CARBOXYACETIC ACID
CARBOXYACETIC ACID = MALONIC ACID = Propanedioic acid = Carboxyacetic acid = Dicarboxymethane = Methanedicarboxylic acid = Methanedicarboxylic acid = 1,3-Propanedioic acid = Malonsäure = Dibasic organic acid
Other names: Malonic acid; Carboxyacetic acid; Dicarboxymethane; Methanedicarboxylic acid; CH2(COOH)2; USAF EK-695; Kyselina malonova; Methanedicarbonic acid; NSC 8124
CAS #: 141-82-2
EC Number: 205-503-0
Formula: C3H4O4 / COOHCH2COOH
Molecular mass: 104.1
Decomposes at 135°C
Density: 1.6 g/cm³
Solubility in water, g/100ml at 20°C: 7.3
Octanol/water partition coefficient as log Pow: -0.91/-0.18 (calculated)
Malonic Acid IUPAC Name
Malonic acid is a dicarboxylic acid with structural formula CH2(COOH)2 and chemical formula C3H4O4. The name malonic acid originated from the word ‘Malon’ which is Greek for ‘apple’. The IUPAC name of malonic acid is Propanedioic acid. Methane Dicarboxylic acid is another name for malonic acid. The ester and salts of malonic acid are called malonates. The dicarboxylic acid has organic reactions similar to the monocarboxylic acid where amide, ester, anhydride, and chloride derivatives are formed. Lastly, the malonic ester malonate as a coenzyme A derivative malonyl CoA that is as important a precursor as Acetyl CoA in the biosynthesis of fatty acids.
Malonic 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.
Malonic acid is a substance found in some fruits that occurs naturally.
Fruits generated in organic farming contain greater concentrations of malonic acid in citrus compared to fruits generated in conventional farming.
The systematic name for malonic acid IUPAC is propanedioic acid.
Malonic acid is the archetypal instance of a competitive inhibitor: it functions in the respiratory electron transport chain against succinate dehydrogenase.
Malonic acid is correlated with deficiency of malonyl-CoA decarboxylase, an inborn metabolism mistake.
Industrially, malonic acid is produced by the hydrolysis of diethyl malonate or dimethyl malonate.
Malonic acid is a forerunner to polyester specialities. Malonic acid is used to generate countless useful compounds as a construction block chemical.
Application Notes: Carboxyacetic acid is used to prepare barbiturates. Its derivative diethylmalonate is used in Knoevenagel condensation reactions as well as reacts with acetone to form Meldrum’s acid. Carboxyacetic acidis used to control acidity, preservative additive for foods and as an excipient in pharmaceutical formulation. Carboxyacetic acid acts as a precursor to polyesters and as an active component in alkyd resins. Further, it is used as a building block in chemical synthesis. In addition to this, it is used to prepare starch-based resin.
Uses of Malonic acid – (C3H4O4)
The uses of malonic acid are listed below:
Malonic acid is used in electroplating.
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 appears as white crystals or crystalline powder.
Malonic 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 malonic 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 Uses
Malonic 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.
Malonic 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.
Malonic Acid is used in cosmetics as a buffering and as a flavouring agent in food.
Malonic acid is used as a component of alkyd resins, used in coating applications to protect from UV rays, oxidation, and corrosion.
Malonic 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.
Properties of Malonic Acid
Malonic acid molecular weight: 104.061 g.mol-1
The density of malonic acid is 1.619 g/cm3.
Malonic Acid appears as a crystalline powder that is white or colourless.
At the boiling point above 140oC the compound decomposes. The melting point is 135-137o C.
If heated to decomposition under fire it emits carbon oxide fumes and acrid irritating smoke.
Acidity pKa = 2.85 at 25oC. pKa1 = 2.83, pKa2 = 5.69
The molar heat of combustion is 864 kJ/mol. The heat of vaporization is 92 kJ/mol.
Malonic Acid is soluble in water. Solubility 763 g/L.
Malonic Acid has a white crystal or crystalline powder structure. The compound is naturally occurring and can be found in many vegetables, fruits. The dicarboxylic acid compound was first prepared by Victor Dessaignes by the oxidation reaction of malic acid.
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 Malonic Acid 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.
Malonic Acid 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.
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’.
Malonic acid (MA), also known as propanedioic acid, is a dicarboxylic acid. Malonic acid may be used as a cross-linking agent between corn starch and potato starch to improve its mechanical properties.
Malonic acid sublimes in vacuum
Malonic acid is an alpha,omega-dicarboxylic acid in which the two carboxy groups are separated by a single methylene group. It has a role as a human metabolite.
It is a conjugate acid of a malonate(1-).
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. Beta ketoacyl synthase domain.
In addition, malonic acid and coenzyme A can be biosynthesized from malonyl-CoA through its interaction with the enzyme fatty acid synthase. malonyl/acetyl transferase domain.
An Malonic acid in which the two carboxy groups are separated by a single methylene group.
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.
Definition: An α,ω-dicarboxylic acid in which the two carboxy groups are separated by a single methylene group.
Malonic 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.
Malonic 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.
Malonic 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.
Malonic acid, formally propanedioic acid, is the second-smallest aliphatic dicarboxylic acid. (Oxalic acid is the smallest.)
