A Facile and Versatile Synthesis of Energetic Furazan-Functionalized 5-Nitroimino-1,2,4-Triazoles

Article abstract of DOI:10.1002/anie.201701659

An analogue-oriented synthetic route for the formulation of furazan-functionalized 5-nitroimino-1,2,4-triazoles has been explored. The process was found to be straightforward, high yielding, and highly efficient, and scalable. Nine compounds were synthesized and the physicochemical and energetic properties, including density, thermal stability, and sensitivity, were investigated, as well as the energetic performance (e.g., detonation velocities and detonation pressures) as evaluated by using EXPLO5 code. Among the new materials, compounds 4–6 and 11 possess high densities, acceptable sensitivities, and good detonation performances, and thereby demonstrate the potential applications as new secondary explosives.

Full text of DOI:10.1002/anie.201701659

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Communications
Chemie
International Edition: DOI: 10.1002/anie.201701659
German Edition: DOI: 10.1002/ange.201701659
Energetic Materials
A Facile and Versatile Synthesis of Energetic Furazan-Functionalized
5-Nitroimino-1,2,4-Triazoles
Zhen Xu, Guangbin Cheng, Hongwei Yang,* Xuehai Ju, Ping Yin, Jiaheng Zhang,* and
Jeanꢀne M. Shreeve*
Abstract: An analogue-oriented synthetic route for the for-
mulation of furazan-functionalized 5-nitroimino-1,2,4-tri-
azoles has been explored. The process was found to be
straightforward, high yielding, and highly efficient, and
scalable. Nine compounds were synthesized and the physico-
chemical and energetic properties, including density, thermal
stability, and sensitivity, were investigated, as well as the
energetic performance (e.g., detonation velocities and detona-
tion pressures) as evaluated by using EXPLO5 code. Among
the new materials, compounds 4–6 and 11 possess high
densities, acceptable sensitivities, and good detonation per-
formances, and thereby demonstrate the potential applications
as new secondary explosives.
these compounds are highly sensitive towards external
mechanical stimuli (impact sensitivity for 1 and 2 is 1.5 and
3 J, respectively), and it greatly limits their practical applica-
tions.[4]
Quantum chemical calculations give rise to the most
appropriate method to understand the relationship between
impact sensitivity and the charge distribution in energetic
materials.[5] Politzer and co-workers have applied general
interaction properties functions (GIPF), based on quantum
chemical calculations, to the correlation and prediction of
a number of properties of energetic molecules.[5] According to
Paulingꢀs electroneutrality postulation, the electrostatic
potential of a molecule under steady-state conditions tends
to be as uniform as possible.[6] Therefore, the GIPF electro-
static balance parameters (n), which can be obtained from
ab initio methods, should be close to 0.2500. Deviations from
this value suggests either instability or sensitivity.[6] In our pre-
study, the GIPF balance parameters of several classic
energetic materials along with some nitramino-functionalized
azoles have been calculated by application of this method.
The GIPF balance parameter (n) for the very insensitive
explosive 2,4,6-triamino-1,3,5- trinitrobenzene (TATB) has
the maximum value of 0.2500, whereas the corresponding
values for 1 and 2 are much lower than 0.2500, and is thus in
agreement with their high sensitivity. Unexpectedly, com-
pounds which are structurally similar to 1 and 2, compounds
such as nitramino-functionalized azoles, 3-amino-4-(5-nitra-
mino-1, 2, 4-triazol-3-yl)furazan (3), 3-nitro-4-(5-nitramino-1,
2, 4-triazol-3-yl)furazan (4), and 3-nitramino-4-(5-nitramino-
1, 2, 4-triazol-3-yl)furazan (5), have balance parameters of
0.2325, 0.2143, and 0.1951, respectively (close to 0.2500).
Based on quantum chemical calculations, furazan-functional-
ized 5-nitroimino-1, 2, 4-triazoles should possess a fine
balance between high detonation performance and low
sensitivity.
