Presently, very few compounds of commercial interest are directly accessible from carbohydrates by using nonfermentive approaches. We describe here a catalytic process for the direct formation of methyl lactate from common sugars. Lewis acidic zeotypes, such as Sn-Beta, catalyze the conversion of mono- and disaccharides that are dissolved in methanol to methyl lactate at 160 degrees C. With sucrose as the substrate, methyl lactate yield reaches 68%, and the heterogeneous catalyst can be easily recovered by filtration and reused multiple times after calcination without any substantial change in the product selectivity.
Zeozymes: Sn‐Beta zeolite is found to be a highly active catalyst for the conversion of triose sugars. If the solvent is water, isomerization of the triose sugars takes place to form lactic acid in 90 % yield at 125 °C. If methanol is used as the solvent, an overall isomerization–esterification reaction takes place and methyl lactate is formed in quantitative yields at 80 °C. This represents one of the most selective zeolite‐catalyzed biomass transformation reactions.
Isomerization reactions of glucose were catalyzed by different types of commercial zeolites in methanol and water in two reaction steps. The most active catalyst was zeolite Y, which was found to be more active than the zeolites beta, ZSM-5, and mordenite. The novel reaction pathway involves glucose isomerization to fructose and subsequent reaction with methanol to form methyl fructoside (step 1), followed by hydrolysis to re-form fructose after water addition (step 2). NMR analysis with (13)C-labeled sugars confirmed this reaction pathway. Conversion of glucose for 1 h at 120 °C with H-USY (Si/Al = 6) gave a remarkable 55% yield of fructose after the second reaction step. A main advantage of applying alcohol media and a catalyst that combines Brønsted and Lewis acid sites is that glucose is isomerized to fructose at low temperatures, while direct conversion to industrially important chemicals like alkyl levulinates is viable at higher temperatures.
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