Aminonitro Groups Surrounding a Fused Pyrazolo-triazine Ring: A

Subscriber access provided by LUNDS UNIV

Article

Aminonitro Groups Surrounding a Fused Pyrazolo-triazine Ring: A Superior Thermally Stable and Insensitive Energetic Material Yongxing Tang, Chunlin He, Gregory H. Imler, Damon A. Parrish, and Jean'ne M. Shreeve ACS Appl. Energy Mater., Just Accepted Manuscript • DOI: 10.1021/acsaem.9b00049 • Publication Date (Web): 12 Feb 2019 Downloaded from http://pubs.acs.org on February 14, 2019

Just Accepted “Just Accepted” manuscripts have been peer-reviewed and accepted for publication. They are posted online prior to technical editing, formatting for publication and author proofing. The American Chemical Society provides “Just Accepted” as a service to the research community to expedite the dissemination of scientific material as soon as possible after acceptance. “Just Accepted” manuscripts appear in full in PDF format accompanied by an HTML abstract. “Just Accepted” manuscripts have been fully peer reviewed, but should not be considered the official version of record. They are citable by the Digital Object Identifier (DOI®). “Just Accepted” is an optional service offered to authors. Therefore, the “Just Accepted” Web site may not include all articles that will be published in the journal. After a manuscript is technically edited and formatted, it will be removed from the “Just Accepted” Web site and published as an ASAP article. Note that technical editing may introduce minor changes to the manuscript text and/or graphics which could affect content, and all legal disclaimers and ethical guidelines that apply to the journal pertain. ACS cannot be held responsible for errors or consequences arising from the use of information contained in these “Just Accepted” manuscripts.

is published by the American Chemical Society. 1155 Sixteenth Street N.W., Washington, DC 20036 Published by American Chemical Society. Copyright © American Chemical Society. However, no copyright claim is made to original U.S. Government works, or works produced by employees of any Commonwealth realm Crown government in the course of their duties.

Page 1 of 21 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

ACS Applied Energy Materials

Aminonitro Groups Surrounding a Fused Pyrazolotriazine Ring: A Superior Thermally Stable and Insensitive Energetic Material Yongxing Tang,a Chunlin He,a Gregory H. Imler,b Damon A. Parrishb and Jean’ne M. Shreeve*a a Department of Chemistry, University of Idaho, Moscow, Idaho, 83844-2343 USA. Fax: (+1) 208-885-9146 E-mail: [email protected] b Naval Research Laboratory, 4555 Overlook Avenue, Washington, D.C. 20375 USA KEYWORDS. Energetic compound; Pyrazole; Triazine; Fused compound; Heat-resistant explosive

ABSTRACT. Nitrogen-rich heterocyclic compounds offer promising potential backbones for constructing various high energy-density compounds. Selective diazotization of 3,5diamino-4-nitropyrazole (1) with tert-butyl nitrite followed by treatment with the sodium salt of nitroacetonitrile gives rise to a fused pyrazolo-triazine ring (5) surrounded by amino

ACS Paragon Plus Environment

1

ACS Applied Energy Materials 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 2 of 21

and nitro groups. Compound 5, confirmed by single-crystal X-ray diffraction, has a remarkable thermal decomposition temperature of 355 oC, a high density of 1.90 g cm-3 and low impact and friction sensitivities. The detonation performance is also superior to TATB. These advantages make 5 a promising candidate as a heat-resistant explosive.

Introduction The continuing successful development of high energy density materials (HEDMs) is indispensable on the way to high-performance and insensitive molecules.1–9 In addition, increasing thermal stability appears to be a prime goal in the evolution of next-generation HEDMs, especially in the field of heat-resistant explosives.10–14 Relying on nitro-benzene, traditional heat-resistant explosives always show excellent thermal stability and low pressure encountered in space applications, but they have a low detonation performance and have to face many environmental issues during the process of manufacture.15–21 In recent years, nitrogen-rich heterocylic compounds have appeared to be ideal candidates for the preparation of novel heat-resistant explosives. Some of them do show high thermal stabilities with good detonation performance; however, their thermal decomposition temperatures are always lower than 300 oC22–24 which is still a big challenge that needs to be addressed for applications in this field. Examination of the relationships between crystal structure and properties demonstrates that there are two main approaches to enhance thermal stability: a) vicinal amino and nitro groups in an acyclic array on an aromatic or heterocyclic compound which leads to a stabilization effect by extensive intra/inter-molecular hydrogen bonding;25,26 and b) conjugation which results in a planar


