A π-Stacked Highly Stable, Insensitive, Energy-Containing Material with a Useful Planar Structure

Shuliang Liu; Yuan Qi; Peng-cheng Zhang; Qiuhan Lin

doi:10.1055/s-0043-1775365

Synlett, Table of Contents

Synlett 2024; 35(17): 1997-2002
DOI: 10.1055/s-0043-1775365

letter

Energetic Molecules

A π-Stacked Highly Stable, Insensitive, Energy-Containing Material with a Useful Planar Structure

Shuliang Liu

^aSchool of Chemistry and Chemical Engineering, Nanjing University of Science and Technology, Nanjing 210094, P. R. of China

,

Yuan Qi

^aSchool of Chemistry and Chemical Engineering, Nanjing University of Science and Technology, Nanjing 210094, P. R. of China

,

Peng-cheng Zhang∗

^bResearch Institute of Chemical Defense, Academy of Military Sciences, Beijing 102205, P. R. of China

,

Qiuhan Lin∗

^aSchool of Chemistry and Chemical Engineering, Nanjing University of Science and Technology, Nanjing 210094, P. R. of China

› Author Affiliations

Abstract

All articles of this category

Abstract

π-Stacking is common in materials, but different π–π stacking modes remarkably affect the properties and performances of materials. In particular, weak interactions, π-stacking and hydrogen bonding often have a significant impact on the stability and sensitivity of high-energetic compounds. A fused [5,7,5]-tricyclic energetic compound with a conjugated structure has been designed and synthesized. 4H-[1,2,5]Oxadiazolo[3,4-e][1,2,4]triazolo[3,4-g][1,2,4]triazepin-8-amine is obtained in 48% yield from 3-amino-4-carboxy-1,2,5-oxadiazole through an efficient two-step reaction. Owing to its layered planar structure and weak π interactions between layers, 4H-[1,2,5]oxadiazolo[3,4-e][1,2,4]triazolo[3,4-g][1,2,4]triazepin-8-amine exhibits high thermal stability (T _d = 318 °C), low sensitivity (IS = 40 J, FS = 360 N), and relatively excellent detonation performance (D = 7059 ms^–1, P = 20.2 GPa). This detonation performance is superior to that of the conventional explosive TNT. The developed procedure provides a new method for the synthesis of fused ring compounds.

Key words

energetic materials - explosives - nitrogen heterocycles - π-stacking - detonation - planar structure

Full Text

References

References and Notes

1a Feng Y, Deng M, Song S, Chen S, Zhang Q, Shreeve JM. Engineering 2020; 6: 1006
1b Hermann TS, Karaghiosoff K, Klapötke TM, Stierstorfer J. Chem. Eur. J. 2017; 23: 11984

2a Sun Q, Li X, Lin Q, Lu M. Org. Biomol. Chem. 2018; 43: 7987
2b Zhang J, Shreeve JM. J. Phys. Chem. A. 2015; 119: 12781
2c Rylott EL, Jackson RG, Edwards J, Womack GL, Seth-Smith HM. B, Rathbone DA, Strand SE, Bruce NC. Nat. Biotechnol. 2006; 24: 216
2d Wang Y, Liu Y, Song S, Yang Z, Qi X, Wang K, Liu Y, Zhang Q, Tian Y. Nat. Commun. 2018; 9: 2444
2e Bayat Y, Eghdamtalab M, Zeynali V. J. Energetic Mater. 2010; 28: 273
2f Fischer N, Fischer D, Klapötke TM, Piercey DG, Stierstorfer J. J. Mater. Chem. 2012; 22: 20418

3a Yu Q, Yin P, Zhang J, He C, Imler GH, Parrish DA, Shreeve JM. J. Am. Chem. Soc. 2017; 139: 8779
3b Haubenreisser S, Wöste TH, Martínez C, Ishihara K, Muñiz K. Angew. Chem. Int. Ed. 2016; 55: 1
3c Tang Y, Zhang J, Mitchell LA, Parrish DA, Shreeve JM. J. Am. Chem. Soc. 2015; 137: 15984

