反应详情

Anhydrous ethanol (460 mL) and sodium (0.57 g, 25 mmol, 0.1 eq) were added to a round bottom flask and stirred under argon until all of the sodium disappeared. 4-nitrobenzonitrile (38.0 g, 257 mmol, 1.0 eq) was then added. The suspension was stirred for 15 h at room temperature under argon. 1,3-diamino-2-methylpropane (22.0 g, 249 mmol, 0.97 eq) was added. The mixture was heated to reflux for 4 days. After removal of the solvent under reduced pressure, the resulting red residue was mixed with ethyl acetate (800 mL) and extracted with 2N HCl (3×200 mL). The combined aqueous mixture was washed with ethyl acetate (250 mL) and the organic layer was removed. The acidic aqueous mixture was basified with solid Na2CO3 and then 5N NaOH until pH was 13. The emulsion was extracted with ethyl acetate (1×400 mL, 2×250 mL). The combined organic layers were washed with brine (400 mL) and then dried over Na2SO4. Upon concentrating, compound 3 was obtained as a yellow solid (12.8 g, 23% yield).

1. temperatureThe mixture was heated
2. temperatureto reflux for 4 days
3. customAfter removal of the solvent under reduced pressure
4. additionthe resulting red residue was mixed with ethyl acetate (800 mL)
5. extractionextracted with 2N HCl (3×200 mL)
6. washThe combined aqueous mixture was washed with ethyl acetate (250 mL)
7. customthe organic layer was removed
8. extractionThe emulsion was extracted with ethyl acetate (1×400 mL, 2×250 mL)
9. washThe combined organic layers were washed with brine (400 mL)
10. dry with materialdried over Na2SO4
11. concentrationUpon concentrating