rdf-syntax-grammar
mods:
  schema location: http://www.loc.gov/mods/v3 http://www.loc.gov/standards/mods/v3/mods-3-2.xsd
  title info:
    title: Use of N-hydroxypyridine-2-thioneoxycarbonyl derivatives in free radical kinetics measurements and synthetic applications
  name:
    name part: Kaplan, Jere Kent
    name part: 1961-
    role:
      role term: creator
  name:
    name part: Newcomb, Martin
    role:
      role term: degree supervisor.
  name:
    name part: Hall, K. R.
    role:
      role term: degree committee member.
  name:
    name part: Harding, Kenn E.
    role:
      role term: degree committee member.
  name:
    name part: Wong, C. H.
    role:
      role term: degree committee member.
  name:
    name part: Texas A & M University
    role:
      role term: degree granting institution.
  type of resource: text
  genre: bibliography
  genre: Academic theses
  origin info:
    place:
      place term: xx
    date issued: 1988
    issuance: monographic
  language:
    language term: eng
  physical description:
    form: print
    extent: x, 117 leaves : illustrations ; 29 cm
  abstract: Rate constants for radical reactions were determined using Barton's N-hydroxypyridine-2-thione esters as the source of radicals. Arrhenius functions of the rate constants (k[T]) for the self-propagating reaction were determined for the octyl and undecyl derivatives of the Barton esters 45 and 48. The Arrhenius functions for the self-propagating reactions allowed the use of the esters as "radical clocks" in competition experiments over a range of temperatures. The second order rate constants for halogen atom abstraction (k[X]) from 1°, 2°, and 3° alkyl halides were measured. As expected, among a class of halides, the order of k[X] was 3° > 2° > 1°; for halides of the same carbon frame, the order of k[X] was I > Br > Cl. Values for the pseudo first order rate constants for hydrogen atom abstraction (k[H],) from tetrahydrofuran (THF), ether, and methylene chloride were measured. These rate constants were used to analyze the reactions in the proposed single electron transfer mechanism for the reduction of alkyl halides with metal hydrides. Second order rate constants were also measured for two synthetically useful processes. Rate constants for bromine and iodine atom abstraction by alkyl radicals from ethyl haloacetates were measured as models for the halides used in Curran's atom transfer reactions. Rate constants for nitrile abstraction k[CN] by an alkyl radical from isonitriles, as used in one carbon homologating reactions, were also measured. Intermolecular aminium radical additions to olefins were also investigated. The aminium radical was formed by protonating the aminyl radical generated from the Newcomb carbamate analogs 73 and 74 to the Barton esters. The aminium radicals generated from 73 and 74 were added to ethyl vinyl ether with some success. Also, reactions where intramolecular cyclizations followed the intermolecular aminium radical addition where a pyrrolidine ring was formed are discussed.
  note: Typescript (photocopy).
  note: Vita.
  note: "Major subject: Chemistry."
  note: Ph. D. Texas A & M University 1988
  note: Includes bibliographical references.
  subject:
    topic: Free radicals (Chemistry)
  subject:
    topic: Free radical reactions
  subject:
    topic: Physical organic chemistry
  subject:
    topic: Major chemistry
  identifier: http://gateway.proquest.com/openurl
  identifier: http://proxy.library.tamu.edu/login
  related item:
    location:
      url: http://proxy.library.tamu.edu/login
  related item:
    location:
      url: http://gateway.proquest.com/openurl
  record info:
    record content source: TXA
    record creation date: 900126
    record change date: 20200904152423.0
    record identifier: in00000869996
    language of cataloging:
      language term: eng