SYNTHESIS OF BIFUNCTIONAL ORGANOPHOSPHORUS COMPOUNDS

COMMUNICATION 5. DIALLYL (ALKYLPHOSPHINIDENE)-, (PHENYLPHOSPHINIDENE)-,

AND (E THOXYPHOSPHINIDENE) DIA CE TA TE S

G. M. Vinokurova and S. G. Fattakhov UDC542.91+661.718.1

We have previously repor ted the synthesis of diallyl 3, 3 '-(phenylphosphinidene)dipropionate and all ied compounds [11 and descr ibed "organic glasses" p repared f rom the corresponding phosphinylidene and phos- phinothioylidene compounds [2]. Continuing this line of investigation, we considered it to be of in te res t to synthesize and study a number of diallyl phosphinidenediacetates, including (alkoxyphosphinidene)diacetates (phosphinous acid derivat ives) , and also the corresponding phosphinylidene- and phosphinidinediaeetates and thei r der ivat ives have been prepared , readi ly and in good yields, by the react ions of ( tr ialkylstannyl)- acet ic e s t e r s with te rva len t phosphorus acid chlorides [3-5]. Diallyl phosphinidenediacetates were p r e - viously unknown.

We have now shown that these compounds can be p repa red analogously by the react ions of allyl ( t r i - a lkyls tannyl)acetates with te rva lent phosphorus acid chlorides. We studied the react ions of allyl ( t r ie thyl- s tannyl)acetate with methyl- , ethyl- , and phenylphosphonous dichlorides and ethyl phosphorodichloridi te , which went in accordance with the scheme

2RaSnCH2COOCH2CH =-= CH2 + tt'PC12--~ WP (CH~COOCH2CH--=CH2) 2 + 2BzSnC1,

in which R = C2H 5 and R' = CHa, C2H5, C6H5, and C2H50.

The reac t ions were exothermic , and the products were obtained in yields of 51-77%. The products were readi ly isolated by vacuum distillation. They a re co lor less liquids which readi ly combine with sulfur and oxygen. By the addition of sulfur we obtained the corresponding diallyt phosphinothioylidenediacetates in yields of 86-93%, and by oxidation we obtained the corresponding diallyl phosphinylidenediacetates. How- ever , in the oxidation reac t ions we were able to isolate only diallyl (ethoxyphosphinylidene)diacetate in the pure state. The diallyl (alkylphosphinylidene)- and (phenylphosphinylidene)-diacetates po lymer ized when distil led. All a t tempts to f rac t ionate them, even in a high vacuum_ and with stabil ization with copper s t ea r - ate, were unsuccessful in spite of the fact that the diallyl (alkylphosphinylidene)- and (phenylphosphinylid- ene)-d iaceta tes were p repa red by different methods: oxidation with hydrogen peroxide, oxidation with a t - mospher ic oxygen, and the t ranses te r i f i ca t ion of dimethyl (alkylphosphinylidene)- and (phenylphosphinyl- idene)-diaceta tes , p r epa red special ly for this purpose [5], with allyl alcohol. The constants of all the com- pounds synthesized a re given in Table 1.

Until r ecen t ly there has been no informat ion in the chemical l i t e ra tu re on the s tar t ing compounds: t r ialkyl(al lyloxy)t ins and ally1 ( t r ia lkylstannyl)acetates . However, these compounds a re of in te res t as in- te rmedia te products for the synthesis of the most var ied organic compounds containing the (al lyloxycarbonyl)- methyl group and for the prepara t ion of t in-containing polymers . We have synthesized (allyloxy) tr iethylt in, (al- lyloxy)tr ibutylt in, and allyl ( t r iethylstannyl)- and ( t r ibutyls tannyl)-acetates . Trialkyl(al lyloxy)t ins were p r e - pared readi ly in good yields by the t ranse ther i f ica t ion of known tr ia lkylmethoxytins with allyl alcohol. Atlyl (trialkylstannyl} ace ta tes were p repa red by the react ions of tr ialkyl(al lyloxy)tins with ketene. The con- stants of the conpounds obtained a re given in Table 2.

