Conjugated energetic salts based on 3,3′-((1E,1′E)-(2,4,6-trinitro-1,3-phenylene)bis(ethene-2,1-diyl))bis(2,4,6-trinitrophenol)

Article abstract of DOI:10.1039/c4nj01091d

Based on a design strategy that has resulted in conjugated energetic materials, 3,3′-((1E,1′E)-(2,4,6-trinitro-1,3-phenylene)bis(ethane-2,1-diyl))bis(2,4,6-trinitrophenol) and its nitrogen-rich salts were obtained and characterized via spectral and elemental analyses. These new molecules exhibit good thermal stability (T_d = 268.4-311.3 °C), especially for hydrazinium salt 4c, which is comparable to that of the benchmark HNS. Also, they exhibit low impact sensitivity (>40 J), high density (1.67-1.88 g cm^-3), acceptable detonation properties (7268-8527 m s^-1, 26.7-34.1 GPa) and brisance parameters (103.9-144.4). The energetic properties of the salts suggest potential applications to new energetic materials.

Full text of DOI:10.1039/c4nj01091d

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DOI: 10.1039/C4NJ01091D
Conjugated Energetic Salts Based on 3,3'-((1E,1'E)-(2,4,6-trinitro-
,3-phenylene)bis(ethene-2,1-diyl))bis(2,4,6-trinitrophenol)
1
Junhui Xu, Jianping Wei, Fangmei Li, Qingguo Ma and Xinhua Peng*
Colour graphic:
Highly conjugated energetic salts exhibit remarkable thermostability and insensitivity.

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PAPER
Conjugated Energetic Salts Based on 3,3'-((1E,1'E)-(2,4,6-
trinitro-1,3-phenylene)bis(ethene-2,1-diyl))bis(2,4,6-
trinitrophenol) †
Cite this: DOI: 10.1039/x0xx00000x
a
a
a
a
a
Junhui Xu, Jianping Wei, Fangmei Li, Qingguo Ma and Xinhua Peng*
Received 00th January 2012,
Accepted 00th January 2012
Based on a design strategy that has resulted in conjugated energeticmaterials, 3,3'-((1E,1'E)-(2,4,6-trinitro-
1
,3-phenylene)bis(ethane-2,1-diyl))bis(2,4,6-trinitrophenol) and its nitrogen-rich salts were obtained and
characterized via spectral and elemental analyses. These new molecules exhibit good thermal stability (T
268.4–311.3 °C), especially for hydrazinium salt 4c, which is comparable to that of the benchmark HNS.
DOI: 10.1039/x0xx00000x
www.rsc.org/
d
=
-3
Also, they present low impact sensitivity (> 40 J), high density (1.67–1.88 g cm ), acceptable detonation
-1
properties (7268–8527 m s , 26.7–34.1 GPa) and brisance parameters (103.9–144.4). The energetic
properties of the salts suggests potential applications to new energetic materials.
Introduction
more nitro groups. The presence of nitro groups tends to decrease the
Energetic materials form an integral part of weapon systems as well heat of formation, but contributes greatly to the overall energetic
as a large number of new high energy density materials (HEDMs) performance. Also, the nitro group enhances the oxygen balance and
including thermally stable explosives, high-performance explosives, density, which improves the detonation performances (pressure and
[7]
melt-castable explosives, insensitive high explosives and energetic velocity). Conventionally, nitroaromatic compounds such as 2,4,6-
[1]
binders have been reported in the literature in recent years.
Synthesis chemists are combining their long-held expertise in combustion of the carbon backbone, while consuming the oxygen
trinitrotoluene (TNT) and TATB produce energy mainly from the
[3g, 8]
manipulating atoms and molecules with physical scientists and provided by the nitro groups.
engineers to create materials with designed functions. Much effort has
been expended to meet the main challenge of the desired combination
of large energy content with maximum possible chemical stability to
[2]
ensure safe synthesis and handling.
Energetic materials are
experiencing tremendous growth to meet the increasing demand for
high-performing materials with high thermal and mechanical stability
in the last decades.[3] In the quest for higher detonation performance
and lower sensitivity, energetic salts have gradually become a popular
choice, as these salts possess low volatility, high thermal stability.
Also, energetic salts with readily modified properties are usually
formed in a simple synthesis process. This provides a powerful
methodology for the design and synthesis of HEDMs for specific
purposes.
Recently, polynitro azoles have attracted more and more attention
due to their advantages of high detonation performance based on the
Fig. 1 Design of thermally stable energetic materials
In the continuing effort to seek more powerful, less sensitive,
thermally stable energetic materials, we intended to extend the
[4]
presence of polynitro groups and high-nitrogen content.
[9]
Unfortunately, compounds in this category also appear to have limits, chemistry of BiHNS-like compounds. The two C=C unsaturated
which include high impact sensitivity and low decomposition double bonds were introduced by Knoevenagel condensation between
[4b, 5]
2,4,6-trinitro-m-xylene (TNMX) and two equivalents of aromatic
temperature in particular.
Nitroaromatic compounds (e.g.
aldehydes in boiling benzene with piperidine catalyzed. The
hexanitrostilbene (HNS) and 1,3,5-triamino-2,4,6-trinitrobenzene
(
TATB)) as traditional energetic materials, have received special condensed products with the expanding π-π conjugation effect
[6]
attention because of their ability to withstand the high temperatures.
facilitated the application. Since the performance of the energetic
(
Figure 1) The examples of imparting higher thermal stability through materials was affected by the introduction of additional energetic
the introduction conjugation and delocalization effects in explosive groups, further introduction of nitro groups into the benzene rings
molecules are HNS and 1,1-diamino-2,2-dinitroethene (FOX-7). should be worthwhile. However, the electrophilic nitration of benzene
Based on structure-performance relationships, introduction of rings in nitrostilbenes was generally accompanied by the oxidization
[
10]
of the C=C double bond. Thereby the synthesis and isolation of
conjugation effects can improve the thermal stability of explosive
molecules. Our aimed design was a combination of conjugation and
[1b]
such energetic materials with more nitro groups introduced and the
This journal is © The Royal Society of Chemistry 2013
J. Name., 2013, 00, 1-3 | f1

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sound C=C double bond existed usually pose an interesting but
challenging design strategy.
