Energy and Biocides Storage Compounds: Synthesis and Characterization of Energetic Bridged Bis(triiodoazoles)

Article abstract of DOI:10.1021/acs.inorgchem.7b02277

Energetic bridged triiodopyrazoles and triiodoimidazoles were designed and synthsized by reacting potassium triiodopyrazolate or triiodoimidazolate with corresponding dichloro compounds. All compounds were fully characterized by ¹H and ^13<

Full text of DOI:10.1021/acs.inorgchem.7b02277

Article
Cite This: Inorg. Chem. XXXX, XXX, XXX-XXX
pubs.acs.org/IC
Energy and Biocides Storage Compounds: Synthesis and
Characterization of Energetic Bridged Bis(triiodoazoles)
†
†
‡
,†
Chunlin He, Gang Zhao, Joseph P. Hooper, and Jean’ne M. Shreeve*
†
Department of Chemistry, University of Idaho, Moscow, Idaho 83844-2343, United States
‡
Department of Physics, Naval Postgraduate School, Monterey, California 93943, United States
S Supporting Information
*
ABSTRACT: Energetic bridged triiodopyrazoles and triiodoimidazoles were designed and synthsized by reacting potassium
1
triiodopyrazolate or triiodoimidazolate with corresponding dichloro compounds. All compounds were fully characterized by H
and 13C NMR spectroscopy, IR spectroscopy, and elemental analyses. The structure of compound 1 was further confirmed by
single-crystal X-ray diffraction. All of the compounds exhibit good thermal stability with decomposition temperatures between
3
1
99 and 270 °C and high densities ranging from 2.804 to 3.358 g/cm . The detonation performances and the detonation
−
1
−1
products were calculated by CHEETAH 7. Compound 3 (D = 4765 m s ; P = 17.9 GPa) and compound 7 (D = 4841 m s ; P
v
v
=
18.5 GPa) show comparable detonation pressure to TNT, and high iodine content makes them promising as energy and
biocides storage compounds.
INTRODUCTION
nearly quantitative amounts of gaseous iodine (I ) upon
detonation; therefore, active agents can be neutralized or
destroyed effectively.
2
■
Ongoing threats of bioterrorism highlight the need for Agent
Defeat Weapons (ADWs), which can be used not only to
eliminate weapons of mass destruction (WMD) in the target
but also to destroy or neutralize the active agents released.
However, the conventional warheads, which rely on a “thermal
kill” mechanism, have limited destructive impact on biological
agents while the blast could also have the undesirable effect of
airborne dispersal of the biological agents. Thus, it is
appropriate to design a new class of materials which could
defeat a biological weapon effectively. The preferred materials
should have the capacity to store both energy and biocides and
release them upon ignition. The energy released will destroy a
storage facility and the biocides released can destroy or
neutralize the active agents.
Figure 1. Previously synthesized iodine-rich compounds.
While high iodine content is beneficial for increasing the
killing efficiency of biological agents, it also results in a low
energy content which may be insufficient to destroy ADWs.
The introduction of an energetic explosophore into a molecule
should improve the energy level of the target biocidal agents.
One strategy often used is partial replacement of iodo groups in
Recently, the study of novel energetic biocidal agents has
attracted increasing interest among researchers.
1
−8
Iodine
exhibits high efficiency in killing certain bacteria, amoebic
10,11
9
the molecules;
however, due to a limited number of iodo
cysts, and viruses. Since iodine-rich compounds which can
groups in aromatic rings, the substitution of iodine with a nitro
release iodine upon decomposition or detonation are of
increasing interest as potential ingredient candidates for
ADWs, many were developed by our research group in the
Received: September 4, 2017
4
,10−13
past few years (Figure 1).
