Synthesis, characterization and thermal behaviors of 4-amino-5-nitro-1,2,3-triazole (ANTZ) and its derivatives

Article abstract of DOI:10.1002/cjoc.201090146

4-Amino-5-nitro-1,2,3-triazole (ANTZ) and its derivatives, such as 2-(4-amino-5-nitro-1,2,3-trazole-1-yl)-1,3,5-trinitrobenzene (T-ANTZ) and 4-amino-5-nitro-1,2,3-triazole (M-ANTZ), were synthesized and characterized, whose structures were confirmed by IR

Full text of DOI:10.1002/cjoc.201090146

FULL PAPER
Synthesis, Characterization and Thermal Behaviors of
4-Amino-5-nitro-1,2,3-triazole (ANTZ) and Its Derivatives
Wang, Bozhou(王伯周)
Fan, Xuezhong(樊学忠)
Li, Jizhen*(李吉祯)
Huo, Huan(霍欢)
Fu, Xiaolong(付小龙)
Zhou, Cheng(周诚)
Xi'an Modern Chemistry Research Institute, Xi'an, Shaanxi 710065, China
4-Amino-5-nitro-1,2,3-triazole (ANTZ) and its derivatives, such as 2-(4-amino-5-nitro-1,2,3-trazole-1-yl)-1,3,5-
trinitrobenzene (T-ANTZ) and 4-amino-5-nitro-1,2,3-triazole (M-ANTZ), were synthesized and characterized,
whose structures were confirmed by IR, NMR and elemental analysis. The thermal behaviors of ANTZ, T-ANTZ
and M-ANTZ were studied by the methods of DSC and TG-DTG, and the results showed that there is an obvious
melting process of ANTZ with melting point of 278.38 ℃, while there is no melting process in the thermal behav-
ior of T-ANTZ and M-ANTZ (the derivatives of ATNZ).
Keywords organic chemistry, synthesis, 4-amino-5-nitro-1,2,3-triazole, thermolysis
Introduction
and purified according to a reported method6 by Xi'an
Modern Chemistry Research Institute, and other re-
agents were of A.R. grade.
4-Amino-5-nitro-1,2,3-triazole (ANTZ), recently
being identified as a kind of potential high performance
insensitive explosive,1-6 has some desirable attributes,
including a high nitrogen content of 54%, high density
Apparatus and measurement methods
IR spectrum was recorded using a Nicolet Model
NEXUS 870 FT-IR instrument and a model DTGS de-
tector. KBr pellet samples, well mixed by about 0.7 mg
of sample and 150 mg of KBr, were used. The 13C NMR
1.837 g•cm－ (at 25 ℃ with measuring method of
3
401.1, GJB772A-97), combustion heat of 1350.501
kJ•mol－ and relatively low sensitivity to shock or im-
1
1
pact-included ignition with H50 of 154 cm [with
drop-weight of 10 kg and measuring method of 601.2,
GJB772A-97, while that of cyclotetramethylenetetrani-
troamine (HMX) is 32 cm under the same measuring
condition], which can be used as a main insensitive en-
ergetic component of cast explosives and propellants7-9
in order to substitute 1,3,5-triamino-2,4,6-trinitro-
benzene (TATB), cyclotrimethylenetrinitramine (RDX)
or HMX. There are several reports on the synthesis
methods, characterization and the detonation properties
and H NMR spectra were performed on a Bruker AV
500 MHz superconducting NMR spectrometer (Bruke
Biospin International AG., Switzerland). DMSO-d6 was
used as the solvent and tetramethyl silane (TMS) as an
internal standard. Elemental analyses of carbon, hydro-
gen and nitrogen were carried out with an Elementary
vario EL-III microanalyzer. DSC measurements were
carried out on TA instruments, Model DSC 910S under
static atmosphere of N2 at the pressure of 0.1 MPa and 1
MPa with heating rate of 10.0 ℃•min－ 1. Samples
weighting from 0.5 to 1.0 mg, loaded in an aluminium
sample cell, were used. TG-DTG measurement was
made using TGA instruments, Model TA2950 under
flowing N2 gas with heating rate of 10.0 ℃•min－ 1 with
samples weighting from 1.0 to 2.0 mg.
