反应详情

Using a methylation procedure described in Synthesis 144 (1978), to a stirred solution of 2.08 g (0.010 mole) of 4-hydroxy-6-nitro-1,2-benzopyrone, derived from the nitration of commercial 4-hydroxy-1,2-benzopyrone described in the Example 7, in 10 ml of anhydrous hexamethylphosphoramide (HMPA, Aldrich Chemical Co.), sodium hydride (0.24 g, 0.010 mole) is added at room temperature. After evolution of hydrogen gas is complete, dimethyl sulfate (1.51 g, 0.012 mole) in 5 ml of HMPA is added and the mixture is stirred for 1 hour and then transferred into a separatory funnel containing 100 ml of ethyl acetate. The organic layer is washed with 50 ml of 1M aqueous hydrochloric acid and then with a portion of water. After drying over sodium sulfate, the solvent is stripped off by rotary evaporation and the residue is dissolved and crystallized from hot ethanol. The methylated nitro-compound is then dissolved in methanol (500 ml) and reduced by adding it to a stirred suspension of 10% palladium catalyst on activated carbon in an aqueous solution of potassium borohydride (2.50 g, 0.046 mole) in 50 ml of water at room temperature. After 15 minutes, the mixture is filtered to remove the catalyst, stripped of solvent by rotary evaporation, and the dry residue as the amine free base crystallized from ethanol giving 4-methoxy-6-amino-1,2-benzopyrone (B).

1. customtransferred into a separatory funnel
2. washThe organic layer is washed with 50 ml of 1M aqueous hydrochloric acid
3. dry with materialAfter drying over sodium sulfate
4. customthe solvent is stripped off by rotary evaporation
5. dissolutionthe residue is dissolved
6. customcrystallized from hot ethanol
7. dissolutionThe methylated nitro-compound is then dissolved in methanol (500 ml)
8. additionby adding it
9. waitAfter 15 minutes
10. filtrationthe mixture is filtered
11. customto remove the catalyst
12. customstripped of solvent by rotary evaporation
13. customthe dry residue as the amine free base crystallized from ethanol