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Diethyl Malonate, also known as DEM, is the diethyl ester of malonic acid.
Diethyl Malonate occurs naturally in grapes and strawberries as a colourless liquid with an apple-like odour, and is used in perfumes.
Diethyl Malonate is also used to synthesize other compounds such as barbiturates, artificial flavourings, vitamin B1, and vitamin B6.
EC Number: 203-305-9
CAS Number: 105-53-3
IUPAC Name: Diethyl propanedioate
Chemical Formula: C7H12O4
Other names: DIETHYL MALONATE, 105-53-3, Diethyl propanedioate, Ethyl malonate, Propanedioic acid, diethyl ester, Malonic ester, Carbethoxyacetic ester, Dicarbethoxymethane, Malonic acid, diethyl ester, 1,3-diethyl propanedioate, Ethyl propanedioate, Malonic acid diethyl ester, Ethyl methanedicarboxylate, Methanedicarboxylic acid, diethyl ester, Ethyl malonate (VAN), FEMA No. 2375, NSC 8864, EINECS 203-305-9, MFCD00009195, propanedioic acid diethyl ester, CCRIS 9480, UNII-53A58PA183, AI3-00656, NSC-8864, Propanedioic acid, 1,3-diethyl ester, 53A58PA183, DTXSID7021863, HSDB 8438, EC 203-305-9, NSC-136903, DTXCID701863, CAS-105-53-3, Malonic acid diethyl, dietyl malonate, malonic acid-diethylester, CH2(COOEt)2, Diethyl propanedioate, 9CI, SCHEMBL8636, ETHYL MALONATE [MI], WLN: 2OV1VO2, DIETHYL MALONATE [FCC], CHEMBL177114, DIETHYL MALONATE [FHFI], FEMA 2375, Diethyl malonate, >=98%, FG, NSC8864, CHEBI:167785, STR00319, Tox21_201362, Tox21_302931, BBL027742, BDBM50502172, Diethyl malonate, analytical standard, s6208, STL281878, AKOS000118957, CS-W020637, Diethyl malonate, ReagentPlus(R), 99%, NCGC00249033-01, NCGC00256502-01, NCGC00258914-01, DB-051013, Diethyl malonate, purum, >=97.0% (GC), M0029, NS00001108, Diethyl malonate, puriss., >=99.0% (GC), EN300-19208, D78522, Diethyl malonate, Vetec(TM) reagent grade, 98%, Q-200975, Q27887610, F1908-0063, Z104473166, PROPANEDIOIC ACID,DIETHYL ESTER (MALONIC ACID,DIETHYL ESTER), InChI=1/C7H12O4/c1-3-10-6(8)5-7(9)11-4-2/h3-5H2,1-2H
Structure and properties
Malonic acid is a rather simple dicarboxylic acid, with two the carboxyl groups close together.
In forming diethyl malonate from malonic acid, the hydroxyl group (-OH) on both of the carboxyl groups is replaced by an ethoxy group (-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)-).
The hydrogen atoms on the carbon adjacent to the carbonyl group in a molecule is significantly more acidic than hydrogen atoms on a carbon adjacent to alkyl groups (up to 30 orders of magnitude).
(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 the carbonyl groups help stabilize the carbanion resulting from the removal of a proton from the methylene group between them.
Preparation
Diethyl malonate may be prepared by reacting the sodium salt of chloroacetic acid with sodium cyanide, followed by base hydrolysis of the resultant nitrile to give the sodium salt of the malonic acid.
Reactions
Malonic ester synthesis
Main article: malonic ester synthesis
One of the principal uses of this compound is in the malonic ester synthesis.
The carbanion (2) formed by reacting diethyl malonate (1) with a suitable base can be alkylated with a suitable electrophile.
This alkylated 1,3-dicarbonyl compound (3) readily undergoes decarboxylation with loss of carbon dioxide.
In general, salts of the alkoxide anion whose alkyl part corresponds to the one used in the above alkylation are preferred as the base.
The use of a conventional base may give base hydrolysis products- for example, sodium hydroxide would simply produce sodium malonate and the alcohol- while other alkoxide salts will cause scrambling by transesterification.
Only the "same" alkoxide anion as the one that one used to alkylate the deprotonated active methylenic site will prevent both base hydrolysis and transesterification.
Other reactions
Like many other esters, this compound undergoes the Claisen ester condensations.
The advantage of using this compound is that unwanted self-condensation reactions are avoided.
Like other esters, this compound undergoes bromination at the alpha position.
Diethyl malonate can be nitrosated with excess sodium nitrite in acetic acid to afford diethyl oximinomalonate, catalytic hydrogenolysis of which in ethanol over Pd/C affords diethyl aminomalonate (DEAM).
DEAM can be acetylated to produce diethyl acetamidomalonate (useful in amino-acid synthesis), or can be added with 3-substituted 2,4-diketones to boiling acetic acid to afford in maximal yield variously substituted ethyl pyrrole-2-carboxylates of interest for porphyrin synthesis.
(Ref. J.B. Paine III, D. Dolphin, J. Org. Chem. 1985, 50, 5598-5604.)
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.
Diethyl Malonate is a flavor ingredient commonly found in perfumes, artificial flavorings, alcoholic beverages, various wines and spirits due to its natural pleasant odor.
Diethyl Malonate 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.
Diethyl Malonate 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.
