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Mechanistic Investigations into the photochemistry of 4-allyl-tetrazolones in solution: a new approach to the synthesis of 3,4-dihydro-pyrimidinones

2006Journal article Restricted access
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dc.contributor.authorFrija, L.
dc.contributor.authorKhmelinskii, Igor
dc.contributor.authorCristiano, Maria Lurdes Santos
dc.date.accessioned2014-06-09T12:36:45Z
dc.date.available2014-06-09T12:36:45Z
dc.date.issued2006
dc.date.updated2014-06-05T10:15:07Z
dc.description.abstractPhotolysis (ì ) 254 nm) of 4-allyl-tetrazolones 2a-c was carried out in methanol, 1-propanol, 1-hexanol, acetonitrile, and cyclohexane. The sole primary photochemical process identified was molecular nitrogen elimination, with formation of pyrimidinones 6a-c. Following the primary photocleavage, secondary reactions were observed in acetonitrile and cyclohexane, leading to phenyl-isocyanate (7), aniline (9), and 1-phenylprop-1-enyl-isocyanate (10a). In alcoholic solutions, the primary products, 6a-c, remained photostable even under extended irradiation, making possible the isolation of 3,4-dihydro-pyrimidinones as stable compounds in very high yields. The observed photostability of pyrimidinones 6a-c in alcohols is ascribed to the excited state quenching via reversible proton transfer, facilitated by the solvent cage stabilization due to formation of hydrogen bonds. The viscosity of alcohols is directly related to the cage effects observed. The photocleavage of 4-allyl-tetrazolones leads probably to a caged triplet radical pair. This hypothesis is confirmed by the solvent viscosity effect on the photolysis quantum yields. Additionally, dissolved molecular oxygen sensitizes the formation of pyrimidinones, as should be expected for a triplet intermediate that can only form the product molecule after T-S conversion, which is accelerated by oxygen.por
dc.identifier.citationFrija, Luís M. T.; Khmelinskii, Igor V.; Cristiano, M. Lurdes S. Mechanistic Investigations into the Photochemistry of 4-Allyl-tetrazolones in Solution:  A New Approach to the Synthesis of 3,4-Dihydro-pyrimidinones, The Journal of Organic Chemistry, 71, 9, 3583-3591, 2006.por
dc.identifier.doihttp://dx.doi.org/10.1021/jo060164j
dc.identifier.issn0022-3263
dc.identifier.otherAUT: IKH00165; MCR00716;
dc.identifier.urihttp://hdl.handle.net/10400.1/4252
dc.language.isoengpor
dc.peerreviewedyespor
dc.publisherAmerican Chemical Societypor
dc.titleMechanistic Investigations into the photochemistry of 4-allyl-tetrazolones in solution: a new approach to the synthesis of 3,4-dihydro-pyrimidinonespor
dc.typejournal article
dspace.entity.typePublication
oaire.citation.endPage3591por
oaire.citation.issue9por
oaire.citation.startPage3583por
oaire.citation.titleJournal of Organic Chemistrypor
oaire.citation.volume71por
person.familyNameKhmelinskii
person.familyNameCristiano
person.givenNameIgor
person.givenNameMaria de Lurdes
person.identifier0000000420541031
person.identifier.ciencia-id0D1A-CB6C-6316
person.identifier.ciencia-idE411-6006-5A01
person.identifier.orcid0000-0002-6116-184X
person.identifier.orcid0000-0002-9447-2855
person.identifier.ridC-9587-2011
person.identifier.ridG-2345-2012
person.identifier.scopus-author-id6701444934
person.identifier.scopus-author-id9238724800
rcaap.rightsrestrictedAccesspor
rcaap.typearticlepor
relation.isAuthorOfPublicationfcb9f09f-2e99-41fb-8c08-7e1acbc65076
relation.isAuthorOfPublicationb16751a6-748e-44b0-9c59-058cbd5b2cc3
relation.isAuthorOfPublication.latestForDiscoveryfcb9f09f-2e99-41fb-8c08-7e1acbc65076

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