Russian Chemical Bulletin, Vol. 42, No. 10, October, 1993 1627

14. I. Rajca, Pol. J. Chem., 1981, 55, 775. 15. A. F. Borovski, Transition Met. Chem. (Weinheim, Ger.),

1983, 8, 226. 16. K. R. Yanuszkiewicz and H. Alper, Organometallics, 1983,

2, 1055. 17. A. F. Borowski and I. Rajca, Transition Met. Chem. (Wein-

heim, Get.), 1984, 9, 109. 18. J. E. Hamlin, K. Hirai, A. Milan, and P. M. Maitlis, J.

Mol. Catal., 1980, 7, 543. 19. Cf R. H. Crabtree, M. F. Mellea, J. M. Mihelcic, and J.

M. Quirk, J. Am. Chem. Soc., 1982, 104, 107. 20. D. Anton and R. H. Crabtree, Organometallics, 1983, 2,

855. 21. I. Amer, T. Bernstein, M. Eisen, J. Blum, and K. P. C.

Vollhardt, J. Mol. Catal., 1990, 60, 313. 22. I. Amer, J. Blum, and K. P. C. Vollhardt, a r. Mol. CataL,

1990, 60, 323. 23. Y. Badrieh, J. Blum, I. Amer, and K. P. C. Vollhardt, J.

Mol. Catal., 1991, 66, 295.

24. J. Blum, H. Huminer, and H. Alper, J. Mol. CataL, 1992, 75, 153.

25. Y. Badrieh, A. Greenwald, H. Schumann, and J. Blum, Chem. Ber., 1992, 125, 667.

26. E. Miiller, R. Thomas, and G. Zountsas, Liebigs Ann. Chem., 1972, 758, 16.

27. J. Blum, Y. Badrieh, O. Shaaya, and L. Meltser, Phospho- rus, Sulfur, Silicon, in press.

28. C. Rottman, M. Ottolenghi, R. Zusman, O. Lev, M. Smith, G. Gong, M. L. Kagan, and D. Avnir, Mater. Lett., 1992, 13, 293.

29. A. Slama-Schwock, M. Ottolenghi, and D. Avnir, Nature, 1992, 355, 240.

30. S. Braun, S. Shtelzer, S. Rappoport, D. Avnir, and M. Ottolenghi, J. Non-Cryst. Solids, 1992, 147/148, 739.

31. A. Roslenfeld, D. Avnir, and J. Blum, J. Chem Soc., Chem. Commun., 1993, 583.

32. Cf, e.g., O. Arad and Y. Sasson, J. Org. Chem., 1989, 54, 4993 and references cited therein.

Received July 21, 1993

Syntheses based on elemental phosphorus, sulfur, and their derivatives

E. S. Batyeva

A. E. Arbuzov Institute of Organic and Physical Chemistry, Kazan" Scientific Center of the Russian Academy of Sciences, 8 ul. Akad. Arbuzova, 420083 Kazan, Russian Federation.

Fax: + 7 (843) 275 2253

This review summarizes the data on the synthesis of various phosphorus-and-sulfur- containing organic compounds based on the reactions of elemental phosphorus and sulfur and their derivatives (various types of esters of trivalent phosphorus thioacids) with a variety of organic compounds.

Key words: elemental phosphorus and sulfur; esters of phosphorus(n0 thioacids; electrophilic and nucleophilic agents; acid catalysis.

One of the urgent problems of the chemistry of organophosphorus compounds is the development of ecologically clean methods for their preparation. The main techniques for their synthesis are based on the use of phosphorus chlorides, and the formation of one mole- cule o f the target product is usually accompanied by the evolution of several molecules o f aggressive hydrogen chloride. 1 The discovery o f the reactions of elemental phosphorus with disulfides 2 and, later on, with thiols 3 to yield trialkyl trithiophosphites made it possible to use

the latter as starting compounds for the synthesis of a variety of organophosphorns compounds. However, the chemistry of esters of thioacids of trivalent phosphorus has remained little investigated until recently, and the studies performed prior to our investigations4, 5 were concerned for the most part with classical Arbuzov reactions, i.e., with transformations involving alkyl and acyl halides. 6-9

Based on these data (see Refs. 6--9) it has been c o n c l u d e d that on going from phosphinites to phosphites

Translated from lzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 1706--1711, October, 1993.

