Study on Dynamic Molecular Behaviors in Crystal
Study on Dynamic Molecular Behaviors in Crystal
批准号:
09044091
负责人:
TODA Fumio
金额:
$4.35万
依托单位国家:
日本
项目类别:
Grant-in-Aid for Scientific Research (B).
财政年份:
1997
资助国家:
日本
项目状态:
已结题
起止时间:
1997 至 1999
中文摘要
当diallene衍生物(A)的晶体加热至1h时,dimethylencecyclene衍生物(B)由循环反应产生。自从晶体上有一个S-反式结构,从S-反式配置到一个S-反式结构中的异构反应应该在循环化反应之前发生。这是非常有趣的,因为它在水晶的小空间里的大分子运动场。这也证实了热转换过程是立体电的,当一个原型分子包含在一个手性主机复合体中,而前分子则被安排在一个手性形式中,它的嵌入式晶体中,并引入了光学活性的光电产品。在水晶、水晶、水晶晶格的包容性化合物中的摄影反应最多的情况下,由于反应过程而被摧毁。关于环己酮、香豆素和三硫氰胺在包含复合晶体中的对比、光二聚氰胺中的对比、光处理,从单晶体到单晶体和负电地给予对光学活性二聚体的光处理。这些反应是由X射线分析研究的,其他有机固体状态反应也是开发的。例如, Dieckmann反应、偶氮素形成反应和Michael Addition反应都在固体状态中有效地进行。在这些反应中,偶氮素形成反应是通过AFM方法研究的,无溶剂反应也是通过选择性地进行澄清的。例如,在固体状态gave meso-和Erythro-Addition产品中对苯乙烯和糖进行治疗,对丁二烯和糖醇进行治疗,尊重。这些数据清楚地显示了晶体容易移动的分子,以及在固体状态下选择性和有效地发生的反应。
英文摘要
When crystals of diallene derivative (A) is heated for 1h, dimethylencecyclobutene derivative (B) is produced by a cyclization reaction. Since A has a s-trans structure on crystal, isomenzation reaction from the s-trans configuration to a s-cis one should be occurred before the cyclization reaction. It is very interesting that such the big molecular motion occurs in a small space of crystal. It was also confirmed that the thermal conversion proceeds stereoselectively.When a prochiral molecule is included in a chiral host compound, the former is arranged in a chiral form in its inclusion crystal and its inadiation gave optically active photoreaction product. In most cases of the photoreaction in crystal, crystalline lattice of the inclusion compound is destroyed as the reaction proceeds. On the contrary, photodimerzation of cyclohexenone, coumarin, and thiocoumarin in inclusion complex crystal with optically active host compound proceeded from single-crystal-to-single-crystal and enantioselectively to give corresponding optically active dimer. These reactions were studied by X-ray analysis.Some other organic solid state reactions were also developed. For example, Dieckmann reaction, azomethine formation reaction, and Michael addition reaction were found to proceed efficiently in the solid state. Of these reactions, azomethine formation reaction was studied carefully by AFM method.Solvent-free reactions were also clarified to proceed selectively. For example, treatment of stilibene and chalcone with pyridine-HBr-BrィイD22ィエD2 salt in the solid state gave meso- and erythro- addition product, respectively. These data clearly show that molecules in crystal move easily and that reaction occurs selectively and efficiently in the solid state.
