Organophosphorus Chemistry

A Specialist Periodical Report Organophosphorus Chemistry Volume 1 A Review of the Literature Published up to June 196...

Author: S. Trippett

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A Specialist Periodical Report

Organophosphorus Chemistry Volume 1

A Review of the Literature Published up to June 1969

Senior Reporter S. Trippett, Department of Chemistry, The University, Leicesfer

Reporters R. S. Davidson, The University, Leicester D. W. Hutchinson, University of Warwick R. Keat, Glasgow University R. A. Shaw, Birkbeck College, London J. C. Tebby, North Staffordshire College of Technology

SBN: 85186 006 0 @ Copyright 1970

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

Organicformulae composed by Wright’s Symbolset method

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

Foreword

This Report was designed to cover all significant work in organophosphorus chemistry available to the Reporters in the year ending 30th June, 1969. As this is the f i s t of an annual series most of the literature from the beginning of 1968 has been included. Hopefully, therefore, future Reports will be substantially smaller. The material has been organised on a compound type rather than a mechanistic basis and this may have tended to obscure the essential unity of the subject. Certainly the more theoretical aspects have not been adequately covered and a volunteer here would be welcome ! It is inevitable that next year’s Report will have been organised before this one is published and that changes resulting from criticism may therefore be delayed. We should, however, be grateful for comments and suggestions for improvement.

Contents

Chapter 1 Phosphines and Phosphonium Salts By S. Trippett

I Phosphines 1 Preparation A From Halogenophosphine and Organometallic Reagent B From Metallated Phosphines C By Reduction D By the Radical Addition of P-H to Olefins E Miscellaneous F Optically Active Phosphines

2 Reactions A Nucleophilic Attack on Carbon (i) Activated Olefins (ii) Activated Acetylenes (iii) Carbonyls etc. (iv) Miscellaneous B Nucleophilic Attack on Halogen C Nucleophilic Attack on Other Atoms D Miscellaneous

1

9 9 9 12 14 15

16 19 21

I I Phosphonium Salts 1 Preparation

21

2 Reactions A Alkaline Hydrolysis B Additions to Vinylphosphoniurn Salts C Miscellaneous Reactions

24

3 Miscellaneous

33

24 29 31

vi

Contents

I I I Phosphorins and Phospholes 1 Phosphorins A Preparation B Structure C Reactions

34 34 34 35

2 Phospholes

38

Chapter 2 Quinquecovalent Phosphorus Compounds By S. Trippetf

1 Pseudorotation

40

2 2,2’-Biphenylylenephosphoranes

42

3 1,3,2-Dioxaphospholens

45

4 1,3,2-Dioxaphospholans

48

5 1,2-Oxaphospholens

51

6 1,3-Oxaphospholans

53

7 Penta(ary1oxy)phosphoranes

53

8 Miscellaneous

53

Chapter 3 Halogenophosphines and Related Compounds By S. Trippett 1 Halogenophosphines A Preparation B Reactions (i) Nucleophilic Attack on Phosphorus (ii) Nucleophilic Attack by Phosphorus (iii) Miscellaneous

55 55 56 56 57

2 Halogenophosphoranes A Dihalogenophosphoranes (i) Structure (ii) Reactions B Hydridofluorophosphoranes C Hydridofluorophosphate Anions

60

60 60 60 61 63 63

vii

Contents

3 Phosphines Containing a P-X (X = Si, Ge, Sn, Pb) Bond A Phosphorus-Silicon B Phosphorus-Germanium C Phosphorus-Tin and Phosphorus-Lead

64 64 65 66

Chapter 4 Phosphine Oxides By S. Trippetf 1 Preparation A Using Organometallic Reagents B From Olefins and Dienes C From Alkyl Phosphinites D Miscellaneous

68 68 70 71 71

2 Reactions A Metallated Phosphine Oxides B Additions to Unsaturated Phosphine Oxides C Miscellaneous

74 74 76 77

Chapter 5 Tervalent Phosphorus Acids By D. W . Hutchinson 1 Introduction

80

2 Phosphorous Acid and its Derivatives A Nucleophilic Reactions (i) Attack on Saturated Carbon (ii) Attack on Unsaturated Carbon (iii) Attack on Nitrogen (iv) Attack on Oxygen (v) Attack on Halogen (vi) Attack on Hydrogen B Electrophilic Reactions C Rearrangements D Cyclic Esters of Phosphorous Acid E Miscellaneous Reactions

80

87 88 88 90 90 93 93 95

3 Phosphonous Acid and its Derivatives

97

4 Phosphinous Acid and its Derivatives

97

80 80 81

...

Vlll

Contents

Chapter 6 Quinquevalent Phosphorus Acids By D. W. Hutchinson 1 Phosphoric Acid and its Derivatives A Phosphorylation Methods B Hydrolysis of Phosphate Esters C Reactions of Derivatives of Phosphoric Acid (i) Dephosphorylation Reactions (ii) P-N Systems (iii) P-S Systems (iv) Miscellaneous Reactions D Cyclic Derivatives of Phosphoric Acid

98 98 105 112 112 114 115 118 119

2 Phosphonic Acid and its Derivatives A Synthetic Methods B Hydrolysis of Phosphonate Esters C Reactions of Derivatives of Phosphonic Acid (i) Dephosphorylation Reactions (ii) a,P-Unsaturated Phosphonic Acids (iii) P-N and P-S Systems (iv) Cyclic Derivatives of Phosphonic Acid (v) Miscellaneous Reactions

121 121 125 126 126 127 128 129 129

3 Phosphinic Acid and its Derivatives A Synthetic Methods B Hydrolysis of Derivatives of Phosphinic Acid C P-S Systems D Miscellaneous Reactions

134 134 135 137 138

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

141

2 Nucleotides and their Phosphonate Analogues A Oligonucleotide Synthesis on Polymer Supports B Mononucleotides C Nucleoside Polyphosphates D 01igonucleot ides E Nucleoside Thiophosphates F Phosphonic Analogues of Nucleotides G Nucleotide Structure H Sequence Studies I Analytical Techniques

141 142 143 145 147 149 152 154 154 157

ix

Contents 3 Coenzymes and Cofactors A Phosphoenolpyruvate B CoenzymeA C Nicotinamide Nucleotides D Vitamin Bla E Nucleoside Diphosphate Sugars

157 157 159 160 161 161

4 Aminophosphonates A Occurrence and Biosynthesis B Synthesis of Lipid Analogues C Catabolism of Phosphonic Acids

162 162 164 165

5 Oxidative Phosphorylation A Hydroquinone Esters B Metal Complexes

165 166 167

6 Sugar Phosphates A Pentoses B Hexoses and Other Sugars C Phosphonates

168 168 170 170

7 Inositol Phosphates

171

8 Terpene Phosphates

172

9 Other Phosphorus Compounds of Biological Interest

175

Chapter 8 Ylides and Related Compounds By S. Trippeff 1 Methylenephosphoranes A Preparation B Reactions (i) Inorganic Reagents (ii) Halides (iii) Carbonyls (iv) Esters (v) 1,3-Dipoles (vi) Miscellaneous

176 176 178 178 180 184 190 190 193

2 Phosphoranes of Special Interest

197

3 Selected Applications of the Wittig Olefin Synthesis A Macrocyclics B Heterocyclics C Natural Products D Carbohydrates

201 201 203 203 204

Contents

X

4 Synthetic Applications of Phosphonate Carbanions

205

5 Wide Aspects of Iminophosphoranes

207 207 20s

A Preparation B Reactions

Chapter 9 Phosphazenes By R. Keat and R. A. Shaw 1 Introduction

214

2 Synthetic Routes to Phosphazenes A Acyclic Derivatives B Cyclic Derivatives

215 215 219

3 Reactions Involving Displacement of Halogen Atoms A By Other Halogen Atoms B Halogen Displacement by Amines C Halogen Displacement by Alcohols D Aryl-derivatives of Cyclophosphazenes

225 225 225 23 1 233

4 Formation of Polymeric Phosphazenes

236

5 Structure and Bonding

238

6 Miscellaneous Physical Measurements

239

Chapter 10 Radicals, Photochemistry, and Deoxygenation Reactions By R. S. Davidson 1 Photochemistry

246

2 Radical Reactions

25 1

3 Electrochemical Generation of Radicals

255

4 Phosphinidenes and Related Species

256

5 Deoxygenation of Peroxides and Desulphurisation of

Disulphides

258

6 Deoxygenation of Ozone and Ozonides

260

7 Deoxygenation of Alcohols and Desulphurisation of Thiols

261

xi

Contents

8 Deoxygenation of Carbonyl Compounds

263

9 Deoxygenation of Nitrile Oxides and Nitrones

265

10 Deoxygenation of Nitro- and Nitroso-compounds

267

Chapter 11 Physical Methods By J. C. Tebby 1 Nuclear Magnetic Resonance Spectroscopy A Chemical Shifts and Shielding Effects B Relaxation Times C Studies of Equilibria and Reactions D Pseudorotation E Restricted Rotation F Other Temperature and Medium Effects G Inversion and Configuration H Spin-Spin Coupling

(9 JPP (ii) JPC (iii) JPF (iv) JPHand JHH I Paramagnetic Effects

273 273 279 279 28 1 286 289 29 1 292 292 294 294 295 301

2 Electron Spin Resonance Spectroscopy

302

3 Vibrational Spectroscopy A Band Assignments and Structural Elucidation B Stereochemical Aspects C Studies of Bonding

303 304 305 307

4 Microwave Spectroscopy and Dipole Moments

309

5 Electronic Spectroscopy

31 1

6 Magnetic Rotation and Susceptibilities

313

7 Circular Dichroism and Refraction

313

8 Diffraction

3 14

9 Electrochemical Studies

316

10 Mass Spectrometry

317

11 pK and Reaction Rate Studies

321

12 Cryoscopic Studies

322

Author Index

323

Abbreviations

The following abbreviations have been used AIBN bisazoisobutyrylnitrile DCC dicyclohexyl carbodi-imide DMF NN-dimethylformamide DMSO dimethyl sulphoxide MO molecular orbital PPi inorganic pyrophosphate n.q.r. nuclear quadrupole resonance THF tetrahydrofuran t .1.c . thin-layer chromatography

1 Phosphines and Phosphonium Salts BY S. TRIPPETT

PART I: Phosphines

1 Preparation A. From Halogenophosphine and Organometallic Reagent.-For the preparation of tertiary phosphines this continues to be the method of choice when applicable. The lithioacetylide (1) with phosphorus trichloride gave the phosphine (2) whose stability at 283" contrasted sharply with the thermal instability of triethynylphosphine. The silicon analogue (3) was prepared in a similar way as well as from bis(trimethylsily1)acetylene and phosphorus trichloride.

-

Li C iC CMe,

PCI,

(1)

P(C i C CMe,), (2) 98%

Li*CiC.SiMe,

-

Me,% C !C SiMe,

PCI,

49%

P(C t C-SiMe,),

dA

(3)

The previously described preparation of tris(trifluoroviny1)phosphine from trifluorovinylmagnesium iodide and phosphorus trichloride is now reported to give only polymeric material. Phosphorus tribromide gave the required phosphine. Among other syntheses of this type, those of the phosphines (4)5 and ( 5 ) and of many fl~oroalkylphosphines,~ e.g. (6), may be mentioned. H. F. Reiff and B. C. Pant, J. Organometallic Chem., 1969, 17, 165. W. Siebert, W. E. Davidsohn, and M. C. Henry, J. Organometallic Chem., 1969, 17, 65. R. N. Sterlin, R. D. Yatsenko, L. N. Pinkina, and I. L. Knunyants, Izuest. Akad. Nauk S.S.S.R.,Ser. khim., 1960, 1991. A. H. Cowley and M. W. Taylor, J. Amer. Chem. Soc., 1969,91, 1929. G. Marr and T. Hunt, J . Chem. SOC.(C), 1969, 1070. M. A. Bennett, W. R. Keen, and R. S. Nyholm, Inorg. Chem., 1968,7, 552. K. Gosling, D. J. Holman, J. D. Smith, and B. N . Ghose, J. Chern. SOC.(A), 1968, 1909.

2

Organophosphorus Chemistry

o-"""""

Li

7Ph2

@ H W 2 PhBPCl

(4) 78%

GF, Li + CF, * PC1,

-

CF,P(GF,), (6)

p-Ketoalkyltin compounds with halogenophosphines gave the correwhich are otherwise difficult to sponding p-ketoalkylphosphines *+O prepare, e.g.

Et,Sn .CH2-C02*Et ~

h

PhP(CH,d C02Et), 70%

Bu,Sn*CH2*CO*Me phzpcl > Ph,P-CH,*CO.Me 57%

B. From Metallated Phosphines.-The synthesis of phosphiran from sodium phosphide and 1,Zdichloroethane in liquid ammonia l1 has been extended12 to the preparation of both 1- and 2-substituted phosphirans. The 2-ethylphosphiran was a mixture of cis- and trans-isomers.

* M. V. Proskurnina, I. F. Lutsenko, Z. S. Novikova, and N. P. Voronova, Khirn. Org. lo

l1

l2

Soedinenii Fosfora, 1967, 8 (Chem. Abs., 1968, 69, 52217). G. M . Vinokurova, Zhur. obshchei Khim., 1967, 37, 1652. 2. S. Novikova, M. V. Proskurnina, L. I. Petrovskaya, I. V. Bogdanova, N. P. Galitskova, and I. F. Lutsenko, Zhur. obshchei Khim., 1967, 37, 2080. R. I. Wagner, Lev. D. Freeman, H. Goldwhite, and D. G. Rowsel1,J. Amer. Chem. Soc., 1967,89, 1102. S. Chan, H. Goldwhite, H. Keyzer, D. G. Rowsell, and R. Tang, Tetrahedron, 1969, 25, 1097.

3

Phosphines and Phosphonium Salts

R

Me Et

H

H

R’

H

H

Ph

Me

%

30

25

63

30

1-Deuteriophosphiran was obtained from 1,2-dichloroethane and sodium dideuteriophosphide prepared in tris(dimethy1amino)phosphine oxide. Alkylphosphines (7) were similarly obtained, e.g. EtPH, (78%), CH2:CH*CH2*PHI(55%). PH,

T~. NaPH,

R Hal

RPH,

(7) Convenient syntheses of methyl l3 and dimethylphosphine l4 have been described using dimethylsulphoxide as solvent. Other syntheses using nietallated phosphines and alkyl halides include those of the amines (8) l6 and (9)la and of the diphosphine (10).17 Whereas lithium diethyl-18 and dicyclohexyl-phosphideslsare stable in refluxing tetrahydrofuran, the corresponding dimethylphosphide 2o rapidly cleaves the solvent to give (11). N(CH,

PhPH*CH, * CH2*PHPh

M+P)2

Li THF

[Me2PLil

THF

Me2P.(CH2),.OLi

MeaSiCl

(1 1)

Me2P.(CH,),. 0 SiMe, 91% 3

la l6

l6 l8

l9

ao

W. L. Jolly, Inorg. Synth., 1968, 11, 124. W. L. Jolly, Inarg. Synth., 1968, 11, 126. L. Sacconi and I. Bertini, J. Amer. Chem. Soc., 1968, 90, 5443. K. Isslieb, R. Kiimmel, H. Oehme, and I. Meissner, Chem. Ber., 1968, 101, 3613. K. Isslieb and H. Weichmann, Chem. Ber., 1968, 101, 2197. W. Hewertson and H. R. Watson, J . Chem. SOC.,1962, 1490. K. Isslieb and H.-R. Roloff, Chem. Ber., 1965, 98, 2091. R. E. Goldsbury, D. E. Lewis, and K. Cohn, J . Organometallic Chem., 1968, 15, 491.

4

Organophosphorus Chemistry Typical of syntheses using vinyl halides were those of the diphosphine (12) 21 and of diphenyl-1-phenylvinylphosphine (13).22 Perfluoroacyldiphenylphosphines have been obtained from the corresponding perfluoroacid halides or anhydride^.,^ Bu,PLi+ CI.CH:CH.Cl trans

THF

Bu,P.CH:CH.PBu, trans (12) 25%

Ph,PNa

+ PhCBr :CH,

Ph,P.CPh:CH, (13) 65%

Aguiar showed2* that the ready reaction of aryl halides with lithium diphenylphosphide does not involve an aryne. Isslieb has now shownz5 that such intermediates are involved in similar reactions with lithium di-t-butylphosphide (14) and aryl fluorides but not with the diethyl- or dibutyl-phosphides. While this difference was ascribed to the greater nucleophilicity of (14) it may be due to steric hindrance round the phosphorus. The reactions of lithium phosphides with aryl bromides are complicated by metal-halogen exchange. Thus (14) and p-bromotoluene gave only (15) together with the biphosphine (16).

M e O B r

+

(14)

____+

Me

0 \ /

Li

+

But,P2

(19

BrPButz

(15)

Metallated diphenylphosphine with carbon disulphide in tetrahydrofuran at -50" gave the pale orange-yellow salts (17) which formed stable red solutions in acetone and ethanol and did not react with nitrogen.26 The corresponding reaction with the tetraphosphine (1 8) at 60"gave a rearranged salt (19) whose ochre solutions in polar solvents 'greedily' absorbed two 21 2a

as 24 25

28

M. A. Weiner and G. Pasternak, J. Org. Chem., 1969, 34, 1130. M. P. Savage and S. Trippett, J. Chem. SOC.(C), 1968, 591. E. Lindner and H. Kranz, Chem. Ber., 1968, 101, 3438. A. M. Aguiar, H. J. Greenberg, and K. E. Rubenstein, J. Org. Chem., 1963,28,2091. K. Isslieb, A. Tzschach, and H.-U. Block, Chem. Ber., 1968,101, 2931. R. Kramolowsky, Angew. Chem. Znternat. Edn., 1969, 8, 202.

5


molecules of nitrogen to give a species ( y ~ t e2090 ~ cm-l) assigned a structure of which (20) is one of the contributing forms.27

C. By Reduction.-Lithium aluminium hydride and trichlorosilane continue to be the reagents of choice. Among applications of the former are syntheses of the diphosphines (21)28 and (22)2g and of dimethylphosphine (70-8 1%) from tetramethyldiphosphine disulphide 30 [(Pr’O)RP(:0). CH,],

LiAlHa

.

RPH CH, * CHz*PHR (21) R = Et, Ph, C6Hll

[(EtO),P(: O)I,(CH,)Ta

LiAlH4 &-)>

H,P*(CHZ),. PHZ (22) n = 1 (19%), 3 (54%), 4 (89%)

The triarylphosphines (23) containing functional groups sensitive to lithium aluminium hydride have been obtained 31 by the trichlorosilane reduction of the corresponding oxides. The use of hexachlorodisilane or octachlorotrisilane in refluxing benzene or in chloroform at room temperature has been recommended32 for the reduction of optically active 27

28

29

30

31

aa

J. Ellerman, F. Poersch, R. Kunstmann, and R. Kramolowsky, Angew. Chem. Infernat. Edn., 1969, 8, 203. K. Isslieb and H. Weichmann, Chem. Ber., 1968, 101,2197. B.P. 1,130,487. G. W. Parshall, Inorg. Synrh., 1968, 11, 157. G. P. Schiemenz and H.-U. Siebeneick, Chem. Ber., 1969, 102, 1883. K. Naumann, G . Zon, and K. Mislow, J. Amer. Chem. SOC.,1969,91,2788.

6 Organophosphorus Chemistry phosphine oxides. Almost complete inversion of configuration occurs and the mechanism shown has been suggested. The same reagents reduce acyclic phosphine sulphides and cyclic phosphine oxides with retention of configuration.

(23) X = CN, CO,H, C0,Me

Si,CJ6

+

O=PcR2 /R1

R3

-

CI,Si-0

+,R1 R2

-pi..

+

Sic&-

R3

D. By the Radical Addition of P-H to 0lefins.-Primary phosphines with allylamine in the presence of 2,2'-azobis-(2-niethylpropionitrile) gave mixtures of the secondary (24)and tertiary (25) 3-arninopropylpho~phines.~~

+

RPH2 CH2 :CH CH2 NH2

-

RPH CH2 CH2 CH2 NH2 (24)

+RP(CH2 CH2 CH2 NH2)2 *

R = Ph, BU

(25)

Similar addition of phenyl phosphine to the terminal dienes (26) gave the diphosphines (27).s4 (PhPH. CH,. CH,),X PhPH2+ CH2:CH-X. CH: CH,

% (27) 27

19

32

52

Diallyl ether also gave 18% of the monophosphine CH2:CH CH, 0 CH2 CHz PHPh. A series of additions of bicyclic secondary phosphines (28) to octa-197-diene has been described.36a The photochemical cyclisation of unsaturated secondary phosphines leads to cyclic tertiary phosphines (29).36b 88

84

86

K. Isslieb, H. Oehme, and E. Leissring, Chem. Ber., 1968, 101, 4032. V. V. Korshak, V. A. Zamyatina, A. I. Solomatina, E. I. Fedin, and P. V. Petrovskii, J. Organometallic Chem., 1969, 17, 193. (a) F.P. 1,502,250. (*) F.P. 1,488,936.

7

Phosphines and Phosphonium Salts (CH,),

+

(CH2:CH*CHz-CH2)2

AIBN

(28)

E. Miscellaneous.-Tetraphenyldiphosphine on refluxing in aqueous ethanol with formaldehyde and diethylamine gave diethylaminomethyldiphenylphosphine (30) and the corresponding oxide.S8 A four-centre mechanism is proposed leading to diphenylphosphine and the phosphinite (31). Ph2y-PPh2

- f

r

:

-

H2N- CH2- 0-H

Ph2P*O*CH2*NEt2 H20 > Ph2P(:O)H (3 1) __I_, + PhzPH EtSN. CHSOH I

I

P+CH90H

Ph2P(:O)CH2*NEt2

Ph2P*CH,.NEt, (30)

Treatment of tris-(hydroxymethy1)phosphine with phenacyl bromides followed by internal acetal formation and base-catalysed elimination of formaldehyde gave the interesting bicyclic phosphines (32).37 Oxidation with hydrogen peroxide in methanol gave the acyclic oxides.

F. Optically Active Phosphines.-t-Butylmethylphenylphosphine has been resolved via the asymmetric platinum(I1) complex (33) obtained from the binuclear compound (34) and ( +)-de~xyephedrine.~* Fractional crystallisation of (33) gave two diastereoisomers. Treatment of one of these with methanolic potassium cyanide liberated the optically active phosphine which was characterised as the oxide and as the optically active complex 36 s7

38

L. Maier, Helv. Chim. Acta, 1968, 51, 1608. E. S . Kozlov, A. I. Sedlov, and A. V. Kirsanov, Zhur. obshchei Khim., 1968, 38, 1881. T. H. Chan, Chem. Comm., 1968, 895.

-

8 (HOCH,),P

+

Ar.CO-CH,Br


+

(HOCH,),P-CH,.CO Ar

H2C -0

/ \

Br-

\ /

:P CH2- C -Ar

-

H2C 0 (32) 48-88%

BdMePliP

K2PtCld

trans-L,PtCl,

PtCl, ~y~ene

'

(35)

(34)

I

(+)-Deoxyephedrine

KaPtCIh

B U ~ M ~ P ~ P ( 4: O )o, D I . [

KCN [ ] < MeOH

[4,= + 10"

ti

3. 10"

L\Pt C1'

DI.[

=

+ 16"

\NH-CH-CH2Ph I I Me Me (3 3)

(35) having [a]== - 11". The extension of this method to the resolution of other tervalent phosphorus compounds, e.g. phosphites, was proposed. A method for determining the optical purity of phosphines has been described,39 which involves quaternisation of the phosphine with the optically active bromide (36) and analysis of the lH n.m.r. spectrum of the resulting salt taking advantage of the chemical shift non-equivalence of the diastereotopic protons in the product mixture. PhCH(OMe).CH,Br+ R1R2R3P (36)

-

+

R1R2R3P.CH2.CH(OMe).PhBr

Inversion of configuration at the phosphorus of the phosphetans (37) has been studied by n.m.r. t e c h n i q ~ e s .The ~ ~ methyl phosphetans did not invert at 162" for 4 days while the t-butyl and phenyl phosphetans inverted remarkably rapidly in view of the increased strain expected in the fourmembered ring in the transition state. *O

J. P. Casey, R. A. Lewis, and K. Mislow, J. Amer. Chem. SOC.,1969, 91, 2789. S. E. Cremer, R. J. Chorvat, C. H. Chang, and D. W. Davis, Tetrahedron Letters, 1968, 5799.


9

R (37) AH* (kcal/mole) AS*(e.u.)

R

28 30

But Ph

k,/k-, 1.3

-8 -8

1.5

2 Reactions A. NucIeophilic Attack on Carbon.-(i) Activated Olefins. Tricyclohexylphosphine catalysed the addition of acrylonitrile and ethyl acrylate to aldehydes41 to give the unsaturated alcohols (38), presumably via the betaines (39; R = C,H,,). In contrast, the corresponding betaines from triphenylphosphine transfer a proton to give the ylides (40) before reacting with the aldehyde in a normal Wittig olefin synthesis.42 R3P

+ CH2:CHX q R,i!.CH,.CHX

X = CN, C02Me R

= Ph

(39)

II

R3$ CH CH2X (40)

;

i R'CHO

+

R3P(:O) + RCH:CHX

R3$ CH2 CX CH(0H) R'

I

R3P + CH2:CX * CH(0H) R' (38) 70-90%

Triphenylphosphine and N-substituted maleimides in acetic acid gave the stable ylides (41).45 The reaction is analogous to that previously described with maleic anhydride.44 With either cis- or trans-/3-haloacrylic acids, esters, or nitriles, tributyl- and triphenyl-phosphines in benzene at 41

48

K. Morita, Z. Suzuki, and H. Hirose, Bull. Chem. SOC.Japan, 1968, 41, 2815. R. Oda, T. Kawabata, and S. Tanimoto, Tetrahedron Letters, 1964, 1653. E. Hedaya and S. Theodoropulos, Tetrahedron, 1968,24, 2241. R. F. Hudson and P. A. Chopard, Helv. Chim. Acta, 1963,46,2178.

10

/c\o NR

-


+

nn

Ph3P-HC’L\V I NR -HC.&

room temperature gave the trans-vinylphosphonium salts (42), probably by an addition-elimination mechanism.45 No reaction occurred with the a- or jg-methyl-/I-haloacrylates. P-Bromoacrylic acid and triphenylphosphine also gave the bis-salt (43) which was formed exclusively at R,P + Hal. CH :CH. X cis or trans

-

+

R,P.CHHal.EH-X

+

R3P* CH :CHX Haltrans (42)

X = C02H, CO,Me, CN Hal = C1, Br

higher temperatures. The salt (42; R = Ph, X = C02H) was not an intermediate in this reaction which may involve dehydrobromination of the p-bromoacrylic acid and addition of triphenylphosphonium bromide to the resulting propiolic acid. The last reaction is now reported to give a high yield of the bis-salt (43). Ph,P

+ BrCH:CH.CO,H trans

\ Ph,$ CH, CH, *6Ph, 2Br (43)

Ph&H Br -t HCiC.CO,H

1,2-Dichloroperfluorocycloalkenes(44) and perfluorocycloalkenes with tertiary phosphines in wet acetic acid 47 gave the stable ylides (45) when n = 1 or 2 but not when n = 3, the major product in this case being the phosphine oxide together with tars and the l-chlorocyclohexene (46). 469

46

47

G. Pattenden and B. J. Walker, J. Chem. SOC.(C), 1969, 531. R. F. Stockel, F. Megson, and M. T. Beachem, J. Org. Chem., 1968,33,4395.

S. E. Ellzey, Canad. J. Chem., 1969,47, 1251.

11


n = 1 (29%), n = 2 (36%)

(44)

(46)

Triphenylphosphine and an excess of perfluorocyclobutene formed a 1 : l - a d d ~ c twhich , ~ ~ with water gave the ylide (45, R = Ph, n = l), and for which, on the basis of 31Pand lSFn.m.r. data, the unlikely looking structures (47) or (48) were suggested.

Fj--fF F -

Ff2

F

F PPh,

+

PPh3

+

(47)

‘PPh,

Diphenylphosphine with 1,2-dichlorotetrafluorocyclobutenein dimethylformamide48 gave the mono- (49, 46%) and di-phosphines (50, 20%) whereas in the absence of solvent only trifluorodiphenylphosphorane and diphenylphosphinyl fluoride had been identified.4g The same phosphine with 1,2-dichlorohexafluorocyclopentene in dimethylformamide 6o gave only the monophosphine (51; R = Ph, 78%) while dicyclohexylphosphine also gave 8% of the diphosphine (52; R = C8Hll). The diphosphine (50) had previously been obtained (11%) from diphenylphosphinerand perfluorocyclobutene in the absence of Ph,P

‘1.c: F F F

48

4@ 6o

Ph,PH DMF’

n;

P h y ; h 2

F F F (49)

F F (50)

R. F. Stockel, Cunad. J. Chem., 1969, 47, 867. W. R. Cullen, D. S. Dawson, and P. S. Dhahival, Canad. J . Chem., 1967, 45, 683. R. F. Stockel, Cunad. J . Chem., 1968,48, 2625.

Organophosphorus Chemistry Preparation of the phosphanone (53) has been improved51 by catalysis with sodium alkoxides at 120-130". 12

fi 0

0

+ PhPH,

Me&. Me

Me Me MeMe

Me

I

Ph (53) 70%

The addition of dimethylphosphine to vinylsilanes is catalysed by lithium dimethylph~sphide,~~ although with diphenyldivinylsilanevigorous polymerisation resulted. MqSi CH :CH,

-

+ Me,PH

Me,Si(CH :CH,),

+ Me,PH

-

Me2PLi

> Me,% CH, CH, PMe, 83% MeaPLi > Me,Si(CH, CH, PMe,),

-

85%

Potassium diphenylphosphide added to 1 1-diphenylethylene gave a low yield of the phosphine (54).69 Carbonation of the intermediate anion from the addition to stilbene resulted in the isolation of 6% of the acid (55).

+

PhaPK PhzCH :CH, Ph,PK+Ph*CH:CH*Ph

-

Ph2P. CH, * CHPh, (54) 20% [I

COS

PhaP(:O).CHPh.CH(CO,H).Ph (55)

(ii) Activated Acetylenes. The initial adducts (56) from the addition of triphenylphosphine to the acetylenic carboxylic esters (57) have been trapped 64 in the presence of sulphur dioxide and water as the betaines (58), also obtained, when R = Ph, CO,Me, by the addition of bisulphite anion to the vinylphosphonium salts (59). The yellow 1 :2 adduct formed from triphenylphosphine and dimethyl acetylenedicarboxylate in refluxing ether 66 has now been shown 66 to be the stable ylide (60)formed by rearrangement of an intermediate phosphorane. Compound (60) gave a colourless perchlorate and reduction with zinc and acetic acid gave the oxide (61). It seems probable that the yellow 1 : 2adduct formed from 1,2,5-triphenylphospholeand the same acetylene 67 s1 s2

64 66 6e

F. Asinger, A. Saus, and E. Michel, Monarsh., 1968,99, 1695. J. Grobe and U. Moller, J. Organomerallic Chem., 1969, 17, 263. F. Rudolph, Jenaer Jahrb., 1966, 221 (Chern. Abs., 1968, 68, 114,707). M. A. Shaw, J. C. Tebby, R. S. Ward, and D. H. Williams, J. Chem. Sac. (C), 1968, 2795. A. W. Johnson and J. C. Tebby, J. Chem. SOC.,1961,2126. N. E. Waite, J. C. Tebby, R. S. Ward, and D. H. Williams, J. Chem. SOC.(0,1969, 1 100. A. N. Hughes and S. Vaboonkul, Tetrahedron, 1968, 24, 3437.

13

Phosphines and Phosphonium Salts Ph3P

+

+

R*CiC.CO,Me + Ph,P*CR:C-CO,Me (56)

(57)

R

=

H, Ph, C0,Me

I

I was the result of a similar rearrangement and has the structure (62; X = C0,Me). For the reactions of diphenyl-1-phenylvinylphosphinewith this acetylene, with epoxides, and with activated olefins see Chapter 8, section 1A. Dibutylphosphine and dibutylethynylphosphineoxide at 80" gave a low yield of the trans-oxide (63).68a

x x (62) X = C0,Me 68

M. A. Weiner and G. Pasternack, J , Org. Chem., 1969,34, 1130. J. C. Kauer and H. E. Simons, J. Org. Chem., 1968, 33, 2720. A. N. Hughes and M. Woods, Tetrahedron, 1967, 23, 2973.

-

14

+

Bu~P(:0)* C i CH BuZPH

Organophosphorus Chemistry Bu,P( :0) CH :CH PBu, (63) 20%

The tetramer of dimethyl acetylenedicarboxylatewith triphenylphosphine gave68b the red ylide (63a), probably identical with the compound previously obtained from (impure) dimer.68c

ox Ph,P

x‘

x

(634

(iii) Carbonyls, etc. Secondary phosphines added to keten6g and to bis(trifluoromethy1)-keten6o to give the acylphosphines (64). For the reaction of tris(dimethy1amino)phosphine with dimethylketen see Chapter 2, section 6. R2PH+ R’& :C :0

-

R,P* CO * CHR’, (64)

Fluorosulphonyl isocyanate and triphenylphosphine in ether at room temperature gave a dipolar adduct (65).61 N-Isothiocyanatodi-isopropylamine with trimethyl and triethylphosphine formed similar 1 :1-adducts Ph3P+FS0,.NC0

Ph,$.CO.G-SO,F (65)

(66).82 With secondary phosphines the products were di-isopropylamine thiocyanate and the diphosphine. A six-membered cyclic transition state is suggested.

-s R,N.NCS

1

+

R’3P

il

3

+

R,N*N-C-PRZ (66)

R’ZPH

R’2 69

8o 61 62

R. G. Kostyanovsky, V. V. Yakshin, and S . L. Zimont, Tetrahedron, 1968,24,2995. R. G. Kostyanovsky, V. V. Yakshin, S . L. Zimont, and I. I. Chervin, Izvest. Akad. Nauk S.S.S.R., Ser. khim., 1968, 190. H.Hoffmann, H. Forster, and G. Tor-Poghossian, Monarsh., 1969, 100, 311. U. Anthoni, 0. Dahl, C. Larsen, and P. H. Nielsen, Acra Chem. Scand., 1969,23,943.

Phosphines and Phosphoniurn Salts

15

Diphenylphosphine and cyanic acid gave the amide (67) 6 3 which with toluene-p-sulphonyl isocyanate did not form a urea but instead a low yield of a compound assigned the structure (68).

.

Ph,P. CO NH,

+ Ar *SO2 NCO

-

0-c:o 1

1

Ph,P( :0)C-N *SO2.Ar I

Addition of diphenylphosphine to the Schiff’s bases (69) gave the phosphines (70).64 R*CH:N*SO,F+PhaPH (69)

PhaP*CHR*NH.SO2F (70)

____j

(iv) Miscellaneous. The mode of quaternisation of tertiary phosphines with triphenylmethyl chloride has been found to depend on the size of the ph~sphine.~ Small ~ phosphines, e.g. Et3P, PhPMe,, gave the expected triphenylmethylphosphonium salts (7 1) but more bulky phosphines, e.g. Ph3P, Ph,PMe, PhBut PMe, gave instead the 4-(diphenylmethy1)-phenylphosphonium salts (72).

+

R3P*CPh3 51

Ph3CCl

+

R,P

The quaternisation of triphenylphosphine with a-bromoketones is base catalysed.g6 Thus a-bromopropiophenone in acetonitrile at room temperature gave none of the salt (73) in the absence of base while in the presence of a catalytic amount of triethylamine 56% of (73) formed in 2 hr. Other

-

- -

Ph$ CHMe CO Ph (73)

&

effective catalysts included aqueous potassium cyanide and hydroxide. Phenacyl bromide and triphenylphosphine in refluxing benzene-methanol 6s

e4 68

L. G. Vaughan and R. V. Lindsey, J. Org. Chem., 1968,33, 3088. H. Hoffmann and H. Forster, Monatsh, 1968, 99, 380. H. Hoffmann and P. Schellenbeck, Chem. Ber., 1968, 101, 2203. I. J. Borowitz, K. C. Kirby jun., P. E. Rusek, and R. Virkhaus, J. Org. Chem., 1968,33 3687.

16


gave acetophenone (87%) via nucleophilic attack on halogen, while in the presence of triethylamine at room temperature in the same solvent mixture 92% of the phenacylphosphonium salt was produced. These remarkable effects were thought to involve addition of the base to the carbonyl group followed by attack of the phosphine, the transition state being ‘stabilised by mesomeric electron release from the negatively charged oxygen atom.’ B

I

Ph.CO*CH,Br

B: > Ph-C-CH,Br

Ph3P

+

> Ph.CO-CH,.PPh,&

I

+ B:

0 The hindered isobutyrophenones (74; X = C1, Br, O*SO,*Me) with triphenylphosphine in aprotic solvents gave methacrylophenone in an elimination reaction.67 Subsequent addition of triphenylphosphonium salt then gave the 3-ketophosphonium salts (75). In protic solvents the bromo-compound gave isobutyrophenone. Similar elimination-additions had previously been observed with a-halogenocyclohexanones.6*$ Ph.CO*CXMe, $. Ph,P (74)

-

Ph*CO.CMe:CH, + Ph,$H

x

I

Ph-CO.CHMe-CH,.$Ph, (75)

B. Nucleophilic Attack on Halogen.-The conversion of alcohols into chlorides on treatment with a tertiary phosphine and carbon tetrachloride has been shown to involve inversion of configuration at the carbon and undoubtedly proceeds via the alkoxyphosphonium chloride (76).70171 Thiols are similarly converted into chlorides with inversion 71 and carbon tetrabromide may be used for the preparation of alkyl bromides.70 Trioctyl, R3P C1-&C13

+

R,PC1

+ R’OH

-

R 3 h cC13

+

R3P-OR

el

R,P(:O)

+ R’CI

(76)

triphenyl, and tris(dimethy1amino)phosphine have been used, the last allowing particularly easy isolation of The intermediate alkoxyphosphonium salt in the reaction of tris(dimethy1amino)phosphine 67

68 60

70

71

K. Fukui, R. Sudo, M. Masaki, and M. Ohta, J . Org. Chem., 1968,33, 3504. P. A. Chopard and R. F. Hudson, J . Chem. Suc., 1966, 1089. I. J. Borowitz, K. C. Kirby jun., and R. Virkhaus, J. Org. Chem., 1966,31,4031. J. Hooz and S. S . H. Gilani, Cunud. J. Chem., 1968,46,86. R. G.Wells and E. I. Snyder, Chem. Comm., 1968, 1358. I. M. Downie, J. B. Lee, and M. F. S. Matough, Chem. Comm., 1968, 1350.

17


with pentan-1-01 and carbon tetrachloride has been trapped as the hexafluoroph osphat e. Benzotrichloride has been used in similar reaction^,^^ the ease of reaction increasing with the nucleophilic character of the phosphine, and the sequence is suggested as a method for reducing suitable trichloromethyl to dichloromethyl compounds. PhCCI,

+EtOH + R,P

-

PhCHCl,

+ EtCl+ R,P(: 0)

With the trichloromethylcyclohexadienone(77) competitive reactions using tris(dibuty1amino)phosphine showed that (77) was almost as reactive as benzotrichloride, and homoallylic stabilisation of the anion (78) was suggested.74

YCCI,

Me

(77) The trichloromethyl anion formed from carbon tetrachloride and tris(dimethy1amino)phosphine has been trapped 75 by addition to carbonyl compounds to give the alcohols (79).

+

(Me,N),PC1 + CCl,

0

Ri'Co*R:

I R~-C,R~ I CCl,

....._________ ?- CC13.CR1R2.0H (79) 50%

-

A similar sequence using esters or amides of trichloroacetic acid 76 gave the glycidic esters (80) or amides, while tributyltin trichloroacetate (81) and triphenylphosphine in the presence of benzaldehyde gave," after treatment with aqueous sodium hydrogen carbonate, the dichloro-acid (82). The suggested intermediates here were dichloroketen and the p-lactone (83). Debromination of a,d-dibromodibenzylsulphone (84) with triphenylphosphine was stereospecific78 involving inversion at both centres, the rneso-form giving cis-stilbene and the ( -I )-form leading to trans-stilbene. The mechanism is illustrated for the former case. The dechlorination of dichlorodiphenylmethane with tributylphosphine to give tetraphenylethylene (50%) was unaffected by the presence of butanol 7p

74 76

76

77

l8

I. M. Downie and J. B. Lee, Tetrahedron Letters, 1968, 4951. B. Miller, J . Amer. Chem. SOC.,1969, 91, 751. B. Castro, R. Burgada, G. Lavielle, and J. Villieras, Compt. rend., 1969,268, C, 1067. J. Villieras, G. Lavielle, R. Burgada, and B. Castro, Compt. tend., 1969, 268, C, 1164. M. Ohara, T. Okada, and R. Okawara, Tetrahedron Letters, 1968, 3489. F. G. Bordwell, R. B. Jarvis, and P. W. R. Corfield,J. Amer. Chem. SOC.,1968,90,5298.

18

Organophosphorus Chemistry (Me2NI3P

CI2C-C02R

+

+

CI3C*CO2R+ (Me2N),PCl -1- C12C-C02R

+ R1*CO*R2

-

Rt CP) R2' 'CCl

C02R

CAI

I Bu,Sn.OCOCCI,

-t-

Ph,P --+ C1,C:C:O

(81)

PhCHO

Ph-CH-CCI, I I

0-c:o

Ph.CH(OH)*CCI,*C02H (82) 33% f

and was therefore held not to involve the formation of BU,PC~.'~ Debromination of the dibromide (85) formed a convenient preparation of diphenylketen,BO the dibromophosphorane being insoluble in the reaction mixture.

cis-stilbene

@ '

-

Ph3$ CH CH. CO R I

(40)

N3

R = Alk., OMe, Ph

PhsP

+

I

HC -C CO R //

\\

Ph3p-HC-CH*C0

*R

~

NYN H (41)

3695% Cyclisation of the initially formed vinylphosphonium salt occurred 36 when diphenylvinylphosphine was treated with (42). The structure of the product (43) was shown by hydrolysis. Similar cyclisations accompanied the quaternisations of the acetylenicphosphines (44) with a-brom~ketones.~~ Ph2P CH :CHB

+ PhNH

N :CCI Ph

.>

HC=CH, Ph2P:f J H P h

PhCHO

+

H+ Ph,P(:O)*CH,*CH2*NPh*NH2 H,O

C1'

C=

(42)

I Ph

HSC-CH, \ Ph2P/" NPh

\c=d I

C1-

Ph

(43) 3s 36

M. Rasberger and E. Zbiral, Monatsh., 1969, 100, 64. I. G. Kolokol'tseva, V. N. Chistokletov, and A. A. Petrov, Zhur. obshchei. Khim., 1968, 38, 2819.

87

M. Simalty and H. Chahine, Compt. rend., 1968, 266, C, 1098.

Phosphines and Phosphonium Salts Ph2P.CiC*R

+

(44) R = Me, Ph

R1*CO*CH2Br R1= Me,

-

31 HC=CR1 /

\

Ph2P\C /0 HC=CR

Br-

Ph

When a dilute solution of dimethyl acetylenedicarboxylatewas added to diphenylvinylphosphinein wet ether s8 a low yield of the 1 : 1 : l-adduct (45) was obtained via cyclisation of the initial betaine (46). Reverse addition led to the 1 :2 : 1-adduct (47), addition of the second molecule of acetylene to (48) being as shown in (49). Ph2P*CH:CH2

+

(MeO,C.Ci),

-

0

Hc=T -

Ph2$

\

-

C= C02Me 1 C0,Me

(6)

<MeO,C.C 2)i

x X /80

H /

+ Ph2F(:O)*CH2*CH:CX*CH,X (45) 5%

(47) 5%

(49)

C. Miscellaneous Reactions.-The 13-ketoalkylphosphoniumisothiocyanates (50) with lead tetra-acetate 39 gave the allenes (51) and/or the acetylenes (52) the ratio depending on the nature of the groups R1and R2. s8 s9

A. N. Hughes and M. Davis, Chem, and Znd., 1969,138. E. Zbiral and H. Hengstberger, Monatsh., 1968,99,412.

32 Ph3$. CHR. CO - CHR1R2 SEN (50)

P b ( OAch

Organophosphorus Chemistry R1R2C:C: CR-SCN + (51)

R1R2C(NCS).CiC*R (52)

Thus when R1,R2 = H the allene was formed but with R1,R2 = Me the acetylene was isolated. The mechanism envisages the acetylene being produced by rearrangement of the allene. With the salts (50; R = OMe) the ketones (53) were produced by hydrolysis of the intermediates (54) followed by rearrangement. Ph3$ .CHR CO CHR1R2 SCN (50)

\

Pb(OAc),

PhJ' CR(SCN) CO CHRlRZ 6Ac (54)

+ Pb(OAc), + AcOH

\R=

OMe

RHC(SCN) CO CHR1R2

(51)

+ Ph,PO

t--------

Ph3$*CR(SCN)*C(E):CR1R2

1

RHC(NCS) CO * CHR1R2

(53) Pyrolysis of the betaine ( 5 5 ) gave the phosphine (56) with migration of phenyl from phosphorus to oxygen.40

(55)

Investigation of the electrolytic reduction of phosphonium salts 4 1 showed that with groups which do not interact with the phosphonium centre, e.g. Me, Ph, the percentage splitting off of a group depends only on the number andfptitude of that group, so that from data for one of the the results for the other members of the series can be series R1mR2(4--n)P 40 41

H. J. Bestmann and G. Hofmann, Annalen, 1968,716,98. L. Horner and 3. Haufe, G e m . Ber., 1968,101,2903.

Phosphines and Phosphonium Salts 33 predicted. This is not the case with groups such as p-anisyl; more anisole is produced when several such groups are attached to phosphorus than would be expected on the basis of the mono-p-anisylphosphonium salt. Treatment of tetraphenylphosphonium bromide with potassium diarylphosphides in refluxing tetrahydrofuran gave triphenylphosphine and the diarylphenylphosphines (57), with transfer of a phenyl group.42 This establishes part of the scheme originally proposed43to account for the products formed in the photolysis of triphenylphosphine. Ph,;

+ Ar,P

-

Ph3P+ Ar,PhP (57)

Ketones and triphenylphosphine were obtained from the action of Grignard reagents on a,a-disubstituted 16-ketoalkyltriphenylphosphonium Ph36.CR1R2.C0.R3

x+2R4MgBr

R42+Ph,P+R1R2CH.C0.R3

3 Miscellaneous The structures of the phosphonium salts (22)44 and (58)45 have been determined by X-ray analysis. The ring in (58) is planar and there is no evidence of delocalisation of charge. Me

2Br-

For a discussion of the magnetic non-equivalence of the methylene hydrogens in the lH n.m.r. spectra of benzylphosphonium salts see Chapter 11. Triarylmethylphosphonium salts have been shown 46 by n.m.r. measurements in chloroform to associate to contact ion pairs in which the anionic charge is localised on the phosphorus. Hammett constants determined in the same medium and by the same method have therefore been used to provide information on the non-inductive portion of the electronic effect of 'onium phosphorus. This ipdicates that R3P+is a strong - M substituent. The reactivity of the salts PhXMe, (X = N, P, As, Sb) towards nitration in sulphuric acid has also been discussed in these 42 43

44 46 48

p7

L. Horner, P. Beck, and R. Luckenbach, Chem. Ber., 1968, 101, 2899. (a) L. Horner and J. Dorges, Tetrahedron Letters, 1965, 763. ( b ) T. Mukaiyama, R. Yoda, and I. Kuwajima, Tetrahedron Letters, 1969, 23. C. Moret and L. M. Trefonas, J . Amer. Chem. SOC.,1969, 91, 2255. R. Majeste and L. M. Trefonas, J . Heterocyclic Chem., 1969, 6, 269. G . P. Schiemenz, Angew. Chem. Internat. Edn., 1968, 7 , 544. A. Gastaminza, T. 0. Modro, J. H. Ridd, and J. H. P. Utley, J. Chem. SOC.(B), 1968, 534.


34

PART 111: Phosphorins and Phospholes 1 Phosphorins A. Preparation.-The preparation of phosphorins from pyrylium salts and tris(hydroxymethy1)phosphine has been extended to the synthesis of 2,4,6-tri-t-butylphosphorin (1). Oxidation of this with ethanolic hydrogen peroxide gave the furan (2). But

But

9-Phospha-anthracene (3) and 9-phosphaphenanthrene (4) have been prepared in solution by dehydrochlorination of the relevant chlorophosphines with 1,5-diazabicyclo[5,4,O]undec-5-ene, and their U.V. spectra ti was much more stable than recorded. 10-Phenyl-9-phospha-anthracene the parent (3) and was isolated as a crystalline solid which, however, reacted with oxygen much more rapidly than did monocyclic phosphorins.

A comparison of the spectra of the phosphacyclohexadienone ( 5 ) with those of its oxide and methiodide did not entirely rule out a contribution from the ‘phosphapyrylium’ form (6). However, the alcohol (7), obtained from ( 5 ) and phenyl-lithium, protonated on phosphorus to give the salt (8) rather than form a phosphapyrylium salt. The U.V. spectrum of the salt (9) did not support any contribution from the aromatic form (lo).’ B. Structure.-X-Ray analysis of 2,6-dimethyl-4-phenylphosphorinhas supported the concept of a delocalised aromatic nucleus. The ring is planar and symmetrical with P-C bonds of 1.74 A intermediate between the single and double bond values. Similar results have been obtained for the phosphorins (11). G. Markl, Angew. Chem., 1966, 78, 907. K. Dimroth and W. Mach, Angew. Chem. Inernat. Edn., 1968, 7 , 460. P. de Koe and F. Bickelhaupt, Angew. Chem. Internat. Edn,, 1967, 6, 567. P. de Koe, R. van Veen, and F. Bickelhaupt, Angew. Chem. Internat. Edn., 1968,7,465. P. de Koe and F. Bickelhaupt, Angew. Chem. Internat. Edn., 1968,7, 889. G. Mark1 and H. Olbrich, Tetrahedron Letters, 1968, 3813. M. Simalty and H. Chahine, Bull. SOC.chim. France, 1968, 4938. J. C. J. Bart and J. J. Daly, Angew. Chem. Internat. Edn., 1968, 7 , 81 1. W. Fischer and E. Hellner, Tetrahedron Letters, 1968, 6227.


35 0

Me3SibSiMe3 Ph +/ Ph Ph

~

M e 3 S i o S i M e 3 PhLi ‘Ph Ph P Ph

I

Ph I v kP3hS‘ i G ; ‘MP eh 3

Ph

(5)

1\

Ph

H (8)

c10,-

Molecular orbital calculations on phosphorins have been reported.1° The models which agreed with the experimental data on electronic spectra and reactivity involved strong interaction between the .rr-orbital of the phosphorus and those of the neighbouring atoms. The stability and possible existence of (n+ 1)-phosphonia[n,n]spirarenes has been discussed.ll These, e.g. (12) and (13), are aromatic systems, the two parts being at right angles but fully conjugated through (d-p)n interaction. to air of a solution of the phosphorin (14; R = Ph) in benzene gave l2the phosphinic acid (15 ) and the anhydride (16). The phosphorin (14; R = But) under similar conditions formed the

C. Reactions.-Exposure

lo l1

la

R. ViIceanu, A. Balint, and Z. Simon, Rev. Roumaine Chim., 1968, 13, 533. A. J. Ashe, Tetrahedron Letters, 1968, 359. K. Dimroth, K. Vogel, W. Mach, and U. Schoeler, Angew. Chem. Internat. Edn., 1968, 7 , 371.

36

0rganophosphor us Chemistry

phosphonic acid (17) which was also obtained using other oxidising agents. Both (1 5 ) and (17) were hydrogen-bonded dimers. R

Ph

Ph

€ ' h o g

d 'OH

But 0 B uH t

R\ 0 OH

Oxidation of phosphorins with mercury(@ acetate in the presence of alcohols or phenols l3 proceeded via radical cations to give the 1,l-dialkoxyor 1,l-diphenoxy-phosphorins(18). These were protonated by strong acids at the 2- or the 4-position. Two isomeric methyl phosphinates (19) and (20) were obtained on oxidation of the 1,l-dimethoxyphosphorin (21). Both isomers with trifluoracetic acid gave the deep blue cation (22). Similar cations may be responsible for the blue colorations obtained l2 when (15) and (16) were dissolved in trifluoracetic acid and when a solution of the phosphorin (14; R = Ph) in benzene was shaken with oxidising acids. The ambident anion (23) formed from 2,4,6-triphenylphosphorin (24) and phenyl-lithium was alkylated on phosphorus with alkyl halides in tetrahydrofuran but at the 2-position in benzene.14 The same anion (23) has also been obtained l5 by reduction of the pentaphenylphosphorin (25) with sodium-potassium. The phosphorin (24) did not react with maleic anhydride or with diethyl acetylenedicarboxylate.l8 However, with hexafluorobut-2-yne at 100" the 1-phosphabarralene (26) was formed.le Arylation15 of the phosphine (24) or of (27) with mercury diaryls at 240-270" gave the 1,l-diarylphosphorins (28) formed via the radicals (29). With the 2,4,6-triphenylphenoxy radical, (27) gave a stable yellow compound for which structure (30) was proposed. The cation (31) was obtained from (27) and trityl perch10rate.l~ With phenyl-lithium it gave (25). The ambident nature of (31) was shown by its l3

l4 l5 l6

K. Dimroth and W. Stade, Angew. Chem. Internat. Edn., 1968, 7 , 881. G. Markl and A. Merz, Tetrahedron Letters, 1968, 3611. G. Markl and A. M e n , Tetrahedron Letters, 1969, 1231. G . Markl and F. Lieb, Angew. Chem. Internat. Edn., 1968, 7 , 733.

37


/ \

R 2 0 OR2 (18)

B

HSO CFBCOaH

Ph Ph O

P

h

P h o P h / \

(24)

Ph R

Ph

Ph

P h O P h / \

Ph Ph (25)

I Ph

38


Ph

Ph

Ph

Ph

reaction with water from which the oxides (32) and (33) have been obtained.ls~

PhG

P Hh

I Ph (27)

Ph&+

0 OH

Ph

Ph

+

Ph

Ph

/ \

Ph

0

2 Phospholes Similar syntheses of 1-methyl- and 1-phenyl-phosphole lB have been described. Their spectroscopic and chemical properties agreed with previous data for more highly substituted phospholes in indicating considerable aromatic character in the phosphole nucleus. 1-Phenylphosphole (34) was obtained as a distillable liquid which did not dimerise at room temperature in contrast to the oxide and sulphide (in which aromatic l7

l9

C . C. Price, T. Parasan, and T. V. Lakshminarayan, J. Amer. Chem. SOC.,1966, 88, 1034. L. D. Quin and J. G . Bryson, J. Amer. Chem. SOC.,1967, 89, 5948. G. Mark1 and R. Potthast, Tetrahedron Letters, 1968, 1755.

39


stabilisation is not possible) which were isolated as the dimers (35). The sulphide of 2,5-dimethyl-1-phenylphosphole was monomeric possibly because of steric hindrance to dimerisation.

