Synthesis, Characterization, and Properties of Energetic Compounds Based on a CH2-Bridged Dinitromethyl Explosophore

Article abstract of DOI:10.1002/ejoc.201701528

A series of energetic salts based on the 1,1,3,3-tetranitropropane-1,3-diide (TNP) dianion have been prepared and fully characterized by NMR and IR spectroscopy, elemental analysis, and single-crystal X-ray diffraction. Their thermal stability (T_d = 111.0–180.9 °C) and sensitivities to mechanical stimuli (IS = 2–5 J; FS = 80–128 N) have been measured. Additionally, their heats of formation (–369.8 to 347.1 kJ mol^–1) and detonation performances (P = 25.0–37.0 GPa; v_D = 7675–9104 m s^–1) have been calculated.

Full text of DOI:10.1002/ejoc.201701528

A Journal of
Accepted Article
Title: Synthesis, Characterization and Properties of Energetic
Compounds Based on CH2-Bridged Dinitromethyl Explosophore
Authors: Haifeng Huang, Yameng Shi, Yao Yu, and Jun Yang
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To be cited as: Eur. J. Org. Chem. 10.1002/ejoc.201701528
Link to VoR: http://dx.doi.org/10.1002/ejoc.201701528
Supported by

10.1002/ejoc.201701528
European Journal of Organic Chemistry
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Synthesis, characterization and properties of energetic
compounds based on CH2-bridged dinitromethyl explosophore
Haifeng Huang,[a] Shiyameng Shi,[a] Yao Yu[b] and Jun Yang*[a]
Abstract:
A
serial of energetic salts based on 1,1,3,3-
anion have been synthesized before. In view of introducing the
alkyl bridge into energetic materials being a good method of
tuning their properties, we reported here the synthesis,
characterization and properties of energetic salts based on
methylene-bridged bis(dinitromethanide) anion.
tetranitropropane-1,3-diide (TNP) anion were prepared and fully
characterized by NMR, IR, elemental analysis and single-crystal X-
ray diffraction. Their thermal stability (Td=111.0-180.9 oC) and
sensitivities to mechanical stimuli (IS=2-5 J; FS=80-128 N) were
measured. Additionally, their heats of formation (-369.8-347.1 kJ
mol-1) and detonation performances (P=25.0-37.0 GPa; vD=7675-
9104 m s-1) were calculated.
Results and Discussion
Synthesis: The synthetic route for TNP-based energetic salts is
illustrated in Scheme 1. Nitration of 4,6-dihydroxyl-2-
methylpyrimidine followed by hydrolysis with water gave
potassium dinitromethanide (KDNM) and 1,1-diamino-2,2-
dinitroethylene (FOX-7), and FOX-7 can be further converted
into KDNM by alkaline hydrolysis[14]. For the preparation of
potassium dinitroethanol (KDNE), it was first performed by the
reaction of KDNM with formaldehyde at 92 oC[15], however, it was
found that the reaction always accompanied with the formation
of some K2DNP (13%) and the yield of KDNE was only 41% . In
order to improve the yield of KDNE and avoid the generation of
K2DNP in this step, the reaction temperature was lowered to 25
oC and pure KDNE was smoothly obtained with a high yield of
90%. K2DNP was synthesized from KDNM with a higher yield
81% compared to that of 63% reported by Klapötke [13a]. The pH
value of the reaction mixture is the key factor affecting the yield
of K2DNP and should be controlled at pH=4. Silver 1,1,3,3,-
tetranitropropane-1,3-diide (Ag2TNP) was obtained by the
reaction of K2TNP with AgNO3 in the yield of 89%. The
metathesis reaction of Ag2TNP with various chlorides in water
gave rise to TNP-based energetic salts. The hydrazinium (1),
guanidinium (2), aminoguanidinium (3) and triaminoguanidinium
(4) were successfully prepared in the yield of 75-84%. All of the
new salts were fully characterized by NMR, IR spectroscopy,
elemental analysis and single-crystal X-ray diffraction.
