SU1397452A1 - Method of producing 2-chloralkyldichlorophosphites - Google Patents

Abstract

The invention relates to phosphorus substances, in particular the preparation of 2-chloroalkyldichlorophosphites of the total fi l Cl-A-OPClj, where A is unsubstituted or 1,2-substituted alkylene, are semi-products for the synthesis of useful organophosphorus products. The goal is to simplify the process and increase the yield of target substances. Their synthesis is carried out by the reaction of alkylene oxide with PC1, in the presence of the bottom residue formed during the vacuum-distillation of the reaction mixture. The process is carried out in the presence of alkylene chlorohydrin. Simplification of the process is achieved by eliminating heat,

Description

The invention relates to organic chemistry, namely to an improved method for the preparation of 2-chloroalkyldichlorophosphites of the general formula

CI-A-OPCl, where A is unsubstituted or 1,2-substituted alkylene, which are the starting materials for the synthesis of organophosphorus co-IQ substances.

74522

20.15 g (83.5%) of the desired substance is obtained,

G. Under similar conditions, g (mol) is used: phosphorus trichloride

52 (0.38); epichlorohydrin 9.25 (0.1); 2,2-dichloroisopropanol 0.64 (5 mol.% VAT residue from option B 7.5 and get 21.85 g (90.5%) of the target

unity with useful properties

The purpose of the invention is to simplify the process and increase the yield of the target product.

Example 1, Preparation of 2,2-dichloroisopropyl dichlorophosphite.

A К A mixture of 9.25 g (0.1 mol) of epichlorohydrin and 0.64 g (5 mol,%) is added to 55 g (0.4 mol) of a mixture of phosphorus with stirring and at a temperature of 40-50 ° C. ) relative to epichlorohydrin 2,2-dichloroisopropanol, the reaction mass is kept under these conditions for 1 hour. Excess phosphorus trichloride is distilled, increasing the bath temperature to 130-140 ° C. Distillation of the residue in vacuo gives 16.1 g ( 66.5% in the calculation. On epilchloroschr and 2.2 -dichlorisopropanol) of the target substance, t, kip, 102-104 C / 15 mm Hg, Art., 1.5202, p 1.5195, GF 46.03 calculated 46543.

Found% C 15.63; H 2.31, C1 61.58; P 13.42,

20

25

Calculated,%: C 15,, 67j H 2.20; C1 61, 69; R 13,47-,

After isolating the desired pre-powder in the reaction flask, 5.6 g of 40 cubic m of the remaining mobile liquid remains.

B „A flask is charged with g (yol) phosphorus phosphorus 6.5 (0.27) regenerated in variant A, a new portion of phosphorus trichloride 13.75 (o, 1), vat residue from variant A and this mixtures under conditions of option A add a mixture of 9.25 g (0.1 mol) of epichlorohydrin and 0.64 g (5 mol,%) of 2,2-dscorisisopropanol. Distillation recovered 18.5 g (76%) of the desired substance.

B, Under similar conditions of use, g (mol): phosphorus trichloride (including regenerated in variant B) (0.4), epichlorohydrin 9.25 (0.1); 2,1-dichloroisopropanol 0.64 (5. mol%) vat residue from variant B 6.7 and

15

thirty

50

55

D, Under similar conditions, g (mol): phosphorus trichloride 54 (0.39) i epichlorohydrin 9.25 (O,); 2,2-dichloroisopropanol 5.29 (10 mol.%) I VAT residue from option D 9.8 and get 25.3 g (100%) of the target substance,

E. Under similar conditions, the use of cosiness g (mol): phosphorus trechloride 54 (0.39), epichlorohydrin 9.25 (0.1) 2.2-dichloroisopropanol 1.29 (Yu mol,%); vat, the remainder of variant D 10.5-and get 28.5 g (114%) of the target substance.

The total yield of 2,2-dichlorbrizopropyl-dichlorophosphite (calculated on the used epichlorohydrin and 2, 2- dichloroisopropanol) in six cycles 130.8 g

. (88.57) ..

Example 2. Preparation of 2-chloroisopropyl dichlorophosphite.

A. To 35 g (0.4 mol) of phosphorus trichloride with stirring and a temperature of 15-20 C add a mixture: 5.6 g (0.096 mol) of propylene oxide and 0.47 g (mol%) of 2-chloro-propane g la The reaction mass is maintained under these conditions for 2 hours. The excess phosphorus trichloride is distilled off at atmospheric pressure and 14.8 g (14%) are distilled off by distillation of the residue in vacuo.

chlorisopropanol and propylene oxide

77. go

target substance, t. Kip, 79 C / 6.m1 Hg, Art .; 1.4927-, pi, 1.3803, MRj. 41.13; calculated 41.22.