Q I Ph

I

Ph

/

Ph

(34)

J

1

PhSiH,

Br

tjBr

K O B ~ 2 7

Ph'

\*

2 Quinquecovalent Phosphorus Compounds BY S. TRIPPETT

The use of 3d-orbitals in bonding by phosphorus has been discussed and re~iewed.~ 1 Pseudorotation Pseudorotation, that is the interconversion of trigonal bipyramids (1) and (3) by way of the square pyramid (2) which may be a transition state or an

intermediate, has been reviewed by Westheimer and the general question of ligand reorganisation in trigonal bipyramids 6--7 and in hexaco-ordinate structures * has been discussed. Peterson graphs are useful for following pseudorotations and for exploring the consequences of stereochemical restrictions which may be imposed on the process, for example by including in the molecule a small ring which will prefer to be apical-equatorial. One such graphs is given in (4); each vertex corresponds to one of the ten BC AD

CD

(4)

* ti

K. A. R. Mitchell, J. Chem. SOC.( A ) , 1968,2677. B. C. Webster, J. Chem. SOC.( A ) , 1968,2909. K. A. R. Mitchell, Chem. Rev., 1969, 69, 157. F. H. Westheimer, Accounts Chem. Res., 1968, 1, 70. E. L. Muetterties, Inorg. Chem., 1967, 6, 635. J. D. Dunitz and V. Prelog, Angew. Chem. Internat. Edn., 1968, 7 , 725. P. C. Lauterbur and F. Ramirez, J. Amer. Chem. SOC.,1968,90, 6722. E. L. Muetterties, J. Amer. Chem. SOC.,1968, 90, 5097.

Quinquecounlent Phosphorus Compounds

41

possible trigonal bipyramids, designated by the groups occupying apical positions, and each edge represents a possible pseudorotation. Conclusions which have been emphasised by several authors include: ( i ) a trigonal bipyramid may be converted into its mirror image by a series of five successive pseudorotations ; and (ii) this process of racemisation is not possible if the restriction is imposed that two groups cannot both be equatorial at the same time. It follows from the first that a stereospecific substitution at phosphorus cannot involve a trigonal bipyramidal intermediate which is sufficiently long lived to pseudorotate without restriction. The outstanding need in this area of organophosphorus chemistry is for quantitative data on the preference of electronegative groups for apical positions, and on the energy barrier to pseudorotation and how it varies with substituents. Such information is beginning to appear. Calculation from spectroscopic data of the energy barrier to pseudorotation in phosphorus halides gave values, for example, of 7.6 for PFBand 15.0 kcal/mole for MePF,. Molecular orbital calculations lo on the cyclic phosphate ester ( 5 ) and the intermediates in its hydrolysis gave an upper value to the barrier between (6) and (7) of 12-15 kcal/mole and fully supported the mechanism for the hydrolysis of ( 5 ) proposed by We~theimer.~ CfHOM : . 7

0-P, I 0-

CtH

0-P -OMe /

-.

The temperature-dependent l11 n.m.r. spectrum of the bis(2,2'-biphenyly1ene)phosphorane (8 ; R = o-isopropylphenyl) was interpreted l1 in

terms of pseudorotation in which the o-isopropylphenyl group remained equatorial, i.e. occupied the apical position of the intermediate square pyramid, and with activation parameters of E = 20.8 k 0-4 kcal/mole and log A = 15.0 f-0.3. Similar studies l2 on a wide variety of phosphoranes lo l1

l2

R. R. Holmes and Sr. R. M. Deiters, J. Amer. Chem. SOC.,1968, 90, 5021. D. B. Boyd, J. Amer. Chem. SOC.,1969,91, 1200. G. M. Whitesides and W. M. Bunting, J . Amer. Chem. SOC.,1967, 89, 6801. D. Hellwinkel, Chimia (Swifz.), 1968, 22, 488.

42


(8; R = alkyl, aryl) gave free energies of activation for pseudorotation (at the coalescence temperature of the signals due to the biphenylylene methyls) varying from 11.9 (R = /3-naphthyl) to 17.1 kcal/mole (R = 01napht hyl). A study l3 of the temperature-dependent lH n.m.r. spectra of (9) and (10) has given data for the energy requirements for forcing the 1,3,2-dioxaphospholan ring into a diequatorial position. Two processes of pseudorotation were identified : those [(11) + (12)] in which the rings remained apical-

equatorial were rapid at - 70" whereas the pseudorotations [(11) + (13)] which involved placing a ring diequatorial were slow on the n.m.r. timescale. The observed spectral changes led to values for the free energy difference between (11) and (13) of 15.6 kcal/mole in the case of (9) and of 18.4 kcal/mole in the case of (10). A major development in the chemistry of quinquecovalent phosphoranes has been the appreciation that small rings stabilise such compounds. This may be because the small ring partly offsets crowding difficulties in the quinquecovalent state, or because the ring is less strained when spanning an apical-equatorial position of a trigonal bipyramid than when it contains a tetrahedral phosphorus. Several examples of this stabilisation are contained in the following account.

2 2,2'-Biphenylylenephosphoranes Details have appeared l4 of the preparation of bis(2,2'-diphenylylene)phosphorane (14) by reduction of the salt (15). A benzene solution of (14) in the dark became deep violet due to the radical (16) which decayed over a period of weeks to give mainly the phosphines (17) and (18) with small ld

D. Houalla, R. Wolf, D. Gagnaire, and K. B. Robert, Chem. Comm., 1969, 443. D. Hellwinkel, Chem. Ber., 1969, 102,528.

43

Quinquecovalent Phosphorus Compounds

quantities of (19) and (20). In benzene-methanol the sole product was compound (18) and deuterium labelling showed that the transfer of hydrogen involved was from (14) to (16) and did not involve the solvent.

+

Oxidation of the phosphorane (14) with air gavel4 the phosphine oxide (21) from which the phosphinic acid (22) was obtained following an unusual reduction with lithium aluminium hydride. The anion (23) from (14) was in equilibrium with the phosphine anion (24), an equilibrium which could be established from either side.l* When compound (14) was treated with t-butyl-lithium in benzene or ether and the solution quenched with deuterium oxide the resulting phosphine (18) was predominantly undeuteriated, i.e. it was present in the reaction mixture before hydrolysis. A catalytic conversion of (14) into (18) via the radical anions (25) and (26) was suggested.14 The phosphoranes (27; R = Me, CH2Ph) with bromine gave the phosphonium salts (28).15 D. Hellwinkel, Chem. Ber., 1969, 102,548.

44


(24)

I

ButLi-THF


45

(18)

+

R-

3 1,3,2-Dioxaphospholens The synthesis of 1,3,2-dioxaphospholens from a-diketones and phosphites has been extended to the use of glyoxallB and of cyclic phosphites and phosph~ramidites.~'The glyo.xa1-trimethyl phosphite adduct (29) was much less sensitive to water than the corresponding biacetyl adduct and has been used in the synthesis of various sugar-like phosphates, e.g. (30). The bicyclic adducts, e.g. (3 l), had remarkable thermal stability. Biacetyl with the aminofluorophosphine (32) gave the dioxaphospholen (33)-1s Successive exchange of the methoxy-groups of the biacetyl-trimethyl phosphite adduct (34) for benzyloxy-groups occurred when (34) was heatedlg with benzyl alcohol at 100". With acyl chlorides (34) gave the phosphate esters (35) of a-hydroxy-p-diketones.20This is an example of the nucleophilic addition of phospholens to carbonyl compounds, a wide variety of which has been investigated by Ramirez and his co-workers. Among F. Ramirez, S. L. Glaser, A. J. Bigler, and J. F. Pilot, J . Amer. Chem. SOC.,1969,91,496. F. Ramirez, M. Nagabhushanam, and C. P. Smith, Tetrahedron, 1968, 24, 1785. G. I. Drozd, S. 2. Ivin, and V. V. Sheluchenko, Zhur. obshchei Khim., 1968, 38, 1906. F. Ramirez, K . Tasaka, N. B. Desai, and C. P. Smith, J. Amer. Chem. Soc., 1968, 90, 751. 2o

F. Ramirez, S. B. Bhatia, A. J. Bigler, and C. P. Smith, J . Org. Chem., 1968,33, 1192.

46


Me MePF.NEt,

+

CHzClz

(MeC0)2

-*+

(32)

Me I MeC0.C.CO.R I 0

I f(0Meh

c1-

-

Et2N... ,P-0

Me

I

F

Me I MeCO *C*CO R I 0 I P(:O)(OM&

-

(35)


47

recent examples are additions to carbon suboxide,21 ap-unsaturated 23 acyl iso~yanates,:!~ and sulphonyl i s ~ c y a n a t e s . ~ ~ aldehydes,22* Carbon suboxide 21 gave the lactones (36); the suggested mechanism is as shown. Acraldehyde 2 2 and crotonaldehyde 23 with (34) gave the phospholans (37); the complex hydrolyses and methanolyses of these compounds have been described.

R1 R’CO- C-C / -0

R1

I

I+

\

CC-P-OM,;. L c H I R2 0’”

I

R’CO-C-C

-6

“

R2 At-0Me

0,

II 0

R2

RICO-C-C:O t---

I

0, P

\ ,c=c=o

/I\

M e 0 RZR2

I

-*

RlCO -C-C - 0 M e 0, I ,C-PR2 \\

c

II 0

II 0

(36)

The initial betaines (38) formed from dioxaphospholens and acyl isocyanates 24 cyclised with expulsion of trialkyl phosphate to form the oxazolinones (39). Similar cyclisation of the intermediate from the reaction of (34) with two molecules of benzenesulphonyl isocyanate gave the NN’-ditosylhydantoin (40).24 21 22

23

a4

F. Ramirez and G . V. Loewengart, J. Amer. Chem. SOC.,1969,91, 2293. F. Ramirez, H. J. Kugler, A. V. Patwardhan, and C. P. Smith, J . Org. Chem., 1968,33, 1185. F. Ramirez, H. J. Kugler, and C . P. Smith, Tetrahedron, 1968, 24, 3153. F. Ramirez and C. D. Telefus, J . Org. Chem., 1969, 34, 376.

48

Organophosphorus Chemistry Me

I

MeCO-C-CH*CH:CH.R

CH.CH:CH*R

O,

II 0

/o

P (OMe),

I

___j

0

I

1

0-

+P(OMe),

R =H, Me

(34)

H

J

I

MeHMe 0, P /O (OMc), (34)

+

2 P h S 0 , - NCO

1

MeCO -C-CO I \ P h - SO,-N\ ,,N.SO,-Ph C 0 (40)

4 1,3,2-Dioxaphospholans Tertiary phosphines and hexafluoroacetone formed the 1,3,2-dioxaphospholans (41).25 That from trimethylphosphine had only one doublet in its lH n.m.r. spectrum at - 62" showing that pseudorotation was rapid on the n.m.r. time-scale even at this temperature. The 1,3,2,-dioxaphospholans rearranged on heating to give the 1,2-oxaphosphetans (42) which at higher temperatures formed phosphinates and olefins.2s The rates of rearrangement were in the order Et,P> Et,PhP> EtPh,P> Me3P and the rates of olefin formation in the order Me,P > Et,PhP > Et3P> EtPh,P. The oxaphosphetan from diethylphenylphosphine was obtained as the two diastereoisomers (43) and (44) which equilibrated on heating. This equilibration could be by a process of pseudorotation only if the fourmembered ring became diequatorial in an intermediate trigonal bipyramid. 26

26

F. Ramirez, C. P. Smith, J. F. Pilot, and A. S. Culati, J. Org. Chem., 1968, 33, 3787. F. Ramirez, C. P. Smith, and J. F. Pilot, J . Amer. Chem. Soc., 1968, 90, 6726.

49


R R.. I )P-0

AJe3

F,CpcF3

The 1,3,2-dioxaphospholan(45) was formed from ninhydrin and trialkyl phosphites but with triphenylphosphine the stable ylide (46) and triphenylphosphine oxide were ~btained.:!~

C/ 0

0

f3>C=PPh3

+

Ph3P0

0

27

A. Mustafa, M. M. Sidky, S. M. A. D. Zayed, and M. R. Mahran, Annalen, 1968,712,

116.

50


The 1,3,2-dioxaphospholans (47),formed from triethyl phosphite and the fluorenones (48), when dissolved in acetonitrile at 43-46' for 20 hr. gave 28

X

X

X

X (47)

(48)

X = H, Br

Me I

X P(oE~),

(49)

X

the spiro-ketones (49)-also formed and the oxazolines (50). 28

2Q

29v

30

Me

x

on heating the adducts to 160°-

I. J. Borowitz, P. D. Readio, and P. Rusek, Chem. Comm., 1968, 240. F. Ramirez and C. P. Smith, Chem. Comm., 1967, 662. I. J. Borowitz and M. Anschel, Tetrahedron Letters, 1967, 1517.

QuinquecovalentPhosphorus Compounds

51

The tetraoxyphosphorane ( 5 1) has been condensed with benzaldehyde and with trichloroacetaldehyde to give the alcohols (52).31 The corresponding alcohol from benzaldehyde and the tetraoxyphosphorane derived

from cis-cyclohexan-l,2-diol was shown from its lH n.m.r. spectrum to contain three diastereoisomers. See Chapter 10, section 1 for the photolysis of 1,3,2-dioxaphospholans. 5 1,2-0xaphospholens The addition of trimethyl phosphite to 3-benzylidene-2,4-pentandioneto form a 1,Zoxaphospholen 32 has been extended to the use of phosphonite A study of the lH n.m.r. spectrum 33s 34 of the and phosphinite dimethyl phenylphosphonite adduct showed that at low temperatures the two isomers (53) and (54) were stable but that at higher temperatures (> 52”) they were in rapid equilibrium by a process involving four successive

MeC0,-,CO-Me C

31

sa 33

34

R. Burgada and H. Germa, Compt. rend., 1968, 267, C, 270. F. Ramirez, 0. P. Madan, and S. R. Heller, J . Amer. Chem. SOC.,1965, 87, 731. F. Ramirez, J. F. Pilot, 0. P. Madan, and C. P. Smith, J. Amer. G e m . SOC.,1968,90, 1275. D. Gorenstein and F. H. Westheimer, Proc. Nat. Acad. Sci. U.S.A., 1967, 58, 1747.

52


R

1

= OMe 60"


53

pseudorotations. Above 70" opening of the ring began and at 125" the adduct was entirely the dipolar form ( 5 5 ) . 6 1,3-Oxaphospholans

The 1,3-oxaphospholans (56) were the initial products from the reactions 35 of phosphites and aminophosphines with dimethylketen at - 75". The trimethyl phosphite adduct (57) gave the keten dimer (58) quantitatively at 60". Dimerisation of dimethylketen to (58) in the presence of phosphites had previously been The reactions of the adduct (57) are indicative of a highly polarised carbon-phosphorus bond.

7 Penta(ary1oxy)phosphoranes Pentaphenoxyphosphorane has been prepared 37 by the addition of phenol ( 5 moles) in benzene to a hexane solution of y-collidine ( 5 moles) at 0" containing phosphorus pentachloride (1 mole). None of the previously reported syntheses was successful. With catechol in benzene the phosphorane readily exchanged two phenoxy-groups to give (59) while a further

exchange occurred in methylene chloride at 25" to give the bicyclic phosphorane (60).38 This is a striking demonstration of the stabilising effect of five-membered rings on phosphoranes. 8 Miscellaneous The minor products in the preparations of the phosphinites (61) from catechol and dichlorophosphines in the presence of triethylamine have been identified 39 as the phosphoranes (62). These were also formed from :he phosphinites (61) on prolonged heating at 100" in the presence of an icid catalyst or on treatment with o-benz~quinone.~~

36

36 37 38 3e

W. G. Bentrude and W. D. Johnson, J. Amer. Chem. Soc., 1968,90, 5924. E. U. Ullam, J. Org. Chem., 1967, :32, 215. F. Ramirez, A. J. Bigler, and C. P. Smith, J. Amer. Chem. SOC.,1968, 90, 3507. F. Ramirez, A. J. Bigler, and C. P. Smith, Tetrahedron, 1968, 24, 5041. M. Wieber and W. R. HOOS, Tetrahedron Letters, 1968, 5333.

54


The phosphorane (63) was the major product formed from o-aminophenol and various halogenocyclophosphazenes in refluxing ~ylene.~O While undoubtedly existing as the phosphorane in solution there was some i.r. evidence that in the solid state the hexaco-ordinate betaine structure (64) might be present.

6””’ \

The phosphorane (65) was obtained *l from bis(trifluoromethy1)phosphine and the stable radical (66).

The slow exchange of ligands on treatment of pentaphenylphosphorane with phenyl-lithium has been followed kinetically 4 2 using tritium labelling, and compared with similar exchange in the pentaphenyl derivatives of arsenic, antimony, and bismuth.

42

H. R. Allcock and R. L.Kugel, Chem. Comm., 1968, 1606. H. G . Ang, Chem. Comm., 1968, 1320. H. Daniel and J. Paetsch, Chem. Ber., 1968, 101, 1451.

3 Halogenophosphines and Related Compounds BY S. TRIPPETT

1 Halogenophosphines A. Preparation.-p-Dihalogenobenzenes with white phosphorus and phosphorus trichloride at 340"in the presence of iodine gavep-bis(dich1orophosphin0)-benzene (38%). Under similar conditions the chlorophosphine (1) was obtained.2

(1)

Methane, ethane, and benzene passed over phosphorus pentachloride at 200°, and the resulting vapour then passed over heated quartz chips, gave

the corresponding dichloropho~phine.~ Terminal olefins with phosphorus pentachloride in benzene or phosphorus trichloride followed by reduction with dichloromethoxyphosphirie gave the dichlorovinylphosphines (2) in 38-87% yield.* R1R2C:CH2+PCI,

---+

[R1R2C:CH'PCI,]

Meo'PCb

+

R1R2C:CH-PC12 MeCl+ 0pc13 (2)

Difluoropentafluorophenylphosphinehas been prepared by the action of sodium fluoride in acetonitrile (not sulpholan 5, or of antimony trifluoride on the corresponding dibromo- or dichloro-compound.6 The same reagents gave fluorodi(pentafluoropheny1)phosphine from the chloride or bromide. 1,2-Dibromo-1,2-diphenyldiphosphine(3) has been obtained in a variety of ways as shown.' Yu. I. Baranov, 0.F. Filippov, S. L. Varshavskii, and M. I. Kabachnik, DukZady Akad. Nauk S.S.S.R., 1968, 182, 337. U.S.S.R.P.210,155. E. A. Smirnov, Yu. M. Zinov'ev, and V. A. Petrunin, Zhur. obshchei Khim., 1968, 38, 1551. Ya. A. Levin, V. S. Galeev, and E. K. Trutneva, Zhur. obshchei Khim., 1967,37, 1872. J. M.Miller, J . Chem. Suc. (A), 1967, 828. M. Fild and R. Schmutzler, J, Che.m. Soc. ( A ) , 1969, 840. M. Baudler, 0. Gehlen, K. Kipker:,and P. Backes, 2. Naturforsch., 1967,22b, 1354.

56


47%

Ph2P212

B. Reactions.-(i) Nucleophilic Attack on Phosphorus. Sodium cyanate and dichlorophenylphosphine gave successively the mono- (4) and di-(isocyanato)phosphine (5).* The latter polymerised slowly in an inert atmosphere.

+

PhPCI, NaNCO

MeCN

PhPCl NCO (4)

-

PhP(NCO), (5)

57% 67% The carbodi-imide (6) was obtained from the reaction of chlorodiphenylphosphine with silver cyanamide as a complex with silver chloride and s ~ l v e n t .Addition ~ of sulphur gave the disulphide (7), and the urea (8) was obtained on oxidation with aqueous hydrogen peroxide. The same chlorophosphine with calcium carbide gave carbon and tetraphenyldiphosphine isolated as the dioxide or disulphide in 50% yield.1°

PhZP *N:C :N PPh2 (6)

Y

x

Ph2P(: S) *N:C: N *P(:S)Ph2

(7) Ph,P(:O) *NH*CO.NH*P(:O)Ph,

(8)

Whereas hydrazine gave no recognisable products, the expected hydrazinophosphines were obtained from 1 , l -dimethylhydrazine and trimethylhydrazine on treatment with trifluoromethyldi-iodophosphine and with di(trifluoromethyl)iodophosphine,llP l2 e.g.,

+

(CF3),PI Me2N NHMe 6

Ether ~

+ (CF,),P. NMe - NMe, 83%

The first diaminophosphine (9) was obtained from t-butyldichlorophosphine and ammonia in ether at -50". Compound (9) was extremely sensitive to oxygen and water and with trimethylchlorosilane gave the bis(trimethylsily1) derivative (10). J. J. Pitts, M. A. Robinson, and S. I. Trotz, Inorg. Nuclear Chem. Letters, 1968, 4, 483. A. Weisz and K. Utvary, Monatsh., 1968, 99, 2498. E. J. Spanier and F. E. Caropreso, Tetrahedron Letters, 1969, 199. l1 L. K. Peterson and G. L. Wilson, Canad. J. Chem., 1968, 46, 685. l 2 L. K. Peterson, G. L. Wilson, and K. I. ThC, Canad. J . Chem., 1969, 47, 1025. lS 0. J. Scherer and P. Klusman, Angew. Chem. Infernat. Edn., 1968, 7, 541. @

lo

57

Halogenophosphines and Related Compounds NHa

ButPC1,

>

MeaSiCl

B~P(NH,), (9)60%

ButP(NH*SiMe,), (10) 70%

Sodium arylsulphinates with chlorodiphenylphosphine in dimethylformamide gave the aryl diphenylphosphinothiolates (1 l).l* There was no reaction with diphenylphosphinic chloride, and aliphatic chlorophosphines gave only diphenyl disulphide and the phosphinic acids. Sodium arylsulphonates did not react with chlorophosphines. Ph,PCl

+ Ar - S0,Na

___j

-

Ph,P( :0). S Ar (1 1)

Phenyl diphenylphosphinoselenolate (12) has been obtained in a variety of ways as shown.15 The route from the dioxide was thought to involve the intermediate PhzP 0 Se Ph which rearranged to (12).

-

PhSe SePh

Ph,PCl

+ or PhSeH

or PhSeMgBr Ph,PMgCI

-1 L

J

O2

Ph,P(:O).Se.Ph (12)

I

+ PhSeBr

PhSeBr

Ph,P(: 0)*P(:O)Ph, Chlorodimethylphosphine with metallated pentaborane(9) gave p-dimethylphosphinopentaborane(9:) (1 3) containing a B-P-B three-centre two-electron bond.ls The n.m.r. spectrum of (13) showed the two methyl groups to be in different environments and chloro(methy1)trifluoromethylphosphine gave rise to two similar isomeric compounds. However, chlorobis(trifluoromethy1)phosphine gave l-bis(trifluoromethy1)phosphinopentaborane(9) with no evidence of bridging phosphorus. H

P

/ \

Me

Me

(13)

(ii) Nucleophilic Attack by Phosphorus. The formation of benzoyl and alkyl chlorides together with the phosphine oxides (14) from the reactions of l4

l6

l6

H. Schindlbauer and W. Prikoszovich, Monatsh., 1968, 99, 1792. N. Petragnani, V. G. Toscano, and M. de Moura Campos, Chem. Ber., 1968,101,3070. A. B. Burg and H. Heinen, Znorg. Chem., 1968,7, 1021.

58


chlorodiphenylphosphine with benzoate esters has been rationalised in terms of competing nucleophilic attacks of the chlorophosphine on the carbonyl carbon or on the alkyl oxygen as sh0wn.l' PhC02-

+ RPh2k1

Ph.CO*OR + Ph2PCI

Ph.CO*O*$Ph2.R

cl

Ph CO .C1 + RPh,P(:O)

I

(14)

Ph*CO*$Ph2-C16 R

Ph.CO*$Ph,.OR el

[Ph*CO-P(:0)-Ph2] t RCl

Aliphatic carboxylic anhydrides with diethylchlorophosphine gave the vinylphosphine oxides ( 1 5 ) presumably via the highly reactive acylphosphine oxides (16).18 For other reactions of these oxides see Chapter 4, section 1D. Et,PCl+ (RCH2.CO)20

-

R.CH2.C0.6Et2.C1e RCH,.C6, R*CH,*CO.P( :O)Et2 RCH2 CO .C1

+

F:CH2 :O)Et2 R*CH:C(0.C0.CH2R)*P( (1 5 )

- CO)20

R*CH2*C(0.CO*CH2R)2.P( :O)Et,

2-Cyanoethylphosphinic chlorides (17) resulted from the addition of dichlorophosphines to acrylamide, perhaps via the cyclic intermediates (18).l8#2o Dichloro(methy1)phosphine with methacrylic acid gave the acid l7

IQ 2o

S. T. McNeilly and J. A. Miller, Chem. Comm., 1969, 620. V. S. Tsivunin, Yu. N. Afanas'ev, R. G. Ivanova, T. A. Zyablikova, and G. Kh. Kamai, Zhur. obshchei Khim., 1968, 38, 1523. V. K. Khairullin, R. M. Kondrat'eva, and A. N. Pudovik, Izvest. Akad. Nauk S.S.S.R., Ser. khim., 1967, 2097. V. K. Khairullin, T. I. Sobchuk, and A. N. Pudovik, Zhur. obshchei Khim., 1968,38, 584.

Halogenophosphines and Related Compounds

59

chloride (19) and with propiolic acid followed by ethanol gave the ester (20)

RP( :0)Cl-CH, CH, * CN (17) 37-56%

fl

MeP(: 0)Cl. CH, .CHMe CO C1 (19) 86%

Me2PC1 ‘-relc.

[]

EtoH z

MeP( :O)(OEt) CH :CH * C0,Et (20)

Chlorodiphenylphosphine arid triethyl orthoformate reacted exothermically 22 to give the acetal (21). Acetals, dithioacetals, and ethoxymethylamines similarly gave the oxides (22) and (23). The acetals (24) were obtained from triethyl orthoformate and dichlorophosphines.

(22) x = 0, s

‘h %‘-r

Ph,P(: 0) CH, *NR2

RPCl2

-I- HC(0Et);

-

RP(: 0) (OEt) CH(0Et)a (24)

Details have appeared 23 of the reaction between chlorodiphenylphosphine and benzoyl peroxide which gave benzoyl chloride, benzoic anhydride, and diphenylphosphinic anhydride. The intermediate mixed anhydride (25) 21

22

23

V. K. Khairullin, R. M. Kondrat’eva, and A. N. Pudovik, Zhur. obshchei Khim., 1968, 38, 288. W. Dietsche, Annalen, 1968, 712, 21. G. Sosnovsky and D. J. Rawlinson, J . Org. Chem., 1968, 33, 2325.

60


was detected by its characteristic carbonyl absorption at 1740 cm-l. Authentic (25) in refluxing benzene rapidly formed an equilibrium mixture of the two symmetrical anhydrides and an appreciable proportion of (25).

Ph2P(:0)0.P( :O)Ph2

+(PhCO)zO

-

+

PhzP(:0). 0.CO Ph PhCO * C1 (25)

(iii) Miscellaneous. Attempts to extend to other ketones the reaction of benzophenone with dichlorophenylphosphine in the presence of partially hydrated aluminium chloride to give the phosphinic chloride (26) met with limited success.23 Alkyl aryl and acyclic dialkyl ketones gave complex mixtures of neutral products but cyclohexanone gave the phosphinic acid (27). Biphthalyl (34%) was formed from phthalic anhydride and dichlorophenylphosphine in the absence of catalyst at 100" in a reaction analogous to that using triethyl p h ~ s p h i t e . ~ ~ Ph2CO+PhPCI2

AlCla HzO

-

> Ph2CCl P( :0) Ph * CI a

(26)

A study 6 v 28 of the disproportionation of difluorophosphines (28) to give tetrafluorophosphoranes and cyclopolyphosphines has shown that the rates of disproportionation are in the order R = Me > Ph > CUFB > CF,. RPF, (28)

-

RPF4+(RP),

2 Halogenophosphoranes A. Diha1ogenophosphoranes.-(i) Structure. Examination of the 31Pn.m.r. spectra of the chlorine adducts of the phosphines PhnPC13-, (n = 3 , 2 , or 1) showed 27 that in this solvent they exist as pentaco-ordinate species but that an excess of chlorine promotes dissociation to the ion pairs R 4 6 el,. This ionisation is less ready as the number of chlorines attached to the phosphorus increases. Hydrogen chloride also promotes the dissociation of dichlorotriphenylphosphorane to give P h , h H&. 24

25 28

K. L. Freeman and M. J. Gallagher, Austral. J . Chem., 1968, 21, 2297; Tetrahedron Letters, 1966, 121. F. Ramirez, H. Yamanaka, and 0. H. Basedow, J. Amer. Chem. Soc., 1961,83, 173. H. G. Ang and R. Schmutzler, J . Chem. SOC.(A), 1969, 702. D. B. Denney, D. Z. Denney, and B. C. Chang, J . Amer. Chem. SOC., 1968,90, 6332.


61

The tetra(diha1ogenophosphoranes) (29) are covalent in rnethylene chloride but in strongly polar solvents such as dimethylformamide and acetonitrile the chlorine adduct forms a 1 :2, the bromine adduct a 1 : 3, and the iodine adduct a 1 :4 electrolyte.28 These were formulated as the spirocyclic (30), bicyclic (31), and bridge-free (32) structures.

3Br/I

1

\

C[CH,h.Ph,l, 41 (3 2)

Br

(3 1)

Spectroscopic evidence has shown 2B that dichlorotriphenylphosphorane in chloroform or brornoform solutions forms hydrogen-bonded nonionic dimeric species (33) with chlorine bridges between the phosphorus atoms. The solvates are crystalline and stable under anhydrous conditions.

(33)

(ii) Reactions. Dichlorophosphoranes have been reduced 30 to phosphines on heating with yellow phosphorus at 150-180”. In contrast to the behaviour of the arsenic analogue, dibromotriphenylphosphorane with silver nitrate, NzOa, or N20, gave only triphenylphosphine oxide with no evidence of a nitrato-phosphorus compound.31 The dehydration of arnides to mitriles using dibromotriphenylphosphorane (34) in the presence of triethylarnine 32 has been extended 33 to the synthesis of aminonitriles, e.g. (35). With the same reagent N-alkylformamides gave isocyanides, NN’-dialkylureas gave carbodi-imides, e.g. (36), and the substituted amides (37) gave ketenimines. 28

29

30

31

32

33

J. Ellermann and D. Schirmacher, Chem. Ber., 1969, 102, 289. G. G. Arzoumanidis, Chem. Comm., 1969, 217. G.P. 1,247,310. G. C. Tranter, C. C. Addison, and D. B. Sowerby, J . Organometnllic Chem., 1968, 12, 369. L. Horner, H. Oediger, and H. Hoffmann, Annalen, 1959, 626, 26. H. J. Bestmann, J. Lienert, and L. Mott, Annalen, 1968, 718, 24.

62


-

Me,N CO * NH,

+ Ph,PBr,

-

EtzN

(35) 67%

+ CO .NH.BLI+ (34)

R - N H . CHO (34) Ph N H

+

Me,N CN Ph3P0

(34)

R1R2CH*C0.NH.R3+(34)

EtaN

> R-NC

EtaN

$zz12

Ph.N:C:N*Bu (36) 72% R1R2C:C: N * R3

(37)

Vilsmeier formylation has been carried out33 with (34) and dimethylformamide presumably via the intermediate (38). Indole gave the 3-aldehyde (78%) and phenylacetylene gave /%bromocinnamaldehyde(60%). Ph,PBr,+Me,N.CHO

-

Ph3PBr.O*6H.NMe, Er (38)

+

+

R1R2C:CR3.CHO Ph3P0 Me,NH

(38)+ R1R2C:CHR3

o-t-Butylphenols on heating with (34) gave t-butyl bromide and steam distillation of the residues gave triphenylphosphine oxide and the dealkylated phenols.34 Thus o-t-butylphenol was obtained from 2,6-di-tbutylphenol at 200", 4-methyl-2,6-di-t-butylphenolgave 4-methyl-2-tbutylphenol, and o-t-butylphenol at 240" gave phenol. The suggested intermediate in the last case (39) could not be isolated. It is, however, a known compound 35 and is thermally stable up to 350" (see Chapter 1, Part 11, section 2C).

+

+ QOH

(34)

Ph,PO

-

2 HO

a'ph3 +

ButBr

6

(39)

A series of perfluoroalkylfluorophosphoranes has been prepared.36 19F N.m.r. studies on the trifluorophosphoranes R2PF3(R = CF3, C2F,) have shown that the fluorines attached to phosphorus are in apparently equivalent environments and it was suggested that the perfluoroalkyl groups are sufficiently electronegative to prefer apical positions. 34

36 36

D. G. Lee, Chem. Comm., 1968, 1554. H. J. Bestmann and G. Hofmann, Annalen, 1968, 716, 98. J. F. Nixon, J. Znorg. Nuclear Chem., 1969, 31, 1615.


63

B. Hydridofluorophosphoranes.--Interest in hydridofluorophosphoranes continues. Difluorohydridodimethylphosphoranewas obtained by the action of hydrogen fluoride on both Buorodimethylphosphine and tetramethyldiph~sphine.~'The same reagent with alkyl and aryldichlorophosphines at - 20"gave the hydridophosphoranes (40)which on chlorination followed by treatment with primary or secondary amines gave the aminotrifluorophosphoranes (41).38These with the same amines at 40-60" gave the diaminodifluorophosphoranes (42).39 HE'

RPCI, -----+

RPHF, (40)

el2

--lo" >

[]

R1R2NH

RPF3(NR1R2)

(41) RIR'NH

------+ RPF,(NR1R2), 40-60" (42)

Aminodifluorohydridophosphoranes (43) have been obtained from primary and secondary amines and alkyldifluorophosphines as stable distillable Ethylenedjamine gave the diphosphoranes (44) with interesting possibilities of isomerism.41 In all cases the apical positions were occupied by the two fluorine atoms. F

R .* I

(R1,N)R2PHF2

H'I

(43)

P- NH.CH2 CH2* NH-P

F.

(44)

F I H a,.

R'I F

C. Hydridoffuorophosphate Anions.-Potassium difluoride added to fluorobis(trifluoromethy1)phosphine and to difluoro(trifluoromethy1)phosphine either at 60-100" without solvent or in acetonitrile at room temperature to form hexaco-ordinate phosphorus salts, e.g. (49, containing phosphorus-hydrogen The 19F n.m.r. spectrum of (45) favours the structure (46). (CF,),PF

+ HF,

> (CF,),PF,H (45)

CF3 (46) 37 38

39

40

41

42

F. See1 and K. Rudolph, 2. anorg. Chern., 1968, 353, 233. G. I. Drozd, S. Z. Ivin, V. V. Sheluchenko, B. I. Tetel'baum, and A. D. Varshavskii, Zhur. obshchei Khim., 1968, 38, 567. G. I. Drozd, S. Z. Ivin, M. A. Landau, and V. V. Sheluchenko, Zhur. obshchei Khim., 1968,38, 1654. G. I. Drozd, S. Z. Ivin, V. V. Shduchenko, B. I. Tetel'baum, G. M. Luganskii, and A. D. Varshavskii, Zhur. obshchei Khim., 1967, 37, 1631. G. I. Drozd, S. Z. Ivin, and V. V. Sheluchenko, Zhur. obshchei Khim., 1968, 38, 1655. J. F. Nixon and J. R. Swain, Chern. Comm., 1968, 997.

64


3 Phosphines Containing a P-X (X = Si, Ge, Sn, Pb) Bond A. Phosphorus-Silicon.-Tris(trimethylsilyl)phosphine treated with stoicheiometric amounts of water, methanol, or deuterium oxide in tetrahydrofuran is a convenient source of trimethylsilylphosphine and bis(trimethy1sily1)phosphine and their deuterium analogue^.^, The lH n.m.r. and i.r. spectra of these silylphosphines suggested pyramidal structures and did not support p,-d, interaction in the phosphorus-silicon bonds.

The polyphosphines and phosphino-arsines (47) and (48), all extremely sensitive to oxygen, have been obtained from trimethylsilylphosphines and arsines as (Me3Si),M1+ 3Ph2M2C1 F (Me,Si),MlPh+ 2Ph,M2C1

Ether

~

(Ph2M2),M1 . (47)

(Ph2M2)2M1Ph (48)

MI, M2 = P, AS Bis(trifluoromethy1)trimethylsilylphosphine (49) was obtained as indi~ a t e d With . ~ ~ hydrogen bromide it gave bis(trifluoromethy1)phosphine and with methyl iodide the phosphine (50). (CF3),PH or (CF,),PI

1

HgW Me3h

(CF,),P.SiMe,

(CF,),PH

-I-(Me,Si),PH

(49) HBr

Me,SiBr

Me,SiI

+ (CF3)2PMe

+ (CF3)J'H

The insertion reactions of diphenyl(trimethylsily1)phosphine have been explored.46 While definite structural assignments were not possible in all 43 44 46 46

H. Burger and U. Goetze, J. Organometallic Chem., 1968, 12, 451. H. Schumann, A. Roth, and 0. Stelzer, Angew. Chem. Internat. Edn., 1968, 7 , 218. J. Grobe, Z. Naturforsch, 1968, 23b, 1609. E. W. Abel and I. H. Sabherwal, J. Chem. SOC.(A), 1968, 1105.


65

cases, the available evidence indicated that in the products from CO,, CS,, phenyl isothiocyanate, and hexafluoroacetone the phosphorus was attached to carbon. A minor product in the last case was the oxide (51). Phenyl isocyanate gave only its dimer whereas with keten, insertion occurred in the carbon-carbon double bond to give the phosphine (52). The product from sulphur dioxide decomposed on attempted distillation and gave a crystalline product formulated as the sulphoxide (53). Other reported reactions of this silylphosphine include those with silver halides and chlor odipheny lphosphine .47 Ph2P(:0) 0 * SiMe, Q

Ph2P* CS S SiMe,

-

-

Ph,P CO * 0 SiMe, < co2

(Ph,P),

+ Ag + Me,SiX

Ph,P SiMe,

PhNCS.

Ph,P CS -NPh.SiMe,

Iph2pcx

AY’

(PhZP),

Ph2P SiMe,

-

Ph2P CO CH, * SiMe,

[I

k

(Ph,P),SO

+ (CF,),CO

+ (Me,Si),O + SO,

(53)

PhJ’.C(CF,),*O.SiMe,

+ Ph2P(:O).C(CF,),.SiMe, (51)

B. Phosphorus-Germanium.-T)iethyl(triethylgermyl)phosphine (54) with keten and diphenylketen 4D gave the phosphines (55) formed by insertion into the carbonyl groups of the keten (contrast the behaviour of the silylphosphine above). Hydrolysis of (55; R = H) gave acetyldiethylEt,P.GeEt,

+ R,C:C:O

(54)

----+

Et,P.C(O-GeEt,):CR, (55) R

\

R

= H, =

58%

Ph, 74%

Et,P *CO CHR, 47 48

E. W. Abel, R. A. N. McLean, and I. H. Sabherwal, J. Chem. SOC.( A ) , 1968, 2371. J. Satgk and C. Couret, Compt. rend., 1968, 267, C, 173. J. Satge and C. Couret, Bull. SOC.chim. France, 1969, 333.

66


phosphine (79%) whereas hydrolysis of ( 5 5 ; R = Ph) led to a mixture of acylphosphine (80%) and diethylphosphine (20%). The acylphosphines were also obtained from (54) on treatment with the corresponding anhyd r i d e ~ .Similar ~~ additions of (54) to the carbonyls of aldehydes produced the phosphines (55) while with a,!?-unsaturated aldehydes 1,4-addition gave the phosphines (56) from which the aldehydes (57) were obtained on hydrolysi~.~~ Et,P.CHR.O.GeEt,

(54)

\ -

(55) 70%

1'.

Et,P*CHR*CH:CH -0. GeEt, cis, trans (56)

Et2P.CHR.CH:CH.CHO (57)

C. Phosphorus-Tin and Phosphorus-Lead.-The six-membered heterocyclic compounds (58; R = Me, Bu, Ph) were obtained 50 from phenylphosphine and the tin dichlorides (59). Pyrolysis of (58; R = Me) gave phenylbis(trimethylstannyl)phosphine, tin, and the cyclophosphine (60). R2 R,SnCl,

+ PhPH,

Et3N

Benzene

(PhP)5

PhP'

I R,Sn,

+

Sn

Sn 'PPh

I ,SnR,

P Ph

+

PhP(SnMe3I2

(60)

The insertion reactions of the (triphenylstanny1)phosphine (61) into carbonyl and thiocarbonyl groups have been i n ~ e s t i g a t e d . ~ They ~ were very similar to those of phosphorus-germanium compounds, the phosphorus always adding to carbon. Migration of the organometallic groups from phosphorus to nitrogen occurred 5 2 when (61) and the lead analogue were treated with phenyl azide, 60

61 62

H. Schumann and H. Benda, Angew. Chem. Internat. Edn., 1968,7, 812. H. Schumann and P. Jutzl, Chem. Ber., 1968, 101, 24. H. Schumann and A. Roth, J. Organometallic Chem., 1968, 11, 125.


67

the product from (61) being the phosphine-imine (62). Successive migrations occurred starting with the bis(triphenylstanny1)- or bis(tripheny1plumby1)-phosphines (63), but with phenylbis(trimethylstanny1)phosphine the only organometallic compound isolated was phenylbis(triniethy1stanny1)amine. No reaction occurred between triphenylsilylazide or triphenylstannylazide and organotin or organolead phosphines in refluxing benzene or between phenyl azide and tris(triphenylstanny1)phosphine or tris(triphenylplumby1)phosphine at 100".

-

-

Ph,P CS * S SnPh, 4

Ph2P CC12 S SnPh,

Ph,P.CS.O.SnPh,

Ph,P*CO-NPh*SnPh, < PhNCo

Ph2P*SnPh,

CS(NHa)a

Ph,P.C(NH,),*S*SnPh,

(61)

Ph,P.SnPh,

+ PhN,

Ph2P(:N.Ph) vNPh-SnPh,

+=

Ph,Sn.PPh,:N.Ph

Ph2P-NPh*SnPh,

(62)

PhP(MPh3), + 3PhN3 (63)

------------+

Ph3M*NPh.PPh(:NPh) *NPh*MPh3

4 Phosphine Oxides BY S. TRIPPETT

1 Preparation A. Using Organometallic Reagents.-Diethyl phosphite with alkyl magnesium halides gave initially the tervalent magnesium salts (1) which reacted with further reagent to form the phosphinous acid salts (2). These with aqueous potassium carbonate gave the corresponding secondary phosphine oxides. This method had previously failed with lower alkyl Grignard reagents. The salts (2) are useful intermediates for the preparation of phosphine oxides of various types. (EtO),PH(:O)

+ R-MgX

-----+

(EtO),P.OMgX+ (1)

R,P-OMgX (2)

R,PH(: 0)

H2C-CHR

R2P(:O).CH2-CHR*OH

\

EtCH: CH.P(: O)Me, R=Me

Me,P(:O).CHEt-CH,-P(:O)Me2 The reaction of phenyl magnesium bromide with diethyl phenylphosphonate was slowed by the presence of magnesium halides possibly due to the formation of a sterically hindered complex between the phosphonate and the magnesium halide., The reaction between phenyl magnesium bromide and ethyl diphenylphosphinate in tetrahydrofuran has been investigated kineti~ally.~The results were interpreted in terms of a moderately strong 1 : 1-complex between the reactants which slowly rearranged to give a complex of triphenylphosphine oxide with magnesium salt. A careful reinvestigation of the formation of diphosphine disulphides from thiophosphoryl halides and phosphonothioic dihalides with Grignard a

H. R. Hays, J. Org. Chern., 1968, 33, 3690. H. R. Hays, J . Org. Chern., 1968, 33, 4201. H. R. Hays, J . Arner. Chern. SOC.,1969, 91, 2736. P. C. Crofts and 1. S . Fox, J . Chern. SOC.(B), 1968, 1416.

69

Phosphine Ox ides

reagents has supported a mechanism in which a complex (3) between the halide and the Grignard reagent leads to a phosphinidine sulphide (4). This then gives the diphosphine disulphide either via insertion into a phosphorus halogen bond or by reaction with the Grignard reagent to give an intermediate phosphinothioyl magnesium halide (5).

(5)

(4)

(3)

Of several buta-l,3-dienylphosphonic dichlorides only (6) gave an acceptable yield of phosphine oxide with Grignard reagent^.^ Other buta1,3-dienylphosphine oxides were therefore prepared via the corresponding 4-chlorobut-2-enylphosphineoxides (7). Me.(CH :CH),.P(: O)C1, (6)

LMgX > Me.(CH :CH),P(: O)Rz R = Et (57%)

CICH2*CR:CH *CH2*P(:O)Cl,

RMgX >

ClCH2.CR:CH * CH, *P(:O)R, (7) R

1

= H (22%) EtOH-KOH

-

CH,: CR CH :CH * P(: O)R,

Tertiary di(chloromethy1)phosphine oxides have been prepared from alkyl and aryl magnesium halides and di(chloromethy1)phosphinyl chloride.6 Dialkylphosphinic chlorides with ethynyl magnesium bromide gave the ethynylphosphine oxides (S),' R2P(:O)C1+ HC :C .MgBr

THF

R,P( :0 ) C i CH (8)

L. N. Mashlyakovskii, B. I. Ionin, 1. S . Okhrimenko, and A. A. Petrov, Zhur. obshchei Khirn., 1968,38,2124. L. Maier, Helv. Chim. Acta, 1969, 52, 845. W.Hagens, H. J. T. Bos, W. Voskuil, and J. F. Arens, Rec. Trav. chim., 1969, 88, 71.


70

Full details have appeared * of the synthesis of optically active tertiary phosphine oxides by the action of Grignard reagents on diastereoisomeric menthyl phosphinates. The menthyl esters are in general highly crystalline and readily separated into diastereoisomers. Reaction with the Grignard reagent proceeds with inversion of configuration at the phosphorus. B. From Olefins and Dienes.-Full details have appeared of the addition of dihalophosphines to 1,3-dienes to give, after treatment with water, phospholene oxides. Methyldichlorophosphine and phenyldibromophosphine with isoprene or penta-l,3-diene gave the 3-phospholene oxides (9) while phenyldichlorophosphine with the same dienes gave the 2-phospholene

(9)

oxides (10). 2-Chlorobuta-l,3-diene with methyldichlorophosphine gave a 9 : 1 mixture of the 3- and 2-phospholene oxides1° from which the 3-methoxy-phospholene oxide (11) was obtained on treatment with sodium methoxide. Acidic hydrolysis of this gave the ketone (12) which is in tautomeric equilibrium with the enol form (13). Crystalline material is largely the enol form, which is probably a strongly hydrogen-bonded dimer, while dilute solutions in chloroform contain predominantly the ketone. OMe

(--$ Me

0

OH

H2° H+

/N

0

The synthesis of a phosphetan by the action of phosphorus trichloride l1 has been extended l2 and aluminium chloride on 2,4,4-trimethylpent-2-ene to include the use of alkyl and aryl dichlorophosphines and of various methyl substituted t-butylethylenes. Some of the resulting oxides (14; R1 = H) exist as geometrical isomers; the ratio of isomers produced in a given case depended on the mode of decomposition of the intermediate. Thus when R1,R2, R3 = H and R4 = Ph slow addition of water to the

lo l1

l2

0. Korpiun, R. A. Lewis, J. Chickos, and K. Mislow, J. Amer. Chem. SOC.,1968,90, 4842. L. D. Quin, J. P. Gratz, and T. P. Barket, J. Org. Chem., 1968, 33, 1034. L. D. Quin and J. A. Caputo, Chem. Comm., 1968, 1463. J. J. McBride, E. Jungermann, J. V. Killhefer, and R. J. Clutter, J. Org. Chem., 1962, 27, 1833. S. E. Cremer and R. J. Chorvat, J. Org. Chem., 1967, 32, 4066.

71

Phosphine Oxides

reaction mixture gave a 19 : 1 ratio of isomeric oxides while slow addition of the reaction mixture to an excess of water gave a 7 : 3 ratio of oxides.

Optimum conditions have been described l3 for the preparation of phosphine oxides, e.g. (15) and (16), by the addition of phosphorus pentachloride or trichlorodiphenylphosphorane to styrene and phenylacetylene.

+

PhCH :CH2 Ph2PC13

110"

PhzP(: 0)* CH :CHPh (15) 22% (PhCCl :CH),P(: 0)

+

PhC i CH PCl,

(16) 25%

C. From Alkyl Phosphinites.- Arbusov reactions using alkyl phosphinites and chloromethylphosphine oxides have been used l4-I6 to prepare a wide range of di-, tri-, and tetra-phosphine oxides, e.g. (17) and (18).

D. Miscellaneous.-The rearrangement of alk-2-enyl diphenylphosphinites via a five-membered cyclic transition state has been shown la by deuterium labelling to be >95% specific and the activation parameters for the rearrangement of (19) to (20) have been determined. /O, PhZP ICHZ D,C=CH

(19) l3

l4

l5 lB

l7

-.

H0

PhZP\ I/'HZ D,C-CH

AH* 23 kcal./mole AS* - 14 e.u.

(20)

G . K. Fedorova, Ya. P. Shaturskii, L. S. Moskalevskaya, Yu. S. Grushin, and A. V. Kirsanov, Zhur. obshchei Khim., 1967, 37, 2686. M. I. Kabachnik, T. Y. Medved, 'Y. M. Polikarpov, and K. S . Yudina, Izuest. Akad. Nauk S.S.S.R., Ser. khim., 1967, 591. L. Maier, Angew. Chem. Internat. Edn., 1968, 7 , 384, 385. T. Y. Medved, Y. M. Polikarpov, S. A. Pisareva, E. I. Matrosov, and M. 1. Kabachnik, Zzvest. Akad. Nauk S.S.S.R., Ser. khim.,1968, 2062. M. P. Savage and S . Trippett, J. Chem. SOC.( C ) , 1966, 1842. A. W. Herriott and K. Mislow, Tetrahedron Letters, 1968, 3013.

72


Tris(chloromethy1)phosphine on oxidation with hydrogen peroxide l9 gave the methylphosphine oxide (21) while treatment with methanolic sodium methoxide 2o gave the methylphosphine oxide (22). Both reactions are thought to involve intermediate ylides (23). (C1CH,)

,P(:0)Me

(22)

Oxidation of 1 -diphenylphosphinoanthracene or its oxide 21 with sodium chlorate and vanadium pentoxide in glacial acetic acid gave the anthraquinone (24). Oxidation of acetyldiphenylphosphine with oxygen has now 0

P(:O)Ph,

_____, 0' (24) 70%

been reported 22 to give the a-hydroxydiphosphine dioxide (25) formed by the addition of diphenylphosphine oxide to the very reactive acetyldiphenylphosphine oxide. CH, * CO * PPhz

O2

. -

CH, CO P(: O)Ph2

PhzPHO

CH,.C(OH)[P(: O)Phz]2 (25)

Similar acylphosphine oxides were intermediates in the reactions of tetraphenyldiphosphine with carboxylic acids.22 The resulting a-hydroxydiphosphine dioxides (26) rearranged rapidly (R = aryl) or slowly (R = alkyl) to the corresponding phosphinyloxyalkylphosphine oxides (27). The alkylations of red phosphorus and of P214by alkyl iodides at 250" were unaffected by the presence of dibenzoyl peroxide or on irradiation with U.V. light.23 Treatment of the reaction mixtures with water gave high yields of tertiary phosphine oxides. lD 2o

21 22

aa

L. Maier, Helu. Chim. Acta, 1969, 52, 858. I. 0. Shapiro, E. N. Tsvetkov, A. I. Shatenshtein, and M. I. Kabachnik, Dokludy Akad. Nauk S.S.S.R., 1968, 179, 888. H. Schindlbauer, Munatsh., 1969, 100, 567. R. S. Davidson, R. A. Sheldon, and S. Trippett, J. Chem. Soc. ( C ) , 1968, 1700. N. G . Feshenko, T. I. Alekseeva, and A. V. Kirsanov, Zhur. obshchei Khirn., 1968,38, 122.

73

Phosphine Oxides (Ph,P),

-

+ RC0,H

-I.-------+ R .CO P(: O)Ph2

R, ,0*P(:O)Ph2 H'

R C(OH)[P(: O)Ph212

'C' \ P (: 0)1Ph2 (27)

(26)

Secondary phosphine oxides have been obtained2*by the reduction of phosphinate esters with lithium! aluminium hydride and the synthesis has been extended to that of the optically active secondary phosphine oxide (28) by reduction of the high-melting diastereoisomeric menthyl ester (29).

Ph\p/p PhH,C/

\OM

LiAlH,

Ph\

(29) [a],, =

-65.4"

/p

P PhH,C' 'H

(28) [.ID

=

-0.52"

Optically active (28) exchanged its proton rapidly in deuteriornethanol with no loss of activity except in the presence of acid or base. Exchange with retention of activity, and configuration, was suggested to occur via the deuterioxyphosphine (30), and racemisation in the presence of base to

X

Ph...I ,P-H PhH,C

&

a4

T. L. Emmick and R. L. Letsinger, J. Amer. Chem. SOC.,1968, 90, 3459.

74


be via the anion (31). Acid-catalysed racemisation may have involved the symmetrical phosphorane (32). Secondary phosphine oxides have also been obtained 24 by the reaction of Grignard reagents with monosubstituted phosphinate esters (33).

-

+

RIHP(: 0) OEt R2MgBr (33) R1 = Ph, Bu R2 = aryl, aralkyl

R1R2HP(:0) 25-75%

2 Reactions A. Metallated Phosphine Oxides.-Metallated phosphine oxides with 26 The p-toluenesulphonyl azide gave the a-diazophosphine oxides (34).25~ base used to generate the anion was usually butyl-lithium or potassium t-butoxide. With the a-formylphosphine oxide (35) cyclisation of the intermediate and elimination of the diphenylphosphinate anion gave the triazine (36). R,P(: 0)* e H-R1 + N3.S02.Ar---+ R2P(:0).CHR1.N: N.N-SO, .At

R,P(: 0)*CN2*R1+ fiH *SO, Ar

I

-

R2P(:0) CR1ON :N * N H .SO, Ar

(34) 1 6 8 3 % Ph,P(:O)*CH(CHO)*Ph + N3*S0,*Ar (3 5)

0

II

Piperidine

PhzP62 i- Ph*C-N .\\

I

HC-N

/N

I

SO,. Ar

-

Ph

I

Ph,P-C-

N \\ N -/ O=C N I I H SO,.Ar

I

0 Ph

II

I

Ph2P-C-N

I /

\N

6-C-N I 1 H SO,.Ar

(36) 26

26

G. Petzold and H. G. Henning, Naturwiss., 1967, 54, 469. M. Regitz, W. Anschutz, W. Bartz, and A. Liedhegener, Tetrahedron Letters, 1968, 3171.

Phosphine Oxides

75

Photochemical decomposition of the oxide (37) in aqueous dioxan 26 gave as the major product the a-hydroxyphosphine oxide (38) together with a small amount of the phosphinic acid (39) formed by a Wolff rearrangement of the intermediate carbene. The oxide (37) had previously been obtained 27 from nitrous acid and the corresponding amine. PhaP(:0)*CH(OH).Ph Ph,P(:O).CN,*Ph (37)

y/

(38)

> Ph,P(: 0)* c * P h

PhP(:0):CPh,

------+

/H/O

J.

