Studies on the synthesis and properties of polynitro compounds based on esteryl backbones

Article abstract of DOI:10.1039/C6NJ02198K

Four esteryl-bridged energetic compounds have been derived from 2,2,2-trinitroethanol with polynitro benzoic acids and characterized via IR, multinuclear NMR spectroscopy, elemental analysis and differential scanning calorimetry (DSC). The structures of 2,2,2-trinitroethyl-2,4,6-trinitrobenzoate (5), bis(2,2,2-trinitroethyl)-4,6-dinitroisophthalate (6), bis(2,2,2-trinitroethyl)-2,5-dinitroterephthalate (7) and bis(2,2,2-trinitroethyl)-2,4,6-trinitroisophthalate (8) were further confirmed by X-ray diffraction studies, which show favorable densities (1.804-1.850 g cm^-3). Interestingly, most of the polynitro esters decompose at temperatures over 180 °C (except for 6: 171.6 °C), which thus exhibit good thermal stability. In addition, performance calculations give detonation pressures and velocities for the ester derivatives in the range of 30.4-32.9 GPa and 8267-8559 m s^-1, respectively. The esteryl-bridged compounds possess acceptable impact sensitivities (14-22 J), friction sensitivities (240-360 N), and electrostatic sensitivities (0.20-0.32 J). These values indicate that polynitro esters can be candidates as promising energetic materials.

Full text of DOI:10.1039/C6NJ02198K

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Studies on the synthesis and properties of polynitro compounds
based on esteryl backbones
Zhen Xu, Hongwei Yang and Guangbin Cheng*a
Received 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
Four esteryl-bridged energetic compounds were derived from 2,2,2-trinitroethanol with polynitro
benzoic acids and characterized by IR, multinuclear NMR spectroscopy, elemental analysis as well as
www.rsc.org/
differential scanning calorimetry (DSC). The structures of 2,2,2-trinitroethyl 2,4,6-trinitrobenzoate(
bis(2,2,2-trinitroethyl) 4,6-dinitroisophthalate( ), bis(2,2,2-trinitroethyl) 2,5-dinitroterephthalate(
and bis(2,2,2-trinitroethyl) 2,4,6-trinitroisophthalate ( ) were further confirmed by X-ray diffraction
5),
6
7)
8
studies, which show favorable densities (1.804-1.850 g cm-3). Interestingly, most of the polynitro
esters decompose at temperatures over 180 °C (expect for 6 : 171.6 °C), exhibit good thermal
stability. In addition, the performance calculations gave detonation pressures and velocities for the
ester derivatives in a range of 30.4-32.9 GPa and 8267-8559 m s-1, respectively. The esteryl-bridged
compounds possess acceptable impact sensitivities (14-22 J), friction sensitivities (240–360 N), and
electrostatic sensitivities (0.20-0.32 J). These values indicate that polynitro esters can be candidates
as promising energetic materials.
Introduction
Over the past decades, research on the energetic materials that correlated with their energetic performances.4-12
combine high performance and low sensitivities is ongoing in Molecules which contain polynitro groups are one of the important
many research groups worldwide.1 However, these classes of useful high energetic materials, such as triaminotrinitro
requirements are somewhat mutually exclusive. Materials with benzene (TATB), 1,3,5-trinitrotriazacyclohexane (RDX), 1,3,5,7-
higher stability and lower sensitivity often exhibit poorer tetranitrotetraazacyclooctane (HMX), and octanitrocubane (ONC)
energetic performance and vice versa. The goal is often to are well-known. Of the nitro-based functional groups, the
discover an optimum balance between them. Driven by trinitroethyl group is a fascinating energetic unit in a lot of high-
increasing demands from both military and civilian applications,2 energy, high-density compounds. The incorporation of the
structural design of energetic molecules has to meet diverse trinitroethyl group into nitro-rich parent compounds is helpful to
standards, such as performance properties, environmental enhance the oxygen balance and density of the energetic materials,
compatibility, as well as safety concerns.3 Given these which improves the detonation performances.13-15 Additionally,
backgrounds, rational introduction of polynitro groups requires 2,2,2-trinitroethanol has long been recognized as a useful building
not only pursuing the highest detonation velocity and pressure, block for such materials.16 In the past few years, many efforts have
but also addressing the problems of thermal stability and impact been undertaken in the chemistry of trinitroethyl esters to evaluate
insensitivity in order to obtain final products with acceptable
properties. Polynitro functionalized compounds are one of the
C(NO2)3
O
C(NO2)3
O
most significant structural motifs in High-energy density
materials (HEDMs) since most of them have positive oxygen
balance values and high densities, which are positively
O
H2N
O
N
N
N
N
O
O
O
ii
i
N
N
C(NO2)3
C(NO2)3
O
O
O
O
O2N
N
N
O
O
O
(O2N)3C
N
N
N
N
O
O
iii
iv
Scheme 1 Trinitroethyl esters derivatives based on furazan rings.