Such compounds produce
©
XXXX American Chemical Society
A
DOI: 10.1021/acs.inorgchem.7b02277
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Inorganic Chemistry
Article
Table 1. Synthesis of Energetic Bridged Triiodopyrazoles, 1−4
Table 2. Synthesis of Energetic Bridged Triiodoimidazoles, 5−8
group also decreases iodine content dramatically. The linkage
of triiodopyrazole or triiodoimidazole with energetic groups can
improve the energy of the molecule and maintain the iodine
content at a high level. Inspired by the good thermal stability
and detonation performances of nitramine-linked 1,2,4-
RESULTS AND DISCUSSION
■
Synthesis. Potassium triiodopyrazolate or triiodoimidazo-
late was prepared in situ by reacting a suspension of
triiodopyrazole or triiodoimidazole with potassium hydroxide
in acetonitrile until a clear solution was achieved. The dichloro
16
compounds, 1,3-dichloro-2-nitrazapropane, 1,5-dichloro-2,4,-
14,15
1
7
triazoles, imidazoles, and pyrazoles,
a series of triiodopyr-
nitrazapentane, 1,7-dichloro-2,4,6-trinitro-2,4,6-triazahep-
18
19
azoles or triiodoimidazoles linked by 2-nitrazapropane, 2,4-
nitrazapentane, 2,4,6-trinitro-2,4,6-triazaheptane, or 2,2-dinitro-
propane moieties were synthesized. These new compounds
provide an efficacious method to store both energy and
biocides.
tane, and 1,3-dichloro-2,2-dinitropropane, were synthesized
according to known methods. The energetic-bridged triiodo-
pyrazoles or triiodoimidazoles (1−8) were synthesized by
adding the dichloro compounds to acetonitrile solution of
potassium triiodopyrazolate or triiodoimidazolate, respectively.
The reaction mixture was stirred for 4 h at room temperature;
B
DOI: 10.1021/acs.inorgchem.7b02277
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Inorganic Chemistry
Article
the precipitate was collected by filtration and washed with
acetonitrile and water to give the desired product in moderate
yield (Tables 1 and 2).
Heat of Formation. The heats of formation were calculated
20
using the Gaussian 03 (Revision E.01) program suite based
on isodesmic reactions. For the calculation of iodine
21
NMR Spectroscopy. All of the new compounds were
compounds, the (15s, 11p, 6d) basis of Stromberg et al.
1
13
1
characterized by H and C{ H} spectroscopy with
was augmented with another p shell and the five valence sp
exponents optimized, resulting in a [5211111111, 411111111,
3111] contraction scheme in conjunction with 6-31+G** for
first- and second-row elements. Single point energy (SPE)
refinement on the optimized geometries was performed with
the use of the MP2/6-311++G** level. The heat of sublimation
[
D ]DMSO as solvent. The resonance bands of the protons
6
13
were observed in the range from 5.46 to 6.24 ppm. In the
{
C
1
H} NMR spectra, chemical shifts for the methylene group are
found between 56.65 and 66.12 ppm. Three peaks were
observed for the carbon atoms bonded to iodine, ranging
between 88.51 and 110.71 ppm on the pyrazole ring and
between 86.59 and 101.03 ppm on the imidazole ring,
respectively.
Single-Crystal X-ray Analysis. Suitable single colorless
plate crystals were grown by dissolving 1 in THF and the
solvent slowly evaporated at room temperature. Compound 1
22
was calculated based on Trouton’s rule by using the equation
ΔH = 0.188 × T. Heats of formation for compounds 1−8 are
sub
−1
in the range between +797.1 (5) and +1508.1 kJ mol (3).
The bistriiodopyrazole analogues have slightly higher heats of
formation compared to the corresponding bistriiodoimidazoles.
