反应详情

A suspension of 5-nitrobenzo[b]thiophene-2-carboxylic acid ethyl ester (2.5 g, 10 mmol) and 10% palladium on carbon (250 mg) in ethanol (100 mL) was stirred at room temperature under an atmosphere of hydrogen for 16 h. The mixture was filtered through a pad of celite which was subsequently washed with dichloromethane (3×50 mL). The combined filtrates were concentrated under reduced pressure to give a colourless oil that was suspended in methanol (25 mL). To this mixture was added a 37% aqueous solution of formaldehyde (2.1 mL, 25.9 mmol). To this mixture was added at 0° C. a solution of sodium cyanoborohydride (2.2 g, 35 mmol) and zinc chloride (2.35 g, 17 mmol) in methanol (140 mL). The mixture was stirred at room temperature for 16 hours then concentrated under reduced pressure. The residue was taken up in ethyl acetate (150 mL) and aqueous solution of sodium hydroxide (100 mL, 2M). The organic layer was washed with aqueous sodium hydroxide (100 mL), distilled water (2×100 mL) and brine (3×50 mL), dried over anhydrous MgSO4, filtered and concentrated under reduced pressure to give an oil that was purified by flash chromatography (20:80:1 diethyl ether:40-60° C. petroleum ether:triethylamine) to give a solid that was recrystallised from ethanol to give the title compound (1.0 g, 60%) as a solid, mp 95-96° C.

1. filtrationThe mixture was filtered through a pad of celite which
2. washwas subsequently washed with dichloromethane (3×50 mL)
3. concentrationThe combined filtrates were concentrated under reduced pressure
4. customto give a colourless oil that
5. stirringThe mixture was stirred at room temperature for 16 hours
6. concentrationthen concentrated under reduced pressure
7. washThe organic layer was washed with aqueous sodium hydroxide (100 mL)
8. distillationdistilled water (2×100 mL) and brine (3×50 mL)
9. dry with materialdried over anhydrous MgSO4
10. filtrationfiltered
11. concentrationconcentrated under reduced pressure
12. customto give an oil that
13. customwas purified by flash chromatography (20:80:1 diethyl ether:40-60° C. petroleum ether:triethylamine)
14. customto give a solid
15. customthat was recrystallised from ethanol