2170-03-8

Usage

Uses

Used in Enzyme Immobilization:
Itaconic anhydride is used as a crosslinking agent for the immobilization of β-glucosidase, a crucial enzyme in various industrial applications, such as biofuel production and the synthesis of valuable chemicals.
Used in Polymer Synthesis:
Itaconic anhydride is used as an alternating monomer in the production of itaconates through esterification. This process facilitates the introduction of polar functionalities in polymers, enhancing their properties and expanding their range of applications.
Used in Emulsion Polymerization:
Itaconic anhydride is utilized in emulsion polymerization to obtain suitable monomers for the synthesis of itaconate-based polymers. These polymers have potential applications in various industries, such as coatings, adhesives, and pharmaceuticals, due to their unique properties.

Preparation

To a flask equipped with a 12 mm diameter ground glass adaptor tube bent for downward distillation and joined to a 100 cm condenser is added 200 gm (0.95 mole) of citric acid monohydrate. An ice-cooled flask and a cold trap are connected to the condenser. The flask containing the citric acid is heated rapidly with a wide flame of the Meker burner so that in 12-15 min the distillation at 175-190°C is complete. The distillation is stopped earlier if the vapors in the reaction flask become yellow. Superheating of the citric acid will cause rearrangement to citraconic anhydride. The water is quickly separated from the distillate and the itaconic anhydride layer dried to afford 40-50 gm (37-47%), m.p. 67-68°C. Long time contact of the water with the anhydride causes it to hydrolyze to itaconic acid, m.p. 162-165°C.

Synthesis Reference(s)

Tetrahedron Letters, 25, p. 6027, 1984 DOI: 10.1016/S0040-4039(01)81751-2

Purification Methods

Crystallise the anhydride from CHCl3/pet ether. It can be distilled under reduced pressure. Distillation at atmospheric pressure, or prolonged distillation causes rearrangement to citraconic anhydride (2-methylmaleic anhydride). If the material (as seen in the IR spectrum) contains much free acid, then heat with acetyl chloride or SOCl2, evaporate and distil at as high a vacuum as possible. The crude anhydride deposits crystals of itaconic acid on standing probably due to hydrolysis by H2O — store it in sealed ampoules under dry N2. [Skinner et al. Org Synth Coll Vol II 368 1943, IR: Nagai Bull Chem Soc Jpn 37 369 1964, Kelly & Segura J Am Chem Soc 56 2497 1934, Beilstein 17/11 V 66.]

InChI:InChI=1/C10H10O7/c1-5(3-7(11)12)9(15)17-10(16)6(2)4-8(13)14/h1-4H2,(H,11,12)(H,13,14)

Upstream product

• 6318-55-4 cis-aconitic anhydride 
• 14556-16-2 2,6-dioxo-3,6-dihydro-2H-pyran-4-carboxylic acid 
• 97-65-4 2-methylenesuccinic acid 
• 108-24-7 acetic anhydride 
• 60-29-7 diethyl ether 
• 75-36-5 acetyl chloride 
• 499-12-7 1 propene 1,2,3 tricarboxylic acid 
• 77-92-9 citric acid 
• 7719-09-7 thionyl chloride 
• 108-88-3 toluene 

Downstream Products

• 57718-07-7 2-methylene-succinic acid 4-ethyl ester 
• 139114-33-3 1-(4-hydroxy-phenyl)-3-methylene-pyrrolidine-2,5-dione 
• 91569-76-5 1-(2-methoxy-phenyl)-3-methylene-pyrrolidine-2,5-dione 
• 51318-98-0 2-(carboxymethyl)bicyclo[2.2.1]hept-5-ene-2-carboxylic acid 
• 73926-98-4 1-(4-methoxyphenyl)-3-methylenepyrrolidine-2,5-dione 
• 67504-35-2 3-methyl-endo-bicyclo<2.2.2>oct-5-ene-2,3-dicarboxylic anhydride 
• 616-02-4 citraconic acid anhydride 
• 4100-80-5 2-methylsuccinic anhydride 
• 531548-27-3 N-(4-ethoxyphenyl)itaconimide 
• 408308-26-9 4-(methyl(phenyl)amino)-2-methylene-4-oxobutanoic acid 
• 498-23-7 citraconic acid 
• 498-21-5 2-methylbutanedioic acid 
• 97-65-4 2-methylenesuccinic acid 
• 1931-60-8 3-methylenebutanedioyl dichloride 

Relevant academic research and scientific papers

Four component Passerini polymerization of bulky monomers under high shear flow

We introduce a four component Passerini polymerization utilizing sterically bulky isocyanide monomers. Under typical Passerini conditions, bulky isocyanides do not react within standard Passerini reaction timescales (hours). We overcome this challenge via the unique physiochemical conditions present in a vortex fluidic device, reducing the reaction time to 2 h on average. Under these high-shear thin-film conditions, bulky isocyanides are readily incorporated into the multicomponent polymerization without the need of high-pressure or temperature. Finally, we demonstrate that the four component approach using functional cyclic anhydrides allows for post-polymerization modification.

Thermal behaviour of the copolymers of acrylonitrile with methyl acrylate and itaconic acid or its derivatives

Itaconic acid monoesters and monoamides, such as 2-carbamoylmethacrylic acid, N-octyl-2-carbamoylmethacrylic acid and 2-methoxy- carbonylmethacrylic acid, smoothed the peak of heat release upon the thermal cyclization of acrylonitrile copolymers with commensurable effectiveness, and they can serve as competitive substitutes for itaconic acid in the synthesis of carbon fiber precursors.

