The new role of 1,1-diamino-2,2-dinitroethylene (FOX-7): two unexpected reactions

Article abstract of DOI:10.1039/C6NJ03370A

Two novel derivatives of FOX-7, 2-methyl-5-nitro-1,2,3-triazole-4-amine (MNTzA) and 1,5-bis(1-amino-2,2-dinitrovinyl)carbonohydrazide (BADCh), were synthesized by two unexpected reactions of FOX-7 and hydrazino compounds, and the two reaction processes were analyzed. The reaction to form MNTzA is unusual among the syntheses of 2,4,5-trisubstituted 1,2,3-triazole compounds. The structures of the two compounds were studied by NMR, single crystal X-ray crystallography and theoretical calculations. MNTzA crystallizes in the monoclinic P2(1)/n space group with four molecules per unit cell, and each molecule exhibits good coplanarity. However BADCh shows serious structural distortion giving it a 'W' shape and possesses two highly polarized C-C double bonds. The DSC analyses and detonation properties of the two compounds were compared with those of FOX-7 and RDX, and the results indicate that MNTzA is an available intermediate for the synthesis of other complicated 2,4,5-trisubstituted 1,2,3-triazole compounds, and BADCh is an excellent energetic material and exhibits good thermal stability (thermal decomposition peak temperature >250 °C), with lower sensitivity (impact sensitivity >19.6 J and friction sensitivity 16%) and similar detonation properties (detonation pressure 32.1 GPa and detonation velocity 8.6 km s^-1) when compared to FOX-7 and RDX.

Full text of DOI:10.1039/C6NJ03370A

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Page 1 of 19
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The New Role of 1,1-Diamino-2,2-dinitroethylene (FOX-7)：Two
Unexpected Reactions
[a]
[a]
[a],[b]*
[a]
[c]
Tianhong Zhou , Yanfeng Li , Kangzhen Xu
, Jirong Song and Fengqi Zhao
[a]
School of Chemical Engineering, Northwest University, Xi’an 710069, China
[
b]
Department of Electrical and Computer Engineering, Missouri of University, Columbia 65211,
USA
[c]
Xi’an Modern Chemistry Research Institute, Xi’an 710065, China
Abstract: Two novel derivatives of FOXꢀ7, 2ꢀmethylꢀ5ꢀnitroꢀ1,2,3ꢀtriazoleꢀ4ꢀamine (MNTzA) and
,5ꢀbis(1ꢀaminoꢀ2,2ꢀdinitrovinyl)carbonohydrazide (BADCh), were synthesized by two
1
unexpected reactions of FOXꢀ7 and hydrazino compounds, and the two reaction processes were
analyzed. The reaction for MNTzA is infrequent to the syntheses of 2,4,5ꢀtrisubstituted
1
,2,3ꢀtriazole compounds. The structures of the two compounds were studied by NMR, single
crystal Xꢀray crystallography and theoretical calculation. MNTzA crystallizes in monoclinic P2(1)/n
space group with four molecules per unit cell, and each molecule exhibits good coplanarity. But
BADCh presents a serious structural distortion of ‘W’ shape and possesses two highly polarized
CꢀC double bonds. DSC analysis and detonation properties of the two compounds were compared
with those of FOXꢀ7 and RDX, and the results indicated that MNTzA is an available intermediate
to synthesize other complicated 2,4,5ꢀtrisubstituted 1,2,3ꢀtriazole compounds, and BADCh is an
excellent energetic material and exhibits good thermal stability (thermal decomposition peak
temperature >250 ºC), lower sensitivity (impact sensitivity >19.6 J and friction sensitivity 16 %)
and similar detonation properties (detonation pressure 32.1 GPa and detonation velocity 8.6 km)
to FOXꢀ7 and RDX.
Keywords: 1,1ꢀDiaminoꢀ2,2ꢀdinitroethylene (FOXꢀ7); 2ꢀMethylꢀ5ꢀnitroꢀ1,2,3ꢀtriazoleꢀ4ꢀamine
(MNTzA); 1,5ꢀBis(1ꢀaminoꢀ2,2ꢀdinitrovinyl)carbonohydrazide (BADCh); Synthesis；Energetic
materials
1
. Introduction
The design and synthesis of new highꢀenergy insensitive compounds are still an
1
important research direction of energetic materials. 1,1ꢀDiaminoꢀ2,2ꢀdinitroethylene
(FOXꢀ7) as a new highꢀenergy insensitive material has been considered as the applied
component of insensitive ammunitions and solid propellants in future, possessing a
ꢀ3
ꢀ1
density of 1.885 g cm , a heat of formation of 133.7 kJ mol , a same insensitivity to
*
Corresponding author. Tel.: +86 29 88307755
Eꢀmail address: xukz@nwu.edu.cn (K. Xu)
1

