RESEARCH FRONT
CSIRO PUBLISHING
Aust. J. Chem. 2014, 67, 1037–1043
http://dx.doi.org/10.1071/CH14060
Synthesis and Characteristics of Energetic Materials
Based on 1,2-Dinitroguanidine
Bingcheng Hu,A,B Xinghui Jin,A Huanqing Jia,A
Zuliang Liu,A and Chunxu Lv A
A
School of Chemical Engineering, Nanjing University of Science
and Technology, Nanjing, Jiangsu, 210094, China.
B
Corresponding author. Email: hubingcheng210094@163.com
A series of energetic salts based on 1,2-dinitroguanidine were successfully synthesised and fully characterised using
1
H NMR, 13C NMR, and IR spectroscopy, mass spectrometry, elemental analysis, and differential scanning calorimetry.
The results show that all the salts possess higher detonation properties (detonation pressures and velocities ranging from
24.8 to 30.3 GPa and 7665 to 8422 m s
1, respectively) than those of trinitrotolouene (TNT, 2,4,6-trinitromethylbenzene).
The thermal stability and thermal kinetic parameters were also investigated to give a better understanding of the physical
and chemical properties of these energetic salts.
Manuscript received: 8 February 2014.
Manuscript accepted: 2 May 2014.
Published online: 16 June 2014.
Introduction
During the past decades, considerable effort has been focussed
on the development of nitrogen-rich high energy density mate-
rials (HEDMs) with high performance and decreased sensitivity
as well as environmental compatibility.[1–3] In the pursuit of
HEDMs, people found that high performance shows some
contradicting aspects according to thermal stability and sensi-
tivity. To avoid such contradictions, one possible approach is to
introduce strong hydrogen bonds (especially the hydrogen
bonds between –NH2 and –NO2 groups) into the crystal struc-
ture. Inter- and intramolecular hydrogen bonding networks
between –NH2 and –NO2 groups cannot only help to stabilise the
compounds substantially and decrease their toxicities and sol-
ubility in common solvents, but also can markedly increase the
density of energetic compounds.[4,5] On the other hand, ener-
getic salts can also be utilised to balance contradictions through
the combination of different anions and cations with different
physical and chemical properties. This is primarily because
salt-based energetic materials often possess advantages over
non-ionic molecules since these salts tend to exhibit lower
vapour pressures and higher densities than their atomically
similar non-ionic analogues.[6–8] The above-described approa-
ches provide powerful methodologies for the design and syn-
thesis of new HEDMs for specific purposes.
1,2-Dinitroguanidine, which has inter- and intramolecular
hydrogen bonding networks between the –NH2 and –NO2
groups, has been receiving much attention for its excellent
energetic properties and simple synthetic process.[9,10] Consid-
erable studies have also demonstrated that R–NHNO2 can
normally act as a moderately strong acid, and that the stability
of this compound can be dramatically increased by transforma-
tion of the –NHNO2 moiety into –NNO–2 to form a salt.[11,12]
Not surprisingly, 1,2-dinitroguanidine consists of this type of
structure and can form energetic salts when paired with bases.
Journal compilation Ó CSIRO 2014
Full Paper
Previous work also demonstrated its feasibility.[13,14] In this
work, we report the synthesis and characterisation of some
novel salts based on 1,2-dinitroguanidine in combination with
different nitrogen-rich cations. Their thermal stabilities and
detonation properties are also investigated.
Results and Discussion
1,2-Dinitroguanidine (1) was obtained by nitration of nitro-
guanidine using 100 % nitric acid and 20 % oleum according to
the literature.[9] The guanidinium salts 4, 5, and 7 were syn-
thesised using silver 1,2-dinitroguanidine (2), which was
prepared by the metathesis of 1,2-dinitroguanidine and an
equivalent amount of aqueous silver nitrate, with the corre-
sponding chloride salts. After stirring for 3 h at ambient tem-
perature, silver chloride was filtered off and the filtrate was dried
slowly in air. The aqueous solubility of 2 is very low but it is
more soluble than the silver halides causing these reactions to
proceed smoothly. For example, to a suspension of 2 (1 mmol) in
water (10 mL) was added a solution of diaminoguanidinium
chloride (1 mmol) in water (5 mL). After stirring at 508C for
several hours, the mixture was filtered, and the filtrate was
concentrated. Compound 4 was obtained in excellent yield by
recrystallisation from methanol and water. The energetic salts
3 and 6 were obtained by the acid–base reaction between
1,2-dinitroguanidine and the energetic bases in methanol
aqueous solutions and the corresponding energetic salts
obtained as solids. All of the salts were recovered as highly
crystalline materials in excellent yields and purities.
The structures of the energetic salts were supported by IR,
1
H, and 13C NMR spectroscopic data and electrospray ionisation
mass spectrometry (ESI-MS) as well as elemental analysis. In
the 1H NMR spectra, the hydrogen signals of the cations could
be easily observed and assigned. In the 13C NMR spectra, the
signals assigned to the 1,2-dinitroguanidine anion are detected
www.publish.csiro.au/journals/ajc
1038 B. Hu et al.

