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

Abstract

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.