Malonic acid (IUPAC systematic name: propanedioic acid) is a dicarboxylic acid with structure CH2(COOH)2. The ionized form of malonic acid, as well as its esters and salts, are known as malonates. For example, diethyl malonate is malonic acid's diethyl ester. The name originates from the Greek word μᾶλον (malon) meaning 'apple'.
|Preferred IUPAC name
3D model (JSmol)
CompTox Dashboard (EPA)
|Molar mass||104.061 g·mol−1|
|Melting point||135 to 137 °C (275 to 279 °F; 408 to 410 K) (decomposes)|
|Acidity (pKa)||pKa1 = 2.83 |
pKa2 = 5.69
Related carboxylic acids
|Safety data sheet||External MSDS|
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
Malonic 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 malonic acid than fruits produced in conventional agriculture.
Structure and preparationEdit
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. A classical preparation of malonic acid starts 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 malonic acid. Industrially, however, malonic acid is produced by hydrolysis of dimethyl malonate or diethyl malonate. It has also been produced through fermentation of glucose.
Malonic 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, malonic acid condenses with urea to form barbituric acid. Malonic acid may also condensed be with acetone to form Meldrum's acid, a versatile intermedate in further transformations. The esters of malonic 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.
Preparation of carbon suboxideEdit
Malonic acid is a precursor to specialty polyesters. It can be converted into 1,3-propanediol for use in polyesters and polymers and a projected market size of $621.2 million by 2021. 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 malonic 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 malonic 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.
Malonic acid was listed as one of the top 30 chemicals to be produced from biomass by the US Department of Energy.
In food and drug applications, malonic acid can be used to control acidity, either as an excipient in pharmaceutical formulation or natural preservative additive for foods.
Malonic 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.
Malonic 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.
Malonic 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 malonic acid is a natural components of many foods, it is present in mammals including humans.
Salts and estersEdit
Malonic acid is diprotic; that is, it can donate two protons per molecule. Its first is 2.8 and the second is 5.7. Thus the malonate ion can be HOOCCH
2COO− or CH
2. Malonate or propanedioate compounds include salts and esters of malonic acid, such as
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