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1
1
,3,5ꢀtriaminoꢀ2,4,6ꢀtrinitrobenzene (TATB) and a similar energyꢀdensity with
,3,5ꢀtrinitroꢀ1,3,5ꢀtriazinane (RDX) and cyclotetramethylenetetranitramine (HMX)
2
(
Scheme 1). Many researches on FOXꢀ7 have been reported every year since first
2
a, 3
4
synthesized by Latypov in 1998.
Recently, Zhou et al studied the mechanical
5
anisotropy of the FOXꢀ7’s crystal, Lempert et al explored the energy potential of
6
solid composite propellants based on FOXꢀ7 and Wang et al also studied the
configuration and stability of FOXꢀ7 embedded in graphene.
NO
2
NO
2
O
2
N
NO
2
N
N
N
N
H
2
N
N
NH
2
O
2
2
N
N
NH
2
2
N
O
2
O
NH
NO
2
N
N
O
2
N
NO
2
O
2
N
NO
2
NH
2
FOX-7
RDX
TATB
HMX
Scheme 1 Chemical structures of FOXꢀ7, RDX HMX and TATB
FOXꢀ7 is a magic compound for its surprising chemical reactivity. Though the
molecular composition and structure of FOXꢀ7 is very simple, its chemical reactivity
is abundant, including acidꢀbase reaction, coordination reaction, nucleophilic
substitution reaction, acetylate reaction, oxidiating reaction, reduction reaction and
7
electrophilic addition reaction. More than 130 derivative compounds of FOXꢀ7 have
been reported through the above reactions. These reactions were systematically
7
summarized and analyzed in the two reviews just published in this year.
Lately, Vo et al reported their exciting discovery of the first cations based on
FOXꢀ7 and its derivative 1ꢀaminoꢀ1ꢀhydrazinoꢀ2,2ꢀdinitroethylene, and amphoteric
8
properties of the two compounds were demonstrated. Gao et al also reported some
complicated multinitro derivatives of FOXꢀ7, and those compounds exhibit good
thermal stability, high density, positive HOF, acceptable oxygen balances and
9
excellent detonation properties. He et al theoretically studied two potential
derivatives of FOXꢀ7, 5ꢀ(dinitromethylene)ꢀ1,4ꢀdinitraminoꢀtetrazole(NNAT) and
1
,1’ꢀdinitroꢀ4,4’ꢀdiaminoꢀ5,5’ꢀbitetrazole (DNABT), and found they all presents good
10
detonation properties. The study on reactivity of FOXꢀ7 is still an active field of
energetic materials.
In this paper, we also report two unexpected reactions of FOXꢀ7, and the structure
and properties of two reaction products will be meticulously studied. The work further
2

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enriches the research of FOXꢀ7.
2
. Experimental Section
2
.1. Materials
FOXꢀ7 was obtained form Xi’an Modern Chemistry Research Institute, and the purity
is over 99%. Methylhydrazine aqueous solution and carbohydrazide were purchased
from commercial sources and used as received.
2
.2. Physical Measurements
NMR spectra were recorded with a AV500 NMR spectrometer (BRUKER). IR
spectra were determined on NEXUS870 (THERMO NICOLET) with KBr pellets.
Elemental analyses were performed on a Vario EL Ш elemental analyzer
(
ELEMENTAR). MS spectra were recorded on a GCMSꢀQP2010 mass spectrometer
SHIMADZU). SEM images were recorded using a Zeiss SIGMA scanning electron
(
microscope. DSC experiments were performed using a DSC200 F3 apparatus
−1
(
NETZSCH, German) under a nitrogen atmosphere at a flow rate of 80 mL min .
TGꢀDTG experiment was performed using a SDTꢀQ600 apparatus (TA, USA) under a
ꢀ1
nitrogen atmosphere at a flow rate of 100 mL min . The combustion energy was
determined by using a IKA C5000 oxygenꢀbomb calorimeter (German). The impact
and friction sensitivities were determined by using a ZBLꢀB impact sensitivity
instrument (NACHEN, China) and a MGYꢀ2 friction sensitivity instrument
(NACHEN, China), respectively. The mass of drop hammer is 5.0 kg. The swing
angle and gauge pressure are 50 º and 0.6 MPa. The mass for each test is 30 mg. All
other reagents were purchased from commercial sources and used without further
purification.
2
.3. Crystal Structure Determinations
Singleꢀcrystal Xꢀray diffraction data were collected on a Bruker SMART APEX CCD
Xꢀray diffractometer using graphiteꢀmonochromated MoꢀKα radiation (λ=0.071073
nm). The structures were solved by the direct methods (SHELXTLꢀ97) and refined by
2
the fullꢀmatrixꢀblock leastꢀsquares method on F with anisotropic thermal parameters
11
for all nonꢀhydrogen atoms. The hydrogen atoms were added according to the
3