(Ph,CH)PhP(: 0 ) OH a

(39)

Methyldiphenylphosphine oxide with butyl-lithium and trimethylchlorosilane gave the oxide (40)28 which was stable at 180" in contrast to the corresponding sulphoxide. The same lithiomethyl oxide with cuprous chloride in tetrahydrofuran at -- 40" followed by oxygenation at 20" gave the diphosphine dioxide (41).29

The product previously obtained from triphenylphosphine oxide and phenyl-lithium was not a tetraphenylphosphonium salt but probably the adduct (Ph,P :0),- LiI.,O Phenyl-lithium metallated the oxide at the meta position(s) ; treatment of the reaction mixture with benzophenone gave the oxides (42; 56%) and (43; 19%). Ligand exchange occurs prior to metaloxide gave naphthalene lation. Thus biphenylyl-a-naphthylphenylphosphine (27%) and biphenyl (2%) on treatment with p-tolyl-lithium in ether at room temperature. The intramolecular version of the aryl-lithium plus phosphine oxide reaction has given phosphonium the oxide (44) when treated successively with butyl-lithium and acid giving 24% of the spirocyclic salt (45). 27

2n 29

30 31

L. Horner, H. Hoffmann, H. Ertel,, and G . Klahre, Tetrahedron Letters, 1961, 9. A. G. Brook and D. G. Anderson, Canad. J . Chem., 1968,46, 2115. T. Kauffmann, G. Beissner, H. Berg, E. Koppelmann, J. Legler, and M. Schonfelder, Angew. Chem. Znternat. Edn., 1968, 7 , 540. G . Wittig and H.-J. Cristan, Bull. SOC.chim. France, 1969, 1293. M. A. Weiner and G. Pasternack, J. Org. Chem., 1969, 34, 1130.

76


Ph,P(:O)

+ PhLi

I:'

1

[

Ph,COH PhzCo

+

-&P(:O)Ph2

+

(44) (45) Phenyl-lit hium with tripheny lpho sphine sulphide O gave triphenylphosphine (56%) and lithium thiophenoxide (41%), a reaction formally analogous to that of phenyl-lithium with the methylthiophosphonium salt (46) which gave triphenylphosphine and methyl phenyl sulphide, the suggested intermediate here being (47). Ph3$SMe BF, (46J

-PhLi

Ph,P=SMe.Ph

-

Ph3P + Ph.S.Me

62.5%

1

55%

Ph3&-sMe.Ph (47)

B. Additions

to Unsaturated Phosphine Oxides.-Addition of dibutylphosphine to the ethynylphosphine oxide (48; R = Bu) at 80" gave a low yield of the trans-oxide (49).32 However, addition of HX (X = R12N, RlO, RIS, or halogen) to the oxides (48;R = Me or Bu) led initially to the

cis-oxides (50) which isomerised on distillation to the trans-oxides, the ease of isomerisation being in the order X = Rl2N> R1O, RIS> halogen. In contrast ethynylphosphines are not susceptible to nucleophilic addition.33 Buzp~BuZP CH :CH P(: O)BU, R,P(:O)*CZH / (49) 20% trans R2P(:0) CH :CHX a

(50) cis 3z

D. Hellwinkel, Chem. Ber., 1969, 102, 548. W. Voskuil and J. F. Arens, Rec. Trav. chim., 1962, 81, 993.

77

Phosphine Oxides

1 : 3-Dipoles with diphenylvinylphosphine oxide and sulphide gave heterocyclic 2-pyrazolines (5 1) from nitrile-imines, 2-isoxazolines from nitrile oxides, and isoxazolidines from nitrones.

C. Miscellaneous.-Baeyer-Villiger oxidations occurred 3s when tetraphenyldiphosphine dioxide and disulphide were treated with perbenzoic acid in methylene chloride, the high migratory aptitudes of the phosphinyl and thiophosphinyl groups leading to the anhydrides (52). Triphenylphosphine sulphide with perbenzoic acid gave the phosphine oxide (70%).

xx II II

II

x x

x3I

II

II

(X =O,S)

Addition of the secondary phosphine oxide (53) to diethyl maleate 36 led eventually to the oxide (54). However, all attempts to resolve both this and the oxide (55) were unsuccessful.

I

(i) 6~ (ii) A

J l 0 Ph (55) 34

s6

36

I. G. Kolokol’tseva, V. N. Chistokletov, B. I. Ionin, and A. A. Petrov, Zhur. obshchei Khim., 1968, 1248. N. Inamoto, T. Emoto, and R. Okazaki, Chem. andznd., 1969, 832. I. G. M. Campbell, J. Chem. Soc. (C), 1968, 3026.

78 Organophosphorus Chemistry Debenzylation and decarboxylation occurred when the phosphinylThe resulting diphenylformate ester (56) was treated with iodide phosphinyl anion has been trapped with carbonyl compounds and with iodine.

-

0 0 II II

Ph2P(:0)*C(6)R1R2

-R

Ph2F(:0)

Ph2s-C-O-CH2Ph 1-

[Ph2P(:-O)I]

(56)

/toH Ph2P(:0)*OR

Tris(chloromethy1)phosphineoxide with phosphorus pentachloride gave as the major product a yellow crystalline compound from which the trichlorophosphorane (57) was obtained on crystallisation from chloroform.38 This remarkable compound was stable to boiling water but

+

(ClCHJ,P(: 0) PCI,

-

[]

+ CCI4

CHCla

.

(Cl,C)2PCI3 (57)

hydrolysis with aqueous ethanolic sodium hydroxide gave bis(trich1oromethy1)phosphinic acid. Pyrolysis gave hexachloroethane and phosphorus trichloride. Similar ready fissions of phosphorus-carbon bonds occurred when chloromethylphosphonic dichloride and di(chloromethy1)phosphinic chloride were treated with phosphorus pentachloride. The conversion of phenyl isocyanate into diphenylcarbodi-imide in the presence of the phospholene oxides (58) has been investigated k i n e t i ~ a l l y . ~ ~ The catalytic (second-order) rate constants obeyed a linear crop relationship ( p = -0.75), where cro is the ‘normal’ substituent constant in agreement with the lack of conjugation between the aromatic ring and the phosphoryl group.

41 Phosphine oxides form 1 : 1 hydrogen-bonded adducts with With triphenylphosphine oxide the aromatic rings could be substituted by 37

38 4o

41

S. Warren and M. R. Williams, Chem. Comm.,1969, 180. A. W. Franks, Canad. J. Chem., 1968, 46, 3573. G. Ostrogovich, F. Kerek, A. B U Z ~ Sand , N. Doca, Tetrahedron, 1969, 25, 1875. H. Schindlbauer and H. Stezenberger, Monatsh., 1968, 99, 2468, 2474. G. Aksnes and P. Albriktsen, Acta Chem. Stand., 1968, 22, 1866.

79

Phosphine Oxides

Me but not by C1, NH,, NO,, or COOH. The product from triphenylphosphine and tetrachloro-o-beinzoquinone was the adduct of triphenylphosphine oxide with tetrachlo:rocatechol.40 The phospholan oxide (59) was particularly efficient at intermolecular hydrogen bonding with phenols and it was suggested that this may be due to the ease with which the five-membered ring can be accommodated in an adduct (60) having the The ~ poor hydrogen-bonding ability geometry of a trigonal b i ~ y r a r n i d . ~ of the phosphetan oxide (61) was probably due to steric hindrance.

F

The optical rotatory dispersions and circular dichroisms of several tertiary phosphine oxides and sulphides have been There are indications that compounds of absolute structure (62), where A and B are alkyl or aralkyl groups and A is larger than B, show a negative Cotton effect in the region of thep-band (200-225 nm) and a positive effect in the region of the a-band (260-280 nm).

The structures of the disulphide (63)43and the oxide (64)44 have been determined by X-ray crystallography. 42 43

W.-D. Baker, Tetrahedron Letters, 1968, 1189. J. D. Lee and G. W. Goodacre, Naturwiss., 1968, 55, 543. Mazhar-UI-Haque and C. N. Caughlan, Chem. Cornrn., 1968, 1228.

5 Tervalent Phosphorus Acids BY D. W, HUTCHINSON

1 Introduction The oxyacids of phosphorus have been the subject of several reviews' which describe the field up to the present, and as a very large number of papers on tervalent phosphorus acids appear annually, a considerable amount of selection has been exercised in the preparation of this Chapter. In general, papers which contribute to the understanding of the reactions and properties of phosphorus oxyacids have been included, while papers of a purely preparative nature (in particular many papers from the Russian literature) have been omitted owing to lack of space.

2 Phosphorous Acid and its Derivatives A. Nucleophilic Reactions.-(i) Attack on Saturated Carbon. In a recent example of the Arbusov reaction,2 l-chloro-2-hydroxy-3-alkoxypropanes (1) when heated with triethyl phosphite at 120-1 50" give rise to the expected 2-hydroxyphosphonates (2).s Ester exchange can also occur under these (EtO),P

+ ClCH,CHOHCH,OR (1)

120-150"

0 II

(EtO),PCH,CHOHCH,OR

(2)

+

CH,CI

/

1 8&-200°

0 II EtO- P- CH- CH,OR

I

(Et0)zPOCH

t

EtO CHzCl

\ CH,OR

(3)

w o

EtOP-CHCH20R II I

I

0-CH,

(5) Grayson and E. J. Griffith (eds.), 'Topics in Phosphorus Chemistry', Interscience. m A. J. Kirby and S. G. Warren, 'The Organic Chemistry of Phosphorus', Elsevier, 1967. R. F. Hudson, 'Structure and Mechanism in Organophosphorus Chemistry', Academic Press, 1965. R. G. Harvey and E. R. De Sombre, Topics in Phosphorus Chemistry, 1964, 1, 57. H. G. Hemming and M. Morr, Chem. Ber., 1969,101, 3963. ( a ) M.

a

Tervalent Phosphorus Acids

81

conditions producing the phosphite (3) which rearranges to the phosphonate (4) among other products at higher temperatures. Elimination of ethyl chloride from (4) can then take place to generate the /3-phostone (5). (ii) Attack on Unsaturated Carbon. The synthesis of aryl phosphonates can be achieved if the Arbusov reaction is initiated either by g°Co-y rays or by U.V. i r r a d i a t i ~ n and , ~ in both cases the reaction presumably proceeds via free radical intermediates. In general, however, ready displacement of halogen from an unsaturated carbon atom by tervalent phosphorus only occurs when the carbanion intermediate is stabilised by delocalisation or by d-rr orbital overlap. Thus, 1,2-tlichloroperfluorocyclopentene(6, R = C1) and 1-chloro-2-ethylthioperfluorocyclopentene (6, R = SEt), both of which can give rise to stabilised carbanions, undergo substitution of chlorine by alkyl phosphites to give the phosphonates (7) and (8).6 With (6, R = C1) only the diphosphonate (8) is produced, and it has been suggested that (7, R = Cl) must react with the phosphite more rapidly than (6, R = Cl). One reason for this increased reactivity may be because the phosphonate group can stabilise carbanions very effectively and hence it is easier to form a carbanion from (7, R = C1) than from (6, R = Cl). Both trans-/3-bromoviny phenyl sulphone (9) and gem-a-bromovinyl phenyl sulphone (10) undergo

p"' Ph 0,s (9)

Br

)=

Ph0,S

(10)

G. Caspari, H. Drawe, and A. Henglein, Radiochim. Acta, 1967, 8, 102 (Chem. Abs., 1968, 68, 105,304). P. Obrycki and C. E. Griffin, J . Org. Chem., 1968,33, 632. J. D. Park and 0. K. Furuta, Tetrahedron Letters, 1969, 393. W. S. Wadsworth jun. and W. D. Emmons, J . Amer. Chem. SOC.,1961,83, 1733.

82 Organophosphorus Chemistry displacement reactions with phosphite esters;* here the carbanion intermediates are stabilised by the sulphonyl group. Numerous papers on the addition of tervalent phosphorus compounds to Mannich phenol bases (e.g. 11) have appeared recently9 and a kinetic investigation lo reveals that the reaction is first order with respect to (1l), and the rate of decomposition of (1 1) to the quinone methide (12) is some 20 times slower than the reaction of (12) with triethyl phosphite. A similar addition reaction can take place with 2-benzylidene-3(2H)-thianaphthenone1,l-dioxide (13) when (14),ll5 (15),llb or (16) lla can be formed depending on the reaction conditions. Pentaco-ordinate products are also formed by the addition of trialkyl phosphites to ethyl ethylidene acetoacetate (17) l 2 or 1,3-dienes,13although in the last instance tetraco-ordinate products can also be obtained. The formation of pentaco-ordinate products from a-diketones and phosphite esters is reviewed in Chapter 2. Triethyl orthoformate will react with tervalent phosphorus halides giving rise to phosphonates,14 presumably by nucleophilic attack by the phosphorus on (18) and ethanolysis of the intermediate. When tris(triethylsily1)phosphiteis added to acetyl chloride the products include triethylsilyl chloride and bis(triethy1silyl)a~etylphosphonate.~~ Chloride ion will attack the electrophilic organosilyl group in the phosphonium intermediate by either an intra- or inter-molecular process in preference to an ethyl group. The Perkow reaction has continued to attract attention, and evidence has been presented16 that the reaction can take place with attack by phosphorus on positive halogen. In trichloroacetylthiourea (19) the halogen

@

lo

l1

l2 lS

l4

l6

l6

E. G. Kataev, F. R. Tantesheva, E. G. Yarkova, and E. A. Berdnikov, Doklady Akad. Nauk S.S.S.R., 1968, 179, 862 (Chem. Abs., 1968, 69, 77,350). E.g. (a) B. E. Ivanov and L. A. Valitova, Izuest. Akad. Nauk S.S.S.R., Ser. khim., 1967, 1087, 1090 (Chem. Abs., 1968,68, 39,723, 39,724). (*) B. E. lvanov, A. B. Ageeva, and R. R. Shagidullin, Izuest. Akad. Nauk S.S.S.R., Ser. khim., 1967, 1994 (Chem. Abs., 1968, 68, 69,079). B. E. Ivanov, L. A. Valitova, and T. G. Vavilova, Izvest. Akad. Nauk S.S.S.R., Ser. khim., 1968, 768 (Chem. Abs., 1968, 69, 76,330). (a) A. Mustafa, M. M. Sidky, S. M. A. D. Zayed, and W. M. Abdo, Tetrahedron, 1968, 24,4725. ( b ) B. A. Arbusov, T. D. Sorokina, and V. S. Vinogradova, Doklady Akad. Nauk S.S.S.R., 1967, 177, 1337 (Chem. Abs., 1968, 68, 105,301). B. A. Arbusov, N. A. Polezhaeva, and V. S. Vinogradova, Izuest. Akad. Nauk S.S.S.R., Ser. khim., 1967, 2281 (Chem. Abs., 1968, 68, 4984). (a) Z. L. Evtikhov, N. A. Razumova, and A. A. Petrov, Zhur. obshchei Khim., 1968, 38, Doklady Akad. Nauk S.S.S.R., 1968, 181, 2341 (Chem. A h . , 1969, 70, 37,879). 877 (Chem. Abs., 1969,70,78,084). N. A. Razumova, Z. L. Evtikhov, L. I. Zubtsova, and A. A. Petrov, Zhur. obshchei Khim., 1968, 38,2342 (Chem. Abs., 1969,70,47,546). ( d ) K. I. Novitskii, N. A. Razumova, and A. A. Petrov., Khim. Org. Soedin. Fosfora, Akad. Nauk S.S.S.R. Otd. obshchei Tekh. Khim., 1967, 248 (Chem. Abs., 1968, 69, 43,981). (a) S. S. Krokhina, R. I. Pyrkin, Y . A. Levin, and B. E. Ivanov, Izvest. Akad. Nauk S.S.S.R., 1968, 1420 (Chem. Abs., 1968, 69, 67,478). l b ) W. Dietsche, Annaien, 1968, 712, 21. N. F. Orlov and B. L. Kaufman, Zhur. obshchei Khim., 1968, 38, 1842 (Chem. A h . , 1969, 70, 4193). J. S. Ayres and G. 0. Osborne, Chem. Comm., 1968, 195.


83 OH

.+ (1 1)

HC(OEt),

~

HC

>

i: ,a 1 HC=OEt

(18)

+ EtOH

+

CI,P-CH(OEt),

84

+ MeCOCl

(Et,SiO),P

-

Organophosphorus Chemistry Et,SiO 0 +I Id Et,SiO-P-C--Me

SiEt,

Et,SiCl

+ (Et',SiO),P(O)COMe

atoms have considerable positive character and, as attack on the carbonyl group is sterically hindered, attack at halogen is a favoured process. The reaction products, dichloroacetylthiourea (20), S-ethyltrichloroacetylisothiourea (21), and diethyl phosphorochloridate, support the proposed mechanism, (21) arising from the dealkylation of the phosphonium intermediate by the isothiouronium ion. This example of the Perkow reaction appears to be an exception to the more usual case when initial attack by (EtO),kl S-

1

CC1,CONHCNH2

CHCI,CON=C-NH,

II S

(19)

S-

I

CCI,CONHCNH,

II

CCl,CON=C-NH,

S

___,

f

S-

3-

CHCl,CONHCNH,

I

I1

CHCI,CON=C-NH,

S

(20) (EtO),PCl

II

(EtO)3kl

0

+

4-

S-

SEt

I

I

CCl,CON=C-NH,

CCl,CON=C-NH, (21) 0

I1

ClCH,CSR

(22)


85

phosphorus occurs at carbonyl carbon followed by rearrangement of the interrnediate.l7" Sulphur can expand its outer valence shell by the use of d orbitals and this could reduce the electron availability on the carbonyl oxygen atom of chlorothiolacetates (22). The synthesis of 1 -thiovinyl phosphates from (22) and trialkyl phosphites has been cited17bas an example of the Perkow reaction in which nucleophilic attack by phosphorus occurs on carbonyl oxygen. There appears, however, to be little evidence for this mode of attack and the reaction probably proceeds in the normal manner. The relative yield of enol phosphate formed by the action of triethyl phosphite and p-substituted phenacyl halides (23) increases when Y is electron releasing and decreases with alteration of X in the order C1> Br > I.I* Irradiation of a mixture of chloroacetone (24) and triethyl phosphite gives the ketophosphonate (25), the enol phosphate (26), and other products.l@ The yield of (25) is decreased on addition of a radical scavenger while the yield of (26) is unaffected. It is suggested that the primary process of this reaction is the n -+r* excitation of the carbonyl group, and addition of methanol or acetic acid which inhibit such excitation suppresses the entire reaction. The byproducts in the photo-Perkow reaction could arise from the photoisomerisation of triethyl phosphite to diethyl ethylphosphonate (27). E.s.r. studies of this isomerisation show 2o that the radical (28) is formed initially and then rapidly decays to (29). Combination of the latter with an ethyl radical leads to (27). When a-bromo-a,/%dicyanopropionates (30, X = C0,Et) are treated 21 with trimethyl phosphite, a reaction analogous to the Perkow reaction takes place to produce a ketenimine (31). On the other hand, when a-bromo-a,/3-dicyanopropionitriles (30, X = CN) are used,22(32) is formed rather than a ketenimine. It has been proposed22 that attack by the phosphite on (30, X = CN) occurs at the comparatively positive halogen atom to generate the bromophosphonium cation (33) together with the mesomeric anion (34), and that. further interaction of (33) and (34) gives rise to the observed product. N-Fluorosulphonyl isocyanates (35) will form zwitterionic, crystalline adducts (36) with triphenyl phosphine, phosphorous trisdimethylamide and triethyl p h ~ s p h i t e . (36, ~ ~ R = OEt) does not dealkylate to (37, R = Et) at room temperature but is converted into (37, R = H) by the action of hydrogen chloride. N-Fluorosulphonyl carbodi-imides are not formed l7

lS

l9 2o

21 2a

23

A. Chopard, V. M. Clark, R. F. Hudson, and A. J. Kirby, Tetrahedron, 1965,21, 1961. ( b ) L. F. Ward jun., R. R. Whetstone, G. E. Pollard, and D. D. Phillips, J. Org. Chem., 1968,33,4470. A. Arcoria and S. Fisichella, Ann. Chim. (Ifaly), 1967, 57, 1228. H. Tomoika, Y. Izawa, and Y. Ogata, Tetrahedron, 1968, 24, 5739. K. Terauchi and H. Sakurai, Bull. Chem. SOC.Japan, 1968, 41, 1736. A. Foucaud and R. Leblanc, Tetrahedron Letters, 1969, 509. R. Leblanc and A. Foucaud, Tetrahedron Letters, 1969, 2441. H. Hoffmann, H. Forster, and G. Tor-Poghossian, Monarsh., 1969, 100, 311.

( a ) P.

4

86


2 enol phosphonium salt

keto phosphonium salt

-EtCl

-EtCI

(EtO),P’

II

0

Atk (EtO)2PEt II 0

(29)

(27)

R,C(CN>C=C=NP(O)(OMe),

I X

N 4,8

Br

+

BrP (OMe),

C

+

CN -

(30)

(34)

R,C-C=C-N=P(OMe),

I

NP

l

l

CNRr

I‘


87

from (35) and the phospholeme oxide (38),24 as the reaction does not proceed beyond the formation of the N-fiuorosulphonyl phospholene imine (39). Carbodi-imides are, however, postulated as intermediates in the reaction between monoaryl amidophosphites (40) and aromatic isocyanates 25 when imidoyl phosphonates (41) are produced. R,P

-+

OCNSO,F

----+ R,~CONSO,F (36)

(35) where R

=

f

Ph, Me,N, or EtO

(EtO),P(O)CONRSO,F (37)

Ph'

PhNHC=NAr +-(RO),P-O 4- PhN=C==NAr 1 I P(O)(OR), (41)

(R'O),P

f

\

OR,

(42)

0 II

0

0 4

MeP-NR*Cl

~

>

II

MeP-NR2 - P(OR'),

I

OR3

(43)

(iii) Attack on Nitrogen. N-Alkyl-N-chloro-methylphosphonamides(42) undergo nucleophilic attack by trialkyl phosphites to give aza-analogues of mixed anhydrides (43)26 which can also be synthesised by the action of 24 26

26

T. W. Campbell, I. I. Monagle, and V. S. Foldi, J. Amer. Chem. Soc., 1962, 84, 3673. A. N. Pudovik and E. S. Betyeva, Zhur. obshchei Khirn., 1968, 38, 285 (Chem. Abs., 69, 52,231). V. A. Shokol, G. A. Golik, and G. I. Derkach, Khim. Org. Soedin. Fosfora, Akad. Nauk S.S.S.R., Otd. obshchei Tekh. Khim., 1967, 96 (Chem. Abs., 1968, 69, 10,511).

88


alkyl phosphorochloridates on the corresponding N-alkyl-methylphosphonamides. (iu) Attack on Oxygen. The oxidation of trialkyl phosphites to the corresponding phosphates by the action of p-benzoquinone and benzyl alcohol 27 can be regarded as an example of nucleophilic attack on oxygen by a tervalent phosphorus derivative. The quinone is reduced in the initial reaction to the hydroquinone anion which can then debenzylate the phosphonium cation to produce hydroquinone benzyl ethers which can be isolated from the reaction.

(RO),P=O i-

0 I

OH

(u) Attack on Halogen. Alkyl chlorides can be synthesised under mild conditions by treating the alcohol with carbon tetrachloride and a tertiary phosphine 28a or trialkyl phosphite.28bPhosphorous trisdimethylamide can be used 29 in place of the phosphine and the alkyl chlorides can be readily separated from the phosphoric trisdimethylamide by extraction with water. The isolation of chloroform and the phosphonium intermediate (44)from the reaction supports an earlier suggestion for the mechanism of this reaction. The reaction between trialkyl phosphites, alkyl thiols, and bromotrichloromethane which leads to OO-dialkyl S-alkyl phosphonothiolates is a complex 32 and appears to be ionic when carried out in hexane ; whereas in the presence of azobis-isobutyronitrile, radical intermediates are involved. The anion of diethyl phosphite will displace halide ion from pentachlorobenzene (45) in the presence of ethanol to generate 1,2,4,5-tetrachlorobenzene and triethyl phosphate.33 This reaction could take place by attack by 27

28

28

31 32

3s

0. Mitsonobu, K. Kodera, and T. Mukaiyama, Bull. Chem. SOC.Japan, 1968, 41, 461. (a) J. Hooz and S. S. H. Gilani, Canad.J. Chem., 1968,46,86. ( t j ) H. R. Hudson, J. Chem. SOC.(B), 1968, 664. I. M. Downie, J. B. Lee, and M. F. S. Matough, Chem. Comm., 1968, 1350. B. Miller, Topics in Phosphorus Chemistry, 1965, 2, 133. L. L. Murdock and T. L. Hopkins, J . Org. Chem., 1968,33, 907. R. E. Atkinson, J. I. G . Cadogan, and J. T. Sharp, J. Chem. SOC.(B), 1969, 138. M. C. Demarcq, Bull. SOC.Chim. France, 1969, 1716,


+ CCI, fast

(Me,N),P

<Me,N),PO

89

+ RCI

slow dealkylat ion

+-

(Me2N)3kl CCI,

(Me,N),hOR Ci

+ CHCI,

(44)

+ BrCCI,

(EtO),P

0

II (EtO),PSR

+ EtBr

---+

(EtO),$Br CCl,

-

/-uH

(EtO),$SR Br

+ CHCI,

phosphorus on halogen to form diethyl phosphorochloridate and the relatively stable anion of 1,2,4,5-tetrachlorobenzene; these would then react with ethanol to give the observed products. In the absence of ethanol a mixture of products is formed including the diethyl ester of 2,3,5,6tetrachlorobenzenephosphonic ;acid. Diethyl bromomalonate reacts with sodium diethyl phosphite to give 1,1,2,2-ethanetetra~arboxylate;~~~ here again the initial reaction is attack

(EtO),P(O)CI

A (Et0)2P-0

+ ha +

CI

CI

c1'

c1

0 +

+ Na

\

c1

c1

Cl

c1

@

BrCH(CO,Et),

(EtO),P(O)Br

(EtO,C)2CHzCHz(CO2Et)Z 84

+ &a -+ cH(C0,Et)2

(EtO),PO

K. H. Takemura and D. J. Tuma, J . Org. Chem., 1969,34,252.

+ CH,(CO&t),

90


on positive halogen, When ethanol is added to the reaction only triethyl phosphate and diethyl malonate are observed. (ui) Attack on Hydrogen. The acetolysis of trialkyl phosphites with acetic acid involves protonation of the phosphorus atom followed by dealkylation of the intermediate to produce acetate esters and dialkyl p h o ~ p h i t e s .The ~~ use of trialkyl phosphites in the synthesis 360 and alkylation of 00-dialkyl dithiopho~phates,~~~ together with the synthesis of mixed anhydrides by the action of carboxylic acids on acetyl p h ~ s p h i t e s ,may ~ ~ proceed by a similar mechanism.

+ HX

(RO),P

> [(RO),pfH

(RO),PH

II

+

X-1

RX

0 where X = OAc or S-P(OR1)2

II

S 0

II

(RO),POAc

0 II

(RO),PH

+

Ac,O

-

+

OAc

(RO) ,PH -0-C

i? -Me

’t/I

0,

CMe

II

0

B. Electrophilic Reactions.-Transesterification reactions of phosphorous esters appear to involve a four-centre aggregate (46)in which the phosphorus atom acts as an ele~trophile.~~ Phosphorous trisdialkylamides undergo ready exchange with imidoyl ethers, possibly by a similar r n e c h a n i ~ m . ~ ~ 86

37

38 39

E. S. Huyser and J. A. Deiter, J. Org. Chem., 1968, 33, 4205. (a) I. S. Akhmetzhanov, Zhur. obshchei Khim., 1968, 38, 1090 (Chem. Abs., 1968, 69, 66,829). ( b ) A. N. Pudovik and V. K. Krupnov, Zhur. obshchei Khim., 1968, 38, 304 (Chem. Abs., 1968, 69, 77,369). E. E. Nifant’ev and I. V. Fursenko, Zhur. obshchei Khim.,1968,38, 1295 (Chem. Abs., 1968, 69, 58,786). A. N. Pudovik and G. I. Evstaf’ev, Doklady Akad. Nauk S.S.S.R., 1968,183,842 (Chew. Abs., 1969, 70, 67,280). Y. Charbonnel, R. Burgada, and J. Barrans, Compt. rend., 1968, 266, C 1241.

Terualent Phosphorus Acids

91

When acyclic 00-dialkyl thiophosphites are treated with nitrosyl chloride, 00-tetra-alkyl monothiopyrophosphates (47) are formed.4o Cyclic thiophosphites [e.g. 2-thiono-5,5-dimethyl-l,3,2-dioxaphosphorinan (48)], however, give rise 41 to a mixture of the asymmetric (49, X = Y = S , Z = 0) and the symmetric42 (149, X = Z = S , Y = 0) dithiopyrophosphates under the same conditions. Studies with 180-labelled nitrosyl S

chloride and dialkyl phosphites show 43 that the bridge oxygen atom of the tetra-alkyl pyrophosphate produced in this reaction originates from the nitrosyl chloride which is behaving as an ambident nucleophile. Electrophilic attack on nitrosyl chloride can, therefore, occur on nitrogen or oxygen and the difference in products when acyclic or cyclic thiophosphites are used may be due to a difference in the mode of electrophilic attack by the two thiophosphites. There appears to be little reason for such a difference except for steric reasons. From a comparison of the rate of reaction of dialkyl phosphites with nitrosyl chloride and with halogens,44 it is considered unlikely that tautomerisrn of the dialkyl phosphite occurs to give the tercovalent phosphite in the reaction with nitrosyl chloride, though this appears to be the rate-determining step in the reaction with halogens. Electrophilic substitution at phosphorus has been reviewed 46 and the reactions classified according to mechanism and to the co-ordination number of the phosphorus atom. 40 41

42 43 44

45

L. Almasi and L. Paskucz, Chem. .Ber., 1963, 96, 2024. A. Zwierzak and J. Michalski, Carnad.J . Chem., 1969, 47, 1163. J. Michalski, M. Mikolajczyk, and B. Mlotkowska, Ckem. Ber., 1969, 102, 90. D. Samuel and B. Silver, J. Chem. SOC.,1963, 3582. Z. Luz and B. Silver, J. Amer. Chem. SOC.,1962,84, 1091, 1095. S. G. Warren, Angew. Chem. Znternat. Edn., 1968, 7 , 606.

92


0 II

hv

RCCH,P(OMe),

MeO, ,OMe '0 *P\o I / R-T-CHZ

MeO,.

>

OlP\O \ I C-CH, /*

(MeO),POCR

II II

0 CH, (51)

OH R,

OH

/,CH,OP

b

(b)

@Me), Me

(52)

(53)

R1= -CMe(CO,Et)C=CH,

Eta\/ q ./*\ TC-Me EtO

oJ

R2= Me, R3= C0,Et

-

,OMe

1 /" *

, 2 \

4-

P-C-Me Etd

I"\

0-


93

C. Rearrangements.-Dimethyl vinyl phosphates (5 1) can be synthesised by the photorearrangement of dimethyl p-ketoethyl phosphites (50).46 Dimethyl phosphite is also formed in this reaction and the product ratio depends on the availability of readily abstractable hydrogen atoms in the solvent. For example, when the reaction is carried out in cyclohexene, little (51) is obtained and (52) is the major product. Presumably (53) which is formed initially, undergoes a photo-Arbusov rearrangement 47 to yield (52). Several papers concerned with the Arbusov rearrangement of phosphite esters have appeared in the past 49 These include a kinetic investigation of the rearrangement of propargyl catechol phosphite (54a) and the first-order rate constant of this rearrangement has been determined over a acetylene-allene rearrangement [that range of t e r n p e r a t ~ r e s .Another ~~~ (54b) with following treatment of ethyl 2.-hydroxy-2-methylbut-3-ynoate phosphorus trihalides] has been studied both in the presence and absence of p ~ r i d i n e .As ~ ~ the rearrangement occurs with ease in the absence of pyridine, an ,S"i type of mechanism is suggested for this transformation rather than an intermolecular two-step process. Diethyl acetyl phosphite (55) rearranges on heating to the a-ketophosphonate (56)51 which can then break down to keten and diethyl phosphite; alternatively (56) can react with a second molecule of (55) to form (57). D. Cyclic Esters of Phosphorous Acid.*-It has been deduced 5 2 from dipole moment and lH n.m.r. measurements that the cyclic phosphites (58a) and (58b) together with their borine adducts have chair conformations in which the methoxy-groups attached to phosphorus are axial. Two signals, which can be ascribed to the ring protons, are observed in the lH n.m.r. spectrum, the relative areas of which vary with temperature due to interconversion of (58a) and (58b) by inversion at phosphorus. This interconversion is a 46

47 48

49

50

I1

62

C. E. Griffin, W. G. Bentrude, and G. M. Johnson, Tetrahedron Letters, 1969, 969. R. B. LaCount and C. E. Griffin, Tetrahedron Letters, 1965, 3071. Y. A. Kondrat'ev, V. V. Tarasov, A. S. Vasil'ev, N. M. Ivakina, and S. Z. Ivin, Zhur. obshchei Khim., 1968, 38, 1'791 (Chem. Abs., 1968, 69, 106,074). t b ) S. Z. Ivin V. N. Pastushkov, Y. A. Kondrat'cv, K. F. Oglobin, and V. V. Tarasov, Zhur. obshchei Khim., 1968, 38, 2069 (Chem. Abs., 1969, 70, 11,759). Y. A. Kondrat'ev, V. V. Tarasov, A. S. Vasil'ev, N. M. Ivakina, S. Z. Ivin, and V. M. Pastushkov, Zhur. obshchei Khim., 1969, 38, 2590 (Cliem. Abs., 1969, 70, 47,031). ( d ) L. V. Nesterov and R. I. Mutalapova, Zhur. obshchei Khim., 1967, 37, 1843, 1847 (Chem. Abs., 1968, 68, 38,804, 38,895). N. I. Rizpolozhenskii and F. S. Mukhametov, Izuest. Akad. Nauk S.S.S.R., Ser. khim., 1968, 2163 (Chem. Abs., 1969, 70, 78,092). M. Verny and R. Vessibre, Bull. SOC.chim. France, 1968, 3004. ( a ) A. N. Pudovik, T. K. Gazizov,, and A. P. Pashinkin, Khim. Org. Soedin. Fosfora, Akad. Nauk S.S.S.R., Otd. obshchei Tekh. Khim., 1967, 25 (Chem. Abs., 1968, 69, 59,333). ( b ) A. N. Pudovik and T. K. Gazizov, Zhur. obshchei Khim., 1968, 38, 140 (Chem. Abs., 1968, 69, 96,836). D. W. White, G. K. McEwen, and J. G. Verkade, Tetrahedron Letters, 1968, 5369.

* Although Ring Index nomenclature can be used for these compounds, it is simpler to name them as esters of the appropriate oxyacids of phosphorus when derivatives can be recognised without difficulty.

94


relatively slow process and attainment of equilibrium can take several days; moreover, the methyl resonances do not broaden over a wide temperature range, which may explain reports 63 that such cyclic phosphites are conformationally immobile. Cyclic phosphates appear to possess conformational mobility.6* Analysis of the lH n.m.r. spectra of ethylene phosphites suggests 65 that the ring has the twisted conformation (60) rather than the simple envelope (59) as the P-0-C-HA and P-0-C-HB couplings indicate markedly different dihedral angles in the two P-0-C-H systems.

where Y = electron pair or BH, I;EB

(59)

where X = OMe, OPh or C1 The enhanced reactivity of cyclic phosphoramidites towards benzaldehyde has been attributed,66 by analogy with the hydrolysis of cyclic p h ~ s p h a t e s to ,~~ the release of steric strain on formation of the transition state. The heats of hydrolysis of some cyclic and acyclic phosphoramidites have been determined 5 8 and are very similar, suggesting that release of ring strain may not be the major factor in determining the relative reactivity of these compounds. However, the rate of reaction of (61, R = Ph) with phenyl isocyanate 69 to give the insertion product 8o is considerably greater than the rate of reaction of (61 ,R = OMe). This could mean that release of ring strain still does have some influence on the relative reactivities of these compounds. D. Gagnaire, J. B. Robert, and J. Verrier, Bull. SOC.chim. France, 1968, 2392. R. S. Edmundson, Tetrahedron Letters, 1969, 1905. 65 P. Haake, J. P. McNeal, and E. J. Goldsmith, J. Amer. Chem. SOC.,1968, 90, 715. 66 R. Greenhalgh and R. F. Hudson, Chem. Cumm., 1968, 1300. 6 7 F. H. Westheimer, Accounts Chem. Res., 1968, 1, 70. 6 8 R. Greenhalgh, J. E. Newberry, R. Woodcock, and R. F. Hudson, Chem. Cumm., 1969, 22. m R. F. Hudson and R. J. G. Searle, J. Chem. SOC.(B), 1968, 1349. 60 R. F. Hudson and A. Mancuso, Chem. Comm., 1969, 522.

6s 64

95

Terualent Phosphorus Acids

R

Me

E. Miscellaneous Reactions.-A. new method for the synthesis of dialkyl phosphites consists of treating a mixture of the alcohol and methanol with phosphorus trichloride. Elimination of methyl chloride from the intermediate occurs smoothly and removal of the volatile products in vacuo leaves the phosphite ester.s1 The synthesis of phosphonites and phosphinites by the action of trimethyl phosphite on alkyl chlorides is a similar process.62 Phosphorus fluorides react with trialkyl phosphines or aminophosphines to give 1 : l-adducts with P-:P bonds.s3 When trimethyl phosphite is treated with phosphorus pentafluoride, a 1 : l-adduct is formed in the first place which breaks down to tetrafluoro(methoxy)phosphorane (62) and fluoro(dimethoxy)phosphine (63).64 Interaction of (62) and (63) gives a complex mixture of products. A range of products is also formed when phosphorus trifluoride reacts with trimethyl phosphite. 2ROH PFs

+ lMeOH + PCl,

+ (MeO),P

-

[(RO),POMe]

PF,OMe

(62!)

(MeO),+Me PF,

MeOPF,

HCl

(RO),P(O)H

+ MeCl

+ (MeO),PF

I

(63)

+ MeOP(O)F, + MeP(O)F, + MeOPF, + (MeO),PF PF', + (MeO),P

+ MeP(O)(F)(OMe) + MeP(O)(OMe), + MeP(O)F,

Esters of pyrophosphoric and pyrothiophosphoric acids are formed when sodium diethyl phosphite is treated with sulphur dioxide.65 The mechanism

82

63

64

66

Y. A. Mandel'baum, A. L. Itskova, and N. N. Mel'nikov, Khim. Org. Soedin. Fosfora, Akad. Nauk S.S.S.R., Otd. obshchei Tekh. Khim., 1967, 288 (Chem. Abs., 1968, 69, 43,338). I. Hechenbleikner and K. R. Molt, U.S.P. 3,316,333 (Chem. Abs., 1968, 68, 49,765). D. H. Brown, K. D. Crosbie, G. W. Fraser, and D. W. A. Sharp, J. Chem. SOC.(A), 1969, 551. D. H. Brown, K. D. Crosbie, G. W. Fraser, and D. W. A. Sharp, J. Chem. SOC.(A), 1969, 872. W. Stec, A. Zwierzak, and J. Michalski, Tetrahedron Letters, 1968, 5873.

96


of this reaction is uncertain, but since dialkyl phosphites can function as ambident nucleophiles, two of the intermediates may be (64) and (65) which must interact with dialkyl phosphite and/or sulphur dioxide to generate the anhydrides. Tervalent phosphorus compounds can be determined by means of the Karl Fischer reagent 66 when the sulphur dioxide again acts as an oxidising agent. Phosphonium salts and quinquevalent phosphorus derivatives do not interfere with the determination. 0 0 0 II II II '+ (EtO),P-S-O+ (EtO),P-O--S-O(EtO),P-0 SO2

?

+

(64)

(6.9

I

(EtO),PO

(EtO),POP(OEt), < II II

-

+ so3'

(EtO),P-O--P(OEt),

0 0

Diethyl phosphite has been used in a study of the interaction of thiamine with nucle~philes.~~ Nucleophilic attack by the phosphorus atom occurs to produce phosphonates.

(67)

J R1R3PSR2

II

J

R2SR3 + R1PSR2

I

X

S (69)

(70) 0

HP(OH),

\ (RCO),O

%.+

I1

> RCOPH

I

OH 0 (71)

II

HOP-CRCH,

I

I

H NHRl (72) E7

B. Hayton and B. C. Smith, J. Inorg. Nuclear Chem., 1969, 31, 1369. A. Takamizawa, K. Hirai, Y.Hamashima, Y. Matsumoto, and S. Tanaka, Chem. and Pharm. Bull (Japan), 1968, 16, 1764.

Tevvalent Phosphorus Acids

97

3 Phosphonous Acid and its Derivatives Reaction conditions appear to have no effect on the reaction between dithioesters of alkylphosphonoiis acids (66) and alkyl halides.&*The alkyl halide can undergo nucleophilic attack either by phosphorus atom or one of the sulphur atoms to generate (67) and (68) respectively. Attack by halide ion on (67) and (68) produces either (69), or a thioether and (70). Hypophosphorous acid can react as a nucleophile and the lone pair on phosphorus can add on to carbonyl groups 69 or enamines 70 to form (71) and (72) respectively.

4 Phosphinous Acid and its Derivatives The kinetics of hydrolysis of phenyl (di-a-haloalky1)phosphinates have been investigated both in water and in dilute aqueous alkali.?l The entropies of activation of the alkaline hydrolysis have the values expected if the reaction were an &2 process. The values for the aqueous hydrolysis are higher and suggest a more ordered structure in the transition state. The rate constant of the second-order reaction between diethylchlorophosphine and chloromethyl butyl ether can be deterrnined 72 from the change in resistance during the reaction, as an ionic intermediate, presumably (73), is produced.

0 2

Ph2PNEt2 (74)

-hydrocarbon solvent

'

Ph2P(0)NEt2

Solutions of the diethylamide of diphenylphosphinous acid (74) in non-polar solvents are subject to aerial oxidation while solutions of (74) in polar solvents are not.73 In the latter case, the electron availability on phosphorus could be reduced either by protonation or by co-ordination to a polar group in the solvent making oxidation difficult. 68

69

70

71

7a

73

E. A. Krasil'nikova, A. M. Potapov, and A. I. Razumov, Zhur. obshchei Khim., 1968, 38, 609 (Chem. Abs., 1968, 69, 43.,993). F. Kasparek, 2. anorg. chem., 1968, 362, 205. N. Kreutzkamp, C. Schimpfky, iind K. Storck, Arch. Pharm., 1968, 301, 247 (Chem. Abs., 1968, 69, 19,260). V. E. Bel'skii, M. V. Efremova, and A. R. Panteleeva, Izvest. Akad. Nauk S.S.S.R., Ser. khim., 1968, 2278 (Chem. Abs., 1969, 70, 28,109). V. S. Tsiwnin, L. N. Krutskii, and G. K. Kamai, Zhur. obshchei Khim., 1967,37,2752 (Chem. Abs., 1968, 69, 66,604). A. E. Myshkin and V. P. Evdakov, Zhur. obshchei Khim., 1968,38, 1776 (Chem. Abs., 1969,70, 4229).

Q uinq uevalent Ph0 s pho rus Acids BY D. W. HUTCHINSON

1 Phosphoric Acid and its Derivatives A. Phosphorylation Methods.-Phosphoryl transfer reactions using mixed anhydrides (e.g. phosphorochloridates or tetra-esters of pyrophosphoric acid), when expulsion of Z (a group bonded to the phosphorus atom) occurs during the phosphoryl transfer, are well kn0wn.l Phosphoryl transfer can also occur from a molecule when the leaving group Z is joined to the phosphoryl residue by two atoms X and Y provided the electrons in the P-X bond can be formally accommodated on Z.2 During the reaction, the bond order between X and Y must increase, and the bond order between Y and Z must decrease, each by one.unit. The atoms X, Y, and Z of the P-XYZ system (1) can be of any element but most commonly are hydrogen, carbon, nitrogen, oxygen, sulphur or halogen. If a lone pair

(5) a

D. M.Brown, Advances in Organic Chemistry, 1963, 3, 76. V. M. Clark and D. W. Hutchinson, Progr. Org. Chem., 1968, 7 , 75.

Quinquevalent Phosphorus Acids

99

of electrons is present on X the efficiency of the P-XYZ system as a phosphorylating agent is reduced since pn-dn bonding between X and P can O C C U ~ . ~This bonding can be reduced by introducing more effective pn bonding between X and Y (e.g. 2). Nitriles bearing electron-withdrawing substituents react smoothly with phospho-monoesters to give sym-pyrophosphates ;4 the same condensation can be carried out with less reactive nitriles at elevated temperature^.^ Prior addition of a reactive alkyl or aralkyl halide [e.g. a chloromethyl ether (3, X = OMe)] to the reaction mixture facilitates phosphoryl transfer, presumably by alkylating the imidoyl phosphate (4). Chloromethyl ethers are powerful alkylating agents and might be expected to react with a phospho-monoester to give (9,which is a P-XYZ system and hence could be a phosphorylating agent. No such interaction has been observed with chloromethyl ethers ; however, gem-dihalides (e.g. 3, R = 4-MeOC,H4, X = C1) can promote phosphoryl transfer.6s 6,7-Dichloroquinoline-5,8-quinone (6) has been used in the presence of transition metal ions to promote phosphorylation reactions.* However, halogenoquinones can be regarded as vinylogous acyl halides and can promote the formation of sym-pyrophosphates from phospho-monoesters at elevated temperatures in the absence of metal ions.@ Addition of a heterocyclic tertiary base (e.g. pyridine) to the reaction mixture at room temperature results in the rapid formation of the sym-pyrophosphate together with the zwitterionic quinone (7). Aliphatic tertiary bases (8) inhibit the phosphorylation reaction, as oxidation of (8) will generate an enamine which can displace halide ion from a second molecule of halogenoquinone to form the dialkylaniinovinyl quinone (9). The selective phosphorylation of amines can be achieved in aqueous media using 1-methylmonophosphoimidazole (1 0),lo and for example, ethanolamine will react with (10) to give the N-phosphorylated but not the O-phosphorylated derivative. Alternatively, y-picoline and phosphorus oxychloride can be used, when the intermediate is the highly reactive (11, R = Me).lo 4-Methoxypyridine and 4-pyridone give more stable phosphorylating agents (e.g. 11, R = OMe) leading to increased yields of product. 2-Pyridone, however, produces the O-phosphoryl derivative (1 2) l1 which is a P-XYZ system and has been used previously as a phosphorylating agent.12

*

lo l1 la

H. Goldwhite and D. G. Rowsell, Chem. Comm., 1969, 713. F. Cramer and G. Weimann, Chem. Ber., 1961,94,996. V. M. Clark, D. W. Hutchinson, and P. F. Varey, J. Chem. SOC.(C), 1969, 74. H. Kaye and Lord Todd, J. Chem. SOC.(C), 1967, 1420. V. M. Clark, D. W. Hutchinson, and P. F. Varey, J . Chem. SOC.(C), 1968, 3062. E. J. Corey and H. Konig, J . Amer. Chem. SOC.,1962, 84, 4904. V. M. Clark, D. W. Hutchinson, A. R. Lyons, and R. K. Roschnik J. Chem. SOC.(C), 1969, 233. E. GuibC-Jampel, M. Wakselman, and M. Vilkas, Tetrahedron Letters, 1968, 3533. E. Guibd-Jampel and M. Wakselman, Chem. Comm., 1969, 720. W. Kampe, Chem. Ber., 1965, 98, 1031, 1038.

100

Organophosphorus Chemistry 0

0 /WH2yRz

OH

+

R’CH=CHNRZ

1

ROP(O)OH

+

OH

H20

HO

OH (32)

3-phosphoglyceric acid under these conditions. A rapid procedure for the determination of orthophosphate in the presence of labile organic phosphates has been developed.57b This consists of the formation of a phosphomolybdovanadate complex which can be extracted from an aqueous medium into butanol. The phosphorylation of a phosphorothioate to generate a pyrophosphorothionate occurs by direct attack of phosphorus on the oxygen atom of the ambident thioate anion and not by the isomerisation of a P(O)SP(O) intermediate.68 Thiophosphorylation appears to proceed in a similar manner as the stability of the P(S)SP(O) system renders its rearrangement unlikely.59 Thus, phosphorylation and thiophosphorylation of optically active phosphorothioates should lead to optically active pyrophosphorothionates with the same configuration and optical purity as the original thioacid. A number of optically active pyrophosphonothionates have been

58

J. Michalski, M. Mikolajczyk, and A. Ratajczak, Bull. Acad. polon. Sci., Sgr. Sci. chim., 1965, 13, 277. L. Almasi and L. Paskucz, Munatsh., 1968, 99, 187.

111

Quinquevalertt Phosphorus Acids HC-O-

II

CH,OPO,'-

C-OH _I_,

HO &>:OH

.Ho\

&.

OH

OH

CHZOH CH,OH I

co

I CH,OH

I

+

J

dH20PO,'.(3 5)

COOH tOH

+

HP04'-

CH3

prepared 6o and inversion of configuration occurs during alkaline hydrolysis. This observation appears to exclude pseudorotation of a pentaco-ordinate transition state in these reactions. The activation energy of the aqueous hydrolysis of OO-diethyl dithiopyrophosphate61a is much larger than that of its monothio analogue.61b It has been claimed6lGthat d,-p, bonding has little effect in the transition state during nucleophilic attack on phosphoryl or thiophosphoryl compounds and that reactivities are determined by the inductive effect of substituents. The rate of acid-catalysed hydrolysis of aliphatic acyl phosphates depends on the size of the acyl group,62and the acid-catalysed hydrolysis occurs by attack by water on carbonyl carbon followed by expulsion of inorganic phosphate. This behaviour is in direct contrast to the mode of reaction at higher pH values.g3 60

61

62

63

J. Michalski, M. Mikolajczyk, B. M€otkowska,and J. Omelanczuk, Tetrahedron, 1969, 25, 1743. (a) V. E. Bel'skii and M. V. Efremova, Izvest. Akad. Nauk S.S.S.R., Ser. khim., 1968, 409 (Chem. Abs., 1968, 69, 66,596). ( b ) V. E. Bel'skii, M. V. Efremova, and Z. V. Lustina, Izvest. Akad. Nauk S.S.S.R., Ser. khim., 1967, 1236 (Chem. Abs., 1968, 68, 21,342). ( e ) A. A. Neimysheva, V. I. Savchuk, M. V. Ermolaeva, and I. L. Knunyants, Izvest. Akad. Nauk. S.S.S.R., Ser. khim., 1968, 2222 (Chem. Abs., 1969, 70, 56,923). D. R. Phillips and T. H. Fife, J . Amer. Chem. SOC.,1968, 90, 6803. G. Di Sabato and W. P. Jencks, J. Amer. Chem. SOC.,1961, 83, 4400.

112 Organophosphorus Chemistry C. Reactions of Derivatives of Phosphoric Acid.-(i) Dephosphorylation Reactions. The synthesis of alkynes from enol phosphates and other enol esters has been reviewed.64 Both cis- and trans-elimination can occur and the highest yields of alkynes are obtained when the reaction is carried out in

a non-aqueous medium. A structurally specific olefin synthesis has been developed 6e which consists of elimination of a diethyl phosphate residue from an enol phosphate by reduction with lithium in ammonia. The enol phosphates can be prepared by treatment of the enolate anion with diethyl phosphorochloridate 65 or by the Perkow reaction.66 The acidolysis and halogenation of a-alkoxy enol phosphates takes place with fragmentati~n.~'The acid (or halogen) adds on to the carbon-carbon double bond of the enol phosphate to give (36) which can then undergo unimolecular decomposition with C-0 bond fission. The reaction between N-bromophthalimide and dimethyl esters of enol phosphates is complex as a-bromoketones, trimethyl phosphate, and e6s

.

OEt

CCI,(OEt)CCI,X

P( S )NHCHzCH2CI

R'/

+

'O

72

98 74

E. Cherbuliez, 3. Baehler, 0. Espejo, E. Frankenfeld, and J. Rabinowitz, Helo. Chim. A d a , 1968, 49, 2608. (a) G. F. Ottmann and H. Hooks jun., U.S.P. 3,409,656 (Chem. Abs., 1969,70, 37,437). ( b ) R. R. Engel, Canad. J. Chem., 1969, 47, 1258. P. Savignac and P. Chabrier, Compt. rend., 1968, 268, C , 861. P. Chabrier and P. Savignac, Compt. rend., 1968, 267, C, 1166. P. Savignac, T. N. Thanh, and P. Chabrier, Compt. rend., 1968, 266, C, 1791; P. Savignac, T. N. Thanh, and P. Chabrier, Compt. rend., 1968,267, C, 183.


115

The chlorination of 00-diethyl phosphoramidate with gaseous chlorine is a strongly exothermic reaction giving rise to 00-diethyl NN-dichlorophosphoramidate (40) which adds on to unsaturated hydrocarbons to give N-chloro-N-(chloroalky1)phosphoramidates(41).75a Reduction of (41) followed by treatment with aqueous acid liberates 2-chloroalkylamines. The reaction between isoquinoline, potassium cyanide, and a phosphorochloridate or phosphorothiochloridate leads to the formation of phosphorus-containing analogues of Reissert Acid hydrolysis

aN L

+

where Z

=

0 or S

II KCN 3. (KO),PCI

J

A

H CN

NaH-Me1

of the Reissert compounds affords isoquinoline, while they can be alkylated in the presence of base. (iii) P--S Systems. The inhibition of acetyl cholinesterase by organophosphorus compounds (e.g. 42, n = 2) occurs as a result of phosphorylation of the active site of the enzyme. 0-Dealkylation of the inhibitor reduces its effectiveness as a phosphorylating agent and hence reduces its inhibitory power.76 Analogues of (42) have been prepared and their properties compared;77their effectiveness as inhibiting agents increases as n increases reaching a maximum at n = 6.78 The findings are interpreted as indicating the presence of a hydrophobic site of limited size near the active site of the enzyme. Trialkyl thiophosphates can be prepared in high yields from the reaction between a dialkyl phosphite and a salt of an 00-dialkyl thiophosphoric acid,79when the latter functions as an ambident nucleophile and dealkylates the phosphite. Direct alkylation of salts of 00-dialkyl thiophosphoric acid has also been investigated.80 'Is 76

77 78

79

(a) A.

Zwierzak and A. Koziara, Attgew. Chem. Internat. Edn., 1968, 7 , 292. ( b ) D. M. Spatz and F. D. Popp, J. Heterocyclic Chem., 1968, 5 , 497. A. H. Aharoni and R. D. O'Brien, Biochemistry, 1968, 7, 1538, P. Bracha and R. D. O'Brien, Biochemistry, 1968, 7 , 1545. P. Bracha and R. D. O'Brien, Biochemistry, 1968, 7, 1555. Y. A. Mandel'baum, P. G. Zaks, N. N. Mel'nikov, and V. V. Ivanov, Khim. Org. Soedin. Fosfora, Akad. Nauk S.S.S.R., Otd. obshchei Tekh. Khim., 1967, 262 (Chem. A h . , 1968, 69, 2457). N. T. Thanh, P. Chabrier, N. H. Philong, and M. J. Ferrere, Compt. rend., 1969,268, C , 1714.

116

Organophosphorus Chemistry (EtO),P(O)S( C H z),rNEt, (42) (RO),P(O)H

+ (R’O),P(S)O-

,NH-bPr P Me0 S

NH,+

---+

(R‘O),P(O)SR

ArO\ /NH-i-Pr P MeS’

ArO,

/ \

(45)

(44) where Ar = 2,4-C12C6H3-

RHN,

,SCHzCH20P MeO’ ‘ 0

(43)

I

+

c s 0 ... I

,p-o-

RHN h

RHN,

e

’0-

P MeO’ \O

+ w S

Aqueous solutions of sodium methyl N-cyclohexylphosphoramidothioate (43) on treatment with an excess of ethylene oxide liberate ethylene sulphide.81 The migration of the phosphoryl residue from sulphur to oxygen can be explained in terms of the formation of a pentaco-ordinate intermediate followed by pseudorotation and expulsion of ethylene sulphide. Stereochemical aspects of phosphorus chemistry are the subject of a recent review.82 The optical isomers of O-2,4-dichlorophenyl O-methyl isopropylphosphoramidothioate(44) and O-2,4-dichlorophenyl S-methylisopropylphosphoramidothioate (45) have been ~ynthesised.~~ Racemic (44) was demethylated with methylamine and the acid liberated was resolved as its quinine salt. Methylation of the optically active quinine salts with diazomethane gave (44) and (45). The value of the optical 8a

8s

N. K. Hamer, Chem. Comm., 1968, 1399. M. J. Gallagher and I. D. Jenkins, Topics Stereochem., 1968, 3, 1. J. N. Seiber and H. Tolkmith, Tetrahedron, 1969, 25, 381.

