Sisal-Derived Acid-Char Molybdenum Catalyst for Reductive Deoxygenation of Sulfoxides

Abstract

The deoxygenation of sulfoxides is a rather important reaction from both synthetic and biological points of view, due to the potential of sulfides as intermediates in a variety of processes. Homogenous Mo-based catalysts successfully perform the reduction of diphenyl sulfoxide to diphenyl sulfide with high yields but present the well-known limitations regarding recovery and recycling. Thus, in the present work, two new composite materials were prepared through the immobilization of molybdenum compounds [MoO2Cl2(H2O)2] and Na2MoO4·2H2O, onto sisal-derived acid-char (S13.5), obtained from rope industry wastes by acid-mediated carbonization. The heterogenous Mo-based materials were characterized by IR spectroscopy, elemental analysis, ICP, solid state NMR, XPS, and SEM, and were evaluated as catalysts for the reduction of sulfoxides to sulfides in the presence of phenylsilane as reducing agent under different reaction conditions. The influence of various experimental parameters, including reducing agent type and amount, solvent type, and acid promoter were investigated. Catalytic studies revealed that both catalysts deoxygenate sulfoxides at 120 °C in toluene solution with high yields (up to 97%). The MoO2Cl2 derived catalyst shown to be highly efficient in the reduction of diaryl, alkylaryl, dibenzyl, and dialkyl sulfoxides to the corresponding sulfoxides using phenylsilane as reductant and no need of acid promoter.

Keywords: Sisal, Acid-mediated carbonization, Molybdenum complexes, Immobilized heterogeneous catalysts, Deoxygenation, Sulfoxide reduction