One Step Synthesis of γ-Chlorobutyrolactones via Thionyl Chloride Re-Investigated Action on γ-Ketoacids

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• All NMR spectra were taken on an AC 200 Bruker machine (200 MHz) in CDCl3, and the chemical shifts are expressed as δ ppm. For a typical experimental sequence for the preparation of 3, 4 and 5, see ref.5. 4: 1H: 2.96 (2H, s), 2.82 (4H, s), 1.58 (2H, quad., J=7.5Hz), 0.87 (3H, t, J=7.5Hz). 13C: 215.86, 176.40, 57.10, 37.98, 35.52, 28.16, 8.29. Typical experiment for the preparation of 6, 7, and 8: A solution of γ-diketoacid (3) (170 mg, 1 mmol) in thionyl chloride (5 mL) was refluxed for 15 min (or left overnight at room temperature). The yellow solution was concentrated in vacuo, and the resulting residue flash-chromatographed (silica gel; ethyl acetate/hexane - 15/85) to afford the corresponding γ-chlorobutyrolactone as a white solid (160 mg, 85%). 6: 1H: 3.02—2.45 (6H,m), 1.33 (3H, s); 13C: 213.65, 171.58, 109.12, 57.32, 36.39, 35.28, 34.40, 17.83. 7: 1H: 3.04—2.44 (4H, m), 2.01 (1H, sextet, J=7.5Hz), 1.79 (1H, sextet, J=7.5Hz), 0.96 (3H, t, J=7.5Hz); 13C: 213.51, 171.58, 109.11, 61.41, 35.84, 35.40, 35.23, 25.96, 8.95; IR (CHCl3) hμ (cm−1): 1818, 1733; EI-MS m/z (I%): M+ 188 (25), 152 (11), 125 (100), 124 (14), 110 (16), 69 (42). 8: 1H: 3.35 (1H, d, J=17Hz), 2.78 (1H, d, J=15Hz), 2.65—2.43 (4H, cm), 1.98—1.92 (1H, cm), 1.83—1.72 (1H, cm), 1.48 (3H, s); 13C: 207.01, 172.58, 110.28, 60.49, 37.02, 35.81, 35.78, 20.50, 20.45. 9: PCl5 (2 eq.), Et2O, RT, 12h, microdistillation, 90%. 1H: 3.44 (2H, s), 2.86 (4H, s), 1.61 (2H, quad., J=7.5Hz), 0.89 (3H, t, J=7.5Hz); 13C: 214.06, 173.83, 58.09, 49.97, 35.41, 28.06, 8.14; IR (neat) hμ (cm−1): 1800, 1725. 10: MeOH, reflux, 3h, 95%. 1H: 3.60 (4H, s), 2.96—2.73 (5H, m), 1.55 (2H, quad., J=7.5Hz), 0.83 (3H, t, J=7.5Hz); 13C: 216.24, 172.13, 57.13, 52.21, 38.72, 35.65, 28.27, 8.34. 11: BnNH2 (2.2 eq.), THF, reflux, lh, flash-chromatog. silica-AcOEt/Hexane : 25/75, 84%. 1H: 7.35—7.17 (5H, m), 5.47 (1H, s), 4.74 (1H, d, J=15.5Hz), 4.14 (1H, d, J=15.5Hz), 2.64 (1H, d, J=17Hz), 2.33 (1H, d, J=17Hz), 2.30—1.56 (6H, m), 0.90 (3H, t, 7.5Hz); 13C: 218.00, 175.30, 137.44, 57.21, 42.46, 37.23, 35.13, 28.84, 23.63, 8.93.
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