NDLI: The Ambident Reactivity of 2,4,6-Tris(trifluoromethanesulfonyl)anisole in Methanol: Using the $SO_{2}CF_{3}$ Group as a Tool to Reach the Superelectrophilic Dimension in σ-Complexation Processes

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The Ambident Reactivity of 2,4,6-Tris(trifluoromethanesulfonyl)anisole in Methanol: Using the $SO_{2}CF_{3}$ Group as a Tool to Reach the Superelectrophilic Dimension in σ-Complexation Processes

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The Ambident Reactivity of 2,4,6-Tris(trifluoromethanesulfonyl)anisole in Methanol: Using the $SO_{2}CF_{3}$ Group as a Tool to Reach the Superelectrophilic Dimension in σ-Complexation Processes

Content Provider	World Health Organization (WHO)-Global Index Medicus
Author	El Guesmi, Nizar Boubaker, Taoufik Goumont, Regis Terrier, François
Description	Author Affiliation: El Guesmi N ( Unité de Recherche de Chimie Théorique et Réactivité, Faculté des Sciences de Monastir, Avenue de l'Environnement, 5019 Monastir, Tunisia.)
Abstract	The kinetics of σ complexation of 2,4,6-tris(trifluoromethanesulfonyl)anisole (7 d) have been investigated over a large pH range of 2–13.70 at T=20 °C in methanol. Two competitive processes associated with the initial addition of $MeO^{−}$ at the unsubstituted 3-position of 7 d to give a 1,3-dimethoxy adduct (9 d-Me) and a subsequent and slow conversion of this species into a 1,1-dimethoxy isomer (8 d-Me) have been identified. Both adducts 8 d-Me and 9 d-Me are $10^{5}–10^{6}$ times more stable than the related adducts 8 a-Me and 9 a-Me of 2,4,6-trinitroanisole (7 a), a conventional reference aromatic electrophile in Meisenheimer complex chemistry. The high stability of 8 d-Me and 9 d-Me is shown to derive from greater rates of formation and lower rates of decomposition than previously determined for 8 a-Me and 9 a-Me, thereby emphasising the especially high activation of a benzene ring by $SO_{2}CF_{3}$ group(s). Analysis of the collected rate and equilibrium data for σ complexation in the anisole series $2,4,6-tris(SO_{2}CF_{3})-,$ $2,6-bis(SO_{2}CF_{3})-4-nitro-,$ $4-SO_{2}CF_{3}-2,6-dinitro-$ and 2,4,6-trinitro- supports the idea that the especially high capacity of resonance stabilisation of the negative charge of the adducts through an $F_{π}-type$ (as defined in ref. 49) polarisation effect is a major factor that accounts for the strong activation provided by $SO_{2}CF_{3}$ groups. A most significant result is the finding that the 1,1-dimethoxy adduct 8 d-Me is by far the most stable benzene σ adduct so far reported. With a p value of 7.32, this adduct is formed exclusively through methanol addition up to pH≈10. This is consistent with the location of 7 d in the superelectrophilic region defined by p≤9.5–10.5. For comparison, the solvent contribution is negligible in the formation of the 1,3-isomer 9 d-Me, the p (10.59) of which is situated on the upper limit of the boundary. Taking advantage of the simple relationship linking $pK_{a}$ values for σ complexation in methanol and water, a ranking of the triflone 7 d on the general thermodynamic scale constructed for Meisenheimer electrophiles in water is informative. An approximate calibration on the electrophilicity scale kinetically derived by Mayr et al. has also been made.
ISSN	09476539
e-ISSN	15213765
Journal	Chemistry - A European Journal
Issue Number	44
Volume Number	15
Language	English
Publisher	Wiley-VCH;ChemPubSoc Europe
Publisher Date	2009-11-09
Publisher Place	Germany
Access Restriction	Open
Subject Keyword	Chemistry
Content Type	Text
Resource Type	Article
Subject	Organic Chemistry Catalysis

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