Studies directed towards the synthesis of metal-containing ketones

Abstract

The photochemistry of organometallic compounds is receiving increasing attention in the current literature, but as yet, little work has been reported on the photochemistry of metal-containing ketones. The objective of the work reported in this thesis was the synthesis of ligands for the formation of suitable metal-containing ketones. The initial studies were directed at the preparation of β- and ϒ-hydroxyketones by a variety of methods, but the major effort was later concentrated on the synthesis of phosphorus derivatives of o-hydroxyphenyl alkyl ketones . The reaction of o-hydroxyphenyl alkyl ketones with phosphorus trichloride afforded 2-chloro- 1,3,2-dioxaphosphorinans which were readily converted to the corresponding 2-alkoxy derivatives by reaction with various alcohols. Extension of the study to acteylacetone indicated that an analogous reaction occurs to give highly labile products. This part of the work has been accepted for publication in Chemical Communications. The reaction of o-hydroxyphenyl alkyl ketones with other phosphorus halides, such as dichlorophenyl phosphine and chlorodiphenylphosphine, has also been investigated. Reaction of the former reagent with o-hydroxyacetophenone gave a crystalline phosphorus-containing derivative; spectroscopic evidence indicates that this compound possesses an unusual structure and it is currently being studied by X-ray crystallography.