PHENYL-a-CARBETHOXYGLUTARONITRILE

In a 500-ml. three-necked flask equipped with a stirrer, a dropping funnel, and a thermometer is placed a solution of 57.0 g. (0.30 mole) of ethyl phenylcyanoacetate 1 in 80 ml. of tert.-butyl alcohol. The solution is heated to 40°, and with stirring the drop-wise addition of a solution of 33.0 g. (0.62 mole) of acrylonitrile (Note 1) in 30 ml. of tert.-butyl alcohol is started. After the addition of about 10-15 drops, 1.0 ml. of a 30% solution of potassium hydroxide in methanol is added, and the temperature is maintained at 40-45° by occasional external cooling while the remaining solution is added slowly. When about one-half of the acrylonitrile has been added, an additional 1.0 ml. of the potassium hydroxide solution is added to ensure the presence of a basic catalyst throughout the reaction. When the addition is completed (after about 30 minutes) and the temperature is no longer maintained above 40° by the exothermic reaction (another 30 minutes), the mixture is heated with a hot-water bath to keep the temperature at 40-45° for 1 hour. 

The solution is diluted with 250 ml. of water and acidified with 30-40 ml. of 10% hydrochloric acid. The product is separated after the addition of 100 ml. of ether, and the aqueous solution is extracted with two 50-ml. portions of ether. The combined extracts are washed with 50 ml. of water and dried over anhydrous magnesium sulfate. The ether is distilled at atmospheric pres- 

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In a 500-mI. flask equipped with a reflux condenser are placed 48.4 g. (0.20 mole) of a-phenyl-a-carbethoxyglutaronitrile/ 225 ml. of hydrochloric acid (sp. gr. 1.19), and 50 ml. of acetic acid. The mixture is heated under reflux for 10 hours. The solution is cooled, transferred to a 1-1. separatory funnel, and diluted with 300 ml. of water. The a-phenylglutaric acid is extracted with five 100-ml. portions of ether-ethyl acetate (1 1) (Note 1). The extracts are combined, washed once with saturated sodium chloride solution, and dried over anhydrous magnesium sulfate. The solvents are removed as completely as possible by distillation from a steam bath, and the residue is transferred to a 200-ml. flask. Acetic anhydride (50 ml.) is added, and the solution is heated under gentle reflux for 1 hour. The excess acetic anhydride is removed by distillation at atmospheric pressure, and the residue is distilled under reduced pressure through a short (15-cm.) Vigreux column with an air-cooled side arm. The product is collected at 178-188°/0.5-l mm. (Note 2). The yield is 31.1-32.7 g. (82-86%) m.p. 90-94°. 

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