1066-5285/93/4210-1627 $12.50 �9 1994 Plenum Publishing Corporation

1628 Russ.Chem.Bull., Vol. 42, No. 10, October, 1993 Batyeva

the regioselectivity of alkylation of the ambident >P- -S- - system changes completely (the S atom, instead of the P atom, is subjected to the attack).

However, recently we found that in the reactions of trialkyl trithiophosphites with alkyl halides, not substitu- tion, but the classical Arbuzov reaction occurs to give S,S-dialkyl alkyltrithiophosphonates, l~

(RS)aP + R'X --> [(RS)aP+R'X -] -4, (RS)zP(S)R' + RX

R = Me, Et, PhCH 2 X = I , Br, C1

This reaction can be used as a general method for the preparation of compounds with a P=S bond.

It was shown previously 7 that acyl halides only react with esters of pIIl thioacids through substitution of a halide atom for a thioalkyl group, regardless of the environment of the P atom.

o C o -1 II (RS)zP + R'OX.---.~ L(RS)2P-SI+-C-R'X-J - ~

R 0 II

(RS)2PX + R'CSR

More recently we have found that these reactions are, as a rule, acid-catalyzed and depend on the pre- sence of admixtures of acids in the reaction mixture. 12

(RS)3P + R'COX ~ (RS)2PX + R'COSR

R' = Me, CCI 3 X = CI, Br

Since these transformations are presumably based on the interaction of esters of pIIl thioacids with acids, we have studied the reactions of this type of esters with mineral and organic acids. 4,5 It was found that in these reactions one of the alkylthio groups at the triva- lent phosphorus atom is replaced to form pill acid anhydrides and a thiol. The reaction is reversible. By changing the reaction conditions (temperature, pressure, the solvent, the removal of one of the reactants from the reaction mixture by binding it to a third reactant) the equilibrium can be shifted toward the final products. We assume that this reversible interaction of esters of pII I thioacids is the basis of the catalytic effect of acidic reagents on the process of the cleavage of the P--S bond, and that the catalysis is not necessarily accom- plished via the pIII acid anhydride and the thiol. The nucleophilic attack can apparently occur as well in any of the intermediate steps (via the hydrogen-bonded com- plex or an onium compound). The general rule is electrophilic participation in nucleophilic substitution (Scheme 1).

Scheme 1

HX

+ . x -

1L H

_

HX H �9

+HY �9 ) + HX P--Y + RSH

According to this scheme, acid catalysis presumably occurs in the above-mentioned reactions with acyl chlo- rides. It should be expected that the equilibrium shown below would be shifted to the formation of ptlI acid anhydride when the thiol evolved is bound into thiocarboxylate and when the acid is recovered.

R'coc~ ~P-Cl (1) ~P-SR+ H C I ~ ~P-C! + R S H ~ R'COSR +

Thus, whereas the interaction of S-esters of pIII thioacids with alkyl halides proceeds via the Arbuzov reaction, in the case of acyl halides the substitution of a halide atom for an alkylthio group occurs.

A study of the reactions of thioesters of phosphinous, phosphonous, and phosphorous acids with haloacetic acids has shown 13 that they occur at a 2 : 1 ratio between the reactants and afford the corresponding pill acid halides, the products of oxidation of the original thioesters, and the esters of the corresponding thiol- carboxylic acids. The formation of these products can result when the reactions proceed according to Eqs. (2)--(4), in which sulfenyl halide RSX (Eqs. (2), (3)) and acyl halide (Eqs. (3), (4)) are assumed to be the intermediate products.

