CN1248992C - Preparation of oligomer and monomer from tannin by catalytic hydrogen degradation - Google Patents
Preparation of oligomer and monomer from tannin by catalytic hydrogen degradation Download PDFInfo
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- CN1248992C CN1248992C CNB2004100226165A CN200410022616A CN1248992C CN 1248992 C CN1248992 C CN 1248992C CN B2004100226165 A CNB2004100226165 A CN B2004100226165A CN 200410022616 A CN200410022616 A CN 200410022616A CN 1248992 C CN1248992 C CN 1248992C
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Abstract
The present invention discloses a preparation method for degrading vegetable tannin into products of oligomers and monomers through catalytic hydrogenolysis. The present invention is characterized in that vegetable materials containing rich tannin are selected and are not pulverized or pulverized into granules with the granule diameter of 1 to 15mm, water or alcohol or ketone mixed with water with arbitrary proportions is used as solvent, the vegetable materials are soaked, and extraction is carried out for 1 to 8 hours at normal pressure, or extraction is carried out for 1 to 4 hours under the conditions of reduced pressure and forced circulation, or extraction is carried out for 4 to 6 times through counterflow circulation. Solvent is recovered from the obtained extract through pressure reduction, filtration is carried out, gum and lipid substances are purified, and subsequently, components with different grades are obtained through extraction and grading with different kinds of solvent. One grade component in the components is selected to be used as reactants, catalytic hydrogenolysis reaction is carried out, and crude products of vegetable polyphenol monomers and oligomers are obtained. The crude products are purified through extraction and column chromatography or preparative chromatography, and refined and pure chemical industry products of oligomer proanthocyanidin, ellagic acid and gallic acid or glucose gallic acetyl ester.
Description
One, technical field
The present invention relates to the catalytic hydrogenolysis preparation method that a kind of vegatable tannin is degraded to oligomer, monomeric compound.This method can be used for by condensed tannin (poly proanthocyanidin) preparation oligomeric proanthocyanidins (OPC ' s), and prepare ellagic acid, tangerine acid, tangerine acyl ester glucose biological activeconstituents by hydrolysable tannins, also can be used for the degradation modification of tannin extract or tackiness agent, belong to field of fine chemical.
Two, background technology
Vegatable tannin is the plant polyphenol kind secondary substance that the plant secondary metabolism produces, and it extensively is present in leaf, wood, skin and the fruit of plant, is reproducible green resource.For example: tannin content is up to 20%-40% in the confierophyte bark, and there is the output of counting in hundred million tons in only this item whole world every year, so tannin is the important object of plant resources comprehensive utilization.Studies show that in a large number both at home and abroad over nearly 30 years: defence close relation such as tannin and plant resistance to environment stress physiology and adaptation physical abuse; Simultaneously, the local flavor and the hobby property of its participation formation numerous food product such as tealeaves, coffee, cocoa, grape wine etc.; In addition, when people eat grain, vegetables, fruit, also taken in tannin, it and human lives are with healthy closely bound up thereupon.There is viewpoint to think that plant polyphenol is " the 5th nutrient substance " after sugar, fat, protein, mineral element and VITAMIN.Particularly eighties of last century is since the fifties, along with the reaction mechanism of polyphenol and protein, polysaccharide, alkaloid, microorganism, enzyme, metal ion etc. is revealed, biological activitys such as it is anti-oxidant, removing free radical, inhibitory anti-virus, reducing blood-fat obtain a large amount of experiment confirms, deep day by day to this class natural product in the research work in fields such as Chinese medicine preparation, functional food, daily chemical products, use more extensive.The green Di Ying of stone. " plant polyphenol ". Science Press, 2000, P1-4.
