PART I PREPARATION OF NOVEL LACTONES AND THEIR PRECURSORS DERIVED FROM METHYL SALICYLATE PART II NUCLEOPHILIC AROMATIC SUBSTITUTION IN A DINITROSALICYLIC LACTONE WITH RING OPENING AND ELIMINATION VIA MEISENHEIMER INTERMEDIATES

<p>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.</p><p>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.</p>

Name thesis:degree_name

Doctor of Philosophy

Level thesis:degree_level

Dissertation

Year

1985

Author dc:creator

• ROTHENBERGER, SCOTT DANIEL

• Chemistry
• Organic

Repository record dc:identifier

https://scholars.unh.edu/dissertation/1462

OAI identifier oai:identifier

oai:scholars.unh.edu:dissertation-2461