N-trinitroethyl-substituted azoxyfurazan: High detonation performance energetic materials

Article abstract of DOI:10.1039/c5ra03230j

Azoxyfurazan derivatives based on the trinitroethyl functionality were synthesized. These energetic N-trinitroethyl-substituted azoxyfurazans were fully characterized by using ¹H and ¹³C NMR spectroscopy, IR, elemental analysis, differential scanning calorimetry (DSC), thermogravimetric analysis (TG) as well as single crystal X-ray diffraction, and, in the case of N-trinitroethylamino azoxyfurazan 4, with ¹⁵N NMR spectroscopy. Furthermore, compound 4 and nitramine 5 have been tested for their responses to impact, friction, and electrostatic discharge. The detonation pressures and velocities of the azoxyfurazan derivatives were calculated, ranging from 35.8 GPa to 41.2 GPa and 8861 m s^-1 to 9458 m s^-1, respectively. Additionally, compound 5 having an oxygen balance of near zero (+2.5%), exhibits a favorable measured density (1.92 g cm^-3) and excellent detonation property (Δ_fH_m, 962.1 kJ mol^-1; P, 41.2 GPa; D, 9458 m s^-1). Thus, these compounds could be potential high detonation performance energetic materials.

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N-Trinitroethyl-substituted azoxyfurazan: high
detonation performance energetic materials†
Cite this: DOI: 10.1039/x0xx00000x
a
a
a
a
b
a
Qiong Yu, Zhixin Wang, Hongwei Yang,* Bo Wu, Qiu Han Lin, Xuehai Ju, Chunxu
a
a
Lu, Guangbin Cheng*
Received 00th January 2012,
Accepted 00th January 2012
The azoxyfurazan derivatives based on the trinitroethyl functionality were synthesized. These
1
13
energetic
N
ꢀtrinitroethylꢀsubstituted azoxyfurazan were fully characterized by using H and
C
DOI: 10.1039/x0xx00000x
NMR spectroscopy, IR, elemental analysis, differential scanning calorimetry (DSC),
thermogravimetric analysis (TG) as well as single crystal Xꢀray diffraction, and, in case with
www.rsc.org/
1
5
N
ꢀtrinitroethylamino azoxyfurazan
and nitramine have been tested with their responses to impact, friction, and electrostatic
discharge. The donation pressures and velocities of the azoxyfurazan derivatives were
4, with N NMR spectroscopy. Furthermore, compound 4
5
ꢀ
1
ꢀ1
calculated, ranging from 35.8 GPa to 41.2 GPa and 8861 m s to 9458 m s , respectively.
Additionally, compound having an oxygen balance of near zero (+2.5%), exhibits favorable
measured density (1.92 g cm ) and excellent detonation property (ꢀfHm, 962.1 kJ mol ;
5
ꢀ
3
ꢀ1
P
,
ꢀ
1
4
1.2 GPa;
D, 9458 m s ). Thus, these compounds could be potential high detonation
performance of energetic materials.
Introduction
Highꢀenergy density materials (HEDMs) are the focus of
advanced energetic materials research aimed at future needs in
1
the defense and space sectors. Fundamental properties such as
high nitrogen content, high density, high heat of formation,
high detonation velocity and pressure, good oxygen balance,
high thermal stability and low sensitivity, must be considered
2
during the development of these energetic ingredients.
However, the development of such materials is complex, owing
to the fact that the contradictory nature of high detonation
performance and low sensitivity usually poses interesting but
3
challenging problems for the synthesis of new HEDMs.
Therefore, it is necessary to find suitable strategies to guide the
synthesis of energetic materials.
Polynitrofunctionalized compounds are one of the most
4
ꢀ10
significant structural motifs in HEDMs.
Owing to the
presence of polynitro fragments in the molecules, most of them
Fig. 1 Tetrazole derivatives containing a trinitroethyl group.
1
1
have positive oxygen balance values and high densities.
Energetic materials containing trinitroethyl moieties have high
1
6ꢀ20
1
2ꢀ20
group of trinitroethyl has attracted considerable interest.
density and good detonation performance.
Moreover, they
2
1
Recently, two
compounds (Fig. 2, iv and
have been reported, which were obtained by the oneꢀpot
Nꢀnitration product of furazanꢀderived
can be readily synthesized by the addition of trinitroethanol
2
2,23
v
) with the trinitroethyl functionality
(
or trinitromethane and formaldehyde
) to an amine.
Recently, some tetrazole and imidazole derivatives containing
trinitroethyl fragments have been reported. However, further
nitration of these compounds is difficult to be achieved because
the effect of the electronꢀwithdrawing of tetrazole and
1
8
reaction using ionic liquids as solvents. Actually, nitrating
trinitroethyl amine compounds to obtain nitroamine compounds
1
9
has not been widely concerned. In addition, the additional
oxygen atom coordinated to the azo group was considered
which not only enhances density and performance, but also
1
2,15
imidazole rings (Fig.1).
The furazan ring is an effective fragment for improving the
performance of explosives, a fact that is probably attributable to
its high density, high positive heat of formation, and good
2
5,26
tends to stabilize the entire molecule.
vi vii), two examples of azoxyfurazan derivatives bearing the
trinitroethyl group were reported recently, but their detonation
As shown in figure
2
( ,
2
4
oxygen balance. The design of new energetic compounds
based on a combination of amino furazan with an explosophore
1
6,17
properties are not quite satisfying.
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Fig. 2 Furazan-derivatives containing one or two trinitroethyl groups.
In a continuing effort to search for more powerful, better
thermal stability, ecoꢀfriendly energetic materials, we are
interested in designing and synthesizing some trinitroethyl
derived compounds based on azoxyfurazan containing a high
percentage of both oxygen and nitrogen content and owning
good oxygen balance. Herein we describe the synthesis of two
trinitroethyl derivatives of azoxyfurazan and one
Nꢀnitration
product which contain one or two trinitroethyl fragments and
display potentially significant physical and energetic properties.
These compounds exhibit high densities, high heats of
formation, and thereby excellent detonation properties.
Scheme 1 Synthesis of trinitroethyl substituted amino azofurazan (
3-
4
) and nitroamino furazan ( ).
5
Results and Discussion
Synthesis
The raw material 3,3’ꢀdiaminoꢀ4,4’ꢀazoxyfurazan
1 was readily
synthesized according to the literature, which can be obtained
TM
by treatment of OXONE (a strong oxidant) with 3,4ꢀdiamino
2
7,28
furazan (DAF).
