反应详情

To 4-(3-cyclopentyloxy-4-methoxyphenyl)-1,1-(ethylenedioxy)-4-(3-nitrophenylethynyl)cyclohexane (0.17 g, 0.35 mmol) in methanol (1 mL), acetic acid (1.2 mL) and water (1.2 mL) under an argon atmosphere was added titanium trichloride (0.3 g, 2 mmol). After stirring for 1.5 h at room temperature, titanium trichloride (0.3g, 2 mmol) and water (1.2 mL) were added, and the mixture was stirred for 0.5 h at room temperature and for 0.5 h at 45°-50°C., then was cooled to room temperature. Water (1.2 mL) and ammonium hydroxide (2.5 mL) were added. After stiinng an additional 1 h, methanol (17.5 mL), 5% sodium carbonate (17.5 mL) and dichloromethane (35 mL) were added, and stirring was continued for 2 h. The suspension was filtered through Celite®, was washed well with dichloromethane and the extract was evaporated. The residue was diluted with dichloromethane, the organic layer was washed with 5:95 ammonium hydroxide:water, was dried (potassium carbonate) and was evaporated. Purification by flash chromatography, eluting with 3:7 ethyl acetate:hexanes, provided a mixture of 4-(3-cyclopentyloxy-4-methoxyphenyl)-4-(3-anminophenylethynyl)-cyclohexan-1-one and 4-(3-cyclopentyloxy-4-methoxyphenyl)-1,1-(ethylenedioxy)-4-(3-aminophenylethynyl)cyclohexane (0.07 g). This mixture and a spatula-tip of pyridinium p-toluenesulfonate in acetone (4 mL) and water (1 mL) was refluxed for 3 days, then was evaporated. Water was added, the mixture was extracted three times with dichloromethane, the extract was dried (magnesium sulfate) and was evaporated. Purification by flash chromatography, eluting with 35:65 ethyl acetate:hexanes provided 4-(3-cyclopentyloxy-4-methoxyphenyl)-4-(3-aminophenylethynyl)cyclohexan-1-one as a colorless oil. 1H-NMR (400 MHz, CDCl3) δ 7.22 (d, J=2.2 Hz, 1H), 7.14 (m, 2H), 6.87 (m, 2H), 6.82 (d, J=2.8 Hz, 1H), 6.66 (dd, J=9.0, 2.4 Hz, 1H), 4.81 m, 1H), 3.85 (s, 3H), 3.7 (br, 2H), 3.04 (dt, J=14.3, 6.0 Hz, 2H), 2.47 (br d, J=14.6 Hz, 2H), 2.2-2.3 (m, 4), 1.8-2.0 (m, 6H), 1.61 (m, 2H).

1. stirringthe mixture was stirred for 0.5 h at room temperature and for 0.5 h at 45°-50°C.
2. temperaturewas cooled to room temperature
3. waitAfter stiinng an additional 1 h
4. stirringstirring
5. waitwas continued for 2 h
6. filtrationThe suspension was filtered through Celite®
7. washwas washed well with dichloromethane
8. customthe extract was evaporated
9. additionThe residue was diluted with dichloromethane
10. washthe organic layer was washed with 5:95 ammonium hydroxide
11. dry with materialwater, was dried (potassium carbonate)
12. customwas evaporated
13. customPurification by flash chromatography
14. washeluting with 3:7 ethyl acetate
15. customhexanes, provided
16. customwas evaporated
17. additionWater was added
18. extractionthe mixture was extracted three times with dichloromethane
19. dry with materialthe extract was dried (magnesium sulfate)
20. customwas evaporated
21. customPurification by flash chromatography
22. washeluting with 35:65 ethyl acetate