Abstract
We present a kinetic and theoretical study of electrophilic aromatic substitution (SEAr) involving 2-(2′,4′,6′-trinitrophenyl)-4,6-dinitrobenzotriazole 1-oxide 1 with a series of 5-R-substituted indoles 2a-e (R = CN, Cl, H, Me and NH2) in acetonitrile at 20 °C. Single electron transfer (SET) mechanism was proposed and confirmed by the agreement between the rate constants (k) and the oxidation potentials (Epox) of these series of indoles. Using Mayr's equation, the electrophilicity parameter (E) of 1 at C-7 position is derived and compared with the same parameter estimated using empirical equation E versus. pKa. Density Functional Theory (DFT) calculations were performed to confirm the suggested reaction mechanisms and elucidate the origin of the electrophilic reactivity of 1. Notably, a linear correlation (R2 = 0.9957) between the experimental nucleophilicity (N) and the theoretical model of nucleophilicity (ω−1) determined in this work of various 5-R-substituted indoles has been obtained and discussed.
Graphical abstract
Mayr and Parr's approaches were combined with the correlation N vs ω−1 established in the present work, to evaluate the empirical electrophilicity parameter (E) of 2-(2′,4′,6′-trinitrophenyl)-4,6-dinitrobenzotriazole 1-oxide and the unknown nucleophile specific parameters (N and sN) of four new 5-R-substituted indoles (R = NO2, F, H and N(CH3)2) in acetonitrile.
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OA, AH, and TS achieved their experimental works with the help of TB. Theoretical calculations were conducted by SA. The manuscript was jointly written and arranged under TB, and SA guidance.
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Amamou, O., Hedhli, A., Slama, T. et al. Combined kinetic, and theoretical approaches for the study of the SEAr reactions of 2-(2′,4′,6′-trinitrophenyl)-4,6-dinitrobenzotriazole 1-oxide with 5-R-substituted indoles in acetonitrile. Chem. Pap. (2024). https://doi.org/10.1007/s11696-024-03440-3
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DOI: https://doi.org/10.1007/s11696-024-03440-3