CN104086613B - A kind of method being separated Cucurbitacin B from muskmelon rattan by catalyzed reaction - Google Patents
A kind of method being separated Cucurbitacin B from muskmelon rattan by catalyzed reaction Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 67
- CVKKIVYBGGDJCR-SXDZHWHFSA-N Cucurbitacin B Natural products CC(=O)OC(C)(C)C=CC(=O)[C@@](C)(O)[C@@H]1[C@@H](O)C[C@]2(C)C3=CC[C@@H]4C(C)(C)C(=O)[C@H](O)C[C@@]4(C)[C@@H]3CC(=O)[C@@]12C CVKKIVYBGGDJCR-SXDZHWHFSA-N 0.000 title claims abstract description 64
- IXQKXEUSCPEQRD-NRNCYQGDSA-N (2S,4R,23E)-2,16beta,20-trihydroxy-9beta,10,14-trimethyl-1,11,22-trioxo-4,9-cyclo-9,10-secocholesta-5,23-dien-25-yl acetate Chemical compound C([C@H]1[C@]2(C)C[C@@H](O)[C@@H]([C@]2(CC(=O)[C@]11C)C)[C@@](C)(O)C(=O)C=CC(C)(C)OC(=O)C)C=C2[C@H]1C[C@H](O)C(=O)C2(C)C IXQKXEUSCPEQRD-NRNCYQGDSA-N 0.000 title claims abstract description 57
- IHTCCHVMPGDDSL-ZJNDIJRCSA-N Cucurbitacin A Natural products O=C([C@@](O)(C)[C@H]1[C@@H](O)C[C@]2(C)[C@]1(C)CC(=O)[C@]1(CO)[C@H]2CC=C2C(C)(C)C(=O)[C@H](O)C[C@@H]12)/C=C/C(OC(=O)C)(C)C IHTCCHVMPGDDSL-ZJNDIJRCSA-N 0.000 title claims abstract description 57
- QZJJDOYZVRUEDY-UHFFFAOYSA-N Dihydrocucurbitacin B Natural products CC12C(=O)CC3(C)C(C(C)(O)C(=O)CCC(C)(C)OC(=O)C)C(O)CC3(C)C1CC=C1C2CC(O)C(=O)C1(C)C QZJJDOYZVRUEDY-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 235000009847 Cucumis melo var cantalupensis Nutrition 0.000 title claims abstract description 31
- 241000345998 Calamus manan Species 0.000 title claims abstract description 23
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 23
- 235000012950 rattan cane Nutrition 0.000 title claims abstract description 23
- 244000064895 Cucumis melo subsp melo Species 0.000 title description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 41
- 239000000284 extract Substances 0.000 claims abstract description 24
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000000605 extraction Methods 0.000 claims abstract description 17
- 238000003756 stirring Methods 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 claims abstract description 12
- 239000012043 crude product Substances 0.000 claims abstract description 10
- 238000010992 reflux Methods 0.000 claims abstract description 10
- 238000002386 leaching Methods 0.000 claims abstract description 8
- 238000001914 filtration Methods 0.000 claims abstract description 7
- 238000007654 immersion Methods 0.000 claims abstract description 7
- 238000001953 recrystallisation Methods 0.000 claims abstract description 7
- 238000001291 vacuum drying Methods 0.000 claims abstract description 7
- 244000241257 Cucumis melo Species 0.000 claims abstract 6
- 238000001035 drying Methods 0.000 claims description 14
- 239000000469 ethanolic extract Substances 0.000 claims description 6
- 239000000178 monomer Substances 0.000 claims 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims 2
- 229920002554 vinyl polymer Polymers 0.000 claims 2
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 abstract description 21
- 239000000047 product Substances 0.000 abstract description 19
- 239000002994 raw material Substances 0.000 abstract description 17
- 238000004519 manufacturing process Methods 0.000 abstract description 15
- 230000006378 damage Effects 0.000 abstract description 4
- 230000001351 cycling effect Effects 0.000 abstract description 2
- 239000000419 plant extract Substances 0.000 abstract description 2
- 239000002351 wastewater Substances 0.000 abstract description 2
- 230000002950 deficient Effects 0.000 abstract 1
- 239000007788 liquid Substances 0.000 abstract 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 14
- 239000000463 material Substances 0.000 description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 238000002425 crystallisation Methods 0.000 description 8
- 230000008025 crystallization Effects 0.000 description 8
- 235000011167 hydrochloric acid Nutrition 0.000 description 8
- LNSXRXFBSDRILE-UHFFFAOYSA-N Cucurbitacin Natural products CC(=O)OC(C)(C)C=CC(=O)C(C)(O)C1C(O)CC2(C)C3CC=C4C(C)(C)C(O)C(O)CC4(C)C3(C)C(=O)CC12C LNSXRXFBSDRILE-UHFFFAOYSA-N 0.000 description 7
