 Methylmethoxytriphenylphosphorane is covalent in the crystalline state, but its solutions are tinged with the yellow of the ylide. Me,P=CH,

+ ROH

Me,POR (5)

Acyclic phosphoranes containing at least two alkoxy-groups undergo exchange reactions with 1,2- and 1,3-glycols to give phosphoranes containing one or two rings.17 Thus pentaethoxyphosphorane with an equimolar amount of ethylene glycol gave the monocyclic phosphorane (6), whereas with two molar equivalents of glycol the bicyclic phosphorane (7)

was obtained. Other diols used included dZ-butane-2,3-diol,styrene glycol, cis- and trans-cyclohexane-1,2-diol, and propylene glycol. However, in the same reaction butane- 1,4-diol and pentane- 1,5-diol gave tetrahydrofuran and tetrahydropyran, respectively, and this heterocyclic synthesis has been extended l8 to other diols and to aminoalcohols. Thus 2-aminoethanol gave aziridine in 70% yield. The mechanism of the reaction is clearly shown by the formation of the oxide (8) from trans-cyclohexane-l,4-diol. l5

l8

H. Schmidbauer, K.-H. Mitschke, and J. Weidlein, Angew. Chem. Internat. Edit., 1972, 11, 144. H. Schmidbauer and H. Stuhler, Angew. Chem. Internar. Edn., 1972, 11, 145. B. C. Chang, W. E. Conrad, D. B. Denney, D. Z . Denney, R. Edelmann, R. L. Powell, and D. W. White, J. Amer. Chem. SOC.,1971, 93, 4004. D. B. Denney, R. L. Powell, A. Taft, and D. Twitchell, Phosphorus, 1971, 1, 151.

Quinquecovalent Phosphorus Compounds

33

U

The equilibrium between phosphonium methoxide and methoxyphosphorane has been ObservedlO in some cases by 31Pn.m.r. Thus the 31P chemical shift of a solution of the salt (9) in methanol changes from + 14.5 to + 91.7 p.p.m. as the methoxide ion content is increased to 3 molar

equivalents. The equilibration is slow at low temperature and at - 80 "C the separate phosphonium and phosphorane resonances can be seen. Molybdenum hexafluoride has been used 2o for the preparation of difluorophosphoranes from phosphines and of trifluorophosphoranes from chlorophosphines.

4 Four-membered Rings Data on the relative apicophilicities of groups have been obtained6 from a study of the variable-temperature 1°F n.m.r. spectra of the hexafluoroacetone adducts of 1-substituted phosphetans. The pseudorotation that can be followed is that which places the four-membered ring diequatorial, i.e. (10) + (11).21 The results (Table 1) were discussed in terms of apicophilicity being a balance between electronegativity, increase in which

H Me M e H M e

Me

CF, (10) l9 2o

*l

D. W. Allen, B. G. Hutley, and M. T. J. Mellor, J. C. S. Perkin 11, 1972, 63. F. Mathey, and J. Bensoam, Compt. rend., 1972, 274, C, 1095. A. E. Duff, R. K. Oram, and S. Trippett, Chern. Comm., 1971, 1011.

34

Organophosphorus Chemistry

favours occupation of the apical position, and ability to back-bond into phosphorus d-orbitals, increase in which favours occupation of the equatorial positions (see also Section 1).

Table 1 R Ph CH=CMe, AG*/kcalmol-l > 22 19.1

Pri Me NMe, OPh OCH(CF,), H 17.8 16.9 16.2 9 0°C

=

Ph or Me Br or C1

-

196°C

=

RPF, (54)

PCIF4 (55)

56

H. Schmidbaur, K.-H. Mitschke, and J. Weidlein, Angew. Chem. Internat. Edn., 1972, 11, 144.

57

F. See1 and K. Velleman, 2. anorg. Chem., 1971, 385, 123.

63

Halogenophosphines and Related Compounds

trigonal-bipyramidal structure, with axial fluorines. The addition of chlorine or bromine to difluorophosphines yields the mixed halogenophosphoranes (53), but these disproportionate readily to give (54).1° A related reaction leads to improved yields of chlorotetrafluorophosphine ( 5 3 , provided the vacuum temperature is kept very low.68 Perfluoro-t-butyl hypochlorite has been used to prepare the phosphoranes (56),6Din which the fluorines are equivalent (from n.m.r.) at room temperature. The exchange with aryloxysilanes to give (57) appears to be general and quantitative.60 Detailed l9F and 31Pn.m.r. data on (57) have been

RnPF5-,

I::::&

+

Rn I ArOSiMe3 * (ArO),-,PF, (57) 11 = 0, 1, or 2

+ RPF4

/m

J O T f\

0 (58)

presented, and earlier work 61 in this area questioned.60 Related reactions have been used to prepare the phosphoranes (58), and the variabletemperature n.m.r. spectra analysed.62 Aminotetrafluorophosphorane (59) has been prepared from ammonia, and a detailed analysis of the n.m.r. data (lH, I9F, and 31P)indicates that it has a trigonal-bipyramidal structure, in which the equatorial nitrogen has a planar config~ration.~~ The axial fluorines (JPF760 Hz) are chemically equivalent, but show different coupling to the hydrogens, while the equatorial fluorines (Jpp 936 Hz) are equivalent in both respects. This has been interpreted on the basis of the amino-hydrogens lying in an axial plane, as in (59), with resultant strong hydrogen-bonding to the axial fluorines. Variable-temperature n.m.r. studies have revealed a high barrier to rotation F

Me,NPF4

W. B. Fox, D. E. Young, R. Foester, and K. Cohn, Znorg. Nuclear Chem. Letters, 1971, 7 , 861. D. E. Young and W. B. Fox, Inorg. Nuclear Chem. Letters, 1971, 7 , 1033. Bo S. C. Peake, M. Fild, M. J. C. Hewson, and R. Schmutzler, Znorg. Chem., 1971,10,2723. R. A. Mitsch, J. Amer. Chem. SOC.,1967, 89, 6297. 6 2 M. Eisenhut and R. Schmutzler, Chem. Comm., 1971, 1452. 83 A. H. Cowley and J. R. Schweiger, J . C. S. Chem. Comm., 1972, 560.

64

Organophosphorus Chemistry

[above 15 kcal mol-l, compared with 9 kcal mol-1 for the dimethylaminoanalogue (60)] 64 which has been ascribed to this intramolecular hydrogenbonding.63 N-Methylaminotetrafluorophosphorane (61) has now been prepared by the silane route, and found to give three 19F resonances at - 80 "C, presumably owing to hindered rotation.65 A similar route to the piperidyl derivatives (62) has been described, and the dependence of the non-equivalence of the fluorines upon the position of the methyl group Me,SiNHMe -t PF,

-

SiMe,

r7

X

N-I'FZXZ

W

+

+

Me,SiF

SbF3

(61)

-

Fbi.-,L,PPh, (62) IZ

-1 SbF3

=

0, 1, or 2

n N-PF,

X

W

(63) X

PhN=P(NEt,)Cl,

MeNHPF,

A

=

CH, or 0

Et,NPF.j

(64)

has been rationalized on the same basis.66 Unsubstituted piperidyl- and morpholino-phosphoranes (63) have been prepared by the antimony trifluoride exchange and the same reagent has been used in a more unusual exchange involving the iminophosphorane (64).68 An elegant and stimulating MO analysis of the problems of bonding and structure in phosphoranes has appeared.69 Of particular relevance to the current topic is a discussion of the interactions of the lone pairs of donor substituents with the orbitals on phosphorus. The authors conclude that donor substituents will prefer equatorial sites (except where electronegativity becomes the dominating influence, as with fluorine), and moreover, that the highest occupied donor orbital will prefer to lie in the equatorial plane of the phosphorane, rather than in the axial plane, i.e. (65) is preferred over (66). Although only limited experimental data are available, it would appear that these predictions are fully supported, e.g. the preferred conformation of (67) 7 0 and the features of the phosphoranes (59) and (61), 64 66 66

67

68 69

70

G . M. Whitesides and H. L. Mitchell, J. Amer. Chem. SOC.,1969, 91, 5384. J. S. Harman and D . W. A. Sharp, Znorg. Chem., 1971, 10, 1538. M. J. C. Hewson, S. C. Peake, and R. Schmutzler, Chem. Comm., 1971, 1454. G. I. Drozd, M. A. Sokal'skii, 0. G. Strukov, and S. Z. Ivin, Zhur. obshchei Khim., 1970,40, 2396. M . Bermann and J. R. Van Wazer, Angew. Chem. Internat. Edn., 1971, 10, 733. R . Hoffmann, J. M. Howell, and E. L. Muetterties, J. Amer. Chem. SOC.,1972,94,3047. S. C. Peake and R. Schmutzler, J . Chern. Soc. ( A ) , 1970, 1049.

65

Halogenophosphines and Related Compounds

i65)

(47)

(66)

discussed above. Thus the hindered rotation observed in the aminophosphoranes can be explained on the basis of orbital interactions, and it remains to be seen how important any hydrogen-bonding interactions are in relation to this. Bis(trifluoromethy1) peroxide and disulphide have been used in a novel preparation of the difluorophosphoranes (68) from tertiary p h o ~ p h i n e s . ~ ~ The phosphetan derivative (69), prepared by this route, has been shown to exist as a mixture of two isomers at -1OO"C, one of which has a (CF3X)z

+

R3P

X

=

OorS

II =

R,PF, (48)

1, 2, or 3

diequatorial heterocyclic ring.71 Boron trifluoride catalyses the exchange of ligands in the phosphorane (70).72 Reactions.-An intermediate (7 1) has been isolated from the bromination of alcohols using triphenylphosphine dibromide in dimethylformamide (Scheme 12).73 This implies that these reactions are closely related to the Vilsmeier reaction, and further evidence for this view comes from the isolation of a formylated product (72) from the analogous reaction of cholest-5-ene-3/3,4/3-diol(73).74 The other product (74) appears to be the result of an enol-bromination of the 3-ket0ne.~~Two related reactions which substantiate this are the mild reaction between pentane-2,4-dione and triphenylphosphine dibromide in DMF, to give (75),75and the formation of l-chlorocyclohex-l-ene (76) from cyclohexanone and a solution of 71 72

73 14

76

N. J. De'ath, D. Z. Denney, and D. €3. Denney, J. C. S . Chem. Comm., 1972, 272. H. Binder, 2. anorg. Chem., 1971, 384, 193. M. E. Herr and R. A. Johnson, J. Org. Chem., 1972, 37, 310. J. Dahl, and R. Stevenson, and N. S. Bhacca, J . Org. Chem., 1971, 36, 3243. J. Carnduff, J. Larkin, J. A. Miller, D. C. Nonhebel, B. R. Stockdale, and H. C. S. Wood. J . C. S . Perkin I, 1972, 692.

66

+

Me,NCH=O

+ Me,N=CHOR

Organophosphorus Chemistry +

Ph,PBr,

+

Me,N=CHOPPh,Br

RoHll

t--- Me,N-yHOPPh,Br

Ph,P=O

OR

@ MeNCOPh

OR =

o,H , .

-

Scheme 12

triphenylphosphine in carbon tetra~hloride.'~Thus the conversion of ketones into halogeno-olefins appears to be a promising synthetic reaction of halogenophosphoranes, or their phosphonium relatives, although

+

I

OH

(73)

0 0 I1 II MeCCH,CMe

+

ox

Ph,P-CCI, I1 = 3

(76)

76

DMF

Ph,PBr,

O H C W (72)

0 II MeCCH=C(Br)Me (75)

0 II

/c\

CH,

'(CH,),,

CH,

)

2\

Ph,P-CCI, n = 2

'

6

N. S. Isaacs and D. Kirkpatrick, J. C. S. Chem. Comm., 1972, 443.

(77)

67

Halogenophosphines and Related Compounds

competing pathways clearly exist, as in the reaction of cyclopentanone to give (77).76 The formation of equal amounts of methyl chloride and (78) from phosphorus pentachloride and bis(hydroxymethy1)phosphinic acid has been rationalized (Scheme 13) in terms of the intermediate methyl ester (79).77 0 II (HOCH2)POH

0 II ClCH2PC12

+ PCl,

-

OH I CliPOP-CH2OH / \ O-CH2

+ HCI

1 + CH3Cl

0 II

t---C14P0P0CH3 I

(78) Scheme 13

CH20H (79)

A slightly modified version of this rationalization is presented below. Diols can be converted into oxirans via the corresponding acetals, which fragment via the orthoester derivatives (80) on treatment with phosphorus pentachloride (Scheme 14).78 The sequence is primarily of interest because

Scheme 14

of its stereospecificity, since the final oxiran has the same absolute configuration at carbon as the initial diol, in appropriate cases. Ethers and certain sulphides are cleaved by triphenylphosphine dibromide to give alkyl bromides (Scheme 15), although the reaction is not general 77

Yu. V. Nazarov, A. A. Muslinkin, and V. F. Zmeltukhin, Izvest. Akad. Nauk S.S.S.R., Ser. khim., 1971, 1806. M. S. Newman and C. H. Chen, J. Amer. Chem. SOC.,1972,94,2149.

Organophosphorus Chemistry

68

R10R2

+

Ph,PBr2 - R2Br

+

+

RlBr

Ph3P=0

Scheme 15

for epoxides, as shown by the reactions yielding (81) and (82), and (83).7s Alkyl iodides result from a similar reaction of the phosphorane (84) with alcohols or ethers such as tetrahydrofuran.*O Further examples of the preparation of vinylphosphonate derivatives from ethers and phosphorus Ph3PBr2 +

0 0--+

i-

+

OPPh3

aBr

Br Br

Ph,PBr, 4-

Me

4Me-

CI (88) 79

A. G. Anderson and F. J. Freenor, J. Org. Chem., 1972, 37, 626. N. G. Feshchenko, I. K. Mazepa, S. I. Shila, and A. V. Kirsanov, Zhur. obshchei Khim., 1971, 41,2375.

Halogenophosphines and Related Compounds 69 pentachloride are the reactions leading to (85) 81 and (86).82983 The contrast between (80) and 2-methyl-1,3-dioxolone (87) is clearly related to the ease of fragmentation of (80) to give chloride ion. Since a previous study of the reaction leading to (85) has described the formation of 1,4-dichlorobutane (88) [cf. (84) 3, the reaction conditions would appear to be critical.84 The exchange reactions between fluorophosphoranes and silane derivatives have been utilized for the fluorination of alcohols, via their trimethylsilyl ethers (89).85,86 According to one of these reports, the ~~ pentaalkyl fluoride is generally accompanied by ~ l e f i n .Phosphorus fluoride similarly fluorinates siloxanes such as (90).87 ROSiMe3 (89)

+

PhPF4 --+

RF

+

PhP(O)F,

+

FSiMe,

Further examples of the preparation of phosphonates from acetals and and (92).90 phosphorus pentachloride include those leading to (91) The reaction of phosphorus pentachloride with t-butanol yields the phosphonate (93), which eliminates hydrogen chloride on treatment with base.Ol The phosphorus-carbon bond-forming steps of the reactions appear to involve the addition of phosphorus leading to (91)-(93) pentachloride to electron-rich olefins. 88s

81 82

83 84

86 86 87 88

89

90 91

S. V. Fridland, G. Kh. Kamai, L. V. Voloboeva, Zhur. obshchei Khim., 1970,40, 595. S . V. Fridland, S. K. Chirkunova, V. A. Kataeva, and G. Kh. Kamai, Zhur. obschchei Khim., 1971, 41, 554. S. V. Fridland, T. V. Zykova, S. K. Chirkunova, V. A. Kataeva, and G. Kh. Kamai, Zhur. obshchei Khim., 1971, 41, 1041. N. I. Shuikin, I. F. Bel'skii, and I. E. Grushko, Izoest. Akad. Nauk S.S.S.R., Otdel. Khim. Nauk, 1963, 557. D. U. Robert and J. G. Reiss, Tetrahedron Letters, 1972, 847. H. Koop and R. Schmutzler, J. Fluorine Chem., 1971, 1, 252. E. W. Kifer and C. H. Van-Dyke, Inorg. Chem., 1972,11,404. V. V. Moskva, G. F. Nazvanoya, T. V. Zykova, and A. I. Razumov, Zhur. obshchei Khim., 1971, 41, 1489. V. V. Moskva, G. F. Nazvanoya, T. V. Zykova, and A. I. Razumov, Zhur. obshchei Khim., 1971,41, 1493. V. V. Moskva, L. A. Bashirova, T. V. Zykova, and A. I. Razumov, Zhur. obshchei Khim., 1970, 40, 2764. V. V. Moskva, L. A. Bashirova, and A. I. Razumov, Zhur. obshchei Khim., 1971, 41, 2577.

70

Organophosphorus Chemistry CH,=CHCH(OEt),

+

so,

Pc15

0

II

+ CI,PC=CH(OEt)

I CH,CI (92)

PCI5

+

i benzene

Me3COH

0 CI 11 I Cl,PCH,CMe,

(93)

0

II

CI,P CH=C Me,

Salts are produced by the reaction of fluorophosphoranes with N-silylimines (94).O2. 93 Vinyl isocyanate reacts with phosphorus pentachloride to give a hexachlorophosphate salt (93, which yields the phosphonic dichloride (96) on hydrolysis and di~tillation.~~ Butyl cyanate reacts with phosphorus pentachloride to give two products, (97) and (98).s5 Me3SiN=PR3

+ Me,PF3

--+

(94)

C Hz = C Ho N= C = O

+

PCI,

[Me,PF,l- [Me,P(N=PK,),l+

-

[CI,PCH=CHNHCOCll+ P a 6 (95) i, SO, ii, A

+ O2

O3 O4

+

RCl

W. Stadelmann, 0. Stelzer, and R. Schmutzler, Chem. Comm., 1971, 1456. W. Stadelmann, 0. Stelzer and R. Schmutzler, 2. anorg. Chem., 1971, 385, 142. V. V. Doroshenko, E. A. Stukalo, and A. V. Kirsanov, Zhur. obshchei Khim., 1971,41, 1645.

s6

CldP-N=C=O

N. K. Kulibaba, V. I. Shevchenko, and A. V. Kirsanov, Zhur. obshchei Khim., 1971, 41, 2105.

71

Halogenophosphines and Related Compounds

3 Phosphines containing a P-X Bond (X = Si, Ge, or Sn) Mislow’s group has continued to study inversion barriers in phosphines and arsines, and test the generality of the theoryQ6that barrier height is controlled by the electronegativity of the ligands. For example, the barrier in (99) is 18 kcal mol-1 less than that in (loo), and the difference was explained on this basis.Q7 The trimethoxysilylphosphine (101a) has a barrier 2 kcal mol-1 less than that of the trimethylsilylphosphine (101b),Q8 SiMe3

L4CPh Me (100)

(99)

Ph-P,

A

+)-

Ph-P,

SR3 (a)R = OMe (b)R = Me

6Me

‘Si(0Me)a

(101)

contrary to the predictions of the above theory,Qs and negative hyperconjugation [implying a contribution from (102) to the ground state of (101a) ] has been suggested as an e x p l a n a t i ~ n . ~ ~ The synthesis and uses of alkali-metal tetraphosphinoaluminates (103) continue to be of interest,O@and further examples of the synthesis of silylphosphines have appeared.loo Phenyl(trimethy1silyl)phosphine (104) has MAI(PHR1)4 (103) M = N a or Li R1 = H or Me

XSiR2,R3, -

PhPHK

+

R1HP.SiR2, R33--n

R1 = R3 = H, R2 = M e f o r n R1 = R2 = Me, R3 = H for n

MesSiCI

= =

0, I , or 2 0-3

PhPHSiMe3 (104) -

been prepared.lol A new synthesis of silylphosphine involves heating a mixture of phosphine and silane at 300 OC.lo2 The silicon-phosphorus bond of dimethyl(trimethylsily1)phosphine (105) is readily cleaved by a variety of covalent halides, as shown in Scheme 16.1°3 Further examples of insertion by carbon multiple bonds R. D. Baechler and K. Mislow, J. Amer. Chem. Soc., 1971, 93, 773. R. D. Baechler, J. P. Casey, R.J. Cook, G. H. Senkler, and K. Mislow, J. Amer. Chem. SOC.,1972, 94, 2859. Bs R. D. Baechler and K. Mislow, J. C. S . Chem. Comm., 1972, 185. J. A. Miller, in ‘Organophosphorus Chemistry’ ed. S. Trippett (Specialist Periodical Reports), The Chemical Society, 1971, vol. 2, p. 52; 1972, vol. 3, p. 53. l o o G. Fritz and H. Schafer, Z. anorg. Chem., 1971, 385, 243. l o l M. Baudler and A. Zarkadas, Chem. Ber., 1971, 104, 3519. lo2 I. H. Sabherwal, and A. B. Burg, Inorg. Nuclear Chem. Letters, 1972, 8, 27. loS J. E. Byrne and C. R. RUSS,J. Organometallic Chem., 1972, 38, 319. g6

72

ISlCl,

Mc,PSiMe (105)

CEiI

! ,

SO,CI,

Organophosphorus Chemistry

Me3SiCI

Me3SiI MesSiCl

+ +

Me,PSiCI,

Me,PCF3

+ Me,PS02CI J.

Me,P(O)CI

+ SO,

Scheme 16

into germylphosphines have appeared, and confirm the trends previously established.lo4elo5 These are illustrated in Scheme 17 for the trialklygermylOMe (MeCO), R = Me

II I

> MeCCOGeMe3

I

PEt, R,GePEt,

CH,=CHCN

R=Et

Et,PCH,CH(CN) GeEt,

( I 06) MeCO,CH= CH, > R = Me

Me3GeOCH=CH2

Scheme 17

+

Me COP Et,

diethylphosphines (106). The n.m.r. spectra of a number of phenylphosphines of general formula (107) have been studied, and 31P shifts,lo6JPHvalues,1o7 and Jpsn values lo*measured, R,MPHPh M = Si, Ge, or Sn R = Me or Ph ( 107)

J. Satgd, C. Couret, and J. Escudie, J. Organometallic Chem., 1971, 30, C70. J. Satgd, C. Couret, and J. Escudie, J. Organometallic Chem., 1972, 34, 83. l o 6 G. Engelhardt, 2. anorg. Chem., 1972, 387, 52. lo' D. G. Harrison, S. E. Ulrich, and J. J. Zuckermann, Inorg. Chem., 1972, 11, 25. l o 8 W. B. Fox, D. E. Young, R. Foester, and K. Cohn, Inorg. Nuclear Chem. Letters,

lo4

lo5

1971, 7, 865.

4

Phosphine Oxides and Sulphides BY J. A. MILLER

Phosphine oxides are clearly not in vogue this year! For the first time since the inception of these Reports the number of new literature citations has gone down. The chapter has been divided into sections on the physical properties, the preparation, and the chemical properties of phosphine oxides. 1 Physical Aspects X-Ray determinations of structure have included the oxides (1) and (2),l the latter of which is shown2 to have a planar heterocyclic ring. The pK, values of a series of phosphine oxides (3) have been measured in d i g l ~ m e . The ~ mass spectra of 10-phenylphenoxaphosphineoxides (4a) and sulphides (4b),4 of ap-unsaturated phosphine oxide^,^ and of 0

CI

0 II Ph- P-CH,R1

I

R2

(a) R' (b) R' (c)

a

*

= =

R1 =

R2 = Ph; pK, 22.5 H, R2 = Ph; pK, 31.3 H, R2 = Me; pK, 31.7

(a) X = 0 (b)X = S

(3)

(4)

T. S. Cameron, J. C. S. Perkin ZZ, 1972, 591. L. Hungerford and L. M. Trefonas, J. Herocyclic Chem., 1972, 9, 347. E. S. Petrov, E. N. Tsvetkov, M. I. Kabachnik, and A. I. Shatenshtein, Zhur. obshchei Khim., 1971, 41, 1172. I. Granoth, J. B. Levy, and C. Symmes, J . C. S. Perkin ZZ, 1972, 697. G. M. Bogolyubov, V. F. Plotnikov, V. M. Ignat'ev, and B. I. Ionin, Zhur. obshchei Khim., 1971, 41, 517.

73

14

0rgan ophosphor us Chemistry R R 4\ X R (a) X (b)X

= =

0 S

R

=

H or Ph

(5)

3-phospholen 1-oxides (5a) and sulphides (5b) have been reported. E.s.r. spectra have been studied ’ for radical-anions generated by alkalimetal treatment of the oxides (6). The applications of n.m.r. to stereochemical problems in phosphine oxides have included the structure of phosphetan 1-oxides,*and the barriers to rotation in the oxide (7a) and the sulphide (7b).9 Extensive use of n.m.r. X II Ph-P-N(Pri), I CI (a)

X

(b) X

= 0 =

S

(7)

shift reagents has been made in the past year, particularly in the solution of structural problems in phosphine oxides.1°-14 More detailed discussion of some of this work appears in Chapter 11. 2 Preparation From Secondary Phosphine Oxides and Su1phides.-A novel reaction of phosphinates with sodium bis-(2-methoxyethoxy)aluminium hydride has been used to synthesize phosphine 0 ~ i d e s . l The ~ complex hydride is believed to generate a secondary phosphine oxide anion from the phosphinate, and this ion may be trapped by an alkyl halide to give a phosphine oxide. The reaction is general for tetrahedral esters, and is G. M. Bogolyubov, L. I. Zubtsova, N. N. Grishin, N. A. Razumova, and A. A. Petrov,

Zhur. obshchei Khim., 1971, 41, 517.

’ C. Thomson and D. Kilcast, Chem. Comm., 1971,782.

G . A. Gray and S. E. Cremer, Tetrahedron Letters, 1971, 3061. W. B. Jennings, Chem. Comm., 1971, 867. lo J. R. Corfield and S. Trippett, Chem. Comm., 1971, 721. l1 K.C.Yee and W. G. Bentrude, Tetrahedron Letters, 1971, 2775. l2 B. D.Cuddy, K. Treon, and B. J. Walker, Tetrahedron Letters, 1971, 4433. l3 G. P. Schiemenz and M. Rast, Tetrahedron Letters, 1971, 5685. l4 Y. Kashman and 0. Awerbouch, Tetrahedron, 1971, 27, 5593. l6 R. B. Wetzel and G. L. Kenyon, J. Amer. Chem. SOC.,1972, 94, 1774.

Phosphines Oxides and Sulphides

75

illustrated (Scheme 1) for the preparation of benzylmethylphenylphosphine oxide (8). The problem of the formation of diphosphine disulphides from phosphonothioic dichlorides and Grignard reagents has received further 0

II I

+

ph-P-OMe

H-

+ Ph-P-0 I Me

+

MeOH

I

Me

PhCH,CI

0 II Ph - P- CH,Ph

I

Me (8)

Scheme 1

study.la Although the dichloride (9a) gave only tertiary phosphine oxides (10a) with alkylmagnesium bromides, the corresponding phosphonothioic dichloride (9b) gave (lob) together with the disulphides (ll), all in low yield (Scheme 2). The Russian group rationalize the formation of (11) in X II

PhCH=CHPRZ

X II

R I

(a) X = 0

(b)X

=

S

PhCH=CHP- S

(9)

(12)

S

I PhCH=CHPCI II

l

k

Scheme 2 l6

B. V. Timokhin, E. F. Grechkin, A. V. Kalabina, V. V. Dorokhova, G. V. Ratovskii, and N. A. Sukhorukova, Zhur. obshchei Khim., 1971, 41, 2658.

76

Organophosphorus Chemistry

terms of an anionic intermediate (12), largely on the basis of analogy with the known behaviour of Grignard reagents towards phosphorus pentach1oride.l' A similar explanation of diphosphine disulphide formation has been presented previously.18 ,3-Cyanoethylphosphine oxides (1 3a) and sulphides (13b) are produced by the base-catalysed addition of secondary phosphine oxides or sulphides X II R,PCH, CH,CN (a) X (b) X

=

=

0, R S, R

= =

Ph o r alkyl Ph or alkyl

(13)

to acry10nitrile.l~ Further full details have appeared of the addition reactions of diphenylphosphine oxide and dimethyl phosphonate to cyclopentadienones.20 Despite the large volume of work 21 in this field, it is still not easy to distinguish the factors which control the additions of tervalent phosphorus compounds to molecules like tetraphenylcyclopentadienone (tetracyclone). For example, diphenylphosphine oxide reacts only at the a-carbon, giving adducts (14a-~),~O and methyl

/ Ph

I

Ph V 0P

I

Ph

h

0 (b) R'

(144

'

(cj R'

0 I1

+Me)ki

= =

H,R'

0

Ph, R2

= Ph = H

(14)

P I 1 f l Ph (a) K' (b) R'

= =

0 H, K' = Ph Ph, R2 = H

(15)

Scheme 3 l7 l8

lS

2o

B. V. Timokhin, E. F. Grechin, N. A. Tran'kova, and 0. A. Yakutina, Zhur. obshchei Khim., 1971, 41, 103. N. K. Pate1 and H. J. Harwood, J. Org. Chem., 1967, 32, 2999. A. N. Pudovik and T. M. Sudakova, Zhur. obshchei Khim., 1971, 41, 1962. J. A. Miller, G. M. Stevenson, and B. C. Williams, J . Chem. SOC.(C), 1971, 2714.

Phosphines Oxides and Sulphides

77

phenylphosphinite reacts only at the ,%carbon, giving adducts (1 5a, b) (Scheme 3),21a but analogous reactions of dimethyl phosphonate 21b can involve attack at either atom of the carbonyl group, as well as at the ring positions. In reactions with trialkyl phosphites,21b-dor with tertiary phosphines,z1c3 cyclopentadienones generally react at the carbonyl oxygen, although one clear exception to this rule has been observed.21~ 2oy

f

By Arbusov and Related Reactions.-Details have been presented 22 of the formation of phosphine oxides from alkyl benzoates and diphenylphosphinous chloride (16), although this route is not likely to be of preparative significance [see Chapter 3, Section 1, p. 521. The sulphides (17) have been prepared from alkyl chloroacetate~.~~ Further syntheses of benzoylphosphine oxides (18) have appeared, and their dipole moments Ph,PCI

+ ArC0,R

(16)

R'zPOR2

+

-

PhCOCI

h

0

II Ph,PR

-

00

II II

R'2PCPh R 1 = Et or Ph (18)

Clearly these oxides are extremely sensitive to experimental ~onditions.~~ By Oxidation of Phosphines.-The kinetics of the AIBN-catalysed autoxidation of various tervalent phosphorus compounds have been slb 21c 21d 21e

slf

22

23

I4 26

M. J. Gallacher and I. D. Jenkins, J. Chem. SOC.(C), 1971, 210. M. J. Gallacher and I. D. Jenkins, J. Chem. SOC.(0,1969, 2605. I. J. Borowitz, M. Anschel, and P. D. Readio, J. Org. Chem., 1971, 36, 553. A. J. Floyd, K. C. Symes, G. I. Fray, G. E. Gymer, and A. W. Oppenheimer, Tetrahedron Letters, 1970, 1735. R. C. Cookson and M. J. Nye, J . Chem. SOC.,1965, 2009. D. M. Roundhill and G. Wilkinson, J. Org. Chem., 1970, 35, 3561. A. I. Razumov, I. A. Krivosheea, and L. S. Alfonskaya, Trudy Kuzunsk Khim.-Technol. Znst., 1969, 40, 207 (Chem. Abs., 1971, 75, 140939.) S. T. McNeilly and J. A. Miller, J . Chem. SOC.(C), 1971, 3007. A. I. Razumov, E. A. Krasil'nikova, N. A. Moskva, T. V. Zykova, and L. A. Chemodanova, Zhur. obshchei Khim., 1971, 41, 2402. E. A. Ishmaeva, M. G. Zimin, R. M. Galeeva, and A. N. Pudovik, Zzuest. Akud. Nuuk S.S.S.R., Ser. khim., 1971, 538. J. A. Miller, in 'Organophosphorus Chemistry', ed. S. Trippett (Specialist Periodical Reports), The Chemical Society, 1971, vol. 2, p. 56.

78

Organophosphorus Chemistry

y"\./f CN CN

~

R.

O,--PPh,

~

Ph3kOOR (19)

Ph3P=O

studied, and the relatively slow autoxidation of triphenylphosphine was ascribed to the stability of the radical chain carrier (19).2s Trifluoroacetyldiphenylphosphine is known 25 to oxidize to the phosphine oxide (20), and a rather unusual explanation of this reaction has been suggested by the same workers (Scheme 4). 27 The formation of 2,2,2-trifluoroethanol by 0 II F,CCPPh,

0 2

__j

0I + F3CC-PPh, I I 0-0

H,O

--+

Ph,$=O

+ CF3H + OH + C O , CFzCPPhZ

CF,CH,OH

-OH

t---

0 CF, 0 II I II PhzP-CH--O-PPh,

+

PhzP 0 II II t-- F3CCOPPhZ H,O

(20) Scheme 4

alkaline hydrolysis of (20) is not commented upon, although it might result from a disproportionation of trifluoroacetaldehyde, produced by cleavage of (20) by hydroxide ion. A number of phosphine oxides and sulphides have been prepared by the oxidation of the corresponding phosphine using standard reagents, e.g. (21),28,(22),29(23),30and (4a) and (4b).4

26 27 28

Y.Ogata, and M. Yamashita, J. C. S . Perkin ZZ, 1972, 730.

E, Lindner and H.-D. Ebert, Angew. Chem. Internat. Edn., 1971, 10, 565. L. Maier, Helu. Chim. Acta, 1971, 54, 1651. L. Maier, Helv. Chim. Acta., 1971, 54, 1434. H. Oehme, K. Issleib, and E. Leissring, Tetrahedron, 1972, 28, 2587.

79 By Miscellaneous Routes.-The synthesis of cyclic phosphine oxides from a,w-dibromides and tetraphenyldiphosphine has been described (Scheme 5 ) . The intermediate phosphonium salts are converted into the

Phosphines Oxides and Sulphides

Me

6

Ph,PPPh,

Br

/ \

/ \

Ph

Ph

Ph

0

(24)

Scheme 5

corresponding oxides by alkaline hydrolysis, e.g. (24), the first phosphocane reported, and (25).31 Good yields of tris(a-hydroxyalky1)phosphine oxides are reported from the electrolytic reduction of phosphorus in the presence Me

of aldehyde polymers, e,g. (26) from f o ~ m a l i n . ~ The ~ synthesis and resolution [using ( + )-9-camphorsulphonic acid] of a phospholen 1-oxide (27) has been 3 Reactions At the P=O or P=S Group.-An extremely simple and efficient synthesis of thiirans by treating oxirans with the phosphine sulphides (28) has been The reaction is catalysed by molar quantities of 31

s2

33 a4

K. L. Marsi, D. M. Lynch, and G . D. Homer, J. Heterocyclic Chem., 1972, 9, 331. I. M. Osadchenko, and A. P. Tomilov, Zhur. obshchei Khim., 1970, 40,698. G . Ostrogovich and F. Kerek, Angew. Chem. Internat. Edn., 1971, 10, 498. T. H. Chan and J. R. Finkenbine, J. Amer. Chem. SOC.,1972, 94,2880.

80

Organophosphorus Chemistry R,P=S

-t

0

H’\

57( S

+

R,p=O

trifluoroacetic acid, and the oxiran geometry (and the chirality at phosphorus in appropriate examples) is retained. The phosphetan 1-oxide (29) has been prepared with an l80label, and this compound used in a study of both l80exchange and epimerization reactions at different pH values.35 The epimerization is always slower than the lSO exchange, especially in acidic conditions, and in the pH 2 region this is believed to be the result of rate-limiting pseudorotation, in which the phenyl group and one of the phosphetan ring carbons are placed axially, as in (30). The

v

V

(Ep i iiie r i za t i o11)

corresponding intermediate (3 1) for exchange only requires that one of the ring carbons be placed axially. These results do not solve one of the main problems of our current picture of the role of quinquecovalent intermediates in phosphine oxide reactions: that of the rapid exchange of the oxide (32), observed several years ago 36-a point made by the author.

(32)

Previous suggestions 37 that the peracid oxidation of secondary phosphine oxides involves (33) as an intermediate have been confirmed from studies se 37

D. G. Gorenstein, J. Amer. Chem. SOC.,1972, 94, 2808. K. L. Marsi, J. Amer. Chem. SOC.,1969, 91, 4724. J. A. Miller, in ‘Organophosphorus Chemistry’, ed. S. Trippett (Specialist Periodical Reports), The Chemical Society, 1972, vol. 3, p. 63.

