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A process for synthesizing vanillin by bio-enzyme-catalyzed oxidation

A technology for catalytic oxidation and vanillin, applied in the direction of fermentation, etc., can solve the problems of low yield of the process route, complex medium components, unstable product quality, etc., and achieve the effects of simple process operation, easy amplification, and small side effects.

Active Publication Date: 2017-12-08
BOTON SHANGHAI BIOLOGICAL TECH CO LTD
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

For example, "Enterobacter mulberry and its biotransformation method for ferulic acid to produce ferulic acid natural vanillin" (Chinese patent CN103215197A) and "A Bacillus subtilis and its method for biotransformation of ferulic acid to produce vanillin" (Chinese Patent CN102443551A), although the reaction steps are simple, the conditions are mild, and the cost of carbon source and nitrogen source is low, but it takes a long time, the composition of the culture medium is complicated, the cost is large, and the yield of the process route is not high (50-60%), it is difficult to industrialize zoom in
Another example is "Preparation Process of Aromatic Carbonyl Compounds from Olefins" (US6331655, U.S. Patent) and "A Method for Preparing Vanillin" (Chinese Patent, CN102367222), respectively using lipase and hemoglobin as biocatalysts to catalyze the oxidation of hydrogen peroxide Isoeugenol prepares vanillin. Although the reaction steps are simple, the conditions are mild, and the time is short, it is difficult to scale up industrialization due to the low yield of the process route (40-55%) and unstable product quality.

Method used

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Examples

Experimental program
Comparison scheme
Effect test

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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PUM

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Abstract

A method for preparing vanillin catalyzed by lipase. In a reaction kettle, solvent, substrate coniferyl alcohol / coniferaldehyde / ferulic acid, lipase, dibasic acid or dibasic acid derivative, hydrogen peroxide are sequentially added The step of urea, wherein the lipase mass is 1%-4% of the substrate isoeugenol mass; the molar mass of dibasic acid or dibasic acid derivative is 0.75-1.5 times of the substrate molar mass; the molar mass of urea hydrogen peroxide is 1-2 times the molar mass of the substrate; the addition temperature of urea hydrogen peroxide is 15-35 degrees, the reaction temperature is 20-40 degrees, and after the reaction time is 14-36 hours, filter, separate and recover urea and enzyme catalyst filtrate is diluted with water , organic solvent extraction, edible alcohol recrystallization, and drying to obtain vanillin. The mother liquor after organic solvent extraction is complexed by sodium bisulfite or sodium sulfite, and the by-product of aldehyde is recovered. The vanillin yield of the method can reach 85%, the reaction steps are simple, the conditions are mild, the catalytic specificity is strong, by-products are not easy to be produced, the product yield is high, the method is friendly to the environment, and can be easily scaled up.

Description

technical field [0001] The invention relates to a technique for synthesizing vanillin catalyzed by biological enzymes. Background technique [0002] Vanillin (Vanillin), also known as vanillin, vanillin, etc., is the main component of vanillin beans, the chemical name is 3-methoxy-4-hydroxybenzaldehyde, the relative molecular weight is 152.1, and the appearance is white To light yellow needle-like crystal or powder, showing the unique aroma of vanilla orchid pods, slightly sweet. Vanillin is one of the largest and most widely used spices in the world. Widely used in chocolate, ice cream, candy and other foods as well as cigarettes, beverages and high-end cosmetics. It can not only be used as a flavor enhancer, but also as a preservative, fresh-keeping agent, antioxidant, flavoring agent or fixative in food, among which beverages, candies, pastries, biscuits, bread and roasted seeds and nuts are mostly used in food, and In other industries, such as medicine, electroplating...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C12P7/24
CPCC12P7/24
Inventor 李斌彭春睿
Owner BOTON SHANGHAI BIOLOGICAL TECH CO LTD