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theoretical models.
.4. Theoretical Calculation Investigation
2
A molecular unit of BADCh generated from Chem3D software was optimized by
minimize energy of MOPAC method repeatedly to nonꢀchange, and then selected as
the initial model, while B3LYP/6ꢀ31+G method in Gaussian 03 package was used to
12
further optimize the structure and compute its frequencies at different temperatures.
Meanwhile, the optimized parameters were used to further compute molecular volume
for 100 times, and the average value was regarded as the credible molecular volume.
All convergent precisions were the system default values, and all calculations were
carried out on the Lenovo T260 server.
2
.5. Preparation
2
ꢀMethylꢀ5ꢀnitroꢀ1,2,3ꢀtriazoleꢀ4ꢀamine (MNTzA) was prepared according to the
following method: FOXꢀ7 (0.02 mol, 2.96 g) was dispersed in 12 mL of water and to
it methylhydrazine aqueous solution (about 0.05 mol, 18 mL) was added dropwise.
After stirred reaction at 100 ºC for 1.5 h, the resulting solution was slowly cooled to
ambient temperature, then diluted with water, filtered, washed with water and dried
under vacuum to obtain the pale yellow crystals of MNTzA. These pale yellow
crystals present regularly rodlike as shown in Figure 1. Yield 1.78 g (62%).
ꢀ1
m.p.167ꢀ169 ºC. IR (KBr, v, cm ), 3440(vs), 3321(vs), 3237(w), 3188(m), 3047(w),
2
1
685(w), 1643(vs), 1574(vs), 1473(w), 1448(w), 1354(m), 1299(s), 1207(m), 1114(w),
13
1
070(m), 866(m). C NMR(DMSO, 500MHz, δ, ppm) 149.745, 137.845, 43.472. H
+
+
NMR(DMSO, 500MHz, δ, ppm) 4.057, 6.773. MS (m/z, %) 143(M , 60), 53(M , 35),
+
+
4
3(M , 100), 30(M , 30). Anal. Calcd. for C
Found. C 25.11, N 48.87, H 3.59.
,5ꢀBis(1ꢀaminoꢀ2,2ꢀdinitrovinyl)carbonohydrazide (BADCh) was prepared
according to the following method: FOXꢀ7 (0.01 mol, 1.48g) was dispersed in 30 mL
of H O and to it carbohydrazide (0.02mol, 1.82 g) was added. After reaction at 105 ºC
3 5 2 5
H O N (%): C 25.18, N48.94, H 3.52.
1
2
for 28 h, the resulting solution was slowly cooled to ambient temperature and diluted
with proper amount of water. Many brown solid were formed, which were filtered,
washed with water, and dried under vacuum, yielding 0.472 g (26.8 %). Figure 1
4