81

Phosphines Oxides and Sulphides 0 II Ph+) PhCOO 4Ph' \H

0

d

0

II I Ph PhCOOP: I Ph H

0 II Ph2POH

-Q

-+OH

o"'

\

+ PhH

04 ' 0

P11

(34)

of deuterium isotope effects.38Cleavage of the oxide (34) with alkali results in loss of the phenyl

Additions to Unsaturated Phosphine Oxides.-Two very similar papers have described the addition of amines to bis-(1 -alkynyl)phosphine oxides, 0

/A'

R'

= Ph

I1 ,C=CR1 Php\CH2COR'

0

I1 ,C=CR1 PhP, CH=CR1 I

\

R'NH,

0

(

NHRj2 %

0

PhP CH=C, /R' I'

Scheme 6 38

II

PhP(CH2COR1)2

R. Curci and F. Difuria, Tetrahedron, 1971, 27, 4601. J. L. Suggs and L. D. Freedman, J . Org. Chem., 1971, 36,2566.

82 Organophosphorus Chemistry and the subsequent conversion of the initial adducts to new heterocycle^.^^^ 41 In one case40 the monoenamine adduct (35) cyclized directly during hydrolysis, and in the other 41 the hydrolysis of the bisenamine (36) led to a bisp-ketoalky1)phosphine oxide (37), which cyclized on treatment with ammonium carbonate (Scheme 6). Pyrazoles (38) are formed in good yields by the dipolar addition of N-phenylsydnone to diphenyl(prop- 1-ynyl)phosphine oxide at high temperature^.^^ Similar additions of diazodiphenylmethane to a series of vinylphosphine oxides result in the formation of 1-pyrazolines (39), which 0 II MeCGCPPh,

0 II R2 PCH=CH2

+

Ph2CN,

H

+

+ 4c\

P h N\ - - I C=O N-0

< S O T

R1 h y ( N R2 Me, R2 = P(O)Ph, S5:(: Me, R1 = P(O)Ph, 15;,’,

5p R1 = R2 =

(38)

0 I1 R2P- CF-CH2 \ N. CPh, qN’

I>

(39)

0

50 C

0

on further heating either isomerize to 2-pyrazolines or eliminate nitrogen to give cyclopropanes (40).43 The analogous reactions of allylphosphine oxides proceed sluggishly at 120 “C and give low yields of the cyclopropane Miscellaneous Reactions.-Details have appeared of a series of rearrangements of the phosphine oxides (41a, b) in which the diphenylphosphinyl group migrates to a carbonium centre /3 to the p h o ~ p h o r u s . ~ ~ 40

I1

M. Maumy, Bull. SOC.chim. France, 1972, 1600. J. C. Williams, J. A. Kuczkowski, N. A. Portnoy, K. S. Yong, J. D. Wander, and A. M. Aguiar, Tetrahedron Letters, 1971, 4749. A. N. Pudovik, N. G. Khusainova, and T. I. Frolova, Zhur. obshchei Khirn., 1971, 41, 2420.

43

Q4

A. N. Pudovik, R. D. Gareev, A. V. Aganov, 0.E. Raevskaya, and L. A. Stabrovskaya, Zhur. obshchei Khim., 1971, 41, 1008. P. E. Cann, D. Howells, and S. Warren, J. C. S. Perkin ZI, 1972, 304.

83

Phosphines Oxides and Sulphides

These migrations involve a 1,2-shift of the diphenylphosphinyl group from a tertiary to a primary carbon, but in a further paper 45 migrations from a tertiary carbon to a tertiary carbonium centre, in the oxides (41c, d), have been described (Scheme 7). Evidence for the intermediacy of the ion

(a) X (b) X (c)X (d) X

=

= = =

NH,, R1 = R2 = H OTS, R' = R2 = H OMS, R1 = H,R2 = Me OH, R1 = R? = Me

(41)

(4 14

Ph2!&

Brz

>

(43)

Scheme 7

(44)

(42) in the reaction of (41d) with hydrogen bromide comes from the related reactions of the oxide (43), e.g. the deterium incorporation from deuteriotrifluoroacetic acid into the methyl groups of (43), and bromination of (43) to give (44). 0

0

II II Ph, PCH2CNHOCOPh

Ph2PCH,N= C = O

0 I1

(EtO)Y (44)

Ph, PCH,CONHOH

Scheme 8 45

(45)

P. F. Cann, D. Howells, and S. G. Warren, Chem. Comm.,1971, 1148.

84

Organophosphorus Chemistry

Bis(N-diphenylphosphinylmethy1)urea (45) has been prepared by two routes (Scheme S), both involving migration of a (diphenylphosphiny1)methyl group to electron-deficient nitrogen and formation of the isocyanate (46).46 Further examples have appeared of the photolytic decomposition of a-diazoalkyldiphenylphosphineoxides (47), to give pho~phinylcarbenes.~~ The subsequent reaction pathway is highly dependent upon R, but the major competing reactions involve solvent trapping of the carbene, either directly [to give (48)] or after rearrangement [to give (49) 1. The a-azidophosphine oxide (50) has been prepared and used in the synthesis of the oxide (51) by standard

(37)

\

(48)

McOIl

0

II PhPCH(Ph)R I OMe

(49)

CH,PPh,

II

0 (51)

A detailed studyihas:been-made of the base-catalysed deoxygenation of carbonyl compounds with diphenylphosphine oxide (52) at high temperat u r e ~ .The ~ ~known 5 0 formation of good yields of trans-stilbene (56a) from benzaldehyde (53a) has been shown 49 to involve the intermediate formation of cis- and trans-stilbene epoxides, and their subsequent deoxygenation by (52). Similar deoxygenation of benzoylferrocene (53b) results in the formation of the ketones (54) and ( 5 3 , as well as the hydrocarbons (56b) and (57).49 The rationalization given in Scheme 9 has been presented to explain these ob~ervations.~~ 46

0. A. Mukhacheva, V. G . Nikolaeva, and A. I. Razumov, Zhur. obshchei Khim., 1971, 41, 1873.

49

M. Regitz, A. Liedhegener, W. Anschutz, and H. Eckes, Chem. Ber., 1971, 104,2177. D. Seyferth and P. Hilbert, Org. Prep. and Proced. Znternat., 1971, 3, 51. W. M. Horspool, S. T. McNeilly, J. A. Miller, and I. M. Young, J . C. S . Perkin I , 1972,

so

L. Horner, P. Beck, and V. G . Toscano, Chem. Ber., 1961, 94, 1323.

47 48

1113.

Phosphines Oxides and Sdphides

(a) R' (b)

R'

= =

Ph, R2 Ph, R2

= =

85

i

H FC

R'COR'

(53) 0 II R22RCCR1 R' = Ph R2 = FC

0

+

(55)

0 II PhzPO

11 R12R2CR2 R' = Ph R2 = FC

I,2-shift

f---

(54)

+

R1R2C=CR1R2 +-----

(a) R1 = Ph, R2 = H (b) R1 = Ph, R2 = FC

(56)

R'R2CHCHR1R2 R' = Ph, R 2 = FC (57)

Scheme 9

Ozonolysis of unsaturated phosphine oxides (58a) leads to the expected products (58b).51 Catalytic hydrogenation of arylphosphine oxides (59a) gives moderate yields of the corresponding cyclohexyl compounds (59b).52 Dimethylphosphine oxide (60) undergoes a complex sequence of exchange reactions with dimethylphosphinous Two of the suggested initial steps involve attack by the oxygen of (60) on halogenophosphines, as shown in Scheme 10 (see Chapter 3 for further details). The first-order J. L. Eichelberger and J. K. Stille, J. Org. Chem., 1971, 36, 1840. L. P. Zhuraleva and M. G. Suleimanova, Zhur. obshchei Khim., 1971, 41, 1944. F. See1 and K.-D. Velleman, Chem. Ber., 1971, 104, 2972.

I1 62

63

4

86

Organophosphorus Chemistry 0

0 II Ph PR2

I1 R'P[(CHZ)n R212 (a)

(a) R = -CH,CH=CH2

(b)R

=

R2

(b) R2

-CH2C02H

= =

Ph, n

=

C6Hll, n

0 or 1 = 0 or 1

(59)

(58)

thermal rearrangement of bis(diphenylphosphiny1) peroxide (61) has been shown to proceed with retention of phosphoryl l80labels,54an observation which is compatible with either a concerted process via the intermediate (62) or an intimate ion-pair reaction. In contrast, the analogous photolytic reaction results in scrambling of the lSO labels.54b Me2P(0)H

+

Me,PCI

--+

Me,P(O)CI

Me2P(0)OH Scheme 10 O* O* Ph2P II /0,0/PPh2II

64

A

o*

+ Me2PH

+

Me,PCl

o*

II II PhZP-0-P-OPh I Ph

(a) R. L. Dannley, R. L. Waller, R. V. Hoffman, and R. F. Hudson, Chem. Comm., 1971,

1362; (6)R. L. Dannley, R. L. Waller, R. V. Hoffman, and R. F. Hudson, J. Org. Chem., 1972, 37, 418.

5

Tervalent Phosphorus Acids BY B. J. WALKER

1 Introduction A great deal of the work published in the past year in this area of phosphorus chemistry has involved minor variations on old themes, and in this chapter only work which has some novelty is discussed in any detail. The use of phosphorous acid derivatives in synthesis has been reviewed.l 2 Phosphorous Acid and its Derivatives Nucleophilic Reactions.-Attack on Saturated Carbon. The Arbusov reaction has been used extensively as a preparative method.2 Halogen has been the group most commonly displaced by phosphorus, although amino,4 alkoxy,6and acetate leaving groups have also been used. Under more forcing conditions, sulphur analogues [e.g. EtSPEtJ of tervalent phosphorus acids also undergo the Arbusov reaction with alkyl halides. The low reactivity of aromatic halides in the Arbusov reaction has been partially overcome through the use of palladium catalysts.s The reaction of phosphites with diphenyliodonium iodide in the presence of copper salts gives arylphosphonates (l), presumably by initial nucleophilic substitution and an Arbusov r e a ~ t i o n . ~ Anionic resins also appear to catalyse the 2

6

*

J. Barycki, Wiad. Chem., 1971, 25, 123 (Chem. Abs., 1971, 75, 4859). E.g. P. Burns, G . Capozzi, and P. Haake, Tetrahedron Letters, 1972, 925; 0. F. Voziyanova, S. N. Baranov, and S. V. Krivun, Zhur. obshchei Khim., 1970, 40, 1905 (Chem. Abs., 1971, 75, 6028). E.g. M. B. Gazizov, D. B. Sultanova, A. I. Razumov, L. P. Ostanina, and A. M. Pusalkina, Zhur. obshchei Khim., 1971, 41, 2575 (Chem. A h . , 1972, 76, 113 302). E.g. B. E. Ivanov and S. S. Krokhina, Izvest. Akad. Nauk S.S.S.R., Ser khim., 1971,2493 (Chem. Abs., 1972, 76, 127 085). E.g. B. E . Ivanov and S. S. Krokhina, Izvest. Akad. Nauk S.S.S.R., Ser. khim., 1970,2629 (Chem. Abs., 1971, 75, 6034.) E.g. M. B. Gazizov, D. B. Sultanova, V. V. Moskva, A. I. Maikova, and A. I. Razumov, Zhur. obshchei Khirn., 1971, 41,932 (Chem. Abs. 1971, 75, 49 216); B. E. Ivanov, L. A. Valitova, and S. S. Krokhina, Izvest. Akad. Nauk S.S.S.R., Ser. khim., 1971, 1502 (Chem. Abs., 1971, 75, 986 276). E.g. A. I. Razumov, E. A. Krasilnikova, N. A. Moskva, T. V. Zykova, and R. A. Salakhutdinov, Zhur. obshchei Khim., 1971, 41, 1498 (Chem. Abs., 1971, 75, 129 890); E. A. Krasil'nikova, N. A. Moskva, and A. I. Razumov, Zhur. obshchei Khim., 1970,40, 2765 (Chem. Abs., 1971, 7 5 , 2 0 516). Ger. Offen. 2 118 223 (Chem. Abs., 1972,76, 34 399). A. G. Varvoglis, Tetrahedron Letters, 1972, 31.

87

88

Organophosphorus Chemistry 0

MeOCHMe Meo

H CH,OPO,H,

HO (55)

s01ution.l~~This observation is in agreement with the results obtained from an earlier n m r . but is in direct contradiction to conclusions based on U.V. spectroscopy.166 Even though the keto-form of (55) is an obligatory intermediate in many enzymic reactions only minute amounts are present in aqueous solution under normal conditions. From the reaction between fructose 1,6-diphosphatase and structural analogues of (%),la'it has been deduced that the furanose ring and the C-3 and C-4 hydroxy-groups of (55) are essential for activity. Oxidation of D-glucuronic acid 6-phosphate by vanadium pentoxide and chlorate ion gives ~-ara.-hex-2-ulosonic acid 6-phosphate (56), which is a known intermediate in carbohydrate metabolism.ls8 In the presence of alkali, (56) is unstable and breaks down by a retro-aldol reaction to a triose phosphate. CO,H I

co

I I HCOH I HCOH I

HOCH

OH-

CHO I HCOH

I

CH,OPO,H,

CH,0P03H,

(56) H. Nomura, M. Shimomura, and S. Morimoto, Chem. andPharm. Bull. (Japan), 1971, 19, 1433. l e 3 E. E. Nifant'ev, L. T. Elepina, and V. N. Bakakhontseva, Zhur. obshchei Khim., 1971, 41, 707 (Chem. Abs., 1971,75, 64 140). 164 G. R. Gray, Biochemistry, 1971, 10, 4705. l65 G. R. Gray and R. Barker, Biochemistry, 1970, 9,2454. 186 G. Avigad, S. Englard, and I. Listowsky, Carbohydrate Res., 1970, 14, 365. 167 S. J. Benkovic, J. J. Kleinschuster, M. M. deMaine, and I. J. Siewers, Biochemistry, 1971,10,4881. 1e8 F. Trigalo and L. Szabb, European J . Biochem., 1972, 25, 336.

lli2

Phosphates and Phosphonates of Biochemical Interest

7H 2 0H

169

CH,OPO,H, I

OP0,H2

HO

HO

HO

(58)

(57)

The syntheses of sucrose 6’-pho~phate,l~~ methyl a-mannopyranoside

4- and 6-pho~phates,l~~ and 3-deoxy-3-fluoro-~-g~ucose 1- and 6-phosphates [ (57) and ( 5 8 ) ] 171have been described. Neither (57) nor (58) was a substrate for UDPGlc-pyrophosphorylase or phosphoglucomutase, although (58) was a poor substrate for glucose 6-phosphate dehydrogenase.171

7 Phospholipids D-1 -Deoxy- 1-fluoroglycerol 3-phosphate (59), a potential anticancer

agent,172 has been prepared from D-mannitol (60) by a stereospecific route which should be suitable for the synthesis of the L-isomer of (59).173Transformation of (60) into D-1-tosyl-2,3-O-isopropylideneglycerol, followed by displacement of tosyl ion by fluoride ion, removal of the isopropylidene group, and treatment with dibenzyl phosphorochloridate gave the dibenzyl ester of (59). A m-mixture of this dibenzyl ester was CH20H

CH20Ts

HO

-

i, KF ii, H 3 0 + i i i , phosphorylate

OH

18

CH,F

HtOH CH20P03H2

3 7 OCHZ

I 18H3’10CH I

CH, I ,oCHzP II ‘CH,CH2&Me3 0 (61) 169

170 171 i m

179

J. G. Buchanan, D. A. Cummerson, and D. M. Turner, Carbohydrate Res., 1972, 21, 283 (Chem. Abs., 1972, 76, 86038). T. N. Cawley and R. Letters, Carbohydrate Res., 1971,19,373 (Chem. Abs., 1971,75, 118 529). J. A. Wright, N. F. Taylor, R. V. Brunt, and R. W. Brownsey, J. C . S. Chem. Comm., 1972, 691. T. P. Fondy, G. S. Ghangas, and M. J. Reza. Biochemistry, 1970, 9, 3272. G. S. Ghangas and T. P. Fondy, Biochemistry, 1971, 10, 3204.

170 Organophosphorus Chemistry obtained from the reaction between epifluorohydrin and dibenzyl phosphoric acid. Diether phosphinate analogues of lecithin, e.g. (61), have also been prepared from (60).17* 2-Chloromethyl-4-nitrophenyl phosphorodichloridate (62) has been used as a bifunctional phosphorylating agent in the preparation of a-glycerophosphorylcholine (63).175The 2-chloromethyl4-nitrophenyl group is readily removed by treatment with aqueous pyridine ;

XI

o/

\OCH,CH,CI

i, C,H,N ii, Me,N iii, H:J) +

-

:o\/H

H

presumably displacement of the benzylic chlorine atom by pyridine is followed by the rapid decomposition of the quaternary compound (64). The synthesis of dl-a-tocopheryl phosphoric diesters using (62) has also been rep orted .l7 The use of arylsulphonyl chlorides in place of DCC in the synthesis of phosphatidyl cholines gives products with a higher molar rotation than has been obtained previ0us1y.l~~ Resolution of 1,2,4,5,6-penta-0-acetyl-myo-inositols has been achieved by means of their acid oxalates; selective removal of the oxalyl residues with base followed by phosphorylation of the hydroxy-groups with phosphoryl chloride and benzyl alcohol produced the dibenzyl phosphates of the inositol penta-acetates. Removal of the protecting groups liberated either 1-D-myo-inositol 1-phosphate (65) or the ~ - i s o r n e r . ~ ~ * 174

175

176 17'

178

A. F. Rosenthal, L. Vargas, and S. C. H. Han. Biochim. Biophys. Acta, 1972,260,369. Y . Mushika and N. Yoneda, Chem. and Pharm. Bull. (Japan), 1971, 19, 696. Y. Mushika and N. Yoneda, Chem. and Pharm. Bull. (Japan), 1971, 19, 687. R. Aneja and J. S. Chadha, Biochim. Biophys. Acta, 1971, 248, 455. J. G. Molotkovsky and L. D. Bergelson, Tetrahedron Letters, 1971, 4791.

171

Phosphates and Phosphonates of Biochemical Interest

Signals in the lH n.m.r. spectra of phosphatidylcholine residues are broadened 17g on the addition of the spin-labelled phosphatidylcholine (66).180 This has been interpreted as indicating that rapid diffusion occurs in the plane of the phosphatidylcholine bilayer as the broadening does not appear to be due to collision exchange of spin-label or fusion of the ve~ic1es.l~~ 31P Nuclear magnetic relaxation times have been determined using several phospholipid dispersions, and from the temperature dependence of the spin-spin relaxation times it has been concluded that these relaxation times reflect the mobility of the hydrophobic lipid head group.lS1 Bacterial glycophospholipidslE2and the metabolism and function of membrane phospholipids of E. coli lS3 have been reviewed.

8 Enzymology The use of paramagnetic probes in magnetic resonance studies on phosphoryl transfer enzymes, e.g. creatine kinase, has been reviewed,ls4 and model reactions with phosphoroguanidates have led to new ideas on the mechanism of action of this enzyme.lS5 The pH-rate profile for the

(67)

NMe,

I

Me R. D. Kornberg and H. M. McConnell, Proc. Nut. Acad. Sci. U.S.A., 1971, 68,2564. R. D. Kornberg and H. M. McConnell, Biochemistry, 1971, 10, 1111. m1 R. W. Barker, J. D. Bell, G. K. Radda, and R. E. Richards, Biochem. Biophys. Res. Comm., 1972,260, 161. 18* N. Shaw and A. Stead, F.E.B.S. Letters, 1972, 21, 249. la3 J. E. Cronan, jun., and P. R. Vagelos, Biochim. Biophys. Acta, 1972, 265, 25. la4 M. Cohn and J. Reuben, Accounts Chem. Res., 1971,4,214. P. Haake and G. W. Allen, Proc. Nut. Acad. Sci. U.S.A., 1971, 68, 2691. 170

la0

172

Organophosphorus Chemistry

hydrolysis of NN-dimethyl-N’-phosphoroguanidate(67) has a maximum at pH 2.0 and the rate of cleavage of the P-N bond in (67) is very high, suggesting that a metaphosphate intermediate may be involved in its reactions. Further support for the involvement of a metaphosphate in phosphoryl transfer from (67) comes from the indiscriminate phosphorylation of alcohol-water mixtures by this compound. It is suggested that the phosphorylation of ADP by phosphocreatine (68) catalysed by creatine kinase also proceeds by a metaphosphate intermediate and that the enzyme functions as a proton-transfer agent in the generation of this intermediate. A phosphoryl-enzyme intermediate is formed during reactions catalysed by alkaline phosphatase.lss 0-4-Nitrophenyl phosphorothioate is hydrolysed 1000 times more slowly by alkaline phosphatase than is its oxygen analogue, suggesting an &2(P) mechanism for the phosphorylation of the enzyme.ls7 From a kinetic study of the reaction between a series of alkyl-, aryl-, and arylamido-phosphates and alkaline phosphatase, it has been shown that steric factors are important in these reactions.la8 Moreover, although amidophosphates [e.g. (69) ] are substrates for this enzyme lg9

they react some 60000 times too slowly for an &1(P) mechanism, which is additional evidence for an &2(P) reaction. Covalent phosphorylenzyme intermediates have also been demonstrated recently for acid phosphatase,lgO acetate kinase,lgl and succinyl CoA synthetase from E. ~ 0 Z i . l ~A~ phosphopeptide containing 25 amino-acid residues and four of the five phosphorus atoms present in p-casein type A1 has been isolated from a tryptic digest of the protein.lg3 The phosphorus atoms are present as phosphoserine residues situated close together and it has been suggested that phosphoserines could be involved in phosphoryl transfer reactions. Under mild conditions, chloro- and bromo-acetol phosphates (70), reactive analogues of dihydroxyacetone phosphate, inactivate yeast fructose XCH,COCH ,OPO,H, (70) X = Br o r C1 J. H. Schwartz, Proc. Nat. Acad. Sci. U.S.A., 1963, 49, 871. I. Katz and R. Breslow, J. Amer. Chem. SOC.,1968, 90, 7376. lS8 A. Williams and R. N. Naylor, J . Chem. SOC.(B), 1971, 1973. lS8 S. L. Snyder and 1. B. Wilson, Biochemistry, 1972, 11, 1616. R. L. VanEtten and M. E. Hickey, Fed. Proc., 1972, 31,451Abs. lgl R. S. Anthony and L. B. Spector, J . Biol. Chem., 1972, 247, 2120. la2 T. Wang, L. JuraSek, and W. A. Bridger, Biochemistry, 1972, 11, 2067. lg3 W. Manson and W. D. Annan, Arch. Biochem. Biophys., 1971, 145, 16.

lS6

Phosphates and Phosphonutes of Biochemical Interest

173

diphosphate aldolase by alkylation of approximately one thiol group per molecule of catalytic subunit, probably near the active site of the enzymes.1s4 a-Glutamyl phosphate (7 l), a possible intermediate in reactions catalysed by glutamine synthetase,ln5cyclizes rapidly to a pyrrolidone (72) with expulsion of phosphate, which renders isolation of (71) difficult. However, when cis-l-amino-l,3-dicarbox~c~clohexane (73), which is an analogue of c02-

I CHz

H3N' C0,(71)

CO,H HQ)C (H , ~N"'

C0.0P03H2

HOC H ,(), ~ N . . (74)

(73)

glutamate, is incubated with glutamine synthetase and ATP, an enzymesubstrate complex can be isolated by gel-fi1trati0n.l~~An acidic compound which has the properties of the mixed anhydride (74) can be isolated from the complex. The effect of a number of oximes derived from pyridines on rat-brain acetyl cholinesterase which had been inactivated by isopropyl methylphosphonofluoridatehas been studied, the most effectiveat restoring enzymic activity being (75).ls7 Acetyl cholinesterase is also inhibited by aryl

2Br(75)

methylphosphonochloridates, both the reactivation and ageing of the enzyme being dependent on the substituents on the aromatic ring.ls8 Reactivation of the phosphonylated enzyme is due to hydrolysis of the phosphonoserine bond, and since substitution in the aryl group of aryl methylphosphonochloridates would have an effect on the electrophilicity of the phosphonyl group, the rate of reactivation would be affected. The lB4

lg5

lQ8 lB7

lg8

Y. Lin, R. D. Kobes, I. L. Norton, and F. C. Hartman, Biochem. Biophys. Res. Comm., 1971,45,34; M. C. Paterson, I. L. Norton, and F. C. Hartman, Biochemistry, 1972,11, 2070. A. Meister, Adv. Enzymol., 1968, 31, 183.

Y. Tsuda, R. A. Stephani, and A. Meister, Biochemistry, 1971, 10, 3186. J. PatoEka, Coll. Czech. Chem. Comm., 1972, 37, 899. J. W. Hovanec and C. N. Lieske, Biochemistry, 1972, 11, 1051.

1 74 Organophosphorus Chemistry ageing of phosphonylated acetyl cholinesterase is due to cleavage of the P-0-aryl bond which should be very sensitive to substitution in the aryl ring. Both tris-(4-nitrophenyl) phosphate and bis-(4-nitrophenyl)carbonate react rapidly with the active site of a-chymotrypsin with the release of one equivalent of 4-nitrophen01.~~~ The resulting phosphorylated or acylated enzyme then releases a second equivalent of 4-nitrophenol in a reaction which involves the participation of a group on the enzyme with a pK, near 7, probably His-57. 9 Other Compounds of Biochemical Interest 2-(Dansy1amino)ethyl triphosphate (76) is a fluorescent substrate for heavy meromyosin-ATPase, behaving like ATP.200 Marked increases in the excitation and emission spectra of (76) on addition of heavy meromyosin are observed and the maximum of the emission spectra undergoes a slight

(76)

(77)

hypsochromic shift. This suggests that (76) is in a hydrophobic environment when bound to the enzyme. L-threo-Neopterin 2',3'-cyclic phosphate (77) has been isolated from Methylococcus capsulatus and its structure proved by degradative means.2o1 Like a similar dihydroneopterin cyclic phosphate which has been isolated from a strain of Comamonus,20athe pteridine moiety and the phosphate group are derived from the same GTP molecule. Further evidence on the structure of presqualene pyrophosphate (78) 203 has been put forward confirming earlier and the enzymic

(78) lgB 201

aoa

203 204

M. L. Bender and F. C. Wedler, J. Amer. Chem. Soc., 1972, 94, 2101. M. Onodera and K. Yagi, Biochim. Biophys. Acta, 1971, 253, 254. T. Urushibara, H. S. Forrest, D. S. Hoare, and R. N. Patel, Biochem. J., 1971,125,141. J. Cone and G. Guroff, J. Biol. Chem., 1971, 246, 979. J. G. Edmond, G. Popjhk, S. M. Wong, and V. P. Williams, J. Biol. Chem., 1971, 246,6254.

H. C. filling, C. D. Poulter, W. W. Epstein, and B. Larsen, J. Amer. Chem. SOC.,1971,

93, 1783; R. M. Coates and W. H. Robinson, ibid., p. 1785.

175

Phosphates and Phosphonates of Biochemical Interest

formation of squalene homologues from homologues of farnesyl pyrophosphate has been reported.20sThe inhibition of enzymic dephosphorylation of a C,,-isoprenyl pyrophosphate by the antibiotic bacitracin is abolished by the addition of chelating agents.2o* Various bivalent metal cations appear to participate in complex formation between the antibiotic and the isoprenyl pyrophosphate, and such metal complexes may be important in the mode of action of bacitracin on membranes. A new microbial metabolite, phosphoramidon (79),has been isolated from a strain of Streptomyces and its structure determined.207 The

CH-CH,CH( I NH I O=P-OH

Me

I

M 4 k O - r HO HO-f-+H OHHO

metabolite, which is hydrolysed by acid to leucyltryptophan, L-rhamnopyranose, and inorganic phosphate, is unusual in possessing a phosphoramidate bond. 205 ao6

207

K. Ogura, T. Koyama, and S. Seto, J . Amer. Chem. SOC.,1972, 94, 307. K. J. Stone and J. L. Strominger, Proc. Nut. Acad. Sci. U.S.A., 1971, 68, 3223. S. Umezawa, K. Tatsuta, 0. Izawa, and T. Tsuchiya, Tetrahedron Letters, 1972, 97.

8

Ylides and Related Compounds BY S. TRIPPETT

1 Methylenephosphoranes Preparation.-The preparation of methylenephosphoranes has been reviewed.l Pure methylenetriphenylphosphorane has been obtained as shown in Scheme 1, together with the pure trimethylsilylmethylene- and

bis(trimethylsilyl)methylene-phosphoranes.2 Ph3P: CH, 85%

+

Ph,PMe Br-

I

iii

I

Me4$ Br-J.

ii ----+

Me4; Br-J.

+ Ph,P: CH. SiMe, 77%, m.p. 12-13

Ph,P: C(SiMe,),

+ Ph,P: CH, 82%

iV

-+=

"C

&

49%,m.p. 139-140 "C

+

P$P. CH(SiMe,), Br-

1-

[ I

Reagents: i, NaH, THF; ii, Me3P:CH,, ether; iii, Me,P:CH.SiMe,, ether; iv, Me,SiBr; v, BuLi; vi, 270-300 "C, 0.1 mmHg

Scheme 1

Further examples have appeared of the use of epoxides as the source of the base in olefin synthesis, among them the synthesis of crocetin dialdehyde (1) shown in Scheme 2., Additional polymeric Wittig reagents have been described and used in olefin ~ynthesis.~ 1 3 4

H. J. Bestmann and R. Zimmermann, Fortschr. Chern. Forsch., 1971, 20, 1. H. Schmidbaur, H. Stuhler, and W. Vornberger, Chem. Ber., 1972, 105, 1085. G.P. 2 037 935-6 (Chem. Abs., 1971, 75, 20 707, 49 365). S. V. McKinley and J. W. Rakshys, jun., J . C . S. Chem. Comm., 1972, 134; W. Heitz and R. Michel, Angew. Chem. Internat. Edn., 1972, 11, 298.

176

177

Ylides and Related Compounds

I

(1) /

0

\

Reagents: i, MeCH,CH-CH,,

CH,Cl,, 75 "C Scheme 2

-

Phosphines and the imine (2) gave the stable ylides (3).5 R3P

+ PhCH: CH-N:C(CF3)Z

R3P:CPh- CH: N - CH(CF3), R = Ph or Pri (3)

(2)

The equilibrium established between methylenetriphenylphosphorane and ethyltriphenylphosphonium bromide in THF has been investigated by quenching with benzaldehyde. Ph3P:CH2

+ + Ph3PEt Br- 7 Ph3$Me Br- + Ph3P:CHMe 15:l

Reactions.-Halides. The stable ylides (4) are C-alkylated by p-nitrobenzyl bromide.' Methyl and ethyl iodides alkylate the formylstabilized ylides ( 5 ) exclusively on oxygen8 to give mixtures of cis- and trans-isomers not necessarily in ratios corresponding to the isomer compositions of the ylides. Dibromo- and di-iodo-methane gave the bisphosphonium salts (6). 2 Ph3P:CH-C 0 . R

+ p-NO,. C,H,. CH,Br

(4; R = OEt or Ac)

-

Ph3P:C(CO.R).CH,.C,H,.NO,-p

+ + Ph,P.CH,.CO*R Br-

Methylenetriphenylphosphorane with 1,Zdibromopropane gave the cyclobutylphosphonium salt (7), which was used in olefin synthesis. The @

K. Burger, J. Fehn, J. Albanbauer, and J. Friedl, Angew. Chem. Internat. Edn., 1972,11,

319.

A. Piskala, M. Zimmermann, G. Fouquet, and M. Schlosser, Coll. Czech. Chem. Comm., 1971,36,1482.

M. I. Shevchuk, A. F. Tolochko, and A. V. Dombrovskii, J. Gen. Chem. (U.S.S.R.),

1971, 41, 534. C. J. Devlin and B. J. Walker, Tetrahedron Letters, 1971, 4923. J. E. Baldwin and R. H. Fleming, J. Amer. Chem. Soc., 1972, 94,2140.

178

Organophosphorus Chemistry

stable a-chloro-ylides ( 8 ) were obtained as shown.lo

R’

‘OMe

PPh, 2 Ph,P:CH,

+

P h 3 k H , C O * R C1-

R

=

+

McCHBr.CH,Br

Br-

p-Me *C6H,.S0,.NHCI -+ Ph,P:CCI*CO*R

OMc, OEt, Me, or Ph

(8) > 70;/,

Carbonyls. The stable ylides (9) react with a-diketones to givell the 1,4-diketones (10). The allenic ketones (11) have been shown12 to be intermediates in the formation of 4-pyrans from diphenylketen and the ylides (9). The acridinium betaines (13) were formed l3 from the 2-aminonaphthoquinones (12) and arylidenephosphoranes under vigorous conditions, oxidation or disproportionation occurring at some stage. Wittig olefin syntheses in hydroxylic solvents may proceed via vinylphosphonium salts (14) and not via the usual oxaphosphetans when the double bond formed is stabilized by a n-bonding substituent.14 In some

(9) R1

10

11

12

lS

14

=

Me or Ph

H. J. Bestmann and R. Armsen, Synthesis, 1970, 590. E. Ritchie and W. C. Taylor, Austral. J. Chem., 1971, 24, 2137. M.Duprt and H. Strzelecka, Cumpt. rend., 1972, 274, C, 1091. H.J. Bestmann, H. J. Lang, and W. Distler, Angew. Chem. Internat. Edn., 1972, 11,59. E. E. Schweizer, D. M. Crouse, T. Minami, and A. T. Wehman, Chem. Cumm., 1971, 1000.

179

YIides and Related Compounds

(13) 11-46x

cases, e.g. (15), the vinylphosphonium salt may be isolated. However, the optically active benzylphosphonium salt (1 6) with benzaldehyde and ethanolic sodium ethoxide gives16 the oxide (17) with almost complete retention of configuration at phosphorus, and the vinylphosphonium salt Ph,P:CHR'

+

R2R3C0

Ph,;*CR': CR2R3 HO-

I

(14)

Ph,PO

+ +

ePh,6-CHR1.C(0)R2R3

-

Ph,6*CHR1.C(OH)R2R3 R40-

R'CH:CR2R3

Ph3P.CH2CH:CH2 +

M e E t P h k H , P h Br-

+

PhCHO

Br-

EtOH EIONa+

EtoH

+

PPh, Br-

o z k * C H : C H 2

Me Et PhPO

+

(17)

(16)

MeEtPh6CPh:CHPh (18)

l*

D. J. H. Smith and S. Trippett, J. C. 5'. Chem. Comm., 1972, 191.

PhCH:CHPh

180

Organophosphorus Chemistry

f

+

I

s3 t

(18) is therefore unlikely to be an intermediate unless it undergoes alkaline hydrolysis with complete retention of configuration at phosphorus. Vinylphosphonium salts have also been implicated in the complex reactions occurring when 2-hydroxyalkylphosphonium salts are treated with base in hydroxylic solvents,16 and l7 in the previously observed formation of the ethers (20) and (21) from the salt (19) and sodium methoxide. The stereospecificity of the /%oxido-ylide synthesis using formaldehyde as one of the aldehyde components is dependent on the order of use of the a1deh~des.l~Thus, starting from the ethylidenephosphorane, use of hexaldehyde and paraformaldehyde in that order gave almost pure isomer (22), while their use in the reverse order gave a mixture of the isomers (22) and (23) in the ratio 36 : 64. 16 '1

l9

J. W. Rakshys, jun., and S. V. McKinley, Chem. Comm., 1971, 1336. E. E. Schweizer, T. Minami, and D . M. Crouse, J , O r g . Chem., 1971, 36, 4028. E. E. Schweizer, C. J. Berninger, D. M. Crouse, R. A. Davis, and R. S. Logothetis, J. Org. Chem., 1969, 34, 207. M. Schlosser and D. Coffinet, Synthesis, 1971, 380.

181

Ylides and Related Compounds C5H11

Ph,P:CHMe

\

CH,OH

I

.'

The unexpected formation of ethyl a-safranate (26) from allylidenetriphenylphosphorane and the keto-ester (24) could involve coupling between the y-carbon of the ylide and the /I-carbon of the unsaturated ketone to give the betaine (25), followed by proton transfer and an intramolecular Ph,P:CH-CH:CH,

+

XC02EI 0

~

R 0 2 E t

f -

Ph,P+

(24)

(25)

Ph,P C0,Me

M~o-> M

e

0

R

Ii

1

(28) PIi,,P: Ct I M C

Meo C0,Me

R H

7

(29)

Organophosphorus Chemistry

182

Wittig reaction.20 Among other unusual olefin syntheses is the formation 21 of the six-membered olefin (29) from the five-membered ketone (27) and an excess of ethylidenephosphorane in DMSO. This probably involves initial base-catalysed isomerization of (27) to the six-membered ketone (28). A full account has appeared22of the use of ylides in the synthesis of cyclopropyl-substituted ethylenes. Among unsuccessful Wittig reactions noted is the failure of cyclohexylidenetriphenylphosphorane to give the olefin (30) on reaction with cycl~hexanone.~~

Ph,P :CCI,

+

PI1C0.CN

- PhC(CN):CCI, (31) 73;!