Sensitivities and Detonation Performances. The
impact sensitivities were measured using a BAM drop hammer,
and the detonation properties were calculated with CHEETAH
crystallizes in the monoclinic P2 /c space group with four
1
−3
formula units per unit cell; its calculated density is 3.413 g cm
at 173(2) K. The crystal structure of 1 is shown in Figure. 2. All
2
3
7
by using the calculated heat of formation and measured
density as shown in Table 3. Compounds 1 and 2 have the
lowest sensitivity toward impact (10J), and 8 has the highest
sensitivity toward impact (4J). The detonation velocities and
pressures range from 3767 to 4841 m/s and 9.4 to 18.5 GPa,
respectively. Because of the higher densities of bistriimidazoles,
slightly higher detonation performances are found compared to
their bistriiodopyrazole analogues. An increase in the number
of N-NO2 groups aids in improving the energy of the
compounds. Compounds 3 (D : 4765 m/s, P: 17.9 GPa) and
ν
7
(D : 4841 m/s, P: 18.5 GPa) are the most powerful in this
ν
series; their detonation pressures are comparable to that of
TNT (P: 19.53 GPa).
Detonation Products. In order to determine the ability of
these new materials to destroy active agents, the detonation
products of 1−8 were calculated by using CHEETAH 7
thermochemical code. The major detonation products are listed
in Table 4. The bistriiodoimidazole and bistriiodopyrazole
isomers release the same major composition of products upon
detonation. All of the iodine in these molecules is converted to
I2 and HI after ignition (Figure 3), which indicates high
efficiency as biocidal agents.
Figure 2. Crystal structure of 1; thermal ellipsoids are drawn at the
0% probability level.
5
of the bond lengths and angles are in the expected range
7
reported for triiodopyrazole compounds. The crystallographic
data and refinement details as well as the packing diagrams are
given in the Supporting Information.
Thermal Stability. All of the compounds are thermally
stabile with decomposition temperatures ranging between
CONCLUSIONS
1
99.4 and 270.2 °C. Introduction of the energetic bridges
causes a slight decrease in thermal stability compared to 3,4,5-
13
■
In summary, a series of energetic bridged triiodoimidazoles and
triiodopyrazoles were designed and synthesized. Their
structures were fully characterized by H, C NMR, infrared,
and elemental analyses. The structure of 1 was determined by
single-crystal X-ray diffraction. The combination of an energetic
1
3
triiodopyrazole (Tdec 282 °C) or 2,4,5-triiodoimidazole
1
13
(
Tdec 252 °C). The nitro-aza bridged bistriiodopyrazoles (1−3)
melt before decomposing, while the other compounds
decompose without melting (Table 3).
Table 3. Physicochemical Properties of Compounds 1−8
a
b
(g/cm3)
c
d
e
f
compd
Td (°C)
d
ΔH ° (kJ/mol)
Dν (m/s)
P (Gpa)
% iodine
IS (J)
f
g
1
220.0 /270.2
3.265
2.941
2.804
2.920
3.358
3.021
2.851
2.983
1.65
864.8
1164.6
1508.1
858.6
3767
4321
4765
3818
3840
4409
4841
3869
6881
9.5
12.4
17.9
9.4
77.89
72.40
67.64
74.53
77.89
72.40
67.64
74.53
0
10
10
8
g
2
242.0 /243.9
g
3
239.3 /244.6
4
218.1
199.4
220.8
234.3
205.0
5
5
797.1
9.9
9
6
1129.3
1436.1
822.5
13.1
18.5
9.8
5
7
5
8
4
g
TNT
80.4 / 295
−31.70
19.53
15
a
b
c
d
Decomposition temperature (onset). Measured density at 25 °C. Calculated heat of formation. Detonation velocity calculated with CHEETAH
e
f
g
7
. Detonation pressure calculated with CHEETAH 7. Impact sensitivity measured via BAM method. Melting point.
C
DOI: 10.1021/acs.inorgchem.7b02277
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Inorganic Chemistry
Article
became a clear solution. After stirring for another 10 min, the solution
was filtered to remove the excess potassium hydroxide, and the filtrate
was transferred into a 25 mL round-bottom flask. The dichloro
compound (1 mmol) in acetonitrile (5 mL) was added in one portion.
