Diethyl ketomalonate Chemical Properties

Melting point:

-70°C

Boiling point:

208-210 °C (lit.)

Density 

1.142 g/mL at 25 °C (lit.)

refractive index 

n20/D 1.415

Flash point:

>230 °F

storage temp. 

Inert atmosphere,Room Temperature

solubility 

Chloroform (Slightly), Methanol

form 

liquid

color 

green-yellow

Specific Gravity

1.142

Water Solubility 

Fully miscible with water.

Sensitive 

Moisture Sensitive

Merck 

14,5913

BRN 

971873

InChIKey

DBKKFIIYQGGHJO-UHFFFAOYSA-N

CAS DataBase Reference

609-09-6(CAS DataBase Reference)

NIST Chemistry Reference

Propanedioic acid, oxo-, diethyl ester(609-09-6)

EPA Substance Registry System

Propanedioic acid, oxo-, diethyl ester (609-09-6)

Safety Information

Hazard Codes 

Xi

Safety Statements 

24/25

WGK Germany 

3

F 

21

Hazard Note 

Irritant

TSCA 

TSCA listed

HazardClass 

IRRITANT, MOISTURE SENSITIVE

HS Code 

29183000

MSDS

• Language:English Provider:SigmaAldrich
• Language:English Provider:ACROS
• Language:English Provider:ALFA

Diethyl ketomalonate Usage And Synthesis

Chemical Properties

Clear yellow liquid

Uses

Diethyl ketomalonate, reagent employed in Wittig and Aza-Wittig reactions for synthesis of triazoles, and 2-azadienes, respectively.

Application

Diethyl ketomalonate can be used in electron-deficient heterodienophile; Diels-Alder reaction; heterodipolarophile; [3 + 2] cycloaddition; 1,3-diyl trapping agent; 1,4-dipolar cycloaddition; [2 + 2] cycloaddition; enophile; ene reaction; electrophilic addition; Wittig reactions; condensation with amines; Pictet-Spengler reactions.

Preparation

Diethyl ketomalonate can be prepared by bromination of Diethyl Malonate to the dibromomalonic ester, exchange of one bromine atom for acetate and α-elimination of acetyl bromide. Alternatively, diethyl malonate is condensed with benzaldehyde to afford the Knoevenagel product which is cleaved by ozonolysis.

Synthesis Reference(s)

Synthetic Communications, 24, p. 695, 1994 DOI: 10.1080/00397919408012648
The Journal of Organic Chemistry, 46, p. 2598, 1981 DOI: 10.1021/jo00325a039

Synthesis

The general procedure for the synthesis of diethyl ketomalonate from diethyl methylidenemalonate was as follows: 258 g of diethyl methylidenemalonate prepared by Knoevenagel condensation reaction of malonic acid and formaldehyde was dissolved in 1 liter of methanol, followed by ozonation reaction. Upon completion of the reaction, 5 g of 10% Pd-on-C was added as a hydrogenation catalyst and placed in 200 ml of methanol to carry out the hydrogenation reaction, with a hydrogen consumption of 28.9 standard liters (86% of the theoretical value was reached). The reaction mixture was post-treated according to the method of Example 5 and subsequently concentrated under vacuum to give 214 g of diethyl ketomalonate with a boiling point of 10.0-112°C/20 mmHg in 82% yield of the theoretical value.

storage

Diethyl ketomalonate is stable for at least 6 months if stored in the refrigerator.

References

[1] Patent: US4769464, 1988, A
[2] Tetrahedron Letters, 1981, vol. 22, # 46, p. 4607 - 4610

Diethyl ketomalonate(609-09-6)Related Product Information

• Diethyl dipropylmalonate
• Diethyl isopropylmalonate
• Diethyl chloromalonate
• DIETHYL DIMETHYLMALONATE
• Diethyl malonate
• Diethyl fluoromalonate
• Dimethyl malonate
• DIETHYL BROMOMALONATE
• Diethyl 2-ethyl-2-phenylmalonate
• Diethyl ethylmalonate
• Diethyl butylmalonate
• Malonic acid
• Diethyl methylmalonate
• 2-AMINODIETHYLMALONATE
• Diethyl bis(hydroxymethyl)malonate
• Diethyl phenylmalonate
• DIETHYL DIETHYLMALONATE
• Diethyl allylmalonate