An Efficient and Solvent-Free Method to Synthesize HMX by Nitrolysis of DPT Catalyzed by Reusable Solid Acid Catalysts

Toosi, Foad Shaghayeghi; Jadidoleslami, Mahdi

doi:10.1080/15533174.2014.900800

Synthesis and Reactivity in Inorganic, Metal-Organic, and Nano-

2015

DOI: 10.1080/15533174.2014.900800

|View full text |Cite

An Efficient and Solvent-Free Method to Synthesize HMX by Nitrolysis of DPT Catalyzed by Reusable Solid Acid Catalysts

Foad Shaghayeghi Toosi

Mahdi Jadidoleslami

Help me understand this report

Search citation statements

Order By: Relevance

Paper Sections

Select...

Citation Types

Supporting

Mentioning

Contrasting

Year Published

2018

2024

Publication Types

Select...

Article5

Relationship

Self Cite0

Independent5

Authors

Journals

Cited by 7 publications

References 13 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

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

View full text Add to dashboard Cite

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.

show abstract

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

View full text Add to dashboard Cite

show abstract

Mechanism Improvement and Process Optimization of the One‐Pot Synthesis of 3.7‐Dinitro‐1,3,5,7‐Tetraazabicyclo[3,3,1]nonane from Urea

Zhu

Meng

Liu

et al. 2018

Propellants Explo Pyrotec

View full text Add to dashboard Cite

As a key precursor in the preparation of octahydro‐1,3,5,7‐tetranitro‐1,3,5,7‐tetrazocine (HMX), 3,7‐dinitro‐1,3,5,7‐tetraazabicyclo[3,3,1]nonane (DPT) prepared from urea by a modified one‐pot method has a bright future. On the basis of our previous work (Reaction Mechanism of One‐Pot Synthesis of Dinitro Pentamethylene Tetramine, Chinese Journal of Organic Chemistry 2010, 30 (3), 414–418.) [1], a novel intermediate 3‐nitro‐1,3,5,7‐tetraazabicyclo[3,3,1]nonane was captured and isolated, and the key reactive intermediate hexahydro‐1‐nitro‐1,3,5‐triazine was directly captured and confirmed by HPLC‐MS. Thus, a modified synthetic mechanism for DPT was elaborated, and based which DPT preparation process was optimized.

show abstract

A Stepwise Strategy for the Synthesis of HMX from 3,7‐Dipropionyl‐1,3,5,7‐Tetraazabicyclo[3.3.1]Nonane

Zhang

Ruan

et al. 2018

Propellants Explo Pyrotec

View full text Add to dashboard Cite

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 3,7dipropionyl-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 N 2 O 5 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 %.A Stepwise Strategy for the Synthesis of HMX from 3,7-Dipropionyl-1,3,5,7-Tetraazabicyclo[3.3.1]Nonane

show abstract

scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.

Contact Info

customersupport@researchsolutions.com

10624 S. Eastern Ave., Ste. A-614

Henderson, NV 89052, USA

This site is protected by reCAPTCHA and the Google Privacy Policy and Terms of Service apply.

Blog Terms and Conditions API Terms Privacy Policy Contact Cookie Preferences Do Not Sell or Share My Personal Information

Made with 💙 for researchers

Part of the Research Solutions Family.

An Efficient and Solvent-Free Method to Synthesize HMX by Nitrolysis of DPT Catalyzed by Reusable Solid Acid Catalysts

Cited by 7 publications

References 13 publications

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

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

Mechanism Improvement and Process Optimization of the One‐Pot Synthesis of 3.7‐Dinitro‐1,3,5,7‐Tetraazabicyclo[3,3,1]nonane from Urea

A Stepwise Strategy for the Synthesis of HMX from 3,7‐Dipropionyl‐1,3,5,7‐Tetraazabicyclo[3.3.1]Nonane

Contact Info

Product

Resources

About