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indicates that the crystalline solids of BADCh are irregular blocky structure. The try
1
for the single crystal all failed. H NMR(DMSO, 400MHz, ppm), δ=8.788, 3.346,
1
3
2
3
3
2
.509. C NMR(DMSO, 400MHz, ppm), δ=43.477, 137.005, 149.745. IR(KBr) υ:
ꢀ1
421, 2360, 1635(vC=O), 1396, 1132, 752, 619 cm . MS [m/z(%), 351(M+, 30),
07(M+, 100), 263(M+, 35), 105(M+, 30)]. Anal. Calcd. for C H N O : C 17.05, H
5
8
10
9
.290, N 39.77 %; found: C 17.09, H 2.263, N 39.49 %.
Figure 1. SEM images of MNTzA and BADCh
3
. Results and Discussion
3
.1. Synthesis of MNTzA
ꢀAminoꢀ1ꢀhydrazinoꢀ2,2ꢀdinitroethylene (AHDNE) as a nucleophilic substitution
derivative of FOXꢀ7 exhibits high reactivity for its special adjacent aminoꢀhydrazino
1
7b,13
group.
AHDNE can react with potassium nitrite in organic acid solution to
synthesize a richꢀnitrogen compound 5ꢀ(dinitromethylene)ꢀtetrazole (DNMT)
14
(
Scheme 2). However, AHDNE and DNMT are unstable, even AHDNE can
9
, 13b, 13c
selfꢀexplode or selfꢀignite at ambient temperature.
So we design to substitute
methylhydrazine for hydrazine to prepare a stable energetic compound. However, the
result is unexpected. The designed compound was not got, but an unusual
2
,4,5ꢀtrisubstituted 1,2,3ꢀtriazole compound, 2ꢀmethylꢀ5ꢀnitroꢀ1,2,3ꢀtriazoleꢀ4ꢀamine,
MNTzA) was surprisingly synthesized (Scheme 2). 1,2,3ꢀTriazole compounds were
largely reported every year since the publication of “Click Chemistry” by Sharpless in
(
15
2
001, and the main “Click Reaction” (Cycloaddition) is to use azide and acetylide
5

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with the action of catalysts to obtain 1,2,3ꢀtriazole or tetrazole compounds. However,
getting 1,4,5ꢀtrisubstituted or 2,4,5ꢀtrisubstituted 1,2,3ꢀtriazole compounds needs
16
much more complicated multistep reactions and the yield is very low. However, a
,4,5ꢀtrisubstituted 1,2,3ꢀtriazole compound can be easily synthesized in this work,
not involving in “Click Chemistry”. Though the compound was reported by Zhang et
2
1
7
al in 2013, whose synthesis method was very complicated and needed about 13 step
reactions, using acetic anhydride as initial raw material. MNTzA is not a complicated
compound, but its amino group, nitro group and methyl group are active groups and
can be further substituted or reacted to prepare other complicated 1,2,3ꢀtriazole
1
7
compounds. The reaction for MNTzA may be a good way to synthesize complicated
,4,5ꢀtrisubstituted 1,2,3ꢀtriazole compounds, and MNTzA may be an available
2
intermediate to synthesize other complicated 2,4,5ꢀtrisubstituted 1,2,3ꢀtriazole
compounds.
H
O
2
2
N
N
NHNH
2
N
NO
2
2
NH
2
NH
2
KNO
H+
N
N
2
O
NH
2
N
H
NO
AHDNE
DNMT
H
N
O
2
2
N
N
NH
2
2
O N
NHNHCH
3
2
NO
2
CH
3
NHNH
2
KNO
H+
2
N
N
O
NH
2
O N
NH2
N
NO2
FOX-7
CH
3
2
O N
N
N
N
3 2
CH NHNH
CH
3
2
H N
MNTzA
Scheme 2. Syntheses of FOX-7’s derivative
The conjectural reaction process for MNTzA is shown in Scheme 3. Firstly,
FOXꢀ7 reacts with methylhydrazine to form an unstable intermediate,
1
ꢀaminoꢀ1ꢀmethylhydrazinoꢀ2,2ꢀdinitroethylene.
Secondly,
1
ꢀaminoꢀ1ꢀmethylhydrazinoꢀ2,2ꢀdinitroethylene becomes the format of tautomers and
3aꢀ3c
resonances (1-3).
3
Thirdly, with the action of electronꢀdonating CH ꢀ group, the H
ꢀ
atom of –NH– dissociates to the adjacent O atom, so the middle N atom of
ꢀ
methylhydrazino group exhibits obvious electronegativity (4). Finally, N atom with
+
lone pair electrons attacks adjacent N atom to form stable 1,2,3ꢀtriazole ring in the
6

