Theoretical Study on Reaction Mechanism ofLutidine Derivative Formation

Abstract

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．

Figures

Figure 1.

 Reaction mechanism of the formation of lutidine derivative.

Figure 2.

 Relative energies of Dimethyl compound along the reaction coordinate at B3LYP/6-31G** level. Units are shown in kcal/mol.

Figure 3.

 Schematic view of 4, TS, and 5 of Dimethyl compound with one H₂SiO molecule at PCM MP2/6-31G** level. Thick arrows show the movement of the protons.

Figure 4.

 Schematic view of 4, TS, and 5 of Dimethyl compound with one water molecule at PCM MP2/6-31G** level.

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