A full account has appeared 24 of the reactions of polyhalogenoacroleins, keto-acetals, ethyl pyruvate, and various halogenated unsaturated ketones with dichloro- and dibromo-methylenetriphenylphosphoranes generated in situ. This dichloro-ylide reacted 25 with the carbonyl of benzoyl cyanide in a normal olefin synthesis to give the unsaturated nitrile (31).

+ 0

Ph,P:CHR

R

0

(32)

R

=

21

23 24 26

I4

+

CO,E1 o r CN

(33)

2o

*OonC

---+

RR H H

R

(34)

G . Biichi and H. Wiiest, Helu. Chim. Acta, 1971, 54, 1767. E. G. Brain, F. Cassidy, A. W. Lake, P. J. Cox, and G . A. Sim, J. C. S. Chem. Comm., 1972,497. T . Teraji, I. Moritani, E. Tsuda, and S. Nishida, J . Chem. SOC.( C ) , 1971, 3252. J. B. Jones and P. W. Marr, Canad. J. Chem., 1970, 49, 1300. C. Raulet and E. Levas, Bull. SOC.chim. France, 1971, 2598. R. L. Soulen, D. B. Clifford, F. F. Crim, and J. A. Johnston, J. Org. Chem., 1971,36, 3386.

183

Ylides and Related Compounds

The bicyclic imide (32) reacted under vigorous conditions with stable ylides to give mixtures of the mono- and bis-olefins.26 The homologue (33) behaved similarly but no reaction was observed with (34). The sulphonamide (35) reacted normally 27 under vigorous conditions. Whereas the ester ylide (36; R = OEt) with N-p-nitrobenzoylaziridine gave the ylide (38) by proton transfer in the intermediate (37), the aroyl ylides (36; R = Ar') catalysed the conversion of the aziridine into the oxazoline (39), presumably uia the same type of intermediate.28 Ph,P:CHCO- R

+

ArCO-Nl

--+ Ph,kH(CO-R)CH,CH2NCO-Ar

(36)

Ph,P:C(CO, Et).CH,CH,N HCO-Ar

(38)

Ar

=

p-NO,.C,;H,

R

= At'

J.

Ph,P:CHCO.Ar'

+

Ar (39)

Among other carbonyl compounds successfully used in olefin synthesis are (40),29(41),30the optically active dione (42),31the pyrroles (43),32and the xanthone (44).33 In the last case the aldehyde was added rapidly to a large excess of the ylide, followed immediately by acetone to remove the excess reagent. Miscellaneous. The unusual reductions of benzyltriphenylphosphonium salts with sodium to give benzyldiphenylphosphine have been shown 34 to involve reduction of the benzylidenephosphorane. This ylide with sulphur in benzene at 70 "C gave 36 triphenylphosphine sulphide, a pentasulphide formulated as (45) or (46), and only traces of isomeric stilbenes. Previous workers 36 reported high yields of stilbenes from the same reaction carried out in refluxing toluene. Benzoylmethylenetriphenylphosphorane (47) with sulphur gave a polymer of the thioaldehyde (48). 2o 27 28 gs

30

32 33 34 35

36

W. Flitsch and B. Muter, Chem. Ber., 1971, 104, 2852. M. Natsume, M. Takahashi, K. Kiuchi, and H. Sugaya, Chem. and Pharm. Bull. (Japan), 1971, 19,2648. H. W. Heine and G. D. Wachob, J. Org. Chem., 1972, 37, 1049. N. N. Belyaev and M. D. Stadnichuk, J. Gen. Chem. (U.S.S.R.), 1971, 41, 1888. L. D. Quin, J. W. Russell, jun., R. D. Prince, and H. E. Shook, jun., J. Org. Chem., 1971,36, 1495. D. A. Lightener and G. D. Christiansen, Tetrahedron Letters, 1972, 883. W. Flitsch and U. Neumann, Chem. Ber., 1971, 104, 2170. H. D. Locksley, A. J. Quillinan, and F. Scheinmann, J. Chem. SOC.( C ) , 1971, 3804. A. W. Herriott, Tetrahedron Letters, 1971, 2547. H. Tokunaga, K. Akiba, and N . Inamoto, Bull. Chem. SOC.Japan, 1972, 45, 506. H. Magerlein and G. Meyer, Chem. Ber., 1970, 103, 2995.

184

Organophosphorus Chemistry 0

R S i C H:C

H

a

("I

C HO

P

(40)

Me

O NC 0 - R ' H

+

Ph,P:CR'*CO,Et 0

(43)

4 6'X

(44)

Ph,P:CHPh

+

Ph,,PS

S8

83;;

+

/

PhCH

S

\

CIIPh

\

/

s.s.s.s

(45) 14:;

Ph,P:CHCO*Ph (47)

+

s8

+ Ph,,PS 4- (PhCO-CHS), (48)

185

Ylides and Related Compounds

Lithiation of the phosphorane (47) in benzene in the presence of HMPT gave 37 a solution containing the 'enolate ylide' (49), which on prolonged refluxing with ketones gave, after work-up, the ,€+unsaturated ketones (50). (47)

Li

Ph,P:C:C(OLi)Ph (49)

R'CH:CR2. CH2CO*Ph (50) 3 0 4 2 : ;

The phosphonium acetates (51) are soluble in organic solvents, in contrast to the previously prepared chlorides. With base in methanol they gave the bisphosphoranes (53), from which the divinylmercury compounds (52) were obtained on reaction with aldehydes.38 Ph,P:CHR'

+

Hg(OAc),

-

P h 3 k H R 1 * H g O A c AcO(51)

I

McOl1 hasc

K'CHO

R2CH:CR1*Hg*CR':CHR2 C-- Ph,P:CR'*Hg.CR':PPh, (52)

(53)

A full account has appeared3g of the reactions of acyl azides with P-keto-a1kylidenephosphoranes. These phosphoranes with ni trile oxides gave isoxazoles (54) 40* 41 and the stable ylides (56) or (57), formed as shown via the quinquecovalent 1 :1 adducts (55).41 The 3-pyrrolines (59) were formed on refluxing the aziridine (58) with the stable ylides Ph,P: CHR (R = CN or C0,Me) in toluene.42Methylenetriphenylphosphorane with benzoyl isocyanate gave a compound that has been assigned structure (60).43 ' 3

38 39 4O 41 42 43

C. Broquet and M. Simalty, Tetrahedron Letters, 1972, 933. N. A. Nesmeyanov, A. V. Kalinin, and 0. A. Reutov, Doklady Chem., 1970,195, 788. P. Ykman, G. L'AbbC, and G. Smets, Tetrahedron, 1971, 27, 5623. T. Sasaki, T. Yoshioka, and Y. Suzuki, Yuki Gosei Kagaku Kyokai Shi, 1970'28,1054 (Chem. Abs., 1971, 74, 125 528). G. L'Abbt, J.-M. Borsus, P. Ykman, and G. Smets, Chem. and Ind., 1971, 1491. F. Texier and R. CarriC, Tetrahedron Letters, 1971, 4163. Y. Ohshiro, Y. Mori, M. Komatsu, and T. Agawa, J. Org. Chem., 1971, 36, 2029.

186

Organophosphorus Chemistry

I

Ph3P:CHC0.R1

f

R 2 C N 0 --+

I

= PI1 -

PhCH-C(CO,Mc),

P 11

(58)

:5R’ N

~1

= M~

K’= PIl’

[

MeCOC:PPh,

MeCO -C: PPh:, I PhNHCO

---+

PhL:NOH]

I’1iJ1’0

PhCO.CH:C:NPh

\ N/

---+

(54)

R’COCH-PPh, / \ , R’C* o N

K’ = K‘

0 ;Ph, I I R’-C-CH I \ 0, ,,CR2 N

CHCO. I’ll

I’IlJ?

Ph,P:C(CO*Ph)-C(NHPh):CHCO.Fh (57)

+ K

Ph,P:CHR =

+

I cllu.;,

Ph,PCHR

-----+

toliicne

PhLH C(CO,Mc), \ /

CN or CO,Me

N Ph

OMe

I
-

N,

PCI, I P

,NMe

s4\ c1 (1)

CH,CI I

CH,CI I

The possibility of obtaining compounds with useful physiological activity still prompts investigations into the properties of phosphazenyltriazines such as (3), which was characterized as its trianilino- and triphenoxy-derivatives. Full experimental details of the reaction of sulphamic acid with phosphorus pentachloride to give the phosphazenyl H. W. Roesky, Chem. Ber., 1972, 105, 1439. L. A. Lazukina, N. G . Kotlyar, V. P. Kukhar', and S. N. Solodushenkov, J . Cen. Chetti. (U.S.S.R.), 1971, 41, 2413.

207

Phosphazenes

derivative, Cl,P=N- SO,CI, have a p p e a ~ e d , ~as~well as further information on the nature of the products of the Kirsanov reactions of carboxylic amides with phosphorus pentachl~ride.~~ lo

From Cyano-compounds and Phosphorus(v) Halides.-The products from the reactions of acetonitrile and chloroacetonitriles with phosphorus pentachloride have been re-examined.ll The formation of compounds of structure (4) from the reaction with acetonitriles is confirmed, as well as the intermediates (9,but there was no evidence for the existence of cisand trans-isomers of (4) or ( 5 ) (X = H) as previously postulated. The

(4)

x,,c=c, ,N=PCI,

CI

P(O)CI,

X

=

so,

+-

(5)

(4)

H,S

s, ,N=PC13 ,c=c, c1 P(S)Cl, X

H or C1

=

H or C1 (7)

(6)

reactions of the compounds (4) with sulphur dioxide and with hydrogen sulphide have been shown to give phosphinyl- (6) and phosphinothioyl- (7) olefins, respectively. In the same way, dichloroacetonitrile and phenyltetrachlorophosphorane give an N-chloroalkylphosphazene in which the olefinic linkage can be readily chlorinated : CHC12CN

+ PhPCI,

CI,C=CCl.N=PPhCl,

c C1,C. CCl, * N=PPhCl,

However, nitriles of the type RCH2CN (R = alkyl or aryl) give resinous products with phenyltetrachlorophosphorane,12 possibly because the T. Moeller, T.-H. Chang, A. Ouchi, A. Vandi, and A. Failli, Inorg. Synth., 1972, 13, 9. 1971, 6, 93. V. P. Rudavskii, D. M. Zagnibida, and V. I. Konchatenko, Farm. Zhur. (Kieu), 1971, 26, 14 (Chern. Abs., 1972, 76, 3496). G. I. Derkach, E. S. Gubnitskaya, and V. A. Shokol, Ref. Zhur. Khim., 1970, Abs. No. lOZh 528 (Chem. Abs., 1971,75, 76 053). E. Fluck and W. Steck, 2. anorg. Chem., 1972, 387, 349. N. D. Bodnarchuk, V. Ya. Semenii, V. P. Kukhar’, and A. V. Kirsanov, J . Cen. Chem. (U.S.S.R.), 1971, 41, 989.

* T. Moeller and R. L. Dieck, Prep. Inorg. Reactions, lo

l1 l2

208

Organophosphorus Chemistry

unsaturated compounds formed initially are chlorinated by the phosphorane. These difficulties have been overcome by simultaneous reaction of these nitriles with dichlorophenylphosphine and chlorine : RCH,CN

+ PhPCI, + Cl,

RCCI,CCI,.N=PPhCI,

-

These compounds were converted to imino-derivatives on reaction with arenesulphonamides : RCCI,CC12.N=PPhCI,

+ ArSO,NH,

ArSO,N= C(CCI,R)N=PPhCI,

Malononitriles undergo interesting reactions with phosphorus pentach10ride.l~ For example (8) is cyclized to a monophosphazene (9) in refluxing chlorobenzene solution and may be re-formed by addition of

A'r

(8)

Ar

=

various methyl-, chloro-, or nitro-substituted phenyl groups

(9)

water to (9) under mild conditions. In addition, the reactions of (9) with formic acid give the hydroxy-phosphazenes (1 0) and P-phenoxy-derivatives of (9) can be obtained by treatment with sodium phenoxide. Alkyl derivatives of (9) have been obtained l4 by the same route and show similar reactivity to nucleophiles. They also form molecular complexes with two molecules of phosphorus pentachloride, but the structure of these complexes is not known. The aryl tricyanides ArHC(CN)CH(CN), undergo a cyclization reaction with phosphorus pentachloride l5 to give the azoles (1 1). This contrasts l3 l4

l6

P. P. Kornuta, A. I. Kalenskaya, and V. I. Shevchenko, J . Gen. Chem. (U.S.S.R.), 1971, 41, 993. P. P. Kornuta, A. I. Kalenskaya, and V. I. Shevchenko, J . Gen. Chem. (U.S.S.R.), 1971, 41, 2416. V. I. Shevchenko and N. R. Litovchenko, J. Gen. Chem. (U.S.S.R.), 1971, 41, 1252.

209

Phosphazenes

with the results obtained last year for analogous alkyl tricyanides, which gave phosphazenes with acyclic N-substituents. Compounds of the type (1 1) undergo reactions typical of trichlorophosphazenyl derivatives, including the conversion of the -N=PC13 group into the -NHP(O)Cl, ArCH(CN)CH(CN),

pclj

Ar-C=C-CN I I CI-C, ,C-N=PCI,

N

\ c1

(1 1)

group by reaction with formic acid. Aroylcyanamides have also been shown l6 to produce monophosphazenes on reaction with phosphorus pentachloride : ArCONHCN

PC16

>

ArCO.N=CCI.N=PCl,

It is probable that these derivatives are formed via the imide ArCO-NH. CC1=N-PCl4, because imides of the type Alk2N*CCl=N-PCl, are obtained from the reactions of dialkylcyanamides with phosphorus pentachlori de. Details have been given l7 of the reaction of tetramethylene dicyanide with phosphorus pentachloride, which produces the expected diphosphazene (CH2),(CC1,CCl2 N=PCl,),.

-

From Azides and Phosphorus(II1) Compounds.-The reactions of azides with phosphorus(II1) compounds continue to be an important general route to monophosphazenes : R1N3

+ R2,P

-

R1N=PR2,

+ N2

New variations on this theme have been included in the synthesis of large numbers of N-alkylcarbamates, AlkO- CO. N=PR3 (R included alkyl,18 dialkylaminoJ8, and alkoxy-groups 19). Phosphazenes of structure (12) with N-phenolic (Xl = OH; X2 = ha1 or NO,)20 and N-aminophenyl

10

17 18

19 20

I. M. Kosinskaya, A. M. Pinchuk, and V. I. Shevchenko, J. Gen. Chem. (U.S.S.R.), 1971,41, 2422. V. I. Shevchenko and V. P. Kukhar’, Ref. Zhur. Khim., 1970, Abs. No. lOZh532 (Chem. A h . , 1971,75, 76 046). V. A. Shokol, L. I. Molyavko, N. K. Mikhailyuchenko, and G . I. Derkach, J. Gem Chem. (U.S.S.R.), 1971, 41, 312. V. A. Shokol, L. I. Molyavko, and G . I. Derkach, J. Gen. Chem. (U.S.S.R.), 1971, 41, 2405. I. N. Zhmurova, A. P. Martynyuk, and A. V. Kirsanov, J. Gen. Chem. (U.S.S.R.), 1971, 41, 787.

210

Organophosphorus Chemistry

(Xl = NH,; X2 = H, hal, or alkyl),l substituents have been similarly obtained, and the basicities of the amino-phenols have been shown to be less than those of the corresponding triphenylphosphazenyl-phenols.20 Monophosphazenes, Ph3P=N. C6H4-p-N=NoC6H4-p-X (X = H, hal, NO,, OH, Me, OMe, NMe,, or N=PPh3) continue to attract attention22 because of the auxochromic action of the triphenylphosphazenyl group, -N= PPh3, which influences colour changes similar to those affected by the dimethylamino-group. N-Phosphinyl phosphazenes, MeP(0)(R1). N=PR2,, have been prepared from the phosphinyl azides Me(R1)P(0)N, and phosphines PR23(R1 included C1, NEt2, NHPh, NH.CO.OAlk, NH- C O . OPh, NH. CO-NHPh, and N=PPh3; R2 included Ph, NEt2, OEt, and OPr').,, N-Trimethylsilylphosphazenesare useful for the characterization 24 of silyl azides, e.g. R1R2Si(N3)2

PPhs

R1R2Si(N=PPh,), (R1 = R2 = Me or Ph; R1 = Me, R2 = Ph)

The crystalline intermediates expected in the reactions of benzoyl azide = 0) and phenylazido formate (n = 1) with tris(dialky1amino)phosphines have been characterized 25 and shown to eliminate nitrogen at 40-90 "C:

(n

R,P

+ N3*CO*(0),Ph

R,P=N*N=N.CO*(O),Ph

-

R,P=N CO * (O),Ph (R = Et,N, piperidino, or morpholino)

The use of monophosphazenes of the type Bu,P=N*C,H,X (X = o-NO,, m-F, m-CF,, or o-CF,), prepared by the azide route, for plant growth retardation has been proposed in a patent application.26 Other Methods.-In an extension of a recently developed synthesis of phosphazenes it has been shown2' that tertiary phosphines react with carbon tetrachloride and methylene diamines to give diaminophosphonium salts: R1,R2P

+ CCI, + H,N(CH2),NH2

-

[R12R2PNH(CH2) ,,NHPR1,R2I2+2 C121

I. N. Zhmurova, A. A. Tukhar', and A. V. Kirsanov, J. Gen. Chem. (U.S.S.R.), 1971,

22

I. N. Zhmurova, R. I. Yurchenko, and A. V. Kirsanov, J. Gen. Chem. (U.S.S.R.),

23

V. A. Shokol, G. A. Golik, and G. I. Derkach, J. Gen. Chenz. (U.S.S.R.), 1971, 41,

24 25 2*

41, 791.

1971, 41, 783.

539. S. S. Washburne and W. R. Peterson, J. Organometallic Chem.. 1971, 33, 153. K. Pilgram, F. Gorgen, and G. Pollard, J . Heterocyclic Chem., 1971, 8, 951. S. J. Kuhn, U.S.P. 3 557 208 (Chem, A h . , 1971, 75, 6096). R. Appel, €3. Blaser, R. Kleinstuck, and K.-D. Ziehn, Chem. Ber., 1971, 104, 1847.

Phosphazenes 21 1 These salts may be deprotonated by ammonia to give the correspond[n = 0, 2, or 3, ing diphosphazenes, R1,R2P=N(CH,),N=PR1,R2 R1 = R2 = Ph; n = 2, R1 = Ph, R2 = Me,S(O)=N-1, and the dimethylene derivative readily gave a diquaternary salt with methyl iodide. In analogous reactions with tris(dimethylamino)phosphine, deprotonation of the diaminophosphonium salt was best effected by potassamide, leaving the strongly basic diphosphazene (Me,N),P=N(CH,),N=P(NMe,),. This route to phosphazenes was also successful 28 in reactions with sulphonamides :

+

+

EtsN

+ Ph2R1P=N*SOzNR2, Ph,PR1 CCI, H,N.S0,NR2, [R1 included Ph and Me,S(O)=N; R2 included H and Me]

With bis(diphenylphosphin0)-ethane and -propane, diphosphazenes RS02N=PPh2(CH,),,,PPh2=N* SOzR (R included NMe,, Ph, and C,H,-p-Me) were formed, but only a monophosphazene was obtained from bis(dipheny1phosphino)methane : (Ph,P),CH,

+ H,N*SO,R

EtaN CClr

Ph,P. CH,. Ph2P=N*S02R

(R = NMe, or Ph) In a related series of reactions,29 monophosphazenes were prepared from phosphorus(II1) amides and carbon tetrachloride in the presence of a base: CCI,

R,P.NHPh R,=Et,,

YO,

(OEt),, (CH,I2,

R

R

[R 28

ae

=

E12NI-1

But; Ar

=

R,Et,NP=N.Ph C Ef Me -0 -

/

,, or (CH,)2-O-

0

R

R R C,;H4-p-X(X = H, Me, OMe, NMe,, or F)] Scheme 1

R. Appel, R. Kleinstuck, and K.-D. Ziehn, Chem. Ber., 1971, 104, 2250. E. E. Nifant'ev, G. F. Bebikh, and T. P. Sakodynskaya, J. Gem Chem. (U.S.S.R), 1971, 41, 2032.

212 Organophosphorus Chemistry A new synthesis of phosphazenes from o-aminophenols and tertiary phosphines has been developed,30which is believed to proceed by addition of the phenoxyl radical, formed by reaction with oxygen, to the phosphine. A possible route is shown in Scheme 1. Good evidence for the formation of the phenoxyl radical was obtained by examination of the e.s.r. spectra of reaction mixtures. 3 Properties of Acyclic Phosphazenes Halogeno-derivatives.-Studies of the alcoholysis of halogenomonophosphazenes have provided some interesting chemistry. For example, in the methanolysis 31 of the N-phosphinothioyl derivative F,P(S). N=PF2Cl hydrogen chloride is evolved, suggesting that reaction occurs initially at the phosphazenyl group. This result might also be expected on the basis of previous studies of the reactivity to amines. However, i.r. and 31Pn.m.r. spectroscopy show unambiguously that the product is the methylthiocompound F2P(0).N=PF,SMe, presumably favoured by the presence of the P=O bond. The possibility of formation of the phosphazane isomer F2P(0).NMe. P(S)F, was eliminated since it was characterized from the reaction : F,P(S)-NMe*SnMe,

+ [F,P(O)],O

----+ F,P(O).NMe.P(S)F,

+ Me3Sn.0.P(0)F,

The products of methanolysis and ethanolysis of a range of N-phosphinothioyl-phosphazenes, X1,P(S). N=PX2&1 (Xl and X2 include Cl and F), have since been shown32to have analogous structures. The solvolysis of F,P(S)-N=PF,CI by carboxylic acids may occur in different ways, depending on the nature of the acid employed: F2P(S)*NH.P(0)F, + HCoP

CO

+

HCI

MeCoa +

F, P (S1.N =P F, C1

F,P(S)-NH-COMe

-

P(O)F,CI

N.m.r. and mass spectrometry show that the alcoholysis of N-sulphonylphosphazenes also occurs 33 at the phosphazenyl group: XS02*N=PCI3

+ ROH

XS02. N=PC12 * OR (R = Me, Et, PP, or Bun)

and that, in the presence of catalytic quantities of diethyl ether, these rearrange to the dichlorophosphinyl derivatives, X*SO,. NR- P(O)Cl,. Possible mechanisms for these rearrangements were discussed. In a closely 30 31

32

H. H. H. H.

B. Stegmann, F. Stocker, and G. Bauer, Annalen, 1972, 755, 17. W. Roesky and L. F. Grimm, Chem. Comm., 1971,998. W. Roesky, B. H. Kuhtz, and L. F. Grimm, 2. anorg. Chem., 1972, 389, 167. W. Roesky and W. Grosse-Bowing, Chem. Ber., 1971, 104, 3204.

213

Phosphazenes

related series of reactions the alcoholysis of the monophosphazenes Y*N=PX3 (Y = MeSO,, C1S02,or N3P3F5;X = F or Cl) was followed.34 The alkoxy-phosphazenes again rearranged in the presence of diethyl ether to give derivatives of the type X,P(O)-NR*Y, with the exception of the derivatives of cyclophosphazenes in which the N3P,F5 N=PX20R structure appears to be stabilized by the presence of the formally unsaturated ring system. However, when the phosphazene linkage was more remote from the ring system, the rearrangement was again observed:

By comparison of these and other reactions with water and silylamines, it

was shown that the reactivity to nucleophilic attack at a phosphazenyl phosphorus atom generally decreased in the order : -N=PF,Cl

> -N=PF3

> -N=PCl,

> -N=PF,NMe,

-

> -N=PC12NMe2

The reactions of sodium t-butyl peroxide with N-sulphonylmonochlorophosphazenes follow 35 the expected course: ArSO,. N=PPh,Cl

+ NaOOBut

ArSO,. N=PPh,OOBut (Ar = C,H,-p-X; X = H, C1, Me, or NO,)

However, phosphoramides were obtained in reactions with analogous dichlorophosphazenes, probably as a result of the presence of traces of water in the reaction mixture : ArSO,.N=P(Ph)Cl,

+ NaOOBut + H 2 0

ArSO,.NH.P(O)(Ph). OOBut (same Ar substituents as above)

Large numbers of N-chloroacyl- and N-aroyl-P-amino-monophosphazenes, RCO N=P(NHR)3-nCln and compounds of closely related structure have been synthesized 36-41 from the analogous P-trichlorophosphazenyl derivatives, because of interest in their herbicidal and fungicidal activity. It is worth noting that in certain cases anionic species containing the phosphazenyl group may be obtained 38 by reactions 379

s4

36 36 37

s8 sD

41

H. W. Roesky and W. Grosse-Bowing, Z. anorg. Chem., 1971,386, 191. T. I. Yurzhenko and A. G. Babyak, J. Gen. Chem. (U.S.S.R.), 1971,41, 1460. V. P. Rudavskii, V. I. Kondratenko, and M. N. Kucherova, J. Gen. Chem. (U.S.S.R.), 1971, 41, 1462.

V. P. Rudavskii and V. I. Kondratenko, J. Gen. Chem. (U.S.S.R.), 1971, 41, 2176. V. P. Rudavskii and V. I. Kondratenko, J . Gen. Chem. (U.S.S.R.), 1971,41,2425. V. P. Rudavskii and N. A. Litoshenko, Khim. Tekhnol. (Kiev), 1971, 48 (Chem. Abs., 1972, 76, 45 845q). V. P. Rudavskii, N. A. Litoshenko, and D. M. Zagnibeda, Khim. Tekhnol. (Kieu), 1971, 19 (Chem. Abs., 1971, 75, 129 895y). V. P. Rudavskii, M. N. Kucherova, and D. F. Shirankov, Khim. Sel. Khoz., 1971, 9, 453 (Chem. Abs., 1971, 75, 108 815g). 8

-

214 with aniline and triethylamine: R.CO-N=PCl,

+ PhNH, + Et,N

Organophosphorus Chemistry

[Et,NH]+[R. CO. N=PC12NPh](R = various chloroalkyl groups)

Reactions of P-chlorophosphazenes with aziridine are also facilitated 42 by the presence of triethylamine : R1R2N=CR3*N=PPhCI,

+ HNC2H,

Et3N

R1R2N=CR3* N=PPh(NC,H,), (R1 = CF, or CCl,; R2 and R3 include O-CO-Alk and CN)

The dialkylaminodichlorophosphazenesPhN=PC12NEt2 form diphosphates on reaction with dialkyl- and diaryl-ureas :43 (R'NI-I) CO

PhN=PCI,NR1, (R1= Et, R2 = Me;

PhNH(R1,N)P(O). 0.P(0)(NR1,)NHPh R1 = Et, R2 = Ph; R1 = Bun, R2 = Me)

The i.r. spectra of the reaction mixtures suggest that are carbodi-imides, R2N=C=NR2, are intermediates in these reactions, although their precise function is not clear. The products of these reactions may also be obtained by controlled hydrolysis of the phosphazene : PhN=PC12-NR12

+ H20

EtsN

-

[PhNH P(0)NR1,],O

The reactions between N-chloroalkylphosphazenes and aldehydic compounds are complex, but generally give imides :44 for example, reactions with dialkylformamides may be formulated : CCI,. CCl,-N=PCI,

+ 2R2N*CH0

. +

CCI,. CO C1 R2N.CHCI, (R = Me or Et)

+ R,NCH=N - POCl,

It seems likely that these reactions proceed via the formation of salt-like complexes, related to those formed in the reactions of dialkylcarboxamides with phosphoryl chloride, e.g. [Me2N.CR. 0.P(O)Cl,]+ C1-. The products from these reactions were compared with those from the reactions of various N-arylsulphonylphosphazenes,ArSO,. N=PC13, with DMF. It is surprising that the phosphazene linkage is not retained when PhN=PCl,NEt2 is fluorinated 45 by antimony trifluoride, PhN=PC12NEt2

+ (excess)SbF,

-

Et,NPF4 42

+ SbC13 + Sb + by-products

L. D. Protsenko, N. Ya. Skul'skaya, and N. D. Bodnarchuk, J. Gen. Chem. (U.S.S.R.), 1971, 41, 1250.

43 44

M. Bermann and K. Utvary, Synth. Inorg. Metal-org. Chem., 1971, 1, 171. V. P. Kukhar', V. Ya. Semenii, and A. V. Kirsanov, J. Gen. Chem. (U.S.S.R.), 1971, 41, 1465.

46

M. Bermann and J. R. Van Wazer, Angew. Chem. Internat. Edn., 1971, 10, 733.

21 5

Phosphazenes

since the cyclophosphazene ring system is generally quite stable to this reagent. Relatively little interest has been shown in the chemical properties of the dimeric monophosphazenes (cyclodiphosphazanes) during the past year. The dimer, (MeNPCI,),, is fluorinated46 by boron trifluoride to give the difluoride, (MeNPCI,F),, with fluorine atoms in axial positions of the approximately trigonal-bipyramidal distribution of bonds about the phosphorus atoms. The same substrate reacts with chlorine under the influence of U.V. irradiation to give 47 the analogous trichloromethyl derivative in which the nitrogen atom is too weakly basic for dimer formation : c1,-U.V.

(MeNPC13)2 CCla soh?

CCl,. N=PCl,

An interesting analogy has been drawn48between the existence of the imino-isocyanate equilibrium R2C=N. COCl

R,CCl. NCO

and that which obtains between certain monophosphazenes and phosphorus(v) isocyanates : (CI,C),CI,P* NCO

-

(Cl,C),ClP=N- COCl

The latter tautomeric mixture was obtained by heating the products from the reaction of the monophosphazene (Cl,C),CIP=NH with oxalyl chloride to 120 "C. The i.r. spectrum of the tautomeric mixture showed that the concentration of the phosphazene form increased as the temperature was lowered in carbon tetrachloride solution. Experimental details of the decomposition of the N-sulphonylphosphazene Cl,P=N* S0,Cl to give the sulphur-nitrogen ring compound (NSOCI,) have been given.49 N-Sulphonylphosphazenes of related structure have been prepared60 by the reaction:

+

-

[C12PR1R2]+C1- H2N*S02Cl R1R2P(Cl)=N- S0,Cl [R1 included C1, Me, and Ph; R2 included C1, Me, Ph, N=PCl,, N=PCI, * N=PCI,, N=PCI(N=PCl,),, N=PPh,Cl, N=CCl. N=PCl,, and N=C(N=PCI,),]

A useful compilation of 31Pn.m.r. data for these derivatives, and for acyclic phosphazenes of related structure, was also given. An upfield 46

47

48

4@

H. Binder, 2. anorg. Chem., 1971, 384, 193. E. S. Kozlov and B. S. Drach, Ref. Zhur. Khim., 1970, Abs. No. lOZh 530 (Chem. A h . , 1971, 75, 88 033v). 0. I. Kolodyazhyi, L. I. Samarai, and S. N. Gaidamaka, J. Gen. Chem. (U.S.S.R.), 1971,41, 1879. T. Moeller, T.-H. Chang, A. Ouchi, A. Vandi, and A. Failli, Inorg. Synrh., 1972, 13, 11. W. Haubold and E. Fluck, 2. Naturforsch., 1972, 27b, 368.

216 Organophosphorus Chemistry trend in 31Pchemical shifts for the monophosphazenes (CCl,),ClP=N* Alk has been related to an opening of the P=N-C bond angle, deduced61 from vibrational spectra and from dipole moment measurements. These upfield shifts also corresponded to increases in the P=N bond order. The 19Fn.m.r. spectra of a series of dimeric monophosphazenes, (F,YPNMe), (Y = F, Me, Et, or Ph), have been obtained 62 over a range of temperatures and used to obtain information on P-N-P coupling constants, molecular conformations, and intramolecular exchange processes. An introductory account 53 of the n.m.r. spectra of monophosphazenes and cyclodiphosphazenes has been given, including a discussion of the upfield 31Pchemical shifts observed on passing from monomers, Cl,P=NR, to dimers, (CI,PNR), (R = fluorophenyl). lH and 31Pn.m.r. data on the structurally related dimers (X,PNMe), (X = C1 or F) have also been Alkyl and Aryl Derivatives.-The cleavage of silicon-nitrogen bonds in N-silylphosphazenes by reactions with phosphorus and silicon halides has been studied in some detail. For example, with phosphorus trichloride a novel tri(phosphazeny1)phosphine is obtained :55 Me,P= N Si Me,

Pc13

(Me,P=N),P

0

A similar reaction occurs with dichloromethylphosphine, but with chlorodimethylphosphine an unexpectedly facile quaternization reaction occurs, so that the N-dimethylphosphinophosphazene,Me,P=No PMe,, is not observed: Me,P=N-SiMe, Me,P=N-SiMe,

+ MePCl, + Me,PCl

-

(Me,P=N),PMe

1

[Me,P=N.PMe,] MetPCl

-

Me,P=N(PMe,), C1-

An analogous result is observed with the sulphur imide Me,S(O)=N. SiMe,: Me,S(O)=N. %Me,

+ Me,PCl

+

Me,S(O)=N(PMe,), C1-

In contrast, the reactions of N-silylphosphazenes with methyl- or phenylfluorophosphoranes R,PF5-, (n = 1 or 2) do not give phosphazenyl51 s2 53

66

E. S. Kozlov, S. N. Gaidamaka, Yu. Ya. Borovikov, V. T. Tsyba, and A. V. Kirsanov, J . Gen. Chem. (U.S.S.R.), 1970, 40, 2539. R. K. Harris, J. R. Woplin, R. E. Dunmur, M. Murray, and R. Schmutzler, Ber. Bunsengesellschaft phys. Chem., 1972, 76,44. K.Utvary, Allg. prakt. Chem., 1971, 22, 301 (Chem. Abs., 1972, 76, 52 568e). H.G. Horn, Chem.-Z., 1971, 95, 849. W. Wolfsberger, H. H. Pickel, and H. Schmidbaur, Z . Naturforsch., 1971, 26b,979.

Phosphazenes

-

[RPF(N=PPri,),]+ [RPF,](R = Me or Ph)

-----+

[Me,P(N=PMe,),]+

217

phosphoranes, but phosphonium ~ a l t s57, e.g. ~~~ RPF, RPF,

+ Me,Si. N=PMe,Ph + Me,%. N=PPri3

Me,PF,

+ Me,%. N=PMe,

[RP(N=PMe,Ph),]+ [RPF5](R = Me or Ph)

[Me,PF,]-

The 31Pchemical shifts of these salts suggest that the phosphonium ions are stabilized by conjugation between the phosphazenyl groups and the central phosphorus (P+) atoms. With methylfluorosilanes, N-silylphosphazenes undergo exchange reactions leading to N-methylfluorosilylphosphazenes in high yield Me,P=N.SiMe,

+ Me,SiF,-,

-

Me,P=N. SiMe,F,-, (n = 0, 1, or 2)

The di- and tri-fluorides may be obtained by fluorination of the analogous (n = 0 or l), which were obtained chlorides, Me,P=N*SiMe,CI,-, independently. The mono- and di-fluorides were monomers, but molecular weight and n.m.r. measurements showed that the trifluoride is a dimer with five-co-ordinated silicon atoms (13). Bis(trimethylphosphazeny1)dimethylsilane, (Me,P=N),SiMe,, gives crystalline 1:1 complexes with

I PMc~

M M

=

=

(13)

Zn; R Cd;R

=

=

Me or Et Me

(14)

dimethyl- and diethyl-zinc, as well as with dimethyl~admiurn.~~ Spectroscopic data suggest that the diphosphazene acts as a bidentate ligand, so that structures of the complexes are as shown in (14). The addition of triphenylphosphazene to a large number of isocyanates has been studied.60 Typical examples of these reactions are: Ph,P=NH

+ RNCO

-

RNH.C0.N=PPh3

[R = aryl, PhSO,, Me,Si, Si(NC0)3, Cl,P(O), or (MeO),P(O)]

+ Si(NCO), + Cl,P(O)NCO

Ph3P=NH (excess) Ph,P=NH (excess)

----+

Si(NH. C O . N=PPh,),NCO

(Ph,P=N),P(O)* NH. CO . N=PPh,

66 5' 5* 69

Bo

W. Stadelmann, 0. Stelzer, and R. Schmutzler, Chem. Comm., 1971, 1456. W. Stadelmann, 0. Stelzer, and R. Schmutzler, Z . anorg. Chem., 1971, 385, 142. W. Wolfsberger, H. H. Pickel, and H. Schmidbauer, Chem. Ber., 1971, 104, 1830. H. Schmidbaur and W. Wolfsberger, Synth. Inorg. Metal-org. Chem., 1971, 1, 111. A. S. Shtepanek, V. A. Zasorina, E. N. Tkachenko, and A. V. Kirsanov, Dopouidi Akad. Nauk Ukrain. R.S.R., Ser. B, 1971, 33, 153 (Chem. Abs., 1971, 75, 76944e).

