Synthesis and characterization of new energetic derivatives containing a high nitrogen content moiety and picryl group: A new strategy for incorporating the picryl functionality

Article abstract of DOI:10.1039/c4ra08084j

New energetic picryl derivatives were synthesized via the reactions of 2,4,6-trinitrobenzaldehyde with high nitrogen content compounds (above 70%) containing the hydrazine group. The resulting compounds 1-3 and 5-7 were characterized well by IR spectroscopy, multinuclear NMR spectroscopy, DSC measurements as well as elemental analysis. Additionally, the structures of compounds 1, 2 and 5 were confirmed by single crystal X-ray diffraction analysis. Except for compound 2, all the remaining products exhibit good thermal stabilities with decomposition onset temperatures above 180 °C. All products possess high heats of formation ranging from 128.62 to 989.52 kJ mol^-1. The calculated detonation velocities lie in the range between 7417 and 8271 m s^-1. The detonation pressures range between 21.8 and 31.1 GPa.

Full text of DOI:10.1039/c4ra08084j

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Journal Name
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View Article Online
DOI: 10.1039/C4RA08084J
ARTICLE
Synthesis and Characterization of New Energetic
Derivatives Containing High Nitrogen Content
Moiety and Picryl Group: A New Strategy for
Incorporating the Picryl Functionality
Cite this: DOI: 10.1039/x0xx00000x
Received 00th January 2012,
Accepted 00th January 2012
Bo Wu, a Hongwei Yang,*a Zhixin Wang, a Qiuhan Lin,a,b Xuehai Ju,a Chunxu Lu,
a and Guangbin Cheng*a
DOI: 10.1039/x0xx00000x
www.rsc.org/
New energetic picryl derivatives were synthesized via the reactions of 2,4,6-
trinitrobenzaldehyde with high nitrogen content compounds (above 70%) containing hydrazine
group. The resulting compounds
multinuclear NMR spectroscopy, DSC measurements as well as elemental analysis.
Additionally, the structures of compounds and were confirmed by single crystal X-ray
diffraction analysis. Except for the compound , all the remaining products exhibit good
1-3 and 5-7 were well characterized by IR spectroscopy,
1
,
2
5
2
o
thermal stabilities with decomposition onset temperatures above 180 C. All products possess
high heats of formation ranging from 128.62 to 989.52 kJ mol-1. The calculated detonation
velocities lie in the range between 7417 and 8271 m s-1. The detonation pressures range
between 21.8 and 31.1 GPa.
2,4,6-trinitrophenyl moiety (picryl moiety) has been used as an
energetic unit in the field of energetic materials.10 As known, the
Introduction
The development of energetic materials continues to focus on these
compounds with high densities, high heats of formation and good
detonation properties.1 The novel energetic compounds possessing
excellent performance and low sensitivity are extremely desirable.
Recently, a new group of energetic materials containing high
nitrogen content moieties has been studied.2 In contrast with
traditional explosives, whose energy is derived from the overall heat
of combustion, the most energy of these energetic compounds
containing high nitrogen fragment derives from their very high heats
of formation. The high heat of formation is directly attributed to
large numbers of N―N and C―N bonds within their structures.3
Additionally, energetic compounds with high nitrogen, but low
hydrogen and carbon content allow a good oxygen balance to be
achieved more easily. Nitrogen-rich parent compounds such as
nitro group is helpful to enhance the oxygen balance and density of
the energetic materials, which improves the detonation performances.
Therefore, picryl moiety plays a remarkable role in preparation of
new energetic materials. Incorporation of a picryl group into the
nitrogen heterocyclic compounds such as triazoles,10c, 10e furazans,10b
trizines10a and tetrazoles10h has been investigated. Among these
energetic picryl derivatives, typical picryl derivatives with high
nitrogen moiety (nitrogen contents above 70%) are the following: 5-
picrylamino-1,2,3,4-tetrazole
trinitrophenyl)guanidine.
(PAT)
contrast
and
to
(2,4,6-
(2,4,6-
In
trinitrophenyl)guanidine, 5-picrylamino-1,2,3,4-tetrazole (PAT) has
been fully investigated. It can be synthesized from the reactions of
picryl
chloride
with
5-amino-1,2,3,4-tetrazole
or
1,5-
diaminotetrazole (Scheme 1).10h It also has been further
characterized for structural aspects, thermal behaviour and explosive
properties. Usually, picryl halogen (halogen = F, Cl) is used as the
starting materials for synthesizing energetic picryl derivatives. In the
present work, 2,4,6-trinitrobenzaldehyde was used as new starting
material for the preparation of new energetic picryl derivatives.
These new picryl derivatives containing high nitrogen content
moieties were synthesized via the condensation reactions of 2,4,6-
trinitrobenzaldehyde with high nitrogen content parent compounds
5
guanidines,4 tetrazoles2c, and tetrazines6 are essential units to
synthesize energetic compounds containing high nitrogen content
moieties. Generally, oxygen-containing energetic substituents such
as nitro (NO2),1c-1e, 2b, 7 nitrato (ONO2),8 and nitramine (NHNO2)1g, 2c,
6e,
9
functionalities are introduced into nitrogen-rich parent
compounds to produce novel energetic derivatives with excellent
detonation performance.
