反应详情

A solution of 14.3g (80.21 mmol) of 4,4-dimethylthiochroman (Compound 61) and 6.76g (86.12 mmol) of acetyl chloride in 65 ml benzene was cooled in an ice bath and treated dropwise with 26.712g (102.54 mmol) of stannic chloride. The mixture was stirred at room temperature for 12 hours, then treated with 65 ml water and 33 ml conc. hydrogen chloride and heated at reflux for 0.5 hours. After being cooled to room temperature, the organic layer was separated and the aqueous layer extracted with 5×50 ml benzene. The recovered organic fractions were combined and washed with 5% sodium carbonate, water, saturated NaCl and then dried (MgSO4). The solvent was removed in vacuo and the residue purified by flash chromatography (silica; 5% ethyl acetate in hexanes) followed by kugelrohr distillation (150 degrees C., 0.7 mm) to give the title compound as a pale yellow oil. PMR (CDCl3) & 1.35 (6H, s), 1.92-1.98 (2H, m) 2.54 (3H, s), 3.02-3.08 (2H, m), 7.13 (1H, d, J~8.6 Hz), 7.58 (1H, dd, J~8.6 Hz, Hz), 7.99 (1H, d, J~2Hz).

1. temperatureheated
2. temperatureat reflux for 0.5 hours
3. temperatureAfter being cooled to room temperature
4. customthe organic layer was separated
5. extractionthe aqueous layer extracted with 5×50 ml benzene
6. washwashed with 5% sodium carbonate, water, saturated NaCl
7. dry with materialdried (MgSO4)
8. customThe solvent was removed in vacuo
9. customthe residue purified by flash chromatography (silica; 5% ethyl acetate in hexanes)
10. distillationfollowed by kugelrohr distillation (150 degrees C., 0.7 mm)