著者:別形式 | Ishikawa, Ryo / Maruo, Yasuko Y. / Kobayashi, Keiji / Teramae, Hiroyuki |
著者:所属(別形式) | Josai University, Faculty of Science, Department of Chemistry / Tohoku Institute of Technology, Department of Environment and Energy / Josai University, Faculty of Science, Department of Chemistry / Josai University, Faculty of Science, Department of Chemistry |
抄録 | ルチジン誘導体生成の反応機構を解明するために, B3LYP/6-31G** レベルおよび一部はMP2/6-31G**
レベルで3, 5-diacetyl-1,4-dihydro-2,6-dimethylpyridine, 3,5-dibenzoyl-1,4-dihydro-2,6-dimethylpyridineおよび
3,5-dibenzoyl-1,4-dihydro-2,6-diphenyl-pyridineの各ルチジン誘導体の対応するβ - ジケトンからの生成反応の
反応機構をab initio 分子軌道法を用いて試みた.全ての素反応について安定構造と遷移状態の構造を求め
た.反応中間体であるFLUORAL-P生成の素反応について,水分子を1 個加えることによりPCM MP2/6-
31G** レベルでの活性化障壁が47.15 kcal/molから25.35 kcal/molへ減少することがわかった. / The reaction mechanism of lutidine derivative formation, 3, 5-diacetyl-1, 4-dihydro-2, 6-Dimethylpyridine, 3,
5-dibenzoyl-1, 4-dihydro-2, 6-dimethylpyridine and 3, 5-dibenzoyl-1, 4-dihydro-2, 6-diphenyl-pyridine from the corresponding
β-diketone is studied by using B3LYP/6-31G** level and partly MP2/6-31G** level. The optimized structures
and the transition state structures of all the elementary reactions are calculated. The activation energy of the
elementary reaction of the formation of reaction intermediate FLUORAL-P is greatly reduced from 47.15 kcal/mol to
25.35 kcal/mol at PCM MP2/6-31G** level when adding one H2O molecule. |