process for the preparation of an oxidizing agent and peroxide based nickel and its use for the selective oxidation of unsaturated alcohols

摘要

1430704 Oxidation of unsaturated alcohols F HOFFMANN-LA ROCHE & CO AG 10 April 1974 [11 April 1973] 15882/74 Heading C2C [Also in Division C1] Nickel peroxide oxidizing agent is made by treating nickel oxide deposited on a fine freeflowing carrier (e.g. graphite of particle size 44-230 microns) with an alkali metal or alkaline earth metal hypohalite or persulphate in an aqueous alkaline medium. The nickel oxide may be deposited on the carrier by forming an aqueous mixture containing a water-soluble nickel salt and the carrier and treating the mixture with alkali (e.g. alkali metal or alkaline earth metal hydroxide). The aqueous mixture may be optionally formed by treating a waterinsoluble nickel salt (e.g. nickel carbonate) with an aqueous acid (e.g. a mineral acid or a lower C 1 -C 4 alkanoic acid). The nickel peroxide oxidizing agent so prepared may be used for the selective oxidation of unsaturated alcohols to carbonyl compounds (e.g. vitamin A alcohol to its aldehyde, geraniol to citral, codeine to codeinone). A range of allylic and benzylic alcohols which may be oxidized is listed.