Investigation of the key active intermediate for the synthesis of 1,3,5,7-tetranitro-1,3,5,7-tetraazacyclooctane: Hydrolysis and nitrolysis of 1-acetoxymethyl-3,5,7-trinitro-1,3,5,7-tetraazacyclooctane
The problem whether 1-hydroxylmethyl-3,5,7-trinitro-1,3,5,7-tetraazacyclooctane is the key active intermediate for the synthesis of 1,3,5,7-tetranitro-1,3,5,7-tetraazacyclooctane (HMX) from urotropine or 3,7-dinitro-1,3,5,7-tetraazabicyclo[3.3.1]nonane (DPT) remains to be illuminated for decades. In...
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| Format: | Article |
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KeAi Communications Co. Ltd.
2020-09-01
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| Series: | Energetic Materials Frontiers |
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| Online Access: | http://www.sciencedirect.com/science/article/pii/S2666647220300154 |
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| author | Yu Zhang Zishuai Xu Luyao Zhang Guangyuan Zhang Dan He Xiaolong Wang Jian Ruan Delong Zhang Guoliang Jin Xiaoping Ma Xiaoliang He Yanming Xu Ying He Jun Luo |
| author_facet | Yu Zhang Zishuai Xu Luyao Zhang Guangyuan Zhang Dan He Xiaolong Wang Jian Ruan Delong Zhang Guoliang Jin Xiaoping Ma Xiaoliang He Yanming Xu Ying He Jun Luo |
| author_sort | Yu Zhang |
| collection | DOAJ |
| description | The problem whether 1-hydroxylmethyl-3,5,7-trinitro-1,3,5,7-tetraazacyclooctane is the key active intermediate for the synthesis of 1,3,5,7-tetranitro-1,3,5,7-tetraazacyclooctane (HMX) from urotropine or 3,7-dinitro-1,3,5,7-tetraazabicyclo[3.3.1]nonane (DPT) remains to be illuminated for decades. In this paper, the hydrolysis and nitrolysis of the esterified intermediate 1-acetoxymethyl-3,5,7-trinitro-1,3,5,7-tetraazacyclooctane (PHX) were studied to solve the long-standing puzzle. The 1H NMR spectrum and 13C NMR spectrum of the 1-hydroxymethyl-3,5,7-trinitro-1,3,5,7-tetraazacyclooctane were detected by tracking the hydrolysis of PHX, which provide direct experimental evidences for its existence. Meanwhile, it was found that 1-nitroso-3,5,7-trinitro-1,3,5,7-tetraazacyclooctane (MNX) is a stable intermediate in the nitrolysis of PHX to generate HMX, and the presence of small amounts of water in the nitrolysis of PHX not only stimulate the redox reaction between nitric acid and formaldehyde but also promote the reaction by hydrolyzing PHX to corresponding N-hydroxymethyl derivative, which verify that 1-hydroxymethyl-3,5,7-trinitro-1,3,5,7-tetraazacyclooctane is the key active intermediate in the synthesis of HMX. |
| first_indexed | 2024-04-10T18:28:56Z |
| format | Article |
| id | doaj.art-82ae879b7b58458d9fbecd63cc71ac3b |
| institution | Directory Open Access Journal |
| issn | 2666-6472 |
| language | English |
| last_indexed | 2024-04-10T18:28:56Z |
| publishDate | 2020-09-01 |
| publisher | KeAi Communications Co. Ltd. |
| record_format | Article |
| series | Energetic Materials Frontiers |
| spelling | doaj.art-82ae879b7b58458d9fbecd63cc71ac3b2023-02-02T04:49:57ZengKeAi Communications Co. Ltd.Energetic Materials Frontiers2666-64722020-09-01126773Investigation of the key active intermediate for the synthesis of 1,3,5,7-tetranitro-1,3,5,7-tetraazacyclooctane: Hydrolysis and nitrolysis of 1-acetoxymethyl-3,5,7-trinitro-1,3,5,7-tetraazacyclooctaneYu Zhang0Zishuai Xu1Luyao Zhang2Guangyuan Zhang3Dan He4Xiaolong Wang5Jian Ruan6Delong Zhang7Guoliang Jin8Xiaoping Ma9Xiaoliang He10Yanming Xu11Ying He12Jun Luo13School of Chemical Engineering, Nanjing University of Science and Technology, Nanjing, 210094, China; College of Engineering and Applied Sciences, Nanjing University, Nanjing, 210093, ChinaGansu Yin Guang Chemical Industry Group Co. Ltd, Baiyin, 730900, ChinaGansu Yin Guang Chemical Industry Group Co. Ltd, Baiyin, 730900, ChinaGansu Yin Guang Chemical Industry Group Co. Ltd, Baiyin, 730900, ChinaGansu Yin Guang Chemical Industry Group Co. Ltd, Baiyin, 730900, ChinaGansu Yin Guang Chemical Industry Group Co. Ltd, Baiyin, 730900, ChinaGansu Yin Guang Chemical Industry Group Co. Ltd, Baiyin, 730900, ChinaGansu Yin Guang Chemical Industry Group Co. Ltd, Baiyin, 730900, ChinaGansu Yin Guang Chemical Industry Group Co. Ltd, Baiyin, 730900, ChinaGansu Yin Guang Chemical Industry Group Co. Ltd, Baiyin, 