AMMONIUM FUMARATE

CAS: 14548-85-7
European Community (EC) Number: 238-594-0
Molecular Formula: C4H12N2O4+2

DESCRIPTION
Fumaric Acid is a non-toxic food additive generally used in beverages and baking powders for which requirements are based on purity.
Ammonium fumarate is a substitute for tartaric acid and occasionally takes the place of citric acid, at a rate of 1.36 gram of citric acid to every 0.91 grams of Fumaric Acid for the same taste. 
Ammonium fumarate is also an essential ingredient in the manufacturing of candy to add sourness, similar to the way malic acid is used.

Ammonium fumarate is a compound with formula (NH4)2(C2H2(COO)2).
Ammonium fumarate is the ammonium salt of fumaric acid.
As a food additive, Tumaric Acid has the E number E368.

Fumaric acid is an organic compound with the chemical formula HO2CCH=CHCO2H.
Together with maleic acid, fumaric acid are isomeric unsaturated dicarboxnic acids.
In maleic acid, carboxylic acid groups are in the cis (Z) form, and in fumaric acid in the trans (E) form.
There are other pronunciations that refer to fumaric acid.
Fumaric Acid has names such as E297, Butenethioic Acid, Allomaleic Acid, Tumaric Acid, Lichenic Acid, Sodium Fumarate, Ammonium Fumarate.
Fumaric acid is found in nature in the contents of bolete mushrooms, lichens, saber grass and Icelandic moss.
The form of fumaric acid found in natural environments is colorless crystalline powder and white in fine form.
Ammonium fumarate also occurs in the human body as well as in plants.
Tumaric Acid is known that the human body, which receives direct sunlight, produces fumaric acid.
Aromatically, Tumaric Acid has a fruity taste.
Fumarate is used so that cells can store the energy we obtain from food in the form of adenosine triphosphate.
With this feature, Tumaric Acid is one of the intermediate products in the citric acid cycle and the urea cycle.
Esters and salts are called fumarates.
Ammonium fumarate is known that dimethyl fumarate greatly inhibits the progression of multiple sclerosis.

How is fumaric acid produced?
In the first step of the fumaric acid production process, maleic anhydride is produced by the catalytic oxidation of suitable hydrocarbons.
Benzene as starting chemicals; n-butane; n-butene mixtures can be used.
The catalysts, which are vanadium and phosphorus oxides, used in the production of Maleic Anhydride are embedded in fixed bed tubular reactors.
Purified Maleic Anhydride is obtained after purification from the water formed as a by-product.
Then, maleic acid is obtained by hydrolysis and fumaric acid is obtained as a result of isomerization of malic acid.

How does fumaric acid look?
Allomalenic acid can be in the form of a white powder or in the form of transparent crystals.
Ammonium fumarate is odorless but has a fruity taste.
Allomalenic acid is 1.5 times more sour and odorless than citric acid.

When Tumaric Acid is above 200 C, Tumaric Acid starts to go from solid state to gas state, that is, it goes into the sublimation stage.
Lichenic Acid loses water when heated at 230 C and turns into maleic anhydride.
Ammonium fumarate evaporates completely at 287 C.

In which sectors is fumaric acid used?
Adhesive production industry
Food industry
Processing of Prepared Foods
Milk and Dairy Products Production Facilities
Pastry Industry
Pharmaceutical Industry – Psoriasis
Production of drugs for veterinary animals
Wine Production Sector