21 8

-

0rganophospho r us Chemistry

The ease with which methyl iodide diquaternizes di(ary1phosphazenes) depends 61 on the separation of the phosphazenyl groups: CH,(Ph,P=NPh),

+ (excess) Me1

(CH,Ph,P=NPh),

+ (excess) Me1

-

(PhN=PPh,. CH,PPh,. NPhMe)+ I(CH,Ph,P- NPhMe),,+ 21-

Pretreatment of the monomethylenediphosphazene with sodium or n-butyl-lithium, followed by methyl iodide, resulted in the formation of a methylenephosphorane, (MePhN. PPh2=CH. PPh,MePh)+ I-. The same compound could also be converted into an imide by reaction with an aldehyde: CH,(PhZP=NPh),

+ 2OZN-p-CGH4CHO

-

CH,(Ph,PO)Z

+ 20,N-p-C,H,CH=NPh

The fact that the monomethylene derivative above only forms a monoquaternary salt may be contrasted with the fact that the diphosphine (Ph,P),CH, forms a diquaternary salt and that the phosphino-phosphazene, Ph,P(=NC6H4X).CH2PPh2 (X = H, p-Br, p-Me, rn-Me, p-OMe, or rn, p-NO,), is preferentially quaternized at the tervalent phosphorus atom.s2 The basicities and quaternization behaviour of these compounds were examined and it was shown that the diphosphazenes [Ph,P(=NC,H,X)],CH, are diacid bases, whereas the diphosphines such as (Ph,P),CH, are monoacid bases. Some of these features are also discussed in an extensive review 63 of the base properties of monophosphazenes, both from chemical and physical standpoints. The P=N bond orders of a series of monophosphazenes have been estimated utilizing 31P chemical shifts.64 As might be anticipated, the order increased with increasing electronegativity of the substituents on phosphorus and decreasing electronegativity of the substituents on nitrogen. The charge distributions and electron energies have been calculated by a self-consistent Hiickel method for phosphazenes of the type (p-X-C,H,),P=N-C,H,-p-NO, (X = H, C1, or NMe,) and (15) and have been Huckel-type MO calculations have compared with their U.V. also been carried out on other N-nitrophenylphosphazenes,66and the 81

62

63 64 85

Yu. V. Kovtun, V. A. Gilyarov, and M. I. Kabachnik, Izuest. Akad. Nauk S.S.S.R., Ser. khim., 1971, 2217 (Chem. Abs., 1972, 76, 46454h). V. Yu. Kortun, V. A. Gilyarov, B. A. Korolev, E. I. Matrosov, and M. I. Kabachnik, J . Gen .Chem. (U.S.S.R.), 1971, 41, 777. M. I. Kabachnik, Phosphorus, 1971, 1, 117. A. S. Tarasevich and Yu. P. Egorov, Teor. i eksp. Khim., 1971, 7, 828 (Chem. Abs., 1972, 76 106 144j). H. Goetz and F. Marschner, Tetrahedron, 1971, 27, 3581. Yu. P. Egorov, V. V. Pen’kovskii, and B. N. Kuzminski, Teor. i eksp. Kltim., 1971, 7, 601 (Chem. Abs., 1972,76, 52003s).

219

Phosphazenes

X

=

II, C1, or NMc,

(15)

extent of m--bonding between nitrogen and phosphorus estimated 67 from the e.s.r. spectra of the anion-radicals of these phosphazenes. The polarographic method of producing these radicals has been described,6sin which reduction occurs at the nitro-group before the phosphazene linkage. Reaction of the phosphazenyl salts [Ph,(H,N)P-N=P(NH,)Ph,]+ (= L) C1- with cobalt(@ or copper(I1) chlorides gives 6B salts of the type L,CoCI, and L,Cu,Cl,, as well as some of their addition compounds with methanol or methylene chloride. Their e.s.r., u.v., visible, and i.r. spectra were discussed. Studies of the reactions of alkoxyphosphazenes with acid chlorides continue. Thus ethoxyphosphazenes are converted 70 into phosphinylamines on reaction with both phosphinyl and silyl chlorides:

4 Synthesis of Cyclic Phosphazenes The compounds Bu,SnCl,, (BuO),Ti, and MePhSiCl, act as catalysts for the preparation of chlorocyclophosphazenes from ammonium chloride and phosphorus penta~hloride.~~ Yields of the methylchlorocyclophosphazenes (NPClMe),,, from the reaction nMePC1,

+ nNH,Cl

-

(NPClMe),

have been improved7, to give up to 58% of cyclic products, by the preparation of finely divided ammonium chloride in situ. Similar findings have previously been reported for the series (NPCI,),. Improvements in the synthesis of the dimethylcyclophosphazenes(NPMe2)3,4have also been 67

V. V. Pen’kovskii, Yu. P. Egorov, and I. N. Zhmurova, Teor. i eksp. Khim., 1970, 6, 819 (Chem. Abs., 1971,75, 13 261j). V. V. Pen’kovskii, Yu. P. Egorov, and G. S. Shapoval, J. Gen. Chem. (U.S.S.R.), 1971, 41, 742.

70

71 72

R. M. Clipsham and M. A. Whitehead, Caiiad. J. Chem., 1972, 50, 75. V. A. Gilyarov, N. A. Tikhonina, and M. I. Kabachnik, J. Gen. Chem. (U.S.S.R.), 1971,41, 2380.

V. V. Kireev, G. S. Kolesnikov, V. P. Popilin, and S. M. Zhivukhin, Trudy Mosk. Khim.-Tekhnol. Inst., 1970, 157 (Chem. Abs., 1971, 75, 94 201q). V. N. Prons, M. P. Grinblat, and A. L. Klebanskii, J. Gen. Chem. (U.S.S.R.), 1971, 41, 475.

220 Organophosphorus Chemistry ~uggested.’~The tetramer is formed via a dihydrochloride, rather than the mixture of acyclic oligomers as previously reported, and yields of ca. 67% have been obtained by flushing the reaction mixture with nitrogen, followed by treatment with triethylamine to remove the last two molecules of hydrogen chloride : NH4Cl

+ Me,PCl,

---+

-

N4P4Me8,2HCl

EtaN

’

-

N4P4Me8

An alternative route to the tetramer (mixed with trimer) is to ammonolyse dimethyltrichlorophosphorane and pyrolyse the product in uacuo : Me,PC13

+ NH,

Me,P(NH,),Cl

A

(NPMe&

Several novel syntheses of new types of cyclophosphazenes have been described. For example, the mono- and di-phosphazenes H2N(R2N)2P=NH (R = Et or Bun) and (16) may be used to insert mono- and di-phosphazene units, respectively, into the triazine molecule (1 7).74 Thus in refluxing benzene solution ammonia was evolved leaving the cyclophosphazatriene (1 8) and the cyclodiphosphazatriene (1 9). lH and 31P NMe,

I

NMe,

I

H,N-I‘=N-I‘=NH I I NMe, NMc,

H N/‘\N II I HC, ,CH N’

H N/C, N II I (R2NN),I‘, ,CH N

n.m.r. spectroscopy showed that both (18) and (19) were quaternized by methyl iodide at the ring nitrogen atom(s) most remote from the phosphorus atom(s). This result would not have been expected had increases in basicity paralleled increased reactivity to methyl iodide, for the cyclotriphosphazatrienes (20) are considerably stronger bases than the triazine (17). The cyclization of linear diphosphazenes can be effected by reaction with trisdirnethylaminoph~sphine.~~ As in the reactions previously reported involving the same diphosphazene and phosphites, (21) was present as the P-H rather than the N-H tautomer. In a related series of reactions it 7s 74 75

F. A. Cotton and A. Shaver, Inorg. Chem., 1971, 10, 2362. A. Schmidpeter and A. Weingand, Angew. Chem. Znternat. Edn., 1971, 10, 397. A. Bermann and J. R. Van Wazer, Znorg. Chem., 1972, 11, 209.

22 1

Phosphazenes

Me,"

(H,N),C=N.C(=NH)(NR'R2)

+

XP(OI'h)2 ---+

'H (21)

H ,N -c/N+c-N R1 KZ II I N y N / \

X H X included Me and Et R1included H and M e R2included H , Me, Ph, Me-p-C,I-I,, and CI-p-C,H,

(22)

was shown76that biguanidines are cyclized by phosphites to give cyclophosphazatrienes (22). It was suggested that the P-H tautomer (22) is stabilized by incorporation of the electrons in the phosphazene rr-bond in the ring rr-system. The P-H bond readily enters into reactions with carbonyl compounds and with carbon tetrachloride, which replaces hydrogen by chlorine. These chlorine atoms may in turn be replaced by amino- or alkoxy-groups : -p
N3P3(NHR)(NMe,),CI (R = PP, Bun, or Pent")

In chloroform solution the fully aminolysed products, N3P3(NHR)(NMe2),, were obtained. It was suggested that the reduced electron supply of the NHR group, relative to that of a dimethylamino-group, is sufficient to prevent a change in mechanism that apparently makes the isolation of the monochloro-derivatives difficult. The monochloro-derivatives were converted to monoalkoxides, and dihydrochlorides of the type N3P3(NMe2)5(NHR),2HCl (R = Prn, Bun, or Pent") were also isolated. New kinetic data on the reactions of chlorocyclophosphazenes with amines have appeared. The reactions of both N3P3C16and N3P3C15.NMe2 with dimethylamine in THF were shown by conductivity measurements to follow a second-order rate law, which was first order in dimethylamine.lll The formation of both mono- and bis-dimethylamino-derivatives was visualized as proceeding by the rapid formation of a five-co-ordinated intermediate, followed by a relatively slow entropy-controlled THFcatalysed dehydrochlorination. It was suggested that the entropy of log ll0 ll1

B. Green and D. B. Sowerby, J. Inorg. Nuclear Chem., 1971, 33, 3687. N. I. Shvetsov-Shilovskii and M. R. Pitina, J . Gen. Chem. (U.S.S.R.), 1971, 41, 1028. J. M. E. Goldschmidt and E. Licht, J. Chem. SOC.(A), 1971, 2429.

228

Organophosphorirs Chemistry

activation increases on going from the mono- to the bis-derivative, mainly because of increased ground-state solvation of the leaving chlorine atom owing to the electron-releasing effects of the substituent, and the participation of the substituent (NMe, group) in the solvation of the chloride ion (necessitating the substituent and the leaving chloride ion to be on the same side of the ring to form a trans-isomer). The reactions of N,P,Cl, with methylaminef12 to give the mono- and bis-methylamino-derivative are also second order and have a lower enthalpy of activation than reactions with dimethylamine, suggesting that steric effects are important. The loss of chloride ion is again entropy controlled and similar solvation effects to those proposed above may be operative here also. These results were compared 113 with those obtained for the reactions: N,P,Cl,- NHMe

N:cye’> N,P,Cl,(NHMe)(N Me,)

( N-\ 11v F K ,P I > F in PIII compounds is anomalous order of the shielding Br a consequence of an inductive effect modified by geminal delocalization between halide substituents l5 rather than the operation of a r-bonding effect.16 The calculations were based on the assumption that the paramagnetic term is dominant and controlled by changes in the ionic character of the phosphorus bonds. PrI1 Compounds. A plot of 8p for a series of diphenylphosphines (R-PPPh,) versus a,,, of R-13CH3 follows a steady curve, which shows that the factors affecting the cheniical shifts are closely related. The point for triphenylphosphine, i.e. R = phenyl, falls on the same line as for alkyl groups. It is suggested that this rules out a d,,-p, intera~ti0n.l~ However, the conclusion ought to be that there is no significant change in any d,--pn bonding upon introducing a third phenyl group. Values of 8p for diphenylalkylphosphines (5 ; Y = H) are virtually unaffected when hydrogen is replaced by a second diphenylphosphino-group (5; Y = PPh2) provided the phosphino-groups are separated by one or more methylene groups.l* The effect of directly bonded diphenylphosphino-groups is not

+

N

l3

l4

l5 l6 17

18

H. Goetz and F. Marschner, Tetrahedron, 1971, 27, 1669, 3581. D. Purdela, J. Magn. Resonance, 1971, 5 , 23. L. Phillips and V. Wray, J.C.S. Perkin II, 1972, 214. J. W. Emsley, J. Feeney, and L. H. Sutcliffe, 'High Resolution Nuclear Magnetic Resonance Spectroscopy', Pergamon Press, Oxford, 1966, Vol. 2, p. 1055. B. E. Mann, J.C.S. Perkin II, 1972, 30. H. G . Horn and K. Sommer, Spectrochirn. Acta, 1971, 27A, 1049.

25 3

Physical Methods

normally so different from that of a phenyl group; however, the cyclic tetraphosphine (6) has Sp - 34.6 p.p.m.ls Protonation of tetramethyldiphosphine leads to considerably less deshielding than for dimethylphosphine.20 The effect of heavy atoms such as silicon, germanium, and tin on phosphorus is to produce a large shielding effect. The application of the theory of Letcher and Van Wazer did not give a satisfactory explanation for the shifts.21 The influence of substitution on 8p of the 23 The cyclic delocalization of the lone phospholes (7) has been studied.22* pair of electrons on phosphorus is interpreted within the Letcher-Van Wazer formalism.22 Mixed halides of methylphosphines, e.g. (8), have chemical shifts between those of the appropriate d i h a l i d e ~ .Likewise ~~ 6p X

UY Me-P,

I

R

/

F

Br

MeO-P,

/CF,

Me

y, Z/p-C-N

(9)

of - 118.8 p.p.m. for the mixed methoxyphosphines (9) is intermediate between the chemical shifts - 124 and - 94.8 p.p.m. of the dimethyland bis(trifluoromethyl)-methoxyphosphines.25 The phosphorus atom in PC=N compounds (10) is in the shielding region of the nitrile group. Consequently replacement of a range of P-substituents, such as methyl, phenyl, and methoxy- and dimethylamino-groups, always produces a shielding effect. The amount of shielding tends to increase with the number of nitrile groups already present.26 The effect was very small in one case: the replacement of a methyl group in trimethylphosphine (Sp rose from 62.0 to 62.6 p.p.m.).26 Cyanodimethylphosphine (10; Y = Z = Me) is probably one of the most polarized cyanophosphines (p. 274 of ref. 8c), and therefore pn-pn bonding may be having a compensating deshielding effect.

+

lS 2o 21 22

23 24 25

36

+

M. Baudler, J. Vesper, P. Junkes, and H. Sandmann, Angew. Chem., Internat. Edn., 1971, 10, 940. F. Seel and K. D. Velleman, Chem. Ber., 1971, 104, 2967. G. Engelhardt, 2. anorg. Chem., 1972, 387, 52. F. Mathey and R. Mankowski-Faveli, Org. Magn. Resonance, 1972, 4: 171. L. D. Quin and S. G. Borleske, Tetrahedron Letters, 1972, 299. H. W. Schiller and R. W. Rudolph, Inorg. Chern., 1972, 11, 187. F. Seel and K. D. Velleman, Chem. Ber., 1972, 105, 406. C. E. Jones and K. J. Coskran, Inorg. Chem., 1971, 10, 1536.

254

Organophosphorus Chemistry

PIv Compounds. Estimations of the degree of protonation of phosphine oxides vary, depending on whether conclusions are drawn from lH. n,m.r. or 31P n.m.r. spectra. A comparison of six oxides indicates that 8p reflects , depends also on the direct protonation to a greater extent than 8 ~which state of the molecule as a A comparison of the shielding effects of oxides and sulphides (1 1; X = 0 or S) showed that the deshielding

(1 1)

effect of the sulphide atom is least when the phosphorus atom bears alkyl groups and most when it bears alkoxy-groups. A change in the structure of the alkyl groups had the usual effect, i.e. a decrease in the number of hydrogens on the a-carbon atom led to deshielding.2s A claim for a linear correlation of 8p with the phosphorus 2pelectron binding energies for a series of triphenylphosphonium salts2Bis not convincing. A study of the effects of cyclization on 8p of phosphites, phosphates, and related compounds has shown that the formation of a six-membered ring causes shielding of the phosphorus nucleus for both PI1*and PIv compounds in accordance with a a-bonding effect of steric origin. A five-membered ring also causes shielding for the PI'' compounds, but the PIv compounds are deshielded in accordance with the onset of a stereoelectronic effect such as p,-& bonding.30 The cyano and ethoxycarbonyl derivatives of the 2-troponyl ylide (12; Y = CN or C0,Et) possess 8p -6.8 and Y

+ 66.9 p.p.m., respectively. X-Ray diffraction shows that the ester has much more Pv character than the nit~-ile.~l Pv Compounds. Further triphenyloxyphosphoranes (1 3) have been prepared. The range of chemical shifts are + 52 k 9 ~ . p . m . 33 ~ ~The s effect of cyclization has been studied for tetra- and penta-oxyphosphoranes. The formation of one six-membered ring, as in (14; It = l), and the 28

so 31

32

33

N. K. Skvortsov, A. V. Dogadina, G. F. Tereshchenko, N. V. Morkovin, B. I. Ionin, and A. A. Petrov, J. Gen. Chem. (U.S.S.R.), 1971, 41, 2839. I. L. Knunyants, V. I. Georgiev, I. V. Galakhov, L. I. Ragulin, and A. A. Neimysheva, Doklady Chem., 1971, 201, 992. W. E. Swartz, jun., and D. M. Hercules, Analyt. Chem., 1971, 43, 1066. G. M. Blackburn, J. S. Cohen, and I. Weatherall, Tetrahedron, 1971, 27, 2903. 1. Kawamoto, T. Hata, Y . Kishida, and C. Tamura, Tetrahedron Letters, 1972, 1611. E. E. Schweizer and W. S. Creasy, J. Org. Chem., 1971, 36, 2244. C. F. Garbers, J. S. Malherbe, and D. F. Schneider, Tetrahedron Letters, 1972, 1421.

255

Physical Methods

(15)

(16)

formation of two six-membered rings, as in (15; n = l), produces consecutive small downfield shifts of up to 4 p.p.m. whereas the formation of one five-membered ring, as in (14; n = 0), and the formation of two fivemembered rings, as in (15; n = 0), produces consecutive large downfield shifts of 17-23 p.p.m. The 8p of + 8 for (15; n = 0) was the lowest of the series.34 It is now possible to make a comparison between the shielding effect of oxygen and sulphur in Pv compounds. It has been found that values of 8p for (16) and for mixed sulphur-oxygen phosphoranes are in the region 0 f 30 p.p.m.lobS36 whereas oxyphosphoranes have shifts in the 36 * Thus the sulphur atom has a marked range +40 f 3 0 ~ . p . m . ~ ~ deshielding effect relative to oxygen, as it does in PIv compounds.1ob Isotope eflects. Deuterium substitution in PH compounds increases the shielding of the phosphorus nucleus. PII1Compounds are changed to a greater extent than PIv compounds and roughly in proportion to the number of protons replaced.37 Deuterium substitution in dialkyl phosphonates (17) shifts 8p by 0.4 p.p.m. upfield, which is commensurate with a decrease of the OPO bond angle of ca, 339

&. The 13C chemical shift ( 8 ~ )for the cis- and trans-vinylphosphines (18) and (19) shows that the P1lr atom deshields both ethylenic carbon atoms. The same trends were observed for the carbon and proton chemical shifts, which suggests that local charge density and not magnetic anisotropy 8p

aa 97 88

B. C. Chang, W. E. Conrod, D. B. Denney, D. Z . Denney, R. Edelman, R. L. Powell, and D. W. White, J. Amer. Chem. Soc., 1971,93,4004. N. J. De'Ath and D. B. Denney, J.C.S. Chem. Comm., 1972, 395. Ref. 8c, p. 257. A. A. Borisenko, N. M. Sergeyev, and Y . A. Ustynyuk, Mol. Phys., 1971, 22, 715. W. J. Stec, N. Goddard, and J. R. Van Wazer, J. Phys. Chem., 1971, 75, 3547.

256

Organophosphorus Chemistry

dominates the hi el ding.,^ The PII1atom of the tris-heteroarylphosphines (20) shifts 6~ downfield for all the carbon The shifts are larger for PIv atoms. The crowding of the methyl and R groups in 3-phospholens, e.g. (21), causes shielding of the carbon nucleus of the methyl group. In fact, relief of this crowding by conversion of the cis-isomer (21) into the corresponding trans-isomer causes a larger downfield shift than its conA 13C n.m.r. study of a wide range of diethyl version into the Y8,

,c=c, 14

(20)

,But

H

(21)

y2p,

,c=c, H

/H Ph

(22)

phosphonate compounds (22) indicates a constant additive effect of -13.2p.p.m. to aC upon replacing a proton in 13CH3Y with the (EtO),P( 0) groups.42 31P and 13C n.m.r. spectroscopy have been used to study the structure of nicotinamide adenine dinucleotide and related compounds in their reduced and oxidized forms. It was concluded that there is an electrostatic interaction between the phosphoryl oxygen in the diphosphate backbone and the quaternary nitrogen of the pyridine ring.43 6 ~ The . PH doublet of the cyclic phosphine (23) in CFCl, at -50 "C disappears when the temperature is raised to +25 "C. Water causes the signal to reappear as a singlet.44 Unlike vinylphosphines and vinylp h o ~ p h o n a t e sthe , ~ ~assignment of the stereochemistry of vinyl phosphates is not assisted by a vicinal coupling constant, and therefore it is necessary to rely on shielding effects. Assignments have been made for the phosphates (24; R = HAor Ph, Y = Hc, Ph, alkyl, C1, or Br) based on the

38

41 42 43 44

46

M. P. Simonnin, R. M. Lequan, and F. W. Wehrli, Tetrahedron Letters, 1972, 1559. H. J. Jakobsen and 0. Manscher, Actu Chem. Scand., 1971, 25, 680. J. J. Breen, S. I. Featherman, L. D. Quin, and R. C. Stocks,J.C.S. Chem. Comnz., 1972, 657. G. A. Gray, J. Amer. Chem. Soc., 1971, 93, 2132. M. Blumenstein and M. A. Raftery, Biochemistry, 1972, 11, 1643. J. B. Lambert and W. L. Oliver, Tetrahedron, 1971, 27, 4245. V. V. Kosovtsev, T. N. Timofeeva, B. I. Ionin, and V. N. Chistokletov, J . Gen. Chem. (U.S.S.R.), 1971, 41, 2671.

257

Physical Methods

known electron-donating property of the phosphate group, which shields Hc more than Hg. The addition of boron trifluoride nullifies this property. In fact it will reverse the shielding effect if an a-phenyl group is present. The shielding constants for the dialkyl phosphate group have been calculated from the chemical shift data; they are - 1.42, geminal; +0.30, cis; and +0.50, trans (to be used with -5.27 as the base value for ethylene).4s The lH n.m.r. spectra of the allylic ylides (25; R = Me R

H

/

'HA

/

d (25b)

(25a)

or H) are in accordance with a very strong deshielding effect on the a-proton, HA, when it is close to the oxygen anion. Thus HA of (25a; R = Me) appears at T 4.42 compared with T 7.1 1 for H ~ i n ( 2 5 bR ; = Me).47 Studies of Equilibria, Reactions, and Solvent Effects.-Lanthanide shift reagents have been found to be effective for phosphines 48 and phosphoryl c o r n p o ~ n d s6o, ~but ~ ~ not for thiophosphoryl c o m p o ~ n d s . 61 ~ * In ~ a comparison of various shift reagents, europium nitrate hexadeuterium oxide (26) was found to give large shifts of 8~ for phosphates and phosphonates. A contact contribution to the 8p shifts was e ~ t a b l i s h e d .When ~ ~ there are two possible sites for co-ordination, as in the aminophosphine (27), steric effects play an important role. Co-ordination occurs at nitrogen in (27; R = H) but at phosphorus in (27; R = Me).48 The n.m.r. parameters 0

H 0 II Ph-P -CH2Ph I

48

47 49

6o

H MeJ&Ms Me

Me It

I. J. Borowitz, S. Firstenberg, E. W. R. Casper, and R. K. Crouch, J . Org. Chem., 1971, 36, 3282. R. K. Howe, J. Amer. Chem. Soc., 1971, 93, 3457. R. C. Taylor and D. B. Walters, Tetrahedron Letters, 1972, 63. J. K. M. Sanders and D. H. Williams, Tetrahedron Letters, 1971, 2813. T. M. Ward, I. L. Allcox, and G . H. Wahl, Tetrahedron Letters, 1971, 4421. K. C. Yee and W. G. Bentrude, Tetrahedron Letters, 1971, 2775.

25 8 Organophosphorus Chemistry obtained using a europium shift reagent with (28) compared favourably with those obtained by the LAOCN analysis of the ordinary second-order Eu(dpm), also developed the non-equivalence of the methylene protons of (29) 5 2 and assisted in the structural studies of the cyclic phosphine oxides (30)53and (31).64 Pr(dpm), was less effective since the shifts must cross over before a good separation is ~ b t a i n e d . ~ , A linear correlation is reported 55 between Gp(phosphine) and the change in chemical shift that occurs upon co-ordination of tertiary phosphines with a number of transition metals. The half-neutralization potential, the Taft o*, and 8p of the complexes of tertiary phosphines and titanium tetrachloride have been found to be related.5s The equilibria involving the co-ordination of phosphoryl compounds and water with metal ions such as A13+are sufficiently slow to be studied by lH n.m.r. and 31Pn.m.r. spectroscopy. Discrete signals from co-ordinated and unco-ordinated ligands are Where this does not occur the equilibrium constant can be estimated from a plot involving chemical shift and concentration of Mono-, di-, and tri-alkyl phosphates have very similar B p values. Separation of the signals may be achieved by the addition of di-(Zethylhe~y1)amine.~~ The methoxide phosphonium salts (32) l1 and (33) have

been shown to be in equilibrium with their Pv oxyphosphoranes, whereas the quasiphosphonium chlorides, bromides, and iodides (34) are not.s1 Many fluoro-oxyphosphoranes, e.g. (35) and (36), are in the Pv form,62

6*

G. P. Schiemenz and H. Rast, Tetrahedron Letters, 1971, 4685. B. D. Cuddy, K. Treon, and B. J. Walker, Tetrahedron Letters, 1971, 4433. J. R. Corfield and S. Trippett, Chem. Comm., 1971, 721. B. E. Mann, C. Masters, B. L. Shaw, R. M. Slade, and R. E. Stainbank, Znorg. Nuclear Chem. Letters, 1971, 7 , 881. F. Calderazzo, S. A. Losi, and B. P. Susz, Helo. Chim. Acta, 1971, 54, 1156. J. J. Delpuech, A. Peguy, and M. R. Khaddar, J. Magn. Resonance, 1972, 6, 325; J. Crea and S. F. Lincoln, Znorg. Chem., 1972, 11, 1131. S. V. Zenin, A. P. Osipov, V. A. Polyakov, and G. B. Sergeev, Russ. J. Phys. Chem.,

58

S. Oshima, K. Asano, T. Nishishita, H. Tsuji, and H. Yokogawa, J. Japan Petrol Inst.,

62

63 64 66

66

67

1971, 45, 867.

6o

61 62

1971, 14, 499. H. Schmidbaur and H. Stuhler, Angew. Chem. Znternat. Edn., 1972, 11, 145. L. V. Nesterov, R. I. Mutalapova, S. G. Salikhov, and E. I. Loginova, Bull. Acad. Sci. U.S.S.R., 1971, 346. S. C. Peake, M. Fild, M. J. C. Hewson, and R. Schmutzler, Znorg. Chem., 1971, 10, 2723.

Physical Methods

259

but the volatility and absence of PF coupling in the tetra-alkyl- and tetraaryl-fluorophosphoranes suggest that these compounds exist as rapidly interconverting mixtures of PIv and Pv species.63

Pseudorotation.-LCAO-MO calculations on the hypothetical molecule PH5 confirm (a) that the trigonal bipyramid (t.b.p.) is the most stable configuration, (b) that the apical orbitals of the t.b.p. are more electropositive than the radial orbitals, (c) that there would be an equilibrium of t.b.p. structures, but those with the most electronegative groups in apical orientations will be more stable and predominate extensively over other t.b.p. configurations, and ( d ) that the lowest fundamental frequency of a t.b.p. corresponds to the equatorial in-plane bending motion as shown in (37), the force constants being nearly four times smaller than those of the

apical bending motion.64 EHMO calculations on the hypothetical molecules HnPFb-n indicate that r-acceptors prefer apical sites of the t.b.p. structure and n-donors prefer radial Pentafluorophosphorane has also been examined separately using LCAO-MO calculations.66 A system of nomenclature, useful for intramolecular exchange processes, has been described. The process leading to positional exchange of identical ligands is called ‘topomerization’, and the indistinguishable species involved are called ‘topomers’. Positional exchange between distinguishable chemical and/or magnetic environments is called ‘heterotopomerization’, e.g. exchange of apical and radial ligands in a t.b.p. phosphorane, and positional exchange between identical environments is called ‘homotopomerization’, e.g. interconversion of staggered conformers of CH3CF3by rotation about the carbon-carbon bond.67 The evidence for Berry pseudorotation and turnstile rotation has been reviewed.68 Further evidence for the turnstile rotation for spiro-pentaoxyphosphoranes has been presented, based on the lowering of the exchange barrier as the distortion of the t.b.p. of the phosphorane increase^.^^ A H. Schmidbaur, K.-H. Mitschke, and J. Weidlein, Angew. Chem. Internat. Edn., 1972, 11,144. O4 A. Rauk, L. C. Allen, and K. Mislow, J. Amer. Chem. SOC.,1972, 94, 3035. IsR. Hoffmann, J. M. Howell, and E. L. Muetterties, J. Amer. Chem. SOC.,1972, 94, 3047. O0 J. B. Florey and L. C. Cusachs, J. Amer. Chem. SOC.,1972, 94, 3040. G. Binsch, E. L. Eliel, and H. Kessler, Angew. Chem. Internat. Edn., 1971, 10, 570. P. Gillespie, P. Hoffman, K. Klusacek, D. Marquarding, S. Pfhol, F. Ramirez, E. A. Tsolis, and I. Ugi, Angew. Chem. Internat. Edn., 1971, 10, 687. OS F. Ramirez, S. Pfohl, E. A. Tsolis, J. F. Pilot, C. P. Smith, I. Ugi, D. Marquarding, P. Gillespie, and P. Hoffman, Phosphorus, 1971, 1, 1.

260 Organophosphorus Chemisiry comparison of intramolecular exchange for five- and six-membered monoand bi-cyclic oxyphosphoranes (14) and (15) has shown that exchange is restricted to radial-apical switching for the five-membered cyclic compounds whereas the compounds with six-membered rings are not so re~tricted.,~A study of the bicyclic oxyphosphorane (38), indicated that non-bonded interactions are also an important factor determining Small ring inhi bits exchange via ionization and thisproexchange cess is absent from the ligand-exchange processes for (38) and (39). As the

ring size increases ionization becomes important and loss of POCH coupling occurs in (40) at 100 "C and loss of coupling in (41) occurs at 25 O C . ? l The exchange process in the bicyclic dioxyphosphorane (42; Y = CF,), which occurs uia the high-energy t. b.p. structure (43 ;Y = CF,), is readily observed. This process involves placing the group Z in an apical position. The exchange

barriers for a series of compounds (43; Y = CF,) with a variety of substituents Z have given estimates of the relative apicophilicities of Z, i.e. the tendencies of the Z groups to occupy an apical position. For carbon substituents the order of apicophilicity decreased with electronegativity, which is the reverse of what might be expected. It appears that the apicophilicity may depend on a balance of electronegativity and ability to back-bond to phosphorus from a radial po~ition.'~Confirmation that the placing of a four-membered ring in a diradial position does not present an insurmountable barrier is obtained from the n.m.r. spectra of (44). The spectrum at - 100 "C corresponded to a mixture of (44) and (45) in a ratio of 2.3 to 1 . In (45) the strain of placing the small ring diradial is balanced by the placing of all the carbon atoms radial and the fluorine 70

71 72

D. W. White, N. 5. De'Ath, D. Z . Denney, and D. B. Denney, Phosphorus, 1971,1,91. D. B. Denney, D. Z . Denney, C. D. Hall, and K. L. Marsi, J. Arner. Chem. SOC.,1972, 94, 245. R. E. Duff, R. K. Oram, and S. Trippett, Chem. Comm., 1971, 1011; R. K. Oram and S. Trippett, J.C.S. Chem. Comm., 1972, 554.

Physical Methods

But Q

oI 0-P'

atoms

F F... I P-N y'l I ..Y N-P, I F F

F

I'F F

Variable-temperature spectra of the fluorophosphoranes

(46),74(47),76and (36)62are also reported. It is believed that the marked

changes which occur in the variable-temperature spectra of (36) may be related to slow rotation about the P-S bond.62 Restricted Rotation.-Several studies have been reported on P-N c o r n p o ~ n d s . ~Restricted ~-~~ rotation about the P-N bond in the dimethylaminophosphines (48) is observed with a variety of phosphorus substituents ; the barrier was largest for (48; Y = C1, Z = Ph).7s However, in the (methoxymethy1amino)phosphines (49) slow rotation was not detected

x,

Y

Me,CH-N

,P-Nl

Me

OMe

/ ii

\ !l

X

down to - 130 "C for the dihalogenophosphines (49;X = Y = halogen) or those with a P-F group, but only for the chloro- or bromodiaminophosphines (49; X = C1 or Br, Y = NMeOMe).77 The PIv 73

'*

75

76

77 78 79

N. J. De'Ath, D. Z . Denney, and D. B. Denney, J.C.S. Chem. Comm., 1972,272. M. Eisenhut and R. Schmutzler, Chem. Comm., 1971, 1452. R. K. Harris, J. R. Woplin, R. E. Dunmur, M. Murray, and R. Schmutzler, Ber. Bunsengesellschaftphys. Chem., 1972, 76, 44. M. P. Simonnin, C. Charrier, and R. Burgada, Org. Mugn. Resonance, 1972, 4, 113. A. Hung and J. W. Gilje, J.C.S. Chem. Comm., 1972, 662. W. B. Jennings, Chem. Comm., 1971, 867. M. J. C. Hewson, S. C. Peake, and R. Schmutzler, Chem. Comm., 1971, 1454. T. T. Bopp, M. D. Havlicek, and 5. W. Gilje, J. Amer. Chem. Soc., 1971, 93, 3051.

262

Organophosphorus Chemistry

compound (50) contains a chiral phosphorus group, which means that slow rotation about the P-N bond would give two diastereotopic isopropyl groups, and indeed four methyl doublets were observed in the spectrum run at -100 "C. The rotational barrier is believed to depend on steric and n-bonding effects.78 The low-temperature 19Fn.m.r. spectra of 2-methylpiperidyltetrafluorophosphorane (5 1) showed distinct apical and radial fluorine atoms, as expected, but in addition non-equivalent radial fluorine

Me

atoms were observed. This is attributed to a preference for the conformation shown in (51). On the other hand, the phenyl derivative (52) shows non-equivalent radial fluorine atoms, in accordance with a preference for the conformation shown in (52), i.e. the one with the methyl group oriented away from the bulky phenyl group.79 The variabletemperature 19Fn.m.r. spectra of the hydrazine derivative (53) are very interesting. The spectra contain a doublet at 160 "C, two doublets at -40 "C, and six doublets at - 145 "C. The spectra may be rationalized

(534

(534

(53b)

if (a) (53) possesses an sp2nitrogen within a planar PNNP framework, (b) there is slow interconversion of (53) and its trans-isomer (AG* = 13.0 kcal mol-l), and (c) there is restricted rotation about the P-N bond (AG* = 6.4 kcalmol-l). Thus at - 145 "C the spectrum shows the presence of three conformations of the cis-isomer (53a-c) and another three similar conformations for the trans-isomer.80 The equilibria involving the cis- and trans-conformations of the stable ylides (54a) and (54b) are dependent on the solvent and on the nature of the a-substituent R, the trans-conformer (54a) being favoured by polar solvents and R = Me.81 Ph3P

\

H

Ph,P

6

R

I

cc-cv

R R! ! o

0

I / \ / / /

c-c -~

/

/

H

(544

C. J. Devlin and B. J. Walker, Tetrahedron Letters, 1971, 4923.

263

Physical Methods

Inversion, Non-equivalence, and Configuration.-Analysis of SCF-LCAO calculations indicates that whereas the inversion of ammonia is dominated by electronic repulsions, the inversion of phosphine is controlled by nuclear repulsion. The phosphorus d-orbital functions markedly affected the properties of both the pyramidal and planar states.82 An n.m.r. study of the inversion of phosphole derivatives such as (55) has shown that even in complex spin systems a relatively accurate estimate of the inversion barrier may be obtained without recourse to a complete lineshape analysis. In this study, alkyl and aryl substituents did not Me /'p'

(55)

OMe

I

OMe

Ph

Ph

(57)

significantly influence the unusually low inversion barriers. The spectra of the phosphindole (56) and the dibenzophosphole (57) show a significant increase in the barrier height (ca. 8 and 10 kcal mol-l, respectively). The increase is attributed to the disruption of the phosphole 'aromaticity' which is responsible for the low inversion barrier in (55).83 Estimates of the influence of bond angles on inversion barriers indicate that the barrier for shallow pyramidal structures is dependent mainly on the ground-state geometry whereas the barrier for deep pyramidal structures is dependent on the bending force c ~ n s t a n t . ~A* limit to the application of free-energy relationships has been found for inversion barriers of less than 5-10 kcal m01-l.~~The lowering of the inversion barrier of the trimethoxysilylphosphine (58) compared to the trimethylsilyl derivative has been attributed to negative hyperconjugation, since the same effect was observed for a similar nitrogen compound (59).86 N.m.r. was used to follow the rate of conversion of (60) into the cis-isomer, which is presumed to occur via the Prrr form (61). The activation energy was estimated to be 23 kcal m01-l.~' Non-equivalence of the methylene protons of (62) was observed for a solution in carbon tetrachloride but not for a solution in deuterium oxide - a solvent which could break up the intramolecular hydrogenbonding shown in (62).88 Also, non-equivalence of the methyl groups was 82

84 86

88

J. M. Lehn and B. Munsch, Mol. Phys., 1972, 23, 91. W. Egan, R. Tang, G. Zon, and K. Mislow, J. Amer. Chem. SOC.,1971, 93, 6205. J. Stackhouse, R. D. Baechler, and K. Mislow, Tetrahedron Letters, 1971, 3437. J. Stackhouse, R. D. Baechler, and K. Mislow, Tetrahedron Letters, 1971, 3441. R. D. Baechler and K. Mislow, J.C.S. Chem. Comm., 1972, 185. E. Ye Nifant'ev and A. A. Borisenko, Tetrahedron Letters, 1972, 309. D. W. White, Phosphorus, 1971, 1, 33.

