The Synthesis of Sn-Containing Silicates Coated with Binaphthol and Their Specific Application for Catalytic Synthesis of 6-Hydroxyhexanoic Acid and Cyclohexylformate through Baeyer-Villiger Oxidation

Abstract

The Baeyer–Villiger oxidation (BVO) of ketone and aldehyde can produce ester and formate, which both have wide applications in many areas. In this work, a series of Sn-containing silicates were prepared through the sol-gel process by using structure-directing and crystallizing agents and post-synthetic coordinated modification of binaphthol. Characterizations revealed that loading of (L)-sodium lactate as the crystallizing agent decreased the crystal size of the synthesized catalyst, and there were SnO2 nanoparticles with sizes of 17–19 nm on the catalyst. Furthermore, quite differently from the 3D mesoporous structure of classical Sn-beta zeolites, the synthesized catalysts had a silt-like mesoporous structure. In the catalysis, when cyclic aliphatic ketones were used as the substrate, only BVO-type products and corresponding ring-opening products were obtained. BVO of aliphatic aldehyde produced both an aerobic oxidation product (carboxylic acid) and a BVO-type product. The presented transformation of aromatic aldehyde (benzaldehyde) only gave an aerobic oxidation product (benzoic acid). The post-synthetic coordinating attachment of (S)-binaphthol to the Sn-containing silicate backbone worsened the BVO of aliphatic ketones but improved the BVO of aliphatic aldehyde and the aerobic oxidation of aromatic aldehyde. In addition, this work also developed two new routes for the synthesis of high-value-added 6-hydroxyhexanoic acid and cyclohexylformate under catalytic BVO conditions.