Reactivity of nucleophiles toward phenyl radical

dc.contributor.author Anderson, James
dc.contributor.department Chemistry
dc.date 2018-08-15T08:33:17.000
dc.date.accessioned 2020-07-02T06:04:58Z
dc.date.available 2020-07-02T06:04:58Z
dc.date.copyright Wed Jan 01 00:00:00 UTC 1986
dc.date.issued 1986
dc.description.abstract <p>The mechanism of the aromatic S(,RN)1 reaction was studied using the competitive reaction kinetics. Evidence has been presented that supports the existence of only one intermediate in the aromatic S(,RN)1 reaction. The relative reactivity of nucleophiles competing for an intermediate in the aromatic S(,RN)1 reaction and phenyl radical generated from the thermolysis of PAT were very similar;Initial relative rate studies competing two nucleophiles versus each other with iodobenzene under S(,RN)1 conditions indicate another important product forming step in the early stages of the reaction other than radical-nucleophile coupling. Photolysis of a charge transfer complex between iodobenzene and the enolates of pinacolone and 1-phenyl-3,3-dimethyl-2-butanone results in electron transfer and cage recombination of a phenyl radical and an alpha-keto radical. A competition occurs between the photochemical process and the photostimulated free radical chain process;Absolute rate constants for the coupling of phenyl radical with various nucleophiles have been determined using competitive reaction kinetics. The rate constants are well below the diffusion limit and are on the order of 10('7) to 10('8) M('-1)s('-1) in DMSO at 45(DEGREES)C. The reactivity of nucleophiles toward phenyl radical appears to be related to the basicity of the nucleophile and the stability of the radical anion formed from coupling.</p>
dc.format.mimetype application/pdf
dc.identifier archive/lib.dr.iastate.edu/rtd/8135/
dc.identifier.articleid 9134
dc.identifier.contextkey 6329029
dc.identifier.doi https://doi.org/10.31274/rtd-180813-3085
dc.identifier.s3bucket isulib-bepress-aws-west
dc.identifier.submissionpath rtd/8135
dc.identifier.uri https://dr.lib.iastate.edu/handle/20.500.12876/81090
dc.language.iso en
dc.source.bitstream archive/lib.dr.iastate.edu/rtd/8135/r_8703682.pdf|||Sat Jan 15 02:07:04 UTC 2022
dc.subject.disciplines Organic Chemistry
dc.subject.keywords Chemistry
dc.subject.keywords Chemistry
dc.subject.keywords Organic
dc.title Reactivity of nucleophiles toward phenyl radical
dc.type article
dc.type.genre dissertation
dspace.entity.type Publication
relation.isOrgUnitOfPublication 42864f6e-7a3d-4be3-8b5a-0ae3c3830a11
thesis.degree.level dissertation
thesis.degree.name Doctor of Philosophy
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