Publication Date

2015

Document Type

Dissertation/Thesis

First Advisor

Klumpp, Douglas A.

Degree Name

M.S. (Master of Science)

Legacy Department

Department of Chemistry and Biochemistry

LCSH

Organic chemistry; Analytical chemistry; Organic compounds--Synthesis--Research; Biomass energy--Research; Superelectrophiles--Research

Abstract

This thesis describes two main areas of research. The first is the development of synthetic strategies to afford products with biorenewable carbon. Biodiesel has been widely accepted as a plausible alternative to replace petroleum based products for transportation purposes. These bio-based diesel fuels are commonly referred to as fatty acid methyl esters (FAME's), because of the long fatty acid hydrocarbon chain that is attached to ester functionality. The ability to modify FAME's allows for an improvement in properties such as density, viscosity, volatility, and gelation points simply by incorporating increasing degrees of unsaturation, shortening carbon chains, and adding aromaticity which results in a blended fuels with increased performance. These modifications may be accomplished through catalytic reforming; utilizing cross-metathesis of the C-C double bond in FAME and the C-C double bond in light olefins. This area of research also seeks new bio-derived octane additives through the alkylation of furans followed by subsequent hydrogenation to achieve highly branch alkanes. Furans are derived from biorenewable sugars through the oxidative dehydration of hexoses. In the case of octane additives we are seeking to create more hydrocarbon species derived from biorenewable resources that will resist premature ignition during compression. Reactions such as the Friedel-Crafts alkylation and the electrophilic addition reactions were attempted. These types of reactions are used to alkylate aromatic rings through use of acidic catalysis.;The second area of research is the synthesis of superelectrophilic intermediates to afford important heterocyclic products. We sought to utilize the aza-Diels-Alder type reaction in which we will be using conjugated nitrogen dienes along with low cost ethylene to create new efficient routes to synthesis N-heterocycles. Since we wanted to use ethylene, a cheap light olefin from the petroleum industry, as our dienophile we will have to create an electrophilic diene to allow for inverse electron demand cycloaddition, since ethylene alone is a poor dienophile. Through the use of acidic media we were able to make our aza-diene superelectrophilic causing a decrease in it LUMO energy resulting in an overall lower energy barrier to overcome for cyclization.

Comments

Advisors: Douglas A. Klumpp.||Committee members: Timothy Hagen; Narayan Hosmane; Douglas A. Klumpp.

Extent

96 pages

Language

eng

Publisher

Northern Illinois University

Rights Statement

In Copyright

Rights Statement 2

NIU theses are protected by copyright. They may be viewed from Huskie Commons for any purpose, but reproduction or distribution in any format is prohibited without the written permission of the authors.

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