New Types of Functionally Substituted Methylphosphonites and Their Derivatives

Abstract

Organophosphorus compounds containing a functional group in the a-position of the alkyl radical are of great interest in both theoretical fundamental investigations and for practical applications. Functionally substituted methyl-phosphonites and their derivatives, belonging to this broad class of organophosphorus compounds, are convenient objects for investigating mutual effects of trivalent phosphorus and a heteroatom, or functional groups attached to it in the a-position. They have also become key substances in obtaining new organophosphorus compounds. Functionally sub-stituted compounds of tetracoordinated phosphorus have been intensively investigated in recent years; rather convenient methods of synthesis of these compounds have been proposed and their properties have been studied in detail¹. However, the corresponding compounds of tricoordinated phosphorus are not available or difficult to obtain. Recently we re-ported on the properties of halogen-substituted methylphos-phines and their derivatives². The present paper is devoted to the synthesis and investigation of the reactivity of alkoxy-, dialkylamino- and carbonyl substituted methylphos-phonites and their derivatives. In synthesis of alkoxymeth-ylphosphonites and their analogs we were the first to use labile alkoxymethylmagnesium chlorides in the reactions with tricoordinated phosphorus acid chlorides³. Previously unknown dialkoxymethylphosphonites and their analogs were obtained from hypophosphorous acid and trialkylorthofor-mates. The process of esterification and dialkoxymethylat-ion of hypophosphorous acid, being dependent on a catalyst, proceeds in different ways and results in the formation of dialkoxymethylphosphonite structures