4a Wang Q, Shao Y, Lu M. Cryst. Growth Des. 2019; 19: 839
4b Zhang C, Wang X, Huang H. J. Am. Chem. Soc. 2008; 130: 8359
4c Zhang J, Mitchell LA, Parrish DA, Shreeve JM. J. Am. Chem. Soc. 2015; 137: 10532
4d Zhang J, Jin B, Peng R, Niu C, Xiao L, Guo Z, Zhang Q. Dalton Trans. 2019; 48: 11848
4e Geng W.-J, Ma Q, Chen Y, Yang W, Jia Y.-F, Li J.-S, Zhang Z.-Q, Fan G.-J, Wang S.-M. Cryst. Growth Des. 2020; 20: 2106
4f Dippold AA, Klapötke TM. J. Am. Chem. Soc. 2013; 135: 9931
4g Tang Y, Huang W, Imler GH, Parrish DA, Shreeve JM. J. Am. Chem. Soc. 2020; 142: 7153
4h Fei T, Lai Q, Cai J, Zhang J, He C, Pang S. Cryst. Growth Des. 2022; 22: 1943

5 Lei C, Tang J, Zhang Q, Yang H, Cheng G. Org. Lett. 2023; 25: 2461

6a Cheng Y, Chen X, Yang N, Zhang Y, Ma H, Guo Z. CrystEngComm 2021; 23: 1953
6b Bu R, Xiong Y, Zhang C. Cryst. Growth Des. 2020; 20: 2824
6c Yin P, Mitchell LA, Parrish DA, Shreeve JM. Angew. Chem. Int. Ed. 2016; 55: 14409

7 Wang Y, Ye J, Yang N, Ma H, Zhang Y, Guo Z. CrystEngComm 2021; 23: 7635

8a Zhang J, Zhang Q, Vo TT, Parrish DA, Shreeve JM. J. Am. Chem. Soc. 2015; 137: 1697
8b Zhang J, Jin B, Song Y, Hao W, Huang J, Guo J, Huang T, Guo Z, Peng R. Langmuir 2021; 37: 7118
8c Lei C, Yang H, Zhang Q, Cheng G. Dalton Trans. 2021; 50: 14462
8d Chand D, Parrish DA, Shreeve JM. J. Mater. Chem. A 2013; 1: 15383

