Date of Graduation

12-2025

Document Type

Dissertation

Degree Name

Doctor of Philosophy in Chemistry (PhD)

Degree Level

Graduate

Department

Chemistry & Biochemistry

Advisor/Mentor

McIntosh, Matt

Committee Member

He, Maggie

Second Committee Member

Zheng, Nan

Third Committee Member

Kilyanek, Stefan

Keywords

Free Radical; Organic Chemistry; Organic Synthesis

Abstract

Radical reactions have known for over a century but have only been thought of as useful synthetic strategies for the last 70 years. During this period, much work has been done to develop theoretical explanations for their reactivity and modes of termination, resulting in them becoming a fundamental type of organic reaction in academia and industry. Previous studies by the McIntosh group have shown that a radical [1,3]-Rearrangement occurs when N-substituted pyridines are heated. Here, the scope of this new reaction is expanded to include polycyclic pyridines including neocuproine (2,9-dimethylphenanthroline) and 2-methylquinoline while also expanding the range of reactions available to the sterically-hindered 2,6-lutidine. Of particular interest is the confirmation of a double rearrangement occurring when using 4-ethylpyridine as a substrate. A second project involved the use of radical chemistry to develop a new pathway to a commercial product, benzophenone-6, sold by a company in Southwest Arkansas. This was achieved by Friedel-Crafts acylation of 1,3-dimethoxybenzene followed by a regioselective dealkylation using water.

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