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Scheme 3 Three pathways for esterification of 2,2,2-trinitroethanol
Scheme 2 Trinitroethyl esters derivatives based on modified aliphatic acids.
their potential as energetic materials.16-21 The esterification of
1,2,5-oxadiazolylacetic acids with 2,2,2-trinitroethanol was
reported.16, 17 Nevertheless, their detonation performances have
not been described (scheme 1). Recently, a series of energetic
polynitro esters were derived from amino acid glycine and oxalyl
chloride (scheme 2).20 The effective method is remarkable to
improve the pressure and velocity of explosives. However, their
thermal and energetic performance are not quite satisfying
because of relatively low decomposition temperatures and high
sensitivity towards impact and friction, as well as electrical
discharge. To address these issues, the multi-nitrophenyl
structures were introduced into the polynitro esters. As known,
phenyl-containing energetic compound is more stable toward
thermal and external stimuli.
Herein, a new family of trinitroethyl esters based on polynitro
benzoic acids were synthesized. The combination of polynitro
benzoic acid and trinitroethyl moieties into one molecule is
expected to increase the oxygen balance so as to improve the
detonation performance. All the energetic compounds were well
characterized by IR and multinuclear NMR spectroscopy,
differential scanning calorimetry (DSC), elemental analysis and
further supported by single crystal X-ray diffraction. Their key
detonation properties and sensitivity towards impact, friction
and electrical discharge were determined by experimental and
theoretical methods.
Scheme 4 synthesis of compounds 5-8
following pathway a, owing to the chlorides are unstable
compounds and decompose in the attempt of isolating them in the
individual state. While pathway b was used in this trial, polynitro
benzoic acids decomposed at high temperatures by sulfuric acid
catalyzed esterification. Hence, to afford trinitroethyl derivatives of
polynitro benzoic acids, we turn to try the transesterification
reaction in pathway c. The polynitro benzoic acids were dissolved in
2,2,2-trinitroethylsulfuric acid prepared from 2,2,2-trinitroethanol
and chlorosulfonic acid led to polynitro esters in good yields. The
synthetic pathway to all of the new energetic materials 5-8 is
illustrated in Scheme 4, the starting compounds such as 2,4,6-
trinitrobenzoic acid (1), 4,6-dinitroisophthalic acid (2), 2,5-
dinitroterephthalic acid (3) 2,4,6-trinitroisophthalic acid (4) and
2,2,2-trinitroethanol were synthesized according to the literatures.
The 2,4,6-trinitrobenzoic acid (1) was dissolved in 2,2,2-
trinitroethylsulfuric acid led to 2,2,2-trinitroethyl 2,4,6-
trinitrobenzoate (5). When reaction temperature is below 60 °C, the
reaction of 1 with 2,2,2-trinitroethylsulfuric acid affords a low yield
of 5 (˂40%). Enhancing of temperature from 60 °C to 80 °C is
favorable to improve yield of 5 to 86 %. Further increase of
temperature resulted in yield decline, which could be attributed to
the decomposition of 1 by the decarboxylation at 90-100 °C. In
addition, excess of 2,2,2-trinitroethanol (2-fold) and chlorosulfonic
acid (3-fold) were used to increase the reaction rate and they are
easily removed by washed with cold water. Bis(2,2,2-trinitroethyl)
4,6-dinitroisophthalate (6), bis(2,2,2-trinitroethyl) 2,5-
Results and discussion
Synthesis
In general, trinitroethyl esters were synthesized from the
esterification of carboxylic acids and 2,2,2-trinitroethanol in three
pathways (scheme 3). The primitive way is to adopt the so-called
sulfuric acid catalyzed esterification, such as the direct reaction of
benzoic acids with the easily available 2,2,2-trinitroethanol in the
sulfuric acid medium at high temperatures (scheme 3, pathway a).
