ナノ空間反応メディアによる炭素結合形成反応制御法の開発

利用纳米空间反应介质开发碳键形成反应控制方法

• 批准号: 10132209
• 负责人: 尾中 篤
• 金额: $ 1.6万
• 依托单位: The University of Tokyo
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research on Priority Areas (A)
• 财政年份: 1998
• 资助国家: 日本
• 起止时间: 1998 至 无数据
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-10132209/
• 关键词: ナノ空間; 反応場; 固体酸; ハニカム構造アルミノシリケート; Diels-Alder反応; ゾル-ゲル法; シクロペンタンジエン; アクリル酸メチル

本研究ではナノメートル領域の細孔と固体酸性を合わせ持つメソ多孔体アルミノシリケートが,酸性反応場として有用であることを明らかにするために,Diels-Alder反応に焦点を当てた.まず,固体酸性を示すナノ空間触媒は,テトラエトキシシランとトリイソプロポキシアルミニウムの混合物を出発物質,第一級アミンを鋳型剤とするゾル-ゲル法により,ハニカム骨格アルミノシリケート(AI-H MS)を調製した.モデルDiels-Alder反応として,反応性が比較的低く,副反応であるジエン,ジエノフィル自身の重合反応が起こりやすい,シクロペンタジエンとアクリル酸メチルの組合せを選んだ.均一系ルイス酸であるBF_3・OEt_2を用いると,生成物の立体選択性は高いものの,副反応の重合反応が優先し,Diels-Alder付加物の収率は低かった.これに対して,本研究で開発したAl-HMS触媒は,反応速度が速く且つDiels-Alder付加物の収率が高く,重合副生物が少なく,更に立体選択性も高いという理想的な触媒性能を示すことがわかった.Al-HMSに含まれるAlの含有量が多いほど触媒活性が高く,Si/Al比が7の時最大収率を与えた.しかしさらにAl含有量を増やすと,ハニカム構造がくずれて,逆に収率が低下した.また,鋳型剤のアルキル鎖が長いほど活性は向上し,ヘキサデシルアミンを用いて合成されたAl-HMSが最高活性を示した.ハニカム構造のAl-HMSがDiels-Alder反応用触媒として優れている理由は,細孔径が約25オングストロームと大きく,反応基質が細孔内を自由に拡散できること,固体酸性発現の要因となるアルミニウムが高分散でしかも高濃度で組み込まれていること,および細孔空間が生み出す極性環境により,極性を帯びたDiels-Alder反応遷移状態が安定化されること,などの相乗効果であると考えられる.

The purpose of this study is to analyze the characteristics of the porous materials in the field, the solid acid concentration in the porous body, the acid concentration in the porous body and the acid field in this study. The solid acid indicates that the space catalyst is used, the mixture of the solid acid and the solid acid is out of the mixture, and the first-stage temperature is used for the determination of the space catalyst. the solid acid indicates that the space catalyst is sensitive, the solid acid indicates that the space catalyst is used, and the mixture is released. The first stage is the first stage, and the bone structure is used. The temperature (AI-H MS) is determined. You need to know that the Diels-Alder is low, and that you have a low sex ratio, and that you have a problem with each other, and that you have a problem with each other. The homogenized BF _ 3 ·OEt _ 2 is used in homogenization, the product is stereoselective, the product is highly selective, the sub-product is coincident, and the addition rate of Diels-Alder is low. In this study, we developed an Al-HMS catalyst with high speed and high loading rate of Diels-Alder. The performance of the ideal catalyst with high selectivity, high concentration of Al and high concentration of Al in this study showed that the activity of the catalyst was high, and the maximum activity of the catalyst was high when the Si/Al ratio was 7. The content of Al is low, and the reverse rate is low. The highest activity of Al-HMS is shown by the synthesis of the highest activity. The reason for the use of the catalyst for the anti-Al-HMS Diels-Alder is that the aperture is about 25 kHz, and that the temperature in the hole is free to disperse, and the solid acid solution is due to the high dispersion temperature, the high dispersion temperature and the environmental pollution in the air space. Sex, Diels-Alder, anti-stabilization, stability, stability, stability and stability.

项目成果

Makoto Onaka: "Catalysis by Solid Acid : Selective Diels-Alder Reactions Promoted by Mesoporous Aluminosilicates Having Honeycomb-like Openings in Nanometer Dimensions" Macroporous Mater. (1999)

Makoto Onaka：“固体酸催化：纳米尺寸蜂窝状开口的介孔铝硅酸盐促进选择性狄尔斯-阿尔德反应”大孔材料。