Proanthocyanidins tannin in plant materials (being condensed tannin) is the structural material that constitutes vegetable cell and tissue, and its significant proportion is with polymer, and association existence such as the form of derivative and xylogen, Mierocrystalline cellulose, hemicellulose.Industrial common employing extraction, separation means are produced the proanthocyanidins tannin, are that 500～3000 poly-proanthocyanidin is called as tannin as molecular weight, are produced by tannin extract factory, make vegetable tanning material and are used for process hides; And the oligomeric proanthocyanidins (OPC) for preparing in the catechin for preparing from tealeaves (monomer proanthocyanidin) and Semen Vitis viniferae or the Cortex Pini is as natural antioxidants and pharmacy intermediate; In addition, contained monomer or the oligomer proanthocyanidin of many Chinese medicinal materialss is its main curative effect composition.Existing studies show that, monomer that molecular weight is low or oligomer have stronger biology, chemically reactive and pharmacological effect.Xu Li plants in state. pycnogenols, plant amedica [J], " external medicine (plant amedica fascicle) " 1996,11 (1): P196 with broad development prospect.
Yet what only obtain with above-mentioned traditional method usually is polymer part in the proanthocyanidin, and getable oligomer and amount of monomer are very limited.In addition, for the tannin that makes extraction better as tanning material and glue paste use properties, the modification of tannin is the method for using always, be means such as applying biological, chemistry or physics, adopt methods such as degraded, synthetic or derivatize, directional transformation, processing so that improve the performance of product, improve the utility value of resource.
At present, the degraded of tannin or modification generally have several method: 1) oxidation degradation method: adopt hydrogen peroxide, Potcrate degraded black wattle plant skin tannin extract, valonex, the green Di Ying of stone." plant polyphenol ". Science Press, 2000, P262; 2) acid degradation method: prepare ellagic acid by the Ellagitannins acidolysis, Leonard J.The polyphenolic constituents of thepellicle ofthe walnut " J ". " J.Am Chem Soc " 1956,78:3445-3448; 3) alkaline bleach liquor degradation method: generate thioether as the torch pine tannin in highly basic condition and benzyl sulfhydrate reaction, be used to prepare the tannin glue paste, Sun Dawang. " tannin chemistry ". China Forest press, 1988, P223; 4) sulphiting modification: handle tamarack and the sulfonation of torch pine tannin takes place simultaneously with degraded with S-WAT, be used for the tannin extract modification industrial; 5) biological degradation method: utilize the degraded hydrolysable tannins such as tannase of microorganism secretion, the green Di Ying of stone. " plant polyphenol ". Science Press, 2000, P.361.
In the aforesaid method 1), 3), 4) be mainly used in tannin extract modification or glue paste production; 2) be detected in experimental study, and hydrolysis temperature is very high, produces dangerous big; 5) not too suitable to condensed tannin.Chemical reagent such as the acid of aforesaid method use, alkali, oxygenant easily cause equipment corrosion, environmental pollution in addition; The more important thing is that aforesaid method is difficult to avoid the oxidation of the active phenolic hydroxyl group of proanthocyanidins tannin, makes product lose the biological and chemical activity thus.For this reason, the degradation modification method of existing tannin also is not suitable for preparing proanthocyanidin oligomer and monomeric products, and other bioactive product.
Three, summary of the invention
The objective of the invention is at the deficiency of art methods and a kind of catalytic hydrogenolysis preparation method who is degraded to oligomer, monomeric compound from vegatable tannin is provided.
Purpose of the present invention is realized that by following technical measures wherein said raw material umber is parts by weight except that specified otherwise.
Vegatable tannin is degraded to the catalytic hydrogenolysis preparation method of oligomer, monomeric compound:
1. the preparation of reaction raw materials
Choosing the plant material that is rich in tannin, is the particle of 1～15mm without pulverizing or powder particle diameter, removes impurity through screening.Water or with water and arbitrary proportion blended methyl alcohol, or ethanol, or in the solution of acetone etc. any one made extraction agent.Raw material in room temperature through soaking or without immersion treatment, press material: the weight ratio of extraction agent=1: 6～40, add in the extractor, 30～75 ℃ of temperature, atmospheric pressure reflux was extracted 1～8 hour or employing decompression pump circulation was extracted 1～4 hour or 4～6 circulated in countercurrent are extracted.The extraction filtrate of gained is reclaimed solvent through concentrating under reduced pressure earlier, filters, add sherwood oil or light oil then, back deresinate and class ester material are left standstill in concussion or stirring, obtain the concentrated aqueous solution of tanning extract crude product, then, take one of following two kinds of methods to obtain various fractions:
(1) in the said extracted thing aqueous solution, by extracting solution: the volume ratio of extraction solvent=1: 1～2 adds the ethyl acetate extraction agent in extraction container, concussion or stirring, after leaving standstill, aqueous phase produces precipitation, filtration gained precipitation, drying is tannin high polymer level part; The filtrate standing demix obtains extract layer and extracting phase water layer respectively, and the latter through extraction agent extraction 3～5 times, merges extraction phase again, and concentrating under reduced pressure reclaims solvent, and drying obtains tannin oligomer level part; The extracting phase water layer, drying gets tannin polymer level part.
(2) in the said extracted thing aqueous solution, add a large amount of quartz sands or silica gel absorber, in vacuum-drying below 60 ℃, and eliminate moisture, and resulting dry thing is ground a little, dismiss agglomerate, pack in the chromatography column, use anhydrous ethyl acetate successively, ethanol, water, aqueous methanol, the drip washing successively of moisture propionic acid, collect various elutriants respectively, concentrating under reduced pressure reclaims solvent, drying, obtain not at the same level part thus, select for use above-mentioned tanning extract crude product or arbitrary number of level part wherein a kind of standby as reactant.
2. catalytic hydrogenolytic cleavage
With 10～200 parts of above-mentioned reactants with add 0.2～20 part of palladium-carbon (Pd-C) catalyzer, 80～3500 parts of the aqueous ethanolic solutions of adding 5～80% volume ratios, mixing the back adding has in the autoclave of agitator, temperature regulator, feed hydrogen, increase hydrogen pressure gradually, make it to reach 0.2～20MPa, disconnect the hydrogen loop, power-on heating again, under agitation is in 40～100 ℃ of temperature, reacted 0.6～6 hour, stop heating, open water coolant, when treating temperature near room temperature, discharge remaining hydrogen, obtain liquid reaction product.
3. the purifying of reaction product
Above-mentioned catalytic hydrogenolysis product is filtered, ethanol in the reclaim under reduced pressure filtrate, the concentrated solution drying of gained obtain containing plant polyphenol monomer and the thick product of oligomer, are condensed tannin as raw material, then obtain the thick product of proanthocyanidin monomer and oligomer, its purity is more than 78%; Perhaps filtrate is obtained the elaboration of different level parts respectively behind extraction fractionations such as ethyl acetate, ethyl butyrate, ethanol, acetone, butanols, its purity is more than 93%; Perhaps further separate, separate with cellulose column earlier, separate with sephadex lh-20 again with post layer watchman's clapper, or with obtaining the pure product of compound behind the preparation HPLC chromatogram purification.
Extraction agent be hot water or with water arbitrary proportion blended alcohol or ketone.
Extraction solvent is any in sherwood oil, light oil, ethyl acetate and/or the ethyl butyrate.
Eluting solvent is any in water, methyl alcohol, ethanol, acetone or the ethyl acetate.
Advantage of the present invention:
1. reaction raw materials adopts the plant material be rich in tannin or extract such as tannin extract, tannin crude product and different fractions to comprise: acetone level part, methyl alcohol level part, ethanol level part, water level part etc.
2. reaction makes spent hydroprocessing catalyst according to the catalytic hydrogenation principle of (promptly comprising shortening and catalytic hydrogenolysis), at lesser temps, under the participation of hydrogen, makes active phenolic hydroxyl group be preserved and recover, and the product biological activity of preparation is strong.
3. this reaction has certain specificity, can make the C between the Flavonol monomer of vegatable tannin such as condensed tannin
4-C
8, C
4-C
6Singly-bound; The fractures such as ester bond of glucose and tangerine acyl group or the phenol acyl group that contracts in the Hydrolysable Tannins, and form monomer and oligomer, provide natural product has been carried out the novel method that the artificial orientation transforms, processes.
4. reaction is not used reagent such as the strong acid of environmental hazard, alkali, oxygenants, and waste discharge is few, belongs to Green Chemistry and cleaner production category.