2

Page 3 of 21 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


structure and π-π stacking interactions.27–31 Typical representatives are 2,4,6-triamino-1,3,5trinitrobenzene (TATB),32,33 and 2,6-diamino-3,5-dinitropyrazine-l-oxide (LLM-105).34,35 Due to the highly critical applications in the field of heat-resistant explosives, additional more reliable, safer and more thermally stable energetic molecules are in great demand. Encouraged by previous work where mild cyclization was obtained by reaction of a diazonium salt of a triazole or a pyrazole with nitroacetonitrile,36–38 azolotriazine systems with vicinal C-NH2/C-NO2 moieties show higher thermal stability (> 50 oC) than the parent single ring molecules (Figure 1). The unique structure of 3,5-diamino-4-nitropyrazole (1) with two amino groups on both sides of a C-NO2 group and one non functionalized NH in the pyrazole ring, is a potential precursor to many energetic compounds.39–41 Thus, it is envisioned that 1 can be used as a substrate for developing a novel molecule 5 with two vicinal amino-nitro groups in the fused ring. Such a compound should show remarkable thermal stability and be insensitive in addition to exhibiting good detonation performance. H2N N

N NH N

O2N T d: 227 oC

O2N T d: 272 oC

N NH N

O2N T d: 198 oC

NH2

N N

N

H2N O2N

NO2

N

N

NO2

N N

O2N

NH2

O2N T d: 246 oC

Figure. 1 Increased thermal stability from single ring to amino-nitro fused ring

Results and Discussion 3,5-Diamino-4-nitropyrazole (1) was prepared according to the literature.42–44 One equivalent of sodium nitrite was reacted with 1 to form unknown products. However, when tert-butyl nitrite was used, only one of the amino groups was converted to the corresponding diazonium salt 3


3


Page 4 of 21

(Scheme 1), which was immediately treated with the sodium salt of nitro acetonitrile in dilute sulfuric acid to form 4. Refluxing 4 in a mixture of methanol and water resulted in 5. When excess gaseous HCl was bubbled into a suspension of 1 in methanol, the hydrochloride salt 2 was formed. Unfortunately, 2 was not converted to the corresponding diazonium salt 3 with either sodium nitrite or tert-butyl nitrite. Attempts to introduce the N-oxide moiety into 5 by using HOF or a mixture of TFAA and 50% hydrogen peroxide was tried;45–48 however, 5 is resistant to oxidation.

Scheme 1. Synthesis of 5 50 eqv. HCl (g)

H2N

NO2

HN N H

NO2

HN N 1

H2N

2

NH2

NH2 Cl-

t-BuONO t-BuONO HCl (g)/CH3OH

H2N

HN N 3

CN Na+

NO2 N2

Cl

NO2

20% H2SO4

H2N

H2N

NO2 NH N

HN N 4

CN

CH3OH/H2O reflux

NO2

NO2 N N

N N H2N

NO2 5

Suitable crystals for single-crystal X-ray diffraction were obtained from the solution of 5 in DMSO. Compound 5 crystallizes as a DMSO adduct (5·DMSO) in the triclinic space group P-1 with two formula units per unit cell (Z = 2) and a crystal density of 1.681 g cm-3 at 20 oC. The molecular structure is shown in Figure 2a. The amino groups, nitro groups and fused ring are essentially in the same plane ( ∠ N10-C9-C11-N12 = -2.1(6)o; ∠ C(9)-C(11)-N(12)-O(13) = 0.2(6)o; ∠N(3)-C(4)-C(5)-N(6) = -1.9(6)o; ∠O(1)-N(3)-C(4)-C(17) = -1.6(6)o ). Intramolecular N–H···O hydrogen bonds (N10-H10B···O13 and N(6)–H(6B)···O(2)) are formed between the adjacent amino and nitro groups (Figure 2b). In addition, intermolecular hydrogen bonds are also present. The details are given in the Supporting Information. Such extensive hydrogen bonding


4

Page 5 of 21 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


causes the molecules to form a planar layer along the b axis. The distance between the layers is 3.09 Å (Figure 2c).

(a)

(b)

(c) Figure. 2 (a) Molecular structure of 5·DMSO; (b) Inter-/intramolecular hydrogen bonds of 5·DMSO; (c) packing diagram of 5·DMSO viewed from b axis.

