Thiolophosphohydrides: New Reagents in the Organo-Phosphorus Synthesis

Abstract

A simple and effective method has been developed for synthesizing a new type of organophosphorus compounds, thiolophosphohydrides, with the general formula R(R′S)PH based on the selective reduction of thioesters of P(III) acids by di- or trialkylstannanes. Stable S-alkylalkylthiophos-phonites and S-alkylalkyldithiophosphonites have been obtained for the first time by using the processes of oxidation and sulfurization. The functionally substituted phosphorus (111) thio derivatives have been obtained by the addition reactions of thiolophosphohydrides with compounds containing carbon-carbon and carbon-oxygen multiple bonds, with the cleavage of the P-H bonds and the preservation of P-S bonds. Factors affecting the rate of interaction, stability and the structure of additional products have been elucidated. Depending on the reaction conditions of thiolophosphohydrides with halogen containing electrophilic reagents and on the nature of the latter, the process can lead to the cleavage either of the P-H bond or the P-S bond. Thiolophosphohydrides as new reagents in organophosphorus synthesis open up new vistas for obtaining a variety of functionally substituted phosphor- and sulfur-containing compounds.     

TETRAPHOSPHORUS TRISULFIDE IN REACTIONS WITH THIOACETALS,AMINALS, SULFENAMIDES AND DISULFIDES. INFLUENCE OF AMINES AND BENZOYL PEROXIDE

Abstract

The reactions of tetraphosphorus trisulfide with thioacetals, aminals, sulfenamides and disulfides were studied. The reactions were found to give organothiophosphorus compounds and to be facilitated by organic amines and benzoyl peroxide.     

The reaction of 1,3-dibutyl-2-ethoxy-4,5-dimethyl-2-oxo-1,3,2-diazaphosphol-4-ene with tetracyanoethylene

The reaction of 1,3-dibutyl-2-ethoxy-4,5-dimethyl-2-oxo-1,3,2-diazaphosphol-4-ene with tetracyanoethylene gives 6-amino-1,3-dibutyl-5-cyano-2-ethoxy-4-(1-imino-2-cyanoethyl)-2-oxo-1,3,2-diazaphosphindane.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 303–305, February, 1994.     

Synthesis and some properties of tetrakis-3,5-di-<Emphasis Type="Italic">tert</Emphasis>-butyl-4-hydroxybenzylated calix[4]resorcinols

A method for the synthesis of new calix[4]resorcinols tetra-3,5-di-tert-butyl-4-hydroxybenzyl derivatives is developed. Their interaction with methyldichlorophosphonate, dimethyldichlorosilane in the presence of a base leads to formation of organophosphorus-organosilicon cavitands. Acetylation of hydroxybenzylated calix[4]resorcinols with acetic anhydride leads to products of either incomplete or full acetylation depending on experimental conditions.