The reaction mixture was stirred for 4 h at room temperature. The
precipitate formed was collected by filtration, washed with acetonitrile
Table 4. Calculated Major Decomposition Products (in
Weight Percent) at T = 298 K, P = 1 atm
compd
N (g)
2
I2 (g)
HI (g)
C (s)
CH (g)
CO (g)
4
2
1
2
3
4
5
6
7
8
8.6
77.11
71.54
66.73
73.76
77.11
71.54
66.73
73.76
0.78
0.86
0.91
0.77
0.78
0.86
0.91
0.77
7.39
6.31
5.37
7.08
7.39
6.31
5.37
7.08
1.61
2.25
2.82
1.54
1.61
2.25
2.82
1.54
4.49
8.35
10.66
12.44
8.22
(
2 mL), and then with water (2 mL). The solid was air-dried to give
the target compound.
,3-Bis(3,4,5-triiodopyrazolyl)-2-nitrazapropane (1). Yield: 82%.
11.71
8.60
1
8.6
4.49
−1
M.P. 242.0 °C; Tdec: 243.9 °C; IR (cm ) ν = 3036, 3002, 1545, 1436,
1
859, 778, 748, 672, 648, 614, 497; H NMR (DMSO-d6): 6.24 (4H, s,
10.66
12.44
8.22
8.35
406, 1364, 1306, 1292, 1277, 1243, 1228, 1172, 1097, 1024, 975, 943,
1
11.71
8.60
13
CH ); C NMR (DMSO-d6): δ 65.51, 88.84, 99.62; 110.52. EA
2
(
C H I N O , 977.58): Calcd, C: 9.83; H: 0.41; N: 8.60; Found, C:
8 4 6 6 2
9
.87; H: 0.47; N: 8.52.
,5-Bis(3,4,5-triiodopyrazolyl)-2,4-nitrazapentane (2). Yield: 76%.
bridge with an iodine-rich aromatic compound provides an
efficient way for the storage of both energy and biocide.
Compounds 3 and 7 exhibit detonation performances
comparable with that of TNT, suggesting great potential as
ingredient candidates as biocidal agents.
1
−1
M.P. 220.0 °C; Tdec: 270.4 °C; IR (cm ) ν = 3030, 2917, 1562, 1547,
1
9
436, 1409, 1397, 1316, 1273, 1243, 1220, 1168, 1117, 1064, 1021,
1
75, 924, 868, 759, 650, 632, 605, 477; H NMR (DMSO-d6): 6.07
13
(2H, s, CH ); 6.20 (4H, s, CH ); C NMR (DMSO-d6): δ 64.66,
2
2
6
1
6.01, 88.51, 99.52; 110.42. EA (C H I N O , 1051.62): Calcd, C:
0.28; H: 0.58; N: 10.66; Found, C: 10.32; H: 0.55; N: 10.56.
9 6 6 8 4
EXPERIMENTAL SECTION
■
General Methods. Reagents purchased from Aldrich, Acros
1,7-Bis(3,4,5-triiodopyrazolyl)-2,4,6-trinitro-2,4,6-triazaheptane
−
1
1
13
(3). Yield: 85%. M.P. 239.3 °C; Tdec: 244.6 °C; IR (cm ) ν = 3032,
1
8
Organics, and AK Scientific were used as received. H and C spectra
were recorded on a 300 MHz (Bruker AVANCE 300) nuclear
magnetic resonance spectrometer operating at 300.13, and 75.48 MHz,
respectively. Chemical shifts in the 13C spectra are reported relative to
560, 1437, 1409, 1315, 1273, 1230, 1168, 1135, 1088, 1021, 974, 928,
1
57, 762, 709, 643, 619, 606; H NMR (DMSO-d6): 5.98 (4H, s,
13
CH ); 6.20 (4H, s, CH ); C NMR (DMSO-d6): δ 64.51, 66.04,
2
2
8
8.52, 100.06; 110.71. EA (C H I N O , 1125.66): Calcd, C: 10.67;
Me Si. The melting and decomposition points were obtained on a
10 8 6 10 6
4
H: 0.72; N: 12.44; Found, C: 10.24; H: 0.56; N: 12.14.