of ANTZ, whose detonation velocity is 8909.403 m•s－
1
and detonation pressure 35.657 GPa,10,11 but there is no
report about the derivatives of ATNZ.
The aim of this work is to study the synthesis meth-
ods, characterization and thermal behaviors of the de-
rivatives of ANTZ, such as 2-(4-amino-5-nitro-1,2,3-
trazole-1-yl)-1,3,5-trinitrobenzene (T-ANTZ) and guan-
ylureaium 4-amino-5-nitro-1,2,3-triazole (M-ANTZ).
Results and discussion
Synthesis of 4-amino-5-nitro-1,2,3-triazole (ANTZ)
According to the synthetic method in the reference,6
4-amino-5-nitro-1,2,3-triazole was synthesized using
4-amido-5-nitro-1,2,3-triazole as the initiative material
by the reaction of rearrangement (Scheme 1).
Experimental
Material
4-Amido-5-nitro-1,2,3-triazol (≥99.5%), guanyl-
urea hydrochloride and picryl chloride were all prepared
*
E-mail: jizhenli@126.com
Received November 19, 2009; revised January 13, 2010; accepted February 24, 2010.
Project supported by the National 973 Project (No. 613740102).
Chin. J. Chem. 2010, 28, 781— 784
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Wang et al.
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Scheme 1 Synthetic route of ANTZ
NaOH (0.9 g, 2.26 mmol) was transferred into a
three-necked round-bottomed flask fitted with a me-
chanical stirrer and a dropping funnel and 18 mL of
water added to it. Then, to this, Cl2 was entered until
pH＝10 at 0 ℃. 4-Amido-5-nitro-1,2,3-triazol was
added slowly at ambient temperature. After 4-amido-
5-nitro-1,2,3-triazol was added completely, it was
stirred further for 0.5 h at 60 ℃ and subsequently
cooled down to ice temperature. Its pH was adjusted to
1—2 with hydrochloric acid. The yellow precipitate was
filtered and 0.4 g yellow solid was obtained with a yield
of 80%.
Figure 3 13C NMR spectrum of ANTZ.
benzene (T-ANTZ) was designed and synthesized
(Scheme 2).
1H NMR (CD3CN) δ: 7.44 (s, 2H, NH2), 2.09 (s, 1H,
Scheme 2 Synthetic route of T-ANTZ
13
NH); C NMR (CD3CN) δ: 136.59 [C(5)-NO2], 142.96
[C(4)-NH2]; IR (KBr) ν: 1352, 1645 (NO2), 3241 (NH),
3374 (NH2), 1601, 1476 (triazole) cm－ 1 (Figures 1—3).
Anal. calcd for C2H3N5O2: C 18.92, H 2.43, N 53.31;
found C 18.61, H 2.33, N 54.24.
ANTZ (0.4 g, 3.1 mmol) followed by addition of 20
mL of DMF was placed in a three-necked round-bot-
tomed flask with a stirrer. To the reaction mixture, pyri-
dine (0.32 g, 4.0 mmol) was added. Then picryl chloride
(0.76 g, 3.1 mmol) was added slowly and the stirring
was continued for another 6 h at 80 ℃. The reaction
mixture was poured into crush ice. The precipitate thus
obtained was filtered and washed with ice water and
finally dried to obtain 0.6 g product with a yield of
56.9%.
1H NMR (DMSO) δ: 8.058 (t, 2H, NH2), 8.585,
8.929 (t, 2H, CH, benzene); 13C NMR (DMSO) δ:
146.40, 141.699 (triazole), 140.958, 125.942, 125.200
(benzene); IR (KBr) ν: 3435 (NH2), 1545, 1346 (NO2),
1601, 1482 (triazole), 806, 730, 681 (benzene) cm .
Anal. calcd for C8H4N8O8: C 28.23, H 1.176, N 32.94;
found C 27.95, H 1.346, N 32.45.
Figure 1 IR spectrum of ANTZ.
－
1
Synthesis of guanylureaium 4-amino-5-nitro-1,2,3-
triazole (M-ANTZ)
Guanylureaium 4-amino-5-nitro-1,2,3-triazole (M-
ANTZ) was designed and synthesized (Scheme 3).
Scheme 3 Synthetic route of M-ANTZ
Figure 2 1H NMR spectrum of ANTZ.
Synthesis of 2-(4-amino-5-nitro-1,2,3-trazole-1-yl)-
1,3,5-trinitrobenzene (T-ANTZ)
2-(4-Amino-5-nitro-1,2,3-trazole-1-yl)-1,3,5-trinitro-
782
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Chin. J. Chem. 2010, 28, 781— 784

