MALONIC ACID

MALONIC ACID

Malonic Acid= 1,3-Propanedioic Acid=Dicarboxymethane =Carboxyacetic acid=Dicarboxylate    

CAS NUMBER:141-82-2
EC NUMBER:205-503-0
Molecular Weight:104.060
Molecular Formula:C3 H4 O4 or COOHCH2COOH

DEFINITION OF MALONIC ACID:
Malonic acid, formally propanedioic acid, is the second-smallest aliphatic dicarboxylic acid. (Oxalic acid is the smallest.) 
Chemically, it is an organic dicarboxylic acid with a methylene group separating the two carbonyl moieties.
Malonic acid should not be confused with malic or maleic acid, both of which also contain two carboxyls.
In its purified form, malonic acid is a white, crystalline substance, water-soluble and easily decomposed by heat.
Malonic acid has a role as a human metabolite. 
Malonic acid is a conjugate acid of a malonate(1-).
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 of Malonic acid originates from the Greek word μᾶλον (malon) meaning 'apple'.
Malonic acid (MOA), one of the major dicarboxylic acids (DCAs) in aerosols, has been identified experimentally and computationally to be a strong acid.
Malonic acid (MOA) acts as a mediate bridge for the formation of pure SA-A-based clusters.

USES/BENEFITS OF MALONIC ACID:
Malonic acid was listed as one of the top 30 chemicals to be produced from biomass by the US Department of Energy.
Malonic acid has numerous commercial uses.
Malonic acid is mainly used in pharmaceutical intermediates, also used in perfumes, adhesives, resin additives, electroplating polishes, etc
Malonic acid  is  used as a complexing agent, 
Malonic acid is also used in the preparation of barbitur salts
Malonic acid is an intermediate of the fungicide rice blast spirit and an intermediate of the plant growth regulator indyl ester
Malonic acid and its esters are mainly used in perfumes, adhesives, resin additives, pharmaceutical intermediates, electroplating polishing agents, explosion control agents, thermal welding flux additives and so on. It is used in the pharmaceutical industry to produce rummina, barbiturate, vitamin B1, vitamin B2, vitamin B6, amino acids, and the like.
Malonic acid is used as an aluminum surface treatment agent. Since only water and carbon dioxide are generated during thermal decomposition, there is no pollution problem.
In this regard, Malonic acid has great advantages compared with acid-based treatment agents such as formic acid used in the past.
The diethyl ester of Malonic acid is used chiefly as an intermediate in the synthesis of barbiturates.
Malonic acid is also used to synthesize vitamins B1 and B6 as well as and numerous other organic compounds. 

Malonic acid is used as a precursor in polymers and polyester.
Malonic acid is used in flavours as well as the fragrance industry.
Malonic acid is used to control the acidity.
Malonic acid is used in pharmaceutical products.
Malonic acid is used as a cross-linking agent between potato starch and cornstarch to enhance its mechanical properties.
Malonic acid is used in the preparation of barbituric salt.
Malonic acid is used in electroplating.
Malonic acid is used to produce vitamin B1, vitamin B6, vitamin B2, and amino acids.
Malonic acid is used in chemical synthesis as a building block.
Malonic acid is used in the manufacture of barbiturates, biodegradable containers.

APPLICATIONS OF MALONIC ACID:
Malonic acid is a precursor to specialty polyesters. 
Malonic acid can be converted into 1,3-propanediol for use in polyesters and polymers with a projected market size of $621.2 million by 2021.
Malonic acid 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.

Malonic acid 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.

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.
Eastman Kodak company and others use malonic acid and derivatives as a surgical adhesive.

