Synthetic manifestation of nitro substituted tetrazole-N-(hetero)aryl derivatives and energetic studies

Article abstract of DOI:10.1039/c6ta10621h

A workable cost-efficient synthetic method for the construction of nitro substituted tetrazole-N-aryl/heteroaryl derivatives is discussed here. The energetic functional groups-NO₂,-NHNO₂ and-N₃ are reliably inserted into the molecular backbone, making the tetrazole-N-aryl derivatives highly energetic and insensitive to heat and impact. For example, the tetrazole derivatives 7 and 8, bearing a-NO₂ or a-NHNO₂ group, exhibit energetic properties close to RDX, but with enhanced insensitivity. Most of the synthesized compounds show exothermic decomposition and are consequently useful for energetic material applications.

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Kun Chang, Zhaorong Chang et al.
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Synthetic Manifestation of Nitro Substituted Tetrazole-N-
(Hetero)Aryl Derivatives and Energetic Studies
Nagarjuna Kommu,[a] M. Balaraju,[a] Vikas D. Ghule,[b] Akhila K. Sahoo *[a, c]
Received 00th January 20xx,
Accepted 00th January 20xx
A workable cost-efficient synthetic method for the construction of a wide range of tetrazole-N-aryl/heteroaryl derivatives
is discussed here. The energetic functional groups -NO2, -NHNO2 and -N3 are reliably inserted into the molecular backbone,
making the tetrazole-N-aryl derivatives highly energetic and insensitive to heat and impact. For example, the tetrazole
derivatives 7 and 8, bearing -NO2 or a -NHNO2 group, exhibits energetic property close to RDX, but with enhanced
insensitivity. Most of the synthesized compounds show exothermic decomposition, and are consequently useful for
energetic material applications.
DOI: 10.1039/x0xx00000x
www.rsc.org/
and good detonation performance. In general, energetic
materials with high-nitrogen contents and better detonation
Introduction
Construction of small nitrogen-rich compounds for energetic
material applications has always garnered significant
attention.[1] Thus, synthesis of N-bearing molecules having
positive heats of formation, less sensitivity to friction and
impact, high thermal stability, and good detonation
performance remains intriguing.[2] Importantly, the five-
membered nitrogen-containing imidazole, pyrazole, triazole,
and tetrazole moieties are core units that are invariably
present in energetic molecules (Figure 1).[3]
performances are sensitive, especially to impact and friction.[7]
Despite the performance of tetrazole, oxidizer groups in the
molecular backbone astutely tune the energetic properties of
the molecule.[8] Thus, the concept of tetrazole-bearing small
molecules with high N and O-contents as insensitive energetic
materials (with high performance and good thermal stability)
garners significant attention, despite being challenging.[9]
Figure 2 comparison of energetic properties of N,N’ ethylene bridged trinitropyrazole -
tetrazole and trinitrobenzene-tetrazole.
Figure 1 Five-membered nitrogen containing heterocycles.
The N,N’-ethylene-bridged 5-aminotetrazole substituted 3,4,5-
tri-nitropyrazole (
I), a recent demonstration from Shreeve’s
Among these moieties, tetrazole is a unique building block that
finds application in energetic materials,[1a] in gas generating
agents,[4] and in pharmaceuticals.[5] Owing to the high
group, as an energetic material has an impact sensitivity (IS) of
30 J, a decompostion temperature (DT) of 135 °C, and a
moderate energetic property (detailed in Figure 2).[10] The
percentage of nitrogen and the large number of N
bonds, the tetrazole skeleton conserves more energy than the
other azole derivatives (Figure 1).[6] Consequently,
the
−N and C−N
ethylene-linkage in the two N-heteroaryls especially
contributes to the stability of I; however, it largely affects the
energetic property. Intrigued with these results, we design and
attempt the synthesis of N-nitroarene-bearing tetrazole
derivatives as insensitive compounds with better energetic
properties (Figure 2). Herein, we discuss a reliable synthetic
method for the construction of tetrazole-N-aryl/heteroaryl
tetrazole scaffold exhibits a high positive heat of formation
a.Advanced Center of Research in High Energy Materials(ACRHEM), University of
Hyderabad, Hyderabad-500046, INDIA.
b.Department of Chemistry, National Institute of Technology, Kurukshetra-136119,
Haryana, INDIA.
derivatives bearing
−NO2, −NHNO2 and −N3 groups in high
c. School of Chemistry, University of Hyderabad, Hyderabad 500046, INDIA.
