Ethyl phenylcyanoacetate

1 Work done under contract with the Office of Rubber Reserve. 

12 Frank, Blegen, Dearborn, Myers, and Woodward, J. Am. Chem. Soc., 68, 1368 (1946). 

ETHYL PHENYLCYANOACETATE (Acetic acid, cyanophenyl-, ethyl ester) 

Submitted by E. C. FIorninc and A. F. Finelli. Checked by William S. Johnson and H. Wynuerg. 

Sodium ethoxide is prepared from 12.0 g. (0.52 gram atom) of sodium and 300 ml. of anhydrous ethanol in a 1-1. three-necked round-bottomed flask fitted with a reflux condenser carrying a calcium chloride tube. After the sodium has dissolved completely, the condenser is arranged for distillation under reduced pressure and the excess ethanol is removed by heating the flask on a steam bath while the system is maintained at the pressure obtained with an ordinary aspirator (Note 1). 

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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... 

Creosol, 33, 17 Crotonaldehyde, 33, IS 34, 29 diethyl acetal, 32, 5 Cupric acetate monohydrate, 36, 77 Cuprous oxide-silver oxide, 36, 36, 37 Cyanamide, 34, 67 36, 8 Cyanoacetamide, 32, 34 Cyanoacetic acid, 31, 25 Cyanoacetylurea, 37, 16 >-Cyanobenzaldehyde, 30, 100 >-Cyanobenzaldiacetate, 36, 59 3-Cyano-5,6-dimethyl-2(l)-pyridone, 32,34 N-2-Cyanoethylaniline, 36, 6 N-2-Cyanoethyl- -anisidine, 36, 7 Cyanoethylation, of aniline, 36, 6 of ethyl phenylcyanoacetate, 30, 80 N-2-Cyanoethyl-m-chloroaniline, 36, 7 Cyanogen, 32, 31 Cyanogen iodide, 32, 29 Cyanogen iodide, complex with sodium iodide, 32, 31... 

A high yield could be achieved in the amination of ethyl phenylcyanoacetate with A,A-dimethyl 0-(mesitylenesulfonyl)hydroxylamine 3b (equation 15) . ... 

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 in 80 ml. of tert.-hnty 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 fer/.-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. 

N-2-Cyanoethylaniline, 36, 6 N-2-Cyanoethyl-/>-anisidine, 36, 7 Cyanoethylation, of aniline, 36, 6 of o-chloroaniline, 38,14 of ethyl phenylcyanoacetate, 30, 80 N-2-Cyanoethyl-ftt-chloroaniline,... 

Dowtherm gives 3-ethoxycarbonyl-4//-pyrazino[l,2-a]pyrimidin-4-one (275) in good yield. Ethyl phenylcyanoacetate also condenses with the starting pyrazine to give 2-hydroxy-4-imino-3-phenyl-4H-pyrazino[l,2-a]pyrimidine (276). Condensation of (274) with ethyl phenylmalonate gives zwitterion (277) (68JMC1045). 

Ethyl phenylacetate, 35, 31 Ethyl phenylazoacetoacetate, 32, 85 Ethyl phenylcyanoacetate, 30, 43, 80... 

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