6946-35-6Relevant articles and documents
Catalytic Activity of Quaternary Ammonium Poly(methylstyrene-co-styrene) Resin in an Organic Solvent/Alkaline Solution
Wu, Ho-Shing,Lee, Chun-Shen
, p. 217 - 223 (2001)
The reaction of 4-methoxyphenylacetic acid with n-bromobutane using triphase catalysis in a dichloromethane/alkaline solution was investigated. Meanwhile, the lab-produced resins and the commercial ion-exchange resin (triphase catalyst) were characterized in terms of the density of active sites, thermal stability, imbibed solvent composition, and reuse of the resin. The amount of active sites in the resin was characterized by EA, TGA, and Volhard methods. The imbibed amounts of organic solvent and water and the volume ratios for lab-produced resins were larger than those for commercial resins. The degradation of the catalyst due to temperature is greater than that due to base concentration.
Encapsulation of heteropolyacids within hollow microporous polymer nanospheres for sustainable esterification reaction
He, Zhiwei,Huang, Kun,Song, Chunmei,Wang, Huaqing,Yu, Haitao,Zhang, Li
, (2021/10/25)
Herein, the Keggin structural phosphotungstic acid (HPW) has been successfully encapsulated within hollow microporous polymer nanospheres (H-MPNs) by a “ship-in-bottle” approach. The H-MPNs are formed by self-assembly induced by hyper-crosslinking of polylactide-b-polystyrene (PLA-b-PS). The obtained catalysts (HPW@H-MPNs) exhibit more sustainable availability than the previously reported HPW-supported catalysts in esterification reaction. This excellent sustainability can be attributed to the stable microporous channels in H-MPNs which are smaller than the molecular size of HPW, thereby effectively preventing the HPW from leaking out. Moreover, such catalysts also perform well in terms of catalytic activity and universality because of the combination of a hollow structure in the interior and permeable pore channels in the shells. This type of polymer carrier and general encapsulation method may provide a new strategy for developing more sustainable catalysts for various chemical reactions.
Enolate-Based Regioselective Anti-Beckmann C-C Bond Cleavage of Ketones
Jahn, Ullrich,Ma?ek, Tomá?
, p. 11608 - 11632 (2021/09/02)
The Baeyer-Villiger or Beckmann rearrangements are established methods for the cleavage of ketone derivatives under acidic conditions, proceeding for unsymmetrical precursors selectively at the more substituted site. However, the fragmentation regioselectivity cannot be switched and fragmentation at the less-substituted terminus is so far not possible. We report here that the reaction of ketone enolates with commercial alkyl nitrites provides a direct and regioselective way of fragmenting ketones into esters and oximes or ω-hydroxyimino esters, respectively. A comprehensive study of the scope of this reaction with respect to ketone classes and alkyl nitrites is presented. Control over the site of cleavage is gained through regioselective enolate formation by various bases. Oxidation of kinetic enolates of unsymmetrical ketones leads to the otherwise unavailable "anti-Beckmann"cleavage at the less-substituted side chain, while cleavage of thermodynamic enolates of the same ketones represents an alternative to the Baeyer-Villiger oxidation or the Beckmann rearrangement under basic conditions. The method is suited for the transformation of natural products and enables access to orthogonally reactive dicarbonyl compounds.