4-Bromomethyl-3-nitrobenzoic acid → 4-Hydroxymethyl-3-nitrobenzoic acid

Participants

Reaction Steps

In a round-bottom flask provided with reflux system, 4.5 g (17.3 mmols) of 4-bromomethyl-3-nitrobenzoic acid were placed, and an aqueous NaHCO3 saturated solution is added (135 mL). The reaction was stirred and allowed to stand at 90-95° C. The progress of the reaction was monitored by thin layer chromatography (TLC) (chloroform/MeOH/AcOEt, 100:50:0.1, v/v) or by HPLC of an acidified aliquot in a linear gradient 0-100% MeCN in 15 minutes in a Symmetry C18 column (150×4.6 mm×5 μm, 100 Å, Waters) retention time for the final product: 7.12 min; retention time for the initial product: 10.39 min. The reaction was completed in 30 minutes. The solution obtained was hot filtered and the reaction was quenched with HCl (12N) to a pH between 1-2 and was extracted with AcOEt (3×100 mL), the different organic fractions were combined, washed with a satured NaCl aqueous solution and dried over MgSO4 anh. The AcOEt was evaporated in vacuo. The product was obtained as a pale yellow solid in a 80% yield. The product has been characterized by HPLC (tr) 7.12 min (linear gradient 0-100% in 15 minutes), HPLC-MS (196 Da) and Rf=0.3 by TLC (Chloroform/MeOH/AcOEt, 100:50:0.1, v/v), NMR-1H 400 MHz in CD3OD: Signals: 2H: singlet 4.98 ppm, 1H: doublet, 7.96 ppm (J: 21 Hz), 1H: doublet of doublets, 8.26 ppm (4 Hz, 20 Hz), 1H: doublet, 8.56 ppm (4 Hz).

Provenance & Evidence