2-Cumaranone
Names | |
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IUPAC name
3H-1-benzofuran-2-one
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Identifiers | |
3D model (
JSmol ) |
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ChEMBL | |
ChemSpider | |
ECHA InfoCard
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100.008.230 |
EC Number |
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PubChem CID
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UNII | |
CompTox Dashboard (EPA)
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Properties | |
C8H6O2 | |
Melting point | 49–51 °C[1] |
Hazards | |
GHS labelling:[2] | |
Warning | |
H315, H317, H319 | |
P261, P264, P264+P265, P272, P280, P302+P352, P305+P351+P338, P321, P332+P317, P333+P317, P337+P317, P362+P364, P501 | |
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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2-Cumaranone is a
.Occurrence and synthesis
In 1884, Adolf von Baeyer and Paul Fritsch disclosed the synthesis of 2-coumaranone, which they described as the lactone of o-oxyphenylacetic acid, through the distillation "over free fire" of (2-hydroxyphenyl)acetic acid.[4]
The lactone 3H-benzofuran-2-one forms in this process under intramolecular water splitting at high temperature and in an impure state.
A similar fragmentation by oxidative intramolecular ring closure from phenylacetic acid also yields only modest returns (< 20%) due to the oxidation sensitivity of the methylene group and the formation of several by-products 2-coumaranone.[5]
The
On an industrial scale, the well-filtered starting materials
An alternative process that uses glyoxylic acid methyl ester methylhemiacetals rather than glyoxylic acid as a starting material has not gained widespread acceptance.[10]
Properties
Pure 2-coumaranone manifests as an off-white to pale yellow solid with an aromatic odor.[1] On purification by distillation, "a colorless oil passes which solidifies in the receiver into splendid, transparent, well-formed crystals".[11] 3H-benzofuran-2-one is soluble in hot water, diethyl ether[4] and acetonitrile.[10] The lactone hydrolyzes slowly in hot water and rapidly in aqueous alkalis to form 2-hydroxyphenylacetic acid or its alkali salt.[4]
Applications
5-Nitro-3H-benzofuran-2-one is formed during the nitration of 2-coumaranone with nitrating acid.[12][13]
The 5-amino-3H-benzofuran-2-one can be obtained from the nitro compound using
Lactones such as 2-coumaranone ('I) are readily cleaved by
Condensation of 5-nitro-3H-benzofuran-2-one (II) with a mixture of valeric acid (III) and valeric anhydride (IV) results in the enollactone (V), which upon heating rearranges to the substituted benzofurancarboxylic acid (VI), a key precursor for the
The basic structure of 2-coumaranone also underlies a class of
A
The most notable application of 2-coumaranone by volume is as a starting material for the synthesis of the
References
- ^ a b Sigma-Aldrich Co., product no. {{{id}}}.
- ^ "2-Coumaranone". pubchem.ncbi.nlm.nih.gov.
- ^
- ^ EP 1481959, W. Jary, "Verfahren zur Herstellung von Lactonen und von aromatischen Hydroxycarbonsäuren", published 2004-12-01, assigned to DSM Fine Chemicals Austria Nfg GmbH & CO., KG
- ISBN 0-8247-1929-8
- ^ US 5616733, J.-C. Vallejos; A. Perrard & Y. Christidis et al., "Preparation method for 2-coumaranone", published 1997-4-1, assigned to Société Française Hoechst
- ^ EP 0818451, N. Carmona; L. Carmona & A. Perrard et al., "Procédé de préparation de l'énollactone de l'acide 2-oxocyclohexylidène acétique et application à la préparation de la 2-coumaranone", published 1998-01-14, assigned to Clariant Chimie S.A.
- ^ a b EP 149838, M. Stanek; P. Hildebrand & C. Zimmermann et al., "Verfahren zur Herstellung von 2-Coumaron und substituierten 2-Coumaronen", published 2004-08-25, assigned to DSM Fine Chemicals Austria Nfg GmbH & CO., KG
- ^ a b Christopher E. Malmberg (2015). "Total Synthesis of Clavatadine A Analogs to Produce a Viable Reversible Inhibitor for Factor XIa" (PDF). MS Thesis. Central Washington University Central Washington University. p. 14. Retrieved 2022-06-20.
- ^ a b US 7070630, M.-I. Lim, Y.-G. Pan, "Primary intermediates für oxidative coloration of hair", published 2006-4-7, assigned to The Procter & Gamble Co.
- ^ EP 2508517, A. Shoutteeten, F. Bleger, F. Mordacq, J. Piron, "Process for the preparation of N-alkyl-2(hydroxy-4-benzoyl)-3-benzofurans and its intermediates thereof", published 2012-10-10, assigned to Clariant Specialty Fine Chemicals (France)
- ^ EP 2500341, C.-F. Chiu, C.-Y. Su, S. Lee, "Benzofuranone derivatives and application of the same", published 2013-06-26, assigned to Chitec Technology Co., Ltd., Double Bond Chemical Ind., Co., Ltd., FDC, Lees Chemical Industry Co. Ltd.
- S2CID 107893512
- ^ S. Schramm; et al. (2013), "Investigations on the synthesis and chemiluminescence of novel 2-coumaranones", Arkivoc, vol. 3, pp. 174–188
- ^ S. Schramm; et al. (2015), "Investigations on the synthesis and chemiluminescence of novel 2-coumaranones – II", Arkivoc, vol. 5, pp. 44–59
- ^ "2-Coumaranone-1-L" (PDF; 170 kB). caymanchem.com. Cayman Chemical Co. Retrieved 2022-06-20.
- ^ WO 199208703, J.D. Jones, G.A. DeBoos, P. Wilkinson, B.G. Cox, J.M. Fielden, "Process for the preparation of pyrimidine compounds", published 1992-5-29, assigned to Imperial Chemical Industries PLC