Methanedicarboxylic acid
Methanedicarboxylic acid = Propanedioic acid = 1,3-Propanedioic acid = Malonic Acid = Carboxyacetic acid = Dicarboxymethane= Kyselina malonova =
EC / List no.: 205-503-0
CAS no.: 141-82-2
Methanedicarboxylic acid is acts as a building block in organic synthesis. Methanedicarboxylic acid is also useful as a precursor for polyesters and alkyd resins, which is used in coating applications, thereby protecting against UV light, corrosion and oxidation.
Methanedicarboxylic acid acts as a cross linker in the coating industry and surgical adhesive.
Methanedicarboxylic acid finds application in the production of specialty chemicals, flavors and fragrances, polymer cross linkers and pharmaceuticals.
Methanedicarboxylic acid is a dicarboxylic acid CH2(COOH)2 used especially in the form of its diethyl ester in organic synthesis (as of barbiturates and vitamins of the B complex)
IUPAC name: Malonic acid
Preferred IUPAC name: Propanedioic acid
Other names: Methanedicarboxylic acid
Chemical formula: C3H4O4
Molar mass: 104.061 g·mol−1
Density: 1.619 g/cm3
Melting point: 135 to 137 °C (275 to 279 °F; 408 to 410 K) (decomposes)
Boiling point: decomposes
Solubility in water: 763 g/L
Acidity (pKa)
pKa1 = 2.83
pKa2 = 5.69
Magnetic susceptibility (χ): -46.3·10−6 cm3/mol
Malonsäure
Propanedioic acid
propanedioic acid
Trade names
Methanedicarboxylic acid
MS
Propanedioic acid
Methanedicarboxylic acid, also called Propanedioic Acid, (HO2CCH2CO2H), a dibasic organic acid whose diethyl ester is used in syntheses of vitamins B1 and B6, barbiturates, and numerous other valuable compounds.
Methanedicarboxylic acid itself is rather unstable and has few applications.
Its calcium salt occurs in beetroot, but the acid itself is usually prepared by hydrolyzing diethyl malonate.
Methanedicarboxylic acid undergoes the usual reactions of carboxylic acids as well as facile cleavage into acetic acid and carbon dioxide.
Diethyl malonate, CH2(CO2C2H5)2, also called malonic ester, is prepared by the reaction of ethyl alcohol with cyanoacetic acid.
Its utility in synthesis arises from the reactivity of its methylene (CH2) group; a hydrogen atom is easily removed by sodium ethoxide or other strong base, and the resulting derivative reacts readily with an alkyl halide to form a diethyl alkylmalonate.
A second alkyl group may be similarly introduced.
The diethyl dialkylmalonates are converted by reaction with urea to barbiturates. Diethyl malonate is a colourless, fragrant liquid boiling at 181.4° C.
Methanedicarboxylic acid, formally propanedioic acid, is the second-smallest aliphatic dicarboxylic acid. (Oxalic acid is the smallest.)
It should not be confused with malic or maleic acid, both of which also contain two carboxyls.
Methanedicarboxylic acid is a white crystalline solid with a decomposition point of ≈135 °C.
It is highly soluble in water and oxygenated solvents.
It has numerous commercial uses: It is a precursor to specialty polyesters; it is used in the manufacture of barbiturates, coatings, and biodegradable containers; and it is even a component of surgical adhesives.
French chemist Victor Dessaignes reported the first synthesis of Methanedicarboxylic acid in 1858; he made it by oxidatively decomposing four-carbon malic acid with potassium dichromate. Since then, it has been synthesized commercially starting from chloroacetic acid, diethyl malonate, and even sodium acetate.
Uses of Methanedicarboxylic acid:
Methanedicarboxylic acid is used as a precursor in polymers and polyester.
Methanedicarboxylic acid is used in flavours as well as the fragrance industry.
Methanedicarboxylic acid is used to control the acidity.
Methanedicarboxylic acid is used in pharmaceutical products.
Methanedicarboxylic acid is used as a cross-linking agent between potato starch and cornstarch to enhance its mechanical properties.
Methanedicarboxylic acid is used in the preparation of barbituric salt.
