New Aspects of Synthesis of the Compounds with P-C Bonds

Abstract

Industrial realization of practically useful compounds with P-C bonds is restrained by lack of simple methods of their production. The use of tri(2-chloroethyl)phosphite and its transformation products for binding aluminium chloride in reactions of phosphorus trichloride with arenes has allowed to improve aryldichloro- and diarylchlorophosphines synthesis methods, as the indicated bases form with AlCl₃ liquid complexes which do not mix with the expected product. Complexones have also been successfully used in the synthesis of organylphosphonyl- and -thionophosphonyldichlorides. New agents of converting adducts of unsaturated compounds and phosphorus pentachloride into organyldichlorophosphonates (aldehydes, ketones, acetyles, ethers and salts of carboxy-lic acids, α-oxides, N-oxides, hexamethyldisiloxane) have been found. Isoalkylallylethers are shown to react with PCl₅ in two directions producing i-PrOCH=C(CH₂Cl)P(O) C1₂and CH₂=CH-CH₂OC(CH₃)=CHP(O)Cl₂ Alkylmetallylethers react under mild conditions with PCl₅ at the double bond, at 3O°C dealkoxylation takes place resulting in dichloroanhydride ClCH₂C(CH₃)=CHP(O)Cl₂. Allyl- and propargylacetales undergo phosphonylation exceptionally at the vinyl group generated during a reaction. Original phosphorus-containing ethers, acetales, cyclical aldehydes, aromatic nitro-, amino-, hydroxycompunds, and phosphorus-containing azodyes have become accessible as a result of the studied transformations.