264 Pri

OMe

\

/

/

\

P-Si-OMe

Ph

OMe

-

Organophosphorus Chemistry Pr'

\+

-OMe

P=Si-OMe

/

Ph

\

OMe

(58)

0

OH

observed in the alkyl phosphinates (63; R = alkyl) but not in the corresponding phenyl phosphinate (63; R = Ph).s9 The diastereomeric salt of (- )-a-phenylethylamine with the (-)-thioic acid (64)has a 8p at lower field than that with the (+)-thioic acid.90 Spin-Spin Coupling.-The use of double-resonance techniques g1 is increasing rapidly. Heteronuclear PH decoupling has been used to determine the structures of p h o ~ p h a t i d e s ,and ~ ~ the Overhauser effect has assisted in conformational studies of dinucleotide~.~~ Some studies of spin systems containing phosphorus are discussed in the Specialist Periodical Report on n.m.r. (ref. 1, p. 205). Jpp and JPM. The PP coupling constants of a stereoisomeric mixture of 1,2-dimethyl-l,2-diphenyldiphosphine(65) and (66) (- 215 and - 234 Hz, respectively) were determined by double irradiation of the weak 31Ptransition. The difference is attributed to a difference in internal rotation about the P-P bond.g4 The couplings between the PIr1and PIv atoms in the corresponding mono- and di-sulphides were remarkably as W. G . Bentrude, W. D. Johnson, W. A. Khan, and E. R. Witt, J. Org. Chem., 1972, s1

sa

s3 s4

37, 631. M. Mikolajczyk and J. Omelanczuk, Tetrahedron Letters, 1972, 1539. W. von Philipsborn, Angew. Chem. Internat. Edn., 1971, 10, 472. M. Kates and A. J. Hancock, Biochem. Biophys. Acta, 1971, 248, 254. M. Kainosho and Y. Kyogoku, Biochemistry, 1972, 11, 741. H. C. E. McFarlane and W. McFarlane, Chem. Comm., 1971, 1589.

265

Physical Methods O

..

Me

Ph

.Me

(65)

Ph

(66)

Y

Y

P11

/ \

Ph

OEt

(67)

similar (-230 and -240 Hz respecti~ely).~~ In contrast, a change from 198 to 78 Hz was observed on co-ordinating nickel carbonyl with the PII1 atom in (67).95 Hydrogen-bonding had a considerable effect on lJpp of the mixed oxide sulphides (68) and (69). Coupling constants of 591 and

401 Hz in deuteriochloroform were raised to 618.5 and 513 Hz in trifluoroacetic acid. CNDO-SCF calculations indicate that hydrogenbonding to the phosphoryl oxygen of (68) (which is expected to predominate) has a small effect on coupling whereas hydrogen-bonding to the sulphur (which presumably occurs to a lesser degree) has a much larger effect. For (69) the maximum calculated effect occurred when both oxygen and sulphur were hydrogen-bonded.ss The magnitude of JpNPvaries from 0 to nearly 500Hz. A larger temperature-dependence of JPNPfor the tetrafluoro-derivatives (70) of ca. 435 Hz at + 60 "C and ca. 470 Hz at - 60 "C suggests that steric 0

FZP,

'N I

R

(70)

PF2

..

II (MeO),P,N,P(OMe), I Me (71)

MeS

0

\

4

/

\

F-P=N-P-F F

F

(72)

interactions are i m p ~ r t a n t .The ~ ~ PNP coupling tends to decrease as P I I I atoms are converted into PIv, e.g. it falls to 54 Hz for (71) and 8.3 Hz for the corresponding mixed oxide sulphide.s8 However, it is high again, J p ~ p= 107 Hz, in (72) and similar compounds with a PN multiple bond.Qg The magnitudes of J p B of borane adducts with PIr1compounds have been 95

g6 @'

O8

@O

G. Bergerhoff, 0. Hammes, J. Falke, B. Tchanyi, J. Weber, and W. Weisheit, Tetrahedron, 1971, 27, 3593. W.J. Stec, J. R. Van Wazer, and N. Goddard, J.C.S. Perkin 11, 1972, 463. E. Niecke and J. F. Nixon, Z . Nuturforsch., 1972, 27b,467. I. A. Nuretdinov, V. V. Negrebetskii, A. 2. Yankelevich, A. V. Kessenikh, L. K. Nikonorova, and E. I. Loginova, Bull. Acad. Sci. U.S.S.R.,1971, 2460; I. A. Nuretdinov, V. V. Negrebetskii, A. Z. Yankelevich, A. V. Kessinikh, E. I. Loginova, L. K. Nikonorova, and N. P. Grechkin, Dokludy Chem., 1971,196,161 ; R. Keat, Phosphorus, 1972, 1, 253. H. W. Roeski and L. F. Grimm, Chem. Comm., 1971, 998.

266

Organophosphorus Chemistry

measured lol and examined as a possible means of measuring dative bond strengths. The coupling was largest (97 Hz) for (73; X = OMe) and smallest (39 Hz) for (73; X = F).lo0 Values of lJpse have been determined for several selenides (74) and fall in the range 840-1100 Hz,lo2and values ~JPc,-J and lJpsn are reported.lo3*lo* loot

X

/

JPc. Values of lJpc and 2 J p ~of trialkylphosphines fall in the range 11-34 Hz, whilst 3 J p ~is 11-13 Hz. The coupling constant lJpc was negative for trimethylphosphine (- 13.6 Hz). This was rationalized in terms of reduced s-character of the phosphorus bonding orbitals as estimated from bond angles. This approach leads to a change in sign from positive to negative when the s-character falls below 0.15. The large magnitude of lJpc (33.9 Hz) for tri-t-butylphosphine may then be attributed to the reverse of this effect. In fact, if the coupling is positive, the calculated bond angle is identical with the experimental However, on examining the coupling constants for a wide range of phosphines, it is disconcerting to find an absence of coupling constants below 12.5 Hz, i.e. there is a rather large gap (25 Hz) in the middle of the range if the couplingconstant passes through zero. A zero l J p ~ ( ~ lis k )reported for the diphosphine (75) and also for the trans-isomer of (76), but a coupling constant of 7.9 Hz is recorded for the cis-isomer of (76) and 25 Hz for Ph2PCH,CH2PPh2

Ph2PCH=CHPPh3

(75)

(76)

6,Me d" (78a)

\*

Me

(7W

R. W. Rudolph and C. W. Schultz, J. Amer. Chem. SOC.,1971, 93, 6821. C. Jouany, G . Jugie, and J. P. Laurent, Bull. SOC.chim. France, 1972, 880. Io2 I. A. Nuretdinov and E. I. Loginova, Bull. Acad. Sci. U.S.S.R., 1971, 2252. lo3 B. E. Mann, Inorg. Nuclear Chem. Letters, 1971, 7 , 595. l o 4 P. G. Harrison, S. E. Ulrich, and J. J. Zuckerman, Znorg. Nuclear Chem. Letters, 1971, 7, 865. lo6 See ref. 17.

loo

lol

267 Physical Methods (77).loS Crowding appears to cause the larger couplings. Thus lJpc is 21.5 Hz for (78a) and 17.5 Hz for its isomer (78b).41 The effect is more dramatic for 2 J p but ~ in reverse. Thus 2 J p to ~ the crowded methyl groups (Me*) in (78a) 41 and (79) lo' is very small ( 0 - 5 Hz), and the coupling to MeB in (78b) and (79) is much larger (27-34 Hz). The corresponding one- and two-bond coupling constants to the vinyl carbon atoms in (18) and (19) also vary considerably (1-33 Hz). As more data become available it will be interesting to see whether the very low magnitude (1.4 Hz) of the cis three-bond PC coupling in (18) is characteristic or The signs of the coupling constants to aromatic sp2 carbon atoms have been determined. Values of lJPc for the tri-2- and 3-thienylphosphines are negative (- 22.7 and - 14.0 respectively) whereas the two-, three-, and four-bond couplings are all positive.40* log Thus the parallel behaviour of the signs of JPc and JFCin aliphatic phosphines and fluorides100also holds for the aromatic series. Likewise, lJpc in the phosphadiazole (80) is also negative. The large negative magnitude of this constant (- 36 Hz) indicates a low s-character for the phosphorus P-C orbita1.ll0

The steric effects of Jpc in PIv compounds are less than in P1Ircompounds but still discernible, as shown by a study of derivatives of the phosphetan (81).ll1 The magnitude of lJpc, which is generally in the region of +30 to + 60 Hz for alkyl phosphonium salts, increases as electronegative substituents are introduced on phosphorus, e.g. lJpc is 88 Hz for (82) 112

+

0 II AcO.CH,.P(CH,Br),

*

+

(82)

+

MeP(OMe)3 BF4(83)

and 132.4 Hz for (83).l13 The effect of carbon substituents has been studied using the phosphonates (22). The values of lJpc were in the range 126-139 Hz and correlated linearly with the calculated P-C s-bond order. H. Marsmann and H. G. Horn, 2. Naturforsch., 1972, 27b, 137. G. A. Gray and S. E. Cremer, J.C.S. Chem. Comm., 1972, 367. lo* H. J. Jakobsen, T. Bundgaard, and R. S. Hansen, Mol. Phys., 1972, 23, 197. log F. J. Weigert and J. D. Roberts, J. Amer. Chem. SOC.,1971, 93, 2361. 110 V. V. Negrebetskii, A. V. Kessenikh, A. F. Vasil'ev, N. P. Ignatova, N. I. ShvetsovShilovkii, and N. N. Mel'nikov, J. Struct. Chem., 1971, 12, 731. G. A. Gray and S. E. Cremer, Tetrahedron Letters, 1971, 3061. J. C. Clardy, G. K. McEwen, J. A. Mosbo, and J. G . Verkade, J. Amer. Chem. SOC.,

loo lo'

1971, 93, 6937.

lla

R. D. Bertrand, F. B. Ogilvie, and J. G. Verkade, J. Amer. Chem. SOC.,1970,92, 1908.

268

Organophosphorus Chemistry

A distinction between the cis and trans geometries of methylphosphinetransition-metal complexes has been possible by considering the triplet nature of the methyl proton signal arising from the virtual coupling in the tmns-isomers, (ref. 8a, p. 293). A similar effect is observed in the 13C n.m.r. spectra, and the effect is not limited to methy1pho~phines.l~~ lJpH. The PrrrH coupling constant tends to increase with P-C conjugation, e.g. 190 i- 10 Hz for dialkylphosphines, 210 rt 10 Hz for phenylphosphines, and ca. 240 Hz for diphenylphosphine. The introduction of trimethyl-silicon, -germanium, and -tin substituents in phenylphosphine (84) lowers l J pto ~ 201, 195, and 187 Hz, in accordance with a

PhPHM Me, (84)

i\

Me H

change in electronegativity The cyclic phosphonium salt (85) possesses l J p ~498 Hz and 2 J p 16.2 ~ ~ Hz. The couplings are opposite in sign, in accordance with positive and negative signs re~pectively.~~ The replacement of a methyl group of trimethylphosphine by SMe or an electronegative group raises 2 J p from ~ ~ 2.7 to 5-9 HZ,,~? 116 and a second such substituent raises it 24 to 8-20 Hz; the largest magnitude is shown by dibromomethylphosphine. Considerable variation of J ~ C H occurs in the vinylphosphines, e.g. 0.1 Hz for (18; Y = NMe,) and +21.4 HZ for (19; Y = NMe2).l17 This reflects the marked dependence of the coupling constant of PI1' compounds on the orientation of the lone pair of electrons, a factor which is absent for PIv compounds.ll* The geminal coupling constant for pure methylenetriphenylphosphorane (86)

JpC,H.

Y

(87; Y = CFJ

in deuteriobenzene 119 is 7.5 Hz, somewhat lower than J ~ C for H trimethylphosphonium ylides or vinylphosphonium salts (ref. 8c, p. 265, and ref. 8a, p. 297). Geminal PCH coupling constants for the oxyphosphoranes (87) were in the range 11-30 Hz.120 114 115 116

11'

118

119 120

B. E. Mann, B. L. Shaw, and R. E. Stainbank, J.C.S. Chem. Comm., 1972, 151. P. G. Harrison, S . E. Ulrich, and J. J. Zuckerman, Inorg. Chem., 1972, 11, 25. F. Seel, W.Gombler, and K. D. Velleman, Annalen, 1972, 756, 181. R. M. Lequan and M. P. Simonnin, Tetrahedron Letters, 1972, 145.

F. A. Carey and A. S . Court, J. Org. Chem., 1972, 37, 939. H. Schmidbaur, H. Stahler, and W. Vornberger, Chem. Ber., 1972, 105, 1084. Mazhar-ul-Haque, C. N.Caughlan, F. Ramirez, J. F. Pilot, and C. P. Smith, J. Amer. Chem. SOC.,1971, 93, 5229.

269

Physical Methods

The vicinal PCCH coupling constants involving the carbon-carbon bond of the cyclopropyl ring in the compounds (88) fall into two ranges, namely 1-4 and 15-17 Hz. The larger couplings are assigned to the cis-compounds, owing to the dihedral angle of O", and the smaller couplings are assigned to the trans-compounds (120" dihedral angle).121 Values of JPCCHare small when a carbonyl group is part of the link (ref. 8b, p. 253) and almost zero when an imino-group interposes, e.g. as in the pyrazolinyl derivatives (89; R = Y = Ph)122 and (89; R = Et, Y = O-).123 The

(88)

(89)

smaller cis PC:CH coupling constants compared to the trans-coupling is well recognized; it is found that an a-halogen substituent reduces the The well-recognized large vicinal coupling cis-coupling further to 7 constants ( 2 8 4 0 Hz) for the PIv compounds apply equally to the dihydroand tetrahydro-derivatives (90) and (91).125 In a study of the methyl derivatives of trithienylphosphines (92) it was found that an ortho-methyl Ph, ,H

Ph

group reduces 3JpH by half, and that 4JpH is more than doubled. The effect was not observed in the sulphide derivatives and therefore appears to be connected with the orientation of the lone pair of electrons on phosphorus.126 A number of derivatives of the oxyphosphoranes derived from (93) have now been prepared. Most of the compounds possessed a value of JPCCH in the range 34-38 Hz or 8-11 Hz. The protons with the larger couplings are attributed to HA, which is anti to the phosphorus atom.32 lZ1

lZs 124

lZ6

H. Gunther, B. D. Tunggal, M. Regitz, H. Scherer, and T. Keller, Angew. Chern. Znternut. Edn., 1971, 10, 563; H. J. Callot and C. Benezra, Cunad. J. Chem., 1972, 50, 1078. E. E. Schweizer and C. S. Kim, J. Org. Chem., 1971, 36, 4033. A. N. Pudovik, R. D. Gareev, A. V. Aganov, 0. E. Raevskaya, and L. A. Stabrovskaya, J . Gen. Chem. (U.S.S.R.), 1971, 41, 1013. V. V. Moskva, T. V. Zykova, V. M. Ismailov, and A. I. Razumov, J . Gen. Chem. (U.S.S.R.), 1971, 41, 89. A. Hettche and K. Dimroth, Tetrahedron Letters, 1972, 829; G. Markl, A. Merz, and H. Rausch, ibid., 1971, 2989; A. Hettche and K. Dimroth, ibid., 1972, 1045. H. J. Jakobsen and M. Begtrup, J . Mol. Spectroscopy, 1971, 40, 276.

0rganophospho rus Chemistry

270

Ph

Cross-conjugation often greatly diminishes spin-spin coupling,122* 123 but this is not without exception because the oxyphosphorane (94) has J ~ C C H= ~ 37 Hz.12’ A long-range coupling has been reported for the phosphine oxide (95); 5JpH is 1.2 Hz, which is not as large as the coupling through an olefinic ~ 5.4 HZ for (96).128 bond, e.g. 6 J p = Me,

I1

,PPh?

,Me C II

H,c\

0 II ,P(OW, CH2

and JPXC,H. The dependence of J p o C H on stereochemistry continues to be used extensively for conformational studies, especially with the cyclic phosphonates (97),12’9 130 and has also been extended to the study of amide derivatives (98).131 Some values of J p s c ~are similar to

JpXH

Me

lZ7 lZ8 lZ9

D. D. Swank, C. N. Caughlan, F. Ramirez, and J. F. Pilot, J . Amer. Chem. SOC.,1971, 93, 5236. T. E. Snider and K. D. Berlin, Phosphorus, 1971, 1, 59. J. P. Majoral, R. Pujol, 5. Navech, and F. Mathis, Tetrahedron Letters, 1971, 3755. W. G . Bentrude and K. C. Yee, J.C.S. Chem. Comm., 1972, 169; J. P. Majoral, R. Pujol, and J. Navech, Compt. rend., 1971, 272, C, 1913. R. Kraemer and J. Navech, Bull. SOC.chim. France, 1971, 3580.

Physical Methods

27 1

those of JPOC~.132 A study of the effect of 0-protonation and -alkylation increases slightly of the oxides (99; Y = OMe or NMe,) showed that JPOCH remains essentially ~ 0 n s t a n t . lThe ~ ~ PNCH coupling constants whilst JPNCH of a wide range of oxides (100) 13* were scattered within the range 8-17 Hz, whereas J ~ N C Hfor the PIr1cyclic compounds (101) fall into two groups, 2.2-3.5 and 5.9-10.9 Hz, depending on the s t e r e ~ c h e m i s t r y .A ~ ~value ~ of the PCNH coupling of 12 Hz is reported for and PNH couplings of 17.7 and 21 Hz for the Pv compounds (103) 13' and (104).138

Relaxation Times, Paramagnetic Effects, and N.Q.R. Studies.-A study of the relaxation times of phosphoryl compounds at two magnetic fields, and of the dependence of spin rotation and dipolar interactions upon viscosity and temperature, led to the approximate separation of dipole-dipole, anisotropy, and spin-rotation interactions, and indicated that second-order paramagnetic shielding was dominant.139 The 31Prelaxation times TI and Tz were determined for several lipid-water phases. Comparisons of changes of T2which occur at the transition temperature for dipalmitoyllecithin indicated that the relaxation times reflect the mobility of the lipid head-group.140 PH Decoupling of trialkyl phosphites and phosphates by paramagnetic reagents only occurs when there is direct co-ordination. In most cases 8p is shifted downfield, but 8~ showed no definite trend. The most effective reagent was cobalt chloride in acetonitrile s01ution.l~~ The H-1 proton of dinucleotide mono- and di-phosphates was identified by the broadening of its resonance that occurred upon the addition of Mn2+ ions.142 A study of the effects of paramagnetic ions on adenosine 5'-monophosphate has also been ~ e p 0 r t e d . l ~ ~ A comparison of the calculated and observed n.q.r. resonances has been used to study the stereochemistry and bonding of chloro-compounds such as (105), (106), and (107). The 35Cl n.q.r. resonances of the thiophosphoryl chlorides were higher than those of the phosphoryl chlorides. This was attributed to reduced p,-d, back-bonding from the sulphur lsa lSs

13' la6 lS6

lS7 lS8 lS9

140

141 143

A. Zwierzak and R. Gramze, Z . Naturforsch., 1971, 26b, 386; B. Krawiecka and J. Michalski, Bull. Acad.polon. Sci., Sbr. Sci. chim., 1971, 19, 377. K. E. DeBruin, A. G. Padilla, and D. M. Johnson, Tetrahedron Letters, 1971, 4279. I. Irvine and R. Keat, J.C.S. Dalton, 1972, 17. J. P. Albrand, A. Cogne, D. Gagnaire, and J. B. Robert, Tetrahedron, 1972, 28, 819. T. Nishiwaki and T. Saito, J. Chem. SOC.(0,1971, 3021. A. H. Cowley and J. R. Schweiger, J.C.S. Chem. Comm., 1972, 560. A. Munoz, M. Koenig, B. Garrigues, and R. Wolf, Compt. rend., 1972, 274, C, 1413. S. W. Dale and M. E. Hobbs, J. Phys. Chem., 1971, 75, 3537. R. W. Barker, J. D. Bell, G. K. Radda, and R. E. Richards, Biochirn. Biophys. Acta, 1972, 260, 161. R. Engel and L. Gelbaum, J.C.S. Perkin I , 1972, 1233. K. N. Fang, N. S. Kondo, P. S. Miller, and P. 0. P. Ts'O, J. Amer. Chem. SUC.,1971, 93, 6647; A. W. Missen, D. F. S. Natusch, and L. J. Porter, Austral. J . Chem., 1972, 25, 129.

272

Organophosphorus Chemistry

atom.143 A similar conclusion was made after a study of the aminophosphine chalcogenides (108; X = 0, S , or Se). It was also found that the occupation number of the nitrogen atom is independent of the phosphorus co-ordination number.144 The 35Cl n.q.r. spectra of alkyldichlorophosphines and their sulphides (109) have been ~ e p 0 r t e d . l N.q.r. ~~ has

also been used to investigate the existence of five-co-ordinate chlorophosphoranes and the orientation of the chlorine atoms in the t.b.p. The phenyl derivatives (1 10) were found to be quasiphosphonium 2 Electron Spin Resonance Spectroscopy y-Irradiation of phosphonium salts and phosphines in sulphuric acid has been studied. The e.s.r. spectra from phosphines corresponded to the radical ( l l l ) , and a comparison with PH3 indicated that the alkyl groups increase the pyramidal character (probably owing to hyperc~njugation).~~~

Although there is chemical evidence for non-equivalence of alkoxy-groups in radicals of the type (112),l4' the e.s.r. resonance of (113) showed no resolvable fine-structure.14* The spectrum of (1 14) indicates that the radical is non-planar, with a phosphorus 3 p character of 0.6 (cf. 0.41 2p character for the planar radical PhzfiO).149The unpaired electron is confined mainly to the sulphur atoms in the thiophosphate radical (115), the spin density in the phosphorus 3s orbital (ca. 0.7%) being similar to that 143 144

146 148 147 148

149

R. M. Hart and M. A. Whitehead, J. Chern. SOC.(A), 1971, 1738. D. Y. Osokin, I. A. Safin, and I. A. Nuretdinov, Doklady Chem., 1971, 201, 981. J. K. B. Bishop, W. R. Cullen, and M. C. L. Gerry, Canad. J . Chem., 1971,49, 3910. A. Begum, A. R. Lyons, and M. C. R. Symons, J. Chem. SOC.(A), 1971, 2290, 2388. W. G. Bentrude and T. B. Min, J. Amer. Chem. SOC.,1972, 94, 1025. A. G. Davies, D. D. Griller, and B. P. Roberts, Angew. Chem. Internat. Edn., 1971, 10, 738. M. Geoffroy and E. A. C. Lucken, Mol. Phys., 1971, 22, 257.

273

Physical Methods

observed for phosphate r a d i ~ a 1 s . lThe ~ ~ reaction of phospholes (1 16) with alkali metals at low temperature gave e.s.r. spectra corresponding to a mono-anion radical. The coupling to the phosphorus nucleus was very large and the spectra support the postulate that there is considerable aromaticity in the phosphole ring.151 The cation-free anion radicals produced by electrochemical reduction of triphenylphosphine, its oxide, and their deuterium analogues had similar e.s.r. spectra, which were independent of solvent. The spectra of the [ 2 H l o ] - ~ ~ m p ~i.e. ~ n(1d17) ~,

and its oxide, did not correspond to superimposed spectra of the [2H15]and [2H,]-compounds in a 2 : 1 ratio, and therefore the electron is delocalized over all three aryl rings in the phosphine and its The e.s.r. spectra of radicals of the type (118) and its PIv derivatives indicated a large, almost isotropic, interaction with the phosphorus atom, which indicates that there is a significant interaction with the valence s-orbital of phosphorus. The interaction is believed to be hyperconjugative 0

and at a maximum for the conformation shown in (118),153 and at a minimum when the p-orbital is at right angles to the C-P bond. The corresponding phosphonite radicals have been examined by e.s.r. spectros c ~ p y . ~In~the * p-dichloro-compounds (1 19) the magnitude of the coupling to H* and the phosphorus nucleus varied in opposite directions, which supports the angular dependence for the i n t e r a ~ t i 0 n . l ~Steric ~ effects 150

161 152

15s

M. Sato, M. Yanagita, Y. Fujita, and T. Kwan, Bull. Chem. SOC.Japan, 1971,44,1423. D. Kilcast and C. Thomson, Tetrahedron, 1971, 27, 5705. A. V. Il'yasov, Y. A. Levin, I. D. Morozova, A. A. Vafina, I. P. Gozman, and E. I. Zoroatskaya, Doklady Chem., 1971, 201, 898. A. R. Lyons and M. C. R. Symons, Chem. Comm., 1971, 1068; J.C.S. Faraday ZI, 1972, 68, 622.

154 156

A. G. Davies, D. Griller, and B. P. Roberts, J. Amer. Chem. SOC.,1972, 94, 1782. W. Damerau, G. Lassmann, and K. Lohs, J. Magn. Resonance, 1971,5,408; 2. Chem., 1971, 11, 182.

274 Organophosphorus Chemistry altering spin transmission, uia hyperconjugation, have also been proposed for the nitroaryl radicals (120; X = 0 or S).156 Spectra are also reported for phosphazenes 15' and for imino-oxyl 15* and peroxyl radi~a1s.l~~ E.s.r. has been used to study paramagnetic proteins which are important in the respiratory chain.160 0

R\

R' 1 20)

3 Vibrational Spectroscopy Band Assignment and Structural Elucidation.-The change in frequency of v(PH) from 2410 to 1753 cm-l upon deuteriation confirmed the presence of a PH bond in (121).lS1 In contrast to v(0H) of acidic and alcoholic OH groups, v(PH) of the phosphonium salt (121) is at higher wavenumber than v(PH) for primary and secondary phosphines (ca. 2300 cm-l), and it is still

(121)

( 122)

higher (ca. 2460 cm-l) for the Pv oxyphosphoranes (122).la2 The fundamental P-C frequencies have been identified in the spectra of difluoroand dichloro-t-butylphosphines and their ~ha1cogenides.l~~ Bands in the OH stretching region, 3200-3300 cm-l, in the spectra of the alcohol (123 ;R = Me or CH,NO,) are assigned to polymeric associates, whereas the bands which appear at 3550-3580 cm-l in dilute chloroform solutions are attributed to monomers with a free hydroxy-group and/or an intramolecular hydrogen-bonded structure. In dilute carbon tetrachloride lS6 lS7

158 159

160 181

le2 163

W. M. Gulick, J . Amer. Chem. SOC.,1972, 94, 29. H. R. Allcock and W. J. Birdsall, Znorg. Chem., 1971, 10, 2495. A. Nakajima, H. Ohya-Nishiguchi, and Y. Deguchi, Bull. Chem. Soc. Japan, 1971,44,

2 120. G. B. Watts and K. U. Ingold, J. Amer. Chem. SOC.,1972, 94, 2528. E. C. Slater, I. Y . Lee, B. F. Van Gelder, S. P. J. Albracht, and J. A. Berden, Biochim. Biophys. Acta, 1972, 256, 14; S. P. J. Albracht and E. C. Slater, ibid., 1971, 245, 508.

R. Churchman, D. G . Holah, A. N . Hughes, and B. C. Hui, J . Heterocyclic Chem., 1971, 8, 877.

A. Schmidpeter and J. Luber, Angew. Chem. Znternat. Edn., 1972, 11, 306. R. R. Holmes and M. Fild, Spectrochim. Acta, 1971, 27A, 1525, 1537.

Physical Methods

275

a band also appears at 3400-3420cm-l,

which may be due to dimeric associates, whereas in THF and acetonitrile bands in the 3450-3480 cm-l region may be due to solute-solvent Similar studies have been reported on the carboxylic acid derivatives (123; R = C02H).166 The CH group in (124) is acidic and gives bands at 2940 and 2875 cm-l. 0

The low frequency is attributed to hydrogen-bonding between the CH group and the phosphoryl oxygen. These bands were weaker in the spectrum of (124) in dichloromethane, and shifted to 3000 cm-l by adding chloroform.les A dilute solution of trimethylphosphine oxide in methanol gives a strong band at 1197 cm-l; bands appear at 1180, then at 1153 and 1120 cm-l as the solution is concentrated.ls7 Donor properties of alkoxy and dimethylamino PI1’ compounds towards hydroxylic solvents have been compared.ls8 A high-wavenumber band at 3615 cm-l in the spectrum of (125) was shown to be due to v(0H) when deuteriation caused P h,P =N Ph (125)

( 126)

a shift to 2665 cm-l.lss The effects of N-protonation, -alkylation, and hydrogen-bonding on the spectra of the phosphinimine (126) have been reported. In all cases the broad and intense band at 1350 cm-l, which these workers attribute to v(PN), is shifted dramatically to low w a v e n ~ m b e r . ~ ~ ~ Some unusual frequencies have been reported for v(C=C) in the spectra of the heterocycles (127) and (128). In (127) it appears 171 at 1565 cm-1 whereas in (128) it occurs as an intense absorption at 1730 k 5 cm-1.172 E. I. Matrosov and M. I. Kabachnik, Spectrochim. Acta, 1972, 28A, 313; E. I. Matrosov, G. M. Baranov, V. V. Perekalin, M. I. Kabachnik, and T. A. Mastryukova, Bull. Acad. Sci. U.S.S.R., 1971, 2439. lt16 A. N. Pudovik, I. V. Gur’yanova, M. G. Zimin, 0. E. Raevskaya, M. A. Shakirova, A. Kh. Mift’akhova, and V. F. Toropova, J. Gen. Chem. (U.S.S.R.), 1971, 41, 1232. 16E E. I. Matrosov, T. Ya. Medved, and M. I. Kabachnik, Bull. Acad. Sci. U.S.S.R., 1971,

16*

1008. E. V. Ryl’tsev, I. E. Boldeskul, A. M. Pinchuk, L. N. Markovskii, and U. P. Egorov, Zhur. priklad. Spectroskopii, 1971, 15, 889. lE8 L. M. Epshtein, Z. S. Novikova, L. D. Ashkinadze, L. M. Rubasheva, and L. A. Kazitsyna, Bull. Acad. Sci. U.S.S.R., 1971, 884. lB0A. A. Pinkerton and R. G. Cavell, J. Amer. Chem. SOC.,1972, 94, 1870. 170 E. I. Matrosov, V. A. Gilyarov, V. Yu. Kovtun, and M. I. Kabachnik, Bull. Acad. Sci. U.S.S.R., 1971, 1076. 171 B. A. Arbuzov, A. P. Rakov, and A. 0. Vizel, Bull. Acad. Sci. U.S.S.R., 1971, 1885. 17a W. G. Bentrude, W. D. Johnson, and W. A. Khan, J. Amer. Chem. SOC.,1972, 94, 3058.

16?

276

Organophosphorus Chemistry

( 1 27)

Stereochemical Aspects.-The methyl torsional frequencies have been obtained for a series of fluoro- and chloro-methylphosphines and their chalcogenidesfrom the spectra in the solid and gas The spectrum of (129) is the same in all phases, and it is concluded that the molecules take up a gauche conformation, with the PNCz section ~ 1 a n a r . lThe ~~ far-i.r. and Raman spectra of trimethylphosphine indicate a CPC bond Me, N -P C I (1 29)

angle of 99.1" and P-C bond length of 1.841 A.175 The electronic effect of stannic chloride on the rotational isomers of the phosphinate (130) has been r e ~ 0 r t e d . l ~ A~gauche conformation (131) has been estimated from the i.r. spectra of some dia1kylpho~phinates.l~~ Thermodynamic parameters have been estimated for the conformational equilibria of the R

P S

cyclic phosphonates (97) from i.r. and n.m.r. data.129 The position of the conformational equilibrium for the cyclic thiophosphinates (1 32) was estimated from the absolute integral intensities of the i.r. bands associated with the different conformers. The more polar conformer was identified by its predominance in the more polar media.178Variable-temperature i.r. spectra (+ 30 to - 130 "C) of the thiophosphinates (133), as expected, indicate a very small energy difference between the rotational 17s 17*

176 176 177 178

17s

J. R. Durig and J. M. Casper, J. Phys. Chem., 1971, 75, 1956. J. R. Durig and J. M. Casper, J. Phys. Chem., 1971, 75, 3837. J. R. Durig, S. M. Craven, and J. Bragin, J. Chem. Phys., 1970, 53, 38.

E. G. Yarkova, A. A. Musina, V. P. Plekhov, A. A. Muratova, and A. N. Pudovik, J . Gen. Chem. (U.S.S.R.), 1971, 41, 2608. 0. A. Raevskii, F. G. Khalitov, and M. A. Pudovik, Bull. Acad. Sci. U.S.S.R., 1971, 2468. E. A. Ishmaeva, 0. A. Raevskii, R. A. Cherkasov, F. G. Khalitov, V. V. Ovchinnikov, and A. N. Pudovik, Doklady Chem., 1971, 197, 302. R. R. Shagidullin and I. P. Lipatova, Bull. Acad. Sci. U.S.S.R., 1971, 940.

277

Physical Methods Mc~C--P, I F F ( 1 33)

The gas- and liquid-phase vibrational spectra and dipole moment of t-butyltetrafluorophosphorane are in accordance with the t.b.p. structure (1 34), with only slight distortion towards a square-pyramidal geometry.lgO Studies of Bonding.-Further work is reported on the force constants of the PC1, PO, and PS bonds.lsl Calculations on some compounds containing the phosphoryl bond indicate that the polarity of the PO bond is reduced by inductive donation by the remaining substituents.ls2 A number of reports of calculations on the bonding in various phosphorus halides have also been pub1i~hed.l~~" The intensities of the NH fundamental band in spirophosphoranes such as (1 35) indicate sp2 character for the nitrogen atoms owing to P-N conjugation.1s3b H

The band positions and intensities of v,,(N02) and v,(NO,) in the i.r. spectra of diphenyl p-nitrophenylphosphine (136; Y = PPh2) were compared with those of other p-substituted nitrobenzenes (136) with the aim of comparing the mesomeric effects of the substituents. The comparison was found to be less useful than anticipated.18* Correlations of ,(PO) and

v ( C 0 ) with Hammett o-constants are reported for the silyl phosphonates (137).lB5 R. R. Holmes and M. Fild, Znorg. Chem., 1971, 10, 1109. N. Fritzowsky, A. Lentz, and J. Goubeau, 2. anorg. Chem., 1971,386, 67, 203. R. M. Archibald and P. G. Perkins, Rev. Roumaine Biochim., 1971, 16, 1137. 18s (a) A. Serafini, J. F. Labarre, A. Veillard, and G. Vinot, Chem. Comm., 1971, 996; I. H. Hillier and V. R. Saunders, J.C.S. Dalton, 1972, 21; M. F. Guest, I. H. Hillier, and V. R. Saunders, J.C.S. Furaduy 11, 1972,68, 114. (b) R. Mathis and R. Burgada, Compt. rend., 1972, 274, C, 1156. lB4 G. P. Schiemenz, Phosphorus, 1971, 1, 133. lB5 V. M. D'yakov, G. S. Gusakova, E. I. Pokrovskii, and T. L. D'yakova, J . Gen. Chem. (U.S.S.R.), 1971, 41, 1040. lB0

lS1

lB2

10

278

Organophosphorus Chemistry 4 Microwave Spectroscopy

The radiofrequency spectrum of phosphine has been measured in a molecular beam electric resonance spectrometer. The suspected inversion doubling was not observed; its dipole moment (p) was 0.574 D.lg6 The calculated rotational barrier between the staggered and eclipsed conformers of methylphosphine is 1.83 and 1.71 kcalmol-l, in agreement with the experimental value of 1.96 from microwave measurements. An orbitalby-orbital analysis of the changes which occur upon rotation suggests a hydrogen-bond contribution when the phosphorus lone pair of electrons and a CH bond are appropriately orientated.lE7 The existence of a 1-2" tilt of a methyl group towards the phosphorus lone pair of electrons in methylphosphines (1 38) was a conclusion drawn from a microwave study

of the deuteriated and non-deuteriated phosphines. The CPC bond angle in trimethylphosphine was estimated to be 98.9O.lSs Co-ordination of methylphosphine and trimethylphosphine with borane decreases the P- C bond lengths, especially for methylphosphine. In fact, whereas r(P-C) of trimethylphosphine is normally the shorter bond of the two phosphines, co-ordination reverses this In the rotation of the P-P bond of diphosphine, calculations indicate that the point of minimum energy occurs between the gauche and semi-eclipsed conformers, as shown in (139).lgo Perhaps this is also the result of a balance between vicinal H,H repulsion and vicinal H,lone-electron-pair attraction. The spectra of H

phosphinodifluorophosphine indicate that the staggered conformation (140) is preferred, and it appears that hydrogen-bonding to fluorine is not sufficient to make the gauche conformer the most ~ t a b 1 e . l A ~ ~similar result was obtained for tetrafluorodiph~sphine.~~~ 186

lS7 188

1813

l90 lgl

P. B. Davies, R. M. Neumann, S. C. Wofsy, and W. Klemperer, J . Chem. Phys., 1971, 55, 3564. I. Absar and J. R. Van Wazer, J. Chem. Phys., 1972, 56, 1284; Chem. Comm., 1971, 611. P. S. Bryan and R. L. Kuczkowski, J. Chem. Phys., 1971, 55, 3049. P. S. Bryan and R. L. Kuczkowski, Inorg. Chem., 1972, 11, 553.