Introduction
There has been a strong demand for developing energetic
materials with high detonation performances and low
sensitivities[1]. The strategy of salt formation and the introduction
of alkyl bridge have been the effective ways to achieve this goal.
In the past decades, a large number of energetic salts have
been reported and many of them show promising energetic
properties[2]. The strategy of introducing alkyl group into
energetic materials has been widely used in the design and
synthesis of new energetic compounds. In 2009, Prof. Shreeve
reported nitraminotetrazoles containing alkyl bridge or alkyl side
chain[3]. In 2014, she reported energetic salts based on N-
ethylene-bridged bis(nitroamino-1,2,4-triazolates) and most of
these salts show low impact and friction sensitivities, and they
retain desirable densities and detonation properties[4]. In 2016,
Prof. Klapötke reported advanced energetic materials based on
bispyrazoylmethanes[5]. There are also some other such
energetic materials[6].
Dinitromethyl has been a hot explosophore in recent years
because it has a good positive oxygen balance
[7]
and its
derivatives usually show better stability compared to their
trinitromethyl counterparts. Many dinitromethyl energetic
derivatives have been synthesized and some of them show
excellent energetic properties, for example, monohydrazinium
salt of 3,5-bis(dinitromethyl)-1,2,4-triazole[8], potassium 4,5-
bis(dinitromethyl)furoxanate[9], potassium 4,4’-bis(dinitromethyl)-
3,3’-azofurazanate[10]
nitraminofurazan [11]. Additionally, dinitromethanide has also
been served as the anion of energetic salts[12]
Potassium
1,1,3,3,-tetranitropropane-1,3-diide (K2TNP) has been
Spectroscopy: In the proton NMR, the signal at about 4.60 ppm
can be assigned to the methylene group in TNP anion, which is
consistent with that of K2TNP[13a], while the other signals are
belonged to the cation. In the 13C NMR, the signals at 29.7 ppm
and 131.7 ppm should be assigned to the methylene and the
carbons connected with nitro groups in the TNP anion.
X-ray crystallography: X-ray quality crystals of salts 1-4 were
obtained by slow cooling and evaporation of their solution in
water and ethanol. Their structures are shown in Figures 1-4,
and the crystallographic data are summarized in Table 1.
and
potassium
3-dinitromethyl-4-
.
Salt 1 crystallizes in the monoclinic space group C 2/c with
four cation/anion pairs per unit cell and a calculated density of
1.822 g cm-3 at 293 (2) K. The length of C-N bondS in the TNP
anion of salt 1 are 1.369(19) and 1.369 (18) Å, which is a little
shorter than those in K2TNP [1.377(3)/1.378(3) Å][13a]. And the
average length of the N-O bond is 1.254 Å. The dinitromethyl
groups of the TNP anion are nearly planar as supported by the
torsion angles of C2-C1-N2-O4=-3.45o and C2-C1-N1-O1=2.84o.
And these two dinitromethyl groups have a dihedral angle of
[a]
[b]
Dr. H. Huang, Y. Shi, Prof. Dr. J. Yang.
Shanghai Institute of Organic Chemistry
Chinese Academy of Sciences
Ling Ling Road 345, Shanghai, 200032, P. R. China
E-mail: yangj@sioc.ac.cn
Y. Yu
Hubei Sanjiang Space Rivers Chemical Technology Co., LTD
Yuanan, Hubei, 444200, P. R. China
Supporting information for this article is given via a link at the end of
the document.
reported[13], but no other salts with organic cations based TNP
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88.38o (C2-C1-N2 and C2-C1-N1), which is larger than that in
K2TNP (72.1o).
Scheme 1. Synthesis of TNP-based energetic salts.
Salt 2 crystallizes in the triclinic space group P-1 with four
cation/anion pairs per unit cell and a calculated density of 1.677
g cm-3 at 296 K. The average length of the N-O bond of salt 2 is
similar with that of salt 1 (2: 1.256 Å vs 1: 1.254 Å). With a
torsion angle C2-C3-C4-N7 of -68.52o, the two dinitromethyl
groups in TNP anion of salt 2 are slightly stronger twisted from
each other in comparison with those in salt 1 of C1-C2-C1-N2=-
57.33o. The planarity of one dinitromethyl group in salt 2 is much
worse than that of salt 1, which is shown by the derivations of
O5, O6, O7 and O8 from the C7-C4-N6 plane being 0.254,
0.259, 0.059 and 0.022 Å, respectively.
