Borane → HCID 70045205, compound

Participants

Reaction Conditions

Reaction Steps

A solution of 3-chloro-4-(4-chlorophenylthio)benzamide (44.7 g, 150 mmol) in tetrahydrofuran (300 ml) was added dropwise over 30 minutes to a stirred 1.0M solution of borane in tetrahydrofuran (450 ml) under a nitrogen atmosphere at ambient temperature. The mixture was refluxed for 16 hours, cooled to 0° C., and quenched by addition of 2.0N hydrochloric acid. The solvent was evaporated under vacuum and the solid residue was slurried in water, filtered, and washed with water (4×300 ml). The solid was partially dried in the air, washed with diethyl ether (3×200 ml), and dried under vacuum at 50° C. for 3 hours and at ambient temperature for 16 hours. The crude product was suspended in diethyl ether (700 ml), vigorously stirred for 30 minutes, filtered, washed with diethyl ether, and dried to provide 27.5 g (57%) 3-chloro-4-(4-chlorophenylthio) benzylamine hydrochloride, m.p. 237°-240° C. The free base was liberated by slurrying the salt (6.77 g) in water (100 ml), basifying with 2.5N aqueous sodium hydroxide, adding diethyl ether (100 ml), and filtering. The biphasic filtrate was separated and the aqueous phase was extracted with diethyl ether. The combined diethyl ether phases were washed with water and brine, dried over anhydrous magnesium sulfate, and evaporated under vacuum. The oily residue was kept under vacuum at ambient temperature for 16 hours to provide 5.80 g (97%) of 3-chloro-4-(4-chlorophenylthio)benzylamine as a colorless oil, 60 MHz 'H NMR (DMSO-d6): 2.22 broad s (2H), 3.37 s (2H), 7.1-7.5 complex m (7H); (DMSO-d6 /D2O/DCl) 4.05 s (2H), 7.03 d (J=9Hz, 1H), 7.3-7.6 broad m (6H).

Provenance & Evidence