SU496283A1 - Method for preparing alkyl ethers of aryl alkyl phosphinic acids - Google Patents

Description

(54) METHOD FOR OBTAINING ALKYL ESTERS OF ARYLALKYLPHOSPHYNIC ACIDS.

 . . -. This invention relates to organophosphorus compounds with a P – C bond, in particular, to an improved method for the preparation of alkyd esters of aryl alkylphosphinic acids, where At is aryl; AC is alkyl; (- alkyl, which are widely used to study the structure and reactivity, the ability of organophosphorus compounds 4G, and also as pesticidal compounds. A known method for producing alkyl ethers of arylalkylphosphonic acids by alcoholysis of amides of phosphine acids when heated. It is also known that the preparation of compounds of this formula by the interaction of arylalkyl acid alcohols in the environment of the organo-stator in the presence of triethylamine hydrogen chloride as an acceptor of hydrogen chloride. The low yield of the product, difficulty; separation of the target product from the impurity of triethylamine hydrochloride, as well as arylalkylphosphine oxide, formed as a result of decomposition of the ester of arylalkylphosphinic acid under the action of triethylamine; The method is technologically simple, and makes it possible to feel the end products with good yields and a high degree of purity. It consists in that arylalkylchlorophosphine is reacted with alcohols in the presence of ethylene oxide in an organic solvent medium. The process is desirable to conduct an excess of ethylene oxide when cooled to a temperature of from -5 to -3S ° C. As a result of the reaction, ethylene oxide is converted to ethylene chloro-i hydrin, which, when interacting with

the starting aripalkylchlorophosphine and ethylene oxide I form α-aryl alkylphosphinic acid chloroethyl ester. The resulting esters differ significantly in boiling point, so they are easily separated by fractionated distillation with a Christmas tree reflux condenser. The absence of an arylalkylphosphine oxide impurity in the reaction products is proved by PMR spectroscopy, and the individuality of the selected esters is shown by p31 NMR data — the copy spectrum.

Example 1. Obtaining ethyl ester of phenylethylphosphinic acid.

To a solution of 6.6 g (0.142 g mol) of ethanol and 12.5 g (O, 284 g mol of ethylene oxide in 25 ml of ether with stirring, in a stream of carbon dioxide and a temperature of from -50 to -45 ° C in 24.5 g (0.142 gmole) of phenylethylchlorophosphine in 2 O ml of ether is added dropwise in an hour for 1 hour. The reaction mixture is stirred for 8 hours at a temperature from -4 to -35 until the traces of anhydride chlorine has disappeared. temperature from –1 ° C to overnight. On the next day after evaporation and two distillations with an electric reflux condenser in vacuum, 14 g are obtained (54.1% of the theoretical w) Ethyl efi1) and feniletilfosfinistoy acid with m. bales. 42-42.5 ° C / 0.038 mm Hg v .;

20

L

0.9810;

1.5251;

-j)

- 124.8 ppm

Literary data: t. Kip. 94.5 - 95.50 / 10 mm Hg v .; (jJO 0.9781

h 1.5250.

Along with ethyl ether, j-ethyl ethylphosphinoic acid and -chloroethyl ester are simultaneously isolated in 9 g yield (29.3% of the theoretical); m.p.

70-7, 012 mm Hg. v; d

1.0968; nf 1.5372; 5,127 ppm

Found C1 16.47%.

Calculated C1 16.36%. Literary data: t. Kip. 8182 0 / mmHg v .; d 11111; fl 1.5430.

Example 2. Preparation of fl-chlorophenylethylphosphinic acid ethyl ester.

A solution of 6.5 g (0.15 gmol) of ethyl 1 alcohol and 17 g (O, 3 gmol) of ethylene oxide in 20 Un ether in a stream of carbon dioxide at a temperature of from -50 to -45 °

treated according to example 1 with 31.5 g (0.15 g. MOLB) fl-chlorophenyl ethyl chlorophosphine in 20 ml of ether. The next day, the reaction mixture was evaporated and distilled with a Christmas tree reflux condenser in a vacuum.

cuome. After two distillations receive. 17.3 g (54.8% of theoretical) ethyl fl-chlorophenylethylphosphinic acid ethyl ester st. kip 57-58.5 ° / 0.12 mm Hg. v .; tiJO 1.1000; ft

DI

 120 ppm

1.5400;

Found C1 16.58 and 17.14%. CioHi4C10P

Calculated C1 16.34%. Literary data: t. Kip. 11420

1, О9ОО;

115.5 / 7 mmHg v .; 25 1.5402.

Example 3. Preparation of L.-chlorophenylethylphosphinic acid n-propyl ester.

30 A solution of 4.9 g (0, O817 g-mol) of absolute n-propyl alcohol and 7 g (0.159 gm) of ethylene oxide in 30 ml of ether is treated as in Example 1 with 16.5 g (O, O8 Gmol) p- chlorophenylethyl

35 chlorophosphine in 2O ml of ether. two. Distillations with the fir-tree reflux condenser in vacuum get 10 g (54.2% of the theoretical) n-chlorine ester of tl-chlorophenylethylphosphinic acid with m.p.

40 72.5-740 / 0.18 mm Hg v .; d

tl 1.5352;

31

(S

- 122 ppm

Found C1 15,, 7 and 16.04%.

 Calculated C1 15.37%. Literary data: t. Kip. 9820

99.5 / 2 mmHg v .;

1.0696; 1.5333.

Along with n-propyl ether, p-chloroethyl ether tl-xno | j4 nipethylphosphinic acid is also simultaneously isolated from the reaction mixture in a yield of 8, O g (4% of the theoretical), b.p.

| 20

95 / 0.25 mm Hg from,;

1,2017; 20

31

S - 127 ppm

J)

Claims (1)

1.5552; Found Cl 26, O%. i Calculated Cl 28.23%, Example 4. Preparation of phenylethylphosphinic acid n-propyl ester To a solution of 5.5 g (0, O91 g-mol) of absolute n-11propyl alcohol and 7 g (o, 159 Gmol) of ethylene oxide in SO ml of ether with stirring in a stream of carbon dioxide and a temperature between -50 and -42 were added according to Example 1 15.7, O91 (Gmol) phenylethyl chlorophosphine in 2 O ml of ether. The reaction mixture is worked up and distilled according to the general procedure. After two distillations in vacuum, 7.37 g (41% of theoretical) of phenylethylphosphinic acid n-propyl ester are obtained with a bale. 38.5-39.50 / 0.08 mmHP P 1.5210; d 0.9736; - 122 ppm Literary data: t. Kip. 81.5mm Hg v .; 0.9663; 82.5 ° / 4 1.5191. Along with n-propyl ether, 5.7 g (28.9% of the theoretical) jj-chloroethyl phenyl ethyl phosphonate was isolated from the reaction mixture. Claim 1. A method of producing alkyl ethers of aryl alkyl phosphonous acids by reacting aryl alkyl chlorophosphines with sp1 fluids, a medium-inert organic solvent in the presence of a hydrogen chloride acceptor and isolating the target product by known methods, such as accepting the owner of the product with a chlorophosporic acid acceptor, in order to simplify the process, you will have to be in the shape of a hologram, you will have to be in a way to accept the same product by accepting the target product by means of a well-known organic ether. 2, the method according to claim 1, which is also distinguished by the fact that the process is carried out in an excess of ethylene oxide at a temperature from -5 to -35 ° C.