in every salt, and other signals were associated with the cations
accordingly. In the IR spectra, several main absorption bands
which belong to the N¼O asymmetric stretch and the N–N
asymmetric stretch were observed at around 1520, 1360, 1320,
and 850 cm
1. The intense absorption bands in the range of
3100–3500 cm
1 can be assigned to the N–H bonds of the salts.
In the ESI-MS spectra, a single signal (m/z ¼ 148) assigned to
the 1,2-dinitroguanidine anion was observed in negative ion
mode, and other signals associated with the cations were
observed accordingly in the postive ion mode. In addition, all
the elemental analysis results are highly consistent with the
calculated values.
Crystal Structure
Crystallographic data (excluding structure factors) for the
structure of 5 has been deposited with the Cambridge Crystal-
lographic Data Centre, CCDC, 12 Union Road, Cambridge
CB21EZ, UK. Copies of the data can be obtained free of
charge on quoting the depository number CCDC-995416
(Fax: þ44-1223-336-033; Email: deposit@ccdc.cam.ac.uk,
http://www.ccdc.cam.ac.uk).
Single crystals suitable for X-ray measurement were obtai-
ned by slow evaporation of a methanol–aqueous solution of salt
5. A crystal with dimensions 0.3 mm  0.3 mm  0.1 mm was
chosen for X-ray determination. The data were collected with
a Bruker SMART APEX II CCD X-ray diffractometer using
graphite-monochromated MoKa radiation (l 0.071073 nm). The
structure was solved by direct methods (SHELXTL-97) and
refined by full-matrix-block least-squares methods on F2 with
anisotropic thermal parameters for all non-hydrogen atoms.
Crystal data and refinement results are summarised in Table 1.
Fig. 1a shows the molecular structure of triaminoguanidi-
nium 1,2-dinitroguanidine (5). It is seen that the molecular
structure of the triaminoguanidinium 1,2-dinitroguanidine salt
was made up of one triaminoguanidinium cation and one 1,2-
dinitroguanidine anion which are distributed in different planes.
The C–N bond lengths range from 1.3065 to 1.3875 Å while the
N–N bond lengths range from 1.3294 to 1.4171 Å. Obviously,
all the C–N or N–N bond lengths are between the normal C–N
and N–N bond lengths (1.47 and 1.45 Å, respectively) and the
normal C¼N and N¼N bond lengths (1.28 and 1.25 Å, respec-
tively). It is indicated that the bonds in the 1,2-dinitroguanidine
cation and dinitroguanidine anion tend to be average. Fig. 1b
presented the three-dimensional packing diagram of the tri-
aminoguanidinium 1,2-dinitroguanidine salt. Since the amino
groups are excellent hydrogen bond donors, and nitro groups are
hydrogen bond acceptors, intra- and intermolecular interactions
were formed. As shown in Fig. 1b, the dashed lines indicate the
strong hydrogen bonding formed between the hydrogen atoms,
nitrogen atoms, and oxygen atoms. The discrete triaminogua-
nidinium cation and 1,2-dinitroguanidine anion are linked into
a 3D network by extensive intra- and intermolecular hydrogen-
bonding interactions. Hydrogen bond lengths are summarised as
follows: N(7)–H(7A)O(2), 2.558(12); N(6)–H(6A)N(9),
2.674(10); N(1)–H(1A)O(2), 3.115(11); N(8)–H(8A)N(11),
2.649(11); N(10)–H(10A)N(7), 2.670(11); N(1)–H(1B)
O(4), 2.558(12)]; N(1)–H(1A)O(3), 3.071(11); N(6)–H
(6A)O(1), 2.987(10); N(7)–H(7A)O(4), 2.924(10); N(8)–H
(8A)O(1), 2.972(10); N(9)–H(9A)N(2), 3.168(10); N(10)–
H(10A)O(3), 2.977(10); N(11)–H(11C)N(4), 3.258(11) Å.
Thermal Decomposition Kinetics
The thermal stabilities of the 1,2-dinitroguanidine-based ener-
getic salts were investigated using differential scanning calo-
rimetry (DSC). Their thermal decomposition kinetics were
studied at the heating rates of 5, 10, 15, and 208C min
1. As a
representative example, thermogravimetric (TG)-DSC curves
for the decomposition process of the aminoguanidinium 1,2-
dinitroguanidine salt 3 which were obtained at different heating
rates are shown in Fig. 2. It was found that, with increasing the
heating rate, the TG-DSC peaks of the decomposition tem-
peratures (Tp) shifted to higher temperatures and the exothermic
peaks of the DSC curves appeared more and more clearly. This