- PIGAXYFCLPQWOD-UHFFFAOYSA-N dihydrocucurbitacin I Natural products CC12C(=O)CC3(C)C(C(C)(O)C(=O)CCC(C)(O)C)C(O)CC3(C)C1CC=C1C2C=C(O)C(=O)C1(C)C PIGAXYFCLPQWOD-UHFFFAOYSA-N 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 150000001904 cucurbitacins Chemical class 0.000 description 6
- 229910052742 iron Inorganic materials 0.000 description 6
- 238000010298 pulverizing process Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- 239000012141 concentrate Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 229930182478 glucoside Natural products 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- 238000001514 detection method Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 150000008131 glucosides Chemical class 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 238000000967 suction filtration Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000004440 column chromatography Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- PXFBZOLANLWPMH-UHFFFAOYSA-N 16-Epiaffinine Natural products C1C(C2=CC=CC=C2N2)=C2C(=O)CC2C(=CC)CN(C)C1C2CO PXFBZOLANLWPMH-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 206010008909 Chronic Hepatitis Diseases 0.000 description 1
- 235000015510 Cucumis melo subsp melo Nutrition 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- FJJCIZWZNKZHII-UHFFFAOYSA-N [4,6-bis(cyanoamino)-1,3,5-triazin-2-yl]cyanamide Chemical compound N#CNC1=NC(NC#N)=NC(NC#N)=N1 FJJCIZWZNKZHII-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000005903 acid hydrolysis reaction Methods 0.000 description 1
- 230000001154 acute effect Effects 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- PQOVWWZVVIGRPP-UHFFFAOYSA-N cucurbitacin B-glucoside Natural products CC12C(=O)CC3(C)C(C(C)(O)C(=O)C=CC(C)(C)OC(=O)C)C(O)CC3(C)C1CC=C(C(C1=O)(C)C)C2CC1OC1OC(CO)C(O)C(O)C1O PQOVWWZVVIGRPP-UHFFFAOYSA-N 0.000 description 1
- -1 cucurbitacin glucoside Chemical class 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000009837 dry grinding Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 208000006454 hepatitis Diseases 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- DHKWOBKCNIDKCO-UHFFFAOYSA-K iron(3+);trichloride;heptahydrate Chemical compound O.O.O.O.O.O.O.[Cl-].[Cl-].[Cl-].[Fe+3] DHKWOBKCNIDKCO-UHFFFAOYSA-K 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 238000005325 percolation Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000001932 seasonal effect Effects 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
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- Saccharide Compounds (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of method being separated Cucurbitacin B from muskmelon rattan by catalyzed reaction.The method step: leaching process: 1 part, muskmelon rattan, alcohol immersion refluxing extraction, extracting liquid filtering is condensed into medicinal extract; Catalyzed reaction: medicinal extract adds concentrated hydrochloric acid, then add Iron(III) chloride hexahydrate stirring reaction, cool to room temperature filters, water wash, dry; Treating process: crude product ethyl acetate stirring and dissolving, then add activated carbon, decolouring, is concentrated to small volume, places crystallise overnight; Recrystallization process: class fine work dissolve with ethanol filtered while hot is concentrated to small volume, places crystallise overnight, filters; Fine work to be positioned in vacuum drying oven dry 8 hours, to obtain Cucurbitacin B fine work.Raw material sources are extensive, and production cost is low, and reduce the destruction of sour environment to Cucurbitacin B, ratio defective product reaches more than 60%, and purity is more than 99.0%, and waste water BOD, below 100, is applicable to suitability for industrialized production cycling use of water, is widely used in plant extract industry.
Description
Technical field
The present invention relates to a kind of method that catalyzed reaction is separated Cucurbitacin B, specifically relate to secondary and a kind of method being separated Cucurbitacin B from muskmelon rattan by catalyzed reaction.
