Melt-cast materials: Combining the advantages of highly nitrated azoles and open-chain nitramines

Article abstract of DOI:10.1039/c6nj00202a

Numerous efforts to substitute TNT as the melt-cast matrix in explosive charges are ongoing due to its low performance and security issues. In this study the syntheses and full structural as well as spectroscopic characterizations of 2-nitrazapropyl substituted polynitroazoles, as potential melt-cast explosives, are presented. This straightforward method of derivatizing the heterocyclic N-H function by introducing a further energetic group improved the stability and energetic properties of the products. X-ray crystallographic measurements were performed for all compounds and afforded insights into structural characteristics such as strong intermolecular interactions. All compounds were characterized in terms of their sensitivities towards impact, friction and electrostatic discharge, and their thermal stabilities. The energetic properties were calculated with the EXPLO5 6.02 program.

Full text of DOI:10.1039/c6nj00202a

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DOI: 10.1039/C6NJ00202A
ARTICLE
Melt-cast Materials: Combining the Advantages of Highly Nitrated
Azoles and Open-chain Nitramines†
Thomas M. Klapötke, Alexander Penger, Carolin Pflüger and Jörg Stierstorfera
Received 00th January 20xx,
Accepted 00th January 20xx
Numerous efforts to substitute TNT as melt-cast matrix in explosive charges are ongoing due to its low performance and
security issues. In this study the syntheses and full structural as well as spectroscopic characterization of 2-nitrazapropyl
substituted polynitroazoles as potential melt-cast explosives are presented. This straightforward method of derivatization
the heterocyclic N-H function by introducing a further energetic group improves the stability and energetic properties.
X-ray crystallographic measurements were performed for all compounds and afforded insights into structural
characteristics like strong intermolecular interactions. All compounds were characterized in terms of sesitivities towards
impact, friction and electrostatic discharge and thermal stabilities. The energetic properties were calculated with the
DOI: 10.1039/x0xx00000x
www.rsc.org/
E
XPLO5 6.02 program.
sufficient separation of melting and decomposition processes,
low vapor pressure to diminish the inhalation toxicity and a
higher density and better performance than the ones already
used. Furthermore, for processing the melt-cast explosives
should show no shrinking and cracking on cooling and no
separation from the shell on casing.
Introduction
Melt-cast explosives are used in mortars, grenades, artillery
shells but also for civil applications e.g. for mining and
demolition. Nowadays, the melt-cast technology is based on
2,4,6-trinitrotoluene (TNT), 2,4-dinitroanisole (DNAN), 1,3,3-
trinitroazetidine (TNAZ), whose structures are depicted in
Figure 1. In general, the melt-cast explosives are molten in
kettles heated at 80 to 120 °C with hot water or steam
ingredients.1 Therefore, an ideal melt-cast explosive or its
formulations should have a low melting point (70–120 °C), a
The drawback of TNT is its low performance (Vdet = 7300 m s−1)
and its formulations are weak and brittle prone to cracking,
which increase the impact sensitivities, exudation and they are
dimensional instable in regard to thermal cycling.2 DNAN did
not show the toxicity drawback, which the manufacturing of
TNT posses, and it is less sensitive but also its performance is
lower. Formulations of TNAZ show issues concerning the
sensitivities and the melt-cast process to perform crack-free
and tension free castings.1 Therefore, the development of new
in all fields improved melt-cast explosives is still pursued.
Polynitrated azoles like 1-methyl-2,4,5-trinitroimidazole
(MeTNI)3 and 1-methyl-3,4,5-trinitropyrazole (MeTNP)4 as well
as 3,4-dinitropyrazole (DNP)5 (Figure 1) show promising
properties as replacement for TNT as melt-cast explosives due
to their high positive heats of formation, which results from
the large number of C–N and N–N bonds as well as from
ring/cage strain.6 The nitro groups lead to an increased acidity
of the heterocyclic proton, which may result in problems
concerning compatibility and storage. A common strategy to
avoid the acidity and diminish the hygroscopicity is their N-
alkylation by methylation or introduction of alkyl chains which
leads to better stabilities and compatibilities in formulations of
explosive charges.4a,7
Fig. 1 Melt-cast explosives.
a.Department of Chemistry, Ludwig Maximilian University, Munich, Butenandtstr. 5-
13, 81377 Munich, Germany. E-mail: tmk@cup.uni-muenchen.de
† Parts of this study have been presented at the 14th Seminar on New Trends in
Research of Energetic Materials, Pardubice, Czech Republic, April 13-15, 2011 and
in the Ph.D. thesis of Alexander Penger.
Alkylation using nitramine containing side groups is an
interesting strategy to improve the energetic properties
because the nitramine group may take part in intermolecular
interactions as acceptor and donor for hydrogen bonds as well
Electronic Supplementary Information (ESI) available: CCDC 1439310-1439321. See
DOI: 10.1039/x0xx00000x
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DOI: 10.1039/C6NJ00202A
O
as for dipolar N∙∙∙O and C∙∙∙O interactions, which should result
in higher densities in comparison to the methylated
derivatives.8 The linkage of two equal azoles by nucleophilic
substitution of 1,3-dichloro-2-nitrazapropane with the
corresponding potassium salts of nitrated azoles has been
investigated in different research groups7c,7i,9 in analogy to
studies of Bottaro and Highsmith.10 The resulting open-chain
nitramines show high thermal stabilities, high detonation
performances and varying sensitivities towards impact and
friction but unfortunately did not melt before decomposition
Therefore, a nitramine function should be introduced without
linking the azoles. Preliminary results using 1-chloro-2-
nitrazapropane and the doubly in situ deprotonated 3-nitro-
1,2,4-triazol-5-one as well as various deprotonated tetrazole
derivatives as azole building blocks reveal promising
properties, especially in regard to their thermal behavior with
respect to melting before decomposition.9,11
N
K
O
.
H2O
NH
N
O2N
N
N
HN
NO2
NO2
acetone, 12 h, rt
N
1
H
O
N
O
O2N
NH
N
N
N
N
NO2
O2N
O2N
O2N
N
N
NEt3, acetone, 12 h, rt
NO2
2
O2N
N
.
NO2
2 H2O
NO2
N
N
N
N
K
N
N
acetone, 24 h, rt
NO2
3
H2N
N
NH2
NO2
N
N
N
N
K
N
N
acetone, 12 h, rt
NO2
N
4
K
We now present an extended study of current work combing
the advantages of highly nitrated azoles and nitramines by
alkylation of the N–H function with 1-chloro-2-nitrazapropane
to obtain potential melt-cast explosives.
O2N
N
N
N
O2N
N
.
2 H2O
NO2
NO2
N
N
N
K
N
N
N
N
acetone, 12 h, rt
N
O2N
N
NO2
NO2
N
5
N
K
O2N
N
NO2
N
Results and discussion
NO2
Cl
N
N
acetone, 12 h, 50 °C
Syntheses
NO2
O2N
NO2
6
1-Chloro-2-nitrazapropane was synthesized in two steps as
shown in Scheme 1.11 After the nitration of 1,3,5-trimethyl-
hexahydro-1,3,5-triazine the conversion of 2-nitro-2-azapropyl
acetate to 1-chloro-2-nitrazapropane was carried out by
heating under reflux with thionyl chloride in dichloromethane
and catalytic amounts of acetic acid and sulfuric acid.
O2N
N
NO2
K
N
N
N
N
CH3CN, 12 h, 50 °C
NO2
O2N
7
O2N
N
NO2
The appropriate nitrogen-rich heterocycles were obtained
from literature-known procedures4a,10b,12 and generally
converted to the corresponding potassium salts by using
potassium hydroxide. The alkylation of the potassium salts
with 1-chloro-2-nitrazapropane in aprotic solvents like acetone
or acetonitrile yielded the desired energetic nitramines as
depicted in Scheme 2.