An alternative to this is the nucleophilic substitution of chlorine
atoms in active benzoic acid chlorides with 2,2,2-trinitroethanol
(scheme 3, pathway b). The third and effective route, is by
transesterification of trinitroethylsulfuric acid with aromatic acids
(scheme 3, pathway c). However, the low reactivity of polynitro
alcohol requires the use of a strong condensing agent or a reactive
carboxylic acid derivative to effect reaction. Initially, we did not
succeed in isolating the desired polynitro benzoic acid chlorides to
2
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dinitroterephthalate
trinitroisophthalate (
(
7
)
and bis(2,2,2-trinitroethyl) 2,4,6- to 98.028(208)°, this shows that a very distorted system is formed
8
3
) can also be obtained from the reaction by the benzene ring and the branch appendage. The length of the
of aromatic acids
in the similar way.
2,
or
4
with 2,2,2-trinitroethylsulfuric acid C8-O3 bond is 1.435 Å, shows typical C-O single bond value, which is
longer than that of C7-O3 (1.337(2) Å) due to the strong electron-
withdrawing influence of the carbonyl group. As shown in Fig.
Spectroscopy
2, crystal packing of
5 shows that the 3D network is criss-
The structures of the new polynitro derivatives 5-8 are crossed. It can be clearly seen that intermolecular hydrogen
1
supported by IR, H and 13C NMR spectroscopic data as well as bonds between the CH2 group and the oxygen atoms of nitro
elemental analysis. In the IR spectra of
asymmetric stretching vibrations νas NO2 are found in the information about crystal
range of 1638–1539 cm-1 and the symmetric stretching Supplementary Information (ESI).
vibrations νs NO2 at 1310-1295 cm-1. The signals lie in the An appropriate crystal of
for X-ray analysis was obtained
5-8
, the characteristic group, C8−H8A
…
O5 and C8−H8B
… O4. Additional
5
can be found in the Electronic
6
range of 1678–1600 cm-1 representing the stretching from dichloromethane, and the structure was determined by
vibrations of C=O, strong absorption peaks at 1350-1010 cm-1 low-temperature X-ray diffraction (Fig. 3). It crystallizes in the
are attributed to the C-O bond of the ester groups. The monoclinic space group P21/c with four formula units in the
vibration around 3100 cm-1 and 1400 cm-1 can be interpreted unit cell (Z= 4) and the calculated density is 1.815 g cm-3 (173 K).
as the stretching vibrations of methylene groups as well as The esteryl groups are twisted out of the benzene ring plane with
signals for valence vibrations of C–H in the polynitro benzene torsion angles of C5–C4–C7–O5, 71.074(231)°; C1–C6–C10–O13, -
ring around 2900 cm-1.
For compounds
, in the 1H NMR spectra, the hydrogen hydrogen bonds and distinction between C1-NO2 group and C3-NO2
38.722(260)°. It is seen that the molecule is asymmetric due to the
5-8
signals of the methylene groups, which are attached to the group in the benzene ring. Therefore, there are small differences
ester side chains appeared between δ = 6.23 and 6.30 ppm. in the parameters of the bond lengths, the N–O bonds in C1-
For compounds
benzene rings are located in the range of δ = 9.43 to 9.49 ppm, significantly longer than that of C3-NO2 moiety (1.179(11)-
which are at a little lower field than that of compounds (δ = 1.197(11)), because of the C3-NO2 has a unstable structure and
8.89, 8.82 ppm) and (δ = 8.66 ppm) owing to the electron- a spatial range of oscillation. In the packing diagram of intra-
withdrawing property of the additional nitro groups. In the 13C molecular hydrogen bond (C8−H8B
O6) and intermolecular
NMR spectra of all compounds, the carbon resonance signals hydrogen bonds (C2−H2 O7, C5−H5 O17, C8−H8B O6,
of the trinitromethyl moieties can be found as weak peaks C11−H11A O14, C11−H11B O16) are observed. These extensive
around the chemical shifts of 125 ppm, which is in good hydrogen-bonding interactions form a complex 3D network within
5 and 8, the proton signals of polynitro NO2 moiety are in the range of 1.218(2)-1.222(2) Å and are
6
7
6,
…
…
…
…
…
…
agreement with previously recorded shifts for similar the structure of
compounds. Moreover, the carbon atoms of the methylene
6.
moiety are identified at δ = 63.46 (
highest field while the carbon signals of carbonyl groups are
observed in a range from δ = 159.34 ( ) to 161.25 ppm ( ).
