Pyrylium

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Pyrylium
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Names
Preferred IUPAC name
Pyrylium[1]
Other names
Pyranium
Identifiers
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3D model (JSmol)
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1421881
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EC Number Page Template:Plainlist/styles.css has no content.
558560
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  • InChI=1S/C5H5O/c1-2-4-6-5-3-1/h1-5H/q+1 ☒N
    Key: WVIICGIFSIBFOG-UHFFFAOYSA-N ☒N
  • InChI=1/C5H5O/c1-2-4-6-5-3-1/h1-5H/q+1
    Key: WVIICGIFSIBFOG-UHFFFAOYAF
  • [o+]1ccccc1
Properties
C5H5O+
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Related compounds
Related compounds
 thiopyrylium, selenopyrylium, telluropyrylium
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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Template:Chembox Footer/trackingTemplate:Short description

Pyrylium is a cation (positive ion) with formula Page Module:Chem2/styles.css has no content.C5H5O+, consisting of a six-membered ring of five carbon atoms, each with one hydrogen atom, and one positively charged oxygen atom. The bonds in the ring are conjugated as in benzene, giving it an aromatic character. In particular, because of the positive charge, the oxygen atom is trivalent. Pyrilium is a mono-cyclic and heterocyclic compound, one of the oxonium ions.

Synthesis

Pyrylium salts are easily produced from simple starting materials through a condensation reaction.[2]

Pyrylium salts with aromatic substituents, such 2,4,6-triphenylpyrylium tetrafluoroborate, can be obtained from two moles of acetophenone, one mole of benzaldehyde, and excess tetrafluoroboric acid.[3] For pyrylium salts with alkyl substituents, such as 2,4,6-trimethylpyrylium salts, the best method uses the Balaban-Nenitzescu-Praill synthesis from tertiary butanol and acetic anhydride in the presence of tetrafluoroboric,[4] perchloric,[5] or trifluoromethanesulfonic acids.[6]

Hydroxide bases open and hydrolyze pyridine to an enedione base that cyclizes in very strong acids to a pyrylium cation.[7]

Enolizing conditions (strong acid) force pyrones to their pyrylium tautomer.[8]

Chemical properties

Pyrylium and its derivatives form stable salts with a variety of anions.[9][10][11][12][13][14]

Like other oxonium ions, pyrylium is unstable in neutral water. However, pyrylium is much less reactive than ordinary oxonium ions because of aromatic stabilization. The highly electronegative oxygen strongly perturbs the orbitals in the aromatic ring, and pyrylium derivatives are extremely resistant to electrophilic aromatic substitution. Pyrylium cations react with nucleophiles at the ortho and para positions, typically through ANRORC.[15]

2,4,6-Triphenylpyrylium salts are converted by hydroxide bases into a stable 1,5-enedione (pseudobase), but 2,4,6-trimethylpyrylium salts on treatment with hot alkali hydroxides afford an unstable pseudobase that undergoes an intramolecular condensation yielding 3,5-dimethylphenol. In warm deuterium oxide, 2,4,6-trimethylpyrylium salts undergo isotopic exchange of 4-methyl hydrogens faster than for the 2- and 6-methyl groups, allowing the synthesis of regioselectively deuterated compounds.[citation needed]

Derivatives

Pyrylium's electrophilicity makes them useful materials for producing other compounds with stronger aromatic character. Pyrylium salts afford pyridines with ammonia,[16] pyridinium salts with primary amines, pyridine-N-oxides with hydroxylamine, phosphabenzenes with phosphine derivatives, thiopyrylium salts with hydrogen sulfide, and benzene derivatives with acetonitrile or nitromethane.

Many important cations are formally derived from pyrylium by substitution of various functional groups for some or all the hydrogens in the ring. 2,4,6-Triphenylpyrylium reacts with primary amines to give pyridinium derivatives called "Katritzky salts"; they are commonly used in metal-catalyzed nucleophilic displacement of the amine.[15]

Pyrones

Script error: No such module "Labelled list hatnote". A pyrylium cation with a hydroxyl anion substituent in the 2-position is not the zwitterionic aromatic compound (1), but the neutral unsaturated lactone 2-pyrone or pyran-2-one (2). Important representatives of this class are the coumarins. Likewise a 4-hydroxyl pyrylium compound is a γ-pyrone or pyran-4-one (4), to which group belong compounds such as maltol.

pyrones
pyrones

2-Pyrones are known to react with alkynes in a Diels–Alder reaction to form arene compounds with expulsion of carbon dioxide. For example:[17]

Pyrone cycloaddition
Pyrone cycloaddition

3-pyrones are too unstable for isolation, but appear as reaction intermediates.