NO2
N
K
NO2
N
O2N
N
NaBr, acetone, 14 h, rt
N
8
NO2
N
N
NO2
N
O2N
O2N
NO2
N
O2N
N
K
NO2
N
+
N
CH3CN, 2 d, rt
N
N
N
In contrast to 1-(3-nitro-1H-1,2,4-triazol-5-on-4-yl)-2-nitraza-
9
O2N
NO2
NO2
O2N
propane (
1
), which was synthesized from the mono potassium
was obtained from the in situ
.
0.5 H2O
10
salt, the two times alkylated
2
NO2
O2N
O2N
Cl
N
N
K
NO2
N
deprotonated free acid 3-nitro-1,2,4-triazol-5-one (NTO) using
triethylamine as base.
N
CH3CN, 2 d, 56 °C
N
N
11
Various studies concerning the chemical stability of alkylated
dinitrotriazoles show elimination of nitrite and formation of
NTO derivatives and bistriazolyl systems under basic reaction
conditions.13 Thus, the alkylation of potassium 3,5-dinitro-
1,2,4-triazolate was carried out at ambient temperature and in
stoichiometric amounts to avoid elimination of nitrite. The
O2N
NH2
.
0.5 H2O
H2N
O2N
NO2
NO2
N
K
NO2
N
N
N
acetone, 12 h, rt
12
Scheme
nitrazapropane.
2 Syntheses of energetic nitramines starting from 1-chloro-2-
nucleophilic substitution of 1-chloro-2-nitrazapropane with the
potassium salt of 3-amino-5-nitro-1,2,4-triazole (ANTA) took
place at the endocylic nitrogen atom to yield selectively
Scheme 1 Synthesis of 1-chloro-2-nitrazapropane starting from 1,3,5-trimethyl-
hexahydro-1,3,5-triazine.
nitramine
4
. Potassium 3,3'-dinitro-5,5'-bi(1,2,4-triazolate) was
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alkylated two times at the nitrogen atoms N1/N1' to afford which also leads to very low yields.DOTIh: 1e0.1s0a3Vm9ie/wCe6ANrrtiJec0lae0cO2tn0iloi2nnAe
nitramine behavior was also observed for the nucleophilic substitution of
5
.
Furthermore, the symmetric and asymmetric dinitroimidazole 1,3-dichloro-2-nitrazapropane with potassium 3,4-dinitro-
and symmetric dinitropyrazole derivatives were successfully pyrazolate as reported previously.7c Additionally to the
alkylated to yield nitramines
reaction velocity of the synthesis of
Finkelstein halogen-exchange using sodium bromide.
6
,
7
, and
8
, respectively. The presented synthesis route for bipyrazolyl systems, they were
was optimized by a solely available by cine substitutions starting from 1,4-
dinitropyrazol derivatives.16
8
Two different substituted nitramines were formed by the The nucleophilic substitution of 1-chloro-2-nitrazapropane
alkylation of the potassium 3,4-dinitropyrazolate. The with potassium 3,4,5-trinitropyrazolate afforded the 5-chloro-
alkylation at N1 of 3,4-dinitropyrazole afforded the desired 3,4-dinitropyrazolate substituted nitramine 11 due to the
nitramine
9. The formation of the other bipyrazolyl based specific reactivity of the C5 position towards nucleophiles. This
nitramine 10 is caused by the high electrophilicity of the C3 behavior was already studied by Dalinger et al. for nucleophilic
position, which leads to a loss of the nitro group.14 The substitution reactions with methylated 3,4,5-trinitro-
supposed intermediate, the existing 3-chloro-4-nitro- pyrazole.17 The reaction of 1-chloro-2-nitrazapropane with
pyrazolate,15 reacted with another equivalent of potassium potassium 4-amino-3,5-dinitropyrazolate in acetone at
3,4-dinitropyrazolate, thereby forming the 3,4,4'-trinitro-1,3'- ambient conditions afforded 12 in good yield.
bipyrazolyl system of nitramine 10. The regioselectivity of the
Spectroscopy
alkylation of 3,4-dinitropyrazole depending on the reaction
Vibrational spectroscopic studies of all synthesized compounds
were performed with IR and Raman spectroscopy and the
frequencies were assigned according to literature.18 A detailed
temperature was studied revealing that the alkylation at N1 is
preferred at low temperatures. The relative ratio of nitramines
1
and 10 was determined by the intensities of the H NMR
9
description is given in the Supporting Information.
1
spectra with a reaction time of 24 h at 25 °C (84:16) and 82 °C
(66:34), respectively. The isolated yields are not related to the
reported ratio of intensities of the 1H NMR due to partial
decomposition during purification by column chromatography,
Compounds
1
–
12 were characterized by H, 13C, and 14N NMR
spectroscopy in d6-acetone. Selected chemical shifts of 1H,
13C{1H}, and 14N resonances of all presented compounds are
Table 1 Assigned 1H, 13C{1H}, and 14N NMR shifts [ppm] in d6-acetone of nitramines 1–12.
1H NMR
Car−H
13C{1H} NMR
C−NO2
14N
CH2
CH3
C−H
−
Cq
CH2
CH3
NO2
1
2
3
4
−
−
−
−
6.02
3.57
146.2
145.3
152.8
58.0
39.6
−30
−34
−31
−34
−32
−37
−21
−25
−26
−23
−30
−32
−24
−30
−34
−25
−30
−28
−31
−20
−25
−26
−28
−31
−18
−23
−26
6.03
5.90
6.81
3.57
3.50
3.65
−
−
−
151.8
−
60.3
58.4
67.0
39.8
38.3
39.0
158.0
151.2
n.o.[a]
6.11
3.60
156.9
61.6
38.5
5
6
−
6.84
6.55
3.68
3.70
n.o.[a]
143.0
−
143.7
−
65.4
65.3
39.1
39.8
8.70
125.5
7
8.28
6.43
3.66
142.3
129.6
138.0
−
62.9
39.6
8
9
7.91
9.03
6.72
6.33
6.33
3.64
3.63
3.59
154.1
103.5
134.0
−
67.9
66.9
63.9
39.9
38.8
39.0
147.7
148.4
−
126.9
10
9.50
8.56
150.1
138.2
137.0
132.0
129.7
128.2
11
12
−
−
6.42
6.64
3.66
3.59
148.4
−
−
130.0
64.4
67.3
39.0
38.8
123.9
130.5-130.4
130.5-130.4
[a] Due to the low solubility in organic solvents some carbon signals could not be observed, although the measurements were performed with elongated pulse delays.
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DOI: 10.1039/C6NJ00202A
atoms of the 3,4,4'-trinitro-1,3'-bipyrazole system (Figure S1).
The assignment is given in Figure 2. The C–H resonance (No. 3)
of the nitramine alkylated pyrazole ring is shifted upfield in
comparison to the C–H resonance of 9, whereas the other C–H
resonance is shifted downfield, because of the neighboring
electron withdrawing substituted pyrazolyl substituent. The
methyl and methylene proton resonances of 10 are in the
Fig. 2 Assigned 1H and 13C{1H} NMR resonances of 10 in d6-acetone.
same range as the ones of 9. Additionally, the assignment of
the carbon atoms is given in Figure 2.
summarized in Table 1. The chemical shifts of methylene
protons of open-chain nitramines were studied in the 1970th
and identified in a range of 5.90–6.10 ppm.19 By introduction
of electron withdrawing substituents like nitro groups in the
azoles the resonances of the methylene protons are shifted
downfield. This effect is considerably observed for the 1,2,4-
Crystal structures
All presented compounds were also characterized by low-
temperature single-crystal X-ray diffraction. Their molecular
structures are depicted in Figure 3. Selected data and
parameters of the measurements and refinements are
summarized in Table S13 to Table S15 in the Supporting
Information.
triazole based nitramines
3 and 5 with resonances at 6.81 ppm
and 6.84 ppm, respectively. The resonance signals of methyl
protons are in a range of 3.50 ppm to 3.70 ppm. The CH
resonances of the imidazolyl and pyrazolyl substituents show
the characteristic downfield shifts of aromatic protons of
nitrogen-rich heterocycles.
