Incorporating Energetic Moieties into Four Oxadiazole Ring Systems for the Generation of High-Performance Energetic Materials

Article abstract of DOI:10.1002/cplu.201800107

The synthesis of three neutral 3,3′-di(1,2,5-oxadiazol-3-yl)-5,5′-bi(1,2,4-oxadiazole) structures in combination with different energetic moieties such as nitramino, trinitroethylamino, and N-nitrated trinitroethylamino is presented. In addition, a novel family of energetic salts based on 4,4′-([5,5′-bi(1,2,4-oxadiazole)]-3,3′-diyl)-bis(1,2,5-oxadiazol-3-nitramide) is synthesized. The new compounds (4, 6–18) are characterized by IR and multinuclear NMR spectroscopy and elemental analysis. The structures of 4?2 C₄H₈O₂, 9, 13, 15, and 16 are further confirmed by single-crystal X-ray diffraction studies. The thermal stabilities of 4 and 6–18 are determined by differential scanning calorimetry. Most of the new compounds have high densities (1.72–1.93 g cm^?3) measured using a gas pycnometer (25 °C). Energetic evaluation indicates that they also have good detonation pressures and velocities (P: 26.4–41.9 GPa; D: 8218–9550 m s^?1).

Full text of DOI:10.1002/cplu.201800107

Accepted Article
Title: Incorporating Energetic Moieties into a Four Oxadiazole Rings
System for the Generation of High-Performance Energetic
Materials
Authors: Bohan Wang, Huanlin Xiong, Guangbin Cheng, and Hongwei
Yang
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Incorporating Energetic Moieties into a Four Oxadiazole Rings
System for the Generation of High-Performance Energetic
Materials
Bohan Wang Hualin Xiong Guangbin Cheng and Hongwei Yang*[a]
[
a]
[a]
[a]
Abstract: The synthesis of three neutral 3,3'-di(1,2,5-oxadiazol-3-
yl)-5,5'-bi(1,2,4-oxadiazole) in combination with different energetic
moieties
like
nitrimino,
trinitroethylamino
and
N-nitrated
trinitroethylamino is presented. In addition,
a
novel family of
energetic salts based on 4,4'-([5,5'-bi(1,2,4-oxadiazole)]-3,3'-diyl)-
bis(1,2,5-oxadiazol-3-nitramide) were synthesized. The new
compounds (4, 6-18) were characterized by IR, multinuclear NMR
spectroscopy and elemental analysis. The structures of 4·2C
4 8 2
H O ,
9, 13, 15 and 16 were further confirmed by single crystal X-ray
diffraction. The thermal stabilities of 4, 6-18 were determined by
differential scanning calorimetry (DSC). Most of the new compounds
have high densities (1.72-1.93 g cm 3) measured using a gas
pycnometer (25 °C), In addition, energetic evaluation indicates that
they also have good detonation pressures and velocities (P: 26.4−
Figure. 1 Oxadiazole rings can exist in different regioisomeric forms. One
1,3,4-isomer and one 1,2,5-isomer and two 1,2,4-isomers (if asymmetrically
substituted).
−
−
1
4
1.9 GPa; D: 8218-9550 m s ).
Introduction
The synthesis towards new energetic materials with excellent
performance characteristics is an ongoing project in many
research groups worldwide.1 Due to practical application
demands, the new materials have to meet many different
standards such as high detonation performance , low sensitivity,
environmental compatibility, safety concerns.2,3 However,
materials with high stability and low sensitivity often exhibit a
poor energetic performance.4 Considerable effort has been
attempted to coordinate the inherent contradiction between the
performance and sensitivity of energetic molecules. An effective
Figure. 2 Energetic compounds with nitroamino fragments.
Figure.
3
Energetic compounds with trinitroethylamino, N-nitrated
approach is the combination of a few of the same or different
heterocyclic subunits in a molecule.5
trinitroethylamino and nitramino furazan fragments.
Compounds containing heterocyclic ring systems are of great
importance both medicinally and industrially.6 For example,
have high nitrogen content and high positive enthalpy. Among
the combinations between functional moiety and azole backbone,
the family of nitramino-furazans has gained considerable
oxadiazoles in different regioisomeric forms (Figure 1), are of
considerable interest in different areas of medicinal and
9
7
attention due to its high detonation performance. For example,
pesticide chemistry and also polymer and material science. In
3
,4-di(nitramino)furazan ( ⅰ )10 (Fig.2) shows good detonation
particular, the energetic materials based on azole frameworks
properties with a detonation pressure of 40.5 GPa and a
are highly desirable, such as tetrazoles, 1,2,5-oxadiazoles
-1
8
detonation velocity of 9376 m s . However, it has a poor
decomposition temperature (99 °C), a high impact sensitivity
(
furazans) and 1,2,5-oxadiazole-2-oxides (furoxans), which
(
<5J) and a friction sensitivity (<5N). Another example is [2,2’-
bi(1,3,4-oxadiazole)]-5,5’-dinitramide (ICM-101), which exhibits a
surprisingly high density (1.99 g cm−3 at 298K) and good
[a]
School of Chemical Engineering,
Nanjing University of Science and
detonation performances (P = 41.9 GPa; D = 9481 m s−1).11
Technology, Xiaolingwei 200, Nanjing, Jiangsu (China)
E-mail: hyang@mail.njust.edu.cn
Many studies have showed that the combination of two or more
nitrogen-rich heterocycles can lead to excellent energetic
properties.12 To gain good detonation performance while
minimizing sensitivity, 1,2,4-oxadiazole and 1,2,5-oxadiazole
were incorporated with nitroamino-furazan.13,14 For example, the
hydroxyammonium salt (ⅱ) and hydrazinium (ⅲ) (Fig.2) show
not only good detonation performances (ⅱ: P = 37.4 GPa; D =
Supporting information for this article is given via a link at the end of
the document.((Please delete this text if not appropriate))
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-1
-1
9
046 m s ; ⅲ : P = 30.1 GPa; D = 8603 m s ) but also
Syntheses
acceptable sensitivities (ⅱ: IS = 16 J; FS = 160 N; ⅲ: IS = 19 J;
FS = 240 N) with good thermal stabilities (ⅱ: T = 193 °C; ⅲ: T
234 °C). Another example is compound ⅳ (Figure. 3), which
exhibits a detonation pressure of 46.1 GPa , velocity of 10114 m
First, the intermediate product 4,4'-([5,5'-bi(1,2,4-oxadiazole)]-
3,3'-diyl)-bis(1,2,5-oxadiazol-3-amine) (3) was prepared by two-
step reactions from malononitrile (1) according to literature
methods.17 The synthetic pathway towards the nitramino product
4 and its energetic salts are illustrated in Scheme 1. Compound
4 was obtained by direct nitration of 3 using 100% nitric acid at
0 °C. The reaction mixture was quenched with ice and with
stirring, then the precipitate was collected by filtration and
washed with ice water. The energetic salts based on 4 were
synthesized in acetonitrile by mixing 4 with a series of bases of
ammonium (6), hydrazinium (7), hydroxylammonium (8),
didiaminouronium (9), guanidinium (10), aminoguanidinium
(11), 1,2,4-triazolium (14), 4-amino-1,2,4-triazolium (15) and 3-
amino-1,2,4-triazolium (16). Salts 12 and 13 were synthesized
by using the silver salt 5 with the corresponding chloride salts.