Table 1. Crystal data and structure refinement details

(a)
Parameter Salt 5
C
Chemical formula C2H11N11O4 O

Formula weight [g mol
1]

N
253.22 H
Temperature [K] 293 (2)
Wavelength [Å] 0.71073
Crystal system Orthorhombic
Space group P na21
a [Å] 22.429(5)
b [Å] 3.6310(7) (b) c
c [Å] 12.307(3) a
a [deg.] 90 b
b [deg.] 90
g [deg.]8 90
Volume [Å3] 1002.3(3) C
O
Z 4 N
Dcalc [g cm
3]
H
1.68
Absorption coefficient [mm
1] 0.150
F(000) 528
y range [deg.] 1.82–25.35
Index ranges 0 # h # 27, 0 # k # 4, 0 # l # 14
Goodness-of-fit on F2 1.002
Final R indices [I . 2s(I)] R1 ¼ 0.0643, wR2 ¼ 0.1628
R indices (all data) R1 ¼ 0.1113, wR2 ¼ 0.1914
Fig. 1. (a) Molecular structure and (b) three-dimensional packing diagram
Largest diff. peak and hole [e Å
3] 0.335,
0.337
of triaminoguanidinium 1,2-dinitroguanidine (salt 5).
Synthesis and Characteristics of Energetic Materials 1039