To afford trinitroethyl derivatives of
azoxyfurazan, we opted to use the Mannich reaction of electron
deficient trinitroethanol which was synthesized according to the
2
9
method reported previously and the weak base
condition (Scheme 1). When reaction temperature is below 70
C, the reaction of trinitroethanol with 3,3’ꢀdiaminoꢀ4,4’ꢀ
azoxyfurazan affords low yield of ’ꢀbis(2,2,2ꢀ
trinitroethyl)ꢀ3,3’ꢀdiaminoꢀ4,4’ꢀazoxyfurazan (≤30%) in 1M
hydrochloric acid. Enhancing of temperature from 70 C to 100
1 under acidic
°
Scheme 2 A plausible mechanism for synthesis of 3.
1
a
N,N
4
°
%
nitric acid solution, the reaction temperature should be
°
o
C is favorable to improve yield of
reaction time of 5 days. Interestingly, further extension of
reaction time resulted in yield decline of accompanied by the
generation of byproduct 3. The identification of byproduct is
proved be monochloroꢀadduct of trinitroethyl derivatives of
azoxyfurazan
mechanism for the formation of
involved two elementary steps (Scheme 2). The first step NMR spectra of compounds
involves the formation of ketone intermediates
by groups attached to the furazan ring appeared at 5.63 and 5.41
hydrolyzation of imine 4, which was formed by the proton ppm, respectively. These proton signals of ꢀNHꢀ groups and ꢀ
transformation from secondary amine of compound
. At the CH ꢀ groups show as triplets and doublets, respectively, owing
second step, the hydroxyl group of intermediates
was attacked to the coupling of ꢀNHꢀ group and ꢀCH ꢀ group. Furthermore,
by hydrochloric acid to form byproduct
, the proton signals were
After condensation on the azoxyfurazan
with easily assigned because only two singlets occurred at δ= 6.16
trinitroethanol , the resulting secondary amine
was subjected ppm and δ= 6.23 ppm; they were shifted downfield compared
4 to 89.55 % with the
strictly controlled at 0~5 C avoiding the nitrification progress
reaction growing extremely violent.
4
3
NMR spectoroscopy
4
by Xꢀray diffraction analysis. The plausible The structures of the three new compounds (3ꢀ5) were
1 13
1
3
from product
4
could be supported by H, and C NMR spectroscopic data. In the H
and , the proton signals of ꢀNHꢀ
3
4
6
4
2
6
2
1
3
.
in the H NMR spectra of compound 5
1
2
4
1
3
to nitration to give
N,
N
'ꢀbis(2,2,2ꢀtrinitroethyl)ꢀ3,3'ꢀ to the parent molecule
4 (δ≈ 5.41 ppm). In the C NMR spectra
dinitraminoꢀ4,4'ꢀazoxyfurazan
5
by 100% nitric acid and acetic of the three new compounds, the signals of carbon atoms
anhydride. When the acetic anhydride was dropped into the 100 bonded to three nitro groups were found at 124ꢀ127 ppm, while
2
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15
Fig. 3 N NMR spectra of compound 4.
those in the furazan ring appeared between 146 and 162 ppm.
The carbon atoms in the furazan rings are influenced by the
conjugated system so that their electron cloud density decreases
a lot, which result in the signals of them shifted downfield more
than 20 ppm compared to those of quaternary carbon atoms(ꢀ
C(NO ) ).
2
3
1
5
The N NMR spectra of compound
4 was measured in
(
CD ) CO solution and chemical shifts are given with respect to
3
2
CH NO as an external standard. As shown in fig. 3, the spectra
3
2
1
5
of compound
4 displays ten signals. The assignments in the N
NMR spectrum are based on the signals of the other nitrogen
atoms in the furazan ring and trinitroethyl group in the
1
6ꢀ20
literature.
The asymmetric bridging azoxy moiety causes
1
5
different N signals between two furazan rings and two kinds
of nitro groups attached to trinitromethyl as well as the two
amino groups. The nitrogen signals (N5 and N9) of the ꢀNHꢀ
group appears at the highest field (δ= ꢀ342.3 ppm, ꢀ340.9 ppm).
The signals for N2, which has oxygen as a neighbor in the
azoxy linkage, appear as expected at lower field compared to
N1.
Fig. 4 (a) Molecular structure of 3. Hydrogen atoms are shown, but are
unlabeled for clarity. (b) Ball and stick packing diagram of 3 viewed down the c
axis. Dashed lines indicate strong hydrogen bonding.
o
the two furazan rings is 4.32 , which indicate that they are
planar (Fig. 4 a). The packing structure of
3 is influenced by
strong hydrogen bonds. These extensive hydrogen bonds (N5ꢀ
H5…O3 2.875(3) Å, N5ꢀH5…N2 2.858(3), C(3)ꢀH(3A)…N(4)
X-ray crystallography
Single crystals of the compounds
Xꢀray diffraction, were obtained by slow evaporation of CH Cl
3ꢀ5 suitable for singleꢀcrystal
2
.835(3), C(3)ꢀH(3A)…O(1) 3.431(3)) are presented in Figure
2
2
4(b) along the c axis (Fig. 4 b), which extend the structure into
a 3D supramolecular structure, and make an important
contribution to enhance the thermal stability of the complex.
solutions. Their crystallographic data are summarized in Table
, and structures are displayed in Fig. 4, 5 and 6, respectively.
1
Further information about crystalꢀstructure determinations is
given in the supporting information†. As expected and found in
the three structures discussed in this work, the furazan ring is
nearly planar, building an aromatic system, which can be seen
since the mean deviation of them are in the range of 0.0004 Åꢀ
Compound
4 crystallizes in the monoclinic space group C2/c
with one molecule in the unit cell, and has a calculated density
of 1.855 g cm (173(2) K). In the unit cell, there are two
oxygen atoms bearing the azo group. The length of ꢀN=N(O)ꢀ
bond is 1.277(3) Å which is slightly shorter than that of 3. The
lengths of the CꢀN bonds in the trinitromethyl are in the range
of 1.517 Å ꢀ1.527 Å and are significantly elongated relative to a
normal CꢀN single bond (1.47 Å). With a lone electron pair of
the nitrogen atoms (N4) attached to the furazan ring, they can
form a pꢀπ conjugation between the nitrogen atoms and the
aromatic ring, so that the lengths of C2ꢀN4 (1.360 Å) bonds are
approaching the length of C=N (1.350 Å) double bond. The
bi(1,2,5ꢀoxadiazole) ring system shows a planar arrangement,
ꢀ
3
0
.0098 Å.