HISTORY
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.
Malonic acid was first prepared in 1858 by the French chemist Victor Dessaignes via the oxidation of malic acid.
French chemist Victor Dessaignes reported the first synthesis of malonic acid in 1858; he made it by oxidatively decomposing four-carbon malic acid with potassium dichromate. 
Since then, Malonic acid has been synthesized commercially starting from chloroacetic acid, diethyl malonate, and even sodium acetate.
In the past two decades, much work has been done on biobased syntheses of malonic acid.
Most recently, the Berkeley, CA, venture-capital startup Lygos raised US$13 million to scale up a process that uses bioengineered yeast strains to produce malonic acid from sugars.

STRUCTURE AND PREPARATION
The structure of malonic acid 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.
Malonic acid has also been produced through fermentation of glucose.

ORGANIC REACTIONS
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 intermediate in further transformations.
The esters of malonic acid are 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
Malonic acid is a key component in the Briggs–Rauscher reaction, the classic example of an oscillating chemical reaction.

Knoevenagel condensation
In Knoevenagel condensation, malonic acid or its diesters are reacted with the carbonyl group of an aldehyde or ketone, followed by a dehydration reaction.
When malonic 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.
Thus, for example, the reaction product of acrolein and malonic 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 and malonic acid.
It reacts in a similar way to malonic anhydride, forming malonates.

BIOCHEMISTRY
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.
it is present in mammals including humans since malonic acid is a natural components of many foods.

SALTS AND ESTERS
Malonic acid is diprotic; that is, it can donate two protons per molecule.
Malonate or propanedioate compounds include salts and esters of malonic acid, such as

-Diethyl malonate
-Dimethyl malonate
-Disodium malonate
-Malonyl-CoA

Metabolite Identification:
Malonic 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.
Malonic acid is a very hydrophobic molecule, practically insoluble (in water), and relatively neutral.
Malonic acid exists in all living species, ranging from bacteria to humans. 
Within humans, malonic acid participates in a number of enzymatic reactions. 
In particular, malonic acid and acetic acid can be converted into acetoacetic acid; which is mediated by the enzyme fatty acid synthase. 
In addition, malonic acid and coenzyme A can be biosynthesized from malonyl-CoA through its interaction with the enzyme fatty acid synthase.
In humans, malonic acid is involved in fatty acid biosynthesis. 
Outside of the human body, Malonic 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 malonic acid a potential biomarker for the consumption of these foods.
Malonic acid, with regard to humans, has been found to be associated with several diseases such as eosinophilic esophagitis, combined malonic and methylmalonic aciduria, and early preeclampsia;
Malonic acid has also been linked to the inborn metabolic disorder malonyl-coa decarboxylase deficiency.

SAFETY MEASURES:
First aid measures
-If inhaled
 If breathed in, move person into fresh air. 
 If not breathing, give artificial respiration.
 Consult a physician.
-In case of skin contact
 Wash off with soap and plenty of water. 
 Consult a physician.
-In case of eye contact
 Rinse thoroughly with plenty of water for at least 15 minutes and consult a physician.
-If swallowed
 Never give anything by mouth to an unconscious person.
 Rinse mouth with water. 

Firefighting Measures
-Suitable extinguishing media
 Use water spray, alcohol-resistant foam, dry chemical or carbon dioxide.
 Use water spray,alcohol-resistant foam, dry chemical or carbon dioxide.
-Unsuitable extinguishing media
 For this substance/mixture no limitations of extinguishing agents are given.
-2 Special hazards arising from the substance or mixture
 Carbon oxides
 Combustible.
-Advice for firefighters
 Wear self-contained breathing apparatus for firefighting if necessary.

Handling and storage
-Advice on safe handling
 Avoid formation of dust and aerosols.
-Advice on protection against fire and explosion
 Provide appropriate exhaust ventilation at places where dust is formed
-Hygiene measures
 Handle in accordance with good industrial hygiene and safety practice.
 Wash hands before breaks and at the end of workday.
-Storage conditions
 Keep container tightly closed in a dry and well-ventilated place. 
 Store in cool place.
 Keep away from sunshine and rain

CATEGORY OF MALONIC ACID:
Malonic acid Belongs to the class of organic compounds known as dicarboxylic acids and derivatives. 
These are organic compounds containing exactly two carboxylic acid groups.

