Exploration of low-melting energetic compounds: Influence of substituents on melting points

Article abstract of DOI:10.1039/d0nj01166e

To investigate the effect of substituents on nitrate-based energetic compounds, a class of energetic compounds based on triazole nitrates were designed, synthesized, and characterized. Crystal structures of some compounds were proved by single crystal X-ray diffraction. The analysis of the melting point of each compound shows that the effect of the substituent on the melting point of the compound follows a trend of -N3 > -NO2 > -ONO2 > -NNO2. To verify the trend, we used Hirshfeld surfaces to analyze the intermolecular effects of the substituents. The compounds (3-nitro-1H-1,2,4-triazol-5-yl)methyl nitrate and (5-azido-1H-1,2,4-triazol-3-yl)methyl nitrate, were found to be potential melt cast explosive carriers or energetic plasticizers. This journal is

Full text of DOI:10.1039/d0nj01166e

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Exploration of Low-melting Energetic Compounds: Influence of
Substituents on Melting Points
Received 00th January 20xx,
Accepted 00th January 20xx
a
a
a
Rui Yang, Zhen Dong and Zhiwen Ye *
DOI: 10.1039/x0xx00000x
To investigate the effect of substituents on nitrate-based energetic compounds, a class of energetic compounds based on
triazole nitrates were designed, synthesized, and characterized. Crystal structures of some compounds were proved by
single crystal X-ray diffraction. Analysis of the melting point of each compound shows that the effect of the substituent on
the melting point of the compound follows a trend of -N
3
>-NO
2
>-ONO
2
>-NNO . To verify the trend, we used Hirshfeld
2
surfaces to analyze the intermolecular effects of the substituents. The compounds, (3-nitro-1H-1,2,4-triazol-5-yl) methyl
nitrate and (5-azido-1H-1,2,4-triazol-3-yl) methyl nitrate, were found to be potential melt cast explosive carriers or
energetic plasticizers.
oxygen balance of compounds, which has attracted attention
13, 14
Introduction
in recent years.
Tang et al. reported a nitrate ester (1-
nitro-3,5-di-(nitroxymethyl)-1,2,4-triazole) which has a low
melting point and good detonation properties. The results
showed that this compound can be used as an attractive melt-
castable explosive. The introduction of nitrate groups into
the triazole ring has been viewed as a new method to develop
new low-melting energetic compounds.
Low-melting energetic compounds are often used as melt
cast explosive carriers or energetic plasticizers in cast
munitions, such as mortars, grenades and artillery shells.1-4
Like TNT, the low detonation velocity as low melting point
energetic compounds and serious environmental pollution
during the production render them no longer suitable for
modern weapons. Research on new types of low-melting
15
In this paper, nitrimino, nitro, azido, and nitrate groups
were introduced into the parent structure of triazole nitrate.
energetic compounds has become
a current priority.
1
All the new energetic materials were characterized by H and
Substituents are one of the main factors affecting the melting
point of azole energetic compounds, including methyl, amino,
nitro, cyano, and azido groups. Substituents can affect the
melting point of compounds primarily because they change
the π electron spatial arrangement of the parent structure,
13
C NMR spectroscopy, IR spectroscopy, thermal stability
analysis and elemental analysis. (5-Nitrimino-1,4-dihydro-
1
1
,2,4-triazol-3-yl) methyl nitrate (
H-1,2,4-triazole ), (3-nitro-1H-1,2,4-triazol-5-yl) methyl
), and (5-azido-1H-1,2,4-triazol-3-yl) methyl nitrate (6)
2), 5-nitro-3-hydroxymethyl-
(3
nitrate (
4
5
that is, the substituent conjugate effect.
were proved by single crystal X-ray diffraction.
Triazole compounds have obtained widespread attention
as high-energy explosives for replace RDX, for example, 5-
6
amino-3-nitro-1,2,4-triazole (ANTA) , 3-azido-N-nitro-1H-1,2,4-
7
8
triazol-5-amine , 4-nitroamino-1,2,4-triazole , 3,5-dinitro-
9
10
1
,2,4-triazole (DNT) , 5-azido-3-nitro-1H-1,2,4-triazole , 3,5-
1
1
12
diazido-1,2,4-triazole , 3-nitro-5-nitramino-1H-1,2,4-triazole
and 1-methyl-5-nitramino-3-nitro-1,2,4-triazole
12
(Fig. 1).
While the study of triazole energetic compounds as melt-cast
explosives has not received much attention from researchers.
The higher oxygen content of nitrate group increases the
a.School of Chemical Engineering, Nanjing University of Science and Technology,
Xiaolingwei 200, Nanjing, Jiangsu, 210094 China. E-mail: yezw@njust.edu.cn
Electronic Supplementary Information (ESI) available. CCDC 1983597 1983595
†
1
983593 1978183. See DOI: 10.1039/x0xx00000x
Fig. 1 Triazole energetic compounds with different substituents.
