SU536191A1 - The method of producing dichloroanhydrides of α-chloro-α-phenylvinylphosphonic acids - Google Patents

Description

;one

The invention relates to the field of chemistry of organophosphorus compounds and relates to a process for the preparation of novel compounds, specifically a-chloro-p-phenylvinylphosphonic acid dichlorides, of the general formula

CgHs-C C-PCl

; I

R 01.

where R is hydrogen, chlorine or bromine, which can be used as intermediates of organophosphorus synthesis.

A number of methods for the preparation of p-phenyl vinylphosphonic acid dichlorides are known, based on the reduction of P-Styryl tetrachlorophosphorane, for example, red 1 and white 2 phosphorus are used as a reducing agent.

The target compounds and the method of their preparation have not been described in the literature, and the known methods for the preparation of 3-styrylphosphonic acid dichlorides are unsuitable for the synthesis of target compounds.

The aim of the invention is to develop a process for the preparation of a-chloro-phenylbenylphosphonic acid dichlorides.

The proposed method for preparing the target compounds is that the corresponding p-phenyl vinyl tetrachlorophosphorane is heated to 120-160 ° C in the presence of a usually equimolar amount of oxychloride or phosphorus thiochloroxy. The starting tetrachlorophosphorane is obtained in a known manner by reacting equimolar amounts of the corresponding styrene and phosphorus pentachloride in dry benzene and then distilling off the solvent. The starting α-chlorophenylvinyl tetrachlorophosphorane can be obtained by reacting phenylacetylene with an equimolar amount of phosphorus pentachloride in dry benzene. The desired compounds are isolated by vacuum fractionation.

The yield of the desired compounds is 16-63%.

The structure of the obtained compounds was confirmed by elemental analysis data and data of the PMR spectra and.

Example 1. Preparation of dichlorohydrin a-chloro-p-phenylvinylphosphonic acid. A. In the presence of phosphorus thiochloroxide.

Claims (2)

93.0 g (0.336 g-mol) of p-styryl tetrachlorophosphorane, obtained by reacting styrene with phosphorus pentachloride in benzene, followed by distilling off the solvent, are placed in a flask with reflux condenser, then 57.0 g (0.336 g-mol) of phosphorus thiochlorooxy and The reaction mixture is heated at 120-160 ° C until the crystalline mass completely disappears and the evolution of hydrogen chloride stops. As a result of fractionation in vacuo, 51.2 g (63%) of the desired product are obtained with a cue of 126-127 ° C / 10.5 mm Hg. v .; df 1.3978; p 1.6379. %: C 41.65; H 2.87; C1 44.50; Found, R 11.90, CsHgClsP Calculated,%: C 41.45; H 2.52; C1 44.45; P 12.10. Chemical shift br / - 158 ppm relative to 85% o-phosphoric acid. PMR spectrum contains a multiplet at 7.77 ppm. (proton in a-position to phenyl drug in styryl radical) and multiplet at 0 7.38 ppm (protons of phenyl core). B. In the presence of phosphorus oxychloride. Similarly, from 76.5 g (0.289 g-mol) of P-Stityl tetrachlorophospho- rop and 44.3 g (0.289 g-mol) of phosphorus oxychloride, after fractionation in vacuum, 41.2 g (60%) of the desired soy is obtained; . 124-126 ° C / 10.5 mm Hg. v .; df 1.3977; 1.6345. Phenylphosphonic acid. According to the procedure of Example 1, of 24.9 g (41%) of the title compound from 60.9 g (0.196 g-mol) | 3-chloro-p-phenpvinyl tetrachlorophosphorane and 33.2 g (0.196 g-mol) of phosphorus thiochloride; 24.2 g (41%) of the title compound. kip 135-137 ° C / 0.15 mm Hg. v .; df 1.4814; p2o 1.6369. Found,%: C 34.85; H 1.85; C1 51.12; R 11.08. CsHsCUP Calculated,%: C 35.00; H 1.83; C1 51.45; R 11.30. The chemical shift ap are 149.5 ppm relative to 85% o-phosphoric acid. The PMR spectrum contains only signals from the irotopes of the phenyl core (, 47 ppm). Example 3. Obtaining dichlorohydrin and - chloro-p-bromo-p - Phenylphosphonic acid. According to the method of Example 1, 118.8 g (0.4 gmol) (3-bromo-p-phenylvinyl tetrachlorophosphorane and 61.4 g (0.4 g-mol) of phosphorus oxychloride) give 20.8 g (16%) of the desired compound140- 142 ° C / 0, 3 mm Hg; d 142 ° C / 0.3 mm Hg; 09; H 1.14; halo (based on chlorine) 44.47; P 9.48. CgHsBrClsP Calculated,%: C 30.27; H 1.27; halo 44.67; P 9.76. Chemical shift br, - 147 ppm, fireproof, 85% o-phosphoric acid Formula of the invention Method for producing a-chloro-p-phenylvipylphosphonic acid dichlorides of general formula SbH5-C-PC1 f IR Oi where R is hydrogen, chlorine or bromine concluding in that the corresponding | 3 - phenyl vinyl tetrachlorophosphorane is heated to 120-160 ° C in the presence of oxychloride or phosphorus thiochloroxy. Sources of information taken into account during the examination: 1. G. K. Fedorova, A. V. Kirsanov, ZHOH, 30 , 4044, 1960 2. E. N. Walsch, T.M. Beck, W.N. Woodstock, IACS, 77,929 (1955).