Four distinct peaks are observed in the polynitroaryl moiety
belong to compounds and
in the 13C NMR spectra, the
resonances of two carbon atoms appear around 149 ppm, and
another two nearly 127 ppm. However, for compounds and
only one carbon signal of the polynitroaryl group locates in the
lower field around 150 ppm and another two ( ) or three (
7) to 64.58 ppm (8) at the
8
6
5
8
6
7,
7
6)
can be detected between δ = 122 and 134 ppm. It can be
attributed to the fact that the electron-withdrawing inductive
effect of trinitroaryl moiety is stronger than dinitroaryl moiety.
Fig. 1 Molecular structure of 5. Hydrogen atoms are shown, but are
unlabeled for clarity.
X-ray crystallography
Single crystals of 5, 6, 7 and 8, suitable for single-crystal X-ray
diffraction, were obtained by slow solvent evaporation method at
room temperature and normal pressure. Selected crystallographic
data are summarized in Table 1. Their structures are shown in Fig.
1-8.
Crystals of
recrystallization from the component solvent of dichloromethane
and n-hexane. It crystallizes in the monoclinic space group 21/c,
5 suitable for crystal-structure analysis were obtained by
P
with a cell volume of 1508.4(2) Å3 and four molecules per unit cell.
A calculated density of 1.850 g cm-3 was determined from the X-ray
crystal structure at 173 K. The torsion angle of O3-C7-C2-C1 is equal
Fig. 2 Ball and stick packing diagram of 5 viewed down the b axis. Dashed
lines indicate strong hydrogen bonding.
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Table 1 Crystallographic data for 5, 6, 7 and 8
Crystals
Formula
5
6
7
8
C9H4N6O14
C12H6N8O20
C12H6N8O20
C12H5N9O22
Formula weight
420.18
582.25
173(2) K
monoclinic
P21/c
582.25
173(2) K
monoclinic
P21/c
627.25
Temperature
173(2) K
173(2) K
Crystal system
monoclinic
monoclinic
Space group
P21/c
P21/c
a(Å)
5.8335(4)
14.3744(16)
8.2651(10)
19.305(2)
90
12.9246(18)
10.0302(15)
8.6402(12)
90
13.8583(10)
b(Å)
10.1818(8)
16.6279(13)
c(Å)
25.563(2)
10．0771(6)
α(°)
90
90
β(°)
96.540(3)
111.692(3)
90
106.913(3)
90
103.879(2)
γ(°)
V (Å3)
90
90
1508.4(2)
2131.2(4)
4
1071.6(3)
2
2254.3(3)
Z
4
1.850
4
1.848
ρcalc (g·cm-3)
GOF on F2
FinalR indexes [I>2σ(I)]
Final R indexes
CCDC
1.815
1.804
1.026
1.027
1.043
1.041
R1 = 0.0362, wR2 = 0.0752
R1 =0.0680, wR2 =0.0866
1447319
R1 = 0.0380, wR2 = 0.0657
R1 = 0.0799, wR2 = 0.0759
1447314
R1 = 0.0426, wR2 = 0.0872
R1 =0.0619, wR2 = 0.0955
1447110
R1 = 0.0398, wR2 = 0.0724
R1 =0.0816, wR2 = 0.0847
1447316
crystallizes in the monoclinic space group
that of , means the molecule packing of
Intuitively, the density of is lower than that of
P21/c with a higher than
6
7
is less compact.
7
6. As shown in Fig.
6, the hydrogen bonds are observed in the packing diagram. The
oxygen atoms (O4, O7 and O10) in the trinitromethyl groups
are involved into the formation of the non-classical hydrogen
bonds with the CH2 fragments ( C3−H3
C5−H5B O4 ) formed a complex 3D network.
crystallizes from dichloromethane in a monoclinic
21/ with four molecules per unit cell. The calculated
owing to the
addition of a nitro group. The C-C bonds of the benzene ring in are
slightly longer than the corresponding bonds in due to the strong
…O10, C3−H3…O7 and
…
Compound
8
space group
P
c
density is 1.848 gcm-3 (173 K), higher than that of
6
Fig. 3 Molecular structure of 6. Hydrogen atoms are shown, but are
unlabeled for clarity.