Nitramine
1 crystallizes from acetone / dichloromethane in the
monoclinic space group P21 with two formula units per unit
cell and a density of 1.721 g cm−3 at 173 K. Its unit cell is shown
in Figure 4. The two times alkylated nitramine
2 crystallizes as
nitric acid adduct from diluted nitric acid in the monoclinic
The carbon resonances of the C–NO2 functions are observed as
small, broadened signals because of their coupling to the
nitrogen cores of the nitro groups. The chemical shifts of the
13C methylene resonances are in a range of 58.0 ppm to
67.0 ppm and the methyl resonances are found in the range
from 38.3 ppm to 39.9 ppm.
space group P21. The N−N bond length of the nitramine groups
of 1 and 2 (1.34 Å) are shorter than the N−N bond length in the
triazolone rings (1.37 Å). In comparison to the C−O bond
length of γ-lactam systems (1.235 Å),20 the C−O bond lengths
of nitramine
1
(1.214(3) Å) is shorter, whereas the
is in the same range
corresponding bond length of
2
The resonance signals of the aromatic C–NO2 and the N–NO2
nitro group nitrogens were observed in the 14N NMR from
−18 ppm to −37 ppm. An unambiguous assignment of these
signals is difficult because of their similar shifts.
(1.230(3) Å). The C−N bond length to the nitro group is
1.457(3) Å and compared to the C−N bond lengths of the
triazolone ring of 1.293(3)–1.400(3) Å considerably elongated.
The significant differences in the bond lengths are an evidence
Two-dimensional NMR spectra (HMBC) of 10 were recorded
for an unambiguous assignment of the protons and carbon
Fig. 3 Molecular structures of the herein presented nitramines 1–12.
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Fig. 4 Unit cell of 1-(3-nitro-1H-1,2,4-triazol-5-on-4-yl)-2-nitrazapropane (1) along
the b axis. Thermal ellipsoids are drawn at the 50 % probability level. Selected
Fig. 5 Selected structure forming dipolar intermolecular C∙∙∙O interactions and non-
classical hydrogen bonds within the crystal structure of 5 are shown black dotted.
hydrogen bonds are shown black dotted.
for the localization of the double bond character. In analogy to
β-NTO,21 the C2−N2 bond length (1.293(3) Å) is the shortest
one, whereas the alkylation leads to an elongated C1−N3 bond
length of 1.400(3) Å instead of 1.378(2) Å.21 The C−NO2
function is twisted out of the triazole plane by 20.4° in contrast
to the almost planar structure in NTO. This twisting enables
various intermolecular interactions within the crystal structure
two dinitropyrazolyl based nitramines
8 and 9 are supported
by various non-classical hydrogen bonds, dipolar N∙∙∙O and C−O
interactions below the sum of the corresponding van der
Waals radii (Table S8 and S9).
1-(3,4,4'-Trinitro-1,3'-bipyrazol-2'-yl)-2-nitrazapropane
(10)
crystallizes from dichloromethane in the triclinic space group
P–1 with two formula units per unit cell and a crystal density of
1.731 g cm−3 at 173 K. The molecular structure of 10 is
depicted in Figure 6. The pyrazole rings are twisted by
55.86(6)°. The almost perpendicular twistings of the nitro
groups N7 and N8 are caused by steric repulsion of the
neighbored nitro group, thereby taking part in intra- and
intermolecular interactions. The pyrazole N−N bond lengths of
1.367(2) Å respective 1.379(2) Å are elongated in comparison
to the nitramine N−N bond of 1.358(2) Å. The alignment of 10
within the crystal structure is formed by non-classical
hydrogen bonds. The C−H funcꢀons of the bipyrazolyl system
and the methylene protons interact with the nitro groups and
the nitrogen atoms of the bipyrazole due to their high acidity
(Table S10). Additionally to the non-classical hydrogen bonds,
dipolar high-grade directed N∙∙∙O and C∙∙∙O interactions of
oxygen O8 are observed, which are shorter than the
corresponding sum of the van der Waals radii.22
of 1. Due to the high acidity of the protons of the 2-nitraza-
propyl substituent, non-classical C−H∙∙∙O and C−H∙∙∙N hydrogen
bonds are formed. Furthermore, high-grade directed dipolar
N∙∙∙O and C∙∙∙O interactions are observed in a range from
2.869–2.970 Å. These dipolar interactions of O2 to the C2−N4
bond are supported by the twisting of the C−NO2 group. The
interactions are summarized in Table S1. The layer-like packing
of
1 is formed by an intermolecular hydrogen bond of the
acidic N−H funcꢀon and the oxygen of the γ-lactam system.
The layers are connected by weak non-classical hydrogen
bonds between the terminal methyl group and the nitro
groups, whereas the non-classical hydrogen bond C3−H3A∙∙∙N2
is found within one layer. The dipolar N6∙∙∙O2 interaction of
2.970 Å is observed in between the layers. Similar interactions
are observed in the crystal structure of nitramine
Table S2.
2 as listed in
The crystal structures of the other 1,2,4-triazole based
nitramines are supported by several non-classical
hydrogen bonds and additionally either classical hydrogen
bonds ( ) or various dipolar interactions (nitramines and
as summarized in Table S3–Table S5. The structure of
nitramine
shows C2 symmetry perpendicular to the C1−C1i
3–5
4
3
5)
5
axis and its triazole rings are twisted by 26.1(1)°. Its crystal
structure is depicted in Figure S8. The molecules of one layer
are connected by
2.920(2) Å) (Figure 5).
a
dipolar
C
∙∙∙
O
interaction (C3∙∙∙O4:
The 4,5-dinitroimidazolyl based nitramine
higher crystal density of 1.767 g cm−3 than the 2,4-dinitro-
imidazole based
(1.735 g cm−3) at 173 K. Furthermore, a
greater extend of non-classical hydrogen bonds and dipolar
interactions are observed within the crystal structure of than
in the one of (Tables S6 and S7). The crystal structures of the
7
crystallizes with a
6
7
Fig.
6 Molecular structure of 1-(3,4,4'-trinitro-1,3'-bipyrazol-2'-yl)-2-nitrazapropane
6
(10). Thermal ellipsoids are drawn at the 50% probability level.
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Table 2 Selected interactions within the crystal structure of 12.
DOI: 10.1039/C6NJ00202A
The neighbored nitro groups of nitramine 11 are less screwed
than the ones of 10. The oxygen atoms of the nitro group N6
as well as the nitramine group are involved in non-classical
hydrogen bonds and additionally dipolar interactions are
observed (Table S11).
