Thermally stable energetic salts based on 3-nitramino-4-tetrazolefurazan

Article abstract of DOI:10.1039/c6ra12109h

In order to develop new energetic materials with high energy and low sensitivity, a series of nitrogen-rich energetic salts based on 3-nitramino-4-tetrazolefurazan were conveniently synthesized through nitration, neutralization and metathesis reaction. All energetic salts were fully characterized by NMR (¹H, ¹³C), IR and elemental analysis. Furthermore, ammonium salt (2) was confirmed by ¹⁵N NMR and hydroxylammonium salt (5) was confirmed by single-crystal X-ray diffraction. Salt 5 crystallized in triclinic space group P1 with four hydroxylammonium cations and two NATF anions per unit cell at a density of 1.815 g cm^-3. The densities of the salts are in the range of 1.621 (6) to 1.815 g cm^-3 (5). Due to the two nitrogen-rich cations in the salts, they show high positive enthalpies of formation falling between 299.2 kJ mol^-1 (2) and 1040.6 kJ mol^-1 (9). All the salts show good thermal stabilities with the decomposition temperatures ranging from 203 °C (4) to 284 °C (6). The impact sensitivities of the energetic salts lie between 5 J (2 and 5) and >40 J (6, 7, 8) and their friction sensitivities range from 108 N (4) to >360 N (6). Their detonation performances were calculated according to Kamlet-Jacobs equations. The detonation pressures of the synthesized energetic salts were found to be in the range of 21.1 GPa (6) to 34.7 GPa (5) and their detonation velocities are between 7117 m s^-1 (6) and 8826 m s^-1 (5).

Full text of DOI:10.1039/c6ra12109h

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DOI: 10.1039/C6RA12109H
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Paper
Thermally Stable Energetic Salts Based on 3-Nitramino-4-
tetrazole-furazan†
Haifeng Huanga, Yameng Shia, Ying Lia,b, Yanfang Liua and Jun Yanga*
Received 00th January 20xx,
Accepted 00th January 20xx
In order to develop new energetic materials with high energy and low sensitivity, a serial of nitrogen-rich energetic salts
based on 3-nitramino-4-tetrazole-furazan were conveniently synthesized through nitration, neutralization and metathesis
reaction. All energetic salts were fully characterized by NMR (1H NMR, 13C NMR), IR and elemental analysis. Furthermore,
ammonium salt (2) was confirmed by 15N NMR and hydroxylammonium salt (5) was confirmed by single-crystal X-ray
diffraction. Salt 5 crystallized in triclinic space group P -1 with four hydroxylammoniumcations and two NATF anions per
unit cell at a density of 1.815 g cm-3. The densities of the salts are in the range of 1.621 (6) -1.815 g cm-3 (5). Due to the two
nitrogen-rich cations in the salts, they show high positive enthalpies of formation falling between 299.2 kJ mol-1 (2) and
1040.6 kJ mol-1 (9). All the salts show good thermal stabilities with the decomposition temperatures ranging from 203oC (4)
to 284oC (6). The impact sensitivities of the energetic salts lie between 5 J (2 and 5) and >40 J (6, 7, 8) and their friction
sensitivities range from 108 N (4) to >360 N (6). Their detonation performances were calculated according to Kamlet-
Jacobs equations. The detonation pressures of the synthesized energetic salts were found to be in the range of 21.1GPa (6)
DOI: 10.1039/x0xx00000x
www.rsc.org/
to 34.7 GPa (5) and their detonation velocities fall between 7117
m m
s-1 (6) and 8826 s-1 (5).
thermally stable, but they show general detonation
performances due to the low density and low oxygen balance.
It is well known that the introduction of nitramino group is an
efficient strategy to improve the density and oxygen balance,
which has been applied in developing new energetic salts.7 The
energetic salts based on 3,4-dinitraminofurzan (DNAF)
reported by Prof. Shreeve8 and our group9 are the nitramino-
containing ones (Figure 1). The DNAF salts show good
detonation performances due to the high oxygen balance of
the DNAF anion. Unfortunately, some of them are quite
sensitive to mechanic stimuli.