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strong reduction system of methylhydrazine, along with the leaving of the two
hydroxyl group to become water.
OH
H
O
2
2
N
N
NO
2
O N
NO2
O N
NO2
O
2
2
N
N
N
O
2
2
1
00
+
3 2
CH NHNH
water
H
NH
2
2
H N
NHNHCH3
2
H N
NNHCH3
H
NNHCH
3
1
2
OH
N
OH
HO
OH
O
2
2
N
N
O
2
2
N
N
O
O
H
2
2
N
N
N
OH
O N
N
N
N
H
2
C
C
2
ꢀH O
N
CH
3
N
CH
3
H
H
NNHCH
3
N
N
CH3
2
H N
N
H
3
4
5
Scheme 3. Reaction process for MNTzA
3
.2. Synthesis of BADCh
7
a
Based on the nucleophilic reactions of FOXꢀ7, carbohydrazide (CHZ) was used as a
nucleophile to prepare new energetic compound. The result indicates that only a
seemingly symmetrical compound 1,5ꢀbis(1ꢀaminoꢀ2,2ꢀdinitrovinyl)carbonohydrazide
(BADCh) was found through the reaction of one CHZ molecule and two FOXꢀ7
molecules with a yield of 26.8 %, but other two expected compounds (A and B) were
not found, regardless of how to change the reaction conditions (Scheme 4).
Compound B is attractive, and we ever doubted that the product should be compound
B, because the compound possesses a stable sixꢀmember ring and should have big
competitive advantage compared with other two compounds. The rule also was found
2b, 7a
1
in other double nucleophilic substitution derivatives.
However, the results of H
NMR (three chemical shifts: 8.788, 3.346, 2.509 ppm) and MS [351(M+, 30)] deny
our guess, and BADCh is the only product. The try for compound B all failed.
O
2
N
NH
2
O
C
（
A
）
O N
NH NH
HN NH
NHNH2
2
O
2
2
N
N
NH
NH
2
2
2
O N
O
C
C
O
B
（ ）
H
2
NHN
NHNH
2
O
2
N
N
N
HN NH
O
CHZ
FOX-7
O
2
2
NH
2
H
2
N
NO
2
O
C
O
NH NH
NH
NH
NO2
BADCh
Scheme 4 Synthesis of BADCh
7

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3
.3. Structure analysis of MNTzA
The single crystal of MNTzA was obtained from the reaction solution cooled very
slowly. The orderly rodlike crystal of MNTzA is pale yellow (Figure 1), and
structured by single crystal Xꢀray crystallography. MNTzA crystallizes in monoclinic
P2(1)/n space group with four molecules per unit cell (Supporting materials). The
structure of MNTzA is simple, consisting of a triazole ring and three small substituent
groups as shown in Figure 2(a). From selected bond lengths, N2ꢀC2 bond (1.346 Å)
is a typical conjugated NꢀC double bond, but N4ꢀC3 bond (1.456 Å) is a typical CꢀN
single bond. In triazole ring, N3ꢀN4 bond (1.299 Å), N3ꢀC1 bond (1.341 Å), N4ꢀN5
bond (1.348 Å), N5ꢀC2 bond (1.339 Å) and C1ꢀC2 bond (1.403 Å) are all conjugated
double bond. Moreover, N2ꢀC2 bond also involves in the conjugative effect of triazole
ring to form a larger conjugated system, which reduces the energy and increases the
stability of molecule. From selected bond angles (N4ꢀN3ꢀC1, 102.667°; N3ꢀN4ꢀN5,
116.56°; N4ꢀN5ꢀC2, 103.82°; N3ꢀC1ꢀC2, 110.37° and N5ꢀC2ꢀC1, 106.58°), it can be
seen that the triazole ring was greatly effected by substituent groups, especially to
amino group. Despite of the influence of substituent groups, all nonꢀhydrogen atoms
in triazole ring and three substituent groups have good coplanarity. The two biggest
torsion angles are 177.86° (C1ꢀN3ꢀN4ꢀC3) and ꢀ177.75° (C3ꢀN4ꢀN5ꢀC2), and the two
smallest are 0° (N4ꢀN5ꢀC2ꢀC1) and ꢀ0.3° (N3ꢀN4ꢀN5ꢀC2), respectively. Each
MNTzA molecule contacts with two surrounding molecules by four hydrogenꢀbond
interactions [only two kinds; N2ꢀH…N5#1 (d(D…A)=3.102 Å, ∠DHA=168.06°),
N2ꢀH…O2#2 (d(D…A)=3.313 Å, ∠DHA=142.65 °); symmetry transformations: #1:
ꢀx+1, ꢀy, ꢀz+2; #2: x+1/2, ꢀy+1/2, z+1/2] (Figure 2(a)), which infinitely extend out to
form an ordered 3D packing of MNTzA as shown in Figure 2(b).
8

