Aliphatic primary, secondary, and tertiary alkyl hydroperoxides rearrange in 60-98% H2S04 at 25°. With tertiary alcohols, the hydroperoxides can be generated in situ and the conversion of tertiary cycloalkanols to -hydroxy ketones is an excellent synthetic reaction with yields of >90%. A novel degradation of primary alcohols to their next lower homolog is developed. The migratory aptitudes propyl « > ethyl » methyl were found. Solutions of K2S20s (effectively HiSCX) in 20-60% H2S04 are advantageous for the Baeyer-Villiger oxidation of ketones. Yields are quantitative and differences in migratory aptitudes are as large as or larger than those found with other peraeids.Migrations to electron deficient oxygen have been extensively studied in connection with the Criegee solvolysis of peresters,1-6 the Baeyer-Villiger oxidation of ketones,3-9 and the rearrangement of benzylic hydroperoxides.3-6•8 All three of these reactions can be considered as 1,2 alkyl or aryl shifts in RO+, though there is ample evidence that the reactions are concerted and that RO + is never a true intermediate.

Xanthene reacts with O2 in 45-96x H2SO4 to produce 2 mol of xanthyl cation/mol of 02. The reaction is first order in xanthene and first order in H + activity. The existence of simple acid catalysis is interpreted as due to an interaction between H+ and 0 2 to form kinetically significant amounts of the hydroperoxy cation, H02+. ualitative observations' had indicated that the oxi-

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Hydroperoxide von primären, sekundären und tertiären Alkoholen werden mit konz. Schwefelsäure behandelt und hierbei verschiedene Umlagerungsreaktionen beobachtet, die z.Tl. angegeben sind und in ihrem Mechanismus diskutiert werden.

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