New Polynitrogen Materials Based on Fused 1,2,4-Triazines

Abstract

The synthesis of several novel polynitrogen materials based on fused 1,2,4-triazines is described. A powerful palladium-catalyzed N-heteroarylation strategy followed by a cyclization provides a straightforward one-pot reaction to these tricyclic materials.

Key words

N-arylation reactions - palladium - energetic materials - 1,2,4-triazines

References and Notes

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9

Typical Procedure for the Pd-Catalyzed N-Arylation Cyclization. A three-necked flask was flushed with N₂ and charged with xantphos (20 mol%) and dry dioxane (5 mL). After degassing, Pd(OAc)₂ (10 mol%) was added and the mixture was stirred under N₂ for 10 min. In another three-necked round-bottom flask, compound 1 (0.100 g, 1.0 equiv), heteroarylamine (1.2 equiv) and K₂CO₃ (20 equiv) were poured into dry dioxane (7 mL). Then, the Pd(OAc)₂/xantphos solution was added via cannula. The resulting mixture was subsequently heated to reflux and vigorously stirred until 1 has disappeared. After cooling down, the solid material was filtered off and washed with CH₂Cl₂ (20 mL) and MeOH (20 mL). The solvent was evaporated and the resulting crude product was purified by flash column chromatography using CH₂Cl₂-MeOH (99:1 v/v) as eluent.
Characterization of Compounds 3a and 3b.
Compound 3a: ¹H NMR (200 MHz, DMSO): δ = 2.10 (s, 3 H, CH₃), 11.97 (br s, 1 H, NH) ppm. ¹³C NMR (50 MHz, DMSO): δ = 13.1 (CH₃), 144.8 (C_10a), 153.7 (C_5a), 154.1 (C₁₀), 154.6 (C_4a), 165.5 (C₇), 178.1 (C₃) ppm. ¹⁵N NMR (30 MHz, DMSO): δ = -296, -258 (NH), -133, -154, -54, -49, 5, 12 (NO₂) ppm. IR: ν = 3223, 2975, 1652, 1521, 1352, 1023 cm^-1. MS: m/z = 281 [M + 1]. Anal. Calcd for C₇H₄N₈O₃S: C, 30.00; H, 1.44; N, 39.99. Found: C, 30.11; H, 1.48; N, 40.05.
Compound 3b: ¹H NMR (200 MHz, DMSO): δ = 1.30 (t, J = 8.1 Hz, 3 H, CH₃), 2.37 (s, 3 H, SCH₃), 4.14 (q, J = 8.1 Hz, 2 H, CH₂), 7.03 (dd, J _{2 ′,4 ′} = 1.1 Hz, J _{3 ′,4 ′} = 7.4 Hz, 1 H, H_{4 ′}), 7.43 (dd, J _{2 ′,3 ′} = 7.9 Hz, J _{3 ′,4 ′} = 7.4 Hz, 2 H, H_{3 ′} and H_{5 ′}), 7.93 (dd, J _{2 ′,4 ′} = 1.1 Hz, J _{2 ′,3 ′} = 7.9 Hz, 2 H, H_{2 ′} and H_{6 ′}), 11.43 (br s, 1 H, NH) ppm. ¹³C NMR (50 MHz, DMSO): δ = 12.1 (CH₃), 14.07 (CH₃), 62.0 (CH₂), 122.9 (C_{4 ′}), 123.5 (C_{2 ′} and C_{6 ′}), 126.6 (C_{3 ′} and C_{5 ′}), 140.5 (C₆), 149.4 (C_{1 ′}), 155.6 (C₅), 163.8 (C=O), 188.1 (C₃) ppm. IR: ν = 3188, 2932, 1726, 1663 cm^-1. MS: m/z = 291 [M + 1]; mp 85-87 °C. Anal. Calcd for C₁₃H₁₄N₄O₂S: C, 53.78; H, 4.86; N, 19.30. Found: C, 54.01; H, 4.54; N, 19.12.