Methanedicarboxylic acid is used in electroplating.
Methanedicarboxylic acid is used to produce vitamin B1, vitamin B6, vitamin B2, and amino acids.
Methanedicarboxylic acid is used in chemical synthesis as a building block.
alonic Acid Uses
Methanedicarboxylic acid acts as a precursor for conversion to 1,3-propanediol, which is a compound used in polyesters and polymers with the huge market size.
Methanedicarboxylic acid is used for the preparation of cinnamic acid, a compound used for the formation of cin metacin which is an anti-inflammatory. The malonates are used in syntheses of B1 and B6, barbiturates, and several other valuable compounds.
It is used in cosmetics as a buffering and as a flavouring agent in food.
Methanedicarboxylic acid is used as a component of alkyd resins, used in coating applications to protect from UV rays, oxidation, and corrosion.
Methanedicarboxylic acid is a building block to many valuable compounds in food and drug applications, pharmaceutical, electronics industry, fragrances, specialty polymer, specialty solvents, and many more.
Methanedicarboxylic acid, also known as malonate or H2MALO, belongs to the class of organic compounds known as dicarboxylic acids and derivatives.
These are organic compounds containing exactly two carboxylic acid groups.
Methanedicarboxylic acid is a very hydrophobic molecule, practically insoluble (in water), and relatively neutral.
Methanedicarboxylic acid exists in all living species, ranging from bacteria to humans. Within humans, Methanedicarboxylic acid participates in a number of enzymatic reactions.
In particular, Methanedicarboxylic acid and acetic acid can be converted into acetoacetic acid; which is mediated by the enzyme fatty acid synthase. Beta ketoacyl synthase domain.
In addition, Methanedicarboxylic acid and coenzyme A can be biosynthesized from malonyl-CoA through its interaction with the enzyme fatty acid synthase.
In humans, Methanedicarboxylic acid is involved in fatty acid biosynthesis. Outside of the human body, Methanedicarboxylic acid has been detected, but not quantified in, several different foods, such as red beetroots, corns, scarlet beans, common beets, and cow milks.
This could make Methanedicarboxylic acid a potential biomarker for the consumption of these foods.
Methanedicarboxylic acid, with regard to humans, has been found to be associated with several diseases such as eosinophilic esophagitis, combined malonic and methylMethanedicarboxylic aciduria, and early preeclampsia; Methanedicarboxylic acid has also been linked to the inborn metabolic disorder malonyl-coa decarboxylase deficiency.
Methanedicarboxylic acid, also called propanedioic acid, is a precursor to specialty polyesters. It is a dibasic organic acid whose diethyl ester is used in syntheses of vitamins B1 and B6, barbiturates, and numerous other valuable compounds.
Molecular Formula: C3H4O4 or COOHCH2COOH
propanedioic acid
Methanedicarboxylic acid appears as white crystals or crystalline powder. Sublimes in vacuum.
CAMEO Chemicals
Methanedicarboxylic acid is an alpha,omega-dicarboxylic acid in which the two carboxy groups are separated by a single methylene group.
Methanedicarboxylic acid has a role as a human metabolite.
Methanedicarboxylic acid is an alpha,omega-dicarboxylic acid and a lipid. It is a conjugate acid of a malonate(1-).
Methanedicarboxylic acid (IUPAC systematic name: propanedioic acid) is a dicarboxylic acid with structure CH2(COOH)2.
The ionized form of Methanedicarboxylic acid, as well as its esters and salts, are known as malonates.
For example, diethyl malonate is Methanedicarboxylic acid's diethyl ester.
The name originates from the Greek word μᾶλον (malon) meaning 'apple'.
History
Methanedicarboxylic acid is a naturally occurring substance found in many fruits and vegetables.
There is a suggestion that citrus fruits produced in organic farming contain higher levels of Methanedicarboxylic acid than fruits produced in conventional agriculture.
Methanedicarboxylic acid was first prepared in 1858 by the French chemist Victor Dessaignes via the oxidation of malic acid.
Structure and preparation
The structure has been determined by X-ray crystallography and extensive property data including for condensed phase thermochemistry are available from the National Institute of Standards and Technology.[8] A classical preparation of Methanedicarboxylic acid starts from chloroacetic acid:
Preparation of Methanedicarboxylic acid from chloroacetic acid.
Sodium carbonate generates the sodium salt, which is then reacted with sodium cyanide to provide the sodium salt of cyanoacetic acid via a nucleophilic substitution.
The nitrile group can be hydrolyzed with sodium hydroxide to sodium malonate, and acidification affords Methanedicarboxylic acid.
Industrially, however, Methanedicarboxylic acid is produced by hydrolysis of dimethyl malonate or diethyl malonate.
It has also been produced through fermentation of glucose.
Organic reactions
Methanedicarboxylic acid reacts as a typical carboxylic acid: forming amide, ester, anhydride, and chloride derivatives.
Malonic anhydride can be used as an intermediate to mono-ester or amide derivatives, while malonyl chloride is most useful to obtain diesters or diamides.
In a well-known reaction, Methanedicarboxylic acid condenses with urea to form barbituric acid.
Methanedicarboxylic acid may also condensed be with acetone to form Meldrum's acid, a versatile intermediate in further transformations.
The esters of Methanedicarboxylic acid are also used as a −CH2COOH synthon in the malonic ester synthesis.
Additionally, the coenzyme A derivative of malonate, malonyl-CoA, is an important precursor in fatty acid biosynthesis along with acetyl CoA.
Malonyl CoA is formed from acetyl CoA by the action of acetyl-CoA carboxylase, and the malonate is transferred to an acyl carrier protein to be added to a fatty acid chain.
Briggs–Rauscher reaction
Methanedicarboxylic acid is a key component in the Briggs–Rauscher reaction, the classic example of an oscillating chemical reaction.
Knoevenagel condensation
In Knoevenagel condensation, Methanedicarboxylic acid or its diesters are reacted with the carbonyl group of an aldehyde or ketone, followed by a dehydration reaction.
Z=COOH (Methanedicarboxylic acid) or Z=COOR' (malonate ester)
When Methanedicarboxylic acid itself is used, it is normally because the desired product is one in which a second step has occurred, with loss of carbon dioxide, in the so-called Doebner modification.[14]
The Doebner modification of the Knoevenagel condensation.
Thus, for example, the reaction product of acrolein and Methanedicarboxylic acid in pyridine is trans-2,4-Pentadienoic acid with one carboxylic acid group and not two.
Preparation of carbon suboxide
Carbon suboxide is prepared by warming a dry mixture of phosphorus pentoxide (P4O10) and Methanedicarboxylic acid.
It reacts in a similar way to malonic anhydride, forming malonates.
Applications
Methanedicarboxylic acid is a precursor to specialty polyesters.
It can be converted into 1,3-propanediol for use in polyesters and polymers (whose usefulness is unclear though).
It can also be a component in alkyd resins, which are used in a number of coatings applications for protecting against damage caused by UV light, oxidation, and corrosion.
One application of Methanedicarboxylic acid is in the coatings industry as a crosslinker for low-temperature cure powder coatings, which are becoming increasingly valuable for heat sensitive substrates and a desire to speed up the coatings process.
The global coatings market for automobiles was estimated to be $18.59 billion in 2014 with projected combined annual growth rate of 5.1% through 2022.
It is used in a number of manufacturing processes as a high value specialty chemical including the electronics industry, flavors and fragrances industry, specialty solvents, polymer crosslinking, and pharmaceutical industry.
In 2004, annual global production of Methanedicarboxylic acid and related diesters was over 20,000 metric tons.
Potential growth of these markets could result from advances in industrial biotechnology that seeks to displace petroleum-based chemicals in industrial applications.
In 2004, Methanedicarboxylic acid was listed by the US Department of Energy as one of the top 30 chemicals to be produced from biomass.
In food and drug applications, Methanedicarboxylic acid can be used to control acidity, either as an excipient in pharmaceutical formulation or natural preservative additive for foods.