D–H∙∙∙A
D–H [Å]
0.981(2)
0.8954(7)
0.8763(7)
0.9902(7)
0.8763(7)
0.8763(7)
0.9904(6)
0.980(2)
0.980(2)
0.9904(6)
H∙∙∙A [Å]
2.3212(16)
2.1781(16)
2.2521(17)
2.4025(17)
2.4858(14)
2.5768(17)
2.6017(14)
2.5903(16)
2.5719(14)
2.5871(15)
D∙∙∙A [Å]
3.174(3)
∠DHA [°]
144.94(13)
122.93(6)
122.54(6)
170.31(6)
118.79(5)
123.13(6)
156.74(5)
150.99(13)
130.43(12)
120.66(5)
C5–H5A∙∙∙O4
N4–H2∙∙∙O3
N4–H1∙∙∙O2
C4–H4A∙∙∙O6
N4–H1∙∙∙O3iv
N4–H1∙∙∙O2iii
C4–H4B∙∙∙O5ii
C5–H5B∙∙∙N2v
C5–H5C∙∙∙O6i
C4–H4B∙∙∙O5i
2.7687(18)
2.8219(18)
3.3827(18)
3.0075(16)
3.1444(18)
3.5332(16)
3.479(3)
1-(4-Amino-3,5-dinitropyrazol-1-yl)-2-nitrazapropane
(12)
crystallizes from acetonitrile / dichloromethane in the
monoclinic space group P21/c with four formula units per unit
cell. The bond lengths and angles in the pyrazole ring are
similar to the corresponding ones in the nitramine alkylated
ring of the bipyrazolyl system 10. In contrast to the crystal
structure of 1-chloro-2-nitrazapropane,23 the nitramine nitro
group is nonplanar with the C4-C5-N7 plane, but twisted out of
the plane by 5.9(1)°. The pyrazolyl ring is turned out of the
CNC-plane by 58.11(5)°. Due to the spatial arrangement of the
nitramine group, various intramolecular non-classical
hydrogen bonds and electrostatic interactions are formed,
involving the methyl and methylene groups as donor and the
nitramine nitro group and as well the O4 of the C-bonded nitro
group as acceptor (Figure 7). These and further selected
interactions are listed in Table 2. The amino group is twisted
out of the pyrazole ring by 3.65(3)°, whereas the nitro groups
are almost in plane with a twist of less than 0.5°. These
twistings enable two intramolecular classical hydrogen bonds
of 2.1781(16) Å and 2.2521(17) Å. Furthermore, intramolecular
dipolar N∙∙∙O and C∙∙∙O interactions considerably below the
sum of the van der Waals radii are observed. The unit cell and
crystal structure are shown in Figure S16. The crystal structure
consists of two different layers, which are opposed staggered
to each other. The layers are connected by a great number of
non-classical and classical hydrogen bonds in a range from
2.40−2.60 Å. Remarkable is a very uncommon four-center
bond, which is formed by proton H1 of the amino group,
interacting intermolecular with the oxygen atoms O3 and O2
and also intramolecular with another O2. Additionally to the
intermolecular hydrogen bonds, an intermolecular dipolar
C∙∙∙O interaction between C3 and O1 of 3.0179(17) Å is
observed. The high amount of intra- and intermolecular
interactions leads to the high density of 1.820 g cm−3 at 173 K,
which is the highest of the herein presented nitramines.
3.293(2)
3.2073(15)
dipolar interactions ΣvdW radii (N∙∙∙O) < 3.07 Å[22]
N4∙∙∙O3 2.7687(18) Å N4∙∙∙O2 2.8219(18) Å
dipolar interactions ΣvdW radii (C∙∙∙O) < 3.22 Å[22]
C4∙∙∙O4 2.9061(17) Å
C3∙∙∙O1v 3.0179(17) Å
Symmetry codes: i) 1−x, 0.5+y, 0.5−z; ii) x, −0.5−y, 0.5+z; iii) −x, −y, 1−z; iv) −x,
−0.5+y, 0.5−z; v) x, −0.5−y, −0.5+z.
Thermal stabilities, sensitivities and energetic properties
The thermal behavior of all presented compounds was
investigated by differential scanning calorimetry (Table 3).
With the exception of 1-(3-nitro-1H-1,2,4-triazol-5-on-4-yl)-2-
nitrazapropane (1) all nitramines melt before decomposition.
For potential applications as energetic ingredients a thermal
stability above 180 °C is desired, which is achieved by the
majority of the compounds. They show thermal stabilities from
151 °C to 264 °C.
Especially for melt-cast applications the pyrazole based
nitramines
below 140 °C and 80–150 °C before decomposition. In general,
the pyrazole based nitramines 12 show higher thermal
stabilities than the imidazole based nitramines and . The
replacement of one nitro group in 1-(3,5-dinitro-1,2,4-triazol-
1yl)-2-nitrazapropane ( ) by an amino group ( ) leads to an
8–11 and 2 are of great interest, which are melting
8
–
6
7
3
4
increase in thermal stability of almost 60 °C. The same effect is
observed for the thermal stability of the twice alkylated 3-
nitro-1,2,4-triazol-5-one
alkylated
2 in comparison to the mono
1
.
The impact, friction and electrostatic discharge sensitivity tests
were carried out for initial safety testing according to BAM
methods.24 All presented nitramines are sensitive towards
friction with the exception of 1-(4-amino-3,5-dinitropyrazol-1-
yl)-2-nitrazapropane (12). The impact sensitivities of the 1,2,4-
triazolyl based nitramines differ strongly depending on the
substituents and vary from sensitive to insensitive. Therefore,
the twice alkylated NTO derivative
nitro-1,2,4-triazol-1-yl)-2-nitrazapropane (
are insensitive towards impact, whereas
sensitivities of 10 J and 7 J. The 2,4-dinitroimidazolyl nitramine
is less sensitive than the 4,5-dinitroimidazolyl nitramine
2
as well as 1-(5-amino-3-
) and the bitriazole
and show
4
5
1
3
6
7
showing impact sensitivities of 38 J and 25 J, respectively. The
pyrazolyl based derivatives are insensitive towards impact with
the exception of 1-(3,5-dinitropyrazol-1-yl)-2-nitrazapropane
Fig. 7 Selected hydrogen bonds within the crystal structure of 12 including a
four-center hydrogen bond formed by proton H1 and two different oxygen
atoms O2 and oxygen O3.
(
11) (19 J). The electrostatic sensitivities of all presented
compounds are within the range of 0.025–0.6 J and greater
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DOI: 10.1039/C6NJ00202A
Table 3 Physical and energetic properties of nitramines 1–12 in comparison to TNT, DNAN and PETN.
1
2
3
4
5
6
7
8
9
Formula
M (g mol−1)
IS (J)[a]
C4H6N6O5
218.13
10
C6H10N8O7
306.20
>40
C4H5N7O6
247.13
7
C4H7N7O4
217.15
>40
C8H10N12O8
402.25
>40
C5H6N6O6
246.14
38
C5H6N6O6
246.14
25
C5H6N6O6
246.14
19
C5H6N6O6
246.14
>40
FS (N)[b]
ESD (J)[c]
N (%)[d]
160
96
160
252
240
120
144
288
n.d.
0.025
38.55
−44.0
–
0.10
36.60
−52.3
117
0.15
39.67
−29.1
136
0.60
45.15
−55.3
202
0.15
41.29
−51.7
225
0.13
34.14
−45.5
130
0.15
34.14
−45.5
142
0.1
n.d.
