University of Illinois Urbana-Champaign

Part One: Radical Cation and Triplex Diels-Alder Reactions. Part Two: Photochemistry of Tri-1-Naphthylboron

Calhoun, Glenn Charles

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Description

Title
Part One: Radical Cation and Triplex Diels-Alder Reactions. Part Two: Photochemistry of Tri-1-Naphthylboron
Author(s)
Calhoun, Glenn Charles
Issue Date
1986
Department of Study
Chemistry
Discipline
Chemistry
Degree Granting Institution
University of Illinois at Urbana-Champaign
Degree Name
Ph.D.
Degree Level
Dissertation
Keyword(s)
Chemistry, Organic
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.
Graduation Semester
1986
Type of Resource
text
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http://hdl.handle.net/2142/70322

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