Salt 3 crystallizes in the monoclinic space group P 21/n with
four cation/anion pairs per unit cell and a calculated density of
1.676 g cm-3 at 293 (2) K, while salt 4 crystallizes in the
monoclinic space group C 2 with four cation/anion pairs per unit
cell and a calculated density of 1.697 g cm-3 at 293 (2) K. Among
the four energetic salts, the hydrazinium salt (1) shows the
highest density of 1.822 g cm-3, while other three new salts have
very similar densities falling between 1.676 and 1.697 g cm-3.
(a)
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(a)
(b)
Figure 1. (a) Displacement ellipsoid plot (30%) of salt
1. (b) Ball-and-
stick packing diagram of salt
bonding.
1. The dashed lines indicate hydrogen
(b)
Figure 3. (a) Displacement ellipsoid plot (30%) of salt
3. (b) Ball-and-
stick packing diagram of salt
bonding.
3. The dashed lines indicate hydrogen
(a)
(a)
(b)
Figure 2. (a) Displacement ellipsoid plot (30%) of salt
2. (b) Ball-and-
stick packing diagram of salt
bonding.
2. The dashed lines indicate hydrogen
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(b)
Figure 4. (a) Displacement ellipsoid plot (30%) of salt 4. (b) Ball-and-stick
packing diagram of salt 4. The dashed lines indicate hydrogen bonding.
Table 1. Crystallographic data and structure refinement parameters for salts1-4.
1
2
3
4
CCDC
1538339
C3H12N8O8
288.21
293(2)
Monoclinic
C 2/c
1538342
C5H14N10O8
342.26
296
1538340
C5H16N12O8
372.30
293(2)
1538341
C5H20N16O8
432.37
293(2)
Formula
FW (g mol-1)
Temperature (K)
Crystal system
Space group
Z
Triclinic
P-1
Monoclinic
P 21/n
Monoclinic
C 2
4
4
4
4
a (Å)
16.718(5)
4.6879(13)
14.053(4)
90
4.6909(15)
17.892(6)
17.909(6)
65.352(6)
83.274(6)
89.138(7)
1355.8(8)
1.677
8.3987(14)
4.8647(8)
36.191(6)
90
22.558(5)
4.3967(10)
20.454(5)
90
b (Å)
c (Å)
α (o)
β (o)
107.409(9)
90
93.682(4)
90
123.466(3)
90
γ (o)
V (Å3)
1050.9(5)
1.822
1475.6(4)
1.676
1692.3(7)
1.697
Dc (g cm-3)
μ (mm-1)
F(000)
0.175
0.154
0.153
0.152
600
0.20×0.16×0.11
712
776
904
Crystal size (mm3)
0.12×0.1×0.05
0.20×0.16×0.12
0.20×0.17×0.10
Index ranges
2.554-25.492
-20≤h≤17
2.117-27.694
-6≤h≤5
2.256-24.996
-9≤h≤9
1.805-25.000
-26≤h≤18
-5≤k≤5
-23≤k≤23
-23≤l≤22
-5≤k≤5
-5≤k≤5
-17≤l≤16
-38≤l≤43
-24≤l≤24
θ (o)
Refl. coll.