Malonic acid should not be confused with malic or maleic acid, both of which also contain two carboxyls.
Malonic acid is a white crystalline solid with a decomposition point of ≈135 °C. It is highly soluble in water and oxygenated solvents.
Malonic acid has numerous commercial uses: It is a precursor to specialty polyesters; malonic acid 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 malonic 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.
In the past two decades, much work has been done on biobased syntheses of malonic acid
Synthesis of Malonic Acid
The synthesis of malonic acid usually begins with chloroacetic acid. It is also synthesized by cyanoacetic acid or by acid saponification reaction of malonates. From monochloroacetic acid, it is produced by sodium or potassium cyanide.
The sodium carbonate primarily breaks down to give sodium salt which reacts with sodium cyanide to give sodium salt of cyanoacetic acid by the process of nucleophilic substitution.
Further, via hydrolyzation, the nitrile group binds with sodium malonate, whose acidification results in the production of malonic acid.
The malonic acid Lewis structure has been found by the X-ray crystallography method. The malonic acid structure CH2(COOH)2 has two carboxylic acids. The salts and esters of malonic acid (malonates) have structures similar to malonic acid.
malonic acid
propanedioic acid
141-82-2
Dicarboxymethane
Carboxyacetic acid
Methanedicarboxylic acid
Kyselina malonova
USAF EK-695
Dicarboxylate
Dicarboxylic acid
Kyselina malonova [Czech]
MFCD00002707
UNII-9KX7ZMG0MK
NSC 8124
Methanedicarbonic acid
Malonic acid, 99%
Thallium malonate
AI3-15375
Propane-1,3-dioic acid
9KX7ZMG0MK
alpha,omega-Dicarboxylic acid
CHEBI:30794
NSC8124
1,3-Propanoic acid
Malonicacid
PROPANEDIOLIC ACID
METAHNEDICARBOXYLIC ACID
1,3-Propanedioic acid
EINECS 205-503-0
BRN 1751370
propanedioicacid
C3H4O4
H2malo
2fah
malonic acid group
Malonic acid (8CI)
1o4m
ACMC-1BSLG
HOOC-CH2-COOH
MLI
C3-120-beta-polymorph
C3-140-beta-polymorph
C3-180-beta-polymorph
C3-220-beta-polymorph
C3-260-beta-polymorph
C3-298-beta-polymorph
Malonate dicarboxylic acid
Propanedioic acid (9CI)
DSSTox_CID_1659
SCHEMBL336
WLN: QV1VQ
CH2(COOH)2
CHEMBL7942
DSSTox_RID_76271
H2Malo ChEBI
HOOC-CH2-COOH ChEBI
Propanedioic acid ChEBI
Propanedioate Generator
Malonate Generator
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
Malonic acid
Malonic acid undergoes Knoevenagel condensations with nearly every type of aldehyde and with very reactive ketones
If condensations with malonic acid are performed in ethanolic ammonia below 70 °C, the methylenemalonic acids are usually obtained.
If, however, the condensations are performed in pyridine (Doebner modification), decarboxylation normally takes place and the acrylic or cinnamic acid is formed.
In these reactions the double bond isomer with the carboxyl group trans to the larger substituent is usually obtained
A problem with condensations of malonic acid is the isomerization of the α,β-isomer to the 3,-y-isomer.
Coumarin-3-carboxylic acid (87) and related compounds are obtained in the reaction of salicylaldehyde and other 3-hydroxy aldehydes with malonic acid.
Finally, reaction of o-aminobenzaldehyde with malonic acid yields 2(1H)-quinolone (88)
The condensation of aldehydes with 2-alkylmalonic acids is of limited synthetic value as the reaction is susceptible to steric hindrance
In these cases the β-hydroxy acids instead of a-alkyl-α β,-unsaturated acids can be obtained, depending on the reaction conditions.
An example from the porphyrin field illustrates the problem of prediction in chemical reactivity.
Condensation of 5-formyloctaethylporphyrin with malonic acid delivers compound (89) which is double decarboxylated under conditions of catalytic hydrogenation to give (90).
The desired compound (92), however, is obtained by hydrogenation of half-ester (91).
Monoalkyl malonates, obtained by partial hydrolysis of dialkyl malonates, show a reactivity similar to malonic acid.
The Knoevenagel reaction is usually accompanied by decarboxylation, giving a cinnamic ester.
