Diethyl propanedioate

The stereochemical outcome and the diastereoselectivity of the addition of the anion of diethyl propanedioate to a,/ -unsaturated sulfoxides is dependent on the reaction solvent, the metal counterion and the geometry of the a,/ -unsaturated sulfoxide1 - 3. 

Trifluoro-l-(4-mcthylphcnylsulfinyl)-l-propcne undergoes addition of the sodium salt of diethyl propanedioate in THF in the same stereochemical sense3. 

Exercise 18-30 Explain why 2,4-pentanedione can be expected to contain much more enol at equilibrium than does ethyl 3-oxobutanoate. How much enoi would you expect to find in diethyl propanedioate In 3-oxobutanal Explain. 

The anions of esters such as ethyl 3-oxobutanoate and diethyl propanedioate can be alkylated with alkyl halides. These reactions are important for the synthesis of carboxylic acids and ketones and are similar in character to the alkylation of ketones discussed previously (Section 17-4A). The ester is converted by a strong base to the enolate anion, Equation 18-18, which then is alkylated in an SN2 reaction with the alkyl halide, Equation 18-19. Usually, C-alkylation predominates ... 

Exercise 18-40 How could you prepare diethyl methylpropanedioate that is free of diethyl propanedioate and diethyl dimethylpropanedioate (Review Section 18-8B to find an alternative synthesis not involving alkylation.)... 

Exercise 18-41 Show how one could prepare cyclobutanecarboxylic acid from diethyl propanedioate and a suitable dihalide. 

Enolate anions of esters, such as ethyl 3-oxobutanoate or diethyl propanedioate, react with aeyl halides or anhydrides to give acylation products. These reactions are carried out best using sodium hydride instead of sodium ethoxide for production of the enol salt, because then no alcohol is liberated to react with the acyl halide or anhydride ... 

The overall reaction is illustrated here by the specific example of the addition of diethyl propanedioate (diethyl malonate) to ethyl 3-phenylpro-penoate (ethyl cinnamate) ... 

The mechanism of this kind of transformation, with diethyl propanedioate as the addend, is outlined in Equations 18-25 and 18-26. The basic catalyst required for the Michael addition (here symbolized as B ) serves by forming the corresponding anion ... 

Exercise 18-47 Explain why the Michael addition of diethyl propanedioate to 3-phenylpropenoic acid is unlikely to be successful. 

Exercise 18-48 The Michael-addition product that results from ethyl 3-phenyl-propenoate and diethyl propanedioate, in principle, also can be formed by sodium ethoxide-catalyzed addition of ethyl ethanoate to ethyl (2-carbethoxy)-3-phenyl-propenoate. Work out the course of this reaction along the lines of Equations 18-25 and 18-26 and explain why it is less likely to be successful than the addition of diethyl propanedioate to ethyl 3-phenylpropenoate. It will be helpful to compare the various possible acid-base equilibria involved in the two possible routes to the same Michael-addition product. 

Diethyl propanedioate, d317 1,1-Diethylpropargylamine, d333 Diethyl pyrocarbonate, d326 Diethyl suberate, d324... 

DIETHYLPHOSPHOROTHIOYL))BENZALDOXIMIN O-N-METHYLCARBAMATE see DJW890 DIETHYL PHTHALATE see DJXOOO DIETHYL-o-PHTHALATE see DJXOOO DIETHYL PROPANEDIOATE see EMA500 DIETHYL-0-2-PYR, ZINYL PHOSPHOROTHIONATE see EPC500... 

Diethyl propanedioate, commonly called diethyl malonate or malonic ester, is more acidic than monocarbonyl compounds pK =13) because its a hydrogens are flanked by two carbonyl groups. Thus, malonic ester is easih converted into its enolate ion by reaction with sodium ethoxide in ethanol. The enolate ion, in turn, is a good nucleophile that reacts rapidh with an alkyl halide to give an a-substituted malonic ester. Note in the following examples that the abbreviation "Et" is used for an ethyl group, CH2CH3. 

DIETHYL PROPANEDIOATE (105-53-3) Combustible liquid (flash point 183 F/84X). Incompatible with oxidizers, nitrates. 

Malonic ester synthesis Synthesis of 2,2-disubstituted carboxylic acids from diethyl propanedioate Imitlonic ester). 

Synonyms Carbethoxyacetic ester DEM Dicarbethoxymethane Diethyl propanedioate Ethyl malonate... 

Diethyl-o-phthalate. See Diethyl phthalate N,N-Diethylpropanediamine N,N-Diethyl-1,3-propanediamine. See3-Diethylaminopropylamine Diethyl propanedioate. See Diethyl malonate N,N-Diethyl-2-propenamide. See N,N-Diethyl acrylamide 2,3-Diethyl pyrazine... 

Malonic ester synthesis (Section 18.7) A reaction in which the a-hydrogen of diethyl propanedioate (diethyl malonate, also called malonic ester ) is removed, creating a resonance-stabilized anion which can serve as a nucleophile in an 5 2 reaction. The a-carbon can be substituted twice the ester functionalities can be converted into a carboxylic acid which, after decarboxylation, will yield a substituted ketone. 

Methylcyclohexanone Diethyl propanedioate Propane-1,2-diol diethanoate Cycloheptane Hept-l-ene Methylcyclohexane Cycloheptanol Heptan-2-one Heptan-3-one Heptan-4-one... 

C7H12O4 105-53-3 Diethyl propanedioate syn. nDiethyl malonate nMalonic acid diethyl ester nPropanedioic acid diethyl ester... 

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