CN102126942B - Method for synthesizing hypericin - Google Patents
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- CN102126942B CN102126942B CN 201010600246 CN201010600246A CN102126942B CN 102126942 B CN102126942 B CN 102126942B CN 201010600246 CN201010600246 CN 201010600246 CN 201010600246 A CN201010600246 A CN 201010600246A CN 102126942 B CN102126942 B CN 102126942B
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- emodin anthrone
- emodin
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- BTXNYTINYBABQR-UHFFFAOYSA-N hypericin Chemical compound C12=C(O)C=C(O)C(C(C=3C(O)=CC(C)=C4C=33)=O)=C2C3=C2C3=C4C(C)=CC(O)=C3C(=O)C3=C(O)C=C(O)C1=C32 BTXNYTINYBABQR-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 229940005608 hypericin Drugs 0.000 title claims abstract description 55
- PHOKTTKFQUYZPI-UHFFFAOYSA-N hypericin Natural products Cc1cc(O)c2c3C(=O)C(=Cc4c(O)c5c(O)cc(O)c6c7C(=O)C(=Cc8c(C)c1c2c(c78)c(c34)c56)O)O PHOKTTKFQUYZPI-UHFFFAOYSA-N 0.000 title claims abstract description 55
- SSKVDVBQSWQEGJ-UHFFFAOYSA-N pseudohypericin Natural products C12=C(O)C=C(O)C(C(C=3C(O)=CC(O)=C4C=33)=O)=C2C3=C2C3=C4C(C)=CC(O)=C3C(=O)C3=C(O)C=C(O)C1=C32 SSKVDVBQSWQEGJ-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 238000000034 method Methods 0.000 title claims abstract description 22
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 38
- CBOKHFLBNZMMAA-UHFFFAOYSA-N Emodin anthrone Natural products OC1=CC(O)=CC2=CC3=CC(C)=CC(O)=C3C(O)=C21 CBOKHFLBNZMMAA-UHFFFAOYSA-N 0.000 claims abstract description 28
- LAJSXCAVRQXZIO-UHFFFAOYSA-N emodin anthrone Chemical compound C1=C(O)C=C2CC3=CC(C)=CC(O)=C3C(=O)C2=C1O LAJSXCAVRQXZIO-UHFFFAOYSA-N 0.000 claims abstract description 28
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 24
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 20
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 18
- RHMXXJGYXNZAPX-UHFFFAOYSA-N emodin Chemical compound C1=C(O)C=C2C(=O)C3=CC(C)=CC(O)=C3C(=O)C2=C1O RHMXXJGYXNZAPX-UHFFFAOYSA-N 0.000 claims abstract description 12
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000001816 cooling Methods 0.000 claims abstract description 10
- 229960000583 acetic acid Drugs 0.000 claims abstract description 9
- 239000012362 glacial acetic acid Substances 0.000 claims abstract description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 6
- 150000002367 halogens Chemical class 0.000 claims abstract description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 4
- 238000010898 silica gel chromatography Methods 0.000 claims description 4
- 238000010792 warming Methods 0.000 claims description 3
- 238000000746 purification Methods 0.000 claims description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 238000000605 extraction Methods 0.000 abstract description 2
- YLILOANQCQKPOD-UHFFFAOYSA-N protohypericin Chemical compound C12=C(O)C=C(O)C(C(C3=C(O)C=C(C=C33)C)=O)=C2C3=C2C3=C1C(O)=CC(O)=C3C(=O)C1=C(O)C=C(C)C=C12 YLILOANQCQKPOD-UHFFFAOYSA-N 0.000 abstract 4
- VWDXGKUTGQJJHJ-UHFFFAOYSA-N Catenarin Natural products C1=C(O)C=C2C(=O)C3=C(O)C(C)=CC(O)=C3C(=O)C2=C1O VWDXGKUTGQJJHJ-UHFFFAOYSA-N 0.000 abstract 1
- 239000010282 Emodin Substances 0.000 abstract 1
- RBLJKYCRSCQLRP-UHFFFAOYSA-N Emodin-dianthron Natural products O=C1C2=CC(C)=CC(O)=C2C(=O)C2=C1CC(=O)C=C2O RBLJKYCRSCQLRP-UHFFFAOYSA-N 0.000 abstract 1
- YOOXNSPYGCZLAX-UHFFFAOYSA-N Helminthosporin Natural products C1=CC(O)=C2C(=O)C3=CC(C)=CC(O)=C3C(=O)C2=C1O YOOXNSPYGCZLAX-UHFFFAOYSA-N 0.000 abstract 1
- NTGIIKCGBNGQAR-UHFFFAOYSA-N Rheoemodin Natural products C1=C(O)C=C2C(=O)C3=CC(O)=CC(O)=C3C(=O)C2=C1O NTGIIKCGBNGQAR-UHFFFAOYSA-N 0.000 abstract 1
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- VASFLQKDXBAWEL-UHFFFAOYSA-N emodin Natural products OC1=C(OC2=C(C=CC(=C2C1=O)O)O)C1=CC=C(C=C1)O VASFLQKDXBAWEL-UHFFFAOYSA-N 0.000 abstract 1
- 230000001678 irradiating effect Effects 0.000 abstract 1
- 239000007791 liquid phase Substances 0.000 abstract 1
- PKUBGLYEOAJPEG-UHFFFAOYSA-N physcion Natural products C1=C(C)C=C2C(=O)C3=CC(C)=CC(O)=C3C(=O)C2=C1O PKUBGLYEOAJPEG-UHFFFAOYSA-N 0.000 abstract 1
- 230000001376 precipitating effect Effects 0.000 abstract 1
- FWPIDFUJEMBDLS-UHFFFAOYSA-L tin(II) chloride dihydrate Chemical compound O.O.Cl[Sn]Cl FWPIDFUJEMBDLS-UHFFFAOYSA-L 0.000 abstract 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000000284 extract Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000004809 thin layer chromatography Methods 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 229960000935 dehydrated alcohol Drugs 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 230000000144 pharmacologic effect Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 241000593508 Garcinia Species 0.000 description 1
- 235000000885 Garcinia xanthochymus Nutrition 0.000 description 1
- 206010061218 Inflammation Diseases 0.000 description 1
- 241000700605 Viruses Species 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000001430 anti-depressive effect Effects 0.000 description 1
- 230000003260 anti-sepsis Effects 0.000 description 1
- 230000000840 anti-viral effect Effects 0.000 description 1
- 239000000935 antidepressant agent Substances 0.000 description 1
- 229940005513 antidepressants Drugs 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 241001493065 dsRNA viruses Species 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 206010022000 influenza Diseases 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- SIOXPEMLGUPBBT-UHFFFAOYSA-M picolinate Chemical compound [O-]C(=O)C1=CC=CC=N1 SIOXPEMLGUPBBT-UHFFFAOYSA-M 0.000 description 1
- 150000003053 piperidines Chemical class 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000000452 restraining effect Effects 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 239000012488 sample solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 210000004881 tumor cell Anatomy 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
The invention relates to a method for synthesizing hypericin. The method comprises the following steps of: (1) dissolving emodin and SnCl2.2H2O in glacial acetic acid, raising the temperature to 100-125 DEG C, adding concentrated hydrochloric acid with the concentration of between 36 percent and 40 percent for reaction of 1-3 hours and cooling to obtain emodin anthrone; (2) dissolving emodin anthrone and potassium tert-butoxide in DMF (Dimethyl Formamide), carrying out reaction in a microwave solid-liquid phase synthesis/extraction instrument for 30-90 minutes and cooling to obtain protohypericin; and (3) dissolving the protohypericin in acetone, irradiating with a halogen lamp for 15-24 hours, concentrating and precipitating to obtain the hypericin. The method has the advantages of easiness in operating, low cost, little pollution, high yield, high purity and the like.
Description
Technical field
The invention belongs to the synthetic field of medicine, relate to the synthetic method of hypericin.
Background technology
Hypericin (hypericin), i.e. hypericin forms for the wounded in the battle herb of Garcinia maingayii Herba Hyperici perforati extracts through processing, and with strong points to virus functions such as influenzas, effect is remarkable.The multiple pharmacological effect such as that hypericin has is antiviral, antidepressant, calmness, antisepsis and anti-inflammation, wound convergence can suppress DNA, RNA viruses, and tumour cell is also had certain restraining effect.The multiple pharmacological effect of hypericin grows with each passing day its market demand.Because the content of hypericin in the Herba Hyperici perforati herb only has about 4/10000ths, at present, the content of hypericin in its extract that extracts from Herba Hyperici perforati both at home and abroad is no more than 1%, even if improve extraction process, the content of the hypericin of extract, separating neither be very high, but also can destroy a large amount of natural vegetations or take a large amount of arable lands.In order to enlarge the medicament sources of hypericin, improve the content of hypericin, only have by effective chemical synthesis process and realize this goal.
Chinese patent application CN1827574A discloses the chemical synthesis process of a kind of hypericin and derivative thereof.The method may further comprise the steps: 1) 1,3,8-trihydroxy-6-methylanthraquinone is dissolved in the analytical pure glacial acetic acid, then adds and contain SnCl
22H
2The 36-40% concentrated hydrochloric acid of O be not higher than 125 ℃ of lower reactions 1-4 hour, and cooling obtains 1,3,8-trihydroxy--6-methyl anthrone; 2) with 1,3,8-trihydroxy--6-methyl anthrone and pyridine, piperidines, nitrogen oxy picolinate and FeSO
47H
2O is dissolved in acetone with reaction product again 100-130 ℃ of lower lucifuge reaction 0.5-3 hour, and is concentrated with halogen lamp irradiation 12-24 hour, uses n-hexane dissolution, and filtering-depositing obtains hypericin.The disclosed synthetic route of the document belongs to traditional synthetic reaction process, has long reaction time, and reacted constituent is complicated, and environmental pollution is large, the shortcomings such as the difficult purifying of troublesome poeration and product.
Summary of the invention
Shortcoming in view of the prior art of synthesizing hypericin exists the purpose of this invention is to provide a kind of cost lower, and yield and productive rate are high relatively, the method for synthesizing hypericin that contaminate environment is few.
In order to realize purpose of the present invention, the contriver improves reaction conditions and method by lot of experiments, has explored a kind of method of effectively synthetic hypericin, and concrete technical scheme is as follows:
A kind of method for synthesizing hypericin comprises the step following steps:
(1) Schuttgelb is converted into emodin anthrone
(2) emodin anthrone is converted into former hypericin
(3) former hypericin is converted into hypericin
Described step (2) is under the condition of microwave, carries out the reaction of emodin anthrone catalyzing and condensing with potassium tert.-butoxide as catalyzer.
Above-mentioned method for synthesizing hypericin, wherein preferred steps (2) is: emodin anthrone and potassium tert.-butoxide are dissolved among the DMF, be combined at microwave solid-liquid/react in the abstraction instrument, cooling, separate obtaining former hypericin, wherein the mol ratio of emodin anthrone and potassium tert.-butoxide is 3-5: 0.5-0.7.Further preferred steps (2) is: emodin anthrone and potassium tert.-butoxide are dissolved among the DMF, be combined at microwave solid-liquid/react in the abstraction instrument, cooling separates obtaining former hypericin, and wherein the mol ratio of emodin anthrone and potassium tert.-butoxide is 3-5: 0.5-0.7; And the reaction of emodin anthrone catalyzing and condensing is with Ar
2Protection, microwave reaction power remains on 250-550W, and temperature of reaction is 130-150 ℃, and the reaction times is 30-90 minute.
Above-mentioned method for synthesizing hypericin, the product that the reaction of described step (2) catalyzing and condensing obtains needs through purification by silica gel column chromatography, and elutriant is that volume ratio is 4: 8: the sherwood oil of 2-0.3: ethyl acetate: methyl alcohol.
