CN103864743B - A kind of synthesis technique of natural active product dihydroquercetin - Google Patents
A kind of synthesis technique of natural active product dihydroquercetin Download PDFInfo
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- CN103864743B CN103864743B CN201410116113.8A CN201410116113A CN103864743B CN 103864743 B CN103864743 B CN 103864743B CN 201410116113 A CN201410116113 A CN 201410116113A CN 103864743 B CN103864743 B CN 103864743B
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- C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
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- C07D311/04—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring
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- C07D311/28—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 4 with aromatic rings attached in position 2 or 3 with aromatic rings attached in position 2 only
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Abstract
The present invention discloses (2R; 3R)-dihydroquercetin synthesis technique; specifically with coffic acid acyl chlorides and Phloroglucinol for raw material; through a gram acidylate of paying through an intermediary in a business deal; double bond peroxide changes into epoxy bond; acidic conditions open loop becomes ether with phenolic hydroxyl group again, and reaction end is carried out being separated, purifying, crystallization obtain high-content and highly purified product.Use in reagent, supplementary material in reaction and all consider with environmental protection, efficiency.Present method has that atom economy type, equipment are simple, production sequence environmental protection, has very large economic and social benefit.
Description
Technical field
The present invention relates to a kind of active skull cap components (2R; the synthesis of 3R)-dihydroquercetin; being specifically related to synthesis material is coffic acid acyl chlorides and Phloroglucinol; relate to reaction and comprise a pair gram acidylate; double bond peroxide changes into epoxy bond; acidic conditions open loop becomes ether with phenolic hydroxyl group again, and separation, purifying obtain (2R, 3R)-dihydroquercetin.
Background technology
Dihydroquercetin chemistry (2R, 3R) by name-3,3', 4', 5,7-penta hydroxy group-flavanone, is also taxifolin, taxifolin and Taxifolin.Dihydroquercetin has extensive biological activity, activity by regulatory enzyme affects metabolism of fat, strong restraining effect is had to malignant lymphocytic growth and leukemia cell, there is stronger bacteriostatic action to streptococcus aureus, intestinal bacteria, dysentery bacterium and Corynebacterium diphtheriae, also have restraining effect and antioxygenation to viral enzyme.As the derivative of Quercetin, its its have biological characteristicses more better than Quercetin, as various activity is stronger, water-soluble better, be more conducive to absorption of human body and biological effectiveness is higher.Therefore, its application widely, uses more and more at food, healthcare products and field of medicaments, and will maintain the trend of sustainable growth in longer for some time in future.
There are three approach in taxifolin source, and one is that extraction and isolation obtains from natural matter, and two is be that raw material is semi-synthetic with catechin, and three is carry out complete synthesis with simple industrial chemicals.
The natural resource of dihydroquercetin mainly contain pinaceae plant tamarack, Pseudotsuga menziesii (Mirbel) Franco, Jin Liumeike plant line elite stand, rosaceous plant black cherry, timber, root of Hairyvein Agrimonia, Anacardiaceae plant Chinese pistache heartwood, and labiate pacifies vigorous sheath stamen floral leaf.The technique of its extraction and isolation, (woods is strong in its Master's thesis for Lin Qiang, the production technique of dihydroquercetin is improved, Northwest University, master thesis, 2009) summarize and extract route and can be divided into two classes: one is offer sacriffices to the gods or the spirits of the dead leaf or Rosa davurica stem etc. for raw material with Huang, first extract sugared former times analog derivative of dihydro canopy skin element, obtain dihydro slack skin element monomer by acid hydrolysis again, this technique document yield is generally about 1%.Two is with larchen bark or wood chip for raw material, and extracting directly goes out dihydro canopy skin element monomer, and this technique document yield is generally at 1-2%.Lin Qiang is the operational path that raw material extracts dihydroquercetin by optimizing with tamarack, makes yield reach 2.6.But total yield is still not high, too large to natural resource consumption, the unit cost of production is high, is unfavorable for Industry Promotion.
