94368-15-7Relevant academic research and scientific papers
An Oxidative Ether Cleavage with p-Nitroperbenzoic Acid
Schneider, Hans-Joerg,Ahlhelm, Alfred,Mueller, Walter
, p. 3297 - 3302 (2007/10/02)
The reaction of p-nitroperbenzoic acid in chloroform with alkyl ethers (1a, 2a) leads by selective attack at C - H bonds in α-position to the ether oxygen to hemiacetals, which decompose to aldehydes and alcohols, yielding carboxylic acids.Secondary alkoxy groups as in 3a, 4a furnish Baeyer-Villiger oxidation products of initially formed ketones. Kinetic measurements with substituted benzyl methyl ethers show a Hammett reaction constant ρ = -0.9, which is in accordance with the observed relatively small discrimination between secondary and tertiary C - H bonds.The results are compared with similar hydroxylations of alkanes and with monooxygenase reactions and point to oxenoid transition states.Radical reactions as found with some alkanes are not observed, which is shown by the small amounts of nitrobenzene ( 10percent) formed during the reaction. 13C-NMR shifts of several ethers and oxidation products are reported.
