Selective Organic Synthesis using Montmorillonite Clay supported Metalloporphyrin Catalysts

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1.Porphyrin Synthesis in Clay Nanospaces : Montmorillonaite clays were treated with 1.0M nitric acid aqueous solution under reflux conditions. The resulting nitric acid-treated clays exhibited considerable catalytic activity for porphyrin synthesis. Its activity was significantly higher than that of a commercial available montmorillonite K-10 catalyst.It was considered that a great increase in the porphyrin yield is due to the presence of mesopores with the average pore diameter of nearly 3.0nm in nitric acid-treated clays.2.Oxidation of Cyclohexene with Molecular Oxygen catalyzed by Cobalt Porphyrin Complexes intercalated into montmorillonaite : It was found that clay supported cobalt porphyrin complexes are highly active catalysts which are stable under the experimental conditions. This is probably due to a prefered orientation of the supported catalyst for an approach of the cyclohexene to the presumed active cobalt site.3.Intercalation of Cobalt Porphyrin Complexes into Alkylammonium-Exchanged Swelling Layred Silicates : Intercalation of cobalt tetra- (N-ethyl-3-pyridyl) porphyrin (CoTEPyP) into cetyltrimethy lammonium-montmorillonaite (CTA-MT) was carried out by solid-solid reactions. The basal spacing of the intercalation compound (CoTEPyP/CTA-MT) increased to 2.82nm from 1.26nm of Na-mont. The gallery height of CoTEPyP/CTA-MT was 1.86nm when the thickness of silicate layrs (0.96nm) was subtracted. This increase in the gallery hight was suggested that the intercalated porphyrin cations were possibly arranged with the molecular plane perpendicular to the interlamellar layrs of monmorillonite.