observation may be attributed to the ‘thermal hysteresis’ of the oxygen balance, detonation velocity, and detonation pressure
heat transfer effect at different heating rates. are summarised in Table 3. In order to assess the potential of
The Kissinger and Ozawa’s methods were also jointly emp- the newly prepared 1,2-dinitroguanidine-based salts, ener-
loyed to calculate the kinetic parameters such as activation getic properties of the traditionally well known energetic
energy (Ea), pre-exponential constant (A), entropy of activa- materials 2,4,6-trinitrotoluene (TNT) and 1,3,5-triamino-2,4,
tion (DS¼6
), enthalpy of activation (DH¼
6
), free energy of activa- 6-trinitrobenzene (TATB) are also listed in the table.
¼
6
tion (DG ), and the critical temperature of thermal explosion (Tb). The onset temperatures for thermal decomposition of the
As shown in Table 2, the apparent activation energy (E) physical properties were determined by using DSC at a heating
obtained using Kissinger’s method (Ek) agreed well with that rate of 58C min
1, and no melting point was observed. As shown
obtained using Ozawa’s method (Eo), and the linear correla- in Table 2, salt 5 has the lowest thermal degradation temperature
tion coefficients (r) are very close to 1. Thus, the results were (Td 1458C) while salt 6 has the highest thermal degradation
credible. The salts possessed an acceptable heat-resistant capa- temperature (Td 2218C). However, all the thermal degradation
bility considering the values of Tb ranging from 416.7 to 504.4 K. temperatures of the salts are lower than those of TNT (Td 2958C)
Additionally, the other thermodynamic parameters such as DS6¼, and TATB (Td 3188C).
DH6¼, and DG6¼ are also given in the table to provide a better Density and heat of formation are two important physical
understanding of the thermal behaviour of these salts. properties for an energetic material since these parameters
are directly related to detonation velocity and detonation pres-
Properties of the 1,2-Dinitroguanidine-Based Salts sure. From Table 2, the densities were found to range from
The physical and chemical characteristics of these energetic 1.59 to 1.69 g cm
1, and salt 7 exhibited the highest density of
salts, such as density, thermal stabilities, heat of formation, 1.69 g cm
1. Although all the densities of these energetic salts
are lower than that of TATB, the densities of salts 6 and 7 were
100 5 K min⫺1 higher than that of TNT. The densities of all the investigated
90 10 K min⫺1 energetic salts are not high enough, especially salts 6 and 7,
80 15 K min⫺1 which are just on par with TNT. This may be the reason why the
70 20 K min⫺1 calculated detonation properties of these materials show disap-
pointing performances. However, all the investigated salts are of
60
nitrogen-rich materials, and large amounts of nitrogen are
50
released during the decomposition process. It is expected that
40 all the above-described materials are applicable in propellant
30 and gas generating compositions.
20 The heat of formation is also an important parameter to be
10 considered since it is usually taken as the indicator of the ‘energy
0 content’ of an energetic material. Recently, significant progress
exo
⫺10 has been made in the theoretical prediction of the thermody-
⫺20
namic properties of energetic salts. The heat of formation can be
calculated for salts with good accuracy (including the heats of
50 100 150 200 250 300 350 400 450 formation of cations and anions, as well as the lattice energy of
T [K] salts). The calculation of the heat of formation of the anion,
cation, and the salts were based on the isodesmic reaction
Fig. 2. Thermogravimetric-differential scanning calorimetry curves of (Scheme 1). It is found that all the cations have a high positive
salt 3 at different heating rates.

Table 2. Thermal decomposition kinetic parameters and thermodynamic parameters

Salt Tb [K]A Kissinger’s method Ozawa’s method Thermodynamic parameters

EBk log AC rD
k EEo rFo TG
p,0 DS6¼&H DH6¼&I DG6¼&J
[kJ mol
1] [s
1] [kJ mol
1] [K] [J mol
1 K
1] [kJ mol
1] [kJ mol
1]

3 481.9 98.3 11.1 0.97 100.5 0.97 462.7
36.1 94.5 111.2
4 420.1 139.2 15.9 0.97 139.6 0.97 409.6 56.83 135.8 112.5
5 416.7 116.2 13.9 0.98 117.3 0.98 404.4 18.7 112.8 105.2
6 441.7 294.5 35.4 0.98 290.9 0.98 436.1 429.6 290.9 103.6
7 504.4 184.6 19.1 0.97 183.5 0.97 492.9 116.6 180.5 123.0
8 225.9 280.8 26.2 0.98 288.5 0.99 491.6
221.9 276.7 376.8
A
Extrapolated onset temperature.
B
Apparent activation energy obtained using Kissinger’s method.
C
Pre-exponential constant.
D
Linear correlation coefficient obtained using Kissinger’s method.
E
Apparent activation energy obtained using Ozawa’s method.
F
Linear correlation coefficient obtained using Ozawa’s method.
G
Extrapolated onset temperature.
H
Activation entropy.
I
Activation enthalpy.
J
Activation Gibbs free energy.
1040 B. Hu et al.

Table 3. Properties of the 1,2-dinitroguanidine-based energetic salts

Salt dA TBm TCd DHf0 D

cation DHf0 Eanion DHf0 Flattice DHf0 G
salt PH DI OBJ
[g cm
3] [8C] [8C] [kJ mol
1] [kJ mol
1] [kJ mol
1] [kJ mol
1] [GPa] [m s
1]

