Studies of organophosphorochloridates. Part VI. Reactions of steroid phosphorochloridates with amines and some alcohols

Abstract

Cholesteryl phosphorodichloridate is best prepared by the action of phosphoryl chloride on cholesterol in the presence of triethylamine. Chromatography and thermal decomposition of the phosphorodichloridate are briefly discussed. Cholesteryl, lanosteryl, and ergosteryl phosphorodichloridates have been treated with selected primary and secondary amines. In all cases nucleophilic substitution at the phosphorus atom took place; only with the ergosteryl derivative was there elimination at C-3.

trans-4-t-Butylcyclohexanol has been converted by phosphoryl chloride or pyrophosphoryl chloride into the phosphorodichloridate. With phosphoryl chloride and a larger proportion of the alcohol, bis-4-t-butylcyclohexyl phosphorochloridate was isolated.

A further study has been made of the reactions of some steroid phosphorodichloridates with alcohols; the mechanisms are briefly discussed.