Organophosphorus compounds. XIII. Synthesis of some 4-Phenylperhydro-1,4-azaphosphorines

Abstract

The reaction of phenylphosphonic dichloride with two mole equivalents of vinylmagnesium bromide in tetrahydrofuran at ? 70º gave 72% of divinylphenylphosphine oxide, which when heated under reflux for 6h with a 20% excess of aqueous methylamine or of aqueous allylamine afforded almost quantitative yields of 1-methyl- or 1-allyl-4-phenylperhydro-1,4-azaphosphorine 4-oxide, respectively. These compounds were converted into the corresponding phosphine sulphides in high yields. An attempt to prepare 4-phenylperhydro-1,4-azaphosphorine 4-oxide by the reaction of divinylphenylphosphine oxide with ammonium hydroxide and sodium hydroxide at 100º for 26h gave, instead, a low yield of 4-phenylperhydro-1,4-oxaphosphorinane 4-oxide. Reaction of vinylmagnesium bromide with diphenylphosphinic, diphenylphosphinothioic and phosphoryl chlorides are described.