9 Cheng B, Yang F, Zhang J, Zhang L, Zhao P, Lin Q. Cryst. Growth Des. 2023; 23: 1466
10 Caution! The target compounds in this article are energetic materials with explosive properties. All synthetic manipulations must be carried out using appropriate equipment (fume hood, safety shield) and protective gear (lab coat, goggles and gloves). Compounds should be synthesized on a small scale and mechanical actions involving scratching or scraping must be avoided.
11 Willer RL, Storey RF, Frisch M, Deschamps JR. J. Heterocycl. Chem. 2012; 49: 227
12 3-Amino-4-(4,5-diamino-1,2,4-triazol-3-yl)-furazan (2) Phosphorus pentoxide (10 g, 70.4 mmol) was slowly added to phosphoric acid (85 wt%, 30 g, 260 mmol) and the mixture was then heated to 50 °C with stirring. A mixture of 3-amino-4-carboxy furazan (3.87 g, 30 mmol) and diaminoguanidine monohydrochloride (6.15 g, 49 mmol) was added to the preheated solution. After the addition was complete, the mixture was heated to 120 °C and the evolution of gaseous HCl was observed. The mixture was kept at 120 °C for 5 h and then cooled to room temperature. Ice water (150 mL) was added to the cooled reaction mixture and a white precipitate was formed. The mixture was made basic (pH 8) using conc. NaOH solution and the precipitate was filtered, washed repeatedly with water and air-dried to obtain crude product 2. Yield: 3.4 g (62%). IR (KBr): 3436, 3352, 1690, 1608, 1404, 1380, 1340, 1183, 1045, 990, 907, 769, 688, 581 cm^–1. ¹H NMR (500 MHz, DMSO-d ₆): δ = 5.91 (2 H, s), 6.26 (2 H, s), 6.58 (2 H, s). ¹³C NMR (125.72 MHz, DMSO-d ₆): δ = 157.18, 154.98, 140.27, 136.58. Anal. Calcd for C₄H₆N₈O (182.15): C, 26.38; H, 3.33; N, 61.52. Found: C, 26.46; H, 3.28; N, 61.31.
13 4H-[1,2,5]Oxadiazolo[3,4-e][1,2,4]triazolo[3,4-g][1,2,4]triazepin-8-amine (3) Compound 2 (0.99 g, 5.4 mmol) was dissolved in acetonitrile (20 mL), the solution was cooled to 0 °C and TCCA (2.325 g, 10 mmol) was added dropwise. The reaction mixture was further stirred at 0 °C for 30 min. The solution was neutralized with solid Na₂CO₃ and then filtered to remove insoluble solids. The filter cake was washed several times with acetonitrile and the combined filtrates were concentrated by vacuum evaporation. The crude product obtained after removal of the solvent under vacuum was purified by silica gel chromatography (eluent: EtOAc/petroleum ether = 1:1) to give product 3 as a light yellow solid. Yield: 0.65 g (48%). T _d = 318 ℃. IR (KBr): 3202, 3049, 2921, 2832, 1693, 1455, 1413, 1390, 1051, 977, 845, 786, 760, 739, 692 cm^–1. ¹H NMR (500 MHz, DMSO-d ₆): δ = 11.15 (s, 1 H), 4.30 (br s, 1 H), 1.29 (s, 2 H). ¹³C NMR (125.72 MHz, DMSO-d ₆): δ = 155.72, 153.1, 140.24, 135.06, 40.2. Anal. Calcd for C₅H₄N₈O: C, 31.26; H, 2.10; N, 58.32, O, 8.33. Found: C, 31.06; H, 2.40; N, 58.02; O, 8.43.
14 Zhang C, Xue X, Cao Y, Zhou J, Zhang A, Li H, Zhou Y, Xu R, Gao T. CrystEngComm 2014; 16: 5905
15 Deng M, Feng Y, Zhang W, Qi X, Zhang Q. Nat. Commun. 2019; 10: 1339
16 Dai C, Chen J, Tang J, Cheng G, Yang H. New J. Chem. 2021; 45: 17960
17 Gao H, Shreeve JM. RSC Adv. 2016; 6: 56271
18 Sućeska M. EXPLO5 V6.05.04. Brodarski Institute; Zagreb, Croatia: 2020
19 Spackman MA, McKinnon JJ. CrystEngComm 2002; 4: 378
20 Spackman MA, Jayatilaka D. CrystEngComm 2009; 11: 19
21 Johnson ER, Keinan S, Mori-Sánchez P, Contreras-García J, Cohen AJ, Yang W. J. Am. Chem. Soc. 2010; 132: 6498
22 Lu T, Chen F. J. Comput. Chem. 2012; 33: 580
23 Frisch MJ, Trucks GW, Schlegel HB, Scuseria GE, Robb MA, Cheeseman JR, Scalmani G, Barone V, Mennucci B, Petersson GA, Nakatsuji H, Caricato M, Li X, Hratchian HP, Izmaylov AF, Bloino J, Zheng G, Sonnenberg JL, Hada M, Ehara M, Toyota K, Fukuda R, Hasegawa J, Ishida M, Nakajima T, Honda Y, Kitao O, Nakai H, Vreven T, Montgomery JA, Peralta JE, Ogliaro F, Bearpark M, Heyd JJ, Brothers E, Kudin KN, Staroverov VN, Kobayashi R, Normand J, Raghavachari K, Rendell A, Burant JC, Iyengar SS, Tomasi J, Cossi M, Rega N, Millam JM, Klene M, Knox JE, Cross JB, Bakken V, Adamo C, Jaramillo J, Gomperts R, Stratmann RE, Yazyev O, Austin AJ, Cammi R, Pomelli C, Ochterski JW, Martin RL, Morokuma K, Zakrzewski VG, Voth GA, Salvador P, Dannenberg JJ, Dapprich S, Daniels AD, Farkas O, Foresman JB, Ortiz JV, Cioslowski J, Fox DJ. Gaussian Inc. Wallingford (CT, USA): 2009
24 Zhang J, Mitchell LA, Parrish DA, Shreeve JM. J. Am. Chem. Soc. 2015; 137: 10532

Supplementary Material

Supporting Information