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Single crystal X-ray structure analysis
Results and discussion
Synthesis
View Article Online
DOI: 10.1039/D0NJ01166E
Slow volatilization of methanol solution
solutions ( and
transparent crystals of
2 or ethyl acetate
3
,
4
6
) at room temperature generated white
, and for single crystal X-ray
diffraction analysis. The unit crystal structures and packing
structures are shown in Fig. 2-5. Detailed crystal data from
single crystal analysis was placed in the ESI. Compound
As shown in Scheme 1, using glycolic acid as raw material,
2
,
3
,
4
6
5
1
1
-amino-3-hydroxymethyl-1H-1,2,4-triazole (
,2,4-triazole-3,5-dimethanol ( ), and 3,5-bis(hydroxymethyl)-
H-1,2,4-triazole ( ) were obtained.
1), 4-amino-4H-
7
1
6, 17
8
(5-Nitrimino-1,4-
) was prepared by
and fuming HNO
4 3
dihydro-1,2,4-triazol-3-yl)methyl nitrate (
nitrating and using a mixture of 98% H SO
in a molar ratio of 3:1 and gave white , the yield was 78.8%.
Subsequently, to increase both performance and stability,
compound was reacted with a nitrogen-rich cation, to obtain
five nitrogen rich salts (2a-e) (Scheme 2). The source of (3-
nitro-1H-1,2,4-triazol-5-yl)methyl nitrate ( ) was first oxidized
with NaNO and H SO and then nitrified in a mixed acid
system of CH COOH-(CH CO) O and fuming HNO . The
temperature was maintained at 0 because a higher
2
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2
3
·CH OH crystallizes in monoclinic space group P 21/n with a
1
2
3
calculated density of 1.662 g/cm at 150 K. The structure is
provided in Fig. 2a. The 5-nitrimino group and triazole ring is
close to coplanar with torsional angles of N4-C3-N5-N6, at
3.93° and N2-C3-N5-N6 at 168.08°. However, the methyl
nitrate moiety is rotated to form an independent plane. The
dihedral angle of the methyl nitrate moiety and triazole ring is
2
2
1
4
2
2
4
7
7.27°. Owing to the strong H-bond between H4 and O6, the
H4···O6 distance is 1.840 Å, and, therefore, one methanol
molecule is involved in the crystallization of compound
3
3
2
3
℃
2
.
temperature aggravate the occurrence of by-products. The
reaction solution was then treated with ice water to obtain a
large amount of white product. After purification, pure
Interestingly, along the b axis, the two triazole rings facing
each other have a centroid distance of 3.570 Å. A π-π
interaction existed with offset face-to-face structure, to form a
wavy layered structure. A great deal of H-bonds exists in the
packing structure to generate a three-dimensional network
structure.
compound
,2,4-triazol-3-yl) methyl nitrate
introducing azido groups with NaN
then, fuming HNO was employed as the nitrating agent. The
4
was obtained with a yield of 72%. (5-Azido-1H-
was obtained by
in the reaction with , and
1
(6)
3
1
3
solution was added into ice water and extracted with ethyl
acetate to obtain a white product in high yield (85%). (1H-
1
,2,4-triazole-3,5-diyl)bis(methylene) dinitrate
(
9
)
was
based on
8. Detailed reaction conditions can be found in the
obtained by directly nitrating with fuming HNO
compound
ESI.
3
a
c
b
Scheme 1. Synthesis of triazole-based nitrate compounds
Fig. 2 (a) Single crystal structure of
c) unit cell of
2; (b) Stacking types of 2 along the b axis;
(
2.
The crystallization mode of compound
space group P 21/n , with crystal density of 1.733 g/cm at 150
K and four moleculars in the unit cell. The structure of with
3 is monoclinic
3
3
atomic labels is provided in Figure 3a. The triazole and 5-nitro
moieties are slightly distorted with torsional angles of O2-N6-
C9-N4 at -7.72° and O2-N6-C9-N5 at 170.63°, while the
hydroxymethyl group alone forms another plane. The plane
and triazole are nearly perpendicular with an included angle of
Scheme 2. Synthesis of compound 2 energetic salts
2
| J. Name., 2012, 00, 1-3
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7.21°. Abundant intermolecular H-bonds form a three- nitrogen atoms of the azide have a linear structure. The angle
View Article Online
DOI: 10.1039/D0NJ01166E
dimensional network.
C2-C3-O1 is 105.68°. Due to this crystal structure (Fig. 5b), two
molecules in the unit cell form hydrogen bonds with each
other, while two adjacent unit cells are unaffected. The
corresponding H···O length is 2.607 Å. The existence of
hydrogen bonds between adjacent molecules constitutes a
bimolecularly layered structure, but, there are no hydrogen
bonds between layers, which may be the reason for the lower
melting point of the compound. Interestingly, because the two
adjacent triazole rings are only 4.526 Å apart, π-π interactions
are formed with a face-to-face structure.
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0
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0
a
b
Fig. 3 (a) Single-crystal structure of
axis.
