Hydrocarbon Functionalization via a New Free Radical-Based Condensation Reaction

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dc.contributor.authorSadeghipour, Mitra Jr.en
dc.contributor.committeechairTanko, James M.en
dc.contributor.committeememberBell, Harold M.en
dc.contributor.committeememberCastagnoli, Neal Jr.en
dc.contributor.committeememberKingston, David G. I.en
dc.contributor.committeememberBrewer, Karen J.en
dc.contributor.committeememberTanko, James M.en
dc.contributor.departmentChemistryen
dc.date.accessioned2014-03-14T20:22:16Zen
dc.date.adate1998-07-17en
dc.date.available2014-03-14T20:22:16Zen
dc.date.issued1998-07-07en
dc.date.rdate1999-07-17en
dc.date.sdate1998-07-07en
dc.description.abstractA new free radical chain process for the allylation of hydrocarbons and some other substrates utilizing substituted allyl bromides (R-H + C=C-C-Br -> R-C-C=C + HBr) has been developed. Good to excellent yields were observed in all cases. Kinetic chain measurements and competition experiments were performed in order to elucidate the mechanism of the reaction. Overall, the results are consistent with a free radical chain process with bromine atom as the chain carrier. Substitution effects on the reactivity of the allyl bromides (CH2=C(Z)CH2Br) and their influence on the overall reaction rate were studied by conducting several competition experiments. The relative rate constants for addition of benzyl radical to CH2=C(Z)CH2Br are: Z=CN(180), COOEt(110), Ph(65), H(1.0). The trend of electronegativity/reactivity of these reactions was very similar to that reported for addition of benzyl radical to substituted alkenes. Other than alkyl aromatics (PhCH3, PhCH(CH3)2), other substrates (i.e., 2- propanol, phenyl cyclopropane) were also tested for this allylation reaction. The magnitude and scope of these reactions, and their synthetic utility is discussed.en
dc.description.degreePh. D.en
dc.identifier.otheretd-61598-21627en
dc.identifier.sourceurlhttp://scholar.lib.vt.edu/theses/available/etd-61598-21627/en
dc.identifier.urihttp://hdl.handle.net/10919/30627en
dc.publisherVirginia Techen
dc.relation.haspartDissertation.PDFen
dc.rightsIn Copyrighten
dc.rights.urihttp://rightsstatements.org/vocab/InC/1.0/en
dc.subjectAdditionen
dc.subjectAllylationen
dc.subjectAllyl bromideen
dc.subjectAlkyl aromaticen
dc.subjectBromineen
dc.subjectCondensationen
dc.subjectFragmentationen
dc.subjectFree Radicalen
dc.subjectHydrocarbonen
dc.subject2-Propanolen
dc.subjectReaction Mechanismen
dc.subjectSynthesisen
dc.titleHydrocarbon Functionalization via a New Free Radical-Based Condensation Reactionen
dc.typeDissertationen
thesis.degree.disciplineChemistryen
thesis.degree.grantorVirginia Polytechnic Institute and State Universityen
thesis.degree.leveldoctoralen
thesis.degree.namePh. D.en

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