3 1.59 – 163 667.4
108.3 490.1 69.0 25.3 7886
32.29

4 1.61 – 168 769.0
108.3 483.5 177.2 26.6 8020
33.61
5 1.68 – 145 871.5
108.3 480.8 286.0 30.2 8419
34.92
6 1.69 – 167 2302.0
108.3 1434.3 759.4 30.3 8422
21.82
7 1.66 – 221 805.3
108.3 446.9 250.1 24.8 7665
43.11
8 1.67 – 225 877.6
108.3 474.2 295.1 26.1 7880
39.5
TNTK 1.65 80.4 295 – – – – 19.5 6881
74.0
TATBK 1.94 – 318 – – – – 31.2 8114
55.8
A
Density.
B
Melting point.
C
Thermal degradation.
D
Calculated molar enthalpy of formation of the cation.
E
Calculated molar enthalpy of formation of the anion.
F
Calculated molar lattice energy.
G
Calculated molar enthalpy of formation of the salt.
H
Detonation pressure.
I
Detonation velocity.
J
Oxygen balance (OB), an index of the deficiency or excess of oxygen in a compound required to convert all C into CO2 and all H
into H2O; for the compound with molecular formula CaHbNcOd (without crystal water), OB (%) ¼ 1600(d
2a
b/2)/Mw (%).
K
Data from Zhang et al.[15]

NO2 NO2
NO2 100 % HNO3
20 % oleum N AgNO3 N Ag ⫹
N ⫺
H2N N NO2 H2N N NO2
H 2N NH2 H
1 2

Energetic
base M⫹Cl⫺

Energetic salts

⫹ ⫹
⫹ H2N ⫹
M⫹ Cation NH2
NH2
NH

H2N N N NH2
H 2N N NH2 H H H2N N N NH2
H H H
3 4 5

H H NH2
⫹ H N N ⫹ N N ⫹
H N
H3N N N NH3 O2N N NH2 H2N NH2
N N N N
H H HN N
⫹
6 7 8

Scheme 1. Synthesis of 1,2-dinitroguanidine and its salts.

heat of formation ranging from 667.4 to 2302.0 kJ mol
1
while the 1,2-dinitroguanidine has a heat of formation of

108.3 kJ mol
1. The lattice energies of the dianionic salts
are ,3 times larger than the monoanionic salts because of
their greater molecular masses and lower densities bringing
about a concomitant decrease in the heat of formation. Besides,
all the salts possess a high positive heat of formation and salt 6
has the highest heat of formation. This may be a result of the
tetrazine skeleton and the higher nitrogen content of salt 7.
With the data of density and heat of formation, detonation
velocity and detonation pressure as other two important para-
meters were calculated using the Kamlet–Jacobs equations. The
calculated detonation pressures of the new salts ranged from
25.3 (salt 3) to 30.3 GPa (salt 6). The calculated detonation
velocities ranged from 7665 (salt 7) to 8422 m s
1 (salt 6). The
calculated data show that the salts exhibit superior detonation
velocity (D) and detonation pressure (P) to those of TNT
(P 19.5 GPa, D 6881 m s
1) and salt 7 has similar values to
Synthesis and Characteristics of Energetic Materials
(a) H8(0.307) H7(0.318)
N6(⫺0.437)
O12(⫺0.078) O2(0.115)
C5(0.256)
N9(⫺0.073)
N11(⫺0.102)
H10(0.323)
N4(⫺0.138)
O13(⫺0.033)
Fig. 3. Optimised structure and charge distribution in (a) 1,2-dinitroguanidine and (b) the anion at B3LYP/6–311þG(d,p) level.
(a) (b)
Fig. 4. (a, c) The highest occupied molecular orbital and (b, d) lowest unoccupied molecular orbital of 1,2-dinitroguanidine and
its anion.
those of TATB (P ¼ 31.2 GPa, D ¼ 8114 m s
1). Unsurprising-
ly, salt 6 has a higher detonation velocity and detonation
pressure than the other five salts because of the difference in
its density and heat of formation. Although the investigated salts
have superior detonation properties to that of TNT, they obvi-
ously show no melting point, and therefore, would not be usable
as melt cast explosives.
Oxygen balance (OB) is the index of the deficiency or
excess of oxygen in a compound required to convert all car-
bon into carbon monoxide, and all hydrogen into water. The
sensitivity, strength, and brisance of an explosive all some-
what depend on the OB. From Table 2, the OBs of the 1,2-
dinitroguanidine salts were between
43.11 (salt 7) and

