Diethyl ethylmalonate

Benzoyl fluoride, 46,3 Benzoy lhydrazine, 46, 85 Benzoyl peroxide, as catalyst for reaction of chloroform with as,as 1,5 cyclooctadiene, 47, 11 reaction with diethyl ethylmalonate, 46, 37... 

C2H,BrMg 925-90-6) see Amfebutamone Dicthylstilbestrol Elhylestrenol Etretinate Fomocaine Indanorex Ketobemidone Mepivacaine Methadone Methallenestril Methohexital Normethadone Olprinone hydrochloride Retinol cthylmalonic acid diethyl ester see under diethyl ethylmalonate ethylmercaptan... 

The mixed carbonic anhydride procedure8-7 has been useful in the preparation of amide linkages and thiol esters. Mixed carbonic anhydrides have successfully acylated, under very mild conditions, the carb-anions derived from diethyl ethylmalonate and diethylcadmium.8 The latter gives as a product the corresponding ketone. Mixed anhydrides derived from acetic and acetylsalicylic acids give results similar to those described here.8... 

Ethyl a-nitrobutyrate may be prepared in 75% yield by the reaction of silver nitrite with ethyl a-iodobutyrate.4 It has been prepared in 18% yield by nitration and subsequent decarboxylation of diethyl ethylmalonate.6 The present method offers the advantage of a direct preparation using sodium nitrite. 

Diethyl Ethylmalonate.—Sodium (4-6 g.) is dissolved, in a small flask fitted with an efficient reflux condenser, in 75 c.c. of absolute alcohol and to the cooled solution 33 g. of diethyl malonate are added (precipitation of diethyl sodio-malonate). To the mixture thus obtained, ethyl bromide (25 g.) or ethyl iodide (35 g.) is added in small portions with shaking and the flask is then heated on the water bath until, after one to two hours, the contents are no longer alkaline. The alcohol is removed by distillation in a vacuum from the water... 

The sodium hydride is obtained from Metal Hydrides Inc., Beverly, Massachusetts the diethyl ethylmalonate from Eastman Organic Chemicals. 

Benzophenone, 46, 36 N-(2-Benzothiazolyl)urea, 46, 72 Benzoyl chloride, reaction with hydrogen fluoride, 46, 4 Benzoyl fluoride, 46, 3 Benzoylhydrazine, 46, 8S Benzoyl peroxide, reaction with diethyl ethylmalonate, 45, 37 2-Benzyl-2-carbomethoxycyclopenta-none, 45, 7... 

To a 1-1., three-necked, round-bottomed flask is added 7.2 g. (0.15 mole) of a 50% dispersion of sodium hydride in mineral oil (Note 1). The sodium hydride is washed several times by decantation with dry ether and is then covered with 300 ml. of dry benzene (Note 2). The flask is equipped with dropping funnel, stirrer, and reflux condenser. Diethyl ethylmalonate (28.2 g., 0.15 mole) (Note 1) is added dropwise over a 5-minute period, and the reaction mixture is stirred for 2 hours until a clear solution forms. The solution is cooled in an ice bath, and 24.2 g. (0.1 mole) of benzoyl peroxide (Note 3) in 300 ml. of dry benzene is added dropwise over a 1-hour period with continuous stirring After another 30 minutes, a peroxide test (Note 4) is made to ensure that all the peroxide has reacted. 

Diethyl malonatc13 gives four products upon reaction with perchloryl fluoride diethyl difluoro-malonate, diethyl ethylmalonate, diethyl ethylfluoromalonate and diethyl fluoromalonate the product distribution depends on the reaction conditions. A number of esters are fluo-rinated,14 15 while (pentafluorophenyl)acetonitrile is converted into mono- and disubstituted products in the presence of cesium fluoride.16... 

Diethyl-ethylmalonate and deriv 5 D1236 diethyl-trinitro-ethylmalonate 5 D1236... 

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