34.14
−45.5
126
34.14
−45.5
80
Ω
CO2 (%)[e]
Tmelt (°C)[f[]
Tdec (°C)[g]
151
211
167
224
228
183
190
210
222
ρ (g cm−3)[h]
ΔfHm (kJ mol−1)[i]
ΔfU (kJ kg−1)[j]
1.69
−71
1.66*
−51
1.74
216
1.65
105
1.66
311
1.70
71
1.73
90
1.65
111
1.67
136
−229
−65
964
586
866
379
456
542
643
E
XPLO5 6.02 values
−ΔExU (kJ kg−1)[k]
Tdet (K)[l]
4598
3210
244
4885
3258
237
5701
3942
305
4756
3205
235
5017
3472
242
5291
3610
263
5374
3630
277
5409
3713
250
5512
3747
259
p
CJ (kbar)[m]
Vdet (m s−1)[n]
V0 (L kg−1)[o]
7941
780
7925
798
8471
757
7983
819
7919
764
8046
739
8184
733
7899
749
8003
746
10
11
12
TNT
DNAN
C7H6N2O5
198.13
> 40
PETN
C5H8N4O12
316.13
3
Formula
C8H7N9O8
357.20
> 40
C5H5ClN6O6 C5H7N7O6
C7H5N3O6
227.13
15
M (g mol−1)
IS (J)[a]
280.59
> 40
288
261.16
> 40
> 360
0.4
FS (N)[b]
ESD (J)[c]
288
> 360
0.7
> 360
n.d.
60
0.2
0.1
0.19
N (%)[d]
38.83
−51.5
133
29.95
−34.2
82
37.54
−45.9
141
18.50
−74.0
81
14.14
−96.9
94
17.72
−10.1
141
ΩCO2 (%)[e]
Tmelt (°C)[f[]
Tdec (°C)[g]
ρ (g cm−3)[h]
ΔfHm (kJ mol−1)[i]
ΔfU (kJ kg−1)[j]
264
214
163
309
315
165
1.70
331
1.76
111
1.78
108
1.65**
−59**
−185**
1.59
1.78**
−534
−1594
−177
−813
1010
466
508
E
XPLO5 6.02 values
−ΔExU (kJ kg−1)[k]
Tdet (K)[l]
pCJ (kbar)[m]
Vdet (m s−1)[n]
V0 (L kg−1)[o]
5406
3751
258
4872
3761
256
5284
3492
298
5022
3452
207
4484
3004
161
5994
3971
309
7986
707
7788
715
8482
753
7241
633
6705
636
8404
743
[a] Impact sensitivity (BAM drophammer 1 of 6). [b] Friction sensitivity (BAM friction tester 1 of 6). [c] Electrostatic discharge (OZM Research). [d] Nitrogen content.
[e] Oxygen balance (Ω=(xO–2yC–0.5zH)1600/M). [f] Melting temperature. [g] Decomposition temperature. [h] Density at ambient temperature. [i] Calculated
enthalpy of formation. [j] Calculated energy of formation. [k] Energy of explosion. [l] Detonation temperature. [m] Detonation pressure. [n] Detonation velocity. [o]
Volume of detonation gases. * Density measured with a He pycnometer. ** Values obtained from the EXPLO5 database.
than the values (0.005–0.02 J) the human body can release.25 solid state enthalpies by Trouton's rule by subtracting the gas-
In comparison to TNT the synthesized nitramines mainly show phase enthalpies with the corresponding enthalpies of
lower impact sensitivities but increased sensitivities towards sublimation.29 If the compound has no melting point, the
friction. In the first instance the performance characteristics of decomposition point was used instead to transform the gas
new energetic materials are calculated to evaluate their utility phase enthalpy to the solid state enthalpy by Trouton's rule.
for possible applications as an energetic material. The The crystal densities at low temperature were corrected to the
detonation parameters of all presented nitramines were corresponding crystal densities at 298 K by Equation 1 and the
calculated using the EXPLO5 (version 6.02) computer code.26 αv coefficient of volume expansion from the related nitramine
The calculations were performed using the maximum densities HMX (αv = 1.6∙10−4 K30).
at 25 °C and the calculated enthalpies of formation. Enthalpies
ρ298K
=
ρ
T/(1+
α
v(298−T))
(1)
of formation were calculated using the atomization method The energetic properties of all presented compounds are
with CBS-4M27 based electronic enthalpies computed with summarized in Table 3. The calculated detonation velocities
Gaussian09 A.02.28 Gas phase enthalpies were transformed to (Vdet) of all compounds range from 7788 m s−1 to 8482 m s−1.
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The detonation pressures (pCJ) of the nitramines at the nitramines
6
and
7
. The most promising potential TNT
DOI: 10.1039/C6NJ00202A
2, 6 and 8 regarding their
Chapman-Jouguet point are calculated in the range from replacements are nitramines
235 kbar to 298 kbar. All nitramines show improved syntheses, sensitivities, energetic performance and especially,
detonation performances in comparison to the widely used their thermal behavior.
melt-cast explosives TNT and DNAN.
Most promising for potential applications as TNT replacements
Experimental section
in melt-cast formulations are nitramines 2, 6, 8 and 9 with
regard to their thermal behavior, sensitivities and
performance.
Caution
All materials prepared are energetic compounds with
sensitivities to various stimuli. While we encountered no issues
in the handling of these materials, proper protective measures
(face shield, ear protection, body armor, Kevlar gloves and
earthed equipment) should be used all the time.
Furthermore, 1-(3,5-dinitro-1,2,4-triazol-1-yl)-2-nitrazaprop-
ane (3) and 1-(4-amino-3,5-dinitropyrazol-1-yl)-2-nitrazaprop-
ane (12) could be of potential use for energetic applications
showing performances comparable to pentaerythritol tetra-
nitrate (PETN), while possessing improved sensitivities.
General methods
All reagents and solvents were used as received (Sigma-
Aldrich, Fluka, Acros Organics), if not stated otherwise.
5-Nitro-2,4-dihydro-1,2,4-triazol-3-one,12k 3,5-dinitro-1,2,4-tri-
azole,10b 5-amino-3-nitro-1,2,4-triazole,12a 3,3'-dinitro-5,5'-
bi(1,2,4-triazole),12j 4,5-dinitroimidazole,12c 2,4-dinitro-imid-
azole,12d 3,5-dinitropyrazole,12e,12f 3,4-dinitro-pyrazole,12f,12g
3,4,5-trinitropyrazole,4a and 4-amino-3,5-di-nitropyrazole12b
were prepared according to literature procedures. Melting and
decomposition points were measured with a Linseis PT10 DSC
using heating rates of 5 °C min−1. 1H, 13C{1H} and 14N NMR
spectra were measured with a JEOL EX 400 or a JEOL Eclipse
400 instrument at ambient temperature. Chemical shifts are
quoted in parts per million relative to TMS (1H, 13C) or
nitromethane (14N). The solvent used was d6-acetone unless
otherwise stated. The solvent residue signal was used as
locking signal for 1H and 13C NMR. Infrared spectra were
measured with a PerkinElmer BX FT-IR spectrometer on a
Smiths DuraSamplIR II diamond ATR unit at ambient
temperature. Following abbreviations were used to
characterize the relative signal intensities: vs (very strong), s
(strong), m (medium), w (weak), vw (very weak) and br
(broad). Raman spectra were recorded on a Bruker BAN II with
a Nd:YAG laser (λ = 1064 nm) with a laser output of 300 mW.
The vibrational spectroscopy data is given in the Supporting
Information. Low-resolution mass spectra were recorded on a
JEOL MStation JMS 700. Elemental analyses were performed
on a Vario EL and a Vario Micro from Elementar Company.
Sensitivity data were determined using a BAM drophammer
and a BAM friction tester. The electrostatic sensitivity tests
were carried out using an Electric Spark Tester ESD 2010 EN
from OZM Research. Single X-ray diffraction studies were
Conclusions
Nucleophilic substitution of 1-chloro-2-nitrazapropane with
nitro-substituted azoles afforded various open-chain
nitramines as reported herein. The alkylation of 3,4-dinitro-
pyrazole yielded additionally to the desired nitramine
9 the
alkylated bipyrazolyl system 10. Prior to this reaction,
bipyrazolyl systems were solely obtained by cine substitutions.