2834
11240
7617
4680
Independ. refl. [Rint]
Data/retraints/parameters
GOF
984 [0.0249]
984/0/111
1.083
6245[0.0420]
6245/0/415
0.913
2591[0.0499]
2591/0/258
1.122
2854[0.0232]
2854/1/263
1.070
Final R indices [I>2θ(I)]
R1=0.0349
wR2=0.0880
R1=0.0376
wR2=0.0902
R1=0.0469
wR2=0.0867
R1=0.01369
wR2=0.1151
R1=0.0662
wR2=0.1378
R1=0.0842
wR2=0.1463
R1=0.0577
wR2=0.1639
R1=0.0605
wR2=0.1684
R indices (all data)
Thermal behavior: The thermal stabilities of the prepared
energetic salts were measured by using Thermal Gravimetric
Analysis-Differential Scanning Calorimeter (TG-DSC) with a
heating rate of 5 K min-1. The obtained DSC curves are shown in
Figure 5, and the corresponding decomposition peak
temperatures are summarized in Table 2. It can be seen that the
guanidinium salt (2) shows the highest decomposition
temperature of 181 oC, while other three new salts show
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obtained from Ref 18. With the HOFs of the cations and TNP
anion and the densities of the new salts in hand, the HOFs of
the TNP-based salts were calculated to be in the range of -369.8
(2) and 347.1 kJ mol-1 based the Born-Harber cycle listed in the
Supporting Information.
comparatively low
thermal
stabilities,
especially the
aminoguanidnium (3, Td=113.7 oC) and triaminoguanidinium
salts (4, Td=111.0 oC). This trend of the thermal stability for
guanidinium analogues is inconsistent with previously reported
examples: the increase of the amino substitution on guanidinium
cation usually results in the worse thermal stability[16]
.
Unfortunately, the thermal stabilities of TNP-based energetic
salts are lower than the corresponding DNM-based ones[2:
Td=180.9 oC vs guanidinium DNM: Td=187 oC; 3: Td=113.7 oC vs
aminoguanidinium DNM: Td=133 oC][12b].
Scheme 2. Isodesmic reaction for calculation of the heat of formation of the
TNP anion.
Sensitivities: The impact sensitivities (IS) and friction
sensitivities (FS) of the newly prepared energetic salts were
measured by using a BAM drop-hammer apparatus (BFH-10)
and
a BAM friction tester (FSKM-10). The results are
summarized in Table 2. As can be seen, the TNP-based
energetic salts in this paper are more sensitive to impact than
1,3,5-trinitro-1,3,5-triazinane (RDX, 7.5 J) and 1,3,5,7-tetranitro-
1,3,5,7-tetrazocane (HMX, 7 J) with the value lying between 2
(1) and
5 J (3). However, their friction sensitivities are
comparable with those of RDX and HMX except of the
hydrazinium salt (1).
Detonation performances: The detonation pressures (P) and
detonation velocities (vD) of the prepared energetic salts were
calculated by using the Kamlet-Jecobs equations shown in the
Supporting Information and the results are summarized in Table
2. Their detonation velocities are between 7675 (2) and 9104 m
s-1 (1) and their detonation pressures lie in the range of 25.0 (2)
and 37.0 GPa (1). Among them, detonation velocity of the
hydrazinium salt (1, 9104 m s-1) is a higher than that of RDX
(8983 m s-1) and is comparable with that of HMX (9221 m s-1).
Figure 5. The DSC curves of salts 1-4 with a heating rate of 5 K min-1.
Higher HOF usually results in better detonation performances.
The HOF of TNP anion was calculated to be -246.0 kJ mol-1
based on the isodesmic reaction shown in Scheme 2 by using
Gaussian 09 (Revision A.01)[17] and that of the cations are
Table 2. Physical properties and thermochemical values of TNP-based energetic salts.
[a]
[b]
[d]
[e]
[f]
[g]
[i]
Compd
Tm
Td
d[c]
△
fHL
△
fHcation
△
fHanion
△
fHsalt
P[h]
vD
IS[j]
2
FS[k]
80
OB[l]
-22.2
-42.1
-43.0
1.822(1.817)
1377.4
1251.2
1211.6
1149.9
-75.2
-369.8
-137.0
347.1
37.0
25.0
26.4
30.2
9104
7675
7883
8394
1
-
-
-
-
139.9
180.9
113.7
111.0
210
774.1
563.7
660.3
871.5
-
-246.0
-246.0
-246.0
-246.0
-
1.677(1.654)
1.676(1.670)
1.697(1.687)
5
128
128
120
2
3
5
3
4
-44.4
-21.6
-21.6
RDX[m]
HMX[m]
205
275
1.806
1.904
-
-
86.3
38.0
41.5
8983
9221
7.5
7
120
112
279
-
-
116.1
[a] Melting point (onset) [oC]. [b] Decomposition temperature (onset) [oC]. [c] Density obtained from single-crystal X-ray diffraction, the values in the
parentheses were measured by using a gas pycnometer at 25oC [g cm-3]. [d] Calculated molar lattice energy [kJ mol-1]. [e] Molar enthalpy of formation
g
h
of cation [kJ mol-1]. [f] Calculated molar enthalpy of formation of anion [kJ mol-1]. Calculated molar enthalpy of formation of salts [kJ mol-1].
