Formation of trinitromethyl functionalized 1,2,4-triazole-based energetic ionic salts and a zwitterionic salt directed by an intermolecular and intramolecular metathesis strategy

Article abstract of DOI:10.1039/c7nj03939e

Ionic salts of 5,5′-bis(trinitromethyl)-3,3′-bi-1H-1,2,4-triazole and an unexpected energetic zwitterion 5-diazonium-3-trinitromethyl-1,2,4-triazolate were synthesized via an intermolecular and intramolecular metathesis strategy. Compared with its ammonium (6), hydrazinium (7) and hydroxylammonium (8) salts, 5,5′-bis(trinitromethyl)-3,3′-bi-1H-1,2,4-triazole (5) exhibits lower sensitivities (IS: 22.5 J and FS: 252 N). It is worth noting that energetic salt 8 exhibits a high density of 1.97 g cm^-3 and an excellent calculated detonation velocity of 9468 m s^-1, and that the energetic zwitterion 5-diazonium-3-trinitromethyl-1,2,4-triazolate (14) exhibits a high density of 1.893 g cm^-3 and an excellent calculated detonation velocity of 9317 m s^-1, which are both superior to that of HMX (9254 m s^-1).

Full text of DOI:10.1039/c7nj03939e

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PAPER
Jason B. Benedict et al.
The role of atropisomers on the photo-reactivity and fatigue of
diarylethene-based metal–organic frameworks
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Ple Na es we dJ oo u nr no at l ao df jCu hs et mm i as tr rgy ins
View Article Online
DOI: 10.1039/C7NJ03939E
Journal Name
LETTER
Formation of trinitromethyl functionalized 1,2,4-triazole-based
energetic ionic salts and a zwitterionic salt directed by a
intermolecular and intramolecular metathesis strategy
Received 00th January 20xx,
Accepted 00th January 20xx
Qing Ma,‡a Hao Gu,‡b Jinglun Huang, Fude Nie, Guijuan Fan* , Longyu Liao* and Wei Yang*
a
a
a
a
c
DOI: 10.1039/x0xx00000x
www.rsc.org/
Ionic salts of 5,5’-bis(trinitromethyl)-3,3’-bi-1H-1,2,4-triazole and characteristics such as density, sensitivity and detonation
an unexpected energetic zwitterion 5-diazonium-3-trinitromethyl- property.
1
,2,4-triazolate were synthesized by
intramolecular metathesis strategy. Compared with its ammonium development of energetic zwitterions such as primary
6), hydrazinium (7) and hydroxylammonium (8) salts, 5,5’- explosives and energetic materials for laser-induced
a
intermolecular and
Very recently, there is a growing interest in the
(
bis(trinitromethyl)-3,3’-bi-1H-1,2,4-triazole (5) exhibits lower explosion.4b,4c In the previous work, the strategy for
sensitivities (IS: 22.5 J, FS:252 N). It is worth noting that energetic incorporating zwitterion into energetic frameworks falls into
salt 8 exhibits 1.97 g cm-3 and an excellent calculated detonation two categories: a) oxygen atom in hydroxyl group as an anion
-1
4
velocity of 9468 m s as well as energetic zwitterion 5-diazonium- and diazolium in neighbouring carbon as a cation; b) nitrogen
3
1
9
-trinitromethyl-1,2,4-triazolate (14) exhibits a high density of atom in azole ring as an anion and diazolium in neighbouring
.893 g cm-3 and an excellent calculated detonation velocity of carbon as a cation. It is worth noting that the property and
5
-1
-1
317 m s , which are both superior to that of HMX (9254 m s ).
application of above-mentioned energetic zwitterions have not
been fully considered during the synthesis except for high
nitrogen content of diazo-group. Meanwhile, researches on
highly energetic zwitterions will be also challenging. Therefore,
the combination of TNM group and zwitterion in one molecule
should lead to interesting structures and different energetic
Trinitromethyl (TNM) group is a very powerful explosophore,
which can increase the oxygen balance in molecules and make
its derivatives attractive candidates for environmentally
friendly high energy and density material (HEDM)
applications.1 A typical protocol for the synthesis of N-
trinitromethylazoles involves N-alkylation of the corresponding
NH azoles with methyl vinyl ketone or bromoacetone in the
presence of a base, followed by nitration of the resulting
intermediates with nitric acid or a mixture thereof with sulfuric
acid.2 In contrast to N-trinitromethyl compounds, the
generation of C-trinitromethyl moieties were more difficult
due to the lack of suitable intermediates and corresponding
chemical activity. Recently, azo-1,2,4-triazole, bis-1,2,4-
oxadiazole and tetrazole featuring TNM moiety have been
released,3 but these researches were still not adequate for
deeply building the relationship between oxidizers bearing
TNM moiety and other significant physicochemical
properties. Herein, we report
a
series of 5,5’-
bis(trinitromethyl)-3,3’-bi-1H-1,2,4-triazole ionic salts as well
as a zwitterion 5-diazonium-3-trinitromethyl-1,2,4-triazolate
via a intermolecular and intramolecular metathesis strategy.
Their interesting chemical reactions, electronic and thermal
stabilities, physicochemical properties and energetic
properties were further investigated in detail.
The starting materials, oxamidrazone (
,2,4-triazol-3-yl) acetic acid (12) were synthesized according
to the literatures.6 As shown in Scheme 1, a mixture of
oxamidrazone with ethyl-3-ethoxy-3-iminopropionate
hydrochloride was cyclized in acetic acid at 105
,5’-bis(acetic acid ethyl ester)-3,3’-bi-1H-1,2,4-triazole (
obtained by neutralizing the above-mentioned mixture at 5
2) and 2-(5-amino-1H-
1
(2)
o
–
110 C and
) was
10
with 0.5M NaOH solution at 10 C and then
5
3
–
oC. Alkalization of
acidification of the above solution with 2M HNO
5,5’-bis(acetic acid)-3,3’-bi-1H-1,2,4-triazole ( ). The desired
was
with concentrated sulphuric
with ammonia
3
o
a.Institute of Chemical Materials, China Academy of Engineering Physics, P.O.Box
9
longyuliao@caep.cn.
b.School of Chemical Engineering, Nanjing University of Science and Technology,
Xiaolingwei 200, Nanjing 210094, China.
o
3
at 0 C led to
19-311, Mianyang 621999, China. E-mail: fanguijuan@caep.cn;
4
5
,5’-bis(trinitromethyl)-3,3’-bi-1H-1,2,4-triazole
(5)
c.
produced from the nitration of 4
Department of chemistry and chemical biology, Harvard University, Cambridge,
Massachusetts, 02138, USA. E-mail: wei_yang@fas.harvard.edu
acid and 96% nitric acid. Further treatment of
5
†
Electronic Supplementary Information (ESI) available: Experimental details, NMR,
solution (7N), hydrazine monohydrate and 50% aqueous
DSC, computational details. For ESI and crystallographic data in CIF or other
electronic format see DOI: 10.1039/x0xx00000x
‡
These authors contributed equally to this work.
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 1
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Ple Na es we dJ oo u nr no at l ao df jCu hs et mm i as tr rgy ins
Page 2 of 6
COMMUNICATION
hydroxylamine resulted in the formation of salts
dipotassium 5,5’-bis(trinitromethyl)- 3,3’-bi-1,2,4-triazolate (
Journal Name
6
–8
. The detected. For compound 14, there are six well resolved signals at
View Article Online
DOI: 10.1039/C7NJ03939E
9
)
δ=–11.00 (N2), –12.28 (N1), –32.59 (N6), –55.13 (N4), –113.07 (N3)
and –154.75 (N5) ppm.
H
2
N
S
N
NH
O
HCl
OEt
N
2
H
4
H
2
O/EtOH
N
NH
N
NaOH/H
COOEt
HCl
2
O
NH
2
NH
2
2
EtO
1) AcOH; (2) KHCO
COOEt
2
H N
H
2
N
(
3
N
NH
N
S
N
2
NH
1
3
NO2NO
NO
2
R
2
N
N
N
N
Basic solution
N
N
NO2
NO
2
R
NO
2
2NO
2
R= NH4
NH
3
2
NO
NO
NH
NH
3
OH
8
COOH
N
N
N
NH
96%HNO
COOH conc.H
2
N
NH
N
6
7
3
NH
2
SO
4
N
NH
N
NO2
NO
NO
N
2
2
4
5
K
NO
2
N
NH
N
NH
2
OH HCl NO
2
KOH
N
NH
N
NO
K
2
NO
2
9
Scheme 1 Synthesis of
5
and its energetic salts.
was obtained by treatment of 5 with an alkaline solution of
hydroxylamine with potassium hydroxide in anhydrous ethanol at
0oC.
i) 0oC, 100%
HNO /conc.H
ii) 25oC, 12h
O
2
N
NO
2
(
3
2
SO
4
NO
2
N
(
N
2
O NHN
N
H
COOH
NH
COOH
COOH
11
N
KOH/H
2
O
13
NH
2
H
2
N
N
H
N
2
H N
HCl
N
H
2
O N
NO
2
Fig.1 Selected 15N NMR spectra of 5, 8 and 14.
2 3
H CO
(
i) -15oC, 96%
HNO /conc.H
NO
2
1
0
12
3
2
SO
4
N
N
2
Single crystals of 5·2H O suitable for single-crystal X-ray
o
N
(
ii) 25 C, 16-24h
N
N
diffraction were obtained by slow evaporation from a solution
of methanol and water in 3:1 volume ratio, whereas 14
14
Scheme 2 Synthesis of energetic zwitterion 14
2
crystallizes from dichloromethane. Compound 5·2H O
Synthesis of 5, 5-diazonium-3-trinitromethyl-1,2,4-triazolate (14)
was obtained with the same nitration methodology by first
cyclization of 10 and 11, followed by the nitration of 12 with
concentrated sulphuric acid and 96% nitric acid (Scheme 2). It is
found that nitration of 12 with concentrated sulphuric acid and 100%
nitric acid could lead to another compound 13 which was revealed
crystallizes as a colorless plate crystal in the monoclinic C2/c
space group with four molecules per unit cell and has a
calculated density of 1.828 g cm-3 at 130(2) K. It is illustrated
from Fig. 2a that 5,5’-bis(trinitromethyl)-3,3’-bi-1H-1,2,4-triazole
2
co-crystallized with two water molecules as well as 4·2H O. The C1–
o
N1–C2–C3 torsion angle of -175.89(10) and C2–N1–C1–C1A torsion
7
by T. Hermann et al. Unexpectedly, a novel energetic zwitterion 14
o
angle of -179.40(14) indicate that the two triazole rings are almost
was achieved by using 96% nitric acid, which could be due to the
coplanar. The N2–N3 bond length of 1.3458(14)Å is close to the N1–
2
presence of HNO in the nitric acid. Diazotization of the primary
N2 bond length of 1.364(2) in 4·2H
shorter than the normal N–N bond length of 1.47 Å. The packing
diagram shows that 4·2H O packs in "V-shaped" packing in Fig. 2b,
2
O (see ESI†), which are all
amine followed by tri-nitration at the α-postion of carboxylic group
make the 2-H of triazole more acidic and led to the zwitterionic
inner salt 14 after deprotonation (Scheme 3). Such a reaction has
rarely been reported and may provide a new method for preparing
high energy zwitterionic compounds.
2
whereas 5·2H
2
O has a parallel-layer packing. Though the single
1
crystal of 5 contained two water molecules, H NMR (see ESI†) of 5
confirmed there was no water in the target product.
