Diethyl malonate

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Diethyl malonate

General
Systematic name	diethyl propanedioate
Other names	diethyl malonate, DEM
Molecular formula	C₇H₁₂O₄
SMILES	CCOC(=O)CC(=O)OCC
Molar mass	160.17 g mol⁻¹
Appearance	colourless liquiud
CAS number	[105-53-3]
Properties
Density and phase	1.05 g cm⁻³, liquid
Solubility in water	negligible
Solubility in ethanol, acetone, diethyl ether, benzene	?
Melting point	−50 °C (223 K)
Boiling point	199 °C (472 K)
Hazards
MSDS	Oxford University MSDS
Main hazards	Harmful (X), Flammable (F)
NFPA 704	1 0 0
Flash point	100 °C
Related compounds
Related compounds	Malonic acid
Except where noted otherwise, data are given for materials in their standard state (at 25 °C, 100 kPa) Infobox disclaimer and references

Diethyl malonate, also known as DEM, is the diethyl ester of malonic acid. It occurs naturally in grapes and strawberries as a colourless liquid with an apple-like odour, and is used in perfumes. It is also used to synthesize other compounds such as barbiturates, artificial flavourings, vitamin B1, and vitamin B6.

1 Chemistry
2 Acidity
3 Malonic Ester Synthesis
4 Reactions
5 See also
- 5.1 External links

[edit] Chemistry

Malonic acid is a rather simple dicarboxylic acid, with two carboxyl groups close together in its molecule. In forming diethyl malonate from malonic acid, the hydroxyl group (-OH) on both of the carboxyl groups are replaced by ethoxy groups (-OEt; -OCH₂CH₃). The methylene group (-CH₂-) in the middle of the malonic part of the diethyl malonate molecule is neighboured by two carbonyl groups (-C(=O)-).

[edit] Acidity

The hydrogen atoms on the carbon adjacent to the a carbonyl group in a molecule is slightly more acidic hydrogens than hydrogen atoms on a carbon adjacent to alkyl groups. (This is known as the α position with respect to the carbonyl.) The hydrogen atoms on a carbon adjacent to two carbonyl groups are even more acidic because on the – the carbonyl groups helps stabilize the carbanion resulting from the removal of a proton from the methylene group between them.

This carbanion can be made from treating diethyl malonate with a base such as sodium ethoxide in ethanol. If aqueous sodium hydroxide were used, base hydrolysis of the ester can happen giving sodium malonate and ethanol. When sodium ethoxide is used, instead, any nucleophilic attack at the carboxylate by the ethoxide will not give any side product. Thus sodium ethoxide is preferred.

This carbanion is neutralized by the sodium cation from the sodium ethoxide. This resulting salt is useful in malonic ester syntheses.

The carbanion formed from diethyl malonate and partially stabilized by conjugation with the two adjacent carbonyl groups

Three tautomeric forms of the conjugate base formed by diethyl malonate

[edit] Malonic Ester Synthesis

Other examples of 1,3-diketo compounds with labile hydrogens include acetylacetone, acetoacetate esters. Synthetically, malonic esters are often used in Claisen ester condensations because unwanted self-condensation reactions are avoided.