Introduction
Demand for energetic materials with high detonation
performance and low sensitivity has been increased by recent
years1 because high sensitivity of the energetic materials tends
to enhance the danger related to the transportation, handling
and processing from production to end-use.2 However,
detonation performance and sensitivity are also contradictory
to each other in the field of energetic materials.3 Energetic
salts especially the nitrogen-rich ones have been found to be a
good way to overcome this problem and a large amount of
energetic salts with high detonation performance and low
sensitivity has been developed.4
Furazan and tetrazole ring are two kinds of nitrogen-rich
heterocyclic rings widely used in the design and synthesis of
new energetic materials.5 Both of them possess high positive
enthalpy of formation and good thermal stability. Nitrogen-
rich energetic salts based on 3-amino-4-tetrazole-furazan (ATF)
have been reported,6 which are insensitive to impact and
Figure 1. Different anions based on furazan.
Aiming at developing energetic salts with better
comprehensive properties, we designed the new energetic
salts by the combination of nitramino and tetrazole with the
furazan ring. Hopefully, the nitramino group will improve the
oxygen balance of the anion (compared with ATF anion) and
the terazole ring will lead to the lower sensitivity of the
resulting salts (compared with DNAF salts). With this in mind,
the energetic salts based on 3-nitramino-4-tetrazole-furazan
(NATF) were prepared and fully characterized by NMR, IR,
elemental analysis and single-crystal X-ray diffraction. Their
a Dr. H. Huang, Y. Shi, Y. Li, Y. Liu. Prof. Dr. J. Yang.
Shanghai Institute of Organic Chemistry
Chinese Academy of Sciences
Lingling Road 345, Shanghai, 200032, P. R. China
E-mail: yangj@sioc.ac.cn
b Y. Li.
Nanjing University of Science and Technology
School of Chemical Engineering
Xiaolingwei 200, Nanjing, 210094, P. R. China
Electronic Supplementary Information (ESI) available: Crystallographic data and
refinement parameters, ab initio computational data and method for calculating
detonation performances. CIF file: CCDC-1476973 (5). For ESI and crystallographic
data in CIF or other electronic format see DOI:10.1039/x0xx00000x
This journal is © The Royal Society of Chemistry 20xx
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thermal stabilities and densities were measured and their curve and the corresponding weight loss on the TG curve was
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DOI: 10.1039/C6RA12109H
enthalpies of formation and detonation performances were 14.6%, which is insistent with the loss of three molecules of
also calculated.
water. The elemental analysis result of salt
that salt has three molecules of co-crystallized water. Salts
were easily synthesized by the metathesis reaction of barium
salt ( ) with equal molar of sulfates in water to give the target
compounds in the yield of 67% to 84%. (Scheme 1) For salts
and the sulfate salts were prepared in situ by the reaction
of chloride salt and Ag2SO4. The chloride salts are hydrazinium
chloride, guanidinium chloride, aminoguanidinium chloride,
diaminoguanidinium chloride and triaminoguanidinium
3 also confirmed
3
4-
9
Results and Discussion
Synthesis. The ammonium (2) and barium salt (3) of 3-
3
4
6-9
nitramino-4-tetrazole-furazan were obtained by the nitration
of 3-amino-4-tetrazole-furazan with the mixed acids of fuming
nitric acid and concentrated sulfuric acid followed by
neutralization with gaseous ammonia or aqueous Ba(OH)2
solution in the same yield of 81% after recrystallization.
(Scheme 1) The thermal gravimetric analysis-differential
chloride. For salt
5, dihydroxyammonium sulfate was used as
purchased. All the salts were fully characterized by NMR, IR
and elemental analysis and salt
single-crystal X-ray diffraction.
5 was further confirmed by
scanning calorimeter (TG-DSC) curve of salt
3 showed an
endothermic peak at the temperature of 151oC on the DSC
Scheme 1. Synthesis of NATF-based energetic salts.
