Shalimov A. PIII-Phosphorylated amides of polyhalogencarboxylic acids

The methods for the synthesis of PIII-phosphorylated trihalogenacetamides and the effect of phosphorus P(III) atom and trihalogenacetamide groups on their structure and reactivity are discussed in the thesis in details. It is shown that phosphorylation regiospecifity of N-substituted amides of trigalogenacetic acids with phosphorus halides is governed by the character of the fragments at nitrogen and phosphorus atoms. A new approach for synthesis of the first representatives of alpha-phosphorylated vinylamides of trifluoroacetic acid was elaborated. It was found that PIII-phosphorylated trihalogenacetamides demonstrate phosphorylation properties to nucleophiles. A hitherto unknown O-PIII-phosphorylated phosphocetenacetal was prepared. For the first time phosphazides with N-acylamide group at phosphorus atom were prepared. For the first time it was shown that the reaction of carboxylic acids N-substituted amides with phosphorus pentachloride proceeds with formation of oxazaphosphetanes as intermediates,rather than via acylic O-tetrachlorophosphoranes, which were postulated before.