As can be seen in Table 1,
3 crystallizes in the orthorhombic
ꢀ
3
3
0
Pbca space group with a calculated density of 1.887 g cm .
The crystal cell of contains separate molecules of without
3
3
water or solvent molecule (Fig. 4 a). The distance between N1
and N2 (1.283 Å) falls in the range between N=N double bonds
(
1.290 Å) and N≡N triple bonds (1.095 Å), which is the result
of the decrease electron cloud density on N=N1A bond owing
to a πꢀπ conjugation system between N1=N2 bond and furazan
ring. The lengths of the CꢀN bonds in the trinitromethyl (1.510ꢀ
o
o
which is reflected in the dihedral angles of almost 0 and ±180
C1ꢀN2ꢀO2ꢀN3 0.1(2) , O2ꢀN3ꢀC2ꢀN4 ꢀ176.69(19) , O2ꢀN2ꢀ
o
o
(
o
1
.526 Å) are longer than the other CꢀN bond distances in the
C1ꢀN1 177.70(19) ). However, the trinitro group is twisted out
of the furazan ring plane with torsion angles of N5ꢀC4ꢀC3ꢀN4, ꢀ
furazan ring and the substituted amino (1.293ꢀ1.437 Å). The
length of C(5)ꢀCl(1) bond is 1.687(2) Å and is shorter than a
normal CꢀCl bond (1.77 Å), which is arising from the
conjugation system between a lone electron pair of the chlorine
atoms Cl(1) and furazan ring. And, the dihedral angle between
o
o
o
4
9.06 ; N6ꢀC4ꢀC3ꢀN4, 71.98 ; N7ꢀC4ꢀC3ꢀN4, 168.35 .
Interestingly, the amino connected to the furazan ring are lie in
the furazan planner (Fig. 5a). As shown in fig. 5(b), crystal
packing of
4 shows that the 3D network is Sꢀshaped. It can be
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Table 1. Crystallographic data for the compounds 3-5
.
3
4
5
CCDC number
Empirical formula
Formula weight
T[K]
994773
ClN10
994770
994775
C
6
H
3
O
9
C
8
H
7
N
14
O
15
8 4 16 19
C H N O
394.63
170(2)
539.28
173(2)
628.27
173(2)
3
Crystal size [mm ]
0.34 × 0.32 × 0.13
Orthorhombic
Pbca
0.20 × 0.18 × 0.12
Monoclinic
C2/c
0.38 × 0.21 × 0.16
Monoclinic
Crystal system
Space group
a [Å]
1
P2 /n
11.3577(6)
9.9015(6)
24.7060(14)
90
21.343(4)
7.8125(16)
11.766(2)
90
7.6635(6)
9.5134(7)
15.1332(12)
90
b [Å]
c [Å]
α [°]
β [°]
90
100.11(3)
90
99.571(3)
90
γ [°]
90
3
V [Å ]
2778.4(3)
8
1931.4(7)
4
1087.94(15)
2
Z
λ(Å)
0.71073
1.887
0.71073
1.855
0.71073
1.918
ꢀ
3
ρ
calcd [mg m ]
ꢀ
1
ꢁ
[mm ]
0.356
0.178
0.189
F (000)
1584
1092
632
θ range [°]
Index ranges
3.19 ꢀ 26.38
1.94 ꢀ 27.87
3.22 ꢀ 25.90
ꢀ12≤
h
≤14
≤12
≤30
ꢀ28≤
ꢀ10≤
ꢀ14≤
h
≤28
ꢀ9 ≤h≤ 8
ꢀ
ꢀ
12≤
29≤
k
k
l
≤10
≤15
ꢀ11≤
ꢀ18≤
k
≤11
≤18
l
l
Reflections collected
15508
11713
6057
Independent reflections/
R
int
2806 / 0.0556
98.5
2303 / 0.0447
99.9
2074 / 0.0412
98.0
Completeness to θ [%]
2
Goodnessꢀofꢀfit on
F
1.037
1.142
1.019
a
R
1
(F) (
I
>2σ(
I
))
0.0439
0.0505
0.0350
b
2
wR [all date]
0.1120
0.1076
0.0727
3
Largest diff. peak / hole [e Å ]
0.370 / ꢀ0.343
0.205 / ꢀ0.256
0.162 / ꢀ0.236
a
b
2
o
2
2
2
o
2
1/2
1
R =Σ|
F
o
| ꢀ |
Fc | /Σ|
F
o
|. wR
2
={Σ[w
(F
ꢀF
c
) ] / Σ[
w
(F
) ]}
clearly seen that intramolecular hydrogen bonds between the ꢀ moieties (such as N15…O15= 2.47 Å, N14…O19= 2.53 Å,
NHꢀ group (N4) and the oxygen atoms (O1) of azoxy group N12…O1= 2.81 Å, N9…O8= 2.55 Å, N8…O6= 2.66 Å,
combined with intramolecular hydrogen (N4ꢀH4…O1 2.784(4), N7…O10= 2.65 Å, N7…O7= 2.87 Å) are shorter than the sum
3
1
N4ꢀH4…O5 2.795(2), C3ꢀH3A…N3 2.867(3)) form a complex of van der Waals radii (N, O= 3.07 Å), which make an
threeꢀdimensional network. important contribution to improve the crystal density. The
Compound crystallizes in the monoclinic crystal system in packing of the atoms of compound is dominated by a threeꢀ
the space group P2 /n. The calculated density is 1.918 g cm dimensional network, which are connected by strong
owing to the intermolecular hydrogen bonds (C3ꢀH3B…N4 2.800(16) Å,
addition of two nitro groups. The crystal structure of is C3ꢀH3A…O3 2.71(2) Å) and intramolecular hydrogen bonds
similar to that of and in which the length of the CꢀN bonds (C3ꢀH3B…O15 2.56(15) Å, C3ꢀH3A…N3 2.705(17) Å). A
5
5
ꢀ
3
1
(
173 K) which shows higher than that of 4
5
3
4
joining the trinitroethyl groups are also longer than that of view of the hydrogen bonds along the a axis is shown in Fig.
furazan ring and the substituted amino (such as C4ꢀN7 1.530 Å, 6(b).
