Nitration of cyclic vinylsilanes with acetyl nitrate: effect of silyl moiety and ring size

Abstract

Reaction of AcONO₂ with common ring vinylsilanes gives the corresponding α,β-unsaturated 1-nitrocycloalkenes, and with medium and large ring vinylsilanes it produces novel 1,1-dinitro 2-nitrates.

References

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7. AcONO₂ was prepared by adding 0.375 g of conc. HNO₃(1.40 density, AR Grade, Merck) to Ac₂O (5 ml, distilled over P₂O₅); see ref. 1..
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9. Selected data for 9: mp 56–58 °C; ν_max/cm^–1 1652, 1595, 1564; δ_H(CDCl₃) 6.19 (dd, J 7.6 and 1.4, 1H), 2.94–2.63 (m, 2H), 2.45–2.30 (m, 1H), 2.12–1.99 (m, 1H), 1.89–1.77 (m, 4H), 1.59–1.44 (m, 4H); δ_C(CDCl₃) 121.5 (s), 78.7 (d), 32.3 (t), 30.6 (t), 25.9 (t), 25.8 (t), 24.8 (t), 21.8 (t); δ_O(CDCl₃) 596.3, 445.2, 352.9; m/z 264 (1%, M⁺+ 1), 171 (3), 95 (37), 81 (34), 67 (37), 55 (72), 46 (100, NO₂⁺), 41 (67)(Found: C, 36.73; H, 5.03;N, 16.01. C₈H₁₃N₃O₇ requires: C, 36.51; H, 4.98; N, 15.96%). For 10: mp 80–82 °C; ν_max/cm^–1 1667, 1595, 1569; δ_H(CDCl₃) 6.08 (d, J 9.9, 1H), 2.58–2.39 (m, 2H), 2.03–1.83 (m, 1H), 1.60–1.28 (m, 17H); δ_C(CDCl₃) 120.4, 74.9, 32.5, 26.6, 25.6, 25.0, 22.3, 22.1, 22.0, 21.8, 21.6, 19.6 (Found: C, 45.11; H, 6.81; N, 12.83. C₁₂H₂₁N₃O₇ requires: C, 45.14; H, 6.63; N, 13.16%). For 11: mp. 89–91 °C; ν_max/cm^–1 1729, 1652, 1636; δ_H(CDCl₃) 5.29 (q, J 3.3, 1H), 2.81–2.71 (m, 1H), 2.50–2.40 (m, 1H), 2.14–1.85 (m, 3H), 1.64–0.88 (m, 15H); δ_C(CDCl₃) 204.3, 85.5, 34.8, 26.2, 26.1, 25.9, 23.7, 22.6, 22.2, 21.8, 21.0, 19.2 (Found: C, 59.05; H, 8.85; N, 5.38.C₁₂H₂₁NO₄ requires: C, 59.24; H, 8.70; N, 5.76%).
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