21.82 % (salt 6). Although all the OBs were negative, they were
less negative than that of TNT (
74.0 %) and TATB (
55.8 %).
For a comparison, dinitroguanidinate salts such as the ammo-
nium salt, hydrazinium salt, guanidinium salt, 1,3,5-triamino-
guanidinium salt (TAG), urea salt (Ur), 5-aminotetrazolium salt
(5-AT), 1-methyl-5-aminotetrazolium salt (1-MAT), 1,4-
dimethyl-5-aminotetrazolium salt (1,4-DMAT), and 1-amino-
3-nitroguanidinium dinitroguanidinate (ANQDNG) reported by
Klapoetke et al. have been also cited.[16,17] It is found that all the
salts reported by Klapoetke et al. have a higher density than the
salts reported in this paper except for GDNQ and 1,4-DMAT,
thus these salts have higher detonation properties according to
Kamlet–Jacobs equations. Among these salts, the compound
hydrazinium 1,2- dinitroguanidinate (HyDNG) has the highest
density, detonation pressure, and detonation velocity which
may be due to inter- and intramolecular hydrogen bonding as
stated in the paper. It also can be seen that the decomposition
temperature of these salts range from 111 to 2258C, and
compound HyDNG has the lowest decomposition temperature
while compound 3,4,5-triaminotriazolium 1,2-dinitroguanidine
(8) has the highest decomposition temperature. This is because
salt 8 has a large p-bond conjugate system in the molecule which
can increase the stability of the compound.
Natural Bond Orbital (NBO) Analysis
In order to give a better understanding of the chemical and
physical properties of 1,2-dinitroguanidine, molecular orbital
1041
(b)
H8(0.294) H7(0.294)
N6(⫺0.479)
O12(⫺0.182) O2(⫺0.182)
C5(0.113)
N1(⫺0.225)
N11(⫺0.264) N9(⫺0.069) N4(⫺0.069) N1(⫺0.264)
O3(⫺0.003)
O13(⫺0.096) O3(⫺0.096)
(c) (d )
and NBO analyses based on the optimised structure of the
neutral molecule and the anion of 1,2-dinitroguanidine (B3LYP/
6–311þG(d,p)) were carried out by using Gaussian 03. As
shown in Fig. 3a, b, all the N and O atoms carry negative charge
while all the C and H atoms carry positive charge and atoms
N6 and H10 carry the highest negative and positive charge
(
0.437 e and 0.323 e, respectively). In the 1,2-dinitroguanidine
anion, all O atoms carry more negative charges (
0.556 e) than
that of the neutral molecule (
0.229 e), and the negative charges
are distributed more symmetrically compared with the neutral
molecule which indicates that the more negative O atoms in the
anion can form stronger hydrogen bonds with the hydrogen
atoms in the cation. In addition, a large p-bond conjugate system
is also found in the 1,2-dinitroguanidine.
The highest occupied molecular orbitals (HOMOs) and
the lowest unoccupied molecular orbitals (LUMOs) of the
neutral molecule and anion of 1,2-dinitroguanidine are shown
in Fig. 4. In the neutral molecule, the atoms N1, N4, O2, and O3
occupy the HOMO and the other part of the 1,2-dinitroguanidine
molecule occupies the LOMO. In the anion, most of the
HOMO and LUMO are overlapped except atoms N6, H7, and
H8 which participate in the LUMO. Obviously, atoms in the
1,2-dinitroguanidine anion occupy more frontier orbitals than
that in the neutral molecule. The results indicate that the
1,2-dinitroguanidine anion is more reactive and easily attacked
by other reagents to form new compounds.
Conclusion
A family of 1,2-dinitroguanidine-based energetic salts were
successfully prepared and fully characterised. The salts exhibit
