Organic acid anhydride

Last updated
Generic example of an anhydride of two carboxylic acids .mw-parser-output .template-chem2-su{display:inline-block;font-size:80%;line-height:1;vertical-align:-0.35em}.mw-parser-output .template-chem2-su>span{display:block;text-align:left}.mw-parser-output sub.template-chem2-sub{font-size:80%;vertical-align:-0.35em}.mw-parser-output sup.template-chem2-sup{font-size:80%;vertical-align:0.65em} R COOH and R COOH, with the blue marked carboxylic acid anhydride functional group, where R stands for any group (typically hydrogen or organyl). FunktionelleGruppen Carbonsaureanhydrid.svg
Generic example of an anhydride of two carboxylic acids R COOH and R COOH, with the blue marked carboxylic acid anhydride functional group, where R stands for any group (typically hydrogen or organyl).

An organic acid anhydride is an acid anhydride that is also an organic compound. An acid anhydride is a compound that has two acyl groups bonded to the same oxygen atom. [1] A common type of organic acid anhydride is a carboxylic anhydride, where the parent acid is a carboxylic acid, the formula of the anhydride being (RC(O))2O. Symmetrical acid anhydrides of this type are named by replacing the word acid in the name of the parent carboxylic acid by the word anhydride. [2] Thus, (CH3CO)2O is called acetic anhydride.Mixed (or unsymmetrical) acid anhydrides, such as acetic formic anhydride (see below), are known, whereby reaction occurs between two different carboxylic acids. Nomenclature of unsymmetrical acid anhydrides list the names of both of the reacted carboxylic acids before the word "anhydride" (for example, the dehydration reaction between benzoic acid and propanoic acid would yield "benzoic propanoic anhydride"). [3]

Contents

One or both acyl groups of an acid anhydride may also be derived from another type of organic acid, such as sulfonic acid or a phosphonic acid. One of the acyl groups of an acid anhydride can be derived from an inorganic acid such as phosphoric acid. The mixed anhydride 1,3-bisphosphoglyceric acid, an intermediate in the formation of ATP via glycolysis, [4] is the mixed anhydride of 3-phosphoglyceric acid and phosphoric acid. Acidic oxides are also classified as acid anhydrides.

Nomenclature

The nomenclature of organic acid anhydrides is derived from the names of the constituent carboxylic acids. In symmetrical acid anhydrides, only the prefix of the original carboxylic acid is used and the suffix "anhydride" is added. For most unsymmetrical acid anhydrides - also called mixed anhydrides- the prefixes from both acids reacted are listed before the suffix, e.g., benzoic propanoic anhydride. [5]

Preparation

Organic acid anhydrides are prepared in industry by diverse means. Acetic anhydride is mainly produced by the carbonylation of methyl acetate. [6] Maleic anhydride is produced by the oxidation of benzene or butane. Laboratory routes emphasize the dehydration of the corresponding acids. The conditions vary from acid to acid, but phosphorus pentoxide is a common dehydrating agent:

2 CH3COOH + P4O10 → CH3C(O)OC(O)CH3 + "P4O9(OH)2"

In addition to symmetrical, acyclic anhydrides, other classes are recognized as discussed in the following sections.

Mixed anhydrides

Mixed anhydrides have the formula RC(O)OC(O)R'. They tend to redistribute upon heating although acetic formic anhydride can be distilled at one atmosphere. [7] Those containing the acetyl group can be prepared using ketene as an acetylating agent:

RCO2H + H2C=C=O → RCO2C(O)CH3

Acid chlorides are also effective precursors as illustrated by the reaction with sodium formate: [8]

CH3C(O)Cl + HCO2Na → HCO2COCH3 + NaCl

Cyclic anhydrides

Examples include maleic anhydride and succinic anhydride. Although these five-membered rings form readily. [9] [10] [11]

Dianhydrides and trianhydrides

Examples are mostly cyclic anhydrides:

These compounds are sometimes useful crosslinking agents.