Synthesis, Characterization and Thermal Behaviors of ANTZ
ANTZ (0.4 g, 3.1 mmol) was transferred into a
three-necked round-bottomed flask fitted with a me-
chanical stirrer and a dropping funnel, then 10 mL of
distilled water was added at constant temperature. After
the addition of water, 1.0 mL of 20% sodium hydroxide
solution was added dropwise to the reaction flask under
stirring at 70 ℃. The stirring was continued for another
0.5 h at 70 ℃. Guanylurea hydrochloride (0.56 g, 3.1
mmol) was added and the resulting reaction mixture
stirred for 3 h and subsequently cooled down to ice
temperature. The precipitate thus obtained was filtered
and washed with ice water and finally dried to obtain
0.4 g product with a yield of 63.4%.
1H NMR (DMSO) δ: 7.953 (s, 2H, M-NH2), 6.072 (s,
2H, triazole-NH2), 7.004 (s, 2H, NH+2 ), 7.353 (s, 1H,
NH); 13C NMR (DMSO-d6) δ: 136.59 [C(1)-NO2],
142.96 [C(2)-NH2], 166.26 [C(3)＝NH2], 163.05 [C(4)
＝O); IR (KBr) ν: 1569, 1357 (NO2), 1716 (C＝O),
3411, 3373 (NH2), 3187 (NH). Anal. calcd for
C4H9N9O3: C 20.82, H 3.896, N 54.51; found C 21.21,
H 3.830, N 51.13.
Figure 6 DSC curves of M-ANTZ.
It is obviously different among the thermal behaviors
of ANTZ, T-ANTZ and M-ANTZ which can be clearly
seen from Figure 4. There are one endothermic peak and
one exothermic peak in the DSC curve of ANTZ, in
which endothermic peak may be the melting process of
ANTZ with melting point of 278.38 ℃ (peak tem-
perature), and the exothermic peak (with peak tempera-
ture of 297.68 ℃) may be the decomposition process
back-to-back of melting. There are two exothermic
peaks (with peak temperatures of 244.01 and 367.83 ℃)
in the DSC curve of T-ANTZ which represent the de-
composition processes of the groups of 4-amino-5-nitro-
1,2,3-trazole and 1,3,5-trinitrobenzene in the molecule
of T-ANTZ, respectively.
Thermal behaviors of ANTZ, T-ANTZ and M-
ANTZ
The thermal behaviors of ANTZ, T-ANTZ and
M-ANTZ were studied by the method of DSC with
－
1
heating rate of 10.0 ℃•min , and the DSC curves of
the three energetic materials are shown in Figures 4—6.
There are one endothermic peak and one exothermic
peak in the DSC curve of M-ANTZ according to the
two obvious mass-loss stages in the TG-DTG curves
(Figure 7). The endothermic peak (with peak tempera-
ture of 201.58 ℃) in the DSC curve represents the en-
dothermic decomposition process of the basic ion group
of guanyl-urea rather than the melting process of M-
ANTZ, which can be confirmed by the first mass-loss
stage (in the temperature range of 184.13—212.37 ℃)
in the TG-DTG curves with mass-loss of 11.72%. The
exothermic peak (with peak temperature of 235.10 ℃)
Figure 4 DSC curve of ANTZ.
Figure 7 TG-DTG curves of M-ANTZ.
Figure 5 DSC curve of T-ANTZ.
Chin. J. Chem. 2010, 28, 781— 784
© 2010 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.cjc.wiley-vch.de
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Wang et al.
FULL PAPER
Table 1 Physical chemistry and detonation properties of ANTZ, T-ANTZ and M-ANTZ
Density/ Combustion heat/ Formation enthalpy/ Detonation velocity/ Detonation
Detonation
Impact sensitive
－
－
－
－
1
3
1
1
(g•cm )
(kJ•mol )
1350.50
—
(kJ•mol )
(m•s )
8909.40
7859.03
5066.18
pressure/GPa temperature/K
(H50)/cm
ANTZ
1.837
134.72
35.66
25.80
—
—
4423.05
—
81.30
132.01
—
T-ANTZ
1.785
378.43
M-ANTZ 1.573
—
－
483.57
represents the decomposition process of the main part of
M-ANTZ, 4-amino-5-nitro-1,2,3-trazole, according to
the second mass-loss stage (in the temperature range of
212.37—280.26 ℃ ) in the TG-DTG curves with
mass-loss of 18.18%.
M-ANTZ (the derivatives of ATNZ).
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Conclusion
4-Amino-5-nitro-1,2,3-triazole (ANTZ), 2-(4-amino-
5-nitro-1,2,3-trazole-1-yl)-1,3,5-trinitrobenzene (T-ANTZ)
and guanylureaium 4-amino-5-nitro-1,2,3-triazole (M-
ANTZ) were designed, synthesized and characterized.
The thermal behaviors of ANTZ, T-ANTZ and
M-ANTZ were studied by the methods of DSC and
TG-DTG. There is an obvious melting process of ANTZ
with melting point of 278.38 ℃, while no melting
process in the thermal behavior of T-ANTZ and
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(E0911191 Pan, B.; Dong, H.)
784
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Chin. J. Chem. 2010, 28, 781— 784