Synthesis and Detonation Properties of 5-Amino-2,4,6-trinitro-1,3-dihydroxy-benzene

Article abstract of DOI:10.1002/open.201600132

5-Amino-4,6-dinitro-1,3-dihydroxy-benzene (6) was synthesized through the ring-opening reaction of macrocyclic compound 4 with the aid of VNS (vicarious nucleophilic substitution of hydrogen) reaction conditions. The mechanism of ring opening of macrocyclic compound 4 was studied. 5-Amino-2,4,6-trinitro-1,3-dihydroxy-benzene (8) was obtained after the nitration of 6 in KNO₃ and concentrated sulfuric acid. The thermal stability, sensitivity, and other detonation performances of 6 or 8 were compared to commercially used 1,3,5-triamino-2,4,6-trinitrobenzene (TATB) or 1,3,5-trinitrotriazacyclohexane (RDX), respectively. All target compounds were characterized by using single-crystal X-ray diffraction, NMR spectroscopy, elemental analysis, and differential scanning calorimetry. The sensitivities were determined by using BAM methods (drop-hammer and friction tests). Performance parameters, including heats of formation and detonation properties, were calculated by using Gaussian 03 and EXPLO5 v6.01 programs, respectively. It is worth pointing out that compound 8 has a remarkable measured density of 2.078 g cm^?3 at 298 K. In addition, compound 8 is more insensitive than RDX (compound 8: IS=11 J; RDX: IS=7 J; IS is the impact sensitivity).

Full text of DOI:10.1002/open.201600132

DOI: 10.1002/open.201600132
Synthesis and Detonation Properties of 5-Amino-2,4,6-
trinitro-1,3-dihydroxy-benzene
Xingcheng Zhang, Hualin Xiong, Hongwei Yang, and Guangbin Cheng*[a]
5-Amino-4,6-dinitro-1,3-dihydroxy-benzene (6) was synthesized
through the ring-opening reaction of macrocyclic compound 4
with the aid of VNS (vicarious nucleophilic substitution of hy-
drogen) reaction conditions. The mechanism of ring opening
of macrocyclic compound 4 was studied. 5-Amino-2,4,6-trini-
tro-1,3-dihydroxy-benzene (8) was obtained after the nitration
of 6 in KNO3 and concentrated sulfuric acid. The thermal stabil-
ity, sensitivity, and other detonation performances of 6 or 8
were compared to commercially used 1,3,5-triamino-2,4,6-trini-
trobenzene (TATB) or 1,3,5-trinitrotriazacyclohexane (RDX), re-
spectively. All target compounds were characterized by using
single-crystal X-ray diffraction, NMR spectroscopy, elemental
analysis, and differential scanning calorimetry. The sensitivities
were determined by using BAM methods (drop-hammer and
friction tests). Performance parameters, including heats of for-
mation and detonation properties, were calculated by using
Gaussian 03 and EXPLO5 v6.01 programs, respectively. It is
worth pointing out that compound 8 has a remarkable mea-
sured density of 2.078 gcmꢀ3 at 298 K. In addition, com-
pound 8 is more insensitive than RDX (compound 8: IS=11 J ;
RDX: IS=7 J; IS is the impact sensitivity).
1. Introduction
The synthesis of high-energy and high-density materials is one
of the important research and development aspects of ener-
getic materials. Development of modern energetic materials is
significant in materials science research. Driven by increasing
demands from both military and civilian applications, the struc-
tural design of energetic molecules has to meet diverse stand-
ards, for example, performance properties, environmental com-
patibility, as well as safety concerns.[1–4] Synthesis of energetic
materials based on a benzene backbone has had a long tradi-
tion since the discovery of 2,4,6-trinitrotoluene (TNT).[5,6] Owing
to its important property as a melt-castable explosive, it is still
in use nowadays, even though it is highly toxic to the environ-
ment.[7] Multi-nitro (or multi-hydroxyl) and multi-amino aromat-
ic explosives are important members in the family of explo-
sives, owing to strong intramolecular hydrogen bonds be-
tween alternating amino and nitro groups. 1,3,5-triamino-2,4,6-
trinitrobenzene (TATB) has a remarkably higher density of
1.930 gcmꢀ3, originating primarily from the hydrogen-bonding
interactions by virtue of additional amino functionalization.
TNPG (1,3,5-trinitro-2,4,6-phloroglucinol) also has a remarkably
high density of 2.170 gcmꢀ3, for the same reason. For many
applications, TATB (H50 =320 cm) shows a meager performance
and is too insensitive to detonation. Similarly, one obvious
weaknesses of TNPG is that it is too strongly acidic for direct
use in military or civilian applications, although it has a better
impact sensitivity value (H50 =27 cm) than TATB. Therefore, al-
ternatives with a better detonation performance, such as less
toxic properties, weaker or no acidity, lower sensitivities to-
wards external stimuli like impact, friction, and electrostatic
discharge, and safer synthesis, are desired.
It is worth pointing out that we originally intended to pre-
pare compound 5 according to the principle of vicarious nucle-
ophilic substitution of hydrogen (i.e. the VNS reaction) by
treatment of 4-amino-4H-1,2,4-triazole (ATA) and compound 4
with sodium methanol in dimethyl sulfoxide (DMSO) solution
(Scheme 1). Compound 5 was expected to be a substitute for
tetranitrodibenzo-1,3a,4,6a-tetrazapentalene (TACOT) as a type
of heat-resistant explosive, because its thermal decomposition
temperature was predicted to exceed the that of TACOT (the
other calculated detonation performances of compound 5
were much better than those of TACOT). However, com-
pound 5 was not obtained from the reaction. Rather, the solu-
tion that was obtained from the reaction was treated with 6m
HCl and purified by column chromatography to obtain com-
pounds 6 and 7. It was unexpected to obtain compounds 6
and 7, because the conditions for the ring-opening reaction of
the macrocyclic compound are usually very demanding and
have not been reported thus far.
[a] X. Zhang, H. Xiong, H. Yang, Prof. Dr. G. Cheng
School of Chemical Engineering
Nanjing University of Science and Technology
Xiaolingwei 200, Nanjing, Jiangsu 210094(P. R. China)
E-mail: gcheng@mail.njust.edu.cn
Supporting Information for this article can be found under:
http://dx.doi.org/10.1002/open.201600132.
ꢀ 2016 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.
This is an open access article under the terms of the Creative Commons
Attribution-NonCommercial-NoDerivs License, which permits use and
distribution in any medium, provided the original work is properly cited,
the use is non-commercial and no modifications or adaptations are
made.
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2.2. Single-Crystal X-ray Structure Analysis
A crystal of 8·H2O, suitable for single-crystal X-ray diffraction,
was obtained by dissolving 8 in a mixed solvent of methanol
and ethyl acetate. The sums of the dihedralangles of com-
pound 8: [a(C2ꢀC1ꢀO1ꢀH1A)=233.898, a(C1ꢀC2ꢀN1ꢀO2)=
240.438, a(N1ꢀO2ꢀH1A)=103.068, a(O1ꢀH1AꢀO2)=139.428,
the sum of the six angles of the hexagon is 716.88 (233.898+
240.438+103.068+139.428=716.88);
a(C3ꢀC2ꢀN1ꢀO3)=
238.048,
a(C2ꢀC3ꢀN2ꢀH4A)=232.518,
(O3ꢀN1ꢀH4A)=
101.618, (O3ꢀH4AꢀO4)=147.038, the sum of the six angles of
the hexagon is 719.198; a(C3»1-C2»1-N»1-O3»1)=238.04,
a(C2»1-C3»1-O4»1-H4A»1)=232.518, a(O3»1-H4A»1-O4»1)=
147.03, a(H4A»1-O3»1-N»1)=101.618, the sum of the six
