2-Coumaranone

2-Cumaranon Struktur.svg 150px 1-Benzofuran-2(3H)-one 553-86-6 correct CAS 284584 61668 209-052-0 68382 4K47Z4Q1E7 1S/C8H6O2/c9-8-5-6-3-1-2-4-7(6)10-8/h1-4H,5H2 ACZGCWSMSTYWDQ-UHFFFAOYSA-N C1C2=CC=CC=C2OC1=O C8H6O2 49–51 °CAldrich 124591 2-Coumaranone 2022-06-10 2-Coumaranone https://pubchem.ncbi.nlm.nih.gov/compound/68382#section=Safety-and-Hazards pubchem.ncbi.nlm.nih.gov en 07 Warning 315 317 319 261 264 264+265 272 280 302+352 305+351+338 321 332+317 333+317 337+317 362+364 501 2-Coumaranone (sometimes also called 2-CumaranonePubChem 2-Coumaranone https://pubchem.ncbi.nlm.nih.gov/compound/2-Coumaranone 2025-01-16 pubchem.ncbi.nlm.nih.gov en) is a bicyclic heteroaromatic compound in which a six-membered benzene ring is annulated with a five-membered γ-butyrolactone ring. The 2(3H)-benzofuranone can also be considered as a lactone of (2-hydroxyphenyl)acetic acid. The benzofuranone basic structure is the basis of some natural products – such as rosmadial,N. Nakatani R. Inatani 1983 10.1080/00021369.1983.10865620 2 353–358 Biosci. Biotechnol. Biochem. A New Diterpene Lactone, Rosmadial, from Rosemary (Rosmarinus officinalis L.) 47 free which is isolatable from rosemary oil, and some substances with high pharmacological activity, such as griseofulvin and rifampicin. Furthermore, 2-cumaranone is utilized as a starting material for the preparation of chemiluminescent and fluorescent dyes, for synthetic pharmaceutical agents, like the antiarrhythmic drug dronedarone, and especially for the fungicide azoxystrobin. 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.A. Baeyer P. Fritsch 1884 10.1002/cber.188401701258 1 973–975 Chem. Ber. Ueber die o-Oxyphenylessigsäure und ihre Derivate 17 300px|center|Synthesis of 2-coumaranone from 2-hydroxyphenylacetic acid 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.T. Fukagawa Y. Fujiwara H. Taniguchi 1982 10.1021/jo00133a055 12 2491–2493 J. Org. Chem. Palladium-catalyzed intramolecular aromatic nuclear acyloxylation: preparation of 2-coumaranone 47 350px|center|synthesis of 2-coumaranone from phenylacetic acid The Ozonolysis of 2-allylphenol obtained by the alkylation of phenol with 3-bromopropene to produce phenylallyl ether and subsequently its Claisen rearrangement, gives rise to 2-hydroxyphenylacetic acid, which, through water splitting, yields 2-coumaranone. Despite this method having good yields, its economic and safety considerations make it unsuitable for an industrial process.EP 1481959 Verfahren zur Herstellung von Lactonen und von aromatischen Hydroxycarbonsäuren 2004-12-01 2004-04-28 W. Jary DSM Fine Chemicals Austria Nfg GmbH & CO., KG 350px|center|2-Coumaranone from 2-allylphenol via ozonolysis On an industrial scale, the well-filtered starting materials cyclohexanone and glyoxylic acid are first transformed in an acid-catalyzed aldol condensation to form the (predominantly) cis-2-oxocyclohexylidene acetic acid (A). This then, in a second step, is transformed into the so-called enollactone (B) through water elimination (90% yield). The enollactone is continuously dehydrogenated at 250 °C in the vapor phase on a palladium catalyst to form 2-coumaranone (C) dehydrogenation (yield approximately 67%).N. Carmona P. Gallezot A. Perrard L. Carmona G. Mattioda J.-C. Vallejos 1998 0-8247-1929-8 New York, NY, U.S.A. 381–390 Marcel Dekker, Inc. Synthesis of 2-Coumaranone by Catalytic Dehydrogenation of α-Carboxymethylidene Cyclohexanone, in Catalysis of Organic Reactions, Frank E. Herkes, editorUS 5616733 Preparation method for 2-coumaranone 1997-4-1 1995-6-7 J.-C. Vallejos A. Perrard Y. Christidis P. Gallezot Société Française Hoechst EP 0818451 Procédé de préparation de l'énollactone de l'acide 2-oxocyclohexylidène acétique et application à la préparation de la 2-coumaranone 1998-01-14 1997-07-02 N. Carmona L. Carmona A. Perrard J.