The semi-synthetic of dihydroquercetin is the report (Nour-EddineEs-Safi in 2007 such as Nour-EddineEs-Safi; SouhilaGhidouehe; PaulHDuerot, Flavonoids, Hemisynthesis; Reaetivity; CharaeterizationandFreeRadiealSeavengingAetivity [J], Moleeules, 2007; 12 (9): 2228-2258) be semi-synthetic raw material with catechin, through benzyl protection, oxidation and deprotection overall yield also less than 10%.Raw materials cost is expensive, does not have further commercial exploitation to be worth.
The representational complete synthesis technique of most by Sun Shuxiang (Sun Shuxiang. the synthesis [J] of flavanonol, modern chemical industry, 1998,18 (12): 27-29) and Li Shaoshun etc. (Li Shaoshun, meter will is loyal. complete synthesis [J] of natural anti-liver cell cytotoxic activity compound 2R, 3R (+) silibinin, China's pharmaceutical chemistry magazine, 1997,7 (2): 107-111) the complete synthesis of taxifolin is all reported.They for raw material, through phenolic hydroxyl group protection, condensation, peroxidation, dephenolize hydroxyl protection with become ether, obtain product with 2,4,6-trihydroxy--methyl phenyl ketone and 3,4-Dihydroxy benzaldehyde.Five step reactions, finally total molar yield is less than 10%, and also used as hazardous chemicals such as NaH, Atom economy is low simultaneously, and by product is many, is difficult to be separated and process, is unsuitable for industrialized production.
Above method is some shortcomings below the method preparing taxifolin exists: (1) natural extract shortcoming has resource utilization low, after extracting dihydroquercetin, affects extraction and the utilization of other activeconstituentss, causes cost too high; Meanwhile, use column chromatography and large water gaging in extraction and isolation process, energy consumption is high, pollution is large, is difficult to obtain high purity and high-content dihydroquercetin.(2) be that starting raw material synthesizing dihydro Quercetin shortcoming is with catechin, reaction requires strict, and productive rate is extremely low, causes by product many, and multi-environment is polluted large, uneconomical.(3) 2,4,6-trihydroxy--methyl phenyl ketone and 3,4-Dihydroxy benzaldehyde is that the complete synthesis shortcoming of raw material is many for reacting step number, and finally total molar yield, less than 10%, has also been used as hazardous chemicals such as NaH simultaneously, Atom economy is low, by product is many, is difficult to be separated and process, is unsuitable for industrialized production.
For solving above-mentioned preparation (2R; the shortcoming of 3R)-dihydroquercetin; present invention process route adopts the complete synthesis route of shorter, environmental protection more, innovation; directly with coffic acid acyl chlorides and Phloroglucinol for raw material; through a gram acidylate of paying through an intermediary in a business deal; double bond peroxide changes into epoxy bond, then acidic conditions open loop becomes ether with phenolic hydroxyl group, and three-step reaction obtains dihydroquercetin.This route prepares that dihydroquercetin cost is low, technique is simple, environmental protection, productive rate are high, has extraordinary using value.
The different characteristics part of the present invention and aforesaid method is: (1) have employed new starting raw material coffic acid acyl chlorides and Phloroglucinol, and make syntheti c route shorter, yield is higher.(2) other supplementary materials are all conventional reaction reagent, gentle, safety, and contamination-free produces, and technique is environmental protection more.(3) complete synthesis dihydroquercetin has that impurity is few, purity is high and the high advantage of content, better than the dihydroquercetin quality of natural extract, cost is low.(4) route is shorter, and equipment is simpler, operates more succinct.The route of excellent suitability for industrialized production is above from economy, environment and Occupational health angle.
Summary of the invention
The present invention needs the key problem solved to be the shortcoming overcoming existing dihydroquercetin preparation technology, sets up environmental friendliness, low cost, succinct from coffic acid acyl chlorides and Phloroglucinol synthesizing dihydro Quercetin industrialized producing technology.
Object of the present invention is achieved through the following technical solutions, and concrete route is shown in Figure of description.
