Date of Graduation

8-2024

Document Type

Dissertation

Degree Name

Doctor of Philosophy in Chemistry (PhD)

Degree Level

Graduate

Department

Chemistry & Biochemistry

Advisor/Mentor

McIntosh, Matthias C.

Committee Member

Zheng, Nan

Second Committee Member

He, Maggie

Third Committee Member

Wang, Feng

Keywords

Benzophenone; Density functional theory; Homolysis; Pyridine; Radical; Rearrangement

Abstract

This work describes two projects centered around radical chemical mechanisms. The first investigation generalized the utility of a C-N bond homolysis followed by a [1,3] – rearrangement synthetic strategy found possible in N-alkylated thiazole & benzothiazole species onto analogous systems. Computational investigation guided the inquiry on structurally analogous systems that would favor a radical, [1,3] – rearrangement. Herein, we describe the implementation of that mechanism to transform Breslow Intermediate-like substrates into tertiary alcohol and amide products under facile conditions. We confer on the proficiency of this strategy with 2-pyridinemethanol and the problematic implementation with 2-(aminomethyl)pyridine. The second investigation solved a production-halting issue an Arkansas company faced in synthesizing one of their signature products, benzophenone-6. Their existing synthesis of benzophenone-6 could not continue due to toxic ingredients required in the production recipe becoming nigh impossible to source. A new, two-step recipe was developed to produce the benzophenone. The new synthetic recipe takes advantage of a radical initiator to produce a Friedel–Crafts acylation product. It also serves a fortunate opportunity for research conducted at the University of Arkansas to be implemented immediately to an Arkansas company.

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