| Popis: |
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. |
