Liquid Crystal Control of uni-to multi-molecular Thermal Reactions

单分子到多分子热反应的液晶控制

基本信息

批准号：
13470496
负责人：
KUNIEDA Takehisa
金额：
$ 9.02万
依托单位：
Kumamoto University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (B)
财政年份：
2001
资助国家：
日本
起止时间：
2001 至 2003
项目状态：
已结题

项目摘要

The aim of this research is to establish the new methodology for highly orientation-regulated reaction system using liquid crystal as medium, with regularity and fluidity. The following typical reactions have tried with a variety of liquid crystal medium :(1)Intramolecular [4+2] cycloaddition (unimolecular reaction) : Intramolecular uncatalyzed thermal cycloaddition reaction of trans-4-cyclohexylcyclohexyl decatrienoic acid esters in smectic liquid crystalline solvents such as bis(4-pentyloxyphenyl)trans-1,4-cyclohexanedicarboxylate (BPCD) was found to give bicyclic cycloadducts with extremely high diastereoselectivity and chemical yields, contrary to the poor results with isotropic medium such as 4-pentyloxyphenyl cyclohexanecarboxylate (PCC) and mesitylene.(2)Intermolecular [4+2] cycloaddition (bimolecular reaction) : Moderate stereoselectivities and reaction accerelation effect were observed for intermolecular cycloaddition with pyrroles and allene diesters in smectic medium.(3)Mitsunobu Reaction (tetramolecular reaction) : Unusual retention of the configuration of hydroxyl group of trans-4-substituted cyclohexanol by Mitsunobu reaction was observed in smectic medium, contrary to the usual result (inversion of configuration) in isotropic medium.

这项研究的目的是使用液晶为培养基，以规律性和流动性来建立高方向调节的反应系统的新方法。 The following typical reactions have tried with a variety of liquid crystal medium :(1)Intramolecular [4+2] cycloaddition (unimolecular reaction) : Intramolecular uncatalyzed thermal cycloaddition reaction of trans-4-cyclohexylcyclohexyl decatrienoic acid esters in smectic liquid crystalline solvents such as发现BIS（4-五氧苯基）trans-1,4-循环甲苯二羧酸盐（BPCD）具有具有极高的非对映选择性和化学产率的双环环载液，与同型培养基（如4-丙烯基氯己式甲基甲苯甲甲基甲基甲苯甲酸苯甲酸甲曲甲苯甲酰基甲基甲基甲基甲酰基甲基甲酰基甲基甲基甲基甲基甲基甲酰基甲基甲基甲基甲酰基甲基甲基甲基甲酰基甲基甲基甲基甲基甲基甲基甲酰基甲基甲基甲基甲基甲酰基甲基甲基甲基甲酰基）相反 mesitylene.(2)Intermolecular [4+2] cycloaddition (bimolecular reaction) : Moderate stereoselectivities and reaction accerelation effect were observed for intermolecular cycloaddition with pyrroles and allene diesters in smectic medium.(3)Mitsunobu Reaction (tetramolecular reaction) : Unusual retention of the configuration of hydroxyl group of在近晶培养基中观察到了反式 - 4次取代的环己醇，与各向同性培养基中通常的结果（构型反转）相反。