SU1694590A1 - Method of 2-chloroheptylphosphonic acid di-(2-chloroalkyl)esters preparation - Google Patents

Abstract

The invention relates to organophosphorus substances, in particular the preparation of di (2-chloroalkyl) esters of 2-chloro-heptyl-phosphonic acid, used as flame retardants and plasticizers in the polymer industry. The goal is to simplify the process. It is carried out by the reaction of 2-chloro-heptyltriphosphonium hexachlorophosphate with "oxides in the medium of an organic solvent at 20-40 ° C in the presence of TICI4. These conditions make it possible to obtain the desired product in one stage from the available starting materials with a yield of 51–91%.

Description

AND

This invention relates to the chemistry of organophosphorus compounds with a P – C bond. Namely, to an improved method for producing di (2-chloroalkyl) esters of 2-chlorheptylphosphonic acid of the general formula

C5NISNS2R (OCHCN2C1) 2

C1

About R

where R is H (a), CH2C1 (b), CH20CH2CH and CH2 (c), which are of particular interest as flame retardants and plasticizers for polymeric materials and monomers for the synthesis of phosphorus-containing high molecular compounds.

The aim of the invention is to simplify the process.

According to the proposed method for the preparation of di (2-chloroalkyl) esters of 2-chloro ether. and soba in 2- od (I)

2 (c)

2-chloro-heptyl-trichlorophosphonium-hexachlorophosphorate is subjected to interaction with L-oxides in a solvent medium in the presence of titanium tetrachloride at 20-40 ° C. The reaction proceeds as follows:

С5НцСНСНСН j№j PCl + 4R-Сн-pr,

about - With nSSHSHSNDoSNSN

About R (

4- POCJj + ZRCHCHjCl

s

where R - has the indicated meanings. The reaction is initially exothermic, so it is desirable to cool the reaction mixture. After dissolving the crystalline 2-chloro-heptyltrichlorophosphonium hexachlorosphosphate, the a-oxide is fed at 20 ° C at a rate such that the temperature in the mixture does not exceed 40 ° C. Such temperature conditions allow to avoid

Os

Yu

Jb 01

yoo o

side reactions of the formation of phosphoric acid 2-chloroalkyl esters. As solvents, it is desirable to use inert organic compounds, such as benzene. Purification of the target esters (I) is carried out by sequential washing of the reaction mixture with a 3% aqueous solution of sodium carbonate or sodium hydroxide, water, drying, and vacuuming at 100 ° C and a pressure of 5-10 mm Hg. d constant weight. The structure of synthetic esters. (I) confirm data

AND

NMR1H and 31P spectra, and composition - by elemental analysis.

In the proposed method, in contrast to the known 2-chlorheptylphosphonic acid instead of dichloride anhydride for the preparation of di (2-chloroalkyl) ethers

2 chlorheptylphosphonic acid 2-chlorheptyltrichlorophosphonium hex.sup.chlorophosphorate is used. This simplifies the process by eliminating the step of producing the corresponding phosphoic acid dichloride.

PRI me R 1. Di (2-chloroethyl) ester 2 | -chlorogetylphosphonic acid.

To a solution of 20 g (0.096 mol) of phosphorus phosphorus in 200 ml of absolute benzene, 4.7 g (0.048 mol) of phptene-1 are added at 5–10 ° C. The mixture is stirred for 48 hours at 20 ° C and the precipitated white precipitate is filtered off with 2-chloro-heptyltrichlorophosphonium hexachloroforforate, washed with benzene, dried under vacuum (May 10 g), suspended in Eenzene, 0.03 ml of tetrachloride titanium is added and at 0-5 ° C begin to supply gaseous ethylene oxide. The crystals gradually turn into a liquid, on which Spent 3 ml of liquid ethylene oxide. The charge continues to pass ethylene oxide at 20 ° C at such a rate that the temperature in the reactor does not exceed 40 ° C. The total consumption of liquid ethylene oxide 10 ml. Heating at 40 ° C is continued for another 1 h, after which unreacted ethylene oxide and the solvent are distilled off in vacuum. The residue (dissolved in 20 ml of benzene and washed with 75 ml of a 2% soda solution, 75 ml of water, dried with magnesium sulfate, benzene is distilled off, the residue is kept to constant weight at 100 ° C and a pressure of 5 mm Hg. Yield 6 g (9Ш; d420 1,30630 till 20 1.4744. IR spectrum, cm

1425, 1380, 1270, 1080, 1030, NMR 31P spectrum: dr 26 ppm Found,%: CI 31.7; P 9.6. ScN22C1ROZR Calculated,%: CI 31.3; R 9, G.

2965, 2935, 2860, 1455, 970, 670.

PRI mme R 2. Di (2-chloro-1-chloromethylethyl) sir 2-chlorheptylphosphonic acid.

To a solution of 25 g (0.121 mol) of phosphorus pentachloride in 250 ml of absolute benzene, 8.4 g (0.061 mol) of heptene-1 is added dropwise at 10 ° C. Stir when. 2 ° C for 48 hours; a white precipitate is filtered off; - 5 ° C is treated with 4.5 g (0.048 mol) of epichlorohydrin. Then it is stirred at 40 ° C for 2 hours, cooled, washed with 50 ml of a 2% soda solution, 50 ml of water, dried with magnesium sulfate, benzene is distilled off, the residue is kept at 110 ° C at 15 mm Hg. to constant weight. 3 g (51%) of the desired product are obtained, d420 1.3315. Pt2 1/881. PC spectrum, 1240, 1080, 1050. NMR31P spectrum: dr + 28 ppm Found %: CI 39.7; R 6.6.

С1зН24С15ОЗР

Calculated,%: CI 40.7; P 7.1. Similarly, 2-chloro-hydroxyphosphonic acid 2-chloro-methylphosphonic acid di (2-chloro-1-allyloxymethyl ethyl) ester is synthesized, yield 65%, d420 1.1192, 20 = 1.4696. IR spectrum, 3080. 2960, 2935, 2865, 1640, 1240. 1040. NMR31R spectrum: (5p + 28m.d.

Found,%: CI24.1; R 7.5. CigH ChOsP

Calculated,%: CI 23.7; R 6.9. The proposed method for the preparation of di (2-chloroalkyl) esters of 2-chlorheptylphosphonic acids is based on available raw materials, does not require complicated instrumentation, and can easily be put into production. This method allows to prepare in one stage esters of formula (I) from p-phosphorus chloride and 1-alkene, mine. It is necessary to obtain 2-chloroheptylphosphonic acid dichloride, which is more economically viable.

Claims (1)

Claims of the invention. A process for the preparation of di (2-chloroalkyl-ov) ethers of 2-chlorheptylphosphonic acid. lots of general formula  S5npsnsn2r (osnsn2a) Cl or 5 where R - N. СНаС or СН20СНаСН СН2. the interaction of phosphorus chlorides with syums in an organic solvent medium in the presence of titanium tetrachloride, which is due to the fact that Neither the process, norhexachlorophosphate or phosphorus chloride, and the process is carried out using 2-chlorheptyltrichlorophospho at 20-40 ° C.