E X P E R I M E N T A L

Prepara t ion of Trialkyl(al lyloxy)t ins. A flask fitted with a rod-and-d isk column was charged with 192.8 g of t r ie thylmethoxyt in and 150 ml of dry allyl alcohol. T h e r e a c t i o n m i x t u r e w a s h e a t e d i n t h e p r e s e n c e of a l i t t le CH3ONa at 125-140 ~ until about 32 ml of methanol had dist i l led off. The reac t ion product was then vacuum-frac t ionated . We obtained 185.3 g (86.5%) of (allyloxy)triethylt in, bp 88-89 ~ (9 ram); nD2~ 1.4820; d42~ 1.2455.

A. E. Arbuzov Institute of Organic and Physica l Chemis t ry , Academy of Sciences of the USSR. Trans la ted f rom Izvest iya Akademii Nauk 8SSR, Seriya Khimicheskaya, No. 8, pp. 1762-1764, August, 1969. Original a r t i c le submitted July 8, 1968.

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TABLE 1. Diallyl (Alkylphosphinidene)-, (Phenylphosphinidene)- , and (Ethoxyphosphinidene)diacetates a n d Corresponding Phos - phinothioylidene and Phosphinylidene Compounds

Compound (p, ram) a~~ ~

Calculated ~a

CHaP(CH,COOCH2CH:CH2)2 C2H~P(CH2C00CH,CH~CH~)~

C6H~p(CH~.C00C H2CH~C H~).

C2H~0P(CH2COOCH2CH:CH2)~

C H,P(CH,COOC HzCH~C H~)e

C~H~P(CH~C 00CH~C H~C H~)~

S C,H~P(CH.C00CH.CH~CHe).

S C~ H~O PI (C I-I~C O O C I-I~C tI-- CI-I~)~

S C~H~0P(C H,C0 0C H.~CH=CH~)~

0

) t.0858 t,493~ 1,0663 1,493(

i, 128t t,54i~

1,0929 1,480(

1,1694' 1,523~

11,t48011, .~'22'~

tt fl946[ 1,563~

1,156411,502i

[1,:~662/I, 47t8

654053,69737 -- 6 5 6 i 5 4 0 9 7 0 i t 2 6 8 6 8 0 661 : 21l 170:2 166: 7: 6

!92,06 56,87 5,75 9,16 91,69 56,79 5,66 9,15 93,05

7 .1, ,0.9016..061,o,2 [77.2 147.07r.2 i o. 2r .4 oo,oT,oo/oT,o /o.?o,o o,ooroT

TABLE 2. Trialkyl(al lyloxy) tins and Allyl (Trialkylstannyl) ace ta tes

Compound bp, ~C (p, ram) d, ~o ~t2o D

Found Calculated

t CaH~)3SnOCH2CH~CH2 C4Ha)aSnOCH:CH~CHz

(CzH~)sS nCH.~COOCH~ CH~CH2 (C4H,)aS nCH2CO OCH2C H~CH2

88--89(9) 1,2455 1,4820/60,5(' 41,00 7,75 60,97 41,07 7,68 86,5 747--t48(9) ~ 1,t266[ t,4800187,52152,0019,10188,68151,9('[9,291 77,29 t20--t22(9) | 1,2~80[ t.4890 |70,46[43.64[7,25170,23143.33~7,29[ 86,0~

t06(0,06) | t.t296[ 1,48~8|98,79~52,71[8,73]97,93t52,04~s,80] 8~.3

(Allyloxy)tributylt in was p r e p a r e d analogously.

P r e p a r a t i o n of Allyl (Tr ia lkyls tannyl )ace ta tes . Ketene was pa s sed into 300.8 g of (al lyloxy)tr iethylt in contained in a t h ree -necked f lask fit ted with bubbler , t h e r m o m e t e r , and ca lc ium chloride tube. During this t r e a t m e n t the t e m p e r a t u r e of the r eac t ion mix tu re ro se to 65-70 ~ . React ion was comple te when the reac t ion mix ture turned yellow and the t e m p e r a t u r e of the mix ture fell. Vacuum fract ionat ion gave 300.2 g (86.04%) of al lyl ( t r ie thyls tannyl)aceta te , bp 126 ~ (11 mm); nD 2~ 1.4890; d420 1.2480.