期刊论文(0)
专著(0)
科研奖励(0)
会议论文
登录
查看更多内容
F.Toda,T.Suzuki,S.Higa: "Solvent-free Dieckmann Condensations of Diethyl Adipate and Pimerate" J.Chem.Soc.,Perkin Trans.1. 3521-3522 (1998)
F.Toda,T.Suzuki,S.Higa:“己二酸二乙酯和庚酸酯的无溶剂迪克曼缩合”J.Chem.Soc.,Perkin Trans.1。
DOI:
--
发表时间:
期刊:
影响因子:
--
作者:
[]
通讯作者:
R.Tamura,H.Takahashi,K.Hirotsu,Y.Nakajima,T.Ushio,F.Toda: "Unusual Disordered Crystal Structure of Racemate Exhibiting a Nobel Enantiomeric Resolution: Preferential Enrichement" Angew.Chem.Int.Ed.Engl.37. 2876-2878 (1998)
R.Tamura、H.Takahashi、K.Hirotsu、Y.Nakajima、T.Ushio、F.Toda:“外消旋物的异常无序晶体结构表现出诺贝尔对映体分辨率:优先富集”Angew.Chem.Int.Ed.Engl。
DOI:
--
发表时间:
期刊:
影响因子:
--
作者:
[]
通讯作者:
F.Toda, H.Takumi, M.Nagami, K.Tanaka: "A Novel Method for Michael Addition and Epoxidation of Chalcones in a Water Suspension Medium" Heterocycles. 47. 469-479 (1998)
F.Toda、H.Takumi、M.Nagami、K.Tanaka:“在水悬浮介质中查耳酮的迈克尔加成和环氧化的新方法”杂环。
DOI:
--
发表时间:
期刊:
影响因子:
--
作者:
[]
通讯作者:
K.Tanaka, A.Moriyama, F.Toda: "Novel Chiral Recognition in Host-Guest lnclusion Complexes Depends on their Molar Ratios" J.Org,Chem.62. 1192-1193 (1997)
K.Tanaka、A.Moriyama、F.Toda:“主客体包合物中的新型手性识别取决于它们的摩尔比”J.Org,Chem.62。
DOI:
--
发表时间:
期刊:
影响因子:
--
作者:
[]
通讯作者:
F.Toda,K.Tanaka,M.Kato: "Stereoselective Photodimerisation of Chalcones in the Molten State" J.Chem.Soc.Perkin Trans.1. 1315-1318 (1998)
F.Toda、K.Tanaka、M.Kato:“熔融状态下查尔酮的立体选择性光二聚”J.Chem.Soc.Perkin Trans.1。
DOI:
--
发表时间:
期刊:
影响因子:
--
作者:
[]
通讯作者:
共 30 条
Creation of Enantioselective Cross- Coupling Reactions in the Solid State
-
批准号:13640595
-
项目类别:Grant-in-Aid for Scientific Research (C)
-
资助金额:$2.18万
-
财政年份:2001
-
负责人:TODA Fumio
-
依托单位:
Study of Extremely Long C - C Bond
-
批准号:11640537
-
项目类别:Grant-in-Aid for Scientific Research (C)
-
资助金额:$2.3万
-
财政年份:1999
-
负责人:TODA Fumio
-
依托单位:
Design of Reactions in Crystals
-
批准号:06242104
-
项目类别:Grant-in-Aid for Scientific Research on Priority Areas
-
资助金额:$23.1万
-
财政年份:1994
-
负责人:TODA Fumio
-
依托单位:
Design of Reactions in Crystals
-
批准号:06242105
-
项目类别:Grant-in-Aid for Scientific Research on Priority Areas
-
资助金额:$82.5万
-
财政年份:1994
-
负责人:TODA Fumio
-
依托单位:
Reactions and Structures of Crystalline Molecular Assembly
-
批准号:05044059
-
项目类别:Grant-in-Aid for international Scientific Research
-
资助金额:$4.48万
-
财政年份:1993
-
负责人:TODA Fumio
-
依托单位:
Development of Inclusion Crystal for Asymmetric Synthesis
-
批准号:05554020
-
项目类别:Grant-in-Aid for Developmental Scientific Research (B)
-
资助金额:$9.98万
-
财政年份:1993
-
负责人:TODA Fumio
-
依托单位:
Self-Assembly of Molecules in Crystal and Its Application to Selective Organic Synthesis
-
批准号:04453102
-
项目类别:Grant-in-Aid for General Scientific Research (B)
-
资助金额:$4.35万
-
财政年份:1992
-
负责人:TODA Fumio
-
依托单位:
Selfassembly of Molecules in Crystal and Its Application to Selective Synthesis
-
批准号:03303002
-
项目类别:Grant-in-Aid for Co-operative Research (A)
-
资助金额:$6.21万
-
财政年份:1991
-
负责人:TODA Fumio
-
依托单位:
DEVELOPMENT OF SEPARATION AND OPTICAL RESOLUTION METHOD OF MATERIALS BY USING INCLUSION COMPOUND
-
批准号:63840017
-
项目类别:Grant-in-Aid for Developmental Scientific Research
-
资助金额:$3.01万
-
财政年份:1988
-
负责人:TODA Fumio
-
依托单位:
Studies on Organic Solid State for Design and Development of the Field of Fine Molecular Recognition
-
批准号:63044103
-
项目类别:Grant-in-Aid for international Scientific Research
-
资助金额:$6.72万
-
财政年份:1988
-
负责人:TODA Fumio
-
依托单位: