CN1252073C - Process for preparation of garcinia acid - Google Patents
Process for preparation of garcinia acid Download PDFInfo
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- CN1252073C CN1252073C CN 200410014061 CN200410014061A CN1252073C CN 1252073 C CN1252073 C CN 1252073C CN 200410014061 CN200410014061 CN 200410014061 CN 200410014061 A CN200410014061 A CN 200410014061A CN 1252073 C CN1252073 C CN 1252073C
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- Prior art keywords
- ether
- morellic acid
- amounts
- extraction
- suction filtration
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- 238000000034 method Methods 0.000 title claims description 35
- 238000002360 preparation method Methods 0.000 title abstract description 3
- ZMJBYMUCKBYSCP-CVYQJGLWSA-N Garcinia acid Chemical compound OC(=O)[C@@H](O)[C@](O)(C(O)=O)CC(O)=O ZMJBYMUCKBYSCP-CVYQJGLWSA-N 0.000 title 1
- PFHZIWAVXDSFTB-UHFFFAOYSA-N hibiscusoic acid Natural products OC(=O)C1OC(=O)CC1(O)C(O)=O PFHZIWAVXDSFTB-UHFFFAOYSA-N 0.000 title 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 174
- XNIZIBPYBUCVEU-UHFFFAOYSA-N Morellic acid Natural products CC1Oc2c(CC=C(C)C)c3OC45C6CC(C=C4C(=O)c3c(O)c2C=C1)C(=O)C5(CC=C(C)/C(=O)O)OC6(C)C XNIZIBPYBUCVEU-UHFFFAOYSA-N 0.000 claims description 81
- COVMVPHACFXMAX-ZVKSWBPMSA-N isomorellic acid Natural products O=C(O)/C(=C\C[C@]12C(=O)[C@H]3C=C4C(=O)c5c(O)c6c(c(C/C=C(\C)/C)c5O[C@]14[C@@H](C(C)(C)O2)C3)OC(C)(C)C=C6)/C COVMVPHACFXMAX-ZVKSWBPMSA-N 0.000 claims description 81
- COVMVPHACFXMAX-OYNOKLRGSA-N (-)-morellic acid Chemical compound C1=CC(C)(C)OC2=C1C(O)=C1C(=O)C3=C[C@@H](C(=O)[C@]4(C\C=C(\C)C(O)=O)OC5(C)C)C[C@@H]5[C@]34OC1=C2CC=C(C)C COVMVPHACFXMAX-OYNOKLRGSA-N 0.000 claims description 78
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 68
- 238000000605 extraction Methods 0.000 claims description 66
- 239000000284 extract Substances 0.000 claims description 58
- 239000000243 solution Substances 0.000 claims description 53
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 48
- 238000000967 suction filtration Methods 0.000 claims description 40
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 38
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 34
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 33
- 238000001035 drying Methods 0.000 claims description 28
- 239000007788 liquid Substances 0.000 claims description 28
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 27
- 238000005406 washing Methods 0.000 claims description 27
- 238000004519 manufacturing process Methods 0.000 claims description 26
- 238000002425 crystallisation Methods 0.000 claims description 24
- 230000008025 crystallization Effects 0.000 claims description 24
- 238000009835 boiling Methods 0.000 claims description 22
- 238000004090 dissolution Methods 0.000 claims description 22
- 238000002156 mixing Methods 0.000 claims description 22
- 239000002994 raw material Substances 0.000 claims description 22
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 19
- 239000000287 crude extract Substances 0.000 claims description 19
- 235000012054 meals Nutrition 0.000 claims description 19
- 239000003960 organic solvent Substances 0.000 claims description 19
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 18
- 239000012153 distilled water Substances 0.000 claims description 18
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 238000010992 reflux Methods 0.000 claims description 14
- 239000003637 basic solution Substances 0.000 claims description 13
- 229940117709 gamboge Drugs 0.000 claims description 13
- 241000598860 Garcinia hanburyi Species 0.000 claims description 12
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 10
- 150000007530 organic bases Chemical class 0.000 claims description 10
- 239000002244 precipitate Substances 0.000 claims description 10
- 230000001186 cumulative effect Effects 0.000 claims description 9
- 239000003208 petroleum Substances 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- 239000012670 alkaline solution Substances 0.000 claims description 3
- 238000005516 engineering process Methods 0.000 abstract description 9
- GEZHEQNLKAOMCA-RRZNCOCZSA-N (-)-gambogic acid Chemical compound C([C@@H]1[C@]2([C@@](C3=O)(C\C=C(\C)C(O)=O)OC1(C)C)O1)[C@H]3C=C2C(=O)C2=C1C(CC=C(C)C)=C1O[C@@](CCC=C(C)C)(C)C=CC1=C2O GEZHEQNLKAOMCA-RRZNCOCZSA-N 0.000 abstract description 8
- GEZHEQNLKAOMCA-UHFFFAOYSA-N epiisogambogic acid Natural products O1C2(C(C3=O)(CC=C(C)C(O)=O)OC4(C)C)C4CC3C=C2C(=O)C2=C1C(CC=C(C)C)=C1OC(CCC=C(C)C)(C)C=CC1=C2O GEZHEQNLKAOMCA-UHFFFAOYSA-N 0.000 abstract 4
- GEZHEQNLKAOMCA-GXSDCXQCSA-N gambogic acid Natural products C([C@@H]1[C@]2([C@@](C3=O)(C\C=C(/C)C(O)=O)OC1(C)C)O1)[C@H]3C=C2C(=O)C2=C1C(CC=C(C)C)=C1O[C@@](CCC=C(C)C)(C)C=CC1=C2O GEZHEQNLKAOMCA-GXSDCXQCSA-N 0.000 abstract 4
- QALPNMQDVCOSMJ-UHFFFAOYSA-N isogambogic acid Natural products CC(=CCc1c2OC(C)(CC=C(C)C)C=Cc2c(O)c3C(=O)C4=CC5CC6C(C)(C)OC(CC=C(C)/C(=O)O)(C5=O)C46Oc13)C QALPNMQDVCOSMJ-UHFFFAOYSA-N 0.000 abstract 4
