反应详情

To a solution of 4-aminophenol (3.27 g, 30.0 mmol) in dichloromethane (50 ml) were added 3,3-dimethyl-butyryl chloride (8.08 g, 60.0 mmol) and pyridine (4.85 ml, 60.0 mmol), while cooling the reaction mixture in an ice bath. After the addition was completed, the cooling bath was removed and stirring was continued overnight at room temperature. The solvent was removed by evaporation and the residue was dissolved in THF (300 ml). 6N NaOH (aq, 35 ml) was added, the mixture was stirred at room temperature overnight and the solvent was removed by evaporation. Water (200 ml) was added and the solid material is collected by filtration, washed with water, dried in vacuo at 40° C. and dissolved in methanol (100 ml). A solution of KOH (3.37 g) in methanol (50 ml) was added. After stirring for 2 days at room temperature water (300 ml) was added, the organic solvent was removed and the aqueous phase was acidified with 1 N HCl. The solids were collected and dried yielding the title compound (1.97 g, 31% yield, pink solid). The mother liquor was extracted with ethyl acetate (3×250 ml). The combined organic phases were washed with saturated sodium bicarbonate (2×250 ml), dried over sodium sulphate, filtered and evaporated yielding a second amount of the title compound (0.67 g, 10%). From the first aqueous extract another portion of product was isolated by extraction with ethyl acetate (4×250 ml). The combined organic phases were washed with water (400 ml), dried, filtered and evaporated yielding a pink thick oil. Crystallisation from ethyl acetate/heptane yielded a third amount of the title compound (2.11 g, 34%).

1. temperaturewhile cooling the reaction mixture in an ice bath
2. additionAfter the addition
3. customthe cooling bath was removed
4. customThe solvent was removed by evaporation
5. dissolutionthe residue was dissolved in THF (300 ml)
6. addition6N NaOH (aq, 35 ml) was added
7. stirringthe mixture was stirred at room temperature overnight
8. customthe solvent was removed by evaporation
9. additionWater (200 ml) was added
10. filtrationthe solid material is collected by filtration
11. washwashed with water
12. customdried in vacuo at 40° C.
13. dissolutiondissolved in methanol (100 ml)
14. additionA solution of KOH (3.37 g) in methanol (50 ml) was added
15. stirringAfter stirring for 2 days at room temperature water (300 ml)
16. additionwas added
17. customthe organic solvent was removed
18. customThe solids were collected
19. customdried