C4ꢀN8 1.529 Å, and C4ꢀN9 1.526 Å). However, the distances
(
1.452 Å) between N5 (N6) and C2 (C6) are longer than the
Physical and energetic properties
similar bond length in compound (C2ꢀN4 1.360 Å), which is
4
To assess the thermal stability of the new materials,
thermogravimetric analysis (TG) and differential scanning
calorimetry (DSC) measurements were carried out for these
because the pꢀπ conjugation between the nitrogen atoms and the
aromatic ring is destroyed resulting from strong electronꢀ
withdrawing effect on the nitrogen atoms (N5, N12) by the
nitro group in the nitroamino moiety. Besides, the two furazan
rings are parallel rather than planar owing to the twist of N1
o
ꢀ1
new compounds at a heating rate of 5 C min using dry
o
o
nitrogen as an atmosphere in ranging from 30 C to 400 C
o
(
Fig. S1ꢀS3†). Compound
3 melted at 185.5 C, the
atom (Fig. 6a). The ꢀNꢀNO group is out of the furazan ring
2
o
o
endothermic stage occurs at a temperature range of 180.2ꢀ188.7
plane with dihedral angles of 65.175 and 41.764 . The
presence of weak attractive electrostatic interactions (short
contacts) between the nitro groups within the trinitromethyl
o
o
C and decomposed at 209.2 C, which shows that the
compound melts without decomposition. Compounds 5
4
ando
o
decomposed without melting at 190.2 C and 144.6 C,
4
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Fig. 6 (a) Molecular structure of 5. Hydrogen atoms are shown, but are
unlabeled for clarity. (b) Ball and stick packing diagram of 5 viewed down
the a axis. Dashed lines indicate strong hydrogen bonding.
Fig. 5 (a) Molecular structure of 4. Hydrogen atoms are shown, but are
unlabeled for clarity. (b) Ball and stick packing diagram of 4 viewed down the
a axis. Dashed lines indicate strong hydrogen bonding.
Heat of formation is an important parameter in evaluating the
performance of energetic compounds, which were calculated by
using the Gaussian 09 suite of program. The geometry
respectively. Compound
than that of due to one side trinitroethyl group attached to
compound was substituted by a chlorine atom in which the
3
is slightly more thermally stable
33
4
optimizations of the molecules and frequency analyses were
3
34
accomplished by using the B3LYP with the 6ꢀ311+G** basis
lone electron pair on the chlorine atom could conjugate with
35
36
set. Atomization energies were calculated by the CBSꢀ4M.
the furazan. There are two steps in the decomposition of
All the optimized structures were characterized to be true local
energy minima on the potential energy surface without
imaginary frequencies. The calculated heats of formation are
summarized in Table 2. It can be seen that all of the
o
compound
5
. One decomposition progress occurs at 144.6 C
o
and the other appeared at 193.1 C. Therefore, these studies
show that and presented here have higher thermal stabilities
than that of , which is attributed to the “explosophore” of
nitramino groups in compound . The weight losses of
compound and are 73.9 % and 99.8 %, respectively, which
both correspond to the thermal decompositions of the
molecules. Compound has two steps of weight loss which has
3
4
5
trinitroethyl derivatives exhibit positive heats of formation,
5
ꢀ1
with
5
having the highest value of 962.1 kJ mol , which is
3
4
more ninefold than that of HMX. Followed by the compound
and , the heats of formation are also remarkably high, which is
almost sevenfold of HMX (104.8 kJ mol ). The heat of
formation of compound was higher than that of and
which was a result of the higher both nitrogen and oxygen
content of compound
3
4
5
ꢀ1
a total weight loss of 99.9%.
Oxygen balance (OB) is used to indicate how clean a
5
3
4,
compound combust completely to N
₂, H₂O and CO₂ etc.
5
.
Compound possesses a negative OB value of ꢀ18.2%, which
3
With the data for molecular weight, density from Xꢀray
is less negative than that of RDX (ꢀ21.6%) (Table 2). With the
increase in the number of nitro group, it is found that compound
o
diffraction and gas pycnometer (25 C), and heat of formation
in hand, the detonation velocity (D) and pressure (P) of the
4
(ꢀ11.9 %) has a less negative OB than
nitration of , compound has an oxygen balance of near zero
+2.5 %), which can almost make full use of chemical energy.
3. Moreover, after
resulting compounds were calculated with KamletꢀJacobs (KꢀJ)
equations. (See ESI†) Their detonation performance data are
summarized in Table 2. The detonation pressures of compounds
4
5
(
Both nitrogen and oxygen content is another very important
property of energetic materials. All the three compounds in this
study have a relatively high both nitrogen and oxygen content
which range from 71.99% to 84.06%.
3
-5 lie in the range between
P=35.8 to P=41.2 GPa (compared
with RDX 35.2 GPa, and HMX 40.3 GPa). Detonation
ꢀ1
ꢀ1
velocities lie in the range between 8861 m s and 9458 m s
(
ꢀ1
ꢀ1
compared with RDX 8977 m s and HMX 9320 m s ).
Among them, owing to high density and high heat of formation,
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Table 2. Physical properties of trinitroethyl derivatives of furazan and azofurazan
a
b
d
e
f
g
h
i
j
k
Comp.
T
[
dec
o
ρ
N+O
[%]
ꢂH
f
D
P
IS
FS
ESD
[J]
OB
[%]
ꢀ3
ꢀ1
ꢀ1
C]
[g cm ]
[kJ mol ]
[m s ]
[GPa]
[J]
[N]
c
3
4
5
209.2
190.2
144.6
230
1.887
71.99
81.02
84.06
81.06
81.06
719.6
759.8
962.1
92.6
8861
9041
9458
8977
9320
35.8
36.7
41.2
35.2
39.6
ꢀ
ꢀ
ꢀ
ꢀ18.2
ꢀ11.9
+2.5
ꢀ21.6
ꢀ21.6
1.84
1.92
1.82
1.91
7.9
3.2
7.5
7.0
130
80
120
112
0.29
0.12
0.1ꢀ0.2
l
l
l
l
RDX
HMX
l
l
287
104.8
0.2
a
o
ꢀ1
b
o
c
Thermal decomposition temperature under nitrogen gas, peak of maximum (DSC, 5 C min ); Density measured by gas pycnometer (25 C); Density from Xꢀray
d
e
f
diffraction; Both nitrogen and oxygen content; Heat of formation calculated with Gaussian 09; Calculated detonation velocities; [g] Calculated detonation
pressure; Impact sensitivities; Friction sensitivity; Electrostatic sensitivity; Oxygen balance (OB, %) for C H N O : OB=1600×(dꢀ2aꢀb/2)/M , M = molecular
a b c d w w
weight (based on carbon dioxide); Ref. 32.
h
i
j
k
l
compound
=41.2 GPa,
HMX.