8
6
Fig. 4 Ball and stick packing diagram of 6 viewed down the b axis. Dashed
lines indicate strong hydrogen bonding.
Fig. 5 Molecular structure of 7. Hydrogen atoms are shown, but are
unlabeled for clarity.
Single crystals of
7 were obtained from acetonitrile solution. It
4
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energetic esters exhibit one exothermic process. Most of these
compounds show broad exothermic peaks, which indicate
extremely slow decomposition. Except for compound
6, which
decompose at 171.6 °C, the decomposition onset temperatures of
the other energetic compounds are observed in a range from 187.3
(8) to 193.2 °C (5), higher than that of trinitroethyl esters reported
( as showing in scheme 2 ).20 As known, a thermal stability above
180 °C is an essential requirement for energetic compounds to
adaptation for practical use.23-24 Compared to TNT and TATB,
compounds
5-8 have lower decomposition temperatures, the
Fig. 6 Ball and stick packing diagram of 7. Dashed lines indicate strong
hydrogen bonding.
undesirable thermal behavior maybe due to the introduction of
trinitromethyl moieties and esteryl structures.
The sensitivities of the resulting compounds 5-8 toward impact
and friction were tested by using standard BAM method.25 As
depicted in Table 2, the impact sensitivity (IS) values of
trinitroaryl derivatives (
5: 17.4 J,
8: 14 J) are lower than that of
dinitroaryl derivatives (
6: 20 J,
7: 22 J), because of the
presence of additional nitro moiety within their structures. All
compounds are less sensitive than RDX (7.5 J), and except for
the compound 8, the IS values of other polynitro compounds
are much higher than that of TNT (15 J). Moreover, similar
trends can be found at the friction sensitivity (FS) values, the
Fig. 7 Molecular structure of 8. Hydrogen atoms are shown, but are
unlabeled for clarity.
FS values of
5-8 are 280 N, 320 N, 360 N and 240 N,
respectively. Additional, all new compounds were tested for
sensitivity toward electrical discharge by an ESD JGY-50 III
electric spark tester.26 As illustrated in Table 2, the
electrostatic sensitivities (ESD) of polynitro derivatives
J), (0.30 J) and (0.32 J) were lower than that of RDX (0.10-
0.20 J). The ESD value of compound (0.20 J) is comparable to
that of RDX. Compared with the trinitroethyl esters have been
5 (0.28
6
7
8
described (as depicted in scheme 2), compounds
good sensitivities.
5-8 exhibit
The heat of formation (HOF) plays an important role in evaluating
the performance of energetic materials. The heats of formation of
the resulting compounds 5-8 were calculated based on appropriate
Fig. 8 Ball and stick packing diagram of 8 viewed down the b axis. Dashed
lines indicate strong hydrogen bonding.
isodesmic reactions. 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 functional with the 6-311 + G** basis set. All of the
optimized structures were characterized by true local energy
minima on the potential energy surface without imaginary
electron-withdrawing influence of the additional nitro group. The
geometry of the trinitromethyl moiety is consistent with that of the
similar moiety in the literature.22 The C-N bond lengths of the
trinitromethyl groups are in the range of 1.515-1.525 Å, longer
than that of normal C-N single bond (1.469(3)-1.480(3) Å),
located on both sides of the benzene ring. A similar difference
is also observed in other compounds. As illustrated in Fig. 8,
frequencies. As summarized in Table 2, the resulting compounds
exhibit unsatisfactory heats of formation. The calculated values
fall in the range from -534.9 ( ) , which are
) to -243.9 kJ mol-1
5-
8
7
(5
non-classical intermolecular hydrogen bonds C8–H8B
…O5 and
extremely negative due to the feature of esteryl backbones.