Anhydrides of Dicarboxylic Acids
Malonic acid anhydride is not a very stable compound. Diethylmalonic acid anhydride is relatively stable and at 160–180°C, decomposes to form diethylketene and CO2
3-(benzyloxy)-3-oxopropanoic acid (CHEBI:84093) has functional parent malonic acid
3-oxo-3-ureidopropanoic acid (CHEBI:49049) has functional parent malonic acid
N-malonyltryptophan (CHEBI:142268) has functional parent malonic acid
O-malonyl-D-carnitine (CHEBI:86047) has functional parent malonic acid
O-malonyl-L-carnitine (CHEBI:85470) has functional parent malonic acid
O-malonylcarnitine (CHEBI:73028) has functional parent malonic acid
S-malonyl-4′-phosphopantetheine (CHEBI:132976) has functional parent malonic acid
aminomalonic acid (CHEBI:17475) has functional parent malonic acid
bumadizone (CHEBI:76119) has functional parent malonic acid
elesclomol (CHEBI:79369) has functional parent malonic acid
ethylmalonic acid (CHEBI:741548) has functional parent malonic acid
heptylmalonic acid (CHEBI:70747) has functional parent malonic acid
hydroxymalonic acid (CHEBI:16513) has functional parent malonic acid
isoprothiolane (CHEBI:6047) has functional parent malonic acid
malonamide (CHEBI:48537) has functional parent malonic acid
malonate ester (CHEBI:38083) has functional parent malonic acid
malonyl-CoA methyl ester (CHEBI:71244) has functional parent malonic acid
methylmalonic acid (CHEBI:30860) has functional parent malonic acid
oxomalonic acid (CHEBI:30842) has functional parent malonic acid
malonate(1−) (CHEBI:30795) is conjugate base of malonic acid
carboxyacetyl group (CHEBI:50650) is substituent group from malonic acid
malonyl group (CHEBI:25134) is substituent group from malonic acid
MALONIC ACID
Submitted by Nathan Weiner
Checked by C. R. Noller and M. E. Synerholm.
1. Procedure
In a 5-l. round-bottomed flask, 500 g. (5.3 moles) of chloroacetic acid (Note 1) is dissolved in 700 cc. of water. The solution is warmed to 50°, neutralized with 290 g. (2.7 moles) of anhydrous sodium carbonate, and again cooled to room temperature. Meanwhile, 294 g. (6 moles) of sodium cyanide (97 per cent) is dissolved in 750 cc. of water warmed to 55°; the solution is cooled to room temperature and then added to the sodium chloroacetate solution, with rapid mixing of the two solutions and cooling under the water tap. When the solutions are completely mixed, cooling is stopped and the temperature allowed to rise. When it reaches 95°, the solution is cooled by adding 200 cc. of ice water, and this is repeated, if necessary, until the temperature no longer rises (Note 2). The solution is then heated on the steam bath for one hour to ensure completion of the reaction.
At the end of this time, the solution is cooled to room temperature and 240 g. (6 moles) of solid u.s.p. sodium hydroxide is slowly dissolved in it.
When solution is complete, the reaction mixture is again heated on the steam bath under a hood. When the temperature reaches 60–70°, evolution of ammonia begins and becomes more vigorous with rise in temperature.
Most of the ammonia is evolved in forty-five minutes, but the solution is heated for at least three hours, and the last traces of ammonia are removed by bubbling steam through the hot solution for forty-five to sixty minutes more.
A solution of 600 g. of anhydrous calcium chloride in 1.8 l. of water warmed to 40° is added slowly with rapid mixing to the hot sodium malonate solution.
A cheese-like precipitate of calcium malonate is formed immediately and becomes coarsely crystalline on standing for twenty-four hours.
After the supernatant solution is decanted, the calcium malonate is washed by decantation four or five times with 500-cc. portions of cold water.
It is then transferred to a filter, sucked as dry as possible, and dried in the air, or at 45–50°, to constant weight.
The yield is 800–900 g.
The dry calcium malonate is placed in a 3-l. round-bottomed flask with sufficient (750–1000 cc.) alcohol-free ether (Note 3) to make a paste which can be stirred.
The flask is surrounded by an ice bath, and the well-stirred salt is treated with 1 cc. of 12 N hydrochloric acid for each gram of salt.
After the acid has been added slowly through a dropping funnel, the solution is transferred to a continuous extractor (Note 4) and extracted with ether until no more malonic acid is obtained. The product, as obtained from the undried ether solution by concentration, filtration, and drying in the air, melts at 130° or higher and is sufficiently pure for most purposes.
The yield is 415–440 g. (75–80 per cent of the theoretical amount).
2. Notes
1. A freshly distilled product boiling over a 3° range was used.
2. If the reaction between the cyanide and the chloroacetate becomes too vigorous, hydrogen cyanide is liberated and partly changed to a brown material, and a corresponding quantity of glycolate is formed. If the temperature of the reaction mixture is allowed to go above 95° spontaneously, the liquid may boil so vigorously and suddenly as to escape from the flask despite the large extra volume provided.
3. Ether is used to avoid unnecessarily increasing the volume of aqueous solution to be extracted.
This ether may be used for further extraction.
It is necessary to use alcohol-free ether to avoid esterifying the malonic acid during the protracted extraction period.
4. A convenient type of extractor used in this preparation was made as follows by modifying that described by J. Friedrichs:1 A 20-cm. calcium chloride tower, or other narrow-necked cylinder with a volume of about 1.3 l., was used as an extraction chamber.
The mantle-tube, conducting the ether vapors to an Allihn condenser, was made of 25-mm. tubing and was about 50 cm. long.
The goose-neck to the extraction flask, of 14-mm. tubing, was sealed to the mantle-tube about 8 cm. from the bottom end.
The inner tube was of 14-mm. tubing, about 65 cm. long, flanged at the top to a diameter of about 20 mm.
