Acid-Catalyzed Nucleophilic Aromatic Substitution: Experimental and Theoretical Exploration of a Multistep Mechanism.
Författare
Summary, in English
The mechanism for the acid-mediated substitution of a phenolic hydroxyl group with a sulfur nucleophile has been investigated by a combination of experimental and theoretical methods. We conclude that the mechanism is distinctively different in nonpolar solvents (i.e., toluene) compared with polar solvents. The cationic mechanism, proposed for the reaction in polar solvents, is not feasible and the reaction instead proceeds through a multistep mechanism in which the acid (pTsOH) mediates the proton shuffling. From DFT calculations, we found a rate-determining transition state with protonation of the hydroxyl group to generate free water and a tight ion pair between a cationic protonated naphthalene species and a tosylate anion. Kinetic experiments support this mechanism and show that, at moderate concentrations, the reaction is first order with respect to 2-naphthol, n-propanethiol, and p-toluenesulfonic acid (pTsOH). Experimentally determined activation parameters are similar to the calculated values (DeltaH(exp) ( not equal)=105+/-9, DeltaH(calcd) ( not equal)=118 kJ mol(-1); DeltaG(exp) ( not equal)=112+/-18, DeltaG(calcd) ( not equal)=142 kJ mol(-1)).
Avdelning/ar
Publiceringsår
2008
Språk
Engelska
Sidor
3954-3960
Publikation/Tidskrift/Serie
Chemistry: A European Journal
Volym
14
Issue
13
Dokumenttyp
Artikel i tidskrift
Förlag
Wiley-Blackwell
Ämne
- Organic Chemistry
Nyckelord
- aromatic substitution
- density functional calculations
- kinetics
- nucleophilic substitution
- reaction mechanisms
Status
Published
ISBN/ISSN/Övrigt
- ISSN: 1521-3765