3
; (b) Stacking types of
3
along the b
The crystallization mode of compound
space group P 21 21. There are four moleculars in a unit cell
and the crystal density was 1.787 g/cm at 152 K. The structure
is provided in Figure 4a. The 5-nitro moiety and triazole ring
are coplanar to form a red plane. the nitrate moiety of
rotates to form the blue plane. The two planes are nearly
perpendicular with an included angle of 80.05°. As seen in Fig.
4 is orthorhombic
3
a
4
4
c, there is a strong hydrogen bond between N on the triazole
and H on the adjacent triazole, and the length of this hydrogen
bond (N3···H4) is 2.139Å. The packing picture is exhibited in Fig.
4
b. The stacking struture presents a wavy layered structure via
the b axis, but now, no H-bonding between the layers exists,
which may be the reason for the lower melting point.
b
c
Fig. 5 Single-crystal structure of
unit cell of 6.
6
; b) Stacking types of
6
along the a axis; c)
Thermal Behavior
For melt cast explosives and energetic plasticizers, the
melting point and decomposition temperature of the
compounds are key parameters. A suitable melting point (70-
20 ) is good for compound casting, and a high
decomposition temperature is good for ammunition stability.
The introduction of different substituent groups on the triazole
ring cause the melting points of the compounds to change. The
melting points and decomposition temperatures of the new
energetic materials were analyzed with differential scanning
calorimetry (DSC) and several energetic materials were
analyzed by thermogravimetric analysis (TGA). The DSC curves
of all compounds are exhibited in Fig. 6, and all show good
18
1
℃
a
thermal stability. The compounds 2e
melting points of 109.95 151.68
8.9 and 104.46
compounds and
cast explosives and energetic plasticizers, and can be
,
3
,
4
,
5
,
6
℃
and
9 have
℃
，
℃，
100.48
，
112.11℃，
9
℃
℃
, respectively. Considering steam casting,
b
c
4
6 have the best ideal characteristics of melt-
Fig. 4 (a) Single-crystal structure of
axis; (c) unit cell of 4.
4
; (b) Stacking types of 4 along the b considered for casting ammunition in military and civilian
applications.
According to Carnelley's symmetry rules, the higher the
The crystallization mode of compound
6
is triclinic space
19
symmetry of a molecule, the higher its melting point. Thus,
compound has a higher melting point than compounds and
. The order in which the substituents decrease the melting
point is shown as: -N >-NO >-ONO >-NNO
3
group P -1, and the calculated density is 1.769 g/cm at 150K.
In the unit cell two molecular moieties are present. Its
structure is provided in Fig. 5a. Not surprisingly, the three
9
4
6
3
2
2
2
.
This journal is © The Royal Society of Chemistry 20xx
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forces (vdW) surfaces of
7
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,
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, and
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are shown in Fig. 7. In Fig.
View Article Online
DOI: 10.1039/D0NJ01166E
a, based on the triazole parent, the ESP of the nitro group is
significantly lower than that of the nitrate group, indicating
that the nitro group has a slight contribution to the reduction
of impact sensitivity of the energetic compounds. As expected,
the azide group has a high positive electrostatic potential.
From the ESP maps of these three compounds, the nitrimino
group has a negative electrostatic potential, indicating that the
nitrimino group may contribute a lot to the reduction of
2 is more insensitive
than compounds and the predicted results of this ESP
models are consistent with the measured conclusions.
The Hirshfeld surfaces and 2D fingerprint spectra are
often used to analyze the relationship between the sensitivity
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impact sensitivity. Therefore, compound
4, 6
21-24
and structure of compounds.
The sensitivities of the
compounds were analyzed by hydrogen bonding and
25-29
intermolecular forces.
The melting points of the energetic
compounds were affected by many factors, of which hydrogen
bonding and intermolecular forces are the main factors.3
The Hirshfeld surfaces and 2D fingerprint spectra are new
methods to analyze the melting points of compounds. The
0-33
Hirshfeld surfaces and 2D fingerprint spectra of the crystal
2, 4
and were studied and exhibited in Fig. 8. All the red dots are
6
related to intermolecular H-bonds (N-H···N, N-H···O and O-
H···N) and the blue parts represent weak interactions of N···O,
N···N, C···N, C···O, and O···O. In the total weak interactions for
6, the total proportion of N···H and O···H is 61.6%,
0.4%, and 37.9%, respectively. The datas represent the
2
,
4
, and
5
strength of the intermolecular hydrogen bonds of the
compounds. However, has a high proportion in N···H and
2
Figure 6. DSC curves of all energetic compounds (heating rate of 10
℃
min-
O···H. This suggests that hydrogen bonds as an important
intermolecular interaction tends to stabilize compounds and
increases the melting temperature. The analysis results of
Hirshfeld surfaces and 2D fingerprint spectra are consistent
with the experimental results.
1)
.