I. Absar, J. B. Robert, and J. R. Van Wazer, J.C.S. Faraday IZ, 1972, 68, 799. R. L. Kuczkowski, H. W. Schiller, and R. W. Rudolph, Znorg. Chem., 1971, 10,2505. E. L. Wagner, Tlteor. Chim. Acta, 1971, 23, 127.

279

Physical Methods

The microwave spectrum of aminodifluorophosphine (141) indicates a planar PNHzgroup with a HNH bond angle of 117.2' and total p 2.58 D.193 The spectra of four phosphorus trihalides are also reported.lg4 Phosphabenzene (142) has been studied; the spectrum is consistent with a CPC bond angle of 101-104', and a planar ring with the phosphorus atom involved in conjugation.^^^ An interesting theoretical study of the

hypothetical methylenephosphorane (143) indicates that there is an essentially zero barrier to C-P bond rotation with or without the inclusion of phosphorus d-0rbita1s.l~~ 5 Electronic Spectroscopy The increase in Am= and E which occurs in the U.V. spectra of tertiary phosphines upon the introduction of aryl groups is largest for mesityl groups (144; Ar = mesityl), less for o-toly' 'oups, and least for phenyl

Et ,PAr

-

3-

(144)

groups. pK, Measurements and estimates of bond angles from 8p indicate that the difference in the effects of the aryl groups is not due to an increase in the energy or p-character of the phosphorus lone pair of A charge-transfer complex between triphenylphosphine and TCNE gives intense absorptions at 502 and 374 nm.lSs A regular change occurs in the U.V. spectra of phosphonium salts (145) as alkyl groups are replaced by aryl groups, except for the dialkyldiaryl salts. This aspect has been studied using pyrrole as a readily identified aryl ~ u b s t i t u e n t .The ~ ~ ~main absorption band of aniline and dimethylaniline is strongly shifted to longer wavelengths by para PIv substituents in a manner typical of groups exerting a - M effect.200The U.V. spectra A. H. Brittain, J. E. Smith, P. L. Lee, K. Cohn, and R. H. Schwendeman, J. Amer. Chem. SOC.,1971,93, 6772. 194 A. H. Brittain, J. E. Smith, and R. H. Schwendeman, Inorg. Chem., 1972, 11, 39; K. Kuchitsu, T. Shibata, A. Yokozeki, and C. Matsumura, Inorg. Chem., 1971, 10, 2584. R. L. Kuczkowski and A. J. Ashe, J. Mol. Spectroscopy, 1972, 42, 457. lS6 I. Absar and J. R. Van Wazer, J . Amer. Chem. SOC.,1972, 94, 2382. lS7 B. I. Stepanov, A. I. Bokanov, and V. I. Svergun, J . Gen. Chem. (U.S.S.R.), 1971, 41, 526. lS8 J. R. Preer, F. D. Tsay, and H. B. Gray, J. Amer. Chem. SOC.,1972,94, 1875. lg9 G. P. Schiemenz, Tetrahedron Letters, 1971, 4689. 2 o o G. P. Schiemenz and K. Rohlk, Chem. Ber., 1971, 104, 1722. 193

0rganoph osphor us Chemistry

280

Y

(147)

( 1 45)

of p-methoxyphenyl PIv compounds (146) are not altered by changes in the p-substituents.201 Aziridine PIv compounds (147) exhibit an intense band in the region 220-247 nm and a less well-defined band near 280 f 20 nm. The bathochromic shift produced by halogens increased with the electronegativity of the halogen.202 The far-u.v. region has been used to study phosphate interactions in aqueous s o l ~ t i o n s . Phosphorus ~~~ is now regularly estimated by (a) absorption spectroscopy using the band at 436nm produced by vanadomolybdophosphate,204(b) by fiame-emission spectroscopy using the emission band at 528 nm produced by HP0,205and (c) by fluorimetry using the intense green-blue fluorescence produced by a transient indoleperoxyphosphoric acid.206 A number of photoelectron spectroscopy studies of organophosphorus compounds have been reported. ESCA spectroscopy may be used to detect changes in gross structure but does not appear to be suitable for studying fine stereochemical aspects such as differentiating between the cis- and trans-isomers of (148).207 Similar limitations were observed for the innerMe

(148)

T (1 49)

orbital photoelectron spectra of thiono-thiolo-compounds such as (149; X, Y = 0 or S).208 Also, there was only a small spread of 2p binding energies in a series of phosphonium As expected, there is a larger difference between phosphines, phosphine oxides, phosphonium salts, and phosphonic acids, but there was a poor correlation with the charge on phosphorus (as estimated by EHMO calculations).20s

208

G. P. Schiemenz, Annalen, 1971, 752, 30. L. D. Protsenko and N. Y. Skul’skaya, J. Gen. Chem. (U.S.S.R.), 1971, 41, 1949. M. Trachtman and M. Halmann, Carbohydrate Res., 1971, 19, 245; H. Descroix, S. Puiseux-Dao, and M. Suard, Compt. rend., 1971, 272, D, 2472. J. Tusl, Analyst, 1972, 97, 111; G. Norwitz, M. Galan, and M. E. Everett, Analyt. Chim. Acta, 1971, 56, 385. W. N. Elliott, C. Heathcote, and R. A. Mostyn, Talanta, 1972, 19, 359; A. Syty, Analyt. Letters, 1971, 4, 531. W. Rusiecki, J. Brzezinski, and M. Szutowski, Acta Polon. Pharm., 1971, 28, 385. W. J. Stec, W. E. Morgan, J. R. Van Wazer, and W. G. Proctor, J. Inorg. Nuclear Chem., 1972, 34, 1100. W. J. Stec, W. E. Moddeman, R. G. Albridge, and J. R. Van Wazer, J. Phys. Chem.,

zos

M. Pelavin, D. N. Hendrickson, J. M. Hollander, and W. L. Jolly, J. Phys. Chem.,

201 202

aos 204 205

206

207

1971,75, 3975.

1970, 74, 1116.

28 1

Physical Methods

Photoelectron spectra, in combination with CND0/2 calculations, have been used to assign molecular orbitals and estimate their energies. This technique has been used to compare the electronic structure of the phosphorin (150) with that of the corresponding pyridine.210 Photoelectron But

( 1 50)

spectra have also been reported for phosphine and various phosphorus halides.211 The K spectra of triphenyl phosphite and triphenyl phosphate have been determined by X-ray emission spectroscopy.212A new theory for estimating phosphorus resonance transition probabilities has been 6 Rotation and Refraction Resolution of two heterocyclic compounds is reported. Partial resolution of the phosphonium salt (151) was achieved using silver D(-)- and L(+)dibenz~yltartrates,~~~ and the phosphine oxide (152) was resolved using ( + )-9-camphorsulphonic

(151)

( 152)

The magnetic rotations of the pyrophosphates (153; Y = alkyl or OR, X = 0) show that the linking oxygen atom interrupts the delocalization of r-electrons.216 A comparison of observed and calculated magnetic rotations of the monothiopyrophosphates shows that they have the thionostructure (153; X = S).217 The Faraday effect and diamagnetic susceptibilities of a number of Prrr-Ncompounds reflect a large variation alo

211

212 213 214

215

216 217

H. Oehling, W. Schafer, and A. Schweig, Angew. Chem. Znternat. Edn., 1971, 10, 656. M. Barber, J. A. Connor, M. F. Guest, I. H. Hillier, and V. R. Saunders, Chem. Comm., 1971, 943; P. J. Bassett and D. R. Lloyd, J.C.S. Dalton, 1972, 248; J, P. Maier and D. W. Turner, J.C.S. Furaday IZ, 1972, 68, 71 1. Y. Takahashi, Bull. Chem. Soc. Japan, 1972, 45, 4. D. R. Beck and 0. Sinanoglu, Phys. Rev. Letters, 1972, 28, 945. C. H. Chen and K. D. Berlin, J . Org. Chem., 1971, 36, 2791. G. Ostrogovich and F. Kereh, Angew. Chem. Internut. Edn., 1971, 10, 498. R. Turpin, D. Troy-Lamire, and D. Voigt, Bull. SOC.chim. France, 1971, 3878. D. Troy-Lamire, R. Turpin, and D. Voigt, Bull. SOC.chim. France, 1972, 889.

282

Organophosphorus Chemistry

o

x

of m character upon changing the electronegativities of the phosphorus substituents.21S Optical rotatory dispersion of normal and 2’4-rnethylated diribonucleoside monophosphate at pH 1, 7, and 11.2 has been used to study the conformation of the ribose part of the m o l e c ~ l e . ~ ~ ~ Circular dichroism of pyrophosphate derivatives of some purine nucleosides indicates a symmetrically stacked syn conformation except when there is restricted rotation of the base.220 Circular dichroism has also been used to study the inhibitor action of guanosine 2’(3’)-monophosphate on a ribonuclease.221 7 Diffraction The number of diffraction studies of phosphorus compounds continues to increase. A timely review of the geometric parameters of acyclic organophosphorus compounds has been published.222 The X-ray diffraction of 1,2,5-triphenylphosphole(1 54) indicates that the phosphole has little if any r-electron delocalization. The P-phenyl

group subtends an angle of 116” to the heterocyclic ring, the C-C bonds of which have typical butadiene distances, and the PC bonds correspond to single The phosphorin ring of (155) has a chair conformation with a CPC bond angle of 100” in the ring.224 The alkaline hydrolysis of 1,2,2,3,4,4-hexarnethyl-l-phenylphosphetaniumiodide gives a spiroderivative of a phosphole oxide. The structure of the corresponding spiro1,l-dimethylphospholaniumsalthas beenexaminedand thering proton found 218

21s 230

221 222 223

224

M. C. Labarre, D. Voigt, S. Senges, M. Zentil, and R. Wolf, J . Chim. phys., 1971, 68, 1216. H. Singh and B. Hillier, Biopolymers, 1971, 10, 2445. M. Ikehara, S. Uesugi, and K. Yoshida, Biochemistry, 1972, 11, 836. N. Yoshida, K. Kuriyama, T. Iwata, and H. Otsuka, Biochem. Biophys. Res. Comm., 1971, 43, 954. L. S. Khaikin and L. V. Vilkov, Russ. Chem. Rev., 1971, 40,1014. W. P. Ozbirn, R. A. Jacobson, and J. C. Clardy, Chem. Comm., 1971, 1062. A. T. McPhail, J. J. Breen, J. C. H. Steele, and L. D. Quin, Phosphorus, 1972, 1, 255.

Physical Methods

283

to be in the 2-position, as shown in (156).22bA comparison of the crystal structures of the 2-troponyl carbonyl-stabilized ylide (157) with that of the corresponding+nitrile-stabilized ylide (158) proved to be very rewarding. Whereas the P a - 0 - bond distance is 236pm in (158), it is much shorter EtO

N

Ill C

\

c=o

( 1 57)

(158)

(214pm) in the ester (157), approaching the bond length of an apical PO bond of oxyphosphoranes (176-179 pni). The distance between the phosphorus atom and the oxygen of the ester carbonyl (305pm) is also less than the sum of the van de Waals radii ( 3 3 O ~ m ) . ~The l bisphosphonium ylide (159) has the NCN group twisted 7.7" out of the PCP plane in the Two enantiomorphs were identified in crystals of the carbodiphosphorane (160). The PCP bond angle of 144" and 130" in Ph,P,

,c--c,

PW+

( I601

,NPh NPh

(161)

each enantiomorph is much greater than the 170" observed for the N=C=N group. The large angle allows two of the phenyl groups, one on each phosphorus atom, to have an almost eclipsed conformation, as shown in (160).227Reaction of this compound with Mn(CO),Br gives the complex (161), in which the triple bond (120 pm) is little changed from X-Ray diffraction studies are also reported for (162) 229 and (1 63).230 226 227 228 229

230

J. N. Brown, L. M. Trefonas, and R. L. R. Towns, J. Heterocyclic Chem., 1972,9,463. F. K. Ross, W. C. Hamilton, and F. Ramirez, Acta Cryst., 1971, B27, 2331. A. T. Vincent and P. 5. Wheatley, J.C.S. Dalton, 1972, 617. S. Z . Goldberg, E. N. Duesler, and K. N. Raymond, Chem. Comm., 1971, 826. A. F. Cameron, N. J. Hair, and D. G . Morris, Chem. Comm., 1971, 918. J. C. Williams, J. A. Kuczkowski, N. A. Portnoy, K. S . Yong, 5. D. Wander, and A. M. Aguiar, Tetrahedron Letters, 1971, 4749.

284

Organophosphorus Chemistry

Crystals of the monohydrate of the diphosphonic acid (1 64) have the PO, groups in nearly eclipsed conformations, with an approximate W arrangement of the OPCPO Co-ordination of this acid with calcium ions occurs with the formation of several types of chelate rings, two involving only phosphoryl groups and one, a five-membered chelate ring, involving an alcoholic and phosphoryl group.232 The crystal and molecular structures of the hexahydrate of disodium DL-glyceryl phosphate (165),233 adenosine 3’,5’-monopho~phate,~~~ and tetramethylamidinium phosphonate (166) 235 are also reported.

X-Ray diffraction of the phosphazene (1 67; X = 2,2’-dioxybiphenyl) When the molecular shows that all the PN bond lengths are dimensions are compared with the electronegativity of the substituents, a correlation can be made for the triniers but not the tetramers. However, correlations in both cases can be achieved if orbital electronegativities are The PN cage molecule (168) has each PNNP link planar within 80 pm. The PN bond lengths are 168 pm, in accordance with a limited ~* PN bond lengths are found in the fouramount of ~ - b o n d i n g . ~Similar membered cyclic compound (169).239 The small ring is bent by 1 l o , which is the same as that observed for the four-membered ring in the oxyphosphorane (170). The apical oxygen and phosphorus atoms of (170) were not collinear (OPO bond angle = 160°).120 The PO bond lengths 331

232 233

234

235

236

237

338

239

V. A. Uchtman and R. A. Gloss, J. Phys. Chem., 1972,76, 1298. V. A. Uchtman, J. Phys. Chem., 1972,76, 1304. R. H. Fenn and G . E. Marshall, Chem. Comm., 1971, 984. M. Sundaralingam and J. Abola, Nature New Biol., 1972, 235, 244. J. 5. Daly, J.C.S. Dalton, 1972, 1048. H. R. Allcock, M. T. Stein, and J. A. Stanko, J. Amer. Chem. SOC.,1971, 93, 3173. A. J. Wagner, J. Inorg. Nuclear Chem., 1971, 33, 3988. W. Vandoorne, G . W. Hunt, R. W. Perry, and A. W. Cordes, Inorg. Chem., 1971,10, 2591. E. H. Ibrahim, R. A. Shaw, B. C. Smith, C. T. Thakur, M. Woods, C. J. Bullen, J . S. Rutherford, P. A. Tucker, T. S. Cameron, K. D. Howlett, and C. K. Prout, Phosphorus, 1971, 1, 153.

Physical Methods Me

x x \ /

\

.//"

\

,N&P ,N--P \ Me N'

( 169)

285

'

\

N-Me

(170; Y = CF,)

indicate that there is negligible d,-p, bonding, and a similar conclusion was made for (94).lZ7 Several electron-diffraction studies have been reported. After the estimation of dihedral angles by electron diffraction, there is usually the problem remaining as to whether the estimate represents an average of many rapidly interconverting conformers or not. Thus the dihedral angle for diphosphine (139) converged to a value of 81", but this result is of doubtful significance since other angles corresponded to parameters not significantly different from that for the final refinement.24oIn the case of methoxydichlorophosphine(171) the dihedral angle probabilities, calculated from the electron diffraction measurements, were high for the range 0-27", and a dihedral angle of 17 k 6" was estimated to correspond to the real molecular conformation. The P-Cl bond length (208.4 pm) was the same as that in dimethylaminodichlorophosphine (172).241A study of Me

C1 (171)

Me,N-PCI, (172)

0 II H3CPC 1 (173)

cyanodifluorophosphine showed it to possess very similar stereochemistry to phosphorus trifluoride, and therefore it appears that the cyanide and fluoride groups have similar stereochemical effects.242 In comparison, the P-Cl bond length of the PIv dichloride (173) was 203.2 pm.243 a40 241 243 243

B. Beagley, A. R. Conrad, J. M. Freeman, J. 5. Monaghan, and B. G . Norton, J. MoE. Structure, 1972, 11, 371. V. A. Naumov, N. M. Zaripov, and V. G . Dashevskii,J . Struct. Chem., 1971,12, 135. G . C. Holywell and D. W. H. Rankin, J. MoE. Structure, 1971, 9, 11. V. A. Naumov and V. N. Semashko, J . Struct. Chem., 1971, 12, 289.

Organophosphorus Chemistry

286

8 Dipole Moments, Conductance, and Polarography Dipole moments (p) were calculated for most of the compounds studied by microwave spectroscopy (see Section 4). The P’II-N bond moment has been estimated to be 0.26 D from the dipole moments of trisdimethylaminophosphine ( p = 1.32 D) and derivatives of (174). However, it is difficult to accept that the PIV-N bond moment of the oxide of (174) is

n

0

\p”\Ph

f-7

0 0 ‘P’

still directed towards nitrogen and with increased magnitude (0.991.13 D).244The dioxaphospholan ring (175) was found to be electrondonating to halogen but electron-accepting from a methoxy-group. The dipole moments of the aryl derivatives (175; Y = Ar) indicated that a phenyl group has weak donor properties towards the ring.245 The dipole moments of a series of vinylphosphines (176; Y = MeO, R,N, Ph, or Et) have been determined. The replacement of an ethoxy-group in triethyl phosphite by a vinyl group lowers the dipole moment. The vinyl group appears to be accepting electrons from the (Et0)2P group since the introduction of electron-donating methyl groups and electron-accepting phenyl groups on the vinyl group (176; Y = OEt, R = Me or Ph) lowered and raised p, respectively. The dimethylamino and ethyl substituents on phosphorus had similar properties to an ethoxy-group. In contrast, phenyl groups on phosphorus caused the phosphorus group to accept electrons from the vinyl group.246 The bond polarities of some P-butyl and P-phenyl phospholes (177) were similar to those of acylic phosphines ( p ca. 1.5 D). This is in contrast to pyrroles and amines, which have dipole moments of ca. 2 and 1 D, respectively.247 The dipole moments of triarylphosphines decrease with the electronegativity of the para-

244

245

246

247

E. A. Ishmaeva, M. A. Pudovik, S. A. Terent’eva, and A. N. Pudovik, Dokiady Phys. Chem., 1971, 196, 63. K. S. Mingaleva, N. A. Razumova, A. A. Petrov, Z . L. Evtikhov, and F. V. Bagrov, J. Gen. Chem. (U.S.S.R.), 1971, 41, 2456. K. S. Mingaleva, Y. N. Chistokletov, V. V. Kosovtzev, and A. A. Petrov, J. Gen. Chem. (U.S.S.R.), 1971, 41, 868. H. Lumbroso, D. M. Berth, and F. Mathey, Compt. rend., 1972, 274, C , 100.

Physical Methods 287 substituents, e.g. p = 1.92, 1.44, 0.65, and 0.61 for (178; Y = Me, H, C1, or F, re~pectively).~~~ Comparisons of measured and calculated dipole moments of formyl-, acyl-, and aroyl-methylenetriphenylphosphoranes(179) are discussed in relation to their conformations and charge delocalizations. The data support a predominance of the cis-forms (179) in benzene Similar comparisons for the ketophosphoryl compounds (180) indicated a predominance (ca. 90%) of the transoid conformation, as shown in (1

,c=c, ,o-

Ph,P(

H

R

o+p-C/ :j Y

R

+o

PhCH=CHPO,Et,

Similar studies have been made on the conformations of alkyl methylphenylphosphinates (131) 177 and on the stereochemistry of the cyclic phosphites (60).251987 The moment for the C(sp2)-P bond is 1.07 D, as estimated from the dipole moments of diethyl styrylphosphonate (1 8 1) and some of its The conductance of quaternary phosphonium salts 253 and diphenylphosphinic acid and its derivatives 254 has been measured, and an indirect polarographic determination of mixed phosphates and arsenates is 9 Mass Spectrometry The mass spectra of methoxydimethylphosphine (182; X = 0 ) and the corresponding sulphur compound (182; X = S) show base peaks corresponding to PO+ and MePSf respectively. Whereas the methoxyphosphine also shows a fragmentation path commencing with loss of a methoxy-group, the positive ions from the sulphur derivative show a strong tendency to

R. F. De Ketelaere, E. G. Claeys, and G. P. Van der Kelen, Bull. Soc. chim. belges, 1971, 80, 253. H. Lumbroso, C. Pigenet, A. Arcoria, and G. Scarlata, Bull. Soc. chim. France, 1971, 3838.

E. A. Ishmaeva, M. G. Zimin, R. M. Galeeva, and A. N. Pudovik, Bull. Acad. Sci.

U.S.S.R.,1971, 473.

E. E. Nifant’ev, A. A. Borisenko, I. S. Nasonovskii, and E. I. Matrosov, Doklady Chem., 1971,196,28. E. A. Ishmaeva, N. A. Bondarenko, and A. N. Pudovik, Bull. Acad. Sci. U.S.S.R., 1971, 2429.

V. M. Tsentovskii, V. P. Barabanov, F. M. Kharrasava, and T. A. Busygina, J. Gen. Chem. (U.S.S.R.), 1971, 41, 1667. D. L. Venezky and J. E. Quick, J. Chem. and Eng. Data, 1972, 17, 23. L. Rozanski, Chem. analit., 1972, 17, 55.

288

Organophosphorus Chemistry

retain the sulphur atom.25 The fragmentation patterns of cyanophosphines showed that loss of a nitrile group is a lower energy process than loss of methoxy, dimethylamino, or phenyl.2s Examination of the spectra of a large number of acetylenic phosphines (1 83 ; R = aryl or alkyl) showed that the fragmentation pathways are strongly dependent on the nature of the

phosphorus and acetylenic s u b s t i t u e n t ~ . ~ The ~ ~ mass spectra of the phosphinoarsines (184) and (1 85) contained ions corresponding to Ph,P+ but not Ph,As+, showing that migration of phenyl to phosphorus is preferred.257 Similar migrations are observed in the spectra of the tetraphospholan (6).Ig The appearance potentials of a series of phosphine oxides (186; R = propyl, propenyl, or propynyl) are all similar to that of acetone, which supports the postulate that the predominant ionization is loss of an electron from oxygen. The fragmentation patterns were examined to see if there is a relationship with alkaline cleavage. The ion at m/e 92 is the base peak in the spectrum of (186; R = propyl) and is attributed to the 0

II Et,PR

fragmentation shown in Scheme 1. The importance of this fragmentation pathway falls for the unsaturated compounds and the rearrangement ion ( M - Et)+ rises in relative intensity. This change is attributed to a lowering of electron density at phosphorus, which stabilizes and retards the fragmentation of the anion leading to [ M - (C2Hp)2]+.258 The spectra of the phospholen oxides (187; X = RO, F, or C1) and the corresponding sulphides in general showed a predominance of heterocyclic ions and few ions resulting from loss of hydrocarbon fragments. This was attributed to the stability of the anion (188). The relative intensity (R.I.) of one such hydrocarbon fragment, C4H6+,correlated (increased) with the susceptibility to hydrolysis of the phosphorus grouping. Possible reasons for this are The relative intensity of the molecular ion of triethylphosphine sulphide is 12.4, nearly six times that of the corresponding oxide 256

257 258

25s

A. J. Carty, N. K. Hota, T. W. Ng, H. A. Patel, andT. J. O’Connor, Canad. J. Chem., 197 1,49, 2706. R. B. King and P. N. Kapoor, J. Amer. Chem. SOC.,1971, 93, 4158. G. M. Bogolyubov, V. F. Plotnikov, V. M. Ignat’ev, and B. I. Ionin, J . Gen. Chem. (U.S.S.R.), 1971, 41, 510. G. M. Bogolyubov, L. I. Zubtsova, N. N. Grishin, N. A. Razumova, and A. A. Petrov, J . Gen. Chem. (U.S.S.R.), 1971, 41, 520.

Physical Met hods

289

0

H+ II Pr -P-CH-CH, 1 Et anion 0

II

R-P-CH,CH, I Et (1 86)

o+

= Prk

-

II Pr-P-H I Et

I

0 II

& Pr-P-H I Et

+ HC-CH,

o+

II Pr-P-H

I

H m/e 92

Scheme 1

0 0 P

/ \

x o (1 87)

P

x o I\

(188)

s s

II II Et,P-PEt, (1 89)

(R.I. = 2.14). Also, the diphosphine disulphide (189) gave a (M/2)+ ion of R.I. 14.2, which is much greater than the R.I. of 1.52 for the parent diphosphine. The energy of the Prv-PIv bond was estimated from the appearance potentials of the (M/2)+ ion of the disulphide (189) and the 01 ion of triethylphosphine sulphide. Its value (2.6 eV) is lower than that (3.7 eV) of the parent diphosphine.260The dissociation energy of the P=S bond was estimated to be 3.7 eV (85 kcal mo1-1).261 The phosphepin (190) gave an abundant ion at m/e 178.262 The fragmentation involves eventual loss of H3P0, to give the ion above with a mass corresponding to that of phenanthrene. The mass spectra of some tertiary-butyl phosphoryl derivatives such as (191; Y = Cl or Ph) can be rationalized if the preferred fragmentations are loss of isobutane from the P-t-butyl groups and loss of a methyl group from the aryl-t-butyl groups.263 260

2e1 262

263

G. M. Bogolyubov, N. N. Grishin, and A. A. Petrov, J . Gen. Chem. (U.S.S.R.), 1971, 41, 817. G. V. Fridlyanskii, V. A. Pavlenko, B. A. Vinogradov, N. N. Grishin, G . M. Bogolyubov, and A. A. Petrov, J. Gen. Chem. (U.S.S.R.), 1971, 41, 1714. J. L. Suggs and L. D. Freedman, J . Org. Chem., 1971, 36, 2566. M. Yoshifuji, R. Okazaki, and N. Inamoto, J.C.S. Perkin I , 1972, 559.

290

Organophosphorus Chemistry

Y The mass spectra are also reported for the thiophosphates (192),264 derivatives of dimethylphosphinic acid (193),265and the phosphadiazoles (194).266 Mass spectra have been used to identify the position of l80labels in phosphinic acid derivatives 267 and to estimate the lSOcontent of inorganic phosphate after silylation.268 The molecular distance between silylated phosphate groups and/or silylated hydroxy-groups has been estimated from the abundance of the rearrangement ions (195) and (196).26a 4-

+

P(OTMS),

HOP(OTMS),

(195)

( 196)

10 pK and Thermochemical Studies The basicities of triarylphosphines (197) in chloroform-acetic acid follow an excellent Hammett correlation which includes halogen substituents. The dimethylaminophenol derivative (197; Y = Me2N) is first protonated on The pK, values of the dialkylphosphinobenzoic acids (198) suggest, rather surprisingly, that the R2P group is very weakly electronaccepting from the aryl ring; values of om = 0.10 and uD = 0.13 were

264 265 266

2G7

268

R. A. Shaw and M. Woods, Phosphorus, 1971, 1, 41. F. See1 and K. Velleman, Chem. Ber., 1971, 104, 2972. R. G. Kostyanovskii, V. G. Plekhanov, N. P. Ignotava, R. G. Bobkova, and N. I. Shvetsov-Schilovskii,Bull. Acad. Sci. U.S.S.R., 1971, 2486. R. L. Dannley, R. L. Waller, R. V. Hoffman, and R. F. Hudson, J. Org. Chem., 1972, 37,418. J. Bar-Tana, 0. Ben Zeev, G. Rose, and J. Deutsh, Biochim. Biophys. Acta, 1972, 264, 214.

269 270

D. 5. Harvey, M. G. Horning, and P. Vouros, Tetrahedron, 1971, 27, 4231. G.P. Schiemenz, Tetrahedron, 1971, 27, 3231.

Physical Methods

291

obtained.271 Acidities determined by conductance and potentiometric titrations of trichloromethyl- and phenyl-phosphonic, phenyl- and diphenyl-phosphinic, and diethyl dithiophosphoric acids are reported.272 The acidities of the thio-acids (199) were weakest and differentiated most in absolute alcohol because the change in energy of ion solvation is Ph

\

Y-P=NZ Ph'

(20 11

probably the governing From a study of the acidity and tautomerism of a di-fLketophosphonium salt it has been concluded that trans-enolization, to give (200), predominate^.^^^ The phosphinimines (201) are dibasic, with pK,'s in the range 11.5-19.4 and 5.9-9.0, but they are only monomethylated by methyl iodide.l16 The acidifying effects of phosphoryl groups on methylene and methyl protons are also Tentative bond energy values have been obtained from heats of reaction of phosphoryl Heats of reaction have been measured, using flow microcalorimetry, for the estimation of cholinesterase activity and its Free energy and enthalpy inhibition by organophosphorus changes,278heat capacities,270and distribution ratios 280 of quaternary phosphonium salts are reported. 11 Surface Properties The use of mass spectrometry as a detector in g.1.c. has the advantage that isomeric materials with the same retention times may still be distinguished, e.g. a phosphate and phosphonate.281 Mono-, di-, and tri-butyl phosphates may be separated by g.1.c. after conversion of the acidic components into their silyl esters.282A dual flame photometric detector has been described for the simultaneous determination of phosphorus-, sulphur-, and chlorinecontaining compounds. The method is based on the measurement of the 271 272

273 274 275

276 277

278

279 280

281

I. G. Malakhova, E. N. Tsvetkov, D. I. Lobanov, and M. I. Kabachnik, J . Gen. Chem. (U.S.S.R.), 1971, 41, 2837. A. Francina and A. Lamotte, Bull. SOC.chim. France, 1971, 1951. T. A. Mastryukova, L. L. Spivak, A. A. Grigor'eva, E. K. Urzhuntseva, and M. I. Kabachnik, J . Gen. Chem. (U.S.S.R.), 1971, 41, 1953. T. A. Mastryukova, V. Rubashevskaya, I. M. Aladzheva, and M. I. Kabachnik, J . Gen. Chem. (U.S.S.R.), 1971, 41, 2358. E. S. Petrov, E. N. Tsvetkov, M. I. Kabachnik, and A. I. Shatenshtein, J. Gen. Chem. (U.S.S.R.), 1971, 41, 1173. A. S. Kertes, J. Inorg. Nuclear Chem., 1972, 34, 796. J. Konickova and I. Wadsoe, Acta Chem. Scand., 1971, 25, 2360. D. H. Berne and 0. Popovych, J. Chem. and Eng. Data, 1972, 17, 178. R. K. Mohanty and J. C. Ahluwalia, J. Chem. Thermodyn., 1972, 4, 53. N. A. Gibson and D. C. Weatherburn, Analyt. Chim. Acta, 1972, 58, 149. C. B. C. Boyce and S. B. Webb, J . Chem. SOC.(C), 1971, 3987. J. W. Boyden and M. Clift, Z . analyt. Chem., 1971, 256, 351.

292

Organophosphorus Chemistry

emission bands of HPO and S , at 526 and 394 nm and of indium chloride at 360 nni, the indium chloride being formed by passing the vapour over indium metal.2aa Similar methods have been developed for specific pesticides,2s4and an inexpensive gas chromatograph for the determination and collection of labile organophosphorus compounds has been described.285 Many methods are now available for the chromatographic separation of polar compounds. Further work is reported on the high-pressure pellicular anion-exchange chromatographic separation of adenosine derivatives,2ss and the pH dependence of the anion-exchange chromatographic separation of tri- and tetra-phosphates has been clarified.287 Thin-layer chromatographic separation of a vinyl phosphate 288 and a dithiolate 289 and paper chromatography of phosphonates 290 have been reported. Gel chromatography, which depends primarily on molecular weight differences, has been used (a) to separate mono-, di-, and tri-alkylated phosphates 291 and (b) for the estimation of organic phosphates in It is interesting to note a reversal of roles; tri-n-octylphosphine oxidetreated cellulose has successfully separated gold, antimony, and thallium.293

12 Radiochemical Studies A non-destructive and rapid (6-8 min) determination of phosphorus and sodium in organophosphorus compounds may be achieved by fast A rapid method of determining 32P and 33P in neutron aqueous solution utilizes a combination of Cerenkov radiation counting and liquid scintillation counting.205 Adsorption on charcoal before scintillation counting of 32Phas also been used.2D6 283 284

285 28E

287

B. Versino and G. Rossi, Chromatographia, 1971, 4, 331. M. C. Bowman and M. Beroza, J. Assoc. Ofic.Analyt. Chemists, 1971, 54, 1086; M. C. Ivey and H. V. Claborn, J . Agric. Food Chem., 1971, 19, 1256. A. F. Machin and C. R. Morris, Analyst, 1972, 97, 289. G. Brooker, J . Biol. Chem., 1971,246, 7810; S . N. Pennington, Analyt. Chem., 1971, 43, 1701 ; H. W. Shmukler, J. Chromatog. Sci., 1972, 10, 137. T. Nakamura, M. Kimura, H. Waki, and S. Ohoshi, BUN. Chem. SOC.Japan, 1971, 44, 1302.

288 289 290

291 292

293 294

295 290

M. Kotakemori and A. Kawagisi, Japan Analyst, 1971, 20, 709. A. Murano and M. Nagase, Japan Analyst, 1971, 20, 665. W. E. Roop, S. A. Tan, and B. L. Roop, Analyt. Biochem., 1971, 44, 77. H. Tanaka and K. Konishi, J. Chromatog., 1971, 60, 430. J. H. Steward and M. E. Tate, J. Chromatog., 1971, 60, 75. J. Blouri and G. Revel, J. Radioanalyt. Chem., 1972, 10, 121. I. P. Lisovskii and L. A. Smakhtin, J. Radioanalyt. Chem., 1971, 8, 75. L. C. Brown, Analyt. Chem., 1971, 43, 1326. T. Chojnacki and Z. Matysiak, Analyt. Biochem., 1971, 44, 297.

