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Diethyl ketomalonate

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Diethyl ketomalonate Basic information
Product Name:Diethyl ketomalonate
Synonyms:2-Oxopropanedioic acid diethyl;2-Oxopropanedioic acid diethyl ester;Ketomalonic acid diethyl;Oxomalonic acid diethyl;Diethyl KETOMALONATE ester;Diethyl ketomalonate ,98%;Diethyl 2-oxomalonate 97%;Diethyl ketomalonate, (Diethyl mesoxalate
CAS:609-09-6
MF:C7H10O5
MW:174.15
EINECS:210-176-2
Product Categories:Pharmaceutical Intermediates
Mol File:609-09-6.mol
Diethyl ketomalonate Structure
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
Fp >230 °F
storage temp. Inert atmosphere,Room Temperature
solubility Chloroform (Slightly), Methanol
form liquid
color green-yellow
Specific Gravity1.142
Water Solubility Fully miscible with water.
Sensitive Moisture Sensitive
Merck 14,5913
BRN 971873
InChIKeyDBKKFIIYQGGHJO-UHFFFAOYSA-N
CAS DataBase Reference609-09-6(CAS DataBase Reference)
NIST Chemistry ReferencePropanedioic acid, oxo-, diethyl ester(609-09-6)
EPA Substance Registry SystemPropanedioic acid, oxo-, diethyl ester (609-09-6)
Safety Information
Hazard Codes Xi
Safety Statements 24/25
WGK Germany 3
21
Hazard Note Irritant
TSCA T
HazardClass IRRITANT, MOISTURE SENSITIVE
HS Code 29183000
MSDS Information
ProviderLanguage
SigmaAldrich English
ACROS English
ALFA English
Diethyl ketomalonate Usage And Synthesis
Chemical PropertiesClear yellow liquid
UsesDiethyl ketomalonate, reagent employed in Wittig and Aza-Wittig reactions for synthesis of triazoles, and 2-azadienes, respectively.
ApplicationDiethyl 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.
PreparationDiethyl 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
diethyl methylidenemalonate

3377-20-6

Diethyl ketomalonate

609-09-6

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.

storageDiethyl 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
Tag: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

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