Electrostatic potentials and Hirshfeld surfaces
Greater positive surface electrostatic potentials (ESPs)
reflect stronger impact sensitivities of compounds.20 The
calculated electrostatic potential (ESP)-mapped van der Waal’s
33.08
5
7.43
58.48(backside)
(backside)
(
backside)
30.19
44.95
2
4.94
41.63
(backside)
19.68
3
5.71
(backside)
(backside)
2
4.71
18.97
2
3.99
19.07
40.97
backside)
23.21(backside)
4
1.92
(
34.49
backside)
a
b
c
63.58
(
Fig. 7 Electrostatic potentials of the compounds (a) 4, (b) 6, and (c) 2.
3
4
Heats of Formation and Energetic Properties
energies , the HOFs of all new energetic compounds were
35
calculated with Gaussian 09W soft, they are shown in ESI.
Using the B3LYP with the 6–311+G** basis set to accomplish
the geometry optimizations and frequency analyses of the
molecules. All new energetic compounds exhibit positive HOF
In studying the energetic performance of energetic
compounds, the heat of formation (HOF) is a key parameter.
According to the isodesmic reaction, which is hypothetical
chemical process in which various forms of chemical bonds at
both ends of the equation remain unchanged and it is a
measure of the difference in the additive of the bond
-1
values, ranging between 102.21 and 556.52 kJ mol , which is
-1
more than TNT (-59.4 kJ mol ). The impact and friction
4
| J. Name., 2012, 00, 1-3
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sensitivities were measured via standard BAM equipment , and the experimental results are exhibited in Table 1.
View Article Online
DOI: 10.1039/D0NJ0116 6- 1
E
and the results are listed in Table 1. All energetic compounds Compound
exhibited good friction sensitivity, with values between 120 N and detonation pressure (33.3 GPa). Except for compound
and 360 N. However, compound has a high impact sensitivity the detonation velocity and detonation pressure of all
5 J) due to the azido group. Others have acceptable impact energetic compounds were higher to those of TNT (6881m s ,
2 exhibits the best detonation velocity (8759 m s )
3
,
6
-1
(
-
1
sensitivities with values ranging from 10 J to 25 J. Using the 19.5 GPa) and NG (7819 m s , 24.4 GPa). Compounds
obtained HOFs and measured densities at 25 , the also have properties of melt-cast explosives, and, thus, they
detonation velocity and detonation pressure of all new can be considered as potential melt-cast explosives or
4 and 6
℃
0
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3
4
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compounds were obtained by the EXPLO5 (v6.01) program , energetic plasticizers.
(
a)
(b)
(c)
(e)
(f)
(d)
Fig. 8 The two dimensional fingerprint picture and Hirshfeld surfaces in crystal structure for
show the individual atomic contact proportion.
2
(a),
4
(b) and 6 (c); the pie charts for 2 (d), 4 (e) and 6 (f)
Table 1. Physical properties and heats of formation of all energetic compounds
[
a]
[b]
d[c] [g cm-3]
1.81(1.662)
1.73
1.725
1.725
OB[d] [%]
-19.70
-29.09
-42.75
-43.32
-45.06
-47.38
H[e] [kJ mol-1]
[f]
[m s-1]
P[g] [GPa]
33.3
IS[h] [J]
20
25
25
15
20
20
20
15
10
5
[i]
Comp.
2
T
m
[
℃]
T
d
[
℃
]
Δ
f
ν
D
FS [N]
240
360
360
240
240
360
360
240
240
120
240
360
353
--
--
--
--
--
208.55
132.84
135.01
127.22
137.10
187.39
187.39
163.18
163.42
145.81
156.96
143
213.5
242.5
202.98
392.76
453.5
556.52
102.21
161.6
421.6
538.4
145.3
-370.8
-59.4
8759
8619
8331
8617
8254
8435
7798
8472
8021
8550
8214
7819
6881
2a
2b
2c
2d
2e
3
4
5
6
9
30.92
27.02
28.91
27.61
28.65
23.90
31.23
23.18
30.07
28.8
1.746
1.75
109.95
151.68
100.48
112.11
98.90
104.46
14
1.695(1.733) -55.55
1.749(1.787) -21.16
1.68
1.73(1.769)
1.73
1.591
1.65
-80
-38.92
-35.47
-3.52
-73.97
20
0.2
15
NG
TNT
24.4
19.5
80.5
295
[a] Melting point (onset). [b] Decomposition temperature (onset). [c] Density measure at 25 , Single crystal density in brackets. [d] Oxygen balance (OB)
℃
for C (without crystal water), C completely produces CO , H completely produces H O, OB(%) = 1600[(d-2a-b/2)/Mw]. [e] Calculated heats of
a
H
b
N
c
O
d
2
2
formation. [f] Detonation velocity [g] Detonation pressure. [h] Impact sensitivity. [i] Friction sensitivity.