Background technology
Cucurbitacin B be a kind for the treatment of for acute and unresolved chronic hepatitis, primary hepatocarcinoma novel
Bulk drug, is widely used in the every field such as medicine, makeup and healthcare products.
According to bibliographical information, the content of Cucurbitacin B in Muskmelon Base is the highest, can reach 0.6%---0.8%, but Muskmelon Base uses as raw material, the limitation of its high cost and raw material result in this product and there is the high of price, and the defect such as the limited amount of product-feed.
Cucurbitacin B is because the new property of spy of Futures Market and both at home and abroad producer are to holding in close confidence the property of operational path, so the patent of having applied for also seldom.
Disclosed " a kind of method extracting Cucurbitacin B " in the Chinese patent (201010235780.X) of application on 07 26th, 2010 by Nanjing Zelang Agricultural Development Co., Ltd., the scope of the claim protection of the method comprises the steps:
1. one kind is extracted the method for Cucurbitacin B, it is characterized in that comprising following steps: the sour water of Muskmelon Base raw material pulverizing ph3-5 is mixed wet, add biological enzyme mixing 30-40 DEG C of enzymolysis 2-4 days, enzymolysis raw material drops into extraction vessel again, add 5-15 times amount alcohol reflux 2-3 times, extracting solution adds activated carbon oxidation aluminium mixing short column, lower fluid injection decompression recycling ethanol is to determining alcohol 30-50%, place crystallization, leach to obtain coarse crystallization, coarse crystallization adds chloroform cold cut, filter and reclaim chloroform to 1/3-1/6 volume, place crystallization, obtain secondary crystal thing, by secondary crystal thing, alcohol reflux dissolves, add activated carbon decolorizing again, filter and place crystallization, namely drying crystalline thing obtains product Cucurbitacin B.
Disclosed a kind of extraction and separation method of Cucurbitacin B in the Chinese patent (200910154837.0) that on November 24th, 2009 applies for by Zhejiang Polytechnical University, the method comprises the steps:
1), by raw material Muskmelon Base pulverize, with ethanol percolation or alcohol reflux, after extracting solution is concentrated, be extracted with ethyl acetate more than three times, reclaim ethyl acetate, obtain total cucurbitacin extract;
2), get total cucurbitacin extract and be dissolved in the aqueous ethanolic solution of volume fraction 25 ~ 45%, be hydrolyzed reaction under acetic acid exists, and fully after reaction, adjust ph, to neutrality, is concentrated into dry; The concentration of described acetic acid is 0.1 ~ 0.3mol/L;
3), step 2) the purified process of gained enriched material obtains the Cucurbitacin B product of Cucurbitacin B content more than 60%; Described purification process is adopted with the following method:
The gained enriched material aqueous ethanolic solution of volume fraction 25 ~ 45% dissolves, then by macroporous resin column chromatography, with the aqueous ethanolic solution wash-out of volume fraction 50 ~ 60%, collects elutriant, concentrate and obtain the Cucurbitacin B product of Cucurbitacin B content more than 60%.
Although aforesaid method can obtain the Cucurbitacin B product of high-content, there is Process Planning Raw source and compare limitation, the defects such as the temperature of enzymolysis and enzymolysis time length.
1. raw material sources problem: according to data measuring and calculating, the muskmelon on 1 mu of ground can about 3-5 kilograms of dry Muskmelon Bases, on market, Bozhou in 2014, the price of Muskmelon Base gradeless and uniformly-priced goods is 800 yuan/kilogram.And the raw material of having no idea to provide tonne.
2. the temperature problem of enzymolysis: enzymolysis is a fermenting process in fact, impact by temperature is very large, there are huge difference in winter and summer, and the change as production season of a product can cause the periodical change of product supply time, and this is concerning very inadvisable Industrial products.
3. in accordance with the technical intelligence of this patent, the enzymolysis time of 2 ~ 4 days, wastes the cost of man power and material greatly, and there are many potential safety hazards in large-scale fermentation vat and place and not environmentally.
As can be seen here, these extraction and separation method raw material sources are restricted, and seasonal effect is obvious, and the production cycle is long, not easily realizes industrialization.
By thaumatropy, the analog (as Cucurbitacin B glucoside) of Cucurbitacin B is converted into Cucurbitacin B in the method leaching process, improves the extraction yield of Cucurbitacin B, production technique is simple, easy and simple to handle.