Spectroscopy. There is no proton in the NATF anion, so all the
1
signals in the H NMR are assigned to the cations and they are
in consistent with the literature data.10 The signals of the 13C
NMR of salt
compared
2
to
(δ=156.9, 150.2, 144.8 ppm) downshifted
that of ammonium 4-amino-3-(5-
tetrazolate)furazan (ATF) (δ=155.9, 151.1, 140.4 ppm) because
of the electron-withdrawing property of the nitro group.9 The
15N NMR spectrum of salt
2 obtained in [D6]DMSO solvent is
shown in Figure 2 in which the chemical shifts are given with
respect to CH3NO2 as external standard. The signal assigned to
the ammonium cation (N1) appears at -356.92 ppm. The
signals corresponding to the nitrogen atoms on the NATF
anion can be assigned based on the chemical shifts in the
literature.7c,11 The signals for N2-N7 in the NATF anion are
observed at -13.28, -150.15, 4.99, 23.38, -61.65 and 10.13 ppm,
respectively.
Figure 2. 15N NMR spectrum of salt 2.
X-ray crystallography. The crystal of salt
5 suitable for single-
crystal X-ray diffraction analysis was obtained by slow
evaporation of its aqueous solution at room temperature. It
crystallized in triclinic space group P-1 with four
hydroxylammonium cations and two NATF anions per unit cell
at a density of 1.815 g cm-3. The NATF anion is almost planar
with the torsion angels of N4-C2-C3-N5, N3-C1-N2-N1 and C1-
N2-N1-O3 being 2.19o, -1.73o and -0.01o, respectively. The
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bonds on the furazan ring near to the nitro group (C1-N3 synthesized salts were measured by TG-DSC with the heating
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1.311Å; N3-O1 1.390 Å) is slightly longer than that near to the rate of 5 K min-1, and the correspondingDDOSI:C10c.u10r3v9e/sC6aRreA1l2i1s0te9Hd
tetrazole ring (C2-N4 1.296Å; N4-O1 1.368 Å), which is in Figure 4. As can be seen, four salts melted before
probably caused by the strong electron-withdrawing property decomposition with the melting points being between 167oC
of the nitro group. Comparing N-O bond lengths of the furazan and 208oC (
5
: 198oC;
decomposed directly without melting. The results
show that these salts are thermally stable with the
decomposition temperatures ranging from 203oC ( ) to 284oC
). The hydrazinium (
, Td=203oC), guanidinium ( , Td=284oC)
and triaminoguanidinium (
, Td=230oC) salts based on NATF
7 8 9
: 208oC; : 167oC; : 189oC). While salts
ring in dihydroxyammonium DNTF (1.398 Å and 1.386 Å) and
2, 4 and 5
salt
5
(1.390 Å and 1.368 Å) further confirmed our deduction.
4
(6
4
6
9
anion exhibit even higher decomposition temperatures than
the corresponding ATF based salts (hydrazinium salt: Td=197oC;
guanidinium salt: Td=257oC; triaminoguanidinium salt:
Td=216oC).6 Additionally, all the NATF salts are more thermally
stable than the corresponding DNTF salts.8 Except for salt
4, all
the prepared salts possess the better thermal stability than
1,3,5-trinitro-1,3,5-triazinane (RDX, Td=230oC).
(a)
Figure 4. The DSC curves of salts 2 and 4-9 with the heating rate of 5 K min-1.
(b)
Enthalpies of formation. The enthalpies of formation (HOF) of
energetic materialswere one of the essential data for
calculating their detonation performances. The HOFs of the
NATF anion was calculated to be 472.1 kJ mol-1 based on the
isodesmic reaction and protonation reaction shown in scheme
2 and 3. All the geometry optimizations were performed by
using B3LYP functional analyses with the 6-31+G** basis set on
the Gaussian 09 (Revision A.01) suite of programs and single
energy points were calculated at the MP2/6-311++G** level.
The HOFs of the cations were obtained from the
Figure 3. (a) Displacement ellipsoid plot (30%) of salt5. (b) Ball-and-stick
packing diagram of salt 5 viewed down the a-axis. The dashed lines indicate
hydrogen bonding.
