1,2,4,5-Tetrazinyl-Substituted Amino-1,2,4,5-Tetrazines

Abstract

The synthesis of 1,2,4,5-tetrazinylamino-1,2,4,5-tetrazines is reported, including the preparation of compounds containing three tetrazine heterocycles in a single compound. These materials were compared to phenylamine derivatives, also synthesized in this study. The UV/Vis and cyclic voltammetry data were collected and are reported, along with the crystal structure of one of the tritetrazine compounds.

Key words

tetrazines - heterocycle - cyclic voltammetry - UV/Vis - nucleophilic addition

• References and Notes

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• 11 See the Supporting Information for further details of the experimental procedures.
• 12 Compound 11; Typical Procedure: Compound 1 (270 mg, 1.0 mmol) was placed in a 50 mL round-bottomed flask. MeCN (10 mL) was added. 1,4-Phenylenediamine (54 mg, 0.5 mmol) was added and the reaction was heated to reflux for 1 h. The reaction was allowed to cool to ambient temperature and the precipitate was isolated by filtration. The product was washed with cold MeCN, and air-dried to give 189 mg of a purple solid (83% yield); mp 299 °C (dec.). ¹H NMR (300 MHz, DMSO-d ₆): δ = 2.24 (s, 6 H), 2.45 (s, 6 H), 7.77 (s, 4 H), 11.03 (s, 1 H). ¹³C NMR (100 MHz, DMSO-d ₆): δ = 12.54, 13.35, 108.95, 120.58, 133.81, 141.62, 150.46, 156.93, 160.37. IR (KBr): ν_max = 3406, 3256, 3163, 3105, 2915, 1587, 1563, 1505, 1475, 1417, 1215 cm^–1. Anal. Calcd for C₂₀H₂₀N₁₄: C, 52.62; H, 4.42, N, 42.96. Found: C, 52.63; H, 4.40; N, 42.95.
• 13 CCDC 1028515 contains the supplementary crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif.