Preparation of HMX by Catalytic Nitrolysis of DPT in AIL-N2O5-HNO3System

He, Zhen; Luo, Jun; Lu, Chunmei; Wang, Ping; Xu, Rong; Li, Jinshan

doi:10.5012/bkcs.2011.32.8.2677

Cited by 10 publications

(8 citation statements)

References 29 publications

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“…The highest yield of 84.1 % was obtained when 40 equivalents of fuming HNO 3 was used. More HNO 3 would reduce the yield due to the destruction of the cyclic structure [14][15][16][17][18]. After that, the reaction temperature was studied in the range of À5 8C~À45 8C.…”

Section: Preparation Of Mnx From Dpt In Hno 3 /Nh 4 No 3 /Nano 2 Systemmentioning

confidence: 99%

“…However, it remained almost unchanged when the amount of NaNO 2 exceeded 1 equivalent (entries 5-7). NH 4 NO 3 plays an important role in the nitrolysis of DPT [3][4][5][14][15][16][17][18]. Therefore, we further studied the effect of the amount of NH 4 NO 3 on the yield of MNX.…”

Section: Preparation Of Mnx From Dpt In Hno 3 /Nh 4 No 3 /Nano 2 Systemmentioning

confidence: 99%

“…In this work, fuming HNO 3 was used to nitrolyze MNX to prepared HMX free of NH 4 NO 3 . The experiments were conducted at 25 8C for 30 minutes, based on previous work [14][15][16][17][18], and the results were listed in Table 4. It is obvious that the yield of HMX was improved continuously with the increasing amount of HNO 3 (entries 1-5).…”

Section: Preparation Of Hmx From Mnx In Fuming Hnomentioning

confidence: 99%

“…Moreover, an extra dose of magnesium oxide or phosphorus pentoxide in fuming HNO 3 -NH 4 NO 3 system could further improve the yield to around 60 % [16,17]. HMX could also be prepared with a yield of 58 % by using HNO 3 -N 2 O 5 as nitrating agent, and the addition of a series of ionic liquids (ILs) as catalysts afforded higher yields up to 65 % [18]. Above all, although various techniques have been developed to enhance the yield of HMX by nitrolysis of DPT, no significant progresses of practically prospective have been achieved.…”

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confidence: 99%

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A Groundbreaking Stepwise Protocol to Prepare HMX from DPT: New Mechanism Hypothesis and Corresponding Process Study

Zhang

Zou

Luo

2017

Propellants Explo Pyrotec

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1,3,5,7-Tetranitro-1,3,5,7-tetraazacyclooctane (HMX) is one of the most powerful and widely used explosives. 3,7-Dinitro-1,3,5,7-tetraazabicyclo[3.3.1] (DPT) is an important precursor in the production of HMX. A new reaction mechanism including nitrolysis, nitrosolysis and nitrolysis processes in fuming HNO 3 was put forward. The stable key intermediate 1-nitroso-3,5,7-trinitro-1,3,5,7tetraazacyclooctane (MNX) was isolated and characterized. Based on the new mechanism, a stepwise method to pre-pare HMX from DPT was developed. The influence factors on the yields of MNX such as reaction temperature, loading amounts of HNO 3 , NaNO 2 and NH 4 NO 3 were investigated. Under the optimized conditions, MNX was obtained with a satisfactory yield of 84.0 %. MNX could be efficiently and smoothly nitrolyzed in fuming nitric acid and afforded pure b-HMX with excellent yield up to 92.8 %. The overall yield of the stepwise procedure was as high as 78.0 %, much higher than traditional one-pot nitrolysis protocols.

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Section: Preparation Of Mnx From Dpt In Hno 3 /Nh 4 No 3 /Nano 2 Systemmentioning

confidence: 99%

Section: Preparation Of Mnx From Dpt In Hno 3 /Nh 4 No 3 /Nano 2 Systemmentioning

confidence: 99%

Section: Preparation Of Hmx From Mnx In Fuming Hnomentioning

confidence: 99%

mentioning

confidence: 99%

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A Groundbreaking Stepwise Protocol to Prepare HMX from DPT: New Mechanism Hypothesis and Corresponding Process Study

Zhang

Zou

Luo

2017

Propellants Explo Pyrotec

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“…The DPT was synthesized according to the Bachmann route [18,19,33]. Two portions of 38% hexamine-acetic acid [36 mL each, containing hexamine (23.17 g, 0.165 mol) dissolved in acetic acid (36 mL, 0.631 mol)] and 47% NH 4 NO 3 -HNO 3 solution [17 mL, containing ammonium nitrate (22.7 g, 0.283 mol) dissolved in nitric acid (17 mL, 0.407 mol)] were prepared.…”

Section: Dpt Synthesis From Hexaminementioning

confidence: 99%

Increasing the Efficiency of the Production of 1,3,5,7-Tetranitro-1,3,5,7-tetrazocane (HMX)

Keshavarz¹,

Afzali²,

Esmaeilpour³

et al. 2016

Cent. Eur. J. Energ. Mater.

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This work introduces a suitable method for the optimization of selective synthesis of 1,3,5,7-tetranitro-1,3,5,7-tetrazocane (HMX), as one of the most wellknown high explosives, from the aspects of production capacity and efficiency, by nitration of 3,7-dinitro-1,3,5,7-tetraazabicyclo[3,3,1]nonane (DPT). The effective factors in the productive capacity of HMX and the synthesis of a product from raw DPT with high capacity, purity, and efficiency have been identified. The required qualitative and quantitative analyses were performed for the identification and confirmation of the product quality. In order to optimize the process of increasing the capacity of HMX production and evaluation of the effects of different factors on the production capacity, a series of experiments were designed and performed by using central composite design (CCD). Practical studies and statistical analyses showed good conformity between the model presented and the actual results, allowing the selective production of HMX with an efficiency of greater than 70% and a high production capacity.

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In situ generated amine as a Lewis base catalyst in the reaction of 3,7‐dinitro‐1,3,5,7‐tetraazabicyclo[3.3.1]nonane in nitric acid: Experimental and DFT study

Zhang

Chi

et al. 2019

J of Physical Organic Chem

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The problem how ammonium nitrate affects the nitrolysis of 3,7‐dinitro‐1,3,5,7‐tetraazabicyclo[3.3.1]nonane (DPT) in nitric acid to prepare 1,3,5,7‐tetranitro‐1,3,5,7‐tetraazacyclooctane (HMX) has puzzled chemists for decades. In this paper, experimental work and theoretical calculation are described to investigate the long‐standing challenge. The experiment results showed that ammonium nitrate or alkylammonium chlorides were in favor of the formation of 1‐nitroso‐3,5,7‐trinitro‐1,3,5,7‐tetraazacyclooctane (MNX) but hindered the conversion of MNX to HMX. A plausible catalytic mechanism was proposed. In which ammonia or amines, in situ generated from the unfavorable balance with their salts, act as Lewis base catalysts. At the same time, the DFT computation results reveal that rigid bicyclic transition states established with 1‐hydroxymethyl‐3,5,7‐trinitro‐1,3,5,7‐tetraazacyclooctane, ammonia (or amines) and three water molecules lead to very low activation energies. Then, a novel process for the preparation of MNX with excellent yield up to 78.5% was developed, which is free of the use of NaNO2 or N2O4 as nitroso resources.

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Preparation of HMX by Catalytic Nitrolysis of DPT in AIL-N₂O₅-HNO₃System

Cited by 10 publications

References 29 publications

A Groundbreaking Stepwise Protocol to Prepare HMX from DPT: New Mechanism Hypothesis and Corresponding Process Study

A Groundbreaking Stepwise Protocol to Prepare HMX from DPT: New Mechanism Hypothesis and Corresponding Process Study

Increasing the Efficiency of the Production of 1,3,5,7-Tetranitro-1,3,5,7-tetrazocane (HMX)

In situ generated amine as a Lewis base catalyst in the reaction of 3,7‐dinitro‐1,3,5,7‐tetraazabicyclo[3.3.1]nonane in nitric acid: Experimental and DFT study

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