I
n the last decade, considerable attention has been directed
toward the synthesis of energetic heterocyclic compounds
with excellent performance characteristics, such as a positive
heat of formation, high density, high detonation velocity and
pressure, high thermal stability, and low sensitivity towards
external forces.[1] The need for highly energetic materials
continues to expand, and of particular interest are nitrogen-
containing heterocycles (triazole, furazan, etc.) in combina-
tion with energetic substituents such as nitro (-NO2), nitrate
(-ONO2), and nitramine (-NHNO2) functionalities because of
their satisfactory comprehensive performances.[2] The com-
pounds functionalized with nitramino groups have been
theoretically and experimentally investigated as energetic
materials.[3]
3,3’-Dinitramino-4,4’-bifurazan
(1:
nD =
9086 msÀ1; P = 40.3 GPa) and 3,3’-dinitramino-5,5’-bis(1H-1,
2, 4-triazole) (2: nD = 8355 msÀ1; P = 30.0 GPa) are two
representative nitramino-based energetic compounds which
show excellent detonation properties.[3a,b] Unfortunately,
[*] Z. Xu, Prof. G. Cheng, Dr. H. Yang, Prof. X. Ju
School of Chemical Engineering
Commonly, the most practical method to prepare nitra-
mino-containing 1, 2, 4-triazoles has been the nitration of 5-
amino-1,2,4-triazoles by either 100% HNO3 or other strongly
acidic systems.[3b,7] The precursors of 5-amino-1,2,4-triazoles
are usually synthesized by condensation of carbonyl com-
pounds with either aminoguanidine hydrochloride or
hydroxyacetimidamides with cyanogen bromide.[8] The draw-
backs of these procedures include narrow applicability to
substrates, harsh reaction conditions, and the inefficiency in
synthesis scale-up. Herein, we report the straightforward and
scalable synthesis, and characterization of a series of energetic
compounds consisting of the 5-nitramino-1,2,4-triazole
moiety and furazan/furoxan rings substituted with methyl,
amino, azo, nitro, and nitramino functional groups. The
Nanjing University of Science and Technology
Nanjing, 210094 (China)
E-mail: hyang@mail.njust.edu.cn
Prof. J. Zhang
School of Materials Science and Engineering
Harbin Institute of Technology
Shenzhen, 518055 (China)
E-mail: jzhang@uidaho.edu
Dr. P. Yin, Prof. J. M. Shreeve
Department of Chemistry, University of Idaho
Moscow, ID 83844-2343 (USA)
E-mail: jshreeve@uidaho.edu
Supporting information and the ORCID identification number(s) for
the author(s) of this article can be found under:
https://doi.org/10.1002/anie.201701659.
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methodology is based on condensation of the readily and
commercially available 1-methyl-1-nitroso-2-nitroguanidine
(MNNG) with furazan-functionalized carboxylic acid hydra-
zides.[9] In the initial case (Scheme 1), compound b reacts with
using the one-pot procedure with MNNG, 3-amino-4-(5-
nitramino-1, 2, 4-triazol-3-yl)methylfurazan (7), bis(5-nitra-
mino-1,2,4-triazol-3-methyl)-azofurazan (8), and 3-methyl-4-
(5-nitramino-1, 2, 4-triazol-3-yl)furoxan (9) were obtained.
The variations of the substrates are shown in Scheme 3. The
Scheme 3. Variations of the substrates of this synthesis strategy and
the preparation of the energetic salts 10 and 11.
Scheme 1. Synthesis route to 3-amino-4-(5-nitramino-1,2,4-triazol-3-
yl)furazan (3) and its azo derivative (6), 3-nitro-4-(5-nitramino-1, 2, 4-
triazol-3-yl)furazan (4), and 3-nitramino-4-(5-nitramino-1, 2, 4-triazol-3-
yl)furazan (5).
reactions of MNNG with furazan/furoxan-based carboxylic
acid hydrazides provide convenient approaches to synthesize
furazan-functionalized 5-nitroimino-1,2,4-triazoles, which are
compounds of potential interest for energetic material
applications. Energetic salts most often possess higher
thermal stability, and lower vapor pressure and acid-induced
corrosivity than their neutral precursors. Hence, a monoam-
monium salt (10) of 3 and dihydroxylammonium salt (11) of 5
were also prepared by typical acid-base reactions (Scheme 3).
