反应详情

温度

-5 °C

To a solution of 3-nitrobenzaldehyde (200 g, 1.32 mol) and chloroform (238 ml, 2.97 mol) in 800 ml of DMF cooled to -9° C. under nitrogen was added dropwise a solution of potassium hydroxide (59.8 g, 0.92 mol) in 180 ml of methanol over a 2.7 hour period. The deep purple reaction mixture was aged for 2 hours at -8° C. before quenching over 40 minutes into 1.8 liter of lN HCl and 1.8 liter of toluene cooled to -5° C. The quench mixture was stirred and cooled for an additional 0.5 hour and then brought to ambient temperature. The toluene layer was separated and washed twice with 1.8 liter of water. After treatment with 35 g of Darco G-60 charcoal for 1 hour and filtration through Super-Cel, the organic layer was washed with 1.8 liter of aqueous 5% sodium bicarbonate solution and then 1.8 liter of water. After evaporation to 550 ml the desired product was crystallized by the addition of 450 ml of hexanes. The resulting slurry was cooled at 0° C. for 2 hours and the solid was collected by filtration and rinsed with hexanes. After drying, 320 g (90% yield) of TMBA was obtained; m.p. 91- 95° C; 1H NMR 3.75 (1H, d, J=1 Hz), 5.25 (1H, d, J=1 Hz), 7.20-8.45 (5H, m).

1. custombefore quenching over 40 minutes into 1.8 liter of lN HCl and 1.8 liter of toluene
2. temperaturecooled for an additional 0.5 hour
3. custombrought to ambient temperature
4. customThe toluene layer was separated
5. washwashed twice with 1.8 liter of water
6. waitAfter treatment with 35 g of Darco G-60 charcoal for 1 hour
7. filtrationfiltration through Super-Cel
8. washthe organic layer was washed with 1.8 liter of aqueous 5% sodium bicarbonate solution
9. customAfter evaporation to 550 ml the desired product
10. customwas crystallized by the addition of 450 ml of hexanes
11. temperatureThe resulting slurry was cooled at 0° C. for 2 hours
12. filtrationthe solid was collected by filtration
13. washrinsed with hexanes
14. customAfter drying