- 238000009776 industrial production Methods 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 24
- 239000002904 solvent Substances 0.000 description 13
- 239000011734 sodium Substances 0.000 description 12
- 238000002474 experimental method Methods 0.000 description 8
- 238000011835 investigation Methods 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- -1 morellic acid pyridinium salt Chemical class 0.000 description 6
- 239000000706 filtrate Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 238000004737 colorimetric analysis Methods 0.000 description 3
- 238000010790 dilution Methods 0.000 description 3
- 239000012895 dilution Substances 0.000 description 3
- 239000006210 lotion Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000003810 ethyl acetate extraction Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- BLDWFKHVHHINGR-FYJGNVAPSA-N neo-gambogic acid Chemical compound C1C2C(C)(C)OC3(C\C=C(/C)C(O)=O)C(=O)C1C=C1C(=O)C(C(O)=C4C(O)CC(OC4=C4CC=C(C)C)(C)CCC=C(C)C)=C4OC123 BLDWFKHVHHINGR-FYJGNVAPSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 241000598812 Garcinia tinctoria Species 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- RTEXIPZMMDUXMR-UHFFFAOYSA-N benzene;ethyl acetate Chemical compound CCOC(C)=O.C1=CC=CC=C1 RTEXIPZMMDUXMR-UHFFFAOYSA-N 0.000 description 1
- MDHYEMXUFSJLGV-UHFFFAOYSA-N beta-phenethyl acetate Natural products CC(=O)OCCC1=CC=CC=C1 MDHYEMXUFSJLGV-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- PJGUSJUWDDRXLN-UHFFFAOYSA-N chloroform;n-ethylethanamine;methanol Chemical compound OC.ClC(Cl)Cl.CCNCC PJGUSJUWDDRXLN-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229960004756 ethanol Drugs 0.000 description 1
- 239000008361 herbal raw material Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 235000015110 jellies Nutrition 0.000 description 1
- 239000008274 jelly Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000000825 pharmaceutical preparation Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to an advanced technology for producing gambogic acid. The gambogic acid obtained by the producing technology is high in purity, the purity of the gambogic acid can reach more than 90%, and the gambogic acid can be directly used for medicinal preparations. The technology of the present invention is suitable for industrial production, and has the advantages of low extracting cost of finished products and high yield of finished products (more than 5%).
Description
Technical field
The present invention relates to a kind of production technique of from herbal raw material, extracting the method, particularly a kind of morellic acid of effective ingredient.
Background technology
In the prior art, application number is the preparation method who discloses 3 kinds of total cambogic acids in 02128822.4 the Chinese patent application: the one, and, the gamboge particle adds the pyridine hot dipping, merge pyridine liquid, add hot water and spend the night, separate out the morellic acid pyridinium salt, the pyridine solution washing, the ether thermosol is used in oven dry, filter, be concentrated in right amount, add isopyknic sherwood oil, separate out solid under the room temperature, with this solids hcl acidifying, extract the dry total cambogic acid that gets; The 2nd,, gamboge particle acetone soaked overnight merges acetone solution, evaporated under reduced pressure gets the brownish black jelly, after adding the pyridine thermosol, add water, solids washs with sherwood oil and 70% pyridine, get orange-yellow morellic acid pyridinium salt, this pyridinium salt is dissolved in ether, and with 1N HCI washing, ether layer adds anhydrous sodium sulfate drying, boil off ether, get total cambogic acid; The 3rd,, the gamboge particle adds the acetone soaked overnight, merges acetone solution, gets the acetone extract of Gamboge, after concentrating,, collect benzene-ethyl acetate (9: 1) wash-out part by silica gel column chromatography, use silica gel G making sheet, chloroform-methanol-diethylamine (15: 1: 1) launches, and extracts R
fThe glassy yellow part of value 0.4, silica gel 0.5%Na
2CO
3Washing is filtered and use the dilute hydrochloric acid acidifying, promptly gets glassy yellow and precipitates, and is washed to neutrality, drain total cambogic acid.Its defective is that the raw material of three kinds of extracting method extractions is to comprise morellic acid, neogambogic acid etc. at interior total cambogic acid mixture, and wherein the content of morellic acid is not high, and yield is low.
Summary of the invention
Technical problem to be solved by this invention is at the deficiencies in the prior art, proposes a kind of production technique suitability for industrialized production, that extract the higher high purity morellic acid of yield that is applicable to.