The impetus of these reactions was the formation of silver
chloride, which had a very low solubility in water and could be
easily removed by filtration. These energetic salts 6-16 were
isolated in high yields (81.65-93.43%) and were stable in air.
d
d
=
-
1
-3
s , a density of 2.12 g cm and a thermal stability of 317 °C. In
addition, introducing trinitroethylamino group into the furazan
ring can increase the oxygen balance and lead to an excellent
energetic performance.15 Recently, the trinitroethyl energetic
derivatives based on aminofurazans have been reported and
demonstrated outstanding performance15e (ⅴ: P = 35.4 GPa, D
-1
-1
=
8900 m s ; ⅵ: P = 40.8 GPa, D = 9486 m s ) (Figure. 3).
As is seen for these furazan-based compounds, combination of
furazan with 1,2,4-oxadiazole could be favorable for obtaining a
high level of detonation performance while meeting the
requirement of insensitivity. In addition, it has been reported that
the more ring structures present in a molecule, the higher the
-1
-1 16
heat of formation of the molecule will gain (in kJ mol /kJ g ). It
can be attributed to the presence of abundant nitrogen atoms
and -C=N- bonds in the two rings system.16f Herein, we reported
and characterization 4,4'-([5,5'-bi(1,2,4-oxadiazole)]-3,3'-diyl)- The trinitroethanol was synthesized according to the method
bis(1,2,5-oxadiazol-3-nitramide) (4), which comprises two
furazan and two 1,2,4-oxadiazole rings. In addition, some
energetic salts (6-16) based on 4 were synthesised and fully
characterized. To seek higher detonation performances of
energetic materials, trinitroethyl fragments were successfully
introduced into the framework of aminofurazan in this paper.
reported previously.18 The N-trinitroethyl derivative 17 were
synthesized via the reactions of the electron-deficient
trinitroethanol with corresponding diamine compound 3 with a
yield of 89%. Then compound 17 was treated with 100% nitric
acid and acetic anhydride to afford the N-nitrated
trinitroethylamino product 18 with a yield of 83%.
Results and discussion
Scheme 1 Synthesis of energetic compounds base on 4,4'-([5,5'-bi(1,2,4-oxadiazole)]-3,3'-diyl)-bis(1,2,5-oxadiazol-3-amine)
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O3A and O4A) are also almost in the same plane with the four
rings (C3-N5-N6-O4 1.1(4)°, C3-N5-N6-O3 179.4(2)°, N6-N5-
C3-C4 -172.5(2)°, N6-N5-C3-N3 8.8(4)°). The anions and
cations are almost in the same plane, which can be seen from
the 2D layer (Figure.5c), and a large amount of hydrogen bonds
can be found between them (Figure.5b), these intramolecular
hydrogen bonds combined with intermolecular hydrogen bonds
to form a face-to-face stacking and make an important
contribution to enhance the density of salt 9.
Spectroscopy
The structures of the compounds 4, 6-18 were fully
1
characterized by IR, NMR and elemental analysis. The H NMR
1
3
and C NMR spectra of these new compounds are shown in the
Supporting Information.
1
In the H NMR spectrum of compound 4 , the proton signal of an
imino group attached to the furazan ring was observed at 7.70
1
ppm. In the H NMR spectrum of 17, the proton signals of –NH–
groups attached to the furazan ring was observed at 6.82. The
proton signals of the methylene group in the H NMR spectrum
1
a)
b)
2
of 17 were observed at 5.62 ppm. However, -CH - protons
1
shows lower field of 6.66 ppm in the H NMR spectrum of 18
because of the electron withdrawing nature of the nitro group. In
1
3
the C NMR spectrum of 4 and 6-18, four signals for two
furazan and two 1,2,4-oxadiazole rings carbon atoms were
found in the expected range as consequence of their symmetric
structure. The carbon resonance of methylene in compound 17
and 18 were found at 47.82 and 53.02 ppm, and the carbon
resonance of trinitromethyl in them were found at 125.55 and
1
22.81 ppm, respectively, which are in good agreement with
18a
previously recorded shifts for similar compounds.
X-ray crystallography
c)
Compound 4, salts 9, 13, 15 and 16 were confirmed by single-
crystal X-ray diffraction. Compound 4 were obtained by the slow
solvent evaporation of 1,4-dioxane solution while salts 9, 13, 15
and 16 were obtained by the slow solvent evaporation of the
water and methanol solution at room temperature. Their crystal
and structure data are listed in Table 1 and their structures are
shown in Figure. 4a-8a. Selected bond lengths, angles, torsion
angles and hydrogen bonds are listed in the Supporting
Information (Table S2- S16).