Similarly, the synthesis of 3,3'-((1E,1'E)-(2,4,6-trinitro-1,3-
phenylene)bis(ethene-2,1-diyl))diphenol from the direct condensation
Since
((1E,1'E)-(2,4,6-trinitro-1,3-phenylene)bis(ethene-2,1- TNMX with 3-hydroxy-benzaldehyde in benzene solution with
diyl))dibenzene (1) could not be nitrated to the nona-nitro derivative piperidine as catalyst was very difficult. Better results were obtained
directly, an hydroxyl group, a strong electron donating substituent, with 1, 4-dioxane as cosolvent and portionwise addition of piperidine.
was introduced into the meta-position of the unnitrated ring to Phenolic substrates which undergo oxidative side reactions could also
enhance the reactivity of its ortho-para positions in a post nitration pose a serious problem. Sulfonic acid groups were electron
reaction. The strong electron-withdrawing effects of the nitro group withdrawing and moderated the nitration step as well as protected the
could deprotonate hydroxyl to form energetic salts when paired with substrate from oxidation. The condensation product 3,3'-((1E,1'E)-
bases. To our knowledge, a few nitroaromatic anion-based energetic (2,4,6-trinitro-1,3-phenylene)bis(ethene-2,1diyl))diphenol was heat-
[
11]
salts have been reported: energetic salts of picric acid
,
ed on a steam bath with excess oleum before nitration. The two-steps
[12]
[13]
dipicrylamine and trinitrophloroglucinol . Our contribution thus sulfonation-nitration processes provided a versatile method for the
lies in the synthesis of the previously unknown 3,3'-((1E,1'E)-(2,4,6- synthesis of 4 and the carefully controlled temperature in this reaction
trinitro-1,3-phenylene)bis(ethene-2,1-diyl))bis(2,4,6-trinitrophenol)
4) as well as its related ionic derivatives. The compounds were
was very important (Scheme 2).
(
characterized using infrared, MS, multinuclear NMR spectroscopy
and elemental analysis. The potential application of the synthesized
compounds of energetic materials was studied and evaluated using the
values obtained in our experiment for the thermal decomposition and
the impact sensitivity data as well as the calculated performance
characteristics.
Scheme 2 Synthesis of 3,3'-((1E,1'E)- (2,4,6- trinitro-1,3-phenylene)bis
(ethene-2,1-diyl))bis (2,4,6-trinitrophenol)
Results and Discussion
The formation of the nitrogen- rich and metal salts (4a−m) was
straightforward. A methanolic solution of the compound 4 was
prepared, and two equiv of the corresponding nitrogen-rich base or
metallic salts were added (Scheme 3). Due to the high solubility of 4
and the low solubility of compounds 4a−m in methanol, all nitrogen-
rich as well as metal ionic derivatives could be isolated in excellent
yields and high purity.
Synthesis
Initially, ((1E,1'E)-(2,4,6-trinitro-1,3-phenylene)bis(ethene-2,1-diyl))
dibenzene (1) was selected as an precursor for the preparation of new
energetic materials BiHNS. The generation of
Knoevenagel condensation between benzaldehyde and TNMX which
was obtained from one-pot nitration of m-xylene at elevated
temperatures in mixed acid. 2,2'-((1E,1'E)-(2,4,6-trinitro-1,3-
phenylene)bis- (ethene-2,1-diyl))bis(nitrobenzene) (2) was achieved
with high selectivity in a solution of nitric acid and acetic anhydride
at the room temperature. Then, nitration of 2 with concentrated
sulfuric and fuming nitric acid yields 4,4'-((1E,1'E)-(2,4,6-trinitro-
1 from the
1
,3-phenylene)bis(ethene-2,1-diyl))bis(1,3-dinitro-benzene) (3) in
acceptable yields (Scheme 1). However, initial nitration directly from
in mixed acid failed to afford the product 3. A strong nitrating agent
1
would lead to many by-products, although the reaction conducted at a
low temperature. The pre-existing nitro groups in aromatic rings were
advantageous by making the C=C double bonds less prone to
oxidation. As more nitro groups were introduced, the C=C double
bonds became more electron deficient and deactivated toward the
electrophilic attack. Also, it was found that conducting the further
Scheme 3 Synthesis of ionic derivatives based on the 3,3'-((1E,1'E)- (2,4,6-
trinitro-1,3-phenylene) bis(ethene-2,1-diyl))bis(2,4,6-trinitrophenol) anion
Spectroscopy
All compounds were fully characterized by IR as well as
nitration of 3 under different conditions, failed to give the final multinuclear NMR spectroscopy, mass spectrometry, elemental
product BiHNS.
analyses and differential scanning calorimetry. The NMR
spectroscopic data of all the salts were collected in DMSO-d . H
6
1
NMR spectroscopic coupling signals assigned to -CH=CH- double
bonds were about 16.60 Hz, which determined the (E)-configuration.
-1
Besides, the infrared spectrum exhibited a band around 970 cm
which refers to C-H deformation in trans -C=C-. For compound 4, the
position of the resonance bands for the protons in the middle of the
benzene ring were observed as a singlet at 8.96 ppm and a signal at
8.74 ppm for the protons on both sides of the benzene rings in the low
field. The signal for hydroxyl group occurred as a weak broad singlet
13
at 8.27 ppm. In the C NMR spectra, the signals at δ= 159.4, 149.1,
Scheme 1 Synthesis of 4,4'-((1E,1'E)-(2,4,6-trinitro-1,3-phenylene)
1
1
47.1, 147.0, 136.0, 130.4, 127.7, 127.7, 125.5, 123.8, 121.9 and
20.4 ppm.
bis(ethene-2,1-diyl))bis(1,3-dinitrobenzene)
2
| J. Name., 2012, 00, 1-3
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ARTICLE
The deprotonation of 4 with nitrogen-
Table 1 Physical properties of 3,3'-((1E,1'E)-(2,4,6-trinitro-1,3-phenylene)bis (ethene-2,1-diyl))bis(2,4,6-
trinitrophenol) (4) and its energetic salts (4a–m) in comparison to other typical energetic materials
rich bases did not have a major effect on
13
1
Tm [a]
Td [b]
D [c ]
OB [d]
ΔfHLat [e]
ΔfH [f]
IS [g]
P [h]
vD [i]
Bri [ j]
signal shifts in the C NMR and H
NMR spectra. On the basis of the values
of the chemical shifts of ammonium
Entry
3
4
226
210
275.1
268.3
1.67
1.88
-95.0
-63.4
-
-
- 69.4
＞40
21.9
26.6
6313
7043
84.7
(
(
(
4a), hydroxylamine (4b), hydrazine
4c), guanidine (4d), aminoguanidine
4e), diaminoguanidine (4f), triamino-
-129.6
31
112.2
4
4
a
dec
245
dec
dec
241
206
210
dec
dec
263
dec
dec
dec
80.4
318
324
282
300.4
299.8
311.3
290.7
272.1
269.5
268.4
291.7
293.2
288.6
290.2
298.1
295.3
295
1.78
1.81
1.79
1.73
1.69
1.74
1.68
1.82
1.68
-
-66.9
-60.1
-66.4
-71.6
-71.0
-70.4
-69.9
-65.8
-76.8
-
936.7
139.1
234.5
438.7
264.0
290.6
495.5
723.9
356.6
350.9
-
＞40
＞40
＞40
＞40
＞40
＞40
＞40
＞40
＞40
-
28.5
29.2
31.4
30.3
30.8
33.9
34.1
30.8
26.7
-
7471
7574
7971
7838
7981
8427
8527
7822
7268
-
114.2
119.3
121.3
123.2
130.2
137.3
144.4
121.2
103.9
-
b
927.5
guanidine (4g) and urea (4h) moieties,
+
+
NH, NH
2
, NH
2
, and NH
3
groups could
4c
924.3
1
be assigned to the resonance peaks in H
NMR spectrum. However, in some of
these energetic salts, the number of
active hydrogen atoms was found less
than the suggested theoretical value. For
example, the protons of ammonium
4
4
4
4
d
e
f
887.8
867.2
865.5
g
842.1
14
cation appeared coupling to N as a
triplet at 7.08 ppm with coupling
constant 51.10 Hz and the number of the
protons were about four rather than
eight. It might be attributed to the
exchange of active hydrogen atoms and
was confirmed by deuterium exchange
4h
905.2
4
4
4
4
i
902.1
j
k
l
-
-
-
-
-
-
-
-
-
-
-
25
-
-
-
-
-
-
24
-
-
-
1
experiments in the H NMR spectrum.