The structures of 3–11 are well-supported by 1H NMR,
13C NMR, and IR spectroscopy, and elemental analysis. The
compounds 3–5 were further investigated by single-crystal X-
ray crystallography.
MNNG in aqueous solution to give the nitroguanidyl-
functionalized intermediate c, from which 3 was synthesized
through intramolecular cyclization by refluxing in aqueous
alkaline solution. The compounds 4 and 5 were prepared by
treating 3 with 30% hydrogen peroxide and 100% nitric acid,
respectively. Notably, the one-pot synthesis of 3 from b was
demonstrated, and further increases the efficiency of this
procedure. The azo-derivative 6 can be obtained from 3
through an oxidative coupling reaction with acidic potassium
permanganate. Additionally, the reaction of e, obtained from
d, and MNNG also provides a feasible route to 6. The broader
applicability of this synthetic strategy was exemplified for
three additional substrates (Scheme 2), that is, methyl-2-(4-
amino- furazan-3-yl)acetate (f) bis(methylacetate)-azofura-
zan (i), and 4-(ethoxycarbonyl)-3-methyl-furoxan (k). By
Suitable crystals of 3·H2O, 4·acetone, and 5·H2O for
single-crystal X-ray diffraction were obtained through slow
evaporation from solvents. In Figure 1, the crystal structures
of these compounds are displayed. The crystals of 3·H2O and
5·H2O crystallize in the monoclinic space group P21/c, which
contains one lattice water molecule, whereas 4·acetone
ꢀ
crystallizes in the triclinic space group P1. Based on the
À
crystal structures, the C C bridged rings, and the amino and
nitranimo moieties of 3·H2O and 5·H2O are nearly planar.
Scheme 2. Synthesis route of 3-amino-4-(5-nitramino-1,2,4-triazol-3-
yl)methylfurazan (7), bis(5-nitramino-1,2,4-triazol-3-methyl)-azofurazan
(8), and 3-methyl-4-(5-nitramino-1,2,4-triazol-3-yl)furoxan (9).
Figure 1. The molecular structures of a) 3·H2O, b) 4·acetone, and
c) 5·H2O.[13] Thermal ellipsoids shown at 50% probability. d) Depicted
are the inter- and intramolecular hydrogen bonds for 5·H2O.
2
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Among these crystals, 5·H2O has the highest crystal density of
(80.12%) and 11 (82.83%) exhibit higher combined nitrogen
and oxygen content values, which are comparable to those of
RDX (81.04%) and HMX (81.04%).
1.896 gcmÀ3, in spite of the presence of a water molecule in
the structure. With a lone electron pair associated with the
nitrogen atom (N3) attached to the furazan ring of 5·H2O,
they form p-p conjugation between the nitrogen atoms and
Heat of formation (HOF) plays an important role in
evaluating the performance of energetic materials. The heats
of formation of 3–11 were calculated based on appropriate
isodesmic reactions by using Gaussian09 program package
(more details about the calculations of heats of formation can
be found in the Supporting Information).[10] As summarized in
Table 1, all new energetic compounds exhibit positive heats of
formation ranging from 327.3 kJmolÀ1/1.01 kJgÀ1 (11) to
1274.4 kJmolÀ1/3.03 kJgÀ1 (6), and are much higher than
those of TNT, RDX, and HMX. The reason for these higher
À
the aromatic ring, so that the lengths of the C1 N3 (1.375 ꢁ)
=
bonds approach the length of the C N (1.350 ꢁ) double bond.
The hydrogen-bonding interactions in 3·H2O, 4·acetone, and
5·H2O are extensive. Additional details involving the crystal
structures, including CCDC numbers,[13] and the polymorph
3·DMF are provided in the Supporting Information.
