Covalently linked ethylmercaptophenyl sulfonic acid and ethylmercaptobenzyl sulfonic acid silica materials—Synthesis and catalytic activity

New covalently linked sulfonic acid modified silicas have been formed and characterised and their catalytic Brönsted activity evaluated. Thus phenylmercaptoethyltrimethoxysilane, (MeO)3SiCH2CH2SC6H5 and benzylmercaptoethyltrimethoxysilane, (MeO)3SiCH2CH2SCH2C6H5, were used to prepare the corresponding T-functional silica derivatives silica ∼ CH2CH2SC6H4-4-SO3H and silica ∼ CH2CH2SCH2C6H4-4-SO3H by grafting on commercial silica, followed by sulfonation of the aryl group. Solid-state NMR, DTA and surface area characteristics of the materials are reported. The mercaptophenylsulfonic acid materials are thermally robust highly efficient solid catalysts for a range of transformations including, esterification, etherification and carbonyl group protection. An apparent pore size effect on rate of conversion was observed. The mercaptobenzylsulfonic acid materials were comparatively unstable.

Graphical abstractIn this paper we report on new silica immobilized ethylmercaptophenyl and ethylmercaptobenzyl sulfonic acid catalysts where the position of the sulfide group has a marked effect on the stability of the catalyst. The mercaptophenylsulfonic acid catalysts are thermally robust and highly efficient for a range of transformations including, esterification, etherification and carbonyl group protection. An apparent pore size effect on rate of conversion was observed. The mercaptobenzylsulfonic acid materials were comparatively unstable. Figure optionsDownload full-size imageDownload as PowerPoint slide