Dihydroquercetin synthesis route is coffic acid acyl chlorides and Phloroglucinol is raw material; through a gram acidylate of paying through an intermediary in a business deal; double bond peroxide changes into epoxy bond, then acidic conditions open loop becomes ether with phenolic hydroxyl group, and reaction end is carried out being separated, purifying, crystallization obtain high-content and highly purified product.Concrete steps are as follows:
1, in enamel reaction still, add methylene chloride and reaction raw materials coffic acid acyl chlorides, chuck is cooled to about 5 DEG C, adds aluminum trichloride (anhydrous) in batches, and control temperature is at 5-10 DEG C, stirring reaction 1-2h, forms complex compound.Continue control temperature within 10 DEG C, add raw material Phloroglucinol in batches, and slowly rise to room temperature, then stirring reaction 3-5h, thin-layer chromatography monitoring raw material coffic acid acyl chlorides complete reaction, is considered as acylation reaction and completes.Be cooled within 10 DEG C, slowly add the sodium hydroxide solution of 5% to about pH9, hydrolysis.Again with 5% dilute hydrochloric acid adjust pH to 6-7, stratification.After separating organic phase, then with dichloromethane extraction once, merge organic phase, dry, concentrating under reduced pressure, obtains 1-coffee acyl-2,4,6-trihydroxy-phenol crude intermediate;
2, in enamel reaction still; add 1-coffee acyl-2,4,6-trihydroxy-phenol with solvent methanol stirring and dissolving; chuck is cooled to about 5 DEG C; add metachloroperbenzoic acid, and control temperature is at 15-20 DEG C, stirring reaction 3-4h in batches; thin-layer chromatography monitoring raw material 1-coffee acyl-2; this disappearance of 4,6-trihydroxybenzene phenolic group, is considered as oxidizing reaction and completes.Be cooled within 10 DEG C, slowly add saturated sodium sulfite solution removing peroxide metachloroperbenzoic acid, concentrating under reduced pressure, reclaims methyl alcohol.Add water and dichloromethane extraction twice again, merge organic phase, dry, concentrating under reduced pressure, obtains 1-(3,4-dihydroxyl)-phenyl, 2-(2,4,6-trihydroxy-) phenyl-oxirane crude intermediate, dry for standby;
3, in enamel reaction still, add the 1-(3 of methylene chloride and reaction raw materials drying, 4-dihydroxyl)-phenyl, 2-(2,4,6-trihydroxy-) phenyl-oxirane intermediate, after stirring and dissolving, chuck is cooled to about 5 DEG C, slowly adds strong acid catalyst, and control temperature is at 0-5 DEG C, stirring reaction 5-8h.Thin-layer chromatography monitoring raw material midbody complete reaction, is considered as into ether and has reacted.With saturated sodium bicarbonate solution adjust pH to 6-7, stratification.After separating organic phase, then with dichloromethane extraction once, merge organic phase, dry, concentrating under reduced pressure, dihydroquercetin crude product.Crude product is with dehydrated alcohol heat of solution, and essence filter, reconcentration, decrease temperature crystalline, obtain high purity, high-content taxifolin fine work.
The invention provides (2R; 3R)-dihydroquercetin synthesis technique; with coffic acid acyl chlorides and Phloroglucinol for raw material; through a gram acidylate of paying through an intermediary in a business deal; double bond peroxide changes into epoxy bond; acidic conditions open loop becomes ether with phenolic hydroxyl group again, and reaction end is carried out being separated, purifying, crystallization obtain high-content and highly purified product.Use in reagent, supplementary material in reaction and all consider with environmental protection, efficiency.Present method has that atom economy type, equipment are simple, production sequence environmental protection, has very large economic and social benefit.
Accompanying drawing explanation
Taxifolin synthetic route is shown in accompanying drawing.
Embodiment
Further illustrate the present invention in the following embodiments, this does not limit the scope of the invention.