Densities. According to Kamlet-Jacobs equations,12 the
detonation velocity of an energetic material is proportional to
its density and its detonation pressure is proportional to the
square of its density. Hence, density is one of the most
important
performances of an energetic material. The densities of salts
and were measured by using gas pycnometer, while the
density of salt was obtained from its single-crystal X-ray
diffraction. As shown in Table 1, the densities of the prepared
energetic salts are in the range of 1.621 ( ),
) -1.815 g cm-3 (
which are much higher than that of 2,4,6-trinitrotolune (TNT),
and the density of salt is even higher than that of RDX.
properties
determining
the
detonation
,14
literatures.13 Then the HOFs of the NATF-based energetic
2
,
salts were calculated to be in the range of 299.2 kJ mol-1
(2
) to
4
6-9
1040.6 kJ mol-1
ESI for details).
(9) according to Born–Haber energy cycles (see
5
6
5
Detonation performances. With the measured densities and
calculated enthalpies of formation in hand,the detonation
pressures (P) and detonation velocities (vD) of the synthesized
energetic salts were calculated according to Kamlet-Jacobs
equations (See ESI for details)12and the results are summarized
in Table 1. The detonation pressures of the synthesized
5
Furthermore, their densities are also higher than that of the
corresponding ATF-based energetic salts.
Thermal behaviors. The thermal behaviors including the
melting point and decomposition temperature of the
energetic salts were found to be in the range of 21.1GPa (6) to
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34.7 GPa (
5
) and their detonation velocities fall between 7117 energetic salts.6,8 Compared with the ATF salts, one more
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DOI: 10.1039/C6RA12109H
m s-1
in
(6 (5). Their detonation performances are cation was introduced into the resulting NATF salts, while only
) and 8826 m s-1
the
following
order:
) > triaminoguanidinium salt (
ammonium salt
) > guanidinium salt ( ). The highest lower detonation performances of NATF-based energetic salts
detonation perfomances of the hydroxylammonium salt ( compared with the ATF salts. In view of the detonation velocity,
(P=8826 m s-1; d=1.815 g
hydroxylammonium
salt one more nitro group was introduced onto the NATF anion.
) > Finally, the NATF salts possess worse oxygen balance than the
(2) > corresponding ATF salts, which may be the reason for the
(
5
) >hydrazinium salt (
diaminoguanidnium salt
aminoguanidinium salt (
4
9
(
8
)
>
7
6
5
)
should be arisen from its best oxygen balance and highest density and thermal stability, salt
5
density. And the relatively high detonation performances of cm-3; Td=233oC) is a promising replacement for RDX (P=8983 m
the triaminoguanidinium salt (9) may be resulted from its s-1; d=1.82 g cm-3; Td=230oC).
highest enthalpy of formation. Their detonation performances
are lower than that of the corresponding ATF and DNTF-based
Table 1. Physical properties and thermochemical values of NATF-based energetic salts.
[a]
[b]
[d]
[f]
d[c]
△
fHsal
P[e]
vD
IS[g]
5
FS[h]
240
108
112
>360
288
240
160
353
N %[i]
60.3
64.1
53.0
62.0
64.2
67.0
68.9
18.5
OB[j]
Compd
Tm
Td
1.667
1.753
1.815
1.621
1.708
1.662
1.686
299.2
613.8
425.6
326.7
538.3
807.3
1040.6
55.7
25.4
31.8
34.7
21.1
25.4
26.2
28.5
7752
8535
8826
7117
7686
7868
8174
7459
2
4
-
232
203
233
284
238
233
230
295
-48.24
-48.82
-30.28
-65.77
-64.69
-63.78
-63.00
-74.0
-
6
5
198
-
5
6
>40
>40
>40
29
15
7
208
167
189
81
8
9
TNT
1.65
23.5
[a] Melting point (peak) [oC] [b] Decomposition temperature (peak) [oC] [c] Density measured by gas pycnometer at 25oC, for salt 5, the density is obtained from the single-crystal
X-ray diffraction [g cm-3] [d] Calculated molar enthalpy of formation of salts [kJ mol-1] [e] Detonation pressure [GPa] [f] Detonation velocity [m s-1] [g] Impact sensitivity [J] [h]
Friction sensitivity [N] [i] Nitrogen content [%] [j] 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 (without crystal water), OB(%)=1600[(d-2a-b/2)/Mw] [%].
MHz. Chemical shifts are reported relative to tetramethylsilane.
13C NMR spectra were recorded on a 400 MHz nuclear
magnetic resonance spectrometer operating at 100 MHz. The
Conclusions
solvent was [D6]dimethylsulfoxide ([D6]DMSO) unless
otherwise specified. 15N NMR spectra was recorded on a 400
MHz nuclear magnetic resonance spectrometer operating at
40.5MHz. The melting and decomposition points were
recorded on a NETZSCH STA 449F3 equipment at a scan rate of
5oC min-1, respectively. Infrared spectra were recorded by
using KBr pellets. Densities were measured at room
A family of nitrogen-rich energetic salts based on 3-nitramino-
4-tetrazole-furazan were conveniently synthesized and fully
characterized by NMR (1H NMR, 13C NMR), IR and elemental
15
analysis. Additionally, ammonium salt (
N NMR and hydroxylammonium salt (
single-crystal X-ray diffraction individually. This kind of
energetic salts show good thermal stability [203oC ( ) to 284oC
)] and high positive enthalpy of formation [299.2 kJ mol-1
to1040.6 kJ mol-1
)]. Their impact sensitivities lie between 5 J
and ) and >40 J ( ) and their friction sensitivities range
from 108 N ( ) to >360 N ( ). Not as we expected, they just
show little lower sensitivities compared with the
2) was confirmed by
5
) was confirmed by
4
temperature using
a MicromeriticsAccupyc Ⅱ 1340 gas
(
6
(2)
pycnometer. Elemental analyses were obtained on an
ElementarVario MICRO CUBE (Germany) elemental analyzer.
3-Amino-4-tetrazole-furazan was synthesized according to
Ref 16.
(9
(2
5
6, 7, 8
4
6
a
X-ray crystallography: Crystal of salt
5 was removed from the
corresponding DNTF salts. The detonation pressures of the
synthesized energetic salts were calculated to be in the range
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 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
BrukerSMART software. The reflection data were also
corrected for Lpfactors. The structure was solved by direct
of 21.1GPa (
6
) to 34.7 GPa (
5
) and their detonation velocities
). In view of the
fall between 7117 m s-1
(6
) and 8826 m s-1
(5
detonation velocity, density and thermal stability, salt
promising replacement for RDX.
5 is a
Experimental Section
General methods:
1H spectra were recorded on a 300 MHz
nuclear magnetic resonance spectrometer operating at 300
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methods and refined by least squares method on F2 using triaminoguanidinium
Paper
chloride.
For
salt
5,
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Bruker SHELXTL program. Structure was solved in the space dihydroxyammoniumsulfate was used as DpOurI:c1h0a.1s0e3d9./C6RA12109H
group P-1 by analysis of systematic absences. In this all-light- Dihydrazinium NATF (4): Recrystallization with the mixture of
atom structure the value of the Flack parameter did not allow water and ethanol to give 400 mg white crystal in 76% yield. 1H
the direction of polar axis to be determined and Friedel NMR (d6-DMSO, 300MHz): δ=7.31 (s, 10H) ppm; 13C NMR (d6-
reflections were then merged for the final refinement. Details DMSO, 100MHz): δ=144.5, 150.1, 156.9 ppm. IR (KBr): 3341,
of the data collection and refinement are given in Table S1.
3012, 1611, 1511, 1438, 1375, 1320, 1157, 1097, 1011, 991,
CCDC-1476973 contains the
(5)
supplementary 970, 913, 869, 827, 771, 737, 581, 542, 453 cm-1. Elemental
crystallographic data for this paper. These data can be analysis for C3H10N12O3 (262.19): Calculated: C: 13.74 H: 3.84 N:
obtained free of charge from The Cambridge Crystallographic 64.11; Measured: C: 13.99 H: 3.94 N: 63.66.
Data Centre via www.ccdc.cam.ac.uk/data_request/cif
.
Dihydroxylammonium NATF
(5): Recrystallization with the
Diammonium NATF (2): 4-Amino-3-(5-tetrazole)furazan (4.4 g, mixture of water and ethanol to give 355 mg white crystal in
1
28.7 mmol) was added in small portions into the mixture of 67% yield. H NMR (d6-DMSO, 300MHz): δ=10.44 (s, 8H) ppm;
98% H2SO4 (25 mL) and fuming nitric acid (95%, 25 mL) cooled 13C NMR (d6-DMSO, 100MHz): δ=143.7, 149.6, 156.3 ppm. IR
with ice-water bath at <5oC. The reaction mixture was allowed (KBr): 3121, 2702, 1618, 1584, 1519, 1441, 1394, 1350, 1221,
to warm to room temperature and stirred for 30 min followed 1185, 1164, 1143, 1097, 1001, 934, 881, 837, 748, 735, 720,
by pouring into 500 mL ice-water. The resulting solution was 594, 551, 453, 405 cm-1. Elemental analysis for
extracted with ethyl acetate, and the combined organic phase C3H8N10O5(264.16): Calculated: C: 13.64 H: 3.05 N: 53.02;
was washed with brine to remove remaining acids. The organic Measured: C: 13.40 H: 3.30 N: 52.28.
phase was dried with MgSO4 for 30 min followed by filtration. Bis(guanidinium) NATF (6): Recrystallization with the mixture
Ammonia gas was bubbled slowly into the filtrate to give of water and ethanol to give 460 mg white crystal in 73% yield.
yellow precipitation. After filtration and washing with water 1H NMR (d6-DMSO, 300MHz): δ=7.16 (s, 12H) ppm; 13C NMR
and ethanol yellow crystal was obtained (5.4 g) in 81% yield. 1H (d6-DMSO, 100MHz): δ=145.0, 150.3, 157.3, 158.0 ppm. IR
NMR (d6-DMSO, 300MHz): δ=7.43 (s, 8H) ppm; 13C NMR (d6- (KBr): 3361, 3183, 1655, 1506, 1427, 1393, 1369, 1337, 1300,
DMSO, 100MHz): δ=144.8, 150.2, 156.9 ppm. IR (KBr): 3185, 1160, 1013, 993, 927, 875, 826, 771, 739, 590, 540 cm-1.
2812, 1697, 1592, 1513, 1437, 1371, 1292, 1155, 1045, 1012, Elemental analysis for C5H12N14O3 (316.24): Calculated: C:
991, 914, 873, 824, 772, 742, 727, 585, 540, 488, 457 cm-1. 18.99 H: 3.82 N: 62.01; Measured: C: 18.76 H: 3.97 N: 61.97.
Elemental analysis for C3H8N10O3 (232.16): Calculated: C: 15.52 Bis(aminoguanidinium) NATF
H: 3.47 N: 60.33; Measured: C: 15.69 H: 3.63 N: 60.25. mixture of water and ethanol to give 520 mg white crystal in
Barium NATF·3H2O
):4-Amino-3-(5-tetrazole)furazan (3.6 g, 75% yield. 1H NMR (d6-DMSO, 300MHz): δ=4.76 (s, 4H) 7.04 (s,
(7): Recrystallization with the
(3
28.7 mmol) was added in small portions into the mixture of 4H), 7.39 (s, 4H), 8.94 (s, 2H) ppm; 13C NMR (d6-DMSO,
98% H2SO4 (25 mL) and fuming nitric acid (95%, 25 mL) cooled 100MHz): δ=145.0, 150.3, 157.4, 158.8 ppm. IR(KBr): 3463,
with ice-water bath at <5oC. The reaction mixture was allowed 3158, 1678, 1648, 1624, 1587, 1509, 1463, 1433, 1390, 1366,
to warm to room temperature and stirred for 30 min followed 1322, 1200, 1162, 1140, 1097, 1043, 1009, 995, 923, 875, 826,
by pouring into 400 mL ice-water. The resulting solution was 770, 734, 692, 616, 543, 507, 453 cm-1. Elemental analysis for
extracted with ethyl acetate, and the combined organic phase C5H14N16O3 (346.27): Calculated: C: 17.34 H: 4.08 N: 64.72;
was washed with brine to remove remaining acids. The organic Measured: C: 16.82 H: 3.76 N: 64.63.