angles of the hexagon is 719.198], which should reflect that
the two CꢀNO2 (2-NO2, 6-NO2) groups, two CꢀOH groups, the
CꢀNH2 group, and benzene ring are nearly coplanar with four
torsion angles, which are less than 3.28 (720ꢀ716.88=3.28). In
addition, the sums of the remaining dihedral angles of com-
pound 8 [a(C3»1-C4ꢀN3ꢀO5)=61.688 or a(C3»1-C4ꢀN3ꢀ
O5»1)=118.328], which should reflect the degree of molecular
twist, are 61.688. Thus, two planes are formed in compound 8,
and have an angle (180ꢀ118.328=61.688) between the plane
of C4ꢀO5ꢀN3ꢀO5»1 and the plane of aromatic ring. Four intra-
molecular hydrogen bonds are formed between the two hy-
droxyl groups, one amino group, and the two nitro groups in
compound 8. The intramolecular H···O distances are O2···H1A=
1.802 ꢁ, H4A···O3=1.863 ꢁ, H4A»1···O3»1=1.863 ꢁ, and
O2»1···H1A»1=1.802 ꢁ, respectively. 5-Amino-2,4,6-trinitro-1,3-
dihydroxy-benzene monohydrate (8·H2O) crystallizes in the tri-
clinic space group P-1 with six molecules per unit cell (Fig-
ure 1b), and has a single-crystal density of 1.960 gcmꢀ3 (when
compound 8 does not contain crystalline water, its measured
density is 2.078 gcmꢀ3) at 298 K. A molecule of water is con-
nected to three molecules of compound 8 by hydrogen bonds.
Two oxygen atoms of the nitro group in compound 8 (not
formed into the intramolecular hydrogen bonds) are connect-
ed through intermolecular hydrogen bonds with two different
water molecules, respectively. The length of the intermolecular
hydrogen bond is 5.659 ꢁ (NꢀO···HꢀO).
Scheme 1. Synthesis of compound 6.
2. Results and Discussion
2.1. Synthesis
Compound 4 was successfully synthesized by employing com-
pound 3 as a common precursor. Compound 3 was prepared
by using a similar synthetic route in a single step by reacting
1,5-difluoro-2,4-dinitrobenzene and resorcinol under basic con-
ditions (Scheme 1).[8–9] First, 1,3-dichlorobenzene was trans-
formed into 1,5-difluoro-2,4-dinitrobenzene in 93% yield. Com-
pound 4 was obtained by nitration of compound 3. The opera-
tion processes of the three reactions are very simple, and post-
processes are also simple (see the Supporting Information).
It is worth pointing out that we originally intended to pre-
pare compound 5 according to a known procedure (VNS
method) by treatment of compound 4 with ATA and sodium
methanol in DMSO solution. However, compound 5 was not
obtained from the reaction (Scheme 1). The mixture was puri-
fied by virtue of a silica gel column and we verified that a new
compound, 5-amino-4,6-dinitro-dibenzene-1,3-diol (6), and an-
other compound, 4,6-dinitrobenzene-1,3-diol (7), were ob-
tained. Then, compound 6 was nitrated with a mixture of KNO3
and concentrated sulfuric acid to get the new compound 5-
amino-2,4,6-trinitro-1,3-dihydroxy-benzene (8) (Scheme 2).
A crystal of compound 6, suitable for single-crystal X-ray dif-
fraction, was successfully obtained by dissolving 6 in ethanol
and letting ethyl acetate (EA) diffuse into the solution. Com-
pound 6 crystallizes in the triclinic space group P-1 with six
molecules per unit cell (Figure 2b). It has a single-crystal densi-
ty of 1.916 gcmꢀ3 at 173 K.
