Synthetic Procedures Yielding Targeted Nitro and Nitroso Derivatives of the Propellant Stabilisers Diphenylamine,N‐Methyl‐4‐nitroaniline,and N,N′‐Diethyl‐N,N′‐diphenylurea

Synthetic methodologies have been developed which yield a variety of diphenylamine (DPA) and 1,3‐diethyl‐l,3‐diphenylurea (ethylcentralite or EC) propellant stabiliser degradation derivatives in high yield. The N‐alkyl nitroanilines (N‐methyl‐2,4,6‐trinitroaniline; N‐methyl‐2,4‐dinitroaniline; N‐ethyl‐2,4,6‐trinitroaniline; N‐ethyl‐2,4‐dinitroaniline; N‐ethyl‐4‐nitroaniline; N‐ethyl‐2‐nitroaniline) have been obtained either by reaction of the parent aniline with the required alkyl halide under mild conditions or via Ullmann type chemistry. A robust and high yielding approach for the synthesis of di, tri and tetranitrodiphenylamines (2,2′,4,4′‐tetranitrodiphenylamine; 2,4,4′‐trinitrodiphenylamine; 2,2′,4‐trinitrodiphenylamine; 2,4,6‐trinitrodiphenyl‐amine; 2,4‐dinitrodiphenylamine) is reported which involves passing the nitroanilines and chloronitrobenzenes down a base activated alumina column. The N‐nitroso‐N‐alkyl compounds (N‐nitroso‐N‐ethyl‐4‐nitroaniline; N‐nitroso‐N‐ethyl‐2‐nitroaniline; N‐nitroso‐N‐Methyl‐4‐nitroaniline; N‐ethyl‐N‐nitrosoaniline; N‐nitroso‐2‐nitrodiphenylamine) have been synthesised using nitrosyl acetate in acetic acid as the N‐nitrosating agent.