Reactions

Acid anhydrides are a source of reactive acyl groups, and their reactions and uses resemble those of acyl halides. Acid anhydrides tend to be less electrophilic than acyl chlorides, and only one acyl group is transferred per molecule of acid anhydride, which leads to a lower atom efficiency. The low cost, however, of acetic anhydride makes it a common choice for acetylation reactions.

In reactions with alcohols and amines, the reactions afford equal amounts of the acylated product and the carboxylic acid:

RC(O)OC(O)R + R'OH → RC(O)OR' + RCO2H
RC(O)OC(O)R + R'2NH → RC(O)NR'2 + RCO2H

Similarly, in Friedel-Crafts acylation of arenes (ArH):

RC(O)OC(O)R + ArH → RC(O)Ar + RCO2H

As with acid halides, anhydrides can also react with carbon nucleophiles to furnish ketones and/or tertiary alcohols, and can participate in both the Friedel–Crafts acylation and the Weinreb ketone synthesis. Unlike acid halides, however, anhydrides do not react with Gilman reagents.[ citation needed ]

The reactivity of anhydrides can be increased by using a catalytic amount of N,N-dimethylaminopyridine ("DMAP") or even pyridine. [12]

Nucleophilic Acyl Substitution on an Anhydride Catalyzed by DMAP.png

First, DMAP (2) attacks the anhydride (1) to form a tetrahedral intermediate, which collapses to eliminate a carboxylate ion to give amide 3. This intermediate amide is more activated towards nucleophilic attack than the original anhydride, because dimethylaminopyridine is a better leaving group than a carboxylate. In the final set of steps, a nucleophile (Nuc) attacks 3 to give another tetrahedral intermediate. When this intermediate collapses to give the product 4, the pyridine group is eliminated and its aromaticity is restored – a powerful driving force, and the reason why the pyridine compound is a better leaving group than a carboxylate ion.

For prochiral cyclic anhydrides, the alcoholysis reaction can be conducted asymmetrically. [13]

Applications and occurrence of acid anhydrides

Acetic anhydride is a major industrial chemical widely used for preparing acetate esters, e.g. cellulose acetate. Maleic anhydride is the precursor to various resins by copolymerization with styrene. Maleic anhydride is a dienophile in the Diels-Alder reaction. [7]

Dianhydrides, molecules containing two acid anhydride functions, are used to synthesize polyimides and sometimes polyesters [14] and polyamides. [15] Examples of dianhydrides: pyromellitic dianhydride (PMDA), 3,3’, 4,4’ - oxydiphtalic dianhydride (ODPA), 3,3’, 4,4’-benzophenone tetracarboxylic dianhydride (BTDA), 4,4’-diphtalic (hexafluoroisopropylidene) anhydride (6FDA), benzoquinonetetracarboxylic dianhydride, ethylenetetracarboxylic dianhydride. Polyanhydrides are a class of polymers characterized by anhydride bonds that connect repeat units of the polymer backbone chain.

Biological occurrence

Natural products containing acid anhydrides have been isolated from animals, bacteria and fungi. [16] [17] [18] Examples include cantharidin from species of blister beetle, including the Spanish fly, Lytta vesicatoria, and tautomycin, from the bacterium Streptomyces spiroverticillatus . The maleidride family of fungal secondary metabolites, which possess a wide range of antibiotic and antifungal activity, are alicyclic compounds with maleic anhydride functional groups. [19] A number of proteins in prokaryotes [20] and eukaryotes [21] undergo spontaneous cleavage between the amino acid residues aspartic acid and proline via an acid anhydride intermediate. In some cases, the anhydride may then react with nucleophiles of other cellular components, such as at the surface of the bacterium Neisseria meningitidis or on proteins localized nearby. [22]

Analogues

Nitrogen

A general linear imide functional group Imide functional group.svg
A general linear imide functional group

Imides are structurally related analogues, where the bridging oxygen is replaced by nitrogen. They are similarly formed by the condensation of dicarboxylic acids with ammonia. The replacement of all oxygen atoms with nitrogen gives imidines, these are a rare functional group which are very prone to hydrolysis.

Sulfur

Sulfur can replace oxygen, either in the carbonyl group or in the bridge. In the former case, the name of the acyl group is enclosed in parentheses to avoid ambiguity in the name, [2] e.g., (thioacetic) anhydride (CH3C(S)OC(S)CH3). When two acyl groups are attached to the same sulfur atom, the resulting compound is called a thioanhydride, [2] e.g., acetic thioanhydride ((CH3C(O))2S).

See also

Related Research Articles

<span class="mw-page-title-main">Amide</span> Organic compounds of the form RC(=O)NR′R″

In organic chemistry, an amide, also known as an organic amide or a carboxamide, is a compound with the general formula R−C(=O)−NR′R″, where R, R', and R″ represent any group, typically organyl groups or hydrogen atoms. The amide group is called a peptide bond when it is part of the main chain of a protein, and an isopeptide bond when it occurs in a side chain, as in asparagine and glutamine. It can be viewed as a derivative of a carboxylic acid with the hydroxyl group replaced by an amine group ; or, equivalently, an acyl (alkanoyl) group joined to an amine group.

<span class="mw-page-title-main">Carboxylic acid</span> Organic compound containing a –C(=O)OH group

In organic chemistry, a carboxylic acid is an organic acid that contains a carboxyl group attached to an R-group. The general formula of a carboxylic acid is often written as R−COOH or R−CO2H, sometimes as R−C(O)OH with R referring to an organyl group, or hydrogen, or other groups. Carboxylic acids occur widely. Important examples include the amino acids and fatty acids. Deprotonation of a carboxylic acid gives a carboxylate anion.

<span class="mw-page-title-main">Ester</span> Compound derived from an acid

In chemistry, an ester is a functional group derived from an acid in which the hydrogen atom (H) of at least one acidic hydroxyl group of that acid is replaced by an organyl group. Analogues derived from oxygen replaced by other chalcogens belong to the ester category as well. According to some authors, organyl derivatives of acidic hydrogen of other acids are esters as well, but not according to the IUPAC.

<span class="mw-page-title-main">Ketene</span> Organic compound of the form >C=C=O

In organic chemistry, a ketene is an organic compound of the form RR'C=C=O, where R and R' are two arbitrary monovalent chemical groups. The name may also refer to the specific compound ethenone H2C=C=O, the simplest ketene.

<span class="mw-page-title-main">Acetyl group</span> Chemical group, –C(=O)CH₃

In organic chemistry, an acetyl group is a functional group denoted by the chemical formula −COCH3 and the structure −C(=O)−CH3. It is sometimes represented by the symbol Ac. In IUPAC nomenclature, an acetyl group is called an ethanoylgroup.

<span class="mw-page-title-main">Acyl group</span> Chemical group (R–C=O)

In chemistry, an acyl group is a moiety derived by the removal of one or more hydroxyl groups from an oxoacid, including inorganic acids. It contains a double-bonded oxygen atom and an organyl group or hydrogen in the case of formyl group. In organic chemistry, the acyl group is usually derived from a carboxylic acid, in which case it has the formula R−C(=O)−, where R represents an organyl group or hydrogen. Although the term is almost always applied to organic compounds, acyl groups can in principle be derived from other types of acids such as sulfonic acids and phosphonic acids. In the most common arrangement, acyl groups are attached to a larger molecular fragment, in which case the carbon and oxygen atoms are linked by a double bond.

<span class="mw-page-title-main">Thioester</span> Organosulfur compounds of the form R–SC(=O)–R’

In organic chemistry, thioesters are organosulfur compounds with the molecular structure R−C(=O)−S−R’. They are analogous to carboxylate esters with the sulfur in the thioester replacing oxygen in the carboxylate ester, as implied by the thio- prefix. They are the product of esterification of a carboxylic acid with a thiol. In biochemistry, the best-known thioesters are derivatives of coenzyme A, e.g., acetyl-CoA. The R and R' represent organyl groups, or H in the case of R.