Compound 4 crystallizes in the triclinic P1 space group, with one
molecule in the unit cell and with a calculated density (1.505 g
-3
cm ) as a dioxane solvate. The non-solvated density of 4 (1.897
-3
g cm ) was calculated by using powder diffraction, more data
can be found in Supporting Information (Table S17). Its
molecular structure is shown in Figure. 4a. The bond lengths of
N1-O1 (1.404(3) Å), C1-N1 (1.303(3) Å), N2-C1 (1.384(3) Å),
C2-O1 (1.383(3) Å) are normal in the 1,2,4-oxadiazole ring.19
The two 1,2,4-oxadiazole rings show a planar arrangement,
Figure. 4 (a) Single-crystal X-ray structure of 4·2C
4 8 2
H O ; (b) Hydrogen bonds
in 4·2C ; (c) Layer assembly and the face-to-face crystal packing for
4
8 2
H O
4 8 2
TATB and 4·2C H O .
which is reflected in the torsion angles C1-N2-C2-C2A
-
a)
b)
176.3(2)°, N2-C2-C2A-O1A -0.7(4)° and the furazan rings are
twisted out of the plane as indicated by the dihedral angle of 12°.
The nitro group is twisted out of the furazan rings plane by 105°
(
N6-N5-C3-N3 109.5(3)°, N6-N5-C3-C4 -78.7(4)°). As can be
seen from Figure. 3c, the 3,3'-di(1,2,5-oxadiazol-3-yl)-5,5'-
bi(1,2,4-oxadiazole) planes form a face-to-face stacking in which
the solvated 1,4-dioxane molecules are parallel to one another.
It has been reported that the highly ordered structures formed in
layer-by-layer arrangements usually show fascinating material
2
0
characteristics. For example, TATB has low sensitivities (IS =
0 J; FS > 360 N), calculations indicate that the layer-stacking
5
structure of this material can absorb the mechanical stimuli-
induced kinetic energy by converting it to layer sliding, which
results in low sensitivity.20 Fortunately, the structure of
compound 4 is very similar to that of TATB with successive
infinite 2D layers and highly ordered face-to-face 3D stacking
c)
(
Fig.4c), which lead to its comparatively low sensitivities (IS = 16
J; FS > 240 N).
The molecular structure of 9, which crystallizes in the monoclinic
-3
1
space group P2 /c, with a density of 1.809 g cm at 173K, is
shown in Figure. 5a. The N6-O3 and N6-O4 bonds of the nitro
groups in salt 9 are elongated by 0.04 Å and 0.021 Å when
compared with its neutral compound 4·2C H O , respectively.
4 8 2
The 1,2,4-oxadiazole rings and furazan rings in salt 9 are almost
in the same plane with torsion angles (N1–C1–C4–C3 3.5(5)°,
N1-O1-C2-C2A
-179.2(2)°,
O1–C2–C2A–N2A
-1.3(4)°).
Figure. 5 (a) Single-crystal X-ray structure of 9; (b) Hydrogen bonds in 9; (c)
Layer assembly and the face-to-face crystal packing for 9.
Interestingly, the exocyclic atom N5, N6, O3 and O4 (N5A, N6A,
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c)
a)
b)
Figure. 8 (a) Single-crystal X-ray structure of 16; (b) Hydrogen bonds in 16; (c)
Wave-like crystal packing for 16.
c)
Salt 13 crystallizes in the monoclinic space group P2
1
/c, with
two molecules per unit cell. The calculated density of 1.733 g
-3
cm was determined from its X-ray crystal structure at 173K
Figure.6a). The four heterocycles in the dianion are in nearly
(
the same plane, the torsion angles N2-C2-C2A-N2A, C2-N2-C1-
C4 and N2-C1-C4-C3 are 180.0(3)°, -178.1(2)° and 177.4(2)°,
respectively. The nitramino groups are also nearly in the same
plane as the furazan rings as indicated by the torsion angles
(
N6-N5-C3-C4 -178.7(2)°, C3-N5-N6-O3 2.9(3)°, C3-N5-N6-O4 -
178.4(2)°). The hydrogen-bonding (Figure.6b) interactions
Figure. 6 (a) Single-crystal X-ray structure of 13; (b) Hydrogen bonds in 13; (c) between the triaminoguanidine cations and the anions (N7-
Layer assembly and the criss-crossed crystal packing for 13.
H7A···O3 2.53(3) Å, N7-H7A···N12 2.27(3) Å, N7-H7A···O4
2
.50(3) Å, N8-H8A···N10 2.52(3) Å, N8-H8A···O4 2.58(3) Å
a)
b)
and so on), playing an important role in forming the criss-
crossed(Fig.6c) crystal packing of salt 13.
Single-crystal X-ray diffraction revealed that salt 15 crystallizes
-3
1
in monoclinic P2 /c space group, with a density of 1.796 g cm
at 173K (Figure. 7a). The length of the N-N bond in salt 15 (N5-
N6 1.337(3) Å) is slight longer than that of salt 9 (N5-N6 1.323(3)
Å). However, the average bond length of the N-O bonds in the
nitro groups of salt 15 (1.248 Å) are slight shorter than that of
salt 9 (1.252 Å). The bonds in the furazan rings and 1,2,4-
oxadiazole rings of salt 15 are nearly the same length as those
in salts 9 and 13. The cations and the anions are not in the
same plane can be seen from Figure.7c. The hydrogen atom in
the cation form intermolecular hydrogen-bond pairings with
neighboring oxygen atoms in the nitramino group (N7-H7A···O4
c)
2.39(3) Å, C6-H6···O3 2.4800 Å, C5-H5···O3 2.4400 Å)
(
Figure.6b). These hydrogen bonds make the packing structure
of salt 15 show a mixing arrangement.
Salt 16 crystallizes in monoclinic P2
1
/c space group with two
-3
molecules in the unit cell and the density is 1.761 g cm , which
is shown in Fig. 8a. The deprotonation of compound 4 with 3-
amino-1,2,4-triazole to give salt 16 results in shorter N-NO2 (N5-
N6 1.314(3) Å) and longer N-O bonds (N6-O3 1.272(3) Å, N6-
O4 1.253(3) Å) than compound 4 (N5-N6 1.391(3) Å, N6-O3
1.222(3) Å, N6-O4 1.221(3) Å ). The C2-C2A bond is 1.466(5) Å,
the C1-C4 bond is 1.465(3) Å, the C-C bonded the two 1,2,4-
oxadiazole rings are essentially planar with a torsion angle (O1-
C2-C2A-O1A -180.0(2)°), the C-C bonded furazan and 1,2,4-
oxadiazole rings shows a planar arrangement, which is reflected
in the torsion angles (N2-C1-C4-C3 -176.9(3)°, N2-C1-C4-N4
Figure. 7 (a) Single-crystal X-ray structure of 15; (b) Hydrogen bonds in 15; (c)
Mixing crystal packing for 15.
