Palladium catalysed oxidation of a-olefins to ketones.

Abstract

The aim of this research project was to investigate the oxidation reactions of olefins to ketones. Initial studies revolved around the oxidation reactions of terminal olefins to symmetrical dialkyl ketones. The inability to isolate pure products, and the consumption of large amounts of the expensive palladium catalyst for each run as well as the extremely low yields that resulted from these oxidation reactions, made it difficult to thoroughly investigate this oxidation system. It was then decided to embark on the investigation of oxidation reactions of a-olefins to methyl ketones. For these studies, six terminal olefins were oxidised to methyl ketones employing seven different oxidation reactions. One of the most important and pioneering reactions m this field is the system employing PdCl2 / CuCl2 / O2 for the oxidation of terminal olefins to methyl ketones, namely the Wacker oxidation reaction. Experimental results, however, indicated that high product contamination from by-products resulted from these oxidation reactions despite the fairly good yields of product from the Wacker oxidation system. Some reaction systems that have been developed from the Wacker oxidation system were also investigated. The oxidation system employing PdCl2 / p-benzoquinone for the oxidation of terminal olefins to ketones was studied. The oxidation reactions resulted in incomplete oxidation with higher olefins (l-decene, l-nonene and l-octene), and complete oxidation of lower olefins (l-heptene, l-hexene and l-pentene) under the same reaction conditions. The products from lower olefins oxidised under these reaction conditions were pure and high yielding Another system that proved efficient both with feasibility and good yields of products was the oxidation system employing Pd(OAc)2 / H202 catalyst to oxidise terminal olefins to methyl ketones. Phase transfer catalysis has been employed in organic chemistry to effect different reactions. In this case two types of phase transfer agents were employed to effect the oxidation of terminal olefins to ketones. The first oxidation system involved the use of a PdCl2 / CuCl2 / O2 catalyst with a quaternary ammonium salt, cetyltrimethylammonium bromide (CTAB), to govern the course of the reaction. Reasonable yields were obtained, and moderate purity of products was also observed. The second phase transfer catalysis system employed polyethylene glycol (PEG-200) as a phase transfer agent, and PdCl2 / CuCl2 / O2 as a catalyst for oxidation of olefins to ketones. This oxidation system resulted in different isomers of a ketone from a terminal olefin. Pure methyl ketones were not isolable from the mixture of methyl and ethyl ketones. The oxidation reactions of olefins to ketones employing Pd(OAc)2 / p-benzoquinone in combination with electrolysis were also investigated. The unique feature about these reactions was the fact that cyclic olefins could also be oxidised under these conditions. Good yields were obtained, and high product purity was observed. One of the important oxidation reactions investigated during the project was the reaction that used an alternative metal to the expensive palladium catalyst for the oxidation reactions to ketones. This oxidation system employs CuCl2 / 18-C-6 / acetaldehyde as a catalyst for the oxidation of hydrocarbons to ketones and alcohols. It was discovered during the investigation that olefins can also be used as substrates and are oxidised to the corresponding ketones. The use of olefins as substrates resulted in higher yields than the hydrocarbon oxidation reactions, and less contamination in the product mixture was also observed.