117


rotation of the two compounds was strongly solvent dependent presumably due to the possibility of hydrogen bond formation between the solvent and the amido group. Racemic methyl 1 -naphthyl phosphorothionic acid has been resolved into its optical antipodes by means of its ephedrine Addition of the sulphenyl chloride (46) to an olefin gives an 00-diethylS-(trcms-2-chloroalkyl) phosphorothioate (47) which on acetolysis with dry acetic acid and sodium acetate affords the diacetate of a trans-2hydroxyalkanethiol (4QE5 Acetolysis with wet acetic acid and sodium acetate gives the trans-2-acetoxyalkanethiol (49) exclusively,86while the

L=/

+

(EtO),P(O)SCl (46)

-

-" c?'(

(EtO),P(O)S: (47)

I

OAc:

AcS

w

SH

OAc

(48)

(49) episulphide is produced with dry acetic acid in the absence of sodium acetate. The retention of configuration during acetolysis suggests the formation of an episulphonium ion which is dephosphorylated by acetic acid to the episulphide. The latter can then undergo attack by acetate ion or water to give the observed products. 00-Dialkyl S-chlorothiolothimophosphates (50) on treatment with alcohols afford the corresponding With sodium alcoholates a more complex reaction takes place and 000-trialkyl thiophosphates, salts of 00-dialkylthiophosphoric acid and bis-(00-dialkyl thiophosphoryl) disulphides are among the products of the reaction. Grignard reagents displace halide ion from (50) and 00-dialkyl S-alkyl and S-aryl dithiophosphates can be prepared in this way.88 SS-2-Acetaminoethyl 00dialkyl thioperoxymonophosphorothioates( 5 1) are of interest as compounds 81

85 8e

13' 88

C. Donninger and D. H. Hutson, letrahedron Letters, 1968, 4871. B. Bochwic and A. Frankowski, Tetrahedron, 1968, 24, 6653. B. Bochwic, A. Frankowski, and A. Kus, Bull. Acad. polon. Sci., Ser. Sci. chim., 1968, 16, 469 (Chem. Abs., 1969, 70, 76,958). L. Almasi and A. Hantz, Monatsh., 1968, 99, 1045. L. Almasi and A. Hantz, Rev. Rouniaine Chim., 1968, 13, 653 (Chem. Abs., 1969, 70, 11,256).

5

118


offering protection against ionising r a d i a t i ~ n . ~Only ~ symmetrical disulphides can be isolated from the reaction between (50) and S-2acetaminoethanethiol; however, on treating 00-dialkyl phosphorodithioic acid with 2-acetaminoethyl 2-acetaminoethane thiolsulphate (52), (5 1) was obtained in moderate yield.

(RO),P( S)SCl

v

(RO),PS 4- (W,P(S)S-

+

“RO),P(S)Sl,

(RO),P(S)SR’

(50)

0

II

AcNHCH,CH,SSCH,CH,NHAc

II

+ (RO),P(S)SH

0

(52)

AcNHCH,CH,SO,H

+

1 (RO),P(S)SSCH,CH,NHAc (5 1)

Changes in P-S force constants due to hybridisation, inductive effects, ionic charge, and T bonding have been discussed in a recent re~iew,~O and it has been shown that the P-S bond, unlike the P-0 bond, never possesses full double-bond character. Internuclear double resonance has been used to investigate the reaction between thiophosphoryl halides and Grignard reagents.91 The mass spectrometric investigation of phosphorothi~nates,~~ phosphine trimethylsilyl derivatives of n u c l e ~ t i d e s and , ~ ~ tris(trimethylsily1) phosphates 96 has been reported recently. One of the decomposition pathways of arylphosphine oxides and phosphorothionates requires the formation of bridged phosphofluorenyl ions ; O 2 ~ 93 an alternative decomposition of phosphorothionates involves the rearrangement of P( :S)O The mass spectrometry of volatile derivatives of to P(:O)S phosphoric acid is being investigated as a potential method for identifying trace constituents in biological systems. (iv) Miscellaneous Reactions. From a study of the kinetic parameters of the reaction between 00-diethyl phosphorodithioic acid and o@-unsaturated 89

ga

ss g4

g6

D. G. Stoffey, J . Org. Chem., 1968,33, 1651. J. Goubeau, Angew. Chem. Internat. Edn., 1968, 8, 328. R. Kosfeld, G. Hagele, and W. Kuchen, Angew. Chem. Internat. Edn., 1968, 7 , 814. R. G. Cooks and A. F. Gerrard, J . Chem. SOC.(B), 1968, 1327. D. H. Williams, R. S. Ward, and R. G. Cooks, J. Amer. Chem. Soc., 1968, 90, 966. J. A. McCloskey, A. M. Lawson, K. Tsuboyama, P. M. Krueger, and R. N. Stillwell, J. Amer. Chem. Soc., 1968, 90, 4182. M. Zinbo and W. R. Sherman, Tetrahedron Letters, 1969, 2811.

119


ketones, esters, and nitriles, it has been proposed g6 that a 1,4-addition takes place with a six-centre transition state. Phosphoryl compounds have been alkylated with triethyloxonium fluoroborate to water-sensitive quasiphosphonium compounds (53),@' the stability of which increases as n increases. Unstable dialkyl t-butylperoxy phosphates (54)can be prepared by treating potassium hydroxide solutions of t-butylhydroperoxide with dialkyl phosphorochloridates.gs

S ==P(OEt),

+ Et,P(OEt), - ?IBF,-

(53)

S =P(OEt),

(RO),P(O)OO-~-BU (54)

3aP-Labelled ferric phosphate will exchange phosphorus with trialkyl phosphates at elevated temperatures ;Dg the rate of exchange is dependent on chain length with trimethyl phosphate exchanging the fastest. The mechanism of the exchange reaction is uncertain but it is postulated that pyrophosphates are involved. D. Cyclic Derivatives of Phosphoric Acid.-The lH n.m.r. spectra of the two 1,3,2-dioxaphosphorinane(55, isomers of 5,5-dimethyl-2-0~0-2-piperidinoX = H, Y = C5HlON)are essentially unchanged over a wide range of temperatures, suggesting that in this instance the ring is conformationally immobile.loOThe lH n.m.r. spectrum of (55, X = C1, Y = CH2Ph)lol also shows. little change with temperature apart from line broadening.lo2 On the other hand, pronounced changes in the lH n.m.r. spectrum of (55, X = Br, Y = Me) occur with variation in temperature, the chemical shifts of groups attached to C(5), and to phosphorus moving to lower fields as the temperature is lowered.lo2 The size of groups attached to phosphorus appears to have an important bearing on the ease of ring inversion as analogous phosphites (55, X = H, Y = lone pair) possess conformational mobility.lo3 A. N. Pudovik and R. A. Cherkasov, Zhur. obshchei Khim., 1968,38,2532 (Chem. Abs., 1969, 70, 57,079). G. Sosnovsky and E. H. Zaret, J . Org. Chem., 1969, 34, 968. L. V. Nesterov and R. I. Mutalapova, Tetrahedron Letters, 1968, 51. L. Termens and K. H. Schweer, Radiochim. Acta, 1968, 9, 125. loo R. S. Edmundson and E. W. Mitchell, J. Chem. Soc. (0, 1968, 3033. Io1 R. S. Edmundson and E. W. Mitchell, J. Chem. SOC.( C ) , 1968,2091. lo2 R. S. Edmundson, Tetrahedron Letters, 1969, 1905. loS J. H. Hargis, and W. G . Bentrude, Tetrahedron Letters, 1968, 5365. ( b ) D. W. White, G . K. McEwen and W. G. Bentrude, Tetrahedron Letters, 1968, 5369. ( e ) C. Bodkin and P. Simpson, Chem. Comm., 1969, 829. O*

120

Organophosphorus Chemistry OR’

(55)

R Me,NH

R

O\ ,OCR,CR,OH P Me,” ‘OPh (57)

2-Oxo-2-phenoxy-l,3,2-dioxaphosphorinanes bearing substituents in the ring (e.g. 56, R = Ph, R’ = i-Pr), which have recently been prepared and reso1ved,lo4are assumed to have the chair conformation. Preliminary data on the acid hydrolysis of (56, R = Et, R’ = H) have appeared.lo5 Dimethylamine will attack 2-oxo-2-phenoxy-l,3,2-dioxaphospholanes to give the phosphoramidate (57); no evidence has been found for the formation of a phosphoramidate containing an intact five-membered ring.108 The effect of catalysts on the polymerisation of ethyl esters of cyclic phosphates (58) has been studied,lo7 and the most effective catalyst when n = 3 is lithium aluminium hydride. Sugar-like phosphates have been obtained by the action of anhydrous acid chlorides on the phospholene (59) prepared from glyoxal (60, R = H) and trimethyl phosphite.lo8 Bromination of (59, R = Me or Ph) gives rise to a-bromo-a-ketol phosphates which can react further with excess trimethyl phosphite to give enediol bisphosphates.log The general reactions of pentaoxyphosphoranes are discussed in detail in Chapter 2. 104 106

106

107 108

J. P. Majoral, A. Munoz, and J. Navech, Compt. rend., 1968,266, C, 235. J. P. Majoral, J. Devillers, and J. Navech, Compt. rend., 1969, 268, C, 1077. M. Revel and J. Navech, Compt. rend., 1969, 268, C, 121. J. P. Majoral, F. Mathis, A. Munoz, J. P. Vives, and J. Navech, Bull. Soc. chim. France, 1968, 4455. F. Ramirez, S. L. Glaser, A. J. Bigler, and J. F. Pilot, J . Amer. Chem. SOC.,1969, 91, 496.

10s

F. Ramirez, K. Tasaka, N. B. Desai, and C. P. Smith, J. Org. Chem., 1968, 33, 25.

121


R

0,

P(OMe)2

II

+

R

MeY

0

where X = H, RCO or Br Y = C1 or Br

2 Phosphonic Acid and its Derivatives A. Synthetic Methods.-Esters of acylphosphonic and acylphosphinic ll1 acids can be prepared by a variant of the Arbusov reaction when an acyl halide is treated with an alkyl phosphite or phosphonite. Oximes of acylphosphonic acids can be reduced to a-aminophosphonic acids (61).1109112 An alternative synthesis of (61) consists of the addition of dialkyl phosphites to Schiff bases.l13 RlCOCl

+ (AlkO),P

--

RICOP(O)(OAlk),

+ AlkCl

1

R20NHz

RICP(0)(OAlk) ,

II

NORa (a) reduce (b) hydrolyse

R1CH=NR8

(A1k0)2p(o% (b) hydrolyse

J. RICHNH,P(0)(OH), (61)

110

111 112 11s

K. D. Berlin, R. T. Claunch, and E . T. Gaudy, J. Org. Chem., 1968,33, 3090. A. I. Razumov and M. B. Gazizov, Zhur. obshchei Khim., 1967,37,2738 (Chem, Abs., 1968, 69, 19,263). K. D. Berlin, N. K. Roy, R. T. Claimch, and D. Bude, J. Amer. Chem. SOC., 1968, 90, 4494. ( a ) H. Hoffmann and H. Forster, Monarsh., 1968, 99, 380. @) N. S. Kozlov, V. D. Pak, and E. S. Elin, Vesti Akad. Navuk. Belarus. S.S.R., Ser. khim. Navuk, 1968, 113 (Chem. Abs., 1969, 70, 20,158).

122


Phosphite esters do not form pentaoxyphosphoranes with phenyl cyclobutenedione (62) as these would be derivatives of c y c l ~ b u t a d i e n e .Quanti~~~ tative yields of 1-alkoxy-3-dialkyl-phosphono-4-oxo-2-phenylcyclobutenes (63) are obtained, and the reactions are too rapid for the formation of phosphonium intermediates to be detected.

(63)

Phosphorus trichloride reacts with cholest4-en-3-one in the presence of benzoic acid to give a stable crystalline phostonyl chloride (64) in addition to the major product 3-chlorocholesta-3,5-diene.115 This reaction has been cited as an example of attack by electrophilic phosphorus on carbonyl oxygen followed by attack by chloride ion at carbonyl carbon and then cyclisation. This mechanism appears to be unlikely as there is little proven precedent for electrophilic attack by phosphorus on carbonyl oxygen. Furthermore, addition of chloride ion to the carbonyl group prior to the cyclisation step would hinder attack by electron-rich phosphorus on the 4,5-double bond. An alternative mechanism would be addition of phosphorus trichloride to the 4,5-double bond followed by proton transfer from the benzoic acid to give the cation (65). Addition of chloride ion to the carbonyl group followed by cyclisation and partial hydrolysis would generate (64). C-Phosphorylated formaldehyde acetals (66) are prepared by treating esters of orthoacids with tervalent phosphorus chlorides; a slow esterification of the phosphorus chloride also takes place.llea Similar products are obtained when dialkyl phosphites are used in place of the ch10ride.l~~ Diethylmethylketen ketal reacts with monoalkyl esters of alkyl phosphonic and alkylphosphonothionic acids in an inert solvent to give ethyl propionate and dialkyl alkylphosphonates or O-alkyl S-alkylphosphonothiolate.116b It is proposed that addition of the phosphonate to the keten occurs followed by a six-centre rearrangement. Phenothiaphosphinic acids (67) can be prepared from p-chlorinated diphenyl thioethers and phosphorus trichloride in the presence of aluminium 11*

R. C. De Selms, Tetrahedron Letters, 1968, 5545.

n5 J. A. Ross and M. D. Martz, J. Org. Chem., 1969, 34, 399. 116 117

W. Dietsche, Annalen, 1968, 712, 21. ( b ) C. D. Hall, J. Chem. SOC.(B), 1968, 708. V. V. Moskva, A. Maikova, and A. I. Razumov, Zhur. obshchei Khim., 1967,37, 1623 (Chem. Abs., 1968, 68, 39,732).

123


CI -

A .

I

I

(a) cyclise (b) hydrolyse

T

(a) cyclise (b) hydrolyse

trichloride.ll*" When bromine is present in either the ortho- or parapositions, p-arylthiophenylphosphonic acids (68) are obtained.llsb The formation of a p-phosphonic acid from either the u- or p-bromo-derivative is unusual and suggests the participation of a common symmetrical intermediate (e.g. 69). Acridinium salts will add on the anion of diethyl phosphite to afford esters of 9,lO-dihydroacridinephosphonic acids (70),ll9 which are converted to the corresponding 9-arylidene derivatives by the action of aromatic aldehydes.lZ0In the presence of Grignard reagents alkyl esters of (70) will rearrange, presumably via the anion. The deoxygenation of aromatic nitro-compounds by triethyl phosphite leads to a complex mixture of products lZ1which include triethyl phosphate, triethyl N-arylphosphorimidates, 3 H - a z e p i n e ~ , and ~ ~ ~ arylphosphonic I. Granoth, A. Kalir, and Z . Pelah, Israel J. Chem., 1968, 6, 651. @) I. Granoth, A. Kalir, Z. Pelah, and E. D. Bergmann, Chem. Comm., 1969, 260. 119 D. Redmore, J. Org. Chem., 1969, 34, 1420. l m W.S. Wadsworth jun. and W. D. Emmons, J. Amer. Chem. SOC.,1961, 83, 1733. l9lR. J. Sundberg, B. P. Das, and R. H. Smithjun., J. Amer. Chem. SOC.,1969, 91, 658. lZa J. I. G. Cadogan, R. K. Mackie, and M. J. Todd, Chem. Comm., 1968,736.

118

124 (RO),PCl

+ HC(OEt),

-

Organophosphorus Chemistry (RO),P(O)CH(OEt),

(a) PCI,-AIC13

(b) hydrolyse

(66)

'

R

Br

or p-isomer

* (68)

R X-

*

&J / / R

(EtO),F(O)

ArCHO

Ar

6a

~

R

H P(O)(OEt), (70)

I

RMgBr

R

R

Et P-OH 0 11 'OEt

CH,CH,O

0

125


The mechanism of deoxygenation reactions is discussed in Chapter 10. B. Hydrolysis of Phosphonate Esters.-The hydrolysis of diethyl2-carboxyphenylphosphonate (71, R1 = Et, R2 = H) proceeds 107-108 times faster than the 4-isomer. On the other hand, the rate of hydrolysis of (71, R1= Et, R2 = Me) is lo5 times slower than the parent carboxylic The very rapid hydrolysis of (71, R1= Et, R2 = H) suggests that neighbouring group participation is an important feature of this reaction. Studies with ’*O-labelled compounds and other kinetic information indicate that a pentaco-ordinate intermediate (72) is formed during the hydrolysis. hydrolyse rapidly in Diesters of 1-cyanovinylphosphonic acids (73) aqueous sodium carbonate s01ution.l~~~ Two reaction pathways are possible: either (73) is hydrolysed to a carbonyl compound and a diester of cyanomethylphosphonic acid, or attack by hydroxide on phosphorus takes place with the liberation of a phospho-diester and an acrylonitrile

O+ ,OR‘

OP>! ‘

P(O)(OH),

COOH

-- o\

c

II 0

P , (0) (ORI)oH COOH

R,C=C(CN)P(O)(OR),

_rrzO’OH;

(73)

I

H,O / OH-

R,C=CHCN

124

lZ5

+ (R’O),P(O)O-

RZCO

+ CHZCNP(O)(OR’)z

J. I. G. Cadogan, D. J. Sears, and D. M. Smith, Chem. Comm., 1968, 1107. G . M. Blackburn and M. J. Brown, J. Amer. Chem. SOC., 1969,91, 525. (a) D. Danion and R. Carrie, Tetrahedron Letters, 1968, 4537. ( b ) D. Danion and R. Carrie, Compt. rend., 1968, 267, C, 735.

126


(74). Alkaline hydrolysis of monoesters of (73) occurs exclusively by the second route, possibly by elimination of a metaphosphate derivative. Data on the hydrolysis of diesters of phosphonic acids,126tetraethyl methylenediph~sphonate,~~~ and S-alkyl alkyl- and aryl-thio-phosphonic acids 128 have been published recently. Cholinesterases which have been poisoned by phosphonic acids containing secondary alkoxy groups undergo relatively rapid dealkylation to the free phosphonic acid, and it has been suggested that a protonated enzyme is involved in this The acid hydrolysis of alkyl esters of methylphosphonic acid, which has been measured lSoin aqueous dioxan, occurs with C-0 bond fission. A qualitative agreement has been observed between the rate of ageing of phosphonylated cholinesterases and the rate of acid hydrolysis of the corresponding diester. C. Reactions of Derivatives of Phosphonic Acid.-The synthesis and properties of aminoalkylphosphonic acids have been reviewed with particular regard to their complexing properties.lS1,132 Organosilicon compounds which contain phosphorus have also been reviewed re~ent1y.l~~ (i) Dephosphorylation Reactions. Anions of activated methylenephosphonates will add on to Schiff bases to afford2-arylaminoethylphosphonates (75).134 On heating in the presence of catalytic amounts of base (75, R = Ph), which is a P-XYZ system,2 cleaves to liberate trans-stilbene and the corresponding N-arylphosphoramidate diester (76).136 This decomposition has been represented as an intramolecular process which can only be true if the groups attached to the C=N of the Schiff base are in a cis-relationship to one another. No mention is made of the geometry of the Schiff base by the authors, and this aspect of the reaction is still unresolved. Both chloromethylphosphonic dichloride (77) and bis(chloromethy1)phosphinic chloride when heated with phosphorus pentachloride give rise to carbon tetrachloride and a phosphorus(1n) compound.136 Attack by PCl,(+) on phosphoryl oxygen could occur followed by rapid chlorination of the chloromethyl groups. Fragmentation to carbon tetrachloride, phosphorus oxychloride, and phosphorus trichloride could then take place. H. Christol, M. Levy, and C. Marty, J. Organometallic Chem., 1968, 12, 459. V. E. Bel’skii and L. A. Kudryavtsevov, Izvest. Akad. Nauk S.S.S.R., Ser. khim., 1968, 2160 (Chem. Abs., 1969, 70, 10,734). lZ8 A. A. Neimysheva, V. I. Savchuk, and I. L. Knunyants, Zhur. obshchei Khim., 1967, 37, 1822 (Chem. Abs., 1968, 68, 58,979). 129 H. P. Benschop and J. H. Keijer, Biochim. Biophys. Acta, 1966, 128, 586. lSo J. I. G. Cadogan, D. Eastlick, F. Hampson, and R. K. Mackie, J. Chem. SOC.(B), 12’

1969, 144. 13a

133 lS4

135 lS8

M. I. Kabachnik, T. Y. Medved’, N. M. Dyatlova, 0. G. Arkhipova, and M. V. Rudomino, Russ. Chem. Rev., 1968, 37, 503. D. Forest and G. Thomas, Bull. SOC.chim. France, 1968, 3441. E. A. Chernyshev and E. F. Bugerenko, Organornetallic Chem. Rev., 1968, 3, 469. M. Kirilov and J. Petrova, Monatsh., 1968, 99, 148. M. Kirilov and J. Petrova, Chem. Ber., 1968, 101, 3467. A. W. Frank, Canad. J. Chem., 1968, 46, 3573.

127

Quinquevalent Phosphorus Acids PhCH,P(O)(OR),

+ PhCH=NAr

-----+PhCHP(O)(OR), I PhCHNHAr

Ph ‘‘II’’hh

+

(RO),P(O)NHAr

(76) (76)

f f -

++-+

P hC H -P (0)(OR)2 PhCH-P(O)(OR),

Ph-CH-NHAr

J

cc1~+PocI~+Pc1~

(ii) a$- Unsaturated Phosphonic Acids. Unsaturated phosphonic acids may be prepared by the condensation of a carbonyl compound with a derivative of methylenephosphonic by elimination reacti0ns,l3~by the reaction of a carbene with a-diazophosphonic acids,130 or by an Arbusov reaction between a trialkyl phosphite and an acetylene 141 The phosphoryl group, like the carbonyl group, is electron withdrawing and hence a$unsaturated phosphonates can undergo the Michael 142 and the Diels-Alder reactions.140,141 Esters of allenylphosphonic acid (79) can be isolated from the reaction between acetylene alcohols (78) and tervalent phosphorus halides.143 Acetylene phosphates are formed initially in this reaction and then isomerise slowly to (79). Conditions for the selective hydrogenation of allenyl157

138

1z9

l40 141 142

143

(a)A. N. Pudovik, G . E. Yastrebova, and V. I. Nikitina, Zhur. obshchei Khim., 1968, 38, 300 (Chem. Abs., 1968,69,27,480. ( b ) A. N . Pudovik, G. E. Yastrebova, and Y . Y. Samitov, Zhur. obshchei Khim., 1968, 38, 292 (Chem. Abs., 1968, 69, 106,815). A. N. Pudovik, G. E. Yastrebova, V. I. Nikitina, and E. K. Mukhametzyanova, Khim. Org. Soedin. Fosfora, Akad. Nauk S.S.S.R., Otd. obshchei Tekh. Khim., 1967, 18 (Chem. Abs., 1968, 69, 59,331). V. S. Abramov, A. L. Shalman, and Z . V. Molodykh, Zhur. obshchei Khim., 1968, 38, 541 (Chem. Abs., 1968, 69, 27,487). D. Seyferth, J. D. H. Paetsch, and R. S. Marmor, J. Organometallic Chem., 1969, 16, 185. G . Peiffer, A. Guillemonat, J. C. Traynard, and M. Faure, Compt. rend., 1969, 286, C, 358. D. Seyferth and J. D. H. Paetsch, J. Org. Chem., 1969, 34, 1483. A. N. Pudovik and N. G. Khusainova, Khim. Org. Soedin. Fosfora, Akad. Nauk S.S.S.R., Otd. obshchei Tekh. Khim., 1967, 53 (Chem. Abs., 1968, 69, 36,223). (‘) V. N. Pastushkhov, E. S. Vdovina, Y . A. Kondrat’ev, S. Z. Ivin, and V. V. Tarasov, Zhur. obshchei Khim., 1968, 38, 1408 (Chem. Abs., 1968, 69, 87,101). ( b ) V .N . Pastushkhov, Y. A. Arbisma, Y . A. Kondrat’ev, S. Z . Ivin, and A. S. Vasil’eva, Zhur. obshchei Khim., 1968, 38, 1405 (Chem. Abs., 1968, 69, 87,102).

128

Organophosphorus Chemistry RC=CCH,OH f (R’O),PCl (78)

RCH=C=CCIP(0)(OR)2

RCrCCH20P(OR),

+ HCI

/

(79)

(80)

phosphonates to vinylphosphonates 144 and the epoxidation of vinylphosphonates 145 have been reported recently. (iii) P - N and P--S Systems. The preparation of phosphonamidates by ester exchange 146 or halide ion displacement 14’ has been described, and it is

where X=O, S:Y=O, S, Se pH

1111

L

W

I OH

(8 7) 144

146

14’

A. A. Petrov, B. I. Ionin, and V. M. Ignat’ev, Tetrahedron Letters, 1968, 15. K. Hunger, Chem. Ber., 1968, 101, 3530. P. M. Zavlin and T. F. Kondyurina, Zhur. obshchei Khim., 1967,37,2787 (Chem. A h . , 1968, 69, 2981). (a) N. N. Mel’nikov, N. V. Lebedeva, N. K. Daragan, and A. F. Grapov, Zhur. obshchei Khim., 1967, 37, 2760 (Chem. Abs., 1968, 69, 19,259). ( h ) N. N. Mel’nikov, L. V. Razvodovskaya, and A. F. Grapov, Zhur. obshchei Khim., 1968,38,2648 (Chem. Abs., 1969, 70, 78,083).


129

claimed that benzoyl hydrazine will react with methylphosphonodichloridate to give heterocyclic products (80)as well as the expected methylphosphonohydra~idate.~~~ Fluorinating agents will convert alkyl phosphonodithioic acid anhydrides into alkylphosphonodithiofluoridates (8 1) 150 which will react with transition metals to form volatile complexes (82).lS1 Sulphur halides act upon (8 1) to afford bis(alky1phosphonothiofluoride)sulphides (S3).152 (iu) Cyclic Derivatives of Phosphonic Acid. The occurrence of geometric isomerism in a seven-memberedring phosphonate (84) has been Crude (84), which can be prepared by treating 1,5-dibrom0-2-methylpentane with triethyl phosphite, has a lH n.m.r. spectrum containing two doublets for the 6-methyl group. The relative areas of these doublets correspond to the relative amounts of the cis- and trans-isomers which can be obtained by g.1.c. Alkylphosphonodichloridates together with their sulphur and selenium analogues give cyclic products (85) with diols and dithi01s.l~~~ 155 Arylphosphonodi-isocyanatidates (86) react with amines to give 1,3,5,2triazaphosphorinanes (87) which are enolised to a considerable extent.15s (u) Miscellaneous Reactions. During the rearrangement of q3-epoxyvinylphosphonates, the phosphonyl group migrates more readily than hydrogen 158 The reactions or an alkyl group, but less readily than a phenyl group.lS7~ of dialkyl aroylphosphonates with peracids,150 thiamine (88),160 and other thiazolium salts all proceed with migration of a phosphonyl group. The photo-reduction of 8-ketophosphonates leads to /I-hydroxyphosphonates,162and if the intermediate acetal radical is stabilised a pinacol is produced. Tetraethyl dimethylaminomethylenediphosphonate (89) can be methylated to a strong acid which ionises to form a stable ylide (90).163a(89) has 1499

148

149

160

151 163

lK4 155

lK6 16’ 168

169

lE0 lel 163

N. N. Mel’nikov, 0. B. Mikhailova, and A. F. Grapov, Zhur. obshchei Khim., 1968, 38, 2099 (Chem. Abs., 1969, 70, 47,539). t a ) H . W. Roesky, Chem. Ber., 1968, 101, 3679. cb)H.W. Roesky, 2. Naturforsch. B, 1969, 24, 5 . V. N. Aleksandrov and V. I. Emel’yanov, Zhur. obshchei Khim., 1967,37,2714 (Chem. A h . , 1968, 69, 2982). H. W. Roesky, Angew. Chem. Internat. Edn., 1968, 7, 815. H. W. Roesky, Inorg. Nuclear Chem. Letters, 1969, 5, 453. K. Bergesen, Acta Chem. Scand., 1968, 22, 1366. M. Wieber and H. U. Werther, Monatsh., 1968, 99, 1153. A. N. Shapovalova and S. M. Shner, Zhur. obshchei Khirn., 1968,38,317 (Chem. Abs., 1968, 69, 27,482). G. Tomaschewski, C. Berseck, and G. Hilgetag, Chem. Ber., 1968, 101, 2073. R. H. Churi and C. E. Griffin, J. Amer. Chem. Soc., 1966, 88, 1824. M. Sprecher and D. Kost, Tetrahedron Letters, 1969, 703. M. Sprecher and E. Nativ, Tetrahedron Letters, 1968, 4405. A. Takamizawa, Y . Mori, H. Sato, and S. Tanaka, Chem. and Pharm. Bull. (Japan), 1968, 16, 1773. A. Takamizawa, Y . Hamashima, and H. Sato, J . Org. Chem., 1968, 33, 4038. H. Tomioka, Y . Izawa, and Y . Ogata, Tetrahedron, 1969, 24, 1501. H. Gross and B. Costisella, Angew. Chem. Internat. Edn., 1968,7,463. H. Gross and B. Costisella, ibid., 391.

130


ArCOP(O)(OR),

+ PhC0,H

(7)

+ Ar -C-P(O)(OR), IJ

I €2-N

A S

I

-0CoPh

where R =

been used to convert aldehydes to carboxylic acids containing one more carbon atom.163b Methylenediphosphonic acid is an analogue of malonic acid and metalated derivatives of the former have been prepared.164 1-Hydroxyalkylidenediphosphonic acids (91) 165a on treatment with acetic anhydride produce diacetates (92) which on treatment with base give bicyclic dimers (93).lesb The products (94) of the reaction between diethyl phosphonate and Grignard reagents contain tervalent phosphorus.lssa* Hydrolysis or alkylation of (94) leads to secondary or tertiary phosphine oxides. Grignard derivatives of dialkyl phosphites react with a-allenyl ketones to give 16*

0. T. Quimby, J. D. Curry, D. A. Nicholson, J. B. Prentice, and C. H. Roy, J . Organometallic Chem., 1968, 13, 199. F. Kalparek, Monatsh., 1968, 99, 2016. ( 2 ~ ) 0. T. Quimby and J. B. Prentice, U.S.P. 3,400,151 (Chem. Abs., 1969, 70, 78,147). ( a ) H. R. Hays, J. Org. Chem., 1968, 33, 3690. ( B ) H. R. Hays, ibid., 4201.

lBS ( a ) 166

131

Quinquevalent Phosphorus Acids Me,NCH(P(O)(OEt),) --+Mel

Me3&CH(P(0)(OEt)2)q

(89)

RCH=C, ,P(o)(oEt), NMe,

H,O+

base

(92)

RCH,COOH

-+

(90)

~

(93)

+unsaturated y-ketophosphonates.ls7 This reaction can be represented as a 1,4-addition followed by isomerisation of the intermediate. Spectroscopic evidence indicates the formation in tetrahydrofuran of a 1 : 1 complex between the phosphoryl oxygen atom of ethyl diphenylphosphinate and phenylmagnesium bromide.168a The reorganisation of this complex to a pentaco-ordinate intermediate obeys first-order kinetics and pseudorotation of the intermediate followed by expulsion of ethoxide leads to triphenylphosphine oxide. This mechanism implies that a racemic product would be expected from the reaction between a Grignard reagent and an optically active phosphinate; however, inversion of configuration has been observed both in this reaction,leeband in the reaction between an optically active phosphinate and an amine.168e Moreover, treatment of dextrorotatory 16'

G. Peiffer, A. Guillemonat, and G.Buono, Bull. SOC.chim. France, 1969, 946. H. R. Hays, J. Amer. Chem. Soc., 1969, 91, 2736. ( b ) 0. Korpiun, R. A. Lewis, J. Chickos, and K. Mislow, J . Amer. Chem. Soc., 1968, 90,4842. A. Nudelman and D. J. Cram, J. Amer. Chem. Soc., 1968,90, 3869. ( d l H. P. Benschop, G. R. Van den Berg, and H. L. Boter, Rec. Trau. chim., 1968, 87, 387.

lea fa)

132


(EtO),P(O)H

P + 2RMgX > R,POMgX

RzP(o)H

% R,P(O)R'

(94)

0-isopropyl S-methyl methylphosphonate (95) with phenylmagnesium bromide affords 0-isopropyl methylphenylphosphinate (96) with inversion of configuration.1ssd (96) in turn can be converted into a phosphine oxide (97) by further treatment with a Grignard reagent. These reactions have been used to deduce that the most active form of the cholinesterase Sarin is R-(- )-isopropyl methylphosphonofluoridate (98). Dimethyl phosphonate when heated with phenyl isocyanate gives inter aZia carbon dioxide and diphenyl carbodi-imide.lsQ This is an example of

--

PhMgBr(THF),

Ph,P(O)(OEt)

Ph3 PO

+ EtOMgBr

lB9

f---

OEt Ph. If ph;P--Ph I M~B:

&

OEt

I

+

Ph2P= OMgBr(THF)+l-I

2 -

OEt Ph ... I ph,P-OMgBr

I

Ph

F. K. Samigulin, I. M. Kafengauz, E. L. Gefter, and A. P. Kafengauz, Zhur. obshchei Khim., 1968,38, 1766 (Chem. Abs., 1969,70,4237).


133

the well-characterised reaction between phosphine oxides and phenyl The equilibrium transalkylation between diesters of phosphonic acid and alkyl halides or tosylates has been studied as a possible method for the synthesis of phosphonate Alkyl methylphosphonochloridates will esterify phosgene oxime (99) to produce (100). Similar compounds can be obtained by the action of trialkyl phosphites on ha loge no nitro alkane^.^^^ (100) is a P-XYZ system and hydrolyses rapidly in alkali. Acyl nitriles of pyruvic and benzoyl formic acids will add on dialkyl phosphonates to give (101) which isomerise on heating to (102).173Presumably the isomerisation involves the formation of a pentaco-ordinate intermediate followed by pseudorotation and fission of the P-C bond. Similar rearrangements have been invoked for the Perkow reacfion.17* Me

Me0

,P\

c1

--

Me

0

\ /

+

CCI,NOH (99)

Me0

\ /

/p\

0 0-N=CCI,

( 100)

where X

170 171

172 173

174

= NH, 0

or S

J. J. Monagle, T. W. Campbell, and H. F. McShane jun., J. Amer. Chem. Soc., 1962, 84, 4288. H. M. Bell, J. Org. Chem., 1969, 34, 681. R. N. Sterlin, B. N. Evplov, and V. M. Izmailov, Zhur. Vses. Khim. Obshchest., 1968, 13, 118 (Chem. Abs., 1968, 69, 19,254).

A. N. Pudovik, Y. Y.Samitov, I. V. Gur’yanova, and L. V. Banderova, Khim. Org. Soedin. Fosfora, Akad. Nauk S.S.S.R., Otd. obshchei Tekh. Khim., 1967, 45 (Chem. Abs., 1968, 69, 67,489). P. A. Chopard, V. M. Clark, R. F. Hudson, and A. J. Kirby, Tetrahedron, 1965, 21, 1961.

134


Aroylphosphonates (103) are usually yellow although their carbon analogues (e.g. benzoyl forniates) are colourless. An examination of the U.V. spectra of (103) indicates that both the T -+ T* and n -+v* transitions occur at longer wavelengths than the carbon analogues, an effect which may be due to involvement of d orbitals in the phosphonyl bond.176 The IH n.m.r. spectra of a number of T excessive heteroarylphosphonates (104) show that d,-p, bonding occurs between the phosphonyl group and the heteroaromatic ring. This effect is more important with (104, X = 0 or S) than with (104, X = NH).178 Substituent effects on geminal P-C-H coupling constants in lH n.m.r. spectra have been measured for a number of organophosphorus 3 Phosphinic Acid and its Derivatives A. Synthetic Methods.-Secondary phosphines (105, R = CgHll or Ph) will react with hexafluoroacetone to generate esters of phosphinic It is suggested that this reaction takes place with attack by phosphorus on carbonyl carbon followed by rearrangement and aerial oxidation. Bis(hydroxymethy1)phosphinic acid (106) can be chlorinated in high yield to produce bis(chloromethy1)phosphinyl chloride (107). Subsequent

176

176

K. Terauchi and H. Sakurai, Bull. Chem. SOC.Japan, 1969,42, 821. R. H. Kemp, W. A. Thomas, M. Gordon, and C. E. Griffin, J. Chem. SOC.(B), 1969, 527.

177

17*

M. J. Gallagher, Austral. J. Chem., 1968, 21, 1197. R. F. Stockel, Chem. Comm., 1968, 1594.


135

treatment of (107) with phosphite esters leads to bis(dia1koxy methylphosphony1)phosphinates (108).170a, Bis(dia1koxy methylphosphony1)phosphine oxides 17Bc and tris(dia1koxy methylphosphony1)phosphinic acids 179d can be prepared in an analogous manner. B. Hydrolysis of Derivatives of Phosphinic Acid.-1 -Ethoxyphosphole l-oxide 180 dimerises readily to 1,8-diethoxy-3a,4,7,7a-tetrahydro-4,7phosphinidenephosphindole 1,8-dioxide (109) whose structure has been confirmed by X-ray crystallography.lB1 (109) can be hydrogenated to (1 10) 182 and both compounds undergo rapid hydrolysis of one of the two ester groups under either acidic or basic 31P-nuclearmagnetic P

4-\

0

OR

H,-cat

.

HO

0

\4 P

resonance studies indicate that the rapid hydrolysis occurs at the phosphorus atom in the bridge position, i.e. the position of maximum strain. While the pH-rate profile above pH 2 corresponds to that usually obtained during the hydrolysis of phosphate esters, the rate does not continue to rise in proportion to the acid strength below this pH value but reaches a maximum in 0 - 2 acid. ~ During the hydrolyses of (109) and (110), water must enter and alcohol must leave from an apical position in the pentaco-ordinate intermediate. To achieve this, pseudorotation must occur and it is Maier, Angew. Chem. Internat. Edn., 1968,7,384. ( b ) L. Maier, Helu. Chim. Acta, L. Maier, ibid., 845. L. Maier, ibid., 858. 1969, 52, 827. 180 I).A. Usher and F. H. Westheimer, J . Amer. Chem. SOC., 1964, 86, 4732. Y.Y . H. Chiu and W. N. Lipscomb, J . Amer. Chem. SOC.,1969,91,4150. lS2 R. Kluger, F. Kerst, D. G . Lee, and F. H. Westheimer, J. Amer. Chem. SOC.,1967, 89, 3918. ( b ) R. Kluger, F. Kerst, D. G. Lee, E. A. Dennis, and F. H. Westheimer, ibid., 3919. lS3 R. Kluger and F. H. Westheimer, J . Amer. Chem. SOC., 1969, 91, 4143.

179

( a ) L.

136


suggested lS3that in solutions of p H < 1 the pseudorotation process itself is rate limiting which would account for the deviation of the pH-rate profiles. Although the alkaline hydrolysis of the phosphinate ester (111, R = Et) might be expected to be very rapid due to relief of steric strain, the rate is approximately the same as that for the alkaline hydrolysis of triethyl phosphate.ls4 Since the alkaline hydrolysis of (112, R = Et) is very rapid, relief of steric strain during the hydrolysis of (111, R = Et) must be counterbalanced by a retardation due to steric hindrance by the neighbouring methyl groups. A similar effect is observed in the hydrolysis of t-butyl phosphinates (1 13, R1 = t-Bu, R2= H). One t-butyl group attached to phosphorus produces little steric hindrance; however, substitution of phosphorus by two t-butyl groups (e.g. 113, R1 = R2= t-Bu) causes a sharp drop in the rate of hydrolysis.lS6 For (113, R1 = R2 = t-Bu) one t-butyl group must occupy an equatorial position in the pentaco-ordinate intermediate (114) while the other t-butyl group occupies an apical position. In the transition state leading to this intermediate, steric hindrance by the ‘equatorial’ t-butyl group inhibits attack by hydroxide ion on phosphorus. The effect of steric hindrance on the alkaline hydrolysis of acyclic and cyclic phosphinates has been determined.186 In the series (1 15), (1 16), and (1 17), additional steric strain due to the introduction of a double bond into the five-membered ring in (116) causes an increase in the rate of alkaline hydrolysis. However, when the double bond is in the a,/I-position relative to phosphorus (e.g. 117), the electron density on phosphorus is reduced and the rate of hydrolysis is lower than for (1 15). 1,4-Addition ofdichlorophenylphosphine to diacetone alcohol leads to 3-hydroxy-2-0~0-2-phenyl-3,5,5trimethyl-1,2-oxaphospholane(118).lS7 Cleavage of the five membered ring occurs on alkaline hydrolysis and the rate is ten times slower than that for the alkaline hydrolysis of 2-ethoxy-1,2-oxaphospholane (1 19) ls8 presumably due to steric hindrance. No exchange of oxygen occurs during the hydrolysis of esters of diphenylphosphinic acid lS9and there is little electronic interaction between the phosphoryl group and aromatic rings. On the other hand, the hydrolytic behaviour of substituted aryl esters of diphenylphosphinic acid is very similar to that of aryl benzoates.lQOKinetic parameters for the alkaline hydrolysis of phenyl bis(a-halogenoalky1)phosphinate.s lgl and the acidic hydrolysis of diarylphosphinamides lg2 have been published. It is of K. Bergesen, Acta Chem. Scand., 1967, 21, 1587. W. Hawes and S. Trippett, Chem. Comm., 1968, 577. lS6 P. Haake, R. D . Cook, W. Schwarz, and D. R. McCoy, Tetrahedron Letters, 1968,5251. K. Bergesen, Acta Chem. Scand., 1969, 23, 696. lS8 G . Aksnes and K. Bergesen, Acta Chem. Scand., 1966, 20, 2508. lSg P. Haake, C. E. Diebert, and R. S. Marmor, Tetrahedron Letters, 1968, 5247. lg0 P. Haake, D. R. McCoy, W. Okamura, S. R. Alpha, S. Y. Wong, D. A. Tyssee, J. P. McNeal, and R. D. Cook, Tetrahedron Letters, 1968, 5243. lgl V. E. Bel’skii, M. V. Efremova, and A. R. Panteleeva, Izoest. Akad. Nauk S.S.S.R., Ser. khim., 1968, 2278 (Chem. A h . , 1969, 70, 28,109). lS2 G . Tomaschewski and G. Kuehn, J. prakf. Chem., 1968, 38,222. 184

ls6

137

Quinquevalent Phosphorus A c i h Me

H

Me

I1

/p

R: Me 0 ’ ‘OR ( I 11)

P

R2’

0’

‘ 0 ~ 3

(113)

‘OR

t-Bu

RO... i ,FOI OH

t - Bu

( 1 14)

4\

0

4 j

OEt

0

OEt

Me

Et,PNMe

R

II

NPh

interest that the heat liberated on hydrolysis of a pyrophosphinate bond is considerably greater than that liberated on hydrolysis of pyrophosphates or triphosphates.lg3 The basicities and rates of methylation of a series of diethylphosphinimidic amides (1 20) have been correlated with Hammett u and p ~ 0 n s t a n t s . l ~ ~

C. P-S Systems.--S-4-Morpholinodithiophosphinates (120), which are obtained by treating thiophosphinous acids with 4-morpholinosulphenyl chloride (121),lg6 will convert thiols into compounds containing S-S G. M. Kosolapoff and H. G. Kirksey, Doklady Akad. Nauk S.S.S.R., 1967, 176 (Chern. Abs., 1968, 69, 18,452). V. A. Gilyarov, A. M. Maksudov, B. A. Korolev, B. I. Stepanov, and M. I. Kabachnik, h e s t . Akad. Nauk S.S.S.R., Ser. khim., 1968, 2019 (Chem. Abs., 1969, 70, 10,930). L. Almasi and L. Paskucz, Chern. Ber., 1969, 102, 1489.

lB3

lg4

lS5

138


bridges. When the thiophosphinous acid is present in excess, dithiophosphinic anhydrides are formed in high yield. The addition of elemental sulphur to alkyl methylphosphinites occurs by a radical mechanism as the reaction is inhibited by hydroquinone and other radical An unusual reaction occurs between diphenylchlorophosphine and salts of arylsulphinic acids,la7 the products being diphenylphosphinyl chloride (122) and S-aryl diphenylphosphinothiolates. The first step in this reaction may be oxygen transfer from the sulphinic acid to diphenylchlorophosphine as pentavalent phosphorus compounds do not deoxygenate sulphinic acids. Disilver cyanamide when heated with (122) or its thio-analogue gives symmetrically substituted products (123), the i.r. spectra of which contain bands indicative of a -N=C=Nsystem rather than a > N-C=N system.las Hydrolysis of the carbodiimides (123) generates NN-diphosphinylureas. R,P(S)H

+

OnNSCl

W

-

u +

R2P(S)SNn0

HCI

H

- R,P(S)SCl 2PhzPC1

+ ArS0,Na

---+

Ph,P(O)SAr

-I-

Ph2P(0)C1 (122)

2Ph,P(X)Cl -I- Ag,CN, where X = 0 or S

Ph,P(X)N=C=NP(X)Ph,

~ _ _ _ 3

(1 23)

Ph,P(O)SePh ( 124)

D. Miscellaneous Reactions.-A number of methods for the synthesis of Se-phenyl diphenylselenophosphinates (124)have been described lg9 and the properties of metal complexes of thiophosphinic together with selenophosphinic acids have been reviewed.200 When the benzyl ester of diphenylphosphinylformate (125) is treated with a solution of iodide ion in acetone, a high yield of the acetone adduct (126) is obtained.201This is an intermolecular s ~ P - reaction 4 202 in which both the electrophilic and electrofugal centres are carbon atoms. Iodine is also an W. A. Mosher and R. R. Irino, J. Amer. Chem. SOC.,1969, 91, 756. H. Schindlbauer and W. Prikoszovich, Monatsh., 1968, 99, 1792. lS8 A. Weisz and K. Utvary, Monatsh., 1968, 99, 2498. Ig9 N. Petragnani, V. G. Toscano, and M. Moura Campos, Chem. Ber., 1968,101, 3070. 2oo W. Kuchen and H. Hertel, Angew. Chem. Internat. Edn., 1969, 8, 89. 201 S. G. Warren and M. R. Williams, Chem. Comm., 1969, 180. 202 S. G. Warren, Angew. Chem. Internat. Edn., 1968, 7 , 606. lS6

197


139

effective electrophile which will convert (125) in the presence of water or methanol to diphenylphosphinic acid or its methyl ester. 0 0

--

0

n Ph2Pd'1-C " 0 -CH Ph

c

II

Ph2P'

Ph2PC1+ PhCO.OO*COPIl

___+

+

(122)

COZ

+

PhCHZI

+ PhCO.O*COPh (127)

PhCOCl

+ PhCO 0 P(0)Ph2 + Ph2P(0)OP(O)Ph2 (128)

A mixture of diphenylphosphinic anhydride, benzoyl chloride, and benzoic anhydride (127) is obtained when a benzene solution of equimolar quantities of diphenylphosphinous chloride and benzoyl peroxide are heated under refl~x.~O~ The first step in this reaction appears to be oxygen transfer from the peroxide to give diphenylphosphinyl chloride (1 22). Interaction of (122) and (127) affords the observed products together with the mixed anhydride (128) which can also be detected in this reaction. The lH n.m.r. spectra of menthyl n-alkylphenylphosphinatescan be used to ascertain the configuration at The configuration (129) has been assigned to the diastereoisomer in which the resonance due to the protons of one of the methyl. groups in the isopropyl residue is shifted upfield due to anisotropic shielding by the phenyl ring. The structures of the unsaturated hydrocarbons obtained on pyrolysis of diphenylphosphinates of menthol, neomenthol, and neocarvomenthol indicate that the elimination reaction proceeds by an El mechanism.2os The mass spectrometric fragmentation pattern of dimethylphosphinic acid differs considerably from the fragmentation patterns obtained from other dialkyl-206and diaryl-phosphinic The base peak for dimethylphosphinic acid corresponds to (130, R = Me) and other peaks corre2os 204 *06

208

a07

G. Sosnovsky and D. J. Rawlinson, J . Org. Chem., 1968,33, 2325. R. A. Lewis, 0. Korpiun, and K. Mislow, J. Amer. Chem. Soc., 1968, 90, 4847. P. Mastalerz and Z. E. Golubski, Roczniki Chem., 1967,41, 1527 (Chem. A h . , 1968, 68, 39,717). P. Haake and P. S . Ossip, Tetrahedron, 1968, 24, 565. P. Haake, M. J. Frearson, and (2. E. Diebert, J . Org. Chem., 1969, 34, 788.

140

Organophosphorus Chemistry H

sponding to (131, R = Me) and PO+ are observed.206For other dialkylphosphinic acids elimination of alkenes is observed and the base peak for diethylphosphinic acid is HP02H+. Diarylphosphinic acids cyclise in the mass spectrometer to biphenyl-2,2’-phosphorus ions which then fragment.207 A general scheme for the fragmentation of pentavalent phosphorus compounds (132) has been put forward.206 The 35Clfrequencies in nuclear quadrupole spectra have been used to correlate the reactivities of dialkylphosphinyl chlorides with the nature of the substituents on phosphormZ0*It is claimed that evidence has been obtained for hyperconjugation between C-H bonds and 3d orbitals of phosphorus.

R

R

From a study of the dipole moments of phospholenes (133) and their oxides (134), it has been shown that the epoxidation of the phospholene ring takes place from the side opposite the phosphoryl group. This suggests that electronic factors rather than steric hindrance control the geometry of the product. *On

20a

A. A. Neimysheva, V. A. Pal’m, G. K. Semin, N. A. Loshadkin, and I. L. Knunyants, Zhur. obshchei Khim., 1967, 37, 2255 (Chem. Abs., 1968, 69, 2386). B. A. Arbusov, A. P. Anastas’eva, A. N. Vereshchagin, A. 0. Vizel, and A. P. Rakov, Izuest. Akad. Nauk S.S.S.R., Ser. khim., 1968, 1729 (Chem. Abs., 1969, 70, 29,008).

7 Phosphates and Phosphonates of Biochemical Interest BY D. W. HUTCHINSON

1 Introduction The widespread occurrence of' phosphate and polyphosphate esters (e.g. nucleic acids and coenzymes*) in living organisms has always been a major factor in promoting their study. However, since this is one of the more prolific areas of biological chemistry, it is impossible to review all recent developments in the space of a single chapter. Many excellent reviews already exist of the biochemical properties and reactions of phosphoric acids and their derivatives, and hence this review is selective in its choice of topics. Only reactions which involve the phosphorus atom of naturally occurring phosphates, polyphosphates, and phosphonates are considered and, for example, important developments in the elucidation of the secondary and tertiary structure of some types of t-RNA have been omitted as has the enzymology of phosphate and polyphosphate esters. Apart from recording new synthetic methods and structural determinations, an attempt has been made to describe some of the reactions mentioned in detail in order to rationalise some of the stages involved. 2 Nucleotides and their Phosphonate Analogues

Two excellent reviews 2* of oligonucleotide synthesis, both originally given as Plenary lectures at I.U.P.A.C. Symposia, have appeared recently. The first is an account of the techniques employed by Khorana and his group in their efforts to synthesise biologically specific nucleic acids. In this review, Khorana favours the use of dicyclohexyl carbodi-imide or aromatic sulphonyl chlorides for the synthesis of internucleotide bonds. The second review, by Cramer., mentions the use of picryl chloride as well as the two main condensing agents for internucleotide bond formation. l

Chapters on biological chemistry in Annual Reports of the Chemical Society, Ann. Rev. Biochem., Progr. Nucleic Acid Res., Adu. Enzymol. H. G . Khorana, Pure Appl. Chem., 1968, 17,313. F. Cramer, Pure Appl. Chem., 1969, 18, 197.

* Standard abbreviations for biochemical compounds are used without definition in this chapter. A detailed key to the abbreviations may be found in the Instructions to Authors of the Journal of Biological Chemistry.

142


Both authors comment on the use of insoluble polymer supports for oligonucleotide synthesis.

A. Oligonucleotide Synthesis on Polymer Supports.-A highly cross-linked rigid polystyrene-divinyl benzene copolymer has been prepared in a bead form which does not swell appreciably under normal reaction conditions and has been used as a support for the synthesis of moderate yields of oligonucleotides. With an aromatic sulphonyl chloride as condensing agent polythymidylic acid containing six monomeric units has been synthesised. Pentathymidine tetraphosphate (TpTpTpTpT) and a variety of di(deoxyribonucleoside) monophosphates and trinucleoside diphosphates have also been synthesised with the aid of insoluble polymer supports. It has been suggested that polyphosphate anhydrides, principally derivatives of cyclic trimetaphosphate (l), are the active phosphorylating

agents in phosphorylation reactions with carbodi-imides. Evidence has now been presented from reactions carried out on polymer supports, that the co-operative interaction of at least three residues is needed before carbodi-imide-promoted phosphorylations can occur, supporting the earlier suggestion.‘ A similar interaction of three or more phosphate residues also appears to be necessary in reactions promoted by aromatic sulphonyl chlorides. The rate of reaction between (1) and an alcohol appears to be slow and the overall reaction proceeds at a much faster rate if (1) undergoes prior attack by a sulphonyl chloride.

*

F. Cramer and H. Koster, Angew. Chem. Internat. Edn., 1968,7, 413. L. R. Melby and D. R. Strobach, J. Org. Chem., 1969, 34, 421. L. R. Melby and D. R. Strobach, J. Org. Chem., 1969, 34,427. G . Weimann and H. G. Khorana, J. Amer. Chem. SOC.,1962, 84,4329. G. M. Blackburn, M. J. Brown, M. R. Harris, and D. Shire, J. Chem. SUC.(C), 1969,676.

Phosphates and Phosphonates of Biochemical Interest RO,

/o, P ,OR

/ o1-0

047 0,

RO, R'OII , slow

>

/o,

OHP HO

KO,

OHP\OR

P RO/ II

(1)

OR

143

o ,

ro /OR

OR

B. Mononuc1eotides.-The following methods have been reported for the synthesis of nwcleotides : (i) 2-cyanoethyl phosphate and dicyclohexyl carbodi-imide ; (2a) and oligomers,lo (2b),11 [3, R = 9H-p~rine-G(lH-thione)],~~ (ii) phosphorus oxychloride ; (2c),I3 (2d),13(2e),14 (2f),14(2g),I5 (iii) diphenyl phosphorochloridate; (2h),16 (iu) di(2,2,2-trichloroethyl) phosphorochloridate (4) ; (2i),17 ( v ) Pl-diphenyl P2-(4-morpholino) pyrophosphorochloridate (5) ; (2j),le (ui) tri-imidazolylphosphine oxide (6) ;lo (2k) 2o and oligomers.20-22 lo

l1 l2 Is

l4 I5 l6

M. P. Mertes and J. Smrt, Coll. Czech. Chem. Comm., 1968, 33, 3304. M. P. Mertes, A. Holy, and J. Smrt, Coll. Czech. Chem. Comm., 1968, 33, 3313. A. R. Hanze, Biochemistry, 1968, 7 , 932. J. P. Bell, Canad. J. Chem., 1969, 47, 1095. K. Kusashio and M. Yoshikawa, Bull. Chem. Soc. Japan, 1968, 41, 142. A. Yamakazi, I. Kumashiro, and T. Takenishi, Chetn. and Pharm. Bull. (Japan), 1968, 16, 338. A. Yamazaki, I. Kumashiro, and T. Takenishi, Chem. and Pharm. Bull. (Japan), 1968, 16, 1561. M. M. Vigdorchik, M. N. Preobrazhenskaya, and N. N. Suvorov, Tetrahedron Letters, 1968,4645.

l7 lS

Is 2o

21 22

K. H. Scheit, Biochim. Biophys. .4cta, 1968, 157, 632. M. Ikehara and M. Murao, Chem. and Pharm. Bull. (Japan), 1968, 16, 1330. F. Cramer, H. Schaller, and H. A. Staab, Chem. Ber., 1961, 94, 1612. K. H. Scheit, Chem. Bet-., 1968, 101, 1141. K. H. Scheit, Biochirn. Biophys. Acta, 1968, 166, 285. K. H. Scheit, Biochim. Biophys. Acta, 1969, 182, 10.