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Scheme 2 Synthesis of picyl derivatives 1-3.
containing hydrazine group such as aminoguanidine derivatives, 5-
hydrazinotetrazolium chloride and 3,6-dihydrazine-1,2,4,5-tetrazine
dihydrochloride. These new energetic picryl derivatives were
characterized for structural aspects, thermal behaviour and explosive
properties by experimental and theoretical methods.
View Article Online
DOI: 10.1039/C4RA08084J
Scheme 1 Synthesis of 5-picrylamino-1,2,3,4-tetrazole (PAT
)
Results and discussion
Synthesis
Scheme 3 The process for the formation of
5
It is known that aromatic aldehyde can readily react with
amines and hydrazines to generate Schiff bases and hydrazones
with the elimination of water molecules. However, 2,4,6-
trinitrobenzaldehyde possesses lower reactivity than common
aldehydes owing to the strong electron-withdrawing inductive
effect of the three nitro groups attached to the benzene ring. In
the beginning, the attempts of reactions between the amino
derivatives of tetrazole (e.g., 5-aminotetrazole and 1,5-
diaminotetrazole) and 2,4,6-trinitrobenzaldehyde did not result
in the desired picryl derivatives. It was probably due to the fact
that the reactivity of the amino group is poorer than that of the
hydrazine group in nitrogen-rich compounds. Then, the
commercially available aminoguanidine hydrochloride reacted
After preparation of these picryl-functionalized guanidine
derivatives, we turned our attention to synthesize picryl-
functionalized tetrazole and 1,2,4,5-tetrazine derivatives. 5-(2-
(2,4,6-trinitrobenzylidene)hydrazinyl)-1
bis-(2-(2,4,6-trinitrobenzylidene)hydrazinyl)-1,2,4,5-tetrazine
were prepared from the reactions of 2,4,6-
H-tetrazole (6) and 3,6-
(7)
trinitrobenzaldehyde with 5-hydrazinotetrazolium chloride and
3,6-dihydrazine-1,2,4,5-tetrazine dihydrochloride in the yield of
80% and 60%, respectively (Scheme 4).
with
trinitrobenzylideneamino) guanidinium chloride
corresponding picryl derivatives and were also synthesized
2,4,6-trinitrobenzaldehyde
to
yield
N
-(2,4,6-
(1). The
2
3
from the reactions of 2,4,6-trinitrobenzaldehyde with
aminoguanidinium nitrate and aminoguanidinium perchlorate
(Scheme 2). Surprisingly, the desired 1,3-bis(2,4,6-
trinitrobenzylideneamino) guanidine (
the reaction of 1,3-diaminoguanidium monohydrochloride with
2,4,6-trinitrobenzaldehyde. 4,6-Dinitro- -(2,4,6-
trinitrobenzylidene)-1 -indazole-1-carbohydrazonamide
was the only ultimate product. It was probably caused by the
intramolecular cyclization of . As reported, the -nitro group
4) was not obtained from
N
H
(5)
4
o
in picryl moiety could be replaced by nucleophiles (Scheme
3).11
Scheme 4 Synthesis of picyl derivatives
6 and 7
NH2
A
NH2
A
Single-Crystal X-ray Analysis
CHO
NO2
HN
N
NH2
H2N
N
H
NH2
O2N
NO2
Three compounds described herein
(1, 2 and 5) were
O2N
NO2
characterized by single-crystal X-ray diffraction analysis.
Selected data and parameters of the measurements and
refinements were gathered in Table1.
EtOH, reflux
NO2
Table 1. Crystal data and structure refinement details of
1, 2 and 5
A= Cl ( ), NO ( ), ClO ( )
1
2
3
3
4
Crystal
1
2
5
2 | J. Name., 2012, 00, 1‐3
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to the steric effect of the –C=N-group. The C7-N4 bond length
formula
C8H8ClN7O6
0.71073
C8H8N8O9
0.71073
C15H8N10O10
0.71075
of 1.277(6) Å, shows typical C-N double bond values.12 The C-
View Article Online
N bond lengths of the protonated guanidine moiety differ in a
DOI: 10.1039/C4RA08084J
λ [Å]
range of 1.311(3) Å to 1.346(3) Å, which are longer than C=N
double bonds (1.277(6) Å) but shorter than the C-N single bond
(1.460(2) Å).12, 13 It indicates that the conjugation system exists
in the protonated guanidine moiety. Classical N6—H6A•••N4
hydrogen bond was found (Figure 1). Further investigation on
crystal
system
orthorhombic monoclinic
orthorhombic
space group
a [Å]
b [Å]
c [Å]
α [°]
Pbca
P21/c
Aba2
hydrogen bonds within the crystal structure of compound
1
shows the infinite chains (Figure 2). The hydrogen atoms of the
protonated guanidine structure together with chlorine atoms add
many intra- and intermolecular hydrogen-bond interactions to
form two dimensional network in the bc-plane. These
hydrogen-bond interactions are helpful to increase the thermal
12.387(3)
11.618(2)
18.866(4)
90
17.6205(13) 24.962(3)
10.4858(7) 16.401(2)
15.8252(10) 9.4116(10)
stability of
1. The details of all hydrogen bonds are gathered in
Supporting Information (see Table S7)
90
90
β [°]
90
111.333(3)
90
90
γ [°]
90
90
V [Å3]
Z
2715.0(9)
4
2723.6(3)
8
3853.2(8)
8
ρcalc
1.633
1.757
1.683
[g cm-3]
Figure 1 Molecular structure of
1 and its labeling scheme.