The crystal structures of all compounds were determined by
low-temperature single-crystal X-ray diffraction and deliver
insight into structural characteristics. A plurality of hydrogen
bonds and dipolar C∙∙∙O and N∙∙∙O interactions is observed
within each crystal structure, which leads to higher densities
compared to the known crystal structures of methylated
parent compounds. Especially, within the crystal structure of
1-(4-amino-3,5-dinitropyrazol-1-yl)-2-nitrazapropane
(
12
)
a
high quantity of intra- and intermolecular interactions was
observed, which leads to the highest density (1.82 g cm−3) of
the herein presented nitramines. With exception of
1, all
nitramines melt before decomposition. The decomposition
temperatures range from 151 to 264 °C. The thermally most
stable one is the bipyrazolyl nitramine 10. Due to the
comparatively low melting points of nitramines
2 and 8–11
(<135 °C) and their considerably higher decomposition points,
they are promising as potential melt-cast explosives.
Their sensitivities towards impact, friction and electrostatic
discharge were investigated by BAM methods. Compounds
1,
3
and 6–8 are found to be sensitive towards impact, while the
others are insensitive. All compounds are sensitive towards
friction between 96 N to 288 N with the exception of 12
(> 360 N, insensitive). However, the sensitivities of the
nitramines are mainly in the range of RDX and PETN or even
improved. The nitramines show calculated performances with
detonation velocities in the range from 7788–8482 m s−1 and
performed on an OXFORD DIFFRACTION XCALIBUR 3 diffractometer
with a KAPPA CCD detector using monochromatic molybdenum
Kα radiation (λ = 0.71073 Å). The data collection was realized
by using CRYSALISP
RO software.31 The structures were solved
detonation pressures between 237–305 kbar. Nitramines
3
with SIR-92 implemented in the program package WINGX32 and
33
and 12 exhibit performances comparable to PETN
accompanied by improved sensitivities towards impact and
friction. However, their thermal stabilities are lower than
180 °C. Therefore, the most promising compounds for
potential application as energetic material are in regard to
their sensitivities and performances the imidazolyl based
finally checked using PLATON
.
The EXPLO5 program is based on the steady-state model of
equilibrium and uses the Becker-Kistiakowsky-Wilson equation
of state (BKW EOS.) for gaseous detonation products and
Cowan-Fickett EOS. for solid carbon.34 It is designed to enable
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the calculation of detonation parameters at the Chapman- 67.0 (CH2), 39.0 ppm (CH3). 14N{1H} NMR (29 MHz): δ −32
DOI: 10.1039/C6NJ00202A
Jouguet point.
(NO2), −37 (NO2), −169 ppm (br). MS (DCI+): m/z (%): 248 (1)
[M+H+]. Sensitivities (grain size: < 100 µm): IS: 7 J; FS: 160 N;
ESD: 0.15 J.
Syntheses
1-(3-Nitro-1H-1,2,4-triazol-5-on-4-yl)-2-nitrazapropane (1). To a
solution of potassium 3-nitro-1,2,4-triazolat-5-one mono-
hydrate (2.86 g, 15.36 mmol) in acetone (30 mL) was added
dropwise 1-chloro-2-nitrazapropane (1.91 g, 15.36 mmol)
dissolved in acetone (10 mL) by stirring at ambient
temperature. The reaction mixture was stirred overnight and
the inorganic solid was filtered off. The organic layer was
concentrated in vacuo to afford a pale yellow solid. The crude
product was washed with 10 mL ethanol and hot water
1-(5-Amino-3-nitro-1,2,4-triazol-1-yl)-2-nitrazapropane (4). 1-
Chloro-2-nitrazapropane (215 mg, 1.73 mmol) was dissolved in
acetone (20 mL) and potassium 5-amino-3-nitro-1,2,4-
triazolate (289 mg, 1.73 mmol) was added. The reaction
mixture was stirred overnight at ambient temperature. The
precipitate was filtered off and the solvent was removed in
vacuo to afford an orange solid. It was washed with ethanol
(10 mL) and water (10 mL). Recrystallization from acetonitrile
yielded beige
4 (67 mg, 0.31 mmol, 18%). DSC: Tmelt = 202 °C,
Tdec = 224 °C. EA (C4H7N7O4, 217.14 g mol−1): calcd C 22.12, H
3.25, N 45.15%; found C 22.65, H 3.14, N 44.52%. 1H NMR
(400 MHz): δ 6.58 (s, 2H, NH2), 6.11 (s, 2H, CH2), 3.60 ppm (s,
(10 mL) to yield 1 (437 mg, 2.00 mmol, 13%) as colorless solid.
DSC: Tdec = 151 °C. EA (C4H6N6O5, 218.13 g mol−1): calcd
C 22.03, H 2.77, N 38.55%; found C 23.44, H 2.85, N 36.08%.
1H NMR (400 MHz): δ 12.00 (s, 1H, NH), 6.02 (s, 2H, CH2),
3.57 ppm (s, 3H, CH3). 13C{1H} NMR (101 MHz): δ 152.8 (CO),
146.2 (br, CNO2), 58.0 (CH2), 39.6 ppm (CH3). 14N{1H} NMR
(29 MHz): δ −30 (NO2), −34 ppm (NO2). MS (DCI+): m/z (%): 219
(16) [M+H+]. Sensitivities (grain size: < 100 µm): IS: 10 J; FS:
160 N; ESD: 0.25 J.
3H, CH3). 13C{1H} NMR (101 MHz):
δ 156.9, 61.6 (CH2),
38.5 ppm (CH3). 14N{1H} NMR (29 MHz): δ −21 (NO2), −25 ppm
(NO2). MS (DCI+): m/z (%) = 218.2 (64) [M+H+], 130.1 (0.5)
+
[C2H3N5O2 ], 89 (26) [C2H5N2O2 ]. Sensitivities (grain size: 100–
+
500 µm): IS: > 40 J; FS: 252 N; ESD: 0.6 J.
5,5'-Bi(1-(2-nitrazapropan-1-yl)-3-nitro-1,2,4-triazole) (5). In
2,4-Bis(2-nitrazaprop-1-yl)-3-nitro-1,2,4-triazol-5-one (2). To
a
acetone
(20 mL)
1-chloro-2-nitrazapropane
(186 mg,
solution of 5-nitro-2,4-dihydro-1,2,4-triazol-3-one (214 mg,
1.64 mmol) in acetone (10 mL) was added dropwise a solution
of triethylamine (331 mg, 3.27 mmol) in acetone (1 mL). After
5 min of stirring, 1-chloro-2-nitrazapropane (610 mg,
4.90 mmol) was added. The reaction mixture was stirred
overnight at ambient temperature and the formed inorganic
solid was filtered off. The organic layer was concentrated in
vacuo and the yellow oily crude product was treated with
dichloromethane. The resulting solid was washed with diethyl
1.49 mmol) was dissolved and of dipotassium 3,3'-dinitro-5,5'-
bi(1,2,4-triazolate) dihydrate (252 mg, 0.75 mmol) was added.
