Issue 10, 2022

pH-Controlled forms of 1-amino-1-hydrazino-2,2-dinitroethylene (HFOX): selective reactivity of amine and hydrazinyl groups with aldehydes or ketones

Abstract

1-Amino-1-hydrazino-2,2-dinitroethylene (HFOX) is a potential reactive intermediate for a new class of energetic materials. Now we describe its condensation with various carbonyl compounds in the presence of acidic and basic catalysts. Condensation of HFOX with α-diones and β-diones gives products of much interest. α-Diones undergo cyclization in the presence of base to form six-membered ring products, while β-diones cyclize to five-membered ring products in the presence of acid. One of the exciting reactions is the formation of ammonium (5,6-dimethyl-1,2,4-triazin-3-yl)dinitromethanide salt, 5c, which was isolated by using aqueous ammonia as a nucleophilic base. All new compounds were fully characterized by advanced spectroscopic techniques. The structures of 5, 5c, 5e, 9, 11, and 12a are supported by single crystal X-ray diffraction analysis. Most of the new six membered ring compounds have good thermostabilities (>200 °C), while the fluorinated five membered ring compound, 12b, has the highest density of 2.04 g cm−3 at 25 °C. Heats of formation and detonation properties were calculated by using Gaussian 03 and EXPLO5 software programs. Nearly all new compounds have very good detonation properties, especially, triazine salts, 5e (Dv = 7513 m s−1; P = 24.45 GPa), and 5f (Dv = 7948 m s−1; P = 26.27 GPa) as well as azide derivative 11 (Dv = 8166 m s−1; P = 25.48 GPa), which are superior to TNT (Dv = 6824 m s−1; P = 19.40 GPa). These findings provide a new perspective for the synthesis of novel high performing energetic materials.

Graphical abstract: pH-Controlled forms of 1-amino-1-hydrazino-2,2-dinitroethylene (HFOX): selective reactivity of amine and hydrazinyl groups with aldehydes or ketones

Supplementary files

Article information

Article type
Paper
Submitted
17 Mar 2022
Accepted
11 Apr 2022
First published
13 Apr 2022
This article is Open Access
Creative Commons BY-NC license

Mater. Adv., 2022,3, 4289-4294

pH-Controlled forms of 1-amino-1-hydrazino-2,2-dinitroethylene (HFOX): selective reactivity of amine and hydrazinyl groups with aldehydes or ketones

A. K. Chinnam, R. J. Staples and J. M. Shreeve, Mater. Adv., 2022, 3, 4289 DOI: 10.1039/D2MA00307D

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