The thermal behavior was determined with DSC at a heating rate of 5 oC min-1. Compound 5 has a remarkably high thermal stability with an onset decomposition temperature of 355 oC (Table 1). This is a little higher than that of traditional heat-resistant energetic compounds, TATB or LLM-105. In addition to excellent thermal stability, 5 exhibits fascinating properties which are


5


Page 6 of 21

inherent in a heat-resistant explosive. The heat of formation for 5 is higher than that of either TATB or LLM-105. It has a high density of 1.90 g cm-3 at room temperature (determined with a gas pycnometer). Additionally, it integrates the insensitivities of TATB and the good detonation performance of LLM 105. It is essentially insensitive with an impact sensitivity > 60 J and a friction sensitivity > 360 N. The calculated detonation performance was obtained by using EXPLO5 v6.01 code49 on the basis of a calculated heat of formation and experimental density. The detonation velocity is 8727 m s-1 and the detonation pressure is 32.6 GPa, which are slightly higher than those of LLM-105. Table 1. Physical and detonation properties of 5 in comparison with TATB and LLM-105 Td a) ρ b) ∆fH c) νD d) P e) Compounds [°C] [g cm-3] [kJ mol-1/kJ g-1] [m s-1] [Gpa]

IS f) [J]

FS g) [N]

5

355

1.90

344/1.43

8727

32.6

>60

>360

TATB

350

1.93

-139.7/-0.54

8179

30.5

50

>360

LLM-105

342

1.92

11/0.05

8639

31.7

20

360

a)

Thermal decomposition temperature (onset) under nitrogen gas (DSC, 5 oC/min); b) Measured densities - gas pycnometer at room temperature; c) Calculated heat of formation; d) Calculated detonation velocity; e) Calculated detonation pressure; f) Impact sensitivity; g) Friction sensitivity.

Since compound 5 shows superior thermal stability, the Kissinger50 and Ozawa51 methods were employed to investigate the thermodynamic properties in comparison with traditional heatresistant explosives, TATB. The DSC curve of 5 at different heating rates is shown in Figure 3. Both the activation energy and extrapolated peak temperature (Tp0) of 5 are higher than those of TATB (Supporting Information, Table S1 and Table S2), showing that 5 has a better heat resistance than TATB, probably because 5 has a larger conjugate system. Moreover, the reaction enthalpy (1701 J/g) of 5 is also larger than that of TATB (628.8 J/g).52 All of the evidence shows that 5 is an excellent candidate as a heat-resistant explosive.


6

Page 7 of 21 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


Figure 3. The DSC curve of 5 at different heating rates.

The nucleus independent chemical shift (NICS) is not only an important tool to describe the aromaticity or magnetic properties of a molecule,53–55 but also is a credible parameter in the evaluation of thermal stability based on the anisotropic effects of π conjugation.56,57 By employing the software Multiwfn v3.5,58 the shielding maps and anisotropic effects of 5 and TATB, visualized as isochemical shielding surfaces (ICSS), were calculated and are given in Figure 4a and Figure 4b. Obviously, in 5, the shielding surfaces are larger and higher than that in TATB, indicating that 5 has a larger increased π conjugation than TATB. Moreover, the area of the high ICSS value at 20 ppm (pink) in 5 is larger than that in TATB (Figure 4c and Figure 4d). Such results support the fact that 5 has a higher thermal stability than TATB.


7


Page 8 of 21

Figure. 4 (a) The shielding map of TATB (1 bohr above the XY plane); (b) The shielding map of 5 (1 bohr above the XY plane); (c) Clipping plane of TATB for multiple iso-chemcal shielding surfaces (ICSS, at 2 ppm in red; at 6 ppm in yellow; at 10 ppm in blue; at 15 ppm in green; at 20 ppm in pink; at -1 ppm in black); (d) Clipping plane of 5 for multiple iso-chemcal shielding surfaces (ICSS, at 2 ppm in red; at 6 ppm in yellow; at 10 ppm in blue; at 15 ppm in green; at 20 ppm in pink; at -1 ppm in black).