Detonation pressure [GPa]. Detonation velocity [m s-1]. Impact sensitivity [J]. Friction sensitivity [N]. Oxygen balance (OB) is an index of the
deficiency or excess of oxygen in a compound required to convert all C into CO2 and all H into H2O, for the compound with the molecular formula of
CaHbNcOd, OB(%)=1600[(d-2a-b/2)/Mw] [%]. m From Ref 19.
i
j
k
l
reaction of Ag2TNP with corresponding chlorides. And they were
fully characterized by NMR, IR, elemental analysis and single-
crystal X-ray diffraction. The TNP-based energetic salts show
comparably low thermal stabilities (Td=111.0-180.9 oC) and high
Conclusions
sensitivities to impact (IS=2-5 J). Among them, detonation
velocity of the hydrazinium salt (1, 9104 m s-1) is a higher than
Four energetic salts based on 1,1,3,3-tetranitropropane-1,3-diide
(TNP) anion were successfully prepared by the metathesis
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Bis(aminoguanidinium) TNP (3): Bright yellow needle; yield: 77% (394 mg). 1 H NMR (d6-
DMSO, 300MHz): δ=4.60 (s, 2H), 4.68 (s, 4H), 6.79 (s, 4H), 7.23 (s, 4H), 8.58 (s, 2H) ppm;
13 C NMR (d6-DMSO): δ=29.7, 131.7, 158.8 ppm. IR (KBr): 3457, 3404, 3344, 1655, 1467,
1372, 1350, 1318, 1254, 1203, 1141, 1080, 945, 854, 844, 770, 745, 734, 685, 649, 531,
463 cm-1. Elemental analysis for C5H16N12O8 (372.26): Calculated: C: 16.13 H: 4.33 N:
45.15; Measured: C: 16.06 H: 4.52 N: 46.54.
that of RDX (8983 m s-1) and is comparable with that of HMX
(9221 m s-1).
Experimental Section
General methods: 1 H spectra were recorded on a 300 MHz nuclear magnetic resonance
Bis(triaminoguanidinium) TNP (4): Bright yellow needle; yield: 75% (444 mg). 1 H NMR
(d6-DMSO, 300MHz): δ=4.48(s, 12H), 4.58(s, 2H), 8.57(s, 4H) ppm; 13 C NMR (d6-DMSO):
δ=29.7, 131.7, 159.0 ppm. IR (KBr): 3319, 1687, 1566, 1458, 1326, 1242, 1197, 1118, 1073,
998, 684, 549 cm-1. Elemental analysis for C5H20N16O8 (432.31): Calculated: C: 13.89 H:
4.66 N: 51.84; Measured: C: 14.46 H: 4.91 N: 52.95.
spectrometer operating at 300 MHz. Chemical shifts are reported relative to
13
tetramethylsilane.
C NMR spectra were recorded on a 400 MHz nuclear magnetic
resonance spectrometer operating at 100 MHz. The solvent was [D6]dimethyl sulfoxide
([D6]DMSO) unless otherwise specified. The melting and decomposition points were
recorded on a NETZSCH STA 449F3 equipment at a heating rate of 5oC min-1, respectively.
Infrared spectra were recorded by using KBr pellets. Densities were obtained from single-
crystal X-ray diffraction. Elemental analyses were obtained on an Elementar Vario MICRO
CUBE (Germany) elemental analyser.