5. by to the classification and the degraded of vegatable tannin, make the product of gained become fine chemical product, purposes is wider, the value of the product height, thus improved the utilization ratio and the value added of resource.
Four, description of drawings
The classification of Fig. 1 tamarack proanthocyanidin and the schema that becomes more meticulous
HPLC figure before Fig. 2 tamarack proanthocyanidin catalytic hydrogenolytic cleavage
The HPLC figure of Fig. 3 tamarack proanthocyanidin catalytic hydrogenolytic cleavage after product
The HPLC of product figure before Fig. 4 Weibull catalytic hydrogenolytic cleavage
The HPLC figure of Fig. 5 Weibull catalytic hydrogenolytic cleavage after product
Five, embodiment
Below by embodiment the present invention is carried out concrete description; be necessary to be pointed out that at this present embodiment only is used for the present invention is further specified; can not be interpreted as limiting the scope of the invention, the person skilled in the art in this field can make some nonessential improvement and adjustment according to the content of the invention described above.
Embodiment 1: tamarack proanthocyanidin extraction fractionation and catalytic hydrogenolysis prepare oligomeric proanthocyanidins
The first step: tamarack proanthocyanidin extraction fractionation
With air-dry bark of dahurian larch is raw material, pulverizes the particle into particle diameter 1～15mm, and impurity is removed in screening.Then, take by weighing the above-mentioned material of 10kg, add the aqueous ethanolic solution 100L of 70% volume ratio, in extractor,, extracted 4 hours discharging with the pump forced refluence in 70 ± 5 ℃ of temperature.Remove the material slag through coarse filtration, gained filtrate is pumped in the vacuum concentration pot, reclaim ethanol, discharging refilters, and precipitation part drying obtains 736g sorrel powder, is proanthocyanidin high polymer (LPE); In filtrate, add sherwood oil or light oil, concussion or stirring, standing demix to remove class ester and natural gum, obtains the 20L extracting solution, the ethyl acetate that adds equivalent is therein made extraction agent, extract 3-5 time combining extraction liquid, reclaim under reduced pressure extraction agent, dry more successively, obtain the 462g red powder, be oligomeric proanthocyanidins (LPC); To obtain the 471g brown powder after extracting phase (water layer) drying, be poly proanthocyanidin (LPW).
Second step: the catalytic hydrogenolytic cleavage of poly proanthocyanidin
Get above-mentioned extraction fractionation product LPW 200g, add palladium-carbon (Pd-C) catalyzer 10g, add the ethanol 3000ml of 75% volume ratio again, mix, in the autoclave of packing into, it is 3.0MPa that feeding hydrogen makes air pressure, in 80 ℃ of temperature, under agitation, reacts 2 hours.Stop heating, treat that temperature reduces to room temperature, be vented to normal pressure earlier, take out reaction product.Filtration, concentrating under reduced pressure, dry product (LPH) 134g that gets.Use the water dissolution products therefrom, through 4 extractions of ethyl acetate, obtain extract layer again, obtain sorrel oligomeric proanthocyanidins (LPHC) 97g after the drying, yield is about 72.18%; And the about 16g of extracting phase water layer (LPHW) accounts for 12.24%.
Embodiment 2: prepare oligomeric proanthocyanidins from the larch extract catalytic hydrogenolysis
Get larch extract (without treating with sulfurous acid) 200g, add Pd-C catalyzer 5g again, add the ethanol 1000ml of 55% volume ratio, mix, in the autoclave of packing into, it is 0.2MPa that feeding hydrogen makes air pressure, in 60 ℃ of temperature, under agitation, reacts 4 hours.Stop heating, when treating that temperature is reduced to room temperature, be vented to normal pressure earlier, take out reaction product.Filtration, concentrating under reduced pressure, dry product (LPH) 135g that gets.Use the water dissolution products therefrom, through 4 extractions of ethyl acetate, obtain extract layer again, get sorrel oligomeric proanthocyanidins (LPHC) 70.7g after the drying and account for 52.37%; And the extracting phase water layer is brown poly proanthocyanidin (LPHW), and heavy 26.6g accounts for 19.70%.The about 37.2g of sorrel polymkeric substance accounts for 27.56%.
Embodiment 3: prepare ellagic acid by the valonex catalytic hydrogenolysis
Get valonex 100g, add palladium-carbon catalyst 2g, add the ethanol 800ml of 45% volume ratio, mix, in the autoclave of packing into, it is 10MPa that feeding hydrogen makes air pressure, in 80 ℃ of temperature, under agitation, reacts 4 hours.Stop heating, when treating that temperature is reduced to room temperature, be vented to normal pressure earlier, take out reaction product, be heated to more than 70 ℃, filtered while hot is removed residue, filtrate through concentrating under reduced pressure, cooling, suction filtration, and, discard filtrate with distilled water wash filter cake 2 to 3 times.With the pyridine washing leaching cake, the dissolving ellagic acid through the several recrystallization, gets faint yellow ellagic acid crystal 13.2g then.
Embodiment 4: prepare tangerine acid by five orange tannin catalytic hydrogenolysiss
Get five orange 50g, be crushed to 1～3mm particle, add palladium-carbon catalyst 1g, add the ethanol 500ml of 35% volume ratio again, mix, in the autoclave of packing into, it is 20MPa that feeding hydrogen makes air pressure, in 80 ℃ of temperature, under agitation, reacts 6 hours.Stop heating, when treating that temperature is reduced to room temperature, be vented to normal pressure earlier, the taking-up reaction product is filtered, is washed filter residue with a little tetrahydrofuran (THF), merging filtrate, and decolorizing with activated carbon is evaporated near doing, and gets white powder 6.1g.
Embodiment 5: prepare tangerine acyl ester glucose by the Weibull catalytic hydrogenolysis
Get Weibull 10g, add palladium-carbon catalyst 0.5g, add the ethanol 200ml of 80% volume ratio again, mix, in the autoclave of packing into, it is 15MPa that feeding hydrogen makes air pressure, in 80 ℃ of temperature, under agitation, reacts 3.5 hours.Stop heating, when treating that temperature is reduced to room temperature, be vented to normal pressure earlier, take out reaction product.Filter, wash filter residue with a little tetrahydrofuran (THF), merging filtrate is evaporated near doing, and gets pewter powder 3.3g.Then, with dextrane gel (Sephadex LH-20) column chromatography, ethanol-water system, gradient elution, collect respectively white solid M-GG 0.96g, Di-GG 1.00g, Tri-GG 0.51g.
Pd-C is a chemical pure, and Chengdu fine chemistry industry trial-production factory produces.
Claims (4)
1. vegatable tannin is degraded to the catalytic hydrogenolysis preparation method of oligomer, monomeric products, it is characterized in that:
(1) preparation of reactant
Select the plant material that is rich in tannin for use, without pulverizing or powder particle diameter is the particle of 1～15mm, water or make solvent with arbitrary proportion blended alcohol or ketone with water, soak, adopt normal pressure to extract 1～8 hour or decompression pump circulation extraction 1～4 hour or 4～6 circulated in countercurrent extractions, the extracting solution of gained is through decompression and solvent recovery, filter, add sherwood oil or light oil, stir or concussion, standing demix is removed natural gum and lipid material, then, take one of following two kinds of methods to obtain various fractions:
A, in the said extracted thing aqueous solution, by extracting solution: the volume ratio of extraction solvent=1: 1～2 adds the ethyl acetate extraction agent in extraction container, concussion or stirring, after leaving standstill, aqueous phase produces precipitation, filtration gained precipitation, drying is tannin high polymer level part; The filtrate standing demix obtains extract layer and extracting phase water layer respectively, and the latter through extraction agent extraction 3～5 times, merges extraction phase again, and concentrating under reduced pressure reclaims solvent, and drying obtains tannin oligomer level part; The extracting phase water layer, drying gets tannin polymer level part,