Safety Precautions
All energetic compounds have the potential to explode during
synthesis. Although we have successfully synthesized these
Experimental Section
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 5
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2
3
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6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
-
1
compounds, the necessary safety measures are not indispensable. 2c: yellow solid; 91% yield. DSC(10℃ min ): 127.22 ℃, 187.76℃
DOI: 10.1039/D0NJ01166E
Goggles and protective masks should always be worn during the (dec., onset). H NMR (300 MHz, DMSO-d ) δ = 4.69(s, 2H), 5.46(s,
6
synthesis process.
General Method
View Article Online
1
1
3
2H), 6.80 (s, 2H), 7.27 (s, 2H), 8.63 (s, 1H). C NMR (126 MHz,
DMSO-d ) δ = 68.6, 152.9, 157.6, 158.9. IR(KBr):ṽ= 3405.67, 3332.31,
160.63, 1678.53, 1623.11, 1518.67, 1441.70, 1374.56, 1281.00,
138.95, 1090.49, 992.35, 933.48, 865.21. elemental analysis calcd
(278.19) C 17.27, H 3.62, N 50.35, O 28.76; found:
C 17.35, H 3.41, N 50.45, O 28.79.
6
3
1
(
In the study, all reagents were purchased from MERYER or
1
13
aladdin. H and C spectra were measured on a 300 MHz (Bruker
AVANCE 300) or 500 MHz (Bruker AVANCE500) nuclear magnetic
4 10 10 5
%) for C H N O
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
resonance spectrometer. DMSO-d
The melting points and decomposition temperature (onset) were
obtained on a DSC at a scan rate of 10 ℃ min in closed Al
containers with a nitrogen flow of 50 ml min . IR spectra were
obtained using KBr pellets for powder on Thermo Nicolet iS10
spectrometer. Elemental analyses were obtained on a vario EL III
CHNOS elemental analyzer.
6
was used as a locking solvent.
-
1
2
1
d: white solid; 89% yield. DSC(10℃ min ): 137.10 ℃(dec., onset).
13
H NMR (300 MHz, DMSO-d6) δ = 5.67 (s, 2H). C NMR (126 MHz,
) δ = 65.1, 144.2, 146.0, 153.7. IR(KBr):ṽ= 3160.86, 3008.03,
875.34, 1659.05, 1603.95, 1561.21, 1438.31, 1298.65, 1223.46,
117.20, 1045.00, 988.34, 855.50, 829.80. elemental analysis calcd
(273.17) C 21.98, H 2.58, N 46.15, O 29.28; found:
C 22.05, H 2.42, N 46.21, O 29.32.
e: white solid; 94% yield. DSC(10℃ min ): 109.95℃(melt, onset),
-1
DMSO-d
2
1
6
-1
(
5 7 9 5
%) for C H N O
(5-Nitrimino-1,4-dihydro-1,2,4-triazol-3-yl) methyl nitrate(2)
-1
2
1
5
-Amino-3-hydroxymethyl-1H-1,2,4-triazole(1)(1 g, 8.77 mmol) was 187.39℃(dec., onset). H NMR (500 MHz, DMSO-d
6
) δ = 5.66(s, 2H),
) δ = 65.3, 144.5, 146.2,
1
3
dissolved in round bottom flask containing fuming nitric acid (4ml) 8.58(s, 2H). C NMR (126 MHz, DMSO-d
6
and 98% sulfuric acid (10ml) at 0 ℃. The reaction mixture was 156.9. IR(KBr):ṽ= 3370.72, 3302.00, 3103.15, 1906.87, 1656.34,
stirred at 0 ℃ for 1 h and was then slowly warming to room 1601.26, 1558.80, 1422.33, 1342.35, 1283.87, 1187.55, 1078.72,
temperature, the reaction was stirred for 24h. After, the reaction 994.50, 972.71, 944.66, 836.28, 717.00. elemental analysis calcd (%)
mixture was added into the mixture of ice and water (50 g), stirred for C H N O (288.18) C 20.84, H 2.80, N 48.60, O 27.76; found: C
5 8 10 5
and the resulting solution extracted with ethyl acetate (3×50 20.91, H 2.75, N 48.76, O 27.58.
ml).The combined organic phases was washed with saturated
brine(2×50 ml). The organic phases were combined and dried with
magnesium sulfate and then filtered. The organic phase was
evaporated under vacuum to obtain a yellow solid (1.41 g, 78.8%).
3
-Nitro-5-hydroxymethyl-1H-1,2,4-triazole (3)
3
-Amino-5-hydroxymethyl-1H-1,2,4-triazole (1) (1 g, 8.77 mmol)
SO (10 ml) at room temperature. Then added
was added in 20% H
2
4
-
1
the above solution to 10 ml water containing sodium nitrite (7.6 g)
under 40 ℃. After the addition was complete, the temperature
rised to 50 ℃ and stirred for another 8 h. After the reaction was
completed, the reaction solution was cooled to room temperature.
