Date of Award

Fall 1985

Project Type

Dissertation

Program or Major

Chemistry

Degree Name

Doctor of Philosophy

Abstract

Part I. The synthesis, characterization, and physical properties of novel lactones and their precursors derived from methyl salicylate are described. The influence of substituents on the aromatic nucleus in affecting ring closure reactions was examined. Experimental results show that ring closure is enhanced when nitro groups are incorporated in the aromatic ring. Investigations were conducted in the preparation of compounds designed to exhibit ring-chain tautomerism.

Part II. Nucleophilic aromatic substitution reactions were carried out on 2-(2-hydroxyethoxy)-3,5-dinitrobenzoic acid, methyl ester and the corresponding seven-membered lactone. Nucleophiles chosen for study included iodide, several amines, hydroxide, methoxide, thiophenoxide, thiosulfate, sulfides, thiocyanate, cyanide, and several enolates. Reaction with a nucleophile was accompanied by the consistent loss of the (beta)-hydroxyethoxy unit. In several of these experiments, the isolation and characterization of Meisenheimer complexes was possible. The Meisenheimer intermediates, in turn, could be converted to aromatic products by means of various nucleophiles.

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