A Witt filter plate of the proper diameter may be sealed into the bottom of the tube to make the ether pass up through the water in a stream of fine bubbles, or this can also be accomplished by sealing off the bottom of the tube and piercing it with 3–6 pinholes.
The mantle-tube was fitted to the chamber by a properly bored rubber stopper, the condenser to the top of the mantle-tube, and the 500-cc. extraction flask to the goose-neck by charred cork stoppers. With this apparatus 395–400 g. of malonic acid was extracted in seventy-two hours, the ether being changed every twenty-four hours, and the final traces were extracted after an additional twenty-four hours.
The extractor as described by Friedrichs is shown in Fig. 12.
Working with Hazardous Chemicals
The procedures in Organic Syntheses are intended for use only by persons with proper training in experimental organic chemistry.
All hazardous materials should be handled using the standard procedures for work with chemicals described in references such as “Prudent Practices in the Laboratory” (The National Academies Press, Washington, D.C., 2011; the full text can be accessed free of charge at http://www.nap.edu/catalog.php?record_id=12654).
All chemical waste should be disposed of in accordance with local regulations. For general guidelines for the management of chemical waste, see Chapter 8 of Prudent Practices.
In some articles in Organic Syntheses, chemical-specific hazards are highlighted in red “Caution Notes” within a procedure.
It is important to recognize that the absence of a caution note does not imply that no significant hazards are associated with the chemicals involved in that procedure.
Prior to performing a reaction, a thorough risk assessment should be carried out that includes a review of the potential hazards associated with each chemical and experimental operation on the scale that is planned for the procedure. Guidelines for carrying out a risk assessment and for analyzing the hazards associated with chemicals can be found in Chapter 4 of Prudent Practices.
The procedures described in Organic Syntheses are provided as published and are conducted at one’s own risk.
3. Discussion
Malonic acid has been prepared by the hydrolysis of malononitrile with concentrated hydrochloric acid; by the hydration of carbon suboxide,and from an alkali cyanide and ethyl bromoacetate,4 ethyl chloroacetate,5 or chloroacetic acid6 followed by hydrolysis.
The preparation using sodium cyanide and chloroacetic acid is the most convenient and economical.
1,3-propanedioic acid
141-82-2 [RN]
1751370 [Beilstein]
212-385-4 [EINECS]
Acide malonique [French]
Kyselina malonova [Czech]
Malonic acid [ACD/IUPAC Name]
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
Malonic acid|Propanedioic acid
Metahnedicarboxylic acid
Methanedicarboxylic acid
Methylmalonic 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]
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.
MALONIC ACID is a carboxylic acid.
Carboxylic acids donate hydrogen ions if a base is present to accept them.
They react in this way with all bases, both organic (for example, the amines) and inorganic.
Their reactions with bases, called “neutralizations”, are accompanied by the evolution of substantial amounts of heat.
Neutralization between an acid and a base produces water plus a salt. Carboxylic acids with six or fewer carbon atoms are freely or moderately soluble in water; those with more than six carbons are slightly soluble in water.
Soluble carboxylic acid dissociate to an extent in water to yield hydrogen ions. The pH of solutions of carboxylic acids is therefore less than 7.0.
Many insoluble carboxylic acids react rapidly with aqueous solutions containing a chemical base and dissolve as the neutralization generates a soluble salt.
Carboxylic acids in aqueous solution and liquid or molten carboxylic acids can react with active metals to form gaseous hydrogen and a metal salt.
Such reactions occur in principle for solid carboxylic acids as well, but are slow if the solid acid remains dry.
Even “insoluble” carboxylic acids may absorb enough water from the air and dissolve sufficiently in it to corrode or dissolve iron, steel, and aluminum parts and containers.
Carboxylic acids, like other acids, react with cyanide salts to generate gaseous hydrogen cyanide.
The reaction is slower for dry, solid carboxylic acids.
Insoluble carboxylic acids react with solutions of cyanides to cause the release of gaseous hydrogen cyanide.
Flammable and/or toxic gases and heat are generated by the reaction of carboxylic acids with diazo compounds, dithiocarbamates, isocyanates, mercaptans, nitrides, and sulfides.
Carboxylic acids, especially in aqueous solution, also react with sulfites, nitrites, thiosulfates (to give H2S and SO3), dithionites (SO2), to generate flammable and/or toxic gases and heat. Their reaction with carbonates and bicarbonates generates a harmless gas (carbon dioxide) but still heat.
Like other organic compounds, carboxylic acids can be oxidized by strong oxidizing agents and reduced by strong reducing agents. These reactions generate heat.
A wide variety of products is possible. Like other acids, carboxylic acids may initiate polymerization reactions; like other acids, they often catalyze (increase the rate of) chemical reactions This chemical is incompatible with strong oxidizers. It is also incompatible with bases and reducing agents. (NTP, 1992)
CARBOXYACETIC ACID
DICARBOXYMETHANE
MALONIC ACID
METHANEDICARBOXYLIC ACID
PROPANEDIOIC ACID
1,3-PROPANEDIOIC ACID
USAF EK-695
Sometimes alternatively referred to as propanedioic acid, malonic acid is a dicarboxylic acid of ethane with a methylene group separating the two carbonyl moieties. The substance occurs in small quantities naturally in urine and beetroot, but is typically prepared by hydrolyzing diethyl malonate.