The reaction mixture was stirred overnight at ambient
temperature. The precipitate was filtered off and the solvent
was concentrated in vacuo. The crude product was washed
with ethanol and water to afford beige
5 (86 mg, 0.21 mmol,
28%). DSC: Tmelt = 225 °C, Tdec = 228 °C. EA (C8H10N12O8,
402.24 g mol−1): calcd C 23.89, H 2.51, N 41.29%; found C
24.36, H 2.46, N 40.79%. 1H NMR (400 MHz): δ 6.84 (s, 4H,
CH2), 3.68 ppm (s, 6H, CH3). 13C{1H} NMR (101 MHz): δ 143.7,
65.4 (CH2), 39.1 ppm (CH3). 14N{1H} NMR (29 MHz): δ −26 ppm
ether and dried at air to afford colorless
2 (166 mg, 0.54 mmol,
33%). DSC: Tmelt = 117 °C, Tdec = 211 °C. EA (C6H10N8O7,
306.19 g mol−1): calcd C 23.54, H 3.29, N 36.60%; found (NO2). MS (DCI+): m/z (%) = 403.3 (45) [M+H+], 89.1 (91)
+
[C2H5N2O2 ], 43.1 (42) [C2H5N+]. Sensitivities (grain size:
1
C 23.78, H 3.19, N 35.43%. H NMR (400 MHz): δ 6.03 (s, 2H,
< 100 μm): IS: > 40 J; FS: 240 N; ESD: 0.15 J.
CH2), 5.90 (s, 2H, CH2), 3.57(s, 3H, CH3), 3.50 ppm (s, 3H, CH3).
13C{1H} NMR (101 MHz): δ 151.8 (CO), 145.3 (br, C–NO2), 60.3
(CH2), 58.4 (CH2), 39.8 (CH3), 38.3 ppm (CH3). 14N{1H} NMR
(29 MHz): δ −31 (NO2), −34 ppm (NO2). MS (DCI+): m/z (%): 307
(6) [M+H+]. Sensitivities (grain size: < 100 µm): IS: > 40 J; FS:
96 N; ESD: 0.10 J.
1-(2,4-Dinitroimidazol-1-yl)-2-nitrazapropane (6). To
a
solution of potassium 2,4-dinitroimidazolate (530 mg,
2.70 mmol) in acetone (10 mL) was added drop wise 1-chloro-
2-nitrazapropane (333 mg, 2.67 mmol) in acetone (1 mL). The
reaction mixture was stirred at 50 °C overnight and the formed
precipitate was filtered off. The organic layer was
concentrated in vacuo and the crude product was purified by
washing with ethanol. The yellow solid was filtered off to
1-(3,5-Dinitro-1,2,4-triazol-1-yl)-2-nitrazapropane (3)
. To a
solution of 1-chloro-2-nitrazapropane (400 mg, 2.52 mmol) in
acetonitrile (5 mL) was added potassium 3,5-dinitrotriazolate
dihydrate (744 mg, 3.19 mmol). The reaction mixture was
stirred for 24 h at ambient temperature. The formed
precipitate was filtered off and the organic layer was removed
in vacuo. The oily crude product was purified by washing with
afford
6 (390 mg, 1.58 mmol, 59%). DSC: Tmelt = 130 °C,
Tdec = 183 °C. EA (C5H6N6O6, 246.14 g mol−1): calcd C 24.40,
H 2.46, N 34.14%; found C 24.50, H 2.29, N 33.83%. 1H NMR
(400 MHz): δ 8.70 (s, 1H, CH), 6.55 (s, 2H, CH2), 3.70 ppm (s,
3H, CH3). 13C{1H} NMR (101 MHz): δ 143.0 (br, CNO2), 125.5
(CH), 65.3 (CH2), 39.8 ppm (CH3). 14N{1H} NMR (29 MHz): δ −23
(NO2), −30 (NO2), −32 (NO2), −210 (br), −215 ppm (br). MS
(DCI+): m/z (%): 247 (3) [M+H+]. Sensitivities (grain size:
< 100 μm): IS: 38 J; FS: 120 N; ESD: 0.13 J.
ethanol (10 mL). After filtration colorless
3
(494 mg,
2.39 mmol, 95%) was obtained. DSC: Tmelt = 136 °C,
Tdec = 165 °C. EA (C4H5N7O6, 247.13 g mol−1): calcd C 19.44,
H 2.04, N 39.67%; found C 19.11, H 1.95, N 38.73%. 1H NMR
(400 MHz): δ 6.81 (s, 2H, CH2), 3.65 ppm (s, 3H, CH3).
13C{1H} NMR (101 MHz): δ 158.0 (br, CNO2), 151.2 (br, CNO2),
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1-(4,5-Dinitroimidazol-1-yl)-2-nitrazapropane (7). To
a
1-(3,4,4'-Trinitro-1,3'-bipyrazol-2'-yl)-2-nitrazapropane (10).
DOI: 10.1039/C6NJ00202A
solution of 1-chloro-2-nitrazapropane (262 mg, 2.10 mmol) in 10 was obtained as side product by the synthesis of 9. Isolation
acetonitrile (15 mL) was added potassium 4,5-dinitro- by column chromatography (silica gel, ethyl acetate/i-hexane
imidazolate (412 mg, 2.10 mmol).The reaction mixture was (70:30)) yielded 10 (103 mg, 0.29 mmol, 14%) as rose solid.
stirred at 50 °C overnight and the precipitate was filtered off. DSC:
Tmelt = 133 °C,
Tdec = 264 °C.
EA
(C8H7N9O8,
The organic layer was removed in vacuo and the crude product 357.20 g mol−1): calcd C 26.90, H 1.98, N 38.83%; found
1
(440 mg, C 26.84, H 1.87, N 34.48%. H NMR (400 MHz): δ 9.50 (s, 1H,
was washed with ethanol. After drying at air
7
1.79 mmol, 85%) was obtained as colorless solid. DSC: CH), 8.56 (s, 1H, CH), 6.33 (s, 2H, CH2), 3.59 ppm (s, 3H, CH3).
Tmelt = 142 °C, Tdec = 190 °C. EA (C5H6N6O6, 246.14 g mol−1): 13C{1H} NMR (101 MHz): δ 150.1 (br, CNO2), 138.2 (CH), 137.0
calcd C 24.40, H 2.46, N 34.14%; found C 24.51, H 2.52, (CH), 132.0 (Cq), 129.7 (br, CNO2), 128.2 (br, CNO2), 63.9 (CH2),
1
N 33.98%. H NMR (400 MHz): δ 8.28 (s, 1H, CH), 6.43 (s, 2H, 39.0 ppm (CH3). 14N{1H} NMR (29 MHz): δ −20 (NO2), −25 (NO2),
CH2), 3.66 ppm (s, 3H, CH3). 13C{1H} NMR (101 MHz): δ 142.3 −26 (NO2), −170 ppm (br). MS (DCI+): m/z (%): 358 (4) [M+H+].
(CNO2), 138.0 (CH), 129.6 (CNO2), 62.9 (CH2), 39.6 ppm (CH3). Sensitivities (grain size: < 100 µm): IS: > 40 J; FS: 288 N; ESD:
14N{1H} NMR (29 MHz): δ −24 (NO2), −30 (NO2), −34 (NO2), 0.20 J. Rf value (silica gel, ethyl acetate/i-hexane (70:30)): 0.83.
−135 (br), −210 ppm (br). MS (DCI+): m/z (%): 247 (11) [M+H+].
