The synthesis and some reactions of N-hydroxycarbamates

Abstract

Hydroxylamine and alkyl chloroformates reacted in alkaline media to form N-,NO-di-, and NNO-tri-alkoxycarbonyl-hydroxylamines, successively. N-Methylhydroxylamine similarly gave N- and NO-di-alkoxycarbonyl-N-methyl-hydroxylamines, and O-methylhydroxylamine produced N- and NN-di-alkoxycarbonyl-O-methylhydroxylamines. N-Phenylhydroxylamine, with 1 equivalent of ethyl chloroformate, gave N-hydroxy-N-phenylurethane. Hydroxylamine hydrochloride and ethyl chloroformate yielded a product which changed into hydroxyurethane. Alkyl N-hydroxycarbamates and hydroxyurea gave O-xanthydryl derivatives. The N-hydroxycarbamates with aqueous dipotassium tetracyanonickelate(II) formed dipotassium tricyanonitrosylnickelate(II). No evidence of a Lossen-type rearrangement during the acid and alkaline hydrolysis of these hydroxylamino-derivatives was seen. The possible mechanisms of hydrolysis are discussed.