REACTIVITY CONTROL IN ORGANIC CHEMISTRY

有机化学中的反应性控制

• 批准号: 63303002
• 负责人: HAYAMI Jun-ichi
• 金额: $ 9.47万
• 依托单位: KYOTO UNIVERSITY
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Co-operative Research (A)
• 财政年份: 1988
• 资助国家: 日本
• 起止时间: 1988 至 1989
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-63303002/
• 关键词: PHYSICAL ORGANIC CHEMISTRY; REACTIVITY; REACTIVITY CONTROL; MOLECULAR INTERACTION; SUBSTITUENT EFFECT; HETEROATOM CHEMISTRY; THEORETICAL CHEMISTRY; ORGANOMETALLIC CHEMISTRY; 基礎有機化学

Twenty four leading physical organic chemists in representative universities and research institutions made up a cooperative research project team.The major aim of the team is to try to establish a comprehensive understanding of the factors governing the reactivity of organic compounds in quantitative sense as far as possible. Approaches are made from the stand points of 1)transmission of the effects of the structural change: 2)chemistry of reactive chemical species and identities: 3)detection and quantilization of interspeclies interaction: 4)identification and characterization of the reaction field covering the topics of molecular aggregates and clusters.Members of the project team are involved both the research of the individual field and the discussion-cooperation of the interlocking aspects of the interesting problems. The results are exemplified by the 192 references in the varieties of the approach which are cited in the Japanese text of the final research report. Representative results are a)the elucidation of the degree of the electron demand common to organic cationic species and transition state; b)elucidation of the importance of the molecular association in the nucleophilic organic reactions such as Griganard Reaction, Wittig Reaction, S_NAr Reaction etc. through both experimental and theoretical approach.

24位来自代表性大学和研究机构的物理有机化学家组成了一个合作研究项目小组，该小组的主要目标是尽可能从定量意义上全面了解影响有机化合物反应性的因素。方法是从以下观点出发的：1）结构变化影响的传递; 2）反应性化学物种和身份的化学; 3）物种间相互作用的检测和量化：4）反应场的识别和表征，涵盖分子聚集体和团簇的主题。项目团队成员既参与单个领域的研究，也参与讨论-有趣问题的连锁方面的合作。最终研究报告的日文文本中引用的各种方法中的192篇参考文献说明了结果。代表性的结果是：（a）阐明了有机阳离子物种和过渡态共同的电子需求程度;（B）从实验和理论两方面阐明了亲核有机反应如Griganard反应、Wittig反应、S_NAr反应等中分子缔合的重要性。

项目成果

Yoshiaki HORIGUDHI,et.al: "Does Me_3SiCl Activate Condugate Addition of Copper Reagents as a Lewis Acid?" Tetrahedron Letters. 7087 (1989)

Yoshiaki HORIGUDHI 等人：“Me_3SiCl 是否会激活作为路易斯酸的铜试剂的共轭加成？”

Nobuaki KOGA,et.al: "An Initio Molecular Orbital Studies of Intermediates and Transition States of Organometallic Elementary Reactions and Homogeneous Catalytic Cycles." Topics in Physical Organometallic Chemistry. 3. 1 (1989)

Nobuaki KOGA 等人：“有机金属基本反应和均相催化循环的中间体和过渡态的从头分子轨道研究”。

Hideyuki MATSUMOTO, et.al.: "Photolysis of Cyclotetrasilanes, a Remarkable Dependenace on Molecular Structure." J. Chem. Soc. Faraday Trans. I, 85, 2369-2379 (1989).

Hideyuki MATSUMOTO 等人：“环四硅烷的光解，对分子结构的显着依赖性。”

Tsutomu ASANO, et.al.: "Mechanism of Geometrical Isomerization about the Carbon-Nitrogen Double Bond." J. Am. Chem. Soc., 112, 0000 (1990).

Tsutomu ASANO 等人：“碳-氮双键的几何异构化机制”。

Masaaki MISHIMA, et.al.: "Gas Phase Substituent Effects. Stabilities of 1-Aryl-2,2,2-trifluoroethyl Cations." Tetrahedron Lett., 685-688 (1990).

Masaaki MISHIMA 等人：“气相取代基效应。1-芳基-2,2,2-三氟乙基阳离子的稳定性”。