2.8(4)°) , while the nitramino group is twisted away from the
a)
b)
furoxan ring with a torsion angle of 14.5°. In the packing diagram
of 16, intermolecular hydrogen bonds (N8-H8A···O3 1.90(2) Å,
N8-H8A···O4 2.55(3) Å, N8—H8A···N6 2.57(2) Å, N9-H9A···O4
2.08(3) Å, N9-H9A···N3 2.25(2) Å, N10-H10A···O4 2.09(3) Å,
N10-H10B···O3 2.34(4) Å, N10-H10B···N5 2.24(4) Å, C6-
H6···N4 2.50(4) Å) are observed (Fig. 8b). All the atoms in the
cation are almost in the same plane, the anion planes
are neatly inserted into the cation planes, as can be seen from
Figure. 8c, making the packing structure of salt 16 show a wave-
like arrangement.
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Table 1 Crystallographic data for 4·2C
4
H
8
O
2
, 9, 13,15 and 16
Crystal
4·2C
4
H
8
O
2
9
13
15
16
Formula
Formula Weight
Temperature (K)
Crystal system
Space group
Volume [Å3]
a [Å]
b [Å]
c [Å]
α[°]
β[°]
C
20
H
26
N
12
O
14
C
10
H
14
N
20
O
10
C
10
H
18
N
24
O
8
C
12
H
10
N
20
O
8
12 10 20 8
C H N O
562.40
173(2)
658.53
173(2)
triclinic
P1
726.54(13)
6.6528(7)
8.9943(9)
12.9685(14)
91.548(4)
102.237(4)
105.854(3)
1
574.41
173(2))
monoclinic
P2 /n
1054.4(2)
10.2856(12)
9.1849(11)
11.2424(10)
90
105.225(4)
90
602.48
173(2)
monoclinic
P2 /c
1154.81(17)
6.6771(5)
7.9630(7)
21.7734(19)
90
94.039(3)
90
2
1.733
1.053
562.40
173(2)
monoclinic
P2 /c
1039.9(2)
8.0298(9)
16.004(2)
8.3865(11)
90
105.225(4)
90
2
1.796
1.023
monoclinic
P2 /c
1060.4(2)
1
1
1
1
11.9498(14)
6.8573(9)
13.2689(18)
90
102.775(5)
90
γ[°]
Z
2
2
-3
ρ(calc) [g cm ]
F2
1.505
1.023
1.809
1.051
1.761
1.055
R
R
1
,wR
,wR
2
[all data]
[I>=2σ (I)]
0.1022, 0.1205
0.0558, 0.1038
1580359
0.1012, 0.1032
0.0520, 0.0895
1580367
0.0793, 0.0942
0.0450, 0.0834
1581858
0.0870, 0.0926
0.0461, 0.0807
1580365
0.0999, 0.0961
0.0485, 0.0824
1581859
1
2
CCDC
Energetic materials properties
functional with the 6-311+G** basis set.22 All the optimized
structures were characterized to be true local energy minima on
the potential energy surface without imaginary frequencies.
The thermal stabilities of these new energetic compounds were
examined using differential scanning calorimetric (DSC)
measurements in the temperature range from 50 to 400 °C at
heating rate of 5 °C min-1 (Table 2). All the newly compounds
It was reported that heterocycles with higher nitrogen content
23
show higher heats of formation. All the new compounds exhibit
(
4, 6-18) are water insensitive and can be stored for long
positive heats of formation ranging between 741.61 (10) and
-1
periods in air. The neutral compound 4 decomposes thermally
at 100.8 °C, its salts (6-16) and the trinitroethylamino derivatives
1573.01 (15) kJ mol . By using calculated values of the heats of
formation and experimental values for densities of the new
compounds, the detonation pressures (P) and detonation
velocities (D) of 4, 6-18 were calculated using the EXPLO5
(17, 18) are more stable
thermally with decomposition
temperatures ranging from 151.8 (18) to 253.1 (10) °C. In
particular, the decomposition process of 13 and 18 possess two
steps with the temperature of 182.7 °C and 212.7 °C (13),
2
4
v6.01 program.
The calculated detonation velocities and
−
1
pressures are in the range from 8218 to 9550 m s and 26.4 to
41.9 GPa, respectively. Of these compounds, the energetic
performances of 8 (D: 8863 m s ; P: 35.0 GPa) and 17 (D: 9062
m s ; P: 37.2 GPa) are comparable to RDX (D: 8795 m s ; P:
34.9 GPa). More strikingly, compound 4 is (D: 9185 m s ; P:
37.5 GPa) comparable to HMX (D: 9144 m s ; P: 39.2 GPa),
compound 18 exhibits higher detonation properties, especially in
terms of detonation velocity (9550 m s ) and pressure (41.9
GPa), which are similar to ICM-101 (D: 9481 m s ; P: 41.9 GPa)
and CL-20 (D: 9455 m s ; P: 46.7 GPa).
1
51.8 °C and 175.9 °C (18), respectively. The thermal stabilities
of 7 (T =215.7 °C), 10 (T =253.1 °C) and 15 (T =219.1 °C) are
higher than RDX (T = 204 °C).
-1
d
d
d
-1
-1
d
-1
The density is an important parameter which plays an important
role in calculation of energetic performance. Densities of
all new compounds were measured by using a gas
pycnometer at 25°C (Table2) and found to fall in the range of
-1
-1
-3
-3
-1
1
.72-1.93 g cm . Among them, 8 (1.82 g cm ) and 17 (1.90 g
-3
-1
cm ) have relatively high densities that are comparable to that of
RDX (1.80 g cm ). More importantly, the densities of 4 (1.92 g
−3
Impact and friction sensitivities (IS and FS) of samples are
−
3
−3
-3
25
cm ) and 18 (1.93 g cm ) are higher than HMX (1.91 g cm ).
In order to study the detonation parameters of these new
compounds, calculations were carried out using the Gaussian 09
program suite. The geometry optimization of the structures and
frequency analyses were carried out using the B3LYPn
measured and evaluated by using the standard BAM method,
as shown in Supporting Information (Table S18). Compound 4
has the relatively low impact sensitivity of 16 J and friction
sensitivity of 240 N, which are comparable to TNT (IS: 15J; FS:
358N). Not surprisingly, compound 18 (IS: 4.5J; FS: 120N) have
relatively high impact and friction sensitivities, which are similar
to ICM-101 (IS: 5J; FS: 60N) and CL-20 (IS: 4J; FS: 48N). In
addition, most of the energetic salts are very insensitive with
IS > 40 J and FS > 360N.
2
1
Table
bi(1,3,4-oxadiazole)]-5,5’-dinitramide (ICM-101), 2, 4, 6, 8, 10, 12-
hexanitrohexaaza)cyclododecane (CL-20), 2,4,6-triamino-1,3,5-
trinitrobenzene (TATB), 2,4,6-trinitrotoluene (TNT), 1,3,5-trinitroperhydro-
,3,5-triazine (RDX) and octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine
2 The physicochemical properties of 4, 6-18 compared with 2,2’-
(
1
(
HMX).
a
ρb [g m-1]
1.92
1.76
1.76
1.82
1.80
1.74
1.74
1.73
1.72
1.75
1.78
1.75
1.90
1.93
1.99
2.04
1.93
1.65
1.80
1.91
c
-1
d
Compounds
T
d
[°C]
D [m s ]
9185
8489
8747
8863
8831
8218
8483
8515
8688
8287
8617
8343
9062
9550
9481
9455
8114
6881
8795
9144
P [GPa]
4
6
7
8
9
1
1
1
1
1
1
1
1
1
100.8
207.2
215.7
165.3
209.2
253.1
211.8
205.5
182.7
176.3
219.1
210.5
187.7
151.8
210.0
215
37.5
30.5
32.2
35.0
32.6
26.4
28.4
28.1
29.3
28.1
30.7
28.2
37.2
41.9
41.9
46.7
31.2
19.5
34.9
39.2
Conclusions
In conclusion, We have successfully synthesized
compound, 4,4'-([5,5'-bi(1,2,4-oxadiazole)]-3,3'-diyl)-bis(1,2,5-
oxadiazol-3-nitramide), which has two furazan rings and two
,2,4-oxadiazole rings linkages in one molecule was synthesized.
a new
0
1
2
3
4
5
6
7
8
1
Subsequently, a series of nitrogen-rich energetic salts (6-16)
were synthesized and fully characterized. In addition, two
trinitroethyl derivatives of compound 3 were synthesized by a
simple way. All new compounds exhibited reasonable physical
-3
properties, such as a relatively high density (1.72-1.93 g cm )
e
d
and good thermal stability (T = 151.8-253.1 °C, except for 4,
ICM-101
ε-CL-20
TATB
TNT
RDXg
HMX
a
e
100.8 °C). More importantly, with a large number of N-O and N-
N bonds in these new structures, the calculated heats of
formation of 4, 6-18 are relatively high and fall in the range of
f
360
295
204
280
f
-1
-1
7
41.61 to 1573.01 kJ mol (1.425 to 2.797 kJ g ). Furthermore,
g
most of the energetic salts have adequately acceptable
sensitivities (IS > 40J, FS > 360N) and attractive detonation
-1 b
Decomposition temperature from DSC (5 °C min ). Density measured
c
d
using a gas pycnometer (25 °C). Calculated detonation velocity. Calculated
detonation pressure. e Ref 9. f Ref 4(a). g Ref 4(c).
-1
properties (D, 8218-8863 m s ; P, 26.4-35.0 GPa). In addition,
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10.1002/cplu.201800107
FULL PAPER
-
1
the detonation performances of compound 4 (D: 9185 m s ; P:
148.22, 141.93 ppm. IR (KBr): 3481, 2747, 1625, 1600, 1516,
1462, 1385, 1308, 1171, 1040, 977, 931, 912, 873, 811 cm .
-1
-1
3
7.5 GPa) are comparable to HMX (D: 9144 m s ; P: 39.2 GPa),
and its sensitivity properties (IS: 16J; FS: 240N) is similar to TNT
IS: 15J; FS: 358N). More importantly, the detonation
Elemental analysis calcd (%) for C
8 2 12 8
H N O (394.18): C 24.38, H
(
0.51, N 42.64; found: C 24.62, H 0.55, N 42.53%.
-1
performance and sensitivities of 18 (D: 9550 m s , P: 41.9 GPa,
Disilver
4,4'-([5,5'-bi(1,2,4-oxadiazole)]-3,3'-diyl)-bis(1,2,5-
-
1
IS: 4.5J; FS: 120N) are even similar to CL-20 (D: 9455 m s , P:
6.7 GPa, IS: 4J; FS: 48N). These positive results suggest that
oxadiazol-3-nitramide) (5).
4
Silver nitrate (0.17 g, 1.0 mmol) was dissolved in water (2 mL)
and then added to a solution of 4 (0.197 g, 0.5 mmol) in
acetonitrile (10 mL). The silver salt precipitated after stirring for 3
h as a light grey powder. The product was filtered to obtain
they might be of interest for applications as energetic materials.
0
.231 g of 5 in a yield of 76.03%.
Experimental
Diaminoguanidine 4,4'-([5,5'-bi(1,2,4-oxadiazole)]-3,3'-diyl)-
bis(1,2,5-oxadiazol-3-nitramide) (12).
Salt 5 (0.304 g, 0.5 mmol) was dissolved in acetonitrile (5.0 mL),
then guanidinium chloride (0.126 g, 1.0 mmol) was added. Silver
chloride started to precipitate immediately and the mixture was
filtered warm under exclusion of light. The solution was
Caution: although we experienced no difficulties in handling
these energetic materials, small scale and best safety practices
(
leather gloves, face shield) are strongly encouraged.
Mechanical actions of these energetic materials involving
scratching or scraping must be avoided.
evaporated to dryness to give 0.253 g of 12 as a light yellow
1
product in a yield of 88.40%. T
DMSO-d
MHz, DMSO-d
ppm. IR (KBr): 3424, 3361, 3292, 1684, 1594, 1524, 1498, 1436,
1383, 1300, 1174, 1136, 1041, 1008, 967, 900, 813 cm .
d
, 205.5 °C. H NMR (300 MHz,
General methods
): δ = 8.59 (s), 7.17 (s), 4.59 (s) ppm. 13C NMR (126
): δ = 163.36, 160.64, 159.71, 158.38, 141.41
6
1H spectra was recorded on a 300MHz (Bruker AVANCE 300)
nuclear magnetic resonance spectrometer operating at 300 MHz
6
1
3
-1
and C was recorded on a 500MHz (Bruker AVANCE 500)
nuclear magnetic resonance spectrometer operating at 126 MHz. Elemental analysis calcd (%) for C10
16 22 8
H N O (572.38): C 20.98,
The d -DMSO and d
6
6
-acetone were selected as locking solvents. H 2.82, N 53.84; found: C 20.97, H 2.85, N 53.72%.
The decomposition temperatures were determined on
differential scanning calorimeter(DSC823e instrument) at
heating rate of 5 °C min . Infrared (IR) spectra were obtained on
a Perkin-Elmer Spectrum BX FT-IR instrument equipped with an
ATR unit at 25 °C. Analyses of C/H/N were performed with a
Vario EL III analyzer. Sensitivity towards impact and friction was
a
a
Triaminoguanidine 4,4'-([5,5'-bi(1,2,4-oxadiazole)]-3,3'-diyl)-
bis(1,2,5-oxadiazol-3-nitramide) (13).
A similar procedure was followed as that described above for 12.
-1
d
0.25 g of 13 as yellowish solid in a yield of 81.65%. T , 182.7 °C.
1
13
H NMR (300 MHz, DMSO-d
6
): δ = 8.59 (s), 4.21 (s) ppm.
C
NMR (126 MHz, DMSO-d ): δ = 163.38, 160.66, 159.02, 158.32,
6
determined using
compounds were determined at room temperature by employing
a gas pycnometer.
a
BAM friction tester. Densities of the
141.43 ppm. IR (KBr): 3338, 3215, 1688, 1586, 1524, 1493,
1425, 1387, 1315, 1272, 1177, 1130, 1004, 966, 932, 897, 809,
538 cm . Elemental analysis calcd (%) for C10H N O (602.41):
18 24 8
-1
C 19.94, H 3.01, N 55.80; found: C 19.92, H 3.02, N 55.81%.
General procedure for the preparation of salts 6-11 and 14-
X-ray crystallography
1
NH
8.
The data for 4, 9, 13, 15 and 16 were collected with a Bruker
three-circle platform diffractometer equipped with a SMART
APEX II CCD detector. A Kryo-Flex low-temperature device was
used to keep the crystals at a constant temperature of 173(2) K
during the data collection. The data collection and the initial unit
cell refinement were performed using APEX2 (v2010.3-0). Data
reduction was performed using SAINT (v7.68A) and XPREP
3
2
·H O (1.0 mmol), hydroxylamine solution (1.0 mmol),
hydrazine hydrate (1.0 mmol), guanidine carbonate (1.0 mmol),
aminoguanidine bicarbonate (1.0 mmol), 1.2,4-triazole (1.0
mmol), 3-amino-1,2,4-triazole (1.0 mmol), 4-amino-1,2,4-triazole
(
1.0 mmol) and carbohydrazide (1.0 mmol) were added to a
solution of (0.197 g, 0.5 mmol) in mL acetonitrile,
respectively, and then stirred for 3 h, filtered and dried at room
temperature.
4
5
(
v2008/2). Corrections were applied for Lorentz, polarization,
and absorption effects using SADABS (v2008/1). Structures
were deduced and refined with the aid of the programs in the
SHELXTL-plus (v2008/4) system of programs. The full-matrix
least-squares refinement on F2 included atomic coordinates and
anisotropic thermal parameters for all non-H atoms. The H
atoms were included in a riding model. The structure was
deduced by direct methods with SHELXS-97 and expanded
using the Fourier technique. The non-hydrogen atoms were
refined anisotropically. The hydrogen atoms were located and
refined.
Ammonium
bis(1,2,5-oxadiazol-3-nitramide) (6)
d
.195 g of 6 was obtained in a yield of 91.07%. T , 207.2 °C. H
4,4'-([5,5'-bi(1,2,4-oxadiazole)]-3,3'-diyl)-
1
0
1
3
NMR (300 MHz, DMSO-d
MHz, DMSO-d ): δ = 163.42, 160.67, 158.28, 141.36 ppm; IR
KBr): 3605, 3209, 1598, 1526, 1503, 1438, 1300, 1187, 1139,
6
): δ = 7.12 (s) ppm; C NMR (126
6
(
-1
1
042, 971, 934, 913, 820, 797, 768, 547 cm ; Elemental
(428.24): C 22.44, H 1.88, N
5.79; found: C 22.45, H 1.89, N 45.75%.
8 8 14 8
analysis calcd (%) for C H N O
4
Hydrazinium
4,4'-([5,5'-bi(1,2,4-oxadiazole)]-3,3'-diyl)-
bis(1,2,5-oxadiazol-3-nitramide) (7)
1
d
0.212 g of 7 was obtained in a yield of 92.52%. T , 215.7 °C. H
Syntheses
13
6
NMR (300 MHz, DMSO-d ): δ = 5.19 (s) ppm; C NMR (126
6
MHz, DMSO-d ): δ = 163.52, 160.76, 158.35, 141.48 ppm; IR
Synthesis of 4,4'-([5,5'-bi(1,2,4-oxadiazole)]-3,3'-diyl)-
bis(1,2,5-oxadiazol-3-nitramide) (4).
Nitric acid (100% 6.0mL) was placed in a 25 mL two-necked
round bottom flask and cooled to -10 °C. Compound 3 (0.61 g
(KBr): 3406, 3336, 3194, 1661, 1587, 1501, 1432, 1391, 1304,
1097, 969, 874, 823, 770 cm ; Elemental analysis calcd (%) for
C H N O (458.27): C 20.97, H 2.20, N 48.90; found: C 20.95,
8 10 16 8
-1
H 2.21,N 48.92%.
2.0 mmol) was slowly added to the cooled nitric acid while
Hydroxylammonium
4,4'-([5,5'-bi(1,2,4-oxadiazole)]-3,3'-
maintaining the reaction temperature below -10 °C. The reaction diyl)-bis(1,2,5-oxadiazol-3-nitramide) (8)
1
mixture was stirred for 2 hours, then poured into ice water (30.0
mL) and stirred for 1 hour. The precipitate was collected by
filtration and washed with ice water and dried at room
d
0.215 g of 8 was obtained in a yield of 93.43%. T , 165.3 °C. H
1
3
6
NMR (300 MHz, DMSO-d ): δ = 7.11 (br) ppm; C NMR (126
MHz, DMSO-d ): δ = 163.43, 160.69, 158.32, 141.42 ppm; IR
6
temperature to give 4 as a colorless solid. Yield 0.58 g (73.73%).