0 ~,i,., ~ X

o II I NSX + ~P-O--&-CH

I

0 0 II

+ RSX ~ / P - - S R + HC-COX ~ p _ ct_t~JH ~ II I

I I

I I ~ II ~P--SR + HC-COX =--- ~ P - - X + HC--C,--SR

I t

(2)

(3)

(4)

These reactions can be used for the preparation of S-esters of thiocarboxylic acids, which contain one less halogen atom than the original acid. These interesting results obtained with halogenated carboxylic acids drew our attention to the reactions of the esters of pII1

Syntheses based on elemental P, S, and their derivatives Russ. Chem.Bull., Vol. 42, No. 10, October, 1993 1629

thioacids with other halogen-containing compounds: sulfenyl chlorides, halogens, phosphorus pentachloride, polyhalomethanes, mono- or dichloroacetylene, etc. 14-19 These reactions at the 2 : 1 ratio between thiophosphite and a halogen-containing compound also involve the cleavage of the >P--S bond and the substitution of a halogen atom for an alkylthio group at the phosphorus atom. Sulfenyl halides are supposedly formed in all cases as intermediate compounds. This has been con- firmed, in particular, in a study of the reaction of trialkyl trithiophosphites with CC14 in the presence of an amine 2~ (Scheme 2). The reaction with sulfenyl halides is acid-catalyzed) s

( R S ) 3 P - -

Scheme 2

x~ (RS)2PX + (RS)3P=S + RX

X=C1, Br~

PCl 5 = (RS)2PCI + (RS)3P=S + RCl + PCl 3

CCls)( -- (RS)2F~C13 + (RS)2PX+ RSSR + X=Cl, Br + (RS)aP=S + RX

EtSCI ~ (RS)2PC1 + EtSSEt + (RS)3P=-S + EtCI

We also carried out for the first time a systematic investigation of the reactivity of the thiol derivatives of pIIl acids with respect to substituted acetylenes. 19 De- pending on the environment of the P atom and on the nature o f the acetylenic compounds, various transforma- tions take place which may involve either the retention or a change in the phosphorus coordination number.

It has been found that esters of pIIl thioacids and amidodithiophosphites react with 1-chloro-2-organyl- acetylenes to give the products of substitution for the alkylthio group with retention of the coordination number of the P atom and do not react according to the Arbuzov reaction (Scheme 3).

Scheme 3

P--SEt + ClC-CR

- ~ EtSCl + ) P - - C - C R

Cl

I ) p - S+Et-C-~= CRI

1 I - - - - C = C - - n t

R n

P(S)SEt + EtCl

P - EtSSEt Cl +

EtSCl + ) P - - SEt

However, the introduction of dialkylamido groups to the pIII atom changes the route of the reaction with haloacetylenes. In fact, the reaction of diamido- thiophosphites with 1-chloro-2-organylacetylene yielded previously unknown derivatives of diamido(alkynyl)thio- phosphonic acids.

(R2N)2PSR' + C[--C=-C--R" - R'Cl~ (R2N)2P(S)__C=_C_R,,

R = Me, Et; R' = Et, Bu; R" = Ph, SEt

In a study of the reaction of esters of pIII thioacids with dichloroacetylene yet another pathway for the re- action was discovered: insertion of dichloroacetylene into the P--S bond, which made it possible to develop an original method for the synthesis of a novel class of phosphorylated ethylenes.

R'S RP(SR') 2 + CtC-=-CCI = R.)P--C(CI)=C(CI)SR'

R = Et, Ph, SEt R' = Et, Pr

The addition of esters of p m thioacids to ethoxyacetylene occurs with the cleavage of the P--S bond, and affords O,S-acetals of phosphory la ted ketenes, 21 which are difficult to obtain.

R2P OEt R2P--SEt + HC---C-OEt ~

H SEt

R = Ph, SEt

The regio- and stereoselectivity of the process were established by i l l , 13C, and 31p N M R spectroscopy.

Regioselective <<insertion,> of oxiranes into the P--S bond of derivatives of pIII thioacids was observed for the first time in a study of the reactions of thiophosphinates and amidothiophosphonates with epoxides.ZZ, 23

RR'P--SEt + ~ 7 -'-R" >- R R ' p " O ' ~ ' 'SEt 0 a"

R, R' = Et, Ph, NEt 2 R" = H, Me

The process is catalyzed by either acidic or basic compounds.

Thus, the esters of pIII thioacids react with dichloro- acetylene, ethoxyacetylene, or epoxides with cleavage of the P--S bond to yield addition products.