Polycyclic oxonium arenes

Chromenylium ion

One bicyclic pyrylium ion is called benzopyrylium ion (IUPAC: chromenylium ion) (formula: Page Module:Chem2/styles.css has no content.C9H7O+, molar mass: 131.15 g/mol, exact mass: 131.04968983). It can be seen as a charged derivative of 2H-1-benzopyran (IUPAC: 2H-chromene, Page Module:Chem2/styles.css has no content.C9H8O), or a (charged) substituted heterocyclic derivative of naphthalene (Page Module:Chem2/styles.css has no content.C10H8).

Flavylium ion

In biology, the 2-phenylbenzopyrylium (2-phenylchromenylium) ion is referred to as flavylium. A class of flavylium-derived compounds are anthocyanidins and anthocyanins, pigments that are responsible for the colors of many flowers.[citation needed]

Naphthoxanthenium cation

Higher polycyclic derivatives of pyrylium also exist. One good example is naphthoxanthenium. This dye is highly stable, aromatic, and planar. It absorbs in the UV and blue region and presents exceptional photophysical properties. It can be synthesized by chemical or photochemical reactions.[18]

  • Benzopyrylium chloride (chromenylium chloride), a salt with chloride as the counterion
    Benzopyrylium chloride (chromenylium chloride), a salt with chloride as the counterion
  • Flavylium cation
    Flavylium cation
  • Naphthoxanthenium cation
    Naphthoxanthenium cation

See also

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Look up pyrylium in Wiktionary, the free dictionary.