Conclusion In conclusion, tert-butyl nitrite is an efficient reagent for selective diazotization of 3,5diamino-4-nitropyrazole which with sodium nitroacetonitrile results in a very stable fused pyrazolotriazine ring (5). The two adjacent amino-nitro groups in the fused ring play an important role in stabilizing the molecule, leading to a superior high decomposition temperature of 355 oC. The high thermal stability was also supported by non-isothermal kinetics analysis and theoretical calculations. In addition, 5 also exhibits good detonation performance (vD: 8727 m s-1; P: 32.6 GPa) and insensitive properties (IS: >60 J; FS: >360 N). These promising properties support 5 as an excellent candidate as a heat-resistant explosive. The strategy of selective diazotization and the fascinating molecular structure with two vicinal amino and nitro groups in a fused ring may prompt a broader study of energetic molecules and lead to the development of other thermally stable compounds.


8

Page 9 of 21 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


ASSOCIATED CONTENT

Supporting Information. The following files are available free of charge. Experimental procedures and characterization, X-ray diffraction details, NMR spectra, and calculation details (.docx) Crystallographic data for 5·DMSO (CIF)

AUTHOR INFORMATION

Corresponding Author *(J.M.S.) E-mail: [email protected]

Notes The authors declare no competing financial interest.

ACKNOWLEDGMENT Financial support of the Office of Naval Research (NOOO14-12-1-0536), the Defense Threat Reduction Agency (HDTRA 1-11-1-0034) is gratefully acknowledged. We are also grateful to the M. J. Murdock Charitable Trust, Reference No.: 2014120: MNL:11/20/2014 for funds supporting the purchase of a 500 MHz NMR spectrometer. REFERENCES


9


Page 10 of 21

(1) Gao, H.; Shreeve, J. M. Azole-based Energetic Salts. Chem. Rev. 2011, 111, 73777436. (2) Dippold, A. A.; Klapötke, T. M. A Study of Dinitro-bis-1,2,4-triazole-1,1’-diol and Derivatives: Design of High-performance Insensitive Energetic Materials by the Introduction of N-oxides. J. Am. Chem. Soc. 2013, 135, 9931-9938. (3) Huynh, M. H. V.; Hiskey, M. A.; Chavez, D. E.; Naud, D. L.; Gilardi, R. D. Synthesis, Characterization, and Energetic Properties of Diazido Heteroaromatic High-nitrogen C−N Compound. J. Am. Chem. Soc. 2005, 127, 12537-12543. (4) Klapötke, T. M.; Petermayer, C.; Piercey, D. G.; Stierstorfer, J. 1,3-Bis(nitroimido)1,2,3-triazolate Anion, the N-Nitroimide Moiety, and the Strategy of Alternating Positive and Negative Charges in the Design of Energetic Materials. J. Am. Chem. Soc. 2012,

134, 20827-20836. (5) Thottempudi, V.; Gao, H.; Shreeve, J. M. Trinitromethyl-substituted 5-Nitro-or 3-azo1,2,4-triazoles: Synthesis, Characterization, and Energetic Properties. J. Am. Chem. Soc. 2011, 133, 6464-6471.


10

Page 11 of 21 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


(6) Thottempudi, V.; Shreeve, J. M. Synthesis and Promising Properties of a New Family of High-Density Energetic Salts of 5-Nitro-3-trinitromethyl-1H-1,2,4-triazole and 5,5’-Bis (trinitromethyl)-3,3’-azo-1H-1, 2, 4-triazole. J. Am. Chem. Soc. 2011, 133, 19982-19992. (7) Tang, Y.; Kumar, D.; Shreeve, J. M. Balancing Excellent Performance and High Thermal Stability in a Dinitropyrazole Fused 1,2,3,4-Tetrazine. J. Am. Chem. Soc. 2017,

139, 13684-13687. (8) Li, Y.; Qi, C.; Li, S.; Zhang, H.; Sun, C.; Yu, Y.; Pang, S. 1,1’-Azobis-1,2,3-triazole: A High-Nitrogen Compound with Stable N8 Structure and Photochromism. J. Am. Chem.

Soc. 2010, 132, 12172-12173. (9) Klapötke, T. M.; Krumm, B.; Pflüger, C. Isolation of a Moderately Stable but Sensitive Zwitterionic Diazonium Tetrazolyl-1,2,3-triazolate. J. Org. Chem. 2016, 81, 6123-6127. (10) Wang, Q.; Wang, S.; Feng, X.; Wu, L.; Zhang, G.; Zhou, M.; Wang, B.; Yang, L. A Heat-resistant and Energetic Metal–organic Framework Assembled by Chelating Ligand.