(KBr): 3182, 1629, 1524, 1477, 1434, 1371, 1288, 1232, 1177,
1040, 1008, 975, 957, 923, 809, 767 cm ; Elemental analysis
1
-1
T
d
, 100.8 °C. H NMR (300 MHz, Acetone-d
6
): δ = 6.80 (s, H)
1
3
6
ppm. C NMR (126 MHz, Acetone-d ): δ = 163.94, 159.31,
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ChemPlusChem
10.1002/cplu.201800107
FULL PAPER
calcd (%) for C
8
8
H N
14
O
10 (460.24): C 20.88, H 1.75, N 42.61;
1H NMR (300 MHz, Acetone-d
NH-), δ = 5.62 (d, J = 6.9 Hz, 2H, -CH
6
): δ = 6.82 (t, J = 6.0 Hz, 1H, -
1
3
found: C 20.85, H 1.76, N 42.57%.
2
-) ppm; C NMR (126
Didiaminouronium 4,4'-([5,5'-bi(1,2,4-oxadiazole)]-3,3'-diyl)-
MHz, Acetone-d ): δ = 163.46, 160.13, 155.18, 135.95, 125.55,
6
bis(1,2,5-oxadiazol-3-nitramide) (9)
47.82 ppm; IR (KBr): 3390, 3011, 1602, 1573, 1505, 1421, 1343,
1
0.254 g of 9 was obtained in a yield of 88.45%. T
d
, 209.2 °C. H
1324, 1300, 1182, 1146, 1023, 978, 947, 910, 866, 810, 788,
1
3
-1
NMR (300 MHz, DMSO-d
NMR (126 MHz, DMSO-d
6
): δ = 8.43 (br), 3.48 (br) ppm;
C
588 cm ; Elemental analysis calcd (%) for C10
H N O
14 20 8
(542.35):
6
): δ = 163.37, 160.67, 159.19, 158.38,
41.42 ppm; IR (KBr): 3349, 3316, 2938, 2780, 1696, 1628,
598, 1524, 1425, 1388, 1282, 1176, 1134, 986, 968, 914, 870,
C 22.87, H 0.96, N 40.61; found: C 22.52, H 0.95, N 40.50%.
Synthesis of N,N'-([5,5'-bi(1,2,4-oxadiazole)]-3,3'-
diylbis(1,2,5-oxadiazole-4,3-diyl))-bis(N-(2,2,2-
1
1
8
-1
10, 544 cm ; Elemental analysis calcd (%) for C10
H
N
14 20
O
10
trinitroethyl)nitramide) (18)
(
4
574.35): C 20.91, H 2.46, N 48.77; found: C 20.88, H 2.31, N
8.77%.
To a stirred nitration reagent with a mixture of 100% nitric acid (5
mL) and acetic anhydride (5 mL) was added 17 (0.315 g, 0.5
mmol) at -5 °C. The reaction mixture was stirred at 0 °C for 2
hours and poured into ice water (50 mL). A white solid was
Diaminomethaniminium 4,4'-([5,5'-bi(1,2,4-oxadiazole)]-3,3'-
diyl)-bis(1,2,5-oxadiazol-3-nitramide) (10)
0
NMR (300 MHz, DMSO-d
MHz, DMSO-d ): δ = 163.48, 160.73, 158.34, 157.98, 141.51
ppm; IR (KBr): 3408, 3344, 3258, 3200, 1661, 1600, 1520, 1499,
1
.235 g of 10 was obtained in a yield of 91.74%. T
d
, 253.1 °C. H
d
filtered and washed with cold water immediately. T , 151.8 °C;
1
3
1
13
6
): δ = 6.93 (s) ppm; C NMR (126
H NMR (300 MHz, Acetone-d
6
): δ = 6.66 (s, 2H,-CH
2
-);
C
6
NMR (126 MHz, Acetone-d ): δ = 164.30, 158.76, 151.40,
6
142.81, 122.81, 53.04 ppm; IR (KBr): 3669, 2988, 2900, 2388,
2347, 2323, 1993, 1584, 1510, 1419, 1333, 1312, 1287, 1176,
-1
1
434, 1414, 1300, 1187, 1139, 970, 821, 586 cm ; Elemental
-1
analysis calcd (%) for C10
4
H N O
12 18 8
(512.32): C 23.44, H 2.36, N
1154, 1028, 989, 938, 908, 876, 806, 777, 590 cm ; Elemental
analysis calcd (%) for C10 (542.35): C 20.01, H 0.56, N
9.21; found: C 23.43, H 2.35,N 49.27%.
14 20 8
H N O
Amino(hydrazinyl)methaniminium
4,4'-([5,5'-bi(1,2,4-
35.00; found: C 20.02, H 0.53, N 34.70%.
oxadiazole)]-3,3'-diyl)-bis(1,2,5-oxadiazol-3-nitramide) (11)
.242 g of 11 was obtained in a yield of 89.24%. T , 211.8 °C.
): δ = 8.59 (s), 7.25 (s), 6.79 (s),
.68 (s) ppm; 13C NMR (126 MHz, DMSO-d
): δ = 163.35,
0
d
1
H NMR (300 MHz, DMSO-d
6
Acknowledgements
4
1
1
9
6
60.64, 158.74, 158.35, 141.41 ppm; IR (KBr): 3449, 3311, 1678,
589, 1524, 1498, 1427, 1389, 1300, 1197, 1172, 1132, 1040,
This work was supported by the Science Challenge Project
(TZ2018004) ， the National Natural Science Foundation of
-1
68, 920, 874, 821, 769, 545, 499 cm ; Elemental analysis
(542.35): C 22.15, H 2.60, N 51.65;
14 20 8
calcd (%) for C10H N O
China (No. 21676147), the Natural Science Foundation of
Jiangsu Province (BK20151483) and“A Project Funded by the
found: C 22.12, H 2.61, N 51.67%.
