Metal Cation-Exchanged Clay-Catalyzed Organic Unit Reactions

我们进行了金属阳离子交换蒙脱土的催化应用（M^<n+>mont），具有层状结构的改性天然粘土，和金属阳离子交换的氟四云母（M^n+-TSM），一种具有层状结构的合成粘土，用于以下有机单元反应：（1）苯酚与4-羟基丁-2-酮的Friedel-Crafts烷基化以产生4-羟基丁-2-酮，（4-羟苯基）丁酮（乌藨子酮），（2）烷基苯基醚重排为相应的烷基酚，（3）苯酚与醛、酮的芳烷基化反应生成相应的偕-双羟苯基烷烃（4）一种简单的和几乎定量的底物选择性缩醛化，（5）用含水叔丁基过氧化氢氧化烷烃，（6）以粘土为Bronsted酸的苯乙烯与醛的Prins反应;（7）以粘土为刘易斯酸的分子间和分子内羰基-烯反应。在几乎所有的情况下，粘土催化剂可以再生，并在过滤，洗涤和干燥后重复使用多次。

We have carried out the catalytic use of metal cation-exchanged montmorillonite (M^<n+>mont), a modified natural clay with a layr structure, and metal cationexchanged fluorotetrasilicic mica (M^<n+>-TSM), a synthetic clay with a layr structure, for the following organic unit reactions : (1) Friedel-Crafts alkylation of phenol with 4-hydroxybutan-2-one to produce 4- (4-hydroxyphenyl) butan-2-one (raspbery ketone), (2) rearrangement of alkyl phenyl ethers to the corresponding alkylphenols, (3) aromatic alkylation of phenol with aldehydes and ketones to produce the corresponding gem-bis (hydroxyphenyl) alkanes (bisphenols) and alkylphenols, respectively, (4) a facile and an almost quantitative substrateselective acetalization, (5) alkane oxidation with aqueous tert-butyl hydroperoxide, (6) Prins reaction of stirenes with aldehydes using a clay as a Bronsted acid, and (7) inter-and intramolecular carbonyl-ene reaction using a clay as a Lewis acidunder similar condition to that of Prins reaction. In almost all cases, the clay catalyst can be regenerated and reused for several times after filtration, washing, and drying.