Mechanism of the reactions of trialkyl phosphites with ?-halocarbonyl compounds

Autor: Valeri I. Kovalenko, A. N. Pudovik, A. M. Pyndyk, Yu. I. Sudarev, T. Kh. Gazizov, V. B. Podobedov
Rok vydání: 1978
Předmět:
Zdroj: Bulletin of the Academy of Sciences of the USSR Division of Chemical Science. 27:2319-2323
ISSN: 1573-9171
0568-5230
DOI: 10.1007/bf00946685
Popis: 1. Trialkyl phosphites react with chloral at low temperatures (from −40 to −70°C) in a 1∶2 ratio to form 1,4,2-dioxaphospholanes, which are converted under the action of HCl into dialkyl α- (1-hydroxy-2,2,2-trichloroethoxy)-β,β,β-trichloroethylphosphonates. 2. The kinetics of the reaction of triethyl phosphite with chloral have been studied by high-speed Raman spectroscopy, and it has been shown that the formation of 2,2,2-triethoxy-3,5-bis(trichloromethyl)-1,4,2-dioxaphospholane is observed at room temperature and that the latter compound slowly decomposes into diethyl β,β-dichlorovinyl phosphate and ethyl chloride with the accompanying splitting off of chloral. 3. It has been postulated that the reaction of trialkyl phosphites with chloral begins with the attack of the phosphite phosphorus atom on the carbonyl carbon atom of chloral. The first step in the process is rapid and is not the rate-determining step of the reaction.
Databáze: OpenAIRE
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