Ellipsoids are drawn at the 50% probability level. Dashed lines
indicate intramolecular hydrogen bond.
GOF on F2
1.041
1.015
0.963
Final
R
R1 = 0.0566, R1
=
=
R1 = 0.0673,
indexes
[I>2σ(I)]
wR2
=
0.0477,
wR2
wR2
=
0.1394
0.1507
0.0880
Final
R
R1 = 0.0810, R1
=
=
R1 = 0.1149,
indexes
wR2
=
0.1057,
wR2
wR2
=
0.1549
0.1815
(all data)
0.1072
Figure 2 Hydrogen bonds viewed on the chains along the b axis in
the structure of 1.
CCDC
996727
996728
996729
N
-(2,4,6-trinitrobenzylideneamino)guanidinium nitrate
crystallizes in the monoclinic space group 21/ as a racemic
twin (Figure 3). There are eight molecules in the unit cell and
the density is 1.757 g cm-3. The molecules are also in an
configuration. In two independent -(2,4,6-
(2)
N
-(2,4,6-trinitrobenzylideneamino)guanidinium chloride
(1)
P
c
crystallizes in the orthorhombic space group
Pbca with a cell
volume of 2715.0(9) Å3 and four molecules in the unit cell. The
density is 1.633 g cm-3. As shown in Figure 1, the molecules
E
N
are
in
an
E
configuration.
In
the
N-(2,4,6-
trinitrobenzylideneamino) guanidinium cations, the atoms in
either benzene ring or guanidinium moiety are planar with
mean deviations from their respective plane of 0.0048, 0.0083,
0.0059 and 0.0589 Å, respectively. The benzene ring and
guanidinium moiety are slightly twisted with the dihedral
angles between them of 3.6 ° and 0.6°, respectively. They are
much smaller than that of compound 1, which is attributed to
the lack of strong hydrogen bonds involving the chlorine atoms
with the bulky guanidinium moiety in the bc-plane within the
trinitrobenzylideneamino) guanidium cation, the atoms in either
benzene ring or guanyl moiety are planar with mean deviations
from their respective plane of 0.0238 and 0.0289 Å,
respectively. The benzene ring and guanidinium moiety are
twisted with the dihedral angle between them of 63.0°. The 4-
NO2 group in the picryl group lies in the plane of the benzene
ring, whereas both nitro groups in the ortho positions are
substantially twisted out of the plane of the aromatic system
with angles of 10.8° (1-NO2 group) and 4.9° (3-NO2 group) due
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crystal structure of compound
2
. As shown in Figure 3, non- deviations from their respective plane of 0.0090, 0.0245 and 0.0151
H15•••O7 hydrogen bonds , respectively. The dihedral angle between the guanidine moiety
were observed. In addition, classical N4 H4B•••O4, N4
H4B•••N2 and N12 H12B•••N9 hydrogen bonds were and benzopyrazole ring is 10.7 °. The bond lengths of C8-N6 and
observed. In the packing diagram of , as depicted in Figure 4, C9-N7 are 1.302(7) and 1.281(7) Å, respectively. In the entire
classical C7
—
H7•••O2 and C15
—
Å
View Article Online
—
—
and benzene ring is 15.3 ° while that between the guanidine moiety
DOI: 10.1039/C4RA08084J
—
2
classical intermolecular hydrogen bonds are found between the molecule, a large conjugation system is formed between the 2,4,6-
protons in guanidinium fragment and the oxygen atoms of nitro trinitrobenzene ring and benzopyrazole ring through two double
groups and nitrate anions. Nonclassical intermolecular bonds (C8-N6 and C9-N7). All the protons possess acidity due to the
hydrogen bonds are also observed between the imine protons electron-withdrawing inductive effect of five nitro groups attached to
and the oxygen atoms of nitrate anions. The details of hydrogen the conjugation system. As depicted in Figure 5, nonclassical C1
bonds are summarized in in Supporting Information (see Table S8) H1•••O3, C4—H4•••N6 and C9—H9•••O10 intramolecular
These interactions build up a 3D network which consists of hydrogen bonds were found. Additionally, intermolecular
—
.
“rhombic shape” unit along
c
direction.
nonclassical interactions were observed between CH protons and the
oxygen atoms of the nitro groups. The details of all hydrogen bonds
are gathered in Supporting Information (see Table S9). In the
packing diagram of 5, as shown in Figure 7, the rows show a zigzag
type pattern and present an angle of 95.72 ° within the rows.
Figure 3 Molecular structure of 2. Ellipsoids are drawn at the 50%
probability level. Dashed lines indicate intramolecular hydrogen
bonds.
Figure 5 Molecular structure of
5 and its labeling scheme.
Ellipsoids are drawn at the 50% probability level. Dashed lines
indicate intramolecular hydrogen bonds.
Figure 4 Ball and stick packing diagram of 2 viewed down the c axis.
Dashed lines indicate strong hydrogen bonds.
Figure 6 Ball and stick packing diagram of 5 viewed down the c axis.