The greatest problem of the method is the simple acid hydrolysis method for transformation utilizing routine, and only transformed the Cucurbitacin B-2-glycoside of part, long sour environment, can cause the destruction of Cucurbitacin B, and the yield of conversion is low, and wastage of material is obvious.
Summary of the invention
The object of this invention is to provide a kind of production process not by affecting in season and temperature, the reaction times is short, and energy consumption is low, a kind of method being separated Cucurbitacin B from muskmelon rattan by catalyzed reaction that production cost is low.
In order to overcome the deficiencies in the prior art, technical scheme of the present invention solves like this: a kind of method being separated Cucurbitacin B from muskmelon rattan by catalyzed reaction, and the method is carried out in the steps below:
A, leaching process:
In mass ratio, by 1 part, the muskmelon rattan pulverizing of drying, use the alcohol immersion 1.5 ~ 2.0 hours of 5 ~ 7 times amount by volume, refluxing extraction 3 times, ethanol extract filtering and concentrating is the medicinal extract of 1.05 ~ 1.10 to proportion;
B, catalytic reaction process:
The medicinal extract obtaining mass ratio to step A adds the concentrated hydrochloric acid of 0.13 ~ 0.17 times amount, add the Iron(III) chloride hexahydrate of 0.01 ~ 0.05 times amount again as catalyzer, DEG C stirring reaction 30 ~ 40 minutes in temperature 70 C ~ 90, cool to room temperature filters, between water wash to pH4 ~ 6, dry;
C, treating process:
In mass ratio, step B is obtained the crude product of dry gained, by 7.5 ~ 8.5 times amount ethyl acetate stirring and dissolving, add the activated carbon of 0.15 ~ 0.25 times amount again, with temperature 55 DEG C ~ 65 DEG C decolouring 1 hour, filtered while hot was concentrated to small volume, places crystallise overnight;
D, recrystallization process:
By the class fine work that step C obtains, be concentrated to small volume by 7.5 ~ 8.5 times amount dissolve with ethanol filtered while hot, place crystallise overnight, filter;
E, drying process:
By the fine work that D step obtains, be positioned in vacuum drying oven, dry 8 hours, obtain Cucurbitacin B fine work.
A kind of described method being separated Cucurbitacin B from muskmelon rattan by catalyzed reaction, the method is carried out in the steps below:
A, leaching process:
In mass ratio, by 1 part, the muskmelon rattan pulverizing of drying, use the alcohol immersion 1.5 ~ 1.8 hours of 5.5 ~ 6.5 times amount by volume, refluxing extraction 3 times, ethanol extract filtering and concentrating is the medicinal extract of 1.05 ~ 1.10 to proportion;
B, catalytic reaction process:
The medicinal extract obtaining mass ratio to step A adds the concentrated hydrochloric acid of 0.14 ~ 0.16 times amount, add the Iron(III) chloride hexahydrate of 0.01 ~ 0.05 times amount again as catalyzer, DEG C stirring reaction 30 ~ 40 minutes in temperature 70 C ~ 90, cool to room temperature filters, between water wash to pH4 ~ 6, dry;
C, treating process:
In mass ratio, step B is obtained the crude product of dry gained, by 7.7 ~ 8.2 times amount ethyl acetate stirring and dissolving, add the activated carbon of 0.17 ~ 0.23 times amount again, with temperature 55 DEG C ~ 65 DEG C decolouring 1 hour, filtered while hot was concentrated to small volume, places crystallise overnight;
D, recrystallization process:
By the class fine work that step C obtains, be concentrated to small volume by 7.7 ~ 8.3 times amount dissolve with ethanol filtered while hot, place crystallise overnight, filter;
E, drying process:
By the fine work that D step obtains, be positioned in vacuum drying oven, dry 8 hours, obtain Cucurbitacin B fine work.
The present invention compared with prior art, has the following advantages:
, the present invention uses raw material sources muskmelon rattan widely, production cost is low, ensure that the maximum utilization of Biological resources, adds the income of melon grower.
, catalytic conversion reaction makes cucurbitacin glucoside material be converted into Cucurbitacin B rapidly, reduce the destruction of sour environment to Cucurbitacin B, considerably increase the yield of target product.
, production process do not affect by season and temperature, the reaction times is short, greatly reduces the energy consumption of production, has saved production cost.
, there is no silica gel or alumina column chromatography process, simple to operate, save solvent greatly reduce production cost.
