Please use this identifier to cite or link to this item: https://hdl.handle.net/1959.11/1615
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dc.contributor.authorNovak, Michaelen
dc.contributor.authorBrinster, Aaron Men
dc.contributor.authorDickhoff, Jill Nen
dc.contributor.authorErb, Jeremy Men
dc.contributor.authorJones, Matthew Pen
dc.contributor.authorLeopold, Samuel Hen
dc.contributor.authorVollman, Andrew Ten
dc.contributor.authorWang, Yue-Tingen
dc.contributor.authorGlover, Stephenen
dc.date.accessioned2009-05-20T11:43:00Z-
dc.date.issued2007-
dc.identifier.citationThe Journal of Organic Chemistry, 72(26), p. 9954-9962en
dc.identifier.issn1520-6904en
dc.identifier.issn0022-3263en
dc.identifier.urihttps://hdl.handle.net/1959.11/1615-
dc.description.abstractQuinol esters '2b', '2c', and '3b' and sulfonamide '4c' were investigated as possible precursors to 4-alkylaryloxenium ions, reactive intermediates that have not been previously detected. These compounds exhibit a variety of interesting reactions, but with one possible exception, they do not generate oxenium ions. The 4-isopropyl ester '2b' predominantly undergoes ordinary acid- and base-catalyzed ester hydrolysis. The 4-tert-butyl ester '2c' decomposes under both acidic and neutral conditions to generate tert-butanol and 1-acetyl-1,4-hydroquinone, '8', apparently by an S(N)1 mechanism. This is also a minor decomposition pathway for '2b', but the mechanism in that case is not likely to be S(N)1. Decomposition of '2c' in the presence of N₃⁻ leads to formation of the explosive 2,3,5,6-tetraazido-1,4-benzoquinone, '14', produced by N₃⁻-induced hydrolysis of '8', followed by a series of oxidations and nucleophilic additions by N₃⁻. No products suggestive of N₃⁻-trapping of an oxenium ion were detected. The 4-isopropyl dichloroacetic acid ester '3b' reacts with N₃⁻ to generate the two adducts 2-azido-4-isopropylphenol, '5b', and 3-azido- 4-isopropylphenol, '11b'. Although '5b' is the expected product of N₃⁻ trapping of the oxenium ion, kinetic analysis shows that it is produced by a kinetically bimolecular reaction of N₃⁻ with '3b'. No oxenium ion is involved. The sulfonamide '4c' predominantly undergoes a rearrangement reaction under acidic and neutral conditions, but a minor component of the reaction yields 4-tert-butylcresol, '17', and 2-azido-4- tert-butylphenol, '5c', in the presence of N₃⁻. These products may indicate that '4c' generates the oxenium ion '1c', but they are generated in very low yields (ca. 10%) so it is not possible to definitively conclude that '1c' has been produced. If '1c' has been generated, the N₃⁻-trapping data indicate that it is a very short-lived and reactive species in H₂O. Comparisons with similarly reactive nitrenium ions indicate that the lifetime of '1c' is ca. 20-200 ps if it is generated, so it must react by a preassociation process. Density functional theory calculations at the B3LYP/6-31G*//HF/6-31G* level coupled with kinetic correlations also indicate that the aqueous solution lifetimes of '1a-c' are in the picosecond range.en
dc.languageenen
dc.publisherAmerican Chemical Societyen
dc.relation.ispartofThe Journal of Organic Chemistryen
dc.titleChemistry of 4-alkylaryloxenium ion "precursors": Sound and fury signifying something?en
dc.typeJournal Articleen
dc.identifier.doi10.1021/jo701853een
dc.subject.keywordsPhysical Organic Chemistryen
local.contributor.firstnameMichaelen
local.contributor.firstnameAaron Men
local.contributor.firstnameJill Nen
local.contributor.firstnameJeremy Men
local.contributor.firstnameMatthew Pen
local.contributor.firstnameSamuel Hen
local.contributor.firstnameAndrew Ten
local.contributor.firstnameYue-Tingen
local.contributor.firstnameStephenen
local.subject.for2008030505 Physical Organic Chemistryen
local.subject.seo780103 Chemical sciencesen
local.profile.schoolSchool of Science and Technologyen
local.profile.emailsglover@une.edu.auen
local.output.categoryC1en
local.record.placeauen
local.record.institutionUniversity of New Englanden
local.identifier.epublicationsrecordpes:5967en
local.publisher.placeUnited States of Americaen
local.format.startpage9954en
local.format.endpage9962en
local.identifier.scopusid37549062659en
local.peerreviewedYesen
local.identifier.volume72en
local.identifier.issue26en
local.title.subtitleSound and fury signifying something?en
local.contributor.lastnameNovaken
local.contributor.lastnameBrinsteren
local.contributor.lastnameDickhoffen
local.contributor.lastnameErben
local.contributor.lastnameJonesen
local.contributor.lastnameLeopolden
local.contributor.lastnameVollmanen
local.contributor.lastnameWangen
local.contributor.lastnameGloveren
dc.identifier.staffune-id:sgloveren
local.profile.orcid0000-0002-9344-8669en
local.profile.roleauthoren
local.profile.roleauthoren
local.profile.roleauthoren
local.profile.roleauthoren
local.profile.roleauthoren
local.profile.roleauthoren
local.profile.roleauthoren
local.profile.roleauthoren
local.profile.roleauthoren
local.identifier.unepublicationidune:1674en
dc.identifier.academiclevelAcademicen
local.title.maintitleChemistry of 4-alkylaryloxenium ion "precursors"en
local.output.categorydescriptionC1 Refereed Article in a Scholarly Journalen
local.search.authorNovak, Michaelen
local.search.authorBrinster, Aaron Men
local.search.authorDickhoff, Jill Nen
local.search.authorErb, Jeremy Men
local.search.authorJones, Matthew Pen
local.search.authorLeopold, Samuel Hen
local.search.authorVollman, Andrew Ten
local.search.authorWang, Yue-Tingen
local.search.authorGlover, Stephenen
local.uneassociationUnknownen
local.identifier.wosid000251653000012en
local.year.published2007en
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School of Science and Technology
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