1
3 2 4
00%HNO /H SO
O
2
N
NO2
NO
COOH
COOH
NO
2
NO2
2
N
N
N
N
N
H
2
N
2
O NHN
N
N
H
N
H
O NHN
2
N
H
1
3
96% HNO
/H
3 2
SO
4
NO
O
2
N
NO
2
2
O N
NO2
COOH
NO
2
N
NO
2
NO
2
- H
N
N
N
N
N
N
N
N
N
N
H
N
N
N
N
H
1
4
Acidity
Fig.2 (a) Thermal ellipsoid plot (50%) and labelling scheme of
Scheme 3 Proposed mechanism for synthesizing 13 and 14 from 12.
5
2 2
·2H O. (b) Ball-and-stick packing diagram of 5·2H O viewed down
The 15N spectra of 5, 8 and 14 are shown in Fig. 1, which are
the a axis. Dashed lines indicate strong hydrogen bonding.
determined based on the literatures.3a,5 Compound 5 and 14 were
Compound 14 crystallizes as an orange prism crystal in the
recorded in acetone-d
For compound 5, there are four well resolved signals at δ=–33.33
N4), –71.94 (N3), –125.95 (N1) and –146.80 (N2) ppm. For
compound 8, five well resolved signals at δ=–22.47 (N4), –51.70
N3), –133.66 (N1), –181.42 (N2) and –286.64 (N5) ppm are
6 6
, and compound 8 was recorded in DMSO-d .
1 1
orthorhombic space group P2 2 with four molecules per unit
cell, and a high calculated density of 1.934 g cm-3 at 130 K. It
(
can be seen from Fig. 3a that the triazole ring and the carbon
atom from trinitromethyl are nearly coplanar, which are
(
2
| J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
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Page 3 of 6
Ple Na es we dJ oo u nr no at l ao df jCu hs et mm i as tr rgy ins
Journal Name
further revealed by the N3
LETTER
o
–
N2
–C2
–C3 torsion angle of
and 8 equal or exceed 200 C.
View Article Online
o
C3 torsion angle of 179.92(18)o.
DOI: 10.1039/C7NJ03939E
1
79.63(18) and the C1
–
N1
–C2
–
Additionally, the triazole ring and the diazo group are
considered to be approximately in the plane, which can be
illustrated from the N2
o
–
N3
–C1–N4 torsion angle of -177.40(18)
o
and the C2–N1–C1–N4 torsion angle of 177.19(19) . The
diazonium bond N4–N5 bond length of 1.095(2) Å in the range of
N≡N triple bond is almost equal to those of other previously
reported diazonium inner salts (1.088(2) Å,11a 1.096(3) Å,11b 1.111(2)
Å 1 and 1.112(2) Å 11d). The packing diagram of 14 from Fig. 3b
shows an irregular packing due to its absent hydrogen bonding
interaction. Fig. 3c gives the physical map of large prism-like yellow
crystals at the ambient temperature.
1c
Fig.4 UV-vis spectroscopy of 5-9 and 14 in anhydrous methanol
solution
5–8 and 14 exhibit positive heat of formation that are
superior to those of pentaerythritol tetranitrate (PETN), 1,3,5-
trinitroperhydro-1,3,5-triazine (RDX) and octahydro-1,3,5,7-
tetranitro-1,3,5,7-tetrazocine (HMX). The experimental
densities of these compounds are in the range of 1.82
cm-3 which equal or exceed those of common oxidizers and
explosives. For dipotassium salt , its theoretical density is up
–1.95 g
9
-3
to 2.15 g cm , which is normally high as well as some reported
9
dinitromethyl dipotassium salts. Impact and friction sensitivity
(IS and FS) are tested using the standard BAM methods. The
diazolium triazolate 14 is a typical hydrogen-free compound of
only C, N and O atoms. It’s very sensitive as well as previously
hydrogen-free explosives such as benzotrifuroxan (BTF)
Fig.3 (a) Thermal ellipsoid plot (50%) and labelling scheme of 14. (b)
Ball-and-stick packing diagram of 14 viewed down the a axis. (c)
Prism-like yellow crystals of 14 grew from dichloromethane at the
ambient temperature.
