Gastrodin synthesizing method

Abstract

The invention relates to a gastrodin synthesizing method, which can effectively solve the preparation problem of gastrodin to meet the requirements of the gastrodin in pharmaceuticals. The method comprises the steps of adding catalyst perchloric acid, acetylating anhydrous dextrose by using acetic anhydride to produce per-acetyl dextrose, feeding hydrogen bromide to bromizing hemiacetal hydroxyl of the per-acetyl dextrose to produce bromo-tetraacethyl glucose, further and dropwise adding a bromo-tetraacethyl glucose solution into chloroform and tetrabutyl ammonium bromide, carbonate and para hydroxybenzene in water to obtain 4-formyl benzene-2', 3', 4', 6'- tetraacetyl-beta-D-glucopyranose, performing re-crystallization with ethanol, adding raney nickel or palladium and carbon, feeding hydrogen and pressurizing to hydrogenate, performing filtering, adding sodium alcoholate or ammonia in to filtrate to perform protecting group removal until the reaction is finished completely, performing pressure reduction and concentration to obtain crude gastrodin, and re-crystallizing the crude gastrodin by using alcohol or an alcohol and ester solvent or an alcohol and ketone solvent to obtain the gastrodin. The gastrodin synthesizing method is abundant and cheap in raw materials, simple in process, recycled in solvent, small in pollution and high in quality.

Description

technical field [0001] The invention relates to medicine, in particular to a method for synthesizing gastrodin. Background technique [0002] Gastrodin is the active ingredient of the traditional Chinese medicine Gastrodia elata. Its chemical name is 4-hydroxymethylphenyl-β-D-glucopyranoside [4-(hydroxymethyl)phenyl-β-D-Glucopyranoside]. The chemical structure is shown in figure 1 As shown, the molecular formula is C 13 h 18 o 7 , the molecular weight is 286.28, it has good pharmacological effects such as sedation and sleep, it is mainly used clinically to treat dizziness and headache, deafness, tinnitus, neurasthenia and so on. [0003] There are many research reports on the synthesis method of gastrodin, mainly including: Zhou Jun first isolated and synthesized gastrodin from Gastrodia elata in 1980. The synthesis method was to use perchloric acid to catalyze acetic anhydride and react with glucose to obtain pentaacetylglucose, and then use red phosphorus and brom...

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Problems solved by technology

[0003] There are many research reports on the synthesis method of gastrodin, mainly including: Zhou Jun first isolated and synthesized gastrodin from Gastrodia elata in 1980. The synthesis method was to use perchloric acid to catalyze acetic anhydride and react with glucose to obtain pentaacetylglucose, and then use red phosphorus and bromine to react with pentaacetyl sugar to obtain bromine Substituting tetraacetylglucose, bromotetraacetylglucose, and p-hydroxybenzaldehyde in acetone solution for condensation reaction, the resulting condensate is then reduced, re-acetylated, saponified, recrystallized and other steps to finally obtain gastroside, in this synthesis process A large amount of toxic red phosphorus and bromine are used, which cause serious environmental pollution and serious harm to the human body; In 1984, Pang Qijie and others proposed an improved method for the synthesis of gastrodin [Pang Qijie, Zhong Yuguo. Improvement of the synthesis method of gastrodin [J] Pharmaceutical Industry, 1984, (03) ], changing potassium borohydride to Raney nickel catalytic addition in one step. Hydrogen, but the Raney nickel used is the most active w-6 type, which is prone to fire; Li Chunqiu et al [Li Chunqiu, Wu Junming, Chen Yao. The application of phase transfer catalysis in the synthesis of gastroside [J] Journal of Yangzhou Normal University (Natural Science Edition), 1983, (02)], initially discussed the use of phase The transfer catalyst synthesizes the condensate, but the chloroform and sodium hydroxide used in it are relatively prone to side reactions, resulting in the generation of impurities in the resulting condensate, and the generated impurities are more difficult to remove from the target product; Dai Xiaochang and others improved the first two steps of gastrodin synthesis [Dai Xiaochang, Peng Xiao, Wu Songfu, Yang Wansong, Mao Yu. Chemical synthesis of gastrodin and its similar phenolic glycosides[J] Yunnan University for Nationalities Journal (Natural Science Edition), 2004, (02)], replaced red phosphorus and bromine with phosphorus tribromide and water, added potassium iodide in the condensation reaction and made this step yield improved, but the price of potassium iodide is expensive and It is not easy to preserve. It can be seen from the above that there are still many problems in the synthesis of gastrodin. The price of phosphorus tribromide is relatively expensive. In the method of condensate, chloroform and sodium hydroxide itself will produce side reactions in the phase transfer reaction, so that the condensate synthesized is not pure, and the impurities generated in the reaction are not easy to completely remove, which has caused the rise of production costs and A waste of time, potassium iodide has a good catalytic effect, but it is more expensive and not easy to store

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