The 5-amino,4,6-dinitro,1,3-dihydroxyl groups and benzene
ring are nearly planar, owing to consecutive hydrogen-bond in-
teractions. The sums of dihedral angles [a(C6ꢀC1ꢀO1ꢀH1c)=
232.828, a(C1ꢀC6ꢀN3ꢀO6)=238.478, a(N3ꢀO6ꢀH1CꢀO1)=
247.558, the sum of the six angles of the hexagon is 718.848;
a(H2CꢀO2ꢀC3ꢀC4)=228.668,
a(C3ꢀC4ꢀN1ꢀO3)=238.198,
Scheme 2. Synthesis of compound 8.
a(N1ꢀO3ꢀH2CꢀO2)=252.748, the sum of the six angles of
the hexagon is 719.598; a(H2BꢀO5ꢀN3ꢀC6)=224.228, a(N3ꢀ
C6ꢀC5ꢀN2)=242.228, a(C5ꢀN2ꢀH2BꢀO5)=253.18, the sum of
the six angles of the hexagon is 719.548; a(H2AꢀN2ꢀC5ꢀ
C4)=240.7, a(C5ꢀC4ꢀN1ꢀO4)=242.02, N1ꢀO4ꢀH2AꢀN2=
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Figure 2. a) Single-crystal X-ray structure of 6. b) Packing diagram of 6.
Figure 1. a) Single-crystal X-ray structure of 8. b) Packing diagram of 8.
235.34, the sum of the six angles of the hexagon is 718.068)],
which should reflect that the two CꢀNO2 (2-NO2, 6-NO2)
groups, two CꢀOH groups, the CꢀNH2 group, and benzene
ring are nearly coplanar with three torsion angles, are less than
28. The two nitro groups lie within the ring plane fixed by the
intermolecular and the lengths of three hydrogen bonds are
1.7632 ꢁ (O1-H1c···O6), 1.728 ꢁ (O2-H2c···O3), and 1.8412 ꢁ (N-
H2B···O5).
A crystal of 4,6-dinitro-1,3-dihydroxy-benzene (7), suitable
for single-crystal X-ray diffraction, was successfully obtained by
dissolving 7 in ethanol and letting the ethanol slowly evapo-
rate into the air. The unit cell of 7 crystallizes in the triclinic
space group P-1 with six molecules per unit cell (Figure 3b). It
has a single-crystal density of 1.824 gcmꢀ3 at 173 K. The sums
of dihedral angles [a(H1AꢀO1ꢀC1ꢀC6)=231.328, a(N2ꢀO6ꢀ
H1AꢀO1)=248.098; a(C1ꢀC6ꢀN2ꢀO6)=239.878, the sum of
the six angles of the hexagon is719.28; a(O3ꢀN1ꢀC4ꢀC3)=
239.928; a(H2AꢀO2ꢀC3ꢀC4)=229.778; a(N1ꢀO3ꢀH2AꢀO2)=
250.238; the sum of the six angles of the hexagon is 719.92],
which should reflect that the two CꢀNO2 (4-NO2, 6-NO2)
groups, two CꢀOH groups group, and benzene ring are nearly
coplanar with two torsion angles, are less than 28. The lengths
of the two hydrogen bonds are 1.865 ꢁ (O3···H2A) and 1.860 ꢁ
(O6···H1A). As can be seen in the crystal structure given in
Figure 3. a) Single-crystal X-ray structure of 7. b) Packing diagram of 7.
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Figure 3, the two CꢀNO2, two hydroxyl groups, and benzene
ring are nearly coplanar. Two nitro and two hydroxyl groups lie
within the ring plane and are fixed by intermolecular hydrogen
bonds.
tion enthalpy of compound 8 is similar to that of RDX. The for-
mation enthalpy of compound 6 is higher than that of TATB.
In addition to the heat of formation, detonation properties
as well as impact and friction sensitivities play a major role in
new energetic materials. With experimental densities and cal-
culated values for heats of formation in hand, the detonation
pressures (P) and velocities (D) were calculated by using
EXPLO5 v6.01 (see the Supporting Information). The calculated
detonation pressures and velocities lie in the ranges from 24.2
to 36.5 GPa, and from 7363 to 8746 msꢀ1. Compound 8 exhib-
its the highest detonation properties (P=36.5 GPa; D=
8750 msꢀ1) among compounds 6–8, which are significantly su-
perior to the highly explosive RDX (P=34.9 GPa; D=
8748 msꢀ1). In addition, the detonation velocity ratio of com-
2.3. Physicochemical Properties
The phase transition and thermal stabilities of all compounds
were determined by using differential scanning calorimetry
(DSC). With the exception of 8·H2O, its thermal decomposition
temperature is only 2058C, which is lower than that of com-
pound 6 (2918C). Being non-coplanar is one of the important
reasons for the decrease in thermal decomposition tempera-
ture (Table 1). The thermal decomposition temperatures are ar-
pound 6 (D=7697 msꢀ1
) is higher than that of TATB
(7606 msꢀ1), but the detonation pressure of compound 6 (P=
27.2 GPa) is lower than that of TATB (31.0 GPa).
Table 1. Physical properties of some of the compounds discussed.