-C. Vallejos Clariant Chimie S.A. 300px|center|Industrial synthesis of 2-coumaranone from cyclohexanone and glyoxylic acid An alternative process that uses glyoxylic acid methyl ester methylhemiacetals rather than glyoxylic acid as a starting material has not gained widespread acceptance.EP 149838 Verfahren zur Herstellung von 2-Coumaron und substituierten 2-Coumaronen 2004-08-25 2001-05-09 M. Stanek P. Hildebrand C. Zimmermann M. Castelijns DSM Fine Chemicals Austria Nfg GmbH & CO., KG Properties Pure 2-coumaranone manifests as an off-white to pale yellow solid with an aromatic odor. On purification by distillation, "a colorless oil passes which solidifies in the receiver into splendid, transparent, well-formed crystals".S. Czaplicki Stanislaus von Kostanecki V. Lampe 1909 10.1002/cber.190904201133 1 827–838 Chem. Ber. Versuche zur Synthese des Chromenols und seiner Derivate 42 https://zenodo.org/record/2308760 3H-benzofuran-2-one is soluble in hot water, diethyl ether and acetonitrile. The lactone hydrolyzes slowly in hot water and rapidly in aqueous alkalis to form 2-hydroxyphenylacetic acid or its alkali salt. Applications 5-Nitro-3H-benzofuran-2-one is formed during the nitration of 2-coumaranone with nitrating acid.2022-06-20 Christopher E. Malmberg 2015 14 Central Washington University Central Washington University Total Synthesis of Clavatadine A Analogs to Produce a Viable Reversible Inhibitor for Factor XIa https://core.ac.uk/download/pdf/51140415.pdf MS ThesisUS 7070630 Primary intermediates für oxidative coloration of hair 2006-4-7 2004-5-3 M.-I. Lim, Y.-G. Pan The Procter & Gamble Co. 500px|center|5-Nitro- and 5-amino-2-coumaranone The 5-amino-3H-benzofuran-2-one can be obtained from the nitro compound using catalytic hydrogenation at a palladium catalyst. Lactones such as 2-coumaranone (I) are readily cleaved by nucleophiles, leading to ring opening. Thus, 5-nitro-3H-benzofuran-2-one reacts with secondary amines to form 2-hydroxyphenylacetic acid amides. Through hydrogenation, these transform into corresponding 3-amino-6-hydroxyphenylethylamines, which are useful precursors for hair dyeing. 350px|center|Hair dye precursors starting from 2-coumaranone 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 antiarrhythmic drug Dronedarone.EP 2508517 Process for the preparation of N-alkyl-2(hydroxy-4-benzoyl)-3-benzofurans and its intermediates thereof 2012-10-10 2004-12-15 A. Shoutteeten, F. Bleger, F. Mordacq, J. Piron Clariant Specialty Fine Chemicals (France) 550px|center|Dronedarone precursor starting from 2-coumaranone The basic structure of 2-coumaranone also underlies a class of antioxidants and radical scavengers, especially for stabilizing polypropylenes. In the synthesis of a model compound, glyoxylic acid reacts with 2 moles of 4-tert-butylphenol in the presence of methanesulfonic acid CH3SO3H to form a phenolic intermediate and is then esterified with benzoic acid.EP 2500341 Benzofuranone derivatives and application of the same 2013-06-26 2011-09-06 C.-F. Chiu, C.-Y. Su, S. Lee Chitec Technology Co., Ltd., Double Bond Chemical Ind., Co., Ltd., FDC, Lees Chemical Industry Co. Ltd. 400px|center|Antioxidants with 2-coumaranone structure A one-pot reaction, carried out as a Tscherniak-Einhorn reaction of fluorophenols (X), glyoxylic acid (Y), and carbamates, such as carbamic acid methyl esterR. Krieg B. Hoffmann D. Weiß C. Biskup 2019 10.1002/hlca.201800243 6 e1800243 Helv. Chim. Acta First synthesis of highly chemiluminescent benzo[b]furan-2(3H)-ones bearing a urea substructure 102 107893512 or carbamic acid mesityl ester (Z'''), yields 2-coumaranones with carbamide side chains. These compounds react with strong bases such as diazabicycloundecene or potassium tert-butanolate, and show pronounced chemiluminescence in the presence of oxygen.S. Schramm etal 2013 174–188 Arkivoc Investigations on the synthesis and chemiluminescence of novel 2-coumaranones http://www.arkat-usa.org/get-file/47206/ 3S. Schramm etal 2015 44–59 Arkivoc Investigations on the synthesis and chemiluminescence of novel 2-coumaranones – II https://www.arkat-usa.org/get-file/52793/ 52022-06-20 PDF; 170 kB en Cayman Chemical Co. 2-Coumaranone-1-L https://cdn.caymanchem.com/cdn/insert/27389.pdf caymanchem.com 300px|center|chemiluminescence molecules with 2-coumaranone structure The most notable application of 2-coumaranone by volume is as a starting material for the synthesis of the fungicide azoxystrobinWO 199208703 Process for the preparation of pyrimidine compounds 1992-5-29 1991-11-12 J.D. Jones, G.A. DeBoos, P. Wilkinson, B.G. Cox, J.M. Fielden Imperial Chemical Industries PLC (known as Amistar from Syngenta) in the class of strobilurins. References Category:Lactones Category:Heterocyclic compounds with 2 rings Category:Benzofurans