反应详情

To a 3-neck round-bottomed flask were added zinc powder (1.96 g, 30 mmol) followed by anhydrous THF (40 mL). To the stirred suspension was slowly added, via syringe, TiCl4 (1.6 mL, 2.77 g, 14.6 mmol) at room temperature. The reaction mixture was heated at reflux with stirring under a nitrogen atmosphere for 2 h. To the refluxing reaction mixture was added a solution of (4-bromophenyl)(4-hydroxyphenyl)methanone (2) (1.1 g, 3.61 mmol) and cyclohexanone (1.1 mL, 1.04 g, 10.6 mmol) in anhydrous tetrahydrofuran (40 mL). The stirred reaction mixture was heated at reflux under a nitrogen atmosphere for 2 h. The oil bath was removed and the reaction mixture was allowed to cool to room temperature. To the reaction mixture was slowly added water (24 mL) followed by 10% aqueous K2CO3 (24 mL). The reaction mixture was filtered through a pad of Celite and the pad was washed with EtOAc. The filtrate was transferred to a separatory funnel with the aid of water and EtOAc and the layers were separated. The organic phase was washed with brine, dried over MgSO4, filtered, and the filtrate was concentrated in vacuo to give the crude product. The crude product was purified by flash chromatography on silica gel with hexanes:EtOAc (100:0 to 60:40) to give 1.17 g (95%) of compound 6 as an off-white solid. 1H NMR (400 MHz, DMSO-d6): δ 1.52 (m, 6H), 2.12 (m, 4H), 6.65 (d, J=8.4 Hz, 2H), 6.82 (d, J=8.4 Hz, 2H), 6.97 (d, J=8.3 Hz, 2H), 7.44 (d, J=8.3 Hz, 2H), 9.32 (s, 1H). HRMS (EI) Calcd for C19H19BrO: 342.0619 (M+). Found: 342.0627.

1. additionTo the stirred suspension was slowly added, via syringe
2. customat room temperature
3. temperatureThe reaction mixture was heated
4. temperatureat reflux
5. customTo the refluxing reaction mixture
6. customThe stirred reaction mixture
7. temperaturewas heated
8. temperatureat reflux under a nitrogen atmosphere for 2 h
9. customThe oil bath was removed
10. filtrationThe reaction mixture was filtered through a pad of Celite
11. washthe pad was washed with EtOAc
12. customThe filtrate was transferred to a separatory funnel with the aid of water and EtOAc
13. customthe layers were separated
14. washThe organic phase was washed with brine
15. dry with materialdried over MgSO4
16. filtrationfiltered
17. concentrationthe filtrate was concentrated in vacuo
18. customto give the crude product
19. customThe crude product was purified by flash chromatography on silica gel with hexanes:EtOAc (100:0 to 60:40)