The synthesis of embodiment 11-coffee acyl-2,4,6-trihydroxy-phenol
In 500L enamel reaction still, add 200L methylene dichloride and reaction raw materials coffic acid acyl chlorides 40.0kg, chuck is cooled to about 5 DEG C, add aluminum trichloride (anhydrous) 13.5kg, and control temperature is at 5-10 DEG C in batches, stirring reaction 2h, forms complex compound.Continue control temperature within 10 DEG C, add raw material Phloroglucinol 26.0kg in batches, and slowly rise to room temperature, then stirring reaction 4h, thin-layer chromatography monitoring raw material coffic acid acyl chlorides complete reaction, is considered as acylation reaction and completes.Be cooled within 10 DEG C, slowly add the sodium hydroxide solution of 5% to about pH9, hydrolysis 0.5h.Again with 5% dilute hydrochloric acid adjust pH to 6-7, stratification.After separating organic phase, then with 100L dichloromethane extraction once, merge organic phase, dry, concentrating under reduced pressure, dry, obtain 1-coffee acyl-2,4,6-trihydroxy-phenol crude intermediate 55.3kg.
Embodiment 21-(3,4-dihydroxyl)-phenyl, 2-(2,4,6-trihydroxy-) synthesis of phenyl-oxirane
In 500L enamel reaction still; add 1-coffee acyl-2,4,6-trihydroxy-phenol 55.0kg with 300L methyl alcohol stirring and dissolving; chuck is cooled to about 5 DEG C; add metachloroperbenzoic acid 40.0kg, and control temperature is at 15 DEG C, stirring reaction 4h in batches; thin-layer chromatography monitoring raw material 1-coffee acyl-2; this disappearance of 4,6-trihydroxybenzene phenolic group, is considered as oxidizing reaction and completes.Be cooled within 10 DEG C, slowly add saturated sodium sulfite solution 12.5L and remove peroxide metachloroperbenzoic acid, concentrating under reduced pressure, reclaim methyl alcohol.Add 150L water and 200L dichloromethane extraction twice again, merge organic phase, dry, concentrating under reduced pressure, obtains 1-(3,4-dihydroxyl)-phenyl, 2-(2,4,6-trihydroxy-) phenyl-oxirane crude intermediate, dry and obtain 51.7kg.
The synthesis of embodiment 3 dihydroquercetin
In 500L enamel reaction still, add the 1-(3 of 200L methylene dichloride and reaction raw materials drying, 4-dihydroxyl)-phenyl, 2-(2,4,6-trihydroxy-) phenyl-oxirane intermediate 50.0kg, after stirring and dissolving, chuck is cooled to about 5 DEG C, slowly adds strong acid catalyst trifluoroacetic acid 10.0L, and control temperature is at 0-5 DEG C, stirring reaction 5h.Thin-layer chromatography monitoring raw material midbody complete reaction, is considered as into ether and has reacted.With saturated sodium bicarbonate solution adjust pH to 6-7, stratification.After separating organic phase, then with 100L dichloromethane extraction once, merge organic phase, dry, concentrating under reduced pressure, drying obtains dihydroquercetin crude product 45.8kg.Crude product is with dehydrated alcohol 230L heat of solution, and essence filter, reconcentration, decrease temperature crystalline, obtain high purity, high-content taxifolin fine work 41.3kg.
Claims (6)
1. a preparation method for (2R, 3R)-dihydroquercetin product, is characterized in that, comprise the steps:
Step one: with coffic acid acyl chlorides and Phloroglucinol for raw material, obtain intermediate product A through paying a gram acylation reaction, the structural formula of described intermediate product A is:
Step 2: described intermediate product A is changed into epoxy bond through double bond peroxide and obtains intermediate product B, the structural formula of described intermediate product B is:
Step 3: by described intermediate product B in acid condition open loop become ether with phenolic hydroxyl group, carry out being separated after reaction terminates, purifying, crystallization obtain (2R, 3R)-dihydroquercetin product, the structural formula of described (2R, 3R)-dihydroquercetin is:
Wherein, the temperature of described pair of gram acylation reaction is room temperature, and the temperature of described peroxidation is 15-20 DEG C, and the temperature of described one-tenth ether reaction is 0-5 DEG C.