144

NHOH

0

R = (a)

I

S

(c) hypoxan t hine (d) guanine 0

0

0

II

(CCI,CH,O) zPCl (4)

HO

(3)

A

(5)

Phosphates and Phosphonates of Biochemical Interest

145

Selective phosphorylation of nucleosides at the 5’-position has been reported with (4) and the preparation of di(2,2,2-trichloroethyl) thymidine 5’-phosphate has been achieved in 75% yield from the unprotected nucleoside.23 Phosphorylation reactions with (5) 24 are carried out in anhydrous media followed by mild acid treatment to remove the protecting groups. Moderate yields of purine nucleotides have been obtained in this manner. urabino-Cytidine 2’,5’-cyclic phosphate (8), prepared by cyclisation of N4-benzoyl-arabino-cytidine 5’-phosphate (7) 25 with carbodi-imide followed by removal of the benzoyl group, is unreactive towards acid, base, and the nucleases present in crude snake venom.26 In the lH n.m.r. spectrum of (8), phosphate anisotropy has only a small effect on the 2’- and 5’-protons but strongly deshields the 3’-protori. A paramagnetic shift of 60 Hz is observed for (8) compared with the 3’-proton of arabino-cytidine. N HCO P h I

(i) DCC (ii) MeOH-NH,

’

(HO) ,P 0

HO (7)

H0’-

HO (8)

A direct synthesis of 3‘,5’-c,yclic mononucleotides has been achieved 27 by the action of a solution of phosphorus oxychloride in trimethyl phosphate on the parent nucleosides. The byproducts which are usually formed during reactions with phosphorus oxychloride in pyridine solution are greatly reduced in absence of the tertiary base.28

C. Nucleoside Po1yphosphates.-A general synthesis of ~ - ~ ~ P - l a b e l l e d nucleoside 5’-triphosphates consists of the treatment of the appropriate P1-(nucleoside-5’) P2-(4-morpholino) pyrophosphate (9) with 32P-labelled o r t h o p h ~ s p h a t e . Enzymic ~~ assay of the products showed that at least 99.8% of the label was in the y-position. The 5’-triphosphates of the nucleoside antibiotics tubericidin (10, R = H),30 toyocamycin (10, R = CN),30 sangivamycin (10, R = CONH2),30s 31 23 24 25 26

27 28

29

30

31

A. Franke, K. H. Scheit, and F. Eckstein, Chem. Ber., 1968, 101, 2998. M. Ikehara and E. Ohtsuka, Chem. and Pharm. Bull. (Japan), 1963,11, 961. W. J. Wechter, J. Medicin. Chem., 1967, 10, 762. W. J. Wechter, J. Org. Chem., 1969, 34, 244. M. Heubert-Habart and L. Goodman, Chem. Comm., 1969, 740. M. Yoshikawa, T. Kata, and T. Takenishi, Tetrahedron Letters, 1967, 5065. A. Adam and J. G. Moffatt, Biochemistry, 1968, 7 , 875. S. C. Uretski, G. Acs, E. Reich, M. Mori, and L. Altwerger, J. Biol. Chem., 1968, 243, 306. R. J. Suhadolnik, T. Uematsu, H., Uematsu, and R. G. Wilson, J. Biol. Chem., 1968, 243, 2761.

146


OH

H 0‘

(9)

N53 4, ‘ I

and formycin (11) 32 have been synthesised and all show some biological activity. Both (10, R = CONH2)31 and (11) 32 could replace ATP in RNA polymerase systems using GTP, CTP, UTP, and a DNA primer. The coding properties of several tubericidin-containing polyribonucleotides were indistinguishable from those of the corresponding adenosine-containing polymers.3o Polyribonucleotides have been synthesised from the 5‘-pyrophosphates of 8-substituted purine ribonucleotides 33 and 2’-O-methyladenosine (12) 34 with the aid of polynucleotide phosphorylase. The 5’-pyrophosphate of (12) was prepared from the corresponding monophosphate using rabbit muscle myokinase. The free 5’-hydroxyl of the RNA chain of the RNA bacteriophages and T4 m-RNA bears a triphosphate group, and consequently the terminal nucleosides are liberated as 2’(3’)-monophosphate 5’-triphosphates (13) 35 on hydrolysis. These have been prepared from nucleoside 2‘,3’-cyclic phosphate 5’-phosphoromorpholidates (14) and inorganic pyrophosphate, the method being analogous to that used for the synthesis of C O A . ~ ~ a2

M. Ikehara, K. Murao, F. Harada, and S. Nishimura, Biochim. Biophys. Acta, 1968, 155, 82.

98 94

8s

M. Ikehara, I. Tazawa, and T. Fukui, Biochemistry, 1969, 8, 736. F. Rottman and K. Heinlen, Biochemistry, 1968, 7, 2634. E. Messens and M. van Montagu, F.E.B.S. Letters, 1968, 1, 326. J. G . Moffatt and H. G . Khorana, J. Amer. Cliem. SOC.,1961, 83, 663.


147

/o\ 0

II

(HO) ,PO ‘ I

Q R0

0

I OH

O=P
(H0)zPCH CH-N

7 2

~

0

0

MeCHO -I- H3P04 0

II (HO),PCH,CHO

Hzo

0 (H0)2kH2CH=N

(47)

0

such will undergo cleavage of the C-P bond without difficulty. Compound (47)has been identified 132 as an intermediate in the degradation of AEP by B. cereus and has recently been synthesised 133 from 2-acetoxy-2-chloroethylphosphonyl dichloride (48). This intermediate is stable in 6~-hydrochloric acid and at high pH, but hydrolyses at pH 5. Similar behaviour has been observed 13* with 2-hydroxyethylphosphonic acid which can be obtained by the diazotisation of AEP in aqueous solution. 0

CH,CO,CH=CH,

II A CH,CO,CHCICH,PCI, PCl--SO-

HO

A (47)

(48) 5 Oxidative Phosphorylation Mitochondria1 oxidative phosphorylation has continued to arouse considerable interest and the main, and rival theories of oxidative phosphorylation-the chemical ( X) and the chemiosmotic-have recently been Much effort is being expended on the study of uncouplers and inhibitors in an effort to separate the various steps in the enzyme N

l30 ls1 132 133 134

136

H. Rosenberg and J. M. La Nauze, Biochim. Biophys. Acta, 1967, 141, 79. A. J. De Koning, Biochim. Biophys. Acta, 1966, 130, 521. J. M. La Nauze and H. Rosenberg, Biochim. Biophys. Acta, 1968, 165, 438. A. F. Isbell, L. F. Englert, and H. Rosenberg, J. Org. Chem., 1969, 34, 755. D. W. Hutchinson and B. D. Place, unpublished observations. D. W. Deamer, J . Chem. Educ., 1969, 46, 198.

166 Organophosphorus Chemistry complex; however, various model chemical reactions have also been investigated as possible begetters of 'high-energy' intermediates. A. Hydroquinone Esters.-Acyl transfer following the oxidation of carboxylic esters of hydroquinones has been demonstrated,lsg the products include anhydrides and esters. Oxidation at room temperature of a pyridine solution of durohydroquinone monoacetate (49), orthophosphate, and ADP by bromine or a high potential quinone gives rise to a low yield of ATP ls7presumably through a derivative of acetyl phosphate. ~

o

Me

~

+

pi

+o A D P

>~ - Br2

~ATP

~

Me

(49) SCOMe

Q

€ 1S CH, CO, H

S P R

(51)

0

Me

where R = H, Ph, Me, Ac

Related syntheses of ATP have been achieved by the oxidation of thiazolid-Zones (50) 138 and mercaptoacetic acid (51) 130 with bromine, although the mechanisms of these two phosphoryl transfer reactions have yet to be elucidated; it is most probable that sulphenyl bromides are involved as intermediates. S-Acetyl-p-thiocresoI(52) is another compound capable of generating a sulphenyl bromide with bromine, and ATP has been synthesised 140 from (52), ADP, and orthophosphate following the addition of bromine.

(i) oxidise

y

R ;$R l R2

R2

OH

(53) 136 137

138 140

:d:'"" 0 (54)

V. M. Clark, M. R. Eraut, and D. W. Hutchinson, J. Chem. SOC.(0,1969, 79. T. Wieland and H. Aquila, Angew. Chem. Internat. Edn., 1968, 7 , 213. T. Wieland and H. Aquila, Chem. Ber., 1968, 101, 3031. T. Wieland and E. Biiuerlein, Angew. Chem. Internal. Edn., 1968, 7 , 893. E. Bauerlein and T. Wieland, Chem. Ber., 1969, 102, 1299.

e

167


In ethanolic solution, tocopherols (53) can be converted into (54, R = Et) ~ intermediate (54, R = POBH2) by the action of iron(m) ~ h l 0 r i d e . lA~ similar has been postulated as being formed when a solution of (53) and orthophosphate in pyridine is oxidised with bromine. Protonation of the oxygen atom in the chroman ring of (54, R = P03H2)generates a phosphorylating agent of the P-XYZ typeg1 which explains the formation of ATP and ADP when nucleoside phosphates are added to this reaction. The enzymic oxidation by horse radish peroxidase of durohydroquinone monophosphate to duroquinone and orthophosphate in lsO-enriched water occurs with negligible C-0 bond fission.142 This implies (see section 2) that the reaction proceeds by nucleophilic attack on phosphorus before the P-0 bond is broken, and hence the transfer of phosphate from hydroquinone phosphates in vivo could be a more efficient process than model chemical studies It appears that the relative amounts of P-0 and C-0 bond fission during the oxidative dephosphorylation of hydroquinone phosphates depend on the oxidising agent employed, and oxidation by periodate in aqueous solution proceeds largely with P-0 f i s ~ i 0 n . l ~ ~ B. Metal Complexes.-The final phosphorylation step in mitochondria1 oxidative phosphorylation is associated with cytochrome-a. A model reaction has been devised 145 in which ATP is produced from orthophosphate and AMP or ADP during the oxidation by molecular oxygen of a ferrohaemochrome in the presence of imidazole. In this case l-phosphoimidazole

I

H,PO,

N

A

u

141 14a 143

144 146

I1

N-P
Me,P

SiMe,

%Ha SiMe, I

Jooo

Me,XCl

J. Me,P:C(XMe,),

,CH2

f-

(157)

+ Me2P,

SiMe,

C( SiMe,),

(161)

when treated with the ethylidenephosphorane (165) gave entirely the silylmethylenephosphorane (166) which disproportionated on heating to give the bis(sily1)methylenephosphorane (167). This stabilising effect is ~ probably due to ( p - d ) bonding.

Et,P:CH.SiH,

+ Et$

el

f \

(166) Et,P(: CHMe) *CH,.SiH,

Et,P: C(SiH,),

+ Et,P:CH,

(167)

3 Selected Applications of the Wittig Olefin Synthesis A. Macrocyc1ics.-The condensation of bisphosphoranes with dicarbonyl compounds has been applied to the synthesis of 9, 10, and ll-membered rings. Biphenyl-2,2’-dialdehyde (168) with the phosphorane from the salt (169) gave the 1l-membered cis,trans isomer (170) 79 and with the phosphoranes from the salts (171; X = 0, S) formed the non-aromatic 10-T electron systems (172; X = 0, S).80 Similar reaction with the furan bisphosphonium salt (173) gave the [101-annulene (174) in two isomeric forms having the internal hydrogens eclipsed or staggered.81 Self-condensation of the phosphorane from the salt (175) gave the complex mixture 8 2 from which small amounts of triepoxy-[181-annulene, 79

82

R. H. Mitchell and F. Sondheimer, Tetrahedron Letters, 1968, 2873. A. P. Bindra, J. A. Elix, P. J. Garratt, and R. H. Mitchell, J. Amer. Chem. Soc., 1968, 90, 7372. A. P. Bindra, J. A. Elix, and M. V. Sargent, Tetrahedron Letters, 1968, 4335. J. A. Elix, Chem. Comm., 1968, 343.

202


OCHO8 3.

QCH0

PI13P* CH,

2 Rr-

-t.

PIi,P- CH,

/

OHC

LiOMe MeOH

(169)

(170) 58%

I-

CH, * PPh3 CI-

LiOMe DMF

O,N O

C

'

H

etc.

: PPh,

Ylides and Related Compounds

203

two isomers of tetraepoxy-[24]-annulene [neither of which may be the allcis isomer (176)], and two isomers of pentaepoxy-[30]-annulenehave been isolated. B. Heterocyclics.--a-Arylidene-y-thiobutyrolactones have been obtained 83 from the stable phosphorane (177). Many 2-furylethylenes have been prepared 85 either using the stable phosphorane (1 78) or from substituted furfuraldehydes and phosphoranes. 84p

C . Natural Products.-H. cecropia juvenile hormone (179) has been synthesised by the sequence of reactions outlined 86 employing three successive Wittig olefin syntheses. The first of these gave olefin containing

(isi) 83

85

86

H. Zimmer, F. Hauper, S. P. Kharidia, H. Pauling, R. G. Gailey, T. Pampalone, T. C. Purcell, and R. Walter, Tetrahedron Letters, 1968, 5435. S . Yoshina, A. Tanaka, and K. Yamamoto, Yukuguku Zusshi, 1968, 88, 65. H. Saikachi and S. Nakamura, Yukuguku Zusshi, 1968, 88, 110. H. Schulz and I. Sprung, Angew. Chem. Internut. Edn., 1969,8, 271.

204


63% of the desired cis-isomer while the second and third were not stereoselective. However, in all cases the desired isomers were separated by fractional distillation. 15-Dehydroprostaglandin El (180) was obtained 87 together with its 11-epi-isomer from the aldehydes (181) and hexanoylmethylenetriphenylphosphorane. Conditions leading predominantly to cis-olefin (‘salt-free’ ylide or dimethylformamide in the presence of iodide) have been used in the syntheses of 14C-labelledoleic and erucic acids,8Qnatural insecticide^,^^ and cis-jasmone and related cis-rethrone~.~~ D. Carbohydrates.-Ylides have been used both in one-carbon chain extensions and in the synthesis of branched-chain carbohydrates. Acetals were usually used as protecting groups. Thus 2,3 :4,5-di-O-isopropylidenealdehyde-L-arabinose with the ylide (182; X = S) gave the thioether (183) readily converted into the acetal (184).92 The ylide (182; X = 0) has also been used in this and similar The branched-chain sugar (185) was obtained from methylenetriphenylphosphorane and the corresponding ketone,04 while the phosphorane (186) was used to prepare vinylphosphonates from protected nucleoside 5’-aldehyde~.~~

f Ph,P:CH,

----+ (185) 60%

R*CHO+Ph3P:CH.P(:O)(OPh), (186)

g*

g8

94 96

R*CH:CH*P(:O)(OPh), trans

M. Miyano and C. R. Dorn, Tetrahedron Letters, 1969, 1615. C. Levron, Bull. Soc. chim. France, 1969, 1198. L. Pichat, J. C. Levron, and J. P. Guermont, Bull. SOC.chim. France, 1969, 1200. P. E. Sonnet, J, Org. Chem., 1969, 34, 1147. L. Crombie, P. Hemesley, and G. Pattenden, J. Chem. SOC.(C), 1969, 1024. J. M. J. Tronchet, S. Jaccard-Thorndahl, and Br. Baehler, Helv. Chim. Acta, 1969, 52, 817. Yu. A. Zhdanov and V. G. Alekseeva, Zhur. obshchei Khim., 1968, 38, 2594; Carbohydrate Res., 1969, 10, 184. D. G. Lance and W. A. Szarek, Carbohydrate Res., 1969, 10, 306. G . H. Jones and J. G. Moffatt, J. Amer. Chem. SOC.,1968, 90, 5337.

** L. Pichat, J. P. Guermont, and J. B1

DMSO


205

4 Synthetic Applications of Phosphonate Carbanions A study has been made 96 of the variation in the proportion of cis (187) and trans (188) esters produced from the phosphonates (189) and aliphatic aldehydes as the groups R1 and R2 varied. As previously established, when R1= H only trans-ester was formed but with R1 = Me the amount of cis-ester increased with the size of R2then decreased when R2= But. The

+

R2,,c=c, / R1

C02E t

H

(188)

effect was more pronounced as R1 increased in size and with R1 = R2 = i-Pr only cis-ester was formed. The same phosphonates (189) with a-ketoesters gave predominantly the substituted maleic esters.97 The variation in the proportions of isomers produced from diethyl cyanomethylphosphonate and aryl alkyl ketones as the alkyl group varies has also been 99 Among other substituted phosphonate esters used in olefin synthesis were (190),loo(191),lo1and (192).lo2 The enamines resulting from the last were readily hydrolysed to acylphosphonates and further to carboxylic acids which were obtained in overall yields of 44-68% from the starting aldehydes.

+

(EtO),P(: 0)CH2.S02Et R. CHO (190)

NaH

R.CH: CH.S02-Et 70-96%

+

(EtO),P( :O)*CH(C0,Et)-(CH2),*C02Et R. CHO (191) NaH R-CH: C(C02Et)*(CH2),C02Et THF 53-86% [(EtO),P(:O)],CH-NMe,

+ R-CHO

R * CH, * C02H 96

97

88 99

100 101

102

NaH

R.CH:C(NMe),.P(:O)(OEt), I

lH+

J. R -CH, CO * P( :O)(OEt),

-

T. H. Kinstle and B. Y. Mandanas, Chem. Comm., 1968, 1699. See also K. Sasaki, Bull. Chem. SOC.Japan, 1968, 41, 1252. R. K. Huff, C. E. Moppett, and J. K. Sutherland, J. Chem. SOC.(C). 1968. 2725. G. Jones and R. F. Maisey, Chem. Comm., 1968, 543. D. Danion and R. Carrie, Tetrahedron Letters, 1968, 4537. I. C. Popoff, J. L. Dever, and G. R. Leader, J. Urg. Chem., 1969, 34, 1128. K. Sato, M. Hirayama, T. Inoue, and S . Kikuchi, Bull. Chem. SOC.Japan, 1969, 42, 250. H. Gross and B. Costisella, Angew. Chem. Znternat. Edn., 1968, 7 , 391.

206 Organophosphorus Chemistry Diethyl cyclohexyliminovinylphosphonate (193) has been used in ‘formylolefination’ of carbonyl compound.lo3 The anion reacted readily with aldehydes and ketones at room temperature and acid hydrolysis of the resulting aldimines in a two-layer system gave +unsaturated aldehydes in overall 63-86% yield. Details have appeared of the use of phosphonamides in olefin synthesis.lo4 The diastereoisomeric p-hydroxyphosphonamides (194) can be separated by fractional crystallisation and undergo cis-elimination on heating, e.g. in refluxing benzene, to give isomerically pure olefins. Alternatively the p-hydroxyphosphonamides (194; R4= H) can be obtained in largely one diastereoisomeric form by reduction of the p-ketophosphonamides (195). (EtO),P(: 0)*CH:CH .NHR

(EtO),P(: 0).CH-m+.NR 0“

(193)

RIRZCO

R1R2C:CH * CHO R1R2CH.P(: O)(NMe,),

H”

C---

.L

R1R2C:CH CH :NR

y

RlR2CLi *P(O)(NMe,),

e

R3R4C(OH).CR1R2*P(:0) (NMe,),

I

I

Rs* COzMe

-N~BH,R3CO*CR1R2*P(: 0) (NMed,

(194)

(195)

R3R4C:CR1R2f (Me,N),P(: 0)OH Phosphonate carbanions have been used in carbohydrate chemistry for the synthesis ofbranched-chain sugars lo5* Io6 and for chain extension to give the phosphonates (196).lo7 Among natural products synthesised with the aid of phosphonate carbanions were H. cecropia juvenile hormone lo8and /3-carotene.10B R*CHO+CH,[P(:O)(OEt)~],

-

R*CH:CH.P(:O)(OEt),

IH2

R-CH2-CH2*P( :O)(OEt), (196) lo8 lo4

lo6 loQ

lo’ lo8

lo9

W. Nagata and Y . Hayase, J. Chem. SOC.( C ) , 1969, 460. E. J. Corey and G. T. Kwiatkowski, J. Amer. Chem. SOC.,1968, 90, 6816. A. Rosenthal and P. Catsoulacos, Canad. J. Chem., 1968, 46, 2868. A. Rosenthal and D. A. Baker, Tetrahedron Letters, 1969, 397. J. A. Montgomery and K. Hewson, Chem. Comm., 1969, 15. K. H. Dahm, H. Roeller, and B. M. Trost, Life Sciences, 1968, 7 , 129. J. D. Surmatis and R. Thommen, J. Org. Chem., 1969, 34, 559.


207

Aliphatic tertiary nitroso compounds with the phosphonates (197) gave aldimines while aniidines were obtained from the a-aminophosphonates (1 98) and aromatic nitroso compounds.111 The benzylphosphonates (199; R = Et, i-Pr) with the Schiff's bases (200) and sodamide in refluxing ether gave stilbene; the intermediates (201) could be isolated under milder conditions.112 (EtO),P(: 0).CH2R'

Na H + R2 NO -

--j

R2.N:CHR' 3840%

(197) R' = C0,Et

or CMe:CH .C02Me

(RO),P(:O)-CH,Ph (199)

t Pha CH :CH Ph

+ Ph*CH:NAr 'NaNHz, 10"

k;r2 (200)

(RO),P(:O)*CHPh.CHPh.NHAr

&

(201)

+ (RO),P(:O).NHAr

5 Ylide Aspects of Iminophosphoranes

A. Preparation.-Isotopic labelling with lSN has been used 113 to show that the 18 and y nitrogens are eliminated when the adduct (202) of triphenylphosphine and toluene-p-sulphonyl azide is pyrolysed to give the iminophosphorane (203).

The potassium salt of aminodiphenylphosphine with methyl iodide in liquid ammonia gave the iminophosphorane (204).Il4 Similar phosphoranes were obtained ll6when hydrazine hydrochloride was treated with dibromoor di-iodo-triphenylphosphorane,while the dichlorophosphorane gave the bisphosphonium salt (205). This, and the corresponding trialkylphosphonium salts, with base formed the bis(iminophosphoranes) (2O6).ll6 l10 ll1 112

114 116

116

J. A. Maassen, T. A. J. W. Wajer, and T. J. de Boer, Rec. Trau. chim., 1969, 88, 5. H.Zimmer, P. J. Bercz, and G. E. Heuer, Tetrahedron Letters, 1968, 171. M.Kirilov and J. Petrova, Chem. Ber., 1968, 101, 3467. H. Bock and M. Schnoller, Chem. Ber., 1969, 102, 38. 0. Schmitz-Dumont and H. Klieber, 2. Nuturforsch., 1968, 23b, 1604. R. Appel and G. Siegemund, Z. anorg. Chem., 1968, 361, 203. R. Appel, B. Blaser, and G. Siegemund, 2. anorg. Chem., 1968, 363, 176.

208 Ph2PNHK

2MeI


[Ph,PMe*N:PMePh,]+ I (204)

While trimethylgermanium azide with trimethylphosphine gave the expected iminophosphorane the corresponding tin azide with a range of phosphines formed only the azides (207), presumably via disproportionation of the tin azide.l17 Me3SnN, + R3P

-

Me,Sn(N,) N :PR3+ [Me,Sn] (207)

Some interesting iminochlorophosphoranes have been obtained as thermally stable distillable liquids by the action of carbon tetrachloride on amino-t-butyl 118 and aminodi-t-butylph~sphines.~~~ The formation of the iminophosphoranes (208) from the N-lithiophosphines (209) and trimethylmetal chlorides did not involve N-metallation followed by rearrangement as X and Y did not become equivalent during the reactions. RzPCl

-A*& NH8

R2PNH2

BuLi Me3XCI

R2PNH.XMe3

kLi

''a

R2PCI:N H

R2P.NLi .XMe3

R2PCl:N -XMe3

(20%

1

Me3YC1

R = t-Bu; X, y = Si, Ge, Sn, or Pb

R2P(YMe3):N*XMe3 (208)

B. Reactions.-Iminotrimethylphosphorane (210) has been obtained as shown as a distillable crystalline compound.120The tetrameric adducts (21 1) with dialkylzincs and dialkylcadmiums had cubic structures. Pyrolysis of the 1,l-adducts with Group I11 metal trialkyls gave the iminophosphoranes 117 118

lZo

H. Schmidbauer and W. Wolfsberger, Chem. Ber., 1968, 101, 1664. 0. J. Scherer and P. Klusman, Angew. Chem. Internat. Edn., 1968, 7, 541. 0. J. Scherer and G. Schieder, Chem. Ber., 1968, 101, 4184. H. Schmidbauer and G. Jonas, Chem. Ber., 1968,101, 1271.

209


(212). Similar adducts have been obtained with other iminophosphoranes.121 The cyclic compounds (213) were obtained lZ2 from the aminoimine (214) and the cyclic salts (215) from the bis(iminophosphorane) (216).12, N3 < ki N,

Me$NH,

Me,P

Me,P:N*$Me,

1-

(21 9)

NaNH,

NH/

TM.1

Me,P:NH

BuLi

------+Me,P:NLi

Me,PCI

> Me,P:N.PMe,

.L

Me,P :NH-tMR,

RH

+ [Me,P:N*MR2], (212)

,NH. SiMe, Ph,P

\

No SiMe,

+

Me,M

M = Al,

SiMes I N, Ga, In > Ph26< ,MMea N

+

CH4

I

PMe,

II

Me$

/ \

N:PMe, N: PMe,

+

Me,M

M = Al, G a

>

lN\

Me,Si\ +,MMe, N

MMe,

The N-lithioiminophosphorane (217) with chlorodimethylphosphine 120 gave the phosphorane (218) which with methyl iodide formed (219) analogous to (204) above. The substituted ureas (220) were obtained from iminotriphenylphosphorane and aryl isocyanates lZ4 or isothiocyanates.lZ6 The thiourea (220; W. Wolfsberger and H. Schmidbauer, J. Organometallic Chem., 1969, 17, 41. H. Schmidbauer, K. Schwirten, and H.-H. Pickel, Chem. Ber., 1969, 102, 564. l Z 8 H. Schmidbauer, W. Wolfsberger, and K. Schwirten, Chem. Ber., 1969,102, 556. lZ4 I. N. Zhmurova and A. P. Martynyuk, Zhur. obshchei. Khim., 1968,38, 876. l z 6 I. N. Zhmurova, A. P. Martynyuk, and G. I. Derkach, Zhur. obshchei. Khim., 1968, 121

laa

38, 163.

210


R = Ph) was also obtained by the dichlorophosphorane route. Arylsulphinyliminophosphoranes (221) were formed from the same imino12’ Oxidation gave the correphosphorane and sulphinyl sponding sulphonyl compounds. Ph,P:NH

+ ArNCX

Ph,P:N.CX.NHAr

1

(220)

T

RSOCl EfN

PhPCI,-Et,N

Ph .NH * CS .NH2

P$P: N *SO R (22 1 )

Ph,P:N*C02Et + CHO*C02Et

THF

> Et02C.CH:N*C02Et (222)

(1 22)

I

NzCH * COZ. Et

J!

II

“‘N+O,E H

f--Ph3P

Et02C-CH*NH*C02Et I N2C C02Et

t

(224)

The highly reactive imine [222; see this chapter, section 1, B(vi)] has been generated in situ from the phosphorane (122) and ethyl glyoxylate and trapped in the presence of nucleophiles.128 Diazoacetic ester gave the diazoester (223) from which the pyrazole (224) was obtained on refluxing in toluene with triphenylphosphine. The same phosphorane (1 22) has also been used 129 to introduce the nitrile group into nucleophilic heterocyclic nuclei, being particularly useful where these are acid sensitive. Thus indole with (122) in the presence of the boron trifluoride-ether complex gave the 3-nitrile (225). These reactions may involve the electrophilic adduct (226).

128 127

128

ias

A. Senning and P. Kelly, Naturwiss., 1968, 55, 543. I. N. Zhmurova and A. P. Martynyuk, Zhur. obshchei. Khim.,1967, 37, 2706. H. Plieninger and D. von der Bruck, Tetrahedron Letters, 1968, 4371. D. von der Bruck, A. Tapia, R. Riechel, and H. Plieninger, Angew. Chem. Internat. Edn., 1968, 7 , 377.

21 1

Ylides and Related Compounds RCHO

Ph,P: N * N:C H - R

R-CH :N*N:CH*'R PhNH

[OCN.NCO] 4 (PhONH*CO.NH:)a

IRCHO

? @ //

(228)

Ph,P:N.N:PPh,

( M e 0 C.C:)2

2Ph,P: C(C0,Me) -C(C02Me):N * N:PPhs Ph,P :N -NH CS N HPh

77%

The ylide reactions of the bis(iminophosphorane) (227) have been explored 130 and are as shown. Outstanding are the reactions with carbon dioxide, in which the product (228) was trapped with aniline, and that with dimethyl acetylene dicarboxylate which presumably involves a fourmembered intermediate in a reaction analogous to those of this ester with stable methylenephosphoranes. The lithium salt of benzoylhydrazonotriphenylphosphorane (229) gave high yields of the 1,3,4-oxadiazoles (230) when treated with aromatic acid chlorides.lS1 Symmetrical 2,5-diaryl-l,3,4-oxadiazolescan be obtained in one step by treating the salt (231) with 2 moles of aromatic acid chloride in the presence of an excess of triethylamine. PhCO*NH*N:PPh,
Ph-C, ,CO*Ar

0

+

NH,.NH.PPh,

(23 1

+

N-N -PPh3

Dh

lao

lS1

DA

Ii

\

R. Appel and G. Siegemund, 2.anorg. Chem., 1968, 363, 183. C. C. Walker and H. Shechter, J . Amer. Chem. SOC.,1968,90, 5626.

Br-

21 2 Organophosphorus Chemistry The phenyliminophosphoranes (232) coupled with tetracyanoethylene 132 at the para position to give the iminophosphoranes (233). Diphenylcarbodi-imide was the major product from benzonitrile oxide and the iminophosphorane (234) but some 8% of the 1,2,4-oxadiazole(235) was also The suggested route to (235), involving an initial equilibrium between (234) and the carbodi-imide and the four-membered compound (236). was supported by the reaction of p-nitrobenzonitrile oxide with the p-methoxyiminophosphorane (237) which gave the symmetrical carbodi-imide (238) and the p-nitroiminophosphorane.

lSz

I. N. Zhmurova, R. I. Yurchenko, and A. V. Kirsanov, Zhur. obshchei. Khim., 1968, 38, 2078.

lSs

R. Huisgen and J. Wulff, Chem. Ber., 1969, 102, 1848.

213

Ylides and Related Compounds p-N02.C6H4.CN0+ 2 p-Me0.C6H4-N:PPh3 (237)

-

------+

-

p-MeO. C6H,. N :C: N C,H4 OMe-p (238) 40% +p-N02*CBH*.N:PPh3+Ph,PO

63%

74%

The nitrone (239) and phenyliminotriethylphosphorane gave the imine (240) in a reaction involving migration of benzoyl in the decomposition of the intermediate.133The nitrileimine (241) with (234) formed the betaine (242) while proton migration in the corresponding compound from (243) and the nitrileimine (244) gave the iminophosphorane (245). The same nitrileimine with (237) formed the stable free radical (246) as shown. P11 I N PhCO.HC' ' 0 \ I N-PEt3

PhCO-CH:&(O)*Ph+ Et,P:N*Ph >-(239)

PhCO*NPh*CH:N*Ph + Et,PO (240)

z

p-Me0 .C6H4. C :N .$.CGH,-NO,-p

I

Ph *N-$Ph3 (242) 89%

+

PhC:N*N.Ph (244)

+

Ph,P:NH (243)

PhC:N*NH*Ph

I

N:PPhs (245)

Ph

8

9 Phosphazenes BY R. KEAT AND R. A. SHAW

1 Introduction Interest, academic as well as industrial, in the phosphazenes has continued to grow. This is clearly reflected in the growth of publications in this field. In 1962 a comprehensive review1 covering the literature since their discovery in 1834 quoted 397 references. Currently, ca. 100 papers and patents appear annually. Perhaps the most significant feature of phosphazene chemistry in recent years has been the relatively rapid accumulation of structural data, obtained from n.m.r. spectroscopic and from X-ray crystallographic studies. This is particularly true of derivatives of cyclic oligomeric phosphazenes. However, no detailed structural data have, as yet, been reported on simple monomers of the type R,P=NR’. The structural data available can often be rationalised in terms of bonding schemes which emphasise the r61e of the 3d-orbitals of the phosphorus atoms, and in terms of various physical properties. However, generalisations on the important subject of halogenatom displacement at phosphorus are still difficult to make. Aspects of this latter subject have recently been r e v i e ~ e d , ~particularly ~t with regard to the reactions and structures of derivatives of hexachlorocyclotriphosphazatriene (1).

For the purpose of this report, the collective name phosphazene will be taken to include monomers and cyclic or linear polymers containing the \ p = ~ - unit. The naming of these compounds will be based on the /

nomenclature suggested by Shaw, Fitzsimmons, and Smith.l The literature is covered for the eighteen months up to June, 1969. R. A. Shaw, B. W. Fitzsimmons, and B. C. Smith, Chem. Rev., 1962,62,247. (a) R. A. Shaw, Endeavour, 1968,27, 74. t b ) Rec. Chem. Progr., 1967, 28,243.

215

Phosphazenes

2 Synthetic Routes to Phosphazenes A. Acyclic Derivatives.-The Kirsanov reaction, whereby 2 moles of hydrogen halide are eliminated between halogenophosphoranes, RnPX6-, (X = halogen; R = other groups, e.g. Ph; n = &3), and organic or inorganic compounds containing one or more primary amino-groups, is still frequently used for the synthesis of new monomeric phosphazenes, e.g. ;

+

P(: O)F2NH2 PCl,

+

P(: O)F2NH2 PCl,Ph, P(:S)XX’NH2+PC1,

-

+ 2HC1 P(: O)F2N=PPh, + 2HC1

P(: O)F,N=PCl,

(refs. 3a, 4a) (1) (ref. 46) (2)

P(:S)XXN=PC13+2HCI (X = X‘ = F) (X = F, X = Cl; X = X = C1) (ref. 3b) (3)

Solvolysis of P( :O)F2N=PC13 by H COOH, P( :O)F20H, or FS020H, occurs preferentially at the P=N linkage to give -NH- bridged derivatives e.g. : of phosphorus or P(: O)F2N=PCl,

+ P( :O)F,OH

P(: O)F,NHP(: O)CI,

+ P(: O)F2Cl

Similarly, the trichlorophosphazenyl derivative (2) is obtained from N3C3F2-NH, and phosphorus pentachloride., Solvolysis of (2) by formic acid gives N3C3F,NHP( :O)C12. Triphenylphosphazenyl derivatives, structurally related to the product of reaction (2), may be obtained from Ph,P=NH.

L

I

+ RSOCl

NEts

> Ph3P=N-SOR+ HCl (R = CC13- or p-CH,C,H,-) (ref. 4b) Ph,P=NH + RNCS Ph,P=NSCNHR (R = alkyl or aryl) (ref. 4c) The derivatives, RNH2 [R = FS02--,6 F2P(:S)-,6v and ClFP(:S)-,7] Ph,P=NH

react with the mixed halogenophosphorane, PC12F3,eliminating hydrogen chloride to give RN=PF3. It may be noted that FS02N=PF3 is reported to be not accessible by fluorination of the chloride, FS02N=PC13.g H. W. Roesky, and P. R. Heinze, Inorg. Nuclear Chem. Letfers, 1968, 4, 179. o, H. W. Roesky, Chem. Ber., 1968, 101, 3679. (a S. Kongpricha and W. C. Preuse, U.S.P. 3,377,14211968 (Chem. Abs., 1968, 68, 114,741). (*) A. Senning and P. Kelly, Naturwiss, 1968, 55, 543; I. N. Zhmurova, A. P. Martynyuk, and G. I. Derkach, Zhur. obshchei. Khim., 1968,38,163 (Chem. Abs., 1968, 69, 52,209). H. W. Roesky and H. H. Giere, Inorg. Nuclear Chem. Letters, 1968, 4, 639. M. Lustig, Inorg. Chem., 1969, 8, 443. H. W. Roesky and L. F. Grimm, Inorg. Nuclear Chem. Letters, 1969, 5, 13. ( a ) 0. Glemser,

216


Phosphorus pentachloride reacts with a range of fluoroanilines to provide derivatives of the type

N=PC13 (n = 2, 3, or 4).* No reaction

was, however, observed with pentafluoroaniline. The products are all dimeric in benzene solution, but the 2,3,4,5-and 2,3,5,6-tetrafluoro-isomers are monomeric in carbon tetrachloride. The distinction between monomers and dimers is particularly marked in the observed 31P chemical shifts. Shifts of 80 p.p.m. for dimers and of 30-40 p.p.m. for monomers (relative to 85% H3P04 solution) were reported. As observed for other derivatives of this type, ammonolysis gives rise to ionic species, formulated as

+

+

NH,

NH2

The monomer-dimer equilibrium was also of interest in phosphazenes of the type, MeCl,P=NAr (Ar = aromatic group), obtained from tetrachloromethylphosphorane and substituted aniline hydrochlorides.ga When Ar = o-C,H4C1, or o-C6H4Br,the products were monomeric in the liquid state, but dimeric in the solid state as shown by i.r. spectroscopy. Reactions of hydrazine dihydrochloride with phosphoranes, Ph3PX2,in the presence of aluminium chloride, are markedly dependent on the nature of the halogen atom, X:nb

+ Ph3PBr, + N2H4,2HC1 Ph3PCl2 N,H4,2HCl

PhSPI,

+ N2H,,2HCI

AlCls

[PhSPNH NHPPhJ ++2C1-

2ooe

AlCls 2ooo

AlCls 2ooo

>

[Ph3P-N=PPh,]+Br-

+NH4Br+Br, + HCl

>

[Ph3P-N=PPh3]+I-+

NH4+13-+ I,+ HCl

Other cationic species containing NH,-groups within the cation have been used to synthesise P=N linkages. Thus, guanidine hydrochloride, NH=C(NH2)2,HC1, and Ph,PCls-, (n = 0-2) give NH II Ph,Cl3-,P=N-C-NH2,HCl and (Ph,C13-,P=N),C=NH, depending on the molar ratio of reactants.1° Pyrolysis of these compounds gives rise to polymeric (NPCl,), ( x = large number; n = 0) and/or oligomeric N3P3Phs(n = 2) phosphazenes. In the same way, the carbonium ions of the salts R+C(NHJaSbCl,- (R = Me, CCls, Ph, or NMe,) and

*

lo

K. Utvary and M. Bermann, Monatsh., 1968,99, 2369. I. N. Zhmurova and I. Yu. Dolgushina, Khim. Org. Soedineniya Fosfora, Akad. Nauk. S.S.S.R., 1967, 195 (Chem. A h . , 1968, 69, 76,781). ( b ) R. Appel and G. Siegemund, Z . anorg. Chem., 1968, 361, 203. F. G. Sherif, J. Inorg. Nuclear Chem., 1968, 30, 1707.

217

Phosphazenes

[C(NH,),]+SbCl,- gave in nitromethane solution with 2 or 3 moles of phosphorus pentachloride respectively the salts formulated as l1

I

R

[

I

CI,P=N-C=N-PCI, (3)

[

N=PC13

I

+SbCI,- and CI,P-N=C-N=PCI3 (4)

I

+SbCI,-

The structures (3) and (4) are consistent with the lH and 31Pn.m.r. data. In the case of (3) (R = Me), a four-bond spin-spin coupling, J(P-N-C-C-H), of 2.55 Hz was taken as evidence of conjugation through the P-N-C-N-P skeleton. Evidence in favour of conjugation between the adjacent nitrogen and carbon atoms, and of slow rotation on the n.m.r. time-scale about this bond, as in ( 5 ) was obtained from the observation of different cis and trans P-N-C-N-C--N spin-spin coupling constants of 2-2 and 3-2 Hz respectively. Me,,

Me N/

I1

CI,P=N

/c,

N=PC13

(5)

Further examples of phosphazene formation by the reaction of phosphorus(xI1) compounds with covalent organic and inorganic azides have been reported : RN, + Ph3P ---+ RN=PPh3 + N, (R = benzothiazolyl, benzimidazolyl, etc.) (ref. 12) ArN,

+ P(NC2HJ3

+

(RO),P(: 0 ) N 3 P(OR),

-

-----+

+

ArN=P(NC,H,), N, (Ar = aromatic group) (ref. 13)

+

(RO),P(: O)N=P(OR), N, (R = alkyl) (ref. 14)

Products containing the grouping =P(OR)3 (R = Alk) can isomerise heating, e.g., (MeO),P(O)N=P(OMe), -----+- (MeO),P(: O).NMe.P(: O)(OMe), Me,SiNH -PBut, But,PNH,

+ Me3SiN, + Me3SiN3

-

-----+

(ref. Me,SiNH. But,P=NSiMe3

(ref. But2P(NH,)=NSiMe3 ( A ) (ref. 15) But,P(NHSiMe,)=NSiMe3 (B)

+

+B u t z h w a N 3 l1

12 la

l4

l6

+ Nz

(0

A. Schmidpeter, K. Dull, and R. Bohm, 2. anorg. Chem., 1968, 362, 58. J. A. Van Allan and G. A. Reynolds, J. Heterocyclic Chem., 1968, 5 , 471. G. I. Derkach and S. K. Mikhailik, Khim. Org. Soedineniya Fosfora, Akad. Nauk S.S.S.R., 1967, 59 (Chem. Abs., 1968, 69, 2757). V. A. Shokol, N. K. Mikhailyuchenko, and G. I. Derkach, Khim. Org. Soedineniya Fosfora, Akad. Nauk. S.S.S.R., 1967, 78 (Chem. Abs., 1968, 69, 10,065). 0. J. Scherer and G. Schieder, Chem. Ber., 1968, 101, 4184.

21 8


Products ( B ) and (C) are believed to be formed by the reaction sequence:

+

( A ) Me3SiN3

But2PNH2+ HN,

-~

+

----+

(B)+HN3 But2P(NH2)=NH

HNs

(C) Notable work on the mechanism of the azide synthesis of phosphazenes has been carried out by Bock and co-workers.le,l7 They established that the decomposition of intermediates such as (6) proceeds by elimination of nitrogen molecules containing y- and 13-nitrogen atoms. This was demonstrated by 15N-labellingat the y- and 13-positions, and a study of the mass spectrum of the nitrogen eliminated in each case. These observations add weight to the suggestion that decomposition proceeds through a fourcentred intermediate of the type (7).

The i.r. spectra of these 15N-labelled derivatives were also discussed in detail as well as the perdeuteriophenyl-derivatives [e.g. (C62H5)3P=N-N=N-S02-p-tolyl]. These workers have also discussed the syntheses and i.r. spectra of 15N-and 2H-labelled derivatives of the type (C6X5)3P=N-N=CY2 (X = lH or 2H, N = 14Nor 15N,Y = lH or 2H).1s Numerous other methods of monophosphazene synthesis have been reported. Compounds of the type, [R2P(:S)I2NH(R = alkyl or phenyl) give on chlorination [ClPR,=N*BR,Cl]Cl-, and on subsequent ammonoDiazomethane methylates similar lysis, [H2N PR2=Nl!R2NH2]Cl-.10 compounds on the sulphur atom:

-

Me,P(: S)NHP(: S)R2+ CH2N2

MeS.P(Me,)=N-P(:S)R,

(R = Ph, Me)

and further reaction of the products with methyl iodide gives rise to further S-methylation at the terminal sulphur atom to give the cationic complex, [MeS*P(Me,)=N$(SMe)R,]I-. The IH and 31Pn.m.r. spectra of these salts were discussed in detail and the lH spectra exhibited ‘virtual coupling’. It was suggested that J(P-C-H) and J(P-N-P-C-H) are of opposite sign.2o It has been shown that certain aminophosphines provide monophosphazenes by an exothermic reaction with carbon tetrachloride :15 l6 *7

l8

l9 20

H. Bock and M. SchnoIler, Aizgew. Chem. Znternat. Edn., 1968, 7 , 636. H. Bock and M. Schnoller, Chem. Ber., 1969, 102, 38. H. Bock, M. Schnoller, and H. tom Dieck, Chem. Ber., 1969, 102, 1363. A. Schmidpeter and J. Ebeling, Chem. Ber., 1968, 101, 815. A. Schmidpeter, H. Brecht, and J. Ebeling, Chem. Ber., 1968, 101, 390.

219

Phosphazenes Me,MNHPBut,

+ CCI,

or (Me,SiNH),PBut

+ CCI,

----+

-

Me,MN=PCIBut,

+ CHCI, (M = Si, Ge, Sn)

(Me,SiNH)ButP(Cl)=NSiMe,

+ CHCI,

This reaction probably proceeds via a nucleophilic attack by the phosphorus on the chlorine atom. Triphenylphosphine and S4N3Cl undergo a complex reaction in the absence of solvent, to give the known salt, [Ph3P=N-PPh3]+C1-. In benzene solution, under anhydrous conditions, a salt tentatively formulated as [(Ph,P=N),SI3+3C1- is obtained. The Lewis acid character of this salt appears to be demonstrated by the fact that it forms an adduct, [(Ph3P=N),SI3+ 3C1-,2PPh3, with triphenylphosphine.2f The compound P(:S)(NCS), and chlorine give a red-brown solid in petrol at -2O", from which C13P=N*CC13can be isolated.22 This compound gives phosphorus pentachloride and cyanuric chloride on heating. The vibrational spectra of this, and other related derivatives, Cl,P=NR [R = CC13, CC12*CC13,and CCl(CCl,),], have been studied and the asymmetricand symmetricP=N-C stretching modes identified. It was suggested that the difference in these A

frequencies indicates changes in the P=N-C

bond angle.,,

B. Cyclic Derivatives.-Modifications of the original synthesis of cyclic oligomeric phosphazenes from ammonium chloride and phosphorus pentachloride continue to be reported. A patent 24 shows that the time for this reaction may be reduced by the introduction of an anhydrous metallic salt capable of complexing with ammonia. Salts claimed to be effective in a variety of solvents include CoCl,, A1C13, MnCl,, CuCl,, SnCl,, MgCl,, ZnCl,, TiC14,CdCI,, and CrCl,. Related to this is the report 25 that addition of metals to the PC15-NH4CI reaction mixture in inert solvents may increase or decrease the rate of hydrogen chloride evolution. The metals Zn, Co, Al, Cu, and Fe, increase the rate, whereas Ni, Mg, Ti, Mn, and Sn decrease the rate. Since the metals are thought to form their anhydrous chlorides in solution, the claim that Mg, Ti, Mn, and Sn slow the rate of hydrogen chloride evolution appears to contradict the claims of the patent.,, Phosphoryl chloride is found to be a good catalyst for this reaction 26 and an 86% yield of cyclic derivatives was obtained in one case. Two Japanese patents indicate that the petrol-insolublelinear polymers from the PC1,-NH,Cl reaction may be converted to cyclic oligomers (NPCI,), on 21

23

24

26 26

H. Prakash and H. H. Sisler, Inorg. Chem., 1968, 7 , 2200. E. Fluck and F. L. Goldman, Z . anorg. Chem., 1968, 356, 307. D. P. Khomenko, G. G. Dyadyusha, and E. S. Koslov, Spectroscopy Letters, 1968, 1, 245. N. L. Paddock and H. T. Searle, U.S.P. 3,407,047/1968 (Chem. Abs., 1969, 70, 3 9,397). E. Kobayashi, Kogyo. Kaguku Zasshi, 1967, 70, 628 (Chem. Abs., 1968, 68, 56,122). J. Emsley and P. B. Udy, Chemical Society Annual Meeting, Nottingham, 1969, Abstract 7.16.

220


reaction with further NH4C1,27and that the yield of cyclic material from the PCl6-NH4C1reaction may be improved by using finely divided NH4C1.28 + The reactivity of Ph3PClPC16 , C5H5N.PCl5, PC14+SbC16-, and PCl, towards NH4C1to form linear salt-like phosphazenes has been The reactions in nitrobenzene solution were followed by 31Pn.m.r. spectroscopy and showed that the reactivity increases in the order PC16- < C5H5NPC15< PC1, < PCl,+. The mass spectra of several oligomeric halogenocyclophosphazenes have been studied in detail. Homologues in the series (NPC12), (n = 3-8),,O (n = 3, 4),31 and (NPF2), (n = 3-16)32 break down to give a series of cyclic and acyclic ions. In the series of nongeminal derivatives, N3P&l,Br+, (x = 0-5),,, the parent ion is of low intensity and the base peak arises from the loss of one bromine atom. Again, cyclic and acyclic ions were identified and the relatively large drop in ionisation potential on the introduction of one bromine atom into N3P&& was interpreted in terms of increased base strengths at the ring nitrogen atoms. Appearance potential data gave AHf" for N,P,Cl,Br as - 168-6 kcal/mole, compared with AHf" for N,P,Cl, = - 1759 kcal/mole. Several examples of six-membered phosphazene ring systems have been obtained by the cyclisation of compounds containing a P-N-P fragment, e . g .: [Ph2P(NHz)-N-P(NHz)Ph,] 'C1-

+

Mc,PCI,

This result 34 differs from previous reports on analogous reactions with PC15, PhPCl,, and Ph2PC13,where the hydrochloride was not normally isolated. It is understandable, however, in terms of basicity substituent constants Me > Ph > C1 (cf. section 6 ) . By use of related reactions it is also possible to introduce boron as a member of the ring 27

28 2o

30 31 32

33 54 35

M. Ura and K. Ogihara, Jap.P. 14,693/1967 (Chem. Abs., 1968, 68, 97,204). E. Kobayashi, Jap.P. 14,694/1967 (Chem. A h . , 1968, 68, 80,074). W. Lehr and M. Schwarz, Z . anorg. Chem., 1968, 363, 43. C. E. Brion and N. L. Paddock, J. Chem. SOC.( A ) , 1968, 388. C. D. Schmulbach, A. G . Cook, and V. R. Miller, Inorg. Chem., 1968, 7 , 2463. C. E. Brion and N. L. Paddock, J. Chem. SOC.( A ) , 1968, 392. G. E. Coxon, T. F. Palmer, and D. B. Sowerby, J. Chem. SOC.( A ) , 1969, 358. M. Bermann and K. Utvary, J . Inorg. Nuclear Chem., 1969, 31, 271. ( a ) M. Becke-Goehring and H . J . Muller, Z . anorg. Chem., 1968,362, 51. ( b ) A. Schmidpeter and K. Stoll, Angew. Chem. Internat. Edn., 1968, 7 , 549.

221

Phosphazenes f

CI,P=N-PCl,CI-

+ + MeNH,CI+

BCl,

The same product was obtained with PCl, instead of [Cl,P=N-~Cl,ICland appears to be covalent in character in spite of the formal charges on some of the ring atoms. Cationic complexes of silicon, germanium, and tin containing the phosphazene linkage have been prepared 3 S b by the reaction: HN(PhnP0)2

+

MX4

_____+

Ph2P-0

3%~~

The reaction has not been observed where M = Sn (X = C1, Br) and a Ph,P=O two-ring derivative, N : is formed. The third ring can

[

Ph,P -0 only be introduced using NaN(Ph2PO), at elevated temperature. Salts with numerous anionic species replacing X have been prepared. When M = Sn, the cations are hydrolytically stable and can be used to precipitate large anions, e.g. Mn0,-. Novel syntheses of compounds containing the elements P, N, and C as ring atoms have been d e ~ c r i b e d . ~ ~ R I H,N-C=NH + [CIP(X,)=N-P(X,)CI]+CI-

R=PhCH, Ph NH, NMe, PhCH, NMe, X = Ph Ph Ph Ph Me Me 86

A. Schmidpeter and J. Ebeling, Chem. Ber., 1968, 101, 3883.

222 Organophosphorus Chemistry The corresponding hydrochlorides are also readily isolated from guanidine hydrochlorides : R I [HZN- C=NH,I+CI-

R =Me X = Ph X ' = Ph

x x

x

+ [CIP =N-PCl]

PhCH2 Ph Ph Ph Ph Ph

'(21-

X'

Me Me Me Ph Me Me

these can be dehydrochlorinated by treatment with an excess of ammonia. At 40°,there is a rapid exchange on the n.m.r. time scale of the proton

between the sites indicated, but at -60°, signals due to the different P-Me groups can be identified from the lHn.m.r. spectrum. A second route to the diphosphazatriazines lies in the elimination of aniline from linear aminophosphazenes and PhNHCH=NPh : H

+ 2PhNH2(X=Ph

or Me)

These ring systems may also be prepared by the reactions:37 R I ,N=PC13

R-C,

2NH,CI

+

N--PCl,SbCI,-

R = M e Ph Me Ph R = M e Me Ph Ph

N /'\N II CI,P,

I PC1.3 N/

11 Cl,P,

,Pa,

I

N

I

R' 37

A. Schmidpeter and R. Bohm, 2. anorg. Chem., 1968,362,65.

+

(R

= Ph)

SbC1,-

Phosphazenes

223

Where R = Me, R' = Me and R = Me, R' = Ph, relatively large J(P-N-C-C-H) coupling constants were observed from the lH n.m.r. spectra (R' = Me, 4.3 Hz; R' = Ph, 4-1 Hz) and cited as evidence of a conjugative interaction within the P-N-C system. There is strong evidence that this is the case in the compound (8) for its crystal structure has been studied3* and it was shown that the ring system was planar. NMe, 1

N/ II Me,P,

c"N. I ,PMe, N' (8)

The lHn.m.r. spectra of species containing P, N, and S as component atoms of a six-membered ring have also been can be cyclised by a Compounds of the type, NH,PR2=N-PR2=NH, variety of reagents, e.g. reactions (7), (8), and (9): NH,PPh,=N-PPh,=NH

3- RP(OPh),

Ph 2 P/N'PPh II I N, /NH P

I R

+ 2PhOH

11

(7) Ref. 40a

Strong evidence for the predominance of the tautomer with a direct P-H bond was obtained from the large value of J(P--H) (500-700 Hz). This appears to be the first example of a cyclotriphosphazatriene with a P-H bond. Related equilibria PrIr+ Pv, where the quinquevalent form contains a P-H bond, have been recently established for a number of mononuclear phosphorus compounds.40b This derivative was also obtained from guanidine (R = H) and its dimethyl derivative (R = Me).41 as 39 40

41

U. Klement and A. Schmidpeter, 2. Naturforsch, 1968, 23b, 1610. L. Siekmann, H. 0. Hoppen, and R. Appel, 2. Naturforsch, 1968, 23b, 1156. (a) A. Schmidpeter and J. Ebeling, Angew. Chem. Internat. Edn., 1968, 7 , 209. m 'C R. Wolf, J. F. Brazier, D. Houalla, and M. Sanchez, Int., Symposium on Organophosphorus Chemistry, Paris, May, 1969. A. Schmidpeter and J. Ebeling, Chem. Ber., 1968, 101, 2602.

