Hydrochloric Acid → Ethyl 4-(4-nitro-3-phenyl-butyrylamino)benzoate

Reaktionsgleichung

[C:1]1([CH:7]=[CH:8][C:9]([NH:11][C:12]2[CH:21]=[CH:20][C:15]([C:16]([O:18][CH3:19])=[O:17])=[CH:14][CH:13]=2)=[O:10])[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.[CH2:22]1CCN2C(=NCCC2)CC1.Cl.[N+:34]([CH3:37])([O-:36])=[O:35]>>[N+:34]([CH2:37][CH:7]([C:1]1[CH:2]=[CH:3][CH:4]=[CH:5][CH:6]=1)[CH2:8][C:9]([NH:11][C:12]1[CH:13]=[CH:14][C:15]([C:16]([O:18][CH2:19][CH3:22])=[O:17])=[CH:20][CH:21]=1)=[O:10])([O-:36])=[O:35]

Komponenten

Edukt 4

HCID 313Hydrochloric Acid

HCID 6375Nitromethane

HCID 811841,8-Diazabicyclo(5.4.0)undec-7-ene

HCID 675852Methyl 4-(3-phenylacryloylamino)benzoate

Produkt 1

HCID 67242330Ethyl 4-(4-nitro-3-phenyl-butyrylamino)benzoateAusbeute 62 %

Versuchsvorschrift

A mixture of 41 (1.340 g, 4.44 mmol) in nitromethane (4 ml) was heated a microwave reactor (Biotage Initiator) at 100° C. for 15 min in presence of DBU (0.811 g, 5.328 mmol, 1.2 eq). After cooling to room temperature, the reaction mixture was poured into HCl 1M (10 ml). The product extracted with ethyl acetate (2×15 ml). The organic extracts were collected, dried over Na2SO4 and the solvent removed under reduced pressure. Chromatography on silica gel (7:3 hexanes/ethyl acetate, Rf 0.20) afforded 47 (0.980 g, 2.75 mmol, 62%) as a yellow oil. 1H NMR (400 MHz, CDCl3) δ 1.37 (3H, t, J 7.6 Hz), 2.79 (1H, dd, J 7.2, 15.2 Hz), 2.86 (1H, dd, J 7.2, 15.2 Hz), 4.07 (1H, quint, J 7.2 Hz), 4.34 (2H, q, J 7.2 Hz), 4.72 (1H, dd, J 7.8, 12.6 Hz), 4.83 (1H, dd, J 6.4, 12.4 Hz), 6.63 (1H, d, J 16 Hz), 7.11 (1H, t, J 7.6 Hz), 7.24-7.26 (2H, m), 7.27-7.36 (2H, m), 7.45 (1H, s), 7.47 (2H, d, J 8.8 Hz), 7.96 (2H, d, J 8.8 Hz). 13C NMR (400 MHz, CDCl3) δ 14.55, 40.67, 40.93, 61.20, 79.50, 119.17, 126.54, 127.53, 128.45, 129.48, 130.98, 138.51, 141.60, 166.30, 168.39. MS (API-ES): m/z found 357 [M+H]+ (100%), HRMS (API-ES) m/z found 357.1344 [M+H]+.