What are the fumaric acid usage areas (processes)?
Lichenic Acid is used as an antioxidant in the preparation of foods.
Ammonium fumarate is used in formulas containing alginate as a calcium-releasing chemical and increases the durability of gels in gelatin form.
Lichenic Acid interferes with chemical regulators called cytokines in the immune system of cells with psoriasis.
Therefore, drugs produced for the treatment of psoriasis contain fumaric acid.
Fumaric acid is used to add flavor to the filling materials used in cake and dessert making.
Lichenic Acid is used to add flavor to milk and dairy products during the production phase.
For example, Tumaric Acid is used in the manufacture of products such as milk powder, milk cream, instant soups containing cream, and chocolate milk.
Again in the food sector, fumaric acid is used in the production of ready-made foods such as cereal-containing breakfast cereal, pudding, instant pasta, noodles, oatmeal.
Tumaric Acid is used to increase the flavor of processed foods such as canned meat, pastrami, sausage.
Vinyl acetate and fumaric acid are used in various adhesive manufactures, thanks to the adhesive properties they contain.
Ammonium fumarate is used as a thickener for latex adhesives. 
Foil lamination adhesives that do not contain casein also contain fumaric acid.
Tumaric Acid is used for the production of glass fiber in the form of Styrene Copolymer.
Ferrous fumarate is produced by replacing Tumaric Acid with ferrous sulfate to treat small red blood cell anemia.
Ammonium fumarate is used with a solution obtained by mixing with substances such as lactic acid and citric acid, to prevent limescale in oil wells and to increase efficiency in oil wells.
Fumaric acid is used as an antioxidant in order to prevent the formation of harmful substances in the feed of cattle, sheep and poultry.
Fumaric acid is used to prevent the formation of bacteria in the wine production process.

The crystal structures of diammonium fumarate, 2NH4+.C4H2O42-, (I) and bis(isopropylammonium) fumarate, 2C3H7NH3+.C4H2O42-, (II), have been determined.
The intermolecular "N-H...O" hydrogen bonds form a three-dimensional network in (I), whereas two-dimensional sheets are formed in (II) and separated by layers of isopropyl groups.
The "N...O" distances are 2.790 (1)-2.903 (1) Å in (I) and 2.747 (1)-2.807 (1) Å in (II).
Differences between the solid-state photoreactivities of the fumaric acid ions in (I) and (II) are rationalized based on the crystal structures.

Fumaric acid is currently produced via the acidcatalysed isomerisation of maleic acid and mainly employed in the manufacture of sizing resins for the paper industry.
Use of this acid as a food acidifying agent (E297) in bakery products, desserts, soluble tea powders, chewing gums and fruit drinks and beverages is allowed by the European Community.
Moreover, fumaric acid is used as raw material to manufacture continuously aspartic acid using immobilised cells of Escherichia coli with high aspartase activity in accordance with the following reaction.

Fumaric acid L − Aspartic acid
In presence of L-phenylalanine, this aminoacid can be converted to aspartame (Chibata et al. 1985).

Tumaric Acid is therefore highly likely that the availability of biotechnologically-produced fumaric acid would positively affect the consumer attitude towards such lowcalorie sweetener since Tumaric Acid would then be of biological origin and this might enhance Tumaric Acids current utilisation.
Under aerobic conditions in a medium containing high concentrations of glucose and limiting amounts of nitrogen, R. arrhizus excretes large amounts of fumaric acid and small quantities of malic and succinic acids (Rhodes et al. 1959, 1962).
However, as the acidic metabolites accumulate in the production medium the pH decreases, thus exerting a progressive inhibitory effect on fumaric acid production.
To prevent this self-inhibition, the addition of a neutralising agent is, therefore, necessary.
In a number of previous investigations (Rhodes et al. 1959, 1962, Goldberg & Stieglitz 1985, Moresi et al. 1991a, b, 1992) fumarate production byR. arrhizus was controlled by the all-at-once addition of calcium carbonate (CaCO3).
However, problems of heavy foam formation (mainly due to calcium fumarate production) (Rhodes et al. 1962) arise that minimise the utilisation of the whole fermenter working volume. Moreover, fumaric acid recovery from a culture broth containing calcium fumarate, residual CaCO3 and mycelium as solid phase is troublesome.

Fumarate is a key intermediate in rumen microbial metabolism.
Fumarate is reduced to succinate, which is then decarboxylated to propionate (Asanuma et al., 1999; López et al., 1999).
During this process, hydrogen is consumed with the production of carbon dioxide.
When hydrogen is used to reduce fumarate, less is available for methanogenesis.
By an alternative pathway, fumarate is metabolized to acetate, but to a much smaller extent than Tumaric Acid is converted to propionate (Demeyer and Henderickx, 1967).
Thus, ruminal fermentation of fumarate could increase both acetate and propionate, although a decrease in acetate to propionate ratio often results (Asanuma et al., 1999; Carro and Ranilla, 2003).

The invention relates to an improved method for the industrial preparation of ammonium salts of fumaric or succinic acid, said salts being used for producing biologically active additives or medicines, as well as in the veterinary and food industries.
The method consists in neutralizing the corresponding acid with ammonium carbonate or bicarbonate at a molar stoichiometric ratio or a ratio which exceeds stoichiometry by 4-5% in a saturated aqueous solution of the salt being synthesized at a temperature of no higher than 40ºC, with subsequent isolation of the product and drying thereof at a temperature of no higher than 70ºC.
The filtrate formed after the isolation of the ammonium salts is suitable for recirculation.
The isolation of the product is preferably carried out by means of cooling the reaction mass to a temperature of 15-18ºC.
The resultant product is generally in crystalline form.
The saturated aqueous solution of the salt being synthesized is prepared by means of reacting ammonium carbonate or bicarbonate with a corresponding acid at a temperature of no higher than 40ºC.
The method is performed under industrial production conditions.
The possibility of preparing ecologically clean salts with a content of the main substance of at least 99.0 mass% and a yield of at least 98% is thereby ensured.
The method makes it possible to increase the yield of the end products and ensures a stably high quality thereof on account of said end products being prepared preferably in crystalline form.

Three novel carboxylate salts, phenylethylammonium fumarate-fumaric acid, phenylethylammonium succinate-succinic acid and anilinium fumarate-fumaric acid, have been prepared and structurally characterized.
Their crystal structures, which all contain unionized acid molecules in addition to the carboxylate di-anion, are closely related to one another.
The solid-state structures of these salts are described, and discussed in the context of the structures of related salts.
Recurrent hydrogen bonding motifs in fumarate and succinate salts containing unionized acid are identified.
Lichenic Acid is shown that the syn-syn hydrogen bonding motif seen in these salts is unusual in fumarate and succinate salts in general.

Applications
Fumaric acid has been used in food and beverage products since 1946.
Ammonium fumarate is currently used in wheat and corn tortillas, sour dough and rye breads, refrigerated biscuit doughs, fruit juice and nutraceutical drinks, gelatin desserts, gelling aids, pie fillings and wine.
Food research shows that Fumaric acid improves quality and reduces costs of many food and beverage products. 
Tumaric Acid is also used in animal feed.

Bakery

Breads
Fumaric acid acts as an instant flavoring agent for rye and sourdough breads.
Fumaric acid is added to dough ingredients during the dry blending step.
Flavor intensity is easily controlled by the amount of Fumaric acid added to the recipe.
In English muffins, Fumaric acid significantly increases porosity.
Dough machinability is improved and more sourness is provided per unit weight.

Fruit Juice Drinks
Fumaric acid provides more sourness per unit weight than other acidulants used in fruit juice drinks.
This substantially reduces the acidulant cost. In fruit juice drinks, Fumaric acid provides more buffering capacity than other acidulants when the pH is near 3.0. Using fumaric acid helps to stabilize the pH of a fruit juice drink, which in turn stabilizes color and flavor.

Wine
Fumaric Acid can economically acidify wine with no detectable difference in flavor.
The replacement ratio of three pounds of fumaric acid to five pounds of Citric acid can significantly reduce acidulant cost. 
Fumaric acid also prevents secondary fermentation after bottling and can act as a clarifier when low concentrations of copper and iron are present.

Confectioneries
Fumaric acid extends the shelf life of acid coated candies because it does not absorb moisture during storage and distribution. 
Maintaining a low moisture level retards sucrose inversion. 
Acidulant cost is also reduced as fumaric acid provides more sourness per unit weight than other acidulants used in dry form.

Jellies and Jams
Fumaric acid can cut food acid costs when used as an acidulant for jams, jellies and preserves. 
As little as two pounds of fumaric acid can be used to replace every three pounds of Citric, Malic or Tartaric acid.
At the 2:3 replacement ratio, fumaric acid does not produce significant differences in gel strength or pH.

Alginate Based Desserts
Fumaric acid is an economical acidulant that liberates calcium.
Ammonium fumarate improves smoothness and optimizes setting times. 
Also, the non-hygroscopicity of fumaric acid means that dry dessert mixes remain free flowing, even in high humidity.
Fumaric acid can be added directly to dry dessert mixes during the manufacturing process without causing degradation of flavor ingredients because of its non-hygroscopic nature.

Gelatin Desserts
Fumaric acid significantly reduces acidulant costs in gelatin desserts.
Depending on the product recipe, each pound of Citric acid can be replaced with 0.6 to 0.7 pounds of fumaric acid.
Reducing moisture pick-up improves flavor stability and lengthens shelf life.
Fumaric acid maintains non-caking and free-flowing qualities.
By keeping the moisture content low, fumaric acid helps to maintain the stability of flavor components and markedly decreases inversion of sucrose in the packaged dry mix.
Tumaric Acid may also be possible to use less expensive packaging if other moisture-sensitive ingredients are not being used in the product formulation.
Fumaric acid also increases gel strength, so food processors may reduce normal gelatin content by about 2%.

Pie Fillings
In pie fillings, Fumaric acid can be mixed directly with the starch and sugar ingredients, as it is non-hygroscopic.
Fumaric acid lowers costs by reducing the quantity of food acid needed in product formulations.
Fumaric acid also improves smoothness and extends the critical cook times for optimum gelation.

Egg White Foams
Fumaric acid can promote maximum volume in both egg-white foams and end products based on egg-white foams.
Fumaric acid can replace the more expensive cream of tartar to control egg-white volume.
With Fumaric acid, egg whites can be overbeaten for as much as double the customary optimum time.
Well suited for continuous flow processes, fumaric acid can be added to both liquid and dried egg whites.

Cleaning Agents for Dentures/Bath Salts
The carbon dioxide generating compounds containing NaHCO3, K2CO3 and powdered Fumaric acid can be tableted with other ingredients to make cleaning agents for dentures and bath salts.

Animal Feed
Fumaric acid has proven to be a particularly effective additive to piglet feed during the post-weaning period.
The inclusion of Fumaric acid and the resultant adjustment of the pH value demonstrate improved weight gain, food consumption and feed conversion ratio.

Industrial Uses

Industrial uses of Fumaric acid include:

Unsaturated Polyester
Alkyd Resins
Printing Inks
Paper Sizing

Chemical and Physical Properties
Computed Properties

Property Name - Property Value
Molecular Weight: 152.15
Hydrogen Bond Donor Count: 4
Hydrogen Bond Acceptor Count: 4
Rotatable Bond Count: 2
Exact Mass: 152.07970687
Monoisotopic Mass: 152.07970687
Topological Polar Surface Area: 76.6 Ų
Heavy Atom Count: 10
Formal Charge: 2
Complexity: 119
Isotope Atom Count: 0
Defined Atom Stereocenter Count: 0
Undefined Atom Stereocenter Count: 0
Defined Bond Stereocenter Count: 1
Undefined Bond Stereocenter Count: 0
Covalently-Bonded Unit Count: 3
Compound Is Canonicalized: Yes