The thermal stabilities of the newly prepared furazan-
functionalized 5-nitroimino-1,2,4-triazoles were determined
using differential scanning calorimetry (DSC) measurements.
As shown in Table 1, all the compounds decompose without
melting, with 3 and 7 being exceptions as they melt at 158.8
and 170.28C, respectively, and then decompose. Amino-
functionalized compounds decompose at higher temperatures
(3: Td = 195.58C; 7: Td = 196.88C) than the other neutral
energetic compounds. In addition, 5 (Td = 128.78C) has the
lowest decomposition temperature. This undesirable thermal
behavior most likely arises from the presence of a second
nitramino moiety in the furazan ring. As expected, the ionic
derivatives 10 (Td = 242.88C) and 11 (Td = 196.98C) have the
best thermal stabilities among the new materials.
Density is a critical physical parameter for energetic
materials. The experimental densities of 3–11 are in the range
of 1.680 to 1.920 gcmÀ3. It should be noted that the densities
of 4–6 and 11 fall within the range designated for new high-
energy-density materials (1.8–2.0 gcmÀ3), and are comparable
with the common high explosives RDX and HMX. Oxygen
balance is the index of the deficiency, that is, the excess of
oxygen in a compound required to convert carbon into either
carbon dioxide or carbon monoxide, and all hydrogen into
water. Based on CO2, 3–11 exhibited negative OB values
ranging between À26.43% (4) and À70.74% (7). In the case
of OBco, 4 (0) and 11 (À7.43%) possess similar values to that
of RDX (0) and HMX (0). Among these compounds, 5
À
À
À
values is attributed to the large number of C N, N N, and N
O bonds within the structures of 3–11.
In the case of energetic materials, the value of energetic
performance depends to a great extent on the detonation
velocity (nD) and detonation pressure (P). Based on exper-
imental densities and calculated heats of formation, detona-
tion properties were determined using EXPLO5 (v6.01).[11]
The calculated detonation velocities and pressures fall in the
range from 8079 to 9258 msÀ1, and from 24.9 to 39.0 Gpa,
respectively. The compounds 4 (9025 msÀ1), 5 (9258 msÀ1),
and 11 (9135 msÀ1) exhibit excellent detonation velocities,
and they are comparable to that of HMX (9144 msÀ1). These
values are due to high density and high combined nitrogen
and oxygen content for these compounds. The high detona-
tion pressure of 5 (39.0 GPa) is slightly lower than that of
HMX (39.2 GPa). To perform a more thorough evaluation of
the energetic compounds, impact and friction sensitivity
measurements were made using a standard BAM Fallhammer
and a BAM friction tester.[12] The compounds 3–11 were
found to be less impact sensitive (18 J to ꢀ 40 J) than TNT. In
addition, the friction sensitivity is higher than 250 N for all
compounds. As shown in Figure 2, the GIPF balance param-
eters of 1–9 showed a relatively consistent trend with their
experimental sensitivity values. Two energetic compounds (7
and 9) with measured IF values above 40 J show higher GIPF
Table 1: Properties of 3–11 compared to 2,4,6-trinitrotoluene (TNT), 1,3,5-trinitroperhydro-1,3,5-triazine (RDX), octahydro-1,3,5,7-tetranitro-1,3,5,7-
tetrazocine (HMX), and TATB.