good physical and chemical properties, such as densities
(from 1.59 to 1.69 g cm
1), heats of formation (from 69.0 to
795.4 kJ mol
1), detonation velocities (from 7665 to 8422 km s
1),
and detonation pressures (from 24.8 to 30.3 GPa). They were
higher than the traditional energetic material TNT and similar to
TATB. Additionally, thermal stabilities of the salts were eval-
uated, and the results showed that these salts possessed
acceptable heat-resistant abilities, with Tb values ranging from
416.7 to 504.4 K. All the results show that these salts can be
potential candidates for energetic materials.
1042
Experimental
CAUTION! Although none of the compounds described herein
have exploded or detonated in the course of this research, these
materials should be handled with extreme care by using best
safety practices (leather gloves, leather coat, face shield, etc.).
General Methods
All chemicals were of pure analytical grade obtained com-
mercially and used as received. 1H and 13C NMR spectra
were recorded on a Bruker 500 MHz nuclear magnetic reso-
nance spectrometer operating at frequencies of 500 and
125 MHz, respectively, and using d6-DMSO as the locking
solvent. The chemical shifts are reported in ppm relative to
TMS. IR spectra were recorded using KBr pellets on a
Thermo Nicolet IS10 IR instrument. ESI-MS results were
recorded on a Finnigan TSQ Quantum ultra AM mass spec-
trometer. Elemental analyses were recorded on a Vario EL III
elemental analyser (Germany). The melting and decomposi-
tion points were recorded by a differential scanning calorim-
eter equipped with an auto-cool accessory and calibrated using
indium at a scan rate of 58C min
1 in a dynamic nitrogen
atmosphere (flow rate: 40 mL min
1). All the samples were
heated from 40 to 4008C at different heating rates of 5, 10, 15
and 208C min
1 to investigate the thermal decomposition
kinetics of the salts, and the transition temperature (Tm) was
taken as the peak maximum.
1,2-Dinitroguanidine (1)
Compound 1 was synthesised according to the literature
method.[9] dH (500 MHz, DMSO-d6,) 9.61 (s, 2H), 13.25 (s, 1H).
dC (DMSO-d6, 125 MHz) 156.44. nmax (KBr)/cm
1 3430, 3330,
3100, 2900, 1655, 1625, 1520, 1420, 1300, 1250, 1140, 1045, 995,
955, 790, 710. m/z (ESI) 148 [M
H]
. Anal. Calc. for CH3N5O4:
C 8.05, H 2.01, N 46.98. Found: C 8.12, H 2.0, N 46.81 %.
General Procedure for the Synthesis of the Salts 3 and 8
To a solution of 1 (149 mg, 1.0 mmol) in methanol (10 mL) was
added dropwise a solution of aminoguanidinium bicarbonate or
3,4,5-triamino triazolium in methanol (5 mL). A white solid was
formed. The suspension was stirred for 2 h at ambient temper-
ature. The insoluble solid was filtered off, washed with cool
methanol several times, and dried under vacuum.
Aminoguanidinium 1,2-Dinitroguanidine (3)
A white solid was obtained (203 mg) in 91.03 % yield.
dH (500 MHz, DMSO-d6,) 4.64 (s, 2H), 6.75 (s, 1H), 7.27
(s, 2H), 8.57 (s, 1H), 9.45 (s, 2H). dC (DMSO-d6, 125 MHz)
159.35, 165.09. nmax (KBr)/cm
1 3460, 3430, 3100, 3372,
2980, 2890, 1655, 1610, 1520, 1420, 1259, 1145, 1063, 971,
784, 644, 468. m/z (ESI) 148 [M
H]
, 75 [M þ H]þ. Anal.
Calc. for C2H9N9O4: C 10.76, H 4.07, N 56.49. Found: C 10.82,
H 4.01, N 56.35 %.
3,4,5-Triamino Triazolium 1,2-Dinitroguanidine (8)
A white solid was obtained (225 mg) in 85.6 % yield.
dH (500 MHz, DMSO-d6,) 5.59 (s, 2H), 7.08 (s, 4H), 9.45
