Selective Organic Synthesis using Montmorillonite Clay supported Metalloporphyrin Catalysts

1.在粘土纳米空间中合成卟啉：用1.0M硝酸水溶液在回流条件下处理蒙脱石粘土。所得的硝酸处理粘土对卟啉的合成表现出相当大的催化活性。其活性明显高于市售蒙脱土K-10催化剂。认为硝酸处理粘土中存在平均孔径接近3.0nm的介孔是导致卟啉产率大幅提高的主要原因。蒙脱石插层卟啉钴配合物催化环己烯的分子氧氧化：粘土负载的卟啉钴配合物是一种高活性催化剂，在实验条件下稳定。这可能是由于负载型催化剂对环己烯接近假定的活性钴位点的倾向。四（n -乙基-3-吡啶基）卟啉（CoTEPyP）通过固固反应嵌入十六烷基三甲基铵蒙脱石（CTA-MT）。插入物CoTEPyP/CTA-MT的基间距由na -月的1.26nm增加到2.82nm。扣除硅酸盐层厚度（0.96nm）后，CoTEPyP/CTA-MT的廊高为1.86nm。通道高度的增加表明，嵌入的卟啉阳离子可能沿垂直于蒙脱石层间层的分子平面排列。

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.