1[c]
[gcmÀ3
N+O[d]
[%]
OBCO
[%]
OBCO
[%]
DfHm
nD
[msÀ1
P[i]
[GPa]
IS[j]
[J]
FS[k]
[N]
[a]
[e]
[f]
[g]
[h]
Compd
Tm
Td[b]
[8C]
2
[8C]
]
[kJmolÀ1]/[kJgÀ1
]
]
3
4
5
6
7
8
9
158.8
–
–
–
170.2
–
–
–
–
195.5
163.2
128.7
174.3
196.8
196.3
180.5
242.8
196.9
295
1.740
1.851
1.920
1.873
1.695
1.704
1.741
1.680
1.850
1.65
75.43
79.30
80.12
76.17
70.77
71.40
71.34
75.95
82.83
60.79
81.04
81.04
69.75
À52.80
À26.43
À28.00
À45.69
À70.74
À64.25
À59.88
À59.37
À27.24
À73.97
À21.61
À21.69
À55.8
À20.87
0
467.52/2.20
524.66/2.17
548.82/2.13
1274.4/3.03
449.0/1.99
1206.2/2.69
443.8/1.95
328.2/1.43
327.3/1.01
8332
9025
9258
8973
8079
8125
8236
8130
9135
6881
8795
9144
8114
27.7
36.0
39.0
34.9
24.9
26.0
28.2
24.6
36.6
19.5
34.9
39.2
31.2
35
20
18
28
>40
31
>40
>40
36
360
280
250
280
>360
300
>360
>360
360
353
120
À3.11
À15.24
À35.40
À28.57
À24.67
À31.14
À7.43
À24.67
0
10
11
TNT
RDX
HMX
TATB
80.5
–
–
À67.0/À0.30
15
204
280
360
1.800
1.905
1.930
70.3/0.32
7.4
7.4
50
0
70.4/0.25
120
>360
–
À18.6
À137.5/À0.54
[a] Melting point. [b] Thermal decomposition temperature (onset) under nitrogen (determined by the DSC exothermal peak, 58CminÀ1). [c] Density
measured by gas pycnometer at 258 C. [d] Combined nitrogen and oxygen content. [e] Oxygen balance [%] based on CO2 for CaHbNcOd: OB
[%]=1600ꢀ(dÀ2aÀb/2)/MW, MW =molecular weight. [f] Oxygen balance [%] based on CO for CaHbNcOd: OB [%]=1600ꢀ(dÀaÀb/2)/MW.
[g] Calculated molar enthalpy of formation in solid state. [h] Detonation velocity. [i] Detonation pressure. [j] Impact sensitivity. [k] Friction sensitivity.
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Academic Program Development of Jiangsu Higher Educa-
tion Institutions (PAPD).
Conflict of interest
The authors declare no conflict of interest.
Keywords: density functional calculations · energetic materials ·
heterocycles · structure elucidation · X-ray diffraction
Figure 2. The general interaction properties function balance parame-
ters and impact sensitivities of representative nitramino-functionalized
energetic compounds compared with classic explosives and targeted
furazan-functionalized 5-nitroimino-1,2,4-triazoles. CL-20 (hexanitro-
hexaazaisowurtzitane).
[1] a) G. Bꢂlanger-Chabot, M. Rahm, R. Haiges, K. O. Christe,
Angew. Chem. Int. Ed. 2015, 54, 11730 – 11734; Angew. Chem.
2015, 127, 11896 – 11900; b) D. E. Chavez, M. A. Hiskey, D. L.
Naud, D. Parrish, Angew. Chem. Int. Ed. 2008, 47, 8307 – 8309;
Angew. Chem. 2008, 120, 8431 – 8433; c) J. Zhang, L. A. Mitchell,
D. A. Parrish, J. M. Shreeve, J. Am. Chem. Soc. 2015, 137,
10532 – 10535; d) T. M. Klapçtke, P. C. Schmid, S. Schnell, J.
Stierstorfer, J. Mater. Chem. A 2015, 3, 2658 – 2668; e) J. Zhang,
Q. Zhang, T. T. Vo, D. A. Parrish, J. M. Shreeve, J. Am. Chem.
Soc. 2015, 137, 1697 – 1704.
[2] a) X. X. Zhao, S. H. Li, Y. Wang, Y. C. Li, F. Q. Zhao, S. P. Pang,
J. Mater. Chem. A 2016, 4, 5495 – 5504; b) D. Fischer, T. M.
Klapçtke, J. Stierstorfer, Angew. Chem. Int. Ed. 2015, 54, 10299 –
10302; Angew. Chem. 2015, 127, 10438 – 10441; c) A. Aizikovich,
A. Shlomovich, A. Cohen, M. Gozin, Dalton Trans. 2015, 44,
13939 – 13946; d) J. Zhang, J. M. Shreeve, J. Am. Chem. Soc.
