Semi-synthesis method of luteolin and galuteolin as well as luteolin rutinoside

Abstract

The invention relates to a semi-synthesis method of luteolin and galuteolin as well as luteolin rutinoside by using hesperidin, a semi-synthesis method of the galuteolin by using hesperetin glucoside, and a semi-synthesis method of the luteolin by using hesperetin, and belongs to the field of chemistry and medicines. The semi-synthesis method comprises the following steps: enabling the hesperidin, the hesperetin glucoside and the hesperetin to be subjected to complexation in pyridine alcohol fluid, dehydrogenizing by using iodine, directly distilling alcohol and pyridine, maintaining for a period of time in an airtight distilled state, and carrying out demethylation reaction, so that the hesperidin is generated into the luteolin rutinoside; generating the galuteolin by demethylation of diosmetin glucoside, and generating the luteolin by diosmetin; and hydrolyzing the luteolin rutinoside, so that the luteolin rutinoside is transformed into luteolin and galuteolin. The semi-synthesis method has the advantages that two steps of dehydrogenation and demethylation are combined into one step, and reaction conditions of dehydrogenation and demethylation are mild and easy to control; few reagents are used and green and environmentally friendly; and the demethylation yield is high, and the industrial production is easy. Compared with disclosed documents and patients, the semi-synthesis method has great advantages in the production of luteolin and glucosides of the luteolin.

Description

technical field [0001] The invention relates to a method for semi-synthesizing luteolin, luteolin, luteolin-rutin, hesperetin-7-O-glucoside, and semi-synthesizing luteolin from hesperetin , whose field belongs to chemistry and medicine. Background technique [0002] Comparison of hesperidin and luteolin resources: Hesperidin widely exists in Rutaceae plants, such as orange peel, etc. Citrus is also the largest fruit in the world. my country has abundant citrus resources, and the utilization of citrus in China is limited. In the utilization of citrus fruit, enough attention has not been paid to the peel, and citrus peel dregs account for 30% to 50% as a by-product of processing. Only a small part is recovered and used as tangerine peel and extracting hesperidin, but most of them are discarded, causing great waste and environmental pollution. The 2010 edition of the Chinese Pharmacopoeia stipulates that the content of hesperidin in green peel should not be less than 5.0%, and...

AI Technical Summary

Problems solved by technology

[0007] Defects of hesperidin semi-synthesis of luteolin: the above three methods of hesperidin semi-synthesis of luteolin are all three steps, and each step uses more organic reagents, some reagents are not recycled, which increases the cost on the one hand On the other hand, it pollutes the environment; every step of the product requires purification, drying and other treatments. On the one hand, the production cycle is long, and on the other hand, the sample will be lost during the process, which reduces the yield of the product and makes separation more troublesome.

Take the demethylation of diosmin as an example: slightly soluble in glacial acetic acid, demethylated with glacial acetic acid-HBr, the same glacial acetic acid-HBr is difficult to recover

Therefore, pyridine-aluminum trichloride is commonly used in its demethylation method, but because pyridine and aluminum trichloride form salts, it is difficult to form a homogeneous solvent, so its dosage is large, because pyridine can form salts with aluminum trichloride and phenol, recovery Limited rate, great environmental pollution

[0008] Luteolin semi-synthesis method and defects: Luteolin is luteolin-7-O-glucoside, which has a small content in plants. For example, the 2010 edition of Chinese Pharmacopoeia Honeysuckle stipulates that luteolin (C 21 h 20 o 11 ) is not less than 0.05%, chrysanthemum contains not less than 0.080% luteolin, while the chlorogenic acid content of mountain silver flower is higher than that of honeysuckle, but it does not contain luteolin. Due to the trace amount of luteolin, the price is 1 of honeysuckle. / 2-1 / 3, but its application range is far less than that of honeysuckle. The reason is that mountain silver flower does not contain luteolin, which makes people more respectful of honeysuckle

[0010] Demethylation and defects of glycoside compounds: In the total synthesis of puerarin, expensive iodotrimethylsilane and relatively expensive reagent acetonitrile were used as solvents for its demethylation ([4] Zhang Peicheng. Flavonoid Chemistry [M]. Chemical Industry Press, 2009, 357), demethylation, resulting in high product costs, and extraction from the natural plant Pueraria radiata, does not have the advantage of synthesis

[0014] O-diphenol has remarkable antioxidation and pharmacological effects: the two benzene rings of A and B are connected by three carbons to form flavonoids. When the A ring has 5-OH and 7-OH dihydroxyl groups, 7-OH often forms a glycosidic bond, and 5 -OH and 4C=O form intramolecular hydrogen bonds, so the A ring has weak oxidation resistance

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