ACS Appl. Mater. Interfaces 2017, 9, 37542-37547.


11


Page 12 of 21

(11) Liu, N.; Shu, Y; Li, H.; Zhai, L.; Li, Y.; Wang, B. Synthesis, Characterization and Properties

of

Heat-resistant

Explosive

Materials:

Polynitroaromatic

Substituted

Difurazano [3,4-b:3’,4’-e] pyrazines. RSC Adv. 2015, 5, 43780-43785. (12) Zhang, M.; Fu, W.; Li, C.; Gao, H.; Tang, L.; Zhou, Z. (E)-1,2-Bis(3,5-dinitro-1Hpyrazol-4-yl)diazene-Its 3D Potassium Metal-Organic Framework and Organic Salts with Super-Heat-Resistant Properties. Eur. J. Inorg. Chem. 2017, 2017, 2883-2891. (13) Wang, Y.; Liu, Y.; Song, S.; Yang, Z.; Qi, X.; Wang, K.; Liu, Y.; Zhang, Q.; Tian, Y. Accelerating the Discovery of Insensitive High-energy-density Materials by a Materials Genome Approach. Nat. Commun. 2018, 9, 2444. (14) Gálvez-Ruiz, J. C.; Holl, G.; Karaghiosoff, K.; Klapötke, T. M.; Löhnwitz, K.; Mayer, P.; Nöth, H.; Polborn, K.; Rohbogner, C. J.; Suter, M.; Weigand, J. J. Derivatives of 1,5Diamino-1H-tetrazole: A New Family of Energetic Heterocyclic-Based Salts. Inorg. Chem. 2005, 44, 4237-4253. (15) Klapötke, T. M.; Witkowski, T. G. 5,5’-Bis(2,4,6-trinitrophenyl)-2,2’-bi(1,3,4oxadiazole)(TKX-55):

Thermally

Stable

Explosive

with

Outstanding

Properties.

ChemPlusChem 2016, 81, 357-360.


12

Page 13 of 21 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


(16) Wu, R.; Zhang, T.; Qiao, X. Synthesis and Characterization of an Intermediary of New Heat-resistant Energetic Materials. Chinese Chem. Lett. 2010, 21, 1007-1010. (17) Zhang, X; Xiong, H.; Yang, H.; Cheng, G. The Synthesis of Energetic Compound on 4, 4'-((2,4,6-trinitro-1,3-phenylene) bis(oxy))bis(1,3-dinitrobenzene)(ZXC-5): Thermally Stable Explosive with Outstanding Properties. Propellants Explos. Pyrotech. 2017, 42, 1203-1207. (18) Zhang, X; Xiong, H.; Yang, H.; Cheng, G. Synthesis and Characterization of New Calixarenes Containing Explosives with High Temperature Stabilities. Propellants Explos.

Pyrotech. 2017, 42, 942-946. (19) Urbański, T.; Vasudeva, S., Heat Resistant Explosives. J. Sci. Ind. Res 1978, 37 (5), 250-255. (20) Kilmer, E. Heat-resistant Explosives for Space Applications. J. Spacecr. Rockets 1968, 5, 1216-1219. (21) Witkowski, T. G.; Sebastiao, E.; Gabidullin, B.; Hu, A.; Zhang, F.; Murugesu, M. 2,3,5,6-Tetra(1H-tetrazol-5-yl)pyrazine: A Thermally Stable Nitrogen-Rich Energetic Material. ACS Appl. Energy Mater. 2018, 1, 589-593.


13


Page 14 of 21

(22) Li, C.; Liang, L.; Wang, K.; Bian, C.; Zhang, J.; Zhou, Z. Polynitro-substituted Bispyrazoles: A New Family of High-performance Energetic Materials. J. Mater. Chem. A 2014, 2, 18097-18105. (23) Tang, Y.; He, C.; Mitchell, L. A.; Parrish, D. A.; Shreeve, J. M. C–N Bonded Energetic Biheterocyclic Compounds with Good Detonation Performance and High Thermal Stability. J. Mater. Chem. A 2016, 4, 3879-3885. (24) Sikder, A.; Sikder, N. A Review of Advanced High Performance, Insensitive and Thermally Stable Energetic Materials Emerging for Military and Space Applications. J.