<span class="mw-page-title-main">Dicarbonyl</span> Molecule containing two adjacent C=O groups

In organic chemistry, a dicarbonyl is a molecule containing two carbonyl groups. Although this term could refer to any organic compound containing two carbonyl groups, it is used more specifically to describe molecules in which both carbonyls are in close enough proximity that their reactivity is changed, such as 1,2-, 1,3-, and 1,4-dicarbonyls. Their properties often differ from those of monocarbonyls, and so they are usually considered functional groups of their own. These compounds can have symmetrical or unsymmetrical substituents on each carbonyl, and may also be functionally symmetrical or unsymmetrical.

In chemical nomenclature, the IUPAC nomenclature of organic chemistry is a method of naming organic chemical compounds as recommended by the International Union of Pure and Applied Chemistry (IUPAC). It is published in the Nomenclature of Organic Chemistry. Ideally, every possible organic compound should have a name from which an unambiguous structural formula can be created. There is also an IUPAC nomenclature of inorganic chemistry.

In organic chemistry, an acyl chloride is an organic compound with the functional group −C(=O)Cl. Their formula is usually written R−COCl, where R is a side chain. They are reactive derivatives of carboxylic acids. A specific example of an acyl chloride is acetyl chloride, CH3COCl. Acyl chlorides are the most important subset of acyl halides.

<span class="mw-page-title-main">Acyl halide</span> Oxoacid compound with an –OH group replaced by a halogen

In organic chemistry, an acyl halide is a chemical compound derived from an oxoacid by replacing a hydroxyl group with a halide group.

<span class="mw-page-title-main">Imide</span> Class of chemical compounds

In organic chemistry, an imide is a functional group consisting of two acyl groups bound to nitrogen. The compounds are structurally related to acid anhydrides, although imides are more resistant to hydrolysis. In terms of commercial applications, imides are best known as components of high-strength polymers, called polyimides. Inorganic imides are also known as solid state or gaseous compounds, and the imido group (=NH) can also act as a ligand.

<span class="mw-page-title-main">Phosphorus pentoxide</span> Chemical compound

Phosphorus pentoxide is a chemical compound with molecular formula P4O10 (with its common name derived from its empirical formula, P2O5). This white crystalline solid is the anhydride of phosphoric acid. It is a powerful desiccant and dehydrating agent.

The Dakin–West reaction is a chemical reaction that transforms an amino-acid into a keto-amide using an acid anhydride and a base, typically pyridine. It is named for Henry Drysdale Dakin and Randolph West. In 2016 Schreiner and coworkers reported the first asymmetric variant of this reaction employing short oligopeptides as catalysts.

<span class="mw-page-title-main">Triflic acid</span> Chemical compound

Triflic acid, the short name for trifluoromethanesulfonic acid, TFMS, TFSA, HOTf or TfOH, is a sulfonic acid with the chemical formula CF3SO3H. It is one of the strongest known acids. Triflic acid is mainly used in research as a catalyst for esterification. It is a hygroscopic, colorless, slightly viscous liquid and is soluble in polar solvents.

Desymmetrization is a chemical reaction that converts prochiral substrates into chiral products. Desymmetrisations are so pervasive that they are rarely described as such except when they proceed enantioselectively. The enantioselective reactions require chiral catalysts or chiral reagents. According to IUPAC]], desymmetrization involves the "... the conversion of a prochiral molecular entity into a chiral one."

<span class="mw-page-title-main">Thioacetic acid</span> Organosulfur compound (CH3C(O)SH)

Thioacetic acid is an organosulfur compound with the molecular formula CH3C(O)SH. It is a thioic acid: the sulfur analogue of acetic acid, as implied by the thio- prefix. It is a yellow liquid with a strong thiol-like odor. It is used in organic synthesis for the introduction of thiol groups in molecules.

Acetyl iodide is an organoiodine compound with the formula CH3COI. It is a colourless liquid. It is formally derived from acetic acid. Although far rarer in the laboratory than the related acetyl bromide and acetyl chloride, acetyl iodide is produced, transiently at least, on a far larger scale than any other acid halide. Specifically, it is generated by the carbonylation of methyl iodide in the Cativa and Monsanto processes, which are the main industrial processes that generate acetic acid. It is also an intermediate in the production of acetic anhydride from methyl acetate.