Impact and friction sensitivity measurements were made by
using a standard BAM Fallhammer and a BAM friction tester.
Not surprisingly, compound 8, with an impact sensitivity (IS) of
11 J and friction sensitivity (FS) of 240 N, is more insensitive to
RDX with an IS of 7 J and FS of 120 N, but it is more sensitive
than TATB with an IS of 50 J and FS of 350 N. In addition, the IS
(30 J) and FS (240 N) of compound 6 are lower than those of
TATB, but are larger than those of RDX, although the detona-
tion properties of compound 6, including detonation velocity,
detonation pressure, and even density, are similar to TATB.
Oxygen balance (OB) is another important index to evaluate
the deficiency or excess of oxygen in a molecule required to
convert all carbon into carbon monoxide and all hydrogen into
water. The OB value of compound 8 is ꢀ36.92%. Compound 8
has an excellent OB value of ꢀ36.92%, which is better than
that of TATB (ꢀ55.81%).
[d]
[e]
Cmpd
1[a]
D[b]
P[c]
[GPa]
DHfm
TDSC
[C]
IS[f]
[J]
FS[g]
[N]
[gcmꢀ3
]
[msꢀ1
]
[kJmolꢀ1
]
4
6
7
8
RDX
TATB
HMX
1.750
1.916
1.824
2.078[h]
1.816
1.930
1.905
7865
7697
7363
8750
8748
7606
9144
28.9
30.7
24.2
36.5
34.9
31
618
ꢀ305
ꢀ295
ꢀ285
80
375
291
302
42
30
24
160
240
240
120
120
350
120
205[i]
204
350
280
11
7
75
104
>50
7
39.5
[a] Single-crystal density. [b] Detonation velocity (calculated with EXPLO5
v6.01). [c] Detonation pressure (calculated with EXPLO5 v6.01). [d] Heat of
formation. [e] Decomposition temperature. [h] Measured density.
[g] Impact sensitivity. [h] Friction sensitivity. [i] Decomposition tempera-
ture of 8·H2O.
ranged from large to small [350 (TATB)>302 (7) >291 (6)>
280(HMX)>205(8·H2O)ffi2048C (RDX)]. At the same time, their
densities are arranged from large to small [2.078 (9)>1.930
(TATB)>1.916 (6)>1.90 (HMX)>1.824 (7)>1.816 gcmꢀ3 (RDX);
except for the density for compound 9, which is a measured
density, those of the others are the single-crystal densities].
Thus, the enhanced inter- and intramolecular interactions in
the molecule give rise to compact packing and smaller
volume, which are conducive to improving the density and sta-
bility of these materials. It is noteworthy that compound 8 has
an impressive measured density of 2.078 gcmꢀ3 at 298 K,
which is higher than those for the currently used energetic
materials, such as RDX (1.816 gcmꢀ3) and cyclo-1,3,5,7-tetrame-
thylen-ene-2,4,6,8-tetranitramine (HMX, 1.91 gcmꢀ3). In addi-
tion, the lowest density compound studied here (among com-
pounds 6–8), that is, compound 7 (1.824 gcmꢀ3), has a higher
density than that of RDX (1.816 gcmꢀ3).