The measurements of impact sensitivities and friction
were realized by
5 exhibits excellent detonation performances
hyang@mail.njust.edu.cn (H. Yang), gcheng@mail.njust.edu.cn (G.
Cheng); Fax: +86 25 8430 3286; Tel: +86 25 8430 3286.
ꢀ
1
(
P
D=9458 m s ), which are better than that of
b
School of Materials Science & Engineering, Beijing Institute of
Technology, South Street No. 5, Zhongguancun, Haidian District,
Beijing, 100081, China.
discharge of the furazan derivatives74 and
5
3
using the standard BAM method. Additionally, they were
tested for sensitivity toward electrical discharge by using an
†
Footnotes should appear here. These might include comments
ESD JGYꢀ50 III electric spark tester. The sensitivity of relevant to but not central to the matter under discussion, limited
compound
nitration product
As can be seen from Table 2, similar trends are observed in the
electrostatic discharge and friction discharge sensitivity results.
The electrostatic sensitivities for compounds
and 0.12 J, respectively, showing that compound
sensitive to electrical discharge than HMX (0.2 J) and
compound is more sensitive than RDX (0.1ꢀ0.2 J). In
addition, compound is less sensitive to friction (130 N) while
the friction sensitivity of HMX is 112 N. Undoubtedly,
compound is sensitive to friction (80 N).
4
(7.9 J) is comparable to that of RDX (7.5 J). The
is more sensitive (4.0 J) than HMX (7.0 J).
experimental and spectral data, and crystallographic data.
5
Electronic Supplementary Information (ESI) available: CCDC 994773,
9
1
94770 and 994775. See DOI: 10.1039/b000000x/
4
and
5
are 0.29
4
is less
a) I. V. Ovchinnikov, N. N. Makhova, L. I. Khmel’nitskii, V. S.
Kuz’min, L. N. Akimova and V. I. Pepekin, Dokl. Akad. Nauk.,
5
1
998, 359, 499ꢀ502; b) A. Hammerl, T. M. Klapӧtke, H. Nӧoth and
M. Warchhold, Inorg. Chem., 2001, 40, 3570ꢀ3575; c) M. H. V.
Huynh, M. A. Hiskey, D. E. Chavez, D. L. Naud and R. D. Gilardi
J. Am. Chem. Soc., 2005, 127, 12537ꢀ12543; d) T. M. Klapӧtke, P.
Mayer, A. Schulz and J. J. Weigand, J. Am. Chem. Soc., 2005, 127
032ꢀ2033; e) Y. Gao, C. Ye, B. Twamley and J. M. Shreeve,
4
,
5
,
Conclusions
2
In summary,
azoxyfurazan
dinitraminoꢀ4,4'ꢀazoxyfurazan
N
4
,
N
’ꢀbis(2,2,2ꢀtrinitroethyl)ꢀ3,3’ꢀdiaminoꢀ4,4’ꢀ
and 'ꢀbis(2,2,2ꢀtrinitroethyl)ꢀ3,3'ꢀ
were synthesized and fully
Chem. ꢁEur. J., 2006, 12, 9010ꢀ9018; f) D. M. Badgujar, M. B.
Talawar, S. N. Asthana and P. P. Mahulikar, J. Hazard. Mater.,
2008, 151, 289ꢀ305; g) M. B. Talawar, R. Sivabalan, T. Mukundan,
H. Muthurajan, A. K. Sikder, B. R. Gandhe and A. S. Rao, J.
Hazard. Mater., 2009, 161, 589ꢀ607; h) Y. C. Li, C. Qi, S. H. Li,
H. J. Zhang, C. H. Sun, Y. Z. Yu and S. P. Pang, J. Am. Chem.
Soc., 2010, 132, 12172ꢀ12173; i) T. M. Klapӧtke and F. X.
Steemann, Propellants, Explos. Pyrotech., 2010, 35, 114ꢀ129; j) H.
Gao, Y.ꢀH. Joo, D. A. Parrish, T. Vo and J. M. Shreeve, Chem. ꢁ
Eur. J., 2011, 17, 4613ꢀ4618; k) Y. Zhang, Y. Guo, Y.ꢀH. Joo, D.
A. Parrish and J. M. Shreeve, Chem.ꢁEur. J., 2010, 16, 10778ꢀ
10784; l) L. Liang, D. Cao, J. Song, H. Huang, K. Wang, C. Bian,
N,N
5
1
13
characterized by H, C NMR spectroscopy, IR, and single
crystal Xꢀray diffraction. These trinitroethyl derivatives have
good both nitrogen and oxygen content, good oxygen balance,
which exhibit high densities, moderate thermal stability and
high detonation velocities (8861 m s to 9458 m s ) and
detonation pressures (35.8 GPa to 41.2 GPa), may serve as a
promising alternative to some known explosive such as RDX.
Especially, compound 5 having an oxygen balance of near zero
ꢀ
1
ꢀ1
(
+2.5 %), exhibits superior detonation properties (ꢀfHm, 962.1
ꢀ
1
ꢀ1
kJ mol ; D, 9458 m s ; P, 41.2 GPa) to HMX. These properties
suggest that trinitroethyl derivatives might be of interest for
future applications as environmentally friendly and nitrogenꢀ
rich energetic materials.
X. Dong and Z. Zhou, J. Mater. Chem. A., 2013, 1, 8857ꢀ8865; m)
Q. H. Lin, Y. C. Li, C. Qi, W. Liu, Y. Wang and S. P. Pang, J.
Mater. Chem. A., 2013, 1, 6776ꢀ6785; n) V. Thottempudi, P. Yin, J.
Acknowledgements
Zhang, D. A. Parrish and J. M. Shreeve, Chem. ꢁEur. J., 2014, 20
,
This work was supported by the National Natural Science
Foundation of China (NSFC) (No. 21376121).
542ꢀ548.
2
a) M.ꢀX. Zhang, P. E. Eaton and R. Gilardi, Angew. Chem. Int. Ed.,
000, 39, 401ꢀ404; b) P. E. Eaton, R. L. Gilardi and M.ꢀX. Zhang,
2
Notes and references
Adv. Mater., 2000, 12, 1143ꢀ1148; c) H. Xue, S. W. Arritt, B.
