Hydrochloric Acid → 2,5-Dimethylbenzoyl chloride

Participants

Reaction Steps

Part A. A 500-mL, three-necked, round bottomed flask equipped with an addition funnel, reflux condenser, and a nitrogen sweep to an HCl gas scrubber was charged with 2,5-dimethylbenzoic acid (50.0 g, 332.9 mmol). The apparatus was cooled in an ice bath and thionyl chloride (125 mL, 1714 mmol) was added over a period of about 5 minutes. After complete addition, the ice bath was removed and the reaction mixture was warmed to about 50° in order to completely dissolve the 2,5-dimethylbenzoic acid. The reaction mixture was allowed to gradually cool with stirring to room temperature overnight. The excess thionyl chloride and the HCl and SO2 reaction side-products were removed by vacuum distillation to afford 2,5-dimethylbenzoyl chloride as an oil, which was used without further purification. This material was transferred immediately to an addition funnel and added dropwise with stirring to a commercial 40% dimethylamine solution (188 mL, 1670 mmol) which was maintained between -5° and 5° by periodic immersion in a dry ice-acetone bath. After complete addition, the reaction mixture was stirred at room temperature for 1 hour. The reaction mixture was diluted with water and extracted with ether. The combined organic extracts were washed with water, dried, and concentrated. The resulting pale yellow oil was distilled under vacuum to afford N,N,2,5-tetramethylbenzamide (29.1 g, 164.2 mmol, 49% yield) as a clear, colorless oil: bp 100° (1.0 torr); IR(CHCl3) 1637 cm-1 ; MS m/e 178(M+ +H); 1H NMR(CDCl3) δ 7.00-7.13(m,2H), 6.90-7.00(m,1H), 3.13(s,3H), 2.84(s,3H), 2.31(s,3H), 2.23(s,3H). Anal. Calcd for C11H15NO: C,74.54; H,8.53; N,7.90. Found: C,74.30; H,8.77; N,7.73.

Provenance & Evidence