Compounds of a similar structure are formed from esters of thioacids of trivalent phosphorus and carbonyl

1630 Russ.Chem.Bull., VoL 42, No. 10, October, 1993 Batyeva

compounds, z4,25 Thus, the reaction of trialkyl trithio- phosphites with aldehydes or ketones proceeds via the <dnsertion>) of the carbonyl moiety into the P--S bond to give derivatives of (1-alkylthio)alkylphosphonic acids. The process is accelerated by the addition of acid.

HC1

0 SR 1 0 SFI I R2PSRI+R2R3C= 0 HCI~, II I 2 3 B II I . R2P-CR R ~ R2P-CRZR~

- B - HCI

R = Alk, Ar, EtS, C1 R 2, R 3 = H, Alk, Ar R 1 = Alk B, base

Evidence for the decisive role of acid catalysis may be seen in the following. Since the preparation of (1-alkylthio)alkylphosphonates in the presence of acid implies the initial reversible replacement of the alkylthio group under the action of HC1, we suggested that the same products would be obtained in the reaction with carbonyl compounds upon addition of pIII acid chlo- rides and thiols which are present in the right-hand side of the equilibrium.

~P - S R + HX ~ ~ P - - X + RSH

In fact, equimolar amounts of pill acid chlorides and chlorophosphines react with mixtures of carbonyl com- pounds and thiols to give derivatives of (1-alkyl- thio)alkylphosphonic acids.

It is noteworthy that this method for the synthesis of (1-alkylthio)alkylphosphonic derivatives differs from the previously known methods by the availability of the original compounds and the possibility of varying the substituents at the phosphorus atom and at the a-carbon atom within wide limits. It is simple and convenient for laboratory implementation, which has resulted in its extension to a large variety of pill chlorides, carbonyl compounds, and thiols.

0 SR 1̂1 I 3 4

R1R2p--cI + R3R2C=O + RSH ~ R I R z P - C R R + HCI

R 1, R 2 = Alk, Ar, AIkS, C1 R s, R 4 = Alk, Ar, H, cyclo-Alk

The products of <dnsertion,> are also formed in the reactions of esters of pill thioacids with a,13-unsaturated acids, e.g., acrylic and methacrylic acids. 26,27

0 0 II II

R2PSEt + CH2=CRCOOH _-- R2PCH2CHRCSEt

R = H, Me

Thus, the investigation of the chemical behavior of pII1 thioacid derivatives has shown that, unlike their oxygen analogs, they react with electrophilic agents with the cleavage of the phosphorus-sulfur bond and replace- ment of the thiol group at the trivalent phosphorus atom rather than according to the Arbuzov scheme.

In our opinion, this behavior is due to the fact that upon the introduction of thi0alkyl substituents to the trivalent phosphorus atom the nucleophilic properties of the latter are reduced. 28 This hypothesis has been sup- ported by C N D O / 2 - M O calculations for trimethyl phos- phite and trimethyl trithiophosphite. The results ob- tained attest to the fact that the HOMO localization at the phosphorus atom in trithiophosphite (30 .1%) is less pronounced than in thimethyl phosphite (50.1%). Con- sequently, the sulfur atom becomes a competing reactive site of the molecule.

+ M - e f f e c t -M-ef fect

A decrease in the -M-ef fec t of the phosphorus atom in the thio-derivatives of pIII acids compared with their oxygen analogs is evident from the geometric parameters of organophosphorus compounds containing P--S and P--O bonds determined by X-ray diffraction analysis and electron diffraction. Shortening of the P--S bond or the approach of the bond angle at the S atom to 180 ~ which would occur in the case of conjugation, are virtu- ally absent (or are observed to only a small extent). The P- -O bond length amounts, on the average, to 1.60 A, which is substantially less than the sum of the covalent radii of the P and O atoms (1.83 A), and the P - - O - - C bond angle is 120 ~ which is considerably greater than the C - - O - - C bond angle (110~ The fact that the mesomeric effect in the P--S system is absent or substantially lower than in the P - -O system should result in destabilization of the quasiphosphonium compounds formed as inter- mediates in addition reactions and should favor reactions at the second nucleophilic site, the S atom.

