Ethyl 0-phenyl- 3-cyanopropionate

The mixture is cooled to 15°, and the precipitated potassium bicarbonate is collected on a Buchner funnel. The solid (weight 70-72 g.) is washed on the funnel with 100 ml. of 95% ethanol. The combined filtrate and wash liquor is transferred to a 5-1. round-bottomed flask and made slightly acid Caution Note 1) with dilute hydrochloric acid (about 15-20 ml. of the 10% acid is required). The solution is then concentrated under reduced pressure to a semi-solid residue (Note 1). The cooled residue is shaken with a mixture of 300 ml. of water and 500 ml. of ether. The material dissolves completely the water layer is separated and washed with 200 ml. of ether. The ether solutions are combined, dried over 20 g. of calcium chloride, filtered into a 2-1. round-bottomed flask equipped with a glass joint, and concentrated by distillation (heating on a steam bath). The crude ethyl /3-phenyl-/3-cyanopropionate remains as a clear red oil weighing 130-140 g. It is sufficiently pure for use in the next step (Note 2). 

A. Ethyl -phenyl-p-cyanopropionate. In a 5-1. round-bottomed three-necked flask suspended in an oil bath and fitted with a mechanical stirrer, a reflux condenser, and a 250-ml. dropping funnel is placed a solution of 200 g. (0.806 mole) of diethyl ben-zalmalonate Mn 2 1. of absolute ethanol. The stirrer is started, and a solution of 56 g. (0.87 mole) of potassium cyanide in 100 ml. of water is added rapidly from the separatory funnel a small amount of the potassium cyanide precipitates. The temperature of the oil bath is raised to 70° and maintained at 65-75° for 18 hours. 

Ethylenimine, 30, 38 toxic properties of, 30, 40 Ethyl o-ethoxybenzoate, 32, 75 Ethyl formate, 32, 32 Ethyl glycidyl ether, 31, 3 2-Ethylhexanaldoxime, 32, 67 2-Ethylhexanamide, 32, 65 2-Ethylhexanoic acid, 32, 66 2-Ethylhexanonitrile, 32, 65 Ethylidene bromide, 32, 55 Ethyl iodide, 31, 34 Ethyl isodehydroacetate, 32, 76 Ethyl lactate, 31, 59, 60 5-ETHYL-2-METHYLPYRIDINE, 30, 41 Ethyl orthocarbonate, 32, 68 Ethyl orthoformate, 32, 5 Ethyl orthosilicate, 32, 5 Ethyl phenylazoacetoacetate, 32, 85 Ethyl phenylcyanoacetate, 30,43,80 Ethyl 0-phenyl-/3-cyanopropionate, 30, 84... 

Recently, Smulik and Vedejs have reported that amination of ester enolates and enim-inates with 0-(p-nitrobenzoyl)hydroxylamine 21 takes place with good yields . However, reaction of enolates derived from ethyl phenylacetate and phenylacetonitrile gave lower yields compared with stabilized enolates derived from diethyl malonate, diethyl 2-phenylmalonate and 2-phenyl-2-cyanopropionate (Scheme 23). 

Hydrolysis, of dihydropyran, 30, 48 of ethyl 3-benzyl-2-cyano-3-methyl-pentanoate, 35, 8 of ethyl enanthylsuccinate, 34, S3 of ethyl 8-phenyl- 3-cyanopropionate,... 

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