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dc.contributor.authorHough, Sarita Elizabethen_US
dc.date.accessioned2019-06-26T08:00:31Z
dc.date.available2019-06-26T08:00:31Z
dc.date.issued2019-06-25
dc.identifier.othervt_gsexam:20323en_US
dc.identifier.urihttp://hdl.handle.net/10919/90657
dc.description.abstractReactions of fluorinated anilines with stoichiometric Ti(NMe2)4 in mesitylene (typically for 23 h at 120 °C) afforded moderate to high yields of the corresponding N,N-dimethyl-o-phenylenediamine derivatives resulting from defluoroamination of a fluorine atom ortho to the NH2 of the starting aniline. Reactivity increased with additional ring fluorination in general accordance with established regiochemical (activating and deactivating) trends. Based on results, we propose a metal-mediated, SNAr-based mechanism. We report the scope and limitations of this reaction and discuss trends in reactivity according to a putative mechanistic scheme.en_US
dc.format.mediumETDen_US
dc.publisherVirginia Techen_US
dc.rightsThis item is protected by copyright and/or related rights. Some uses of this item may be deemed fair and permitted by law even without permission from the rights holder(s), or the rights holder(s) may have licensed the work for use under certain conditions. For other uses you need to obtain permission from the rights holder(s).en_US
dc.subjecttitanium amideen_US
dc.subjectSNAren_US
dc.subjectdefluorinationen_US
dc.subjectanilinesen_US
dc.subjectorganometallicen_US
dc.subjectnucleophilesen_US
dc.titleRegioselective, Nucleophilic Activation of C-F Bonds in o-Fluoroanilinesen_US
dc.typeThesisen_US
dc.contributor.departmentChemistryen_US
dc.description.degreeMaster of Scienceen_US
thesis.degree.nameMaster of Scienceen_US
thesis.degree.levelmastersen_US
thesis.degree.grantorVirginia Polytechnic Institute and State Universityen_US
thesis.degree.disciplineChemistryen_US
dc.contributor.committeechairDeck, Paul A.en_US
dc.contributor.committeememberDorn, Harry C.en_US
dc.contributor.committeememberMorris, Amandaen_US
dc.contributor.committeememberMerola, Joseph S.en_US
dc.description.abstractgeneralThis thesis describes reactions of fluorinated anilines with titanium amides to make fluorinated 1,2-phenylenediamines. The reaction gives high to moderate yields, and is highly selective for ortho substitution. The scope of the reaction, trends in reactivity among substrates, product characterization, and reaction mechanism are discussed. This reaction is of interest because fluorinated aniline derivatives are a privileged structural motif in pharmaceuticals and agricultural chemicals. The first chapter presents an overview of C-F bond activation and key background information. Chapter 2 is a description of the experiments and an in-depth analysis of their results. Chapter 3 presents detailed characterization data for substances generated in this research. Chapter 4 comprises some concluding remarks and plans for possible future extensions of the research.en


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