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    Formation of "methylene" nitrones in some nitrosoarene - olefin reactions

    Author
    Getman, Gerry D.
    View/Open
    174891_thesis.pdf (2.882Mb)
    Other Contributors
    Hepfinger, N. F.; Altwicker, Elmar R.; Bunce, S. C.; Potts, Kevin T.; Wedler, Frederick C.;
    Date Issued
    1975-09
    Subject
    Organic chemistry
    Degree
    PhD;
    Terms of Use
    This electronic version is a licensed copy owned by Rensselaer Polytechnic Institute, Troy, NY. Copyright of original work retained by author.;
    Metadata
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    URI
    https://hdl.handle.net/20.500.13015/1334
    Abstract
    On the basis of preliminary kinetic investigations, the mechanism of addition of nitrosobenzene to styrene and similar compounds was advanced as occurring by an initial 2 + 2 cycloaddition of styrene and nitrosobenzene followed by ring opening to a diradical species which reacts with additional nitrosobenzene to form isomeric 2,3,5-triphenyl-1,2,5-oxadiazolidine-N-oxides.; Unlike the reaction of styrene and nitrosobenzene, the reaction of trifluoronitrosomethane with styrene was found to undergo a multiple Diels-Alder addition to form 4,10-diaza-4,10-bis(trifluoromethyl)-3,9-dioxatricyclo[6.2.2.02,7]dodeca-6,11-diene. Although all isomeric structure for this product were not eliminated from consideration, the fact that two successive Diels-Alder cycloadditions had occurred was confirmed by thermolysis, hydrogenation, and elemental analysis. In a similar manner, 2-phenylpropene formed a multiple Diels-Alder adduct at low temperatures; at elevated temperature an "ene" product, N-(tri-fluoromethyl)-N-(2-phenyl-2-propenyl)hydroxylamine, was preferentially formed.; N-methylenephenylamine-N-oxide, N-methylene(4-methylphenyl)-amine-N-oxide, and N-methylenemethylamine-N-oxide were generated by thermolysis of the corresponding N, N'-dihydroxymethanediamines in the presence of various dipolarophiles. The resulting cycloadditions provided a convenient synthesis for some previously inaccessible isoxazolidines. The same method was used to synthesize stable N-methylene-amine-N-oxides, e.g., N-mesitylamine-N-oxide and N-methylene-tert-butylamine-N-oxide, which were previously prepared through the use of diazomethane.; The addition of nitrosobenzene to styrene and 1,1-diphenyl-ethylene has been shown to proceed through 1,2,5-oxadiazolidine-N-oxide intermediates which undergo subsequent thermal decomposition to N-methylenephenylamine-N-oxide and more highly substituted nitrones. Evidence for the presence of N-methylenephenylamine-N-oxide in reaction media was provided by isolation of its cycloadduct with N-phenylmaleimide, and as an adduct of aniline and nitrosobenzene. Similarly, N-ethylidine-phenylamine-N-oxide was isolated as a cycloadduct of N-phenylmaleimide from the reaction of nitrosobenzene with 1-(3,4-methylenedioxyphenyl)-propene.;
    Description
    September 1975; School of Science
    Department
    Dept. of Chemistry;
    Publisher
    Rensselaer Polytechnic Institute, Troy, NY
    Relationships
    Rensselaer Theses and Dissertations Online Collection;
    Access
    Restricted to current Rensselaer faculty, staff and students. Access inquiries may be directed to the Rensselaer Libraries.;
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