,3-Bis(3,4,5-triiodopyrazolyl)-2,2-dinitropropane (4). Yield: 63%.
differential scanning calorimeter (TA Instruments Co., model Q20) at
a heating rate of 5 °C/min. IR spectra were recorded using KBr pellets
for solids on a Thermo Nicolet AVATAR 370 FTIR. Densities were
determined at 25 °C by employing a Micromeritics AccuPyc II 1340
gas pycnometer. Elemental analyses were carried out using an Exeter
CE-440 elemental analyzer or Elmentar vario MICRO cube elemental
analyzer. Impact sensitivity measurements were made using a standard
BAM Fallhammer.
The starting materials 3,4,5-triiodopyrazole, 2,4,5-triiodoimida-
zole, 1,3-dichloro-2-nitrazapropane, 1,5-dichloro-2,4,-2,4-nitraza-
pentane, 1,7-dichloro-2,4,6-trinitro-2,4,6-triazaheptane, and 1,3-
dichloro-2,2-dinitropropane were prepared according to the
1
−1
Tdec: 218.1 °C; IR (cm ) ν = 3190, 2845, 1680, 1631, 1566, 1541,
504, 1460, 1422, 1339, 1284, 1193, 1154, 1143, 1106, 1066, 1034,
004, 975, 943, 755, 706, 669, 538; H NMR (DMSO-d6): 5.60 (4H,
s, CH ); C NMR (DMSO-d6): δ 53.23, 85.97, 97.27; 106.88;
1
1
1
13
2
130.69. EA (C H I N O , 1021.59): Calcd, C: 10.58; H: 0.39; N: 8.23;
9 4 6 6 4
Found, C: 10.36; H: 0.45; N: 8.13.
7
1,3-Bis(2,4,5-triiodoimidazolyl)-2-nitrazapropane (5). Yield: 80%.
24
16
−1
T
dec: 199.4 °C; IR (cm ) ν = 2999, 2921, 1561, 1452, 1388, 1277,
17
18
1
1247, 1174, 1114, 962, 767, 658; H NMR (DMSO-d6): 6.04 (4H, s,
1
9
13
CH
); C NMR (DMSO-d6): δ 64.62, 87.84, 96.93, 101.03; EA
H I N O , 977.58): Calcd, C: 9.83; H: 0.41; N: 8.60; Found, C:
4 6 6 2
2
literature.
(C
8
General Procedures to Synthesize Energetic-Bridged Triio-
doazoles. To a suspension of triiodopyrazole or triiodoimidazole
10.07; H: 0.46; N: 8.73.
1,5-Bis(2,4,5-triiodoimidazolyl)-2,4-nitrazapentane (6). Yield:
−1
(
0.98 g, 2.2 mmol) in acetonitrile (10 mL) was added potassium
70%. Tdec: 220.8 °C; IR (cm ) ν = 3019, 2917, 1561, 1439, 1421,
1
hydroxide (0.14 g, 2.5 mmol). With stirring, the suspension slowly
1390, 1316, 1282, 1176, 1121, 1100, 962, 927, 859, 769, 657, 629; H
Figure 3. Sum of I and HI in the decomposition products (weight percent).
2
D
DOI: 10.1021/acs.inorgchem.7b02277
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Inorganic Chemistry
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NMR (DMSO-d6): 6.05 (4H, s, CH ); 6.08 (2H, s, CH ); 13C NMR
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2
2
(
1
0
DMSO-d6): δ 65.42, 68.09, 88.36, 96.98; 100.22. EA (C H I N O ,
051.62): Calcd, C: 10.28; H: 0.58; N: 10.66; Found, C: 10.08; H:
.54; N: 10.20.
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,7-Bis(2,4,5-triiodoimidazolyl)-2,4,6-trinitro-2,4,6-triazaheptane
−1
(
1
(
(
1
0
7). Yield: 71%. M.P. T : 234.3 °C; IR (cm ) ν = 3015, 2925, 1561,
dec
1
443, 1390, 1278, 1174, 1136, 1105, 969, 927, 763, 610; H NMR
DMSO-d6): 5.94 (4H, s, CH ); 6.02 (4H, s, CH ); C NMR
DMSO-d6): δ 65.47, 66.12, 87.78, 96.60; 100.29. EA (C H I N O ,
125.66): Calcd, C: 10.67; H: 0.72; N: 12.44; Found, C: 10.98; H:
(5) Bennion, J. C.; Vogt, L.; Tuckerman, M. E.; Matzger, A. J.