The structural formula of morellic acid of the present invention is
Technical problem to be solved by this invention is to realize by following technical scheme.The present invention is a kind of production technique of morellic acid, is characterized in, its step is as follows:
(1) the raw material goa powder is broken into meal,, is concentrated into the 1/4-1/12 of cumulative volume, get medicinal extract shape extract with ethyl acetate or chloroform or the saturated propyl carbinol refluxing extraction that 8-14 doubly measures, suction filtration, united extraction liquid;
(2) medicinal extract shape extract extracts 3-5 time with the basic solution of 5-8 times of volume, divide and get the buck layer, transferring PH with the aqueous hydrochloric acid of 6mol/L is 1-4, and divide the extraction acid liquid 3 times with the ethyl acetate of sour water 3-9 times volume or chloroform or saturated propyl carbinol, divide and to get and merge organic solvent layer, be washed to neutrality, normal pressure is concentrated into and no longer includes organic solvent and steam, the morellic acid crude extract;
(3) the morellic acid crude extract is with the ether or the acetone solution of 3 times of amounts, it is even that each adds ether or acetone volume 1/2-1/4 organic bases and the boiling range petroleum ether and stirring that is 60-90 ℃ doubly, half Sai Changwen places, crystallization, suction filtration, precipitate respectively washs 2-3 time drying with basic solution and the distilled water that 3-10 doubly measures respectively;
(4) get the ether dissolution that above-mentioned dry thing is doubly measured with 2-5, the boiling range that adds the 1/4-3/4 volume is the sherwood oil that 60-90 ℃ sherwood oil or boiling range are 30-60 ℃, water-bath crystallization, suction filtration, the ether of doubly measuring with 3-5-sherwood oil mixing solutions washing 2-3 time, drying;
(5) get the ether dissolution that the dry thing in the step (4) is doubly measured with 1-3, with the HCL of 1mol/L washing 3-5 time, the 1-3 that each consumption is equivalent to be washed liquid doubly is washed till water layer neutrality with distilled water again, and branch is got ether layer, uses anhydrous Na
2SO
4Drying, suction filtration boils off ether layer, gets the arborescens morellic acid, and decompressing and extracting gets orange-yellow Powdered morellic acid.
Optimized technical scheme of the present invention is: a kind of production technique of morellic acid, and its step is as follows:
(1) the raw material goa powder is broken into meal, with ethyl acetate or the chloroform or the saturated propyl carbinol refluxing extraction of 12 times of amounts, suction filtration, united extraction liquid is concentrated into 1/6 of cumulative volume, gets medicinal extract shape extract;
(2) medicinal extract shape extract extracts 3 times with the basic solution of 6 times of volumes, divide and get the buck layer, transferring PH with the aqueous hydrochloric acid of 6mol/L is 3, and divide the extraction acid liquid 3 times with the ethyl acetate of 3 times of volumes of sour water or chloroform or saturated propyl carbinol, divide and to get and merge organic solvent layer, be washed to neutrality, normal pressure is concentrated into and no longer includes organic solvent and steam, the morellic acid crude extract;
(3) the morellic acid crude extract is with the ether or the acetone solution of 3 times of amounts, each add the organic bases of 1/4 times of ether or acetone volume and petroleum ether and stirring that boiling range is 60-90 ℃ even, half Sai Changwen places, crystallization, suction filtration, precipitate respectively wash drying 3 times with the basic solution and the distilled water of 10 times of amounts respectively;
(4) get the ether dissolution of above-mentioned dry thing with 3 times of amounts, the boiling range that adds 1/2 volume is the sherwood oil that 60-90 ℃ sherwood oil or boiling range are 30-60 ℃, the water-bath crystallization, and suction filtration, with the ether of 4 times of amounts-sherwood oil mixing solutions washing 3 times, drying;
(5) get dry thing in the step (4) with the ether dissolution of 2 times of amounts, with the HCL washing of 1mol/L 4 times, each consumption is equivalent to be washed 2 times of liquid, is washed till water layer neutrality with distilled water again, divides and gets ether layer, uses anhydrous Na
2SO
4Drying, suction filtration boils off ether layer, gets the arborescens morellic acid, and decompressing and extracting gets orange-yellow Powdered morellic acid.
Technical problem to be solved by this invention can also further realize by following technical scheme.The production technique of above-described a kind of morellic acid, be characterized in, in step (1), during with ethyl acetate or chloroform or saturated n-butanol extraction raw material gamboge, the consumption of ethyl acetate or chloroform or saturated propyl carbinol is 12 times of raw material, refluxing extraction 3 times, for the first time consumption is 6 times of raw material, refluxed 3 hours, for the second time and for the third time consumption is 3 times of raw material, and each refluxed 1 hour.
Technical problem to be solved by this invention can also further realize by following technical scheme.The production technique of above-described a kind of morellic acid is characterized in, in the step (1), the granularity of described gamboge meal is the 10-30 order.Wherein, most preferred granularity is 20 orders.
Technical problem to be solved by this invention can also further realize by following technical scheme.The production technique of above-described a kind of morellic acid is characterized in, the basic solution described in the step (2) is an inorganic alkaline solution, is selected from 5%NaOH solution, 5%Na
2CO
3Solution, 5%NaHCO
3Solution and 5%Ca (OH)
2Solution.
Technical problem to be solved by this invention can also further realize by following technical scheme.The production technique of above-described a kind of morellic acid is characterized in, the organic bases described in the step (3) is selected from diethylamine, triethylamine or pyridine; Basic solution described in the step (3) is 70% diethylamine, or 70% triethylamine, or 70% pyridine.
