Wikipedia

Itaconic anhydride

Itaconic anhydride is the cyclic anhydride of itaconic acid (an unsaturated, dicarboxylic acid) and is obtained by the pyrolysis of citric acid. It is a colourless, crystalline solid, which dissolves in many polar organic solvents and hydrolyzes forming itaconic acid.[4] Itaconic anhydride and its derivative itaconic acid have been promoted as biobased "platform chemicals" and bio- building blocks.[5][6]) These expectations, however, have not been fulfilled.[7]

Itaconic anhydride
Names
Preferred IUPAC name
3-Methylideneoxolane-2,5-dione
Other names
Methylenesuccinic anhydride
Identifiers
3D model (JSmol)
ChEMBL
ChemSpider
ECHA InfoCard 100.016.835 Edit this at Wikidata
EC Number
  • 218-518-2
UNII
  • InChI=1S/C5H4O3/c1-3-2-4(6)8-5(3)7/h1-2H2
    Key: OFNISBHGPNMTMS-UHFFFAOYSA-N
  • C=C1CC(=O)OC1=O
Properties
C5H4O3
Molar mass 112,09 g·[mol−1
Appearance colorless crystalline solid[1]
Melting point 70–72 °C (158–162 °F; 343–345 K)[3]
soluble in acetone and chloroform, only slightly soluble in Diethylether,[2] reacts with water
Hazards
GHS labelling:
GHS07: Exclamation mark
Warning
H302, H315, H319, H335
P261, P264, P270, P271, P280, P301+P312, P302+P352, P304+P340, P305+P351+P338, P312, P321, P330, P332+P313, P337+P313, P362, P403+P233, P405, P501
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).

Production

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As discovered as early as 1836, attempted distillation of citric acid gives the so-called "pyrocitric acid" ("Brenzcitronensäure"), now known as itaconic anhydride.[8]

 
Synthese von Itaconsäureanhydrid aus Citronensäure

According to an organic synthesis protocol,[4] itaconic anhydride is obtained from the rapid heating of citric acid monohydrate in a modest yield (37-47 %). The by-product is the thermodynamically more stable citraconic anhydride.[9]

Also when heating anhydrous citric acid to 260 °C in a vacuum, a mixture of itaconic and citraconic anhydride is achieved "in good yield".[10]

More productive are processes based on the biotechnologically accessible itaconic acid,[11] which produces exclusively itaconic anhydride in yields of up to 98% at temperatures of 165-180 °C and pressures of 10-30 mmHg in the presence of catalytic quantities of strong acids, such as concentrated sulphuric acid.[12]

 
Synthese von Itaconsäureanhydrid aus Itaconsäure

In order to avoid overheating and thus higher proportions of citraconic anhydride, the dehydration reaction can also be carried out in higher boiling aromatic solvents such as toluene or xylene in the presence of acidic montmorillonite[13] or in cumene in the presence of methanesulfonic acid.[14] In both variants yields of 95-97 % of itaconic anhydride are achieved.

Another process of cyclizing dicarboxylic acids with diethyl carbonate in the presence of a chromium-salen complex with μ-nitrido-bis(triphenylphosphane) chloride as cocatalyst quantitatively provides itaconic anhydride contaminated with citraconic anhydride already at 40 °C in 1 millimolar preparations. However, the reaction is technically uninteresting because of its expensive catalysts.[15]

Reactions

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At temperatures above its melting point, itaconic anhydride converts to citraconic anhydride.[12] Even at significantly lower temperatures, such as in boiling chloroform, isomerization can take place in the presence of tertiary amines.[16]

 
Umlagerung von Itaconsäureanhydrid in Citraconsäureanhydrid

By treating itaconic anhydride with phosphorus pentachloride (PCl5), itaconic acid dichloride (itaconyl chloride) is obtained:[17]

 
Synthese von Itaconylchlorid

from which polyamides with reactive vinylidene groups can be formed with diamines.[18]

Bromination of itaconic anhydride at – 20 °C and subsequent dehydrobromination produces 2-bromomethylmaleic anhydride in 70% yield by shifting the double bond into the five-membered ring.[19]

 
Bromierung-Dehydrobromierung von Itaconsäureanhydrid

Otto Diels and Kurt Alder already described the addition (Diels-Alder reaction) of the dienophile itaconic anhydride to the diene cyclopentadiene in 1928.[20] Also furfuryl alcohol, which is accessible from renewable raw materials, reacts as a diene to form the Diels-Alder adduct, in which the reaction of the alcohol group with the cyclic anhydride structure forms a lactone and a carboxylic acid group, i.e. the cyclic half ester of itaconic acid.[21]

 
Diels-Alder-Reaktionen mit Itaconsäureanhydrid

Itaconic anhydride can react with aromatics such as benzene via Friedel-Crafts acylation. This always happens in such a way that the ring opening occurs at the carbonyl group, which is further away from the methylene group (3-position).[22]

 
Friedel-Crafts-Acylierung mit Itaconsäureanhydrid

Nucleophiles such as thiols can easily be added to the methylene group. With other nucleophiles, such as alcohols, ammonia,[23] amines and hydroxylamine, itaconic anhydride reacts regioselectively in position 3 to the corresponding esters, amides and hydroxamic acids.