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1
,3-Bis(2,4,5-triiodoimidazolyl)-2,2-dinitropropane (8). Yield:
1
−
5
1
(
8%. Tdec: 205.0 °C; IR (cm ) ν = 2983, 2925, 1476, 1435, 1413,
360, 1313, 1249, 1189, 1139, 963, 763, 726, 704, 619; H NMR
DMSO-d6): 5.46 (4H, s, CH ); C NMR (DMSO-d6): δ 50.65,
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6.59; 94.92, 98.62, 130.04. EA (C H I N O , 1021.59): Calcd, C:
9 4 6 6 4
0.58; H: 0.39; N: 8.23; Found, C: 9.07; H: 0.43; N: 7.19.
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ASSOCIATED CONTENT
* Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acs.inorg-
chem.7b02277.
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Jean’ne M. Shreeve: 0000-0001-8622-4897
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characterization, and sensitivity data of some azidomethyl nitramines.
ACKNOWLEDGMENTS
Propellants, Explos., Pyrotech. 2009, 34, 13−23.
■
(19) Borgardt, F. G.; Seeler, A. K.; Noble, P. Aliphatic polynitro
This work was supported by the Office of Naval Research
compounds. I. synthesis of 1,1,1-trinitrochloroethane and its rearrange-
(
N00014-16-1-2089) and the Defense Threat Reduction
ment to dipotassium tetranitroethane. J. Org. Chem. 1966, 31, 2806−
Agency (HDTRA 1-15-1-0028). The authors thank the M. J.
Murdock Charitable Trust, Vancouver, WA (Reference No.:
2
811.
(20) Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.;
2
014120: MNL:11/20/2014), for funds to purchase a 500
Robb, M. A.; Cheeseman, J. R.; Montgomery, J. A., Jr.; Vreven, T.;
Kudin, K. N.; Burant, J. C.; Millam, J. M.; Iyengar, S. S.; Tomasi, J.;
Barone, V.; Mennucci, B.; Cossi, M.; Scalmani, G.; Rega, N.;
Petersson, G. A.; Nakatsuji, H.; Hada, M.; Ehara, M.; Toyota, K.;
Fukuda, R.; Hasegawa, J.; Ishida, M.; Nakajima, T.; Honda, Y.; Kitao,
O.; Nakai, H.; Klene, M.; Li, X.; Knox, J. E.; Hratchian, H. P.; Cross, J.
B.; Bakken, V.; Adamo, C.; Jaramillo, J.; Gomperts, R.; Stratmann, R.
E.; Yazyev, O.; Austin, A. J.; Cammi, R.; Pomelli, C.; Ochterski, J. W.;
Ayala, P. Y.; Morokuma, K.; Voth, G. A.; Salvador, P.; Dannenberg, J.
J.; Zakrzewski, V. G.; Dapprich, S.; Daniels, A. D.; Strain, M. C.;
Farkas, O.; Malick, D. K.; Rabuck, A. D.; Raghavachari, K.; Foresman,
J. B.; Ortiz, J. V.; Cui, Q.; Baboul, A. G.; Clifford, S.; Cioslowski, J.;
Stefanov, B. B.; Liu, G.; Liashenko, A.; Piskorz, P.; Komaromi, I.;
Martin, R. L.; Fox, D. J.; Keith, T.; Al-Laham, M. A.; Peng, C. Y.;
Nanayakkara, A.; Challacombe, M.; Gill, P. M. W.; Johnson, B.; Chen,
MHz NMR spectrometer. We are indebted to Dr. Richard
Staples for crystal structure.
DEDICATION
■
Remembering Professor Malcolm MacKenzie Renfrew.
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