Technical problem to be solved by this invention can also further realize by following technical scheme.The production technique of above-described a kind of morellic acid is characterized in, in the ether in the step (4)-sherwood oil mixing solutions, the blending ratio of ether and sherwood oil is 1-3: 1.
Compared with prior art, the advantage of the production technique of morellic acid of the present invention is: its technology advanced person, and with the morellic acid purity height that this production technique obtains, its morellic acid purity can reach more than 90%, can be directly used in pharmaceutical preparation; Technology of the present invention is applicable to suitability for industrialized production, and the finished product extraction cost is lower; The finished product yield of technology of the present invention is higher, can reach more than 5%.
Embodiment
Embodiment 1.A kind of production technique of morellic acid, its step is as follows:
(1) the raw material goa powder is broken into meal, the granularity of described meal is 20 orders, extract with the ethyl acetate backflow of 12 times of amounts, and suction filtration, united extraction liquid is concentrated into 1/6 of cumulative volume, gets medicinal extract shape extract;
(2) medicinal extract shape extract is with the 5%NaHCO of 6 times of volumes
3Solution extraction 3 times divides and gets the buck layer, and transferring PH with the aqueous hydrochloric acid of 6mol/L is 3, and divide the extraction acid liquid 3 times with the ethyl acetate of 3 times of volumes of sour water, and divide and to get and merge organic solvent layer, be washed to neutrality, normal pressure is concentrated into and no longer includes organic solvent and steam, the morellic acid crude extract;
(3) the morellic acid crude extract is with the ether dissolution of 3 times of amounts, each add the pyridine of 1/4 times of ether volume and petroleum ether and stirring that boiling range is 90 ℃ even, half Sai Changwen places, crystallization, suction filtration, precipitate respectively wash drying 3 times with 70% pyridine solution and the distilled water of 10 times of amounts respectively;
(4) get the ether dissolution of above-mentioned dry thing with 3 times of amounts, the boiling range that adds 1/2 volume is 90 ℃ a sherwood oil, the water-bath crystallization, and suction filtration, with the ether of 4 times of amounts-sherwood oil mixing solutions washing 3 times, drying;
(5) get dry thing in the step (4) with the ether dissolution of 2 times of amounts, with the HCL washing of 1mol/L 4 times, each consumption is equivalent to be washed 2 times of liquid, is washed till water layer neutrality with distilled water again, divides and gets ether layer, uses anhydrous Na
2SO
4Drying, suction filtration boils off ether layer, gets the arborescens morellic acid, and decompressing and extracting gets orange-yellow Powdered morellic acid.
Embodiment 2.A kind of production technique of morellic acid, its step is as follows:
(1) the raw material goa powder is broken into meal, the granularity of described meal is 25 orders, extract with the ethyl acetate backflow of 12 times of amounts, and suction filtration, united extraction liquid is concentrated into 1/4 of cumulative volume, gets medicinal extract shape extract; Wherein, during with ethyl acetate extraction raw material gamboge, refluxing extraction 3 times, consumption is 6 times of raw material for the first time, refluxes 3 hours, is 3 times of raw material with consumption for the third time for the second time, each refluxed 1 hour.
(2) medicinal extract shape extract is with the 5%NaOH solution extraction of 5 times of volumes 4 times, divide and get the buck layer, transferring PH with the aqueous hydrochloric acid of 6mol/L is 2, and with the ethyl acetate of 5 times of volumes of sour water divide 3 times the extraction acid liquid, divide and to get and merge organic solvent layer, be washed to neutrality, normal pressure is concentrated into and no longer includes organic solvent and steam, the morellic acid crude extract;
(3) the morellic acid crude extract is with the acetone solution of 3 times of amounts, each add the diethylamine of 1/2 times of acetone volume and petroleum ether and stirring that boiling range is 60 ℃ even, half Sai Changwen places, crystallization, suction filtration, precipitate respectively wash drying 3 times with 70% diethylamine solution and the distilled water of 5 times of amounts respectively;
(4) get the ether dissolution of above-mentioned dry thing with 4 times of amounts, the boiling range that adds 1/4 volume is 60 ℃ a sherwood oil, the water-bath crystallization, and suction filtration, with the ether of 4 times of amounts-sherwood oil mixing solutions washing 3 times, drying; Wherein, in ether-sherwood oil mixing solutions, the blending ratio of ether and sherwood oil is 3: 1.
(5) get dry thing in the step (4) with the ether dissolution of 2 times of amounts, with the HCL washing of 1mol/L 4 times, each consumption is equivalent to be washed 2 times of liquid, is washed till water layer neutrality with distilled water again, divides and gets ether layer, uses anhydrous Na
2SO
4Drying, suction filtration boils off ether layer, gets the arborescens morellic acid, and decompressing and extracting gets orange-yellow Powdered morellic acid.
Embodiment 3.A kind of production technique of morellic acid, its step is as follows:
(1) the raw material goa powder is broken into meal, the granularity of described meal is 15 orders, and with the chloroform refluxing extraction of 10 times of amounts, suction filtration, united extraction liquid is concentrated into 1/8 of cumulative volume, gets medicinal extract shape extract;
(2) medicinal extract shape extract is with the 5%Na of 7 times of volumes
2CO
3Solution extraction 5 times divides and gets the buck layer, and transferring PH with the aqueous hydrochloric acid of 6mol/L is 4, and divide the extraction acid liquid 3 times with the chloroform of 8 times of volumes of sour water, and divide and get and merge organic solvent layer, be washed to neutrality, normal pressure is concentrated into and no longer includes organic solvent and steam, the morellic acid crude extract;
(3) the morellic acid crude extract is with the ether dissolution of 3 times of amounts, and it is even to add the triethylamine of 1/3 times of ether volume and petroleum ether and stirring that boiling range is 80 ℃ again, and half Sai Changwen places, crystallization, suction filtration, precipitate respectively wash drying 2 times with 70% triethylamine solution and the distilled water of 3 times of amounts respectively;
(4) get the ether dissolution of above-mentioned dry thing with 2 times of amounts, the boiling range that adds 3/4 volume is 80 ℃ a sherwood oil, the water-bath crystallization, and suction filtration, with the ether of 5 times of amounts-sherwood oil mixing solutions washing 2 times, drying; Wherein, in ether-sherwood oil mixing solutions, the blending ratio of ether and sherwood oil is 2: 1.
(5) get dry thing in the step (4) with the ether dissolution of 1 times of amount, with the HCL washing of 1mol/L 5 times, each consumption is equivalent to be washed 3 times of liquid, is washed till water layer neutrality with distilled water again, divides and gets ether layer, uses anhydrous Na
2SO
4Drying, suction filtration boils off ether layer, gets the arborescens morellic acid, and decompressing and extracting gets orange-yellow Powdered morellic acid.
Embodiment 4.A kind of production technique of morellic acid, its step is as follows:
(1) the raw material goa powder is broken into meal, the granularity of described meal is 30 orders, and with the saturated propyl carbinol refluxing extraction of 14 times of amounts, suction filtration, united extraction liquid is concentrated into 1/12 of cumulative volume, gets medicinal extract shape extract;
(2) medicinal extract shape extract is with the 5%Ca (OH) of 8 times of volumes
2Extract 3 times, divide and get the buck layer, transferring PH with the aqueous hydrochloric acid of 6mol/L is 1, and divide the extraction acid liquid 3 times with the saturated propyl carbinol of 6 times of volumes of sour water, and divide and get and merge organic solvent layer, be washed to neutrality, normal pressure is concentrated into and no longer includes organic solvent and steam, the morellic acid crude extract;
(3) the morellic acid crude extract is with the acetone solution of 3 times of amounts, and it is even to add the pyridine of 1/2 times of acetone volume and petroleum ether and stirring that boiling range is 70 ℃ again, and half Sai Changwen places, crystallization, suction filtration, precipitate respectively wash drying 3 times with 70% pyridine solution and the distilled water of 8 times of amounts respectively;
(4) get the ether dissolution of above-mentioned dry thing with 2 times of amounts, the boiling range that adds 1/2 volume is 40 ℃ a sherwood oil, the water-bath crystallization, and suction filtration, with the ether of 3 times of amounts-sherwood oil mixing solutions washing 3 times, drying; Wherein, in ether-sherwood oil mixing solutions, the blending ratio of ether and sherwood oil is 1: 1.
(5) get dry thing in the step (4) with the ether dissolution of 2 times of amounts, with the HCL washing of 1mol/L 4 times, each consumption is equivalent to be washed 3 times of liquid, is washed till water layer neutrality with distilled water again, divides and gets ether layer, uses anhydrous Na
2SO
4Drying, suction filtration boils off ether layer, gets the arborescens morellic acid, and decompressing and extracting gets orange-yellow Powdered morellic acid.
Embodiment 5.A kind of production technique of morellic acid, its step is as follows:
(1) the raw material goa powder is broken into meal, the granularity of described meal is 20 orders, extract with the ethyl acetate backflow of 12 times of amounts, and suction filtration, united extraction liquid is concentrated into 1/12 of cumulative volume, gets medicinal extract shape extract;
(2) medicinal extract shape extract is with the 5%Ca (OH) of 8 times of volumes
2Extract 3 times, divide and get the buck layer, transferring PH with the aqueous hydrochloric acid of 6mol/L is 1, and divide the extraction acid liquid 3 times with the saturated propyl carbinol of 6 times of volumes of sour water, and divide and get and merge organic solvent layer, be washed to neutrality, normal pressure is concentrated into and no longer includes organic solvent and steam, the morellic acid crude extract;
(3) the morellic acid crude extract is with the acetone solution of 3 times of amounts, and it is even to add the diethylamine of 1/2 times of acetone volume and petroleum ether and stirring that boiling range is 70 ℃ again, and half Sai Changwen places, crystallization, suction filtration, precipitate respectively wash drying 3 times with 70% diethylamine aqueous solution and the distilled water of 10 times of amounts respectively;
(4) get the ether dissolution of above-mentioned dry thing with 2 times of amounts, the boiling range that adds 1/2 volume is 40 ℃ a sherwood oil, the water-bath crystallization, and suction filtration, with the ether of 3 times of amounts-sherwood oil mixing solutions washing 3 times, drying; Wherein, in ether-sherwood oil mixing solutions, the blending ratio of ether and sherwood oil is 1: 1.
(5) get dry thing in the step (4) with the ether dissolution of 2 times of amounts, with the HCL washing of 1mol/L 4 times, each consumption is equivalent to be washed 3 times of liquid, is washed till water layer neutrality with distilled water again, divides and gets ether layer, uses anhydrous Na
2SO
4Drying, suction filtration boils off ether layer, gets the arborescens morellic acid, and decompressing and extracting gets orange-yellow Powdered morellic acid.