Physical Description: White crystalline powder
Solubility: (5% in water)Clear, colourless solution
pH: 3.0 - 4.0
Specific Optical Rotation: 18.5 - -16.5 °
Residue on Ignition: ≤ 0.5%
Heavy Metals: ≤ 10ppm
Cadmium (Cd): ≤ 1ppm
Lead (Pb): ≤ 3ppm
Mercury (Hg): ≤ 0.1ppm
Arsenic (As): ≤ 1ppm
Water: ≤ 1.0%
D-Enantiomer: ≤ 1.0%
L-Carnitine Content: 56.5 - 60.5 %
Assay: 97.5 - 102.5 % (L-Carnitine + Fumaric acid, dried basis)
Specification Version: 1.0

Classification
Ontologies
MeSH Tree

MeSH Tree - Chemicals and Drugs Category - Organic Chemicals - Carboxylic Acids - Acids, Acyclic - Dicarboxylic Acids - Fumarates - Supplementary Records - fumaric acid

Names and Identifiers

IUPAC Name: diazanium;(E)-but-2-enedioic acid
InChI=1S/C4H4O4.2H3N/c5-3(6)1-2-4(7)8;;/h1-2H,(H,5,6)(H,7,8);2*1H3/p+2/b2-1+;;
InChI Key: CKKXWJDFFQPBQL-SEPHDYHBSA-P
Canonical SMILES: C(=CC(=O)O)C(=O)O.[NH4+].[NH4+]
Isomeric SMILES: C(=C/C(=O)O)C(=O)O.[NH4+].[NH4+]
Molecular Formula: C4H12N2O4+2

Synonyms

(e)-2-butenedioic acid
(E)-HO2CCH=CHCO2H
[(14) C]fumarate
[U-(13) C]fumarate
1,2-Ethenedicarboxylic acid, trans-
1,2-ethylenedicarboxylic acid
1,2-Ethylenedicarboxylic acid, (E)
2-Butenedioic acid (2E)-
2-Butenedioic acid (E)-
2-Butenedioic acid (E)-, disodium salt
2-Butenedioic acid (E)-, ion(2-)
2-Butenedioic acid (E)-, sodium salt
acide fumarique
AI3-24236
Allomaleic acid
Allomalenic acid
Ammonium fumarate
Boletic acid
BRN 0605763
Butene-1,4-dioic acid
Butenedioic acid
Butenedioic acid, (E)-
Caswell No. 465E
CCRIS 1039
CCRIS 7315
Disodium fumarate
EINECS 203-743-0
EINECS 227-535-4
EINECS 231-725-2
EINECS 241-087-7
EPA Pesticide Chemical Code 051201
FEMA No. 2488
Fema number: 2488
Fumaran sodny
Fumarate
Fumarate dianion
Fumarate(2-)
Fumaric acid
Fumaric acid (e)-butenedioic acid trans-1,2-ethylenedicarboxylic acid allomaleic acid boletic acid
Fumaric acid, disodium salt
Fumaric acid, ion(2-)
Fumaric acid, sodium salt
HSDB 710
Kyselina fumarova
Lichenic acid
Maleic anhydride, mono(castor oil) ester
Monosodium fumarate
NSC 2752
NSC-2752
Sodium 2-butenedioate, (E)-
Sodium fumarate
Sodium fumarate (x-Na)
Sodium hydrogen fumarate
Trans-1,2-ethenedicarboxylic acid
Trans-1,2-Ethylenedicarboxylic acid
Trans-Butenedioic acid
Tumaric acid
U-1149
USAF EK-P-583
(E)-2-Butenedioate
2-(E)-Butenedioate
2-(E)-Butenedioic acid
Allomaleate
Boletate
Lichenate
Trans-1,2-Ethylenedicarboxylate
Trans-2-Butenedioate
Trans-2-Butenedioic acid
Trans-Butenedioate
(2E)-But-2-enedioate
(2E)-But-2-enedioic acid
142-42-7