Date of Award
Doctor of Philosophy
The flash vacuum pyrolysis chemistry of a series of methyl-substituted, furfuryl benzoates and methyl-substituted, 3-furylmethyl benzoates has been investigated. Mechanisms were proposed for the formation of the pyrolysis products, from each of the compounds studied, which involved either (alpha) or (beta) eliminations of benzoic acid after one or more 3,3 sigmatropic shifts of the benzoate group. These reactions provide a method for the preparation of the bis(methylene)-dihydrofurans which are the furan analogs of the ortho- and para-quinodimethanes, an actively investigated group of reactive intermediates. The chemical reactions of the 2,3-bis(methylene)-2,3-dihydrofurans, which were investigated in this study, included thermal dimerization reactions, Diels-Alder reactions and chelatropic reactions with sulfur dioxide;Pyrolysis of diesters of 3,4-bis(hydroxymethyl)-2,5-dimethylfuran formed furanoradialene as the only major, non-polymeric product. Warming the product solutions to room temperature converted furanoradialene into one 4+2 dimer;Several approaches toward the synthesis of 18.104.22.168.(2,3,4,5)furanophane were investigated. The failure to produce the desired furanophane was attributed to a retro-4+4 reaction which occurred during the pyrolysis of 4,4'-bis(acetoxymethyl)-5,5'-dimethyl-2,2(2,3)furanophane.
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Timothy John Cassady
Cassady, Timothy John, "Chemistry of 2,3-dimethylene-2,3-dihydrofurans and other reactive olefins prepared by the flash vacuum pyrolysis of substituted furylmethyl esters " (1983). Retrospective Theses and Dissertations. 8459.