A Facile 1,2-Acetoxychlorination Reaction of Olefins by Using the N,N-Dimethylacetamide/Hydrogen Chloride/M-Chloroperbenzoic Acid (or Oxone) System

Abstract

Various alkenes underwent 1,2-acetoxychlorination by N,N-dimethylacetamide (DMA)/HCl/m-CPBA (or Oxone) system in good yields.

Notes

¹H NMR Data of Products. 1-Acetoxy-2-chloro-1-phenylethane (Entry 1): ¹H NMR (CDCl₃) δ 2.12 (s, 3H), 3.60–3.82 (m, 2H), 5.95 (dd, J=4.85, 7.61 Hz, 1H), 7.35 (s, 5H). 1-Acetoxy-2-chlorocyclohexane (Entry 2): ¹H NMR (CDCl₃) δ 1.18–1.52 (m, 4H), 1.55–1.85 (m, 4H), 2.00 (s, 3H), 3.75 (dt, J=5.10, 9.72 Hz, 1H), 4.71 (dt, J=4.55, 9.10 Hz, 1H). 1-Acetoxy-2-chlorocycloheptane (Entry 2): ¹H NMR (CDCl₃) δ 1.45–1.96 (m, 10H), 2.03 (s, 3H), 4.02 (dt, J=3.88, 7.94 Hz, 1H), 4.95 (dt, J=3.87, 7.86 Hz, 1H). 2-Acetoxy-1-chlorohexane and 1-Acetoxy-2-chlorohexane (Entry 4): ¹H NMR (CDCl₃) δ 0.78–0.95 (m, 3H), 1.17–1.48 (m, 4H), 1.52–1.78 (m, 2H), 2.01 (s, 0.7H), 2.02 (s, 0.3H), 3.44–3.65 (m, 1.4H), 3.93–4.08 (m, 0.3H), 4.15 (m, 0.6H), 4.92–5.08 (m, 0.7H). 2-Acetoxy-1-chloro-3-(2-ethoxycarbonyloxyphenyl)propane (Entry 5): ¹H NMR (CDCl₃) δ 1.29 (t, J=7.27 Hz, 3H), 1.98 (s, 3H), 2.89–2.95 (m, 2H), 3.42 (dd, J=5.03, 11.79 Hz, 1H), 3.55 (dd, 4.43, 11.79 Hz, 1H), 4.26 (q, J=7.13 Hz, 2H), 5.12 (m, 1H), 7.05–7.26 (m, 4H). 1-Acetoxy-2-chloro-3-(2-ethoxycarbonyloxyphenyl)propane (Entry 5): ¹H NMR (CDCl₃) δ 1.29 (t, J=5.44 Hz), 2.00 (s, 3H), 2.95 (dd, J=7.53, 14.13 Hz, 1H), 3.08 (dd, J=5.87, 14.23 Hz, 1H), 4.12–4.28 (m, 5H), 7.09–7.28 (m, 4H). 2-Chloro-1,3-diacetoxy-1-phenylpropane (Entry 6): ¹H NMR (CDCl₃) δ 1.98 (s, 3H), 2.04 (s, 1H), 2.06 (s, 2H), 3.88–4.35 (m, 3H), 5.94 (d, J=6.28 Hz, 1H), 7.20–7.31 (m, 5H).