Dashed lines indicate strong hydrogen bonds.
4,6-dinitro-N'-(2,4,6-trinitrobenzylidene)-1H-indazole-1-
carbohydrazonamide (5) crystallizes in the orthorhombic space
group Aba2 with a cell volume of 3853.2(8) Å3 and eight molecules
in the unit cell. A density of 1.683 g cm-3 was determined from the
X-ray crystal structure. As shown in Figure 6, the molecules are in E
configuration. The atoms in the 2,4,6-trinitrobenzene ring,
benzopyrazole ring and guanidine moiety are planar with mean
Spectroscopy
In the IR spectrum of compounds 1-3 and 5-7, the characteristic
asymmetric stretching vibrations νas NO2 are found in the range of
1638–1539 cm-1 and the symmetric stretching vibrations νs NO2 at
1310–1295 cm-1. The signals lie in the range of 1678–1600 cm-1
4 | J. Name., 2012, 00, 1‐3
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representing the stretching vibrations of C=N. The vibration around
3200 cm-1 can be interpreted as the stretching vibrations of C–H in
the –CH=N– group as well as signals for valence vibrations of C–H
in the trinitrobenzene ring around 3100 cm-1. For all new picryl
derivatives, the signals lying in the range of 3551–3409 cm-1
representing N–H vibrations are observable.
View Article Online
DOI: 10.1039/C4RA08084J
All products were investigated using 1H NMR and 13C NMR.
Additionally, the 15N NMR spectra were recorded for compounds 2
and 3. The multinuclear NMR spectra were measured in [D6]DMSO
and the chemical shifts were given with respect to DMSO or
1
CH3NO2 as external standard. The H and 13C NMR spectra of all
compounds were given in the Supporting Information (Figures S3-
S14). For compunds 1-3 and 6-7, in the 1H NMR spectra, the proton
signals of picryl group appear between δ = 9.06 and 9.14 ppm,
Figure 7 15N NMR spectra of 2 and 3.
which are at
a
little higher field than that of 2,4,6-
trinitrobenzaldehyde (δ = 9.16 ppm). The proton signals of the -
CH=N- groups range from δ = 8.39 to 8.59 ppm, which are
significantly at higher field than that of -CH=O group appearing at δ
= 10.54 ppm in 2,4,6-trinitrobenzaldehyde. In the 13C NMR spectra,
for all compounds, the carbon signals of picryl moiety are identified
around δ = 150, 148, 130 and 125 ppm. The carbon signals of the
C=N double bonds connecting the picryl group to nitrogen-rich
moieties of 1-3 and 5 locate at the lower field ranging from 140.78 to
143.32 ppm than that of 6-7 appearing at 136.2 and 135.53 ppm. It
can be attributed to the fact that the electron-withdrawing inductive
effect of guanidine moiety is stronger than nitrogen-rich
heterocycles .
Thermal Behavior and Sensitivities
Thermal stability is one of the most important physicochemical
properties of energetic materials. The thermal behaviour of all
products was investigated by differential scanning calorimetry (DSC)
o
at a heating rate of 10 C min-11. The plots were shown in the
Supporting Information (Figures S15-S20). As summarized in Table
2, compounds 1, 3, 6 have melting process, whereas the other
compounds decompose directly. Generally, the decomposition onset
temperatures of presented energetic picryl derivatives are higher than
180 °C. A thermal stability above 180 °C is an essential requirement
for energetic compounds to adaptation for practical use. The only
exception is 2, whose decomposition onset temperature is 146.3 °C.
This lower stability may be due to the lack of the hydrogen bonding
network in the structure. For compounds 1, 3, 5, 6, 7, their
decomposition onset temperatures are higher than that of 5-
picrylamino-1,2,3,4-tetrazole (PAT) (Tdec,onset = 183 °C),10h which
probably due to the existence of the large conjugation system within
their structures. The most stable compound is 7, which decomposed
at almost 230 °C. Its decomposition onset temperature is higher than
that of RDX (1,3,5-trinitro-1,3,5-triazinane; Td = 205 oC).15
The sensitivities of the resulting compounds 1-3 and 5-7 towards
impact, friction, and electrostatic discharge were tested by using
standard procedures.16 As depicted in Table 2, the impact sensitivity
values are found to be in the range from 6 (3) to 35 J (6). The
friction sensitivity values differ in the range from 120 (3) to 360 N
(6). Based on the classification standard of sensitivities,17 the ionic
picryl derivatives 1-3 are classified as sensitive due to their impact
sensitivities of 25, 11 and 6 J and friction sensitivities of 192, 168
and 120 N, respectively. The compounds 5 and 7 are less sensitive to
impact and friction than RDX (7.5 J, 120 N) due to their impact
sensitivities of 32 and 30 J and friction sensitivities of 320 and 288
N, respectively. The impact and friction sensitivity values of 6 are 35
J and 360 N, respectively, placing it in the insensitive class. These
picryl derivatives 1-3 and 5-7 differ strongly in their electrostatic
sensitivities. As shown in Table 2, compounds 1, 5-7 are
significantly less sensitive to electrostatic discharge than RDX. The
nitrate 2 is slightly less sensitive than RDX, whereas perchlorate 3 is
more sensitive than RDX.
