The Nitrolysis Mechanism of 3,7-Dinitro-1,3,5,7-tetraazabicyclo[3,3,1]nonane

Wen Jin Liu; Zhi Bin Xu; Ke Jian Cui; Min Xue; Zi Hui Meng; Xiao Chuan Huang; Zhong Xue Ge; Zhi Hui Lin; Guang Ming Qin

doi:10.1002/prep.201500078

The Nitrolysis Mechanism of 3,7-Dinitro-1,3,5,7-tetraazabicyclo[3,3,1]nonane

Wen Jin Liu, Zhi Bin Xu, Ke Jian Cui, Min Xue, Zi Hui Meng, Xiao Chuan Huang, Zhong Xue Ge, Zhi Hui Lin, Guang Ming Qin

School of Chemistry and Chemical Engineering

Research output: Contribution to journal › Article › peer-review

14 Citations (Scopus)

Abstract

Two intermediates, 1,5-dinitroso-3,7-dinitro-1,3,5,7-tetraazacyclooctane (DNDS) and 1-nitroso-3,5,7-trinitro-1,3,5,7-tetraazacyclooctane (MNX), were isolated and characterized in the synthesis of 1,3,5,7-tetranitro-1,3,5,7-tetraazacyclooctane (HMX) from the nitrolysis of 3,7-dinitro-1,3,5,7-tetraazabicyclo[3,3,1]nonane (DPT) for the first time. When the nitrolysis of DPT was slowed down, two intermediates were detected with HPLC. It was proposed that electrophilic NO₂⁺ and NO⁺ from HNO₃ and N₂O₄ might attack nitrogen atoms at positions 3 and 7 of DPT to form the cations of the intermediates, then nucleophilic H₂O attacked the bridge carbon atoms of DPT to produce the intermediates, which were oxidized to form HMX.

Original language	English
Pages (from-to)	645-651
Number of pages	7
Journal	Propellants, Explosives, Pyrotechnics
Volume	40
Issue number	5
DOIs	https://doi.org/10.1002/prep.201500078
Publication status	Published - Oct 2015

Keywords

DPT
HMX
Intermediate
Mechanism
Nitrolysis

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title = "The Nitrolysis Mechanism of 3,7-Dinitro-1,3,5,7-tetraazabicyclo[3,3,1]nonane",

abstract = "Two intermediates, 1,5-dinitroso-3,7-dinitro-1,3,5,7-tetraazacyclooctane (DNDS) and 1-nitroso-3,5,7-trinitro-1,3,5,7-tetraazacyclooctane (MNX), were isolated and characterized in the synthesis of 1,3,5,7-tetranitro-1,3,5,7-tetraazacyclooctane (HMX) from the nitrolysis of 3,7-dinitro-1,3,5,7-tetraazabicyclo[3,3,1]nonane (DPT) for the first time. When the nitrolysis of DPT was slowed down, two intermediates were detected with HPLC. It was proposed that electrophilic NO2+ and NO+ from HNO3 and N2O4 might attack nitrogen atoms at positions 3 and 7 of DPT to form the cations of the intermediates, then nucleophilic H2O attacked the bridge carbon atoms of DPT to produce the intermediates, which were oxidized to form HMX.",

keywords = "DPT, HMX, Intermediate, Mechanism, Nitrolysis",

author = "Liu, {Wen Jin} and Xu, {Zhi Bin} and Cui, {Ke Jian} and Min Xue and Meng, {Zi Hui} and Huang, {Xiao Chuan} and Ge, {Zhong Xue} and Lin, {Zhi Hui} and Qin, {Guang Ming}",

note = "Publisher Copyright: {\textcopyright} 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.",

year = "2015",

month = oct,

doi = "10.1002/prep.201500078",

language = "English",

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pages = "645--651",

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AU - Liu, Wen Jin

AU - Xu, Zhi Bin

AU - Cui, Ke Jian

AU - Xue, Min

AU - Meng, Zi Hui

AU - Huang, Xiao Chuan

AU - Ge, Zhong Xue

AU - Lin, Zhi Hui

AU - Qin, Guang Ming

PY - 2015/10

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N2 - Two intermediates, 1,5-dinitroso-3,7-dinitro-1,3,5,7-tetraazacyclooctane (DNDS) and 1-nitroso-3,5,7-trinitro-1,3,5,7-tetraazacyclooctane (MNX), were isolated and characterized in the synthesis of 1,3,5,7-tetranitro-1,3,5,7-tetraazacyclooctane (HMX) from the nitrolysis of 3,7-dinitro-1,3,5,7-tetraazabicyclo[3,3,1]nonane (DPT) for the first time. When the nitrolysis of DPT was slowed down, two intermediates were detected with HPLC. It was proposed that electrophilic NO2+ and NO+ from HNO3 and N2O4 might attack nitrogen atoms at positions 3 and 7 of DPT to form the cations of the intermediates, then nucleophilic H2O attacked the bridge carbon atoms of DPT to produce the intermediates, which were oxidized to form HMX.

AB - Two intermediates, 1,5-dinitroso-3,7-dinitro-1,3,5,7-tetraazacyclooctane (DNDS) and 1-nitroso-3,5,7-trinitro-1,3,5,7-tetraazacyclooctane (MNX), were isolated and characterized in the synthesis of 1,3,5,7-tetranitro-1,3,5,7-tetraazacyclooctane (HMX) from the nitrolysis of 3,7-dinitro-1,3,5,7-tetraazabicyclo[3,3,1]nonane (DPT) for the first time. When the nitrolysis of DPT was slowed down, two intermediates were detected with HPLC. It was proposed that electrophilic NO2+ and NO+ from HNO3 and N2O4 might attack nitrogen atoms at positions 3 and 7 of DPT to form the cations of the intermediates, then nucleophilic H2O attacked the bridge carbon atoms of DPT to produce the intermediates, which were oxidized to form HMX.

KW - DPT

KW - HMX

KW - Intermediate

KW - Mechanism

KW - Nitrolysis

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The Nitrolysis Mechanism of 3,7-Dinitro-1,3,5,7-tetraazabicyclo[3,3,1]nonane

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