Process for synthesizing vanillin by adopting bio-enzyme catalytic oxidation method
A technology of catalytic oxidation and vanillin, applied in the direction of fermentation, etc., can solve the problems of low yield of process route, complex medium composition, low yield of process route, etc., and achieve simple process operation, easy scale-up, and simple reaction steps Effect
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Embodiment 1
[0021] 1. In a 100ml three-necked flask, add cis-ferulic acid oil (0.1mol, 19.4g), lipase Novozyme 435 (0.19g), and under stirring, add diethyl oxalate (0.15mol, 22 g) dissolved urea hydrogen peroxide (0.2 mol, 18.8 g), the addition was completed within 1 hour, the temperature was kept at 35 degrees, and the reaction was carried out for 36 hours.
[0022] 2. Filtration, separation and recovery of urea and enzyme catalyst. The filtrate was diluted with aqueous solution and extracted with butyl acetate. Add sodium bisulfite to the extracted mother liquor, freeze and crystallize, filter and recover the solid as the by-product of sodium glyoxylate bisulfite adduct; recover butyl acetate from the extract, and crystallize the crude product with edible alcohol to obtain white needles Crystal 11.7 g, yield 77%.
Embodiment 2
[0024] 1. In a 100 ml three-necked flask, add 20 ml of toluene, coniferaldehyde (0.1 mol, 17.8 g), lipase (0.5 g), and under stirring, add oxalic acid (0.15 mol, 13.5 g) at 15 degrees, and then divide into 5 Add urea hydrogen peroxide (0.18mol, 16.9 grams) at a time, 3.38 grams each time, keep the temperature at 15 degrees, complete the addition within 2 hours, keep the temperature at 20 degrees, and react for 16 hours.
[0025] 2. Filtration, separation and recovery of urea and enzyme catalyst. The filtrate was diluted with aqueous solution and extracted with toluene. Sodium bisulfite was added to the extracted mother liquor, frozen and crystallized, and the solid recovered by filtration was the by-product of glyoxal sodium bisulfite adduct; toluene was recovered from the extract, and the crude product was crystallized with edible alcohol to obtain white needle-like crystals 12.6 grams, yield 83%.
Embodiment 3
[0027] 1. In a 100 ml three-necked flask, add 20 ml of methyl tert-butyl ether, coniferyl alcohol (0.1 mol, 18 g), lipase (0.4 g), and under stirring, add malonic acid (0.075 mol, 7.8 grams), then add urea hydrogen peroxide (0.15mol, 14.1 grams) in 5 times, each 2.82 grams, the temperature is maintained at 15 degrees, the addition is completed in 2.5 hours, the temperature is maintained at 30 degrees, and the reaction is 36 hours.
[0028] 2. Filtration, separation and recovery of urea and enzyme catalyst. The filtrate was diluted with aqueous solution and extracted with methyl tert-butyl ether. Sodium bisulfite is added to the extracted mother liquor, frozen and crystallized, and the solid recovered by filtration is the by-product of glycolaldehyde sodium bisulfite adduct; methyl tert-butyl ether is recovered from the extract, and the crude product is crystallized with edible alcohol to obtain 10.6 g of white needle-like crystals, yield 70%.
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