Malonic acid Chemical Properties, Uses and Production
Dibasic acid
Malonic acid is also known as methane dicarboxylic acid, carrot acid, malic acid reduction, beet acid. There are three kinds of crystal forms, of which two are triclinic, and one is monoclinic. That crystallized from ethanol is white triclinic crystals. Its relative molecular mass is 104.06. The relative density is 1.631 (15 ℃). Melting point is 135.6℃. It decomposes to acetic acid and carbon dioxide at 140℃. It does not decompose at 1.067×103~1.333×103Pa vacuum, but directly sublimates. It is not soluble in benzene. It is soluble in water, and the solubility is respectively 61.1 (0 ℃), 73.5 (20 ℃), 92.6 (50 ℃) in water, and 57 (20 ℃)in ethanol, 5.7 (20 ℃) in diethyl ether. It is slightly soluble in pyridine. It can decompose to formic acid and carbon dioxide in case of potassium permanganate. Malonic acid is dibasic acid. It has a typical reactive of dibasic acids, such as that its methylene is active, and it can be an addition, alkylation, amination, halogenation reaction; its two carboxyl groups are very close and they can be dehydrated; esterification with alcohol; decarboxylation by heating; condensation with carbonyl compounds; addition with compounds that containing active double bonds. Hydroxyl in two carboxyl groups of malonic acid were all replaced by ethoxy (see substitution reaction) to produce diethyl malonate. Diethyl malonate is important raw materials in organic synthesis for dyes and drugs synthesis. Because its molecules containing active methylene, which can react with sodium alcohol to generate sodium malonate. Then sodium malonate reacts with a variety of lively halides to generate substituted malonate. Malonate can prepare various monocarboxylic acids, dicarboxylic acids, keto acids and other compounds by hydrolysis reaction to lose carboxyl. As substituted malonate reacts with urea to prepare a commonly used hypnotic barbiturates.
Since that malonic acid generates carbon dioxide and water after heated without pollution problems, it can be directly used as aluminum surface treatment agent; it is also the raw material in the production of pesticides fungicides Fujione, herbicides Alloxydim; malonic acid is used to prepare diuretic sulfinpyrazone medicine, anti-inflammatory drug phenylbutazone paraben, sedatives bromomethyl Jacinto goods in pharmaceutical industries. In addition, malonic acid and its esters are widely used as pharmaceutical intermediates, such as preparing barbiturates, vitamins B1 and B6, etc. Esters of malonic acid are commonly used in organic synthesis. It also can be used as binding agent, perfum, resin additive, electroplating polishing agent, welding flux and so on.
The above information is edited by the chemicalbook of Ge Qian.
Uses
Malonic acid, also known as Propanedioic acid, Methane dicarbonic acid or Carboxyacetic acid, is an organic acid. Mainly used in perfumes, pharmaceutical intermediates, adhesives, resin additives, electroplating polishing agents, etc. Used in the pharmaceutical industry to produce barbituric acid, vitamin B1, vitamin B2, vitamin B6, etc. In agriculture, malonic acid is an intermediate of the fungicide rice pestin and an intermediate of the plant growth regulator indyl ester. In addition, it can also be used in the production of adhesives and resin additives, and can also be used as a surface treatment agent for leather and aluminum products.
Preparation
Chloroacetic acid is used as raw material in Laboratories. It is neutralized by NaOH or Na2CO3 to generate chloroacetic acid sodium salt. The sodium salt reacts with KCN (or NaCN) to yield α-cyano sodium acetate. And then malonic acid can be prepared after alkaline hydrolysis, calcium replacement and acidification. Chemical reaction equation is as follows:
Preparation
Chemical Properties
White crystals. It dissolves easily in water. And it is soluble in alcohol, ether and pyridine.
Uses
1. It mainly can be used as pharmaceutical intermediates. It also can be used as perfumery, adhesives, resin additives, electroplating polishing agent and so on.
2. It can be used as complexing agent. It also can be used to prepare barbituric salt.
3. Malonic acid is the intermediate of fungicides isoprothiolane. It is also the intermediate of plant growth regulator ethychlozate.
4. Malonic acid and its esters is mainly used as perfumery, adhesives, resin additives, pharmaceutical intermediates, electroplating, polishing agent, explosion control agents, heat welding fluxing additives and the like. In the pharmaceutical industry, it can be used to produce phenobarbital, barbiturates, vitamin B1, vitamin B2, vitamin B6, phenylbutazone, amino acids and so on. Malonic acid can be used as the aluminum surface treatment agent since that malonic acid generates carbon dioxide and water after heated without pollution problems. At this point, it has a great advantage when compared with acidic treating agent like formic acid in the past.
5. It can be used as complexing agent in the determination of beryllium, copper, calibration standard alkaline solution, biochemical studies, organic synthesis, preparing barbiturates, gas chromatography analysis of the standard.
