Ethyl 4-bromo-β-oxobenzenepropanoate

Clear yellow to light brown liquid

To a solution of NaH (80 g, 60percent mineral oil dispersion, 2 mol) in toluene (1.2 L) was added diethyl carbonate (295 g, 2.50 mol) at 0 °C. After stirring at rt for 2 hrs, the mixture was added drop wise to a solution of compound 15-1 (99 g, 0.50 mol) in toluene (400 mL) at reflux. After refluxing overnight, the reaction mixture was cooled to rt and sequentially treated with HOAc (140 mL) and aq. HC1 (2 M, 864 mL). The resulting mixture was extracted with EtOAc (400 mL x 3) and the combined organic extracts were washed with water (500 mL x 4) and brine (200 mL x 2) and dried with anhydrous NaIn around bottom flask, 8.04 g (200.96 mmol) of NaH were washed three times with cyclohexane; under argon, 100 ml of dry toluene and 30.4 ml (251.2 mmol) of diethyl carbonate were successively added. Slowly, 10 g (50.24 mmol) of 4'-bromoacetophenone were added and the resulting mixture was stirred one night under reflux. After cooling, 25 ml of acetic acid were added to the reaction mixture, then a solution of 15 ml of concentrated HC1 in 100 ml of cooled water. The mixture was extracted with ethyl acetate and the organic layer was treated with a solution of sodium bicarbonate then dried over MgS0To a stirred solution of NaH (60percent, 4.2 g, 105.5 mmol) in toluene (100 mL) at 0°C, diethyl carbonate (8.9 g, 75.37 mmol) was added and the solution was stirred at rt for 2 h. To this solution, compound a (10 g, g, 50.25 mmol) was added at 110°C and the resulting reaction mixture was stirred at 110°C for 12 h. The progress of the reaction was monitored by TLC. Upon completion the reaction mixture was cooled to rt, diluted with iN HC1 andextracted with ethyl acetate. The combined organic layers were dried over anhydrous Na2SO4 and concentrated under reduced pressure resulting in a crude compound which was purified by column chromatography to afford the compound b (5 g, 37percent).

Molecular Weight:271.11
XLogP3:2.6
Hydrogen Bond Acceptor Count:3
Rotatable Bond Count:5
Exact Mass:269.98916
Monoisotopic Mass:269.98916
Topological Polar Surface Area:43.4
Heavy Atom Count:15
Complexity:232
Covalently-Bonded Unit Count:1
Compound Is Canonicalized:Yes