4m
-
-
-
15
-
-
-
1
From the
H
NMR signals of
TNT[3d]
HNS[14]
TATB[5a]
HMX
1.65
1.74
1.93
1.94
-74.0
-67.5
-55.8
-21.6
-67.0
-67.8
-140
104.8
15
19.5
20.1
31.2
39.6
6881
7000
8114
9320
100
101.6
107
155
methylamine and pyridine salts (4i and
j), it was noted that the deprotoned 4
332
5
4
was well combined with two equiv of the
amines. The carbon signals in nitrogen-
324
50
287
7.4
13
rich cations could be found in C NMR
spectra. Mass spectrometry and
elemental analyses well verified the
structure. The measured values of the
molecular weight for the energetic salts,
[a] Melting point [°C]. [b] Thermal degradation temperature (onset) under nitrogen gas (DSC, 5 °C /min) [°C]. [c]
-
3
[d]
Measured density (gas pycnometer, 25 °C) [g cm ]. Oxygen balance, the compound with the molecular formula
[e]
of CaHbNcOd, OB(%) = 1600[(d - 2a- b/2)/ Mw] [%]; Mw = molecular weight. Calculated molar lattice energy
KJ mol ]. Calculated heat of formation [KJ mol-1]. [g] Impact sensitivity [J]. According to UN recommendations
on the transport of dangerous goods: Impact: insensitive ≥ 40 J, less sensitive ≥ 35 J, sensitive ≥ 4 J, very sensitive
3 J. [h] Calculated detonation pressure [GPa]. [i] Calculated detonation velocity [m s-1]. [j] The calculated brisance
relative to TNT [15] ( = 100).
-
1
[f]
[
7
18 or 719, were in excellent accordance
with molecular weight of the energetic
anion.
≤
degree to which an explosive could be oxidized. The sensitivity,
strength, and brisance of an explosive are all somewhat dependent
upon oxygen balance and tend to approach their maximum values as
the oxygen balance approaches zero. Although all of the salts
described in this paper had negative OB values, all of them presented
better oxygen balance than TNT (-74%) except 4i (-76.8%). As shown
in Table 1, 4b exhibited the least negative oxygen balance of -60.1%.
Densities of the energetic materials were measured with a gas
Physicochemical Properties: Thermal Stability, Heat of
Formation, and Detonation Parameters.
The phase transition temperatures and thermal stability of all the
compounds were studied using differential scanning calorimetry
(
DSC) and digital micro-melting point apparatus (Table 1). All of the
synthesized compounds melted more than 200 °C and prior to
decomposition. Among the 4-based salts, aminoguanidinium salt 4f
showed the lowest melting point (206 °C), whereas the melting points
of hydroxylaminium salt 4b, diaminoguanidinium salt 4e as well as
pyridinium salt 4j were higher than 240 ℃ . The decomposition
temperatures of all ionic compounds were higher than that of
compound 4 in the range from 268.4 °C (4g) to 311.3 °C (4c). The
hydrazinium salt 4c showed the highest decomposition temperature
-3
pycnometer, and found in the range of 1.67–1.88 g cm , which
seemed the densities of salts were lower than that of the parent
-3
compounds 4 (1.88 g cm ). Nevertheless, they were much higher than
-
3
-
the density of TNT (1.65 g cm ) and comparable to HNS (1.74 g cm
3
)
. Among the ionic salts, uronium salt (4h) had the highest density at
.82 g cm . The relatively high densities were presumably ascribed
-3
1
to the high symmetry of the anion and the extensive intra- and
intermolecular hydrogen bonds in these salts.
among the salts (T
benchmark HNS (T
95 °C) and HMX (T
d
= 311.3 °C), which was comparable to the
= 332 °C) and superior to those of TNT (T
d
= 287 °C). Decomposition of explosives might
d
d
=
Impact sensitivity measurements were made by using standard
BAM Fall hammer techniques with 40.0 mg samples. The parameters
of impact sensitivity ranged from 15 J to greater than 40 J. Neutral
compound 4 had an impact sensitivity of 31 J. Salts 4a-i were
insensitive (>40 J), whereas the metallic salts 4k-m were sensitive to
impact, detonating in a loud noise. In general, all of the nonmetallic
energetic salts might be served as candidates for energetic materials.
2
be caused by the reactions in or between molecules at a certain
temperature. They exhibited excellent thermal stability (4a-d, 4h-m
nearly 300°C), which most likely could be attributed to the extensive
and strong hydrogen-bonding interactions and the conjugated system.
Oxygen balance (OB) was an expression that used to indicate the
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The heat of formation was another important parameter to be
considered in the design of energetic salts, obtained by calculations
with Gaussian 03 (Revision D.01) suite of programs. Recently,
significant progress had been made in the theoretical prediction of
where ΔH
L
is the lattice energy of the salts, which could be predicted
[19]
by using the formula suggested by Jenkins et al . [Equation (2)]:
[14, 15]
thermal properties of energetic salts.
The calculated standard
-1
enthalpies of formation for the anion of 4 was -177.0 kJ mol , which
was obtained on the basis of isodesmic reactions and Born–Haber
cycles. The triaminoguanidinium salt possessed the highest heats of
depend on the nature of the ions M p+and
X
In this equation, n
M
and n
q-
X , respectively, and are equal to three for monoatomic ions, five for
-1
formation when paired with the anion (4g: 723.9 kJ mol ). Also, the
diaminoguanidinium salt 4f owned a higher heats of formation of linear polyatomic ions, and six for nonlinear polyatomic ions. The
-1
4
95.5 kJ mol . Ammonium salt 4a possessed large lattice energies, equation for lattice potential energy U [Equation (3)] has the form:
pot
-3
which lead to low positive heats of formation of the salts. As where ρ [g cm ] is the density, M is the chemical formula mass of
m
m
[16]
-1
calculated by Zhu et al. , it showed that the heat of formation of a the ionic material, and values for the coefficients γ [kJ mol cm] and
-1
-1
cation or anion increases as the number of nitrogen atoms increases δ [kJ mol ] are taken from the literature, they are 8375.6 kJ mol cm
-1
[16, 19-20]
and nitrogen-nitrogen bonds usually contribute a lot to positive heat and -178.8 kJ mol , respectively.
of formation.
the anion of 4 were computed by using the method of isodesmic
The heats of formation of
-1
The detonation velocity vD [m s ] and pressure P [GPa] were the reactions and protonation reaction (Scheme 5 and Scheme 6).
most important parameters for evaluating the detonation
characteristics of energetic materials. These parameters were directly
related to the density and heat of formation. They were obtained by
calculation using Kamlet–Jacobs equations [Eqs. (4), (5) and (6), see
below]. As shown in Table 1, for the 4-based salts, the calculated
detonation pressures lied in the range of 26.7–34.1 GPa, which were Scheme 5 Isodesmic reactions for calculations of heats of formation.
higher than that of TNT (19.5 GPa). The calculated detonation
-1
velocities fall in the range of 7268–8527 m s , which were better than
-1
-1
that of TNT (6881 m s ) and HNS (7000 m s ). Thus, the salts could
be acted as competitive energetic materials.