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(
a)
(
b)
Figure 2. Thermal ellipsoids plots shown at 30% and their hydrogen-bond interactions (a)，
and packing diagram of MNTzA along the a-axis (b)
Selected bond lengths(Å): N2ꢀC2, 1.346(3); N3ꢀN4, 1.299(2); N3ꢀC1, 1.341(3); N4ꢀN5, 1.348(2); N4ꢀC3, 1.456(3);
N5ꢀC2, 1.339(3); C1ꢀC2, 1.403(3). Selected bond angles(°): N4ꢀN3ꢀC1, 102.66(17); N3ꢀN4ꢀN5, 116.56(17);
N4ꢀN5ꢀC2, 103.82(16); N3ꢀC1ꢀC2, 110.37(19); N3ꢀC1ꢀN1, 121.62(19); C2ꢀC1ꢀN1, 128.0(2); N5ꢀC2ꢀN2, 123.0(2);
N5ꢀC2ꢀC1, 106.58(18); N2ꢀC2ꢀC1, 130.4(2).
3
.4. Theoretical Calculation Results of BADCh
Vibration analysis showed that the optimized structure is in accord with the minimum
points on the potential energy planes, proving that the optimized structure is stable
12
and the calculation results are reliable. The optimized structure of BADCh and some
selected bond lengths are shown in Figure 3. One CHZ molecule connects with two
FOXꢀ7 molecules by mucleophilic substitution to form a new bigger molecule with
the leave of two amino groups. The new molecule (BADCh) presents a serious
structural distortion of ‘W’ shape around the central CHZ group, which is much
different from the similar plane structure of FOXꢀ7’s molecule and highly ordered
1
8
singleꢀlayer space construction. The structural distortion also can be supported by
those seemingly symmetric chemical bonds, such as bond C5ꢀC7 (1.431 Å) and
C15ꢀC17 (1.430Å), C1ꢀN24 (1.407Å) and C1ꢀN2 (1.399Å), N14ꢀN24 (1.391 Å) and
9

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N2ꢀN4 (1.387Å), and C15ꢀN14 (1.368Å) and C5ꢀN4 (1.368Å) (see Supporting
Materials). From the bond lengths, bond C5ꢀC7 and C15ꢀC17 still are conjugated
double bonds. Bond C15ꢀN14, C15ꢀN16, C5ꢀN4 and C5ꢀN6 are conjugated double
bonds. Comparing with related bond lengths of CHZ [CꢀN (1.348 Å), NꢀN (1.411
1
9
Å)], CꢀN bond was elongated, but NꢀN bond was shortened in BADCh. So, a big
conjugated system forms from C7 to C17 including all middle atoms, which should be
the main reason for BADCh having better thermal stability than FOXꢀ7. The
distribution of atomic net charges indicated that C5 (0.7581e) and C15 (0.6476 e)
have more positive charges than C7 (0.1377 e) and C17 (0.2604 e), also indicating
that BADCh possesses two highly polarized CꢀC double bonds. Carbonyl group
reduces the activities of NꢀN bond and CꢀN bond of both sides, which may be another
reason for BADCh having better thermal stability than FOXꢀ7.
Figure 3 Optimized structure of BADCh and some selected bond lengths
3
.5. DSC analysis
Typical DSC and TG/DTG curves in Figure 4 indicate that the thermal behavior of
MNTzA presents two obvious stages. The first is an intense endothermic
meltingꢀdecomposition process with a mass loss of about 92.8%, and the onset
temperature, peak temperature and decomposition enthalpy at a heating rate of 10 °C
ꢀ1
ꢀ1
min are 169.56, 170.41 ºC and 140.9 J g , respectively. The second is a
slow endothermic decomposition process with a mass loss of only about 4.5 %. The
final residue at 300 ºC is about 3.3 %. No exothermic process can be found in the
whole DSC curve of MNTzA. The introduction of a methyl group and the losing of a
nitro group make the thermal behavior of compound change greatly, compared with
that of parent compound (FOXꢀ7) in Figure 5.
1
0