 
Reaktionen von Itaconsäureanhydrid mit Nukleophilen

The hydroxamic acid formed with O-benzylhydroxylamine can be cyclized in high yields with dicyclohexylcarbodiimide (DCC) to five-membered isoimides (iminofuranones) or with acetanhydride (Ac2O) to imides.[24]

 
ildung von Itaconimiden und Iminofuranonen

A number of five-, six- and seven-membered heterocycles (such as benzothiazepines) are obtainable from itaconic anhydride in useful yields.[25]

 
Bildung von Benzothiazepinessigsäure aus Itaconsäureanhydrid

Polymers of itaconic anhydride

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As an unsaturated cyclic anhydride, itaconic anhydride undergoes radical polymerization[26] and via polycondensation with diols or diamines. The two reactions can also be carried out sequentially – first radical polymerization, then polycondensation or vice versa.[27][28]

Radically produced itaconic anhydride polymers and copolymers can be alkaline hydrolyzed to polyitaconic acids under ring opening or converted into polymeric acid amides or esters subsequent to polymerization.[29]

 
Copolymere von Itaconsäureanhydrid mit Stearylmethacrylat + Hydrolyse

The resulting copolymers show properties that suggest a potential use as biomaterials for therapeutic systems and prostheses.[30]

Functional polymers exclusively from biogenic monomers involves the ring-opening metathesis polymerisation of an oxanorbornene ester produced from itaconic anhydride and furfuryl alcohol by Diels-Alder lactonisation using a Grubbs II catalyst.[31]

 
ROMP-Reaktion mit Itaconsäureanhydrid-Cyclopentadien/Furfurylalkohol-Diels-Alder-Addukt

References

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  2. ^ Entry from Itaconic Anhydride from TCI Europe, retrieved on {{{Date}}}
  3. ^ J.L. Belletire, R.J. Rauh (2001), "Itaconic Anhydride", E-EROS Encyclopedia of Reagents for Organic Synthesis, doi:10.1002/047084289X.ri086, ISBN 0-471-93623-5
  4. ^ a b R.L. Shriner, S.G. Ford, L.J. Roll (1931). "Itaconic Anhydride and Itaconic Acid". Organic Syntheses. 11: 70. doi:10.15227/orgsyn.011.0070.{{cite journal}}: CS1 maint: multiple names: authors list (link)
  5. ^ B. Kamm (2007), "Produktion von Plattformchemikalien und Synthesegas aus Biomasse", Angew. Chem. (in German), vol. 119, no. 27, pp. 5146–5149, Bibcode:2007AngCh.119.5146K, doi:10.1002/ange.200604514
  6. ^ Birgit Kamm (2008-04-14). "Das Konzept der Bioraffinerie – Schlüssel für Ressourceneffizienz". GDCh Aktuelle Wochenschau. Archived from the original on 2018-11-04. Retrieved 2018-10-01.
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  26. ^ D. Stawski, S. Polowinski (2005), "Polymerization of itaconic acid", Polimery, vol. 50, no. 2, pp. 118–122
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  28. ^ T. Okuda, K. Ishimoto, H. Ohara, S. Kobayashi (2012), "Renewable biobased polymeric materials: Facile synthesis of itaconic anhydride-based copolymers with poly(L-lactic acid) grafts", Macromolecules, vol. 45, no. 10, pp. 4166–4174, Bibcode:2012MaMol..45.4166O, doi:10.1021/ma300387j{{citation}}: CS1 maint: multiple names: authors list (link)
  29. ^ T. Otsu, J.-Z. Yang (1991), "Radical polymerization of itaconic anhydride and reactions of the resulting polymers with amines and alcohols", Polymer Int., vol. 25, no. 4, pp. 245–251, doi:10.1002/pi.4990250408
  30. ^ S. Shang, S.J. Huang, R.A. Weiss (2011), "Comb-like ionomers from sustainable resources: Copolymers of itaconic anhydride-co-stearyl methacrylate", Polymer, vol. 52, no. 13, pp. 2764–2771, doi:10.1016/j.polymer.2011.04.025{{citation}}: CS1 maint: multiple names: authors list (link)
  31. ^ Y. Bai, J.H. Clark, T.J. Farmer, I.D.V. Ingram, M. North (2017), "Wholly biomass derivable sustainable polymers by ring-opening metathesis polymerization of monomers obtained from furfuryl alcohol and itaconic anhydride", Polymer Chem., vol. 8, no. 20, pp. 3074–3081, doi:10.1039/C7PY00486A{{citation}}: CS1 maint: multiple names: authors list (link)
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