SU372818A1 - . ^^; ^; BLIOTEKA - Google Patents

Description

one

This invention relates to a process for the preparation of new phosphoric (thiophosphoric) acid diester chlorides of the general formula

OC CXCOOR, I

SNS

where RI and R2 - Ci-Sat-alkyl;

X is hydrogen or chlorine;

Y is oxygen or sulfur,

which can be used for the synthesis of insecticides, acaricides and nematocides. The proposed method is based on the known reaction of the interaction of phosphorus acid chlorides with p-dicarbonyl compounds and consists in the fact that phosphoric (thiophosphoric) acid ester hydrochloride is of the general formula

R,

C1

C1

where RI is Ci-C3-alkyl;

Y is oxygen or sulfur,

treated with acetoacetic acid derivative of general formula

CJijCOCHXCOORa

where R2 is Ci-Sb-alkyl;

X is hydrogen or chlorine,

in the presence of eg triacceptor acid, ethylamine.

The reaction temperature is (-10) -20 ° C. You can carry out the reaction in an inert organic solvent, for example toluene, chlorobenzene, chloroform. If no solvent is used at the beginning of the reaction, it is advisable to add a small amount of the solvent during the reaction;

Target products released by known techniques are colorless oils which are distilled under high vacuum without decomposition.

Example 1. Chloride 0-ethyl-0- (1karbmethoxy-1-propylene-2-yl) - thiophosphoric

acid.

with..

RO-CETSN,

/

C1

I

SNS

to a mixture of 53.7 g (0.3 mol 0-ethyl dichlorophosphate and 34.8 g (0.3 mol) methyl acetoacetate) are added in 1 hour at 10 -12 ° C and 30.5 g (0 , 3 mol} of triethylamine and after adding half of triethylamine 50 ml of toluene are added, stirred for 2 hours at 10 ° C and 17 hours at. Triethylamine hydrochloride is filtered, the filtrate is washed with water, dried, filtered and evaporated in vacuo at 40 ° C. in high vacuum, a pure target product is obtained, bp 53 ° C / / 0.03 mm; n 1.496; mol. weight 258.7.

The ratio between cis and trans isomers in the crotonic acid residue is 9: 1.

Calculated,%: C 32.5; H 4.7; C1 13.7; R 12.0; S 12.4.

CrHizClOiPS.

Found,%: C 32.1; H 5.0; C 14.2; R 12.0; S 13.2.

Example 2. Chloride 0-n-propyl-0- (1carbmethoxy-1-propen-2-yl) -phosphoric acid.

About .N, 0. II

7 F - O - C UNCISS, SGI

sn.

30.5 g (0.3 mol) of triethylamine are added to a mixture of 53.1 g (0.3 mol) of 0-n-propyl dichlorophosphate and 34.8 g (0.3 mole) of methyl acetic acetic acid, and after forming a large amount of precipitate, 50 ml of toluene are added. Then it is stirred for 15 hours at 0 ° C, triethylamine hydrochloride is filtered off, the filtrate is washed several times with a small amount of water, dried, filtered and concentrated in vacuo at 40 ° C. The aqueous phase is extracted with ml of chloroform, dried, the extract is evaporated and distilled under high vacuum to obtain the pure desired product, i.e. bale. 67 ° C / 0.05 mm; p 1,460; a pier weight 256.6.

The ratio between cis- and t / ans-isomers in the crotonic acid residue is 1: 2.

Calculated,%: C 37.4; H 5.5; C1 13.8; R 12.1.

CgHuClOiP.

Found,%: C 38.0; H 5.7; C1 13.0; R 12.2.

The compounds listed in the table are prepared analogously.

Subject invention

Claims (2)

1. Method of producing phosphoric (thiophosphoric) acid diester of phosphoric acid with general formula Y RiO. II ; p-o-c cxcooR ,, cvI sn, where Ri and Ra is Ci-Cz-alkyl; X is hydrogen or chlorine; Y is oxygen or sulfur, characterized in that the phosphoric (thiophosphoric) ester ether dichloride is of general formula Y Rio P-CI / Cl where Ri and Y are as defined above, are treated with an acetoacetic acid derivative of the general formula CHgCOCHXCOORj where R2 and X are as defined above, in the presence of an acid acceptor, followed by isolation of the target product by known techniques. 2. A method according to claim 1, characterized in that triethylamine is used as an acid acceptor.