Diethyl malonate Property

Melting point:

-51--50 °C (lit.)

Boiling point:

199 °C (lit.)

Density 

1.055 g/mL at 25 °C (lit.)

vapor density 

5.52 (vs air)

vapor pressure 

1 mm Hg ( 40 °C)

refractive index 

n20/D 1.413(lit.)

FEMA 

2375 | DIETHYL MALONATE

Flash point:

212 °F

storage temp. 

Store below +30°C.

solubility 

20.8g/l (External MSDS)

pka

13.5(at 25℃)

form 

Liquid

color 

colourless liquid

Odor

Sweet ester odor

Odor Type

fruity

explosive limit

0.8-12.8%(V)

Water Solubility 

Miscible with ethyl alcohol, ether, chloroform and benzene. Slightly miscible with water.

Merck 

14,3823

JECFA Number

614

BRN 

774687

Dielectric constant

7.9（21℃）

Stability:

Stable. Combustible. Incompatible with strong oxidizing agents,

InChIKey

IYXGSMUGOJNHAZ-UHFFFAOYSA-N

LogP

0.96 at 20℃

CAS DataBase Reference

105-53-3(CAS DataBase Reference)

NIST Chemistry Reference

Propanedioic acid, diethyl ester(105-53-3)

EPA Substance Registry System

Diethyl malonate (105-53-3)

Safety

Hazard Codes 

Xi

Risk Statements 

36/37/38-36

Safety Statements 

24/25-26

WGK Germany 

1

RTECS 

OO0700000

Autoignition Temperature

435 °C DIN 51794

Hazard Note 

Irritant

TSCA 

Yes

HS Code 

29171910

Hazardous Substances Data

105-53-3(Hazardous Substances Data)

Toxicity

LD50 orally in Rabbit: 15720 mg/kg LD50 dermal Rabbit > 16000 mg/kg

Hazard and Precautionary Statements (GHS)

Symbol(GHS)

Signal word

Warning

Hazard statements

H319Causes serious eye irritation

Precautionary statements

P264Wash hands thoroughly after handling.

P264Wash skin thouroughly after handling.

P280Wear protective gloves/protective clothing/eye protection/face protection.

P305+P351+P338IF IN EYES: Rinse cautiously with water for several minutes. Remove contact lenses, if present and easy to do. Continuerinsing.

P337+P313IF eye irritation persists: Get medical advice/attention.

Diethyl malonate Chemical Properties,Usage,Production

Description

As an organic compound, diethyl malonate belongs to the diethyl ester of malonic acid, which is present naturally in guava fruits, melons, grapes, pineapples, blackberries and strawberries as a colorless liquid with an apple-like odor. It is a flavor ingredient commonly found in perfumes, artificial flavorings, alcoholic beverages, various wines and spirits due to its natural pleasant odor. It is also used as an essential intermediate in the syntheses of numerous pharmaceuticals, such as barbiturates, vitamins B1 and B6, non-steroidal anti-inflammatory agents. Besides, diethyl malonate is also involved in organic synthesis of other compounds, such as alpha-aryl malonates, mono-substituted and di-substituted acetic acid. And it can react with benzaldehyde for the production of diethyl benzylidenemalonate in Knoevenagel condensation reaction.

uses

Diethyl malonate is the diethyl ester of malonic acid. It naturally occuring in grapes and strawberries, is widely used in the manufacture of pharmaceuticals, antioxidants, and dyes.
Diethyl malonate is used in organic synthesis for the preparation of alpha-aryl malonates, mono-substituted and di-substituted acetic acid, barbiturates and artificial flavorings. It is also involved in the synthesis of pharmaceuticals like chloroquine, butazolidin and barbital. It acts as intermediate in the synthesis of vitamin B1, vitamin B6, non-steroidal anti-inflammatory agents agrochemicals and perfumes. In Knoevenagel condensation reaction, it reacts with benzaldehyde to get diethyl benzylidenemalonate.