Twamley and J. M. Shreeve, Inorg. Chem., 2004, 43, 7972ꢀ7977;
d) H. Xue and J. M. Shreeve, Adv. Mater., 2005, 17, 2142ꢀ2146; e)
a
School of Chemical Engineering, Nanjing University of Science and
Technology, Xiaolingwei 200, Nanjing 210094, P. R. China. Eꢀmail:
6
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ARTICLE
A. R. Katritzky, S. Singh, K. Kirichenko, J. D. Holbrey, M. 10 H. S. Jadhav, M. B. Talawar, D. D. Dhavale, S. N. Asthana and V. N.
Smiglak, W. M. Reichert and R. D. Rogers, Chem. Commun., 2005, Krishnamurthy. Inaian. J. Chem. Technol., 2005, 12, 187ꢀ192.
68ꢀ870; f) H. Xue, Y. Gao, B. Twamley and J. M. Shreeve, Inorg. 11 a) K. F. Mueller, R. H. Renner, W. H. Gilligan, H. G. Adolph and M.
8
Chem., 2005, 44, 5068ꢀ5072; g) M. Gӧbel, T. M. Klapӧtke and P.
Mayer, Z. Anorg. Allg. Chem., 2006, 632, 1043ꢀ1050; h) Y. Guo,
J. Kamlet, Combust. Flame., 1983, 50, 341ꢀ349; b) J. Song, Z.
Zhou, X. Dong, H. Huang, D. Cao, L. Liang, K. Wang, J. Zhang, F.
Chen and Y. Wu, J. Mater. Chem., 2012, 22, 3201ꢀ3209; c) R. P.
Singh and J. M. Shreeve, Chem. ꢁEur. J., 2011, 17, 11876ꢀ11881;
d) R. Duddu, P. R. Dave, R. Damavarapu, R. Surapaneni and R.
Gilardi, Synth. Commun., 2005, 35, 2709ꢀ2714.
H. Gao, B. Twamley and J. M. Shreeve, Adv. Mater., 2007, 19
,
2
4
2
884ꢀ2888; i) Y.ꢀH. Joo and J. M. Shreeve, Org. Lett., 2008, 10
665ꢀ4667; j) Y.ꢀH. Joo and J. M. Shreeve, Angew. Chem
009, 48, 564ꢀ567; k) Y. Guo, G. Tao, Z. Zeng, H. Xiang, D. A.
,
.
Int. Ed.,
Parrish and J. M. Shreeve, Chem. ꢁEur. J., 2010, 16, 3753ꢀ3762; l) 12 Q. Zhang, J. Zhang, D. A. Parrish and J. M. Shreeve, Chem. ꢁEur. J.,
Y.ꢀH. Joo and J. M. Shreeve, Angew. Chem. Int. Ed., 2010, 49
,
2013, 19, 11000ꢀ11006.
7
2
320ꢀ7323; m) Y.ꢀH. Joo and J. M. Shreeve, J. Am. Chem. Soc., 13 a) Y. Oyumi, A. L. Rheingold and T. B. Brill, Propellants, Explos.
010, 132, 15081ꢀ15090; l) V. Thottempudi, H. Gao and J. M.
Pyrotech., 1987, 12, 46ꢀ52; b) V. V. Avdonin, G. A. Volkov, P. V.
Galkin, V. N. Grebennikov, L. T. Eremenko, E. P. Kirpichev, A. G.
Korepin, G. M. Nazin and Y. I. Rubtsov, Lzv. Akad. Nauk SSSR,
Shreeve, J. Am. Chem. Soc., 2011, 133, 6464ꢀ6471; m) N. Fisher,
L. Gao, T. M. Klapӧtke and J. Stierstorfer, Polyhedron., 2013, 51
01ꢀ210; n) D. Fisher, T. M. Klapӧtke, D. G. Piercey and J.
,
2
Ser. Khim., 1992,
Novikova, Russ. J. Org. Chem., 2002, 38, 1873ꢀ1879; e) J. P.
Agrawal and R. D. Hodgson, in Organic Chemistry of Explosives
8, 1857ꢀ1863; d) E. L. Metelkina and T. A.
Stierstorfer, Chem. ꢁEur. J., 2013, 19, 4602ꢀ4613; o) T. M.
Klapӧtke and J. Stierstorfer, J. Am. Chem. Soc., 2009, 131, 1122ꢀ
,
1
134; p) Y.ꢀH. Joo, B. Twamley, S. Garg and J. M. Shreeve,
WILEYꢀVCH, Hoboken. 2007; f) M. Göbel and T. M. Klapötke,
Angew. Chem Int. Ed., 2008, 120, 6332ꢀ6335; q) V. Thottempudi
.
Adv. Funct. Mater., 2009, 19, 347ꢀ365.
and J. M. Shreeve, J. Am. Chem. Soc., 2011, 133, 19982ꢀ19992.
R.Wang, H. Xu, Y. Guo, R. Sa and J. M. Shreeve, J. Am. Chem. Soc.,
14 a) E. Yu. Orlova, Khimiya
i
tekhnologiya brizantnykh
3
4
vzryvchatykhveshchestv, Khimiya, Leningrad, 1981; b)Organic
Energetic Compounds (Ed.: P. L. Marinkas), Nova Science
Publishers, Inc. 1996; c) J. P. Agrawal and R. D. Hodgson, Organic
Chemistry of Explosives, Wiley, Hoboken, 2007.
2
010, 132, 11904ꢀ11905.
a) C. E. Gregory, Explosives for North American Engineers, Trans
Tech Publications, ClausthalꢀZellerfeld, Germany, vol. 5, 1984; b)
T. L. Davis, The Chemistry of Powder and Explosives, Wiley, New 15 P. Yin, Q. Zhang, J. Zhang, D. A. Parrish and J. M. Shreeve, J.
York, vol. 2, 1943. Mater. Chem. A., 2013, , 7500ꢀ7510.
a) A. S. Kumar, V. B. Rao, R. K. Sinha and A. S. Rao, Propellants, 16 A. B. Sheremetev, I. L. Yudin and K. Yu. Suponitsky, Mendeleev
Explos. Pyrotech., 2010, 35, 359ꢀ364; b) H. W. Qiu, V. Stepanov, Commun., 2006, 16, 264–266.