In chemistry, carbonylation refers to reactions that introduce carbon monoxide (CO) into organic and inorganic substrates. Carbon monoxide is abundantly available and conveniently reactive, so it is widely used as a reactant in industrial chemistry. The term carbonylation also refers to oxidation of protein side chains.

α,β-Unsaturated carbonyl compound Functional group of organic compounds

α,β-Unsaturated carbonyl compounds are organic compounds with the general structure (O=CR)−Cα=Cβ-R. Such compounds include enones and enals, but also carboxylic acids and the corresponding esters and amides. In these compounds, the carbonyl group is conjugated with an alkene. Unlike the case for carbonyls without a flanking alkene group, α,β-unsaturated carbonyl compounds are susceptible to attack by nucleophiles at the β-carbon. This pattern of reactivity is called vinylogous. Examples of unsaturated carbonyls are acrolein (propenal), mesityl oxide, acrylic acid, and maleic acid. Unsaturated carbonyls can be prepared in the laboratory in an aldol reaction and in the Perkin reaction.

References

  1. ↑ IUPAC , Compendium of Chemical Terminology , 2nd ed. (the "Gold Book") (1997). Online corrected version: (2006–) " acid anhydrides ". doi : 10.1351/goldbook.A00072
  2. 1 2 3 Panico, R.; Powell, W. H.; Richer, J. C., eds. (1993). "Recommendation R-5.7.7". A Guide to IUPAC Nomenclature of Organic Compounds . IUPAC/Blackwell Science. pp. 123–25. ISBN   0-632-03488-2.
  3. ↑ "Nomenclature of Anhydrides". 8 November 2013.
  4. ↑ Nelson, D. L.; Cox, M. M. "Lehninger, Principles of Biochemistry" 3rd Ed. Worth Publishing: New York, 2000. ISBN   1-57259-153-6.
  5. ↑ "Nomenclature of Anhydrides". 8 November 2013.
  6. ↑ Zoeller, J. R.; Agreda, V. H.; Cook, S. L.; Lafferty, N. L.; Polichnowski, S. W.; Pond, D. M. "Eastman Chemical Company Acetic Anhydride Process" Catalysis Today (1992), volume 13, pp.73-91. doi : 10.1016/0920-5861(92)80188-S
  7. 1 2 Heimo Held, Alfred Rengstl, Dieter Mayer "Acetic Anhydride and Mixed Fatty Acid Anhydrides" Ullmann's Encyclopedia of Industrial Chemistry 2002, Wiley-VCH, Weinheim. doi : 10.1002/14356007.a01_065
  8. ↑ Lewis I. Krimen (1970). "Acetic Formic Anhydride". Organic Syntheses . 50: 1. doi:10.15227/orgsyn.050.0001 .
  9. ↑ Spanedda, Maria Vittoria; Bourel-Bonnet, Line (2021). "Cyclic Anhydrides as Powerful Tools for Bioconjugation and Smart Delivery" (PDF). Bioconjugate Chemistry. 32 (3): 482–496. doi:10.1021/acs.bioconjchem.1c00023. PMID   33662203.
  10. ↑ Chen, Yonggang; McDaid, Paul; Deng, Li (2003). "Asymmetric Alcoholysis of Cyclic Anhydrides". Chemical Reviews. 103 (8): 2965–2984. doi:10.1021/cr020037x. PMID   12914488.
  11. ↑ González-López, Marcos; Shaw, Jared T. (2009). "Cyclic Anhydrides in Formal Cycloadditions and Multicomponent Reactions". Chemical Reviews. 109 (1): 164–189. doi:10.1021/cr8002714. PMID   19140773.
  12. ↑ Kürti, László; Barbara Czakó (2005). Strategic Applications of Named Reactions in Organic Synthesis. London: Elsevier Academic Press. p. 398. ISBN   0124297854.