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-1
Figure 4. Typical DSC and TG/DTG curves of MNTzA at a heating rate of 10 °C min
Figure 5 indicates that thermal behavior of BADCh can be divided into four
stages. The first two stages are crystalꢀphase transition processes, and the peak
−1
temperatures are 116.51 and 169.13 ºC at the heating rate of 5.0 ºC min , respectively.
The last two stages are a continuous exothermic decomposition process with a mass
lose of about 76 %, and the peak temperatures are 252.82 and 286.49 ºC at the heating
−1
rate of 5.0 ºC min , respectively. It is surprising that the thermal behavior of BADCh
was very similar to that of FOXꢀ7 including two crystalꢀphase transition processes,
and the difference for the two compounds is the thermal decomposition temperature
of BADCh is higher than that of FOXꢀ7 (229.70 and 294.33 ºC). The same
phenomenon
also
can
be
found
in
another
derivative
of
20
FOXꢀ7ꢀꢀꢀꢀ1ꢀaminoꢀ1ꢀ(2,4ꢀdinitrophenylhydrazinyl)ꢀ2,2ꢀdinitroethylene (APHDNE),
indicating that 1ꢀaminoꢀ2,2ꢀdinitrovinyl group plays the key role in molecules. The
sequence of thermal stability for the three compounds is BADCh > APHDNE >
FOXꢀ7. The introduction of stable group can raise the thermal stability of compound.
Moreover, the two continuous exothermic decomposition processes of BADCh can
easily become a big and wide exothermic process with the rise of heating rate (10 °C
–1
min ), but FOXꢀ7 still presents two exothermic decomposition processes (Figure 6).
A multiple heating method was employed to obtain the kinetic parameters [the
11

New Journal of Chemistry
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apparent activation energy (E) and preꢀexponential factor (A)]. The DSC data and
results obtained by Kissinger method and Ozawa method of the decomposition
2
1
process for BADCh are listed in Table 1. The apparent activation energy obtained
by Kissinger method agrees well with that by Ozawa method. The linear correlation
coefficients (r) are very close to 1. So, the results are credible. Moreover, the apparent
activation energy is lower, indicating that BADCh easily decomposes at high
temperature.
–1
Figure 5 Typical DSC and TG/DTG curves of BADCh at a heating rate of 5 °C min
–
1
Figure 6 DSC curves of BADCh and FOX-7 at a heating rate of 10 °C min
Table 1. DSC data and results of kinetic parameter at different heating rates (β)
1
2

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β/
E
k
O
E /
ꢀ
1
T
e
/ºC
T
p
/ºC
log(A
k
/s )
r
k
r
O
–
1
ꢀ1
ꢀ1
(
ºC min )
/(kJ mol )
(kJ mol )
5
.0
.5
235.1
238.8
255.3
257.7
252.8
260.8
267.6
269.7
7
1
13.6
8.90
0.9905
116.5
0.9918
1
1
0.0
2.5
Subscript k is data obtained by Kissinger method, Subscript O is data obtained by Ozawa method
The selfꢀaccelerating decomposition temperature (TSADT) and critical temperature
of thermal explosion (T ) are two important parameters required to ensure safe storage
and process operations for energetic materials and then to evaluate the thermal
b
22
stability. TSADT and T
which all are much higher than those of FOXꢀ7 as 206.0 and 207.1 ºC, also
indicating BADCh has higher thermal stability than FOXꢀ7
b
for BADCh are calculated as 213.7 and 222.1 ºC respectively,
3
g
.
3
.6 Detonation Properties
The detonation properties of MNTzA, BADCh and the properties of FOXꢀ7 and RDX
2d, 8
for comparison are summarized in Table 2.
MNTzA, as an energetic material,
exhibits bad detonation properties comparing with FOXꢀ7 and RDX, though having
high nitrogen content (48.9 %) and good insensitivity (>16.9 J, 24 %). The reason
should be the losing of one nitro group and the introduction of a methyl group, which
makes the energy and density of compound decline greatly (the crystal density
ꢀ3
ꢀ3
18
declines from 1.88 g cm of FOXꢀ7 to 1.58 g cm of MNTzA). However,
detonation properties of BADCh are good, whose detonation velocity and detonation
pressure are close to that of FOXꢀ7 and RDX, but the sensitivities are much lower
than that of RDX.
Table 2. Detonation properties
a
b
c
d
e
0
f
g
h
i
j
M
T
m
d
OB
ꢀꢁ
/kJ g
c
H
c
ꢁ
f
H
m
IS
FS
P
D
sample
ꢀ1
ꢀ3
ꢀ1
ꢀ1
ꢀ1
/
g mol
/°C
/g cm
/%
/kJ mol
/J
/%
/GPa
km s
MNTzA
BADCh
FOXꢀ7
RDX
143.12
352.18
148.08
222.12
167.8
1.58
ꢀ72.7
12.38
8.11
ꢀ130.1
ꢀ260.9
ꢀ133.7
96.2
16.9
24
20.7
7.1
k
ꢀ
ꢀ
1.75
ꢀ22.7
ꢀ21.6
ꢀ21.6
19.6
24.7
7.4
16
10
76
32.1
36.1
8.6
8.3
8.7
1.88
7.83
204.5
1.82
9.55
33.7
a
b
c
d
e
f
Molecular mass, Melting point; Crystal density; Oxygen balance; Combustion energy; Enthalpy of
g
h
i
formation; Impact sensitivity; Friction sensitivity; Detonation pressure based on KamletꢀJacobs (KꢀJ)
equations; Detonation velocity based on KamletꢀJacobs (KꢀJ) equations; Theoretical calculation result.
j
k
1
3

