反应详情

温度

-20 °C

31 g (0.398 mol) of benzene was put in a 500 ml four-necked flask equipped with a stirrer, a Liebig condenser having the upper portion thereof provided with a calcium chloride tube, and a thermometer, then stirred under a nitrogen stream at 300 rpm, and then mixed with 53 g (0.398 mol) of aluminum chloride and 17.3 g of dichlorometahne at room temperature. The resulting solution was cooled to -20° C. A solution of 17.5 g (0.398 mol) of ethylene oxide in 146.5 g of dichloromethane was dropwise added to the cooled solution over 4 hours. During this dropwise addition, the temperature of the reaction system was maintained at -20° C. to -30° C. After the completion of the dropwise addition, the resulting mixture was stirred at the same temperature for 15 minutes. Thereafter, 18 g (0.282 mol) of a 47% aqueous solution of formaldehyde was added to this mixture at 5° C. over 30 minutes. The resulting mixture was heated up to a temperature of 20° C. under stirring, and then further stirred at the same temperature for 2 hours and 30 minutes. 100 g of water was carefully added dropwise to the resulting mixture at a temperature of 30° C. or below. The resulting mixture was heated up to a temperature of 40° C. under stirring, and then further stirred at the same temperature for 1 hour. The resulting reaction mixture was allowed to stand still to effect phase separation. After the removal of the lower layer, the remaining organic phase was mixed with 50 g of a 10% aqueous solution of caustic soda. The resulting mixture was stirred at 40° C. for 1 hour, and then allowed to stand still to effect phase separation. After the removal of the lower layer, the remaining organic phase was distilled to remove the solvent. Subsequently, the residue was subjected to vacuum distillation (under 20 Torr) to obtain 37.4 g (0.278 mol) of isochroman as a fraction boiling at 105 to 106.5° C. (under 20 Torr). The yield was 70%.

1. customequipped with a stirrer
2. customthereof provided with a calcium chloride tube
3. additionDuring this dropwise addition
4. temperaturethe temperature of the reaction system was maintained at -20° C. to -30° C
5. additionAfter the completion of the dropwise addition
6. stirringthe resulting mixture was stirred at the same temperature for 15 minutes
7. temperatureThe resulting mixture was heated up to a temperature of 20° C.
8. stirringunder stirring
9. stirringfurther stirred at the same temperature for 2 hours and 30 minutes
10. temperatureThe resulting mixture was heated up to a temperature of 40° C.
11. stirringunder stirring
12. stirringfurther stirred at the same temperature for 1 hour
13. customThe resulting reaction mixture
14. customphase separation
15. customAfter the removal of the lower layer
16. additionthe remaining organic phase was mixed with 50 g of a 10% aqueous solution of caustic soda
17. stirringThe resulting mixture was stirred at 40° C. for 1 hour
18. customphase separation
19. customAfter the removal of the lower layer
20. distillationthe remaining organic phase was distilled
21. customto remove the solvent
22. distillationSubsequently, the residue was subjected to vacuum distillation (under 20 Torr)