Allyl ( t r ibutyls tannyl)aceta te was p r e p a r e d analogously.

P r e p a r a t i o n of Diallyl (Alkylphosphinidene)-, (Phenylphosphinidene)- , and (Ethoxyphosphinidene)-di- ace ta tes . A four -necked f lask fit ted with s t i r r e r , dropping funnel, t h e r m o m e t e r , and ref lux condenser was charged with 68.75 g of al lyl ( t r ie thyls tannyl)aceta te and 60 ml of dry e ther , and a solution of 13.2 g of methylphosphonous dichloride in 20 ml of dry e ther was added dropwise with s t i r r ing . The t e m p e r a t u r e of the reac t ion mix tu re gradual ly ro se to 46 ~ When the whole of the methylphosphonous dichloride had been added, s t i r r ing was continued fu r the r for 30 rain. E ther was dr iven off, and the res idue was v a c u u m - f r a c - t ionated. We obtained 54 g (about 100%) of chlorotr ie thyl t in , bp 45-46 ~ (0.06 mm), and 18.7 g (68%) of di- al lyl (methylphosphinidene)diacetate , bp 86 ~ (0.025 ram); nD 2~ 1.4933; d42~ 1.0858.

The other phosphinidene compounds were p r e p a r e d analogously.

P r e p a r a t i o n of Diallyl (Alkylphosphinothioylidene)-, (Phenylphosphinothioylidene)- , and (Ethoxyphos- phinothioylidene) d iace ta tes . F inely ground sulfur (1,96 g) was added to 15 g of diallyl (methylphosphini- dene)diacetate. The t e m p e r a t u r e of the mix ture ro se to 53 ~ The reac t ion mix ture was then heated for 2 h at 100-130 ~ and vacuum-f rac t iona ted . We obtained 15 g (89.6%) of diallyl (methylphosphinothioylidene)- diacetate , bp 134 ~ (0.03 mm); nD 2~ 1.5235; d42~ 1.1694.

The other phosphinothioylidene compounds were p r e p a r e d analogously.

P r e p a r a t i o n of Diallyl (Ethoxyphosphinylidene)diacetate. Ai r was dried with H2SO 4 and pa s se s through a solution of 8.2 g of diallyl (ethoxyphosphinidene)diacetate in 30 ml of dry e ther . There was an exo thermic r eac t i om When the t e m p e r a t u r e of the reac t ion mix ture fell, the reac t ion was complete . E ther was dr iven off, and the res idue was vacuum-f rac t iona ted~ We obtained 4.7 g (54.2%) of product , bp 135-136 ~ {0.03 mm); nD 2~ 1.4718; d42~ 1.1662.

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CONCLUSIONS

i. A method was developed for the preparation of dtallyl (alkyl-, aryl-, and alkoxy-phosphinidene)- diacetates.

2. Diallyl (methyl-, ethyl-, phenyl-, and ethoxy-phosphinidene) diacetates, (methyl-, ethyl-, phenyI-, and ethoxy-phosphiniothioylidene)acetates were prepared and characterized.

3. (Allyloxy)triethyltin, (allyloxy)tributyltin, and allyl(triethylstannyl)- and (tributylstannyl)-aeetates were prepared and characterized.

io

2. 3. 4.

5.

LITERATURE CITED

G. M. Vinokurova and S. G. Fattakhov, Zh. Obshch. Khim., 3_6, 67 (1966). G. M. Vinokurova and S. G. Fattakhov, Vysokomolecul. Soedin., AI____0, 2126 (1967). M. V. Proskurnina, Z. S. Novikova, and I. F. Lutsenko, Dokl. Akad. Nauk SSSR, 159, 619 (1964). M. V. Proskurnina, I. F. Lutsenko, Z. S. Novikova, and N. P. Voronova, in: Chemistry of Organo- phosphorus Compounds [in Russian], Izd. Nauka (1967), p. 8~ G. M. Vinokurova, Zh. Obshch. Khim., 37, 1652 (1967).

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