Potassium Cyanide → Methyl 2-chloro-4-cyanobenzoate

Participants

Reaction Conditions

Reaction Steps

4-Amino-2-chloro-benzoic acid methyl ester (25 g, 72.7 mmol) was dissolved in 10% aqueous H2SO4 (150 mL) and the solution was cooled to 0° C. A solution of NaNO2 (11.15 g, 16.88 mmol) in water (50 mL) was added dropwise maintaining the temperature between 0-5° C. The mixture was stirred for 10 min., excess nitrous acid was neutralized using a saturated aqueous NaHCO3 solution. The resulting mixture was then added to a precooled (0-5° C.) suspension of CuCN (13.87 g, 155 mmol) and KCN (10.07 g, 155 mmol) in water (200 mL). It was stirred for 10 min., then allowed to attain room temperature. It was stirred for 0.5 h. and finally heated on a steam bath for 0.5 h. Excess saturated FeCl3 solution was then added to the reaction mixture. It was extracted using EtOAc (3×200 mL). The organic extract was washed with water, dried (anhydrous Na2SO4), concentrated and purified using a silica gel column and CHCl3:petroleum ether (60-80° C.) (1:1) as eluant to obtain the title compound.

Provenance & Evidence