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Organic Synthesis in Water Utilizing Inorganic Porous Materials

利用无机多孔材料在水中进行有机合成

基本信息

批准号：
15350057
负责人：
MINAKATA Satoshi
金额：
$ 9.41万
依托单位：
Osaka University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (B)
财政年份：
2003
资助国家：
日本
起止时间：
2003 至 2005
项目状态：
已结题

来源：
https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-15350057/
关键词：
Green Chemistry Environmentally Organic Synthesis Organic Synthesis in Water Inorganic Porous Materials Silica Gel Aziridines Water Soluble Nucleophiles Ring Opening Reaction チアゾリジン水 MCM-41 オレフィンクロラミンT

项目摘要

Although the use of PTC to permit the reaction in aqueous media is a general method, an alternative potential process in water was devised, based on the adsorptive nature of silica gel. While the application of silica gel to organic synthesis has been widely investigated, its use in organic reactions in aqueous media has not been exploited, to the best of our knowledge. Silica would be effective as organic reaction media in water because the organic molecule as a substrate would be adsorbed to the silica by hydrophobic interactions between the surface of the silica and the organic molecule. We investigated here on the iodine-catalyzed aziridination of olefins using Chloramine-T (CT) and the ring opening of the resulting aziridine in a silica-water system, in which the use of silica (silica gel vs. MCM-41) showed unique results. For example, when styrene was treated with CT, K_2CO_3, and a catalytic amount of I_2 in the presence of Silica Gel 60 in water, N-(p-toluenesulfonyl)-2-phenylaziridine was obtained in good yield. A variety of olefins were successfully employed in this silica-mediated olefin aziridination in water using the iodine catalyst-CT system. To show the generality of the present media in organic synthesis, the ring opening of N-(p-toluenesulfonyl)-2-n-hexylaziridine with NaN_3 or KCN was examined. The reaction of aziridines with NaN_3 or KCN in water in the absence of silica did not proceed similarly to the case of the aziridination described above. When Silica Gel 60 was added, however, the desired reaction proceeded to afford the regioselective ring-opening products, respectively. To obtain a ring expansion product by the system, potassium thiocyanate was employed in the reaction. As was expected, a ring expansion product, thiazolidine derivative consisting of one thiocyanate and two aziridines moieties was produced in good yield as a mixture of two diastereomers.

虽然使用PTC允许在水介质中的反应是一种通用的方法，但基于硅胶的吸附性质，设计了一种替代的潜在的在水中的过程。虽然硅胶在有机合成中的应用已被广泛研究，但据我们所知，其在水介质中的有机反应中的应用尚未开发。二氧化硅作为水中的有机反应介质是有效的，因为作为底物的有机分子通过二氧化硅表面和有机分子之间的疏水相互作用而被吸附到二氧化硅上。本文研究了碘催化的烯类氮丙啶化反应，并在硅胶-水体系中进行了氮丙啶的开环反应，其中硅胶（硅胶vs. MCM-41）的使用显示了独特的结果。例如，苯乙烯与CT、K_2CO_3和催化量的I_2在硅胶60存在下于水中反应，得到N-（对甲苯磺酰基）-2-苯基氮丙啶。在碘催化剂-CT体系中，各种烯烃成功地用于这种二氧化硅介导的烯烃氮丙啶化反应。为了显示现有介质在有机合成中的通用性，本文研究了N-（对甲苯磺酰基）-2-正己基氮丙啶与NaN_3或KCN的开环反应。氮杂环丙烷与NaN_3或KCN在水中在没有二氧化硅存在下的反应不进行类似于上述氮杂环丙烷化的情况。然而，当加入硅胶60时，所需的反应进行，分别得到区域选择性开环产物。为了通过该体系获得扩环产物，在反应中使用硫氰酸钾。如所预期的，以良好的产率产生作为两种非对映异构体的混合物的扩环产物，即由一个硫氰酸酯和两个氮杂环丙烷部分组成的噻唑烷衍生物。

项目成果

期刊论文数量（22）

专著数量（0）

科研奖励数量（0）

会议论文数量（0）

专利数量（0）

Unprecedented CO_2-Promoted Aminochlorination of Olefines with Chloramine-T

前所未有的 CO_2 促进氯胺-T 烯烃氨氯化反应

DOI：
发表时间：
2006
期刊：
Organic Letters 8・5
影响因子：
0
作者：
Satoshi Minakata;Satoshi Minakata;Satoshi Minakata
通讯作者：
Satoshi Minakata

Development of New Synthetic Methods of Heterocycles Using Chloramine‐T as a Nitrogen Source

以氯胺-T为氮源的杂环合成新方法的发展

DOI：
10.1002/chin.200348248
发表时间：
2003
期刊：
ChemInform
影响因子：
0
作者：
S. Minakata;M. Komatsu
通讯作者：
M. Komatsu

Introduction of an N1 Unit to Monoenes or 1,6-Dienes Using Chloramine-T-Silver Nitrate a New Route to Aziridines or Bicyclic Pyrrolidines

使用氯胺-T-硝酸银将 N1 单元引入单烯或 1,6-二烯，这是制备氮丙啶或双环吡咯烷的新途径

DOI：
发表时间：
2003
期刊：
Heterocycles 60・2
影响因子：
0
作者：
Satoshi Minakata;Satoshi Minakata;Satoshi Minakata;Satoshi Minakata;Satoshi Minakata;Satoshi Minakata;Satoshi Minakata;Satoshi Minakata;Satoshi Minakata;Satoshi Minakata;Satoshi Minakata;Satoshi Minakata;Satoshi Minakata;Satoshi Minakata;Satoshi Minakata;Satoshi Minakata;Satoshi Minakata;Satoshi Minakata
通讯作者：
Satoshi Minakata

Novel synthesis of gem-dichloroaziridines from imines via the KF/Al2O3-promoted generation of dichlorocarbene from chloroform.