600-17-9Relevant articles and documents
Rambaud
, p. 1348 ()
Influence of the Interaction between a Tin Catalyst and an Accelerator on the Formose-Inspired Synthesis of α-Hydroxy-γ-butyrolactone
Yamaguchi, Sho,Matsuo, Takeaki,Motokura, Ken,Miyaji, Akimitsu,Baba, Toshihide
, p. 1386 - 1391 (2016/04/20)
In this study, we focused on the tin-catalyzed transformation of formaldehyde into α-hydroxy-γ-butyrolactone (HBL) in the presence of an α-hydroxy carbonyl compound as the accelerator. The screening of various accelerators aided in clarifying the structural prerequisites of the accelerator for the formose-inspired synthesis of HBL. To investigate the influence of the interactions between the tin metal and the accelerator on the catalytic activity, we performed a deuterium-exchange experiment with α-hydroxyacetophenone followed by in situ 119Sn NMR spectroscopy and X-ray absorption fine structure measurements. On the basis of the experimental results, we proposed a reaction mechanism to obtain HBL.
Mechanistic Studies on the Cascade Conversion of 1,3-Dihydroxyacetone and Formaldehyde into α-Hydroxy-γ-butyrolactone
Yamaguchi, Sho,Matsuo, Takeaki,Motokura, Ken,Sakamoto, Yasuharu,Miyaji, Akimitsu,Baba, Toshihide
, p. 853 - 860 (2015/06/02)
Abstract The chemical synthesis of commercially and industrially important products from biomass-derived sugars is absolutely vital to establish biomass utilization as a sustainable alternative source of chemical starting materials. α-Hydroxy-γ-butyrolactone is a useful synthetic intermediate in pharmaceutical chemistry, and so novel biomass-related routes for its production may help to validate this eco-friendly methodology. Herein, we report the specific catalytic activity of homogeneous tin halides to convert the biomass-derived triose sugar 1,3-dihydroxyacetone and formaldehyde into α-hydroxy-γ-butyrolactone. A detailed screening of catalysts showed the suitability of tin catalysts for this reaction system, and isotope experiments using [D2]paraformaldehyde, substrate screening, and time profile measurements allowed us to propose a detailed reaction pathway. In addition, to elucidate the activated species in this cascade reaction, the effect of additional water and the influence of additional Bronsted acids on the reaction preferences for the formation of α-hydroxy-γ-butyrolactone, lactic acid, and vinyl glycolate were investigated. The active form of the Sn catalyst was investigated by 119Sna NMR spectroscopy. Specific catalytic activity of homogeneous tin halides: We present a complete map of the synthetic pathway to α-hydroxy-γ-butyrolactone and related byproducts from 1,3-dihydroxyacetone and formaldehyde. Furthermore, we propose a catalytic mechanism and a valence state of the catalyst in the reaction mixture based on the results of 119Sn NMR spectroscopy.