2014, 136, 4437 – 4445; e) I. V. Ovchinnikov, A. O. Finogenov,
M. A. Epishina, Y. A. Strelenko, N. N. Makhova, Mendeleev
Commun. 2009, 19, 217 – 219; f) L. L. Fershtat, N. N. Makhova,
Russ. Chem. Rev. 2016, 85, 1097 – 1145.
[3] a) D. Fischer, T. M. Klapçtke, M. Reymann, J. Stierstorfer,
Chem. Eur. J. 2014, 20, 6401 – 6411; b) A. A. Dippold, T. M.
Klapçtke, Chem. Eur. J. 2012, 18, 16742 – 16753; c) Y. Tang, J.
Zhang, L. A. Mitchell, D. A. Parrish, J. M. Shreeve, J. Am.
Chem. Soc. 2015, 137, 15984 – 15987; d) T. M. Klapçtke, M.
Leroux, P. C. Schmid, J. Stierstorfer, Chem. Asian J. 2016, 11,
844 – 851.
[4] a) Y. Tang, C. He, L. A. Mitchell, D. A. Parrish, J. M. Shreeve,
Chem. Eur. J. 2016, 22, 11846 – 11853; b) Y. Tang, H. Gao, L. A.
Mitchell, D. A. Parrish, J. M. Shreeve, Angew. Chem. Int. Ed.
2016, 55, 1147 – 1150; Angew. Chem. 2016, 128, 1159 – 1162.
[5] a) P. He, J. Zhang, K. Wang, X. Yin, T. Zhang, J. Org. Chem.
2015, 80, 5643 – 5651; b) J. Yuan, X. Long, C. Zhang, J. Phys.
Chem. A 2016, 120, 9446 – 9457; c) P. Politzer, J. S. Murray, Z.
Peralta-Inga, Int. J. Quantum Chem. 2001, 85, 676 – 684; d) P.
Politzer, J. S. Murray, Cryst. Growth Des. 2015, 15, 3767 – 3774.
[6] a) B. M. Rice, J. J. Hare, J. Phys. Chem. A 2002, 106, 1770 – 1783;
b) P. Politzer, P. Lane, J. S. Murray, Cent. Eur. J. Energ. Mater.
2011, 8, 39 – 52; c) E. F. Kjønstad, J. F. Moxnes, T. L. Jensen, E.
Unnebery, Mol. Phys. 2016, 114, 1822 – 1830.
balance parameters of 0.2471 and 0.2499, which are close to
0.25 and indicate that this approach may be a powerful means
for the insensitive energetic materials design. The most
promising compounds for practical use as new secondary
explosives are compounds 4–6 and 11. These compounds
possess high densities, acceptable sensitivities, and good
detonation performances.
In conclusion, inspired by the recently reported highly
energetic compounds functionalized with nitramino groups,
a series of furazan-functionalized 5-nitroimino-1,2,4-triazoles
were designed and synthesized. One-pot reactions based on
condensation of readily and commercially available 1-methy-
1-nitroso-2-nitroguanidine with furazan-functionalized car-
boxylic acid hydrazides were developed. The advantages of
the new strategy were illustrated to be the availability of the
substrates, the high efficiency of the reaction step, and the
possibility of scalable synthesis using a green chemical
process. The new compounds exhibit reasonable physical
properties. The compounds 3–11 possess high measured
densities, high heats of formation, and excellent detonation
velocities and detonation pressures. Also, 4, 5, and 11 exhibit
superior detonation performance relative to RDX and are
comparable to HMX. Importantly, all the novel furazan-
functionalized 5-nitroimino-1,2,4-triazoles exhibit low impact
sensitivities (18 to more than 40 J) and friction sensitivities
(250 to more than 360 N). These features make them
potentially interesting candidates for further investigation as
secondary energetic materials. New advances in the synthesis
of energetic 5-nitroimino-1,2,4-triazoles are expected to
emerge in the foreseeable future by utilization of the new
strategy.
