Anionic Amino-Cope Rearrangement Studies and Development of Designer Sulfur-Rich Materials using Sulfur, Sulfur Monochloride and Dithiophosphoric Acids

This dissertation is divided into six chapters, containing both works related to the explorations of new anionic amino-Cope cascade reaction as well as development and characterizations of new sulfur-rich materials. Chapter 1 presents diverse results of the anionic amino-Cope cascades when strategically employing γ-substituted dienolates nucleophile. In Chapter 2, efforts to challenge anionic amino-Cope reactions with steric effect are reported, resulting in the formation of conjugate di- and trienamides with selective configuration of double bond geometry. Chapter 3 highlights the first comprehensive study of the sulfur-rich polymer material prepared through inverse vulcanization, which undeniably assigns the major microstructure of the polymer through degradation studies, collaborative computational calculations, and solid state NMR analysis. Chapter 4 describes the structural characterization of deuterated poly(S-r-DIB) material. Chapter 5 focuses on the design and synthesis of olefinic monomers for polymerization with S2Cl2, as well as the structural characterization of the polymer through degradation studies. Chapter 6 presents a new polymer functionalization method using dithiophosphoric acid, which resulted in an improving thermomechanical, optical properties and flame retardancy.

Name thesis:degree_name

Ph.D.

Level thesis:degree_level

doctoral

Discipline thesis:degree_discipline

Graduate College

Grantor dc:publisher

The University of Arizona.

Year dc:date.issued

2023

Author dc:creator

• Bao, Jianhua

Advisor dc:contributor.advisor

• Njardarson, Jon

Committee members dc:contributor.committeemember

• Jewett, John
• Gianetti, Thomas
• Mash, Eugene

• Amino-Cope rearrangement
• Degradation
• Polymerization

Statement dc:rights

• Copyright © is held by the author. Digital access to this material is made possible by the University Libraries, University of Arizona. Further transmission, reproduction, presentation (such as public display or performance) of protected items is prohibited except with permission of the author.

Licence dc:rights.uri

• http://rightsstatements.org/vocab/InC/1.0/

Language dc:language.iso

en

Handle dc:identifier.uri

http://hdl.handle.net/10150/670267

OAI identifier oai:identifier

oai:repository.arizona.edu:10150/670267