(3-bromo-4-methylphenyl)methanol

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 14.4 g (72 mmol) of (3-bromo-4-methylphenyl)methanol are placed in 200 ml of dichloromethane in a round-bottomed flask. 62.6 g (72 mmol) of manganese oxide are added and the medium is stirred at room temperature overnight. The mixture is filtered through Celite and the solvent is evaporated off. 11.8 g (85%) of the expected product are obtained in the form of an oil. The mixture is filtered through Celite the solvent is evaporated off

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 15 g (70 mmol) of 3-bromo-4-methylbenzoic acid are placed in 150 ml of anhydrous THF in a round-bottomed flask and under a stream of nitrogen. 84 ml of 1M borane/THF are added dropwise and the reaction medium is stirred overnight at room temperature. A THF/water (50/50) solution is added slowly at 0° C. and the mixture is then poured into saturated aqueous ammonium chloride solution and extracted with ethyl acetate. The organic phase is dried over magnesium sulfate, filtered and then evaporated. 14.4 g (100%) of the expected product are obtained in the form of a yellow oil. extracted with ethyl acetate The organic phase is dried over magnesium sulfate filtered evaporated

Conditions: temp:70.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a stirred solution of 3-bromo-4-methylbenzyl alcohol (4.43 g, 22 mMol) in CHCl3 (100 mL) was added MnO2 (15 g, 172 mMol). The reaction was stirred and refluxed (70° C. oil bath) for 18 h, cooled to RT, filtered through Celite®, rinsed with CHCl3, and concentrated to dryness under vacuum. Purification by flash chromatography on silica gel (10% EtOAc, hexanes) gave the title product (3.0 g, 68%). 1H NMR (400 MHz, CDCl3) δ 9.98 (s, 1H), 7.75 (d, J=1.5 Hz, 1 H), 7.73 (d, J=8.1 Hz, 1 H), 7.57 (dd, J=8.1, 1.5 Hz, 1 H), 7.28 (s, 1 H), 2.50 (s, 3 H). cooled to RT filtered through Celite® rinsed with CHCl3 concentrated to dryness under vacuum Purification by flash chromatography on silica gel (10% EtOAc, hexanes)

Conditions: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Ethyl 3-bromo-4-methylbenzoate was reduced follows: 2 equivalents lithium aluminium hydride (LAH) in THF was cooled to 0° C. Ethyl 3-bromo-4-methylbenzoate in anhydrous THF (10 mL) was added slowly to the cooled solution of LAH over 10 minutes, while stirring. The mixture was stirred at room temperature for 1 hour. The reaction was cooled to 0° C. and poured into ether (100 mL). The mixture was acidified by adding 1N HCl (aqueous) dropwise over 10 minutes. Separate fractions and wash aqueous phase with ether (50 mL). The fractions were combined and dried over magnesium sulfate. Solvent removal left a clear oil. The yield was 90%. 1H NMR (Varian 300 MHz, CDCl3, shifts relative to the solvent peak at 7.24 ppm) δ 7.5 (s, 1H) 7.2 (d, 1H) 7.1 (d, 1H), 4.6 (s, 2H) 2.3 (s, 3H). The mixture was stirred at room temperature for 1 hour Separate fractions and wash aqueous phase with ether (50 mL) dried over magnesium sulfate Solvent removal left a clear oil

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:70.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a stirred solution of 3-bromo-4-methylbenzyl alcohol (4.43 g, 22 mMol) in CHCl3 (100 mL) was added MnO2 (15 g, 172 mMol). The reaction was stirred and refluxed (70° C. oil bath) for 18 h, cooled to RT, filtered through Celite®, rinsed with CHCl3, and concentrated to dryness under vacuum. Purification by flash chromatography on silica gel (10% EtOAc, hexanes) gave the title product (3.0 g, 68%). 1H NMR (400 MHz, CDCl3) δ 9.98 (s, 1H), 7.75 (d, J=1.5 Hz, 1 H), 7.73 (d, J=8.1 Hz, 1 H), 7.57 (dd, J=8.1, 1.5 Hz, 1 H), 7.28 (s, 1 H), 2.50 (s, 3 H). cooled to RT filtered through Celite® rinsed with CHCl3 concentrated to dryness under vacuum Purification by flash chromatography on silica gel (10% EtOAc, hexanes)