A novel rearrangement of substituted phenylhydroxylamines

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dc.contributor.advisorCox, James R.
dc.contributor.committeeMemberGeanangel, Russell A.
dc.contributor.committeeMemberWillcott, Mark Robert, III
dc.contributor.committeeMemberMcElrath, Eby N.
dc.creatorNolen, Robert L.
dc.date.accessioned2022-06-22T19:53:46Z
dc.date.available2022-06-22T19:53:46Z
dc.date.issued1970
dc.description.abstractThe rearrangement in different solvents of a number of substituted phenyl hydroxyl amines has been investigated. Kinetically, the N-acyl-N-phenylhydroxyl amines show a great sensitivity to electronic changes in the molecule. Electron withdrawing substituents decrease the rate, and electron donating substituents increase the rate markedly. In all compounds investigated, 0-dichloroacetyl-N-acetyl-N-(4-methylphenyl)hydroxyl amine and 0-di chioroacetyl-N-acetyl-N-phenylhydroxyl amine, two different compounds could be isolated depending on whether or not a base was present. The compound always isolated when no base was present was the kinetically controlled product X or XIII. The second product was the thermodynamically more stable product XI or XIV. The structure of the kinetically controlled product has been shown to be a novel one. Oxygen-18 tracer studies have shown that the rearrangement of O-dichioroacetyl-[raised 18]O-N-acetyl-N-(4-methylphenyl)hydroxyl amine rearranges in neat solution by an ion pair mechanism, whereby the oxygen-18 strategically placed in the di chioroacetyl carbonyl group was mixed exactly half and half with the phenyl hydroxyl amine oxygen. The rearrangement of O-dichioroacetyl-[raised 18]O-N-acetyl-N-phenylhydroxyl amine in chloroform solution occurred by transfer of all the labelled oxygen to the ortho position. This result indicates a change in mechanism from that of the 4-methyl compound. In dichloroacetic acid, O-dichloroacetyl-[raised 18]O-N-acetyl-N-phenylhydroxyl amine rearranged by three different pathways; one intermolecular, one cyclic, and the third by an intramolecular process. Just by changing the ring substituents, two different mechanisms were detected. Also, the change in solvent produced a marked change in mechanism. Therefore, the solvent and electronic effects indicate a very complex and delicate system.
dc.description.departmentChemistry, Department of
dc.format.digitalOriginreformatted digital
dc.format.mimetypeapplication/pdf
dc.identifier.other13726612
dc.identifier.urihttps://hdl.handle.net/10657/9889
dc.language.isoen
dc.rightsThis item is protected by copyright but is made available here under a claim of fair use (17 U.S.C. Section 107) for non-profit research and educational purposes. Users of this work assume the responsibility for determining copyright status prior to reusing, publishing, or reproducing this item for purposes other than what is allowed by fair use or other copyright exemptions. Any reuse of this item in excess of fair use or other copyright exemptions requires express permission of the copyright holder.
dc.titleA novel rearrangement of substituted phenylhydroxylamines
dc.type.dcmiText
dc.type.genreThesis
thesis.degree.collegeCollege of Arts and Sciences
thesis.degree.departmentChemistry, Department of
thesis.degree.disciplineChemistry
thesis.degree.grantorUniversity of Houston
thesis.degree.levelDoctoral
thesis.degree.nameDoctor of Philosophy

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