Singlet oxygen oxidation of olefin, aromatic, sulfide or heterocyclic substrates, including highly hydrophobic substrates, using hydrogen peroxide and metal compound catalyst in multiphase microemulsion

摘要

In the oxidation of olefin, aromatic, sulfide or heterocyclic substrates (I), using singlet oxygen in presence of a transition or rare earth metal compound catalyst (II) and 2-10 equivalents of hydrogen peroxide (H2O2), (I) is treated in a multiphase microemulsion containing (II) with 3-90% H2O2 (decomposed to singlet oxygen), comprising: an oil-in-water microemulsion in combination with an oil phase; a water-in-oil microemulsion in combination with a water phase; a microemulsion with bi-continuous water and oil phases, a water phase and an oil phase. In the oxidation of organic substrates (I), using singlet oxygen in presence of a catalyst (II) and 2-10 equivalents of hydrogen peroxide (H2O2), (I) is treated in a multiphase microemulsion containing homogeneously distributed (II) with 3-90% H2O2 so that on catalytic decomposition of H2O2 to water and singlet oxygen (I) is oxidized to the required products, where the emulsion comprises: (1) an oil-in-water microemulsion in combination with an oil phase; (2) a water-in-oil microemulsion in combination with a water phase or (3) a microemulsion with bi-continuous water and oil phases, a water phase and an oil phase. Water is optionally selectively removed from the mixture using a membrane during the reaction. (I) are selected from olefins (with 1-10 double bonds), 6-50C aromatics, polycyclic aromatics (with 2-10 aromatic rings), alkyl-, alkenyl- or aryl sulfides (mono- or disubstituted on the S-atom) or 4-50C heterocycles (containing one or more ring O-, N- or S-atoms) (optionally substituted by one or more of halo, CN, =O, OH, 1-50C alkoxy, 1-50C alkyl, 6-50C aryl, 2-50C alkenyl, 2-50C alkynyl, COOH, ester or amide groups, amino, NO2, silyl, silyloxy, sulfone or sulfoxide groups or NR1R2). (II) are based on molybdenum, tungsten, scandium, vanadium, titanium, zirconium, praseodymium, neodymium, neodymium, samarium, europium, terbium, dysprosium, holmium, erbium, ytterbium or lutetium, in the form of oxides, oxo complexes, nitrates, carboxylates, hydroxides, carbonates, chlorides, fluorides, sulfates or tetrafluoroborates. R1, R2H, 1-50C alkyl, CHO, 2-50C acyl or 7-50C benzoyl (sic); or together form a ring.