The brisance parameter could be directly related to detonation Scheme 6 Protonation reactions for calculations of heats of formation.
pressure or detonation velocity and indirectly to heat of detonation. It
was indicated that the detonation performance of energetic The enthalpy of reaction is obtained by combining the MP2/6-311 +
compounds was dependent on their molecular structure. Mohammad + G** energy difference for the reaction, the scaled zero-point
Hossein Keshavarz[17] reported a reliable and simple method for the energies, and other thermal factors. Thus, the heats of formation of the
prediction of the brisance through with the general formula C
H
a b
N O
c d
.
species being investigated can be readily extracted. With values of the
As shown in Table 1, the calculated brisance of 4-4i ranges between heats of formation and densities, the detonation pressure (P) and
1
03.9 (4i) and 144.4 (4g), which were comparable with currently used velocity (vD) were calculated based on Kamlet–Jacobs equations
[7b, 7c]
explosives (TNT: 100, HNS: 101.6, TATB: 107).
[Equations (4) and (5)]:
Theoretical study: Calculations were performed with the Gaussian
0
3 (Revision D.01) suite of programs.[18] The geometric optimization
of the structures were carried out by using the B
3
LYP functional with
6
-31+ G** basis set, and single energy points were calculated at the
a b c d
For the compounds with the molecular formula of C H O N , 2a +
b/2 > c ≥ b/2 (suitable for all the salts in this study), Q can be
calculated according to Equation (6):
MP2/6-311+ + G** level. All of the optimized structures were
characterized to be true local energy minima on the potential energy
surface without imaginary frequencies.
where P is the detonation pressure (GPa), D is the detonation velocity
3
(
km/s), ρ is the packed density (g/cm ), The measured density was
used for the calculation here. N is the moles of gas produced per gram
̅
of explosives, 푀 is the average molar weight of detonation products,
̅
and Q is the chemical energy of detonation (kJ/g). N, 푀, and Q are
decided according to the largest exothermic principle; i.e., for the
Scheme 4 Born–Haber cycle for the formation of energetic salts.
explosives with C H N O elements, all of the N atom converts into N
the O atom forms H O with the H atom first, and the remainder forms
CO with the C atom.
Also, the brisance parameters of pure energetic compounds were
based on the elemental composition. For the C energetic
2
,
2
For an ionic crystal with formula unit M
p q
X , where M denotes the
2
cation and X denotes the anion. The values of heats of formation for
[3d, 5b, 15d]
the cations are available in the literature.
Based on a Born–
a b c d
H N O
Haber energy cycle (Scheme 4), the standard heats of formation of a
salt can be simplified by the formula given in Equation (1):
compounds, the predicted data could be specified according to the
following Equation (7):
4
| J. Name., 2012, 00, 1-3
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ARTICLE
80 °C for 1 h and then elevated to 110 °C for 4 h. After cooling down
to room temperature the mixture was poured in to crashed ice (800.00
g). The precipitate was filtered and crystallized using 100.0 mL 2-
butanone to give a pure product as a white solid (19.30 g, 80%).
where Bris relTNT is the relative brisance with respect to TNT.
Conclusions
(
(1E,1'E)-(2,4,6-trinitro-1,3-phenylene)bis(ethene-2,1-
[
9]
diyl))dibenzene (1) Prepared according to the literature method.
Yellow solid, m. p. 149-150 °C, (lit. 149.5-151.1 °C), IR (ν, cm ):
In this work, we reported an efficient two–step nitration for the
syntheses of 4,4'-((1E,1'E)-(2,4,6-trinitro-1,3-phenylene)bis(ethene-
-
1
1
3
095, 1634, 1588, 1541, 1451, 1395, 1344, 968. H NMR (500MHz,
CDCl ), δ 8.72 (s, 1H), 7.50-7.37 (m, 10H), 7.20 (d, J = 16.60Hz, 2H),
.90 (d, J =16.60Hz, 2H).
,2'-((1E,1'E)-(2,4,6-trinitro-1,3-phenylene)bis(ethene-2,1
2
,1-diyl))bis(1,3-dinitrobenzene) (3) as well as 3,3'-((1E,1'E)-(2,4,6-
trinitro-1,3-phenylene)bis(ethene-2,1-diyl))bis(2,4,6-trinitrophenol)
4) and its nitrogen-rich salts(4a-m), leading to thermally stable
energetic materials. Both the neutral compound and its salts exhibit
good thermal stability (T = 268.4–311.3 °C) and energetic properties
detonation velocity 7268–8527 m s , detonation pressure 26.7–34.1
3
6
2
(
diyl))bis(nitro-benzene) (2) To acetic anhydride (15.0 mL), initially
at room temperature, was added 68 % nitric acid (1.86 g, 20.0 mmol)
over a period of approximately 25 min, maintaining the temperature
about 25 °C. The nitration solution was then cooled to 10 °C and 2
drops of concentrated sulfuric acid was added as catalyst. Following
the addition of compound 1 (0.84 g, 2.0 mmol) in small portions, the
reaction mixture with rapid stirring at 30 °C. The solid was dissolved
first and then a green solid was formed after 5 min. The reaction
mixture then poured into 150.0 mL of water. Finally, after hydrolysis
of the acetic anhydride was complete, the product was collected by
filtration.
d
-1
(
GPa, brisance parameters 103.9–144.4) that exceed those of
conventional TNT. In addition, most of these compounds show higher
-3
density in the range of 1.67–1.88 g cm than TNT and are comparable
with HNS. Also, they were characterized with respect to impact
sensitivity, which exhibit low impact sensitivities (> 40 J). The good
property parameters meet the requirement of high temperature
explosives.
Green yellow solid (0.87 g, 86%), recrystallization from acetone, m.
