A series of "Balanced Catalytic Surfactants" (BCS) [(Cn)2N(C1)2]2MoO4 (n = 8, 9, 10, 12) based on amphiphilic double-tailed quaternary ammonium with molybdate as a counterion has been developed for the dark singlet [4 + 2] cyclooxygenation of organic substrates in three-liquid-phase microemulsion systems. These cationic surfactants form three-liquid-phase microemulsion systems at room temperature in the presence of an appropriate organic solvent and water without addition of any cosurfactant or electrolyte. Comparative peroxidation of rubrene points out the specific advantages of these three-phase media over phase transfer catalysis in two phase systems and on conventional one-phase microemulsions based on sodium molybdate: (i) only three constituents, (ii) low amounts of surfactants, (iii) insensitivity to water dilution, (iv) fast separation of the three phases, (v) straightforward recovery of the product and the surfactant from the oil and microemulsion phases, respectively. The preparative peroxidation of alpha-terpinene and 1,4,5-trimethylnaphtalene was performed in the ternary systems [(C8)2N(C1)2]2MoO4/water/tert-butyl acetate or benzene. The reusability of the catalyst, the catalytic nature of the BCS, and the ability of the systems to oxidize poorly reactive substrates were demonstrated showing the broadness of the applicability of such systems.
A new gemini surfactant phase transfer catalyst, namely diethyl-ether-a,v-bis-(dimethyldodecylammonium molybdate) codified as 12-EO-12-Mo, was prepared by anion exchange from the analogous gemini dichloride (12-EO-12-Cl 2 ). The physico-chemical properties of these compounds such as Krafft temperature, critical micelle concentration, surface activity and binary water-surfactant behavior were compared and the influence of the molybdate counterion was examined. Though both compounds are highly hydrophilic, the cmc of 12-EO-12-Mo (0.4 mmol L S1 ) is about five times lower than of its dichloride analogue (2.2 mmol L S1 ). Moreover, 12-EO-12-Mo exhibits an additional cubic liquid crystal phase between 53 and 64 wt%. The usefulness of 12-EO-12-Mo as an amphiphilic phase transfer catalyst for the dark singlet oxygenation was demonstrated with the peroxidation of two typical organic substrates: a-terpinene which reacts with 1 O 2 according to a [4 R 2] cycloaddition and the less reactive b-citronellol, which provides two hydroperoxides according to the ene-reaction. 12-EO-12-Mo provides a simple reaction medium with only three components for the preparative peroxidation of hydrophobic substrates by chemically generated singlet oxygen.
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