反应详情

A solution of 4-bromomethyl-2'-nitro-1,1'-biphenyl (7.27 g, 24.8 mmol) in acetic acid (50 mL) was treated with potassium acetate (4.88 g, 49.1 mmol). The reaction mixture was heated at reflux for 2 hours. After cooling, the reaction mixture was filtered and the precipitate was washed with acetic acid (2×). The filtrate was evaporated under vacuum and the residue was triturated with ethyl ether. The ether layer was washed consecutively with water, saturated aqueous sodium bicarbonate (3×) and water. The organic layer was dried over magnesium sulfate, filtered and evaporated under vacuum. The residue was dissolved in methanol (50 mL) and treated with a 6 N methanolic potassium hydroxide solution (5 mL). After stirring for 1 hour at room temperature, thin layer chromatography indicated the absence of starting material. The reaction mixture was acidified with acetic acid and evaporated under vacuum. The residue was washed free of acetic acid by washing an etheral solution with aqueous sodium bicarbonate and water. After drying over magnesium sulfate, the ethereal solution was evaporated under vacuum. The residue was purified by preparative high pressure liquid chromatography on silica gel, eluting with hexanethyl acetate (3:1) to give 2'-nitro-1,1'-biphenyl-4-carboxaldehyde (620 mg) followed by 4-hydroxymethyl-2'-nitro-1,1'-biphenyl (3.06 g, 13.4 mmol, 54%).

1. temperatureThe reaction mixture was heated
2. temperatureat reflux for 2 hours
3. temperatureAfter cooling
4. filtrationthe reaction mixture was filtered
5. washthe precipitate was washed with acetic acid (2×)
6. customThe filtrate was evaporated under vacuum
7. customthe residue was triturated with ethyl ether
8. washThe ether layer was washed consecutively with water, saturated aqueous sodium bicarbonate (3×) and water
9. dry with materialThe organic layer was dried over magnesium sulfate
10. filtrationfiltered
11. customevaporated under vacuum
12. dissolutionThe residue was dissolved in methanol (50 mL)
13. additiontreated with a 6 N methanolic potassium hydroxide solution (5 mL)
14. customevaporated under vacuum
15. washThe residue was washed free of acetic acid
16. washby washing an etheral solution with aqueous sodium bicarbonate and water
17. dry with materialAfter drying over magnesium sulfate
18. customthe ethereal solution was evaporated under vacuum
19. customThe residue was purified by preparative high pressure liquid chromatography on silica gel
20. washeluting with hexanethyl acetate (3:1)