Date of Award
2025
Degree Type
Dissertation
Degree Name
Doctor of Philosophy in Chemistry
Department
Chemistry
First Advisor
Brenton DeBoef
Abstract
Pillar[n]arenes, discovered in 2008, have already made their mark as a formidable addition to the field of supramolecular chemistry, largely due to their host-guest chemistry. While the synthesis of pillar[5]arene is well established, the synthesis of pillar[6]arene, with its larger core, has not been so straightforward and mainly accomplished through the use of bulky solvents. Here we present an optimized method for a reproducible, acid-catalyzed synthesis for a brominated pillar[6]arene, starting with a brominated monomer and using chloroform as the templating solvent. Our studies have demonstrated the ratio of brominated pillar[6]arene to brominated pillar[5]arene increases with both decreasing concentration of starting material, and decreasing both time and temperature, providing 39% yield at milligram scale and 20% yield at gram scale. Using 1H NMR, we examined the interplay between brominated pillar[5]arene and brominated pillar[6]arene, where the former was believed to be the kinetic product and the latter the thermodynamic product in the Friedel Crafts Alkylation reaction. Here, we present data to support a two-reaction system, showing no evidence of interconversion. Last, we present a method for the synthesis of a water-soluble cationic pillar[6]arene with a yield of 50%.
Recommended Citation
Gillis, Helice A., "THE RELATIONSHIP BETWEEN PILLAR[5]ARENE AND PILLAR[6]ARENE IN THE SYNTHETIC ROUTE TO A WATER-SOLUBLE PILLAR[6]ARENE: A CASE OF KINETIC AND THERMODYNAMIC PRODUCTS OR TWO DISTINCT, COMPETING REACTIONS" (2025). Open Access Dissertations. Paper 4431.
https://digitalcommons.uri.edu/oa_diss/4431
