Pentaerythritol Trinitrate Substituted s-Tetrazine and s-Triazine

Abstract

The synthesis of pentaerythritol trinitrate persubstituted 1,2,4,5-tetrazine and 1,3,5-triazine is reported. These materials were characterized with respect to their chemical and energetic materials properties. X-ray crystallographic analyses were also performed. The UV/Vis, Raman, and cyclic voltammetry data were collected and are reported.

Key words

tetrazines - triazines - heterocycle - cyclic voltammetry - UV/Vis - energetic materials

• References and Notes

• 1 Chavez DE, Hanson SK, Veauthier JM. Angew. Chem. Int. Ed. 2013; 52: 6876

For other examples of electroactive tetrazines, see:
• 2a Clavier G, Audebert P. Chem. Rev. 2010; 110: 3299
• 2b Malinge J, Allain C, Brosseau A, Audebert P. Angew. Chem. Int. Ed. 2012; 51: 8534
• 3a Zhang H.-X, Kato M, Sasaki Y, Ohba T, Ito H, Kobayashi A, Chang H.-C, Uosaki K. Dalton Trans. 2012; 41: 11497
• 3b Abdi K, Hadadzadeh H, Salimi M, Simpson J, Khalaji AD. Polyhedron 2012; 44: 101
• 3c Hadadzedah H, Maghami M, Simpson J, Khalaji AD, Abdi K. J. Chem. Crystallogr. 2012; 42: 656
• 3d Roy S, Blane T, Lilio A, Kubiak CP. Inorg. Chim. Acta 2011; 374: 134
• 3e Najafpour MM, Boghaei DM, Mckee V. Polyhedron 2010; 29: 3246
• 4a Koc ZE, Bingol H, Saf AO, Toriak E, Coskun A. J. Hazard. Mater. 2010; 183: 251
• 4b Sun C, Hudson ZM, Helander MG, Lu Z.-H, Wang S. Organometallics 2011; 30: 5552
• 4c Dainyte A, Gudeika D, Buika G, Grazulevicius JV. Mol. Cryst. Liq. Cryst. 2014; 590: 73
• 5 Lange K, Koenig A, Roegler C, Seeling A, Lehmann J. Bioorg. Med. Chem. Lett. 2009; 19: 3141
• 6 Rao BV, Dhokale S, Rajamohanan PR, Hotha S. Chem. Commun. 2013; 49: 10808
• 7 Compound 4 – Typical Procedure PETRIN (1, 390 mg, 1.44 mmol) was placed in a 25 mL round-bottomed flask. Compound 3 (555 mg, 1.44 mmol) was then added along with CH₂Cl₂ (2 mL). The reaction was stirred. 4-Dimethylaminopyridine (287 mg, 2.35 mmol) was added and the reaction stirred for 2 h. The reaction was filtered through a short plug of silica, the eluent collected and evaporated to give the desired product, 4, as a reddish-pink solid (735 mg, 82%), mp 139 °C, 147 °C (dec.). ¹H NMR (300 MHz, DMSO-d ₆): δ = 4.68 (s, 2 H), 4.85 (s, 6 H). ¹³C NMR (100 MHz, DMSO-d ₆): δ = 41.54, 66.83, 70.66, 165.54. IR (KBr): ν_max = 3023, 2947, 2916, 1659, 1641, 1629, 1475, 1238, 1389, 1365, 1284, 1082, 1031, 1015, 993, 944, 889, 753 cm^–1. Anal. Calcd for C₁₂H₁₆N₁₀O₂₀: C, 23.23; H, 2.60; N, 22.58. Found: C, 23.21; H, 2.61; N, 22.55.
• 8 Brandt NN, Brovko OO, Chikishev AY, Paraschuk OD. Appl. Spectrosc. 2006; 60: 288
• 9a Audebert P, Sadki S, Miomandre F, Clavier G. Electrochem. Commun. 2004; 6: 144
• 9b Audebert P, Sadki S, Miomandre F, Clavier G, Vernieres MC, Saoud M, Hapiot P. New J. Chem. 2004; 28: 387
• 9c Audebert P, Miomandre F, Clavier G, Vernieres MC, Badre S, Meallet-Renault R. Chem. Eur. J. 2005; 11: 5667
• 10 Pop F, Riobe F, Seifert S, Cauchy T, Ding J, Dupont N, Hauser A, Koch M, Avarvari N. Inorg. Chem. 2013; 52: 5023
• 11 Farzinnejad N, Miran Beigi AA, Fotouhi L, Torkestani K, Ghadirian HA. J. Electroanal. Chem. 2005; 580: 245
• 12 CCDC 1053809 and CCDC 1053814 contain the supplementary crystallographic data for 4 and 6, respectively. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif.