反应详情

温度

60 °C

Magnesium (4.94 g, 0.203 mol) under tetrahydrofuran (15 ml) was activated with a grain of iodine and 1,2-dibromoethane (0.4 ml). After the reaction was finished, 10% of a solution of vinylbromide (21.4 g, 0.2 mol) in tetrahydrofuran (70 ml) was added (dry ice-ethanol condenser, nitrogen atmosphere). The reaction started immediately, and the remaining part of the vinylbromide solution was added dropwise under stirring at such a rate (over 45 minutes) as to maintain the temperature at 58-62° C. The mixture was heated at reflux temperature for 30 minutes and then cooled to 30° C. Over 1 h, a solution of 2-chloro-6,11-dihydrodibenzo[b,e]thiepine (28.9 g, 0.1 mol, prepared as described in Es. farmacie 11, 451, 1962) in tetrahydrofuran (70 ml) was added dropwise under stirring (30-35° C.). The mixture was allowed to stand overnight at room temperature and then quenched under cooling (ice and sodium chloride) with a solution of ammonium chloride (21 g) in water (100 ml). Toluene (100 ml) was added, the mixture was filtered and the aqueous layer was extracted with toluene (3×100 ml). The toluene solutions were combined, dried (MgSO4) and evaporated. The residue was crystallised from a mixture of benzene (50 ml) and hexane (100 ml) to give 27.4 g (95%) of 2-chloro-11-vinyl-6,11-dihydrodibenzo[b,e]thiepin-11-ol.

1. temperatureThe mixture was heated
2. temperatureat reflux temperature for 30 minutes
3. temperaturecooled to 30° C
4. waitOver 1 h
5. stirringunder stirring (30-35° C.)
6. waitto stand overnight at room temperature
7. customquenched
8. temperatureunder cooling (ice and sodium chloride) with a solution of ammonium chloride (21 g) in water (100 ml)
9. additionToluene (100 ml) was added
10. filtrationthe mixture was filtered
11. extractionthe aqueous layer was extracted with toluene (3×100 ml)
12. dry with materialdried (MgSO4)
13. customevaporated
14. customThe residue was crystallised from a mixture of benzene (50 ml) and hexane (100 ml)