224


NH2PPh2=N-PPh,=NH

+ BrCN

+ NH2-PPh2=N-PPh,=N-C=N [Ph P ( NH, ) =N - $ Ph NH, ] Br -

Ph2P+ ,PPh2 N

+ 3[R,NC(NH2),]+C1( R = H , Me)

X I H,N P R = ~ N- P R, =N- P = s I SH

(9) Ref. 42

R = Ph, X = MeO*C6H4R = Ph, X = PhSR = Me,N, X = M e 0 .C6H4-

225

Phosphazenes

The predominance of the NH-tautomer was established by 31Pn.m.r. spectroscopy. This tautomer was converted to the cyclotriphosphazatriene by quaternisation at the sulphur atom and subsequent removal of HI by EtOH or a MeCN-water mixture. 3 Reactions Involving Displacement of Halogen Atoms A. By Other Halogen Atoms.-A comprehensive study of the fluorination of N3P,C16 by NaF in nitromethane or in nitrobenzene and of N4P4Cl, by KS02F has been rep~rted.~,Compounds representing all degrees of and N4P4C18-,F, replacement in the series N3P&16-,Fn (n = 1-6) (n = 1-8) have been obtained. l0FN.m.r. spectroscopy shows that fluorination in both cases proceeds by a geminal replacement pattern. With N4P4C18two alternative geminal routes are available when n > 2 and the one taken is as indicated below: C

CI

c1

KSOzF

KS0,F

etc.

These observations are explicable in terms of a simple electrostatic effect whereby replacement of a chlorine atom at phosphorus by a fluorine atom increases the electrophilicity of the phosphorus atom. Qualitative observations show that the rate of formation of N,P&&F2 is greater than that of N3P3C14F2 from the respective monofluoro-derivatives. This behaviour was accounted for in terms of r-inductive effects within the P-N ring system. Halogen exchange reactions between dimericphosphazenes(MeN=PCl,), and (MeN=PF,), (using a 1 :2 molar ratio in a sealed tube at 1loo)lead to the formation of a series of mixed fluoride-chlorides (MeN=P),F,Cl,-, (n = 2-5) which were separated by fractional di~tillation.~~ The derivatives where n = 1 or 2 were obtained by fluorination of (MeN=PCl,), by NaF in acetonitrile. The structures of the isomers obtained were not established. In contrast, reaction of (Cl,P=N CCl, *CCl,),(CH,), (n = 2-6) with K F in chlorobenzene led to cleavage of the P=N bond and the formation of PF5 and (CHz),(CClzCN)2.46

B. Halogen Displacement by Amines.-Interest has recently been shown in the synthesis and properties of amino-derivatives of N3P3F6,46* 47 and, to a 4s 44

4s

46 47

A. Schmidpeter and C. Weingand, 2. Naturforsch, 1969, 24b, 177. J. Emsley and N. L. Paddock, J. Chem. SOC.(A), 1968,2590. K. Utvary and W. Czysch, Monatsh., 1969, 100, 681. V. I. Schevchenko, V. P. Kukhar, and A. V. Kirsanov, Zhur. obshchei. Khim. 1967, 37, 2361 (Chem. Abs., 1968, 68, 77,683). 0. Glemser, E. Niecke, and H. W. Roesky, Chem. Comm., 1969, 282. T. Chivers and N. L. Paddock, Chem. Comm., 1969, 337.

226


lesser extent, in such derivatives of the homologues, (NPF,), (n = 4-6).46 These amino-derivatives are perhaps best characterised by their 19Fn.m.r. spectra which can also give valuable structural information. Amina’lysis has been carried out using rneth~larnine,~~ dirneth~larnine,~~-~~ dimethylamin~trimethylsilane,~~, 48 and lithium dimeth~lamide.~~ The isomers so far characterised in the series, N,P,F2,-2 (NMe2)2, are n ~ n g e r n i n a l 48 .~~~ These derivatives are sunimarised in Table 1 below together with the Table 1 X =

chloride-fluorides and bromidefluorides obtained by deaminolysis with HCl or HBr respectively.46$ 47 In view of the relatively high P-N bond orders associated with fluorophosphazenes, it is remarkable that the reaction of N3P3F6with diethylamine is reported to lead to cleavage of the P-N ring Chlorofluorodimethylamino-derivatives may be obtained from the reaction of N3P&&-, (NMe,), (n = 2,3) with SbFa or KS0,F. Fluorinations with these two reagents follow different replacement N3P3C14(N

SbFa

LTCl

N3P3CI,F,(NMe2), -----+N,P3F2C14

(two geometric isomers with =P(F)NMe, and =PC12 groups) N3P3C1,(NMe2)2

KSO2F

’ N3P3C12F2(NMe2)2

(two geometric isomers with ZPClNMe, and =PF, groups) N,P3CI,(NMe2)3

SbFs

N2P3F3(NMe2I3

a N3P3C13F3

nongeminal

The course of reactions of N3P3C16with a wide range of amines has been studied in recent years but, even now, little is known of the mechanisms of these reactions and their relation to the stereospecific reaction paths observed. Some light is thrown on this matter by the followingobservations : A. Hawley and G. Nickless, Chemical Society Annual Meeting, Nottingham, 1969, Abstract 7.17. a B. Green and D. B. Sowerby, Chem. Comm., 1969, 628.

227

Phosphazenes

\

\

NH,Et

NH,BU~

CI"

C 'I

In view of the fact that t-butylamine with N3P3Cl, gives entirely geminal N3P3Cl,(NHBut),, and that ethylamine with N3P3C16gives entirely nongeminal N3P3C14(NHEt),, it becomes apparent that at least in some reactions the nature of the nucleophile may be of greater importance than the substituent already present in determining the reaction pattern.60 It is interesting to note that the reactions of four equivalents of piperidine, and of four equivalents of t-butylamine, with one equivalent of the diphosphatriazines (9);'" take a similar route to that observed for the same amines with N,P,C&.

R I

R

=

Mc, Ph

(9)

The former reactions are summarised in the Scheme. lH And n.m.r. data were used to show that the geminal route A is followed by t-butylamine and that the nongeminal route B is followed by piperidine. These conclusions were confirmed by the n.m.r. data obtained on the compounds prepared by replacement of the remaining chlorine atoms in (10) and (11) s1

R. Keat and R. A. Shaw, Angew. Chem. Internat. Edn., 1968, 7,212. (a) A. Schmidpeter and N. Schindler, Chem. Ber., 1969, 102, 856. R. A. Shaw, J. Chem. SOC.( A ) , 1966,908.

(li)

R. Keat and

228

Organophorphorus Chemistry

by methoxy- or dimethylamino-groups. Although it was not experimentally established whether the dipiperidino-derivative (1 1) had the cis- or the trans-structure, the latter was postulated on the basis of the R I

R I

A series of mixed pyrrolidine-aziridine derivatives, N,P,(NC,H,),(NC,H,),-, (n = 1-4) have been prepared starting from aziridinochloro-derivatives of known geminal structure and from chloropyrrolidino-derivatives of unknown structure.62 By a comparison of the isomers obtained, it was possible to establish that pyrrolidine replaces the chlorine atoms in N3P3Cl, by a predominantly nongeminal scheme. Similarly, the preparation of a series of aziridinomorpholino-derivatives of N3PsClswas used to establish a nongeminal reaction scheme with morpholine.63 A series of monoamino-derivatives,N3P3C1,R (R = NHCHPhCO,Me, NHNHPr', and NHCHMePh)s4 and a series of

a-phenylpyrrolidinyl-derivatives,NsP3Cle-, isomer only in each case) s2

ss 54

66

(-jl)(n= 1 4 ) (one

have been described.

A. A. Kropacheva and N. M. Kashnikova, Zhur. obshchei Khim., 1968, 38, 136; J. Gen. Chem. U.S.S.R.,1968, 38, 135.

L. E. Mukhina and A. A. Kropacheva, Zhur. obshchei Khim., 1968, 38, 313; J. Gen. Chem. U.S.S.R.,1968,38, 314. A. A. Kropacheva and N. M. Kashnikova, Khim. Org. Soedineniya Fosfora, Akad. Nauk S.S.S.R.,1967, 186 (Chem. Abs., 1968, 69, 10,066). A. A. Kropacheva and N. M. Kashnikova, Khim. Org. Soedineniya Fosfora, Akad. Nauk S.S.S.R., 1967, 188 (Chem. Abs., 1968, 69, 10,321).

Phosphazenes 229 The N-P bonds in N3P3X6(X = F, C1, Br), N4P4C18,and (NPCl,), (n- 15,000) undergo a novel form of degradation on reaction with orthoaminophenol.56 In all cases the same product is obtained which has properties consistent with the five-co-ordinate phosphorus compound (12), rather than with the analogous six-co-ordinate species (13).

Preliminary information on the mode of reaction of N4P4C18 with dimethylamine has appeared and some indication of the complexity of this system is provided by the detection (in one case by t.1.c. chromatography 68), isolation, and characterisation 67 of five isomeric bisdimethylamino-derivatives, N4P&l,(NMe,),, one of which was geminal. Of these, the two pairs of nongeminal isomers could be interconverted by pyridine hydrochloride. Only two trisdimethylamino-isomers, N4P4C16(NMe2)3,geminal and nongeminal, were isolated from a possible total of 5.67 The reaction of N4P4C18with an excess of the bulky secondary amine, methylcyclohexylamine, is strongly stereospecific and the nongeminal tetrakis-derivative, N4P4C1,(NMe C6H11)4,is formed in high yield.6e The structure of this derivative (14) was established by its reactions with methylamine and phenyl isocyanate, and by lH n.m.r. spectroscopy on these materials. It was also suggested that in this case aminolysis proceeds sequentially at the Me

66

67

68 6a

H. R. Allcock and R. L. Kugel, Chem. Comm., 1968, 1606. W. Lehr, Naturwiss, 1969, 56, 214. R. Stahlberg and E. Steger, J. Inorg. Nuclear Chem., 1968, 30, 737. A. J. Berlin, B. Grushkin, and L. R. Moffett, Inorg. Chem., 1968, 7 , 589.

230


2,6- and 4,s-positions in the ring, a result only partially observed for dinieth~lamine.~' The reactions of the monomeric phosphazenes PhN=PCl,R [R = NMe,, NEt,, NBun2, and N(Me)CH,Ph] with ammonia give products which are the phosphonium salts [PhNHP(R)(NH,),]+Cl-, rather than the salts [PhNH(NH2)RP=N-6(NH,)(NHPh)]C1-. The latter type (where R = H) are obtained from ammonia and (15). It was suggested that the observed products might be due to the enhanced stability of [PhNHPR(NH,),]+Clrelative to [PhNHP(NH2)3]+C1-.60

The Lewis-base properties of aminocyclophosphazenes continue to provide a source of interest. The compound NsP3(NMe2)6undergoes quaternisation at the exocyclic nitrogen atoms by Me30+BF4- to give (16).61 Evidence for the structure of the cation postulated was obtained by hydrolytic degradation of the salt (16) which gave Me,NH,Cl- and Me3&HCc. On the assumption (not necessarily correct) that the ring nitrogen atoms are least hindered to the approach of an electrophile, it was suggested that charge-transfer from the exocyclic nitrogen atoms may not be as extensive as that suggested from protonation studies. On the other hand, X-ray crystallographic evidence shows unambiguously that protonation of a ring nitrogen atom occurs in N3PsCl(NHPri)4,HC1,62 and furthermore on that ring nitrogen which has the largest number of a(NHPri) substituents, confirming earlier deductions from basicity studies (see section 5 on structural studies). It is likely that the nature of the acid may be of considerable significance in any estimation of the relative basicity of cyclic and exocyclic nitrogen atoms. Steric effects are also important in the consideration of solvent effects on the lHn.m.r. spectra of the dimethylamino-derivatives, N3PsX+,(NMeJn (X = C1, n = 1 4 and 6; X = Br, n = 1-3) which generally show an upfield shift on passing from carbon tetrachloride to benzene The shift is most pronounced for n = 1. For a given degree of chlorine or bromine replacement the signals from dimethylamino-groups cis to one another were shifted upfield to a greater extent than those trans to one another. This may reflect a preference of the benzene solvent molecules to approach the phosphazene ring on the side with more dimethylamino-groups than chlorine atoms. 6o

62 6s

K. Utvary and M. Bermann, Inorg. Chem., 1969, 8, 1038. J. N. Rapko and G. R. Feistel, Chem. Comm., 1968,474. N. V. Mani and A. J. Wagner, Chem. Comm., 1968, 658. R. Keat and R. A. Shaw, J. Chem. SOC.(A), 1968, 703.

Phosphazenes

23 1

The reactions of N3P3(NMe2)ewith HX (X = C1, Br, or I) in boiling xylene solution have been studied.64 Adducts of the type N3P3(NMe2)&€X were initially isolated, but prolonged reactions lead to deaminolysis and the formation of cis-N3P3C12(NMe2),and trans- and C ~ ~ - N ~ P , X ~ ( N M ~ , ) ~ (X = C1 or Br), although the latter isomer may not have been a primary reaction product. The cis-isomer, N3P3C12(NMe2),,is also obtained from the dimethylaminolysis of N3P3C16,and its isolation by deaminolysis lends some weight to the suggestion that it is the thermodynamically favoured form. No iododimethylamino-derivatives were isolated. The hydrochlorides, N3P3[NH(CH2),Me],, xHCl (n = 2, x = 2; n = 3, x = 2; n = 4, x = 3) have been obtained from the reaction of the corresponding hexakisamino-derivatives with hydrogen chloride in benzene solution at room t e m p e r a t ~ r e . ~ ~ C. Halogen Displacement by Alcohols.-Relatively little work has recently been reported on the alcoholysis of chlorophosphazenes. Cyclic fluoroalkoxy-oligomers of the type (NPR2), [n = 3-7; R = OCH2(CH2)aY; x = 1-20; Y = H or F] have been prepared from (NPC12), and the corresponding sodium alkoxides or alcohols. Their chemical and thermal stabilities have been investigated.66 The base-catalysed hydrolysis of N3P3(OCH2CF3)6 proceeds by successive removal of two trifluorethoxy-groups at different phosphorus atoms followed by hydrolytic degradation of the P-N ring?'

CF3CH20'A 'ONa

CF3CH20H

+ NH3 +

HSP04

In contrast, the hydrolysis of (17) to give (18) proceeds much more rapidly :67 64 65

E6 67

S. N. Nabi, R. A. Shaw, and C. Stratton, Chem. andInd., 1969, 166. K. Denny and S. Lanoux, J. Inorg. Nuclear Chem., 1969,31, 1531. Olin Mathieson Chem. Corpn., B.P. 1,104,471/1968 (Chem. Abs., 1968, 69, 35,419). H. R. Allcock and E. J. Walsh, J. Amer. Chem. SOC.,1969, 91, 3102.

232


K

This behaviour appears to be connected with the strain within the fivemembered ring for similar rate enhancement effects have been observed in the hydrolysis of mononuclear phosphorus esters containing a related five-membered ring. The esters NaP,(OPh)6and (19) undergo no detectable hydrolytic attack under similar conditions.

(19)

A new rearrangement of linear phosphazenes has been observed and its mechanism formulated :as

R

100-1 30"

/

OR

/

2RO-P=N-P=O \ \ R' OR R = alkyl; R' = alkyl or aryl

The rate of isomerisation decreases with increasing molecular weight of the ester and increases when R' is changed from alkyl to aryl. Heating also induces the elimination reaction: AlkCCI,CC1,N=PCl2( OAlk) 6*

100"

~

AlkCCI,C(Cl)=NP(: O)C1,

+AlkCl

I. M. Filatova, E. L. Zaitseva, A. P. Simonov, and A. Ya. Yakubovich, Zhur. obshchei Khim., 1968, 38, 1304; J. Gen. Chem. U.S.S.R.,1968, 38, 1256.

Phosphazenes 233 Further alcoholysis of the product occurs at both carbon and phosphorus atoms to give AlkCCl,C(OAlk)=NP(: O)Cl(OAlk).69 D. Aryl-derivatives of Cyclophosphazenes.-In contrast to the ring-cleavage reactions commonly observed between N3P&I, and organometallic reagents, phenyl-lithium undergoes reaction with N3P3F6in ether solution to give the monophenyl-derivative, N3P3F5Ph, and a mixture of diphenyl derivatives N3P3F4Ph2[cis- (20), trans- (21), and geminal(22) isomers in the

(20)

(21)

(22)

ratio 3 : 1 :0.25].70 With two equivalents of o-tolyl-lithium, only the nongeminal cis-bis(o-tolyl) derivative, N,P,F,(o-tolyl),, was isolated. Structures were established on the basis of 19Fand 31Pn.m.r. data and from dipole moment measurements. It was suggested that the previously postulated ‘cis-effect’61bshould be modified to account for the fact that an exocyclic group which is able to rr-bond relatively strongly to phosphorus is able to labilise the phosphorus-halogen bond cis to it on the phosphazene ring. This effect can be used to predict the reaction path of dimethylamine and of piperidine with N3P3Cle,in addition to the arylations noted above. The Friedel-Crafts reactions of N3P,F6 with benzene in the presence of aluminium trichloride follow a geminal pattern similar to that observed for N3P3Clc,except that a geminal triphenyl-derivative, N3P3F3Ph3(23), was

(23)

isolated.71 No geminal trichloro-derivative, N3P3C13Ph3,has been isolated in this way. Structures were again established from 19Fand 31Pn.m.r. data and correlations were made between this data and the expected rr-bonding effects, exocyclic to, and within, the P-N ring. The 19Fn.m.r. spectra of a series of monopentafluorophenyl-derivatives, N,P,(C6Fs)F2,-1 (n = 3-43), have been measured and indicate that there is a strong rr-withdrawal from the pentafluorophenyl ring in each case (p,-d, This effect is dependent on the value of n and varies in a 80

70

7l 72

V. I. Shevchenko, A. A. Koval’, and A. V. Kirsanov, Zhur. obshchei Khim., 1968,38, 5 5 5 ; J . Gen. Chem. U.S.S.R., 1968, 38, 541. C. W. Allen and T. Moeller, Inorg. Chem., 1968, 7 , 2177. C. W. Allen, F. Y . Tsang, and T. Moeller, Inorg. Chem., 1968, 7 , 2183. T. Chivers and N. L. Paddock, Chem. Comm., 1968,704.

234 Organophosphorus Chemistry similar manner to changes in base strength and ionisation potential in the series (NPCI,),. Some insight has been gained 73 into the reaction of N3P3Cl,with phenylmagnesium bromide, which has previously been shown to lead to the formation of small quantities of N3P3Ph6and relatively large quantities of unidentified materials. The latter have now been shown to consist of a mixture of fully phenylated acyclic phosphazenes which give, e.g., (24) on [Ph,P=N-PPh,=N-PPh,=&H,]

X-

(X = e.g., Clod

(24)

treatment with Brarnsted acids. The compounds N3P3C14Ph2 and N3P3Cl,Ph, undergo reaction with the same reagent more slowly, but it is believed that in the three cases the initial reaction is one involving ring cleavage by phenylmagnesium bromide. With N3P3C1,, the reaction may be represented as shown, although it is possible that two molecules of the organometallic reagent are involved.

N

‘P/

IN:

c1’ ‘c1

-

Mg + PhPCl,=N-PCI,=N-PCl,=NMgBr I Br

This linear product may then undergo phenylation and subsequent recyclisation:

The proportion of acyclic phenylated products is drastically reduced relative to that in the above reactions, and the nature of the cyclic species is completely changed when NsPsCla is treated with diphenylmagnesium in 1,4-di0xan.~** 76 The major product is formulated as (25) and evidence for

’’ M. Biddlestone and R. A. Shaw, J . Chem. SOC.(A), 1969, 178. 74

M. Biddlestone, R. A. Shaw, and D. Taylor, Chem. Comm., 1969, 320.

75

M. Biddlestone and R. A. Shaw, Chem. Comm.,1968,407.

Phosphazenes 235 this structure is obtained from degradative hydrolysis, from the 31P spectra obtained on a nuclear-electron double-resonance spectrometer, and from the 19Fn.m.r. spectrum of its penta(trifluoroeth0xy)-derivative, N6P6Ph7(OCH2CF3)6.74 A minor product has been identified as (26) which displays remarkable stability considering that it contains a P-P bond which is not cleaved by halogens.75

The arylation of the trichlorophosphazenyl-derivatives,N3P3Cl5N=PCI3 and geminal N3P3C14(N=PC13)2(27), by arylmagnesium halides proceeds by preferential reaction at the terminal phosphorus atom :76 N3P3C15(N=PC13)

N3P3C14(N=PC13)2

ArMgBr EtzO

N,P3C15(N=PAr3) (Ar

’

ArMgBr E ~ ~ O N3P3C14(N=PAr3),

=

Ph)

(Ar = Ph, p-tolyl)

With longer reaction times, ring phenylation was reported to occur geminally to the -N=PPh3 group to give N,P,Cl,Ph(N=PPh),. The latter compound and N3P3C14(N=PPh3),were unreactive to further attempts at arylation. Reaction patterns and 31Pn.m.r. evidence were cited in favour of a geminal structure for the derivatives N3P3ClX(N=PPh3) (X = C1, -NH2, Ph, and -N=PPh,). The ring-contracted geminal derivative, N3P3C1,Ph(N=PPh3), has also been obtained in low yield by the Friedel-Crafts phenylation of N4P4C18:77 N4p4c18

’

AIC13-PhH

- Et3N

+

[X] N3P3C14Ph(N= PPh3)

The second product, X, was not identified, but treatment with dimethylamine gave the tetramer-derivative, N4P4CJ2Ph5 *NMe2,which contains a =PPh- NMe, group, but the relative orientations of the remaining phenyl groups were not established. The hydrolysis of N,P3ClPh5: N3P3C1. Ph5 + H2O + NC5H5

N,P,(OH)Ph,

+ C6H5NHC1

in acetone has been the subject of a kinetic study which suggests that a nucleophilic base-catalysed mechanism may be operative :78 76

77

M. K. Feldt and T. Moeller, J. Inorg. Nuclear Chem., 1968, 30, 2351. V. B. Desai, R. A. Shaw, and B. C. Smith, Angew. Chem. Internat. Edn., 1968,7, 887. C. D. Schmulbach and V. R. Miller, Inorg. Chem., 1968, 7 , 2189.


236

+

ks

N,P,(OH)Ph, 4-C,H,NH

Supporting evidence for the intermediate, N3P3Ph6NC6H5was obtained + ClO, . by the isolation of the perchlorate salt, N3P3Ph5NC6H5 The physical properties and thermal dissociation of the adducts, N3P3Ph6,3C2H2C14 79 and N3P3Ph4C12,C2H2C14 8o have been studied; they are believed to be clathrates. The reactions of nongeminal N4P4C12Phs towards water, amines, and caesium fluoride have been studied as summarised :sl N4P4Cl2Phs

pyridine-Ha0

r -

> N4P4(OH)2Ph6

PCls-CHCla or SOCl2-CHCla

(two isomers of N4P4ClaPh6 were isolated from the reaction with SOCl2, but their structures were not established). PBq N4P4(0H)2Ph6

N4P4C12Ph6

=

R’ = H; R

= H,

N4P4Br2Ph6 N4p4 F2Ph6

’

NHRR’ CHC~~

N4P4(NRR)2Ph6 R’ = Me; R = R‘ = Me; R = R’ = Et;

N4P4C12Ph6

(R

>

CsF CH,CN’

R = Me, R = Ph; RR’ = C5H,,) The preparation of the cis- and trans-isomers of N,P,Br,Ph, has been described in detail :82 PhPBr, + NH,Br N,P3Br3Ph3

-

Interconversion of these two isomers was observed in refluxing acetonitrile or bromobenzene It was suggested that isonierisation occurred by a solvent-assisted ionisation mechanism. 4 Formation of Polymeric Phosphazenes Current work on the synthesis of polymeric phosphazenes is largely reported in the patent literature. Two reviews of recent developments in this aspect of polymer chemistry have appeared as well as a more general, but useful, survey of the technical uses of phosphorus-nitrogen compounds.8a 7s

8o

Ba 84

B6

R. D. Whitaker, A. J. Barreiro, P. A. Furman, W. C. Guida, and E. S. Stallings, J. Znorg. Nuclear Chem., 1968, 30, 2921. R. D. Whitaker and W. C. Guida, J. Znorg. Nuclear Chem., 1969, 31, 875. A. J. Bilbo, C. M. Grieve, D. L. Herring, and D. E. Salzbrunn, Znorg. Chem., 1968, 7, 2670. P. Nannelli, S.-K. Chu, B. S. Manhas, and T. Moeller, Znorg. Synth., 1968, 11, 201. B. S. Manhas, S.-K. Chu, and T. Moeller, J. Znorg. Nuclear Chem., 1968, 30, 322. H. R. Allcock, Chem. Eng. News, 1968,46, 68. H. Saito, Kobunshi, 1968, 17, 391 (Chem. Abs., 1968, 69, 59,570). H.-G. Horn, Chem. Ztg. Chem. App., 1969, 93, 241.

23 7

Phosphazenes

Interest in the polymerisation of oligomeric cyclophosphazenes to give linear polymers, (NPCI,), continues. It is found 8 7 that highly purified N3P3C16polymerises only slowly at 300", whereas with relatively crude N,P,C16 polymerisation was rapid at 270". The polymerisation process is also accelerated by the presence of oxygen. Acyclic ionic phosphazenes with boron- or aluminium-containing anions 88 have been prepared by the reactions : PCI,

+ (NPCI,),

[Cl(Cl,P=N),PCI,]+[PCl,l-

(n = 3,4)

lMCb

(M = A1 or B)

[Cl(Cl,P=N),PCl,]+[MCI,]-

The resultant fluids were heated and the degree of polymerisation of the cation studied. The pyrolysis of mixtures of NbNClz or NbOCl, and (NPCI,),, has been studied.80 There are several reports of condensation polymerisations involving diols and oligomeric cyclophosphazenes, e.g. : Ph

Ph

\ /

Ph

Ph

+ 2nHCl Simple polymer fractionation gave samples with a molecular weight of ca. 500,000. Differential thermal analysis and thermogravimetric analysis on this polymer suggested that thermal degradation is initiated in the phosphazene ring.g0 Similar condensation studies were also conducted with analogous polymers using as bridging groups the following difunctional reagents : 8' 88

R. 0. Colclough and G. Gee, J . Polymer Sci.,Part C, 1968,7, 3639. E. F. Moran, J. Inorg. Nuclear Chem., 1968, 30, 1405. U. A. Buslaev, B. V. Levin, S . M. Sinitsyna, M. A. Polikarpova, Z . G. Rumyautseva, and V. V. Mironova, Izvest Akad Nauk S.S.S.R., Neorg. Materialy, 1968, 4, 1706 (Chem. Abs., 1969, 70, 53,566). A. J. Bilbo, C. M. Douglas, N. R. Fetter, and D. L. Herring, J. Polymer Sci.,Part A , 1968, 6, 1671.

238


The condensation reactions of N,P,Cl, with 2,6-methylol-o-creso1in warm dioxan have been studied.g1 The insoluble polymeric materials obtained from the pyrolysis of N,P,Cl, give, on treatment with ethylene glycol, materials soluble in chloroform, and two hypotheses have been proposed to account for this ~ b s e r v a t i o n .Various ~~ diols and triols of boron have been e.g. : condensed with N3P3Clsand N3P,(OBu), to produce novel

+

BU“OH

Polymers with useful chemical and thermal stability have been obtained by the reaction of pyrolysed N3P,Cl, with a mixture of sodium fluoroalkoxides, NaOR (R = CH2CF3and CHzC3F,).94 The copolymers obtained have a relatively large proportion of [NP(OCH2CF3)(OCH2C,F,)] units. The reader is also referred to the patent literature, where examples of polymeric phosphazenes obtained from reactions involving a l c o h o l ~ , ~ am ~ i- n~e~~ , ~loo ~g and various alkyl phosphorus compounds Io2 are to be found. lo13

5 Structure and Bonding The output of detailed structural information on the phosphazenes steadily increases. This continues to provide some impetus for theories of bonding within these structures, and a useful review lo3of bonding in cyclic phos91

93

94 g5 *6

97

g8

M. Kajiwara and H. Saito, J. Chem. SOC.Japan, Ind. Chem. Sect., 1968, 71, 1470. M. Pornin, Bull. SOC.chim. France, 1968, 759. A. V. Deryabin, S. M. Zhivukhin, V. V. Kireev, and G. S. Kolesnikov, Plast. Massy., 1968,3,29 (Chem. Abs., 1968,69, 3200). S. H. Rose, J. Polymer Sci., Part B, Poly. Letters, 1968, 6, 837. M. E. Hull and D. W. Hoch, U.S.P. 3,402,145/1968 (Chem. Abs., 1968, 69, 103,783). H. R. Allcock and R. L. Kugel, U.S.P. 3,370,020/1968 (Chem. Abs., 1968, 68, 69,55 5). S. M. Zhivukhin and S. I. Belykh, U.S.S.R.P. 212,522/1968 (Chem. Abs., 1968, 69, 19,998). D. J. Jaszka, U.S.P. 3,392,214/1968 (Chem. Abs., 1968, 69, 59,945).

Yu. V. Azhikina, M. Ya. Konoleva, B. M. Maslenikov, and L. Ya. Kulikova, Izuest. Akad. Nauk S.S.S.R., Neorg. Materialy, 1968,4, 1711 (Chem. Abs., 1969,70, 53,572). loo H. R. Allcock and R. L. Kugel, U.S.P.3,364,189/1968 (Chem. Abs., 1968,68, 50,558). lol H. H. Sisler, Fr.P. 1,497,470/1967 (Chem. Abs., 1969, 69, 52648). lo2 E. I. Sokolov, V. A. Bartashiv, A. L. Klebanskii, T. I. Saratovkina, T. L. Chernyavskaya, and V. N. Sharov, U.S.S.R.P. 216,710/1968 (Chem. Abs., 1969, 70, 11,808). lo3 K. A. R. Mitchell, Chem. Rev., 1969, 69, 157. 99

Phosphazenes

239

phazenes has appeared in connection with the more general aspects of 3d-orbital bonding. The utilisation of phosphorus 3d-orbitals for bonding in the planar ring structures, N3P3F6, N4P4FS,and N,P,C16, has been examined in detail lo*and it was suggested that the 3d,,- and 3d,s-,2-orbitals (for axes see ref. 104) are the most effective in 7-bonding. These conclusions are consistent with a bonding scheme that emphasises cyclic electron delocalisation within the two 7-systems, symmetric and antisymmetric to reflection in the molecular plane. Recently reported molecular parameters for cyclic and acyclic phosphazenes are summarised in Table 2. In all molecules where each phosphorus atom has the same pair of substituents the endocyclic P-N bond lengths are equal within experimental error. There have been a number of attempts to identify the ring conformations of N4P4CI, in solution by vibrational spectroscopy. The most likely conformation has a point group Dza (saddle shape),l17,118 but variable symmetry cannot be ruled For samples examined in the solid state, agreement is reached with X-ray crystallographic evidence on the structure of the K(S,) and T(C2h)forms.118 These structures have been further confirmed by n.q.r. studies and these results have been tentatively interpreted in terms of differing n-character in the axial and equatorial P-Cl bonds of the Tform.120 It has been suggested that N4P,Cl, has a planar ring (D4hsymmetry) in the vapour phase.lls The vibrational spectra of NSP5Br10have been interpreted in terms of a distorted DShsymmetry.121 6 Miscellaneous Physical Measurements The variation of vapour pressures of N6P6C112 and N4P4Br,over a range of temperatures has been measured. These observations give lattice energies of 25.3 k 0.42 and 29-42 0.47 kcal/mole respectively.lZ2 K. A. R. Mitchell, J. Chem. SOC.( A ) , 1968, 2683. M. I. Davis and J. W. Paul, Acta Cryst. Supp., 1969, A25, S116. lo6 A. J. Wagner and A. Vos, Acta Cryst., 1968, B24, 707. lo7 A. W. Schlueter and R. A. Jacobson, J . Chem. SOC.( A ) , 1968, 2317. log F. R. Ahmed, P. Singh, and W. H. Barnes, Acta Cryst., 1969, 1325, 316. loo A. J. Wagner and A. Vos, Acta Cryst., 1968, B24, 1423. 110 N. L. Paddock, J. Trotter, and S. H. Whitlow, J. Chem. SOC.( A ) , 1968, 2227. l l 1 G. J. Bullen, P. R. Mallinson, and A. H. Burr, Chem. Comm., 1969, 693. 112 J. Trotter, S. H. Whitlow, and N. L. Paddock, Chem. Comm., 1969, 695. 113 J. C. van de Grampel and A. Vos, Acta Cryst., 1969, B25, 651. 114 U.Klement and A. Schmidpeter, 2. Nuturforsch, 1968, 23b, 1610. 115 M.L. Ziegler, 2. anorg. Chem., 1968, 362,257. 116 J. W. Cox and E. R. Corey, Chem. Comm., 1969, 205. 117 T. R. Manley and D. A. Williams, Spectrochim. Acta, 1969, 24, A , 1661. llS H. C. Hisatsune, Spectrochim. Acta, 1969, 25, A , 301. 118 W. P. Griffith and K. J. Rutt, J. Chem. SOC.( A ) , 1968, 2331. 120 M. Dixon, H.D. B. Jenkins, J. A. S. Smith, and D. A. Tong, Trans. Faraday SOC., lo4 lo5

121

lZa

1967, 63,2852. G. E. Coxon and D. B. Sowerby, Spectrochim. Acta, 1968, 24, A , 2145. S . Cotson and K. A. Hodd, J . Inorg. Nuclear Chem., 1969, 31, 245.

N4P4C18(T form)

Compound

r

2.006 (0.007)

1.992 (0.004)

1 ~804

1.585 (0.010)

1.559 (0.012)

1.597 (0.006) (0.007)

P-x

P-N

n

Average bond distances (&a

117.8 (0.3)

120.5 (0.7)

119.7 (0.3) (average ring angle)

NPN

)-T?----

Comments

103-8 X-Ray study. Slight chair (0.3) conformation. Effects of electronegativity on P-N ring parameters discussed for halogenophenylphosphazenes

103.1 X-Ray study. Chair-shaped (0.2) ring with approximately C,, symmetry. Previously studied (Kform) has boat conformation. Two independent P-N-P angles, 133-6 and 137.6 (0.8"), explained by Cl-Cl interaction. See i.r. studies below

108

106

105

Reference

101.8 Preliminary report of elec(1.2) trondiffraction(e.d.) study. Slight chair of C3p symmetry, ring puckered by 6". Accuracy better than previous e.d. studies

A

XPX

Average bond angles (")"

Fable 2 Molecular structures of phosphazenes obtained by diffraction methods

3

4

3

%

n

2 E

$

$

0

td .b 0

Ph

* Estimated deviations in parentheses.

1

C1

P-CI P-Ph 2.03 1.79

116.7 (0.7)

1.576 (0.013)

1.561 (0.014)

1.57

(0.5)

1.563 (0.010)

120

120-0

(0.8)

1-669 (0.010)

118.4

1.961 (0.009)

1.521 (0.013)

111

X-Ray study. p-transStructure confirms earlier assignments. Ring has chair conformation similar to N,P4C18 (above). Ring symmetryN Czn, Estimated deviations G0.1 A for lengths and RCH(OH).CH2P(: O)(OR), or

(14)

RC(0H) * CH2P(:O)(OR),

I

RC(0H). CH2P(:O)(OR),

hydrogen abstraction rate constant of 6.83 x log M-l sec-l was obtained for the reduction of /3-keto-n-propylphenylphosphonate by diethyl ether. Further work on the photoinduced hydrolysis of substituted phenyl phosphates (1 5) has shown l4 that it occurs by attack of water at the 0P(:0)(0H)

OH

I

ON,, I1v

Hzo>

phosphorus atom which is followed by phosphorus-oxygen bond fission. In strongly alkaline solution hydrolysis occurs by attack of hydroxyl ion at the phosphate-substituted carbon atom and is followed by the loss of phosphate anion. Previous work in this field has been summarised and A study has been made of the riboflavin-sensitised dephosphorylation of menadiol diphosphate (1 6 ) and the conclusion reached l6was

WMeWMe oPo,2-

+

oPo32-

riboflavin hv

0,-NaAc-H Ac

0po:(16)

0~0~’(17)

0

+

2 CH,CO *OPO,”l3 l4 la

H. Tomioka, Y . Izawa, and Y. Ogata, R. 0. De Jongh and E. Havinga, Rec. R. 0. De Jongh and E. Havinga, Rec. P.-S. Song and T. A. Moore, J. Amer.

Tetrahedron, 1969, 25, 1501. Trav. chim., 1968, 87, 1318. Trav. chim.,1968, 87, 1327. Chem. Sac., 1968, 90, 6507.

Radicals, Photochemistry, and Deoxygenation Reactions 25 1 that triplet sensitiser produces singlet oxygen which adds onto the phosphate to give a peroxide (17) which decomposes to give the observed products. Photolysis of a-diazophosphine oxides (18) has been found l7 to give products consistent with the initial production of a phosphorus-substituted carbene. /IY

Ph,P(: 0)CPh ---+

N2 (18)

'kz0

[Ph,P(: O)ePh]

II

(O-HH20Bond Insertion)

1

Wolff Rearrangement

Ph I O=P=CPh,

J.

Ph2P(:O)CH(OH)*Ph

PhP(OH)*CHPh2

ll

0 2 Radical Reactions Several further examples (e.g. 19 and 20) 18-20 have been reported of the radical initiated addition of compounds which contain P-H bonds to olefins. It has been reported 21 that at high temperatures and low pressures, 39

0

+

P(H)6 Na'

H,;GNa+

MeoH-t-BuooH> 5 hr. 145-150"

0

n-BuPH,

+ CH2=CHCH2NH2

A,BN

z n-BuPH .CH,CH,CH2NH, 3-

n-BuP(CH2CH,CH2NH2)%

tetrafluorodiphosphine produces difluorophosphino radicals. Tetraphenyldiphosphine (21) has been shown22to react with phenyl-, diphenyl- and triphenyl-acetic acids to give the corresponding hydrocarbons, toluene, diphenylmethane, and triphenylmethane. 17

M. Regitz, W. Anschiitz, W. Bartz, and A. Liedhegener, Tetrahedron Letters, 1968,

18

K. A. Petrov, T. N. Lysenko, B.-Ya. Libman, and V. V. Pozdnev, Khim. Org. Soedin,

3171.

19 20 21 22

Fosfora, Akad. Nauk S.S.S.R., Otd. obshchei Tekh. Khim., 1967,181 (Chem. Abs., 1968, 69, 67,487g). E. E. Nifant'ev and M. P. Koroteev, Zhur. obshchei Khim., 1967,37, 1366 (Chem. A h . , 1968, 68, 39,739b). K . Issleib, H. Oehme, and E. Leissring, Chem. Ber., 1968, 101, 4032. D. Solan and P. L. Timms, Chem. Comm., 1968, 1540. R. S. Davidson, R. A. Sheldon, and S. Trippett, J . Chem. SOC.( C ) , 1968, 1700.

0rganophosphorus Chemistry

252 A

Ph,P *PPh2+ ArCH,C02H

Ph,POCO * CH,Ar + Ph,PH

(21)

Ph,POCO.CH,Ar

----+

-

ArCH,&O ----+ ArkH, + Ph2PH

+ ArCH2d0

Ph,PO

ArbH,+CO ArCH,

+ Ph,P.

Carbon monoxide, and not carbon dioxide, was shown to be a product of the reaction. Hellwinkel has reported 23 that bi~-2,2’-biphenylenephosphorane (22) at room temperature and in a nitrogen atmosphere decomposes to a radical (23) which subsequently gives the phosphine (24) and the phosphorane (25). The radical (23) has a g value of 2.0025 rf: 0.0001 and a

phosphorus hyperfine coupling constant of 17.9 G . The formation of a radical species in the decomposition was further demonstrated by the observation that the use of good hydrogen donors, such as methanol, as solvents led to the formation of reduced products and that the presence of oxygen gave hydroperoxides. The same radical (23) is formed when the lithium compound (26) reacts with iodine.24 A mechanism for the formation of the radical (23) was not suggested. Formation of the 1,l-diphenylphosphabenzole (27) by reaction of the phosphabenzole (28) with diphenylmercury has been reported and the radical (29) suggested as an intermediate.25 Compound (27) was also obtained by reaction of the reduced phosphabenzole (30) with diphenylmercury. The formation of the 23 ?*

2b

D. Hellwinkel, Chem. Ber., 1969, 102, 528. D. Hellwinkel, Chem. Ber., 1969, 102, 548. G. Mark1 and A. Merz, Tetrahedron Letters, 1969, 1231.

Radicals, Photochemistry, and Deoxygenation Reactions 253 phenoxyphosphabenzole ( 3 1) by reaction of (30) with the 2,4,6-tri-t-butylphenoxy radical was taken as evidence for the feasibility of radical (29)

J Ph'

/ \

?h

Ph Ph

being an intermediate. The reaction of phosphabenzoles with mercuric acetate has been found to give 1,l '-diacetoxyphosphabenzoles (32) which are strongly fluorescent compounds.26 It was stated that the reaction occurs via cation radicals which can be detected by e.s.r. spectroscopy. A preparation of the phenoxy radical (33) has been described and its e.s.r. spectrum analy~ed.~'A phosphorus hyperfine coupling constant of 38.56 G was

(32)

Acd

OAc

H+H P(0Pr- i >

I1

0

26

27

K. Dimroth and W. Stade, Angew. Chem. Znt. Edn., 1968, 7,881. A. Rieker and H. Kessler, Tetrahedron, 1968, 24, 5133.

254


reported for the radical. The variations of the spectrum with change in temperature were interpreted as being due to variation of the rate of rotation about the carbon-phosphorus bond. The reactions of a variety of radicals with trivalent phosphorus compounds to give phosphoranyl radicals (R4$ have been reported. Dimethylamino radicals react with alkyl diphenylphosphinites to give NN-dimethyl diphenylphosphinic amide plus alkyl radicals.28 In some cases alkyldiphenylphosphine oxides (34) were formed and it was suggested that they R . +Ph2POR

-

Ph,P(:O)R+R* (34)

had been produced by attack of the alkyl radicals upon the phosphinite. That this reaction can indeed occur was confirmed29by the finding that phenyl radicals, generated from phenylazotriphenylmethane, react with phosphites to give phenylphosphonates. In the reaction with trimethyl phosphite, l,l,1-triphenylethane was produced but some doubt was expressed as to its formation by the trapping of methyl radicals by triphenylmethyl radicals. Photolysis of chloromethyl methyl ether (35)in the presence MeCOCH,Cl

MeCOeH,

(35) MeCOeH2 + (EtO),P

Et' 3- (EtO),P

+ Ci

MeCOCH$(OEt),

-

MeCOCH,P(: O)(OEt),

EtP(:O)(OEt),

MeCOCH@(OEt),

+ Cf

+ E
FH CH,

(half the doublet was hidden by the ring protons at T 7-5-9.9 p.p.m. and the other half appeared at T 11-4-12-4 p.p.m.);6 the chloromethylphosphine (98) shows l J p + ~ 199.4 Hz (geminal and vicinal coupling constants were also positive).120 Geminal PCH coupling constants for a wide range of acyclic compounds have been reviewed by Gallagher.121 A comparison of 2 J p between ~~ the oximinophosphonium salts (21) and the corresponding phosphorane (22) 116

A. H.Cowley and M. W. Taylor, J. Amer. Chem. SOC.,1969, 91, 1026.

W. McFarlane and R. F. M. White, Chem. Comm., 1969, 744, G. A. OIah and C. W. McFarland, J. Org. Chem., 1969,34, 1832. For correlation of Jwp and vco see S. 0. Grim, P. R. McAllister, and R. M. Singer Chem. Comm., 1969, 38. 120 H. Goldwhite and D. G. Rowsell, J. Phys. Chem., 1968, 72, 2666. lZ1 M. J. Gallagher, Austral. J. Chem., 1968, 21, 1197.

11'

118

296


[see this chapter (lA)] shows a fall in magnitude for the latter series.27 ~ for the salts (21), the change is a positive one in Assuming 2 J pis~negative agreement with the low s-character of the bonding orbitals of the Pv atom. A positive shift for the negative geminal coupling constant is also predicted for increases in the s-character of the bonding orbitals of the carbon atom. In agreement, a series of 9-phosphofluorene salts (99) showed that upon

increasing the electronegativity of X the magnitude of JPCHa decreased ~ constant.la2 A similar trend was shown whereas that of J P - M remained by phosphine oxides. These relatively small increases in the s-character of the bonding orbitals of carbon were sufficient to reduce the negative 2 J p to ~ zero. Larger increases in the s-character of the bonding orbitals of carbon are obtained by considering an sp2 hybridised carbon atom; in such tetraco-ordinated phosphorus compounds 2 J p is~almost ~ certainly p o s i t i ~ e . l ~ ~ - l ~ ~ It is generally in the region 5-23 Hz for vinyl ‘phosphine’ oxides la4* la6 decreasing with increase in electronegativity of Z, but

R

aMc \

x-

7, CH,Ph

Ph

lZ2 lZ3

lz4 lz6

c=c \ /

R

/

/C\

Pli2PN H 0

H,

9

C:P--CH,O--C -R \ C0’ H, /

D. W. Allen, I. T. Millar, and J. C. Tebby, Tetrahedron Letters, 1968, 745. T. N. Timofeeva, B. I. Onin, Yu. L. Kleiman, N. V. Morkovin, and A. A. Petrov, Zhur. obshchei Khim., 1968, 38, 1255 (Chem. Abs., 69, 77,353); J. E. Lancaster, Spectrochim. Acta, 1967, 23, A , 1449. W. Hagens, H. J. T. Bos, W. Voskuil, and J. F. Arens, Rec. Trav. chim., 1969, 88, 71. M. P. Williamson, S. Castellano, and C. E. Griffin, J. Phys. Chem., 1968,72, 175. R. M. Lequan and M. P. Simonnin, Compt. rend., 1969, 268, C, 1400.

297

Physical Methods

24-26 Hz for the cyclic oxides (101);1272 J is 0-8 ~ ~Hz for ~ allenic ‘phosphine’ oxides (102) 128 but much larger (16-28 Hz) for the chlorides (102; Y = Cl); and 2 J p is~17-23 ~ Hz for vinylphosphonium salts (103)129 but 28-7 Hz for the cyclic salt (104).127 An exceedingly large geminal coupling constant (40.8Hz) is observed 89 for the cyclopropenylphosphine oxide (105) and even larger constants (47-52 Hz) for the cyclopropenylphosphonium salts (76) [see this chapter (lF)]. The authors of this report predict that these constants will also be ~ the phosphine (106), its oxide, positive. The sign and magnitude of 2 J pfor sulphide, BH, complexes, and metal carbonyl complexes have been disThe results confirm a change in the sign of 2 J p ~ ~ . The assignment of the stereochemistry about a double bond by n.m.r. does not present any difficulties provided the vinyl protons are not obscured or equivalent. The large values of trans-PC=CH coupling constants (usually 28-5 1 Hz) for tetra-co-ordinated phosphorus derivatives of ethylene are typified by 3 J p = ~ ca. 40 Hz for the phosphole- and dihydrophosphole-oxides and sulphides (107) 131 and (108).127The corresponding

P

(EtO),P,

C=C

/

H

,H \

H

cis-PC=CH coupling constants are much smaller (10-20 Hz), but the inclusion of the double bond as part of a heteroaromatic ring (109; Y = 0, S or N) reduces the constants to the range 2-8 H z . ~On ~ the other hand, 3 J p is ~ 11-8 Hz for triphenylphosphine oxide (1 10; Y = Ph).132Jt is interesting that once again, uiz. (102),128the presence of the POCl2 grouping raises the coupling constant and 3 J p is ~ 17.0 Hz for (1 10; Y = Cl).132In the case of the vinylphosphonate (1 1 1 ) 125 the vinyl protons are almost equivalent and it would not have been possible to analyse the spectrum 127 las

lZ9

130

lal 192

L. D. Quin, J. P. Gratz, and T. P. Barket, J. Org. Chem., 1968, 33, 1034. M. P. Simonnin and C. Charrier, Org. Magn. Resonance, 1969, 1, 27. G. Pattenden and B. J. Walker, J . Chem. SOC.( C ) , 1969, 531. E. J. Boros, R. D. Compton, and J. G. Verkade, Znorg. Chem., 1968, 7 , 165. G. Mark1 and R. Potthast, Tetrahedron Letters, 1968, 1755. R. Keat, Chem. and Znd., 1968, 1362.

298


without making use of the coupling to phosphorus. The relative signs of JPHfor vinyl- and allyl-phosphonates, which in general parallels H-H couplings in the same compounds, have been reviewed.133 The configurations of the vinylphosphine oxides (1 10) were assigned 124 by a comparison of the observed 'JHH with the calculated values for the cis- and trans~ for both isomers with isomers. The constants 3JpH as well as 2 J p decrease increase in the electronegativity of Z. It is also of note that for the series of trans-vinyl 'phosphine' oxides (100; Z = OEt), 3JpCCH varies with the Taft constant q of the phosphorus substituent (Y).lZs The coupling constants of tri-co-ordinated phosphorus compounds are complicated by the presence of the phosphorus lone pair. It has been argued134 that the very high s-character of the lone pair of electrons of phosphines will give these electrons little or no directional properties, and on this assumption the phosphorinane (112) has been assigned the con-

a

L

H

-..czQ

: @R

R

R formation with an axial P-H group as shown. This conclusion follows from the appearance of the P-H proton as a triplet of triplets (JHPCH 12 and 2.5 Hz), the larger coupling constant being associated with axial-axial coupling. However, there is considerable evidence 135 that the geminal and vicinal coupling constants to the phosphorus atom of PI'' compounds, i.e. 2 J p ~ and 'JpH, are strongly dependent on the dihedral angle subtended by the C-H bond and the lone pair of electrons on phosphorus. ~ a The signs and magnitudes of the geminal coupling constant 2 J p for number of cyclic phosphines bearing sp3hybridised carbon atoms have been examined.136 A graph has been drawn which indicates JPCHto be at maximum (ca. +27 Hz) when the proton and lone pair of electrons are closest ( a = 0")and at a minimum (ca. - 5 Hz) when the dihedral angle a is 120". These observations support the existence of two coupling terms of opposite signs.135 An example (1 13) of z J p involving ~~ an sp2 hybridised carbon atom has been rep0~ted.l~'The magnitude (42 Hz) is much larger than those above and is in accordance with a positive 'through space' contribution now being reinforced by the normal bonding contribution which has become positive in sign due to the increased s-character of the bonding orbitals of carbon. G . Mavel and R. Mankowski-Favelier,J . Chim. phys., 1967, 64, 1808. J. B. Lambert, W. L. Oliver jun., and G. F. Jackson, Tetrahedron Letters, 1969, 2027. l a b G. Mavel, J . Chim. Phys. Physicochim. Biol., 1968, 65, 1692. la6 J. P. Albrand, D. Gagnaire, and J. B. Robert, Chem. Comm., 1968, 1469; J. P. Albrand, D. Gagnaire, J. Martin, and J. B. Robert, Bull. Soc. chim. France, 1969, 40. 133

la4

299

Physical Methods

The influence of the orientation of the lone pair of electrons on vicinal coupling constants to phosphorus has also been the subject of several papers. The lH spectrum of the ethylenephosphite (1 14) was in agreement 137

F,

FF3

with the twist envelope conformation shown, possessing 3&HA = ca. 2 Hz and 3 J p H ~= ca. 9 Hz. No change occurred in the spectrum up to 100”. Also no inversion was observed for the cyclic phosphonite (1 15) in the temperature range -50 to 160°.138The spatial arrangement of the phosphorus lone pair is considered to be important, the coupling constant being smaller for the axial proton HA (3JpH = 3--4 Hz) than for the equatorial proton HB (3JpH = 11-20 Hz). The existence of syn- and anti-isomers for similar compounds had been deduced from 8p considerations. 139 Note that in the case of vicinal coupling both the ‘through space’ and the ‘through bond’ coupling are varying with the stereochemistry of the molecule. Several examples of vicinal coupling involving sp2 hybridised /3 carbon atoms in cyclic compounds have been reported. Thus 3 J p is ~ 7 Hz for the phosphabarrelene (116; R = Ph or CMe,), 14 Hz for (116; R = Me),14* and 8 Hz for (117).131 These values are considerably smaller than the corresponding constants in trivinyl phosphine (3Jp~trans + 30.2 Hz ; lS7 13*

139

140

P. Haake, J. P. McNeal, and E. J. Goldsmith, J . Amer. Chem. Soc., 1968, 90, 715. D. Gagnaire, J. B. Robert, and J. Verrier, Bull SOC.chim. France, 1968, 2392. A. V. Bogatskii, A. A. Kolesnik, Yu. Yu. Samitov, and T. D. Butova, Zhur. obshchei Khim., 1967, 37, 1105 (Chem. Abs., 68, 95,896). G. Mark1 and F. Lieb, Angew. Chem. Internat. Edn., 1968, 7 , 733.

300


13.6 Hz). The cis coupling constants, involving the ortho-proton in 2-thienyl phosphines 141and aryl p h ~ s p h i n e sare , ~ ~of~ the order 6-8 Hz and the P-H coupling constants of tri-3-thienylphosphine are all smaller than the equivalent H-H and all have the same sign, presumably positive. From these results it appears that the influence of the orientation of the lone pair of electrons is significant for vicinal atoms especially when coupling occurs through a multiple bond. The normal dependency of vicinal coupling constants on the dihedral angle has been used to establish the configuration and conformation of a phosphoniaethane s ~ l p h o n a t e .The ~ ~ ~threo-form (1 18) was identified from its very small PCCH coupling constant. The cyclic phosphate (119) 3Jp33 cis+

\

C0,Me

(1 18)

nl3 HA '

(1 19)

OPh

OPh ( 120)

possessed J P O C3HHz ~ and J P O C21 H ~Hz. The variation of stereochemistry is also important through four By double irradiation of the C H 2 0 protons in (120), 4 J p H ~and 4 J p ~were B found to be 1 and 2.6 Hz respectively. The constants 3JpH and 4 J p ~ normally fall in the ranges 7-1 3 Hz and 0-3-1 -3 Hz, respectively, for the ethyl esters of phosphonic acids.145 Proton exchange has been identified as the cause of the variable-temperature geminal coupling constants for the alkylidenephosphoranes (1 2 l), (122), and (123). The exchange arises from a transylidation process for the (Me),P=CH, (121)

Ph,P=CHCOR (122)

Ph3P=CHC02R (123)

reactive methylenephosphorane (121),14sbut arises from the presence of traces of conjugate phosphonium salts for the acyl and carboalkoxyis 24.5 Hz for very methylenephosphoranes (122) and (123).14' Thus JPCH pure (122; R = Ph) but is collapsed to a broad singlet at 50" in the presence of 1% Ph3kH2COPhX-. 141 142

14s

144 145

146

14'

M. J. Bulman, Tetrahedron, 1969, 25, 1433. H. J. Jakobsen and J. Aa Nielson, Acta Chem. Scand., 1969, 23, 1070. M. A. Shaw, J. C . Tebby, R. S. Ward, and D. H. Williams, J. Chem. SOC.( C ) , 1968, 2795. L. D. Hall and R. B. Malcolm, Chem. and Znd., 1968, 92. M. P. Williamson and C. E. Griffin, J . Phys. Chem., 1968, 7 2 , 4043. H. Schmidbaur and W. Tronich, Chem. Ber., 1968, 101, 604. F. J. Randall and A. W. Johnson, Tetrahedron Letters, 1968, 2841; H. J. Bestmann, H. G. Liberda, and J. P. Snyder, J. Amer. Chem. SOC.,1968, 90, 2964.