Author Index Abola, J., 284 Abramov, V. S., 109 Absar, I., 187, 278, 279 Abul'khanov, A. G., 238 Adam, W., 245 Aganov, A. V., 82, 269 Agarwal, K. L., 153 Agawa, T., 185 Aguiar, A. M., 82,130,131, 283 Ahluwalia, J. C., 291 Ahmad, M., 151 Ahmed, F. R., 235 Akamsin, V. D., 54 Akiba, K., 22, 183, 245 Akintobi, T., 192 Akiyama, S., 196 Aksenov, V. I., 127 Aladzheva, I. M., 17, 23, 29 1 Alam, S. S., 159 Albanbauer, J., 91, 177 Al'bitskaya, V. M., 49 Albracht, S . P. J., 274 Albrand, J. P., 271 Albridge, R. G., 280 Alekandrova, N. A., 88 Alfonskaya. L. S., 77 Ali, A., i92 Alimov, M. P., 125 Alimov, P. I., 125 Allcock. H. R.. 49. 224, 228, 23 1, 235,274, ' 284 Allcox, I. L., 257 Allen, C. W., 232 Allen, D. W., 6, 19, 33, 251 Allen, G. W., 171 Allen, L. C., 29, 259 Amidou, A. B., 225 Amos, H., 158 Anderson, A. G., 68 Anderson, D. R., 250 Andreae, S., 136 Andrewes, A. G., 195 Andrews, G. C., 106 Aneja, R., 8, 170, 246 Anfinsen, C. B., 143 Ang, H. G., 1 Angelmo, N., 160 Ankel, H., 159 Annan, W. D., 172 Anoshina, N. F., 7 Anschel, M., 77 Anschutz, W., 84 Ansell, G. B., 235 Anstey, R. H., 229 Anthony, R. S., 172

Appel, R., 9, 10, 203, 210, 21 1. Apprion, P., 128 Arbuzov, B. A., 42, 46, 55, 56, 57, 90, 94, 96, 275 Archibald, R. M., 277 Arcoria, A,, 102, 287 Armsen, R., 178 Armstrong, D. R., 224 Asano, K., 258 Ash, A. B., 140 Ashe, A. J., 24, 279 Ashkinadze, L. D., 275 Aspinall, G. O., 160 Auschutz, W., 138 Avigad, G., 168 Aviv, H., 157 Awerbouch, O., 74 Axelrod, E. H., 194 Azzaro, M., 142 Babcock, D., 151, 152 Babler, J. H., 201 Babyak, A. G., 213 Baechler, R. D., 13, 71, 26 3 Bauerlein, E., 166, 167 Bagrov, F. V., 41, 286 Bakakhontseva, V. N., 168 Balasubramanian, S., 110 Bald, R. W., 143, 149 Baldwin, J. E., 177, 246 Ballantyne, W., 151 Banks, G. R., 156 Barabanov, V. P., 287 Baranov, G. M., 275 Baranov, S. N., 87, 129 Baranovskii, L. A., 127 Baranowski, T., 160 Barber, M., 51, 281 Barker, R., 168 Barker, R. W., 171, 271 Barley, G. C., 195 Barr, R. M., 159 Barrans, J., 48, 104 Bar-Tana, J., 290 Bartish, C. M., 116 Barton, D. H. R., 120,236, 246 Bartsch, W., 199 Barycki, J., 87 Bashirova, L. A., 69 Bassett, P. J., 51, 281 Baudler, M., 2, 3, 71, 253 Bauer, B. J., 143 Bauer, G., 212, 237 Bauer, R. J., 147

293

Bauerlein, E., 119 Baukov, Yu. I., 99 Beagley, B., 285 Bebikh, G. F., 211 Beck, D. R., 281 Beck, P., 84 Begtrup, M., 269 Begum, A., 51, 239, 272 Behrens, N. H., 159 Beikirch, H., 156 Bell, J. D., 171, 271 Beloglazova, T. N., 233 Bel'skii, I. F., 56, 69 Belskii, V. E., 125, 135 Belyaev, N. N., 183 Belyaev, Yu. P., 225 Bender, M. L., 174 Benezra, C., 138, 242, 269 Benkovic, S. J., 125, 168 Benrens, N. H., 159 Benschop, H. P., 137 Bensoam, J., 33 Bentlev. T. J.. 120. 236 Bentnide, W: G.,' 41, 47, 48, 74, 101, 141, 237, 257,264, 270, 272, 275 Ben Zeev, O., 290 Berden, J. A., 274 Bergelson. L. D.. 170 Berger, HI, 122 ' Bergerhoff, G., 265 Bergesen, K., 89, 141 Bergmann, E. D., 200 Berlin, K. D., 16, 18, 270, 28 1 Bermann. M.. 64. 214. 220 Bernard, D., 39, 42, 43, _

48.49

,

I

Ber;lk,-D. H., 291 Berninger, C. J., 180 Beroza, M., 292 Bertazzoni, U., 158 Bertin, D. M., 286 Bertrand, R. D., 141, 267 Beslier, L., 44 Bestmann, H. J., 18, 176, 178, 195, 196 Bezzubova, N. N., 135 Bhacca, N. S., 65 Bhalerao, U. T., 194 Bianchini, J. P., 88 Biddlestone, M., 231 Bieniek. T.,233 Bigorgne, M.,112 Bilofsky, H. S., 30 Binder, H., 65, 215, 222, 223 Bindra, A. P., 198

Author Index Binsch, G., 259 Birdsall, W. J., 224, 274 Birnboim, H., 158 Bishop, J. K. B., 51, 272 Bishop, M. J., 167 Bissell, E. C., 49 Blackburn, G. M., 254 Blagoveshchenskii, V. S., 118 Blanchard, C., 140 Blaser, B., 203, 210 Block, H. D., 120 Blouri, J., 292 Blumbergs, P., 140 Blumenstein, M., 256 Bobkova, R. G., 290 Bodalski, R., 89, 132 Bodnarchuk, N. D., 207, 214 Bohler, D., 226 Boehm, W., 187 Boehne, H., 3 Bogatskii, A. V., 88 Bogolyubov, G. M., 73, 74, 288, 289 Bohlmann, F., 195 Boisdon, M. T., 114 Bokanov, A. I., 279 Boldeskul, I. E., 275 Bondarenko, N. A., 287 Bondarenko, V. M., 225 Bondinell, W. E., 163, 194 Bonnafous, J. C., 195 Bonte, B., 13 BODD.T. T.. 261

Borowitz, G. B., 102 Borowitz, I. J., 10, 77, 102, 103,257 . . Borsus, J.-M., 185 Both, W., 196 Bouquet, G., 112 Bowman, M. C., 292 Boyce, C. B. C., 61, 129, 238, 291 Boyden, J. W., 291 Bragin, J., 276 Brain, E. G., 182 Bram. G. M.. 162 Brass; H. J., 134 Braun, H., 1, 15 Braye, E. H., 27, 239 Breen, J. J., 256, 282 Brelivet, J., 128 Brentnall, H. J., 143 Breslow, R., 172 Bridger, W. A., 172 Bright, H. J., 161 Brittain, A. H., 52, 279 Britton, R. W., 195 Brocas, J., 31 Bromilow, R. H., 122, 123 Brooker, G., 292 Broquet, C., 185 Brown, C., 101, 102 '

Brown, D. H., 160 Brown, D. M., 156 Brown, G. M., 117 Brown, J. N., 283 Brown, L. C., 292 Brownsey, R. W., 169 Briimmer, W., 143 Bruenner, H. U., 3 Brun, G., 140 Brunswick, D. J., 148 Brunt, C., 157 Brunt, R. V., 169 Bryan, P. S., 278 Brzezinski, J., 280 Buchanan, J. G., 169 Buchi, G., 15 Buchowicz, J., 149 Buck, H. M., 49, 240 Budovskii, E. I., 143, 149 Biichi, G., 182 Bugerenko, E. F., 127 Bugianesi, R. L., 158 Bullen, G. J., 235, 284 Bundgaard, T., 267 Bunton, C. A., 121 Buono, G., 42, 96 Burg, A. B., 71 Burgada, R., 39, 42, 43, 48, 49, 109, 261, 277 Burger, K., 44,91, 98, 177, 243 Burgers, P. M. J., 154 Burkhardt, J., 233 Burkhardt, T., 195 Burmakina, T. V., 57 Burnaeva, L. A., 37 Burns, P., 87, 136 Burt, D. W., 107 Burtsev, V. A., 90 Bushweller, C. H., 30 Busygina, T. A., 287 Butcher, R. W., 143 Butova, T. D., 88 Byrne, J. E., 71 Cadogan, J. I. G., 48, 133, 248 Calderazzo, F., 258 Callot. H. J.. 138. 242. 269 ' Cama, L. D., 166 Cameron, A. F., 204, 235, 283 Cameron, T. S., 73, 284 Camiener, G. W., 162 Campagnari, F., 158 Cann, P. F., 82, 83 Capka, M., 2 Caplier, I., 27, 239 Capozzi, G., 87, 135, 136 Carey, F. A., 268 Carnduff, J., 65 Carrie, R., 185, 200 Carriuolo, J., 151 Carty, A. J., 2, 288 Casev. J. P.. 71 Cashki, M.,'152 Cashion, P. J., 153 Casper, E. W. R., 103, 257 Casper, J. M., 276 I

,

_

Cassidy, F., 182 Castro. B.. 9. 18, 246 Caughlan,'C. N., 35, 43, 268, 270 Cavell, R. G., 275 Cawley, T. N., 169 Cernv. M.. 2 Chadha, J: S., 170 Challis, J. A., 133 Chan, T. H., 79 Chang, B. C., 32, 44, 49, 255 Chang, T.-H., 207, 215 Charrier, C., 261 Chasle, M.-F., 8 Chatta, M. S., 130, 131 Chatzidakis, A., 27, 244 Chekhmakheva, 0. G., 153 Chemodanova, L. A., 77 Chen, C. H., 16, 67, 281 Chenault, J., 120 Chenery, D. H., 153 Cherkasov, R. A., 276 Chernyshev, E. A., 127 Chikamune, O., 129 Chirkunova, S. K., 69 Chistokletov. V. N., 16,93. 256, 286 Chivers, T., 228, 232 Chladek, S., 151 Chojnacki, T., 292 Chong, K. J., 117, 145 Chone. R.. 192 ChourJ. Y . , 156 Christensen, B. G., 166 Christiansen, G. D., 183 Christol, H., 5 Christophliemk, P., 142 Churchman, R., 28, 274 Claborn, H. V., 292 Claeys, E. G., 287 Clardy, J. C., 267, 282 Clare, P., 226 Clarke, F. B., 27, 131 Clifford, D. B., 182 Clift, M., 291 Clipsham, R. M., 219, 224 Clive, D. L. J., 246 Coates, R. M., 174 Cochrane, J. S., 195 Coerdeler, J., 9 Coffinet. D.. 180 Cogne, A., 271 Cohen, J. S., 254 Cohn, K., 52, 63, 72, 279 Cohn, M., 171 Colbv. T. H.. 118 Collihgton, E. W., 195 Combret, J.-C., 8 Cone, J., 174 Connor, J. A., 51, 281 Conrad, A. R., 285 Conrad, W. E., 32, 255 Cook, A. F., 151 Cook, A. G., 59 Cook, R. J., 71 Cooke, R., 152 Cookson, R. C., 77 Cooper, C. M., 246 ,

,

Author Index Cooperman, B. S., 123, 148 Coppola, J. C., 7, 153 Cordes, A. W., 284 Corfield, J. R., 53, 74, 137, 258 Cori. C. F.. 160 Corre, E., 41 Corrie, J. E. T., 189 Coskran, K. J., 54, 253 Costisella, B., 140 Cosvn. J. P.. 196 Cotion, F. A., 220 Cottrell, I. W., 160 Coulson, C. A., 51 Couret, C., 39, 72 Court, A. S., 268 Cowley, A. H., 31, 63, 27 1 Cox, P. J., 182 Craig, D. P., 223 Cramer, F., 145, 147 Craven, S. M., 276 Crea, J., 258 Creasy, W. S., 23, 42, 191, 254 Cremer, H.-D., 198 Cremer, S. E., 74, 267 Cremlyn, R. J. W., 118, 119 Cresp, T. M., 199 Crim, F. F., 182 Cristau, H.-J., 1, 5 Cronan, J. E., jun., 171 Crosscup, C. J., 154 Crouch, R. K., 10, 103, 257 Crouse, D. M., 19, 178, 180 Crowder, R. D., 162 Cuatrecasas, P., 143 Cuddy, B. D., 74, 258 Cullen, W. R., 51, 272 Cummerson, D. A., 169 Curci, R., 81, 106, 246 Cusachs, L. C., 29, 259 Cushley, R. J., 250 Dahl, J., 65 Dahl, O., 8 Dale, S. W., 271 Daly, J. J., 284 Damerau, W., 273 Daniewski, W. M., 61 Danion, D., 200 Danks, L. J., 15, 241 Dannley, R. L., 86, 137, 243, 290. Dashevskii, V. G., 285 Davidson, N., 158 Davies, A. G., 236, 272, 273 Davies, A. P., 8, 246 Davies, M., 187 Davies, P. B., 278 Davis, M. I., 235 Davis, R. A., 180 Dawson, J. W., 2 Dawson, T. M., 246

295 Day, A. C., 195 Dean, P. D. G., 162 De’ath, N. J., 34, 65, 107, 246, 255, 260, 261 De Bruin, K. E., 139, 271 Degarry, N., 127 Degterev, E. V., 125 Deguchi, Y., 274 De Ketelaere, R. F., 287 Deljac, A., 195 Delpuech, J. J., 258 De Luca, U., 158 de Maine, M. M., 168 Demersemen, B., 112 De Montellano, P. R. O., 97

Denney, D. B., 31, 32, 34, 49, 65, 107, 245, 246, 255. 260. 261 Denney, D.Z.; 31, 32, 34, 65. 245. 246. 255. 260. 261 . . . Denyer, C. V., 246 Depoorter, H., 187 Derkach, G. I., 103, 207, 209. 210 Descroix, H., 280 Deutsch, J., 290 Devanneaux, J., 224 Deventhal, J., 141 Devlin, C. J., 177, 262 de Waal, W., 195 Dewhurst, B. B., 118, 119 Dianova, E. N., 42, 96 Dieck, R. L., 207, 225 Diehl, J. W., 245 Diemert, K., 132 Dietsche, W., 57 Di Furia, F., 81, 106, 246 Dillon, K. B., 251 Dimroth, K., 24, 25, 26, 27, 240, 244, 269 di Sanseverino, L. R., 153 Distler, W., 178 Dixon, J., 246 Dmitrieva, G. V., 60 Doak, G. O., 39 Dobbie, R. C., 61 Dodonov, A. M., 61 Dogadina, A. V., 131, 254 Dombrovskii, A. V., 10, 177, 187, 190 Donini, P., 152 Donohue, J., 137 Dormoy, J.-R., 9, 246 Dorokhova, V. V., 75 Doroshenko, V. V., 70 Doyle, M., 196 Drach, B. S., 127, 215 Drake, G. L., 3 Dreiman, N. A., 233 Drew, M., 120 Drozd, G. I., 52, 64 Druce, P. M., 60 Druet, B., 13 Duesler, E. N., 283 Duwel, H., 198 Duff, R. E., 33,260 Duke, J., 152 ’

Dulog, L., 61, 238 Dumas, L. B., 156 Dunham. L.. 202 Dunmur; R: E., 37, 216, 26 1 Duprk, M., 178 Durig, J. R., 276 Dyadyusha, G. G., 224 D’yakonov, A. I., 49 D’yakonova, N. I., 61 D’yakov, V. M., 101, 277 D’yakova, T. L., 101, 277 Eastlick, D. T., 133 Ebeling, J., 221 Ebert, H.-D., 13, 78 Ecker, A., 132, 241 Eckes, H., 84 Eckstein, F., 144, 151, 152 Eckstein, U., 138 Edelman, R., 32, 255 Edlin, G., 152 Edmond, J. G., 174 Edmonds, M., 157 Edmundson, R. S., 89, 109, 119 Edwards, J. O., 134 Egan, W., 27, 263 Egorov, Yu. P., 218, 219, 275 Eguchi, M., 12, 117 Ehrlich, J., 160, 161 Eichelberger, J. L., 85 Eiki, T., 122 Eisenhut, M., 39, 63, 261 Elegant, L., 142 Elepina, L. T., 168 Eliel, E. L., 259 Eliseenkova, R. M., 54 Elisenkov, V. N., 135 Elix, J. A., 198 Elliott, W. N., 280 Ellis, K., 133 El’natanov, Y. I., 3 Emsley, J., 205 Emsley, J. W., 252 Engel, R., 271 Engelhardt, G., 72, 253 Englard, S., 168 Englund, P. T., 157 Epshtein, L. M., 275 Epstein, J., 135 Epstein, W. W., 174 Erlich, H., 152 Erman, W. F., 194 Ermolaeva, M. V., 135 Ernazarov, M., 56 Escudie, J., 39, 72 Etienne, A., 13 Evans, D. A., 106 Evans, P. J., 159 Everett, J. W., 246 Everett, M. E., 280 Evtikhov, Zh. L., 37, 96, 286 Faerber, P., 144 Fahmy, M. H., 124

296

Author Index

Failli, A., 207, 215 Faizullin, E. M., 56 Falke, J., 265 Fang, K. N., 147, 271 Fanta. W. I.. 194 Farnham, W. B., 177

Faiild, H., 148 Faucher, J. P., 224 Faught. 5. B.. 235 Fearherman, S. I., 256 Feeney, J., 252 Fehn, J., 44, 91, 98, 177, 243 Feldmann, R., 198 Fenn, R. H., 284 Feshchenko, N. G., 54, 68 Fil$,-M., 31, 63, 258, 274, LI I

Fina, N. J., 134 Finkenbine, J. R., 79 Firestone. R. A.. 166 Firstenb&g, S., ' 102, 103, 967

Fi&%, H. U., 148 Fischer, D., 157 Fischer, L. V., 147 Fisichella. S.. 102 Flaskerud, G., 226 Fleming, R. H., 177 Flitsch, W., 183 Florey, J. B., 29, 259 Floyd, A. J., 77 Fluck, E., 207, 215 Foester, R., 63, 72 Fondy, T. P., 169 Forrest, H. S., 174 Fottrell, P. F., 161 Foucaud, A., 8, 41, 201 Fouquet, G., 177 Fouquey, C., 141 Fox, W. B., 63, 72 Frampton, R. D., 125 Francina, A., 291 Frank, A. W., 3 Fray, G. I., 77 Freedman, L. D., 16, 81, 130, 251, 289 Freeman, B. H., 188 Freeman, J. M., 285 Freenor,-F. J., 68 Freist, W., 145 Fridkin, M., 156 Fridland. S. V.. 69 Fridlyanskii, G: V., 289 Frjedl, J., 91, 177 Fritsch, W., 202 Fritz, G., 71 Fritzowsky, N., 52, 277 Frolova. T. I.. 82

42, 94,

Gabbai, A., 152 Gabriel, T. F., 157 Gadreau, C., 201 Gagnaire, D., 271 Gaidamaka, S. N.. 215. 216 Gal, J.-Y., 240 Galakhov, I. V., 254 Galan, M., 280 Galeeva. R. M.. 77. 287 Gallacher, M. J., 77 Gallant, J., 152 Garbers, C. F., 15, 189, 254 Gareev, R. D., 82, 269 Garratt,P. J., 196,198,199, 246 Garrigues, B., 43, 271 Gates, P. N., 251 Gautzdamaka, C. T., 139 Gazizov, M. B., 87 Gazizov, T. Kh., 90 Gelbeland, K., 13 Geider, K., 143 Gelbaum, L., 271 Genkina, G. K., 103, 142 Geoffroy, M., 272 Georgiev, V. I., 254 Germa, H., 109 Gerry, M. C. L., 51 Ghangas, G. S., 169 Gibson, N. A., 291 Gielen, M., 31 Gilham, P. T., 156, 158 Gilje, J. W., 52, 261 Gillespie, P., 29, 259 Gilyarov, V. A., 103, 145, 218,219, 275 Gitel', P. O., 230 Glemser, O., 3, 222 Glonek, T., 166, 251 Gloss, R. A., 284 Goddard, N., 255, 265 Gorgen, F., 210 Goetz, H., 23, 218, 252 Goldberg, S. Z., 283 Gol'dfarb, E. I., 57 Goldman, R., 143 Goldschmidt, J. M. E., 227, 228 Golik, G. A., 210 Gombler, W., 53, 110, 268 Gonzalez-Porque, P., 161 Goodman, L., 147 Goody, R. S., 152 Gorak, R. D., 128 Gorbatemko, Zh, K., 54 Gordon, M., 61 Gorenstein, D. G., 80, 121 Gorzny, K., 90 Goubeau, J., 52,277 Gough, S. T. D., 109 Gozman, I. P., 39, 238, 273 Grace, D. S. B., 48, 248 Graf, R., 199 Graf, U., 195 Gramze, R., 271 Granoth, I., 24, 59, 73 ~~

Grapov, A. F., 133 Graves, G. E., 205 Gravestock, M. B., 194 Gray, G. A., 74, 256, 267 Gray, G. R., 168, 250 Gray, H. B., 279 Gray, R. W., 192 Greber, G., 233 Grechkin, E. F., 1, 75, 76 Grechkin, N. P., 38, 265 Green, B., 226, 227 Greenwald, J., 243 Griffin, C. E., 61 Grigor'eva, A. A., 291 Griller, D., 236, 273 Griller, D. D., 272 Grimm, L. F., 205, 212, 265 Grinblat, M. P., 219 Grishin, N. N., 74, 288, 289 Grobe, J., 4 Groen, M. B., 190 Gross, H., 140 Grosse-Bowing, W., 212, 213 Grossman, L., 156 Gruenwedel, D. W., 158 Grushko, I. E., 69 Gryzlova, G. K., 231 Gubanova, G. S., 38 Gubnitskaya, E. S., 207 Guchhait. R. B., 164 Giinther, .H., 198 GuCron, M., 158, 251 Guest, M. F., 51, 277, 281 Guibe-Jampel, E., 118 Guilford. H.. 148. 162 Gulick, W. M.,240, 274 Gulyaev, N. N., 145 Gunther, H., 269 Gurny, R., 199 Guroff, G., 174 Gur'yanova, I. V., 7, 37, 27 5 Gusakova, G. S., 101, 277 Guskova, L. I., 149 Gutzchebauch, K., 131 Gymer, G. E., 77 Haag, A., 13 Haake, P., 87, 135, 136, 171 Haas, K., 226 Haede, W., 202 Hafferl, W., 202 Hair, N. J., 204, 235, 283 Hall, C. D., 6, 31, 188, 241, 245, 260 Halmann, M., 243, 280 Hamada, A., 6, 189 Hamilton, W. C.. 283 Hammes,-O., 265 Hampl, J., 226 Han, S. C. H., 170 Hancock. A. J.. 264 Hansen, E. R.,'237 Hansen, R. S., 267 Hanson, J. R., 195 Hanson, K. R., 163

Author Index Harman, J. S., 64 Harpp, D. N., 41 Harrjs, R. K., 37, 216, 261 Harris, R. O., 224 Harrison. D. G.. 72 Harrison; P. G.,'266, 268 Harrison, W., 235 Harshman, R. B., 152 Hart, R. M., 272 Hartman, F. C., 173 Hartsuiker, G. J., 235 Hartzler, H. D., 192 Harvey, C. L., 157 Harvey, D. J., 290 Harwood, H. J., 76 Hashimoto, M., 117, 246 Hassan, B. E. M., 129 Hassid, W. Z., 158 Hata, T., 47, 117, 145, 155, 254 Hattaha, T., 1 Hattori, M., 155 Haubold, W., 215 Haussmann, P., 233 Havlicek, M. D., 261 Hayase, Y.,194 Hayashi, T., 224, 233 Hayatsu, H., 153 Hazai, I., 149 Heathcote, C., 280 Heck, K., 141 Hedgeland, R., 228 Heimer, E. P., 151 Heine, H. W., 183 Heitz, W., 176 Hellwinkel, D., 46 Helmreich, E., 160, 161 Hemming, F. W., 159 Henderson, T. O., 166,251 Hendrickson, D. N., 280 Herberg, K., 98 Hercules, D.-M., 254 Herr, M. E., 65 Herriott, A. W., 138, 183 Hesse, R. H., 120, 236 Hetflejs, J., 2 Hettche, A., 25, 240, 269 Hettler, H., 147 Hewitt, G., 246 Hewson, M. J. C., 30, 31, 63, 64, 258, 261 Heyns, K., 154 Hiatt, R., 13, 245 Hickey, M. E., 172 Higashi, F., 114 Hilbert, P., 84 Hilderbrand, R. L., 166, 25 1 Hillier, B., 282 Hillier, I. H., 51, 277, 28 1 Hin, B. C., 28 Hirayama, Y., 1 Hoare, D. S., 174 Hobbs, J., 144 Hobbs, M. E., 271 Hofle, G., 246 Hoffman, R. V., 86, 137, 243, 290 Hoffmann, P., 29, 259

297 Hoffmann, R., 29, 64, 259 Hogness, D. S., 159 Holah, D. G., 28, 274 Hollander, J. M., 280 Holman, M. J., 151 Holmes, A. B., 198, 199 Holmes R. R., 274 277 Holy, 120, 145, 145, 149 Holywell, G. C., 285 Homer, G. D., 79 Honda, H., 145 Horiguchi, M., 165 Horn, H. G., 216, 252, 267 Horner, L.,18, 84 Homing, M. G., 290 Horspool, W. M., 84, 104 Hota, N. K., 2, 224, 288 Houalla, D., 38, 44 Hovanec, J. W., 173 Howe, R. K., 190,257 Howell, J. M., 29, 64, 259 Howells, D., 82, 83 Howlett, K. D., 284 Hudson, H. R., 88 Hudson, R. F., 86, 101, 102, 112, 125, 137, 243,

A.,

290

Hinig, S., 190 Hueske, E. E., 12 Hughes, A. N., 28, 187, 274 Hugl, E., 22, 189 Hui, B. C., 274 Hulla, F. W., 148 Humphrey, R. E., 12 Hung, A., 52,261 Hungerford, L., 73 Hunt, G. W., 284 Hunter, F. E., jun., 167 Huntley, B. G., 19 Hutchins, R. O., 113 Hutchinson, D. W., 143, 162 Hutley, B. G., 33, 251 Ibanez, J. D., 146 Ibrahim, E. H., 284 Ignat'ev, V. M., 73, 288 Ignatova, N. P., 267, 290 Ikehara, M., 119, 145, 153, 155, 156, 282 Il'ina, N. A., 109 Illingworth, B., 160 Il'yasov, A. V., 273 Inamoto, N., 22, 59, 183, 241, 245, 289 Ingold, K. U., 236, 274 Ionin, B. I., 73, 131, 254, 256, 288 Irvine, I., 271 Isaacs, N. S., 8, 66, 246 Isaacs, N. W., 153 Ishizo, H., 122 Ishmaeva, E. A., 77, 276, 286,. 287 Ismagilova, N. M., 52 Ismailov, V. M., 132, 269

Isoe, S., 194 Issleib, K., 3, 4, 7, 78 Itakura, K., 121, 155 Ivanov, B. E., 87, 96, 238 Ivanovskaya, K. H., 57 Ivey, M. C., 292 Ivin, S. Z., 52, 64 Iwashima, A., 162 Iwata, K., 187 Iwata, T., 282 Izawa, O., 175 Jacobson, R. A., 282 Jacques, J., 141 Jaenicke, L.,192 JagodiC, V., 92 Jahns, H.-J., 10, 108 Jakobsen, H. J., 256, 267, 269 Jampel, E., 145 Janik, B., 144 Janssen, E., 225 Janzen, A. F., 136 Jastorff, B., 145, 147 Jencks, W. P., 151 Jenkins, I. D., 77 Jenkins, R. N., 16 Jennings, W. B., 74, 261 Johnson, A. W., 203 Johnson, D. M., 139, 271 Johnson, R. A., 65 Johnson, W. D., 41, 47, 48, 101, 264,275 Johnson, W. S.. 194 Johnston, J. A.; 182 Jolly, W. L., 280 Jones, C. E., 54, 253 Jones, E. R. H., 195 Jones. 5. B.. 182 Jouany, C.,'266 Juds, H., 23 Jugelt, W., 136 Jugie, G., 266 Sung, P., 159 Junkes, P., 3, 253 JuriSek, L., 172 Juvale, C., 157 Kabachnik, M. I., 17, 23, 73,89,103,139,141,145, 218. 219.275. 291 Kabachnik, M.'M., 153 Kainosho, M., 264 Kajiwara, M., 230 Kakurina, V. P., 7 Kalabina, A. V., 75 Kalbacher, B., 152 Kalenskaya, A. I., 208 Kalinin, A. V., 185 Kamai, G. Kh., 52, 56, 57, 58, 69 Kamego, A., 121 Kanai, Y.,145 Kanematsu, K., 11, 241 Kano, T., 4 . Kanter, H., 25 Kapoor, P. N., 4, 288 Kapuler, A. M., 152

Author Index

298 Karimullina, E. Kh., 37 Kashman, Y., 13, 74, 110 Kataeva, V. A., 69 Katchalski, K., 143 Kates, J., 157 Kates, M., 264 Kato, T., 144 Katz, I., 172 Katz, T. J., 30, 46 Katzman, S. M., 93, 247 Kaufmann, G., 156 Kawagisi, A., 292 Kawamoto, I., 47, 254 Kazitsyna, L. A., 275 Kazymov, A. V., 23, 187 Keat, R., 265, 271 Keller, T., 269 Kemp, W., 196 Kennard, O., 7, 153 Kenyon, G. L., 74, 162 Kerek, F., 79, 281 Kerr, C. M. L., 239 Kerr, K. A., 153 Kertes, A. S., 291 Kessel, A. Y., 138 Kessenikh, A. V., 265, 267 Kessler, H., 259 Kettler, M., 151 Khachaturyan, 0. B., 224 Khaddar, M. R., 258 Khaikin, L. S., 282 Khairullin, R. S., 57, 58 Khairullin, V. K., 60, 138 Khalaturnik, M. V., 190 Khalitov, F. G., 276 Khan, S. A., 123 Khan, W. A., 41, 47, 101, 237, 264, 275 Kharrasava, F. M., 287 Khasawinah, A., 124 Khim, C. S., 189 Khomenko, D. P., 224 Khorana, H. G., 153 Khusainova, N. G., 82 Khwaja, T. A., 118, 145 Kifer, E. W., 69 Kilcast, D., 28, 74, 239, 273 Kim, C. S., 19, 21, 269 Kim, Y.-H., 154 Kimball, A. P., 146 Kimura, M., 292 King, J. F., 15, 241 King, R. B., 4, 288 King, R. R., 192 Kirby, A. J., 122, 123, 153 Kireev, V. V., 219, 230, 233 Kirilov, M., 141, 199 Kirizlova, K. M., 187 Kirkpatrick, D., 8, 66, 246 Kirkwood, S., 159 Kirsanov, A. V., 54, 68, 70, 127, 207, 209, 210, 214, 216, 217 Kishida, Y., 47, 254 Kislitsyna, N. M., 99 Kitos, P. A., 158

Kiuchi, K., 183 Kjmen, H., 195 Klebanskii, A. L., 219 Kleinschuster, J. J., 168 Kleinstuck, R., 9, 10, 203, 210,211 Klemperer, W., 278 Klingebiel, U., 222 Klingenfuss, M., 166 Kluba, K., 117 Kluger, R., 163 Klusacek, H., 29 Klusacek, K., 259 Knorre, D. G., 153 Knowles, P. F., 163 Knunyants, I. L., 135, 254 Kobayashi, E., 225, 233 Kobes, R. D., 173 Kochetkov, N. K., 143, 149. Koenig, M., 38, 43, 271 Kosinskaya, I. M., 127, 209 Kosovetsev, V. V., 16,256, 286 Kossel, H., 157 Koster, H., 154 Kottgen, D., 52 Kohl, H., 202 Kolesnik, A. A., 88 Kolesnikov, G. I., 90 Kolesnikov, G. S., 219, 230, 233 Kolesnikova, N. A., 128 Kolodyazhzyi, O., 1, 2, 15 Komatsu, M., 185 Komlev, I. V., 115 Kondo, K., 90 Kondo, N. S., 147, 271 Kondratenko, V. I., 207, 213 Konishi, K., 292 Konickova, J., 291 Konotopova, S. P., 93 Koop, H., 69 Kopay, C. M., 21 Kornberg, R. D., 171 Kornuta, P. P., 208 Korolev, B. A., 142, 218 Korytnyk, W., 160 Kosrov, E. S., 139 Kostikin, L. I., 230 Kostyanovskii, R. G., 3, 290 Kostyuk, A. S., 99 Kotakemori, M., 292 Kotick, M. P., 144 Kotlyar, N. G., 206 Kotovich. B. P.. 128 Kovtun, V. Yu.; 218, 275 Koyama, T., 175 Kozlov, E. S., 127, 215, 216. 224 Kozlova, L. N., 90 Kozuka, S., 112, 247 Kraemer, R., 141, 270 Kraihanzel, C. S., 116 Kranz, E., 18 Krasil’nikova, E. A., 54, 77, 87

Kraus, J., 126 Krawiecka, B., 141, 271 Kreiser, T. H., 144 Kren, R. M., 18 Kresze, G., 202 Kreutzkamp, N., 98 Krivin, S. K., 129 Krivosheea, I. A., 77 Krivun, S. V., 87 Kroeker, K., 153 Krokhina, S. S., 87 Krupnov, V. K., 46 Krutskii, L. N., 56 Kubo, M., 199 KuEerovB, Z., 145 Kuchen, W., 132, 141 Kucherova, M. N., 213 Kuchitzu, K., 279 Kuczkowski, 5. A., 82,283 Kuczkowski, R. L., 278, 279 Kudryavtseva, L. A., 96 Kugel, R. L., 235 Kuhn, S. J., 210 Kuhtz, B. H., 212 Kukhar, V. P., 206, 207, 209, 214 Kukhin, V. P., 127 Kulibaba, N. K., 70 Kulik, S., 248 Kuramshin, I. Y., 140 Kurata, Y., 111 Kuriyama, K., 282 Kurz, J., 98 Kurz, K., 121 Kuwajima, I., 111 Kuzminski, B. N., 218 Kwan, T., 236, 273 Kyllingstad, V. L., 15 Kyogoku, Y., 264 Labarre, J.-F.,51, 224,277 Labarre, M. C., 282 L’Abbe, G., 185 Lacey, J. C., jun., 151 Lachmann, B., 160 Laemmerhir, K., 98 Laffler, T., 152 Lake, A. W., 182 Lam, C. W. K., 162 Lambert, J. B., 256 Lambeth, D. O., 167 Lamotte, A., 291 Lampin, J.-P., 201 Landor, P. D., 202 Landor, S. R., 202 Lane, M. D., 164 Lang, H. J., 178 Lapin, A. A., 7 Lappert, M. F., 60 Lardy, H. A,, 167 Larkin, J., 65 Larsen, B., 174 Larson, A. C., 153 Larsson, P. O., 162 Lassmann, G., 273 Lau, P. T., 1 Laurenco, C., 43 Laurent, J. P., 266 Lavielle, G., 8

Author Index

299

Lazareva, M. V., 132 Lazukina, L. A., 206 Leanza, W. J., 166 Le Corre, M., 190 Leder, P., 157 Lednicer, D., 188 Lee, I. Y., 274 Lee, J., 244 Lee, P. L., 52, 279 Lee, W. W., 147 Lehn, 5. M., 263 Leibovici, C., 224 Leissring, E., 7, 78 Leloir, L. F., 159 Lentz, A., 52, 277 Lequan, R. M., 256, 68 Lesser, J. H., 126 Le Strat, G., 127 Letcher, J. H., 251 Letsinger, R. L., 156 Letters, R., 169 Leva, M. A.. 221 Levas, E., 182 Levin, Y. A., 238, 273 Levy, J. B., 24, 59, 73 Lewars, E. G., 15, 241 Leyshon, L. J., 103, 241 Lezius. A. G.. 156 Liaaen-Jensen, S., 195 Liang, C. R., 165 Licht, E., 227, 228 Liedhegener, A., 84, 138 Lieske, C. N., 140, 173 Lightener, D. A., 183 Lim. P. K. K.. 48. 248 Lin,’Y., 173 Lincoln, S. F., 258 Lindner, C., 9 Lindner, E., 13, 78 Liober. B. G . . 141 Lipatova, 1, P., 276 Lipsky, S. R., 250 Lisovskii, I. P., 292 Listowsky, I., 168 Litoshenko, N. A., 213 Litovchenko, N. R., 208 Littauer, U. Z., 156 Littlewood, P. S., 246 Litvinenko. L. M., 127 Llinas, J., 88 Lloyd, D., 11, 188 Lloyd, D. R., 51, 281 Llovd. G. J.. 123 Lobanov, D: I., 291 Locksley, H. D., 183 Loewengart, G. V., 35, I

105

,

Loginova, E. I., 258, 265, 266 Logothetis, R. S., 180 Lohrmann, R., 147 Lohs, K., 273 Longmuir, G. H., 224 Looker, B. E., 246 Lopez, L., 48, 104 Lord, E., 188 Losi, S. A., 258 Lowe, C. R., 162 Lowe, M., 148 Luber, J., 49, 111, 274

Lucken, E. A. C., 272 Luckenbach, R., 15, 18 Luderer, T. K. J., 49, 240 Lugovkin, B. P., 92 Lumbroso, H., 286, 287 Lustig, M., 205 Lutsenko, I. F., 90, 99 Lynch, D. M., 79 Lyons, A. R., 238, 239, 272, 273 Lythgoe, B., 246 Lyznicki, E. P., 126 McCarry, B. E., 194 McColeman, C., 13, 245 McConnell, H. M., 171 McEwen, G. K., 109, 141, 267