1-(5-Chloro-3,4-dinitropyrazol-1-yl)-2-nitrazapropane (11). To a
mixture of potassium 3,4,5-trinitropyrazolate semihydrate
(575 mg, 2.30 mmol) in acetonitrile was added 1-chloro-2-
nitrazapropane (286 mg, 2.30 mmol) dissolved in acetonitrile
(5 mL). The reaction mixture was stirred under reflux for 2 d
and the precipitate was filtered off. The organic layer was
concentrated in vacuo and the crude oily product was
dissolved in hot dichloromethane. The precipitate was filtered
off and the filtrate was removed in vacuo. The resulting oil was
overlaid with methanol and the formed precipitate was
filtered off and dried at air to afford 11 (116 mg, 0.41 mmol,
18%). DSC: Tmelt = 82 °C, Tdec = 214 °C. EA (C5H5ClN6O6,
280.58 g mol−1): calcd C 21.40, H 1.80, N 29.95, Cl 12.64%;
Sensitivities: (grain size: 100–500 µm): IS: 25 J; FS: 144 N; ESD:
0.15 J.
1-(3,5-Dinitropyrazol-1-yl)-2-nitrazapropane (8). To a solution of
1-chloro-2-nitrazapropane (124 mg, 1.00 mmol) in acetone
(5 mL) was added potassium 3,5-dinitropyrazolate (195 mg,
1.00 mmol) and sodium bromide (192 mg, 0.99 mmol). The
reaction mixture was stirred at ambient temperature for 14 h
and the precipitate was filtered off. The organic layer was
concentrated in vacuo and the crude product was washed with
ethanol. The colorless precipitate was filtered off to yield
8
(139 mg, 0.57 mmol, 57%). DSC: Tmelt = 126 °C, Tdec = 210 °C. EA
(C5H6N6O6, 246.14 g mol−1): calcd C 24.40, H 2.46, N 34.14%;
found C 24.82, H 2.41, N 33.75%. 1H NMR (400 MHz): δ 7.91 (s,
1H, CH), 6.72 (s, 2H, CH2), 3.64 ppm (s, 3H, CH3). 13C{1H} NMR
(101 MHz): δ 154.1 (br, CNO2), 147.7 (br, CNO2), 103.5 (CH),
67.9 (CH2), 39.9 ppm (CH3). 14N{1H} NMR (29 MHz): δ −25
(NO2), −30 (NO2), −178 ppm (br). MS (DCI+): m/z (%): 247 (4)
1
found C 21.71, H 1.78, N 29.78, Cl 12.77%. H NMR (400 MHz):
δ 6.42 (s, 2H, CH2), 3.66 ppm (s, 3H, CH3). 13C{1H} NMR
(101 MHz): δ 148.4 (br, CNO2), 130.0 (CCl), 123.9 (br, CNO2),
64.4 (CH2), 39.0 ppm (CH3). 14N{1H} NMR (29 MHz): δ −28
(NO2), −31 (NO2), −176 ppm (br). MS (DCI+): m/z (%): 281 (38)
[M+H+], 234 (3) [M+–NO2]. Sensitivities (grain size: < 100 µm):
IS: > 40 J; FS: 288 N; ESD: 0.10 J.
+
[M+H+], 200 (2) [M-NO2 ]. Sensitivities (grain size: < 100 µm):
IS: 19 J; FS: 288 N; ESD: 0.10 J.
1-(3,4-Dinitropyrazol-1-yl)-2-nitrazapropane
(9).
To
a
1-(4-Amino-3,5-dinitropyrazol-1-yl)-2-nitrazapropane
(12).
suspension of potassium 3,4-dinitropyrazolate (1.00 g,
4.31 mmol) and sodium bromide (0.44 g, 4.31 mmol) in
acetonitrile was added 1-chloro-2-nitrazapropane (0.54 g,
4.31 mmol) dissolved in acetonitrile. After two days of stirring
at ambient temperature the inorganic solid was filtered off.
The organic layer was concentrated in vacuo and purified via
column chromatography (silica gel, ethyl acetate/i-hexane
(70:30)). Due to decomposition by chromatography only a
1-Chloro-2-nitrazapropane (115 mg, 0.92 mmol) was dissolved
in acetone (15 mL) and potassium 4-amino-3,5-dinitro-
pyrazolate semihydrate (187 mg, 0.85 mmol) was added. The
reaction mixture was stirred overnight at ambient
temperature. The precipitate was filtered off and the organic
layer was concentrated in vacuo. The crude product was
washed with ethanol and diethyl ether to afford 12 (197 mg,
0.75 mmol, 88%) as yellow solid. DSC: Tmelt = 141 °C,
Tdec = 165 °C. EA (C5H7N7O6, 261.15 g mol−1): calcd C 23.00,
H 2.70, N 37.54%; found C 23.19, H 2.65, N 37.25%.
1H NMR (400 MHz): δ 7.01 (s, 2H, NH2), 6.66 (s, 2H, CH2),
3.61 ppm (s, 3H, CH3). 13C{1H} NMR (101 MHz): δ 130.5−130.4
(3C, CNH2, CNO2), 67.3 (CH2), 38.8 ppm (CH3). 14N{1H} NMR
(29 MHz): δ −19 (NO2), −23 (NO2), −26 (NO2), −184 (br),
−318 ppm (br). MS (DEI+): m/z (%): 261 (8) [M+]. Sensitivities
(grain size: < 100 µm): IS: > 40 J; FS: >360 N; ESD: 0.4 J.
small amount of colorless
9 (36 mg, 0.15 mmol, 3%) was
obtained. DSC: Tmelt = 82 °C, Tdec = 234 °C. EA (C5H6N6O6,
246.14 g mol−1): calcd C 24.40, H 2.46, N 34.14%; found
1
C 22.72, H 2.15, N 31.07%. H NMR (400 MHz): δ 9.03 (s, 1H,
CH), 6.33 (s, 2H, CH2), 3.63 ppm (s, 3H, CH3). 13C{1H} NMR
(101 MHz): δ 148.4 (br, CNO2), 134.0 (CH), 126.9 (br, CNO2),
66.9 (CH2), 38.8 ppm (CH3). 14N{1H} NMR (29 MHz): δ −28
(NO2), −31 (NO2), −176 ppm (br). MS (DCI+): m/z (%): 247 (73)
[M+H+], 200 (26) [M+–NO2]. Sensitivities (grain size: < 100 µm):
IS: > 40 J. Rf value (silica gel, ethylacetate/i-hexane (70:30)):
0.72.
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9
a) T. M. Klapötke, A. Penger, C. Pflüger, in New Trends Res.
Energ. Mater., Proc. Semin., 14tDhO, I: P10a.r1d03u9b/iCc6eNJ0(C0z2e0c2hA
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Acknowledgements
The Konrad Adenauer Foundation is gratefully acknowledged
for the award of a Ph.D. scholarship to C.P. Financial support of
this work by the Ludwig-Maximilian University of Munich
(LMU), the U.S. Army Research Laboratory (ARL), the Office of
Naval Research (ONR) under grant no. ONR.N00014-16-1-
2062, and the Bundeswehr – Wehrtechnische Dienststelle für
Waffen und Munition (WTD 91) under grant no.
E/E91S/FC015/CF049 is gratefully acknowledged. The authors
acknowledge collaborations with Dr. Mila Krupka (OZM
Research, Czech Republic) in the development of new testing
and evaluation methods for energetic materials and with Dr.
Muhamed Sućeska (Brodarski Institute, Croatia) in the
development of new computational codes to predict the
detonation and propulsion parameters of novel explosives. We
are indebted to and thank Drs. Betsy M. Rice, Jesse Sabatini
and Brad Forch (ARL, Aberdeen, Proving Ground, MD) for
many inspired discussions. The authors like to thank Stefan
Huber for assistance during the sensitivity measurements.
Nitramine
als
potentielle
Ersatzstoffe
für
Cyclomethylentrinitramin (RDX), dissertation, Ludwig
Maximilian University of Munich, 2011.
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DOI: 10.1039/C6NJ00202A
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Combination of the nitramine 1-chloro-2-nitrazapropane and nitro-substituted azoles yielded
energetic materials for potential use as TNT replacement in melt-cast formulations.