Pillared bentonites were found to be efficient catalysts for the O-methyl bond cleavage of anisoles (e.g., m-methylanisole, guaiacol, and creosol) under very mild, static conditions (150°C, a few hours, inert atmosphere). The O-methyl bond cleavage led to phenolic products. Gas chromatographymass spectrometry and solid-state 13C nuclear magnetic resonance (NMR) techniques used to probe 13C-labeled anisoles revealed that dealkylation and transalkylation reactions occurred to a large extent, and that conversion was efficient at >95% after two days. Ortho- and para-isomers were observed exclusively, without any evidence of meta-substitution. Volatile products were determined by mass spectrometry to be 13CH3OH and (13CH3)2O. Magic-angle spinning 13C NMR experiments showed that the molecules were fairly mobile in the clay micropores prior to catalysis. After catalysis, cross-polarization NMR showed that molecular motion had decreased markedly. Ultraviolet-visible spectroscopy of the colored complexes suggested some quinone formation. The trend of clay reactivity was found to be: pillared bentonite ≫ acid-washed montmorillonite > untreated bentonite > pillared fluorhectorite ≃ untreated fluorhectorite.

Phenol (benzenol) oxidation by three synthetic manganese oxides (buserite, manganite, and feitknechtite) has been studied in aerated, aqueous, acidified suspensions. The rate of reaction was pH dependent. Oxidation was greatly enhanced below pH 4, when diphenoquinone and p-benzoquinone were identified as the first products. Initial reaction rate was correlated with standard reduction potential (E°) of the oxides following the order: feitknechtite > manganite > buserite. A more gradual process of phenol oxidation after the initial reaction was influenced by electrochemical properties of the solution. High soluble manganese activity and increase in pH adversely affected reaction rates. Thus, the reactivity of the oxides was related to their stability and possibly the ability to readsorb Mn(II), following the order: buserite > manganite > feitknechtite. The results indicate that thermodynamic and electrochemical data for oxides and phenols are useful in predicting under which conditions phenols can be oxidized by a given system.