phase was dried with MgSO4 for 30 min followed by filtration. Bis(diaminoguanidinium) NATF (8): Recrystallization with the
Aqueous solution of Ba(OH)2·8H2O (7.4 g, 23.5 mmol) was mixture of water and ethanol to give 620 mg white solid in
added into the filtrate and the reaction mixture was stirred at 82% yield. 1H NMR (d6-DMSO, 300MHz): δ=4.65 (s, 8H), 7.27 (s,
room temperature for 30 min. Yellow solid precipitate was 4H), 8.80 (s, 4H) ppm; 13C NMR (d6-DMSO, 100MHz): δ=145.1,
separated by filatration and recrystallized with water to give 150.3, 157.5, 159.8 ppm. IR(KBr): 3407, 3367, 3281, 3201,
light yellow solid (6.1 g) in 81% yield. IR (KBr): 3562, 3412, 2978, 2875, 1679, 1615, 1502, 1432, 1407, 1386, 1311, 1182,
3269, 2960, 1682, 1611, 1523, 1443, 1420, 1382, 1356, 1293, 1157, 1136, 1052, 994, 932, 875, 827, 773, 740, 656, 544, 514,
1169, 1149, 1085, 1070, 1036, 1019, 998, 924, 877, 847, 778, 427 cm-1. Elemental analysis for C5H16N18O3 (376.30):
736, 707, 545, 455 cm-1. Elemental analysis for Ba C3H6N8O6 Calculated: C: 15.96 H: 4.29 N: 67.00; Measured: C: 15.69 H:
(387.46): Calculated: C: 9.30 H: 1.56 N: 28.92; Measured: C: 4.32 N: 66.17.
8.82 H: 1.58 N: 29.38.
Bis(triaminoguanidinium) NATF
(9): Recrystallization with the
General procedures for the preparation of salts 4-9: Barium mixture of water and ethanol to give 685 mg white solid in
1
NATF (775 mg, 2 mmol) was added to the aqueous solution of 84% yield. H NMR (d6-DMSO, 300MHz): δ=4.51 (s, 12H), 8.62
sulfate salt (2 mmol) and the resulting solution was stirred at (s, 6H) ppm; 13C NMR (d6-DMSO, 100MHz): δ=146.3, 150.4,
room temperature for 4 h. For salts
4 and 6-9 the sulfate salts 158.0, 159.1 ppm. IR(KBr): 3317, 3210, 1691, 1598, 1498, 1427,
were prepared by the reaction of chloride salt (4 mmol) and 1392, 1373, 1309, 1203, 1133, 1033, 986, 910, 864, 820, 773,
Ag2SO4 in 15 mL water at room temperature for 2 h. The 748, 725, 639, 581, 538, 459 cm-1. Elemental analysis for
chloride salts are hydrazinium chloride, guanidinium chloride, C5H18N20O3 (406.33): Calculated: C: 14.78 H: 4.47 N: 68.94;
aminoguanidinium chloride, diaminoguanidinium chloride and Measured: C: 14.34 H: 4.56 N: 68.63.
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Y. Tang, J. Zhang, L. A. Mitchell, D. A. Parrish and J. M.
Acknowledgements
This work was financially supported by Natural Science
Foundation of Shanghai, China (Grant. No. 16ZR1443600).
Thanks to Prof.Guangyu Li for 15N NMR measurement.
Shreeve. J. Am. Chem. Soc. 2015, 137, 15984-15V9ie8w7A. rticle Online
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DOI: 10.1039/C6RA12109H
The combination of nitramino group and tetrazole with furazan ring gave rise to energetic salts
thermally stable up to 284oC.