Synthesis
Step 1: Methyl 2-amino-4-bromobenzoate (500 mg, 2.17 mmol) was dissolved in anhydrous THF (10 mL) and the solution was cooled to -10 °C. Under stirring, lithium aluminum hydride (1 M solution of THF, 6.5 mL, 6.52 mmol) was slowly added dropwise. After the dropwise addition was completed, the reaction mixture was allowed to gradually warm up to room temperature and stirred at room temperature overnight. Upon completion of the reaction, the mixture was cooled in an ice-water bath and the reaction was quenched by sequential addition of methanol and saturated potassium sodium tartrate solution. The mixture was continued to be stirred at room temperature for 6 hours. Subsequently, the reaction mixture was diluted with a mixture of ethyl acetate and water to separate the organic and aqueous phases. The organic phase was dried over anhydrous magnesium sulfate, filtered, and concentrated to dryness under reduced pressure to give (2-amino-4-bromophenyl)methanol (Ex.44a, 326 mg, 74% yield) as a viscous brown solid.
References
[1] Patent: WO2018/138359, 2018, A1. Location in patent: Page/Page column 41; 61
[2] Journal of Organic Chemistry, 2014, vol. 79, # 3, p. 1235 - 1246