Physical Methods

301

Large vicinal coupling constants (34-40 Hz) have been reported for a series of phosphorins (124) 14* and diphospha-s-triazines (1 25 ; Y = Ph, X = Ph or Me).149 For (125; Y = Me) 4JpH was 2-5-3-3 Hz and for (125; Y = NMe,) 5 J pwas ~ 0.45 Hz.

The origin of the exceptionally large four-bond coupling constant ( 4 J P ~ 16 Hz) observed for the ‘phosphine’ (126) 150 may be due to the close proximity of the phosphorus atom and the N-H proton. The N-H doublet becomes a singlet and moves downfield on forming the ‘phosphine’ oxide. A linear relationship has been found between the coupling constants of the allenic ‘phosphines’ (127) and the sum of the inductive and resonance effects of the P substituents;151 4&H (0.5-5 Hz) was negative in most cases but may be positive when the P substituent is a strong donor, e.g. Y = NMe,. The magnitude of 2 J p and ~ 4JpH for the ‘phosphines’ (127) and their oxides varied with temperature and s01vent.l~~ The multiplicity of the proton HA in the phosphine (128) was greater than that expected for the vinyl grouping. The extra multiplicity was

q;? (E tOj,$

HA

(128)

/p

OH / C--cH H, \ CH,OMe

(1 29)

removed by 31P irradiation and is therefore attributed to long-range l z ) . ~A~coupling ~ constant ( 4 J p ~of ) 1.2 Hz is reported coupling ( 5 J p ~ l .H for an interaction through three @-hybrid carbon atoms for the phosphonate (1 29).153 I. Paramagnetic Effects.-The observation of large proton chemical shifts for diamagnetic cations in the presence of certain paramagnetic anions is a very sensitive technique for detecting ion pairing or aggregation in solution. + The n.m.r. spectra of the unsymmetrical diamagnetic cation Ph,PBu in 148 149

150

151 152

153

G . Mark1 and A. Merz, Tetrahedron Letters, 1968, 3611; ibid., 1969, 1231. A. Schmidpeter and J. Ebeling, Chem. Ber., 1968, 101, 3883. R. F. Hudson and R. J. G . Searle, J . Chem. SOC.(B), 1968, 1349. M. P. Simonnin and M. C. Charrier, Compt. rend., 1968, 267, C , 550. A. G. Moritz, J. D. Saxby, and S. Sternhell, Austral. J. Chem., 1968, 21, 2565. C. E. Griffin and S. K. Kundu, J. Org. Chem., 1969, 34, 1532.

302


the presence of paramagnetic anions such as Ph,PNiBr,- or Ph,PCoI,- have been used to estimate inter-ionic distances.15* Comparisons of calculated and observed linewidths and dipolar shifts are consistent with the approach of the cation along the C-3 axis of the anion on the opposite side to the bulky phosphine ligand (130).

i+

Ph,PBu

t 130) Low-field dynamic nuclear polarisation results for phosphorus in different environments are r e ~ 0 r t e d . lThe ~ ~ order of enhancement is found to be: 0

II

(Et0)3P> (EtO),PH > (EtO),P=O which supports an exchange-polarisation interpretation of the molecular encounter. The Overhauser effects on phosphorus oxides, sulphides, and selenides have been measured in CS, in the presence of tributylphenoxyl radicals and large positive enhancements have been observed for the PIII This has enabled the estimation of lJpse (263 f 10 Hz) from the analysis of the 77Sesatellites of P,Se,. 2 Electron Spin Resonance Spectroscopy E.s.r. has been used to investigate the mechanism of the photoisomerisation of triethylphosphite (1 3 1) to diethyl ethylphononate (1 32).ls7 Two signals were observed below 100" corresponding to >P-6 and ethyl radicals. 0

ll

(EtO),P:

(EtO),PEt

(13 1)

(1 32)

At 100" the >P-6 spectrum was replaced by a >6-0 spectrum and at 110" this latter spectrum disappeared leaving the spectrum due to ethyl radicals, with a reduced intensity. ls4 lS6 lS6 lS7

R. H. Fischer and W. D. Horrocks jun., Znorg. Chem., 1968,7, 2659. J. A. Potenza, P. J. Caplan, and E. H. Poindexter, J. Chem. Phys., 1968, 49, 2461. R. A. Dwek, R. E. Richards, D. Taylor, G . J. Penney, and G . M. Sheldrick,J. Chern. SOC.(A), 1969, 935. K. Terauchi and H. Sakurai, Bull. Chem. SOC.Japan, 1968, 41, 1736.

Physical Methods

303

The reaction of alkyl methylphosphinates (1 33) with a-methylbenzylamine and sulphur has been shown to proceed via the stable free radical (1 34) 168 (g value 2.0289) to give the methylthiophosphonate (1 35). 0

II

Me-P-H

I

OR (133)

0

II

Me-P.

I

OR (1 34)

OH

I

Me-P=S

1

OR (1 35)

The reaction of t-butoxy and t-butylthiyl radicals with phosphites and phosphines has also been followed by e.s.r.16@Very clean reactions were observed which can be rationalised in terms of the formation of a fourco-ordinate phosphorus radical, e.g. (136), which fragments to give the

most stable radical. Whereas trialkylphosphites react with t-butoxy and t-butylthiyl radicals to give a t-butyl radical, triallylphosphite gives ally1 radicals,* and triphenylphosphite gives phenoxy radicals.* On the other hand, phosphines give a t-butyl radical only with t-butylthiyl radicals and with t-butoxy radicals the sole radicals produced come from the phosphine, e.g. an ethyl radical from triethylphosphine. By comparing MO calculated and observed e.s.r. isotropic hyperfine splittings, the stereochemistry of the tetrafluorophosphoranyl radical (1 37) has been estimated to be similar to that of a SF4 molecule.lS0 The FlPFl angle is 174 k 5" and the F2PF2angle is 109 k 9". The structure of phosphonium iodide (138) has been determined at liquid nitrogen temperature from the e.s.r. spectrum of I,- centres produced by X-ray irradiation.lsl 3 Vibrational Spectroscopy In addition to the normal extensive use for structural elucidation, vibrational spectroscopy has been applied to stereochemical and conformational problems and the estimation of bonding interactions. Frequencies are expressed in S.I. units mm-l (100 mm-l=l,OOO cm-I). 15*

le0 161

W. A. Mosher and R. R. Irino, J . Amer. Chem. Soc., 1969, 91, 756. J. K. Kochi and P. J. Krusic, J . Amer. Chem. Soc., 1969, 91, 3944. J. Higuchi, J. Chem. Phys., 1969, 50, 1001. C. L. Marquardt, J . Chem. Phys., 1967, 48,994.

* The reaction with butoxy-radicals only was reported.

304


A. Band Assignments and Structural Elucidation.-Analyses of the i.r. and Raman spectra of [2H,]trimethylphosphine,1s2phospl~iranes,spls3 triethylphosphine sulphide, triethylphosphine selenide,ls4 and a series of quasiphosphonium chlorides and antimony hexachlorides ls5have been reported. 1.r. spectra are frequently used to establish the presence of P-phenyl groups166 and the P-phenyl stretching and bending vibrations in the 53-0-10-0mm-1 region have now been assigned.ls7 The i.r. spectra of aromatic ls8 and unsaturated alkyl 160 phosphonates have been studied. It is found that compounds which possess hydroxyl- or amino-groups on a side-chain, e.g. (139),15*or aromatic ring, e.g. (140),168will H-bond, inter.-H\

(1

NCOMe

-CH,C=CH

or intra-molecularly, to the phosphonyl group causing vpo to shift from 124.2-125.8 mm-l down to 120.3-123.0 mm-l. Hydrogen-bonding is also reported for the enol (34) 41 [see this chapter (lC)]. However H-bonding involving acetylenic hydrogen (e.g. 141) did not alter Y ~ = ~ . Further ~ ~ O evidence has been presented which confirms the very low wavenumbers (1 50-1 54 mm-l) of the i.r. bands of carboxylic ester groups bonded to the y position of an allylidenephosphorane such as (68) [see this chapter (lE)]. The i.r. spectra of a series of phosphinimines (142) has been exarninedl7l and VP=N has been identified using 15N isotope effects. Its variation with mass and bonding effects (especially those connected with R1)is discussed. The azophosphinimines (143) 172 and related compounds 173 have also been studied in detail. 1.r. solution spectra of the major product from the reaction of o-aminophenol with hexachlorocyclotriphosphazine (NPCl,), was in accordance with (144).174However, in the solid phase the presence of a broad P. J. D. Park and P. J. Hendra, Spectrochim Acta, 1968, 24, A , 2081. R. W. Mitchell, L. J. Kuzma, R. J. Pirkle, and J. A. Merritt, Spectrochimica Acta, 1969, 25, A , 819. J. R. Durig, J. S. Di Yorio, and D. W. Wertz, J. Mol. Spectroscopy, 1968, 28, 444. 165 A. Schmidt, 2. anorg. Chem., 1968, 362, 129. 106 A. M. Aguiar and M. G. R. Nair, J. Org. Chem., 1968, 33, 579. 167 K. Shobatake, C. Postmas, J. R. Ferraro, and K. Nakamoto, Appl. Spectroscopy, 1969, 23, 12. R. Obrycki and C. E. Griffin, J. Org. Chem., 1968, 33, 632. lBO L. P. Raskina, B. S. El'tsefon, G. S. Radovskii, and A. A. Berlin, Zhur. Priklad. Spektroscopii, 1968, 9,691 (Chem. Abs., 70, 62,574). 170 V. V. Tarasov, Ya. S. Arbisman, N. S. Rylyakova, and Yu. A. Kondrat'ev, Zhur. jiz. Khim., 1968, 42, 2720 (Chem. Abs., 70, 77,083). W. Wiegrabe and H. Boch, Chem. Ber., 1968, 101, 1414. 172 H. Boch, M. Schnoellr, and H. tom Dieck, Chem. Ber., 1969, 102, 1363. 173 H. Boch and M. Schnoellr, Angew Chem. Internat. Edn., 1968, 7 , 636. 17* H. R. Allcock and R. L. Kugel, Chem. Comm., 1968, 1606. 162 163

Physical Methods

305 R3P=NR1 (143)

R3P=N-N=CRI2 (142)

N H,

band at 321-5mm-l and the absence of the NH2 deformation band at 164.0mm-l indicated that (145) may be present. Deuterium studies of ~ YPH occur in the region 95-101 mm-l. (146) 175 indicate that both 8 p and B. Stereochemical Aspects.-1.r. and Raman spectra are commonly used to establish the stereochemistry of fluorophosphoranes. In contrast to microwave spectra [see this chapter (4)] the i.r. and Raman spectra of (147) Me I N: 1 P H / \ F3C . CF3

../

(147)

(148a)

(148b)

favour an equatorial CF, g r 0 ~ p i n g . l Considered ~~ together, these results may indicate the operation of an exchange process. The i.r. spectrum of the aminophosphine (148) has a well-resolved unsymmetrical doublet (346.5 and 343.0 mm-l) in the N-H stretching region in accordance with the presence of unequal amounts of two rotational isomers in thermal eq~i1ibrium.l~~ Overtones were identified at 689.2 and 684-1 mm-l and the spectrum was the same in gas and liquid phases and benzene solution, which rules out doubling due to hydrogen-bonding. Larger groups in place of methyl caused the conformer absorbing at the lower frequency to become more predominant; however, there was no evidence of N-P n-bonding and the results were in accordance with a steric barrier to rotation. 'H N.m,r. confirmed the presence of two rotamers [see this chapter (IE)]. If rapid N inversion occurs, the two conformers could possess the averaged structures (148a) and (148b). 176 176

R. A. Nyquist, Spectrochim. Acta, 1969, 25, A , 47. J. E. Griffiths, J. Chem. Phys., 1968, 49, 1307. N. N. Greenwood, B. H. Robinson, and B. P. Straughan, J . Chem. SOC.( A ) , 1968,230.

306


The i.r. spectra of some acyl phosphines (149) also exhibit two bands, in this case in the 160-180 mm-l region.178 The band at higher frequency S

S

R2PCOR1 (149)

II

II

(MeO),PX (1 50)

H-CGC-CH~OPCI~ (151)

is attributed to the cis-conformer. When the group R1 is larger than methyl or phenyl the cis-conformer is not observed presumably due to steric reasons. There have been further reports of doubling of phosphoryl and thiophosphoryl bands. Restricted rotation about the P-0 bond is believed to account for the doubling in the spectra of phosphorochloridothioates, e.g. (150; X = C1) and (151).179 For trimethyl thiophosphate (150; X = MeO) one of the lines of the Raman v p , ~ doublet disappears on cooling l80 and in (152) one of the two YS-H bands is intramolecularly h~dr0gen-bonded.l~~ In another case, triethyl sulphide, the higher band of a proposed P=S doublet has been assigned to a skeletal stretching vibration.le4 S

II

(R0)ZPSH (152)

The bands due to v p , ~ are reported to be a doublet for a series of aromatic phosphates.lsl The high frequency part of the doublet increases in intensity with temperature due to changes in conformer populations. Contrary to previous reports v p , ~ in 1,3,2-dioxaphosphorinanes(153) is found to be dependent upon conformation.ls2 Carbon tetrachloride 0

( I53a)

Me

(153b)

solutions show two bands in the regions 126.7-129.8 and 130.8-132-2 mm-1 which shift to lower frequencies on the addition of phenol. These bands are assigned to a conformational equilibrium of (153a) and (153b) in which the latter, absorbing at higher frequency, predominates. Phosphoryl groups have been shown, by X-ray diffraction, to occupy an equatorial orientation in the solid state. R. G. Kostyanovskii, V. V. Yakshin, S. L. Zimont, and I. I. Chervin, Izoest. Akad. Nauk S.S.S.R., Ser. khim., 1968, 190, 188 (Chem. Abs., 69, 43,987,43,988). R. A. Nyquist and W. W. Muelder, J. Mol. Structure, 1968, 2465. lSo J. R. Durig, J. S. DiYorio, J. Mol. Structure, 1969, 3179. 181 A. M. Noskov and V. V. Moskovskikh, Zhur. priklad Spektroskopii, 1968, 9, 235 (Chem. Abs., 70, 15,549). lEa M. Kainosho, T. Morofushi, and A. Nakamura, Bull. Chem. SOC. Japan, 1969,42,845.

178

179

Physical Methods

307

Although sodium trimetaphosphate, Na3P309,and triphosphoramidate, Na3(P02NH),, are known to possess C,,symmetry in the solid phase, it is

D,*, symmetry

C,, symmetry

found that, in aqueous solution, the vibrational spectra are in accordance with planar geometry (D3hsymmetry) similar to phosphonitrilic chlorides (PHC1.J3. lg3

C. Studies of Bonding.-The i.r. spectra of triaziridophosphine (154) and corresponding mono- and di-compounds (both PIrrand PI") indicate a lack 0

II

RPXz

0 II RCX

of conjugation other than donation of the N lone pair to P.18* The P - 0 frequencies of trimethylphosphine oxide and a number of its complexes with metal halides have been compared with those of amine oxides.ls6 The shift of vp-0 to lower frequencies upon co-ordination is attributed to a reduction in P-0 T-bonding. The i.r. spectra of a series of phosphinic and carboxylic acid halides (155) and (156) have been compared.186 Although the polarity of the P=O and P-X bonds is little affected compared to that of the C=O bond, an inductive effect raises vpo and reduces the basicity of the oxygen atom. A careful study has been carried out on the force constants relating mainly to P-S bonds. In general the force constants of bonds to phosphorus increase with the percentage s-character of the bond in a magnitude similar to those of C-H bonds.ls7 In the Table the force constants are presented as a percentage of that of the sps hybrid. It was also found that the force constants increased (a) with increased electronegativity of the P-substituents, and (b) on transition from negatively charged ions to neutral molecules. Although vpo increased regularly with the force W. P. Griffith and K. J. Rutt, J . Chem. SOC.(A), 1968, 2331. R. R. Shagidullin and N. P. Grechkin, Zhur. obshchei Khim., 1968,38,150 (Chem. Abs., 69, 66,727). IE6 S. H. Hunter, V. M. Langford, G. A. Rodley, and C. J. Wilkins, J . Chem. SOC.(A), 1968, 305. IE6 A. A. Neimysheva and I. L. Knunyants, Doklady Akad. Nauk S.S.S.R., 1968, 181, 888 (Chern. Abs., 69, 91,515). lE7 J. Goubeau, Angew. Chem. Znternat. Edn., 1969, 8, 328.

lE8 lE4

308


constant ( k p ~ ) vps , did not. This was attributed to strong coupling of the SP stretching vibration with the other stretching vibrations of the molecule Table Bond Hybridisation

Approx. % s

Force constant

Apical Pv Pd 0 61-71

PI1'

PIv

Axial Pv

(SIP

SP3

SP2

10 76-94

25 100

33 101-109

(strong coupling is also reported for triethylphosphine s ~ l p h i d e ) .The ~~~ coupling was largely compensated in the calculation of the force constant kPS,and a plot of k p S us. the sum of the electronegativities of the three substituents gave two straight lines, one for compounds with light substituent atoms (F, 0, N, C) and one for the heavier substituent atoms (Cl, Br, S). It was concluded that the heavier atoms permitted a larger degree of pn-d,, bonding in the P=S bond relative to small atoms with the same electronegativity. The P=S bond orders (1.9-1 -3) calculated from k were significantly less than the P=O bond orders (2-4-1.9). The P=S and P=Se stretching frequencies of the tricyclopropyl phosphine chalcogenides (157) and corresponding tri-isopropyl compounds (158) are

all higher than the values previously reported for tertiary alkyl or aryl phosphine chalcogenides. These observations support a shorter P=Ch bond and could be due to electron withdrawal by the cyclopropyl groups and a steric effect by the isopropyl groups.38 The carbonyl stretching frequencies of the mono-tertiary PI*'complexes 119 and mono- and di-cyclopropylphosphine c o m p l e x e ~ ,(1 ~59) ~ and (160), COCO

I /

co -w- co CO' ; (C- c3 H, l3 (1 59)

fit linear relationships with lJpw. The least basic P'II compound, triphenylphosphite, shows the largest values of vco (195.9 mm-l) and l J p (411 ~ Hz) and the most basic, tributylphosphine, shows the smallest vco (193.4 mm-l) and l J p (200 ~ Hz). The most likely reasons are that the P -+ W u-bond, which transmits the coupling effect, is strengthened by a synergic r-interaction, which is at a maximum for the less basic phosphorus ligands,lls and that the shift of vco to higher frequencies is caused by an increase in

Physical Methods

309

electron-withdrawing power of W resulting from decreased back donation from the metal to the carbonyl ligands. The complex of the tricyclopropyl phosphine possessed vco and Jpw similar to those of diphenylalkylphosphines indicating the former to be a good 7~ N.m.r. studies have indicated that the nuclear charge on P is a dominant factor and therefore the correlation between Jpw and the CO stretching frequency can be interpreted 117 by a mechanism involving a-bonds only. Two reviews have been published la8which include discussions of the information which may be gained from V C O . The stretching frequency V C ~ Cof the bis(dipheny1phosphino)acetylene (161) appears at 209.7 mm-1 in the Raman The low frequency is caused, at least in part, by p,-d, bonding. This 7~ donation to the phosphorus atom is reduced upon complexation or formation of the dioxide or disulphide, as shown by an increase in V C ~ C ,in accordance with a reduction in the phosphine-acetylene interaction. The change in VC=C has been used to estimate the n--bonding ability of a wide variety of metals to the phosphine (161) which acts as a bidentate bridging ligand. The i.r. spectrum of the acetylenic phosphine oxide (162) indicates the presence of a C=C-P interaction but no C=C-P=O interaction. The intensity of v ~ increased = ~ with the electronegative character of P ~ u b s t i t u e n t s . ~ ~ ~

Although weakly basic, due to p,-d, bonding, the diphosphinamine (163) possesses a band at 276-282 mm-l typical of the group )N-R in which the lone pair is not used in bonding.lgl However, the variation of VNH with solvent for spirophosphoranes of the type (164) shows a marked resemblance to pyrrole. This can be interpreted as a result of sp2hybridisation of the N atom andp,-d, N-P conjugation.lg2It was also found that the variation of VPH paralleled l J p ~ .

4 Microwave Spectroscopy and Dipole Moments The microwave spectrum of trifluoromethyltetrafluorophosphorane (147) is consistent lg3with a C,,structure in agreement with the n.m.r. spectrum. However, since the i.r. spectrum indicates a C,, structure it seems reasonL. Vaska, Accounts Chem. Res., 1968,1, 335; E. W. Abei and F. G. A. Stone, Quart. Rev., 1969, 23, 325. lS9 A. J. Carty and A. Efraty, Chem. Comm., 1968, 1559. lBoV. V. Tarasov, Ya. S. Arbisman, Yu. A. Kondrat’ev, and S. Z. Ivin, Zhur. obshchei Khim., 1968,38, 130 (Chem. Abs., 69, 58,713). ID1 J. F. Nixon, J . Chem SOC.(A), 1968, 2689. lea R. Mathis, R. Burgada, and M. Sanchez, Spectrochim. Acta, 1969, 25, A , 1201. IDS E. A. Cohen and C. D. Cornwell, Inorg. Chem., 1968, 7 , 398.

11

3 10


able to conclude that an exchange process occurs in which the CF3 group and fluorine atoms all participate. The stereochemistry of phosphirane (165) has been evaluated from its microwave Of particular H I

c-.

Me

P:

0 II HPF?

"C"' \OEt

note is the repulsion between the &-hydrogens, Hc, and the P-H group. The bond angles indicate that the bonds to P are nearly pure p and the lone pair of electrons nearly pure 3s. The dipole moment was also measured. The microwave spectrum of difluorophosphine oxide (1 66) has been recorded. Its dipole moment was 2.65 f 0.03 D lg5 which is only 0.08 D smaller than the dipole moment calculated by use of the bond moments of PF3, PH3, and F3P0. The dipole moments of the P=S bond decrease in the order SPR3(4.9) > SP(SR)3(3.8) > SPCl, (2.0)> SP(OR)3(1.4), which supports the overriding importance of the inductive effect on the polarity of the P=S bond.lQ8 Dipole moments have been used to establish the stereochemistry of several cyclic compounds. Epoxidation of a phospholene oxide was shown to occur trans to the P=O group to give (167),lg7 and the cyclic phosphates (168) and the corresponding amino-derivatives (1 69) have been found to

possess equatorial P=O groups ;Ig8 also see this chapter (1H and 3B). In the case of the cyclic phosphites (170) advantage was taken of the large dipoles induced by the co-ordination of BH3.1g9The data indicated the methoxygroups to be axial. Together with variable-temperature n.m.r. spectra it was concluded that the phosphite exists in two stereomeric forms (170a) and (170b) in the ratio of 1 : 3.3 at 21" and 1 : 6.9 at - 80". Restricted rotation lg4 lg6

lD6

lg7

lg8 leS

M. T. Bowers, R. A. Beaudet, H. Goldwhite, and R. Tang, J. Amer. Chem. SOC.,1969, 91, 17. L. F. Centofanti and R. L. Kuczkowski, Inorg. Chem., 1968,7, 2582. J. P. Fayet, P. Mauret, M. C. Labarre, and J. F. Labarre, J. Chim. Phys. Physicochim. Biol., 1968, 65, 722. B. A. Arbuzov, A. P. Anastas'eva, A. N. Vereshchagin, A. 0. Vizel, and A. P. Rakov, Izvest. Akad. Nauk S.S.S.R., Ser. khim., 1968, 1729 (Chem. Abs., 70, 29,008). M. Kainosho and T.Shimozawa, Tetrahedron Letters, 1969, 865. D. W. White, G. K. McEwen, and J. G. Verkade, Tetrahedron Letters, 1968, 5369.

Physical Methods

31 1

has been invoked to explain the dipole moments of certain diethyl alkylphosphonates.200 Dipole moments as well as U.V. spectra have been used to study the merocyanine type of mesomerism shown by the phosphinimines (171).201

5 Electronic Spectroscopy The single maximum above 220 nm in the U.V.spectra of vinylphosphines, e.g. A,, 245 nm (log E 2-36) for (172), has been interpreted in terms of promotion of a nonbonded electron on P to the empty T* orbital of the vinyl group.2o2 In this case the bathochromic shift for trans-1,Zvinylene diphosphine (173) (Amax, 263; log E , 6.6) may be attributed to stabilisation

of the excited state by pn--dn conjugation with the PrIratom. The further bathochromic shift of the monoxide of (173) (Amax 273, log E 5-15) and the lack of any maximum above 220 nm for the dioxide of (173) add weight to this explanation. Aroyl phosphonates (174) show bathochromic shifts compared with the corresponding aromatic aldehyde for both the 7~ -+7 ~ *and n T* transitions of the carbonyl group.*OS The interaction (overlap effect), which may involve the phosphorus d orbitals appears to be far less sensitive to rotation around the bond axis than is the pn-pn bonding of a-diketones. An interesting linear correlation between the wavelengths of the intense n -+m* bands and the Hammett substituent constant of Y may be drawn. --f

aoo

K. S. Mingaleva, B. I. Ionin, and A. A. Petrov, Zhur. obshchei Khim., 1968, 38, 560 (Chem. Abs., 69, 76,478). H. Goetz and D. Probst, Annulen, 1968, 715, 1. M. A. Weiner and G. Pasternack, J. Org. Chem., 1969, 34, 1130. K. Terauchi and H. Sakurai, Bull. Chem. Soc. Japan, 1969, 42, 821.

11*

312


The p-tolylphosphonium salts (175) show two bands in the 265-275 nm region which are attributed to lack of conjugation between rings (after Jaffe), +

p-tolyl,PR Hal-

(175) (176)

and a band at 233--234 nm which, from its high intensity, may be due to charge transfer from the halide The spectra of a number of reactive alkylidenephosphoranes have been determined.ll In addition to the phenyl band at 265 nm, methylenephosphorane (Ph,P=CH,) absorbs at 341 nm and this maximum is increased by 35 +_ 2 nm on replacing one a-hydrogen by an alkyl group and by 45 nm on replacing both hydrogens by alkyl groups. Although a 7~ -> T * transition was favoured over a rr -+ d transition, substitution by alkyl groups would raise the rr-bond energy and thereby lower the transition energy in both cases. The electronic spectra of a number of phosphorins (176) have been measured and in addition to a band in the 335-345 region, bands are observed at 394-400 and 513-525 nm.lP8

(178)

(1 77)

Phenylphosphonic acid (177) possesses a band at 270 nm which increases and intensity with concentration of H2S04 and HC104. Benzylin ,A,, phosphonic acid did not show this effect indicating that upon protonation of (177) to give (178) there is increased rr-donation from the phenyl ring towards P.zOs The U.V. spectra of disubstituted phosphazines have been interpreted as exhibiting no absorption bands characteristic of aromatic systems.206 The

( I 79)

two main U.V. bands of the phosphinimines (179) corresponded to bands of p-nitroaniline and diethylarylphosphine indicating that the P=N acts as an aor 2oK *06

M. A. A. Beg and Samiuzzaman, Tetrahedron, 1968, 24, 191. A. Modro, T. Jasinski, and T. A. Modro, Chem. and Ind., 1969, 381. B. Lakatos, A. Hesz, Z . Vetessy, and G. Horvath, Magar kem. Folyoirat, 1968, 74, 468 (Chem. Abs., 70, 15,622).

Physical Methods 313 interrupting link. The pK, values in nitromethane confirmed this interpretation.207

6 Magnetic Rotation and Susceptibilities Further work by French workers208 on magnetic rotation (the Faraday effect) has been directed towards the tetra-alkyldiphosphines (1 80) and the

s s R2P - PR2 ( 1 80)

II

II

R,P--PR, (181)

corresponding disulphides. The rotations due to the P-P and P=S bonds have been calculated. The latter rotations are considerably higher than those of monosulphides (R,P=S) and indicate that the two P=S bonds in (181) are conjugated.208a Work has also been carried out on phosphine-boron complexes 208* including magnetic susceptibility determinations. The magnetic moment of a phosphite cobalt(i1) complex is also reported.200 7 Circular Dichroism and Refraction The cad. curves of methyl phosphine oxides (182) have been compared with those of sulphoxides (1 83) possessing a similar configuration. They

display a remarkable correspondence of Cotton effects. This intersystem matching provides striking evidence that the lone pair on sulphur in the anisyl p-tolylsulphoxides (1 83) is not significantly implied in the generation of the optical active transitions.210

The molar refraction of phosphinous acids (184;R = Et or CH=CH2) has been measured.211 The mean bond refraction of the P1I1-CCphenyl bond in esters of this type is 4.404,similar to that of triphenylphosphine. 2u7

208

209

210 211

T. G . Edel’man and B. I. Stepanov, Zhur. obshchei Khim., 1968, 38, 195 (Chem. Abs., 69, 58,748). (a) D. Voigt, R. Turpin, and M. C. Labarre, Bull. SOC.chim. France, 1968, 3561; ( b ) J. P. Laurent and G. Jugie, Bull. Soc. chim. France, 1969, 26. E. A. Zgadzai, G. P. Naumova, and A. D. Troitskaya, Tr. Kazun Khim-Techno/. Inst., 1967, 96 (Chem. Abs., 69, 100,661). F. D. Saeva, D. R. Raynor, and K. Mislow, J. Amer. Chem. Soc., 1968, 90,4176. F. M. Kharrasova and G. Kamai, Zhur. obshchei Khim., 1968, 38, 359, 617 (Chem. Abs., 69, 43,974,52,215).

314


8 Diffraction X-Ray diffraction has shown that the crystal structure of the reactive alkylidenephosphoranes (185; R = H or Me) has a phosphorus atom with a distorted tetrahedral co-ordination.212 The phenyl groups, which are arranged like a propeller, have unequal rotations about the P-C bonds. The P=CH2 bond length (166 pm) is among the shortest observed so far and is close to the sum of the double bond radii of phosphorus and carbon. The implication of these results on the extent of pn--dn bonding is fully discussed. Ph,P=CR2 (185)

The stereochemistry of the phosphorins (186) 213 and (187) 214 has been determined. Planarity of the phosphorin rings is achieved by expansion of

the PCC and CCC angles to 122-1 26" in order to accommodate the CPC bond angle of 103". The P-C bond lengths (173-175 pm) are intermediate between those of triphenylphosphine (183 pm) and methylene-phosphoranes (1 65-1 68 prn) and compare with those (175-1 76 pm) of the phosphoranylidenephosphetane (188). The planarity of the phosphorin rings and equality of P-C bond lengths are in character with an aromatic

ring. The essentially equal P-C bond lengths2I6and long P-0 bond (201 pm) in (188) indicate that (189) makes an important contribution to the resonance hybrid. A'-Ray diffraction of two other phosphetanes (190) 216 and (191) 217 has been reported. There was no mention of nonplanarity for (190), but in (191) the ring is 24" out of plane with the larger groupings 21p 218 214

J. C. J. Bart, Angew. Chem. Internat. Edn., 1968,7, 730;J. Chem. SOC.(B), 1969,350. J. C. J. Bart and J. J. Daly, Angew. Chem. Internat. Edn., 1968, 7, 811. W. Fisher, E. Hellner, A. Chatzidakis, and K. Dimroth, Tetrahedron Letters, 1968, 6227.

*16 216

p17

G. Chioccola and J. J. Daly, J. Chem. SOC.( A ) , 1968, 568.

D. D. Swank and C. N. Caughlan, Chem. Comm., 1968, 1051. C. Moret and L. M. Trefonas, J. Amer. Chem. Soc., 1969, 91, 2255.

Physical Methods

315 U

Me

occupying the equatorial orientation as shown. Such stereochemical preferences probably play a very important role in the reactions of these compounds.66 The CPC bond angle in the ring was very similar (82.5') for (190) and (191), but it is difficult to believe that the ring bond lengths differ by ca. 10 pm. An unusually short hydrogen bond (249 pm) from the proton of the phosphinic acid grouping to the water of hydration is also reported. Although the highfield chemical shift of the phosphorus atoms (+ 3-5 p.p.m.) of the hexaphenyl analogue of (192) is thought to be due to delocalisation, the hexa-alkyl compound (192; X = Me, Y = Et) possesses P-C and C=C bond lengths of 182 and 130 pm respectively, indicating a diene structure. As expected the ring is planar.218

5,10-Dihydro-5,10-diethylphosphenanthrene is known in two isomeric forms, assigned cis- and trans-geometries. It is now found that the crystal structure of an arsenic analogue has a cis 'butterfly' conformation which adds weight to the earlier conclusion that the major isomer of the phosphorus compound has the cis-configuration (193).210 The crystal structure of a copper derivative of the triphenylmethylphosphonium cation (194) showed the cation to be a nearly perfect tetrahedron 220 with the phenyl rings in the expected propeller arrangement. X-Ray diffraction shows that the aminocyclophosphazine hydrochloride (195) has a distorted boat conformation221and confirms that the ring nitrogen atoms are the stronger basic centres. The stereochemistries of the non-geminally substituted phosphazines (1 96) and the corresponding 218 219

R. Majeste and L. M. Trefonas, J. Heterocyclic Chem., 1969, 6, 269. 0. Kennard, F. G. Mann, D. G. Watson, J. K . Fawcett, and K. A. Kerr, Chem. Comm., 1968,269.

220

221

R. M. Wing, J. Amer. Chem. SOC.,1968, 90, 4828. N. V. Mani and A. J. Wagner, Chem. Comm., 1968, 658.

ll**


316 C!H

+

I

Ph'

Ph,PMe PI1

(194)

(195)

tetramethylamino-compound have been determined and show that substitution of C1 by NHMe proceeds with retention of configuration and causes a considerable reduction in the P-N-P bond angle.222 The ring system of the cyclo-octaphosphazine, [NP(OMe),],, consists of two approximately planar and parallel six-atom segments joined by a step as shown in (197).223The molecular structure as a whole supports earlier conclusions as to the importance of the T system involving orbitals with axes perpendicular to the ring.

(197)

=

P

The crystal structure of the cobalt(rr) chloride and copper(@ chloride complexes of the octamethylcyclophosphazine cation (NPMe2)pH+ shows an alternation of P-N bond lengths which is independent of the conformation of the ring. This is interpreted in terms of the approximate equality of the components of a dual system.^^* Electron diffraction indicates a pyramidal structure for disilylphosphine with an SiPSi angle of 96-97°.225 This is in contrast to earlier evidence for a planar heavy-atom skeleton. 9 Electrochemical Studies The half-wave potentials of phosphonium salts have been determined by rapid polarography.226 The more positive waves corresponded to the formation of PI1' compounds and the more negative waves corresponded 222

223 224

226 226

G. J. Bullen, P. R. Mallinson, and A. H. Burr, Chem. Comm., 1969, 691. N. L. Paddock, J. Trotter, and S. H. Whitlow, J. Chem. SOC.(A), 1968, 2227. J. Trotter, S. H. Whitlow, and N. L. Paddock, Chem. Comm., 1969, 695. B. Beagley, A. G. Robiette, and G. M. Sheldrick, J. Chem. SOC.(A), 1968, 3002. L. Horner and J. Haufe, J. Electroanalyt. Chem. Interfacial. Electrochem., 1969, 20, 245.

Physical Methods

317

to the degradation of tertiary and secondary compounds. The position of the half-wave potentials were influenced by the measuring conditions. Polarography, cyclic voltammetry, and coulometry have been used 227 to study the electroreduction of triphenylphosphine and its oxide. Ph,P:+e

-

Ph,b:-

A

Ph,FHfPh*+A-

J.

0

.1

II Ph2PH Ph-Ph

The conductivity of tungsten chloride 228 and rhodium chloride 229 biphosphine-carbonyl complexes in nitromethane and acetonitrile respectively, confirmed their ionic character and showed them to be 1 : 1 electrolytes. However, chloroform solutions of the former were non-conducting. The semiconductor properties of the adducts of 00-dialkyl dithiophosphates and amines were confirmed by their increase in conductivity with In contrast to earlier experiments but in confirmation of the 31P n.m.r., dichlorotriphenylphosphorane (1 98) dissociates as shown. It does not ionise to P h , k l and Ph,PCl, since the addition of tetraethylammonium chloride did not produce an inflection in the conductance.231 -

+

Ph3PC12 ,~ (198)

+

Ph3PCI C r

The paper electrophoresis of phosphorus oxyacids, phenyl compounds, and hexose or inosine phosphate esters has been examined and a method of estimating dissociation constants and molecular weights has been devised.232 10 Mass Spectrometry

The mass spectra of phenyl, diphenyl, triphenylpho~phines,~~~ and the cyclopentaphosphine (199) 234 all contain an ion at m/e 108 attributed to the phenylphosphinidene ion. This ion is also present in the spectra of most phenyl-substituted phosphine oxides, phosphonium salts, and 236 but are not observed for the halogen compounds, e.g. ylide~,~,~9 227

228 229 230

231 232

K. S. V. Santhanam and A. J. Bard, J. Amer. Chem. SOC.,1968,90, 1118. P. M. Boorman, N. N. Greenwood, and M. A. Hildon, J . Chem. SOC. ( A ) , 1968,2466. J. T. Mague and J. P. Mitchener, Inorg. Chem., 1969, 8, 119. L. Almasi, A. Hantz, E. Weissmann, and E. Hamburg, Rev. Roumaine Chim., 1967,12, 1269 (Chem. Abs., 69, 2399). G . S. Harris and M. F. Ali, Tetrahedron Letters, 1968, 37. Y . Kiso, M. Kobayashi, Y . Kitaoka, K. Kawamoto, and J. Takada, J . Chromatog., 1968, 36, 215.

233

234

B. Zeeh and J. B. Thomson, Tetrahedron Letters, 1969, 111. U. Schmidt, I. Boie, C. Osterroht, R. Schroer, and H. F. Grutzmacher, Chem. Ber., 1968, 101, 1381.

236 236

D. H. Williams, R. S. Ward, and R. G. Cooks,J . Amer. Chem. SOC.,1968, 90,966. R. G. Cooks, R. S. Ward, D. H. Williams, M. A. Shaw, and J. C. Tebby, Tetrahedron, 1968,24, 3289.

318

Organophosphorus Chemistry Ph,PO,Ph,pfRX-, Ph,P=CY,

II Ph,P,Ph2PH,PhPH,

____f

Ph

PhP 108 +

iiije

t---

PhP/ p \ P Ph \

I

PhP- PPh

PhPC12.233Loss of chlorine radicals occurs more readily and in the case of the fluorophenyl compound (200) loss of the aryl ring is also ready.36 A wide variety of compounds, possessing at least two phenyl rings attached to phosphorus, give molecular ions (201) which undergo a bondforming rearrangement and produce abundant M - 1 ions due to the stable phosphafluorenyl ion (202). It has been shown235 for (201; Y = Ph,

X = 0, S , CH2) that the cyclisation occurs without scrambling of the phenyl protons. However, for triphenylphosphine, the major fragmentation pathway involves loss of a phenyl group with scrambling of the phenyl protons with the eventual formation of (203), an ion common to the spectra of most triphenylphosphorus compounds. This ion is not prominent in the spectra of the diphenylphosphinate (201; Y = HO or RO, X = 0). In this case the major fragmentation pathway involves the loss of water or alcohol from the corresponding phosphafluorenyl ion (202) to give the phosphinylium ion (204).237 The cyclic phosphinate (205) also loses water or alcohol to give an analogous ion but the keto-derivative (206) tends to form heteroaromatic ions such as (207).

237

P. Haake, M. J. Frearson, and C. E. Diebert, J. Org. Chem., 1969, 34, 788.

Physical Methods

319 OH

0

0

(206)

(207)

The mass spectra of alkylidenephosphoranes stabilised by CN, C02R,and COR groups have been For the acyl methylenephosphoranes (208) loss of an alkyl or aryl radical was always predominant, but for the carboalkoxy methylenephosphoranes (209 ;Z = CN or C02Me)cyclisation to (210) competed with the loss of methoxy- and carbomethoxy-groups. COR

Ph,P=C

/

\

14

(208)

0-00-0 /

/

/p Ph / P\CH CO, M e

Ph

/

CO, Me

/

Ph,P =C / Z

\C=c=o /

Z

Z

(2 10)

(21 1)

(209)

The transfer of an aromatic hydrogen to a more labile environment is confirmed by the ready loss of methanol from (210) to give (211). When the a-carbon atom already possesses a hydrogen atom loss of methanol can also occur before cyclisation. In the case of the ethyl esters (212) competition arises from a process in which the a-carbon atom gains a hydrogen atom via the cyclic loss of CO, and C2H4;further fragmentation follows a pathway characteristic of Ph,P=CHZ.

Ph2P-BPh2 (214)

The bis(dipheny1phosphino)rnethane (213) is reported 238 to show the migration of phenyl groups to give Ph,P+ cations which fragment in the usual way. Low-abundance ions corresponding to Ph,P+, PhaB+, 238

R. Colton and Q. N. Porter, Austral. J. Chem., 1968, 21, 2215.

320


Ph4P+,and Ph4BP+appear in the spectrum of (214). The dominant pathway involves fission of the P-B bond.239 The mass spectra of the compounds (215 ) have been cited as evidence for their oxyphosphorane structure^.^^ In contrast to the corresponding oximinophosphonium salts, see (21), this chapter (lA), the spectra of the oxyphosphoranes showed no fragment ions above Bu3PO+ indicating a cyclic structure with a preformed P-0 bond.

s

R

Ar

SII (RO) P -N

H

(216)

( 2 15)

(217)

The molecular ion of phosphoramidothioates such as (216) showed loss of SH with cyclisation to form ions, e.g. (217).240This type of fragmentation was less important in the chloridothioates (218), loss of Cl, RO, and other radicals providing an easier pathway. The diphenylphosphorothioates (219) showed the expected P=S + P=O isomerisation but aryl migration to sulphur predominated over alkyl migration. S

II

S

II

(R0)2PCl

ROP(OPh),

(218)

(2 19)

Initial fragmentation by loss of CF3 and in some cases CF, is reported for the trifluoromethyl compounds (220-223). Extensive rearrangement

to species containing P-F bonds was also observedZ4l for the PIrr compounds. Electron bombardment of phosphazines causes similar fragmentations to those produced by pyrolysis.242The most abundant ions in the spectra of P3N3C16and P4N4C18occur from loss of C1. The dominance of evenelectron ions over odd-electron ions is striking.243Chloro-, ~ ~ U O I -and O-,~~~ 239 240 241

212 243

244

E. W. Abel, R. A. N. McLean, and I. H. Sabherwal, J. Chem. SOC.(A), 1968,2371. R. G. Cooks and A. F. Gerrard, J. Chem SOC.(B), 1968, 1327. R. G. Cavell and R. C. Dobbie, Inorg. Chem., 1968,7, 101,690; R. C. Dobbie, L. F. Doty, and R. G. Cavell, J. Amer. Chem. Soc., 1968, 90, 2015. B. Zeeh and R. Beutler, Org. Mass Spectrometry, 1968, 1, 791. C. D. Schmulback, A. G. Cook, and V. R. Miller, Innorg. Chem., 1968, 7 , 2463. C. E. Brion and N. L. Paddock, J. Chem. SOC. ( A ) , 1968, 388, 392.

Physical Methods

321

mixed chlorobromo-phosphonitriles 245 are reported to fragment to cyclic and linear ions. Appearance potentials have been used to estimate the energy of P-P bonds of diphosphine 246 and diphosphine tetrachloride and t e t r a i ~ d i d e . ~ ~ ' 11 pK and Reaction Rate Studies

The majority of kinetic studies has been directed towards the investigation of reaction mechanism. The mechanism of the acid and base hydrolyses of p-nitrophenyl phosp h a t e ~ , with ~ ~ *or without the presence of cationic micelles, has been studied. Also the rates of acid hydrolysis of methylphosphonates have been compared with the ageing of phosphorylated c h o l i n e s t e r a ~ e . The ~ ~ ~ factors which lead to reactivity differencesfor acyclic and cyclic phosphoramidites 250 and acyclic, mono- and bi-cyclic p h o s p h i n a t e ~have , ~ ~ ~been investigated by comparing rate constants and enthalpies. The effect of free radical inhibitors and initiators on the rate of attack of triethylphosphite on carbon tetrachloride has been used to show that the reaction may proceed via heterolytic or homolytic

The transmission of polar effects in phosphinimines (224) has been studied by correlating alkylation rate constants and pK, values with Hammett constants.253 The best correlation is obtained with the nucleophilic substituent constant 0-. Also a successful correlation of ionisation constants and rate constants of benzylations has been achieved using the extended Hammett equation and the 01 and OR substituent constants defined for carbon subst ituent s.254 245

248

G. E. Coxon, T. F. Palmer, and D. B. Sowerby, J. Chem. SOC.(A), 1969, 358. N. N. Grishin, G. M. Bogolyubov, and A. A. Petrov, Zhur. obshchei Khim., 1968, 38, 2683.

247 248

249

A. Finch, A. Hameed, P. J. Gardner, and N. Paul, Chem. Comm., 1969, 391. C. A. Bunton and S. J. Farber, J. Org. Chem., 1969, 34, 767; C. A. Bunton and L. Robinson, J. Org. Chem., 1969, 34, 773, and references therein. J. I. G. Cadogan, D. Eastlick, F. Hampson, and R. K. Mackie, J. Chem. SOC.(B), 1969, 144.

26e

251 252

253 254

R. F. Hudson and R. J. G. Searle, . I Chem. . SOC.(B), 1968, 1349; R. F. Hudson and A. Mancuso, Chem. Comm., 1969, 522, and references therein. R. Kluger and F. H. Westheimer, J. Amer. Chem. SOC.,1969, 91, 4143. R. E. Atkinson, J. I. G. Cadogan, and J. T. Sharp, J. Chem. SOC.(B), 1969, 138. V. A. Gilyarov, A. M. Maksudov, B. A. Korolev, B. I. Stepanov, and M. I. Kabachnik, Izvest. Akad. Nauk S.S.S.R.,Ser. khim., 1968, 7 , 1656 (Chem. Abs., 69, 95,815). M. Charton, J. Org. Chem., 1969, 34, 1877; see also M. Charton, and B. I. Charton, J. Org. Chem., 1969, 34, 1882.

322


The pK, values of a number of phosphines 255 and phosphine oxides 256 have been measured for solutions in nitromethane by potentiometric titrations. 12 Cryoscopic Studies

Pyridine solutions of copper(1) hydride and trialkyl or triarylphosphines have been studied by freezing-point depression. Cryoscopic titration curves for the more basic phosphines show a molality minimum which corresponds to the formation of R,P(CUH),.~~~ 256

B. A. Korolev and B. I. Stepanov, Zzuest. V.U.Z.,Khim. i khim. Tekhnol., 1968, 11,

256

B. I. Stepanov, B. A. Korolev, and A. I. Bokanov, Zhur. obshchei Khim., 1969,39,316,

a57

J. A. Dilts and D. F. Shriver, J . Amer. Chem. SOC.,1969, 91, 4088.

1193.

321.

Author Index Aa Nielson, J., 300 Abdo, W. M.,82 Abel, E. W., 64, 65, 309, 320

Abramov, V. S., 127 Acs, G., 145 Adam, A., 145 Adam, W., 19,258 Adams, W. G., 268 Addison, C. C., 61 Afanas’ev, Yu. N., 58 Agawa, T., 267, 272 Ageeva, A. B., 82 Aguiar, A. M., 4, 29, 364 Aguirre, A. R., 159 Aharoni, A. H., 115 Ahmed, F. R., 239 Akhmetzhanov, I. S., 90 Akjba, K., 178 Akiba, K.-Y., 178 Akitt, J. W., 273 Aksnes, G., 78, 136, 186 Albrand, J. P., 298 Albright, J. D., 154 Albriktsen, P., 78 Aleksandrov, V. N., 129 Alekseeva, T. I., 72 Alekseeva, V. G., 204 Alexander, E. S., 23, 291 Ali, M. F., 317 Alimov. M. P., 103 Alimov; P. I., 103 Allcock, H. R., 54, 229, 231. 236. 238. 304

Allen,’ C. W., 233, 276 Allen, D. W., 24, 29, 296 Almasi, L., 91, 110, 117, 137, 317

Alpha, S. R., 136 Altwerger, L., 145 Ambrus, J. H., 275 Anastas’eva, A. P., 140,310 Anatol, J., 164 Anderson, D. G., 75 Ang, H. G., 23, 54, 60 Angyal, S. J., 171, 172 Anh, N. T., 112 Anschel. M.. 50 Anschutz, W., 74,251 Anthoni, U., 14 Appel, R., 207, 211, 216, 223, 276

Aquila, H., 166 Araki, Y., 162 Arbisma. Y. A. 127 Arbisman, Ya. S., 304,309 Arbusov, B. A., 82, 140, 3 10

Arcoria, A., 85

Arens, J. F., 69, 76, 296 Arkhipova, 0. G., 126 Arnup, P. A., 197 Arpke, C. K., 103 Arzoumanidis, G. G., 61 Ashe, A. J., 35 Asinger, F., 12 Asunskis, J., 193 Atkinson, M. R., 152 Atkinson, R. E., 88, 261, 32 1

A-u-Rahman, 272 Avison, A. W. D., 100 Ayres, J. S., 82 Azhikina, Yu. V., 238 Babkina, E. I., 247 Backes, P., 55 Baehler, B., 114, 204 Baer, E., 164 Bluerlein, E., 166 Baird, M. C., 197 Baker, B. R., 153 Baker, D. A., 206 Balint, A., 35 Ball, W. J., jun., 159 Balzer, W.-D., 23, 290 Banderova, L. V., 133 Baranov, Yu. I., 5 5 Barber, G. A., 161 Bard, A. J., 255, 317 Barket, T. P., 70, 297 Barkulis, S. S., 162 Barlow, C. G., 294 Barlow, M. G., 290 Barnes, W. H., 239 Barrans, J., 90 Barreiro, A. J., 236 Barsukov, L. I., 185 Bart, J. C. J., 34, 197, 314 Bartashiv, V. A., 238 Bartz, W., 74, 251 Basco, N., 247 Basedow, 0. H., 60 Basi, J. S., 275 Basu, H., 164 Battioni, J. P.,277 Baudler, M., 55 Beachem, M. T., 10 Beagley, B., 316 Beaudet, R. A., 310 Beck, P., 33, 247 Becke-Goehring, M.,220 Beg, M. A. A., 312 Beissner, G., 75 Bell, H. M., 133 Bell, J. P., 143 Bel’skii, V. E., 97, 105, 107, 111, 126, 136

Belykh, S. I., 238 Bemiller, J. N., 109 Benda, H., 66 Benkovic, S. J., 158 Bennett, M. A., 1 Benschop, H. P., 131 Bentrude, W. G., 53, 93, 119, 249, 254, 255

Bercz, P. J., 207 Berdnikov, E. A., 82 Berecoechean. J.. 164 Berg, H., 75 Bergelson, L. D., 184, 185 Bergenthal, M. D., 112 Berger. J. E.. 107 Bergesen, K.; 129, 136 Berglund, D., 21 Bergmann, E. D., 123 Berlin, A. A., 304 Berlin, A. J.. 229 Berlin, K. D., 121 Bermann, M., 216, 220, ~~

230

Berner-Fenz, L., 178 Berninger, C. J., 197 Berseck, C., 129 Bertini, I., 3 Bertrand, R. D., 294 Bestmann, H. J., 32, 61,

62, 180, 181, 182, 186, 187, 190, 193, 195, 196, 265, 276, 288, 300 Betyeva, E. S., 87 Beutler, R., 320 Bezzubov, A. A., 184 Bezzubova, N. N., 105 Bhatia, S. B., 20, 45, 265 Bjckelhaupt, F., 34 Biddlestone, M., 234 Bigler, A. J., 45, 53, 120 Bilbo, A. J., 236, 237 Bindra, A. P., 201 Birum, G. H., 186, 197, 198 Blackburn, D. E., 268 Blackburn, G. M., 125, 142,260 Blaser, B., 207 Bliznyuk, N. K., 103 Bloch, B., 256 Block, H.-U., 4 Bloor, J. E., 269 Boch, H., 304 Boche, J., 258 Bochwic, B., 117 Bock, H., 207, 218 Bodkin, C., 119 Bohm, R., 217,221 Bohme, E., 190

Author Index Bogatskii, A. V., 299 Bogdanova, I. V., 2 Bogolyubov, G. M., 260, 231

JL1

Boie, I., 256, 317 Bokanov, A. T., 322 Bond, A., 21 Bond. R. P. M.. 175 Bondinell, W. E., 190 Boorman, P. M., 317 Boozer, C. E., 107 Bordwell, F. G., 17 Borodin, P. M., 279 Borodulina-Shvetz, V. I., 157

Boris, E. J., 297 Borowitz, 1. J., 15, 16, 50 Bos. H. J. T.. 69. 296 Boter, H. L.,'131 BouIton, A. J., 267, 272 Bowers, M. T., 310 Boyd, D. B., 41, 105, 150, 283 Boyer, J. H., 272 Boyer, P. D., 168 Bracha, P., 115 Brazier, J. F., 223 Brecht, H., 218, 274 Breslow, R., 109 Brewer, D., 259 Brinckman, F. E., 247 Brinigar, W. S., 167 Brion, C. E., 220, 320 Brook, A. G., 75 Broom, A. D., 154 Brophy, J. J., 24 Brown, D. H., 95 Brown, D. M., 98,100,105 Brown, M. J., 125, 142 Bryson, J. G., 38 Buddrus, J., 176 Bude, D., 121 Burger, H., 64 Bugerenko, E. F., 126 Bullen, G. J., 239, 316 Bulman, M. J., 300 Bunton, C. A., 107, 108, 109, 167, 321 Buono, G., 131 Burg, A. B., 57, 275 Burgada, R., 17, 51, 90, 309 Burr, A. H., 239, 316 Buslaev, U. A., 237 Butova, T. D., 299 BUZBS,A,, 78 Cadogan, J. I. G., 88, 123, 125, 126, 261, 267, 269, 272, 321 Caesar, F., 290 Cameron, T. S., 102 Campbell, I. G. M., 77 Campbell, T. W., 87, 133 Caplan, P. J., 302 Caputo, J. A., 70, 279 Cargioli, J., 290 Carles, J., 19, 261 Caropreso, F. E., 56 Carrie, R., 125, 205

Carty, A. J., 309 Caserio, M. C., 289 Casev. J. P.. 8. 292 Caspari, G.; 81, 255 Castellano, S, 296 Castro, B., 17 Catsoulacos, P., 206 Caughlan, C. N., 79, 314 Cavell, R..G., 320 Centofanti, L. F., 310 Cerfontain, H., 186 Chabrier, P., 114, 115 Chacko, G. K., 164 Chahine. H.. 30. 34 Chan, S.', 2, '274' Chan, T. H., 7 Chang, B. C., 60, 280 C h a m C. H.. 8 Chanrey, J. D'., 158 Chapman, D., 291 Charbonnel, Y., 90 Charrier, C., 297 Charrier, M. C., 301 Charton, B. I., 321 Charton, M., 321 Chatt, J., 293 Chatterjee, A. K., 170 Chatzidakis, A., 314 Chen, E. H., 265 Chen, W. Y., 154 Cheng, C. Y., 102 Cherbuliez, E., 114 Cherkasov, R. A., 119 Chernyavskaya, T. L., 238 Chernyshev, E. A., 126 Chervin I. I 14 306 Cheung,' K. W., 590 Chickos, J., 70, 131 Chioccola, G., 314 Chistokletov, V. N., 30,77 Chiu, Y. Y. H., 135 Chivers, T., 225, 233 Chizhik, V. I., 279 ChlBdek, S., 147, 156 Chodkiewicz, W., 277 Chopard, P. A., 9, 16, 85, 133 Chorvat, R. J., 8, 27, 70, 28 1 Christol, H., 126 Chu. S.-K.. 236 Churi, R. H., 129 Claeys, E., 278 Clark, V. M., 85, 98, 99, 133. 159. 166. 168 Claunch, R. T.,' 121 Clutter, R. J., 70 Cohen, E. A., 309 Cohen. J. S.. 159 Cohen; M. P., 193 Cohn, K., 3 Colclough, R. O., 237 Colton. R.. 319 Commenges, G., 280 Compton, R. D., 297 Cook, A. F., 152 Cook, A. G., 220, 320 Cook, R. D., 136 Cooks, R. G., 118, 317, 320

Cooper, T. A., 167 Cordes, E. H., 157 CO:,",~, E. J., 99, 173, 206, LJ7

Corfield, J. R., 281 Corfield, P. W. R., 17 Cornforth, J. W., 173 Cornwell. C. D.. 309 Costisella, B., 129, 205 Cotson, S., 239 Cottrell, W. R. T., 255 Coulter, C. L., 161 Couret, C., 65 Cowley, A. H., 1, 278, 279, 283, 286, 289, 292, 295 Cox, J. W., 239 Coxon, G. E., 220, 239, 321 Cram, D. J.. 131 Cramer, F.,'99, 141, 142, 143, 147, 172 Creasy, W. S., 197, 262 Cremer, S. E., 8, 27, 70, 28 1 Crews, P., 288 Cristan, H.-J., 75 Crofts, P. C., 68, 257 Crombie, L., 185, 204 Crosbie. K. D.. 95 Crouse,'D. M.,' 197, 288 Cullen, W. R., 11 Curry, J. D., 130 Cymerman Craig, J., 112 Czysch, W., 225 Dahl, O., 14 Dahm, K. H., 206 Daly, J. J., 34, 314 Daniel, H., 54 Danion, D., 125, 205 Daragan, N. K., 128 Darling, S. D., 18 Das, B. P., 123, 268 Davidsohn, W. E., 1 Davidson, R. S., 72, 251, 254 Davis, D. W., 8 Davis, M., 31 Davis, M. I., 239 Davis, R. A., 197 Dawson, D. S., 11 Dawson, J. W., 294 Deamer, D. W., 165 De'ath, N. J., 28 de Boer, T. J., 207 Degani, C., 109 Deiter, J. A., 90 Deiters, R. M., 281 Deiters, S. R. M., 41 De Jongh, R. O., 250 De Ketelare, R., 278 de Koe, P., 34 De Koning, A. J., 165 Demarcq, M. C., 88 de Moura Campos, M., 57 Denney, D. B., 60,258,280 Denney, D. Z., 60,258,280 Dennis, E. A., 135 Denny, K., 231 Denzel, T., 196

Author Index Derkach, G. I., 87, 103, 209. 215. 217 Derkach. N. Ya.. 23 Deryabin, A. V.,-238 Desai, N. B., 45, 105, 120 Desai. V. B.. 235 De Selms, R’. C., 122, 265 De Sombre, E. R., 80 Dever. J. L., 205 Devillers, J.; 120 Dewar, M. J. S., 286, 289 Dhahival. P. S . . 11 Dhar, M: M., i48 Dheer, S. K., 147 Diebert, C. E., 136, 139, 318 Dietsche, W., 59, 82, 122 Dighe, P. K., 157 Digorio, J. S., 304 Dilts, J. A., 322 Di Mari, S. J., 190 Dimroth, K., 34, 35, 36, 253. 314 Di Sabato, G., 111, 158 Dixon, M., 239 Di Yorio, J. S., 306 Dobbie, R. C., 320 Doca. N.. 78 Dorges, J., 247 Dorges, L., 33 DolejS, L., 175 Dolgushina, I. Yu., 216 Donninger, C., 117 Dorn, C. R., 204 Doty, L. F., 320 Douglas, C. M., 237 Downie, I. M., 16, 17, 88, 262 Drawe, H., 81, 255 Driscoll, J. S., 276 Drozd, G. I., 45, 63, 284, 294 Dubov, S. S., 284 Dull, K., 217 Iunitz, J. D., 40, 105 3urig, J. R., 304, 306 Dutting, D., 154 3wek, R. A., 302 Dyadyusha, G. G., 219 Iyatkin, B. L., 272 Iyatlova, N. M., 126 East, J. L., 157 Eastlick, D., 126, 321 Eaton. D. R.. 280 Ebeling, J., 218, 221, 223, 274, 301 Eckstein, F., 145, 147, 149, 150. 152 Edel’man, T. G., 245, 3 13 Edmundson, R. S., 94,119 Edwards, J. A., 190 Efraty, A., 309 Efremova. M. V.. 97. 111.