, the method product increase rate reach more than 60%, higher than the level of the 7%--10% of routine hydrolysis productive rate, product purity is more than 99.0%, reach as high as 99.9%, each kind solvent obtains the rate of recovery can reach more than 92%, waste water BOD, below 100, is applicable to suitability for industrialized production cycling use of water, is widely used in plant extract industry.
Accompanying drawing explanation
Fig. 1 is conventional process flow figure;
Fig. 2 is process flow sheet of the present invention.
Embodiment
Below in conjunction with drawings and Examples, content of the present invention is described in further detail:
With reference to shown in Fig. 2, a kind of method being separated Cucurbitacin B from muskmelon rattan by catalyzed reaction, the method is carried out in the steps below:
A, leaching process:
In mass ratio, by 1 part, the muskmelon rattan pulverizing of drying, use the alcohol immersion 1.5 ~ 2.0 hours of 5 ~ 7 times amount by volume, refluxing extraction 3 times, ethanol extract filtering and concentrating is the medicinal extract of 1.05 ~ 1.10 to proportion;
B, catalytic reaction process:
The medicinal extract obtaining mass ratio to step A adds the concentrated hydrochloric acid of 0.13 ~ 0.17 times amount, add the Iron(III) chloride hexahydrate of 0.01 ~ 0.05 times amount again as catalyzer, DEG C stirring reaction 30 ~ 40 minutes in temperature 70 C ~ 90, cool to room temperature filters, between water wash to pH4 ~ 6, dry;
C, treating process:
In mass ratio, step B is obtained the crude product of dry gained, by 7.5 ~ 8.5 times amount ethyl acetate stirring and dissolving, add the activated carbon of 0.15 ~ 0.25 times amount again, with temperature 55 DEG C ~ 65 DEG C decolouring 1 hour, filtered while hot was concentrated to small volume, places crystallise overnight;
D, recrystallization process:
By the class fine work that step C obtains, be concentrated to small volume by 7.5 ~ 8.5 times amount dissolve with ethanol filtered while hot, place crystallise overnight, filter, described small volume refers to the volume after concentrating;
E, drying process:
By the fine work that D step obtains, be positioned in vacuum drying oven, dry 8 hours, obtain Cucurbitacin B fine work.
A kind of described method being separated Cucurbitacin B from muskmelon rattan by catalyzed reaction, the method is carried out in the steps below:
A, leaching process:
In mass ratio, by 1 part, the muskmelon rattan pulverizing of drying, use the alcohol immersion 1.5 ~ 1.8 hours of 5.5 ~ 6.5 times amount by volume, refluxing extraction 3 times, ethanol extract filtering and concentrating is the medicinal extract of 1.05 ~ 1.10 to proportion;
B, catalytic reaction process:
The medicinal extract obtaining mass ratio to step A adds the concentrated hydrochloric acid of 0.14 ~ 0.16 times amount, add the Iron(III) chloride hexahydrate of 0.01 ~ 0.05 times amount again as catalyzer, DEG C stirring reaction 30 ~ 40 minutes in temperature 70 C ~ 90, cool to room temperature filters, between water wash to pH4 ~ 6, dry;
C, treating process:
In mass ratio, step B is obtained the crude product of dry gained, by 7.7 ~ 8.2 times amount ethyl acetate stirring and dissolving, add the activated carbon of 0.17 ~ 0.23 times amount again, with temperature 55 DEG C ~ 65 DEG C decolouring 1 hour, filtered while hot was concentrated to small volume, places crystallise overnight;
D, recrystallization process:
By the class fine work that step C obtains, be concentrated to small volume by 7.7 ~ 8.3 times amount dissolve with ethanol filtered while hot, place crystallise overnight, filter;
E, drying process:
By the fine work that D step obtains, be positioned in vacuum drying oven, dry 8 hours, obtain Cucurbitacin B fine work.
The selection of Extraction solvent:
Be widely used in industrial Extraction solvent at present and be mainly methyl alcohol, ethanol, cheaper methyl alcohol, ethanol beyond doubt, because methyl alcohol has stronger injury effect to eyes and considers the dissolvent residual of the finished product, therefore select ethanol just to become first-selected as Extraction solvent.
The determination of catalytic reaction condition:
As catalyzer, can consider the factor of Environmental Factors and cost as the metal such as chromium, platinum, palladium, iron of catalyst applications and their compound, first the material of catalyzed reaction is determined in the scope of iron and compound thereof by applicant.