Hazard. Mater. 2004, 112, 1-15. (25) He, C.; Yin, P.; Mitchell, L. A.; Parrish, D. A.; Shreeve, J. M. Energetic Aminatedazole Assemblies from Intramolecular and Intermolecular N–H⋯O and N–H⋯N Hydrogen Bonds. Chem. Commun. 2016, 52, 8123-8126. (26)

Yin,

P.;

Parrish,

D.

A.;

Shreeve,

J.

M.

Energetic

Multifunctionalized

Nitraminopyrazoles and Their Ionic Derivatives: Ternary Hydrogen-bond Induced High Energy Density Materials. J. Am. Chem. Soc. 2015, 137, 4778-4786.


14

Page 15 of 21 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


(27) Pagoria, P. A Comparison of the Structure, Synthesis, and Properties of Insensitive Energetic Compounds. Propellants Explos. Pyrotech. 2016, 41, 452-469. (28) Meng, L.; Lu, Z.; Ma, Y.; Xue, X.; Nie, F.; Zhang, C. Enhanced Intermolecular Hydrogen Bonds Facilitating the Highly Dense Packing of Energetic Hydroxylammonium Salts. Cryst. Growth Des. 2016, 16, 7231-7239. (29) Ma, Y.; Zhang, A.; Xue, X.; Jiang, D.; Zhu, Y.; Zhang, C. Crystal Packing of Impactsensitive High-energy Explosives. Cryst. Growth Des. 2014, 14, 6101-6114. (30) Ma, Y.; Zhang, A.; Zhang, C.; Jiang, D.; Zhu, Y.; Zhang, C. Crystal Packing of Lowsensitivity and High-energy Explosives. Cryst. Growth Des. 2014, 14, 4703-4713. (31) Zhang, J.; Mitchell, L. A.; Parrish, D. A.; Shreeve, J. M. Enforced Layer-by-layer Stacking of Energetic Salts Towards High-performance Insensitive Energetic Materials.

J. Am. Chem. Soc. 2015, 137, 10532-10535. (32) Boddu, V. M.; Viswanath, D. S.; Ghosh, T. K.; Damavarapu, R. 2, 4, 6-Triamino-1, 3, 5-trinitrobenzene (TATB) and TATB-based Formulations–A Review. J. Hazard. Mater. 2010, 181, 1-8.


15


Page 16 of 21

(33) Cady H. H.; Larson A. C. The Crystal Structure of 1,3,5-triamino-2,4,6trinitrobenzene. Acta Cryst. 1965, 18, 485-496. (34) Pagoria, P.; Mitchell, A. R.; Schmidt, R. D.; Simpson, R. L.; Garcia, F.; Forbes, J. W.; Swansiger R. W.; Hoffman, D. M. Report UCRL-JC-130518, Lawrence Livermore National Laboratory, Livermore, CA, 1998. (35) Pagoria, P. F. Synthesis of LLM-105. Propellants, Explos. Pyrotech. 1995, 20, 3842. (36) Piercey, D. G.; Chavez, D. E.; Scott, B. L.; Imler, G. H.; Parrish, D. A. An Energetic Triazolo-1, 2, 4-Triazine and Its N-Oxide. Angew. Chem. Int. Ed. 2016, 55, 15315-15318. (37) Schulze, M. C.; Scott, B. L.; Chavez, D. E. A High Density Pyrazolo-triazine Explosive (PTX). J. Mater. Chem. A 2015, 3, 17963-17965. (38) Snyder, C. J.; Myers, T. W.; Imler, G. H.; Chavez, D. E.; Parrish, D. A.; Veauthier, J. M.; Scharff, R. J. Tetrazolyl Triazolotriazine: A New Insensitive High Explosive.

Propellants Explos. Pyrotech. 2017, 42, 238-242.


16

Page 17 of 21 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


(39) Guillard, J.; Goujon, F.; Badol P.; Poullain D., New Synthetic Route to Diaminonitropyrazoles as Precursors of Energetic Materials. Tetrahedron Lett. 2003, 44, 5943-5945. (40) Makarov, V. A.; Ryabova, O. B.; Alekseeva, L. M.; Chernyshev V. V.; Granik, V. G. Investigation of the Reaction of 3, 5-Diamidino-4-nitropyrazole with Amines. Chem.

