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Development of Practical Catalysts by an Efficient Integration of A Dynamic Bifunctional Catalyst and Supercritical Fluid Chemistry

通过动态双功能催化剂和超临界流体化学的有效集成开发实用催化剂

基本信息

批准号：
14078209
负责人：
IKARIYA Takako
金额：
$ 30.08万
依托单位：
Tokyo Institute of Technology
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research on Priority Areas
财政年份：
2002
资助国家：
日本
起止时间：
2002 至 2005
项目状态：
已结题

项目摘要

Highly efficient catalytic reaction processes have been developed by a combination of the conceptually new bifunctional catalysts and unique reaction media, supercritical fluids.1. Development of Chiral Bifunctional Molecular Catalysts for Asymmetric C-C Bond Formation : A conceptually new chiral bifunctional transition metal-based molecular catalyst promoted the enantioselective C-C bond formation has been developed. Asymmetric Nicahel reactions with chiral amide complexes proceeds smoothly to give the corresponding chiral adducts with high atom economy and high ee. The present bifunctional molecular catalyst offers a great opportunity to open up new fundamentals for stereoselective transformation including enantioselective C-H and C-C as well as C-N and C-0 bond formation.2. Double Stimuli-Responsive Behavior of Aliphatic Poly(urethane-amine) Copolymers Prepared from 2-Methylaziridine and Supercritical Carbon Dioxide : A reaction of aziridines and carbon dioxide proceeds under superc … More ritical conditions to give random copolymers containing urethane and amine moieties. The resulting copolymeric products obtained from 2-methylaziridine and carbon dioxide exhibit sharp and rapid phase transitions in response to both temperature and pH. The responsive property can be controlled by the reaction conditions under supercritical state.3. Continuous Chemoselective Methylation of Functionalized compounds with Supercritical Methanol over Mulitifunctionalized Solid Catalysts : The chemoselective methylation of phenols and ethanol amine with supercritical methanol over the metal oxide catalysts has been successfully developed using a continuous flow fixed bed reactor. Methylation of phenols over the bifunctional catalyst, Cs-P-Si, having both very weak acidic and basic sites, gives selectively the 0-methylation products, while the weaker acid-base bifunctional catalyst ZrO_2 provids mainly C-methylation products. Whilst, the methylation of aminoalcohols over the Cs-P-Si mixed oxide produces preferentially N-methylated products. The chemoselective outcome of the reaction is highly influenced by the acid-base character on the solid catalysts under supercritical conditions and the nature of the supercritical fluids. Less

高效的催化反应过程已经通过概念上新的双功能催化剂和独特的反应介质，超临界流体的组合而发展。不对称C-C键形成的手性双功能分子催化剂的开发：开发了一种概念上新的手性双功能过渡金属基分子催化剂，促进了对映选择性C-C键的形成。手性酰胺配合物的不对称Nicahel反应可以顺利进行，得到高原子经济性和高ee值的手性加成物，该双功能分子催化剂为立体选择性转化提供了新的基础，包括C-H和C-C以及C-N和C-O键的形成.由2-甲基氮丙啶和超临界二氧化碳制备的脂肪族聚（氮丙啶-胺）共聚物的双重刺激响应行为：氮丙啶和二氧化碳在超临界二氧化碳下的反应 ...更多信息临界条件，得到含有氨基甲酸酯和胺部分的无规共聚物。由2-甲基氮丙啶和二氧化碳得到的共聚物产物对温度和pH值都有明显的响应，其响应性可以通过超临界状态下的反应条件来控制.多功能化固体催化剂上功能化化合物与超临界甲醇的连续化学选择性甲基化反应：利用连续流动固定床反应器，成功地开发了金属氧化物催化剂上苯酚和乙醇胺与超临界甲醇的化学选择性甲基化反应。双功能催化剂Cs-P-Si具有很弱的酸性和碱性，选择性地生成O-甲基化产物，而较弱的酸碱双功能催化剂ZrO_2主要生成C-甲基化产物。而氨基醇在Cs-P-Si混合氧化物上的甲基化优先产生N-甲基化产物。反应的化学选择性结果受超临界条件下固体催化剂上的酸碱性质和超临界流体的性质的高度影响。少