Acknowledgements
This work was financially supported by Natural Science
Foundation of Shanghai, China (Grant. No. 16ZR1443600) and
National Natural Science Foundation of China (NSFC, Grant. No.
21602241).
X-ray crystallography: Crystals of salts 1-4 were removed from the flask and covered with
a layer of hydrocarbon oil, respectively. A suitable crystal was selected, attached to a glass
fiber, and placed in the low-temperature nitrogen stream. The single-crystal X-ray diffraction
data were collected at 293
K (296 K for salt 2) using a Bruker CCD area detector
diffractometer equipped with a graphite-monochromatized MoKα radiation (λ=0.71073 Å)
using omega scans. Data collection and reduction were performed and the unit cell was
initially refined by using Bruker SMART software. The reflection data were also corrected for
Lp factors. The structure was solved by direct methods and refined by least squares
method on F2 using Bruker SHELXTL program. In this all-light-atom structure the value of
the Flack parameter did not allow the direction of polar axis to be determined and Friedel
reflections were then merged for the final refinement. Details of the data collection and
refinement are given in Table 1.
Keywords: Explosive • energetic material • dinitromethyl •
energetic salt • detonation performance
[1]
a) D. G. Piercey, D. E. Chavez, B. L. Scott, G. H. Imler and D. A.
Parrish. Angew. Chem. Int. Ed. 2016, 55, 15318; b) Y. Tang, H. Gao, D.
A. Parrish and J. M. Shreeve. Chem. Eur. J. 2015, 21, 11401-11407; c)
A. A. Dippold and T. M. Klapötke. Chem. Asian J. 2013, 8, 1463-1471.
a) D. Srinivas, V. D. Ghule and K Muralidharan. RSC Adv. 2014, 4,
7041-7051; b) W. Liu, S. –H. Li, Y. –C. Li, Y. –Z. Yang, Y. Yu, S. –P.
Pang. J. Mater. Chem. A 2014, 2, 15978-15986; c) C. Bian, K. Wang, L.
Liang, M. Zhang, C. Li and Z. Zhou. Eur. J. Inorg. Chem. 2014, 2014,
6022-6030; d) T. M. Klapötke, N. Mayr, J. Stierstorfer and M.
Weyrauther. Chem. Eur. J. 2014, 20, 1410-1417; e) W. Liu, Q. –H. Lin,
Y. –Z. Yang, X. –J. Zhang, Y. –C. Li, Z. –H. Lin and S. –P. Pang. Chem.
Asian J. 2014, 9, 479-486; f) V. Thottempudi and J. M. Shreeve, J. Am.
Chem. Soc. 2011, 133, 19982-19992; g) Y. Huang, Y. Zhang and J. M.
Shreeve. Chem. Eur. J. 2011, 17, 1538-1546; h) M. Göbel, K.
Karaghiosoff, T. M. Klapötke, D. G. Piercey and J. Stierstorfer. J. Am.
Chem. Soc. 2010, 132, 17216-17226.
CCDC-1538339 (1), CCDC-1538342 (2), CCDC-1538340 (3) and CCDC-1538341 (4)
contain the supplementary crystallographic data for this paper. These data can be obtained
free of charge from The Cambridge Crystallographic Data Centre via
www.ccdc.cam.ac.uk/data_request/cif.
[2]
Silver TNP (Ag2TNP): K2TNP (130 mg, 0.43 mmol), which was prepared according to the
procedure in ref 13a, was dissolved in 10 mL water followed by the addition of aqueous
AgNO3 (160 mg, 0.95 mmol) in 2 mL water. The resulting reaction mixture was stirred at
room temperature for 20 min and the precipitate was collected by filtration and washed with
water (2 mL×3) and ethanol (2 mL×3). Yellow powder (168 mg, 89%) was obtained after air-
dry. Elemental analysis for C3H2Ag2N4O8 (288.18): Calculated: C: 8.26 H: 0.46 N: 12.80;
Measured: C: 8.42 H: 0.66 N: 12.57.
