反应详情

Commercial grade of 2-chloromethyl-1,4-benzodioxane (10.0 g, 54.7 mmol) and phthalimide potassium salt (12.0 g, 65.0 mmol) were added to N,N-dimethylformamide (350 ml) and subjected to reaction overnight under reflux; thereafter, N,N-dlmethylformamide was distilled off under vacuum. Water (250 ml) was added to the residue and the mixture was stirred well, with the floating solids being subsequently recovered by filtration. The solids were dried, then recrystallized from methanol/methylene chloride, thereby yielding (1,4-benzodioxan-2-ylmethyl)phthalimide as a colorless tabular crystal in an amount of 8.43 g. The thus obtained crystal was dissolved in ethanol (500 ml); to the solution, hydrazine hydrate (4.3 g) was added, followed by refluxing under heating for 3 h. The resulting solids were filtered off and ethanol was distilled off under vacuum, followed by addition of water (300 ml). Thereafter, an aqueous solution of 6N sodium hydroxide was added to adjust pH to 12 and the mixture was subjected to 3 cycles of extraction with methylene chloride. The methylene chloride layers were dried with anhydrous sodium sulfate, and concentrated under vacuum, thereby yielding a crude product of 2-aminomethyl-1,4-benzodioxane as a colorless oil (crude product, 4.3 g).

1. customsubjected to reaction overnight
2. temperatureunder reflux
3. distillationthereafter, N,N-dlmethylformamide was distilled off under vacuum
4. additionWater (250 ml) was added to the residue
5. filtrationbeing subsequently recovered by filtration
6. customThe solids were dried
7. customrecrystallized from methanol/methylene chloride
8. dissolutionThe thus obtained crystal was dissolved in ethanol (500 ml)
9. additionto the solution, hydrazine hydrate (4.3 g) was added
10. temperatureby refluxing
11. temperatureunder heating for 3 h
12. filtrationThe resulting solids were filtered off
13. distillationethanol was distilled off under vacuum
14. additionfollowed by addition of water (300 ml)
15. additionThereafter, an aqueous solution of 6N sodium hydroxide was added
16. extractionthe mixture was subjected to 3 cycles of extraction with methylene chloride
17. dry with materialThe methylene chloride layers were dried with anhydrous sodium sulfate
18. concentrationconcentrated under vacuum