反应详情

9H-thioxanthene-9-carbonitrile [33] (1.20 g, 5.37 mmol) was dissolved in anhydrous Et2O and cooled in an icebath. n-Butyl lithium (2.14 mL, 5.37 mmol, 2.5M soln. in hexanes) was added dropwise over 10 min. with continuous stirring. Stirring was continued for 30 min. at the same temperature and then brought to room temperature. The reaction mixture was heated at reflux (1 hr), cooled in an icebath and ethyl bromo acetate (0.83 mL, 7.52 mmol) was added dropwise via syringe. The resulting mixture was heated at reflux (4 h) cooled and filtered. The residue was washed with ether (25 mL). Water (25 mL) was added to the filterate and the organic layer was separated. The aqueous layer was once again extracted with ether (25 mL). The combined ether extracts were washed with water and brine, dried (MgSO4) and evaporated under reduced pressure to give an oil which was purified by mplc using pet. ether: EtOAc (9:1) as eluent to give 0.97 g (59%) of the product as a colorless oil. 1H NMR (CDCl3)d: 1.08-1.12 (t, J=6 Hz, CH3), 3.08 (s, 2H, CH2), 3.95-4.03 (q, 2H, CH2), 7.31-8.00 (m, 8H, Ar—H). 13C NMR (CDCl3)d: 38.49, 47.63, 60.76, 118.91, 127.00, 127.24, 127.80, 128.15, 130.73, 130.98, 167.66.

1. temperaturecooled in an icebath
2. custombrought to room temperature
3. temperatureThe reaction mixture was heated
4. temperatureat reflux (1 hr)
5. additionwas added dropwise via syringe
6. temperatureThe resulting mixture was heated
7. temperatureat reflux (4 h)
8. temperaturecooled
9. filtrationfiltered
10. washThe residue was washed with ether (25 mL)
11. additionWater (25 mL) was added to the filterate
12. customthe organic layer was separated
13. extractionThe aqueous layer was once again extracted with ether (25 mL)
14. washThe combined ether extracts were washed with water and brine
15. dry with materialdried (MgSO4)
16. customevaporated under reduced pressure
17. customto give an oil which
18. customwas purified by mplc