The 15N NMR spectra for compound 2 shows six singlet resonances.
And five well-resolved resonances are detected in the 15N NMR of
compound 3. The assignments of the nitrogen signals were
determined based on the literature values of compounds with similar
14
structures.4a,
As depicted in Figure 7, in the spectra of 2, the
signals of nitrate anion locate at the lowest field with δ = -4.37 ppm.
In the same N-(2,4,6-trinitrobenzylideneamino) guanidinium
fragment of 2 and 3, the strong nitrogen signals of the nitro groups in
benzene ring appear around -16.78 (N1/N3) and -20.00 (N2) ppm.
The nitrogen signals of -CH=N- group connecting the guanidine
structure to the benzene ring are found around δ = -59.91 ppm while
the nitrogen signals of the -NH- group (N5) are observed at a
relatively higher field (around -231.65 ppm). In addition, for
compounds 2 and 3, the signals at highest field are attributed to
protonated semi-guanidine moieties, which appearing at δ = -304.2
ppm.
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Heats of Formation and Detonation Parameters
resulting compounds
formation. The calculated values fall in the range from 128.62
) to 989.52 (
) kJ mol-1, which are highly positiVvieewdAurtiecletoOntlhinee
1-3 and 5-7 exhibit positive heats of
The heat of formation (HOF) plays an important role in
evaluating the performance of energetic materials. The heats of
(3
7
DOI: 10.1039/C4RA08084J
feature of high nitrogen content.
formation of the resulting compounds
1-3 and 5-7 were
The detonation velocity (D) and detonation pressure (P), which
are used to measure the performance of a high explosive, were
calculated by using the EXPLO5 program (Version 6.01).20 As
summarized in Table 2, for these new energetic picryl
calculated based on appropriate isodesmic reactions (Scheme
S1, Supporting Information). Calculations were carried out
using the Gaussian 09 program suite.18 The geometry
optimization of the structures and frequency analyses were
carried out using the B3LYP functional with the 6-311+G**
basis set.19 All of the optimized structures were characterized
by true local energy minima on the potential energy surface
without imaginary frequencies. For ionic energetic compounds
derivatives 1-3 and 5-7, the calculated detonation velocities lie
in the range between 7417 and 8271 m s-1, most of which are
remarkably higher than that of PAT (7770 m s-1).10h The
detonation pressures range between 21.8 and 31.1 GPa, in
which the highest detonation pressure value of
slightly lower than that of RDX (35.2 GPa).
3 (31.1 GPa) is
1
-3
, the positive heats of formation were calculated using the
Born–Haber energy cycle. As summarized in Table 2, the
Table 2. The physicochemical properties of 1-3 and 5-7 compared with 5-picrylamino-1,2,3,4-tetrazole (PAT) and
1,3,5-trinitroperhydro-1,3,5-triazine (RDX).
Nd
ΔfHm
(kJ/mol) (m/s) (GPa)
Dh
Pi
ISj
[J]
FSk
ESDl
[J]
a
b
g
Tm
[oC]
Td
[oC]
OBc
ρ (g cm-3)
Compound
[%]
[N]
205.7 207.7 -67.14 29.39 1.633e
214.18
134.76
128.62
525.42
652.06
989.52
452.23
70
7417 21.8
8256 29.6
8271 31.1
192
168
120
320
360
288
0.887
0.321
0.119
1.1
1
25
11
6
146.3 -48.86 31.11 1.757e
-
2
3
1.853f
211.1 211.1 -40.24 24.66
-78.64 28.69 1.683e
5
-
189.1
7782
24.8
32
35
30
182.2 184.2 -61.89 39.01 1.765f
8234 28.4
0.714
0.821
6
229.5 -65.27 33.33 1.795f
-
7
8188
28.4
PATm
RDXn
-
-
183
205
-50.02 37.84 1.552
-21.6 37.84 1.80
7770 26.4
8795 35.2o
>60 >360 1.0
120 0.2
7.5
a Melting point. b Thermal decomposition temperature under nitrogen gas. c Oxygen balance (%) for CaHbNcOd: OB (%) =1600 ×
d
e
f
(d-2a-b/2)/ Mw (based on carbon dioxide). Nitrogen content. Density from X-ray structure. Density from theoretical
i
calculation. g Molar enthalpy of the formation. h Detonation velocity. Detonation pressure. j Impact sensitivity measured with a
k
l
m
n
o
2.0 kg hammer. Friction sensitivity. Sensitivity against electrostatic discharge. Data from ref [10h]. Data from ref [15].
Data from ref [2e].
Bruker Avance III 500 instrument at 25 °C. The 13C and 15N
NMR spectra were recorded on a Bruker Avance III 300
instrument at 25 °C. The chemical shifts were given relative to
dimethyl sulfoxide (1H, 13C) or nitromethane (15N) as external
standards. Infrared (IR) spectra were recorded on a Perkin-
Elmer Spectrum BX FT-IR instrument equipped with an ATR
unit at 25 °C. DSC studies were performed at a heating rate of
Experimental
Caution: Although we experienced no difficulties in handling
these energetic materials, small scale and best safety practices
(leather gloves, face shield) are strongly encouraged.
