Development of the enantioselective solid catalyst with high enantioselectivity

高对映选择性固体催化剂的研制

• 批准号: 16550094
• 负责人: OSAWA Tsutomu
• 金额: $ 2.05万
• 依托单位: University of Toyama
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 2004
• 资助国家: 日本
• 起止时间: 2004 至 2005
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-16550094/
• 关键词: Tartaric acid; Modified nickel catalyst; Enantioselective solid catalyst; Surface coverage; Modifier

Enantioselective solid catalyst is important for the syntheses of optically active compounds, which are important for the intermediates for the farmaceuticals or agrochemicals. This study aims at the development of the enantioselective solid catalyst with a high enantioselectivity and its high durability in the repeated use of the recovered catalyst. In this study, enantioselective catalyst was prepared by adsorbing (R,R)-tartaric acid and NaBr on a nickel surface (this process is called modification). Two types of modification methods have been developed, that is i)pre-modification (nickel catalyst is soaked in a solution of (R,R)-tartaric acid and NaBr, is washed by water, methanol and THF, and then uses for the hydrogenation reaction), and ii)in-situ-modification ((R,R)-tartaric acid and NaBr are added to the reaction media). The type of methods significantly influence the enantioselectivity and its durability.In this study, for comparing the features of the pre-modification and tho … More se of the in-situ-modification, effects of the pre-modification conditions in an aqueous solution and in an organic solvent were investigated. As the base nickel catalyst, reduced nickel was used. The reduced nickel was prepared by the reduction of nickel oxide (commercially available one or one prepared by the decomposition and calcinations of nickel hydroxide at 773 K or 1373 K) in a hydrogen stream. As a results, for the modification in an aqueous solution, the modified reduced nickel catalyst prepared from nickel oxide calcined at 1373 K gave the highest enantioselectivity of 88%. The coverage of tartaric acid and Br^- on the catalyst surface was 25% and 13%, respectively. The modified reduced nickel prepared from nickel oxide calcined at 773 K gave the enantioselectivity of 50%. The coverage of tartaric acid and Br^- on the surface was 17% and 16%, respectively. On the other hand, for the modification in an organic solvent (THF), it was revealed that the modification at a high temperature (373 K in an autoclave) and a high hydrogen pressure (9 MPa) were mandatory for attaining a high enantioselectivity and its high durability. In this case, the coverage of tartaric acid and Br^- on the surface was 30% and 38%, respectively. From these results, the coverage of tartaric acid on the surface, which was reported as a crucial factor for attaining a high enantioselectivity in the literature, was not the only factor for determining the enantioselectivity and the durability. The surface of nickel (the type of base nickel) was also very important for determining the enantioselectivity. It was also revealed that a high coverage of Br^- was important, especially for attaining a high durability of the enantioselectivity. Less

对映选择性固体催化剂对于光学活性化合物的合成很重要，这对于中间体对于农生或农化学物质很重要。这项研究旨在开发具有较高的对映选择性的对映选择性固体催化剂，并在反复使用恢复的催化剂中的高耐用性。在这项研究中，通过在镍表面上吸附（R，R） - tart酸和NABR来制备对映选择性催化剂（此过程称为修饰）。已经开发了两种类型的修饰方法，即i）i）修饰（将镍催化剂浸泡在（R，R） - tartaric Acid和NABR的溶液中，用水，甲醇和THF洗涤，然后用来用于氢化反应），以及II），II）在situ sodification中添加了 - （R，R）-tartaric Acid and Nabric Acid and reaction nabir sybire nabir sybire nabr sybir s re反应媒体。方法的类型显着影响对映选择性及其耐用性。在这项研究中，研究了在水溶液中和有机溶液中进行预修饰条件的影响的更多SE。作为基础镍催化剂，使用了还原镍。还原镍是通过在氢水中的氧化镍氧化镍（以773 K或1373 K为单位的分解和钙钙化制备）来制备的。结果，对于在水溶液中的修饰，由1373 K钙化的镍氧化镍制备的改性还原镍催化剂的对映选择性最高为88％。在催化剂表面上的tart酸和Br^的覆盖率分别为25％和13％。从773 K处钙化的镍氧化镍制备的改性还原镍给出了50％的对映选择性。地表上tart酸和Br^的覆盖率分别为17％和16％。另一方面，对于有机溶液（THF）进行的修饰，据揭示了在高温下（高压釜中的373 K）和高氢压（9 MPa）的修饰是具有高较高的对映选择性及其高耐用性的强制性的。在这种情况下，表面上的tart酸和br^的覆盖率分别为30％和38％。从这些结果来看，tart酸在表面上的覆盖范围是在文献中获得高对映选择性的关键因素，这并不是确定对映选择性和耐用性的唯一因素。镍表面（碱镍的类型）对于确定对映选择性也非常重要。还揭示了Br^的高覆盖范围很重要，尤其是对于获得对映选择性的高耐用性。较少的

项目成果

Enantio-differentiating hydrogenation of methyl acetoacetate oven reduced nickel catalysts pre-modified in methanol

甲醇中预改性的乙酰乙酸甲酯烘箱还原镍催化剂的对映异构加氢

• 发表时间: 2005
• 期刊: Catalysis Letters 102
• 作者: T.Osawa;S.Oishi;M.Yoshihisa;M.Megawa;T.Harada;O.Takayasu
• 通讯作者: O.Takayasu

Enantio-differentiating hydrogenation of methyl acetoacetate over reduced nickel catalysts pre-modified in methanol

甲醇预改性还原镍催化剂上乙酰乙酸甲酯的对映异构加氢

• 发表时间: 2005
• 期刊: Catalysis Letters 102
• 作者: Tsutomu Osawa;Sinobu Oishi;Masako Yoshihisa;Miho Maegawa;Tadao Harada;Osamu Takayasu
• 通讯作者: Osamu Takayasu

Modification method studies for the preparation of tartaric acid-NaBr-modified nickel catalyst for the enantio-differentiating hydrogenation of methyl acetoacetate

酒石酸-溴化钠改性乙酰乙酸甲酯对映异构加氢镍催化剂的制备方法研究

• 发表时间: 2006
• 期刊: Stud.Surf.Sci.Catal (in press)
• 作者: Tsutomu Osawa;Mika Kobayashi;Miho Maegawa;Masako Yoshihisa;Tadao Harada;Osamu Takayasu
• 通讯作者: Osamu Takayasu