Diethyl Malonate is also involved in the synthesis of pharmaceuticals like chloroquine, butazolidin and barbital.
Diethyl Malonate 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.
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.
Diethyl Malonate is used in the preparation of barbiturates, artificial flavourings, vitamin B1, and vitamin B6 as well as in perfumes.
Manufacture of barbiturates.
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.
Dimethyl and diethyl malonates are widely used for the production of vitamins, pharmaceuticals, agrochemicals, fragrances, and dyes.
Diethyl malonate was used to investigate Knoevenagel condensation reactions in microreactor using zeolite catalysts obtained by grafting amino groups onto NaX and CsNaX zeolites.
Diethyl Malonate may be used in the synthesis of diethyl benzylidenemalonate by base catalyzed Knoevenagel condensation with benzaldehyde.
Diethyl Malonate may be used in the synthesis of a-aryl malonates
Industry Uses
Odor agents
intermediate for pharmaceutical
Consumer Uses
Air care products
Building/construction materials not covered elsewhere
Non-TSCA use
aroma chemicals
General Manufacturing Information
Industry Processing Sectors
Construction
Miscellaneous manufacturing
Pharmaceutical and medicine manufacturing
Diethyl malonate is diethyl ester of malonic acid.
4Acylation 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 beta,gamma-unsaturated enones.
IDENTIFICATION AND USE:
Diethyl malonate is used in chemical synthesis.
Diethyl Malonate is also used in food, beverages, and in fragrances.
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.
Application
Diethyl malonate was used to investigate Knoevenagel condensation reactions in microreactor using zeolite catalysts obtained by grafting amino groups onto NaX and CsNaX zeolites.
Diethyl Malonate may be used in the synthesis of diethyl benzylidenemalonate by base catalyzed Knoevenagel condensation with benzaldehyde.
Diethyl Malonate may be used in the synthesis of α-aryl malonates.
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.
Diethyl Malonate is also involved in the synthesis of pharmaceuticals like chloroquine, butazolidin and barbital.
Diethyl Malonate 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.
Diethyl malonate, naturally occuring in grapes and strawberries, is used in the synthesis of chemicals.
Diethyl Malonate is sweet green apple fruity pineapple winey-estery soft pleasant fruity-green balsamic apples fresh-top-note-modifier green-citrus-notes grape pear apricot wine-like-notes rose-apple star-fruit berry.
Diethyl malonate belongs to the class of organic compounds known as dicarboxylic acids and derivatives.
These are organic compounds containing exactly two carboxylic acid groups.
Based on a literature review very few articles have been published on Diethyl malonate.
belongs to the class of organic compounds known as dicarboxylic acids and derivatives.
These are organic compounds containing exactly two carboxylic acid groups.
Diethyl Malonate occurs naturally in grapes and strawberries.
Diethyl Malonate is used in the preparation of barbiturates, artificial flavourings, vitamin B1, and vitamin B6 as well as in perfumes.
About this substance
Helpful information
This substance is registered under the REACH Regulation and is manufactured in and / or imported to the European Economic Area, at ≥ 100 to < 1 000 tonnes per annum.
This substance is used by consumers, in articles, by professional workers (widespread uses), in formulation or re-packing, at industrial sites and in manufacturing.
Consumer Uses
This substance is used in the following products: washing & cleaning products, air care products, polishes and waxes, biocides (e.g. disinfectants, pest control products), cosmetics and personal care products and perfumes and fragrances. Other release to the environment of this substance is likely to occur from: indoor use (e.g. machine wash liquids/detergents, automotive care products, paints and coating or adhesives, fragrances and air fresheners) and outdoor use as processing aid.
Other release to the environment of this substance is likely to occur from: outdoor use in long-life materials with low release rate (e.g. metal, wooden and plastic construction and building materials) and indoor use in long-life materials with low release rate (e.g. flooring, furniture, toys, construction materials, curtains, foot-wear, leather products, paper and cardboard products, electronic equipment).
This substance can be found in products with material based on: plastic (e.g. food packaging and storage, toys, mobile phones).
Widespread uses by professional workers
This substance is used in the following products: polishes and waxes, washing & cleaning products, laboratory chemicals, coating products and fillers, putties, plasters, modelling clay.
This substance is used in the following areas: health services and scientific research and development.
Other release to the environment of this substance is likely to occur from: indoor use (e.g. machine wash liquids/detergents, automotive care products, paints and coating or adhesives, fragrances and air fresheners) and outdoor use.
Formulation
This substance is used in the following products: perfumes and fragrances and coating products.
Release to the environment of this substance can occur from industrial use: formulation of mixtures.
Uses at industry
This substance is used in the following products: washing & cleaning products, coating products, laboratory chemicals, adhesives and sealants, pH regulators and water treatment products and pharmaceuticals.
This substance has an industrial use resulting in manufacture of another substance (use of intermediates).
This substance is used in the following areas: printing and recorded media reproduction and building & construction work.
This substance is used for the manufacture of: chemicals, textile, leather or fur, wood and wood products, pulp, paper and paper products, rubber products, plastic products, mineral products (e.g. plasters, cement), fabricated metal products, electrical, electronic and optical equipment, machinery and vehicles and furniture.
Release to the environment of this substance can occur from industrial use: in processing aids at industrial sites, as an intermediate step in further manufacturing of another substance (use of intermediates), in the production of articles and for thermoplastic manufacture.