2.4. Reaction Mechanism of Compound 6
It is believed that the amination of compound 4 proceeds in
accordance with the VNS mechanism.[9–12] In the presence of
a strong base, deprotonation of 4-amino-4H-1,2,4-triazole
(ATA) occurs, resulting in the formation of 4-amino-4H-1,2,4-tri-
azole imide (ATAI). The latter is added onto the aromatic ring
of compound 4 in the middle of the two nitro groups to give
the corresponding ꢀ-adduct. When the ꢀ-adducts are acted
upon by a base, deprotonation with simultaneous elimination
of 1,2,4-triazole takes place to obtain intermediate 12. A more
stable intermediate 13 or 14 is obtained, because of the repul-
sive effect of the electronic cloud of the 5-NH2 group. Accord-
ing to the same mechanism, intermediate 15 is obtained. Inter-
mediate 15 is hydrolyzed with an aqueous solution of 6m hy-
drochloric acid to obtain compounds 6 and 7. (Scheme 3).
When the aqueous solution of 6m hydrochloric acid is re-
placed by an aqueous solution of acetic acid, compounds 6
and 7 are still obtained (Table 2). Compound 4 is synthesized
after the nitration of 3 in nitrosonitric acid and concentrated
sulfuric acid; thus, it is stable and the ring-opening reaction
does not occur in strong acid. Similarly, compound 4 is also
To evaluate the energetic properties, computation of the
heats of formation were performed by using the Gaussian 03
suite of programs (Supporting Information). The calculated
detonation velocities are arranged from large to small: HMX
(9320 msꢀ1
)
>
RDX (8748 msꢀ1
)
ffi
8 ) > 6
(8746 msꢀ1
(7697 msꢀ1) > TATB (7606 msꢀ1) > 7 (7363 msꢀ1). The forma-
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using single-crystal X-ray diffraction. The values of the detona-
tion velocity and thermal decomposition temperature of 5-
amino-2,4,6-trinitro-1,3-dihydroxybenzene is similar to that of
RDX, but its values of impact sensitivity, detonation pressure,
and the measured density (2.078 gcmꢀ3) are much higher than
those of RDX. All of these show that 5-amino-2,4,6-trinitro-1,3-
dihydroxybenzene is a more promising energetic material than
RDX. It can also be found that compound 6 displays an excel-
lent performance for energetic materials. The values of the
density, detonation velocity, and detonation pressure of the
compound 6 are equivalent to those of TATB. However, the
sensitivities of compound 6 lie between RDX and TATB; thus, it
is more sensitive and easy to explode than TATB. In addition,
the ring-opening reaction mechanism of macrocyclic com-
pound 4 has also been studied.
Acknowledgements
This work was supported by the National Natural Science Foun-
dation of China (No. 21376121) and the Foundation Research
Funds for the Central Universities (No. 30916011314)
Conflict of Interest
The authors declare no conflict of interest.
Scheme 3. Reaction mechanism to obtain compound 6.
Keywords: benzene backbone
·
energetic materials
·
macrocyclic compound · mechanism · VNS reaction
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Cmpd.
12m
HCl
6m
HCl
3m
HCl
10m
HOAc
5m
HOAc
5m
HNO3
Yield of 6 [%]
Yield of 7 [%]
81.33
75.23
81.08
75.16
80.92
76.01
81.06
75.47
81.01
75.34
81.12
75.27
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3. Conclusions
From this experimental study the following conclusions can be
drawn. 5-Amino-2,4,6-trinitro-1,3-dihydroxybenzene can be
synthesized in three steps in high purity and on a large scale.
The molecular structures of 6, 7, and 8 were determined by
Received: October 26, 2016
Revised: December 7, 2016
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FULL PAPERS
X. Zhang, H. Xiong, H. Yang, G. Cheng*
Off with a bang! 5-Amino-4,6-dinitro-
1,3-dihydroxy-benzene (6) is synthesized
through a ring-opening reaction of mac-
rocyclic compound 4 with the aid of
VNS (vicarious nucleophilic substitution
of hydrogen) reaction conditions.
&& – &&
Synthesis and Detonation Properties
of 5-Amino-2,4,6-trinitro-1,3-
dihydroxy-benzene
&
ChemistryOpen 2017, 00, 0 – 0
www.chemistryopen.org
6
ꢀ 2017 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
ÝÝ These are not the final page numbers!