SU551336A1 - Method for preparing diaryl esters, -limit phosphonic acids - Google Patents

Description

METHOD OF OBTAINING DIARYL ETHERS a / 3. (54) UNLIMITED PHOSPHONE ACIDS

The invention relates to the chemistry of phosphorus compounds with a C-P bond, namely, an improved method for the preparation of diaryl-B1H esters of a- - unsaturated phosphonic acids. A general formula:

(RI O

where R is aryl or substituted aryl,

RI is hydrogen or lower alkyl.

These compounds can be used as repellents and organic phosphorus intermediates.

A known method for the preparation of dipesch zhirs of a, - unsaturated phosphonic acids by the interaction of diphenylchlorophosphite with fixed ketones at 120 ° C in a sealed tube 1.

This method is not universal, it is difficult to process, besides crawled products contain impurities of an acidic nature, which excludes the possibility of their further use as repellents.

Closest to the invention in terms of technical essence and the achieved result is the method of obtaining the a, ft-unsaturated diaryl ethers of a, ft-unsaturated phosphonate acids by the interaction of hydrochloride a, j3 - unsaturated phosphonic acid with a phenomer at a molar ratio of reagents of 1: 2 respectively and C 2 temperature.

The disadvantages of this method include the need to use 2 mol of phenol per 1 mol of dichloride d, / 3 unsaturated phosphonic; acids and significant reaction time (20-24 hours).

 The purpose of the invention is to simplify the process for the preparation of diaryl ethers, and | 8 - non-specific phosphonic acids.

To this end, it is suggested that dichlorohydrin o, / 3 unsaturated phosphonic acid be reacted with phenol at a molar ratio of 1: 1 and reacting carbon dioxide through the reaction mixture, followed by treatment of the reactive mixture with aqueous sodium hydroxide solution to a pH of 8-9.

The descriptive method for obtaining diaryl ethers of a, / - unsaturated phosphonic acid based on the use of available initial reagents is technologically simple and allows to obtain the target products with a high yield (85-92.5%).

Example. Difeshtelovy ether vikilfospolyuvov acid.

A mixture of 143 g (0.1 g tol) of vinylphosphonic acid dachloride and 9.4 (0.1 g mol) of phenol is stirred and heated at 130–140 ° C for 4 h with a continuous purging of carbon dioxide to remove hydrogenous voloric acid . Cool to room temperature, add sodium hydroxide solution to pH 8 and 20 ml of Beisol. The organic layer is separated, the benzene is distilled off. Obtain 24.5 g (92.5%) of vishphosphonic acid diphenyl ester, t.Kil. 142 ° С / mm, lnJJl, 5575, d 1.1960

. Found,%: C 64.87; H 4.81; R 12.17; C, 4H1eOZR

Calculated,%: C 64.62; H 5.00; R 11.92. T.KSh. 109.5 (IlO mm) nJl, 557L Diaryl esters of unsaturated phosphonic acids are obtained in a similar way, the list and properties of which are given in the table,

Example 2. The repellent properties of diphencleate ester WINSH1PHOSPHONE acid.

Forks of tissues (WcM) are impregnated with acetonium solutions of Vishphosphonic acid diphenyl ester at the rate of 4 and 401 per 1 m according to ADV (active substance). The impregnated tissue pieces are left free hung in room conditions. After 24 hours, 10, 30.50, 90 days, 20 days, and 150 days, the coefficient of the repellent effect (CODE) of the tissues with respect to the laboratory culture of fleas is determined. CODE is determined on the basis of the number of blocks remaining on the experimental and control (non-impregnated) tissue samples after 30, 60, 120, and 180 seconds in the "} ment of stopping the possibility of insect jumping. According to the CODE of four segments, the view is average. The comparison of the effectiveness of difeschvinylphosphot in parallel experiments uses the known renellent hexamide in DETA.

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Formula invented in

I. The method of obtaining diarrheal emirs, kepr, far phosphonic. acids of the general formula

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Claims (2)

I in RI o shch R ar l il emsedyushyar, A | - hydrogen nln is lower glkyl, by the interaction of d-chlorine {waiting for a, P is unsaturated phonoic acid with phenol ri heating, which is due to the fact that, in order to simplify the process, H (MS) and #KS K & imbmbi take molar ratio 8 1: 1 and the process is carried out by blowing carbon dioxide through the reaction mixture, followed by treating the reaction mixture with an aqueous solution of caustic soda to RC q) q 8-9. 2. The method according to claim 1, characterized in that the process is carried out at 130-150 C. Sources of information taken into account in the examination: 1. Nurtdshyuv S.Kh., Hayrupliya R.S., Tsivushsh B.C., Zykova TV, Kamai G.Kh. On the interaction of dash1H01Chlorphosphites with saturation ketones, JOH, 1972t.42, p.123-125. 2. US patent N 2365466, cl. 260-543, 1944 prototype).