3-(BROMOMETHYL)BENZOICACID

Off-White Solid

Methylmethylbenzoic acid (2.0 g, 14.7 mmol)And benzoyl peroxide (BPO, 0.036 g, 0.15 mmol)Was dissolved in dichloromethane (6 mL) and heated to reflux, NBS (2.6 g, 14.7 mmol) was added in portions, Continue to heat reflux 2h, After cooling to room temperature, the reaction was quenched with water (10 mL), extracted with dichloromethane (50 mL), washed with water, washed with saturated NaCl, dried over anhydrous Na2SO4, Concentrated to give a pale yellow solid 2.7 g, yield 86percentTo a suspension of 3-Methyl-benzoic acid (40.0 g, 293 mmol) in carbon tetrachloride (400 mL) were added AIBN (1 g, 0.58 mmol) and N-Bromosuccinamide (52.0 g, 8.07 mmol) at 25 °C. The reaction mixture was refluxed over a period of 3 h. The resulting reaction mixture was filtered when it was hot and the filtrate was diluted with ethyl acetate, washed with water and dried over sodium sulphate. The solvent was evaporated under reduced pressure to obtain 3-Bromomethyl-benzoic acid as a colorless solid (54 g, 85 percent).To a suspension of 3-Methyl-benzoic acid (40.0 g, 293 mmol) in carbon tetrachloride (400 mL) were added AIBN (1 g, 0.58 mmol) and N-Bromosuccinamide (52.0 g, 8.07 mmol) at 25° C.In a 1 L round bottom flask fitted with a reflux condenser, a stirred suspension of 10.00 g m-toluic acid and 14.37 g (1.1 eq.) N-bromosuccinimide in 735 mL chloroform was sparged for 0.5 h with nitrogen. The sparging was discontinued and the stirred suspension was irradiated under a nitrogen atmosphere using a 500 W quartz halogen lamp at 75percent power, causing the solids to dissolve and the reaction to reflux. The red color of the reaction became clear after 1.25 h, and another 14.37 g of N-bromosuccinimide was added. The reaction mixture was stirred and irradiated under nitrogen atmosphere with a 500 W quartz halogen lamp at 75percent power for another 1.5 h, at which time the solution was clear. The solvent volume was reduced in vacuo to about 100 mL, and then the solution was cooled to -20° C., forming crystals. The resultant suspension was vacuum filtered through a bed of dry silica, which was then eluted with 800 mL of chloroform. The chloroform filtrate volume was reduced in vacuo to about 100 mL, and then the chloroform was cooled to -20° C., forming crystals. The crystals were vacuum filtered and washed with 30 mL chloroformn and 50 mL hexanes, then dissolved in 250 mL chloroform and washed in a separatory funnel with 3.x.300 mL volumes of water, followed by one 300 mL volume of brine to remove traces of succinimide. The organic phase was dried over magnesium sulfate, vacuum filtered and concentrated in vacuo to provide 9.56 g (61percent) of Compound 17 as a white crystalline power.a) Synthesis of 3-bromomethylbenzoic acid: In a 1 L round bottom flask fitted with a reflux condenser, a stirred suspension of 10.00 g of m-toluic acid and 14.37 g (1.1 eq.) N-bromosuccinimide in 735 mL chloroform was sparged for 0.5 h with nitrogen. The sparging was discontinued, and the suspension was stirred and irradiated under nitrogen atmosphere using a 500 W quartz halogen lamp at 75percent power, causing the solids to dissolve and the chloroform to reflux. The red color of the reaction mixture disappeared after 1.25 h, and 14.37 g of N-bromosuccinimide was added. The reaction mixture was stirred and irradiated under nitrogen atmosphere with a 500 W quartz halogen lamp at 75percent power for another 1.5 h, at which time the solution became colorless. The solvent volume was reduced in vacuo to about 100 mL, and then cooled to-20 °C. The resultant suspension was vacuum filtered through a bed of dry silica. The silica was washed with 800 mL of chloroform. The chloroform filtrate was reduced in vacuo to about 100 mL, and then cooled to-20 °C. The resultant crystals were vacuum filtered, washed with 30 mL of chloroform followed by 50 mL of hexanes, then dissolved in 250 mL chloroform and washed in a separatory funnel with 3 x 300 mL volumes of water followed by one 300 mL volume of brine to remove traces of succinimide. The organic phase was dried with magnesium sulfate, vacuum filtered, and the solvent was removed in vacuo to provide 9.56 g (61percent) of 3- bromomethylbenzoic acid as a white crystalline power.

Molecular Weight:215.04
XLogP3:2.2
Hydrogen Bond Donor Count:1
Hydrogen Bond Acceptor Count:2
Rotatable Bond Count:2
Exact Mass:213.96294
Monoisotopic Mass:213.96294
Topological Polar Surface Area:37.3
Heavy Atom Count:11
Complexity:147
Covalently-Bonded Unit Count:1
Compound Is Canonicalized:Yes