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Computational Study for the Aromatic Nucleophilic Substitution Reaction on 1-Dimethylamino-2,4-bis(trifluoroacetyl)-naphthalene with Amines
Department of Chemical Science and Engineering, Graduate School of Engineering, Kobe University, Kobe, Japan
Department of Chemical Science and Engineering, Graduate School of Engineering, Kobe University, Kobe, Japan
Department of Chemical Science and Engineering, Graduate School of Engineering, Kobe University, Kobe, Japan
Department of Chemical Science and Engineering, Graduate School of Engineering, Kobe University, Kobe, Japan
Department of Chemical Science and Engineering, Graduate School of Engineering, Kobe University, Kobe, Japan
- 1 Department of Chemical Science and Engineering, Graduate School of Engineering, Kobe University, Kobe, Japan
- 2 Department of Chemical Science and Engineering, Graduate School of Engineering, Kobe University, Kobe, Japan
- 3 Department of Chemical Science and Engineering, Graduate School of Engineering, Kobe University, Kobe, Japan
- 4 Department of Chemical Science and Engineering, Graduate School of Engineering, Kobe University, Kobe, Japan
- 5 Department of Chemical Science and Engineering, Graduate School of Engineering, Kobe University, Kobe, Japan
International Journal of Organic Chemistry·Volume 08 (2018)·Pages 273–281·Published 1 August 2018·DOI10.4236/ijoc.2018.83020
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Abstract
Our previous research showed that aliphatic amines were put in order of high reactivit y as “ethylamine > ammonia > t- butylamine > diethylamine” on the aromatic nucleophilic substitution of 1-dimetylamino-2,4-bis(trifluoroacetyl)-naphthalene 1 in acetonitrile. The DFT calculation study (B3LYP/6-31G* with solvation model) for the reactions of 1 with above four amines rationally explained the difference of each amines reactivity based on the energies of their Meisenheimer complexes 3 which are assumed to formed as the reaction intermediates in the course of the reaction giving the corresponding N-N exchange products 2 . Intramolecular hydrogen bond between amino proton in 1-amino group and carbonyl oxygen in 2-trifluoroacetyl group stabilizes Meisenheimer complexes 3 effectively, and accelerates the substitution reaction from 1 to 2 . Our calculation results also predicted that the above order of amines is also true if less polar toluene is used as a solvent instead of acetonitrile even though more enhanced conditions are required.
Keywords1-Amino-24-bis(trifluoroacetyl)naphthalenesAliphatic AminesMeisenheimer ComplexesAromatic Nucleophilic SubstitutionDFT Calculation
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