C11–H11…O19 were observed within the structure of
8 owing
By using the calculated values of the heats of formation and density
to the acidity of the methylene protons.
from gas pycnometer experiments, the detonation velocities (
D)
and pressures ( ) of compounds were calculated based on the
P
Energetic materials properties
empirical Kamlet-Jacobs (K-J) equations. The detonation
performance data are summarized in Table 2, the detonation
Thermal stability is one of the most important physicochemical
properties of energetic materials. The thermal behavior of all
products was investigated by differential scanning calorimetry (DSC)
at a heating rate of 5 °C min-1 in Al pans. The plots were shown in
velocities of compounds 5-8 range from 8267 (7 (8),
) to 8559 m s-1
which indicates that the detonation velocities of all are comparable
to that of TATB (8114 m s-1, 31.2 GPa). Their detonation pressures
the ESI. As summarized in Table 2, while
134.3 °C, 185.1 °C and 133.3 °C, and
5
,
7
and
do not melt prior to
and 7
8 were melting at
are found in the range between 30.4 (
7
) and 32.9 GPa (
8), in which
6
the highest detonation pressure value of
lower than that of RDX (34.9 GPa).
8
(32.9 GPa) is slightly
decomposition. In particular, the decomposition process of
6
possess two steps with the peak temperatures. However, the other
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Table 2 The physicochemical properties of
trinitroperhydro-1,3,5-triazine (RDX)
5
-
8
compared with trinitrotoluene (TNT), triaminotrinitrobenzene (TATB) and 1,3,5-
a
b
c
d
Tm
Td
ΩCO
ΩCO2
ρe
Df
Pg
△
Hfh
ISi
[J]
FSj
[N]
280
320
360
240
-
ESDk
Compounds
[°C]
134.3
-
[°C]
193.2
171.6
192.7
187.3
295
[100%]
11.43
13.75
13.75
19.14
-24.7
-18.6
0
[100%]
-22.86
-19.24
-19.24
-11.48
-73.8
[g cm-3]
1.839
1.807
1.792
1.832
1.654
1.94
[m s-1]
8389
8320
8267
8559
6881
8114
8795
GPa
31.7
30.9
30.4
32.9
19.5
31.2
34.9
[kJ mol-1]/[kJ g-1]
-243.9/-0.58
-504.2/-0.87
-534.9/-0.92
-500.3/-0.80
-295/-1.30
[J]
0.28
0.30
0.32
0.20
-
5
6
17.4
20
7
185.1
133.3
80.4
-
22
8
14
TNTl
TATBl
RDXm
15
324
-55.8
-154.2/-0.60
50
-
-
-
204
-21.6
1.80
70.3/0.32
7.5
120
0.10-0.20n
a Melting point. b Thermal decomposition temperature under nitrogen gas (determined by the DSC exothermal peak, 5 °C min-1). c Oxygen balance, assuming
the formation of CO; the oxygen balance of ammonium perchlorate is 34.0 %. d Oxygen balance (%) for CaHbNcOd: OB (%) = 1600
(d-2a-b/2)/Mw (based on
*
e
f
g
h
carbon dioxide). Density measured by gas pycnometer at 25°C. Detonation velocity. Detonation pressure. Calculated molar enthalpy of formation in
solid state. i Impact sensitivity. j Friction sensitivity. k Sensitivity against electrostatic discharge. l Data from ref. 27. m Data from ref. 28. n Data from ref. 29.
General methods
Conclusion
1H and 13C NMR spectra were recorded on 300 MHz (Bruker
AVANCE 300) nuclear magnetic resonance spectrometers operating
at 300 and 75 MHz, respectively, by using acetone-d6 as the solvent
and locking solvent unless otherwise stated. Chemical shifts in 1H
and 13C NMR spectra are reported relative to acetone. The
decomposition temperatures were determined by a differential
scanning calorimeter (DSC823e instruments) at a heat rate of 5 °C
min-1. Infrared (IR) spectra were recorded 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. The
electrostatic sensitivity tests were carried out with an Electric Spark
Tester ESD JGY-50 III. The sensitivities towards impact and friction
were determined by using a HGZ-1 drophammer and a BAM friction
tester.
A family of esteryl-bridged energetic compounds was synthesized
by polynitro benzoic acids and the 2,2,2-trinitrorthanol. All of the
new compounds were well characterized. Additionally, the
structures of them were confirmed by single-crystal X-ray
diffraction analysis. According to the DSC results, except for the
compound
6 (Td,onset = 171.6 °C), the decomposition onset
temperatures of other compounds are higher than 180 °C, which
indicates that these new energetic compounds possess good
thermal stabilities. In particular, compared with these esters have
been reported, compounds 5, 7 and 8 are potential candidates for
energetic materials with good thermal stabilities owing to the
existence of multi-nitrophenyl structures. As known, oxygen
balance (OB) is an important parameter to classify energetic
materials, trinitroethyl group introduced into materials is helpful to
enhance the oxygen balance. Assuming the formation of CO2, OB
values of the polynitro esters in the range from -22.86 % to -
11.48 %, which are comparable to RDX (-21.6 %). Nevertheless,
based on CO, OB values of the polynitro esters are rising to the
range from 11.43 % to 19.14 %, much higher than that of RDX (0 %).
