Phenylmalonic ester, ethyl

Ruhemann prepared phenylcarboxylic-aconitic ester by the action of phenylmalonic ester on chlor-fumarlc ester in the presence of sodium ethylate. This ester,OaHsO( OOOCiHs )s-J( COOCgHe ),... 

Fenalamide, a-[[[2-(Diethylamino)ethyl]amino]-carbonylj-a -rlhylberizeneacrlic acid ethyl ester N-[2-(dieth-ylamino)ethylJ 2- thyl 2-phenylmaionamic add ethyl ester ethyl N-[2-(diethy[amino)ethy J-2-ethyl-2-phenylmalon-amate phenylethylmalonic acid (diethylamino)ethylamide ethyl ester Spasmamide. C H NjO, mol wt 334.45. C 68.23%, H 9.04%, N 8,38%. O 14,35%. Smooth muscle relaxant, Prepn Galimberti et aL. U.S. pat. 3.025,317 (1962 to Soc. Ital. Prod. Schering). 

Ethyl phenylethylmalonate. In a dry 500 ml. round-bottomed flask, fitted with a reflux condenser and guard tube, prepare a solution of sodium ethoxide from 7 0 g. of clean sodium and 150 ml. of super dry ethyl alcohol in the usual manner add 1 5 ml. of pure ethyl acetate (dried over anhydrous calcium sulphate) to the solution at 60° and maintain this temperature for 30 minutes. Meanwhile equip a 1 litre threenecked flask with a dropping funnel, a mercury-sealed mechanical stirrer and a double surface reflux condenser the apparatus must be perfectly dry and guard tubes should be inserted in the funnel and condenser respectively. Place a mixture of 74 g. of ethyl phenylmalonate and 60 g. of ethyl iodide in the flask. Heat the apparatus in a bath at 80° and add the sodium ethoxide solution, with stirring, at such a rate that a drop of the reaction mixture when mixed with a drop of phenolphthalein indieator is never more than faintly pink. The addition occupies 2-2 -5 hoius continue the stirring for a fiuther 1 hour at 80°. Allow the flask to cool, equip it for distillation under reduced pressure (water pump) and distil off the alcohol. Add 100 ml. of water to the residue in the flask and extract the ester with three 100 ml. portions of benzene. Dry the combined extracts with anhydrous magnesium sulphate, distil off the benzene at atmospheric pressure and the residue under diminished pressure. C ollect the ethyl phenylethylmalonate at 159-160°/8 mm. The yield is 72 g. 

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). 

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