Greener Alternatives to Selected Organic Oxidation Reactions

Sheppard, Ryan (2015) Greener Alternatives to Selected Organic Oxidation Reactions. Memorial University of Newfoundland. (Unpublished)

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Abstract

The study of green chemistry is dedicated to eliminating or reducing toxic waste. One route to accomplish this goal is to explore alternative reaction conditions and parameters resulting in the development of more benign synthetic routes and reagents. The primary focus of this research is to find optimal reaction conditions for the oxidation of a primary alcohol to an aldehyde. As a case study, the oxidation of benzyl alcohol to benzaldehyde, a common industrial process, was examined. Traditionally carried out using the Jones Reagent, commonly referred to as chromium (IV) oxide or chromium trioxide (CrO3) in sulphuric acid, a great deal of research went into utilizing less toxic reagents, such as MnO2 or KMnO4 supported on a clay base. This research has led to an improvement on these alternatives, using a lithium chloride (LiCl) catalyst in a montmorillonite K10 clay solid phase, together with the oxidizing agent hydrogen peroxide, as even greener alternatives to these traditional oxidizing agents. Experiments were carried out to determine the lifetime of this LiCl/clay system as compared to MnO2 and KMnO4, to investigate its ability to catalyze the oxidation of other aromatic alcohols (such as 4-methoxybenzyl alcohol and diphenylmethanol), and to further improve the system’s adherence to green chemistry principles. Green solvent alternatives were examined by replacing the toluene solvent with dimethylcarbonate (DMC), and reaction conditions were optimized to improve product yield. It was determined that the LiCl/H2O2 system was, in most cases, equally as effective at catalyzing the oxidation of benzyl alcohol to benzaldehyde. Although the catalyst and oxidizing agent eliminated the toxic waste generated from chromium reagents, it offered significant challenges in product isolation, because of an aqueous-organic phase separation.

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