[7] A. A. Dippold, D. Izsꢃk, T. M. Klapçtke, Chem. Eur. J. 2013, 19,
12042 – 12051.
[8] a) R. Wang, H. Xu, Y. Guo, R. Sa, J. M. Shreeve, J. Am. Chem.
Soc. 2010, 132, 11904 – 11905; b) S. D. Shaposhnikov, N. V.
Korobov, A. V. Sergievskii, S. V. Pirogov, S. F. Melꢀnikova, I. V.
Tselinskii, Russ. J. Org. Chem. 2002, 38, 1351 – 1355.
Acknowledgments
[9] T. P. Efimova, O. Y. Ozerova, T. A. Novikova, I. V. Belik, V. M.
Berestovitskaya, Russ. J. Gen. Chem. 2013, 83, 1779 – 1786.
[10] M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A.
Robb, J. R. Cheeseman, V. G. Zakrzewski, J. A. Montgomery,
R. E. Stratmann, J. C. Burant, S. Dapprich, J. M. Millam, A. D.
Daniels, K. N. Kudin, M. C. Strain, O. Farkas, J. Tomasi, V.
This work was supported by the Office of Naval Research
(N00014-16-1-2089), the Defense Threat Reduction Agency
(HDTRA1-15-1-0028), the National Natural Science Foun-
dation of China (No. 21376121, 21676147), and the Priority
4
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Communications
Chemie
Barone, M. Cossi, R. Cammi, B. Mennucci, C. Pomelli, C.
Criteria, 5th ed., United Nations Publication, New York, 2009;
Adamo, S. Clifford, J. Ochterski, G. A. Petersson, P. Y. Ayala, Q.
Cui, K. Morokuma, D. K. Malick, A. D. Rabuck, K. Raghava-
chari, J. B. Foresman, J. Cioslowski, J. V. Ortiz, A. G. Baboul,
B. B. Stefanov, G. Liu, A. Liashenko, P. Piskorz, I. Komaromi, R.
Gomperts, R. L. Martin, D. J. Fox, T. Keith, M. A. Laham, C. Y.
Peng, A. Nanayakkara, C. Gonzalez, M. Challacombe, P. M. W.
Gill, B. Johnson, W. Chen, M. W. Wong, J. L. Andres, C.
Gonzalez, M. Head-Gordon, E. S. Replogle, J. A. Pople, Gaus-
sian09, revisionD. 01; Gaussian, Inc.: Wallingford, CT, 2009.
b) 13.4.2 Test 3 (ii): BAM Fallhammer, pp. 75–82; c) 13.5.1 Test 3
(i): BAM friction apparatus, pp. 104–107.
[13] CCDC 1479423 (3·H2O), 1479439 (4), and 1491824 (5·H2O)
contain the supplementary crystallographic data for this paper.
These data can be obtained free of charge from The Cambridge
Crystallographic Data Centre.
´
[11] M. Suceska, EXPLO5 6.01, Brodarski Institute, Zagreb, Croatia,
2013.
Manuscript received: February 14, 2017
Revised: March 15, 2017
Final Article published: && &&, &&&&
[12] a) Tests were conducted according to the UN Recommendations
on the Transport of Dangerous Goods, Manual of Tests and
Angew. Chem. Int. Ed. 2017, 56, 1 – 6
ꢀ 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.angewandte.org
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These are not the final page numbers!

Angewandte
Communications
Chemie
Communications
Energetic Materials
Z. Xu, G. Cheng, H. Yang,* X. Ju, P. Yin,
J. Zhang,* J. M. Shreeve*
&&&& — &&&&
A Facile and Versatile Synthesis of
Energetic Furazan-Functionalized 5-
Nitroimino-1,2,4-Triazoles
High energy: An analogue-oriented syn-
thetic route for the formulation the title
compounds was developed. The process
was found to be straightforward, high
yielding, and highly efficient, and scalable
for the synthesis of high-performance
energetic materials.
6
www.angewandte.org
ꢀ 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Angew. Chem. Int. Ed. 2017, 56, 1 – 6
These are not the final page numbers!