† Footnotes relaꢀng to the title and/or authors should appear here.
Electronic Supplementary Information (ESI) available: [details of materials,
experimental procedures, characterization of all new compounds, X-ray
crystallography data, CCDC 1515413–1515422, theoretical studies information,
electrostatic potential surfaces and isodesmic reactions for synthesized
compounds. For ESI and crystallographic data in CIF]. See DOI: xx.xxxx/x0xx00000x
yields. The energetic and sensitivity properties of the
representative molecules are studied; some of the molecules
display energetic properties comparable to the established
high-explosive molecules, but with better insensitivities.[9,10]
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Table 1 Nitration of substituted N-aryl-tetrazoles[a]
.
Results and Discussion
The amine moiety can be readily converted to tetrazole. Thus,
a wide range of tetrazole-N-aryl/heteroaryl derivatives 2a 2r
−
were reliably accessed in good yields from the corresponding
anilines through the condensation and cycloaddition with
sodium azide in the presence of triethylorthoformate as shown
in Scheme 1. [11]
T
t
[h]
Entry
2
Yield of 3/4/5 (%)
[°C]
RT
80
1
2a
24
RT
80
2
24
2
3
2b
2c
RT
80
2
24
O2N
N
N
N
RT
80
2
24
4
5
2d
2e
N
O2N
4d
Me
, 75 (80 oC)
RT
0.5
Scheme 1 Synthesis of substituted N-aryl/heteroaryl-tetrazoles.
6
7
2f
RT
80
3
6
Next, the nitration of the N-aryl tetrazoles
independently conducted in a mixture of 98% H2SO4 and 95%
HNO3 (Table 1). The nitration of N-phenyl-1,2,3,4-tetrazole (2a
2 were
)
gave mono nitration product 2m in 78% yield at room
temperature (RT); dissapointingly; the reaction under harsh
2g
RT
0.5
6
o
reaction conditions (80 C) did not provide the corresponding
di-nitration product (entry 1). The desired mono-nitration
products 3b (86%), 3c (83%), and 3d (82%) were respectively
-
82 (RT)
obtained from the methyl substituted N-aryl tetrazoles (2b
when the reaction conducted at RT (entries 2 4). Pleasingly,
the nitration at 80 οC led to the di-nitration products 4b
4c
and 4d in 82%, 78%, and 75% yields, respectively (entries 2 4).
−d),
8
9
2h
2i
RT
RT
6
6
−
,
,
−
Likewise, p-methoxy-substituted aryl tetrazole 2e exclusively
produced 4e (88%) at RT (entry 5). Nitation of m-methoxy
substituted aryl tetrazole 2f at RT yielded products 4f (18%)
and 4f′ (64%) (entry 6); while the reaction at 80 οC explicitly
delivered 4f′ in 78% yield (entry 6). Compounds 3g (29%) and
4g (55%) were isolated from o-OMe substituted aryltetrazole
2g upon nitration at RT; interestigly, the di-nitration product 4g
(82%) was solely obtained when the reaction conducted for 6 h
(entry 7). These results obviously entails that nitration easily
occurred in the electron-rich arenes. The electron deficient
arenes were not prone undergoing electrophilic nitrations;
10
11
2j
90
90
8
8
2k
consequently, the -OCF3, -CF3 substituted N-aryl-tetrazoles 2h
2i 2j, and 2k delivered mononitration products 3h 3i 3i′, 3j
,
,
,
,
,
12
2l
80
24
o
and 3k even at 100 C (entries 8−11). Pleasingly, nitration of
pyrazole substituted aryl-tetrazole (2l) at 80 oC
a) Isolated yield
2 | J. Name., 2012, 00, 1-3
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provided di- and tri-nitro containg products 4l (42%) and 5l crystallographic data of all these compounds are mentioned in
(20%) (entry 12). Disappointingly, electrophilic nitration of the Supporting Information.[12] The crystal density of
electron poor –NO2 substituted aryl-tetrazoles (2m
heteroaryl substituted tetrazoles (2o 2p, 2q
2r) were failed cm−3) were measured at 273 K; while compounds 4b
under the harsh reaction conditions. Pleasingly, the non-nitro , and exhibited crystal densities 1.63, 1.64, 1.65, 1.78, 1.79,
,
2n,) and compounds 4c (1.56 g cm−3), 4e (1.62 g cm−3), and
6
(1.75 g
,
&
,
4f′, 4g, 7,
8
9
bearing compounds 2o−r .
exhibited high HOFs (470.69 to 882.5 1.66 g cm−3, respectively at 293 K
kJ mol−1). Interestingly, the compound 2r showed sharp
exothermic decomposition with high positive heats of
1
formation 882.5 kJ mol− (Figure 4). Structures of 4b
,
4c
,
4e,
4f′, and 4g are once again confirmed by X-ray diffraction
analysis (Figure 3). The compounds 4b 4c 4d 4e 4f 4f′ 4g 4l
,
,
,
,
,
,
,
and 5l exhibited moderate to good detonation performance of
6759 to 7812 m s−1 (based on the computed energetic studies;
Table 2).
