反应详情

Lithium ethoxide (1.0 M in ethanol, 15.0.mL, 15 mmol) was added to a stirred suspension of 3,5-bis[(3,5-di-tert-butylphenyl)vinyl]benzaldehyde (A) (WO99/9921935) (4.00 g, 7.48 mmol) and 4-methylbenzylphosphoniumchloride (8) (3.62 g, 8.98 mmol) in diethyl ether (40 mL), giving a clear orange solution which was stirred at room temperature for 2 h. The solution was washed with water (3×40 mL) and brine (40 mL), dried over anhydrous magnesium sulphate, filtered and the solvent removed, This residue was passed through a plug of silica with dichloromethane—light petroleum (1:4) as eluent to give a white solid, which was found by 1H NMR to be mainly cis isomer. The solid was heated with iodine (210 mg) and toluene (100 mL) at 100° C. under argon for 6 h and allowed to cool. The solution was washed with saturated aqueous sodium metabisulphite (50 mL) and brine (50 mL) and the solvent removed. The residue was recrystallised from a dichloromethane—hexanes mixture to leave 4-({3,5-bis[(3,5-di-tert-butylphenyl)vinyl]phenyl}vinyl)toluene (9) (3.00 g, 64%) as a white solid. δH(400 MHz, CDCl3) 1.40 (36 H, s, t-butyl), 2.39 (3 H, s, CH3), 7.13 and 7.22 (2 H, d, J 16, core vinyl H), 7.17 and 7.28 (4 H, d, J 16, branch vinyl H), 7.21 and 7.48 (4 H, AA′BB′, core phenyl H), 7.39 (2 H, dd, J 1.5, sp H), 7.43 (4 H, d, J 1.5, sp H), 7.59 (2 H, d, J 1, bp H) and 7.62 (1 H s, bp H).

1. customgiving a clear orange solution which
2. washThe solution was washed with water (3×40 mL) and brine (40 mL)
3. dry with materialdried over anhydrous magnesium sulphate
4. filtrationfiltered
5. customthe solvent removed
6. customto give a white solid, which
7. temperatureto cool
8. washThe solution was washed with saturated aqueous sodium metabisulphite (50 mL) and brine (50 mL)
9. customthe solvent removed
10. customThe residue was recrystallised from a dichloromethane—hexanes mixture