Paideno,%: C 54.18J P 15.78,

18.51; H 3.03; C1

C HgCljOP

Calculated,%: C, 18.44; H, 3.10; - C, 54.42; R 15.85,

After isolation of the desired product in the reaction flask, 2.9 g of the bottoms remain,

B, Under similar conditions of use, cosiness, g (mol): phosphorus trichloride

 f -

(including 38 g. regenerated aroma varnish in variant A), 55 (0.4) j propylene oxide

5.8 (.0.10) 5 2-chloroisopropanol 0.47 (5 mol.%), Vat residue from option A and get 16.42 g (80%) of the target substance.

B, Under the same conditions, g (mol) is used: phosphorus trichloride (including 40 g recovered in variant B) 55 (0.4) propylene oxide 5.8 (0.10) 2-chloro-propanol and 0.47 (5 mol,%), VAT residue from, option B 1.5 and get to 19.5 g (95%) of the target substance.

G. Under similar conditions, g (mol) is used: phosphorus trichloride (including 41 g recovered in variant B) 55 (0.4) propylene oxide 5.8 (0.10) 2-chloro-propanol and 0.47 j VAT residue from option B 1.3 and get 21.0 g (102.5%) of the target substance.

The total yield of 2-chloroisopropyl-dichloro-phosphite (based on propylene oxide and 2-chloro-isopropanol) in four cycles is 71.72 g (87.4%).

Example 3. Getting 2-chloroethyl dichlorophosphite ..

A, A mixture of 55 g (0.4 mol) of phosphorus trichloride and 0.8 g (Yu mol.%) Of ethylene chlorohydrin at displacement and a temperature of 0–10 ° C introduces 4.4 g (0.1 mol) ethylene oxide. The temperature of the reaction mass is raised to room temperature, the mixture is kept under these conditions for 1 hour. The excess phosphorus trichloride is distilled off and 14.8 g (81% calculated as ethylene oxide and ethylene chlorohydrin oxide) are recovered by distilling the residue, boil. 73-75 C / 20 mmHg nf 1.5048 1.4728, W, 36.54, calculated 36.60.

Found,%: C 13.13; And 2.20; C1 58.51; P 17.10.

CJl Clausp

. Calculated,%: C 13.24; H 2.23; C1 58.63; 17.07,

After the desired product has been isolated, 2.3 g of the bottoms remain in the reaction flask as a mobile, colored liquid.

B. Under similar conditions, g (mol) is used: phosphorus trichloride (including 37 g recovered in variant A) 65 (0.47); ethylene oxide 4.4 (0.1); ethylene chlorohydrin 0.8 (Yu mol%) stillage residue from option A and get 16.4 g (90.0%) of the target substance.

B. Under similar conditions, g (mol) is used: phosphorus trichloride (including 35 g of B (55) regenerated in variant B) 55 (0.4) i ethylene oxide 4.4 (0, l) J ethylene chlorohydrin 0.8 ( Yu mol.%), Vat residue from option B 2.6 and receive 18.95 g (104%) of the target substance.

G. Under similar conditions, g (, mol) is used; phosphorus trichloride (including 34 g recovered in variant B) 55, ethylene oxide 4.4 (0.1); ethylene chlorohydrin 0.8 (10 mol.%), and the distillation residue from option B 2.8 and receive 20.4 g (112%) of the target substance.

D. Under similar conditions, g (mol) is used: phosphorus trichloride (including 34 g regenerated in variant r) -55j ethylene oxide 4,4 (0,1); ethylene chlorohydrin.- 0.8

(10 mol.%); VAT residue from option D 2.7 and get 18.8 g (103%) of the target substance.

The total yield of 2-chloroethyl dichlorf-phiite (based on ethylene oxide

and ethylene chlorohydrin) on five cycles

89.35 g (98%).

In this way, the proposed method allows to simplify the process of obtaining the target compound by

eliminating the heating of the reaction mixture in an autoclave at 100-300 ° C,

drastically reduce the amount of waste - the bottom residue and increase

jQ yield of the desired product by

carrying out the process in the presence of

VAT residue resulting from

the allocation of 2-chloroalkyldichlorophosphate,

and catalytic amounts of alkylene 45 chlorohydrin.

Claims (1)

Formula isobreni The method of obtaining 2-chloralcic-chlorophosphites of the general formula 0 C1-A-ORF1, where A is unsubstituted or 1,2-substituted alkylene,  by the interaction of alkylene oxide with g phosphorus trichloride followed by isolation of the target product by vacuum distillation, in order to simplify the process and increase the yield 513974526 of the target product, the process is carried out on the product, and the catalytic copy of the presence of the cubic residue, the volumes of the corresponding alkilinity, during the isolation of the desired chlorohydrin at 0-50 C.