1,4-Dicyanobenzene → p-Cyanobenzamide

Temperature

78 °C

Terephthalonitrile (128 g) and ethanol (1700 g) were placed in a four-neck flask, and the mixture was heated to 78° C. with stirring. To the mixture, a 20% aqueous solution (10 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 40%) and 38.4 g of terephthalonitrile (conversion 70%). The reaction mixture was cooled to 25° C., neutralized with concentrated sulfuric acid, and heated under reduced pressure so as to concentrate the mixture and to remove ethanol (1275 g). After normal pressure was restored, the mixture was cooled to 25° C., and water (720 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 55.9 g of crude p-cyanobenzoic acid (yield 38%) and terephthalonitrile (38 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 precipitated terephthalonitrile (36 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 ethanol (309 g) with heat, and the solution was cooled for crystallization, to thereby obtain 52.6 g of p-cyanobenzoic acid having a purity of 95% (yield 34%).

ORD record

ord-74290905d22a4a68a8e47dea1d23bcd6

Source dataset

uspto-grants-2002_08

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US06433211B1