Metal Cation-Exchanged Clay-Catalyzed Organic Unit Reactions

我们利用层状结构的改性天然粘土-金属阳离子交换蒙脱土（M^<n+>-TSM）和层状结构的合成粘土-金属阳离子交换氟四硅云母（M^<n+>-TSM）对以下有机单元反应进行了催化：(1)苯酚与4-羟基丁酮-2- 1的Friedel-Crafts烷基化反应生成4-（4-羟基苯基）丁酮-2- 1（树状酮），(2)烷基苯基醚重排生成相应的烷基酚，(3)苯酚与醛和酮的芳香烷基化反应分别生成相应的双（羟基苯基）烷（双酚）和烷基酚，(4)一个简单且几乎定量的底物选择性缩醛化反应，(5)用过氧化叔丁基水溶液氧化烷烃；(6)用粘土作为布朗斯特酸，乙烯与醛的普林斯反应；(7)用粘土作为刘易斯酸，在与普林斯反应相似的条件下，分子间和分子内羰基烯的反应。在几乎所有的情况下，粘土催化剂经过过滤、洗涤和干燥后可以再生和重复使用数次。

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.