NMR Investigation of the Thermolysis of Citric Acid

The thermolytic decomposition of citric acid in the presence of tin/lead solder has been investigated.The solid reaction products were first examined by solid-state 13C NMR.The samples were then dissolved in D2O, and 1H and 13C 1D and 2D (HMQC, TOCSY) spectra were obtained.Results indicate the presence of a series of compounds including 3-hydroxyglutaric, citraconic, itaconic and aconitic acids, and anhydrides.Solution- and solid-state NMR data are provided for citric acid and a number of metal and alkali metal citrate salts.Results of this work are related to the use of citric acid as a solder flux and to the elimination of chlorofluorocarbon cleaning processes in the electronics industry.Index Headings: NMR; Solid-state NMR; Citric acid; Thermolysis.

Microwave assisted synthesis of diosgenin esters of maleic and itaconic acids

Diosgenin monomaleate and diosgenin monoitaconate were prepared by the esterification of diosgenin with maleic and itaconic anhydride, respectively, in toluene using p-toluenesulphonic acid as catalyst. A domestic microwave oven was modified and used for the synthesis of both products. The reaction time for consuming all the diosgenin according to thin-layer chromatography (TLC) was reduced by around 90% in the synthesis of monomaleate of diosgenin as well as in the synthesis of monoitaconate of diosgenin in comparison with conventional heating, whereas the monomaleate of diosgenin yield increased from 43 to 80-85% and the monoitaconate of diosgenin yield from 34 to 95% under the same experimental conditions. It was easier to purify the diosgenin monoitaconate than the diosgenin monomaleate. Both products were characterized by NMR and FTIR spectroscopy. Copyright Taylor & Francis Group, LLC.

New type of prototropic tautomerism involving carbon, hydrogen, and oxygen atoms

A low-molecular weight analog of the vinyl chloride-maleic anhydride copolymer, chloromethylsuccinic anhydride gives rise to a new type of prototropic tautomerism, cyclic anhydride-enol, with formation of quasiaromatic enol and dienol derivatives. The ratio of the anhydride and enol tautomers in solution at room temperature is 7:1.

FRAGRANCE MIXTURE

A fragrance mixture and its applications, in particular perfume oils, cosmetic agents, application agents or washing and cleaning agents, containing a sensory effective amount of (i) (E)-2-methyl-but-2-endicarboxylic acid diethyl ester, (ii) (Z)-2-methyl-but-2-endicarboxylic acid diethyl ester or (iii) 2-methylenebutanedicarboxylic acid diethyl ester and mixtures thereof and analogous esters derived from these compounds and mixtures.

Heterogeneous catalysts for the cyclization of dicarboxylic acids to cyclic anhydrides as monomers for bioplastic production

Cyclic anhydrides, key intermediates of carbon-neutral and biodegradable polyesters, are currently produced from biomass-derived dicarboxylic acids by a high-cost multistep process. We present a new high-yielding process for the direct intramolecular dehydration of dicarboxylic acids using a reusable heterogeneous Lewis acid catalyst, Nb2O5·nH2O. Various dicarboxylic acids, which can be produced by a biorefinery process, are transformed into the corresponding cyclic anhydrides as monomers for polyester production. This method is suitable for the production of renewable polyesters in a biorefinery process.

(Re)Investigation of the reactivity of uranium hexafluoride toward several organic functions at room temperature

The annual worldwide production of UF6 is very large and this compound is not used. Consequently, it could be interesting to find some applications as organic reagent. UF6 could be considered as an oxidizer of various functions. However, it seems also present some possibilities as a fluorinating reagent in mild conditions.

SULFOMETHYLSUCCINATES, PROCESS FOR MAKING SAME AND COMPOSITIONS CONTAINING SAME

Sulfometh lsuccinates of the formula I, wherein R is an alkyi, alkenyl, alkynyl, alkoxylated alkyi, cycloalkyl, cycloalkenyl, cycloalkynyl, branched alkyi, branched alkenyl, branched alkynyl, branched alkoxylated alkyi, aromatic, substituted alkyi aromatic, substituted alkenyl aromatic or substituted alkoxylated aromatic group; M is a cation, hydrogen, amine or ammonium salt or combinations thereof, and each M may be the same as or different from the other; and n is from 1 to about 6. Processes for synthesizing the sulfomethylsuccinates are also provided. The sulfomethylsuccinates can be used as surfactants, emulsifiers, skin feel agents, film formers, rheological modifiers, solvents, release agents, lubrication agents, conditioners, and dispersants, etc.

4-(2',4'-DIFLUOROBIPHENYL-4-YL)-2-METHYL-4-OXOBUTANOIC ACID AND ITS DERIVATIVES

Friedel-Crafts reaction of itaconic anhydride (III) with 2,4-difluorobiphenyl (II) afforded unsaturated acid IV which was hydrogenated to give 4-(2',4'-difluorobiphenyl-4-yl)-2-methyl-4-oxobutanoic acod (I).A series of functional derivatives and salts of the acid I has been prepared.The antiinflammatory effect of these compounds was compared with that of acid I using selected experimental inflammation models.The analgesic activity in the intraperitoneal iritation test was also evaluated.In the case of (R)-(+)-1-phenylethylamide Vf the ratio of the diastereisomers was determined by HPLC.