IS<3J)10 and trinitrotris(triazolo)benzene (TNTTB) (IS=3J).11 It is
(
worth noting that
comparable to that of 14, expect
6
–
8
showed high impact sensitivities
which is relatively lower.
9
To investigate the electronic structures of these new compounds,
the ultraviolet and visible spectra (UV-vis) of 5–9 and 14 were
collected in anhydrous methanol solution (Fig.4). All compounds are
in the B band of the UV from 250 nm to 400 nm, which mainly
corresponds to n→π* electronic transition. Concretely speaking, it
The phenomenon can be rationalized in terms of extensive
O···O contact interaction between bis(trinitromethyl) groups
and its obvious decreasing in gem-dinitromethyl groups. The IS
and FS of 14 show that it is more sensitive than PETN. The
electrostatic discharge device (ESD) measurements show that
is obvious that
to the electrostatic interaction after the formation of energetic
salts, where neutral compound shows no absorbance.
Different from salts , ziwitterion 14 displays an alternative
absorbance at 273 nm. Interestingly, dihydroxylammonium
salt exhibits an intense absorbance at 354 nm when
compared with other salts bearing the same frameworks. In
addition, the characteristic absorbance of salt has a
6–9 display absorbances around 354 nm owing
only
=0.33J,
Other compounds show that they are easy to be initiated
=0.11 J; =0.15 J; =0.12 J; 14=0.09 J).
Density was measured with helium gas pycnometer at 25 oC
except compound 14 was determined by X-ray diffraction at
98 K. The experimental densities of compounds 5–14 are in
the range of 1.86 The calculated detonation
7
and
9
are less sensitive towards electrostatic discharge
(7
9=0.39 J) than RDX and HMX (RDX=HMX=0.20 J).
5
5–9
(5
6
8
8
8
2
bathochromic shift at 237 nm relative to other compounds
which basically show the consistent absorbances from 205 to
10 nm. This may be explained by different intra- or
2.15 g cm-3
.
–
pressures (P) and detonation velocities (D) were estimated
based on traditional Chapman-Jouget thermodynamic
detonation theory using EXPLO5 program (v6.02).12 The
detonation pressures of the present compounds lie in the
2
intermolecular interactions because the hydrogen bonding
interaction induced by dihydroxylammonium cation is usually
8
stronger than those from other cations. Because no hydrogen
bonding interaction exists in 14, it is rational that no
characteristic absorbance appears at 354 nm.
range of 33.7 to 39.9GPa and detonation velocities lie between
-1
8
800 m s-1 and 9468 m s . Specific impulses (Isp) of the
referenced compounds were also calculated by using EXPLO5
code. Among them, the resulting Isp values of (260.2 s),
As shown in Table 1, the thermal behavior of all the title
compounds was investigated by DSC-TG. They show thermal
5
8
o
o
-1
(262.5 s) and 14 (268.4 s) is comparable to those of RDX (267.7
s), HMX (267.5 s) and PETN (270.1 s), but much higher than
that of common oxidants such as ADN (202 s).15
stability from 127
–
218 C at the heating rate of 5 C min . It is
possess higher thermal decomposition
after the formation of salts, especially
worth noting that
temperature than
6–9
5
7
This journal is © The Royal Society of Chemistry 20xx
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Ple Na es we dJ oo u nr no at l ao df jCu hs et mm i as tr rgy ins
Page 4 of 6
COMMUNICATION
Journal Name
Table 1. Energetic properties and detonation parameters of the title compounds
View Article Online
DOI: 10.1039/C7NJ03939E
Comp.