Methanedicarboxylic acid is used as a building block chemical to produce numerous valuable compounds, including the flavor and fragrance compounds gamma-nonalactone, cinnamic acid, and the pharmaceutical compound valproate.
Methanedicarboxylic acid (up to 37.5% w/w) has been used to cross-link corn and potato starches to produce a biodegradable thermoplastic; the process is performed in water using non-toxic catalysts.
Starch-based polymers comprised 38% of the global biodegradable polymers market in 2014 with food packaging, foam packaging, and compost bags as the largest end-use segments.
Eastman Kodak company and others use Methanedicarboxylic acid and derivatives as a surgical adhesive.
Methanedicarboxylic acid is a dicarboxylic acid with a chemical formula C3H4O4. Dicarboxylic acids are organic compounds containing two carboxylic acid functional groups.
Dicarboxylic acids generally show the same chemical behaviour and reactivity as monocarboxylic acids.
Methanedicarboxylic acid is a substance found in some fruits that occurs naturally. Fruits generated in organic farming contain greater concentrations of Methanedicarboxylic acid in citrus compared to fruits generated in conventional farming.
The systematic name for Methanedicarboxylic acid IUPAC is propanedioic acid.
Methanedicarboxylic acid is the archetypal instance of a competitive inhibitor: it functions in the respiratory electron transport chain against succinate dehydrogenase.
Methanedicarboxylic acid is correlated with deficiency of malonyl-CoA decarboxylase, an inborn metabolism mistake.
Biochemistry
Methanedicarboxylic acid is the classic example of a competitive inhibitor of the enzyme succinate dehydrogenase (complex II), in the respiratory electron transport chain.
It binds to the active site of the enzyme without reacting, competing with the usual substrate succinate but lacking the −CH2CH2− group required for dehydrogenation.
This observation was used to deduce the structure of the active site in succinate dehydrogenase. Inhibition of this enzyme decreases cellular respiration.
Since Methanedicarboxylic acid is a natural components of many foods, it is present in mammals including humans.
1,3-propanedioic acid
141-82-2 [RN]
1751370 [Beilstein]
212-385-4 [EINECS]
Acide malonique [French] [ACD/IUPAC Name]
Kyselina malonova [Czech]
Methanedicarboxylic acid [ACD/IUPAC Name] [Wiki]
Malonsäure [German] [ACD/IUPAC Name]
Methanedicarbonic acid
MFCD00002707 [MDL number]
Propanedioic acid [ACD/Index Name]
118690-08-7 [RN]
3-HYDROXY-PROPANOIC ACID
Benzophenone-1-hydroxy cyclohexyl phenyl ketone mixture
Carboxyacetic acid
CH2(COOH)2 [Formula]
dicarboxylic acid
DICARBOXYLIC ACID C3
dicarboxymethane
DXX
HOOC-CH2-COOH [Formula]
http://www.hmdb.ca/metabolites/HMDB0000691
https://www.ebi.ac.uk/chebi/searchId.do?chebiId=CHEBI:30794
hydrogen malonate
Malonate dicarboxylic acid
Methanedicarboxylic acid|Propanedioic acid
Metahnedicarboxylic acid
Methanedicarboxylic acid
MethylMethanedicarboxylic acid [ACD/IUPAC Name] [Wiki]
MLA
MLI
propandioic acid
Propane-1,3-dioic acid
Propanediolic acid
QV1VQ [WLN]
STR00614
WLN: QV1VQ
α,ω-dicarboxylic acid
丙二酸 [Chinese]
Methanedicarboxylic acid is also known as Propanedioic Acid or Dicarboxymethane. The name is derived from a Greek word Malon which means apple.
Malonates are the ionized form of Methanedicarboxylic acid, along with its esters and salts. It appears as a white crystal or crystalline powder.
It dissolves in alcohol, pyridine, and ether.
Malonic acid was first prepared in the year, 1858 by the French chemist Victor Dessaignes by the oxidation of malic acid.
Malonic acid is found in some fruit’s viz citrus fruits.
The amount of malonic acid produced from fruits through organic farming is greater than the fruits grown through conventional agriculture.
Malonic acid can be produced through the fermentation of glucose.