General Methods
o
10 C min–1 in closed Al containers with a nitrogen flow of 30
All chemical reagents and solvents were obtained by purchase
and were used as supplied without further purification. 2,4,6-
trinitrobenzaldehyde,21 aminoguanidinium perchlorate,4a 5-
mL min–1 on an STD-Q600 instrument. Analyses of C/H/N
were performed with a Vario EL III Analyzer. The electrostatic
sensitivity tests were carried out with an Electric Spark Tester
ESD JGY-50 III. The sensitivities towards impact and friction
hydrazinotetrazolium
chloride,5i
3,6-dihydrazino-1,2,4,5-
tetrazine dihydrochloride22 were prepared according to
published procedures. The 1H spectra were recorded on a
6 | J. Name., 2012, 00, 1‐3
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ARTICLE
were determined by using a HGZ-1 drophammer and a BAM 0.6484 g of
2
was obtained as white solid in a yield of 90%.
o
1
friction tester.
DSC: Tdec= 146.3 C. H NMR (500 MHz, DMSO): δ (ppm)
View Article Online
X-ray Crystallography: The X-ray diffraction measurements 12.34 (s, 1H, -N
H
-), 9.14 (s, 2H, -C
H
), 8.58 (s, 1H, -C
H
DOI: 10.1039/C4RA0=80N8-4)J,
for
1
,
2
and
5
were performed with a Bruker three-circle 7.73 (s, 4H, -NH2). 13C NMR (75 MHz, DMSO):
δ
(ppm) 156.4,
platform diffractometer equipped with a SMART APEX II 150.5, 149.0, 141.3, 129.6, 125.1. 15N NMR (30 MHz, DMSO )
CCD detector. The data collection and the initial unit cell
δ (ppm) -4.37, -16.78, -20.00, -59.91, -231.65, -304.61. IR
refinement was performed by using APEX2 (v2010.3-0). Data (KBr): 3423, 3166, 3104, 2886, 1683, 1631, 1612, 1547, 1400,
Reduction was performed by using SAINT (v7.68A) and 1385, 1348, 1303, 1226, 1149, 1081, 1037, 914, 825, 726 cm−1.
XPREP (v2008/2). Corrections were applied for Lorentz, C, H, N analysis (%): C8H8N8O9 (360.20), calculated result: C
polarization, and absorption effects by using SADABS 26.68, H 2.24, N 31.11; found: C 27.32, H 2.44, N 30.98.
(v2008/1). The structure was solved and refined with the aid of
the programs in the SHELXTL-plus (v2008/4) system of perchlorate (3)
programs. The full-matrix least-squares refinement on F2 0.7316 g of
included atomic coordinates and anisotropic thermal parameters DSC: Tdec= 211.1 C. H NMR (500 MHz, DMSO):
for all non-H atoms. The H atoms were included in a riding 12.30 (s, 1H, -N -), 9.13 (s, 2H, -C ), 8.59 (s, 1H, -C
model. The structure was solved by direct methods with 7.70 (s, 4H, -NH2). 13C NMR (75 MHz, DMSO):
(ppm) 156.4,
SHELXS-97 and expanded by using the Fourier technique. The 150.5, 149.0, 141.4, 129.6, 125.1. 15N NMR (30 MHz , DMSO )
N
-(2,4,6-trinitrobenzylideneamino)
guanidinium
3
was obtained as white solid in a yield of 92%.
o
1
δ
(ppm)
H
H
H=N-),
δ
non-hydrogen atoms were refined anisotropically. The
hydrogen atoms were located and refined.
Preparation of 2,4,6-trinitrobenzaldehyde
δ (ppm) -16.78, -20.00, -59.91, -231.65, -304.61. IR (KBr):
3551, 3472, 3417, 3245, 3106, 1688, 1638, 1617, 1539, 1465,
1401, 1349, 1231, 1146, 1115, 1086, 917, 847, 827, 723, 628,
500 cm−1. C, H, N analysis (%): C8H8ClN7O10 (397.64),
calculated result: C 24.16, H 2.03, N 24.66; found: C 25.07, H
2.11, N 23.12.
Several crystals of I2 were added to a suspension of
2,4,6trinitrotoluene (10 g, 0.044 mol) and
N,N-
dimethylpnitrosoaniline (7 g, 0.047 mol) in pyridine (15 mL).
The reaction mixture was stirred at 30 °C for 48 h. The
resulting precipitate was filtered off, washed with cold acetone
Synthesis of 5
A
solution of 1,3-diaminoguanidine monohydrochloride
and dried in air to yield 11.07 g
trinitrobenzylidene)benzene-1,4-diamine in a yield of 70%. A
suspension of -dimethyl- '-(2,4,6-
N,N-dimethyl-N'-(2,4,6-
(0.2512 g, 0.002 mol) and 2,4,6-trinitrobenzaldehyde (1.2056 g,
0.005 mol) in 30 mL ethanol was refluxed for 48 h. Then, the
reaction mixture was cooled to room temperature and the
N
,
N
N
trinitrobenzylidene)benzene-1,4-diamine (10 g, 0.027 mol) in
80 mL concentrated HCl was stirred at 60 °C for 3 h. The
precipitate was filtered off, washed with water and dried in air
to obtain 4.36 g of 2,4,6-trinitrobenzaldehyde in a yield of 65%.
precipitate was collected by filtration. 0.72 g
was obtained in a yield of 74%. DSC: Tdec= 189.1 oC. 1H NMR
(500 MHz, DMSO): (ppm) 9.10 (s, 6H, -C ), 8.51 (br, -NH2).