4b
4c
4e
The explosophoric groups −NO2, −NHNO2, and/or −N3 improve
energetic performance of the molecule. The synthesized
tetrazole bearing compounds with less number of
explosophoric groups shown in Scheme 1 and Table 1,
therefore exhibited moderate performance. We thus became
interested probing the conversion of easily transformable
−
OMe moiety to an explosophoric group. Gratifyingly,
methoxy moiety of 4e reliably converted to amino-group when
refluxed with aqueous ammonia in CH3CN to produce in 84%
yield (Scheme 2).[2d] As expected, a significant upsurge of
crystal density of
(1.75 g cm−3) over 4e (1.62 g cm−3) has
4f′
4g
6
6
6
been observed (Table 2), clearly reflecting the existence of
strong inter- and intra-molecular hydrogen bonding between
the
HNO3 at 0
aryl-tetrazole
group in under sodium tungstate/H2SO4/H2O2 led to the tri-
−
NH2 and
−
NO2 groups in
6
. The reaction of
5 C successfully delivered nitroamino substituted
(76%) (Scheme 2). Next, oxidation of NH2
6 with fuming
o
−
7
−
7
8
9
6
Figure 3 Molecular structures of compounds 4b, 4c, 4e, 4f′, 4g, 6, 7, 8 and 9; thermal
nitro substituted aryl-tetrazole
our surprise, the nitro group in
8
in 74% yield (Scheme 2). To
was readily replaced by azido
ellipsoids are set at 30% probability and hydrogen atoms are labelled for clarity.
8
Energetic Properties
when exposed to TMS-N3 in DMF at RT for 2 h to afford
9 in
Energetic properties of few representative molecules are
shown in Table 2 and the theoretical informations are detailed
in the Supporting Information.[13] All the calculations are
executed using the Gaussian 03 program suite.[14] The
geometric optimization of the structures and frequency
analysis are determined using B3PW91 functional with 6-31G
(d,p) basis set. Isodesmic transformations are used elucidating
HOF from total energies obtained in the DFT calculations. The
mono, di and tri-nitro substituted tetrazoles showed positive
heat of formation except –CF3 and –OCF3 substituted aryl-
tetrazoles. The nitrogen rich tetrazole 2r exhibited highest
77% yield (Scheme 2). X-ray diffraction analysis unambiguously
elucidated the solid state structures of compounds
3).
6−9 (Figure
1
positive heats of formation 882.5 kJ mol− (Table 2). The
molecular packing calculations using CVFF force field in the
polymorph module of Material Studio Suite are employed
predicting the density of the compound.[15] The density of the
3
3
synthesized compounds displayed 1.46 g cm− to 1.79 g cm−
,
clearly reflecting the increase of density from mononitro to tri-
nitro substituted N-aryl-tetrazoles. It is obvious that the NH2
and NO2 groups contribute to inter- and intra-molecular
−
Scheme 2 Preparation of -NH2/-NO2/-NHNO2/-N3 substituted aryl-tetrazoles
derivatives.
−
hydrogen bonding interactions, which ultimately improves
crystal packing, stability and the density of the molecule.
X-ray Crystallography
Single crystals were grown by the slow evaporation of the
3
Noticeably, compound
6
unveiled crystal density 1.75 g cm−
)
solutions of 4b
temperature and atmospheric pressure. The structures of 4b
4c 4e 4f′, 4g , and were unambiguously elucidated by
, 4c, 4e, 4f′, 4g, 6, 7, 8, and 9 in EtOAc at room
3
than the calculated density from material studio (1.69 g cm− ).