(s, 2H), 12.50 (s, 1H). dC (DMSO-d6, 125 MHz) 150.50,
165.25. nmax (KBr)/cm
1 3371, 3269, 1702, 1658, 1623, 1209,
1143, 1047, 968, 671. m/z (ESI) 148 [M
H]
, 115 [M þ H]þ.
Anal. Calc. for C3H9O4N11: C 13.69, H 3.42, N 58.56 . Found:
C 13.60, H 3.49, N 58.61 %.
B. Hu et al.
General Procedure for the Synthesis
of the Salts 4, 5, and 7
To a suspension of the silver salt 2 (1 mmol) in water (10 mL)
was added slowly a solution of the corresponding halide salt
(1 mmol) in water (5 mL). The resulting reaction mixture was
stirred at 508C for 6 h and filtered. The filtrate was concentrated
under reduced pressure. The collected residue was recrystallised
from methanol/water to afford the corresponding product in
excellent yield.
Diaminoguanidinium 1,2-Dinitroguanidine (4)
Recrystallised from H2O and CH3OH to give a white solid,
yield: 192 mg (80.67 %). dH (500 MHz, DMSO-d6,) 4.58 (s, 4H),
7.14 (s, 2H), 8.55 (s, 2H), 9.45 (s, 2H). dC (DMSO-d6, 125 MHz)
160.29, 165.19. nmax (KBr)/cm
1 3466, 3390, 3325, 3272, 3191,
2971, 1685, 1610, 1507, 1420, 1400, 1245, 1053, 1020, 971,
784, 668, 550. m/z (ESI) 148 [M
H]
, 90 [M þ H]þ. Anal.
Calc. for C2H10N10O4: C 10.09, H 4.23, N 58.81. Found: C 9.98,
H 4.30, N 58.93 %.
Triaminoguanidinium 1,2-Dinitroguanidine (5)
Recrystallised from H2O and CH3OH to give a white solid,
yield: 212 mg (83.80 %). dH (500 MHz, DMSO-d6,) 4.48 (s, 6H),
8.58 (s, 3H), 9.43 (s, 2H). dC (DMSO-d6, 125 MHz) 159.58,
165.32. nmax (KBr)/cm
1 3386, 3360, 3345, 3330, 3273, 3240,
1685, 1610, 1526, 1414, 1276, 1235, 1125, 1050, 1000, 951,
780, 599, 530. m/z (ESI) 148 [M
H]
, 105 [M þ H]þ. Anal.
Calc. for C2H11N11O4: C 9.49, H 4.38, N 60.86. Found: C 9.41,
H 4.45, N 61.71 %.
2-Iminium-5-nitriminooctahydroimidazo[4,5-d]
imidazole 1,2-Dinitroguanidine (7)
Recrystallised from H2O and CH3OH to give a white solid,
yield: 296 mg (88.62 %). dH (500 MHz, DMSO-d6,) 5.84 (s, 2H),
8.07 (s, 2H), 9.41 (s, 6H). dC (DMSO-d6, 125 MHz) 70.56, 159.41,
161.75, 164.93. nmax (KBr)/cm
1 3400, 3355, 3260, 1711, 1580,
1453, 1385, 1285, 1250, 1210, 1145, 1090, 1045, 951, 602. m/z
(ESI) 148 [M
H]
, 186 [M þ H]þ. Anal. Calc. for C5H10N12O6:
C 17.97, H 3.02, N 50.29. Found: C 18. 06, H 3.00, N 50.36 %.
3,6-Dihydrazino-s-tetrazine 1,2-Dinitroguanidine (6)
To a solution of 1 (149 mg, 1.0 mmol) in methanol (10 mL)
was added 3,6-dihydrazino-s-tetrazine (71 mg, 0.5 mmol).
The resulting suspension was stirred at 408C for 3 h and then
filtered. The product was washed with cool methanol several
times and dried under vacuum. Compound 6 was recrystallised
from H2O and CH3OH to give a white solid, yield: 197 mg
(89.55 %). dH (500 MHz, DMSO-d6,) 9.46 (s, 8H), 10.50 (s, 4H).
dC (DMSO-d6, 125 MHz) 161.86, 164.25. nmax (KBr)/cm
1
3351, 3197, 3137, 3309, 1617, 1590, 1551, 1516, 1236, 1159,
1061, 950, 787, 727, 674, 549, 468. m/z (ESI) 148 [M
H]
,
143 [M þ H]þ. Anal. Calc. for C4H12N18O8: C 10.91, H 2.75,
N 57.27. Found: C 11.03, H 2.62, N 57.49 %.
Supplementary Material
Crystallographic and computational details are available on the
Journal’s website.
Acknowledgements
This study was supported by the National Defence Advanced Research
Projects (No. J-KY-2012-1317) and the Priority Academic Program
Development of Jiangsu Higher Education Institutions (PAPD).
Synthesis and Characteristics of Energetic Materials
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