The solution was acidified with 20% sulfuric acid and a small
amount of urea was added. The solution was extracted by ethyl
acetate (3×40 ml), the solvent was evaporated under vacuum to
Single crystal obtained by evaporation in methanol. DSC(10℃ min ):
1
2
2
1
1
08.55 ℃ (dec., onset). H NMR (300 MHz, DMSO-d
H), 5.67 (s, 2H); C NMR (126 MHz, DMSO-d
52.8. IR(KBr):ṽ= 3355.95, 2591.55, 1619.57, 1571.88, 1522.25,
419.93, 1282.21, 1105.00, 989.35, 945.92, 852.74. elemental
6
) δ = 3.84(s,
1
3
6
) δ = 54.4, 151.2,
analysis calcd (%) for C
9.19; found: C 17.60, H 1.87 N 41.22 O 39.31.
General procedure for preparation of 2a-e.
3 4 6 5
H N O (204.10) C 17.65, H 1.98, N 41.18, O
3
-1
obtain a white solid (1.13 g, 89.7%). DSC(10℃ min ): 151.68℃
1
(
melt, onset), 219.17℃ (dec., onset). H NMR (300 MHz, DMSO-d
6
)
13
Compound 2 (0.5 g, 2.45 mmol) was dissolved in acetonitrile (10 ml), δ = 4.67 (s, 2H), 6.02 (s, 1H). C NMR (126 MHz, DMSO-d
then 28% NH ·H O (150 mg, 1.37 mmol), or guanidine carbonate 55.73, 159.42, 162.63. IR(KBr):ṽ= 3215.21, 2977.35, 2762.69,
220.5 mg, 1.225 mmol), or aminoguanidine bicarbonate (340 mg, 1707.12, 1555.38, 1477.63, 1446.02, 1386.71, 1303.61, 1215.07,
6
) δ =
3
2
(
2
1
.45 mmol), or 1,2,4-triazole (169 mg, 2.45 mmol), or 4-amino-4H- 1059.02, 1016.21, 896.60, 837.93, 794.97. elemental analysis calcd
,2,4-triazole (210 mg, 2.45 mmol) was added. The solution was (%) for C (144.09) C 25.01, H 2.80, N 38.88, O 33.31; found:
4 4 4 3
H N O
stirred for 2 h at room temperature. The products were obtained by C 25.04, H 2.75, N 38.93, O 33.28.
filtration to give 2a-e.
(
3-Nitro-1H-1,2,4-triazol-5-yl) methyl nitrate (4)
-1
2
a: white solid; 88% yield. DSC(10℃ min ): 132.84 ℃(dec., onset).
1
13
3 3 2
8 g of glacial CH COOH and 8 g of (CH CO) O were added into a 50
H NMR (300 MHz, DMSO-d
6
) δ = 5.46 (s, 2H), 7.13(s, 4H); C NMR
ml round bottom flask and stirred at 0 ℃, after which 4.5 ml of
fuming HNO was slowly added and stirred for 30 min. Then 3-nitro-
-hydroxymethyl-1H-1,2,4-triazole (3) (1 g, 6.94 mmol) was added
(
1
8
126 MHz, DMSO-d
6
) δ = 68.5, 152.8, 157.3. IR(KBr):ṽ= 3218.01,
613.63, 1530.11, 1434.29, 1272.41, 1147.93, 1081.02, 976.14,
89.52. elemental analysis calcd (%) for C (221.13) C 16.26,
3
5
3 7 7 5
H N O
and continuely stirred for 2 h. Additionally, the solution was stirred
for 2h at room temperature. After, the reaction solution was
poured into crushed ice (50 g), the product was precipitated,
filtered, washed with a amount of cold water, dried in air at room
H 3.19, N 44.34, O 36.18; found: C 16.29, H 3.06 N 44.38, 36.27.
-
1
2
b: light yellow solid; 92% yield. DSC(10℃ min ): 135.01 ℃(dec.,
1
onset). H NMR (300 MHz, DMSO-d
6
) δ = 5.47 (s, 2H), 6.99 (s, 6H);
) δ = 68.4, 152.7, 157.3, 158.1.
IR(KBr):ṽ= 3394.67, 3157.15, 1625.42, 1519.89, 1443.80, 1386.42,
333.38, 1281.89, 1138.18, 1090.79, 934.74, 864.63. elemental
analysis calcd (%) for C (263.17) C 18.26, H 3.45, N 47.90, O
0.40; found: C 18.23, H 3.40, N 47.95, O 30.42.
13
C NMR (126 MHz, DMSO-d
6
-
temperature and obtained white solid (0.94 g, 72%). DSC(10℃ min
1
1
)
: 100.48℃(melt, onset), 163.18℃(dec., onset). H NMR (500 MHz,
DMSO-d ) δ = 5.83 (s, 2H). C NMR (126 MHz, DMSO-d ) δ = 65.0,
6 6
52.2, 162.6. IR(KBr):ṽ= 3074.97, 2917.25, 1663.92, 1637.44,
546.05, 1482.57, 1428.90, 1383.97, 1309.86, 1291.44, 1274.43,
1
13
4 9 9 5
H N O
1
1
3
6
| J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
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Page 7 of 9
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Journal Name
ARTICLE
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
1
(
169.09, 1036.29, 969.74, 840.89, 796.27. elemental analysis calcd
%) for C (189.09) C 19.06, H 1.60, N 37.04, O 42.31; found:
C 19.11, H 1.55, N 37.08, O 42.26.