Applicant successively employs iron powder, ferric oxide, iron(ic) chloride, applicant finds iron powder ferric oxide has added rear effect not to be clearly by experiment, analyze by experiment, applicant knows that first above 2 kinds of materials can react after running into hydrochloric acid and discharges hydrogen G&W.This greatly reduces the effect of this material as catalyzer.
After iron(ic) chloride adds, the moment of meeting water produces amount of heat, and reaction is very violent, through experimental analysis, the generation of this heat be because iron(ic) chloride and water affine, discharge the result that a large amount of heat energy causes.Consider the security of production, applicant terminates the use of iron(ic) chloride.Make his hydrate Iron(III) chloride hexahydrate into.
After Iron(III) chloride hexahydrate adds, reacting balance, the quantity that applicant added reaction times and catalyzer is through many experiments, and curve plotting, obtain the ratio of the acid of medicinal extract weight 0.15 times amount, and the optimum proportion of the catalyzer of medicinal extract weight 0.03 times amount Iron(III) chloride hexahydrate.
The specification requirement of finished product:
Sample detects through HPLC, and Cucurbitacin B content is not less than 98.0%; Fusing point 220 DEG C-225 DEG C; Weight loss on drying is not higher than 2.0%; Water content is not higher than 1%; Organic solvent content is not higher than 0.5%.
In sum, applicant " Tianfeng Biological Science & Technology Co., Ltd., Xi'an " is by the comprehensive analysis to raw material, find the Cucurbitacin B containing 0.15% ~ 0.2% in muskmelon rattan, contain the cucurbit B-2-glycoside of 0.2% ~ 0.3% simultaneously, the class glucoside Cucurbitacin B material that the C=C bond of about 0.25% ~ 0.4% is closed, Cucurbitacin B-2-glycoside can be converted into Cucurbitacin B by the method for hydrolysis, but the Cucurbitacin B of part hydrolysis is destroyed while hydrolysis, the time of 2 hours, by arriving the balance producing and destroy, causes the yield that can only improve 7%--10%.The class glucoside Cucurbitacin B material of C=C bond conjunction is simultaneously because the singularity of structure, it cannot be made to be converted into Cucurbitacin B to the reaction conditions of routine, Tianfeng Biological Science & Technology Co., Ltd., Xi'an establishes a kind of catalyzed reaction by technical research and from muskmelon rattan, is separated the method Cucurbitacin B-2-glycoside of Cucurbitacin B under the condition of catalysis, also the class glucoside Cucurbitacin B material that C=C bond is closed is continued to be converted into Cucurbitacin B while realizing the conversion of maximum range in the shortest time, improve the yield of cucurbitacin greatly.Have that cost is low, efficiency is high, easy-operating feature.
embodiment:
The muskmelon rattan that the preparation of applicant to the main muskmelon place of production, Shaanxi Yan Liang abandons is sampled immediately, obtains 2.7 tons of raw materials, after shining dry grinding, obtains 870 kilograms of dry product muskmelon rattan raw materials altogether, and this batch of raw material is adopted to the process for processing of different charging capacity.
embodiment1:
Get raw material 1.5 kilograms, add the ethanol of 9 liters, the wide-necked bottle heating extraction of 20L three times, each 1 hour, concentrate and obtain 163 grams of medicinal extract, detecting Cucurbitacin B concentration is 18.4 milligrams/gram, 163 grams of medicinal extract, add 24.45 grams of concentrated hydrochloric acids, then add 4.89 grams of Iron(III) chloride hexahydrates, react 30 minutes, after washing, pH is 4 ~ 6, obtains 78 grams of crude products, and detecting Cucurbitacin B content is 61.5 milligrams/gram, the yield of Cucurbitacin B increases to 59.94%, and carries out crystallization, suction filtration according to invented technology.Obtain product 3.53 grams, content detection is 98.33%.
embodiment 2:
Get raw material 15 kilograms, add the ethanol of 90 liters, heat extraction in the extractor of 200L three times, each 1 hour, concentrate and obtain 1576 grams of medicinal extract, detecting Cucurbitacin B concentration is 17.95 milligrams/gram, 1576 grams of medicinal extract, add 236.4 grams of concentrated hydrochloric acids, then add 47.28 grams of Iron(III) chloride hexahydrates, react 30 minutes, washing pH4-6 obtain 791 grams of crude products, detecting Cucurbitacin B content is 56.83 milligrams/gram, and the yield of Cucurbitacin B increases to 58.9%, and carries out crystallization, suction filtration according to invented technology.Obtain product 36.7 grams.
