Donor-Acceptor tetramethylenes have been studied by polymerizations. 1,4-Zwitterionic intermediates are indicated when reactive tetramethylenes initiate homopolymerization. Alternately, 1,4-diradical intermediates initiate copolymerization. This basis for studying intermediates has led to an empirical table for predicting the zwitterionic and diradical nature of addition and polymerization reactions of tetramethylenes. Here we attempted to extend this work to trimethalylenes by studying the thermal ring opening of ethyl chrysanthemate, ethyl 1-cyano-2-(4-methoxyphenyl)-cyclopropane-corboxylate, ethyl 1-cyano-2-(2-methoxyphenyl)-cyclopro-panecroboxylate, and diethyl 1,3-dicyano-w,r-di(2-methoxyphenyl)-cyclobutanedicarboxylate. These compounds were found to be thermally stable to 150°C and did not initiate polymerization in styrene, methyl methacrylate, a series of high boiling acrylates, and dimethyl fumarate. Free radicals were trapped in dimethyl fumarate to give oligomers at temperatures above 110°C. Even though the compounds studied did not initiate polymerization at decomposition temperatures of 175°-200°C, dimethyl fumarate may prove useful in these studies in the future.

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Vita. / Digitized by Kansas Correctional Industries

Includes Publications resultant of the thesis research Includes bibliographical references (leaves 180-196). Electronic publication; full text available in PDF format; abstract in HTML format. A series of new cobalt(II) ℓ-keto iminato complexes and cobalt(II) salens have been made and the effect of chirality in the northern, southern and peripheral quadrants of these catalysts, with respect to induced enantiomeric excess, during ring-opening of 1,2-dioxines has been determined. Electronic reproduction.[Australia] :Australian Digital Theses Program,2001. ix, 206 leaves : ill. ; 30 cm.

Thèse doctorat : Chimie : Paris 12 : 2003. / Version électronique uniquement consultable au sein de l'Université Paris 12 (Intranet). Titre provenant de l'écran-titre. Bibliogr. : 193 réf.

Thesis (Ph. D.)--University of Texas at Austin, 2001. / Vita. Includes bibliographical references (leaves 270-290). Available also in a digital version from Dissertation Abstracts.

Herein describes our approaches to the Daphniphyllum alkaloids. Specifically targeted are the recently isolated daphnicyclidins. The first chapter describes the structural diversity and biological properties of this class of alkaloids. Chapter 2 discusses some exploratory chemistry towards the daphnicyclidin fused tricycle. Chapter 3 describes the use of cyclopropanes in synthesis and their use in our ring expansion strategy. Preliminary results on the key cyclopropane ring expansion and the stereoselective quaternary center formation are also discussed. The chemistry concerning the diasteroselective cyclopropanation of a key intermediate and further details concerning the cyclopropane ring expansion are delineated. Chapter 4 contains the experimental details and characterization data for all new reported compounds. / text

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