N (%)[a]
53.84
53.84
53.84
64.29
33.32
59.14
17.72
37.84
37.84
Ω
CO2 (%)[b]
-3.69
Ω
CO (%)[c]
18.43
6.83
3.21
12.79
3.81
19.67
15.18
0
T
d
[d]
IS (J)[e] FS(N)[f] ESD(J)[g] d (g cm )
-3 [h]
f
∆ I
H (kJ mol-1)[j] P (GPa)[k] D (m s-1)[l]
sp (s)[m]
260.2
250.2
258.6
262.5
194.5
268.4
270.1
267.7
267.5
5
6
7
8
9
148 22.5
252
6
0.11
0.15
0.33
0.12
0.39
0.09
0.10
0.20
0.20
1.89
331.9
-45.1
250.9
44.9
36.2
33.7
34.9
39.9
36.0
37.6
31.4
34.7
39.2
9073
8800
8933
9468
9280
9317
8564
8872
9254
-13.67
-16.06
-6.40
188
218
191
161
127
150
1
3
1.86
1.94
1.97
2.15
1.89i
1.77
1.81
1.90
16
5
144
288
5
-19.03
0
8
-258.2
521.7
-407
14
<1
3
PETN13
RDX14
-10.12
-21.61
-21.61
60
210 7.5
279
120
120
80.0
HMX14
0
7
104.8
[
2
a] Nitrogen content. [b] Oxygen balance assuming the formation of CO . [c] Oxygen balance assuming the formation of CO. [d]
o
-1
Decomposition point from DSC at the heating rate of 5 C min . [e] Impact sensitivity measured by drop-hammer test according to standard
BAM methods. [f] Friction sensitivity measured by a friction tester according to standard BAM methods. [g] Electrostatic discharge device.
o
[
h] Density measured by gas pycnometer at 25 C. [i] Density recalculated from low-temperature X-ray density, ρ298K=ρ
T
/(1+α
v
(298-T
0
))
-4
α
v
=1.5x10 , T
0
is the crystal testing temperature. [j] Calculated solid heat of formation by Gaussian 09 package at M06-2X/6-311++G(d,p)
level.16 [k] Detonation pressure. [l] Detonation velocity. [m] Specific impulse (neat compound).
Chem., 2008, 44, 874–881; (c) I. L. Dalinger, I. A. Vatsadze, T.
K. Shkineva, A. V. Kormanov, M. I. Struchkova, K. Yu.
Suponitsky, A. A. Bragin, K. A. Monogarov, V. P. Sinditskii and
In summary, 5,5’-bis(trinitromethyl)-3,3’-bi-1H-1,2,4-triazole
) and 5-diazonium-3-trinitromethyl-1,2,4-triazolate (14) were
(
5
synthesized by a intermolecular and intramolecular metathesis
strategy. Energetic salts ( ) were synthesized based on 5.
The chemical reaction mechanism of synthesizing unexpected
A. B. Sheremetev, Chem. Asian J., 2015, 10, 1987
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Qi, K. Wang and Q. Zhang, Chem. Eur. J., 2017, 23, 1 9.
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(a) P. Yin, J. Zhang, D. A. Parrish, J. M. Shreeve, Chem. Eur. J.,
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–1996; (d) X.
6
–
9
4
–
–
energetic zwitterion 14 was proposed. Surprisingly, compound
-
3
3
4
5
8
shows high density (1.97 g cm ) and good detonation
–
-1
performance (D: 9468 m s , P:39.9 GPa), which indicates its
potential application as a highly energetic material.
–
ö
–
We are indebted to the NSAF Foundation of National
Natural Science Foundation of China and China Academy of
Engineering Physics (Grant No. U1530262), the National
Natural Science Foundation of China (Grant No. 11402237) and
the Science and Technology Development Foundation of China
Academy of Engineering Physics (Grant No. 2015B0302055) for
funding of this work. Prof. Qinghua Zhang was also gratefully
acknowledged for providing gas pycnometer in the test of
experimental densities.
ö
ć
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Table of content
Energetic trinitromethyl bistriazole and its ionic salts, as well as an unexpected
energetic-zwitterion featuring trinitromethyl and diazonium moieties were synthesized by a
intermolecular and intramolecular metathesis strategy.