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Synthetic Procedures Yielding Targeted Nitro and Nitroso Derivatives of the Propellant Stabilisers Diphenylamine, N‐Methyl‐4‐nitroaniline, and N,N′‐Diethyl‐N,N′‐diphenylurea
Author(s) -
Elliot M. S.,
Smith F. J.,
Fraser A. M.
Publication year - 2000
Publication title -
propellants, explosives, pyrotechnics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.56
H-Index - 65
eISSN - 1521-4087
pISSN - 0721-3115
DOI - 10.1002/(sici)1521-4087(200001)25:1<31::aid-prep31>3.0.co;2-z
Subject(s) - chemistry , diphenylamine , nitroaniline , yield (engineering) , acetic acid , nitroso , alkyl , medicinal chemistry , aniline , organic chemistry , nuclear chemistry , materials science , metallurgy
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.