PHYSICAL PROPERTIES OF MALONIC ACID:
Malonic acid appears as white crystals or crystalline powder.
Malonic acid sublimes in vacuum.
Malonic acid is a white crystalline solid with a decomposition point of ≈135 °C.
Malonic acid is highly soluble in water and oxygenated solvents.

Appearance : White crystal powder (Solid)
Molecular weight : 104.06 (g/mol) 
Monoisotopic Mass:104.01096
Flash point : 157° (314°F)
Density : 1.62
Specific Gravity: 1.63100 @ 25.00 °C.
Melting Point:    135.00 °C. @ 760.00 mm Hg
Boiling Point:    264.00 °C. @ 760.00 mm Hg
Vapor Pressure:    0.001500 mmHg @ 25.00 °C.
Decomposition temperature: > 140 °C -
Water solubility :766 g/l at 20 °C
Odor :odorless
logP (o/w):-0.910
Assay:95.00 to 100.00

SYNONYMS OF MALONIC ACID:
H2Malo    
HOOC-CH2-COOH    
Propanedioic acid    
Propanedioate    
Malonate    
alpha,Omega-dicarboxylic acid    
Carboxyacetic acid    
Dicarboxylate    
Dicarboxylic acid    
Dicarboxymethane    
Kyselina malonova    
Malonate dicarboxylic acid    
Metahnedicarboxylic acid    
Methanedicarbonic acid    
Methanedicarboxylic acid    
Propanedioic acid dithallium salt    
Propanediolic acid    
Thallium malonate    
Malonic acid, 2-(14)C-labeled    
Malonic acid, monocalcium salt    
Malonic acid, 1,3-(14)C2-labeled    
Malonic acid, diammonium salt    
Malonic acid, disodium salt    
Malonic acid, dithallium salt    
Malonic acid, dipotassium salt    
Malonic acid, disodium salt, 1-(14)C-labeled    
Malonic acid, monosodium salt    
Malonic acid, potassium salt    
Malonic acid, sodium salt    
Thallous malonate    
Dithallium malonate    
Monosodium malonate    
kyselina malonova
usaf ek-695 
kyselina malonova czech,

Frequently Asked Questions- FAQs
-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.

-What is Knoevenagel Condensation of Malonic Acid?
 This condensation reaction is named after Emil Knoevenagel. 
 It is a nucleophilic addition reaction. 
 In this reaction malonic acid or its diesters react with an aldehyde or ketone’s carbonyl group. 
 This reaction is then followed by a dehydration reaction.
 Malonic acid when subjected to this reaction gives the desired product through a second step where removal or loss of carbon dioxide occurs.
 This modification step is called Doebner modification. An example of this so-called Doebner reaction would be the reaction between malonic acid and acrolein.
 The reaction product of this reaction is trans-2,4-Pentadienoic acid. 
 Instead of two, this product has only one carboxylic acid group, due to the loss of carbon dioxide in the second step.

-What is the Role of Malonic Acid as an Inhibitor ?
 Malonic acid has a key role in biochemistry as a competitive inhibitor.
 It is the competitive inhibitor of the enzyme succinate dehydrogenase. 
 In the respiratory electron transport chain, the compound malonic acid binds with the active site of the enzyme succinate dehydrogenase without any reaction.
 The competitive inhibitor resembles the actual substrate and binds at the active site of the enzyme.
 The malonate and succinate exhibit very similar structure that causes this competitive inhibition. 
 This inhibits the usual reaction that takes place upon binding with the substrate succinate. 
 Malonic acid lacks the group -CH2CH2- thus inhibiting the dehydrogenation reaction. 
 This inhibition reaction of the enzyme succinate dehydrogenase results in a decrease in cellular respiration.