Content detection is 99.13%.
embodiment 3:
Get raw material 50 kilograms, add the ethanol of 300 liters, heat extraction in the extractor of 500L three times, each 1 hour, concentrate and obtain 4961 grams of medicinal extract, detecting Cucurbitacin B concentration is 17.64 milligrams/gram, 4961 grams of medicinal extract, add 744.15 grams of concentrated hydrochloric acids, then add 148.83 grams of Iron(III) chloride hexahydrates, react 30 minutes, washing pH4-6 obtain 2473 grams of crude products, detecting Cucurbitacin B content is 55.72 milligrams/gram, and the yield of Cucurbitacin B increases to 57.46%, and carries out crystallization, suction filtration according to invented technology.Obtain product 121.7 grams,
Content detection is 98.81%.
Claims (2)
1. from muskmelon rattan, be separated a method for Cucurbitacin B by catalyzed reaction, the method is carried out in the steps below:
A, leaching process:
In mass ratio, the muskmelon rattan l part of drying pulverized, use the alcohol immersion 1.3 ~ 2.0 hours of 5 ~ 7 times amount by volume, refluxing extraction 3 times, ethanol extract filtering and concentrating is the medicinal extract of 1.05 ~ 1.10 to proportion;
B, catalytic reaction process:
In mass ratio, the medicinal extract obtained to step A adds the concentrated hydrochloric acid of 0.13 ~ 0.17 times amount, then the Iron(III) chloride hexahydrate adding 0.01 ~ 0.05 times amount is as catalyzer, DEG C stirring reaction 30 ~ 40 minutes in temperature 70 C ~ 90, cool to room temperature filters, between water wash to pH4 ~ 6, dry;
C, treating process:
In mass ratio, by the crude product of dry for step B gained, by 7.5 ~ 8.5 times amount vinyl acetic monomer stirring and dissolving, then add the activated carbon of 0.15 ~ 0.25 times amount, with temperature 55 DEG C ~ 65 DEG C decolouring 1 hour, filtered while hot was concentrated to small volume, places crystallise overnight;
D, recrystallization process:
By the class fine work that step C obtains, be concentrated to small volume by 7.5 ~ 8.5 times amount dissolve with ethanol filtered while hot, place crystallise overnight, filter;
E, drying process:
By the fine work that D step obtains, be positioned in vacuum drying oven, dry 8 hours, obtain Cucurbitacin B fine work.
2. a kind of method being separated Cucurbitacin B from muskmelon rattan by catalyzed reaction according to claim l, is characterized in that the method is carried out in the steps below:
A, leaching process:
In mass ratio, the muskmelon rattan l part of drying pulverized, use the alcohol immersion 1.5 ~ 1.8 hours of 5.5 ~ 6.5 times amount by volume, refluxing extraction 3 times, ethanol extract filtering and concentrating is the medicinal extract of 1.05 ~ 1.10 to proportion;
B, catalytic reaction process:
In mass ratio, the medicinal extract obtained to step A adds the concentrated hydrochloric acid of 0.14 ~ 0.16 times amount, then the Iron(III) chloride hexahydrate adding 0.01 ~ 0.05 times amount is as catalyzer, DEG C stirring reaction 30 ~ 40 minutes in temperature 70 C ~ 90, cool to room temperature filters, between water wash to pH4 ~ 6, dry;
C, treating process:
In mass ratio, by the crude product of dry for step B gained, by 7.7 ~ 8.2 times amount vinyl acetic monomer stirring and dissolving, then add the activated carbon of 0.17 ~ 0.23 times amount, with temperature 55 DEG C ~ 65 DEG C decolouring 1 hour, filtered while hot was concentrated to small volume, places crystallise overnight;
D, recrystallization process:
By the class fine work that step C obtains, be concentrated to small volume by 7.7 ~ 8.3 times amount dissolve with ethanol filtered while hot, place crystallise overnight, filter;
E, drying process:
By the fine work that D step obtains, be positioned in vacuum drying oven, dry 8 hours, obtain Cucurbitacin B fine work.
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