  13. ↑ Carsten Bolm, Iuliana Atodiresei, and Ingo Schiffers (2005). "Asymmetric Alcoholysis of Meso-Anhydrides Mediated by Alkaloids". Organic Syntheses. 82: 120. doi:10.15227/orgsyn.082.0120.{{cite journal}}: CS1 maint: multiple names: authors list (link)
  14. ↑ Chiang, Wen-Yen; Chiang, Wen-Chang (1988-05-05). "Condensation polymerization of multifunctional monomers and properties of related polyester resins. II. Thermal properties of polyester—imide varnishes". Journal of Applied Polymer Science. 35 (6): 1433–1439. doi:10.1002/app.1988.070350603.
  15. ↑ Faghihi, Khalil; Ashouri, Mostafa; Hajibeygi, Mohsen (2013-10-25). "High Temperature and Organosoluble Poly(amide-imide)s Based on 1,4-Bis[4-aminophenoxy]butane and Aromatic Diacids by Direct Polycondensation: Synthesis and Properties". High Temperature Materials and Processes. 32 (5): 451–458. doi: 10.1515/htmp-2012-0164 . ISSN   2191-0324.
  16. ↑ Saleem, Muhammad; Hussain, Hidayat; Ahmed, Ishtiaq; Draeger, Siegfried; Schulz, Barbara; Meier, Kathrin; Steinert, Michael; Pescitelli, Gennaro; Kurtán, Tibor; Flörke, Ulrich; Krohn, Karsten (February 2011). "Viburspiran, an Antifungal Member of the Octadride Class of Maleic Anhydride Natural Products". European Journal of Organic Chemistry. 2011 (4): 808–812. doi:10.1002/ejoc.201001324.
  17. ↑ Han, Chunguang; Furukawa, Hiroyuki; Tomura, Tomohiko; Fudou, Ryosuke; Kaida, Kenichi; Choi, Bong-Keun; Imokawa, Genji; Ojika, Makoto (24 April 2015). "Bioactive Maleic Anhydrides and Related Diacids from the Aquatic Hyphomycete Tricladium castaneicola". Journal of Natural Products. 78 (4): 639–644. doi:10.1021/np500773s. PMID   25875311.
  18. ↑ Heard, David M.; Tayler, Emyr R.; Cox, Russell J.; Simpson, Thomas J.; Willis, Christine L. (3 January 2020). "Structural and synthetic studies on maleic anhydride and related diacid natural products" (PDF). Tetrahedron. 76 (1): 130717. doi:10.1016/j.tet.2019.130717. hdl:1983/53998d06-9017-4cfb-822b-c6453348000a. S2CID   209714625.
  19. ↑ Chen, Xiaolong; Zheng, Yuguo; Shen, Yinchu (May 2007). "Natural Products with Maleic Anhydride Structure: Nonadrides, Tautomycin, Chaetomellic Anhydride, and Other Compounds". Chemical Reviews. 107 (5): 1777–1830. doi:10.1021/cr050029r. PMID   17439289.
  20. ↑ Kuban, Vojtech (2020). "Structural Basis of Ca 2+-Dependent Self-Processing Activity of Repeat-in-Toxin Proteins". mBio. 11 (2): e00226-20. doi:10.1128/mBio.00226-20. PMC   7078468 . PMID   32184239.
  21. ↑ Bell, Christian (2013). "Structure of the repulsive guidance molecule (RGM)-neogenin signaling hub". Science. 341 (6141): 77–80. Bibcode:2013Sci...341...77B. doi:10.1126/science.1232322. PMC   4730555 . PMID   23744777.
  22. ↑ Scheu, Arne (2021). "NeissLock provides an inducible protein anhydride for covalent targeting of endogenous proteins". Nature Communications. 12 (1): 717. Bibcode:2021NatCo..12..717S. doi:10.1038/s41467-021-20963-5. PMC   7846742 . PMID   33514717.
This page is based on this Wikipedia article
Text is available under the CC BY-SA 4.0 license; additional terms may apply.
Images, videos and audio are available under their respective licenses.