13C NMR (75 MHz, DMSO):
(ppm) 156.8, 155.1, 150.5,
148.9, 147.4, 143.3, 141.2, 139.9, 138.1, 129.9, 125.1, 124.5,
119.5, 116.4. IR (KBr): 3478, 3422, 3367, 3150, 3119, 3092,
1638, 1594, 1537, 1462, 1445, 1401, 1347, 1300, 1189, 1081,
1034, 916, 787, 719, 474 cm−1. C, H, N analysis (%):
C15H8N10O10 (488.29), calculated result: C 36.90, H 1.65, N
28.69; found: C 37.54, H 1.77, N 28.01.
5 as yellow solid
δ
H
δ
1H NMR (500M, DMSO):
2H, -C
). 13C NMR (75M, DMSO):
149.2, 135.7, 126.2.
δ
(ppm) 10.54 (s, 1H, -C
HO), 9.16 (s,
H
δ
(ppm) 189.7, 149.6,
General procedures for preparation of energetic
compounds 1-3
A solution of aminoguanidium salts (2 mmol) and 2,4,6-
trinitrobenzaldehyde (0.7233g, 0.003 mol) in 30 mL ethanol
was refluxed for 24 h. Then, the reaction mixture was cooled to
room temperature. The residue was purified on a silica gel
column chromatography employed by a solvent mixture of
ethyl acetate: methanol = 8 : 1 to afford the desired product.
Synthesis of 6
A solution of 5-hydrazinotetrazolium chloride (0.2731 g, 0.002
mol) and 2,4,6-trinitrobenzaldehyde (0.7233 g, 0.003 mol) in
30 mL ethanol was refluxed for 24 h. Then the reaction mixture
was cooled to room temperature. The mixture was purified on a
silica gel column chromatography employed by a solvent
N
-(2,4,6-trinitrobenzylideneamino) guanidinium chloride (1)
0.5672 g of was obtained as reddish solid in a yield of 85%.
DSC: Tdec= 207.7 C. H NMR (500 MHz, DMSO):
12.88 (br, 1H, -N -), 9.12(s, 2H, -C ), 8.61(s, 1H, -C
7.86 (s, 4H, -NH2). 13C NMR (75 MHz, DMSO):
(ppm) 157.0,
1
mixture of ethyl acetate : methanol = 4 : 1 to afford 0.52 g
6
as
reddish solid in a yield of 80%. DSC: Tdec= 184.2 C. H NMR
(500 MHz, DMSO): (ppm) 15.56 (br, N ), 12.52 (s, 1H, -
-), 9.08 (s, 2H, -C ), 8.39 (s, 1H, -C
=N-). 13C NMR (75
MHz, DMSO): (ppm) 157.7, 150.4, 149.3, 136.2, 130.2,
o
1
o
1
δ
(ppm)
H
H
H=N-),
δ
H
δ
N
H
H
H
150.5, 148.9, 140.8, 129.6, 125.0. IR (KBr): 3409, 3250, 3175,
3108, 3012, 2965, 2361, 2336, 1678, 1606, 1537, 1468, 1401,
1347, 1224, 1176, 1141, 1079,1018, 910, 725, 675, 583, 559,
503 cm−1. C, H, N analysis (%): C8H8ClN7O6 (333.65),
calculated result: C 28.80, H 2.42, N 29.39; found: C 29.12, H
2.56, N 28.78.
δ
124.9. IR (KBr): 3418, 3094, 2956, 2888, 1643, 1605, 1543,
1402, 1346, 1264, 1150, 1122, 1079, 1059, 920, 742, 721 cm−1.
C, H, N analysis (%): C8H5N9O6 (323.18), calculated result: C
29.73, H 1.56, N 39.01; found: C 30.24, H 1.67, N 38.52.
Synthesis of 7
N
-(2,4,6-trinitrobenzylideneamino) guanidinium nitrate (2)
A solution of 2,4,6-trinitrobenzaldehyde (0.7233 g, 0.003 mol),
3,6-dihydrazine-1,2,4,5-tetrazine dihydrochloride (0.2150 g,
This journal is © The Royal Society of Chemistry 2012
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0.001 mol) in 20 mL ethanol was stirred at 80 oC for 18 h. The
resulting precipitate in reaction mixture was filtered off. Then
1
(a) J. P. Agrawal, R. D. Hodgson, Organic Chemistry of Explosives
,
Wiley, New York, 2007; (b) T. M. Klapötke, J. Stierstorfer and A. U.
View Article Online
washed with cold ethanol (50 mL) and dried to afford 0.35 g
as red powder in a yield of 60%. DSC: Tdec= 229.5 oC. 1H NMR
(500 MHz, DMSO): (ppm) 12.75 (s, 2H, -N -), 9.06(s, 4H, -
), 8.54(s, 2H, -C
=N-). 13C NMR (75 MHz, DMSO):
7
Wallek, Chem. Mater., 2008, 20, 4519; (c) M. Göbel and T. M.
DOI: 10.1039/C4RA08084J
Klapötke, Adv. Funct. Mater., 2009, 19, 347; (d) V. Thottempudi, H.
