A Stepwise Strategy for the Synthesis of HMX from 3, 7‐Dipropionyl‐1, 3, 5, 7‐Tetraazabicyclo[3.3.1]Nonane. Issue 12 (26th September 2018)

• Record Type: Journal Article
• Authors: Zhang, Yu; Xu, Zishuai; Ruan, Jian; Wang, Xiaolong; Zhang, Luyao; Luo, Jun
• Is Part Of: Propellants, explosives, pyrotechnics. Volume 43:Issue 12(2018)
• Page Start: 1287
• Page End: 1295
• Publication Date: 2018-09-26
• Subjects: DPPT -- DPNNO -- DPDN -- HMX -- nitrolysis -- nitrosolysis; Propellants -- Periodicals; Explosives -- Periodicals; 662.2
• DOI: 10.1002/prep.201800193
• Languages: English
• ISSNs: 0721-3115

Abstract

Abstract: 1, 3, 5, 7‐Tetranitro‐1, 3, 5, 7‐tetraazacyclooctane(HMX) is one of the most powerful and widely used explosives. A new method for the synthesis of HMX from 3, 7‐dipropionyl‐1, 3, 5, 7‐tetraazabicyclo[3.3.1]nonane (DPPT) was investigated. Two important intermediates, 1, 5‐dipropionyl‐3‐nitroso‐7‐nitro‐1, 3, 5, 7‐tetraazacyclooctane (DPNNO) and 1, 5‐dipropionyl‐3, 7‐dinitro‐1, 3, 5, 7‐tetraazacyclooctane (DPDN), were isolated from the reaction mixture. The reaction mechanism, involving a nitrolysis‐nitrosolysis‐nitrolysis‐nitrolysis process, was proposed and verified by the 1 H‐NMR tracking. Based on the reaction mechanism, a stepwise method to prepare HMX from DPPT was developed. DPPT could be efficiently and smoothly converted to DPNNO in red fuming nitric acid with excellent yield up to 94.2 %. The influence factors on the yields of HMX such as reaction temperature, loading amounts of N2 O5 were investigated. Under the optimized conditions, HMX was obtained with a satisfactory yield of 85.0 %. The overall yield of the stepwise procedure was as high as 80.0 %. Abstract :