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4
. Conclusions
In conclusion, we reported two new reactions of FOXꢀ7 in this work, and two
reaction products, 2ꢀmethylꢀ5ꢀnitroꢀ1,2,3ꢀtriazoleꢀ4ꢀamine (MNTzA) and
,5ꢀbis(1ꢀaminoꢀ2,2ꢀdinitrovinyl)carbonohydrazide (BADCh), are unexpected. The
1
reaction for MNTzA is infrequent to the syntheses of 2,4,5ꢀtrisubstituted 1,2,3ꢀtriazole
compounds, and may be a selectable way to synthesize other complicated
2
,4,5ꢀtrisubstituted 1,2,3ꢀtriazole compounds by the reaction without involving in
wellꢀknown “Click Chemistry”. 1ꢀAminoꢀ2,2ꢀdinitrovinyl group plays the key role to
the thermal behavior of compound, but the introduction of a methyl group and the
losing of a nitro group make the thermal behavior of FOXꢀ7 change greatly.
MNTzA is not a good energetic compound for its bad detonation properties, but
BADCh still exhibits excellent thermal stability, lower sensitivity and similar
detonation properties to FOXꢀ7 and RDX and has a good application potential as
energetic material. This work further enriches the reactivity of FOXꢀ7.
Supporting Information
CCDC-1044208 contains the supplementary crystallographic data for this paper.
These data can be obtained free of charge from the Cambridge Crystallographic Data
Center via www.ccdc.ac.uk/data_repuset/cif.
Crystallographic data, optimized bond lengths, bond angles and atomic net charges,
and energies of combustion.
Acknowledgments
This investigation received financial assistance from the National Natural Science
Foundation of China (No. 21673178 and 21241003) and the Chinese Scholarship
Council (No.201606975010).
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Derivatives
of
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H
N
O
2
N
N
NH
2
O
O
2
N
N
NHNH
2
NO
2
2
NH
2
NH
2
KNO
H+
N
N
2
O
C
O
2
NH
NH
NHNH
2
NH
N
H
NO
2
2
AHDNE
DNMT
O
C
H
O
O
2
N
N
NH
NH
2
2
O
O
2
N
NHNHCH
3
N
NO
2
2
O
2
N
N
HN NH
CH
3
NHNH
KNO
H+
N
N
H N
3
2
N
2
H
3
2
2
C
O
O
2
HN NH
CHZ
2
2
N
NH
2
N
NO
FOX-7
CH
3
2
O N
O
O
2
2
N
N
NH
2
H
2
N
NO
2
N
N
3 2
CH NHNH
O
C
N
CH
3
NH
NH
NH
NH
NO
2
2
H N
BADCh
MNTzA
Two unexpected reactions of FOX-7 were studied. The reaction for MNTzA is infrequent to the
synthesis of 2,4,5-trisubstituted 1,2,3-triazole compounds.