[3]
[4]
Y. H. Joo and J. M. Shreeve. Angew. Chem. Int. Ed. 2009, 48, 564-567.
P. Yin, D. A. Parrish, J. M. Shreeve. Angew. Chem. Int. Ed. 2014, 53,
12889-12892.
General procedure for the preparation of salts 1-4: To an aqueous suspension of freshly
prepared Ag2TNP (600 mg, 1.37 mmol) in 10 mL water was added the aqueous solution of
the corresponding chloride salts (2.74 mmol) in 2 mL water. After stirring for 20 min at room
temperature, the precipitate was removed by filtration and the filtrate was concentrated on
rotary evaporator to give the target product. For salts 1-4, hydrazinium chloride,
guanidinium chloride, aminoguanidinium chloride and triaminoguanidinium chloride were
used respectively.
[5]
[6]
D. Fischer, J. L. Gottfried, T. M. Klapötke, K. Karaghiosoff, J.
Stierstorfer and T. G. Witkowski. Angew. Chem. Int. Ed. 2016, 55,
16132-16135.
a) J. Stierstorfer, K. R. Tarantic and T. M. Klapötke. Chem. Eur. J. 2009,
15, 5775-5792; b) Q. Zhang, J. Zhang, D. A. Parrish and J. M. Shreeve.
Chem. Eur. J. 2013, 19, 11000-11006; c) P. Yin, J. Zhang, D. A. Parrish
and J. M. Shreeve. Chem. Eur. J. 2014, 20, 16529-16536.
Dihydrazinium TNP (1): Bright yellow needle; yield: 81% (320 mg). 1 H NMR (d6-DMSO,
300MHz): δ=4.59 (s, 2H), 6.98 (s, 10H) ppm; 13 C NMR (d6-DMSO): δ=29.7, 131.7 ppm. IR
(KBr): 3359, 3300, 3169, 3097, 2979, 1615, 1594, 1534, 1466, 1362, 1323, 1034, 932, 774,
742, 685, cm-1. Elemental analysis for C3H12N8O8 (288.18): Calculated: C: 12.50 H: 4.20 N:
38.88; Measured: C: 12.76 H: 4.53 N: 38.56.
[7]
[8]
[9]
X. X. Zhao, S. H. Li, Y. Wang, Y. C. Li, F. Q. Zhao and S. P. Pang. J.
Mater. Chem. A 2016, 4, 5495-5504.
J. Zhang, S. Dharavath, L. A. Mitchell, D. A. Parrish and J. M. Shreeve.
J. Am. Chem. Soc. 2016, 138, 7500-7503.
C. He and J. M. Shreeve. Angew. Chem. Int. Ed. 2016, 55, 772-775.
[10] Y. Tang, C. He, L. A. Mitchell, D. A. Parrish and J. M. Shreeve. Angew.
Chem. 2016, 128, 5655-5657.
Bis(guanidinium) TNP (2): Bright yellow needle; yield: 84% (390 mg). 1 H NMR (d6-DMSO,
300MHz): δ=4.59 (s, 2H), 6.94 (s, 12H) ppm; 13 C NMR (d6-DMSO): δ=29.7, 131.7, 157.9
ppm. IR (KBr): 3458, 3400, 3191, 1637, 1564, 1458, 1356, 1329, 1243, 1204, 1121, 1066,
860, 774, 745, 685, 526 cm-1. Elemental analysis for C5H14N10O8 (342.23): Calculated: C:
17.55 H: 4.12 N: 40.90; Measured: C: 17.30 H: 4.10N: 42.65.
[11] Y. Li, H. Huang, Y. Shi, J. Yang, R. Pan and X. Lin. Chem. Eur. J. 2017,
23, 7353-7360.
[12] a) L. He, G. –H. Tao, D. A. Parrish and J. M. Shreeve. Inorg. Chem.
2011, 50, 679-685; b) L. He, G. –H. Tao, D. A. Parrish and J. M.
Shreeve. Chem. Commun. 2013, 49, 10329-10331.
For internal use, please do not delete. Submitted_Manuscript
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[13] a) T. M. Klapötke, B. Krumm and R. Moll. Chem. Eur. J. 2013, 19,
12113-12123; b) F. G. Borgardt, P. Noble, W. L. Reed and A. K. Seeler.