Elix; J. A.; 201 Elleman, J., 5 , 61

325 Ellzey, S. E., 10 El-Nigumi, Y. O., 23 El’tsefon, B. S., 304 Emel’yanov, V. I., 129 Emmick, T. L., 73 Emmons, W. D., 81, 123 Emoto, T., 77 Emslev, J., 219. 225 Engel,-R. R.,I14 Englert, L. F., 165 Epstein, W. W., 173 Eraut. M. R.. 166 Ermolaeva. M.V.. 111 Errington, ‘W., 273 Ertel, H., 75 Espejo, O., 114 Evans. W. J.. 172 Evdakov, V. ’P., 97 Evplov, B. N., 133 Evstaf’ev, G. I., 90 Evtikhov, 2. L., 82 Fackler, J. P., jun., 293 Faltus, H., 287 Farber, S. J., 107, 321 FarkaS. J.. 175 Farley,‘C.’ E., 260 Faure, M., 127, 164 Fawcett, J. K., 315 Fayet, J. P., 310 Feaguson, E., 158 Feakins, D., 245 Fedin, E. I., 6 Fedorova, G. K., 71 Feistel, G. R., 230 Feldt, M. K., 276, 235 Fendler, E. J., 108 Fenz, L., 178 Ferraro, J. R., 304 Ferrere, M. J., 115 Feshenko, N. G., 72 Fetizon, M., 112 Fetter, N. R., 237 Fife, T. H., 111 Filatova, 1. M., 232 Fild, M., 55, 278 Filippov, 0. F., 55 Finch, A., 321 Finer, E. G., 292 Fischer, R. H., 302 Fischer, W., 34, 314 Fish, R. H., 289 Fishwick, S. E., 24, 27 Fisichella, S., 85 Fitchin, J. A., 293 Fitzsimmons, B. W., 214 Fleming, I., 112 Fletcher. H. G.. iun.. 170 Fletcher; I. J., 267 ’ Flint, J., 24, 27 Fliszar, S., 19, 261 Flitsch, W., 187 Flook, A. G., 291 Fluck, E., 219, 280 Forster, H., 14, 15, 85, 121 Fogel, J. S., 27 Foldi. V. S.. 87 Foote, C. S.’, 109 Forest, D., 126

Foucaud, A., 85 Fox, 1. S., 68, 257 Frank, A. W., 78, 126 Frank, D. S., 105 Franke, A., 145, 147 Frankel, L. S., 290 Frankelfeld, E., 114 Frankowski, A., 117 Fraser, G. W., 95 Frearson, M. J., 105, 139, 318 Freeman, K. L., 18, 24, 60 Freeman, L. D., 2 Freiberg, J., 112 Friebolin, H., 286 Fried, J. H., 190 Friedman, H. C., 161 Frolov, V. V., 279 Fromageot, H. P. M., 147 Frrayen, P., 186 Frydman, B., 190 Fryth, P. W., 169 Fu, J.-J. L., 254 Fuchs, G. A., 294 Fukui, K., 16, 192 Fukui, T., 146 Fukuyama, S., 183 Furman, P. A., 236 Fursenko, I. V., 90 Furuta, 0. K., 81 Gabriel, T., 154 Gaertner, V. R., 21 Gagnaire, D., 42, 94, 282, 298,299 Gailey, R. G., 203 Gaj, B. J., 21 Galeev, V. S., 55 Galitskova, N. P., 2 Gallagher, M. J., 18, 24, 60, 116, 134, 273, 295 Gancher, E., 176, 184 Gandiano, G., 192 Gardner, P. J., 321 Garratt, P. J., 201 Garves, K., 181 Gastaminza, A., 33 Gaudiano, G., 277 Gaudy, E. T., 121 Gaydou, E., 113 Gazizov. M. B.. 121 Gazizov; T. K.,‘93 Gee, G., 237 Gefter. E. L.. 132 Gehlen, O., 55 Geike, F., 163 Germa, H., 51 Gerrard, A. F., 107, 118, 320 Gersmann, H., 109 Chose, B. N., 1 Gibb. T. C..273 Giere, H. H., 215 Gilani, S. S. H., 16, 88 Gilham, P. T., 157 Gilyarov, V. A., 137, 321 Gindl, H., 149 Ginsburg, B., 161 Gittler, C., 108 Glasel, J. A., 279

Author Index

326 Glaser, S. L., 45, 120 Gleason, J. G., 20, 259 Glemser. 0.. 215. 225 Goetz, H., 245, $11 Goetze, U., 64 Goldman, F. L., 219 Goldman, L., 154 Goldsbury, R. E., 3 Goldsmith, E. J., 94, 299 Goldwhite, H., 2, 99, 274, 287,295, 310 Gohk, G. A., 87 Golubski, Z. E., 139 Goodacre, G. W., 79 Goodfellow, R. G., 293 Goodman, L., 145 Goodrich, R. A., 284 Gordon, M., 134, 276 Gorenstein. D., 51 Gosling, K:, 1 . Goubeau, J., 118, 307 Gounelle, Y.,256 Gozman. I. P.. 105 Graham.' W. A. G., 278 Granoth, I., 123 Grapov, A. F., 128, 129 Gratz, J. P., 70, 297 Grav. H., 287 Gray, A. H.. Grayson, MI, M., 19, 29, 260 Graison, Grechkin, N. P., 307 Greco, A. E., 157 Green. B.. 226 Green; MI, 21 Green, M. J., 294 Greenberg, H. T., 4 Greenhalgh, R., 94, 105 Greenwood, N. N., 273, 305. 317 Grieve, C. M., 236 Griffin, B. E., 147 Griffin C. E 19, 81, 93, 129,'134, 247, 249, 254, 265. 276. 296, 300, 301, GAffin G. W 249 Griffit;. W. P.: 239. 307 Griffiths, D. E:, 160, 161 Griffiths J. E 305 Grim. S.' 0.. 575. 293.295 Grimm, L. F., 215 ' Grisebach, H., 161 Grishin, N. N., 321 Grisley, D. W., 276 Grobe J., 12, 64 Gross,'H., 112, 129, 205 Griitzmacher, H.-F., 256, 317 Grushin, Yu. S., 71 Grushkin, B., 229 Guermont, J. P., 204 Guib6-Jampe1, E., 99 Guida, W. C., 236 Guillemonat, A,, 113, 127, 131 Gulati, A. S., 48, 263, 275 Gur'yanova, I. V., 133 Haag, A., 186 Haake, P., 94, 136, 139, 299, 318

H[aake, P. C., 100 H[aberlein, H., 180 H[achmann, J., 147 HMgele, G., 118 H[artz, R., 180 H[agens, W., 69, 296 H[aley, R. C., 172 H[all, C. D., 122 H[all, G. E., 273 H[all, L. D., 300 H[almann, M., 109 H[amamura, E. K., 184 H[amashima, Y..96. 129 Hamburg, E., 317 . Hameed, A., 321 Hamer, N. K., 100, 107, 116 Hampson, F., 126, 321 Hanahan, D. J., 164 Hands, A. R., 196 Hansen, B., 105 Hantz, A., 117, 317 Hanze. A. R.. 143 Harada, F., 146 Harding, D., 101 Hargis, J. H., 119, 255 Harlev-Mason. J.. 112 HarpG, D. N.,'20; 259 Harris, G. H., 103 Harris, G. S., 317 Harris, J. E., 276 Harris, J. J., 284 Harris, M. R., 142 Harris, R. K., 292 Harrison, A. W., 107 Hartung, H., 186 Harve , R. G., 80 Haszehine, R. N., 23 Haufe, J., 32, 256 Hauper, F., 203 Haute, J., 316 Havinga, E., 250 Hawes, W., 24,27,28, 136, 28 1 Hawkinson, S. W., 161 Hawlev. A.. 226 Hayas;,' Y.,' 206 Hays, H. R., 68, 130, 131, 280 Hayton, B., 21, 96 Hechenbleikner, I., 95 Hedaya, E., 9 Heeren, J. K., 27 Heinen, H., 57 Heinlen, K., 146 Heinze, P. R., 215 Heller, S. R., 51 Hellner, E., 34, 314 Hellwinkel, D., 41, 42, 43, 76, 252, 275, 285 Hellyer, J., 167 Hemesley, P., 185, 204 Hemming, H. G., 80 Hendra, P. J., 304 Hendricker, D. G., 293 Henglein, A., 81, 255 Hengstberger, H., 31, 176, 179. Henning, H. G., 74 Henrick, C. A., 190

Henry, M. C., 1 Herring, D. L., 236, 237 Herriott, A. W., 71, 280 Hershey, J. W. B., 168 Hertel, H., 138 Hesz, A., 245, 312 H euer, G. E., 207 H ewertson, W., 3 H ewson, K., 153, 206 H eymann, H., 162 H iguchi, H. J., 303 H ildon. M. A.. 317 Hilgetag, G., 129 Hirai, K., 96 Hirayama, M., 205 Hirose. H.. 9 Hisatsune.'H. C., 239 Hoch, D. 'W., 238 Hodd, K. A., 239 Hogben, M. G., 278 Hoffmann, H., 14, 15, 61, 75. 85. 121 H ofmann, G., 32, 62 H olland, R. J., 289 H ollis, D. P., 154 H olman, D. J., 1 H olmann, M. J., 152 H olmes, R. R., 41, 281 H 61y, A., 143, 147 H ooks, H., jun., 114 H oos, W. R., 53 H ooz, J., 16, 88 H opkins, T. L., 88, 262 H oppen, H. O., 223,276 H orbath, G., 245 H orecker, B. L., 170 H origuchi, M., 162, 164 H orii, T., 260 H orn, H.-G., 236 H orner, L., 21, 23, 32, 33, 61,75, 176,247,.256, 316 H orrocks. W. D.. run.. 280. 302 HorskB, K., 175 Horvath, G., 312 Hosoi. K.. 190 Hosokawa, Y.,159, 160 Houalla, D., 42, 223, 282 Hubert-Habart. M.. 145 Hudson, H. R.; 88 ' Hudson, R. F., 9, 16, 80, 85, 94, 105, 133, 267 301, 321 Huff, R. K., 205 Hughes, A. N., 12, 13, 31 Huisgen, R., 25, 190, 192, 212. 265. 267 Hull, 'M. E., 238 Hultquist, D. E., 175 Humeres, E., 109 Hunger, K., 128 Hunt, T., 1 Hunter, S. H., 307 Hutchings, B. L., 169 Hutchinson, D. W., 98, 89 159, 165, 166, 168 Hutson, D. H., 117 Huyser, E. S., 90 I "

~~

Iedema, A. J. W., 178

Author Index Ignat’ev, V. M., 128 Ikehara, M.,143, 145-147 Imanari, M., 178 Imbery, D., 286 Inamoto, N., 77, 178 Inokawa, S., 246 Inoue, T., 205 Ionin, B. I., 69, 77, 128, 294, 31 1 Ireland, R. E., 112 Irgolic, K. J., 103 Irino, R. R., 138, 260, 303 Irvin, S. Z., 294 Isbell, A. F., 165 Ishiguro, T., 168 Ishimoto, N., 162 Isslieb, K., 3-6, 251, 280 Ito, E., 162 Itskova, A. L., 95 Ivakina, N. M., 93 Ivanov, B. E., 82 Ivanov, V. V., 115 Ivanova, R. G., 58 Ivin, S. Z., 45, 63, 93, 127, 284, 309 Iwai, I., 154 Izawa, Y., 85, 129, 250, 254 Izmailov, V. M., 133 Jaccard-Thorndahl, S., 204 Jackson, G. F., 291, 298 Jackson, W. R., 286, 289 Jacobson, R. A 239 Jain, S . R., 276” Jakobsen, H. J., 300 Jardine, R. V., 287 Jarvis, R. B., 17 Jasinski, J., 312 Jaszka, D. J. 238 Jefferson, R.,’294 Jencks, W.P., 100,111,158 Jenkins, H. D. B., 239 Jenkins, I. D., 116, 273 Jennings, W. B., 289 Johnson, A. W., 12, 277, 300 Johnson, G. M., 93, 249 Johnson, L. F., 171 Johnson, W. D., 53 Jolly, W. L., 3 Jonas, G., 208 Jones, A. S., 154 Jones, G., 205 Jones, G. H., 152, 184, 204 Jones, H. L., 277 Jugie, G., 280, 313 Jungermann, E., 70 Jurion, M., 112 Jutzl, P., 66 Kabachnik, M. I., 21, 55, 71, 72, 126, 137, 321 Kafengauz, A. P., 132 Kafengauz, I. M., 132 Kainosho, M., 306, 310 Kajiwara, M., 238 Kalir, A., 123

327 Kamai, G. K., 97, 313 Kametani, T., 258, 267 Kampe W., 99 Kandaisu, M., 162 Kaplan, M. L., 260, 261 Kashnikova, N. M., 228 KaSpBrek, F 97, 130 Kata, T., 143 Kataev E. G., 82 KathaGala, F., 147 Katritzky, A. R., 267 Katz, I.. 109 Kauer, J. C., 13 Kauffmann, T., 75 Kaufman. B. L.. 82 Kaufman; M. L:, 247 Kawabata, T., 9 Kawamoto, K., 317 Kawamura, S., 260 Kaye, H., 99 Ke, C. H., 279 Keat, R., 227, 230, 289, 290,297 Keen, W. R., 1 Keijer, 5. H 126 Kelly, P., 2ib, 215 Kemp, R. H., 134, 276 Kennard, O., 315 Keough, P. T., 19, 29 Kerek, F., 78 Kerr, K. A., 315 Kerst, F., 135 Kessel, A. Ya., 276 Kessler, H., 253, 288 Ketelaar, J., 109 Keyzer, H., 2, 274 Khairullin V. K., 58, 59 Kharidia, k. P., 203 Kharrasova F. M., 313 Khokhlov, 6. S., 103 Khomenko, D. P., 219 Khorana, H. G., 141, 142, 146, 147 Khusainova N. G., 127 Kidwell, R. ’L., 18 Kiely, D. E 170 Kikuchi, S.1’205 Killhefer J. V 70 Kinstle ?. H.,*’2OS Kipker’K 5 5 Kirby, ’A. *i., 80, 85, 100, 108, 133, 158, 162 Kirby K. C. jun., 15, 16 Kiree;. V. V.’. 238 Kirilov, M., 126, 207 Kirksey, H. G., 137 Kirsanov, A. V., 7, 23 71, 72,212, 225, 233 Kiso, Y., 317 Kitaoka, Y., 317 Kittredge, J. S., 162, 164 Klahre, G., 75 Klapper, H., 290 Klebanskii, A. L., 238 Kleiman, Yu. L., 296 Klement, U., 223, 239 Klieber, H., 207 Kluger, R., 135, 321 Klusman, P., 56, 208 Knowles, F. C., 170 9

Knunyants 1. L 1 108, 111, 126,’ 140 z72’ 307 Kobayashi, E., i19, i20 Kobayashi, M., 317 Kochi, J. K., 303 Kodera, K., 88 Konig, H., 99 Koppelmann, E., 75 Koster, H., 142 Koh, L. L., 265 Kokoszka G. F 247 Kolesnik, ’A. A.,‘b99 Kolesnikov, G. S., 238 Kolodjaznij, 0. I., 103 Kolodkina, I. I., 157 Kolokol’tseva, I. G., 30,77 Kolomiets, A. F., 103 Kondo, N. S., 154 Kondrat’ev, N. S., 304 Kondrat’ev, Y. A., 93, 127, 309 Kondrat’eva, R. M., 58,59 Kondyurina, T. F., 128 Kongpricha, S., 215 Konoleva, M. Ya., 238 Konstantinov, Yu. S., 272 Koopmans, K., 109 Kopeckq, J., 148 Km?lev, B. A., 137, 321, 3LL

Koroteev, M. P., 251 Korpiun, O., 70, 131, 139, 292 Korshak, V. V., 6 Kosfeld, R., 118 Koslov, E. S., 219 Kosolapoff, G. M., 103, 137 Kost, D., 129 Kostyanovsky, R. G., 14, 306 Koval’, A. A.. 233 Koziara, A., 115 Kozlov, E. S., 7 Kozlov, N. S., 121,268 Kozlova, N. Y., 109 Kraihanzel. C. S.. 293 Kramolowsky, R.-,4 , 5 Kranz, E., 180 Kranz, H., 4 Krasil’nikova, E. A., 97 Krasna, A. I., 279 Kreutzkamp, N., 97 Krivun, S. V., 23 Krokhina, S. S., 82 Kropacheva, A. A., 228 Krueger, P. M., 118, 157 Krupnov, V. K., 90 Krusic, P. J., 303 Krutskii, L. N., 97 Kuchen, W., 118, 138 Kuczkowski, R. L., 310 Kudchadker, M. V., 103 Kudryavtsevov, L. A., 126 Kuehn, G., 136 Kummel, R., 3 Kugel, R. L., 54, 229, 238, 304 Kugler, H. J., 47, 265 Kukhar, V. P., 225

Author index

328 Kulakova, V. N., 294 Kulikova, L. Ya., 238 Kumamoto, T., 183, 190 Kumar, A,, 147 Kumashiro, I., 143 Kundu, S. K., 301 Kunstmann, R., 5, 190, 196, 265 Kus, A., 117 Kusashio, K., 143 Kuwajima, I., 33 Kvasha, Z. N., 103 Kwiatowski, G. T., 206 Labarre, J. F., 310 Labarre, M. C., 310, 313 L’Abbt. G.. 193 La Count, R. B., 93, 249 Lakatos, B., 245, 312 Lakshminarayan, T. V., 38 Lamb, R. W., 103 Lambert, J. B., 291, 298 La Nauze, J. M., 165 Lancaster, J. E., 296 Lance, D. G., 204 Landau, M. A., 63, 284 Lang, H. J., 187 Langford, V. M., 307 Lanoux, S., 231 Lapidot, A., 159, 167 Larsen, C., 14 Last, W. A., 245 Latscha, H. P., 275, 276 Laurent, J. P., 280, 313 Lauterbur, P. C., 40, 281 Lavielle, G., 17, 280 Lawson, A. M., 118, 157 Leader, G. R., 205 Lebedev, V. B., 294 Lebedeva, N. V., 128 Leblanc, R., 85 Lee, B. K., 162 Lee, D. G., 62, 135 Lee. J. B.. 16, 17. 88. 262 Lee; J. D:, 79 ’ Legler, J., 75 Lehr. W.. 220. 229 Leigh, G.’ J., 293 Leissring, E., 6, 251 Lequan, R. M., 296 Letsinger, R. L., 73, 147 Levin, B. V., 237 Levin, Ya. A., 55, 82 Levron, J. C., 204 Levv. M.. 126 LeGs, D.’ E., 3 Lewis, R. A., 8, 70, 131, 139. 292 Li,-N.’ C., 279 Liang, C. R., 162 Liberda, H. G., 300 Libman, B.-Ya., 251 Lieb, F., 36, 299 Liedhegener, A., 74, 251 Ljehr, J. G., 176 Lienert, J., 61 Light, K. K., 197, 262 Lindner, E., 4 Lindsey, R. V., 15 Lipscomb, W. N., 135 ’

Liptuga, N. I., 103 Lisy, V., 152 Llewellyn, D. R., 109 Lobanov, D. I., 21 Loewengart, G. V., 47 Logothetis, R. S., 197 Longone, D. T., 23,291 Loshadkin, N. A., 140 Luckenbach, R., 21, 33, 247 Luganskii, G. M., 63 Lustig, M., 215 Lustina, Z. V., 107, 111 Lutsenko, I. F., 2 Luz, Z., 91 Lyons, A. R., 99 Lysenko, T. N., 251 Maassen, J. A., 207 McAllister, P. R., 293, 295 McBride, J. J., 70 McCloskev. J. A.. 118.157 McCoy, D.’R., 136 ’ McCrae, W., 185 MacDonald, D. L., 170 McEwen, G. K., 93, 119, 310 McEwen, W. E., 29 McFarland, C. W., 274, 295 McFarlane, W., 290, 292, 295 Mach, W., 34, 35 McIntosh, C. L., 164 Mackie, R. K., 123, 126, 321 McLean, R. A. N., 65. i m

JLW

McNeal, J. P., 94, 136, 299 McNeilly, S. T., 58, 265 McShane, H. F., jun., 133 Madan. 0. P.. 51. 281 Mxercker, A.,’ 181, 197 Markl, G., 34, 36, 38, 252 Mague, J. T., 317 Mahler, H. R., 157 Mahler. W.. 282 Mahran, M: R., 49 Maier, L., 7, 23, 69, 71, 72, 135 Maikova, A., 122 Maisey, R. F., 205 Majeste, R., 33, 315 Majoral, J. P., 120 Maksudov, A. M., 137, 321 Malcolm, R. B., 300 Malisch, W., 200 Mallinson, P. R., 239, 316 Mancuso, A., 94, 321 Mandanas, B. Y., 205 Mandel’baum. Y. A.. 95. 115 Manhas, B. S., 236 Mani, N. V., 230, 3 15 Mankowzki-Favelier, R., 280, 298 Manley, T. R., 239 Mann, F. G., 315 Manoussakis, G., 23 I

,

Maples, P. K., 293 Markl, G., 297, 299, 301 Marmor, R. S., 127, 136 Marquardt, C. L., 303 Marr, G., 1 Marsi, K. L., 28 Martin, J., 298 Martius, C., 167 Marty, C., 126 Martynyuk, A. P., 209, 210, 215 Martz, M. D., 122 Masaki, M., 16, 192 Mashlyakovskii, L. N., 69, 294 Maslenikov, B. M., 238 Mastalerz, P., 139 Mathiason, D. R., 184 Mathis, F., 120 Mathis, R., 309 Matough, M. F. S., 16, 88 Matrosov, E. I., 71 Matsumoto, H., 267 Matsumoto, K:, 190 Matsumoto, Y., 96 Matthews, C. H., 186 Matthews, C. N., 197, 198, 17L

L I V

Matzura, H., 149 Mauret. P.. 310 Mavel, ’G.,’280, 294, 298 Mazhar-U1-Haque, 79 Medved, T. Y., 71, 126 Meek, D. W., 21 Meek, J. S., 265 Megson. F.. 10 Mehner, I.-, 3 Melby, L. R., 142 Mel’nichenko, I. V., 109 Mel’nikov. N. N.., 95., 115. 128, 129 Mercer, A. J. H., 196 Merritt, J. A., 304 Mertes, M. P., 143 Merz, A., 36, 252, 301 Messens, E., 146 Meyhew, J., 293 Mian, A. M., 154 Michalski, J., 91, 95, 110, 111 Michel, E., 12 Michelson, A. M., 160 Michniewicz, J. M., 147 Mikhailik, S. K., 217 Mikhailova, 0. B., 129 Mikhailyuchenko, N. K., 217 Miki, H., 267, 272 Mikolajczyk, M., 91, 110, 111 Miles. M. G.. 272 Millar, I. T.,‘24, 29, 296 Miller, B., 17, 88 Miller, D. L., 100 Miller, J. A,, 58, 172, 173 265 Miller, J. M., 55 Miller, N. E., 184 Miller, P. S., 147 Miller, V. R., 220,235, 320 I

329

A uthor Index Mills, J. L., 279 Minami, T., 267, 272 Mingaleva, K. S., 311 Mingos. D. M. P.. 293 Mironoba, V. V., 237 Mislow, K., 5 , 8, 70, 71, 131, 139, 280, 292, 313 Mitani, M., 176 Mjtchard, D. A., 186 Mitchell. E. W.. 119 Mitchell; K. A. R., 40, 238, 239 Mitchell. R. H.. 201 M itchell; R. W., 304 M itchener, J. P., 317 M itchenko, Yu. I., 279 M itsonobu, O., 88 M iyano, M., 204 M lotkowska, B., 91, 111 M ochalina, E. P., 272 M odro, A., 312 M odro, T. A., 312 M‘odro, T. O., 33 M oeller, T., 233, 235, 236, 276 M oller, U., 12 M offatt, J. G., 145, 146, 152, 184, 204 M offett. L. R.. 229 M olodykh, Z.’V., 127 M olt, K. R., 95 M[onaco, D. J., 176 M onagle, I. I., 87 M onagle,, J. J., 133 M ondelli, R., 192, 277 M ontgomery, J. A., 153, 206 M oore, C. E., jun., 161 M oore, D. R., 21 M oore, T. A., 113, 250 M oppett, C. E., 205 M oran, E. F., 237 M oravek, J., 148 M oret, C., 33, 314 M ori, M., 145 M ori, Y., 129 M orimoto, S., 168 M orita, K., 9 M‘oritz, A. G., 301 M orkovin, N. V., 296 M[orofushi, T., 306 M[on, M., 80 M[orris, R. A. N., 255 M osher, W. A., 138, 260, 303 Moskalevskaya, L. S., 71 Moskovskikh, V. V., 306 Moskva, V. V., 122 Mott, L., 61 Moura Campos, M., 138 Muelder, W. W., 306 Mueller, D. C., 291 Muller, H. J., 220 Muetterties, E. L., 40, 282, 284 Mukaiyama, T., 33, 88, 183, 190 Mukhametov, F. S., 93 Mukhametzyanova, E. K., 127

M ukherjee, P. P., 169

M ukhina, L. E., 228 M unoz, A., 120 M urao, K., 146, 147 M urao, M., 143 M urdock, L. L., 88, 262 M urray, A. W., 152 M urray, R. W., 260, 261 M usina, A. A., 276 M ustafa, A., 49, 82 M utalapova, R. I., 93, 119 M uylle, E., 278 M yshkin, A. E., 97 Nabi, S. N., 245 Nagabhushanan, M., 45 Nagase, O., 159, 160 Nagata, W., 206 Nagpal, K. L., 148 Nair, M. G. R., 304 Nakabayashi, T., 260 Nakamoto, K., 304 Nakamura, A., 306 Nakamura, S., 183, 203 Nakatani, T., 162 Nannelli, P., 236 Narang, S. A., 147 Nash, J. A., 290 Nativ, E., 129 Naumann, K., 5 Naumova, G. P., 3 13 Navech, J., 120 Neimysheva, A. A., 108, 111, 126, 140, 307 Nesterov, L. V., 93, 119, 276 Neumann, H., 175 Newberry, J. E., 94 Newmark, R. A., 292 Nichols, D . I., 278 Nicholson, D . A., 130 Nickless, G., 226 Niecke, E., 225 Nielsen, P. H., 14 Nifant’ev, E. E., 90, 251 Nikitina, V. I., 127 Nishimura, H., 148 Nishimura, S., 146, 279 Nishimura. T.. 154 Nixon, J. F., ’62, 63, 292, 294, 309 Nomura. H.. 168 Norman; A.’D., 292 Noskov, A. M., 306 Novikova, Z. S., 2 Novitskii, K. I., 82 Nudelman, A., 131 Nurrenbach, A., 195 Nussbaum, A. L., 152, 154 Nyholm, R. S., 1 Nyquist, R. A,, 305, 306 Nyu, K., 267 O’Brien, R. D., 115 Obrycki, B., 254 Obrycki, P., 81 Obrycki, R., 304 Ochoa-Solano, A., 108 Oda, R., 9

Oediger, H., 61, 176 Oehme, H., 3, 6, 251 Ogasawara, K., 258, 267 Ogata, Y.,8 5 , 129, 250, 254 Ogihara, K., 220 Ogilvie, K. K., 147 Ogilviea, F., 294 Oglobin, K. F., 93 Ohara, M., 17 Ohshiro, Y., 267 Ohta, M., 16, 192 Ohtsuka, E., 145, 147 Okada, T., 17 Okamura, W., 136 Okawara, R., 17 Okazaki, R., 77 Okhrimenko, I. S., 69, 294 Olah, G. A., 274, 295 Olbrich, H., 34 Oldham, K. G., 109 Oliver, W. L., jun., 298 OKs, W. D., 260 Olson, R. S., 103 Omelanczuk, J., 111 Onin, B. I., 296 Orlov, N. F., 82 Orth, D., 160 Ortiz de Montellano, P. R., 173 Osborne, G. O., 82, 101, 102 Ossip, P. S., 139 Osterroht, C., 256, 317 Ostrogovich, G., 78 Ottmann, G. F., 114 Paddock, N. L., 219, 220, 225, 233, 239, 316, 320 Paetsch, J., 54 Paetsch, J. D. H., 127 Page,. G., 102 Pahnia. D. N.. 157 P a k , v : D., 121 Pal, B. C., 164 Pal’m, V. A., 140 Palmer. T. F.. 220. 321 Pampaione, T., 203 Pant, B. C., 1 Panteleeva, A. R., 97, 136 Pappas, J. J., 176, 184 Parasan, T., 38 Park, J. D., 81 Park. P. J. D.. 304 Parshall, G. W., 5 Parvin, R., 109 Pashinkin, A. P., 93 Paskucz, L., 91, 110, 137 Pasternack, G., 4, 13, 75, 31 1

Pa%, D. J., 181 Pastushkov, V. N., 93,127 Pattenden. G.. 10. 185. 204, 297 Patwardhan, A. V., 265 Paul, J. W., 239 Paul, N., 321 Pauling, H., 203 Payne, D. S., 289 I

Author Index

330 Peake, S. C., 284, 286 Pearson, S. C., 21 Peer, H. G., 168 Peiffer, G., 113, 127, 131 Pelah, Z., 123 Penkett, S. A., 291 Penney, G. J., 302 Peters, H., 187 Peterson, L. K., 56 Petragnani, N., 57, 138 Petrellis, P., 249 Petrov, A. A., 30, 69, 77, 82. 128. 260. 294. 296.

Petrunin. V. A.. 5 5

Phipps,’D. A.,‘186 Phuong, N. H., 115 Pichat, L., 204 Pickel. H.-H.. 209 Pidcock, A., 293 Pignolet, L. H., 280 Pilot, J. F., 45,48, 51, 120, 275. 281. 282 Pinkina, L: N., 1 Pirkle, R. J., 304 Pisareva, S. A., 71 Pitts, J. J., 56 Pizer, L. I., 109 Place, B. D., 165 Plieninger, H., 210 Poersch, F., 5 Pogell, B. M., 169 Poindexter, E. H., 302 Polezhaeva, N. A., 82 Polikarpov, Y. M., 71 Polikarpova, M. A,, 237 Pollard. G. E.. 85 Pommer, H., 195 Pon, N. G., 170 Ponti. P. P.. 192. 277 Popoff, I. c., 205 Popp, F. D., 115 Pornin, M., 238 Porter, Q. N., 319 Postmas, C., 304 Potapov, A. M., 97 Potenza, J. A., 302 Potthast, R., 38, 297 Pozdnev, V. V., 251 Prakash, H., 219 Prelog, V., 40, 105 Prentice, J. B., 130 Preobrazhenskaya, M. N., 143 Preobrazhenski, N. A., 157 Preuse, W. C., 215 Price, C. C., 38 Prikoszovich, W., 57, 138 Probst, D., 245, 311 Proskurnina, M. V., 2 Prout, C. K., 102

Puchalski, C., 193 Pudovik, A. N., 58, 59, 87, 90, 93, 119, 127, 133 Pulav. P.. 245 Purckll, T., 203 Purdela, D., 274 Pustinger, J. V., 276 Pyrkin, R. I., 82 Quimby, 0. T., 130 Quin, L. D., 38, 70, 279, 297 Rabinowitz, J., 114 Radovskii, G. S., 304 Raghanan Nair, M. G., 29 Rahman, R., 259 Raison, J. K., 172 Rakov, A. P., 140,310 Rakshys, J. W., 275 Ramirez, F., 20,40, 45, 47, 48, 50, 51, 53, 60, 120, 263, 265, 275, 281, 282 Ramirez, F. B., 105 Ramirez, R. J., 19, 258 Randall, E. W., 293 Randall, J. F., 300 Rapko, J. N., 230 Rasberger, M., 30, 178, 184 Raskina, L.P., 304 Rast, H., 291 Ratajczak, A., 110 Rawlinson, D. J., 59 Rawlinson, D. W., 139 Raynor, D. R., 313 Razumov, A. I., 97, 121, 122 Razumova, N. A., 82 Razvodovskaya, L. V., 128 Readio, P. D., 50 Rebello, P. F., 169 Redmore, D., 123 Reese, C. B., 147, 148 Reesor, J. B., 287 Regitz, M., 74,251 Rehak, J., 287 Reich, E., 145 Reich, H., 103 Reiff, H. F., 1 Reilly, C. A., 294 Reilly, G. J., 29 Revel, M., 120 Reynolds, G. A., 217 Richards, E. M., 24 Richards, R. E., 302 Ridd, J. H., 33 Riechel, R., 210 Riecker, A,, 253, 288 Rilling, H. C., 173 Rittersdorf, W., 172 RizDolozhenskii. N. I.. 93 Robert, J. B., 42, 94, 282, 298,299 Roberts, E., 162, 164 Robiette. A. G.. 316 Robinson, B. H:, 305 Robinson, L., 108, 321 Robinson, M. A., 56

Robinson, R., 164 Rodley, G. A., 307 Roeller, H., 206 Roesky, H. W., 129, 215, 225 Roloff, H.-R., 13 Roschnik, R. K., 99 Rose, S. H., 238 Rose, 2. B., 109 Rosenberg, H., 162, 165 Rosenthal, A., 206 Ross, J. A., 122 Roth, A., 64, 67 Rottman, F., 146 Rowsell, D. G., 2, 99, 274, 287,295 Roy, C. H., 130 Roy, N. K., 121 Rubenstein, K. E., 4 Rudakova, I. P., 157 Rudner, B., 284 Rudolph, F., 12 Rudolph, K., 63 Rudolph, R. W., 292 Rudomino, M. V., 126 Rumyautseva, Z. G., 237 Runquist, O., 258 Rupert, D., 181 Rusek, P. E., 15, 50, 255 Rushizky, G. W., 157 Russell, A. F., 171, 172 Rutt, K. J., 307 Rylyokova, N. S., 304 Saalfank, R., 193 Sabherwal, I. H., 64,65,320 Sacconi, L., 3 Saeva, F. D., 313 Safe. S.. 259 Saffhill,’R., 148 Saikachi, 183, 203 Saito, H., 236, 238 Sakurai, H., 85, 134, 247, 302, 311 Salmond, W. G., 185 Salsburg, N. J., 291 Salzbrunn, D. E., 236 Samaray, L. I., 103 Samek, Z., 175 Samigulin, F. K., 132 Samitov, Y. Y., 127, 133, 276, 299 Samiuzzaman, 312 Samuel, D., 100, 167 Samuel, S., 91 Sanchez, M., 223, 309 Sandermann, H., jun., 161 Santhanam, K. S. V., 255, 317 Saratovkina, T. I., 238 Sargent, M. V., 201 Sarma, G. R., 164 Sasaki, K., 205 Satgk, J., 65 Sato, H., 129 Sato, K., 205 Saunders, D. G., 267 Saus, A., 12 Savage, M. P., 4, 29, 71, 178

331

Author Index Savchuk, V. I., 111, 126 Savignac, P., i i 4 Saxby, J. D., 301 Schaffer, E. T., 197 Schaller. H.. 143 Schechter, H., 193 Scheit, K. H., 143, 145, 147 Schellenbeck, P., 15 Scheluchenko. V. V.. 63 Scher, B., 161 Scherer, 0. J., 56, 208, 217 Schieder, G., 208, 217 Schiemenz. G. P.. 5 . 33. 29 1 Schim fky C., 97 Schinsbader, H., 57, 72, 78, 138 Schindler, N., 227 Schirmacher. D.. 61 Schleyer, P. R., 109 Schlueter, A. W., 239 Schmidbauer, H., 184, 198, 200, 208, 209, 276, 200 Schmidpeter, A., 217, 218, 220, 221, 222, 223, 225, 227, 239, 274, 301 Schmidt, A., 304 Schmidt U., 256, 317 SchmitzlDurnont, O., 207 Schmulbach, C. D., 220, 235, 320 Schmutzler, R., 55, 60, 278, 284, 286 Schneider, G., 147 Schnoller, M., 207, 218, 304 Schoeler, U., 35 Schonfelder, M., 75 Schray, K.J., 158 Schroer, R.,256, 317 Schulz, H., 203 Schumann, H., 64, 66, 67 Schwarz, M.,220 Schwarz, W., 136 Schweer, K. H., 119 Schweizer, E. E., 176, 197, 262, 288 Schweizer. M. P.. 154 Schwirten; K., 209 Searle, H. T., 219 Searle. R. J. G.. 94. 267. 301,' 321 Sears, D. J., 125, 272 Sebesta, K., 175 Sedlov, A. I., 7 Seegmiller, J. E., 170 Seel, F., 63 Sejber, J. N., 116 Seidel. W. C.. 293 Segal,'W., 162 Sekiya, T., 148 Semm, G. K., 140 Sen Gupta, A. K., 186 Senning, A., 210, 215 Sepulveda, L,, 108 Sevenair, J. P., 181 Seyferth, D., 27, 127 Shaffer, E. T., 262 Shagidullin, R. R., 82, 307 Shah, D. H., 157 I

,

I

.;

'

I

,

I

Shalman, A. L., 127 Shapiro, I. O., 72 Shapovalova, A. N., 129 Sharman. S. H.. 172 Sharov, V. N., 238 Sharp, D. W. A., 95 Sharp, J. T., 88, 261, 321 Shatenshtein. A. I.. 21. 72 Shaturskii, Ya. P.,'71 Shavel, J., jun., 193 Shaw, D., 293 Shaw, M. A., 12, 300, 317 Shaw, R. A., 102,214,227, 230, 231, 234, 235, 245, 290 Shechter, H., 188,211 Sheldon, R. A., 72, 251 Sheldrick, G. M., 302, 316 Sheluchenko. V. V.. 45.63. 284,294 Shemyakin, M. M., 184, 185 Sheppard, W. A., 275 Sherif, F. G., 216 Sherman, W. R., 118 Shevchenko, V. I., 225, 233 Shimwu, B., 154 Shimizu, M., 159, 160 Shimozawa, T., 310 Shinkai, I., 190 Shire, D., 142 Shlyk, Yu. N., 260 Shner, S. M., 129 Shobatake, K., 304 Shokol, V. A., 87, 217 Shono, T., 176 Shriver, D. F., 322 Shutt, J. R., 281 Sidky, M. M., 49, 82 Siebeneick, H.-U., 5 Siebert, W., 1 Siegemund, G., 207, 211, 216 Siekmann, L.,223, 276 Silver, B., 91, 100 Silver, D., 91 Sim, W., 289 Simalty, M.,30, 34 Simon, Z., 35 Simonnin, M. P., 296, 297, 301 Simonov, A. P., 232 Simons, H. E., 13 Simonsen, D. G., 162, 164 Simpson, P., 119 Singer, R. M., 295 Singh, P., 239 Sinitsyna, S. M., 237 Sisler H. H 219 238, 276 Skod;, J., lg8, 132 Smallcombe. S. H.. 289 ' Smets, G., 193 Smirnov, E. A., 55 Smith, B. C., 21, 96, 214, 235 Smith, C. P.,45,47,48, 50, 51, 53, 120, 263, 265, 275,281,282 Smith, D. M., 125, 272 '

_

,

I

Smith, G. P., 20 Smith, J. A. S., 239 Smith J. D., 1 Smith: R. A,, 109 Smith, R. H., 268, 269 Smith, R. H., jun., 123 Smrt, J., 143, 147 Smyrniotis, P. Z.,170 Snyder, E. I., 16, 262 Snyder, J. P., 20, 193, 259, 276,288, 300 Sobchuk, T. I., 58 Sokolov, E. I., 238 Solan, D., 251 Solomatina, A. I., 6 Sondheimer, F., 185, 201 Song, P.-S., 113, 250 Sonnet, P. E., 204 Sorm, F., 147, 175 Sorokina, T. D., 82 Soshin, V. A,, 268 Sosnovsky, G., 59,119,139 Sowerby, D. B., 61, 220, 226, 239, 321 Spanier, E. J., 56 Spatz, D. M., 115 Sprecher, M., 129 Sprung, I., 203 Srivastava, P. C., 148 Staab, H. A., 143 StBde, W., 36, 253 Stahlberg, R., 229 Stallings, E. S., 236 Stanclift, W.E., 293 Stavenski, I. H., 157 Stec, W., 95 Steger, E., 229, 287 Stelzer, O., 64 Stepanov, B. I., 137, 245, 313, 321, 322 Sterlin R. N., 1, 133 Sterlin: S. R., 272 Sternhell, S., 301 Stewart, C. J., 159 Stezenberger, H., 78 Stillwell, R. N., 118, 157 Stockel, R. F., 10, 11, 19, 134 Stoffey, D. G., 118 Stoll K., 220 Stonk F. G. A., 309 Storcl;, K., 97 Strating, J., 178 Stratton, C., 231 Straughan, B. P., 273, 305 Strel'tsov, R. V., 103 Streuli, C. E., 260 Strobach, D. R., 142 Strominger, J. L., 162 Sturtz, G., 280 Suart. S. R.. 280 Sudo,' R., 16 Suhadolnik, R. J., 145, 169 Sullivan, W. W., 188 Sulston, J. E., 147, 148 Sundbern. -_R. J., 123, 268, 269 Surmatis, J. D., 173, 206 Sutherland, J. K.,205 Suvorov, N. N., 143

Author Index

332 Suzuki, Z., 9 Swain, J. R., 63, 294 Swank, D. D., 314 Swift, T. T., 293 Sventitskii, E. N., 279 Szarek, W. A., 204

Trebst, A., 163 Trefonas, L. M., 33, 314, 315 Treichel, P. M., 284 Trippett, S., 4, 24, 27, 28, 29. 71. 72, 136, 178. 251, 281 Trivedi, B. C., 281 Troitskaya, A. D., 313 Tronchet. J. M. J.. 204 Tronich, ’W., 184, 198, 200, 276, 300 Trost, B. M., 206 Trotter, J., 239, 316 Trotz, S. I., 56 Trutneva, E. K., 55 Tsai, S.-C., 19, 258 Tsang, F. Y., 233, 276 Tsivunin, V. S., 58, 97 Ts’o, P. 0. P., 154 Tsubota, M., 262 Tsuboyama, K., 118, 157 Tsuge, O., 190 Tsurugi, J., 260 Tsvetkov, E. N., 21, 72 Tukada, T., 317 Tuma, D. J., 89 Turdin, R., 162 Turpin, R., 313 Tyssee, D. A., 136 Tzschach, A., 4 ’

Taft, R. W., 275 Tagawa, H., 160 Takamizawa, A,, 96, 129 Takemura, K. H., 89 Takenishi, T., 143, 145 Tanaka, S., 96, 129, 203 Tang, R., 2, 274, 310 Tanimoto, S., 9 Tantesheva, F. R., 82 Tapia, A., 210 Tarasov, V. V., 93, 127, 304, 309 Tasaka. K.. 45. 120 Tashiro, M:, 190 Tate, M. E., 171 Taylor, A., 259 Taylor, D., 234, 302 Taylor, G. A., 186 Taylor, M. D., 278, 283 Taylor, M. W., 1, 295 Tazawa, I., 146 Tebbe, F. N., 284 Tebby, J. C., 12, 24, 289, 296, 300, 317 Tedder, J. M., 178 Telefus, C. D., 47 Terauchi, K., 85, 134, 247, 302. 311 Termens, L., 119 Tetel’baum, B. I., 63, 284 Thanh, T. N., 114 115 The. K. I.. 56 Theaker, G., 178 Theodoropulos, S., 9 Thomas, G., 126 Thomas, J. O., 159 Thomas, W. A., 134, 276 Thommen, R., 173, 206 Thompson, G. A.,Jun., 162 Thompson, J. G., 197 Thomson, J. B., 257, 269 317 Ticozzi, C., 192, 277 Timms, P. L., 251 Timofeeva, T. N., 296 Tisue, G. T., 161 Todd (Lord), 99 Todd, M. J., 123 Tolkmith, H., 116 Tomaschewski, G., 129, 136 tom Dieck, H., 218, 304 Tomikawa, M., 159 Tomioka, H., 8 5 , 129, 250, 254 Tomoskozi. I., 182 Tong, D. A., 239 Tor-Poghossian, G., 14, 85 Toscano. V. G.., 57., 138 Toth, G.’, 245 Tranter, G. C., 61 Traynard, J. C., 113, 127 ’

’

’

’

Ubasawa, M., 147 Udy, P. B., 219 Uematsu, H., 145 Uematsu, T., 145 Uhlenhopp, E. L., 279 Ukena, T., 100 Ukita, T., 148 Ulff, J. W., 25 Ullam, E. U., 53 Ullman, D., 188 Ulrich, T. A., 197 Umani-Ronchi. A.. 277 Underwood, A: L.,’ 161 Ura, M., 220 Uretski, S. C., 145 Usher, D. A., 105, 135 Utley, J. H. P., 33 Utvary, K., 56, 138, 216, 220, 225, 230

Varshdvskaya, L. S., 157 Varshavskii, A. D., 63,284 Varshavskii, S. L., 55 Varvoglis, A. G., 108, 158 Vasil’ev, A. S., 93, 127 Vaska, L., 309 Vaughan,-L. G., 15 Vaver, V. A., 184 Vavilova. T. G . . 82 Vdovina,’ E. S , ’127 Venanzi, L. M., 294 Vereshchagin, A. N., 140, 711)

Vereshchinskii, I . V., 247 Verkade, J. G., 93, 294, 297. 310 Vernon, C. A., 109 Verny, M., 93 Verrier, J., 94, 299 Vessiere, R., 93 Vetessey, Z., 245, 3 12 Vigdorchik, M. M., 143 Vilceanu, R., 35 Vilkas, M., 99 Villieras, J., 17 Vinogradova, V. S., 82 Vinokurova, G. M., 2 Virkhaus, R., 15, 16 Vives, J. P., 120 Vizel, A. O., 140, 310 Vogel. K.. 35 Vorgt,’ D.; 313 von der Bruck, D., 210 voii Strandtmann, M., 193 Voronova, N. P., 2 Vos, A., 239 Voskuil, W., 69, 76, 296 Vullo, W. J., 280 Wadsworth, W. S., jun., 81, 123 Wagner, A. J., 230, 239, 315 Wagner, F., 161 Wagner, R. I., 2 Waite, N. E., 12, 289 Waier. T. A. J. W.. 207 Wikselman, M., 99 Wilinder, O., 175 Walker. B. J.. 10. 24. 297 Walker; C. C:, 211 Walker, R. T., 154 Waller, C. W., 169 Walsh, E. J., 231 Walter, R., 203 Walther, B., 280 Wang, C. C., 170, 246 Wang, J. H., 167, 168 Ward. L. F.. iun.. 85 Ward; R. S.; -12, ’1 18, 289, 300, 317 Warren, S. G., 78, 80, 91, 138. 162. 163 Wasserman, E., 261 Watson, D. G., 315 Watson, H. R., 3 Watson, P., 245 Webster, B. C., 40 Wechter, W. J., 145, 277 ’

Vaboonkul, S., 12 Valitova, L. A., 82 Van Allan, J. A., 217 van de Grampel, J. C., 239 Van den Berg, G. R., 131 Van de Ouweland, G. A. M., 168 Van Der Kelen, G. P., 278 Vanermen, W., 278 van Gorkon, M., 273 Vankovh, J., 175 Van Leusen, A. M., 178 van Montagu, M., 146 Van Valkenburg, C. F., 186 van Veen, R., 34 Van Woerden, H. F., 186 Varey, P. F., 99

A uthov Index Weeks, M., 293 Wehman, A. J., 288 Weichmann, H., 3, 5 Weigrabe, W., 304 Weimann, G., 99, 142 Weiner, M. A., 4, 13, 75, 31 1 Weingard, C., 225 Weingarten, H., 272 Weiss, R. G., 262 Weissmann, E., 317 Weisz, A., 56, 138 Wells, R. G., 16 Werther, H. U., 129 Wertz, D. W., 304 West, B. O., 23 Westheimer, F. H., 40, 51, 94, 100, 105, 108, 135, 281, 321 Wheatland, D. A., 293 Whetstone, R. R., 85 Whistler, R. L., 170, 246 Whitaker, R. D., 236 White, D. W., 93, 119, 310 White, R. F. M., 295 White, W. D., 292 Whitesides, G. M., 41 Whiting, W. M., 41 Whitlow, S. H., 239, 316 Wieber, M., 53, 129 Wieland, T., 160, 166 Wielesek, R. A., 255 Wilcox, R. D., 103 Wilkins, C. J., 307 Williams, D. A., 239 Williams, D. H., 12, 118, 289, 300, 317

333 Williams, J. H., 169 Williams, M. R., 78, 138 Williamson, M. P., 296, 300 Wilson, G. L., 56 Wilson, L. A., 258 Wilson, R. G., 145 Wing, R. M., 315 Winstein, S., 172 Wittig, G., 75, 186 Wittner E. 107 Wodak,’J.,’167 Wolf, R.,42 223, 280, 282 Wolfsberger,’ W., 208, 209 Wong, S. Y., 136 Wood, H. C. S., 172 Woodcock, R., 94 Woods, M., 13 Woodyard, J. D., 272 Wulff, J., 190, 192, 212, 265, 267 Wysocki, D. C., 19, 265 Yager, W. A., 261 Yagi, H., 267 Yakovleva, E. A., 21 Yakshin, V. V., 14, 306 Yakubovich, A. Ya., 232 Yamakazi, A., 143 Yamamoto, K., 203 Yamanaka, H., 60 Yamanaki, T., 267 Yang, K. U., 108 Yarkova, E. G., 82 Yasnikov, A. A., 109 Yastrebova, G. E., 127 Yatsenko, R. D., 1

Yee, K. K., 247 Ykman, P., 193 Yoda, R., 33 Yoshikawa, M., 143, 145 Yoshina, S., 203 Young, W. G., 172 Yudina, K. S., 71 Yurchenko, R. I., 212 Yurkevich, A. M., 157 Zaitseva, E. L., 232 Zaks, P. G., 115 Zamyatina, V. A., 6 Zaret, E. H., 119 Zavlin, P. M., 128 Zayed, S. M. A. D., 49, 82 Zbiral, E., 30,31, 176, 178, 179, 184 Zeeh, B., 257, 317, 320 Zelinger, H. I., 288 zemli6ka, J., 147, 156 Zgadzai, E. A., 313 Zhdanov, Yu. A., 204 Zhivukhin, S. M.,238 Zhmurova, I. N., 209, 210, 212, 215,216 Ziegler, M. L., 239 Zimmer, H., 203, 207 Zimmermann, R., 195 Zimont, S. L., 306 Zinbo, M., 118 Zingaro, R. A., 103 Zinov’ev. Yu. M., 55 Zon, G.,.5 Zubtsova, L. T., 82 Zwierzak, A., 91,115 Zyablikova, T. A., 58

Organophosphorus Chemistry

Organophosphorus Chemistry

Organophosphorus Chemistry