REACTION OF GRIGNARD REAGENTS WITH PHOSPHINOUS CHLORIDES HAVING THE ANTI-7-PHOSPHANORBORNENE FRAMEWORK

Abstract

Trichlorosilane-pyridine converts the bridging phosphorus function in dimers of 1-aminophosphole derivatives to the phosphinous chloride with the anti configuration. The chlorine was replaced by phenyl with retention of configuration (as confirmed by stereospecific features in ³¹P and ¹³C NMR spectra) on attack of phenylmagnesium bromide in ether. Reactions with methylmagnesium bromide or tert-butyl-magnesium chloride were not useful for producing tertiary phosphines. The anti-P-phenyl phosphine derivative was oxidized to the phosphine oxide which was readily isomerized by amines to the syn-compounds. In the mass spectra of these oxides, a peak for the P(II) species [C₆,H₅P=O)⁺ was present.