反应详情

温度

75 °C

To a suspension of sodium sulfide (3.26 g, 41.8 mmol) in DMF (42 mL) was added a solution of 3-chloro-4,4-dimethylpent-2-enenitrile (6.0 g, 41.8 mmol, Ohta, H.; Ishizaka, T.; Tatsuzuki, M.; Yoshinaga, M.; Iida, I.; Yamaguchi, T.; Tomishima, Y.; Futaki, N.; Toda, Y.; Saito, S. Bioorg. Med. Chem., 2008, 16, 1111-1124) in DMF (21 mL) at rt for 5 min and stirred the mixture at 70-80° C. for 2 h. Then chloroacetonitrile (5.3 mL, 83.6 mmol) was added dropwise to the reaction mixture and again stirred at 70-80° C. for 2 h. Then, a solution of sodium methoxide (2.26 g, 41.8 mmol) in dry methanol (42 mL) was added dropwise and stirring was continued for 2 h at the same temperature. The mixture was allowed to rt and poured into cold water and stirred for 30 min. The solution was extracted with chloroform (3×100 mL) and the combined chloroform layer was washed with water, brine and dried over sodium sulfate. The solution was filtered and evaporated the solvent. The residue was chromatographed over silica gel column using hexane-EtOAc (90:10) as eluent to give the product as a pale brown color solid (4.9 g, 65%), mp 118-122° C. 1H NMR (400 MHz, CDCl3): δ 6.32 (1H, s), 4.37 (2H, br s), 1.33 (9H, s); LC-MS (negative ion mode): m/z 179 (M−H)−.

1. stirringagain stirred at 70-80° C. for 2 h
2. stirringstirring
3. waitwas continued for 2 h at the same temperature
4. customwas allowed to rt
5. stirringstirred for 30 min
6. extractionThe solution was extracted with chloroform (3×100 mL)
7. washthe combined chloroform layer was washed with water, brine
8. dry with materialdried over sodium sulfate
9. filtrationThe solution was filtered
10. customevaporated the solvent
11. customThe residue was chromatographed over silica gel column