Phosphorylation of diamines

Abstract

Alkanediamines react with diphenyl phosphite (1 mol. equiv.) and triethylamine in carbon tetrachloride, or with diphenyl phosphorochloridothionate (1 mol. equiv.), to give bis(diphenoxyphosphinylamino)alkanes and related compounds, and not ω-aminoalkylphosphoramidic esters. m- and p-Phenylenediamines behave similarly, but m-phenylenediamine may also be monophosphorylated. o-Phenylenediamine behaves anomalously and gives phenyl hydrogen N-(2-aminophenyl)phosphoramidate. Piperazine and phenyl phosphorodichloridothionate give NN′-bis(phenoxyphosphinothioyl)piperazine or 7-phenoxy-1,4-diaza-7-phosphabicyclo[2,2,1]heptane-7-thione, depending on the reaction medium.