反应详情

温度

55 °C

Copper (II) acetate monohydrate (3.70 g, 0.05 eq) and bis-camphorethylenediamine (N1,N2-bis[(1R,2R,4R)-1,7,7-trimethylbicyclo[2.2.1]hept-2-yl]-1,2-ethanediamine) (7.38 g, 0.06 eq) were charged to a reactor, followed by ethanol (200 mL, 2 vol). The contents were heated to 50-60° C. for ˜1 h or until all solids dissolved, then cooled to room temperature and stirred, at which time a solution of 3-({3-[(phenylmethyl)oxy]propyl}oxy)benzaldehyde in ethanol (100 g, 1 eq in 50 mL, 0.5 vol) was charged. The reaction mixture was cooled to −10° C. to −20° C., whereupon nitromethane (112.7 g, 5 eq) was added slowly to the reaction, maintaining a temperature below −10° C., followed by diisopropylethylamine (1.94 mL, 1.44 g, 0.03 eq). The reaction temperature was maintained at −10° C. for ˜22-30 h. When the reaction was complete, a room temperature solution of 1 N HCl (250 mL, 2.5 vol) and t-butyl methyl ether (TBME, 500 mL, 5 vol) were charged to the reaction vessel. Following the addition, the contents were stirred for ˜5 minutes and brought to 20° C. (˜room temperature), and then the layers were allowed to separate and the aqueous phase removed. The organic phase was then washed 2× with water (250 mL, 2.5 vol) and each time the aqueous phase removed. TBME was then distilled off and replaced with absolute ethanol.

1. dissolutiondissolved
2. temperaturecooled to room temperature
3. additionwas charged
4. additionwas added slowly to the reaction
5. temperaturemaintaining a temperature below −10° C.
6. temperatureThe reaction temperature was maintained at −10° C. for ˜22-30 h
7. customwas complete, a room temperature
8. additionwere charged to the reaction vessel
9. additionthe addition
10. custombrought to 20° C.
11. custom(˜room temperature)
12. customto separate
13. customthe aqueous phase removed
14. washThe organic phase was then washed 2× with water (250 mL, 2.5 vol)
15. customeach time the aqueous phase removed
16. distillationTBME was then distilled off