730900, ChinaGansu Yin Guang Chemical Industry Group Co. Ltd, Baiyin, 730900, ChinaGansu Yin Guang Chemical Industry Group Co. Ltd, Baiyin, 730900, ChinaSchool of Chemical Engineering, Nanjing University of Science and Technology, Nanjing, 210094, ChinaSchool of Chemical Engineering, Nanjing University of Science and Technology, Nanjing, 210094, China; Key Laboratory of Special Energy Materials, Ministry of Education, Nanjing University of Science and Technology, Nanjing, 210094, China; Corresponding author.The problem whether 1-hydroxylmethyl-3,5,7-trinitro-1,3,5,7-tetraazacyclooctane is the key active intermediate for the synthesis of 1,3,5,7-tetranitro-1,3,5,7-tetraazacyclooctane (HMX) from urotropine or 3,7-dinitro-1,3,5,7-tetraazabicyclo[3.3.1]nonane (DPT) remains to be illuminated for decades. In this paper, the hydrolysis and nitrolysis of the esterified intermediate 1-acetoxymethyl-3,5,7-trinitro-1,3,5,7-tetraazacyclooctane (PHX) were studied to solve the long-standing puzzle. The 1H NMR spectrum and 13C NMR spectrum of the 1-hydroxymethyl-3,5,7-trinitro-1,3,5,7-tetraazacyclooctane were detected by tracking the hydrolysis of PHX, which provide direct experimental evidences for its existence. Meanwhile, it was found that 1-nitroso-3,5,7-trinitro-1,3,5,7-tetraazacyclooctane (MNX) is a stable intermediate in the nitrolysis of PHX to generate HMX, and the presence of small amounts of water in the nitrolysis of PHX not only stimulate the redox reaction between nitric acid and formaldehyde but also promote the reaction by hydrolyzing PHX to corresponding N-hydroxymethyl derivative, which verify that 1-hydroxymethyl-3,5,7-trinitro-1,3,5,7-tetraazacyclooctane is the key active intermediate in the synthesis of HMX.http://www.sciencedirect.com/science/article/pii/S26666472203001541,3,5,7-Tetranitro-1,3,5,7-tetraazacyclooctane (HMX)1-Acetoxymethyl-3,5,7-trinitro-1,3,5,7-tetraazacyclooctane (PHX)1-Hydroxymethyl-3,5,7-trinitro-1,3,5,7-tetraazacyclooctaneReaction mechanismNitrolysisNitrosolysis |
| spellingShingle | Yu Zhang Zishuai Xu Luyao Zhang Guangyuan Zhang Dan He Xiaolong Wang Jian Ruan Delong Zhang Guoliang Jin Xiaoping Ma Xiaoliang He Yanming Xu Ying He Jun Luo Investigation of the key active intermediate for the synthesis of 1,3,5,7-tetranitro-1,3,5,7-tetraazacyclooctane: Hydrolysis and nitrolysis of 1-acetoxymethyl-3,5,7-trinitro-1,3,5,7-tetraazacyclooctane Energetic Materials Frontiers 1,3,5,7-Tetranitro-1,3,5,7-tetraazacyclooctane (HMX) 1-Acetoxymethyl-3,5,7-trinitro-1,3,5,7-tetraazacyclooctane (PHX) 1-Hydroxymethyl-3,5,7-trinitro-1,3,5,7-tetraazacyclooctane Reaction mechanism Nitrolysis Nitrosolysis |
| title | Investigation of the key active intermediate for the synthesis of 1,3,5,7-tetranitro-1,3,5,7-tetraazacyclooctane: Hydrolysis and nitrolysis of 1-acetoxymethyl-3,5,7-trinitro-1,3,5,7-tetraazacyclooctane |
| title_full | Investigation of the key active intermediate for the synthesis of 1,3,5,7-tetranitro-1,3,5,7-tetraazacyclooctane: Hydrolysis and nitrolysis of 1-acetoxymethyl-3,5,7-trinitro-1,3,5,7-tetraazacyclooctane |
| title_fullStr | Investigation of the key active intermediate for the synthesis of 1,3,5,7-tetranitro-1,3,5,7-tetraazacyclooctane: Hydrolysis and nitrolysis of 1-acetoxymethyl-3,5,7-trinitro-1,3,5,7-tetraazacyclooctane |
| title_full_unstemmed | Investigation of the key active intermediate for the synthesis of 1,3,5,7-tetranitro-1,3,5,7-tetraazacyclooctane: Hydrolysis and nitrolysis of 1-acetoxymethyl-3,5,7-trinitro-1,3,5,7-tetraazacyclooctane |
| title_short | Investigation of the key active intermediate for the synthesis of 1,3,5,7-tetranitro-1,3,5,7-tetraazacyclooctane: Hydrolysis and nitrolysis of 1-acetoxymethyl-3,5,7-trinitro-1,3,5,7-tetraazacyclooctane |
| title_sort | investigation of the key active intermediate for the synthesis of 1 3 5 7 tetranitro 1 3 5 7 tetraazacyclooctane hydrolysis and nitrolysis of 1 acetoxymethyl 3 5 7 trinitro 1 3 5 7 tetraazacyclooctane |
| topic | 1,3,5,7-Tetranitro-1,3,5,7-tetraazacyclooctane (HMX) 1-Acetoxymethyl-3,5,7-trinitro-1,3,5,7-tetraazacyclooctane (PHX) 1-Hydroxymethyl-3,5,7-trinitro-1,3,5,7-tetraazacyclooctane Reaction mechanism Nitrolysis Nitrosolysis |
| url | http://www.sciencedirect.com/science/article/pii/S2666647220300154 |
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