Highly Stereoselective Nitration of Chalcone Derivatives with Nitric Oxide

Abstract

A novel nitration of chalcone derivatives with nitric ­oxide affords E-α-nitropropenones exclusively in good yield. The reaction is most likely initiated by electrophilic addition of nitric ­dioxide to the C=C double bond at the α-position.

stereoselective - nitration - chalcone - nitric oxide - E-2-nitropropenone

References and Notes

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9

Typical Procedure A stock solution was prepared by dissolving 1a (104 mg, 0.5 mmol) in anhyd CH₂Cl₂ (100 mL). NO was produced by the reaction of a 1 M H₂SO₄ solution with a sat. aq solution of NaNO₂ under an argon atmosphere (H₂SO₄ was added dropwise). NO was carried by argon and purified by passing it through a series of scrubbing bottles containing distilled water, 4 M NaOH, and CaCl₂ (in this order; bottles were kept under an argon atmosphere). Purified NO was bubbled through the stock solution, which was previously degassed with argon for
6 min. In the course of degassing, the argon flow rate was controlled by regulating the flow-meter at 0.8 Lmin^-1 and the stock solution was kept at a pressure of up to +10 mm (water column over local atmospheric pressure at 10 °C). The total amount of NO was passed through the solution estimated to be roughly 300 mmol at local atmospheric pressure using the ideal gas law. After completion of the reaction, as indicated by TLC, the reaction mixture was dried over anhyd MgSO₄, concentrated under vacuum, and purified by column chromatography on silica gel (200-300 mesh, EtOAc-PE), giving pure 2a (98 mg, 78%); mp 92 °C. IR (KBr): 3062, 2923, 1679, 1638, 1522, 1316, 1231, 947, 765, 687 cm^-1. ¹H NMR (300 MHz, CDCl₃): δ = 7.35 (m, 2 H), 7.42 (m, 3 H), 7.49 (m, 2 H), 7.63 (m, 1 H), 7.96 (m, 2 H), 8.34 (s, 1 H). ¹³C NMR (75 MHz, CDCl₃): δ = 128.9, 129.2 (2 C), 129.3, 131.0, 132.3, 133.5, 134.9, 137.3, 144.7, 188.2. MS-EI: m/z = 253 (M⁺), 191, 132, 105, 102, 77, 63. HRMS-ESI: m/z calcd for C₁₅H₁₂NO₃: 254.0812; found: 254.0811.

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