| Project/Area Number |
14550795
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| Research Category |
Grant-in-Aid for Scientific Research (C)
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| Allocation Type | Single-year Grants |
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| Section | 一般 |
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| Research Field |
工業物理化学
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| Research Institution | Gifu University (2004)
Osaka Sangyo University (2002-2003) |
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Principal Investigator |
SAKAI Shogo Gifu University, Faculty of Engineering, Professor, 工学部, 教授 (40221262)
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| Project Period (FY) |
2002 – 2004
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| Project Status |
Completed (Fiscal Year 2004)
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| Budget Amount *help |
¥2,800,000 (Direct Cost: ¥2,800,000)
Fiscal Year 2004: ¥600,000 (Direct Cost: ¥600,000)
Fiscal Year 2003: ¥800,000 (Direct Cost: ¥800,000)
Fiscal Year 2002: ¥1,400,000 (Direct Cost: ¥1,400,000)
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| Keywords | Aromaticity / IDA / CiLC / Diels-Alder Reaction / Pericyclic Reaction / Cope Rearrangement / 1,3-Dipolar Reaction / Pseudopericyclic Reaction / Claisen反応 / 環化反応機構 / 溶媒効果 / IMiC MO法 / スイッチング分子 / 置換基効果 / ぺり環状反応機構 / 軌道対称性理論 / CiLC解析法 / コープ転位反応 / Mills-Nixon効果 |
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| Research Abstract |
We studied the following projects.
(1)New Definition of Aromaticity and the Applications : A new criterion of aromaticity for cyclic π-conjugated compounds is proposed on the basis of CiLC analysis founded on ab initio molecular orbital methods. The new criterion states that the all bonds should have equivalent electronic structures and the difference between weights for the singlet coupling and polarization terms should be small.
(2)Diels-Alder Reaction Mechanisms : The concerted and stepwise mechanisms of the hetero-Diels-Alder reaction of butadiene with formaldehyde and thioformaldehyde were studied by a CASSCF molecular orbital method. The concerted pathways for both systems are more favorable than the stepwise pathways. Substitution effects for concerted and stepwise mechanisms of the Diels-Alder reaction between butadiene and ethylene were also studied.
(3)1,3-Dipolar Cycloaddition Mechanisms : The reaction mechanisms can be calssifled into two classes : ionic electrocyclic and diradical coupling mechanisms. Ionic electrocyclic mechanism occurs in reaction systems with a large difference in electronegativies between the two atoms of the dipolarophile and their atoms react with the atoms with each opposite charge of a 1,3-dipole. Diradical coupling mechanism occurs through two process : the first process is a one-electron movement from the edge atom to the center atom of a 1,3-dipole, which leads to a biradical state.
(4)Cope Rearrangement Reaction Methanisms : The mechanism of the Cope rearrangement in the reaction of 1,5-hexadiene and its monophenyl and diphenyl deviatives was studied. CiLC analysis was performed for the potential energy surface of the C_<2h> cut in the reaction of 1,5-hexadiene, giving the typical electronic character for the aromatic transition state, diradical intermediate, and the transition state between them.
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