Organophosphides, from phosphorus

Reaction of the organophosphide from phosphorus and phenyllithium with propylene oxide, followed by hydrolysis, gave bis(2-hydroxypropyl)-diphenylphosphonium bromide in 19% yield and 2-hydroxypropyldi-phenylphosphine (6). The latter was obtained as the methiodide in 19% yield. Reaction of the complex lithium phenylphosphide with benzaldehyde gave bis(a-hydroxybenzyl)phenylphosphine oxide in 12% yield (6). 

The organophosphides derived from phosphorus and organometallic compounds were found to react with alkyl halides in a manner typical of phosphides, to give unsymmetrical tertiary phosphines (6). Thus, phosphorus, plienyllithium, and butyl chloride gave dibutylphenyl-phosphinc and butyldiphenylphosphine in 37% and 44% yields, respectively. 

The results from reactions with phenyllithium and phenylsodium indicated that the phosphorus-derived organophosphides were of complex structure (6). The alkyl halide reactions demonstrated the presence of structural units having two phenyl groups bonded to phosphorus, yet only small yields of diphenylphosphine were obtained on hydrolysis. Lithium diphenylphosphide was thus ruled out as an important intermediate, since it hydrolyzes cleanly to diphenylphosphine. Moreover, hydrolysis of the organophosphide from plienylsodium and phosphorus failed to give simple phosphine products at all, but reaction of the sodium... 

White phosphorus also reacts with carbon nucleophiles in ether or tetrahydrofuran to give dark red solutions believed to be complex organophosphides (Rauhut and Semsel). Hydrolysis of a mixture obtained from reactions of white phosphorus with organolithium and organomagnesium compounds gives the primary phosphine as the major product, with small amounts of secondary and tertiary phosphines being formed under some conditions. 

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