Gao and J. M. Shreeve, J. Am. Chem. Soc., 2011, 133, 6464; (e) V.
δ
H
C
H
H
δ
Thottempudi and J. M. Shreeve, J. Am. Chem. Soc., 2011, 133
,
(ppm) 161.3, 150.2, 147.9, 135.5, 129.9, 124.1. IR (KBr): 3422,
3215, 3093, 2989, 2880, 2361, 2338, 1600, 1539, 1450, 1348,
1303, 1178, 1084, 1055, 968, 923, 738, 722, 569 cm−1. C, H, N
analysis (%): C16H8N14O12 (588.32), calculated result: C 32.66,
H 1.37, N 33.33; found: C 33.15, H 1.41, N 32.94.
19982; (f) A. A. Dippold and T. M. Klapötke, J. Am. Chem. Soc.,
2013, 135, 9931; (g) J. Zhang and J. M. Shreeve, J. Am. Chem. Soc.,
2014, 136, 4437.
2
3
(a) H. Gao and J. M. Shreeve, Chem. Rev., 2011, 111, 7377; (b) V.
Thottempudi, F. Forohor, D. A. Parrish and J. M. Shreeve, Angew.
Chem. 2012, 124, 10019; Angew. Chem. Int. Ed. 2012, 51, 9881; (c)
Conclusions
T. M. Klapötke, F. A. Martin, and J. Stierstorfer, Chem. Eur. J.
2012, 18, 1487; (d) Q. Zhang, C. He, P. Yin, and J. M. Shreeve,
Chem. Asian J., 2014, , 212.
,
The new energetic picryl derivatives
1-3 and 5-7 were
9
synthesized via the condensation reactions of 2,4,6-
trinitrobenzaldehyde with high nitrogen content (above 70%)
compounds containing hydrazine group. All products were well
characterized by means of IR spectroscopy, multinuclear NMR
spectroscopy, DSC measurements as well as elemental analysis.
Single crystal X-ray measurements were accomplished for
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compounds
1
,
2
and
5
. According to the DSC results, Except
for the compound
2
(Td, onset = 146.3 °C), the decomposition
onset temperatures (Td, onset) of the remaining energetic picryl
derivatives are higher than 180 °C, which indicates that these
new energetic picryl compounds possess good thermal
stabilities in contrast with 5-picrylamino-1,2,3,4-tetrazole
4
5
(a) T. M. Klapötke and J. Stierstorfer, Cent. Eur. J. Energ. Mater.
,
2008, , 13; (b) R. Wang, Y. Guo, Z. Zeng and J. M. Shreeve, Chem.
5
Commun., 2009, 2697; (c) R. Wang, Y. Guo, Z. Zeng, B. Twamley
and J. M. Shreeve, Chem. Eur. J., 2009, 15, 2625; (d) Y. Huang, Y.
Zhang and J. M. Shreeve, Chem. Eur. J., 2010, 17, 1538.
(PAT). In particular, the most stable compound is 7, which
decomposed at almost 230 °C. Its decomposition onset
o
temperature is higher than that of RDX (Td = 205 C). The
(a) T. M. Klapötke , P. Mayer, A. Schulz and J. J. Weigand, J. Am.
Chem. Soc., 2005, 127, 2032; (b) T. Abe, G. H. Tao, Y. H. Joo, Y.
calculated detonation velocities lie in the range between 7417
and 8271 m s-1. The detonation pressures range from 21.8 to
Huang, B. Twamley and J. M. Shreeve, Angew. Chem., 2008, 120
,
31.1 GPa. Ionic picryl derivative
3 has a detonation pressure
7195; Angew. Chem., Int. Ed., 2008, 47, 7087; (c) T. M. Klapötke
and J. Stierstorfer, J. Am. Chem. Soc., 2008, 131, 1122; d) Y. -H.
Joo, J. M. Shreeve, Angew. Chem. 2009, 121, 572; Angew. Chem.,
Int. Ed., 2009, 48, 564; (e) T. M. Klapötke, F. A. Martin and J.
Stierstorfer, Angew. Chem., 2011, 123, 4313; Angew. Chem., Int.
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and velocity of 31.1 GPa and 8271 m s-1, respectively, which is
significantly higher than those of PAT (26.4 GPa and 7770 m s-
1). Except
3, most new picryl derivatives are less sensitive to
impact, friction and electrostatic discharge than RDX. In
conclusion, the way to synthesize new picryl derivatives
starting from 2,4,6-trinitrobenzaldehyde enriches the
methodology for development of new energetic picryl
compounds.
Acknowledgements
A
. 2013,
1
, 6776; (i) D. Chand, D. A. Parrish and J. M. Shreeve, J.
, 15383.
This work was supported by the Natural Science Foundation of
Jiangsu Province (BK2011696) and the National Natural
Science Foundation of China (No. 21376121).
Notes and references
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17 Impact: insensitive > 40 J, less sensitive ≥ 35 J, sensitive ≥ 4 J, very
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DOI: 10.1039/C4RA08084J
Synthesis of new picryl derivatives containing high nitrogen content moiety from new
starting materials are now reported.

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DOI: 10.1039/C4RA08084J
29x10mm (600 x 600 DPI)