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|Title:||Part One: Radical Cation and Triplex Diels-Alder Reactions. Part Two: Photochemistry of Tri-1-Naphthylboron|
|Author(s):||Calhoun, Glenn Charles|
|Department / Program:||Chemistry|
|Degree Granting Institution:||University of Illinois at Urbana-Champaign|
|Abstract:||Part One. The Diels-Alder reactions of electron-rich alkenes and alkadienes in a photochemical electron transfer system are presented. In acetonitrile, the Diels-Alder dimerization of 1,3-cyclohexadiene (1) is shown to be the result of the reaction of the radical cation of 1. A chain mechanism and a fast rate constant for addition of the radical cation of 1 to a neutral molecule of 1 are applied to explain a similar reaction using an aminium salt catalyst. In benzene, the Diels-Alder adducts are produced via a triplex intermediate. Product and spectroscopic studies for five triplex reactions are presented. Some preliminary observations about this reaction also are discussed.
Part Two. Irradiation of tri-1-naphthylboron in cyclohexene does not give evidence for the formation of 1-naphthylborene. No cis-1,2-cyclohexanediol is detected after oxidative hydrolysis and 1,1'-binaphthyl, a primary photoproduct, is observed only in low yield. These findings are in contrast to the results of Ramsey and Anjo, which were used to support formation of 1-naphthylborene.
Thesis (Ph.D.)--University of Illinois at Urbana-Champaign, 1986.
|Date Available in IDEALS:||2014-12-15|