Saturated alcohols, reaction with manganese dioxide

Nickel peroxide is a solid, insoluble oxidant prepared by reaction of nickel (II) salts with hypochlorite or ozone in aqueous alkaline solution. This reagent when used in nonpolar medium is similar to, but more reactive than, activated manganese dioxide in selectively oxidizing allylic or acetylenic alcohols. It also reacts rapidly with amines, phenols, hydrazones and sulfides so that selective oxidation of allylic alcohols in the presence of these functionalities may not be possible. In basic media the oxidizing power of nickel peroxide is increased and saturated primary alcohols can be oxidized directly to carboxylic acids. In the presence of ammonia at —20°, primary allylic alcohols give amides while at elevated temperatures nitriles are formed. At elevated temperatures efficient cleavage of a-glycols, a-ketols... 

Acetaldehyde—Acetic aldehyde—Acetyl hydrid——44 —is formed in all reactions in which alcohol is deprived of H without introduction of O. It is prepared by distilling from a capacious retort, connected with a well-cooled condenser, a mixture of HjSOj, 6 pts. HgO, 4 pts. alcohol, 4 pts. and pow dered manganese dioxid, G pts. The product is redistilled from calcium ehlorid below 50° (123° P.). The second distillate is mixed with two volumes of ether, cooled by a freezing mixture, and saturated with dry NHg there separate crystals of ammonium acetylid, CgHiO, NHi, -which are -washed with ether, dried, and decomposed in a distilling apparatus, over the water-bath, with tho proper quantity of dilute HjS04 the distillate is finally dried over calcium ehlorid and rectified below 35° (95° P.). 

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