J. Org. Chem. 1970,35, 4236-4238; c) K. Klager, J. P. Kispersky and E.
Hamel. J. Org. Chem. 1961, 26, 4368-4371; d) M. J. Kamlet, R. E.
Oesterling and H. G. Adolph. J. Chem. Soc. 1965, 5838-5849; e) K.
Klager, US2984689, 1961; f) S. S. Novikov, A. A. Fainzil’berg, S. A.
Shevelev, I. S. Korsakov, K. K. Babievskii, Dokl. Akad. Nauk SSSR
1959, 124, 589-591; g) E. E. Hamel. Tetrahedron 1963, 19, 85-95; h) H.
Piotrowska and K. Wejroch. Liebigs Ann. Chem. 1992, 871-875; i) R.B.
Kaplan and H. Shechter. J. Am. Chem. Soc. 1961, 83, 3535-3536.
[14] M. Anniyappan, M. B. Talawar, G. M. Gore, S. Venugopalan and B. R.
Gandhe. J. Hazard. Mater. 2016, B137, 812-819.
Petersson, H. Nakatsuji, M. Caricato, X. Li, H. P. Hratchian, A. F.
Izmaylov, J. Bloino, G. Zheng, J. L. Sonnenberg, M. Hada, M. Ehara, K.
Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O.
Kitao, H. Nakai, T. Vreven, J. A. Montgomery, Jr., J. E. Peralta, F.
Ogliaro, M. Bearpark, J. J. Heyd, E. Brothers, K. N. Kudin, V. N.
Staroverov, R. Kobayashi, J. Normand, K. Raghavachari, A. Rendell, J.
C. Burant, S. S. Iyengar, J. Tomasi, M. Cossi, N. Rega, J. M. Millam, M.
Klene, J. E. Knox, J. B. Cross, V. Bakken, C. Adamo, J. Jaramillo, R.
Gomperts, R. E. Stratmann, O. Yazyev, A. J. Austin, R. Cammi, C.
Pomelli, J. W. Ochterski, R. L. Martin, K. Morokuma, V. G. Zakrzewski,
G. A. Voth, P. Salvador, J. J. Dannenberg, S. Dapprich, A. D. Daniels,
O. Farkas, J. B. Foresman, J. V. Ortiz, J. Cioslowski, and D. J. Fox,
Gaussian, Inc., Wallingford CT, 2009.
[15] O. A. Ivanova, E. M. Budynina, E. B. Averina, T. S. Kuznetsova, Y. K.
Grishin and N. S. Zefirov. Synthesis, 2007, 13, 2009-2013.
[18] a) T. M. Klapötke, C. Petermayer, D. G. Piercey and J. Stierstorfer. J.
Am. Chem. Soc. 2012, 134, 20827−20836; b) Y. Guo, G. Tao, Z. Zeng,
H. Gao D. A. Parrish and J. M. Shreeve. Chem. Eur. J. 2010, 16, 3753-
3762.
[16] a) W. Fu, B. Zhao, M. Zhang, C. Li, H. Gao, J. Zhang and Z. Zhou. J.
Mater. Chem. A 2017, 5, 5044-5054; b) H. Huang, Y. Shi, Y. Li, Y. Liu
and J. Yang. RSC Adv. 2016, 6, 64568-64574.
[17] M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A. Robb,
J. R. Cheeseman, G. Scalmani, V. Barone, B. Mennucci, G. A.
[19]
N. Fischer, D. Fischer, T. M. Klapötke, D. G. Piercey and J Stierstorfer.
J. Mater. Chem. 2012, 22, 20418-20422.
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Haifeng Huang, Yameng Shi, Yao Yu,
Jun Yang*
Page No. – Page No.
Synthesis, characterization and
properties of energetic compounds
based on CH2-bridged dinitromethyl
explosophore
A serial of energetic salts based on 1,1,3,3-tetranitropropane-1,3-diide (TNP) anion
were prepared and fully characterized.
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