Malonic acid Synthesis – C3H4O4
Preparation of malonic acid starts with chloroacetic acid which is also known as MCA (monochloroacetic acid).
Step 1: Sodium carbonate produces sodium salt.
Step 2: It is made to react with sodium cyanide.
Step 3: cyanoacetic acid salt is generated through nucleophilic substitution.
Step 4: The nitrile group is hydrolyzed with sodium hydroxide to produce sodium malonate.
Step 5: The acidification results in malonic acid.
Industrially, malonic acid is produced by the hydrolysis of diethyl malonate or dimethyl malonate. Never give anything by mouth to an unconscious person. Rinse the mouth with water. Malonic acid is a forerunner to polyester specialities. Malonic acid is used to generate countless useful compounds as a construction block chemical.
Malonic acid Health Risks
It is a strong irritant and is harmful when harmful by inhaled, ingested or absorbed by the skin leading to skin damage and damage to mucous membranes.
A few laboratory animal toxicity studies of malonic acid, but the studies are insufficient to define extra health impacts.
If inhaled, it may be dangerous. Causes irritation of the respiratory tract. If absorbed through the skin, it may be dangerous. It causes irritation of the skin.
When breathed in, move fresh air into the individual. Give artificial respiration if you don’t breathe. Consult a doctor.
What happens when malonic acid is heated?
On heating malonic acid produces acetic acid and carbon dioxide.
Is malonic acid strong?
Malonic acid is a diprotic acid. pKa value of first loss of proton is 2.83, and second loss proton is 5.69 . Higher the pka value, the less acidic strength. So that the malonic acid is a medium strong acid.
What is the source of malonic acid?
Malonic acid is found in many fruits and vegetables. The calcium salt of malonic acid occurs in high concentrations in beetroot.
What is malonic acid soluble in?
Malonic acid is soluble in water, It is a polar molecule, form H+ ion in aqueous solution , it is also soluble in methyl alcohol but insoluble in hexane.
Is maleic acid optically active?
Maleic acid does not have any chiral centre, so it does not exhibit optical isomerism.
Malonic Acid is incompatible with bases, oxidizing agents and reducing agents.
Salts and esters
Chemical structure of the malonate dianion.
Malonic acid is diprotic; that is, it can donate two protons per molecule. Its first {\displaystyle pK_{a}}{\displaystyle pK_{a}} is 2.8 and the second is 5.7.
Thus the malonate ion can be HOOCCH2COO− or CH2(COO)2−
2. Malonate or propanedioate compounds include salts and esters of malonic acid, such as
Diethyl malonate
Dimethyl malonate
Disodium malonate
Malonyl-CoA
Health Hazards of Malonic Acid
Upon exposure, Malonic acid can cause a range of symptoms in the eyes, skin, and respiratory tract. It can irritate eyes, skin. The compound if inhaled can irritate the respiratory tract. It may also cause serious eye damage or eye irritation. Hence, if exposed eyes should be washed with normal water or with a saline solution. If redness or irritation is observed in the affected skin, the area should be immediately washed with water. The contaminated clothes should be removed.
If ingested it may cause gastrointestinal irritation such as nausea, vomiting, etc. The mouth should be immediately rinsed with water several times and further medical help should be taken.
It is a strong irritant that can affect both skin and mucous membranes.
If heated the compound releases toxic fumes of carbon dioxide and monoxide and gases that may irritate the respiratory tract if inhaled.
In its purified form, malonic acid is a white, crystalline substance, water-soluble and easily decomposed by heat. Chemically, it is an organic dicarboxylic acid with a methylene group separating the two carbonyl moieties. The diethyl ester of this chemical is used chiefly as an intermediate in the synthesis of barbiturates. It is also used to synthesize vitamins B1 and B6 as well as and numerous other organic compounds. The free acid is rather unstable and has few uses other than being a biochemical diagnostic probe for intermediary metabolism.
The calcium salt of malonic acid occurs in beetroot, but the acid itself is usually prepared by hydrolyzing diethyl malonate. It undergoes the usual reactions of carboxylic acids as well as facile cleavage into acetic acid and carbon dioxide.