Conclusions
View Article Online
DOI: 10.1039/D0NJ01166E
A series of energetic compounds based on triazole nitrate were
designed, synthesized and characterized. The effects of nitramine,
nitro, azide, and nitrate groups on the melting points of the
3 3 5 5
H N O
5
-Azido-3-hydroxymethyl-1H-1,2,4-triazole (5)
5
-Amino-3-hydroxymethyl-1H-1,2,4-triazole (1)(1.14 g, 10 mmol) compounds were determined by DSC. Analysis of the melting point
SO
(25 mL) under 5 ℃. Then, sodium of each compound shows that the effect of the substituent on the
nitrite (0.76 g, 5.5 mmol) was added and the solution was stirred for melting point of the compound follows a trend of -N >-NO >-
Two low-melting energetic compounds were
(0.78g, 6mmol) was added. obtained that can be used as potential melt-casting explosive
was dissolved in 25% H
2
4
3
2
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2 2
h. After that, a small amount of urea was added to remove ONO >-NNO .
dissolved nitrogen oxides. Then, NaN
3
Addition completed, the solution was stirred for 3h at 25 ℃ and carriers or energetic plasticizers namely (5-Nitro-1H-1,2,4-triazol-3-
then neutralized to pH 6-7 with NaHCO
extracted by ethyl acetate (3×30 mL), and the combined organic 1,2,4-triazol-3-yl) methyl nitrate (T
phase was dried by anhydrous magnesium sulfate. Evaporation of provide reference for the development of new types of melt-cast
-1
solution. The solution was yl) methyl nitrate (T
m
D
=100.48 ℃, ν =8472 m s ) and (5-Azido-1H-
3
-1
m
D
=98.9 ℃, ν =8550 m s ), which
the solvent in under vacuum obtained 2 (80%) as a white solid. explosive carriers or energetic plasticizers.
-1
1
DSC(10℃ min ): 112.11℃(melt, onset), 163.43℃(dec., onset). H
NMR (500 MHz, DMSO-d ): δ= 13.85 (s, 1H), 5.76 (s, 1H), 4.55 (s,
H); 3C NMR (126 MHz, DMSO-d
) δ= 55.7, 156.8, 157.9.
IR(KBr):ṽ=3145.83, 3060.52, 2864.66, 2412.76, 2227.91, 2143.06, There are no conflicts to declare.
6
1
Conflicts of interest
2
6
1
1
560.11, 1509.16, 1450.83, 1356.18, 1326.85, 1282.83, 1207.94,
143.32, 1067.96, 1044.07, 1026.96, 784.37, 757.9, 731.25, 640.4
-1
cm ; elemental analysis calcd (%) for C
.88, N 59.98, O 11.42; found: C 25.84, H 2.65, N 60.03, O 11.48.
5-Azido-1H-1,2,4-triazol-3-yl)methyl nitrate (6)
-Azido-3-hydroxymethyl-1H-1,2,4-triazole (5) (1.0 g, 6.94 mmol)
was added in fuming HNO (10 mL) under 0 ℃. After, the solution
3
H
N
4 6
O(140.04): C 25.72, H Acknowledgements
2
The author thanks Mr. Chong Zhang (University of Science and
(
Technology) for using EXPLO5 software to calculate the
explosion performance, and also thank Dr. Qi Sun (University
of Science and Technology) for his guidance on the calculation.
5
3
was stirred for an additional 12 h at room temperature andthen
poured into crushed ice. The solution was extracted by ethyl
acetate (3×25 mL), washed with cold water(2×20 ml), and the
combined organic phase were dried by anhydrous magnesium
sulfate. Evaporation of the solvent in under vacuum obtained 3
Notes and references
1
2
3
4
T. M. Klapötke, A. Penger, C. Pflüger and J. Stierstorfer, New J.
Chem, 2016, 40, 6059-6069.
R. Yang, Z. Dong and Z. Ye, ChemistrySelect, 2019,
4213.
4, 14208-
(
85%) as a white solid. Compound 6 was crystallized from ethyl
1
-1
acetate and used single crystal X-ray analysis. DSC(10 ℃ min ):
J. C. Bennion, Z. R. Siddiqi and A. J. Matzger, Chem Commun
(Camb), 2017, 53, 6065-6068.
1
9
8.9℃(melt, onset), 145.81℃(dec., onset). H NMR (500 MHz,
13
A. S. Ermakov, E. Y. Petrov, D. B. Vinogradov, F. Van Toai, A. P.
6 6
DMSO-d ): δ= 5.65 (s, 2H); C NMR (126 MHz, DMSO-d ) δ=65.9,
Denisyuk and D. L. Rusin, Theor. Found. Chem. Eng., 2007, 41
,
1
1
1
8
51.9, 155.6. IR(KBr):ṽ= 3055.51, 2399.83, 2247.51, 2149.48,
633.37, 1565.57, 1521.29, 1445.28, 1396.94, 1349.03, 1320.04,
281.45, 1228.71, 1200.41, 1148.69, 1045.76, 1026.06, 985.47,
6
60-667.