Di(1,2,4-triazolium) 4,4'-([5,5'-bi(1,2,4-oxadiazole)]-3,3'-diyl)-
Priority Academic Program Development of Jiangsu Higher
Education Institutions” (PAPD).
bis(1,2,5-oxadiazol-3-nitramide) (14)
1
0.242 g of 14 was obtained in a yield of 92.05%. T
d
, 176.3 °C. H
1
3
NMR (300 MHz, DMSO-d
NMR (126 MHz, DMSO-d
6
): δ = 10.28 (br), 9.18 (s) ppm;
C
6
): δ = 163.49, 160.42, 157.00, 143.79,
41.53 ppm; IR (KBr): 3102, 2912, 1598, 1553, 1519, 1430,
400, 1378, 1305, 1254, 1176, 1101, 1040, 970, 940, 913, 882,
Key words high-energy-density materials · 3,3'-di(1,2,5-
oxadiazol-3-yl)-5,5'-bi(1,2,4-oxadiazole) · detonation
performance·sensitivity·X-ray diffraction
1
1
8
-1
8 18 8
52, 826, 628 cm ; Elemental analysis calcd (%) for C12H N O
(
4
532.31): C 27.08, H 1.51, N 47.36; found: C 27.12, H 1.52, N
7.29%.
Di(4-amino-1,2,4-triazolium) 4,4'-([5,5'-bi(1,2,4-oxadiazole)]- Reference
3
,3'-diyl)-bis(1,2,5-oxadiazol-3-nitramide) (15)
1
0.259 g of 15 was obtained in a yield of 92.12%. T
d
, 219.1 °C. H
[1] (a) T. M. Klapötke, D. G. Piercey and J. Stierstorfer, Dalton Trans., 2012,
41, 9451-9459; (b) V. Thottempudi, H. Gao and J. M. Shreeve, J. Am.
Chem. Soc., 2011, 133, 6464-6471; (c) D. Fischer, T. M. Klapötke, M.
Reymann and J. Stierstorfer, Chem. Eur. J., 2014, 20, 6401-6411; (d) J.
Zhang, L. A. Mitchell, D. A. Parrish and J. M. Shreeve, J. Am. Chem. Soc.,
1
3
NMR (300 MHz, DMSO-d
NMR (126 MHz, DMSO-d
6
): δ = 9.47 (s), 8.08 (br) ppm;
C
6
): δ = 163.44, 160.55, 157.72, 144.04,
41.45 ppm; IR (KBr): 3350, 3115, 3026, 1602, 1526, 1497,
430, 1399, 1275, 1215, 1188, 1139, 1027, 986, 939, 913, 871,
1
1
8
2015, 137, 10532-10535; (e) J. Zhang and J. M. Shreeve, Dalton Trans.,
-1
11, 622 cm ; Elemental analysis calcd (%) for C12
H N
10 20
O
8
2016, 45, 2363-2368. (f) C. H. Lim, T. K. Kim, K. H. Kim, K. H. Chung and
J. S. Kim, B. Korean Chem. Soc. 2010, Vol. 31, No. 5. (g) Q. Sun, C.
Shen, X. Li, Q. Lin and M. Lu, J. Mater. Chem. A, 2017,
(
4
562.34): C 25.63, H 1.79, N 49.82; found: C 25.63, H 1.74, N
9.85%.
Di(3-amino-1,2,4-triazolium) 4,4'-([5,5'-bi(1,2,4-oxadiazole)]-
10.1039/C7TA02209C.
3
,3'-diyl)-bis(1,2,5-oxadiazol-3-nitramide) (16)
[2] (a) D. E. Chavez, J. C. Bottaro, M. Petrie and D. A. Parrish, Angew. Chem.
Int. Ed., 2015, 54, 12973-12975; (b) J. Zhang, S. Dharavath, L. A. Mitchell,
D. A. Parrish and J. M. Shreeve, J. Am. Chem. Soc., 2016, 138, 7500-
1
d
0.253 g of 16 was obtained in a yield of 89.98%. T , 182.7 °C. H
): δ = 8.31 (s), 8.02 (br) ppm; 13
NMR (300 MHz, DMSO-d
NMR (126 MHz, DMSO-d
6
C
7503. (c) L. E. Fried, M. R. Manaa, P. F. Pagoria and R. L. Simpson,
6
): δ = 163.36, 160.65, 158.26, 150.73,
41.04, 139.24 ppm; IR (KBr): 3419, 3308, 3191, 2775, 1697,
592, 1518, 1498, 1428, 1323, 1253, 1179, 1039, 970, 949, 911,
Annu. Rev. Mater. Res., 2001, 31, 291-321; (d) W. Yang, Z. Li, Q. Zhou,
Y. Zhang, H. Huang, S. Li and D. Nie, Cryst. Growth Des., 2012, 12,
5155-5158; (e) X. Zhang, E. Eaton and R. Gilardi, Angew. Chem. Int. Ed.,
2000, 39, 401-404; (f) M. Goobel, K. Karaghiosoff, T. M. Klapötke, D. G.
Piercey and J. Stierstorfer, J. Am. Chem. Soc., 2010, 132, 17216-17226.
1
1
8
-1
75, 842, 767, 716 cm ; Elemental analysis calcd (%) for
(562.34): C 25.63, H 1.79, N 49.82; found: C 25.63,
12 10 20 8
C H N O
H 1.76, N 49.77%.
Synthesis of 4,4'-([5,5'-bi(1,2,4-oxadiazole)]-3,3'-diyl)-bis(N-
[
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white solid was obtained, washed with cold water and dried in
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air. 0.886 g of 17 was obtained in a yield of 70.33%. T , 187.7 °C;
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Entry for the Table of Contents (Please choose one layout)
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Energetic compounds based on 4,4'-
Bohan Wang, Hualin Xiong, Guangbin
Cheng and Hongwei Yang*
(
[5,5'-bi(1,2,4-oxadiazole)]-3,3'-diyl)-
bis(1,2,5-oxadiazol-3-amine) were
synthesized and fully characterized.
Most of these compounds have high
heat of formation, high density,
moderate sensitivities and good
detonation performance.
Page No.1 – Page No.8
Incorporating Energetic Moieties into
a Four Oxadiazole Rings System for
the Generation of High-Performance
Energetic Materials
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