1,4-Dicyanobenzene → p-Cyanobenzamide

Participants

Reaction Conditions

Reaction Steps

Terephthalonitrile (128 g) and tert-butanol (2432 g) were placed in a four-neck flask, and the mixture was heated to 80° C. with stirring. To the mixture, a 20% aqueous solution (13.4 g) of sodium hydroxide was added over three hours by use of a tube pump. Liquid chromatographic analysis revealed that the reaction mixture contained 71.5 g of p-cyanobenzamide (yield 49%) and 64 g of terephthalonitrile (conversion 50%). The reaction mixture was cooled to 25° C., neutralized with concentrated sulfuric acid (98% by weight), and heated under reduced pressure so as to concentrate the mixture and to remove tert-butanol (1824 g). After normal pressure was restored, the mixture was cooled to 25° C., and water (540 g) was added thereto. Subsequently, an aqueous solution (887.5 g) of sodium hypochlorite (effective chlorine 12%) was added to the reaction mixture over six hours while a 50% aqueous solution of sulfuric acid was added so as to maintain the pH of the mixture at 5-6. Liquid chromatographic analysis revealed that the reaction mixture contained 69.1 g of crude p-cyanobenzoic acid (yield 47%) and terephthalonitrile (64 g). Subsequently, the residual solvent (1090 g) was removed from the reaction mixture through distillation under reduced pressure. To the resultant mixture, a 48% aqueous solution of sodium hydroxide was added to thereby adjust the pH to 8, and the terephthalonitrile precipitated (60.2 g) was recovered through filtration. To the filtrate, concentrated sulfuric acid was added so as to adjust the pH to 3.0 and precipitate p-cyanobenzoic acid from its salt. The precipitate was dissolved by adding methanol (309 g) with heat, and the solution was cooled for crystallization, to thereby obtain 60.0 g of p-cyanobenzoic acid having a purity of 98% (yield 40%).

Provenance & Evidence