反应详情

To a stirred suspension of 4-chlorobenzoic acid (31.3 g, 200 mmol) in toluene (200 mL) was added oxalyl chloride (30 mL, 350 mmol) followed by DMF (0.1 mL). The resulting suspension was heated at reflux until all solids dissolved. The solvent was removed under reduced pressure by rotary evaporation. The resulting semi-solid residue was dissolved in ethyl acetate (200 mL) and cooled in an ice bath under nitrogen with mechanical stirring. A solution of tert-butylamine (53 mL, 500 mmol) in ethyl acetate (50 mL) was carefully added to the mixture dropwise keeping the internal temperature below 10° C. During addition the initially clear solution became thick colorless slurry. Ethyl acetate (50 mL) was added followed by sat. aq. NaHCO3 (300 mL) and the resulting mixture was stirred until two clear layers resulted. The biphasic mixture was transferred into a separatory funnel, and the organic layer was separated. The organic layer was then washed with water (100 mL), brine (100 mL), and dried over anhydrous Na2SO4. Recrystallization from ethyl acetate/hexanes afforded N-tert-butyl-4-chlorobenzamide (35.5 g, 84% yield) as colorless needles (mp 136-137° C.).

1. temperatureThe resulting suspension was heated
2. temperatureat reflux until all solids
3. dissolutiondissolved
4. customThe solvent was removed under reduced pressure by rotary evaporation
5. dissolutionThe resulting semi-solid residue was dissolved in ethyl acetate (200 mL)
6. temperaturecooled in an ice bath under nitrogen with mechanical stirring
7. customthe internal temperature below 10° C
8. additionDuring addition the initially clear solution
9. customresulted
10. customThe biphasic mixture was transferred into a separatory funnel
11. customthe organic layer was separated
12. washThe organic layer was then washed with water (100 mL), brine (100 mL)
13. dry with materialdried over anhydrous Na2SO4
14. customRecrystallization from ethyl acetate/hexanes