反应详情

A 25-mL, three-necked, round-bottomed flask was equipped with a magnetic stirrer, a standard condenser with a N2 inlet, a 10-mL addition funnel and two glass stoppers. To a mixture of the amine (31, 0.60 g, 3.57 mmol) in CH2Cl2 (5 mL) and 10% NaOH (3.58 g, 8.93 mmol) was added dropwise a solution of 4-chlorobenzoyl chloride (0.69 g, 3.92 mmol) in CH2Cl2 (5 mL) over 15 min. Stirring of the mixture was continued for an additional 3 h under N2. An aqueous mixture, formed upon addition of H2O (30 mL), was extracted (CH2Cl2, 4×25 mL). Combined extracts were dried (Na2SO4, 2 h), filtered, and concentrated to give a viscous yellow oil. Chromatography of the oil was performed by adding an ether solution of the oil to a neutral alumina column (69 g, 1.7 cm×30 cm) and then using 60:40 hexanes/ethyl acetate as eluant. Fractions (Rf =0.41) were saved and concentrated (rotary evaporator then vacuum pump, overnight, RT/0.2 mm Hg) to give 0.86 g (80.4%) of off-white solid (33); mp 97°-98° C. IR (KBr) cm-1 3085, 3070 (Ar C--H), 2965, 2935, 2865, 2800, 2770 (C--H), 1630 (C=O); 1H NMR (DCCl3) δ0.95 (d;, 3H, CH3, J=6.5 Hz), 1.05 (d, 3H, CH3, J=6.4 Hz), 1.63-1.75 [m, 3H, H(5) and H(9)], 1.97 [bs, 1H, H(1)], 2.41 [bd, 1H, H(4)ax, J=10.6 Hz], 2.50 [bd, 1H, H(6)ax, J=11.2H], 2.59 [heptet, 1H, CH(CH3)2, J=6.5 Hz] , 2.71 [bd, 1H, H(6)eq, J=11.0 Hz], 3.03-3.06 [m, 2H, H(2)ax and H(4)eq ], 3.31 [bd, 1H, H(8)ax, J=12.8 Hz], 3.71 [bd, 1H, H(8)eq, 13.1 Hz], 4.77 [bd, 1H, H(2)eq, J=13.2 Hz], 7.27-7.37 (m, 4H, Ar--H); 13C NMR (DCCl3) ppm 16.37, 19.35 (CH3), 29.07 [C(1)], 29.07 [C(1)], 29.80 [C(5)], 32.29 [C(9)], 46.68 [C(2)], 52.22 [C(4)], 52.56 [C(8)], 54.38 [CH(CH3)2 ], 54.79 [C(6)], 128.35, 128.51, 134.67, 136.11 (Ar-- C), 169.03 (C=O). Anal. Calcd. for C17H23ClN2O: C, 66.55; H, 7.56. Found: C, 66.45; H, 7.71.

1. customA 25-mL, three-necked, round-bottomed flask was equipped with a magnetic stirrer, a standard condenser with a N2 inlet, a 10-mL addition funnel
2. extractionwas extracted (CH2Cl2, 4×25 mL)
3. dry with materialCombined extracts were dried (Na2SO4, 2 h)
4. filtrationfiltered
5. concentrationconcentrated
6. customto give a viscous yellow oil
7. concentrationconcentrated (
8. customrotary evaporator