Reaction Steps
Acetylacetone (4.5 mL, 44 mmol) was added dropwise over 30 minutes to a cooled (ice/H2O bath) suspension of 95% NaH (0.95 g, 41 mmol) in anhydrous THF (150 mL). After H2 evolution had ceased, a solution of p-bromobenzyl bromide (10.2 g, 40.8 mmol) in anhydrous THF (20 mL) was added at once with stirring. The reaction mixture was heated to 50° C. (internal temperature) for 48 h, cooled to room temperature, and poured into saturated aqueous NH4Cl (250 mL). The organic phase was separated and the aqueous phase was extracted with EtOAc (3×125 mL). The combined organic extracts were dried (Na2SO4). The drying agent was removed by filtration and the filtrate was concentrated under reduced pressure to give an oily residue. Flash column chromatography (EtOAc:hexane (1:8)) gave 4d as a clear amber oil which solidified upon standing at room temperature (9.01 g, 82%). 1H NMR (300 MHz, CDCl3): δ 7.42 (d, J=8.4 Hz, 2H, enol), 7.39 (d, J=8.4 Hz, 2H, keto), 7.03 (d, J=8.4 Hz, 2H, keto), 7.02 (d, J=8.4 Hz, 2H, enol), 3.95 (t, J=7.5 Hz, 1H, keto), 3.60 (s, 2H, enol), 3.10 (d, J=7.5 Hz, 2H, keto), 2.13 (s, 6H, keto), 2.05 (s, 6H, enol). 13C NMR (75 MHz, CDCl3): δ 203.3, 192.1, 138.9, 137.3, 132.0, 130.6, 129.4, 120.0, 120.9, 108.1, 70.0, 33.7, 32.6, 29.9, 23.5. IR (neat, cm−1): 3409, 3010, 3004, 2927, 1896, 1728, 1699, 1594, 1487, 1405, 1358, 1072, 1010. GC/MS (ET): m/z 268 (M+). Anal. Calcd. for C12H13BrO2: C, 53.55; H, 4.87; O, 11.89. Found: C, 53.27; H, 4.77; O, 11.61.
