General procedure for the synthesis of 4-chloro-3-(hydroxymethyl)phenol from 2-chloro-5-hydroxybenzoic acid: to a solution of 2-chloro-5-hydroxybenzoic acid (4 g, 23.2 mmol) in tetrahydrofuran (200 mL) was slowly added lithium aluminum hydride (1 M in ether, 25 mL, 25 mmol) under ice bath cooling conditions. The reaction mixture was heated to reflux for 6 hours. Upon completion of the reaction, the reaction mixture was diluted with a mixture of tetrahydrofuran and water, followed by acidification with 1M hydrochloric acid to acidity. Extraction was carried out with ethyl acetate and the organic phases were combined and dried over anhydrous sodium sulfate. The organic phase was concentrated under reduced pressure to give 4.3 g of 4-chloro-3-(hydroxymethyl)phenol in quantitative yield.
[1] Patent: US2006/35922, 2006, A1. Location in patent: Page/Page column 31
[2] Angewandte Chemie - International Edition, 2015, vol. 54, # 41, p. 12044 - 12048
[3] Angew. Chem., 2015, vol. 127, p. 12212 - 12216,5
[4] Patent: WO2010/122089, 2010, A1. Location in patent: Page/Page column 51