Production method
The preparation method is that firstly sodium carbonate aqueous solution is added chloroacetic acid in the reaction vessel to get sodium chloroacetate aqueous solution. And then 30% sodium cyanide solution is slowly dripped at a predetermined temperature to generate sodium cyanide. After the reaction of cyanide finishes, sodium hydroxide is added to hydrolyze under heating in order to form sodium malonate solution. After the solution is concentrated, added dropwise to generate malonic acid, filtered and dried, then the product is obtained.
Description
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 (malon) meaning ‘apple’.
Chemical Properties
Crystalline
Uses
Malonic acid is used as building block in chemical synthesis, specifically to introduce the molecular group -CH2-COOH. Product Data Sheet
Uses
Malonic acid is used as an intermediate in the manufacture of barbiturates and other pharmaceuticals.
Definition
ChEBI: An alpha,omega-dicarboxylic acid in which the two carboxy groups are separated by a single methylene group.
Preparation
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 cyano acetic acid salt via a nucleophilic substitution. The nitrile group can be hydrolyzed with sodium hydroxide to sodium malonate, and acidification affords malonic acid.
Reactions
In a well – known reaction, malonic acid condenses with urea to form barbituric acid. Malonic acid is also frequently used as an enolate in Knoevenagel condensations or condensed with acetone to form Meldrum’s acid. The esters of malonic acid are also used as a – CH2COOH synthon in the malonic ester synthesis.
General Description
White crystals or crystalline powder. Sublimes in vacuum.
Air & Water Reactions
Water soluble.
Reactivity Profile
Malonic acid is a carboxylic acid. Carboxylic acids donate hydrogen ions if a base is present to accept them. They react in this way with all bases, both organic (for example, the amines) and inorganic. Their reactions with bases, called “neutralizations”, are accompanied by the evolution of substantial amounts of heat. Neutralization between an acid and a base produces water plus a salt. Carboxylic acids with six or fewer carbon atoms are freely or moderately soluble in water; those with more than six carbons are slightly soluble in water. Soluble carboxylic acid dissociate to an extent in water to yield hydrogen ions. The pH of solutions of carboxylic acids is therefore less than 7.0. Many insoluble carboxylic acids react rapidly with aqueous solutions containing a chemical base and dissolve as the neutralization generates a soluble salt. Carboxylic acids in aqueous solution and liquid or molten carboxylic acids can react with active metals to form gaseous hydrogen and a metal salt. Such reactions occur in principle for solid carboxylic acids as well, but are slow if the solid acid remains dry. Even “insoluble” carboxylic acids may absorb enough water from the air and dissolve sufficiently in Malonic acid to corrode or dissolve iron, steel, and aluminum parts and containers. Carboxylic acids, like other acids, react with cyanide salts to generate gaseous hydrogen cyanide. The reaction is slower for dry, solid carboxylic acids. Insoluble carboxylic acids react with solutions of cyanides to cause the release of gaseous hydrogen cyanide. Flammable and/or toxic gases and heat are generated by the reaction of carboxylic acids with diazo compounds, dithiocarbamates, isocyanates, mercaptans, nitrides, and sulfides. Carboxylic acids, especially in aqueous solution, also react with sulfites, nitrites, thiosulfates (to give H2S and SO3), dithionites (SO2), to generate flammable and/or toxic gases and heat. Their reaction with carbonates and bicarbonates generates a harmless gas (carbon dioxide) but still heat. Like other organic compounds, carboxylic acids can be oxidized by strong oxidizing agents and reduced by strong reducing agents. These reactions generate heat. A wide variety of products is possible. Like other acids, carboxylic acids may initiate polymerization reactions; like other acids, they often catalyze (increase the rate of) chemical reactions Malonic acid is incompatible with strong oxidizers. Malonic acid is also incompatible with bases and reducing agents.
Hazard
Strong irritant.
Fire Hazard
Flash point data for Malonic acid are not available; however, Malonic acid is probably combustible.
Biotechnological Applications
The calcium salt of malonic acid occurs in high concentrations in beetroot. It exists in its normal state as white crystals. Malonic acid is the classic example of a competitive inhibitor: It acts against succinate dehydrogenase (complex II) in the respiratory electron transport chain.
Purification Methods
Crystallise malonic acid from *benzene/diethyl ether (1:1) containing 5% of pet ether (b 60-80o), wash with diethyl ether, then recrystallise it from H2O or acetone. Dry it under vacuum over conc H2SO4. [Beilstein 2 IV 1874.]
