Benzoic acid, 3-acetyl-, methyl ester

Methyl 3-bromobenzoate (110 g, 0.51 mol), dry acetonitrile (500 mL), ethynyl(trimethyl)silane (60.0 g, 0.61 mol), diisopropylamine (62.0 g, 0.61 mol) and tetra(triphenylphosphine)palladium (23.6 g, 0.02 mol) were placed under an atmosphere of argon in a three-necked round-bottomed 1 liter flask, equipped with a magnetic stirrer and a thermometer. The mixture was stirred for 30 minutes and then cooled to 10 3.95 g (24.06 mmol) of 3-acetylbenzoic acid were initially charged in 100 ml of toluene and 75 ml of methanol. After dropwise addition of 4.12 g (36.09 mmol) of trimethylsilyldiazomethane 2M in diethyl ether at RT, an instant evolution of gas in the reaction solution was observed. Another 0.27 g (2.4 mmol) of trimethylsilyldiazomethane 2M in diethyl ether was added until the reaction solution remained yellow, and the mixture was stirred at RT for 10 min. The reaction solution was evaporated. Yield: 4.28 g (100percent of theory) LC-MS (Method 4): Rconcentrated sulfuric acid (4 mL) was added to methanol (60mL) solution of 3-acetyl-benzoic acid 20 (2.02 g, 12.3 mmol) and was refluxedwith stirring for 26.5 hours. After removing the solvent, the residue waspoured into water, and extracted with ethyl ether, and after washing theorganic layer with water and brine, it was dried over anhydrous sodium sulfate.Then, the filtrate was concentrated in vacuum to obtain compound 21 as a whitesolid 2.12 g (97percent yield).3-acetylbenzoic acid (200 g) was dissolved in 2 L methanol (or ethanol, propanol) and 128 ml concentrated sulfuric acid was slowly added at room temperature. The mixture was heated to reflux overnight. After the reaction was completed, the methanol was removed by concentration under reduced pressure. The remaining oil was dissolved in 2 L ethyl acetate and washed with 1 L water for once, 1 L saturated sodium bicarbonate for twice, and 0.5 L saturated brine for once. The organic phase was dried by using anhydrous sodium sulfate and the ethyl acetate was removed by concentration under reduced pressure to obtain a red oil, cooled at room temperature to obtain yellow solid (189 g), yield: 87percent, The 3 - acetyl benzoic acid (compound 1) (5.00g, 30 . 7mmol) dissolved in 147 ml of methanol, slowly dropping 10 ml concentrated sulfuric acid, stirring reflux, the reaction 24h and reducing pressure to evaporate the methanol, add 80 ml water, extracted with ethyl acetate 3 times, the combined organic phase are water and saturated salt water washing, then drying with anhydrous sodium sulfate, filtered, concentrated to obtain yellow liquid 4.54g, yield is 83percentTo a solution of 3-acetylbenzoic acid (1) (5.00 g, 30.7 mmol) in MeOH (147 mL) added into 10 mL concentrated HGeneral procedure: The starting aldehydematerials (1 mmol) were dissolved in MeOH (5 mL), and Oxone (1 mmol) and 10 mol percent of In(OTf)3 were added atroom temperature. The reaction mixture was heated at reflux, and was monitored for completion by TLC. After the reactionmixture was filtered, the filtrate was condensed using arotary evaporator. Flash column chromatography on silica gelfurnished the corresponding products, which were confirmedby spectroscopy.

Molecular Weight:178.18
XLogP3:1.9
Hydrogen Bond Acceptor Count:3
Rotatable Bond Count:3
Exact Mass:178.062994177
Monoisotopic Mass:178.062994177
Topological Polar Surface Area:43.4
Heavy Atom Count:13
Complexity:210
Covalently-Bonded Unit Count:1
Compound Is Canonicalized:Yes