The calculated detonation velocities lie in the range between 8267
and 8559 m s-1. The detonation pressures range from 30.4 to 32.9
X-ray crystallography
The data for 5, 6, 7 and 8 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 173(2) K during the data collection. The data
collection and the initial unit cell refinement were performed by
using APEX2 (v2010.3-0). Data Reduction was performed by using
SAINT (v7.68A) and XPREP (v2008/2). Corrections were applied for
Lorentz, polarization, and absorption effects by using SADABS
(v2008/1). The structure was solved 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 solved by direct methods with SHELXS-97 and expanded by
using the Fourier technique. The non-hydrogen atoms were refined
anisotropically. The hydrogenatoms were located and refined.
GPa. Particularly, compounds
5 8
(31.7 GPa and 8389 m s-1) and
(32.9 GPa and 8559 m s-1) also exhibit moderate detonation
properties, which are significantly higher than those of TATB (31.15
GPa and 8114 m s-1). Additionally, for all energetic polynitro esters,
their impact sensitivity values are found in the range between 14 (
and 22 J ( ). The friction sensitivity values range from 240 ( ) to 360
N ( ), which shows that they are significantly less sensitive than RDX
8)
7
8
7
(7.5 J, 120 N). The simple synthetic route and the good detonation
properties of these compounds suggest potential application as
energetic materials.
Syntheses
Experimental
6
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ARTICLE
Journal Name
Caution: Although we experienced no difficulties in handling these for C12H6N8O20 (582.22): C 24.76, H 1.04, N 19.25; found C 24.12, H
energetic materials, small scale and best safety practices (leather 0.98, N 19.04 .
gloves, face shield) are strongly encouraged.
Synthesis of bis(2,2,2-trinitroethyl) 2,4,6-trinitroisophthalate (8)
2,4,6-trinitrobenzoic acid (
1
),30 4,6-dinitroisophthalic acid (
2
),31 2,5-
33
dinitroterephthalic acid (
3
), 32 2,4,6-trinitroisophthalic acid (
4
)
and A similar procedure was followed as that described above for
: 0.38 g, 1.25 mmol) was subjected
as brown solid in a yield of
6,
2,2,2-trinitroethanol34 were synthesized according to the literatures 2,4,6-trinitroisophthalic acid (
4
procedures.
to the same method to obtain 0.596 g 8
83 %. DSC: Td,onset = 187.3 °C. 1H NMR (300 MHz, Acetone-d6): δ =
9.46 (s, 1H, -CH-), 6.28 (s, 4H, -CH2-) ppm. 13C NMR (75 MHz,
Synthesis of 2,2,2-trinitroethyl 2,4,6-trinitrobenzoate (5)
2,2,2-trinitroethanol (0.9 g, 5.0 mmol) was added slowly to Acetone-d6) δ = 159.34 (-COO-), 149.10 (-C(NO2)(C(COO-))), 147.61
chlorosulfonic acid (0.5 mL, 7.5 mmol) at -10 °C. The reaction (-C(NO2)(C(COO-))(-CH-)), 127.88 (-C-C(COO-)), 127.75 (-CH-), 123.64
mixture was gradually warmed to 50 °C and stirred for 1 h, then (-C(NO3)3), 63.49 (-CH2-) ppm. IR (KBr): 3439(w), 3106(w), 3015(w),
2,4,6-trinitrobenzoic acid (1: 0.64 g, 2.5 mmol) was added, keeping 2964(w), 2895(w), 1777(s), 1604(s), 1550(s), 1439(m), 1390(m),
the temperature at 80 °C for 2 h, the reaction mixture was cooled to 1343(s), 1298(s), 1219(s), 1149(s), 1089(m), 1041(w), 924(w),
room temperature and poured on ice. The precipitate was filtered 854(w), 795(m), 736(m). Elemental analysis calcd (%) for C12H5N9O22
off, washed with water and dried in vacuo to afford 0.903 g yellow (626.95): C 22.98, H 0.80, N 20.10; found C 22.19, H 0.83, N 19.51 .