Malonic acid Preparation Products And Raw materials
Raw materials
Diethyl ester Chloroacetic acid Acetone CALCIUM MALONATE Sodium cyanide Hydrochloric acid Cyanoacetic acid MALONIC ACID DISODIUM SALT Diethyl malonate Sodium chloroacetate
oic Acid Impurity 2 (Malonic Acid)
• Malonic acid 141-82-2
• 141-82-2 Malonic acid 1,3-Propanedioic acid
• Sodium Valproate Impurity 24
• Malonic acid, AR,99.5%
• Malonate, AR,99.5%
• Malonic acid anhydrous, free-flowing, Redi-Dri(TM), ReagentPlus(R), 99%
• Malonic acid ReagentPlus(R), 99%
• Malonic acid sublimed grade, >=99.95% trace metals basis
• Malonic acid Vetec(TM) reagent grade, 98%
• Malonic acid, synthesis grade
• Malonate standard fo
• Propane-1,3-dioic acid
• CH2(COOH)2
• Kyselina malonova
• kyselinamalonova
• Methanadicarboxylicacid
• Methanedicarbonic acid
• Methanedicardonicacid
• USAF ek-695
• usafek-695
• Malonic acid, 99% 250GR
• Malonic acid,anhydrous, free-flowing
• Malonsure
• Propanedioic acid Methane acid
• Methane acid
• MALONIC ACID FREE ACID
• Malonate Ion Chromatography Standard Solution Fluka
• MALONIC ACID REAGENTPLUS(TM) 99%
• MALONIC ACID 500MG NEAT
• MALONIC ACID, REAGENTPLUS, 99%
• MALONIC ACID PURE
• MalonicAcid Gr
• MalonicAcid For Synthesis
• Malonic Acid-1-13C2
• Malonic Acid-13C3
• malonate standard for ic
• MALONICACID,REAGENT
• Malonsαure(α-Form)
• Daucic acid
• 1,3-Propanedioic acid
• Malonic acid, Reagent Grade, 99.5+%
• Malonic acid: (Carboxyacetic acid)
• MALONIC ACID extrapure AR
• Malonic acid, Propanedioic acid
• Propandioic acid
• RARECHEM AL BO 0098
• PROPANEDIOIC ACID
• MALONIC ACID
• MALONATE ION CHROMATOGRAPHY STANDARD
• MAAC
• METHANEDICARBOXYLIC ACID
• DICARBOXYLIC ACID CO
• DICARBOXYMETHANE
• CARBOXYACETIC ACID
• Malonic acid ,99.5%
• AKOS BBS-00003780
Malonic acid has the chemical formula C3H4O4 and is a dicarboxylic acid. Organic compounds with two carboxylic acid functional groups are known as dicarboxylic acids. Dicarboxylic acids have similar chemical properties and reactivity to monocarboxylic acids. Malonic acid is a naturally occurring compound present in certain fruits. Organically grown citrus fruits have higher levels of malonic acid than conventionally grown citrus fruits.
Malonic acid is IUPAC’s systematic name for propanedioic acid. Malonic acid is the prototypical competitive inhibitor, acting against succinate dehydrogenase in the respiratory electron transport chain.
Malonic acid is linked to a malonyl-CoA decarboxylase deficiency, which is an inborn metabolic error.
Propanedioic acid, or Dicarboxymethane, is another name for malonic acid. The name Malon is derived from a Greek word that means apple. Malonates, as well as its esters and salts, are the ionised form of malonic acid. It appears as a crystalline powder or a white crystal. Alcohol, pyridine, and ether dissolve it.
By oxidising malic acid, the French chemist Victor Dessaignes produced malonic acid for the first time in 1858. Some fruits, such as citrus fruits, contain malonic acid.
The amount of malonic acid released by organically grown fruits is higher than that produced by conventionally grown fruits. Glucose fermentation can be used to manufacture malonic acid.
C3H4O4 is the chemical formula for malonic acid.
PROPERTIES
Chemical formula: C3H4O4
Molecular Weight/ Molar Mass: 104.061 g/mol
Density: 1.619 g/cm³
Boiling Point: Decomposes
Melting Point: 135 to 137°C
SYNTHESIS OF MALONIC ACID
Malonic acid is made from chloroacetic acid, which is also known as MCA (monochloroacetic acid).
Step 1: Sodium carbonate is converted to sodium salt in the first step.
Step 2: It’s made to react with sodium cyanide in step two.
Step 3: A nucleophilic substitution produces cyanoacetic acid salt.
Step 4: Sodium malonate is made by hydrolyzing the nitrile group with sodium hydroxide.
Step 5: Malonic acid is generated as a result of the acidification.
Malonic acid is made industrially by hydrolyzing diethyl malonate or dimethyl malonate.
Never give something by mouth to someone who is unconscious.
Using spray, rinse your mouth.
Polyester specialties are forerunners of malonic acid.
As a building block chemical, malonic acid is used to make a variety of useful compounds.
APPLICATIONS
The following is a list of malonic acid’s applications.
In polymers and polyester, malonic acid is used as a precursor.
It’s used in the fragrance industry as well as in flavourings.
It’s used to keep the acidity in check.
It’s used in a variety of pharmaceutical products.
To improve the mechanical properties of potato starch and cornstarch, it is used as a cross-linking agent.
Barbituric salt is made with this ingredient.
It’s used in the electroplating process.
It’s used to make B vitamins, B vitamins, B vitamins, B vitamins, B vitamins, B vitamins, B vitamins, B vitamins, and B vitamins, as well as amino acids.
It is used as a building block in chemical synthesis.
HEALTH CONSEQUENCES OF MALONIC ACID
It is a potent irritant that causes skin damage and damage to mucous membranes when inhaled, swallowed, or absorbed through the skin.
There have been a few laboratory animal toxicity studies of malonic acid, but they are inadequate to determine any additional health effects.
It may be harmful if inhaled. The respiratory tract is irritated as a result of this substance. It may be toxic if absorbed through the skin. The skin becomes irritated as a result of it.
