Metal Cation-Exchanged Clay-Catalyzed Organic Unit Reactions

我们进行了金属阳离子交换蒙脱石(M^&lt；n+&gt；mont)，一种具有层状结构的改性天然粘土和金属阳离子交换氟四硅云母(M^&lt；n+&gt；-TSM)，一种具有层状结构的合成粘土，用于下列有机单元反应：(1)苯酚与4-羟基丁烷-2-酮的Friedel-Craft烷基化反应生成4-(4-羟基苯基)丁烷-2-酮，(2)烷基苯基醚重排为相应的烷基酚，(3)苯酚与醛和酮的芳香烷基化反应，分别产生相应的宝石-双(羟基苯基)烷烃(双酚)和烷基酚，(4)一种简便的和几乎定量的底物选择性的乙酰化反应，(5)用叔丁基氢过氧化氢水溶液氧化烷基(6)以粘土为B酸的二茂铁与醛的Prins反应；(7)以粘土为Lewis酸的分子间和分子内的羰基-烯反应。在几乎所有的情况下，粘土催化剂经过过滤、洗涤和干燥后都可以再生和重复使用几次。

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.