SU1694589A1 - Method of producing di-(2-chloroethyl) esters of alkenylphosphonic acids - Google Patents

Abstract

The invention relates to organophosphorus substances, in particular the preparation of di (2-chloroethyl) esters of alkenylphosphonic acids of the total CRiR2 CH-P (OHO-CH2-CH2CI) 2, where Ri is CeHs and R2-H or CH3, or RI is 1-naphthyl, which as flame retardants and plasticizers are used in polymer production. The goal is to simplify the process. It is carried out by the reaction of alkenyltrichlorophosphonium hexachlorophosphorate with ethylene oxide at 20-40 ° C in the presence of TICU. These conditions allow in one stage from the available raw material to obtain the target product with a yield of 64-90%. 3 table.

Description

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This invention relates to the chemistry of organophosphorus compounds with a P – C bond, namely to an improved process for the preparation of di (2-chloroethyl) alkenylphosphonic acid esters of the general formula

R

Ri

(OCH2CH2CI) 2

H

ABOUT

(I)

where Ri is SbH5. R2 - H (a). SNS (b);

Ri - 1-SyuN, R2 - H (c), which can be used as flame retardants and plasticizers of polymeric materials, monomers and comonomers for the preparation of fire-resistant high molecular compounds, as well as plant growth stimulants.

The aim of the invention is to simplify the process.

According to the proposed method for the preparation of alkenylphosphonic acid di (2-chloroethyl) ethers, alkenyltrichlorophosphonium hexachlorophosphate is reacted with ethylene oxide in the presence of titanium tetrachloride at 20-40 ° C.

The process is described by the following scheme:.

RlR2O CHPC 3 PCl6 + 4o ---- -RiR2C "

CHP (OXOCH2CH2C02 + 2CICH2CH2CH + POC1 where RI and R2 are as indicated.

The process can be carried out both without solvent and in inert organic solvent. The reaction is initially exothermic, therefore it is necessary to apply cooling of the reaction mixture so that the temperature does not exceed 20 ° C. After dissolving crystalline alkenyl trichlorophosphonium hexachlorophosphonate

ABOUT

2

01 00 About

the ethylene oxide feed is carried out at 20 ° C at such a rate that the temperature in the mixture does not exceed 40 ° C. This temperature mode allows you to avoid side reactions of formation of phosphoric acid 2-chloroethyl ethers. The supply of ethylene oxide is finished after the cessation of self-heating of the reaction mixture or the negative sample with silver nitrate for active chlorine is stopped. The target esters are purified by sequential washing 3% solution, sodium hydroxide, water, drying and evacuating at 100 ° C and a pressure of 5-10 mm Hg to constant weight.

The structure of the obtained esters (I) was supported by the data of IR, NMR P spectroscopy, and the composition by elemental analysis.

In the proposed method, in contrast to the alkene phosphonic acids, which are known instead of dichlorohydrides of alkenyl phosphonic acids, alkenyl trichlorophosphonium hexachlorophosphorates are used to prepare alkenyl phosphonic acid esters. This allows one to simplify the process by reducing the formation of esters of formula (I) to one stage.

PRI me R 1. Di (2-chloroethyl) ether styrylphosphonic acid.

The crystalline styryltrichlorophosphonium hexachlorophosphorate obtained from 10.4 g (0.1 mol) of distilled styrene and 42 g (0.2 mol) of phosphorus pentachloride in 100 ml of absolute benzene is filtered off, washed with benzene, dried in a vacuum desiccator, transfer t to the reactor, add 0.05 ml of titanium tetrachloride to the reactor, cool with ice and start feeding gas-gap ethylene oxide. The crystals gradually turn into liquid. Then continue to pass ethylene oxide at room temperature at such a rate that the temperature does not exceed 40 ° C. Upon completion of the exothermic reaction, feeding of ethylene oxide is stopped. Overall

and

(2-Chloroethyl) esters of alkenylphosphonic acid RP (OCH2CH2C1) 2

sn3 sn sn

64

1.3056

consumption of liquid ethylene oxide 22 ml. Heat another 1 hour at 40 ° C, at 25-30 mm Hg. highly volatile are distilled off. The residue is washed at 40 C with 100 ml of a 3% sodium hydroxide solution, then

water, dried with anhydrous magnesium sulphate, filtered and the filtrate was kept in vacuo at 5 mm Hg. and temperature, 100 ° C to constant weight. Obtain 26 g (86%) of the desired product.

Di (2-chloroethyl) ethers and methylstyryl- and 2- (1-naphthyl) vinylphosphonic acids are synthesized in a similar way.

The constants and data of elemental analysis, IR and NMR spectra are given in Table.

1-3.

The proposed method for producing di (2-chloroethyl) ethers of alkenylphosphonic acids is based on available raw materials, does not require complex instrumentation, and can easily be put into production. This method permits the preparation of esters of formula (I) from phosphorus pentachloride and alkene in one stage, and the preparation of the dichloride anhydride is mined.

alkenylphosphonic acids, which is economically viable.

Claims (1)

The invention of the method for producing di (2-chloroethyl) esters of alkenylphosphonic acids of the general formula Ru R2 (OCH2CH2C) 2 AND ABOUT where RI is CeHs; R2 is H or CH3 Ri-1-CioH7; R2-H, the interaction of phosphorus chlorides with ethylene oxide in the presence of titanium tetrachloride, characterized in that, in order to simplify the process, alkenyl trichlorophosphonium hexachlorophosphorate is used as phosphorus chloride and the process is carried out at 20-4.0 ° C. (Table 1.5695 20.2 8.4 ЈCHj2,4l; J (PH) 3.6 Hz. Continuing iaCxn.1