A. R. Di Stasio, T. M. Chou and W. Y. Lee, J. Hazard. Mater., 17 T. V. Romanova, M. P. Zelenov, S. F. Melˈnikova and I. V.
1
5
6
7
8
2
011, 185, 489ꢀ493; c) J. D. Zhang, X. L. Cheng and F. Zhao,
Tselinsky, Russ. Chem. Bull., 2009, 58, 2188ꢀ2190.
18 A. B. Sheremetev, N. S. Aleksandrova, N. V. Palysaeva, M. I.
Struchkova, V. A. Tartakovsky and K. Y. Suponitsky, J. ꢁEur.
Chem., 2013, 19, 12446ꢀ12457.
Propellants, Explos. Pyrotech., 2010, 35, 315ꢀ320.
a) V. M. Boddu, D. S. Viswanath, T. K. Ghosh and R. Damavarapu,
J. Hazard. Mater., 2010, 181,1ꢀ8; b) J. Sun, B. Kang, C. Xue, Y.
Liu, Y. X. Xia, X. F. Liu and W. Zhang, J. Energ. Mater., 2010, 19 Q. Yu, Z. Wang, B. Wu, H. Yang, X. Ju, C. Lu and G. Cheng, 2015,
28, 189ꢀ201; c) C. M. Tarver, J. Phys. Chem. A., 2010, 114, 2727ꢀ
unpublished.
2
736.
20 a) H. Gao and J. M. Shreeve, RSC Adv., 2014, 4, 24874ꢀ24880; b) D.
a) G. Herve, G. Jacob and N. Latypov, Tetrahedron., 2005, 61, 6743ꢀ
748; b) N. V. Latypov, J. Bergman, A. Langlet, U. Wellmar and
U. Bemm, Tetrahedron., 1998, 54, 11525ꢀ11536; c) N. V. Latypov,
M. Johansson and E. Holmgren, Org. Process Res. Dev., 2007, 11
6ꢀ59.
E. Chavez, T. M. Klapötke, D. G. Piercey, D. Parrish and J.
6
Stierstorfer, New Trends in Research of Energetic Materials,
7th
Proceedings of the Seminar, 1 , Pardubice, Czech Republic, April
9ꢀ11, 2014, , 4ꢀ14.
21 a) M.ꢀG. A. Shvekhgeimer, Russ
,
1
5
. Chem. Rev., 1998, 67, 35ꢀ68; b) H.
a) C. W. An, J. Y. Wang, W. Z. Xu and F. S. Li, Propellants, Explos.
Pyrotech., 2010, 35, 365ꢀ372; b) Y. Bayat, M. Eghdamtalab and V.
Feuer and T. Kucera, J. Org. Chem., 1960, 25, 2069ꢀ2070; c) M.ꢀG.
A. Shvekhgeimer, Russ. Chem. Rev., 1998, 67, 35ꢀ68.
Zeynali, J. Energ. Mater., 2010, 28, 273ꢀ284; c) Y. Q. Wu and F. 22 P. Noble, F. G. Borgardt and W. L. Reed, Chem. Rev., 1964, 64, 19ꢀ
L. Huang, J. Hazard. Mater., 2010, 183, 324ꢀ333; d) G. X. Zhang 57.
and B. L. Weeks, Propellants, Explos. Pyrotech., 2010, 35, 440ꢀ 23 S. S. Novikov, M.ꢀG. A. Shvekhgeimer, V. V. Se vostyanova and V.
4
45.
A. Shlyapochnikov, Khimiya alifaticheskikh i alitsiklicheskikh
nitrosoedinenii Khimiya, Moscow, 1974.
9
a) F. H. Crocker, K. J. Indest and H. L. Fredrickson, Appl. Microbiol.
Biotechnol., 2006, 73, 274ꢀ290; b) U. R. Nair, R. Sivabalan, G. M. 24 a) A. Gunasekaran, T. Jayachandran, J. H. Boyer and M. L. Trudell,
Gore, M. Geetha, S. N. Asthana and H. Singh, Combust. Explos.
Shock Waves., 2005, 41, 121ꢀ132; c) H. Singh, Explosion., 2005,
J. Heterocycl. Chem., 1995, 32, 1405ꢀ1407; b) A. K. Zelenin and
M. L. Trudell, J. Heterocycl. Chem., 1997, 34, 1057ꢀ1060; c) A. B.
Sheremetev, V. O. Kulagina, I. A. Kryazhevskikh, T. M.
15
, 120ꢀ132; d) S. V. Sysolyatin, A. A. Lobanova, Y. T.
Chernikova and G. V. Sakovich, Russ. Chem. Rev., 2005, 74, 757ꢀ
64.
Melnikova and N. S. Aleksandrova, Russ. Chem. Bull., 2002, 52
,
7
1533ꢀ1539; d) M. Deng and J. Wang, Chin. J. Energ. Mater., 2002,
10, 56ꢀ58; e) R. S. Kusurkar, S. K. Goswami, M. B. Talawar, G. M.
This journal is © The Royal Society of Chemistry 2012
J. Name., 2012, 00, 1-3 | 7

RSC Advances
Page 8 of 9
View Article Online
ARTICLE
5RA03230J
DOI: 10.1039Jo/Curnal Name
Gore and S. N. Asthana, J. Chem. Res., 2005,
4
, 245ꢀ247; f) Z. Ge,
Barone, M. Cossi, R. Cammi, B. Mennucci, C. Pomelli, C. Adamo,
S. Clifford, J. Ochterski, G. A. Petersson, P. Y. Ayala, Q. Cui, K.
Morokuma, D. K. Malick, A. D. Rabuck, K. Raghavachari, 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.
HeadꢀGordon, E. S. Replogle and J. A. Pople, Gaussian 09,
revision A. 01; Gaussian, Inc.: Wallingford, CT, 2009.
X. Wang, J. Jiang, B. Wang and X. Fu, Chin. J. Synth. Chem.,
2
2
008, 16, 260ꢀ263; g) K. Baum and B. H. Abdollah, U.S. Pat.
0090137816, 2009; h) M. V. Jacqueline, E. C. David, C. T. Bryce
and A. P. Damon, J. Energ. Mater., 2010, 28, 229ꢀ249; i) A. A.
Denisaev, B. L. Korsunskii, V. I. Pepekin and Y. N. Matyushin,
Combust. Explos. Shock Wave., 2010, 46, 74ꢀ80; j) P. Ravi, D. M.
