反应详情

Sodium hydride (79.6 mg, 1.99 mmol, 60% dispersion in mineral oil) was washed with n-hexane (3×2 mL). Dimethyl sulfoxide (2 mL) was introduced via a syringe and the mixture was heated at 75° C. until the evolution of hydrogen ceased. The clear solution was cooled in an ice-water bath and a solution of the n-decylphosphonium bromide (874 mg, 1.99 mmol) in DMSO (4 mL) was added dropwise. The resulting solution was stirred at room temperature for 15 minutes. A solution of the bromobenzophenone, 5,5'dibromo-2,2'-dimethoxy-3,3'dicarbomethoxybenzophenone, (642 mg, 1.24 mmol) in warm DMSO (5 mL) was added dropwise and the reaction mixture heated at 55° C. for 22 hours. It was cooled in an ice-water bath. A solution of ammonium chloride (200 mg) in water (5 mL) was added and the reaction mixture was extracted with ethyl ether (5×5 mL). The organic extracts were washed twice with brine, dried over sodium sulfate, and evaporated in vacuo. A flash chromatography on silica gel (230-400 mesh), elution with n-hexane/ethyl acetate, 4:1, yielded decene, 1,1-[di(5'-bromo-2'-methoxy-3'-methoxycarbonyl) phenyl]-1-undecene, (466 mg, 64%) as an oil: IR (KBr) 3072, 2925, 2853, 1736, 1570, 1436, 1285, 1253, 1195, 1164, 1149, 1006 cm- 1 ; 1H NMR (CDCl3, 200 MHz) δ7.88 (d, J=2.5 Hz, 1H), 7.79 (d, J =2.5 Hz, 1H), 7.55 (d, J=2.5 Hz, 1H), 7.50 (d, J=2.5 Hz, 1H), 6.07 (t, J=7.3 Hz, 1H), 3.88 (s, 3H), 3.87 (s, 3H), 3.52 (s, 3H), 3.49 (s, 3H), 2.09 (m, 2H), 1.26 (m, 14H), 0.88 (t, J=6.3 Hz, 3H); CIMS m/e (relative intensity) 641 (MH+, 4), 609 (MH+ -MeOH, 100).

1. temperatureThe clear solution was cooled in an ice-water bath
2. temperaturethe reaction mixture heated at 55° C. for 22 hours
3. temperatureIt was cooled in an ice-water bath
4. extractionthe reaction mixture was extracted with ethyl ether (5×5 mL)
5. washThe organic extracts were washed twice with brine
6. dry with materialdried over sodium sulfate
7. customevaporated in vacuo
8. washA flash chromatography on silica gel (230-400 mesh), elution with n-hexane/ethyl acetate, 4:1