Diethyl ethylene malonate

Amidines of perfluorocarboxylic acids are excellent synthons for the preparation of fluoroalkyl pyrimidines. The reaction of 35 with diethyl ethoxy ethylene malonate or malononitrile results in the formation of the corresponding 2-trifluoromethylpyrimidines 36 and 37 in high yield (Fig. 7.11). ... 

Incorporation of a carbonyl group into the alkyl side chain also proved compatible with biologic activity. The key intermediate (76) is obtainable by Michael addition of the anion from diethyl malonate to methylvinyl ketone followed by ketalization with ethylene glycol. Condensation of 76 with hydrazobenzene leads to the pyrazolodione hydrolysis of the ketal group affords ketasone (78). ... 

Diethyl malonate was reacted with 4-chlorophenyl isothiocyanate in the presence of sodium hydride in dioxane at room temperature for 1 hr to give the sodium salt of mercapto-(4-chlorophenylamino)methylenemalonate, which was then treated with ethylene dibromide in DMF at room temperature overnight. In this way, diethyl [3-(4-chlorophenyl)-l,3-thiazolidin-2-ylidene]malonate was obtained in 88% yield (82EUP58392). 

Cyclopropane carboxylic acid (1) Cyclopropane bromide + KCN - cyclopropane cyanide followed by hydrolysis (2) Ethylene dibromide + diethyl malonate - cyclopropane dicarboxylic acid followed by saponification and monodecarboxylation via heating... 

Finally, Cope and his co-workers discovered that tetra(bromomethyl)ethylene can be multiply alkylated in low yield by diethyl malonate to give 3,3,7,7-tetracarbe-thoxybicyclo[3.3.0]oct-l(5)-ene (13).40 This substance can be decarboxylated and further modified structurally. 

Alkylation of malonic ester with an equimolar ponion of ethylene bromide or trimethylene bromide produces ring closure to give diethyl esters of 1,1-cyclopropane- and 1,1-cyclobutane-dicarboxylic acids, respectively. Five- and six-membered rings also have been formed in this manner. ... 

Monomers. The following monomers were obtained from Eastman Organic Chemicals and used as received diethylene glycol, ethylene glycol, hexamethylene glycol, diethyl succinate, diethyl malonate, diethyl adipate, and 1,4-cyclohexane dimethanol. The following monomers were... 

Quinoxaline-2-carboxaldehyde has been converted into the 2-carboxylic acid by oxidation with potassium permanganate in acetone and reduced to the 2-hydroxymethyl compound by treatment with formalin and potassium hydroxide. It also undergoes other typical reactions of aromatic aldehydes such as benzoin formation on reaction with potassium cyanide - and condensation reactions with malonic acid and its diethyl ester and Schiff base formation. Acid-catalyzed reaction of quinoxaline-2-carboxaldehyde with ethylene glycol gives the cyclic acetal the diethylacetal has been prepared by reaction of 2-dibromomethylquinoxaline with sodium ethoxide. " An indirect preparation of the oxime 11 is achieved by treatment of 2-nitromethyl-quinoxaline (10) with diazomethane followed by thermolysis of the resulting nitronic ester. 

Materials. Terephthaldicarboxaldehyde (Aldrich), diethyl bis(hydroxymethyl) malonate (Aldrich), p-toluenesulfonic acid (Aldrich), potassium hydroxide (85 wt%, Fisher), pyridine (Fisher), glutaric dialdehyde (50wt% aqueous solution, Aldrich), ethylene glycol divinyl ether (Aldrich), ethyl glycolate (Aldrich), isophthalic dicarboxaldehyde (Lancaster), propionaldehyde (Eastman Chemical), isovaleraldehyde (Aldrich), 2-ethyl-2-oxazoline (Acros), ammonia (7M in methanol, Acros), l-methoxy-4-(methylthio)benzene (Aldrich), silver... 

Ethylene oxide added to an ice-cold suspension of diethyl acetamido-(5-amino-3-indolylmethyl) malonate in methanol containing p-toluenesulfonic acid, and stirred 18 hrs. at room temp. diethyl acetamido-[5-bis-(2-hydroxyethyl)-amino-3-indolylmethyl] malonate (Y 99%) dissolved in pyridine, treated with methanesulfonyl chloride, and heated 20 min. in an oil bath at 80-90° after the exothermic reaction has subsided -> diethyl acetamido- [5-bis- (2-chlorethyl) -amino-3-indolylmethyl]malonate (Y 40-50%).—Other chlorodehydroxylation methods were not successful. J. DeGraw and L. Goodman, J. Org. Ghem. 27, 1395 (1962). 

Show how the scheme for formation of 4-butanolactone in Problem 19.47 can be used to synthesize lactones (a) and (b), each of which has a peach odor and is used in perfumery. As sources of carbon atoms for these syntheses, use diethyl malonate, ethylene oxide, 1-bromoheptane, and 1-nonene. 

ChCl is choline chloride. Gly is glyceroL EG is ethylene glycoL MAc is malonic acid. EtjtElOHlNCl = N,N-diethyl ethanol ammonium chloride. 

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