Recently we managed to experimentally confirm the participation of both of the nucleophilic sites of trialkyl trithiophosphites, the P and S atoms, in the reaction with cuprous halides. According to the X-ray diffraction analysis data, the resulting crystalline products are poly- mers with a regular structure, in which the copper atom is coordinated with the phosphorus and sulfur atoms of the trithiophosphite ligand to form a six-membered ring 29 (Scheme 4).

Thus, the competitive participation of the second nucleophilic site (the S atom) in the reaction results in cleavage of the P--S bond and the replacement of the thioalkyl group at the phosphorus atom.

Therefore, the preparation of compounds that retain the thioalkyl group at the phosphorus atom presents definite difficulties. We have suggested that the intro-

Syntheses based on elemental P, S, and their derivatives Russ.Chem.Bull., VoL 42, No. 10, October, 1993 1631

S c h e m e 4

n (RS)aP + n CuX ~ [(RS)aP'CuX] n

R = Et; X = C 1 , Br, I

o, - . ; _ s / \ / \ / ,, / Cu' Cu Cu"

/ \ e l / ~ t \ S--P-... / I

duction of various functional groups that favor the Arbuzov reaction into pIII thioacid derivatives would allow the retention of thioalkyl groups at the phosphorus atom.

For this purpose, dithio- and monothiophosphine derivatives were synthesized. 3~ Alkylthiophosphines were prepared by the reduction of the corresponding dithiophosphonites and trithiophosphites with organotin mono- and dihydrides. 3~ It was shown that di(alkylthio)- and alkyl(alkylthio)phosphines react with carbonyl com- pounds or unsaturated compounds with retention of the thioalkyl group at the P atom. Only with acetyl chloride (in the absence of a base) has the exchange reaction with cleavage of the P--S bond and replacement of the RS group at the P atom been observed. In the presence

S c h e m e 5

EtS-.pH RP(SEt)2 + 1R'4_nSnH n ~ R f + 1R'4_nSn(SEt)2

R = Me, Et, BU t, Ph; R' = Et, Bu; n = 1, 2

(4-n)(RS)aP + BUnSnH4_ n .-.'. (4-n)(RS)2PH + BU nSn(SR)4_ n

R = Me, Et, P r ; n = 2 , . 3

RS "PH

R ' /

RS OH \ I R"CHO �9 R ' - - P - C H R "

RS CH2=CH--CN I

R'--P-CH2CH2CN

RS ClC=-CCI I

R'--P--CCI=CHCI

X 0 2 or S 8 fl

�9 R ' - -P - -H X = O, S I SR

O R"COCl, B R L II . - - B - H C I ~ R s / P . C R

R"COC1 R'.x. �9 c I / P - - H + R"COSR

X RS II

PhN=C=X �9 .~P- CNHPh X = O , S FI'

of a base, proton migration occurs to afford the cor- responding a-oxophosphinite (Scheme 5).

S,S'-Dialkyl trimethylsilyldithiophosphites, which we prepared for the first time from S,S'-dialkyl dithio- chlorophosphites and bis(trimethylsilyl)acetamide, react with electrophilic reagents, such as alkyl or acyt halides, sulfenamides, aldehydes, isocyanates, and ethoxy- acetylene. In all of these cases, the alkyl and silyl groups at the phosphorus atom migrate to give thioalkyl- or thionophosphonates depending on the nature of the electrophilic reagent (Scheme 6).

S c h e m e 6

(RS)2PCl + (M%Si)2NC(O)Me -~ (RS)2POSiM % + MeCN

(RS)zPOSiM %

S 0 R'SNEt 2 II II

RS--POSiMe 3 + (RS)2 PSR' + P I R'

+ Et2 NSiMe 3

O O R'COCI II II

(RS)2P-CR ' + Me3SiCI

R'COBr 0

(RS)2PBr + R'COSiMe 3

S R'X il

X=Cl, B r ~ (RS)2P-Q~Me3R' + RX

(RS)2P(O)R' + MeaSiX

R'R"C=O, B O O~Me 3 II I

(RS)2 P - C R ' R "

R' = H; R" = Me, Ph, 2-NO2C6H4; B = Et3N , Py

It is of interest that the replacement of one of the thioalkyl groups at the P atom by an amino or acetoxy group results in reactions with acyl halides that involve cleavage of the P- -N or P--O bond rather than the P--S bond (see Refs. 34,35).