powder in a yield of 86 %. DSC: Td,onset = 193.2 °C. 1H NMR (300 MHz,
Acetone-d6) δ = 9.43 (s, 2H, -CH-), 6.29 (s, 2H, -CH2-) ppm. 13C NMR
Acknowledgements
(75 MHz, Acetone-d6) δ = 160.42 (-COO-), 150.08 (-C(NO2)(C(COO-))),
148.20 (-CNO2), 127.52 (-C(COO-)), 126.61 (-CH-), 125.00 (-C(NO3)3), This work was supported by the National Natural Science
64.37 (-CH2-) ppm. IR (KBr): 3547(s), 3011(w), 2964(w), 2893(w), Foundation of China (No. 21376121, No. 21676147), the
1764(s), 1613(s), 1550(s), 1459(m), 1438(m), 1344(s), 1304(s), Natural Science Foundation of Jiangsu Province (BK20151483)
1258(s), 1178(m), 1117(s), 1088(s), 1067(s), 926(m), 881(w), 850(w), and the Fundamental Research Funds for the Central
800(m), 781(m), 732(m). Elemental analysis calcd (%) for C9H4N6O14 Universities (No. 30916011314).
(420.16): C 25.73, H 0.96, N 20.00; found C 25.12, H 1.02, N 19.84 .
Synthesis of bis(2,2,2-trinitroethyl) 4,6-dinitroisophthalate (6)
Notes and references
2,2,2-trinitroethanol (0.9 g, 5.0 mmol) was added slowly to
chlorosulfonic acid (0.5 mL, 7.5 mmol) at -10 °C. The reaction
mixture was gradually warmed to 50 °C and stirred for 1 h, then 4,6-
1
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dinitroisophthalic acid (2: 0.32 g, 1.25 mmol) was added, keeping
the temperature at 80 °C for 2 h, the reaction mixture was cooled to
room temperature and poured on ice. The precipitate was filtered
off, washed with water and dried in vacuo to afford 0.582 g
yellowish powder in a yield of 80 %. DSC: Td,onset = 171.6 °C. 1H NMR
(300 MHz, Acetone-d6) δ = 8.89 (s, 1H, -CH(C-NO2) ), 8.84 (s, 1H, -
CH(C-COO)), 6.23 (s, 4H, -CH2-) ppm. 13C NMR (75 MHz, Acetone-d6)
δ = 161.25 (-COO-), 150.95 (-CNO2), 133.56 (-C(COO-)), 129.08 (-CH-
C(NO2)), 124.77 (-CH-C(COO-)), 122.46 (-C(NO3)3), 62.42 (-CH2-) ppm.
IR (KBr): 3503(w), 3112(m), 3056(m), 3018(m), 2968(m), 2892(m),
1763(s), 1598(s), 1549(s), 1437(m), 1387(m), 1350(s), 1296(s),
1235(s), 1183(m), 1153(m), 1116(m), 852(w), 832(w), 799(s), 778(s).
Elemental analysis calcd (%) for C12H6N8O20 (582.22): C 24.76, H 1.04,
N 19.25; found C 24.12, H 0.98, N 19.04 .
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A similar procedure was followed as that described above for
dinitroterephthalic acid ( : 0.32 g, 1.25 mmol) was subjected to the
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8.89 (s, 1H, -CH(C-NO2) ), 8.84 (s, 1H, -CH(C-COO)), 6.23 (s, 4H, -CH2-)
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CNO2), 133.56 (-C(COO-)), 129.08 (-CH-C(NO2)), 124.77 (-CH-C(COO-
)), 122.46 (-C(NO3)3), 62.42 (-CH2-) ppm. IR (KBr): 3503(w), 3112(m),
3056(m), 3018(m), 2968(m), 2892(m), 1763(s), 1598(s), 1549(s),
1437(m), 1387(m), 1350(s), 1296(s), 1235(s), 1183(m), 1153(m),
1116(m), 852(w), 832(w), 799(s), 778(s). Elemental analysis calcd (%)
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Four polynitro esters were derived from 2,2,2-trinitroethanol with multi-nitrobenzoic
acids by transesterification.