Heterocycl. Compd. 2002, 38, 947-953. (41) Makarov, V. A.; Solov'eva, N. P.; Ryabova O. B.; Granik, V. G. Synthesis of Pyrazolo[1,5-a]-pyrimidines by Reaction of 3,5-Diamino-4-nitropyrazole with Acetoacetic Ester in the Presence of Alkaline Agents. Chem. Heterocycl. Compd. 2000, 36, 65-69. (42) Latli, B.; Jones P.; Krishnamurthy D.; Senanayake C. H. Synthesis of [14C]-, [13C4]-, and [13C4, 15N2]- 5-amino-4-iodopyrimidine. J. Label. Compd. Radiopharm. 2008, 51, 5458. (43) Clark, J.; Gelling, I.; Southon, I. W.; Morton, M. S. Heterocyclic Studies. Part XIII. Ready Ring Cleavage of Some Pyrimidine Derivatives to Give Highly Substituted Ethylenes. J. Chem. Soc. C: Org. 1970, 0, 494-498.


17


Page 18 of 21

(44) Solov'eva, N. P.; Makarov, V. A.; Granik, V. G. Highly Polarized Enamines. Chem.

Heterocycl. Compd. 1997, 33 (1), 78-85. (45) Chavez, D. E.; Parrish, D. A.; Mitchell, L.; Imler, G. H. Azido and Tetrazolo 1, 2, 4, 5-Tetrazine N-Oxides. Angew. Chem. Int. Ed. 2017, 56, 3575-3578. (46) Wei, H.; Gao, H.; Shreeve, J. M. N-Oxide 1,2,4,5-Tetrazine-Based High-Performance Energetic Materials. Chem. Eur. J. 2014, 20, 16943-16952. (47) Wei, H.; Zhang, J.; Shreeve, J. M. Synthesis, Characterization, and Energetic Properties of 6-Amino-tetrazolo[1,5-b]-1,2,4,5-tetrazine-7-N-oxide: A Nitrogen-Rich Material with High Density. Chem. Asian J. 2015, 10, 1130-1132. (48) Tang, Y.; He, C.; Shreeve, J. M. A Furazan-fused Pyrazole N-oxide via Unusual Cyclization. J. Mater. Chem. A 2017, 5, 4314-4319. (49) M. Sućeska, EXPLO5, Version 6.01, 2013. (50) Kissinger, H. E. Reaction Kinetics in Differential Thermal Analysis. Anal. Chem. 1957, 29, 1702-1706. (51) Ozawa, T. A New Method of Analyzing Thermogravimetric Data. Bull. Chem. Soc.

Jpn. 1965, 38, 1881-1886.


18

Page 19 of 21 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


(52) Cao, X.; Luo, S.; Xu L.; Meng, R. Thermal Decomposition of TATB and Its Thermal Explosion Characteristics in [Emim]Ac/DMSO Solvent. Chin. J. Explos. Propellants 2016,

39, 52-55. (53) Chen, Z.; Wannere, C. S.; Corminboeuf, C.; Puchta R.; Schleyer, P. v. R. Nucleusindependent Chemical Shifts (NICS) as An Aromaticity Criterion. Chem. Rev. 2005, 105, 3842-3888; (54) Schleyer, P. v. R.; Maerker, C.; Dransfeld, A.; Jiao H.; Hommes, N. J. R. v. E. Nucleus-independent Chemical Shifts: A Simple and Efficient Aromaticity Probe. J. Am.

Chem. Soc. 1996, 118, 6317-6318; (55) Wang, Y.; Li, S.; Li, Y.; Zhang, R.; Wang D.; Pang, S. A Comparative Study of the Structure, Energetic Performance and Stability of Nitro-NNO-azoxy Substituted Explosives. J. Mater. Chem. A 2014, 2, 20806-20813. (56) Ghule, V. D.; Radhakrishnan, S.; Jadhav P. M.; Tewari, S. P. Quantum Chemical Studies on Energetic Azo-bridged Azoles. J. Energ. Mater. 2013, 31, 35-48; (57) Ghule, V.; Sarangapani, R.; Jadhav P.; Tewari, S. Theoretical Studies on Nitrogen Rich Energetic Azoles. J. Mol. Model. 2011, 17, 1507-1515.


19


Page 20 of 21

(58) Lu T.; Chen, F. Multiwfn: A Multifunctional Wavefunction Analyzer. J. Comput. Chem. 2012, 33, 580-592.

Table of Contents


20

Page 21 of 21 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60



21

Aminonitro Groups Surrounding a Fused Pyrazolo-triazine Ring: A

Recommend Documents