,
3
The tri-nitro-substituted N-aryl-tetrazoles
8
7
(1.78 g cm− ;) and
,
,
,
6,
7,
8
9
(1.79 g cm−3;) exhibited highest density among all the
single-crystal X-ray diffraction analysis (Figure 3). The
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synthesized tetrazole derivatives; the crystal density of 7 and 8
is comparable to RDX (1.80 g cm−3). Detonation velocities (Dv)
and detonation pressures (P) are calculated using Explo5
To our delight, compounds
J). Energetic properties of 2m
3h 3i 3i′ 3j
Information.[16]
6
–
9
are insensitive to impact (>40
,
2n, 2o, 2p, 2q, 3b, 3c, 3d, 3g,
,
,
,
, and 3k are shown in the Supporting
version 6.02. Compounds
7899, 8208, 8298, and 7734 m s−1, respectively. The impact
sensitivity (IS) of the compounds (with better
performance) are determined using BAM Fall hammer
6–9 showed detonation velocity
The TG-DTA measurements determined the thermal stabilities
of the compounds. Interestingly, the synthesized tetrazole
bearing compounds displayed broad or sharp exothermic
decomposition (in DTA; Figure 4), a potential requirement for
the energetic material application. The molecules decomposed
6–9
apparatus with 5 Kg drop weight on 15
the values are detailed in Table 2.
−20 mg samples and
Table 2 Energetic properties of 1,2,3,4-tetrazole derivatives
[b]
in 93
−224 °C, showcasing the thermal stability of the
IS[f]
[J]
[d]
Td
ρ[a]
Dv
P[c]
HOF[e]
1
compounds.
Compound
1
3
(m s− )
(GPa) (οC) (kJ mol− )
(g cm− )
2r
4b
4c
4d
4e
4f
1.59
1.66 (1.63)
1.63 (1.56)
1.62
7120
7432
7305
7243
7274
7268
17.2
20.4
19.5
19.1
19.9
19.7
224
178
168
194
156
152
882.5
403.9
408.7
392.9
302.7
287.4
−
−
−
−
−
−
−
Conclusions
In summary, a reliable synthetic approach for the construction
of various nitro and nitrogen-rich N-aryl/ heteroaryl-1,2,3,4-
1H-tetrazole derivatives is revealed and their structures are
elucidated by single-crystal X-ray diffraction analysis. Some of
the compounds possess high positive heats of formation
1.70 (1.62)
1.62
(882.5 kJ mol− ), good density (1.79 g cm−3) close to RDX,
1
4f′
1.65 (1.64)
7432
21.0
177
322.4
4g
1.66 (1.65)
1.64
7442
7142
7812
7899
8208
8298
7734
8172
6881
8795
21.1
18.9
21.9
24.1
28.0
28.4
26.2
27.0
19.5
34.9
171
167
−
293.7
654.3
628.0
369.0
495.4
470.5
744.3
423.0
67
−
−
−
better thermal stability (224
°
C), reasonable detonation
and pressure (28.4), and impact
insensitivity (>40 J). Interestingly, most of the synthesized
1
4l
velocity (8298 m )
s−
5l
1.68
6
1.69 (1.75)
1.76 (1.78)
1.83 (1.79)
1.70 (1.66)
1.71
223
93
>40 tetrazoles show exothermic decompositions, amenable for
>40 energetic material applications. Notably, the energetic
7
8
175
191
135
295
230
>40 properties of
7 & 8 are appealing and suitable for insensitive
9
I[10]
TNT[17]
RDX[17]
>40 explosive application.
30
15
1.65
Cautions!
7
1.80
85.0
All the 1,2,3,4-tetrazoles derivatives are energetic materials
and it tends to explode under certain conditions unpredictably.
However, none of the compounds described herein has
[a] Calculated density (at 298.15 K); the crystal density measured at 273 K/293 K and
shown in parenthesis. [b] Detonation velocity (calculated with Explo5 version 6.02).[18]
[c] Detonation pressure (calculated with Explo5 version 6.02). [d] Heat of formation. [e]
1
Thermal decomposition (Td) temperature under nitrogen gas (10 οC min− ). [f] Impact exploded or detonated in the course of this research. Caution
sensitivity.
should be exercised at all times during the synthesis,
characterization, and handling of any of these materials, and
mechanical actions involving scratching or scraping must be
avoided. Ignoring safety precautions can lead to serious
injuries.
Acknowledgements
NK and MB thank the ACRHEM, University of Hyderabad for
financial support. We thank CMSD and School of Chemistry,
University of Hyderabad for providing computational and
experimental facilities. NK and MB special thanks to Dr. A.
Sudheer Kumar for his support. NK thanks to Mr. P. Krishna
Chary, B. Geetha and Mr. D. Maddileti (School of Chemistry,
University of Hyderabad) for performing the X-ray
crystallography studies.
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4 | J. Name., 2012, 00, 1-3
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