Ethyl enanthylsuccinate

ETHYL ENANTHYLSUCCINATE (Succinic acid, heptanoyl-, diethyl ester) 

Submitted by Tracy M. Patrick, Jr., and Floyd B. Erickson.1 Checked by T. L. Cairns and R. D. Cramer. 

A mixture of 228 g. (2.0 moles) of enanthaldehyde (Note 1) and 172 g. (1.0 mole) of ethyl maleate (Note 2) is placed in a jacketed flask (Fig. 3) (Note 3) with condensers attached to the flask and the jacket openings. The jacket is charged with trichloroethylene (Note 4), which is heated to reflux, and, when the reaction mixture reaches 84—85°, 0.5 g. of benzoyl peroxide is added to the mixture through the condenser. After 3-8 hours an additional 0.5-g. portion of benzoyl peroxide is added, and heating is continued for a total of 18-24 hours (Note 5). 

Good-quality enanthaldehyde such as the white label grade supplied by the Eastman Kodak Company was distilled before use. It is best stored in a brown bottle under nitrogen for protection against oxidation. 

Ethyl maleate from Commercial Solvents Corporation, Terre Haute, Indiana, was distilled before use. Ethyl fumarate can be used also, but the yield of product is lower since a much greater proportion of high-boiling compounds is obtained. Aldehydes do not undergo free-radical addition to maleic anhydride under these conditions. 

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Ethyl diazoacetate, 36, 25 Ethyl dichloroacetate, 32, 47 Ethyl diethoxyacetate, 35, 59 Ethyl enanthylsuccinate, 34, 51 Ethylene, 32, 100 37, 65 Ethylene, 1,1-dichloro-2,2-dipi.uoro-,... 

The submitters state that ethyl enanthylsuccinate can be hydrolyzed and decarboxylated to 7-oxocapric acid. The reaction is carried out by heating 57 g. of the keto ester with a solution of 140 ml. of concentrated sulfuric acid in 250 ml. of water. The mixture is stirred while the ethanol is removed gradually by distillation over a period of 3 hours. The acid is taken up in benzene, extracted from the benzene with aqueous alkali, and liberated from the alkaline solution by acidification with concentrated hydrochloric acid. After recrystallization from 50% ethanol about 29 g. (78% yield) of 7-oxocapric acid is obtained as colorless crystals, m.p. 69-70°. 

Ethyl enanthylsuccinate has been prepared by the free-radical addition of enanthaldehyde to ethyl maleate.2... 

METHYL-, HYDROCHLORIDE, 31, 37 N-methyl-1,2-diphenyl-, 34, 64 Ethyl benzoylacetate, 32, 85 Ethyl bromide, 34, 58 O-Ethylcaprolactim, 31, 73 Ethyl chloroacetate, 30, 7 34, 54 Ethyl chloropluoroacetate, 34, 49 Ethyl /3-chloroisocrotonate, 32, 78 Ethyl cyanoacetate, 32, 45 Ethyl dichloroacetate, 32, 47 Ethyl enanthylsuccinate, 34, 51 Ethylene, 32, 100 Ethylene, tetraphenyl-, 31,104 Ethylene chloride, 34, 85, 86 Ethylene chlorohydrin, 30, 11 33, 11 Ethylene dibromide, 30, 35 Ethylene diisothiuronium bromide, 30, 36... 

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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