(RS)2P--NEt 2 + R'COX ~ (RS)2PX + RCONEt 2 O O II II

(RS)2P--OOCMe + R'COX ~ (RS)2PX + R'--COC-Me

R = Me, CCla, Ph X = C1, Br

Thus, the derivatives of the thioacids of trivalent phosphorus can be used for the synthesis of a wide variety of organophosphorus compounds with either re- tention or cleavage of the P--S bond.

1632 Russ.Chem.Bull., VoL 42, No. 10, October, 1993 Batyeva

Scheme 7

4 P(red) + !~S8

S 6 RSSR II

4 (RS)2Ps- S-- SR

8 R'OSnRa..._ 4 (R'O)2~:G-SrlR 3 + (R3S1"1)2S

4 (R sio)2 R" z 0,, I'~ I a -"- 4 R';~ ,,PSSiR 3 + 2 (R3Si)2S

0

R, R' = AIk R" = --(CH2) n -

Recently we prepared phosphorus-and-sulfur-con- taining compounds on the basis of the reaction of mix- tures of elemental (red) phosphorus and sulfur with organic reactants. By treating dialkyl disulfides, silylated diols, or stannylated alcohols with a mixture of red phosphorus and elemental sulfur the corresponding de- rivatives of dithio- and tetrathiophosphoric acids were synthesized (Scheme 7) (aprotic reagents were selected with the aim of avoiding the formation of toxic hydro- gen sulfide).

Since the same organothiophosphorus compounds are formed upon the reactions of dialkyl disulfides, trialkylalkoxystannanes, or disilylated diols with phos- phorus sulfide (P4S10), one cannot rule out that the interaction of these reactants with elemental phosphorus and sulfur occurs via the formation of phosphorus sulfides, for the most part, tetraphosphorus decasulfide, or phosphorus thioacid anhydrides having an analogous structure.

Thus, as a result of these studies of the reactivity of the derivatives of thioacids of trivalent phosphorus and e lemental phosphorus and sulfur with respect to electrophilic and nucleophilic organic agents, novel me- thods for the synthesis of organothiophosphorus com- pounds, different from the known methods associated with the use of phosphorus chlorides and the evolution of hydrogen chloride, have been developed. With the aid of the new methodology novel representatives of the family of organic phosphorus-and-sulfur-containing com- pounds have been prepared.

References

1. D. Purdela and R. Vylchanu, Khimiya organicheskikh soedinenii fosfora [Chemistry of Organic Compounds of Phos- phorus], Khimiya, Moscow, 1971 (in Russian).

2. US Pat. 2542370, Chem. Abstrs., 1954, 45, 5712. 3. Ch.Wu, J. Am. Chem. Soc., 1965, 87, 2522. 4. E. N. Ofitserov, O. G. Sinyashin, E. S. Batyeva, and A. N.

Pudovik, Zh. Obshch. Khimii, 1980, 50, 222 [J. Gen. Chem. USSR, 1980, 511 (Engl. Transl.)].

5. E. N. Ofitserov, O. G. Sinyashin, N. V. Ivasyuk, E. S. Batyeva, and A. N. Pudovik, Zh. Obshch. Khimii, 1980, 511, 1217 [J. Gen. Chem. USSR, 1980, 511 (Engl. Transl.)].

6. A. E. Arbuzov, Zh. Russ. Fiz.-Khim. Obshch., 1910, 42, 549 [J. of Russ. Phys.-Chem. Soc. (in Russian)].

7. A. F. Divinskii, M. I. Kabachnik, and V. V. Sidorenko, Dokl. AN SSSR 1948, 60, 999 [DokL Chem., 1948, 60 (Engl. Transl.)].

