SU1067004A1 - Process for preparing 1-chloro-2-alkoxyvinylphosphonic anhydrides - Google Patents

Abstract

1. METHOD OF OBTAINING 1-CHLOR-2-ALKOXIVINYLPHIPHIPHONEIC DICHPORANUM HYDRONES by the interaction of phosphorus pentachloride with alkyl ethers of alcohols in an organic solvent, decomposition of the resulting adduct and release of the desired product by distillation, and a & in order to increase the yield of the target products, decomposition of the adduct is carried out with dimethyl sulfate at 20-35 C. 2. The method according to claim 1 is also characterized in that the reaction of phosphorus pentachloride with alkyl ethers of alcohols is carried out at 840 ° C.

Description

4 The invention relates to the chemistry of organophosphorus compounds with a C-P bond, and specifically to a method for preparing 1-chloro-2-alkoxyvinylphosphonic acid dichlorohydrides of the general formula JOSN C 54 P (O) Coll. where E-alkyl which are widely used as organophosphorus synthesis intermediates. A known method for producing 1-chloro-2-alkoxyvinylphosphonic acid dichloride anhydrides by reacting 2-alkoxyvinylphosphonic acid dichlorohydrides with chlorine gas in carbon chloride at 15-20 ° C til. The disadvantages of this method are the inaccessibility of the initial acid hydrides, as well as the use of chlorine gas, which is closest to the proposed technical essence and the achieved result, is the method of Cheney dichlorohydrin 1-chloro-2-alkoxyvinylphosphonic acid, which means that the alkyl esters are alcohols, for example alkyl vinyl ethers, reacting with phosphorus pentachloride in diluent e, consisting of absolute benzene and phosphorus oxychloride, at 5-6 ° C, followed by repeated exposure ktsionnoy mixture at 12 C for The resulting adduct was then heated at 80-90 C for 2 h, then at - up to complete dissolution of the crystals, and the desired product isolated by distillation. Products yield up to 23% SI. The disadvantage of this method is the low yield of the target products. The purpose of the invention is to increase the yield of the target products. This goal is achieved by the fact that according to the method for producing 1-chloro-2-apkoxyvinylphosphonic acid dichlorides, which is apkyl esters. the alcohols are reacted with phosphorus pentachloride in an organic solvent, followed by treating the adduct formed with dimethyl sulfate at 20-35 °. Example. 1-Chloro-2-ethoxyvinylphosphonic acid dichloride, A, B four-necked flask equipped with a stirrer, a calcium chloride tube cooler, a thermometer and a dropping funnel, placed 58 g {0., 279 g-mole) of phosphorus chloride and 80 mp absolute benzene. To the resulting suspension with vigorous stirring and cooling is added dropwise 10 g (0.139 g-mol) of ethyl vinyl ether ether while maintaining the temperature of the reaction mass. The reaction mixture is then kept at room temperature for 3 hours. The resulting adduct is treated with 35.1 g (0.279 g-mol) of dimethyl sulfate. To complete the reaction, the mixture is heated for 1-2 hours. A clear yellow solution is formed which is distilled and 16.5 g of the desired product are obtained, yield 53%. Tcmp 90-92 C (2.5 mm Hg), 1.4051, p 1.5087. Literature data: Tstsch 72-74 0 (0.05 mm Hg), ti 1,5082. Found,%: SS 47.25; R 13.57 C H CtjOjP Calculated,%: C1 47.60; R 13.86. NMR spectrum P: (5p + 29 ppm. B. To a suspension of 97 g (0.466 g-mol) of phosphorus pentachloride in 150 ml of absolute benzene while adding. T 14 g (0.189 g-mol) of diethyl ether and peremethe the mixture is added dropwise to 6.6 g (0.480 g-mol) of dimethyl sulfate and heated at 35 ° C until complete dissolution of the crystals is obtained by distillation of the resulting solution to obtain 23.7 g of the target solution. product, yield 55% J Tkip 112-114 C (4 mm Hg), 3985 ,, 5075. Found: Cf 47.31; P 13.71. JK-spectrum, 3040; 2975, 2930, 2885, 1.625, 1275, 1230, 860, 830, 685, 560.V Example 2. 1-Chloro-2-butoxyvinylphosphonic acid dichloride.Crystalline adduct obtained similarly to example 1A from 10 g (0.1 gmol) butylvinyl ether and 41.7 g (0.2 gmol) p phosphorous phosphorus in 50 MP absolute benzene, treated at 25.5 g (0.2 g-mol) of dimethyl sulfate and stirred at this temperature until the reaction mixture is completely homogenized. 12.6 g of the expected product are obtained by distillation, yield 50%, Bp 112114 e (2 mm pT.CT.), D5 ° l, 3053, n | f 1,5012. Literary data: 124 "C (1 mm Hg), p 1.5050. Found,%: St. 42.05; R 12.11. CgH jClaOjP Calculated,%: ce 42.29; R. 12.32. NMR P spectrum: s + 30.0 ppm. PMR spectrum ((9, ppm, hexamethyldisioxane vnutr.): 7.73 in., d (PH) 6 Hz (SI); 4.30, t., 3j (HH) 6 Hz (OCHj); 1 , 63 m., (CHgCHg); 0.96 T., J (HH) 6 Hz. IR spectrum, cm: 3035, 2969, 883, 1620, 1470, 1385, 1270, 1210, 840.

J1067004, 4

The proposed method for producing di-by eliminating highly toxic

1-chloro-2-alkoxy-amino-phosphorus oxychloride; Conducting phosphoric acid allows more under mild temperature conditions.

than doubling the output of the target- allows to simplify {instrumental

out ° of products. Carrying out the process of designing the process, which is based on an available raw material and is easy, based on an inert organic solvent.

benzene, improves working conditions, can be implemented in production.

Claims (2)

1. METHOD FOR PRODUCING DICHLOR— 1-CHLORO-2-ALCOXYVINYL PHOSPHONIC ACID ANHYDRIDES by the interaction of phosphorus pentachloride with alkyl ethers of alcohols in an organic solvent, decomposition of the formed adduct and isolation of the target product by distillation, characterized in that, in order to increase the yield of target products, 20 -35 ° C. 2. The method of pop. 1, with the fact that the interaction of phosphorus pentachloride with alkyl ethers of alcohols is carried out at 840 ° C.