References

https://en.wikipedia.org/wiki/Diethyl_malonate
https://pubchem.ncbi.nlm.nih.gov/compound/7761#section=Safety-and-Hazards
https://www.alfa.com/zh-cn/catalog/A15468/
http://www.hmdb.ca/metabolites/HMDB29573
http://www.chemicalland21.com/industrialchem/organic/DIETHYL%20MALONATE.htm

Description

Diethyl malonate is a diester derivative of malonic acid, a dicarboxylic acid with two carboxyl groups (-COO-) separated by one methylene group (-CH2-). Diethyl malonate is formed by the replacement of the hydroxyl groups (-OH) of malonic acid with ethoxy groups (-OCH2CH3). The hydrogen atoms on the methylene carbon between the two carboxyl groups make this compound acidic. Because of its unique structure, diethyl malonate is reactive and functions as a reagent for organic synthesis and to make products such as barbiturates, pigments, and agrochemicals. Volatile esters are known to have fruity scents and are often used as fragrances and flavorings. Diethyl malonate is a volatile diester that occurs naturally in fruits such as grapes, strawberries, guava, melon, pineapple, and blackberries.

Chemical Properties

Diethyl malonate has a faint, pleasant, aromatic odor.

Occurrence

Reported found in pineapple, bilberry, Cape gooseberry, cognac, malt whiskey, apple brandy, grape brandy, port, cider, sherry and red, white, strawberry and bilberry wines.

Uses

Diethyl Malonate occurs naturally in grapes and strawberries. It is used in the preparation of barbiturates, artificial flavourings, vitamin B1, and vitamin B6 as well as in perfumes.

Uses

manufacture of barbiturates.

Uses

Diethyl malonate is used in organic synthesis for the preparation of alpha-aryl malonates, mono-substituted and di-substituted acetic acid, barbiturates and artificial flavorings. It is also involved in the synthesis of pharmaceuticals like chloroquine, butazolidin and barbital. It acts as intermediate in the synthesis of vitamin B1, vitamin B6, non-steroidal anti-inflammatory agents agrochemicals and perfumes. In Knoevenagel condensation reaction, it reacts with benzaldehyde to get diethyl benzylidenemalonate.

Definition

ChEBI: Ethyl malonate is a dicarboxylic acid.

Preparation

Reacting chloroacetic acid to cyanoacetic acid using sodium cyanide and subsequent saponification; malonic acid is finally esterified by azeotropic distillation with ethanol in benzene

Taste threshold values

Taste characteristics at 50 ppm: sweet and fruity with apple and pineapple nuances.

Synthesis Reference(s)

The Journal of Organic Chemistry, 46, p. 3151, 1981 DOI: 10.1021/jo00328a041
Tetrahedron Letters, 36, p. 3997, 1995 DOI: 10.1016/0040-4039(95)00697-B

General Description

Diethyl malonate is diethyl ester of malonic acid. Acylation of diethyl malonate using magnesium chloride and triethylamine is reported. K₂CO₃-catalyzed 1,4-addition reaction of diethyl malonate with various substituted 1,2-allenic ketones yields polyfunctionalized β,γ-unsaturated enones.

Safety Profile

Mildly toxic by ingestion. A skin irritant. Combustible liquid when exposed to heat or flame; can react with oxidizing materials. To fight fire, use water to blanket fire, foam, CO2, dry chemical. When heated to decomposition it emits acrid smoke and irritating fumes. See also ESTERS.

Metabolism

When the ester was fed to chicks at a level of 5% in the diet, 32% of the energy from diethyl malonate was available (Yoshida et al. 1970). Hydrolysis of diethyl malonate would produce ethanol and malonic acid, which is a relatively strong acid and acts as an inhibitor of enzymes, including succinic dehydrogenase (Fassett, 1963). Malonic acid injected into rats or rabbits is excreted largely unchanged, but also causes increased excretion of citric and a-ketoglutaric acids (Krebs, Salvin & Johnson, 1938). Some malonate may be metabolized through the tricarboxylic acid cycle, with decarboxylation to acetate followed by transformation to succinate, which has been detected in rat urine (Lee & Lifson, 1951). Diethyl malonate was hydrolysed by adipose-tissue lipase (Lynn & Perryman, 1960) and to the monoester by α-chymotrypsin (Cohen & Crossely, 1964). It was oxidized in 110 min to the extent of 34% by the homogenized mycelium of urethane-grown Streptomyces nitrifica (Schatz, Trelawny, Schatz & Mohan, 1957).

Purification Methods

If too impure (IR, NMR) the ester (250g) is heated on a steam bath for 36hours with absolute EtOH (125mL) and conc H2SO4 (75mL), then fractionally distilled under reduced pressure. Otherwise fractionally distil it under reduced pressure and collect the steady boiling middle fraction. [Beilstein 2 IV 1881.]