Alkyl N-Nitro- and N-Nitrosopiperidin-2-yl Carbamates

摘要

The conversions of N-nitro- and N-nitrosopipecolic acid gave the carbamatederivatives of 1-nitro-and 1-nitroso-2-aminopiperidine. Previously two alpha-aminonitrasamines, isolated as ureas R'N(NO)CH(R)NHCOHN2, were known I and alpha-aminonitramines were unknown. The primary alpha-amino derivatives (masked or free) of nitra-mines or nitrosamines are needed for investigations on new preparations of cyclic and caged nitramines (energetic materials that are sought for explosives, propellants, and other energy storage systems). Treatment with triethyl amine and ethyl chloroformate followed by the addition of sodium azide converted N-nitro-pipecolic acid 1 to the azide that gave the isocyanate quantitatively on thermolysis. The isocyanate reacted with methanol to give methyl N-(1-nitropiperidin-2-yl)carbamate and with water to give N,N'-di-(1-nitropiperidin-2-yl)-urea 12.