反应详情

温度

0 °C

A stirred, 0° C. solution of 1-chloro-3,5-dimethylbenzene (10.9 g, 77.2 mmol) and 4-chlorobenzoyl chloride (13.6 g, 77.2 mmol) in carbon disulfide (165 ml) was treated with aluminum chloride (11.4 g, 85.0 mmol) in portions over 15 minutes. The mixture was stirred 15 minutes at 0° C., 60 minutes at ambient temperature, 20 hours at reflux and 3 days at ambient temperature. The mixture was cooled to 0° C. and quenched by addition of ice (250 g) followed by concentrated hydrochloric acid (60 ml). The mixture was extracted twice with diethyl ether and the combined extracts were washed with water (3X), saturated aqueous sodium carbonate, and brine, dried over anhydrous magnesium sulfate, and evaporated to dryness of 30° C. under vacuum. The residue was chromatographed in three approximately equal batches on silica gel (500 g) eluted with 97:3 (v/v) hexane-ethyl acetate using a preparative high performance liquid chromatograph to provide 7.3 g (34%) 1-(4-chlorobenzoyl)-2-chloro-4,6-dimethylbenzene, m.p. 84°-87° C. [IR (neat): 2100, 1660 cm-1 ; 60 MHz 'H NMR (CDCl3): 2.11 s (3H), 2.34 s (3H), 6.94 bs (1H), 7.04 bs (1H), 7.34 dm (J= 9 Hz, 2H), 7.70 dm (J=9 Hz, 2H)] and 3.4 g (16%) 1-(4-chlorobenzoyl)-4-chloro-2,6-dimethylbenzene, m.p. 41°-52° C. [IR (neat): 2100, 1660 cm-1 ; 60 MHz 'H NMR (CDCl3) 2.08 s (6H), 7.07 s (2H), 7.38 dm (J=9 Hz, 2H), 7.69 dm (J=9 Hz,2H)].

1. temperatureat reflux and 3 days at ambient temperature
2. temperatureThe mixture was cooled to 0° C.
3. customquenched by addition of ice (250 g)
4. extractionThe mixture was extracted twice with diethyl ether
5. washthe combined extracts were washed with water (3X), saturated aqueous sodium carbonate, and brine
6. dry with materialdried over anhydrous magnesium sulfate
7. customevaporated to dryness of 30° C. under vacuum
8. customThe residue was chromatographed in three approximately equal batches on silica gel (500 g)
9. washeluted with 97:3 (v/v) hexane-ethyl acetate using a preparative high performance liquid chromatograph