Reactions of ketene acetals—IX: The synthesis of naphthoquinones from benzoquinones

Halogenobenzoquinones react with ketene acetals and give benzofurans, but in the presence of acetic acid, naphthoquinones are produced in variable yields. Some aspects of the reaction have been studied and the method has been applied to the synthesis of useful intermediates and of derivatives of some naturally occurring naphthoquinones such as tri-O-methylflaviolin 20 and tetra-O-methylspinochrome B23. Benzoquinones also react with conjugated ketene acetals without acid catalysis, providing convenient syntheses of ramentaceone 43, O-methylstypandrone 45 and 1,3,6,8-tetramethoxyanthraquinone 34.