2. the preparation method of (2R, 3R) according to claim 1-dihydroquercetin product, is characterized in that paying gram acylation reaction catalyst is aluminum trichloride (anhydrous), needs, at low temperature 5-10 DEG C, to form complex compound with reaction raw materials coffee acyl chlorides.
3. the preparation method of (2R, 3R) according to claim 2-dihydroquercetin product, is characterized in that the reaction of formation complex compound and a pair gram acylation reaction solvent are methylene dichloride, described pair gram of acylation reaction time 3-5h.
4. the preparation method of (2R, 3R) according to claim 1-dihydroquercetin product, it is characterized in that peroxidation reagent is metachloroperbenzoic acid, feed temperature controls at 3-7 DEG C.
5. the preparation method of (2R, 3R) according to claim 1-dihydroquercetin product, it is characterized in that into ether reaction and use strong acid to comprise hydrogenchloride, tosic acid, methylsulfonic acid and trifluoroacetic acid, reaction solvent is methylene dichloride.
6. the preparation method of (2R, 3R) according to claim 1-dihydroquercetin product, it is characterized in that crystallization is take dehydrated alcohol as solvent, and crystallization mode is cooling stirred crystallization.
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| CN102070592A (en) * | 2011-01-26 | 2011-05-25 | 陕西嘉禾植物化工有限责任公司 | Synthesis method of dihydroquercetin |
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| CN102070592A (en) * | 2011-01-26 | 2011-05-25 | 陕西嘉禾植物化工有限责任公司 | Synthesis method of dihydroquercetin |
Non-Patent Citations (3)
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| Non-heme manganese complexes of C1-symmetric N4 ligands: Synthesis, characterization and asymmetric epoxidations of α,β-enones;Bin Wang et al.;《Journal of Organometallic Chemistry》;20120915;第715卷;9-12 * |
| Synthesis and antibacterial activity of epoxides derived from chalcones;Asif Husain et al.;《Asian Journal of Chemistry》;20051231;第17卷(第1期);624-626 * |
| Synthesis of Isobavachalcone and Some Organometallic Derivatives;John P. Grealis er al.;《Eur. J. Org. Chem.》;20121109;第2013卷;332–347 * |
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Denomination of invention: Synthetic process of natural active product dihydroquercetin Effective date of registration: 20210930 Granted publication date: 20160420 Pledgee: Agricultural Bank of China Limited Zhangjiagang branch Pledgor: ZHANG JIA GANG VINSCE BIO-PHARM Co.,Ltd. Registration number: Y2021320010400 |
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Address after: No. 2, Nanjing Middle Road, Jiangsu Yangzijiang Chemical Industrial Park, Zhangjiagang Free Trade Zone, Suzhou City, Jiangsu Province, 215634 Patentee after: Wison Biomedical (Suzhou) Co.,Ltd. Address before: 215634 No. 2 Nanjing Middle Road, Yangtze River Chemical Industrial Park, Zhangjiagang Free Trade Zone, Suzhou City, Jiangsu Province Patentee before: Weisheng Biomedical (Suzhou) Co.,Ltd. Address after: 215634 No. 2 Nanjing Middle Road, Yangtze River Chemical Industrial Park, Zhangjiagang Free Trade Zone, Suzhou City, Jiangsu Province Patentee after: Weisheng Biomedical (Suzhou) Co.,Ltd. Address before: 215634 Building D, No. 7 Guangdong Road, Zhangjiagang Free Trade Zone, Suzhou City, Jiangsu Province (Weisheng) Patentee before: ZHANG JIA GANG VINSCE BIO-PHARM Co.,Ltd. |
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Date of cancellation: 20221031 Granted publication date: 20160420 Pledgee: Agricultural Bank of China Limited Zhangjiagang branch Pledgor: ZHANG JIA GANG VINSCE BIO-PHARM Co.,Ltd. Registration number: Y2021320010400 |