SU721447A1 - Method of preparing 1-alkoxy-3-chloro-1-propene-2-phosphonyl(thiophosphonyl) dichlorides - Google Patents

Description

Body at 0-70 ° C, followed by decomposition of the resulting complex with sulfur dioxide, ethyl alcohol, formic acid, acetic anhydride or hydrogen sulfide at О-10®С. The process can be conducted both without a solvent, and in the solvent medium. A distinctive feature of the method is the use of alkyl alkyl ether as the ally containing reagent, decomposition of the complex obtained by sulfur dioxide, ethyl alcohol, formic acid, acetic anhydride or hydrogen sulfide under the specified conditions. The method of obtaining 1-alkoxy-3-chloro-1-propec-2-phosphonic acid (thiophosphonic) acid disulfur is characterized by simplicity and availability of initial reagents and allows to obtain high purity target products as by reacting phosphorus pentachloride with alkyl lilium a single phosphorylation product is formed containing an olefinic bond. Example 1. 1-megoxy-3-chloro-1-propen-2-phosphopic acid dichloride. a) In a four-necked flask equipped with a stirrer, thermometer, dropping funnel and reflux condenser with a calcium chloride tube, place 208.3 g (1 mol) of phosphorus chloride, 450 ml of absolute benzene and add O-10 C with vigorous stirring 36 g (0.5 mol) of methylallite ether. Then the temperature of the reaction mixture is slowly raised to 60-70 ° C and held for 3-5 hours. The resulting crystalline and complex is treated at O-IO C with syringate gas until the reaction mixture is completely clarified. Vacuum distillation gives 39 g (35%) of 1-methoxy-3-chloro-1-propen-2-phosphonic acid dichloride (constants and product yields are given in Table 1. In the IR spectrum of 1-dichlorohydrin alkoxy-3-chloro-1-propen-2-phosphonic acids were found to have characteristic absorption bands in the region of 500-6OO cm V (P – C $), 12751265 cm V (), 123 O – 1 O 2 O cm (“C – O– C), 1616-1620 (The parameters of the NMR spectra are circumvented in Table 2. 74 The PMR spectra were recorded on a PYa 23O8 spectrometer, 60 MGy, carbon tetrachloride solvent, and the tetramethylsilane standard of the morning. e NMR-KGU-4, 10.2 MHz; external standard-85% phosphoric acid. IR spectra were recorded on a SpelcttKJinOM-SOOO spectrophotometer in a thin layer. b) A crystalline complex obtained from 60 g (0.28 mol) phosphorus pentachloride and 10 g (0.14 mol) of methyl ellar ether under conditions of example la are treated with formic acid until the reaction mixture is clarified. 6.5 g (20%) of 1-methoxy-3-chlorohydride dichloride is obtained by vacuum distillation 1-propene-2-phosphonic acid. PRI mme R 2. Dichloride 1-ethoxy-3-chloro-1-propen-2-phosphonic acid. a) From 290 g (1.39 mol) of phosphorus pentachloride and 6O g (0.69 mol) of ethyl lilyl ether under conditions of example 1a, 69 g (41%) of dichlorohydride I-ethoxy- are obtained; chloro-1-propen-2-phosphonic acid. b) 60.5 g (0.29 mol) of phosphorus pentachloride is gradually added to 25 g (0.29 mol) of ethyl allied ether so that the temperature of the reaction mixture does not rise above, after which the temperature of the reaction mixture is raised to 68-70лЗ, the resulting crystalline complex decompose 13 g of ethanol. 12 g (17%) of 1-ethoxy-3-chloro-1-propen-2-phosphonic acid dichloride are obtained by distillation. c) A crystalline complex, prepared from 72.5 g (0.35 mol) of phosphorus pentachloride and 15 g (0.17 mol) of ethyl lilyl ether under the conditions of Example 1 a, is treated at 0-10 with acetic anhydride until the crystals are completely dissolved. Vacuum distillation gives 1O g (24%) of 1-ethoxy-3-chloro-1-propen-2-phosphonic acid dichloride. In a similar manner, 1-propoxy-3-chloro-1-propen-2-phosphonic acid dichloride is synthesized. PRI me R 3. Dichlorohydrin 1-methoxy-3-chloro-1-propen-2-thiophosphonic acid. White crystalline complex, rep.

ISO-stranded g (0.72 mop) of phosphorus pentachloride and 26 g (0.36 mol) of methipallate ether under the conditions of Example la are treated at 0 ° C with hydrogen sulfide until the crystals completely disappear.

By distillation in vacuo, 32 g (37%) of 1-methoxy-chloro-1-propei-2-thiophosphonic acid dihydramine are obtained.

Similarly, the synthesis of dichlorohydrin 1-ethoxy-3-chloro-1-propene-2-thiophosphonic acid.

721447

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X SIDSE

Parameters of the NMR spectrum of dichlorogens of 1-alcokoi-3-chloro-1-propvn-2-phosphonic (thiophosphonic) acids

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T (} fi l and It ft 2

Chemical shifts of methoxy groups.

Claims (2)

Invention Formula I. Method of producing 1-alkoxy-3-chloro-1-propen-2-h (2) h) osphonic (thiophosphonic) acid dichlorogens by reacting an allyl-containing reagent phosphorus with phosphorus followed by the decomposition of the complex obtained, characterized in that, in order to simplify the process, alkyl allyl ether is used as the allyl-containing reagent and the sulfur complex is dissolved in 1) gas, ethyl alcohol, formic acid lot, acetic gangistimide or hydrogen sulfide at about 10 s. 2. A method according to claim 1, wherein t and h and and so that alkyl alkyl ether is reacted with phosphorus chloride at O-7CV. Sources of information taken into account in the examination 1. USSR Author's Certificate No. 174627, cl. C O7 F 9/42, 1964. 2. Moscow V.V. et al. Interaction of phosphorus pentachloride with acrolein acetal. - JOH, 197О, 4О, .№ 12 with. 2764 (prototype).