НОВЫЕ АСПЕКТЫ РЕАКЦИИ ФОСФОРИЛИРОВАНИЯ СЛОЖНЫХ ЭФИРОВ ПЕНТАХЛОРИДОМ ФОСФОРА И КОНФОРМАЦИОННЫЕ ОСОБЕННОСТИ ПРОДУКТОВ ПРЕВРАЩЕНИЯ

It has been obtained and characterized the products of the reaction of phosphorous pentachloride with esters that are the mixture of geometric isomers of dichloroanhydrides of β- chloro-β-alkoxyvinylphosphonic acid, which are intermediates in formation of threechloroanhydries of phosphonchlorocarboxylic acid.It was established, that in excess of phosphorous pentachloride, ethylacetate forms as products showed above so threechloroanhydride of phosphonoacetic acid. Proposed the sequence of obtaining of threechloroanhydrides of phosphonoacetic acid.In opposite of ethylacetate, phosphorylation of ethyl ester of propionic acid with phosphorous pentachloride gives only two products: threechloroanhydride of α-chloro-α-phosphonpropionic acid and dichloroanhydride of α-metyl- β-chloro-β-etoxyvinylphosphonic acid in the form of just one geometric isomer, that were separated and characterized. Formation of every vinylphosphonate can be explained by conformational feature of intermediates phosphorylation.On the base of these reasonings, 1H and 13C NMR spectras of theeethyl ester of α-phosphonpropionic acid and diethylacetal of phosphonoacetic aldehyde were analyzed and using conformational characteristics of called phosphonates an explanation of ambiguity of spectras is given. [ABSTRACT FROM AUTHOR]