B, in the said extracted thing aqueous solution, add a large amount of quartz sands or silica gel absorber, in vacuum-drying below 60 ℃, and eliminate moisture, resulting dry thing is ground a little, dismiss agglomerate, in the chromatography column of packing into.Use anhydrous ethyl acetate successively, ethanol, water, aqueous methanol, various elutriants are collected in the drip washing successively of moisture propionic acid respectively, and concentrating under reduced pressure reclaims solvent, drying, obtain not at the same level part thus, select for use above-mentioned tanning extract crude product or arbitrary number of level part wherein a kind of standby as reactant
(2) catalytic hydrogenolytic cleavage
With above-mentioned reactant 10～200 weight parts, palladium carbon catalyst 0.2～20 weight part, aqueous ethanolic solution 80～3500 weight parts of 5～80% volume ratios, add and to have in the reactor of agitator, temperature regulator, high pressure hydrogen is fed in the reactor, emptying three times is to remove the air in the reactive system, increase pressure to 0.2～20MPa gradually, disconnect the hydrogen loop, then, the power-on heating, under agitation, in 40～100 ℃ of temperature, reacted 0.6～6 hour, stop heating, cool to room temperature, discharge remaining hydrogen, obtain liquid reaction product
(3) purifying of reaction product
Above-mentioned catalytic hydrogenolysis product is filtered, reclaim under reduced pressure ethanol wherein, drying obtains containing the thick product of plant polyphenol monomer and oligomer; Perhaps with filtrate respectively through ethyl acetate, ethyl butyrate, acetone, ethanol, butanols extraction fractionation obtain the elaboration of different levels part; Perhaps further use column chromatography, separate through cellulose column earlier, separate with sephadex lh-20 again; Or with getting the pure product of compound after the preparation HPLC chromatographic separation.
2. vegatable tannin is degraded to the catalytic hydrogenolysis preparation method of oligomer, monomeric products according to claim 1, it is characterized in that extraction agent be hot water or with water arbitrary proportion blended alcohol or ketone.
3. vegatable tannin is degraded to the catalytic hydrogenolysis preparation method of oligomer, monomeric products according to claim 1, it is characterized in that extraction solvent is any in sherwood oil, light oil, ethyl acetate or the ethyl butyrate.
4. vegatable tannin is degraded to the catalytic hydrogenolysis preparation method of oligomer, monomeric products according to claim 1, it is characterized in that eluting solvent is any in water, methyl alcohol, ethanol, acetone or the ethyl acetate.
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| CN101284022B (en) * | 2007-06-01 | 2011-06-15 | 山西省农业科学院农产品综合利用研究所 | Complexation extraction method of plant polyphenols substances |
| CN102746806A (en) * | 2012-07-19 | 2012-10-24 | 上海尤尼特生物科技有限公司 | Corrugated carton penetrant made of tannin of natural quebrachos and preparation method of corrugated carton penetrant |
| CN102732180A (en) * | 2012-07-19 | 2012-10-17 | 上海尤尼特生物科技有限公司 | Natural quebracho tannin drying agent and preparation method thereof |
| CN103990551B (en) * | 2014-05-29 | 2016-04-13 | 西安建筑科技大学 | A kind of zinc flotation of sulfur minerals is separated preparation method and the application thereof of inhibitor |
| CN108164572B (en) * | 2018-02-06 | 2021-04-02 | 黔西南州成章农业发展有限公司 | Method for extracting tannic acid by using dendrobe |
| CN110423360B (en) * | 2019-08-09 | 2021-04-13 | 南京林业大学 | Ultrasonic-assisted photocatalytic selective degradation of condensed tannin and degradation degree control method thereof |
| CN111134245A (en) * | 2020-01-19 | 2020-05-12 | 中国林业科学研究院林产化学工业研究所 | Valonea extract feed additive for broiler chickens and application thereof |
| CN111675683A (en) * | 2020-05-22 | 2020-09-18 | 西北农林科技大学 | Preparation method of proanthocyanidin polymer and proanthocyanidin polymer |
| CN114376130A (en) * | 2020-10-22 | 2022-04-22 | 四川博明龙商务咨询有限公司 | Plant beverage and preparation method thereof |
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