Synthetic studies towards anthraquinones

by Anthony Stewart. Mitchell

Institution: Deakin University
Year: 1994
Keywords: Anthraquinones; Phenols
Record ID: 1032367
Full text PDF: http://hdl.handle.net/10536/DRO/DU:30023347


The oxidation of substituted phenols with phenyliodonium diacetate in methanol was found to afford 2,4-cyclohexadienones, 2,5-cyclohexadienones or mixtures of isomers depending on the substrate being oxidized. A reaction mechanism was proposed for this oxidation which involved an intermediate aryloxenium ion. A strong correlation was observed between the experimentally determined product ratios and the results predicted by calculation of the LUMO coefficients of the proposed intermediates, Annulation of these cyclohexadienones with the anion derived from cyanophthalide afforded substituted anthraquinones in high yields. The chemistry relating to the annulation of Michael acceptors with phthalide anions was comprehensively reviewed. A mild selective method for the oxidation of hydroquinones to quinones using dibenzoyl peroxide and base is presented. A general synthetic approach to C-glycosylanthraquinones was presented, based on the annulation of a C-glycosylcyclohexadienone with the anion derived from cyanophthalide, A suitable precursor to a C-glycosylcyclohexadienone, 2-(2’,3’,4’,6’-tetra-0-acetyl-|3-D-glucopyranosyl)benzyloxybenzene, was prepared via the reaction of benzoylbromoglucose with 2-benzyloxyphenylmagnesium bromide, A group of molecules were prepared by a Marschalk reaction between /ewcoquinizarin and aldehydo-sugsrs. These compounds are potential bioreductive alkylating agents in which molecular simplicity can be achieved without overly sacrificing DNA binding ability.