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

具有均匀孔结构的介孔硅（MS）成功制备了。化学活性基，例如氨基丙基，辛基和环己基基团分别锚定在MS表面上，分别为MS-NH2，MS-C8和MS-EP。还获得了框架结构中的介孔有机物，包括乙烯链，氨基丙基，硫醇和吡啶基团（分别为MOS-EY，MOS-NH2，MOS-SH，MOS-SH和MOS-PY）。通过使用这些样品进行了以下研究。1。乙醛对MS-NH2上的吸附：乙醛的刺激性通过氨基丙基基团的锚定极大地改善。特别是，在MS-NH2中，低浓度下的刺激性增加，孔径较窄。 1 nm.2。表面稳定性和疏水/氢电输液控制：MS-C8暴露的疏水性特征。 MS-EP表现出比MS的亲水性更多，而在吸水后稳定保留了孔结构。 MOS-EY是疏水性的，并且暴露了……烷烃蒸气的OD吸附性更高。3。通过氧化MOS-SH的氧化位点形成：MOS-SH表面上的硫醇基团通过氧化处理转化为磺酸酸的一（-SO_3H）。 Solid acidity of the MOS-SO_3H Characterized by ammonia adsorption microcalorimetry was comparable to that of aluminumisolicate 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用于催化性不对称环丙谁反应的固体催化剂。在重氮酯和烷烃的催化不对称环丙烷化反应中，该反应在水相和两个相的Pybox/Ru（II）催化剂中成功进行，以使相应的环丙基植物以及超过95％的对照率进行。此外，在333K的333K上，在333K上支持Mos-Py催化的Sonogashira偶联反应的单羟唑啉基苯基（Phemox）/钯络合物在333K上催化了Sonogashira偶联反应。在MOS-PY上支持的Phemox/PD催化剂的效率几乎与非支撑催化剂相同。较少的