8. B. A. Arbuzov, N. I. Rizpolozhenskii, and M. A. Zvereva, Izv. Akad. Nauk SSSR, OKhN, 1957, 179 [Bull. Acad. Sci. USSR, Div. Chem. Sci., 1957 (Engl. Transl.)]. E. A. Krasirnikova, Usp. Khim., 1977, 46, 1638 [Rus. Chem. Revs., 1977, 46 (Engl. Transl.)]. V. A. Al'fonsov, G. U. Zamaletdinova, E. S. Batyeva, and A. N. Pudovik, Zh. Obshch. Khim., 1986, 56, 713 [J. Gen. Chem. USSR, 1986, 56 (Engl. Transl.)].

11. M. I. Kabachnik, A. N. Pudovik, E. S. Batyeva, V. A. Al'fonsov, and G. U. Zamaletdinova, [zv. Atcad. Nauk SSSR, Set. Khim., 1987, 1871 [Bull. Acad. Sci. USSR, Div. Chem. Sci., 1987, 36, 1734 (Engl. Transl.)].

12. V. A. Arfonsov, G. U. Zamaletdinova, E. S. Batyeva, and A. N. Pudovik, lzv. Akad. Nauk SSSR, Set. Khim., 1982, 1386 [Bull. Acad. Sci. USSR, Div. Chem. Sci., 1982, 31, 1235 (Engl. Transl.)].

13. O. G. Sinyashin, Sh. A. Karimullin, E. S. Batyeva, and A. N. Pudovik, lzv. Akad. Nauk SSSR, Set. Khim., 1982, 1671 [Bull. Acad. Sci. USSR, Div. Chem. Sci., 1982, 31, 1491 (Engl. Transl.)].

14. O. G. Sinyashin, Sh. A. Karimullin, E. S. Batyeva, and A. N. Pudovik, Zh. Obshch. Khim., 1984, 54, 540 [J. Gen. Chem. USSR, 1984, 54 (Engl. Transl.)].

15. O. G. Sinyashin, Sh. A. Karimullin, E. S. Batyeva, and A. N. Pudovik, Zh. Obshch. Khim., 1984, 54, 2463 [Y. Gen. Chem. USSR, 1984, 54 (Engl. Transl.)].

16. O. G. Sinyashin, Sh. A. Karimullin, D. A. Pudovik, E. S. Batyeva, and A. N. Pudovik, Zh. Obshch. Khim., 1984, 54, 2458 [J. Gen. Chem. USSR, 1984, 54 (Engl. Transl.)].

17. O. G. Sinyashin, Sh. A. Karimullin, E. S. Batyeva, and A. N. Pudovik, Zh. Obshch. Khim., 1985, 55, 453 [d. Gen. Chem. USSR, 1985, 55 (Engl. Transl.)].

18. O. G. Sinyashin, Sh. A. Karimullin, V. P. Kostin, E. S. Batyeva, and A. N. Pudovik, Zh. Obshch. Khim., 1986, 56, 1700 [J. Gen. Chem. USSR, 1986, 56 (Engl. Transl.)].

19. O. G. Sinyashin, V. A. Zubanov, E. S. Batyeva, and A. N. Pudovik, Izv. Akad. Nauk SSSR, Set. Khim., 1986, 1215 [Bull. Acad. Sci. USSR, Div. Chem. Sci., 1986, 35, 1101 (Engl. Transl.)].

20. E. Herrman, S. Albracht, and A. John, Z. Anorg. Allg. Chem., 1987, 545, 202.

21. O. G. Sinyashin, V. A. Zubanov, R. Z. Musin, E. S. Batyeva, and A. N. Pudovik, Zh. Obshch. Khim., 1989, 59, 512 [J. Gen. Chem. USSR, 1989, 59 (Engl. Transl.)].

22. O. G. Sinyashin, Sh. A. Karimullin, E. S. Batyeva, and A. N. Pudovik, [zv. Akad. Nauk SSSR, Ser. Khim., 1984, 796 [Bull. Acad. Sci. USSR, Div. Chem. Sci., 1984, 33, 676 (Engl. Transl.)].

