Diethyl propanedioate malonate

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

Diethyl propanedioate (malonic ester) is the starting material for preparing 2-aIkylated and 2,2-dialkylated acetic acids, a method called the malonic ester synthesis. 

Propose a synthesis of cyclohexanecarboxylic acid from diethyl propanedioate (malonate), CH2(C02CH2CH3)2, and l-bromo-5-chloropentane, Br(CH2)5Cl. 

In Summary jS-Dicarbonyl compounds such as ethyl 3-oxobutanoate (acetoacetate) and diethyl propanedioate (malonate) are versatile synthetic building blocks for elaborating more complex molecules. Their unusual acidity makes it easy to form the corresponding anions, which can be used in nucleophilic displacement reactions with a wide variety of substrates. Their hydrolysis produces 3-ketoacids that are unstable and undeigo decarboxylation on heating. 

Propose a synthesis of veronal from diethyl propanedioate (malonic ester. Section 23-2) and urea (Section 20-6). (Hint In the presence of a base, such as an alkoxide, amides are in equilibrium with the corresponding amidates Section 20-7.)... 

Recall that A-alkylation of 1,2-benzenedicarboxylic imide (phthalimide) anion followed by acid hydrolysis furnishes amines (Section 21-5). To prepare an amino acid instead, we can use diethyl 2-bromopropanedioate (diethyl 2-bromomalonate) in the first step of the reaction sequence. This alkylating agent is readily available from the bromination of diethyl propanedioate (malonate). Now the alkylation product can be hydrolyzed and decarboxylated (Section 23-2). Hydrolysis of the imide group then furnishes an amino acid. 

Diethyl cyclopropylcarbonylmalonate Malonic acid, (cyclopropylcarbonyl)-, diethyl ester (8) Propanedioic acid, (cyclopropylcarbonyl)-, diethyl ester (9) (7394-16-3)... 

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) ... 

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. 

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

Malonic acid, diethyl ester Malonic ester Methanedicarboxylic acid, diethyl ester Propanedioic acid diethyl ester... 

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. 

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

Maleic anhydride see l-Oxacyclopent-3-en-2,5-dione Malonic acid diethyl ester see Diethyl propanedioate MEK see Butan-2-one... 

Ethyl ethanoate Diethyl propanedioate (Ethyl acetate) (Diethyl malonate)... 

Acetoacetic ester is a common name for ethyl acetoacetate, Its systematic, but rarely used, name is ethyl 3-oxobutanoate. Malonic ester is a common name for diethyl malonate, which is an acceptable alternative for diethyl propanedioate. 

---