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.

尽管使用PTC允许在水性培养基中反应是一种通用方法，但根据硅胶的吸附性，设计了水中的替代潜在过程。尽管已经广泛研究了硅胶在有机合成中的应用，但据我们所知，尚未利用其在水性培养基中的有机反应中使用。二氧化硅将作为水中的有机反应培养基有效，因为有机分子作为底物将通过二氧化硅表面与有机分子之间的疏水相互作用吸附到二氧化硅上。我们在这里研究了使用氯胺T（CT）（CT）的碘催化的氧化替象，以及在二氧化硅水系统中所产生的氮杂氨酸的环开口，其中硅胶（硅胶与MCM-41）的使用显示出独特的结果。例如，当苯乙烯被CT，K_2CO_3处理时，在水中有硅胶60的情况下，I_2的催化量n-（p-toluenesulfonyl）-2- 2-苯基嘧啶的产量良好。使用碘催化剂-CT系统，该二氧化硅介导的氧化纤维中的氧化烯二烯酸化成功成功地使用了各种烯烃。为了显示当前培养基在有机合成中的普遍性，检查了N-（p-toluenesulfonyl）-2-N-己糖酰氮杂胺与NAN_3或KCN的环。在没有二氧化硅的情况下，氮杂胺与NAN_3或KCN在水中的反应与上述的氮杂化情况相似。但是，当添加硅胶60时，所需的反应分别提供了区域性开环产物。为了通过系统获得环膨胀产物，反应中采用了硫氰酸钾。正如预期的那样，作为两个硫氰酸酯和两个氮杂胺部分组成的环噻唑胺衍生物作为两个非对映异构体的混合物的产量良好。

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）

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：制备氮丙啶或双环吡咯烷的新路线

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;Satoshi Minakata;Satoshi Minakata
通讯作者：
Satoshi Minakata

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

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

Silica Gel-Promoted Synthesis of 3,4,5-Triaryltetrahydro-1,4-thiazine Derivatives from β,β'-Dichloro Sulfides and Aromatic Amines

硅胶促进 β,β-二氯硫化物和芳香胺合成 3,4,5-三芳基四氢-1,4-噻嗪衍生物

DOI：
发表时间：
2005
期刊：
Tetrahedron Letters 46・47
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
通讯作者：
Satoshi Minakata

Satoshi Minakata: "Introduction of an NI Unit to Monoenes or 1,6-Dienes Using Chloramine-T-Silver Nitrate : a New Route to Aziridines or Bicyclic Pyrrolidines"Heterocycles. 60・2. 289-298 (2003)

Satoshi Minakata：“使用氯胺-T-硝酸银将 NI 单元引入单烯或 1,6-二烯：氮丙啶或双环吡咯烷的新路线”杂环 60・2。