反应详情

Triethylamine (17.0 g, 0.168 mol) is added in one portion to allyl bromide (105.9 g, 0.875 mol) under a nitrogen atmosphere. The resulting white emulsion gives an exotherm to 70° C. and becomes a thick white solid mass within 5 minutes. The solution formed with the addition of ~100 ml of DMF is stirred for 1 hour at 70°-95° C. A solution of 4'-amino-2-bromo-3',5'-dichloroacetophenone (25.0 g, 0.088 mol) in 50 ml of DMF is added in one portion and the resulting brown reaction mixture is maintained at 80°-90° C. for 2 hours. The progress of the reaction is frequently checked by thin layer chromatography (SiO2 /CH2Cl2 /hexanes (1/1)) since prolonged heating results in the decomposition of both starting material and products. The reaction mixture is poured into 1.51 of H2O and is stirred for 0.5 hours. After a second aqueous trituration, the residual brown semi-solids are stirred with ~150 ml of CCl4 for 0.5 hours to form a suspension. The yellowish-brown solids are collected by filtration and are air dried to give 14.9 g (59.6%) of recovered phenacyl bromide starting material. The CCl4 filtrate is stirred with MgSO4, filtered and concentrated to yield 9.42 g of a brown syrup. Gradient elution (hexanes/CH2Cl2 (10/0→8/2) flash chromatography on a 9"×2" column of Silica Gel 60 gives two major fractions:

1. customThe resulting white emulsion gives an exotherm to 70° C.
2. customwithin 5 minutes
3. temperaturethe resulting brown reaction mixture is maintained at 80°-90° C. for 2 hours
4. temperaturesince prolonged heating
5. customresults in the decomposition of both starting material and products
6. stirringis stirred for 0.5 hours
7. customto form a suspension
8. filtrationThe yellowish-brown solids are collected by filtration
9. customdried