Shift fresh air into the person while breathing in. If you are unable to breathe, have artificial respiration. Consult a physician.
Malonic acid (also called Propanedioic Acid ) is a white crystalline C-3 dicarboxylic acid; melting at 135 -136 C; readily soluble in water, alcohol and ether; solution in water is medium-strong acidic.
It can be derived by oxidizing malic acid or by the hydrolysis of cyanacetic acid.
Malonic acid itself is rather unstable and has few applications.
It’s diethyl ester (diethyl malonate) is more important commercially. Diethyl malonate, a colourless, fragrant liquid boiling at 199 C, is prepared by the reaction of monochloroacetatic acid with methanol, carbon monoxide or by the reaction cyanoacetic acid (the half nitriled-malonic acid) with ethyl alcohol. Malonic acid and its esters contain active methylene groups which have relatively acidic alpha-protons due to H atoms adjacent to two carbonyl groups. The reactivity of its methylene group provide the sequence of reactions of alkylation, hydrolysis of the esters and decarboxylation resulting in substituted ketones. The methylene groups in 1,3-dicarboxylic acid utilize the synthesis of barbiturates; a hydrogen atom is removed by sodium ethoxide, and the derivative reacts with an alkyl halide to form a diethyl alkylmalonate.
The diethyl dialkylmalonates are converted to barbiturates by reaction with urea.
Malonic acid and its esters are characterized by the large number of condensation products.
They are important intermediates in syntheses of vitamins B1 and B6, barbiturates, non-steroidal anti-inflammatory agents, other numerous pharmaceuticals, agrochemicals and flavors & fragrances compounds.
Malonic 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.
Malonic 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. It undergoes the usual reactions of carboxylic acids as well as facile cleavage into acetic acid and carbon dioxide.
Dicarboxylic acid is a compound containing two carboxylic acid, -COOH, groups. Straight chain examples are shown in table. The general formula is HOOC(CH2)nCOOH, where oxalic acid’s n is 0, n=1 for malonic acid, n=2 for succinic acid, n=3 for glutaric acid, and etc. In substitutive nomenclature, their names are formed by adding -dioic’ as a suffix to the name of the parent compound. They can yield two kinds of salts, as they contain two carboxyl groups in its molecules. The range of carbon chain lengths is from 2, but the longer than C 24 is very rare. The term long chain refers to C 12 up to C 24 commonly. Carboxylic acids have industrial application directly or indirectly through acid halides, esters, salts, and anhydride forms, polymerization, and etc. Dicarboxylic acids can yield two kinds of salts or esters, as they contain two carboxyl groups in one molecule. It is useful in a variety of industrial applications include;
Plasticizer for polymers
Biodegradable solvents and lubricants
Engineering plastics
Epoxy curing agent
Adhesive and powder coating
Corrosion inhibitor
Perfumery and pharmaceutical
Electrolyte
There are almost infinite esters obtained from carboxylic acids. Esters are formed by removal of water from an acid and an alcohol. Carboxylic acid esters are used as in a variety of direct and indirect applications. Lower chain esters are used as flavouring base materials, plasticizers, solvent carriers and coupling agents. Higher chain compounds are used as components in metalworking fluids, surfactants, lubricants, detergents, oiling agents, emulsifiers, wetting agents textile treatments and emollients, They are also used as intermediates for the manufacture of a variety of target compounds. The almost infinite esters provide a wide range of viscosity, specific gravity, vapor pressure, boiling point, and other physical and chemical properties for the proper application selections.
C length (Straight)
Product
CAS #
Melting Point
Boiling Point
C 2
Oxalic Acid
(Ethanedioic Acid) 144-62-7
189 – 191 C
Sublimes
C 3
Malonic Acid
(Propanedioic Acid)
141-82-2 131 – 135 C
Decomposes
C 4
Succinic Acid
(Butanedioic Acid)
110-15-6
185 – 190 C
235 C
C 5
Glutaric Acid
(Pentanedioic Acid)
110-94-1
95 – 99 C
302 C
C 6
Adipic Acid
(Hexanedioic Acid)
124-04-9
151 – 153 C
265 C at 100 mmHg
C 7
Pimelic Acid
(Heptanedioic Acid)
111-16-0
105 – 106 C
212 C at 10 mmHg
C 8
Suberic Acid
(Octanedioic Acid)
505-48-6
143 – 144 C
230 C at 15 mmHg
C 9
Azelaic Acid
(Nonanedioic Acid)
123-99-9
100 – 103 C
237 C at 15 mmHg
C 10
Sebacic Acid
(Decanedioic Acid)
111-20-6
131 – 134 C
294 at 100 mmHg
C 11
Undecanedioic acid 1852-04-6
109 – 110 C
C 12
Dodecanedioic acid 693-23-2
128 – 129 C
245 C at 10 mmHg
C 13
Brassylic acid
(Tridecanedioic acid) 505-52-2
112 – 114 C
C 14
Tetradecanedioic acid 821-38-5
126 – 128 C
C 15
Pentadecanedioic acid 1460-18-0
C 16
Thapsic acid
(Hexadecanedioic acid) 505-54-4
124 – 126 C
C 18
Octadecanedioic acid
871-70-5