A Facile Synthesis of N-Alkoxyacylimidoyl Halides from α-Nitro Ketones and Alkyl Halides in the Presence of NaHSO₄/SiO₂

Abstract

A novel method was developed for the synthesis of N-alkoxyacylimidoyl halide by the reaction of α-nitro ketone and alkyl halides in the presence of NaHSO₄/SiO₂. Nitrile oxides that are generated from α-nitro ketones by silica gel supported acid catalysts are the possible intermediate, which react with alkyl halides to form N-alkoxyacylimidoyl halides. Novel 17 N-alkoxyacylimidoyl halides were synthesized by this procedure.

Key words

alkoxyacylimidoyl halide - nitrile oxide - solid acid - one pot - stereoselective

• References and Notes

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• 22 Typical Procedure for the Synthesis of N-Alkoxyacylimidoyl Halide: A mixture of α-nitro ketone 1 (1 mmol), alkyl halide 2 (6 mmol) and NaHSO₄/SiO₂ (2.1 mmol/g, 0.5 g) in toluene (10 mL) was stirred at 80 °C for 8 h, and then the used supported reagent was removed by filtration. The filtrate was evaporated to leave the crude product, which was purified by column chromatography (hexane–EtOAc) to obtain N-alkoxyacylimidoyl halide 3 (see Supporting Information). Typical Data for Representative Compound; N-Diphenylmethyloxy(benzoylformimidoyl Bromide) (3ag): white solid; mp 71–72 °C (n-hexane). ¹H NMR (400 MHz, CDCl₃): δ = 7.62–7.64 (m, 2 H), 7.49–7.53 (m, 1 H), 7.34–7.42 (m, 10 H), 7.24–7.28 (m, 2 H), 6.46 (s, 1 H). ¹³C NMR (100 MHz, CDCl₃): δ = 183.6, 139.6, 134.2, 133.5, 131.1, 130.9, 128.6, 128.3, 128.1, 127.5, 89.2. IR (neat): 1665, 1559 cm^–1. HRMS (ESI, MeOH): m/z [M + Na] calcd for C₂₁H₁₆NO₂NaBr: 416.0262; found: 416.0264. Anal. Calcd for C₂₁H₁₆NO₂Br: C, 63.97; H, 4.09; N, 3.55. Found: C, 64.06; H, 3.95; N, 3.53.