308 N-Heterocycles
NO 2NO 2
100
(SDATO / BTATNB)O 2 NN
H NNHN
N
HN
HN
NCl
NO 2Cl
NO 2
85O 2 N
N
N
H
98NH 2 N+ 2DMF, 125 °C
76 %Figure 7.38Agrawal and co-workers^62 synthesized 1,3-bis(1,2,4-triazol-3-amino)-2,4,6-trinitroben-
zene (SDATO or BTATNB) (100) from the reaction of two equivalents of 3-amino-1,2,4-
triazole (98) with styphnyl chloride (85). The performance of SDATO (calculated VOD
∼7609 m/s) is slightly higher than PATO while showing more insensitivity to impact.
COOHCl
101COOHCl
102O 2 N NO 2NH 2Cl
103O 2 N NO 2NClNO 2NO 2O 2 NO 2 NNO 2NO 2O 2 NClO 2 NNNHNO 2NO 2O 2 NO 2 NNO 2NO 2O 2 NNHO 2 NNNHNHN NN NHNNH 2 Noleum, HNO 3 ,
92–95 °C
81 %oleum, NaN 3
reflux
84 %H 2 SO 4 , HNO 3 ,
85–90°C, 78 %MeOH, 64 %105 104
(BTDAONAB)N NFigure 7.39N,N′-Bis(1,2,4-triazol-3-yl)-4,4′-diamino-2,2′,3,3′,5,5′,6,6′-octanitroazobenzene (BT-
DAONAB) (105) has recently been synthesized by Agrawal and co-workers^63 by tandem
nitration–oxidative coupling of 4-chloro-3,5-dinitroaniline (103) followed by displacement of
the chloro groups with 3-amino-1,2,4-triazole. This is a thermally stable explosive with some
impressive properties, exceeding TATB in both thermal stability and explosive performance
(VOD∼8321 m/s,d= 1 .97 g/cm^3 ). This compound doesn’t melt and the DTA exotherm is
not seen until 550◦C.
NO 2
107N
H NNHNNO 2NO 2
106O 2 NO 2 NN NNNNO 2NO 2NO (^2) NO
2
Figure 7.40
C-Nitration of 1,2,3-triazole and 1,2,4-triazole rings can be achieved with either mixed acid
or solutions of nitric acid in acetic anhydride.N-Nitration is usually achieved with nitric acid
in acetic anhydride at ambient to subambient temperatures. Thermal rearrangement of theN-
nitro product to the more stableC-nitro product often occurs at higher nitration temperature.