Experimental Section
-1
p. 212-213 °C, IR (ν, cm ): 3097, 1629, 1603, 1550, 1524, 1341, 975;
1
H NMR (500MHz, DMSO-d
6
), δ 9.07 (s, 1H）8.09 (d, J =8.15Hz,
Safety Precautions
2
2
1
1
5
5
4
H), 7.86 (d, J=3.95Hz, 2H), 7.69-7.66 (m, 4H), 7.50 (d, J =16.45Hz,
13
H), 7.21 (d, J =16.45Hz, 2H); C NMR (126MHz, DMSO-d
6
), δ
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 using the best safety practices.
49.77, 147.23, 146.48, 133.59, 131.04, 129.89, 129.54, 128.33,
+
13 5
27.86, 124.23, 122.43, 121.96. HRMS calc. for C22H N O10 (M+H) :
08.0210, found (M+H) 508.0206, (M+ Na) 530.0121, (M+ K）
45.9988.
,4'-((1E,1'E)-(2,4,6-trinitro-1,3-phenylene)bis(ethene-2,1-
General Methods
All chemical reagents and solvents (analytical grade) were used as diyl))bis(1,3-dinitrobenzene) (3) Fuming nitric acid (1.33 g, 20.0
supplied unless otherwise stated. All experiments were monitored by mmol) was added slowly by funnel to a concentrated sulfuric acid
thin-layer chromatography (TLC), TLC plates were visualized by (20.0 mL) solution of compound 2 (1.01 g, 2.0 mmol）below 10°C.
1
13
exposure to ultraviolet light (254 nm). H and C spectra were The mixture was kept at room temperature, and gave a red-brown
recorded on a Bruker Avance III 500 MHz Digital NMR Spectrometer, solution. The reaction was quenched by pouring into 150.00 g of
using CDCl
reported in δ (ppm) values. Coupling constants were reported in hertz by filtration and crystallized by acetone to give a pure product.
3 6
or DMSO-d
as a solvent and the chemical shifts were crashed ice, and pale yellow solid was formed. The solid was collected
-
1
(
Hz). Mass spectra were obtained using an electrospray (ESI-TOF) Pale yellow solid (0.57 g, 48%), m. p.226-227 °C, IR (ν , cm ): 3098,
1
mass spectrometer 6500 Series and a Bruker Daltonics flexAnalysis 1625, 1608, 1555, 1530, 1342, 970; H NMR (500MHz, DMSO-d
instrument. Infrared spectra were recorded using Bruker Tensor 27 δ 9.10 (s, 1H), 8.79 (d, J =2.30Hz, 2H), 8.66-8.64 (dd, J =2.30Hz, J
with the sample dispersed in a KBr pellet and were reported in terms =8.65Hz, 2H), 8.11 (d, J =8.65Hz, 2H), 7.73 (d, J =16.45Hz, 2H), 7.26
6
),
1
2
-
1
13
of frequency of absorption (cm ). The melting points were (d, J =16.45Hz, 2H); C NMR (126MHz, DMSO-d
6
), δ 149.57,
determined on digital micro-melting point apparatus. The 147.00, 146.82, 146.71, 135.27, 129.95, 129.58, 129.38, 127.63,
+
decomposition points were recorded using differential scanning 125.33, 122.61, 119.80. HRMS calc. for C22
calorimeter (DSC). The following procedures were used in 597.0364, found (M+H) 597.0349, elemental analysis, calcd (%) for
experiments for each sample: cooling from 50 °C and heating to
14: C: 44.23; H: 1.86; N: 16.41; Found, C: 44.18; H: 1.82;
11 7
H N O14 (M+H) :
22 11 7
C H N O
-1
4
50 °C at 5 °C min . Densities were measured at room temperature N: 16.33.
using gas pycnometer. Elemental analyses were performed on a CE- 3,3'-((1E,1'E)-(2,4,6-trinitro-1,3-phenylene)bis(ethene-2,1-
40 Elemental Analyzer. Impact sensitivity (IS) was measured diyl))diphenol. To a mixture of 2,4,6-trinitro-m-xylene (1.21 g, 5.0
through using 10 kg mass dropped from 40 cm. Detonation pressures mmol), 3-hydroxybenzaldehyde (1.22 g, 10.0 mmol), and mixed
P) and detonation velocities (D) were calculated according to the solvents of benzene (30.0 mL) and dioxane (25.0 mL) in a 100 mL
4
(
Kamlet–Jacobs equations.
round-bottomed flask was added piperidine (1.0 mL) in portions and
the resulting mixture was heated to reflux using a condenser
connected through a Dean-Stark trap. The reaction mixture was a
Syntheses
2
,4,6-trinitro-m-xylene 21 m-Xylene (10.62 g, 0.10 mol) was added homogeneous solution at reflux temperature, initially a light orange
slowly to a mixture of concentrated sulfuric acid (50.0 mL) and color which gradually deepened to dark brown during the heating
fuming nitric acid (20.0 mL) below 20 °C. The mixture was heated at period. After 10 h at reflux, heating was discontinued and the solvents
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ARTICLE
New Journal of Chemistry
Journal Name
were collected to give the crude product. The bright yellow solid was 159.37, 149.07, 147.10, 146.94, 135.97, 130.39, 127.76, 127.72,
isolated via silica gel column chromatography (Hexane/ Ethyl 125.52, 123.85, 121.91, 120.47. Hydrogen/deuterium exchange
1
acetate= 5/1).
experiments, H NMR (500 MHz, D
2
O-DMSO-d
6
), δ 8.92 (s, 1H),
-1
Bright yellow solid (2.04 g, 91%), m. p. 194-196 °C, IR (ν , cm ): 8.72 (s, 2H), 7.03 (d, J =16.75Hz, 2H), 6.71 (d, J =16.75Hz, 2H). MS
400, 3095, 1635, 1609, 1586, 1514, 1395, 1323, 972; H NMR (FAB ): 717.8, elemental analysis, calcd (%) for C22H N O20: C:
15 11
1
−
3
(
500MHz, DMSO-d
6
), δ 9.60 (s, 2H), 9.00 (s, 1H), 7.29 (d, J = 35.07; H: 2.01; N: 20.45; Found, C: 35.00; H: 1.98; N: 19.59.
1
6.60Hz, 2H), 7.23 (t, J = 7.85Hz, 2H), 6.98 (d, J = 7.70Hz, 2H), 6.94 Dihydroxylammonium
3,3'-((1E,1'E)-(2,4,6-trinitro-1,3-
(
=
s, 2H), 6.81-6.78（dd, J
1
=8.10Hz, J
2
=1.75Hz, 2H), 6.78 (d, J phenylene)bis(ethene-2,1-diyl)) bis(2,4,6-trinitrophenolate) (4b)
13
-1
16.60Hz, 2H). C NMR (126MHz, DMSO-d ), δ 157.26, 149.90, Yellow solid (0.70 g, 89%), m.p. 245 °C, IR (ν , cm ): 3424, 3203,
6
1
1
45.98, 136.58, 135.74, 129.96, 129.49, 122.13, 117.87, 116.63, 3096, 1604, 1542, 1451, 1341, 1308, 1262, 1157, 1071, 1005, 964,
+
1
16.31, 112.99. HRMS calc. for C22
15
H N
O
3 8
(M+H) : 450.0968, 910, 825, 788, 755, 707. H NMR (500MHz, DMSO-d
6
), δ 10.08 (s,
found 450.0975, 511.0722( M+Na+K).
