Synthesis of bifunctional organophosphorus compounds

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    G . M. V inokurova and S. G. Fat takhov UDC542.91+661.718 .1

    We have previously reported the synthesis of diallyl 3, 3'-(phenylphosphinidene)dipropionate and allied compounds [11 and described "organic glasses" prepared from the corresponding phosphinylidene and phos- phinothioylidene compounds [2]. Continuing this line of investigation, we considered it to be of interest to synthesize and study a number of diallyl phosphinidenediacetates, including (alkoxyphosphinidene)diacetates (phosphinous acid derivatives), and also the corresponding phosphinylidene- and phosphinidinediaeetates and their derivatives have been prepared, readily and in good yields, by the reactions of (trialkylstannyl)- acetic esters with tervalent phosphorus acid chlorides [3-5]. Diallyl phosphinidenediacetates were pre- viously unknown.

    We have now shown that these compounds can be prepared analogously by the reactions of allyl (tri- alkylstannyl)acetates with tervalent phosphorus acid chlorides. We studied the reactions of allyl (triethyl- stannyl)acetate with methyl-, ethyl-, and phenylphosphonous dichlorides and ethyl phosphorodichloridite, 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 reactions were exothermic, and the products were obtained in yields of 51-77%. The products were readi ly isolated by vacuum distillation. They are colorless liquids which readily 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 reactions we were able to isolate only diallyl (ethoxyphosphinylidene)diacetate in the pure state. The diallyl (alkylphosphinylidene)- and (phenylphosphinylidene)-diacetates polymerized when distilled. All attempts to fractionate them, even in a high vacuum_ and with stabilization with copper stear- ate, were unsuccessful in spite of the fact that the diallyl (alkylphosphinylidene)- and (phenylphosphinylid- ene)-diacetates were prepared by different methods: oxidation with hydrogen peroxide, oxidation with at- mospheric oxygen, and the transester i f icat ion of dimethyl (alkylphosphinylidene)- and (phenylphosphinyl- idene)-diacetates, prepared specially for this purpose [5], with allyl alcohol. The constants of all the com- pounds synthesized are given in Table 1.

    Until recently there has been no information in the chemical l i terature on the starting compounds: trialkyl(allyloxy)tins and ally1 (trialkylstannyl)acetates. However, these compounds are of interest as in- termediate products for the synthesis of the most varied organic compounds containing the (allyloxycarbonyl)- methyl group and for the preparation of tin-containing polymers. We have synthesized (allyloxy) triethyltin, (al- lyloxy)tributyltin, and allyl (triethylstannyl)- and (tributylstannyl)-acetates. Trialkyl(allyloxy)tins were pre- pared readi ly in good yields by the transetherif ication of known trialkylmethoxytins with allyl alcohol. Atlyl (trialkylstannyl} acetates were prepared by the reactions of trialkyl(allyloxy)tins with ketene. The con- stants of the conpounds obtained are given in Table 2.


    Preparat ion of Trialkyl(allyloxy)tins. A flask fitted with a rod-and-disk column was charged with 192.8 g of tr iethylmethoxytin and 150 ml of dry allyl alcohol. Thereact ionmixturewasheated in thepresence of a little CH3ONa at 125-140 ~ until about 32 ml of methanol had distil led off. The reaction product was then vacuum-fractionated. We obtained 185.3 g (86.5%) of (allyloxy)triethyltin, bp 88-89 ~ (9 ram); nD2~ 1.4820; d42~ 1.2455.

    A. E. Arbuzov Institute of Organic and Physical Chemistry, Academy of Sciences of the USSR. Translated from Izvestiya Akademii Nauk 8SSR, Seriya Khimicheskaya, No. 8, pp. 1762-1764, August, 1969. Original art ic le submitted July 8, 1968.


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

    Compound (p, ram) a~~ ~

    Calculated ~a


    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~)~


    ) 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,:~662/I, 47t8

    654053,69737 -- 656i540970it268680 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(allyloxy) tins and Allyl (Trialkylstannyl) acetates

    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)tributyltin was prepared analogously.

    Preparat ion of Allyl (Trialkylstannyl)acetates. Ketene was passed into 300.8 g of (allyloxy)triethyltin contained in a three-necked flask fitted with bubbler, thermometer , and calcium chloride tube. During this t reatment the temperature of the react ion mixture rose to 65-70 ~ . Reaction was complete when the reaction mixture turned yellow and the temperature of the mixture fell. Vacuum fractionation gave 300.2 g (86.04%) of allyl (tr iethylstannyl)acetate, bp 126 ~ (11 mm); nD 2~ 1.4890; d420 1.2480.

    Allyl (tr ibutylstannyl)acetate was prepared analogously.

    Preparat ion of Diallyl (Alkylphosphinidene)-, (Phenylphosphinidene)-, and (Ethoxyphosphinidene)-di- acetates. A four-necked f lask fitted with s t i r re r , dropping funnel, thermometer , and reflux condenser was charged with 68.75 g of allyl (tr iethylstannyl)acetate and 60 ml of dry ether, and a solution of 13.2 g of methylphosphonous dichloride in 20 ml of dry ether was added dropwise with st irr ing. The temperature of the reaction mixture gradually rose to 46 ~ When the whole of the methylphosphonous dichloride had been added, st i r r ing was continued further for 30 rain. Ether was driven off, and the residue was vacuum-f rac - tionated. We obtained 54 g (about 100%) of chlorotriethyltin, bp 45-46 ~ (0.06 mm), and 18.7 g (68%) of di- allyl (methylphosphinidene)diacetate, bp 86 ~ (0.025 ram); nD 2~ 1.4933; d42~ 1.0858.

    The other phosphinidene compounds were prepared analogously.

    Preparat ion of Diallyl (Alkylphosphinothioylidene)-, (Phenylphosphinothioylidene)-, and (Ethoxyphos- phinothioylidene) diacetates. Finely ground sulfur (1,96 g) was added to 15 g of diallyl (methylphosphini- dene)diacetate. The temperature of the mixture rose to 53 ~ The reaction mixture was then heated for 2 h at 100-130 ~ and vacuum-fract ionated. 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 prepared analogously.

    Preparat ion of Diallyl (Ethoxyphosphinylidene)diacetate. Air was dried with H2SO 4 and passes through a solution of 8.2 g of diallyl (ethoxyphosphinidene)diacetate in 30 ml of dry ether. There was an exothermic react iom When the temperature of the reaction mixture fell, the reaction was complete. Ether was driven off, and the residue was vacuum-fract ionated~ We obtained 4.7 g (54.2%) of product, bp 135-136 ~ {0.03 mm); nD 2~ 1.4718; d42~ 1.1662.



    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.



    G. M. Vinokurova and S. G. Fattakhov, Zh. Obshch. Kh im. , 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. Kh im. , 37, 1652 (1967).



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