McEwen, W. E., 15 McFarlane, H. C. E., 264 McFarlane. W.. 264 Machin, A: F.,’292 MacKay, W. D., 195 McKennon, D. W., 205 Mackey, J. K., 156 McKinley, S. V., 176, 180 McMurray, T. B. H., 57 McNeilly, S. T., 52, 77, 84, 104 Macomber. R. S.. 111 M cPhail, A. T., 282 M aeba, I., 190 M agerlein, H., 183 M arkl, G., 24 M aichuk, D. T., 151 M aier, J. P., 281 M aier, L., 78, 89, 92, 142 M‘aikova, A. I., 87 M aitra, U. S., 159 M ‘ajewski, P., 132 M[ajewski, P. J., 89 Mjajoral, J. P., 141, 270 M .akitie, O., 142 M ;alakhova, I. G., 291 M[alevannaya, R. A., 89 M[alherbe, J. S., 15, 189, 254 Mammino, J., 225 Mamonov, V. I., 90 Mancuso, A., 112 Mandel, N., 137 Mankowski-Faveli, R., 253 Mann, B. E., 252,258,266, 268 Manscher, O., 256 Manson, W., 172 Mareev, Yu, M., 90 Maria, P. C., 142 Marjoral, J. P., 142 Markl, G 269 Markovskh, L. N., 275 Marquarding, D., 29, 259 Marr, P. W., 182 Marschner, F., 23, 218, 252 Marshall, G. E., 284 Marsi, K. L., 18, 31, 79, 80, 245, 260 Marsmann, H., 267 Martin, M., 138

Martin, R. H., 196 Martynyuk, A. P., 209 Maryanoff, B. E., 113 Mashoshina, S. N., 90 Maslennikov, V. P., 126 Mastalerz, P., 139 Masters, C., 258 Mastryukova, T. A., 17, 23, 132, 141, 275, 291 Matheson, I. B. C., 244 Matheson, N. K., 160 Mathey, F., 33, 201, 253, 286. Mathiaparanam P., 41 Mathis F 109’270 Mathis: R:: 277 Matrosov, E. I., 23, 103, 218, 275, 287 Matschiner, H., 3 Matsumura, C., 279 Matysiak, Z., 292 Maumy, M., 82 Maxwell, E. S., 159 Mazepa, I. K., 68 Mazhar-ul-Haque, 35, 268 Mebazaa, M. H., 19 Medved, T. Ya., 275 Medvedeva, M. D., 114 Meister, A., 173 Mellor, M. T. J., 19, 33, 251, Melnikov, L. L., 133 Mel’nikov, N. N., 267 Merz, A., 24, 269 Meunier, J. C., 233 Meyer, G., 183 Meyers, A. I., 195 Mhala, M., 121 Michalski, J., 89, 113, 128, 132, 141, 271 Michel, R., 176 Mift’akhova, A. Kh., 275 Mikhailova, 0. B., 133 Mikhailvuchenko. N. K.. 209 Mikolajczyk, J., 113 Mikolajczyk, M., 141, 264 Miller, B., 104 Miller, 5. A., 52, 58, 65, 71, 76, 77, 80, 84, 94, ~~

104

Min, T.-B.T 237, 272 Minami, T., 19, 178, 180 Mingaleva, K. S., 286 Mirttinen, S., 142 Mislow, K., 13, 21, 27, 29, 71, 137,259,263 Missen, A. W., 271 Mitchell, A. R., 158 Mitchell, C. M., 46 Mitchell, E. W., 89 Mitchell, H. L., 64 Mitsch, C. C., 251 Mitsch. R. A.. 63 Mitschke, K.IH., 32, 62, 259

300 Mitsunobu, O., 12, 117 Miyata, Y., 145 Mizrakh, L. I., 90 Moddeman, W. E., 280 Moeller, T., 207, 215, 225 Moller, U., 4 Moffat, J., 93, 247 Mohanty, R. K., 291 Moll, E., 44, 98 Molotkovsky, J. G., 170 Molyavko, L. I., 103, 209 Monaghan, J. J., 285 Mondig, F., 226 Monson, R. S., 127 Montgomery, J. A., 160 Moore, D. R., 225 Moore, J., 205 Moreland, C. G., 251 Morgan, W. E., 280 Mori, Y., 185 Morimoto, S., 168 Morioka, S., 119, 145, 153 Moritani, I., 182 Morkovin. N. V.. 254 Morozova, I. D.,*273 Morris, C. R., 292 Morris, D. G., 204, 235, 283 Mortell, T. R., 201 Mosbach, K., 148, 162 Mosbo, J. A., 267 Moskova, 0. F., 129 Moskva, N. A., 77, 87 Moskva, V. V., 69,87,132, 269 Mostyn, R. A., 280 Motherwell, W. D. S., 7, 153 Mousseron-Canet, M., 195 Mu, P. T. K., 162 Muller, D. G., 192 Muter, B., 183 Muetterties, E. L., 29, 64, 259 Mukaiyama, T., 117, 155, 246 Mukasa, S., 202 Mukhacheva, 0. A., 84 Mukhametov, F. S., 57 Mukhametzyanova,. E. Kh., 61 Muller, A., 142 Mundrv. K. W.. 158 Munoi‘A., 38; 43, 114, 371

L.11

Munsch, B., 263 Murakami, Y., 121, 122 Muramova, A. A., 140 Murano. A.. 292 Murata,‘M.; 11, 241 Muratova, A. A., 114, 276 Murayama, A., 147 Murch, R. M., 233 Mureyama, K., 143 Murray, M., 37, 216, 261 Murray; R. -K.,-137 . Mushika, Y., 170 Musina,+A. A., 138, 276 Muslinkin, A. A., 67

Author Index Mutalapova, R. I., 258 Mutterer, F., 120, 236 Myers, T. C., 166, 251 Naan, M. P., 6, 188, 241 Nagase, M., 292 Nagyvary, J., 151 Nakajima, A., 274 Nakamura, A., 4 Nakamura, K., 233 Nakamura, T., 292 Nakanishi, A., 112, 128, 247 Nakayama, S., 241 Nakazato, H., 157 Napier, R. P., 109 Narang, S. A., 121, 155 Nasonovskii, I. S., 287 Natsume, M., 183 Natusch, D. F. S., 271 Naumov, V. A., 285 Navech, J,, 141, 142, 270 Naylor, H. G., 229 Naylor, R. A., 134 Naylor, R. N., 172 Nazar, R. N., 152 Nazarov, Yu. V., 67 Nazvanoya, G. F., 69 Nechaev, Y. D., 131 Negrebetskii, V. V., 265, 267 Neilson, G. W., 238 Neilson, T., 154 Neimysheva, A. A., 254 Nelsestuen, G. L., 159 Nemysheva, A. A., 135 Nesmeyanov, N. A., 185 Nesterov, L. V., 88, 138, 258 Neumann, R. M., 278 Neumann, U., 183 Newman, M. S., 67 Ng, T. W., 2, 288 Nicholson, D. A., 101, 131 Niecke, E., 205, 226, 265 Nierlich, F., 61, 238 Nifant’ev, E. E., 99, 113, 115, 118, 168, 211, 263, 287 Nikaido, H., 158 Nikolaev, A. F., 225, 233 Nikolaeva, V. G., 84 Nikolenko, L., 125 Nikonorova, L. K., 265 Nikonova, L. Z., 55, 56, 1n4

Nishida, S., 182 Nishino, H., 162 Nishishita, T., 258 Ni?$waki, T., 10, 90, 93, L I 1

Nitzsche, S., 233 Nixon, J. F., 265 Nohara, A., 145 Nohira, H., 1 Nomura, H., 168 Nonhebel, D. C., 65 Norman, A. D., 2 Norton, B. G., 285

Norton, I. L., 173 Norwitz, G., 280 Nose, Y., 162 Novikova, Z. S., 90, 275 Noyce, D. S., 115, 135 Nuretdinov. I. A.. 265. 266, 272 ’ Nuretdinova, 0. N.,. 55,56, . 104 Nurtdinov, S. Kh., 52, 57. 5 8 Nussbkum, A. L., 151 Nye, M. J., 77 Nys, J,, 187 Oae, S., 112, 128, 247 O’Bryan, J. M., 162 O’Connor, T. J., 2, 288 Odenwtilder, H., 24 Oehling, H., 27, 281 Oehme, H., 3, 7, 78 Ogata, Y., 13, 31, 78, 97, 23 8 Ogawa, H., 196, 199 Ogilvie, F. B., 267 Ogilvie, K. K., 153 Ogura, K., 175 Ohlsson, R., 148, 162 Ohoshi, S., 292 Ohshiro, Y., 185 Ohtsuka, E., 119, 145, 153 Ohya-Nishiguchi, H., 274 Ojala, D., 151, 152 Okada, T., 13 Okamoto, Y., 129, 138 Okawara, R., 13 Okazaki, R., 59, 241, 289 Okram, R. K., 53 Okruszek, A., 128 Okulevich, P. O., 230 Oliver, W. L., 256 Omelanczuk, J., 141, 264 Ondracek, L., 226 O’Neill, I., 195 Onodera, M., 174 Oppenheimer, A. W., 77 Oram, R. K., 30, 33, 137, 260 Orgel, L. E., 147 Oritani, T., 195 Oro. J., 146 Orth, D., 11 Orth, H. D., 143 Ortiz de Montellano, P. R., 244 Osadchenko, I. M., 79 Osborne, M. J., 159 Oshima, S., 258 Osipov, A. P., 258 Osipova, L. F., 230 Osokin, D. Y., 272 Ossip, P. S., 135 Ostanina, L. P., 87 Ostrogovich, G., 79, 281 Oswald, A. A., 126 Otsuka, H., 282 Otsuka, S., 4 Ouchi, A., 207, 215 Ovchinnikov, V. V., 276

301

Author Index Owen, G. R., 154 Ozbirn, W. P., 282

Pollard, G., 210 Polyakov, V. A., 258 Pomazanov. V. V.. 55. 104 Pongs, O., 146 Poon, R., 157 Popilin, V. P., 219 Popjhk, G., 174 Pouolin. V. P.. 233 Popovych, 0.,’291 Porter, L. J., 271 Portnoy, N. A., 82, 283 Posternak, T., 152 Potapov, A. M., 54 Potapov, V. K., 153 Poulter, C. D., 174 Powell. R. L.., 6., 32. 49. 24 1,‘255 Prabha, S., 121 Preer, J. R., 279 Prmtrazhensjkaya, N. N., ~~

Paddock, N. L., 223, 232, 23 5

Padilla, A. G., 139, 271 Painter, A. A., 167 Pan, C. S. J., 195 Panda, C. A., 248 Pantzer, R., 52 Parmeggiani, A., 151 Parodi, A. J., 159 Patel, H. A., 2, 288 Patel, N. K., 76 Patel, R. N., 174 Paterson, M. C., 173 PatoEka, J., 173 Paul, J. W., 235 Paulsen, H., 199 Pavlenko, V. A., 289 Peake, S. C., 30, 31, 63, 64, 258, 261 Pechet, M. M., 120, 236 Peguy, A., 258 Peiffer, G., 42, 88, 96 Pelavin, M., 280 Penev, P., 187 Pen’kovskii, V. V., 218, -Ai1n7

Pennington, S. N., 292 Perahia, D., 153 Perekalin, V. V., 132, 275 Peretz. J.. 136 Perkins, P. G., 224, 277 Perry, R. W., 284 Peterson, W. R., 210 Petrov, A. A., 16, 37, 42, 60, 74, 93, 96, 131, 254, 286, 288, 289 Petrov, E. S., 29, 73 Petrov, G., 141, 199 Petrova, M. V., 96 Petrovskii, P. V., 23, 141 Pfeuffer, T., 160, 161 Pfohl, S., 29, 259 Pfuller, H., 195 Phillips, L., 52, 252 Phillips, W. G., 107 Pickel, H. H., 216, 217 Piers, E., 195 Pietrusiewicz, M., 132 Pigenet, C., 287 Pilgram, K., 210 Pilot, J. F., 29, 35, 43, 259, 268, 270 Pinchuk, A. M., 127, 209, 275 Pinkerton, A. A., 275 Piskala, A., 177 Pitina, M. R., 227 Plakhanov, V. G., 3, 290 Plekhov, V. P., 276 Ploger, W., 92, 130, 131 Plotnikov, V. F., 73, 288 Pohl, H. H., 26 Pokrovskii, E. I., 101, 277 Polakis, S. E., 164 Pollard, D. R., 235

I

~

1L.J

Priess, H., 158 Prince, R. D., 183 Proctor, W. G., 280 Prokof’ev, M. A., 153 Prons, V. N., 219 Protsenko, L. D., 214, 280 Prout, C. K., 284 Pudovik, A. N., 7, 37, 56, 60, 76, 77, 82, 90, 99, 114, 135, 138, 140, 269, 275, 276, 286, 287 Pudovik, M. A., 276, 286 Puiseux-Dao, S., 280 Pujol, R., 270 Pullman, B., 153 Purdela, D., 252 Pusalkina, A. M., 87 Quick, J. E., 287 Quillinan, A. J., 183 Quin, L. D., 183,253, 256, 282 Radda, G. K., 171, 271 Radler, R., 225 Radscheit, K., 202 Raevskaya, 0. E., 82, 269, 275 Raevskii, 0. A,, 39, 276 Raftery, M. A., 256 Raylin, L. I., 254 Raigorodskii, I. M., 230, 233 Rainer, W., 233 Rajagopalan, P., 187 Rakov, A. P., 275 Rakshys, J. W., jun., 176, 180 Ramel, A., 151 Ramirez, F., 29, 35, 43, 105, 259, 268, 270, 283 Rammler, D. H., 149 Rane, D. F., 57 Ranganathan, S., 248 Rankin, D. W. H., 285 Rao, V. V. K., 142 Raphael, A., 126 Rapoport, H., 194 Rast, H., 258

Rast, M., 74 Rath, U., 156 Ratner, M. A., 51 Ratovskii, G. V., 75 Ratts, K. W., 107 Rauk, A., 29,259 Raulet, C., 182 Rausch, H., 24, 269 Rawlings, H. L., 233 Raymond, K. N., 283 Razumov, A. I., 54 69 77, 84, 87, 132, 141,’266 Razumova, N. A., 37, 41, 42, 46, 60, 74, 96, 286, 288 Razvodovskaya, L. V., 133 Readio, P. D., 10, 77 Redmore, D., 241 Rees, R. G., 88 Reese, C. B., 118, 145, 154 Regitz, M., 84, 138, 269 Reich, E., 152, 156 Reichel, L., 10, 108 Reiss, E., 3 Reiss, J. G., 69 Renz, M., 147 Reuben, J., 171 Reutov 0. A 185 Revel. b..295 Reverman, L. F., 144 Reza, M. J., 169 Rice, V. T., 102 Richards, J. B., 159 Rjchards, R. E., 171, 2 1 Richardson C. C 157 Richtaski, k.. 139’ Rigby, C.*W.; 188 Rilling, H. C., 174 Rjtchie, E., 178 Rizpolozhenskii, N. I., 54, 57, 135 Robberson, D. L., 158 Robert, D. U., 69 Robert, J. B., 271, 278 Roberts, B. P., 236, 272, 273 Roberts, J. D., 267 Robins, R. K., 143, 147 Robinson, W. H., 174 Robison G. A 143 Rockstr&h, C.1’3 Rodnyanskaya E. R 49 Roesky, H. W?., 205;’206, 212, 213, 225, 265 Rogers, P. E., 237 Rohlk, K., 279 Romanov, G. V., 7 Ronen, H., 13 Roop, B. L., 292 Roop, W. E., 292 Rose, G., 290 Rose, I. A., 163 Rosenberg, H., 165 Rosenberg, M., 158 Rosenthal, A. F., 170 Ross, F. K., 283 ROSS, S. E., 225 Rossi, G., 292 Rothius, R., 49, 240 Roundhill, D. M., 77

302 Rowe, M. J., 156 Roy, S., 151 Roychoudhury, R., 157 Rozanski, L., 287 Rubasheva, L. M., 275 Rubashevskaya, V., 17,291 Rudavskii, V. P., 207, 21 3 Rudolph, R. W., 253, 266, 278 Ruell, T., 127 Runge, W., 202 Ruschig, H., 202 Rusek, P. E., 10 Rusiecki, W., 280 RUSS,C. R., 71 Russell, J. W., jun., 183 Ruth, E., 202 Rutherford, J. S., 284 Ryan, E., 161 Ryl’tsev, E. V., 275 Sabherwal, I. H., 71 Sabin, J. R., 51 Saffhill, R., 154 Safin, I. A., 272 Saikachi, H., 196, 199 Saito, H., 224, 230, 233 Saito, T., 93, 271 Sakan, T., 194 Sakodynskaya, T. P., 211 Saksena, A. K., 246 Sakurai, H., 129, 138 Salakhutdinov, R. A., 52, 57, 87, 141 Salikhov, S. G., 258 Salomon, Y., 148 Salser, W., 157 Sam, T. W., 245 Samarai, L. I., 215 Samitov, Y. Y., 138 Sammes. P. G.. 246 Sampson, E. J.; 125 Sanchez, M., 44 Sanders, J. K. M., 257 Sandmann, H., 31, 253 Sanger, F., 157 Sanno, Y., 145 Sano, T., 12 Saran, A., 153 Sarantakis, D., 192 Sargent, M. V., 198, 199 Sasaki, T., 11, 185, 241 Sasse, K., 58 Satchell, D. P. N., 163 SatgC, J., 39, 72 Sato, K., 196 Sato, M., 236, 273 Sato, S.-J., 111 Saunders, D. G., 103, 241 Saunders, V. R., 51, 277, 28 1 Saussez, R., 27, 239 Savchenko, L. Ya., 94 Savelova. V. A.. 127 Savelpevh, N. I.’, 99 Savicheva, G. A., 141 Savignac, D., 120 Savignac, P., 49

Author Index Saxon, G., 158 Scarlata, G., 287 Schadenberg, H., 190 Schafer, H., 71 Schafer, W., 26, 27, 281 Schaffer, O., 27, 244 Schattka, K., 145 Scheider, D. F., 15 Scheinmann, F., 183 Scheit, K. H., 144 Scherer, A., 125 Scherer, H., 269 Schiemenz, G. P., 15, 74, 258, 277, 279, 280, 290 Schiller, H. W., 253, 278 Schindler, N., 92, 130 Schliebs, R., 120 Schlosser, M., 177, 180 Schmidbaur, H., 32. 62, 176, 216, 217, 258, 259, 248 Schmidpeter, A., 49, 89, 91, 111, 203, 220, 221, 223, 274 Schmidt, U., 132, 241 Schmidt-Samoa, E., 98 Schmutzler, R., 30, 31, 37, 39, 63, 64, 69, 70, 204, 216,. 217, 258, 261 Schneider, D. F., 189, 254 Schubert, G., 136 Schuessler, D., 102 Schultz, C. W., 266 Schulz, D. N., 15 Schuman, D. A., 143 Schwartz, J. H., 172 Schweig, A., 27, 281 Schweiger, J. R., 31, 63, 27 1 Schwkzer, E. E., 19, 21, 23, 42, 178, 180, 189, 191. 254. 269 Schwendeman, R. H., 52, 279 Schwyzer, R., 148 Scott, M., 148, 162 Seel, F., 53, 62, 85, 110, 253. 268. 290 Seeliger, A’., 10, 246 Selinger, Z., 148 Selve, C., 18, 246 Semashko, V. N., 285 Semenii, V. Ya., 207, 214 Semenii, Y. Y., 127 Senges, S., 282 Senkler, G. H., 71 Sepulveda, L., 121 Serafini, A., 51, 277 Sergeev, G. B., 258 Sergeeva, V. P., 126 Sergeyev, N. M., 255 Seto, S., 175 Seyferth, D., 84 Shabana, R., 92 Shabarova, Z. A., 153 Shagidullin, R. R., 276 Shahak, I., 136 Shakirova, M. A., 275 Shapoval, G. S., 219 Sharp, D. W. A., 64

Shatenshtein, A. I., 73, 29 1 Shaver, A.. 220 Shaw, B. L., 258, 268 Shaw, N., 171 Shaw, R. A., 231,284, 290 Shchelkina, E. P., 187 Shealy, Y. F., 160 Shen. T. Y.. 158 Sheleton, R:, 157 Shermergorn, I. M., 61 Shevchenko, V. I., 70, 127, 208, 209 Shevchuk, M. I., 10, 177, 187, 190 Shibata, T., 279 Shikanian, K., 153 Shila, S. I., 68 Shilov, I. V., 99 Shimada, Y., 109, 119 Shimomura, M., 168 Shipov, A. E., 141 Shirankov, D. F., 213 Shmukler, H. W., 292 Shokol, V. A., 103, 207, 209, 210 Shook, H. E., jun., 183 Shostenko, A. G., 61 Shpak, S. T., 10 Shtepanek, A. S., 217 Shuikin, N. I., 56, 69 Shukla, R., 98 Shurukhin, B. B., 37, 96 Shushunov, V. A 126 Shvetsov-Shilovsl&. N. I.. 227, 290 Shvetsov-Shilovskii, Y., 267

Sidky, M. M., 92 Siewers, 1. J., 168 Silman, I., 143 Sim, G. A., 182 Simalty, M., 19, 185 Simon, L. N., 143, 147 Simonnin, M. P., 256, 261, 268 Simpson, P., 107 Sinanoglu, O., 281 Singer, M. F., 156 Singer, M. I. C., 11, 188 Singh, H., 282 Sisler, I-I. H., 18 Sklarz, B., 247 Skoda, J., 145 Skul’skaya, N. Ya., 214, 280 Skvortsov, N. K., 254 Skylarskii, L. S., 118 Slade, R. M., 258 Slater, E. C., 274 Sletzinger, M., 166 Smakhtin, L. A., 292 Smets, G., 185 Smith, B. C., 284 Smith. C. P.. 29. 35. 259. 268’ Smith, D. J. H., 133, 179 Smith, D. J. M., 53, 137 Smith. J. E.. 52. 279 Smith; M. A., 156 I

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303

Author Index Smrt, J.. J., 154 Smyrl, T. G., 136 Smythe, R. J., 13, 245 Snider, T. E., 18, 270 Snyder, C. D., 194 Snvder. E. I.. 8 Snider; S. L.’, 172 Sokal‘skaya, L. I., 101 Sokal’skii, M. A., 52, 64 Sokolov, M. P., 141 Sokurenko, A. M., 118 Soliman, F. M., 92 Solodushenkov, S. N., 206 Solomonovici, A., 200 Sommer, K., 252 Sommer, R. G., 144 Sondheimer, F., 198, 199 Sorm, F., 143 Sorokina, T. D., 90 Soulen, R. L., 182 Southern, E. M., 158 Sowerby, D. B., 226, 227 Spector, L. B., 172 Spencer, N., 163 Spivak, L. L., 291 Sprecher, M., 163 Sprinson, D. B., 163 Spruegel, W., 187 Stabrovskaya, L. A., 82, 269 Stache, U., 202 Stackhouse, J., 263 Stadelmann, W., 70, 204, 217 Stadnichuk, M. D., 183 Stade, W., 25 Stahler, H., 268 Stainbank, R. E., 258, 268 Stanko, J. A., 235, 284 Starkovsky, N. A., 154 Stary, H., 221 Stead, A., 171 Stec, W., 128, 207 Stec, W. J., 255, 265, 280 Steele, J. C. H., 282 Stegmann, H. B., 212, 237 Stein, M. T., 235, 284 Steinberg, G. M., 140 Steinmetzer, H.-C., 190 Stelzer, O., 70, 204, 217 Stepanov, B. I., 224, 231, 279 Stephani, R. A., 173 Sternbach, H., 144 Stevenson, G., 94 Stevenson, G. M., 76 Stevenson. R., 65 Steward, J. HI, 292 Stille, J. K., 85 Stockdale, B. R., 65 Stocks. R. C.. 256 Stocker, F., 212, 237 Stoll, H., 52 Stoll, K., 221 Stone, F. G. A., 46 Stone, K. J., 175 Straus, D. B., 143 Streeter, D. G., 156 Strizhov, N. K., 90 Stroh, E. G., 235

Strominger, J. L., 161, 175 Struck, R. F., 160 Strukov, 0. G., 64 Strzelecka, H., 178 Stubbe, J. A., 162 Stuhler, H., 32, 176, 258 Stukalo, E. A., 70 Sturtz, G., 126 Suard, M., 280 Sudakova, T. M., 76, 90 Suerbaev, Kh. A., 23 Sugaya, H., 183 Suggs, J. L., 81, 130, 289 Sukhorukova, N. A,, 75 Suleimanova, M. G., 85 Sultan, M. K., 247 Sultanova, D. B., 87 Sumskaya, E. B., 23, 187 Sunamoto, J., 121, 122 Sundaralingam, M., 284 Suoboda, P., 2 Susz, B. P., 258 Sutcliffe, L. H., 252 Sutherland, E. W., 143 Sutherland, J. K., 245 Suzuki, H., 233 Suzuki, Y., 185 Svergun, V. I., 90, 279 Swan, J. M., 16 Swank, D. D., 43, 270 Swartz, W. E., jun., 254 Swiatek, K. R., 147 Symes, K. C., 77 Symmes, C., 24, 59, 73 Symons, M. C. R., 51,238, 239, 272, 273 Szab6, L.! 168 Szutowski, M., 280 Tachikawa, R., 195 Taft, A., 32 Tagaki, W., 122 Tait. B. S.. 48. 248 Tajima, K:, 155 Takahashi, M., 183 Takahashi, Y.,281 Takaku, H., 109, 119 Takanisji, T., 144 Takeuchi, Y., 10, 246 Takizawa, T., 6, 189 Tamura, C., 47, 254 Tan, H.. 141 Tan; S. A., 292 Tana, I., 122 Tanaka, H., 292 Tang, R., 27, 263 Tani, K.. 4 Tanner, W., 159 Tarasevich, A. S., 218 Tarasova, R. I., 99 Tasaka, K., 35, 105 Tate, M. E., 292 Tatsuta, K.,175 Taunton-Rigby, A., 154 Taylor, M. V., 246 Taylor, N. F., 169 Taylor, R. C., 257 Taylor, W. C., 178 Tazawa, I., 156 Tchanyi, B., 265

rebby, J. C., 6 reraji, T., 182 Terent’eva, S. A., 286 rereshchenko, G. F., 254 Tesoro, G. C., 225 Tesser, G. I., 148 Teste, J., 128 Tewari, R. S., 98 Texier, F., 185 Thakur, C. T., 284 Thaller, V., 195 Thamm, H., 226 Thanwalla, C. B., 140 Thedford, R., 143 Thiem, J., 199 Thompson, A. R., 102 Thomson, C., 28, 74, 239, 273 Thorstenson, P. C., 97, 244 Tidwell, T. T., 125, 126 Tikhonina, N. A., 219 Timmler, H., 98, 121 Timofeeva, T. N., 256 Timokhin, B. V., 1, 75, 76 Titov, S. S., 142 Tkachenko, E. N., 217 Tokunaga, H., 183 Tolochko, A. F., 177 Tomaszewski, M., 149 Tomilov, A. P., 79 Toropova, V. F., 275 Torrence, P. F., 143, 155 Toscano, V. G., 84 Tossidis, I., 142 Towns, R. L. R., 283 Trachtman, M., 280 Tran’kova, N. A., 1, 76 Traynard, J. C., 88 Trefonas, L. M., 73, 283 Treon, K., 74, 258 Tribout, J., 196 Trigalo, F., 168 Trippett, S., 30, 33, 53, 74, 133, 137, 179, 258, 260 Tronchet, J. M. J., 199 Trotter, J., 235 Troy-Lamire, D., 28 1 Trutneva, E. K., 238 Tsay, F. D., 279 Tsentovskii, V. M., 287 Tsivunin. V. S..I 52., 56.I 57, 58‘ Ts’o, P. 0. P., 146,147,271 Tsolis, E. A., 29, 35, 105, 259 Tsou, K. C., 153 Tsuchiva. T.. 175 Tsuda,-E:, 182 Tsuda, Y., 173 Tsuji, H., 258 Tsujimoto, N., 128, 247 Tsvetkov, E. N., 73, 89, 29 1 Tsyba, V. T., 216 Tu, S. I., 167 Tucker, P. A., 284 Tudrii. G. A.. 42. 96 Tukhar, A. A’., 210 Tulloch, C. D., 196

304 Tunggal, B. D., 269 Turchinsky, M. F., 149 Turnblom, E. W., 30, 46 Turner, D. M., 169 Turner, D. W., 281 TurDin. R.. 281 Tusek, ‘Lj.,.92 Tusl, J., 280 Twitchell, D., 32 Tzschach, A., 3 Ubasawa, M., 145 Uchida, M., 111 Uchtman, V. A., 284 Udy, P. B., 205 Uesugi, S., 282 Ugi, I., 29, 259 Ulrich, S. E., 72, 266, 268 Umezawa, S., 175 Underwood, W. G. E., 246 Urushibara, T., 174 Urzhuntseva, E. K., 291 Ustynyuk, Y. A., 255 Utvary, K., 214, 216 Uzlova, L. A., 199 Vafina, A. A., 273 Vagelos, P. R., 171 Vaisberg, M. S., 141 Valitova, L. A., 87 van Boom, J. H., 154 Van der Kelen, G. P., 287 Vandi, A., 207, 215 Vandoorne, W., 284 Van Dormael, A., 187 Van-Dyke, C. H., 69 Van Etten, R. L., 172 Van Gelder, B. F., 274 Van Leemput, R., 233 van Tamelen, E. E., 194 Van Wazer, J. R., 64, 187, 214, 220, 251, 255, 265, 278, 279, 280 Vargas, L., 170 Varvoglis, A. G., 87, 130 Vasil’ev, A. F., 267 Vasyanima, M. A., 138 Vaughan, M. H., jun., 157 Vaughn, H., 101, 131 Vaziyanova, P. F., 129 Vedejs, E., 8 Veillard, A., 51, 277 Velleman, K. D., 53, 62, 85, 110, 253, 268, 290 Venanzi, L. M., 2 Venezky, D. L., 287 Vere Hodge, R. A., 195 Verhelst, A., 61, 238 Verkade, J. G., 109, 141, 267 Versino, B., 292 Vesper, J., 3, 253 Vikane, T., 89, 141 Vilkas, M., 118, 145 Vilkov, L. V., 282 Villieras, J., 8 Vilsmaier, E., 187 Vincent, A. T., 283 Vinogradov, B. A., 289

Author Index Vinogradova, V. S., 42, 90, 96 Vinot, G., 51, 277 Virgilio, J. A., 115, 135 Viterbo, R., 141 Vizel, A. O., 46, 57, 275 Vizgert, R. V., 138 Vnek, J., 163 Vogel, E., 198 Vogt, w., 110 Voigt, D., 281, 282 Volashin, M. P., 138 Vollhardt, K. P. C., 196, 198, 199 Voloboeva, L. V., 69 Volynskaya, E. M., 187 von Philipsborn, W., 264 Vornberger, W., 176, 268 Vouros, P., 290 Voziyanova, 0. F., 87 Voznesenskaya, A. K., 42, 96 Wachob, G. D., 183 Wada, M., 12 Waddington, T. C., 251 Wadsoe, I., 291 Wagner, A. F., 158 Wagner, A. J., 224, 235, 284

Wagner, E. L., 278 Wahl, G. H., 257 Waite. N. E.. 6 Wakagawa, h., 196 Wakeford, D. H., 118, 119 Waki, H., 292 Wakselman, M., 118, 145 Walker, B. J., 74, 177, 258, 262 Waller. R. L.. 86. 137.243. 290 Walsh, E. J., 228, 231 Walters, D. B., 257 Wampler, D. L., 153 Wander, J. D., 82, 283 Wanek. W.. 226 Wang, J. H:, 167 Wang, T., 172 Ward, D. C., 156 Ward, T. M., 257 Warren, S., 82, 83, 153 Warren, W. A., 165 Washburne, S. S., 210 Wasserstein, P., 163 Waters, J. A., 155 Watson, D. G., 153 Watts, G. B., 236, 274 Weatherall, I., 254 Weatherburn, D. C., 291 Webb, S. B., 61, 129, 238, 29 1 Weber, J., 265 Wedler, F. C., 174 Weeks, J. E., 88 Weetall, H. H., 161 Wehman, A. T., 178 Wehrli, F. W., 256 Weibel, M. K., 161 Weichmann, H., 4 Weidlein, J., 32, 62, 259 I

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I

,

Weigert, F. J., 267 Weingand, A., 220 Weinstein. B.. 192 Weisheit, -W.,’265 Weiss, D., 10 Werstiuk, E. S., 154 Westheimer, F. H., 27, 131 Wetzel. R. B.. 74 Whalley, W. B 192 Wheatley, P. J.Y283 White, D. W., 32, 34, 49, 113, 141, 255, 260, 263 White, G. F., !63 White, W. E., jun., 151 Whitehead, M. A., 219, 224, 272 Whitesides, G. M., 64 Wieland, T., 119, 166, 246 Wiesner, K., 195 Wjesner, K. J., 195 Wightman, R. H., 121, 155 Wilchek, M., 148 Wilkerson, C., 245 Wilkes, J. S., 156 Wilkinson, G., 77 Williams, A., 134, 172 Williams, B. C., 76, 94 Willjams, D. H., 257 Williams, F., 239 Willjams, J. C., 82, 283 W/ll!ams, V. P., 174 Willis, B. J., 246 Willson, M., 109 Wilson, D. B., 159 Wilson. D. P.. 144 Wilson; I. B., ’172 Wilt, E. M., 157 Wingfield, J. N., 235 Witkop, B., 143, 155 Wltt, E. R., 41, 101, 264 Wittia. G.. 1. 15 Wofslkjr, S: C., 278 Wolf, R., 38, 43, 44, 114, 271, 282 Wolfsberger, W., 216, 217 Wollmann, K., 131 Wong, J. T., 152 Wong, S. C. K., 203 Wong, S. M., 174 Wood, H. C. S., 65 Woodcock, R., 125 Woods, A. E., 162 Woods, M., 284, 290 Woplin, J. R., 37, 216, 261 Worms, K. H., 131 Wray, V., 52, 252 Wreland, T., 10 Wright, J. A., 169 Wright, S. H. B., 16 Wuest, H., 15, 182 Wynberg, H., 190, 196 Yagi, K., 174 Yakovleva, T. V., 46 Yakshin, V. V., 101 Yakutina, 0. A., 1, 76 Yamada, K., 22, 245 Yamada, S., 10, 246 Yamashita, K., 195

305

Author Index Yamashita, M., 13, 31, 78, 97,238 Yamazaki, A., 153 Yamazaki. H.. 152 Yamazaki; N.; 114 Yanagita, M., 236, 273 Yankelevich, A. Z., 265 Yarkova, E. G., 114, 140, 276 Yato, T., 188 Yee. K. C.. 74. 141. 257.

Yoneda; S.,’187, 188 Yong, K. S., 82, 283 Yoshida, H., 156 Yoshida, K., 282 Yoshida, N., 282 Yoshida, Z., 187, 188 Yoshifuji, M., 59, 241, 289 Yoshikawa, M., 144

Yoshina, S., 190 Yoshioka, T., 185 Young, D. E., 63, 72 Young, I. M., 84, 104 Young, V. A., 125 Yount, R. G., 151, 152 Yuki, R., 156 Yurchenko, R. I., 210 Yurzhenko, T. I., 213 Yvernault, T., 240 Zagnibida, D. M., 207, 213 Zagorets, P. A., 61 Zaripov, N.-M., 285 Zarkadas, A., 2, 71 Zarytova, V. F., 153 Zasorina, V. A., 217 Zavalishina, A. I., 115 Zavlin, P. M., 49 Zawadzki, S., 120 Zbiral, E., 22, 189 Zeiss, W., 89, 91, 203, 223 Zeleneva, T. P., 224 Zemlyanskii, N. I., 128 Zenin, S. V., 258 Zentil, M., 282 Zhdanov, Yu. A., 199

Zhivukhin, S. M., 219, 233 Zhmurova, I. N., 209,210, 219 Zhukov, V. P., 56 Zhuraleva, L. P., 85 Ziehn, K. D., 9, 10, 203, 210,211 Zimin, M. G., 77, 275,287 Zimmer, G., 125 Zimmermann, R., 176, 177 Zinkovskii, A. F., 94 Zmeltukhin, V. F., 67 Zoer, H., 235 Zon, G., 27, 137, 263 Zoroastrova, V. M., 42,96 Zoroatskaya, E. I., 273 Zubtsova, L. I., 46, 60, 74, 96, 288 Zuckermann, J. J., 72, 266, 268 Zurflueh, R., 202 Zutra, A., 156 Zwierzak. A.. 113. 117. 120, 271 Zykova, T. V., 52, 57, 58, 69, 77, 87, 141, 269 Zyryanova, T. A., 233 ~~

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