Badgujar, G. M. Gore, S. P. Tewari and A. K. Sikder, Propellants,
Explos. Pyrotech., 2011, 36, 393ꢀ403; k) G. B. Manelis, G.M.
Nazin and V. G. Prokudin, Russ. Chem. Bull., 2011, 60, 1440ꢀ1447;
l) B. Wang, H. Li, Y. Li, P. Lian, Y. Zhou and X. Wang, Chin. J. 34 a) A. D. Becke, J. Chem. Phys. 1993, 98, 5648ꢀ5652; b) P. J.
Energ. Mater., 2012, 20, 385ꢀ390; m) H. Li, B. Wang, Q. Yu, Y. Li
and Y. Shang, Chin. J. Energ. Mater., 2012, 20, 18ꢀ21; n) H.
Stephens, F. J. Devlin, C. F. Chabalowski and M. J. Frisch, J. Phys.
Chem,., 1994, 98, 11623ꢀ11627.
Martinez, Z. Zheng and W. R. Dolbier, J. Fluorine Chem., 2012, 35 P. C. Hariharan and J. A. Pople, Theor. Chim. Acta., 1973, 28, 213ꢀ
43, 112ꢀ122; o) A. B. Sheremetev, I. L. Yudin, N. V. Palysaeva 222.
and, K. Yu. Suponitsky, J. Heterocycl. Chem., 2012, 49, 394ꢀ401; 36 J. W. Ochterski, G. A. Petersson and J. A. Montgomery, J. Chem.
p) V. P. Sinditskii, A. V. Burzhava, A. B. Sheremetev and N. S. Phys., 1996, 104, 2598.
Aleksandrova, Propellants, Explos. Pyrotech., 2012, 37, 575ꢀ580; 37 a) Test methods according to the UN Recommendations on the
1
q) L. Liang, K. Wang, C. Bian, L. Ling and Z. Zhou, Chem. ꢁEur.
J., 2013, 19, 14902ꢀ14910.
Transport of Dangerous Goods, Manual of Tests and Criteria,
United Nations Publication, New York, 4th edn, 2003; b) 13.4.2
Test 3 (a) (ii) BAM Fallhammer, pp. 75ꢀ82; (c) 13.5.1 Test 3 (b)
(i): BAM friction apparatus, pp. 104ꢀ107.
2
5 a) F. Boneberg, A. T. Kirchner, M. Klapötke, D. G. Piercey and M. J.
Stierstorfer, J. Chem.ꢁAsian. J., 2013,
Dippold, D. Izsák and T. M. Klapötke, Chem.ꢁEur. J., 2013, 19
2042ꢀ12051; c) D. Fisher, T. M. Klapötke and J. Stierstorfer,
8, 148ꢀ159; b) A. A.
,
1
Chem.ꢁEur. J., 2013, 19, 4602ꢀ4613; d) T. Harel and S. Rozen, J.
Org. Chem., 2010, 75, 3141ꢀ3143; e) D. E. Chavez and M. A.
Hiskey, J. Energ. Mater., 1999, 17, 357ꢀ377; f) A. M. Churakov
and V. A. Tartakovsky, Chem. Rev., 2004, 104, 2601ꢀ2616; g) M.
Noyman, S. Zilberg and Y. Haas, J. Phys. Chem. A., 2009, 113
376ꢀ7382; h) M. Göbel, K. Karaghiosoff, T. M. Klapötke, D. G.
Piercey and J. Stierstorfer, J. Am. Chem. Soc., 2010, 132, 17216ꢀ
7226; i) K. R. Jorgensen, G. A. Oyedepo and A. K. Wilson, J.
,
7
1
Hazard. Mater., 2011, 186, 583ꢀ589; j) T. M. Klapötke, D. G.
Piercey, J. Stierstorfer and M. Weyrauther, Propellants, Explos.
Pyrotech., 2012, 37, 527ꢀ535; k) A. A. Dippold and T. M.
Klapötke, J. Am. Chem. Soc., 2013, 135, 9931ꢀ9938.
2
6 a) H. Li, B. Wang, X. Li, J. Tong, W. Lai and X. Fan, Bull. Korean
Chem. Soc., 2013, 34, 686ꢀ688; b) C. J. Underwood, C. Wall, A.
Provatas and L. Wallace, New. J. Chem., 2013, 36, 2613ꢀ2617; c) J.
Zhang and J. M. Shreeve, J. Am. Chem. Soc., 2014, 136, 4437ꢀ
4
445.
7 a) A. Gunasekaran, M. L. Trudell and J. H. Boyer, Heteroat.
Chemistry., 1994, , 441ꢀ446; b) L. Gao, H. Yang, B. Wu, G.
2
2
5
Cheng and C. Lu, Chin. J. Energ. Mater., 2013, 21, 226ꢀ229.
8 C. Li, Y. Ma, Y. Xue, J. Yang and B. Wang, Chin. J. Energ. Mater
.
2
012, 20, 151ꢀ154.
2
3
9 H. Feuer and T. Kucera, J. Org. Chem., 1960, 25, 2069ꢀ2070.
0 A. F. Holleman, Lehrbuch der Anorganischen Chemie, 101st ed., de
Gruyter, Berlin (Germany), New York (USA), 1995, p. 1842.
1 A. Bondi, J. Phys. Chem., 1964, 68, 441ꢀ451.
3
3
2 R. Mayer, J. Köhler and A. Homburg, in: Explosives, vol. 5, Wileyꢀ
VCH, Weinheim, Germany, 2002, P. 334.
3
3 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.
8
| J. Name., 2012, 00, 1-3
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Page 9 of 9
RSC Advances
View Article Online
DOI: 10.1039/C5RA03230J
N-Trinitroethyl-substituted azoxyfurazan: high detonation performance
energetic materials
Qiong Yu, Zhixin Wang, Hongwei Yang*, Bo Wu, Qiuhan Lin, Xuehai Ju, Chunxu Lu, Guangbin Cheng*
Detonation property: High nitrogen energetic compounds with good oxygen balance
are reported. These compounds display excellent detonation properties and extra high
heat of formation. Especially, an N-nitrated trinitroethylamino azoxyfurazan
derivative reported here possesses oxygen balance of near zero (+2.5 %) and exhibits
-1
-1
f m
outstanding properties (ꢀ H , 962.1 kJ mol ; D, 9458 m s ; P, 41.2 GPa).