Synthesis of N-trinitroethyl derivatives of linear and heterocyclic nitrogen-containing compounds

Abstract

Earlier unknown N trinitroethyl derivatives of acetylhydrazine, 4 amino 1,2,4 triazole, and 2,4,6 triamino 1,3,5 triazine, which are potential components for gas generating formu lations, were synthesized.

N‐Oxide 1,2,4,5‐Tetrazine‐Based High‐Performance Energetic Materials

“…3‐Amino‐6‐nitro‐1,2,4,5‐tetrazine‐2,4‐di‐N‐oxide ( 16 ) : Compound 16 was prepared using the general procedure and the starting material was 3‐amino‐6‐nitro −1,2,4,5‐tetrazine ( 16 a ) 21e. Yellow solid; yield: 52 %; IR (KBr): $\tilde \nu $ =3421, 3314, 1649, 1585, 1532, 1432, 1348, 1337, 1125, 840, 819 cm −1 ; 1 H NMR: δ =7.88 ppm (s, 2 H); 13 C NMR: δ =149.3, 150.4 ppm; 15 N NMR: δ =−27.9, −90.2, −94.6, −309.4 ppm; elemental analysis calcd (%) for C 2 H 2 N 6 O 4 (174.01): C 13.82, H 1.16, N 48.28; found: C 13.79, H 1.14, N 47.59.…”

Synthetic Routes to a Triazole and Tetrazole with Trinitroalkyl Substitution at Nitrogen

“…Compound 2: DTA (5 °C min −1 ) 67 °C (onset dec.); IR (ATR, cm −1 ) ν 3362 (w), 3283 (w), 2200 (m), 2170 (m), 1589 (vs), 1488 (w), 1427 (m), 1378 (m), 1305 (s), 1266 (m), 1204 (m), 805 (m), 782 (m), 662 (w), 634 (w), 517 (w); Raman (1064 nm, 800 mW, cm −1 ) 2957 (6), 2604 (4), 2264 (7), 2232 (48), 2200 (100), 2158 (5), 2137 (6), 2061 (4), 1625 (15), 1592 (46), 1380 (15), 1347 (9), 857 (20), 784 (6), 642 (6), 516 (5), 476 (6), 410 (5), 377 (14), 217 (7); 1 4,5-Dicyano-1N-(trinitroethyl)-1,2,3-triazole (3). 2-Amino-3-(2,2,2-trinitroethylamino)maleonitrile (2, 2.7 g, 10 mmol) was slowly added to 10 mL of the colorless fuming nitric acid at −10 °C with good stirring, accompanied by a heavy reaction.…”

“…The trinitromethyl group is an important building block in the research for new energetic materials with a good availability of the sources nitroform or trinitroethanol. − In combination with already oxygen-rich energetic materials, many potent replacements for the common but harmful oxidizer ammonium perchlorate were investigated, such as trinitroethyl nitrocarbamate ( A ) and bis­(trinitroethyl)­oxalate ( B ). , In the ongoing research to replace the secondary explosive RDX, the combination of the trinitromethyl moiety with different azoles results in interesting compounds (Figure ) ( C – F ). − In general, either trinitroethanol was reacted with heterocyclic amines to incorporate the trinitromethyl unit , or the exhaustive nitration of activated methylene groups forms the trinitromethyl moiety, e.g. in azolylacetic acids. ,, However, only very sparse information exists about azoles with nitrogen-substituted trinitroalkyl units. ,, In those few examples, rather sensitive N -trinitromethyl triazoles were obtained either by exhaustive nitration mentioned above or by nitration of dinitromethyl derivatives with nitronium tetrafluoroborate.…”

“…1,4 In the ongoing research to replace the secondary explosive RDX, the combination of the trinitromethyl moiety with different azoles results in interesting compounds (Figure 1) (C−F). 5−8 In general, either trinitroethanol was reacted with heterocyclic amines to incorporate the trinitromethyl unit 8,9 or the exhaustive nitration of activated methylene groups forms the trinitromethyl moiety, e.g. in azolylacetic acids.…”

Delving into Autocatalytic Liquid-State Thermal Decomposition of Novel Energetic 1,3,5-Triazines with Azido, Trinitroethyl, and Nitramino Groups

“…To this end, Zeman et al have studied the thermal decomposition of 4,6-diazido-2-amino-1,3,5-triazine (DAAT) and 4,6-diazido- N -nitro-1,3,5-triazine-2-amine (DANT) using quantum chemistry and nonisothermal thermokinetic analysis . In line with the idea of the introduction of high molecular weight groups, the N -trinitroethyl moiety has been introduced in the triazine framework. − Additionally, the introduction of the N -trinitroethyl group will supposedly increase the gas-generating ability of the substance. The resulting 2,4,6-tris­(2,2,2-trinitroethylamino)-1,3,5-triazine (TTET) compound is claimed to be more energetic and less sensitive than the benchmark nitramine hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) …”