Metal Cation-Exchanged Clay-Catalyzed Organic Unit Reactions

金属阳离子交换粘土催化有机单元反应

• 批准号: 07555279
• 负责人: UEMURA Sakae
• 金额: $ 1.6万
• 依托单位: KYOTO UNIVERSITY
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (A)
• 财政年份: 1995
• 资助国家: 日本
• 起止时间: 1995 至 1996
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-07555279/
• 关键词: montmorillonite; clay-catalyst; catalytic organic reaction; environmentally benign; Friedel-Crafts reaction; aromatic alkylation; acetalization; alkane oxidation; フリーデル-クラフツ反応; 核アルオル化; 雲母; フリーデル・クラフツ型反応; プリンス反応; アセタール化; 転位反応

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.

我们进行了金属阳离子交换蒙脱石的催化利用（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。

项目成果

Uemura, S.: "Ce^<3+>Exchanged Montmorillonite as a Useful Substrate-Selectire Acetalization Catalyst" J. Org. Chem.60. 4039-4043 (1995)

Uemura, S.：“Ce^<3>交换蒙脱土作为有用的底物选择性缩醛化催化剂”J. Org。

S.Uemura 他 2名: "Cation-Exchanged Fluorotehasilicic Mica-Catalysed Oxidation of Alkanes with t-BuDOH" Journal of Chemical Society Perhin Trans.2. 8. 2013-2017 (1995)

S. Uemura 和其他 2 人：“Cation-Exchanged Fluorotehasilicic Mica-Catalysed Oxidation of Alkanes with t-BuDOH” Journal of Chemical Society Perhin Trans.2. 8. 2013-2017 (1995)

S.Uemura 他 4名: "Cation-Exchaugcol Mont-Catalyzed Facile Friedel-Crufts Alkylation of Hydroxy and Methexy Aromahes" Journal of Organic Chemistry. 59. 5901-5904 (1994)

S. Uemura 和其他 4 人：“羟基和 Methexy Aromahes 的阳离子-Exchaugcol Mont-Catalyzed Facile Friedel-Crufts 烷基化”有机化学杂志 59. 5901-5904 (1994)。

S.Uemura et al.: "Cation-Exchanged Fluorotetrasilicic Mica-Catalyzed Oxidation of Alkanes with t-BuOOH" J.Chem.Soc., Perkin Trans. 2, No.8. 2013-2017 (1995)

S.Uemura 等人：“阳离子交换氟四硅云母-用 t-BuOOH 催化烷烃氧化”J.Chem.Soc.，Perkin Trans。

S.Uemura et al.: "Cation-Exchanged Mont-Catalyzed Prins Reaction" Bull.Chem.Soc., Jpn.69. 2361-2368 (1996)

S.Uemura 等人：“Cation-Exchanged Mont-Catalyzed Prins Reaction”Bull.Chem.Soc.，Jpn.69。