References

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  1. ^ Page Module:Citation/CS1/styles.css has no content.International Union of Pure and Applied Chemistry (2014). Nomenclature of Organic Chemistry: IUPAC Recommendations and Preferred Names 2013. The Royal Society of Chemistry. p. 1097. doi:10.1039/9781849733069. ISBN 978-0-85404-182-4.
  2. ^ Page Module:Citation/CS1/styles.css has no content.Balaban, A. T.; Wray, V. (1977). "13C n.m.r. spectra of some pyrylium salts and related compounds". Organic Magnetic Resonance. 9 (1): 16–22. doi:10.1002/mrc.1270090105.
  3. ^ Page Module:Citation/CS1/styles.css has no content.Dimroth, Karl; Reichardt, C.; Vogel, K. (1969). "2,4,6-Triphenylpyrylium tetrafluoroborate". Organic Syntheses. 49; Page Module:Citation/CS1/styles.css has no content.Collected Volumes, vol. 5.
  4. ^ Page Module:Citation/CS1/styles.css has no content.Balatan, A. T.; Boulton, A. J. (1969). "2,4,6-Trimethylpyrylium tetrafluoroborate". Organic Syntheses. 49; Page Module:Citation/CS1/styles.css has no content.Collected Volumes, vol. 5, pp. 1112–1113.
  5. ^ Page Module:Citation/CS1/styles.css has no content.Balaban, Alexandru T.; Nenitzescu, Costin D. (1968). "2,4,6-Trimethylpyrylium perchlorate". Organic Syntheses. 44; Page Module:Citation/CS1/styles.css has no content.Collected Volumes, vol. 5, pp. 1088, 1106, 1114, 1135.
  6. ^ Page Module:Citation/CS1/styles.css has no content.Balaban, Alexandru T.; Boulton, A. J. (1973). "2,4,6-Trimethylpyrylium trifluoromethanesulfonate". Organic Syntheses; Page Module:Citation/CS1/styles.css has no content.Collected Volumes, vol. 5, pp. 1112, 1114–1116.
  7. ^ Page Module:Citation/CS1/styles.css has no content.Gómez-Palomino, Alejandro; Ghiazza, Clément; Busch, Julia; Wagner, Lucas; Cornella, Josep (2023). "Preparation of Pyrylium tetrafluoroborate (Pyry-BF4)". Organic Syntheses. 100: 361–381.
  8. ^ Page Module:Citation/CS1/styles.css has no content.Agyemang, Nana B.; Murelli, Ryan P. (2019). "Synthesis of 5-hydroxy-4-methoxy-2-methylpyrylium trifluoromethanesulfonate from Kojic acid". Organic Syntheses. 96: 494–510.
  9. ^ Page Module:Citation/CS1/styles.css has no content.Gilchrist, T. L. (1997). Heterocyclic Chemistry. Longman. ISBN 0-582-27843-0.
  10. ^ Page Module:Citation/CS1/styles.css has no content.Balaban, A. T.; Schroth, W.; Fischer, G. (1969). "Pyrylium Salts Part I. Syntheses". In Katritzky, A. R.; Boulton, A. J. (eds.). Advances in Heterocyclic Chemistry Volume 10. Vol. 10. New York: Academic Press. pp. 241–326. doi:10.1016/S0065-2725(08)60499-7. ISBN 978-0-12-020610-0.
  11. ^ Page Module:Citation/CS1/styles.css has no content.Balaban, A. T.; Dinculescu, A.; Dorofeenko, G. N.; Fischer, G. W.; Koblik, A. V.; Mezheritskii, V. V.; Schroth, W. (1982). Katritzky, A. R. (ed.). Pyrylium Salts. Syntheses, Reactions and Physical Properties. Advances in Heterocyclic Chemistry: Supplement. Vol. 2. New York: Academic Press. ISBN 978-0-12-020652-0.
  12. ^ Page Module:Citation/CS1/styles.css has no content.Balaban, A. T. (1979). "The Pyrylium Cation as a Synthon in Organic Chemistry". In Mitra, R. B.; Ayyangar, N. R.; Gogte, V. N.; Acheson, R. M.; Cromwell, N. (eds.). New Trends in Heterocyclic Chemistry. Studies in Organic Chemistry. Vol. 3. Amsterdam: Elsevier. pp. 79–111. ISBN 978-0-444-41737-4.
  13. ^ Page Module:Citation/CS1/styles.css has no content.Balaban, A. T. (1987). "Pyrylium Salts as Useful Synthons". In Chizov, O. (ed.). Organic Synthesis: Modern Trends. Oxford: Blackwell. pp. 263–274. ISBN 0-632-02014-8.
  14. ^ Page Module:Citation/CS1/styles.css has no content.Balaban, T. S.; Balaban, A. T. (2003). "Pyrylium Salts". Hetarenes and Related Ring Systems, Six-membered Hetarenes with one Chalcogen. Science of Synthesis; Houben-Weyl Methods of Molecular Transformations. Vol. 14. Stuttgart: Georg Thieme Verlag. pp. 11–200. ISBN 978-3-13-118641-6.
  15. ^ a b Page Module:Citation/CS1/styles.css has no content.Pang, Yue; Moser, Daniel; Cornella, Josep (2020). "Pyrylium Salts: Selective Reagents for the Activation of Primary Amino Groups in Organic Synthesis". Synthesis. 52 (4): 489–503. doi:10.1055/s-0039-1690703. S2CID 208705148.
  16. ^ Page Module:Citation/CS1/styles.css has no content.Anderson, A. G.; Stang, P. J. (1981). "2,6-Di-tert-Butyl-4-Methylpyridine". Organic Syntheses. 60: 34; Page Module:Citation/CS1/styles.css has no content.Collected Volumes, vol. 7, p. 144.
  17. ^ Page Module:Citation/CS1/styles.css has no content.Delaney, P. M.; Moore, J. E.; Harrity, J. P. A. (2006). "An Alkynylboronic Ester Cycloaddition Route to Functionalised Aromatic Boronic Esters". Chemical Communications. 2006 (31): 3323–3325. doi:10.1039/b607322k. PMID 16883424.
  18. ^ Page Module:Citation/CS1/styles.css has no content.Bucher, G.; Bresolí-Obach, R.; Brosa, C.; Flors, C.; Luis, J. L.; Grillo, T. A.; Nonell, S. (2014). "β-Phenyl quenching of 9-phenylphenalenones: a novel photocyclisation reaction with biological implications". Physical Chemistry Chemical Physics. 16 (35): 18813–18820. Bibcode:2014PCCP...1618813B. doi:10.1039/C4CP02783C. PMID 25079707.
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