23. V. P. Kostin, O. G. Sinyashin, E. S. Batyeva, and A. N. Pudovik, Zh. Obshch. Khim., 1985, 55, 1860 [Z Gen. Chem. USSR, 1985, 55 (Engl. Transl.)].

24. V. A. Arfonsov, I. S. Nizamov, E. S. Batyeva, and A. N. Pudovik, Zh. Obshch. Khim., 1985, 55, 1634 [Z Gen. Chem. USSR, 1985, 55 (Engl. Transl.)].

25. V. A. Al'fonsov, I. S. Nizamov, E. S. Batyeva, and A. N. Pudovik, Zh. Obshch. Khim., 1986, 56, 709 [J. Gen. Chem. USSR, 1986, 56 (Engl. Transl.)].

26. E. N. Ofitserov, O. G . Sinyashin, N. V. Ivasyuk, E. S. Batyeva, and A. N. Pudovik, Zh. Obshch. Khim., 1981, 51, 468 [o r. Gen. Chem. USSR, 1981, 51 (Engl. Transl.)].

9.

10.

Syntheses based on elemental P, S, and their derivatives Russ.Chem.Bull., 1Iol. 42, No. 10, October, 1993 1633

27. O. G. Sinyashin, T. N. Sinyashina, E. S. Batyeva, A. N. Pudovik, and E. N. Ofitserov, Zh. Obshch. Khim., 1982, 52, 2438 [Z Gen. Chem. USSR, 1982, 52 (Engl. Transl.)].

28. E. S. Batyeva, O. G. Sinyashin, Sh. A. Karimullin, V. A. Al'fonsov, and A. N. Pudovik, Khimiya i Primenenie Fosfororganicheskikh Soedinenii, Tr. 11111 Vsesoyuznoi Konferentsii po Khimii Fosfororganicheskikh Soedinenii [Chemistry and Application of Ovganophosphorous Compounds, Proc. of the VIII All-Union Conference on the Chemistry of Organophosphorous Compounds], Eds. A. N. Pudovik and O. A. Erastova, Nauka, Moscow, 1987, 104 (in Russian).

29. E. S. Batyeva, L. I. Kursheva, O. V. Kataeva, I. A. Litvinov, and O. G. Sinyashin, Zh. Obshch. Khim., 1993, 63, 225 [Z Gen. Chem., 1993, 63 (Engl. Transl.)].

30. O. G. Sinyashin, I. Yu. Gorshunov, N. V. Ivasyuk, E. S. Batyeva, and A. N. Pudovik, Izv. Akad. Nauk SSSR, Ser. Khim., 1986, 1394 [Bull. Acad. Sci. USSR, Div. Chem. Sci.,

1986, 35, 1267 (Engl. Transl.)]. 31. O. G. Sinyashin, I. Yu. Gorshunov, E. S. Batyeva, and

A. N. Pudovik, Zh. Obshch. Khim., 1988, 58, 1458 [Z Gen. Chem. USSR, 1988, 58 (Engl. Transl.)].

32. V. A. Arfonsov, I. S. Nizamov, A. G. Trusenev, E. S. Batyeva, and A. N. Pudovik, Zh. Obshch. Khim., 1988, 58, 2799 [J. Gen. Chem. USSR, 1988, 58 (Engl. Transl.)].

33. V. A. Al'fonsov, I. S. Nizamov, A. G. Trusenev, E. S. Batyeva, and A. N. Pudovik, Zh. Obsheh. Khim., 1989, 59, 2671 [J. Gen. Chem. USSR, 1989, 59 (Engl. Transl.)].

34. O. G. Sinyashin, V. P. Kostin, E. S. Batyeva, and A. N. Pudovik, Zh. Obshch. Khim., 1982, 52, 2701 [J. Gen. Chem. USSR, 1982, 52 (Engl, Transl.)].

35. V. P. Kostin, O. G. Sinyashin, E. S. Batyeva, and A. N. Pudovik, Izv. Akad. Nauk SSSR, Set. Khim., 1982, 1673 [Bull. Acad. Sci. USSR, Div. Chem. Sci., 1982, 31, 1494 (Engl. Transl.)[.

Received August 2, 1993