,3'-((1E,1'E)-(2,4,6-trinitro-1,3-phenylene)bis(ethene-2,1-
diyl))bis(2,4,6-trinitrophenol) (4) The addition of 3,3'-((1E,1'E)- DMSO-d
3H), 8.95 (s, 1H), 8.74 (s, 2H), 7.09 (t, J = 51.15Hz, 1H), 7.06 (d, J =
13
3
16.80Hz, 2H), 6.74 (d, J = 16.80Hz, 2H). C NMR (126MHz,
), δ 159.35, 149.07, 147.10, 146.95, 135.99, 130.42, 127.74,
6
−
(
2,4,6-trinitro-1,3-phenylene)bis(ethene-2,1- diyl))diphenol (2.25 g, 127.69, 125.50, 123.81, 121.88, 120.43. MS (FAB ): 718.0, elemental
5
.0 mmol) to 96% sulfuric acid (10.0 mL) produced a dark green analysis, calcd (%) for C22
15
H N
11
O
22: C: 33.64; H: 1.92; N: 19.62;
colored slurry. This slurry was chilled in an ice and water bath and 30% Found, C: 33.48; H: 1.88; N: 19.56.
oleum was added (15 mL) slowly with stirring, keeping the Dihydrazinium
3,3'-((1E,1'E)-(2,4,6-trinitro-1,3-
temperature of the mixture under 30 °C. The resulting dark brown phenylene)bis(ethene-2,1-diyl))bis (2,4,6-trinitrophenolate) (4c)
-1
solution was allowed to stand at room temperature for 15 min, then Yellow solid (0.72 g, 92%), IR (ν , cm ): 3369, 3224, 3105, 1626,
heated to 90 °C on the steam bath and held at that temperature for 2 h. 1596, 1547, 1452, 1343, 1263, 1165, 1067, 964, 924, 826, 781, 754,
1
After cooling to room temperature this solution was added slowly, 703. H NMR (500MHz, DMSO-d
6
), δ 8.96 (s, 1H), 8.75 (s, 2H), 7.43
13
with rapid stirring, during 30 min., to a mixture of 68% nitric acid (8.0 (s, 6H), 7.06 (d, J = 16.75Hz, 2H), 6.74 (d, J = 16.75Hz, 2H).
mL) and 96% sulfuric acid (8.0 mL) at room temperature and then NMR (126 MHz, DMSO-d ), δ 159.16, 149.07, 147.01, 146.95,
heated to 50 °C for 1 h. Initially the reaction mixture was a black- 136.00, 130.36, 127.78, 127.69, 125.47, 124.06, 121.89, 120.51. MS
C
6
−
brown solution, but after about 10 min the color of the mixture turned (FAB ): 717.9, elemental analysis, calcd (%) for C22
to red accompanied by some foams. The mixture was then drowned 33.73; H: 2.19; N: 23.24; Found, C: 33.68; H: 2.21; N: 23.16.
in crashed ice and water (300 mL). The product was filtered, washed Diguanidinium 3,3'-((1E,1'E)-(2,4,6-trinitro-1,3-
with water, and dried. phenylene)bis(ethene-2,1-diyl))bis (2,4,6-trinitrophenolate) (4d)
Light yellow solid (1.51 g, 42%)，crystallized from methanol/water, Bright yellow solid (0.75 g, 90%), IR (ν , cm ): 3463, 3419, 3362,
17 13
H N O20: C:
-1
-1
m. p. 209-210 °C, IR (ν, cm ): 3422, 3212, 3107, 2908, 1630, 1595, 3198, 3091, 1650, 1604, 1535, 1482, 1452, 1337, 1302, 1251, 1155,
1
1
1
553, 1451, 1343, 1167, 966, 923, 825, 778, 754, 701. H NMR 1065, 958, 927, 907, 825, 790, 755, 717. H NMR (500MHz, DMSO-
500MHz, DMSO-d ), δ 8.96 (s, 1H), 8.74 (s, 2H), 8.27 (br, 2H), 7.06 ), δ 8.94 (s, 1H), 8.73 (s, 2H), 7.04 (d, J = 16.80Hz, 2H), 6.89 (s,
d, J =16.75Hz, 2H), 6.74 (d, J =16.75Hz, 2H). C NMR (126MHz, 12H), 6.72 (d, J = 16.80Hz, 2H). C NMR (126MHz, DMSO-d
(
(
6
d
6
13
13
6
), δ
DMSO-d
6
), δ 159.35, 149.07, 147.10, 146.95, 135.99, 130.42, 127.74, 159.38, 158.24, 149.08, 147.11, 146.95, 135.99, 130.42, 127.77,
+
+
1
27.69, 125.50, 123.81, 121.88, 120.43. HRMS calc. for C22
9 9
H N O
20
127.71, 125.52, 123.87, 121.89, 120.46. MS (FAB ):59.3 (CN
H
3 6
);
−
(
M):718.9174, found 718.9176, elemental analysis, calcd (%) for (FAB ): 717.8, 718.9, elemental analysis, calcd (%) for C24
19 15 20
H N O :
C
22
H
9
N
9
O
20: C: 36.73; H: 1.26; N: 17.52; Found, C: 36.61; H: 1.14; C: 34.42; H: 2.29; N: 25.09; Found, C: 34.38; H: 2.22; N: 24.89.
Diaminoguanidinium 3,3'-((1E,1'E)-(2,4,6-trinitro-1,3-
phenylene)bis(ethene-2,1- diyl))bis(2,4,6-trinitrophenolate) (4e)
N: 17.44.
-1
General procedures for the preparation of 3,3'-((1E,1'E)-(2,4,6- Yellow solid (0.75 g, 86%), m.p. 241°C, IR (ν , cm ): 3439, 3361,
trinitro-1,3-phenylene)bis(ethene-2,1-diyl))bis(2,4,6-trinitrophen
ol) based salts (4a–m):
3095, 1669, 1601, 1543, 1453, 1338, 1301, 1257, 1155, 1070, 959,
926, 907, 825, 789, 754, 708. H NMR (500MHz, DMSO-d ), δ 8.94
6
1
The 4 (0.72 g, 1.0 mmol) was dissolved in methanol (13.0 mL) (s, 1H), 8.73 (s, 2H), 8.53(s, 2H), 7.23(br, 8H), 7.05 (d, J = 16.75Hz,
13
followed by adding a solution of 2 equiv ammonium chloride, 2H), 6.73 (d, J = 16.75Hz, 2H), 4.66(s, 4H). C NMR (126 MHz,
hydroxylamine hydrochloride, hydrazine monohydrochloride, DMSO-d ), δ 159.37, 157.36, 149.07, 147.11, 146.95, 135.99, 130.42,
guanidine hydrochloride, aminoguanidine hydrochloride, 127.77, 127.70, 125.51, 123.86, 121.88, 120.45. MS (FAB ): 718.0,
diaminoguanidine monohydrochloride, triaminoguanidine 719.0, elemental analysis, calcd (%) for C24 20: C: 33.23; H:
monohydrochloride, urea, methylamine, pyridine, potassium nitrate, 2.44; N: 27.45; Found, C: 33.33; H: 2.42; N: 27.49.
silver nitrate or 0.5 equiv copper nitrate (50 wt% in water), Di(diaminoguanidinium) 3,3'-((1E,1'E)-(2,4,6-trinitro-1,3-
respectively. After stirring at room temperature for 1 h, the yellow phenylene)bis(ethene-2,1- diyl))bis(2,4,6-trinitrophenolate) (4f)
6
−
21 17
H N O
-1
precipitate was filtered off and dried in an oven at 70 °C for 4 h.
