The reaction of thioanisole with tetraperoxomolybdate ion in comicelles of Aliquat-336 and cetyl trimethylammonium mesylate

Addition of sparingly soluble Aliquat-336 (methyl tri-n-octylammonium chloride) to cetyl trimethylammonium mesylate (CTAOMs) in two-fold molar excess generates comicelles, as shown by changes in 1H and 35Cl NMR spectra, and conformational changes in Aliquat allow it to enter the comicelles. These comicelles behave similarly to micelles and comicelles of cetylpyridinium chloride (CPyCl) as reaction media for the oxidation of thioanisole (PhSMe) mediated by tetraperoxomolybdate ion (Mo(O2)42−). Second-order rate constants in terms of local concentrations in the micellar interfacial regions are consistently lower than second-order rate constants in H2O-t-BuOH (7:3, v/v) and are slightly lower in micelles and comicelles of CTAOMs than in those of CPyCl. In some conditions sodium “percarbonate” (Na2CO3, 1.5 H2O2) can replace hydrogen peroxide (H2O2), although this system was not examined quantitatively.