Aromatic sulfonation with sulfur trioxide: mechanism and kinetic model. Issue 1 (19th September 2016)

• Record Type: Journal Article
• Authors: Moors, Samuel L. C.; Deraet, Xavier; Van Assche, Guy; Geerlings, Paul; De Proft, Frank
• Is Part Of: Chemical science. Volume 8:Issue 1(2017)
• Page Start: 680
• Page End: 688
• Publication Date: 2016-09-19
• Subjects: Chemistry -- Periodicals; 540.5
• DOI: 10.1039/c6sc03500k
• Languages: English
• ISSNs: 2041-6520

Abstract

Abstract : Electrophilic aromatic sulfonation of benzene with sulfur trioxide is studied with ab initio molecular dynamics simulations in gas phase, and in explicit noncomplexing (CCl3 F) and complexing (CH3 NO2 ) solvent models. Abstract : Electrophilic aromatic sulfonation of benzene with sulfur trioxide is studied with ab initio molecular dynamics simulations in gas phase, and in explicit noncomplexing (CCl3 F) and complexing (CH3 NO2 ) solvent models. We investigate different possible reaction pathways, the number of SO3 molecules participating in the reaction, and the influence of the solvent. Our simulations confirm the existence of a low-energy concerted pathway with formation of a cyclic transition state with two SO3 molecules. Based on the simulation results, we propose a sequence of elementary reaction steps and a kinetic model compatible with experimental data. Furthermore, a new alternative reaction pathway is proposed in complexing solvent, involving two SO3 and one CH3 NO2 .