Diammonium 3,3'-((1E,1'E)-(2,4,6-trinitro-1,3- 3236, 1681, 1604, 1539, 1454, 1395, 1338, 1302, 1258, 1154, 1069,
phenylene)bis(ethene-2,1-diyl))bis (2,4,6 –trinitrophenolate. (4a) 997, 958, 927, 828, 787, 754, 704. H NMR (500MHz, DMSO-d
Yellow solid (0.76 g, 85%), m. p. 206 °C, IR (ν , cm ): 3441, 3315,
1
6
), δ
Yellow needle-shaped crystal (0.65 g, 86%), IR (ν , cm ): 3423, 3175, 8.96(s, 1H), 8.75 (s, 2H), 8.55(s, 4H), 7.14(s, 4H), 7.07 (d, J =16.75Hz,
-1
13
3
9
(
087, 1604, 1520, 1451, 1406, 1340, 1304, 1257, 1153, 1066, 955, 2H), 6.74 (d, J =16.75Hz, 2H), 4.36(s, 8H). C NMR (126MHz,
24, 825, 788, 752, 712, 687. H NMR (500MHz, DMSO-d ), δ 8.94 DMSO-d ), δ 159.37, 159.20, 149.08, 147.11, 146.95, 136.00, 130.43,
6 6
s, 1H), 8.73 (s, 2H), 7.08 (t, J =51.10Hz, 4H), 7.04 (d, J =16.75Hz, 127.76, 127.71, 125.52, 123.83, 121.89, 120.44. MS (FAB ): 740.0
1
−
13
2
H), 6.72 (d, J =16.75Hz, 2H). C NMR (126MHz, DMSO-d
6
), δ
6
| J. Name., 2012, 00, 1-3
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DOI: 10.1039/C4NJ01091D
New Journal of Chemistry
Page 8 of 9
Journal Name
ARTICLE
(
2
M+Na), elemental analysis, calcd (%) for C24
.58; N: 29.65; Found, C: 32.03; H: 2.46; N: 28.99.
H
23
N
19
O
20: C: 32.12; H: 1543, 1480, 1451, 1342, 1269, 1161, 1078, 964, 927, 782, 758, 714.
+
MS (FAB ): 64.3.
Ditriaminoguanidinium
3,3'-((1E,1'E)-(2,4,6-trinitro-1,3-
phenylene)bis(ethene-2,1- diyl))bis(2,4,6-trinitrophenolate) (4g) Acknowledgements
-1
Yellow solid (0.77 g, 83%), m. p. 210 °C, IR (ν , cm ): 3425, 3344, This project was funded by the Priority Academic Program
3
1
110, 2997, 1628, 1548, 1454, 1338, 1300, 1260, 1154, 1102, 1072, Development of Jiangsu Higher Education Institutions (PAPD).
046, 956, 912, 827, 788, 752, 683. H NMR (500MHz, DMSO-d ), We are indebted to thank Qiong Wu for discussions about
6
1
δ 10.19 (s, 6H), 8.95 (s, 1H), 8.74 (s, 2H), 7.06 (d, J =16.75Hz, 2H), Gaussian calculations.
1
3
6
1
1
.73 (d, J =16.75Hz, 2H). C NMR (126MHz, DMSO-d
6
), δ 159.37,
59.20, 149.08, 147.11, 146.95, 136.00, 130.43, 127.76, 127.71, N† otes and references
−
25.52, 123.83, 121.89, 120.44. MS (FAB ): 717.9, 718.9; elemental
20: C: 32.08; H: 2.72; N: 31.71;
Dedicated to Professor Hitomi Suzuki on occasion of his 80th birthday.
a
analysis, calcd (%) for C24
Found, C: 32.04; H: 2.66; N: 31.86.
Diuronium 3,3'-((1E,1'E)-(2,4,6-trinitro-1,3-phenylene)bis(ethene- Fax: (+) 86-025-84317639; Tel: (+) 86-025-84315520
H
25
N
21
O
School of Chemical Engineering, Nanjing University of Science and
Technology, Nanjing 210094, China. E-mail: xhpeng@mail.njust.edu.cn
2
8
1
,1-diyl))bis(2,4,6- trinitrophenolate) (4h) Yellow solid (0.67 g, Electronic Supplementary Information (ESI) available: NMR and
-1
0%), IR (ν , cm ): 3475, 3176, 3090, 1706, 1600, 1542, 1452, 1403, MS Spectra of related compounds. See DOI: 10.1039/b000000x/
1
341, 1306, 1258, 1155, 1066, 960, 924, 825, 783, 753, 712. H NMR
1
.
(a) H. Gao, J. M. Shreeve, Chem. Rev. 2011, 111, 7377-7436; (b) A.
K. Sikder, N. Sikder, J. Hazard. Mater. 2004, 112, 1-15; (c) J. P.
Agrawal, Prop., Explos., Pyrotech. 2005, 30, 316-328; (d) M. B.
Talawar, R. Sivabalan, T. Mukundan, H. Muthurajan, A. K. Sikder, B.
R. Gandhe, A. S. Rao, J. Hazard. Mater. 2009, 161, 589-607; (e) Q.
Zhang, J. M. Shreeve, Angew. Chem. Int. Ed., 2013, 52, 8792-8794.
(a) P. F. Pagoria, G. S. Lee, A. R. Mitchell, R. D. Schmidt, Thermochim.
Acta 2002, 384, 187-204; (b) U. R. Nair, S. N. Asthana, A. S. Rao, B.
R. Gandhe, Defence Sci. J. 2010, 60, 137-151; (c) D. M. Badgujar, M.
B. Talawar, S. N. Asthana, P. P. Mahulikar, J. Hazard. Mater. 2008,
151, 289-305; (d) X. Peng, H. Suzuki, Org. Lett. 2001, 3, 3431-3434;
(
500MHz, DMSO-d
6
), δ 8.96 (s, 1H), 8.75 (s, 2H), 7.10 (t, J =
5
5
1
1
7
2
1.15Hz, 2H), 7.06 (d, J = 16.80Hz, 2H), 6.74 (d, J = 16.80Hz, 2H),
13
.35 (br, 8H). C NMR (126MHz, DMSO-d
6
), δ 160.36, 159.25,
49.08, 147.05, 146.95, 136.00, 130.38, 127.78, 127.69, 125.48,
+
+
−
24.00, 121.89, 120.49. MS (FAB ):61.2 (CH
19.0; elemental analysis, calcd (%) for C24
.04; N: 21.69; Found, C: 34.22; H: 2.00; N: 21.76.