Embodiment 6.Extract the investigation experiment of solvent.
Take by weighing 5 parts of gamboge meal (20 order), every part of about 1 gram, respectively with dehydrated alcohol, ethyl acetate, acetone, chloroform, each 10ml of water-saturated n-butanol, refluxing extraction is 3 hours in the water-bath of 80-90 degree, behind the extracting solution suction filtration, with each 5ml washing dregs of a decoction of same solvent, merging filtrate and washing lotion, concentrating under reduced pressure reclaims solvent to doing, and is washed till in the 25ml volumetric flask, with methanol constant volume with the small amount of methanol gradation.Behind 1000 times of this solution dilutions, by the content assaying method (ZrOcl of this product morellic acid
2Colorimetry), survey uv-absorbing, calculate the extraction yield of morellic acid, the results are shown in Table 1 at the 410nm place:
Table 1: the investigation result who extracts solvent
By table 1 as seen, higher with ethyl acetate, chloroform, water-saturated n-butanol as its extraction yield of solvent.
| Extract solvent | Sample weighting amount (gram) | Carry yield (%) |
| Ethanol | 1.0033 | 39.6 |
| Ethyl acetate | 1.0060 | 54.9 |
| Acetone | 1.0052 | 42.8 |
| Chloroform | 1.0027 | 52.1 |
| Water-saturated n-butanol | 1.0086 | 55.2 |
Embodiment 7.The orthogonal test of extraction conditions.
Three principal elements that influence extraction conditions are solvent and medicinal material ratio (A), extraction time (B) and extraction time (C), and each factor is got three levels (seeing Table 2) and carried out orthogonal test, and experimental technique is as follows:
The level of factor table that table 2 extracts
Accurately take by weighing gamboge meal (20 order), every part of about 1 gram is respectively with each orthogonal experiment condition refluxing extraction in 80-90 ℃ of water-bath.After each extraction finished, the extracting solution suction filtration was got filtrate, and the dregs of a decoction (when needing) extract once more by test requirements document, handle with method.After extracting end, with the ethyl acetate 5ml washing dregs of a decoction, merging filtrate and washing lotion, concentrating under reduced pressure reclaims solvent to dried, is washed till in the 25ml volumetric flask, with methanol constant volume with the small amount of methanol gradation.Behind 1000 times of this solution dilutions, by the content assaying method (ZrOCl of this product morellic acid
2Colorimetry), surveying uv-absorbing at the 410nm place, is contrast with the morellic acid methanol solution, calculates the extraction yield of morellic acid.
Calculate the k and the K value of each each level of factor respectively according to each experiment extraction yield.The k1 value of the 1st level is the extraction yield sum that contains three orthogonal experiments of A1, K1=k1/3.According to the K value, calculate the D value of each factor, be example with factor A, D=K
Amax-K
AminoThe D value is big more, and the influence of this factors on extraction rate is big more.The results are shown in Table 3
Table 3 orthogonal array
| Experiment number (%) | A | B | C | Sample weighting amount (g) | A | C(mg/ml) | Extraction yield |
| 1 2 3 4 5 6 7 8 9 K 1 K 2 K 3 K 1 K 2 K 3 D | A 1 A 1 A 1 A 2 A 2 A 2 A 3 A 3 A 3 129.6 148.0 146.7 43.2 49.3 48.9 6.1 | B 1 B 2 B 3 B 1 B 2 B 3 B 1 B 2 B 3 138.7 143.8 141.8 46.2 47.9 47.3 1.7 | C 1 C 2 C 3 C 2 C 3 C 1 C 3 C 1 C 2 128.7 143.6 152.0 42.9 47.9 50.7 7.8 | 1.065 1.032 1.011 1.014 1.009 1.083 1.004 1.053 1.025 | 0.439 0.444 0.501 0.526 0.577 0.472 0.473 0.506 0.547 | 0.0170 0.0172 0.0194 0.0204 0.0224 0.0183 0.0183 0.0196 0.0212 | 39.9 41.7 48.0 50.3 55.5 42.2 48.5 46.6 51.6 |
From last table as seen, D
C＞D
A＞D
B, so extraction time is to the having the greatest impact of extraction yield, and three best separately levels of factor are respectively A
2B
2C
3, promptly the ethyl acetate extraction of 6 of medicinal material times of amounts is 3 hours, carries altogether 3 times.
Be the confirmatory experiment of extraction time below.
Because selected extraction time factor (3 times) be the edge level, the result that so carry out confirmatory experiment, the investigation extraction is more than three times (3 times, 4 times, 5 times).
Precision takes by weighing three parts of each 1.0 grams of gamboge meal (20 order), respectively extracts 3 times, 4 times, 5 times with the ethyl acetate of 6 times of amounts, and each three hours, after each extraction finished, the extracting solution suction filtration was got filtrate, and the dregs of a decoction (when needing) extract once more by test requirements document, handle with method.After extracting end, with the ethyl acetate 5ml washing dregs of a decoction, merging filtrate and washing lotion, concentrating under reduced pressure reclaims solvent to dried, is washed till in this 25ml volumetric flask, with methanol constant volume with the small amount of methanol gradation.Behind 1000 times of this solution dilutions, by the content assaying method (ZrOCl of this product morellic acid
2Colorimetry), surveying uv-absorbing at the 410nm place, is contrast with the morellic acid methanol solution, calculates the extraction yield of morellic acid.The results are shown in Table 4.
The proof test of table 4 extraction time
| Extraction time | Sample weighting amount (g) | A | C(mg/ml) | Extraction yield (%) |
| 3 times 4 times 5 times | 1.007 1.019 1.102 | 0.566 0.557 0.621 | 0.0219 0.0216 0.0241 | 54.4 53.0 54.7 |
The result shows, extracts can reach the optimum extraction effect 3 times.Therefore, selected extraction time is three times.
In influencing each factor of extraction efficiency, extraction time is a principal element, and the consumption of solvent and extraction time are secondary cause.In process of the test, find that also most effective constituent concentrates in the primary extracting solution.Therefore under the prerequisite that guarantees extraction yield, for cutting down the consumption of energy and the consideration of cost, the solvent load of second and third time is decided to be 3 times, extraction time be 1 hour for best.So best former real extracting method is, reflux extraction extracts 3 times, and solvent load is 12 times of amounts of raw material, and consumption is 6 times of medicinal material for the first time, refluxes 3 hours; The 2nd time and the 3rd consumption are 3 times of amounts of medicinal material, and each refluxed 1 hour.
Embodiment 8.The investigation of separation and purification condition.
1, select for use basic solution to separate the foundation of utmost point morellic acid.
Morellic acid is a ketone compounds, contains carboxyl in the structure, and acidity is stronger relatively, can be dissolved in 5%NaOH solution, 5%Na
2CO
3Solution, 5%NaHCO
3Solution and 5%Ca (OH)
2In the solution.And other the main ketone compounds in the gamboge does not contain carboxyl, and 1-2 phenolic hydroxyl group only arranged, and 6 phenolic hydroxyl groups and 8 carbonyls formation intramolecular hydrogen bonds, and acidity is less relatively, can not be dissolved in above-mentioned inorganic alkaline solution, they can be separated whereby.
2, select the salifiable foundation of organic bases for use.
Morellic acid and neogambogic acid are the arborescens organic compound, only depend on solvent extraction method can not reach and other compound separation purpose.In experimentation, NaOH, Na have been investigated
2CO
3, NaHCO
3, alkaline reagentss such as diethylamine, triethylamine, pyridine, organic basess such as diethylamine, triethylamine, pyridine can generate the crystallization of stable salt in mutually at organic solvent with them, so selected organic bases for use in this technology.
It is 3, selected that ether-organic bases-sherwood oil is the foundation of recrystallisation solvent
Because morellic acid solubleness in the ether of heat is bigger, and solubleness is little when cold.This technology adds a small amount of organic bases in ether-sherwood oil, can make its salify crystallization on the one hand, has reached the purpose of purifying, compares with document on the other hand, has reduced the consumption of organic bases such as triethylamine, pyridine, diethylamine in a large number.
4, the investigation of ether or acetone consumption in the step (3).
With the ether is example, has investigated the ether dissolution morellic acid crude extract of 1 times, 1.5 times, 2 times, 2.5 times, 3 times and 5 times amount respectively.When consumption is lower than 2.5 times, be difficult to dissolve fully, be higher than 3 times and all can dissolve fully, so the consumption of selected ether is 3 times of morellic acid.
5, the investigation of step (3) PetroChina Company Limited. ether consumption.
Investigated 1/10,1/5,1/4,1/2 of ether or acetone respectively, the sherwood oil consumption of 1 times of volume influences crystalline.Get each 1g of morellic acid pyridinium salt crude product, use the 10ml ether dissolution, and add 1,1.5,2,2.5,5 and the sherwood oil mixing of 10ml respectively, room temperature was placed three hours, suction filtration, and it is dry under infrared lamp to get solid, weighs, and calculates yield.Crystallization sees Table 5.
With when 1/4 times of consumption, all can in a few hours, separate out solid during 1/2 times of volume, eduction rate does not have notable difference; When being 1/10,1/5 times of volume, solid generates very slow, and eduction rate is lower in the time of three hours; Yet, when consumption is 1 times, but can not separate out solid, only at the bottom of bottle, have one deck oily matter.The 1/4-1/2 that therefore selected sherwood oil consumption is ether or acetone doubly.
The investigation of table 5 sherwood oil consumption
| The sherwood oil consumption | 1/10 times 1/5 times | 1/4 times 1/2 times | 1 times |
| Phenomenon is described | Crystallization speed is slower | Crystallization | Can not crystallization |
| Yield (%) | 21.1 37.9 | 56.2 54.7 |
Claims (7)
1, a kind of production technique of morellic acid is characterized in that, its step is as follows:
(1) the raw material goa powder is broken into meal,, is concentrated into the 1/4-1/12 of cumulative volume, get medicinal extract shape extract with ethyl acetate or chloroform or the saturated propyl carbinol refluxing extraction that 8-14 doubly measures, suction filtration, united extraction liquid;
(2) medicinal extract shape extract extracts 3-5 time with the basic solution of 5-8 times of volume, divide and get the buck layer, transferring PH with the aqueous hydrochloric acid of 6mol/L is 1-4, and divide the extraction acid liquid 3 times with the ethyl acetate of sour water 3-9 times volume or chloroform or saturated propyl carbinol, divide and to get and merge organic solvent layer, be washed to neutrality, normal pressure is concentrated into and no longer includes organic solvent and steam, the morellic acid crude extract;
(3) the morellic acid crude extract is with the ether or the acetone solution of 3 times of amounts, it is even that each adds ether or acetone volume 1/2-1/4 organic bases and the boiling range petroleum ether and stirring that is 60-90 ℃ doubly, half Sai Changwen places, crystallization, suction filtration, precipitate respectively washs 2-3 time drying with basic solution and the distilled water that 3-10 doubly measures respectively;
(4) get the ether dissolution that above-mentioned dry thing is doubly measured with 2-5, the boiling range that adds the 1/4-3/4 volume is the sherwood oil that 60-90 ℃ sherwood oil or boiling range are 30-60 ℃, water-bath crystallization, suction filtration, the ether of doubly measuring with 3-5-sherwood oil mixing solutions washing 2-3 time, drying;
(5) get the ether dissolution that the dry thing in the step (4) is doubly measured with 1-3, with the HCL of 1mol/L washing 3-5 time, the 1-3 that each consumption is equivalent to be washed liquid doubly is washed till water layer neutrality with distilled water again, and branch is got ether layer, uses anhydrous Na
2SO
4Drying, suction filtration boils off ether layer, gets the arborescens morellic acid, and decompressing and extracting gets orange-yellow Powdered morellic acid.
2, the production technique of a kind of morellic acid according to claim 1 is characterized in that, its step is as follows:
(1) the raw material goa powder is broken into meal, with ethyl acetate or the chloroform or the saturated propyl carbinol refluxing extraction of 12 times of amounts, suction filtration, united extraction liquid is concentrated into 1/6 of cumulative volume, gets medicinal extract shape extract;
(2) medicinal extract shape extract extracts 3 times with the basic solution of 6 times of volumes, divide and get the buck layer, transferring PH with the aqueous hydrochloric acid of 6mol/L is 3, and divide the extraction acid liquid 3 times with the ethyl acetate of 3 times of volumes of sour water or chloroform or saturated propyl carbinol, divide and to get and merge organic solvent layer, be washed to neutrality, normal pressure is concentrated into and no longer includes organic solvent and steam, the morellic acid crude extract;
(3) the morellic acid crude extract is with the ether or the acetone solution of 3 times of amounts, each add the organic bases of 1/4 times of ether or acetone volume and petroleum ether and stirring that boiling range is 60-90 ℃ even, half Sai Changwen places, crystallization, suction filtration, precipitate respectively wash drying 3 times with the basic solution and the distilled water of 10 times of amounts respectively;
(4) get the ether dissolution of above-mentioned dry thing with 3 times of amounts, the boiling range that adds 1/2 volume is the sherwood oil that 60-90 ℃ sherwood oil or boiling range are 30-60 ℃, the water-bath crystallization, and suction filtration, with the ether of 4 times of amounts-sherwood oil mixing solutions washing 3 times, drying;
(5) get dry thing in the step (4) with the ether dissolution of 2 times of amounts, with the HCL washing of 1mol/L 4 times, each consumption is equivalent to be washed 2 times of liquid, is washed till water layer neutrality with distilled water again, divides and gets ether layer, uses anhydrous Na
2SO
4Drying, suction filtration boils off ether layer, gets the arborescens morellic acid, and decompressing and extracting gets orange-yellow Powdered morellic acid.
3, the production technique of a kind of morellic acid according to claim 2, it is characterized in that, in step (1), during with ethyl acetate or chloroform or saturated n-butanol extraction raw material gamboge, the consumption of ethyl acetate or chloroform or saturated propyl carbinol is 12 times of raw material, refluxing extraction 3 times, for the first time consumption is 6 times of raw material, refluxed 3 hours, for the second time and for the third time consumption is 3 times of raw material, and each refluxed 1 hour.
4, the production technique of a kind of morellic acid according to claim 2 is characterized in that, in step (1), the granularity of described gamboge meal is the 10-30 order.
5, the production technique of a kind of morellic acid according to claim 1 and 2 is characterized in that, the basic solution described in the step (2) is an inorganic alkaline solution, is selected from 5%NaOH solution, 5%Na
2CO
3Solution, 5%NaHCO
3Solution and 5%Ca (OH)
2Solution.
6, the production technique of a kind of morellic acid according to claim 1 and 2 is characterized in that, the organic bases described in the step (3) is selected from diethylamine, triethylamine or pyridine; Basic solution described in the step (3) is 70% diethylamine, or 70% triethylamine, or 70% pyridine.
7, the production technique of a kind of morellic acid according to claim 1 and 2 is characterized in that, in the ether in the step (4)-sherwood oil mixing solutions, the blending ratio of ether and sherwood oil is 1-3: 1.
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| CN101921283B (en) * | 2010-07-20 | 2013-04-24 | 辽宁大学 | Extraction technology of gambogic acid |
| CN102372725A (en) * | 2010-08-26 | 2012-03-14 | 苏州宝泽堂医药科技有限公司 | Purification method for high-content gambogic acid |
| CN102603767A (en) * | 2012-03-07 | 2012-07-25 | 广州牌牌生物科技有限公司 | Gambogic acid separating and purifying production process |
| CN103893227B (en) * | 2012-12-28 | 2016-07-06 | 上海中医药大学 | Mountain papaw branch extract and application thereof |
| CN104557966B (en) * | 2015-02-12 | 2017-04-12 | 内蒙古昶辉生物科技股份有限公司 | Method for extracting active ingredients from cambogia |
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