J. Wei, Ind. Eng. Chem. Res., 1999, 38, 5019-5027.
K. Y. Lee, C. B. Storm, M. A. Hiskey and M. D. Coburn, J. Energ.
Mater, 1991, , 415-428.
K. Wang, D. A. Parrish and J. M. Shreeve, Chem.-Eur. J., 2011,
, 14485-14492.
5
6
-1
68.96, 837.98, 773.03, 749.57, 725.15, 685.02, 666.15, 587.17 cm .
9
7
8
9
elemental analysis calcd (%) for C
N 52.97, O 25.93; found: C 19.54, H 1.70, N 52.51, O 26.25.
1H-1,2,4-triazole-3,5-diyl)bis(methylene) dinitrate (9)
,5-Bis(hydroxymethyl)-1H-1,2,4-triazole (8) (1.5 g, 1.16 mmol) was
dissolved in fuming HNO (15 mL) under 0 ℃. After, the reaction
3 3 7 3
H N O (185.03): C 19.47, H 1.63,
1
7
T. P. Kofman, G. Y. Kartseva and M. B. Shcherbinin, Russ. J.
Org. Chem., 2002, 38, 1343-1350.
(
Y.-N. Li, N. Liu, P.-F. Su, Y.-L. Wang, Z.-X. Ge, H. Li and B.-Z.
Wang, Asian J. Chem, 2014, 26, 7151-7156.
3
3
10 V. V. Tolstyakov, Chem. Heterocycl. Compd, 2017, 53, 719-
mixture was stirred for 12 h at room temperature andthen poured
into ice water. The solution was extracted by ethyl acetate (3×25
mL), washed with cold water (2×30 ml), and the combined organic
phase was dried by anhydrous magnesium sulfate. Evaporation of
the solvent in under vacuum obtained 3 (80%) as a white solid.
721.
1
1
1 S.-H. Li, S.-P. Pang, X. T. Li, Y.-Z. Yu and X.-Q. Zhao, Chinese J
Org Chem, 2008, 28, 727-731.
2 A. A. Dippold, T. M. Klapötke, F. A. Martin and S. Wiedbrauk,
Eur. J. Inorg. Chem, 2012, 2012, 2429-2443.
13 D. E. Chavez, M. A. Hiskey, D. L. Naud and D. Parrish, Angew
Chem Int Ed Engl, 2008, 47, 8307-8309.
14 N. Wingborg and C. Eldsäter, Propellants, Explos., Pyrotech,
-1
1
DSC(10℃ min ): 104.46℃(melt, onset), 156.96℃(dec., onset). H
13
NMR (500 MHz, DMSO-d
DMSO-d ) δ = 66.52, 153.77. IR(KBr):ṽ= 2903.29, 2639.56, 1625.46,
464.04, 1369.60, 1275.04, 1164.70, 1069.44, 992.15, 935.64,
49.97, 787.40, 752.22. elemental analysis calcd (%) for
(219.11) C 21.93, H 2.30, N 31.96, O 43.81; found: C 21.98,
6
) δ =5.69 (s, 4H); C NMR (126 MHz,
2
002, 27, 314 - 319.
6
1
5 Y. Tang and J. M. Shreeve, Chem. -Eur. J., 2015, 21, 7285-
1
9
C
7291.
16 M. Liu, Q. Xu, S. Guo, R. Zuo, Y. Hong, Y. Luo, Y. Li, P. Gong
4
H
5 5
N O
6
and Y. Liu, Bioorg Med Chem, 2018, 26, 2621-2631.
H 2.25, N 32.04, O 43.73.
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 7
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2
2
2
2
2
2
2
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3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
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5
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5
5
5
5
5
5
6
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7 M. Raidt, M. Neuburger and T. A. Kaden, Dalton Trans, 2003,
292–1298.
8 Q. Zhang and J. M. Shreeve, Chem Rev, 2014, 114, 10527-
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1 S. Chen, Y. Liu, Y. Feng, X. Yang and Q. Zhang, Chem Commun
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2 W. Huang, Y. Tang, G. H. Imler, D. A. Parrish and J. M.
Shreeve, J Am Chem Soc, 2020, 142, 3652-3657.
View Article Online
DOI: 10.1039/D0NJ01166E
1
1
1
,
1
2
2
2
2
2
2
2
2
2
2
1
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
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4
5
6
7
8
9
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1
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3
4
5
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9
0
3 L. Tian, Y. Xu, Q. Lin, P. Wang and M. Lu, Chem Asian J, 2019,
14, 2877-2882.
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The substituent effect of low melting point compounds reduces sensitivity and improves
explosive performance.