3,3'-((1E,1'E)-(2,4,6-trinitro-1,3-
phenylene)bis(ethene-2,1-diyl)) bis(2,4,6-trinitrophenolate) (4i)
5 2
N
O ), (FAB ): 718.0,
17 13
H N O22: C: 34.34; H:
Dimethanaminium
2
.
-1
Bright yellow solid (0.67 g, 86%), IR (ν , cm ): 3426, 3258, 3080,
1
7
7
2
1
1
603, 1543, 1470, 1336, 1303, 1259, 1156, 1070, 960, 932, 826, 790,
1
53, 707. H NMR (500MHz, DMSO-d
6
), δ 8.94 (s, 1H), 8.73 (s, 2H),
.49 (s, 6H), 7.04 (d, J = 16.75Hz, 2H), 6.72 (d, J = 16.75Hz, 2H),
13
6
.36 (s, 6H). C NMR (126MHz, DMSO-d ), δ 159.40, 149.08,
(
(
e) X. Peng, H. Suzuki, C. Lu, Tetrahedron Lett. 2001, 42, 4357-4359;
f) X. Peng, N. Fukui, M. Mizuta, H. Suzuki, Org. Biomol. Chem. 2003,
47.10, 146.95, 135.97, 130.40, 127.78, 127.71, 125.52, 123.94,
−
21.90, 120.48. MS (FAB ): 718.0; elemental analysis, calcd (%) for
1
, 2326-2335. (g) K. Smith, S. Almeer, S. J. Black, Chem. Commun.
24 19 11
C H N O20: C: 36.89; H: 2.45; N: 19.72; Found, C: 36.82; H: 2.34;
N: 19.66.
Dipyridinium
phenylene)bis(ethene-2,1-diyl))bis (2,4,6-trinitrophenolate) (4j)
2000,17, 1571-1572. (h) K. Smith, M. H. Alotaibi, G. A. El-Hiti, J.
Catal. 2013, 297, 244–247.
3,3'-((1E,1'E)-(2,4,6-trinitro-1,3-
3
(a) V. Thottempudi, F. Forohor, D. A. Parrish, J. M. Shreeve, Angew.
Chem. Int. Ed. 2012, 51, 9881-9885; (b) T. M. Klapötke, C. Petermayer,
D. G. Piercey, J. Stierstorfer, J. Am. Chem. Soc. 2012, 134, 20827-
-1
Yellow solid (0.80 g, 91%), m. p. 263°C, IR (ν, cm ): 3424, 3242,
3
9
8
8
1
096, 2750, 1597, 1538, 1486, 1455, 1307, 1265, 1156, 1069, 963,
1
25, 786, 755, 708. H NMR (500MHz, DMSO-d
.93 (d, 5.20Hz, 5H), 8.61-8.58 (tt, J = 7.85Hz, J
.73 (s, 2H), 8.08-8.05 (dd, J = 6.7Hz, J = 0.95Hz, 5H), 7.05 (d, J =
6.75Hz, 2H), 6.73 (d, J = 16.75Hz, 2H). C NMR (126 MHz,
), δ 159.37, 149.07, 147.10, 146.95, 145.58, 141.85, 135.99,
30.42, 127.77, 127.71, 126.61, 125.52, 123.86, 121.91, 120.46. MS
6
), δ 8.95 (s, 1H),
1
2
= 1.45Hz, 2H),
2
0836; (c) V. Thottempudi, J. M. Shreeve, J. Am. Chem. Soc. 2011,
33, 19982-19992; (d) R. Wang, H. Xu, Y. Guo, R. Sa, J. M. Shreeve,
1
2
1
13
J. Am. Chem. Soc. 2010, 132, 11904-11905; (e) A. A. Dippold, T. M.
Klapötke, J. Am. Chem. Soc. 2013, 135, 9931-9938; (f) T. T. Vo, J.
Zhang, D. A. Parrish, B. Twamley, J. M. Shreeve, J. Am. Chem. Soc.
DMSO-d
1
6
−
(
FAB ): 718.0, 719.0; elemental analysis, calcd (%) for C32
C: 43.80; H: 2.18; N: 17.56; Found, C: 43.82; H: 2.22; N: 17.51.
Potassium 3,3'-((1E,1'E)-(2,4,6-trinitro-1,3-phenylene)bis(ethene-
19 11 20
H N O :
2
013, 135, 11787-11790; (g) W. Liu, Q. Lin, Y. Yang, X. Zhang, Y. Li,
Z. Lin, S. Pang, Chem. Asian J. 2014, 9, 479-486.
2
8
1
,1-diyl))bis (2,4,6-trinitrophenolate) (4k) Yellow solid (0.64 g,
-1
4
5
(a) J. Zhang, J. M. Shreeve, J. Am. Chem. Soc. 2014, 136, 4437-4445;
(b) M. A. Kettner, T. M. Klapötke, Chem. Commun. 2014, 50, 2268-
0%), IR (ν, cm ): 3413, 2073, 2021, 1659, 1532, 1461, 1354, 1248,
−
122, 1086, 961, 930, 776, 757, 716. MS (FAB ): 718.
Silver 3,3'-((1E,1'E)-(2,4,6-trinitro-1,3-phenylene)bis(ethene-2,1-
2
270; (c) Q. Zhang, J. Zhang, D. A. Parrish, J. M. Shreeve, Chem. Eur.
diyl))bis (2,4,6-trinitrophenolate) (4l) Yellow solid (0.77 g, 82%), IR
J. 2013, 19, 11000-11006.
-
1
(
1
ν , cm ): 3445, 2081, 2011, 1602, 1544, 1452, 1343, 1256, 1112,
−
(a) Q. Lin, Y. Li, Y. Li, Z. Wang,W. Liu, C. Qi and S. Pang, J. Mater.
Chem., 2012, 22, 666–674.P. Yin, Q. Zhang, J. Zhang, D. A. Parrish, J.
M. Shreeve, J. Mater. Chem. A 2013, 1, 7500-7510; (b) V. Thottempudi,
P. Yin, J. Zhang, D. A. Parrish, J. M. Shreeve, Chem.Eur. J. 2014, 20,
056, 962, 927, 788, 755, 706. MS (FAB ): 717.9.
Copper 3,3'-((1E,1'E)-(2,4,6-trinitro-1,3-phenylene)bis(ethene-2,1-
diyl))bis (2,4,6-trinitrophenolate) (4m) Green yellow solid (0.66 g,
-1
8
5%), IR (ν, cm ): 3644, 3615, 3569, 3419, 3203, 3117, 1608, 1574,
5
42-548.
This journal is © The Royal Society of Chemistry 2012
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