TY - JOUR
T1 - Electronic and solvent effects on kinetics of SNAr substitution reactions of substituted anilines with 2,6-bis(trifluoromethanesulfonyl)-4- nitroanisole in MeOH-Me2SO mixtures of varying composition
T2 - One reaction with two mechanistic pathways
AU - El Guesmi, Nizar
AU - Berionni, Guillaume
AU - Asghar, Basim H.
PY - 2013
Y1 - 2013
N2 - The kinetics and mechanism of the aromatic nucleophilic substitution reactions of 2,6-bis(trifluoromethanesulfonyl)-4-nitroanisole with para-X-substituted anilines (X = OH, OMe, Me, H, F, I, Cl) were studied in MeOH-Me2SO mixtures and pure Me2SO at 25.0 C. The second-order rate coefficients depend on the substitutent in aniline and give good Hammett and Brønsted correlations; a polar SNAr reaction is proposed for the reaction in different MeOH-Me2SO mixtures. The measured rate coefficients of the reaction demonstrated dramatic variations for aniline donor with the increasing dimethyl sulfoxide composition in MeOH-Me 2SO mixtures. In this case, the Hammett and Brønsted plots are biphasic and concave upwards with a break point at 4-methylaniline. These results indicate a change in mechanism from the polar (SNAr) for less basic nucleophiles (X = 4-Cl, 4-I, 4-F, and H) to the single electron transfer (SET) for more basic nucleophiles (X = 4-OH, 4-OMe and 4-Me). The changes of the structure of the transitions states with substituents and solvent are in accordance with the results of kinetics studies. The solvation model described is well supported by the solvatochromism exhibited by aniline in the solvent mixture under investigation. These results provide an ideal framework for understanding the paramount importance of the specific molecular structure of solvent molecules in determining chemical reactivity versus solvent effects. Graphical abstract: [Figure not available: see fulltext.]
AB - The kinetics and mechanism of the aromatic nucleophilic substitution reactions of 2,6-bis(trifluoromethanesulfonyl)-4-nitroanisole with para-X-substituted anilines (X = OH, OMe, Me, H, F, I, Cl) were studied in MeOH-Me2SO mixtures and pure Me2SO at 25.0 C. The second-order rate coefficients depend on the substitutent in aniline and give good Hammett and Brønsted correlations; a polar SNAr reaction is proposed for the reaction in different MeOH-Me2SO mixtures. The measured rate coefficients of the reaction demonstrated dramatic variations for aniline donor with the increasing dimethyl sulfoxide composition in MeOH-Me 2SO mixtures. In this case, the Hammett and Brønsted plots are biphasic and concave upwards with a break point at 4-methylaniline. These results indicate a change in mechanism from the polar (SNAr) for less basic nucleophiles (X = 4-Cl, 4-I, 4-F, and H) to the single electron transfer (SET) for more basic nucleophiles (X = 4-OH, 4-OMe and 4-Me). The changes of the structure of the transitions states with substituents and solvent are in accordance with the results of kinetics studies. The solvation model described is well supported by the solvatochromism exhibited by aniline in the solvent mixture under investigation. These results provide an ideal framework for understanding the paramount importance of the specific molecular structure of solvent molecules in determining chemical reactivity versus solvent effects. Graphical abstract: [Figure not available: see fulltext.]
KW - Biphasic concave upward free energy relationship
KW - Kinetics
KW - Single electron transfer (SET) pathway
KW - Solvatochromic parameters
KW - Solvent effect
UR - http://www.scopus.com/inward/record.url?scp=84885295021&partnerID=8YFLogxK
U2 - 10.1007/s00706-013-1030-7
DO - 10.1007/s00706-013-1030-7
M3 - Article
AN - SCOPUS:84885295021
SN - 0026-9247
VL - 144
SP - 1537
EP - 1545
JO - Monatshefte fur Chemie
JF - Monatshefte fur Chemie
IS - 10
ER -