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Functionalization of Mesoporous Silica Surface by Anchoring of Chemically-active Groups and Applications to Precise Organic Synthesis

通过锚定化学活性基团实现介孔二氧化硅表面的功能化及其在精密有机合成中的应用

基本信息

批准号：
14350426
负责人：
TSUTSUMI Kazuo
金额：
$ 8.51万
依托单位：
Toyohashi University of Technology
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (B)
财政年份：
2002
资助国家：
日本
起止时间：
2002 至 2004
项目状态：
已结题

项目摘要

Mesoporous silicas(MS) with uniform pore structure were successfully prepared. Chemical active groups such as aminopropyl, octyl, and epoxycyclohexyl groups were anchored on MS surfaces, designated as MS-NH2,MS-C8 and MS-ep, respectively. Mesoporous organosilicas including ethytene chains, aminopropyl, thiol and pyridinium groups in the framework structures were also obtained (abbreviated as MOS-Ey,MOS-NH2,MOS-SH and MOS-Py, respectively). The following researches were performed by use of these samples.1.Acetaldehyde adsorption on MS-NH2 : The sorptivity of acetaldehyde was drastically improved by the anchoring of aminopropyl groups. Especially, the sorptivity at low concentration increased in MS-NH2 with narrower pore sizes of ca. 1 nm.2.Surface stability and hydrophobe/hydrophile control : MS-C8 exhibited hydrophobic character. MS-Ep showed more hydrophilic character than MS, while the pore structure stably retained after water sorption. MOS-Ey was rather hydrophobic and exhibited go … More od sorptivity for alkane vapor.3.Acid sites formation by oxidation of MOS-SH : Thiol groups on MOS-SH surface were converted to sulfonic acid ones (-SO_3H) by an oxidation treatment. Solid acidity of the MOS-SO_3H characterized by ammonia adsorption microcalorimetry was comparable to that of aluminosilicate zeolites.4.Application to organic synthesis : We found that asymmetric 2,6-bis(oxazolinyl)pyridine(pybox)/ruthenium catalyst was adsorbed on silica such as MS and MS-NH2 and acted as solid-supported catalyst for a catalytic asymmetric cyclopropanation reaction. In the case of catalytic asymmetric cyclopropanation reactions of diazoester and alkenes, the reaction was successfully proceeded with pybox/Ru(II) catalyst in both water phase and two phases to give the corresponding cyclopropylesters along with over 95% enantioselectivities. Furthermore, monooxazolinylphenyl (phemox)/palladium complexes supported on MOS-Py catalyzed Sonogashira coupling reactions of iodonitrobenzene and ethynybenzene derivatives at 333K without any other co-catalysts such as CuI. The efficiency of phemox/Pd catalyst supported on MOS-Py was almost same as the non-supported catalyst. Less

成功制备了孔结构均匀的介孔氧化硅。化学活性基团如氨丙基、辛基和环氧环己基被锚定在MS表面上，分别命名为MS-NH 2、MS-C8和MS-ep。还获得了在骨架结构中包含乙烯链、氨丙基、硫醇和吡啶鎓基团的介孔有机二氧化硅（分别缩写为MOS-Ey、MOS-NH 2、MOS-SH和MOS-Py）。1.乙醛在MS-NH_2上的吸附：氨丙基的锚定大大提高了乙醛的吸附性能。特别是在低浓度下，吸附剂在MS-NH 2中的吸附能力随着孔径的减小而增加。2.表面稳定性和疏水/亲油控制：MS-C8表现出疏水特性。MS-Ep比MS具有更好的亲水性，但吸水后孔结构保持稳定。MOS-Ey是相当疏水的，并且表现出去 ...更多信息 3.氧化形成的酸中心：氧化处理使MOS-SH表面的巯基转化为磺酸基（-SO_3H）。4.在有机合成中的应用：我们发现不对称2，6-二（恶唑啉基）吡啶（pybox）/钌催化剂被吸附在硅胶（如MS和MS-NH 2）上，并作为固载催化剂用于催化不对称环丙烷化反应。对于重氮酯和烯烃的催化不对称环丙烷化反应，在Pybox/Ru（II）催化剂上，在水相和两相体系中都成功地进行了反应，得到了相应的环丙酯，沿着大于95%.此外，在333 K下，在没有CuI等助催化剂的情况下，单恶唑啉苯基（phemox）/钯（Pd/MOS-Py）配合物催化碘代硝基苯和乙炔苯衍生物的Sonogashira偶联反应。以MOS-Py为载体的phemox/Pd催化剂的催化效率与未负载的催化剂几乎相同。少