Part I. Mechanism of the Rearrangement of Fenchone. Part II. Mechanism of the Diels-Alder Reaction

Citation

Lutz, Raymond Paul (1962) Part I. Mechanism of the Rearrangement of Fenchone. Part II. Mechanism of the Diels-Alder Reaction. Dissertation (Ph.D.), California Institute of Technology. doi:10.7907/0GDS-G649. https://resolver.caltech.edu/CaltechTHESIS:08032011-144903807

Abstract

Part I: The rearrangement of fenchone (1,3,3-trimethylbicyclo[ 2.2.1]-heptan-2-one) to 3,4-dimethylacetophenone has been carried out using a sample labeled with carbon-14 in the methyl groups of the 3-position. In concentrated sulfuric acid at 90°, 96% of the reaction takes the following course: […]

Part II: Optically active methacrolein dimer, labeled with deuterium at the aldehyde hydrogen, rearranges thermally with complete retention of optical activity to the isomer in which the deuterium is shifted to the vinyl position on the ring. The rearrangement is accompanied by […]

substantial competitive formation of methacrolein by a Diels–Alder dissociation, lending support to the presumption that this and analogous isomerizations represent partial reverse Diels-Alder reactions. The results rule out the intervention of a linear intermediate in the Diels-Alder reaction of methacrolein, and make it unlikely that similar intermediates are involved in other Diels-Alder reactions.

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