Brad Miller
Appalachian State University
Subject Listing - Chemistry
Advisor: Dr. Michael Ramey
Friday, Poster Session 4, Presentation Kiosk 29 C, Health & Fitness Center
AMINE SUBSTITUTED MACROMOLECULAR ELECTROLYTES
The long term objective of this research is to synthesize and develop a set of functionalized hexaphenylbenzene polyelectrolytes with the ability to transport a variety of ionic species (H+, Li+, Cl-, etc.). These materials will be candidates for use in fuel cell and rechargeable battery applications. The initial synthetic target is a hexaphenylbenzene molecule in which each of the phenyl rings is substituted in the para position with (N,N-diethylamine)-1-oxapropyl groups. The amine groups can be reacted with acid (HCl, HBr) or alkylhalides (methyl or ethyl bromide) to provide a single molecule with six positively charged quaternized amine sites. Production of this molecule hinges on the synthesis of 3 distinct components: a) Diethyl-[2-(4-iodo-phenoxy)-ethyl]amine, Compound A; b) 4,4'-(3-[N,N-diethylamino]-1-oxapropyl)diphenylacetylene, Compound B; and c) cobalt octacarbonyl promoted cyclization of the substituted diphenylacetylene into the hexaphenylbenzene molecule. Synthesis of Compound A has been optimized using a variety of Williamson etherification techniques. Para-iodophenol was reacted with 1.1 equivalents of 2-chloroethyldiethylamine hydrochloride and an excess of potassium carbonate. Acetone and a mixed acetone/water solvent system were explored, along with the use of standard reflux versus microwave promoted heating. The conditions leading to the highest percent yield (80%) and simplest workup were sealed tube microwave reactions in acetone solvent at a temperature of 100 0C (~ 80 psi) for 30 minutes. Upon cooling, the reaction mixture was extracted using methylene chloride and 3M aqueous sodium hydroxide, followed by evaporation of the organic solvent. Using this method, approximately 0.5 grams of product could be isolated in 1 hour. Gas chromatography/mass spectroscopy indicated the iodoamine compound was 98% pure. With a useable protocol developed for Compound A, attention is now turning towards the synthesis of Compound B via Sonogashira coupling reactions.
Advisor: Dr. Michael Ramey, Assistant Professor of Chemistry, Department of Chemistry, Appalachian State University, Boone, NC