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  • pH-Controlled forms of 1-amino-1-hydrazino-2,2-dinitroethylene (HFOX): selective reactivity of amine and hydrazinyl groups with aldehydes or ketones
Title: pH-Controlled forms of 1-amino-1-hydrazino-2,2-dinitroethylene (HFOX): selective reactivity of amine and hydrazinyl groups with aldehydes or ketones
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 ( D v = 7513 m s −1 ; P = 24.45 G P a), and 5f ( D v = 7948 m s −1 ; P = 26.27 G P a) as well as azide derivative 11 ( D v = 8166 m s −1 ; P = 25.48 G P a), which are superior to TNT ( D v = 6824 m s −1 ; P = 19.40 G P a). These findings provide a new perspective for the synthesis of novel high performing energetic materials.  more » « less
Award ID(s):
1919565
PAR ID:
10346972
Author(s) / Creator(s):
; ;
Date Published:
Journal Name:
Materials Advances
Volume:
3
Issue:
10
ISSN:
2633-5409
Page Range / eLocation ID:
4289 to 4294
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
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