Above-mentioned any method for synthesizing hypericin, described step (1) is: with Schuttgelb and SnCl
22H
2O is dissolved in the glacial acetic acid, is warming up to 100-125 ℃, then adds concentrated hydrochloric acid in batches, keeps 100-125 ℃ of temperature of reaction, reaction 1-3 hour, and cooling separates obtaining emodin anthrone; Wherein Schuttgelb and SnCl
22H
2The mol ratio of O is 1: 3.5-5, glacial acetic acid and concentrated hydrochloric acid volume ratio are 5: 1-3.Further preferred steps (2) is: with Schuttgelb and SnCl
22H
2O is dissolved in the glacial acetic acid, is warming up to 100-125 ℃, then adds concentrated hydrochloric acid in batches, keeps 100-125 ℃ of temperature of reaction, reaction 1-3 hour, and cooling separates obtaining emodin anthrone; Wherein Schuttgelb and SnCl
22H
2The mol ratio of O is 1: 1.5-3.5, and glacial acetic acid and concentrated hydrochloric acid volume ratio are 5: 1-3; And in the whole reaction process with Ar
2Protection reaches 100-125 ℃ in temperature of reaction, and slowly adds concentrated hydrochloric acid when backflow phenomenon occurring in batches.
Above-mentioned any method for synthesizing hypericin, described step (3) is: after former hypericin is dissolved in acetone, halogen lamp irradiation 15-24 hour, concentrated, obtain hypericin; Wherein said former hypericin and acetone mol ratio are 0.5-0.7: 3-10.Further preferred steps (2) is: after former hypericin is dissolved in acetone, and Ar
2Protection, and with Ar
2Pass into below the liquid level, halogen lamp irradiation 15-24 hour, concentrated, obtain hypericin; Wherein said former hypericin and acetone mol ratio are 0.5-0.7: 3-10.
Compared with prior art, method for synthesizing hypericin of the present invention has following useful technique effect: the contriver is creatively take the condensation reaction of potassium tert.-butoxide as alkali catalyst catalysis emodin anthrone, so that the preparation hypericin is simple to operate, preparation cost is lower, yield and purity are higher relatively, low in the pollution of the environment, obtained comparatively desirable effect.
Embodiment
Below be specific embodiments of the invention, technical scheme of the present invention is done further the description, but protection scope of the present invention is not limited to these embodiment.Every do not deviate from the change of the present invention design or be equal to substitute include within protection scope of the present invention.
Method therefor is ordinary method if no special instructions among the following embodiment.
The method synthetic hypericin of current series invention, specific examples may further comprise the steps:
(1) Schuttgelb is converted into emodin anthrone
Get Schuttgelb 2g (7.4mmol), add among the glacial acetic acid 120mL Ar
2The lower SnCl of adding is stirred in protection
22H
2O2.8g (12.4mmol) begins heating with mixture, and temperature of reaction reaches 115 ℃, begins to occur backflow phenomenon.About 110 ℃, dropwise add concentrated hydrochloric acid 48mL, finish back flow reaction 2h (TLC tracking).After placing cooling, filter with Büchner funnel, residue is washed till neutrality with deionized water, weighs after the vacuum-drying to obtain emodin anthrone 1.766mg, productive rate 93%.
When TLC follows the tracks of reaction mechanism, every half hour, draw 20 μ L reaction solutions, add an amount of dehydrated alcohol and make it dissolve fully, the preparation sample solution.Then accurately take by weighing emodin anthrone 1mg and add anhydrous alcohol solution, use the pipettor sucking-off, move in the 25mL volumetric flask, with absolute ethanol washing repeatedly, add dehydrated alcohol and be dissolved to 25mL, raw materials solution.With the reaction solution for preparing and emodin anthrone ethanolic soln point on thin layer chromatography board, select chloroform: the volume ratio of methyl alcohol be 3: 1 as developping agent, the variation of reactant yellow spotting and resultant fluorescence spot in the observing response system is judged the degree that reaction is carried out as index.
(2) emodin anthrone is converted into former hypericin
Get emodin anthrone 1.024g (4mmol) and 0.062g (0.55mmol) potassium tert.-butoxide is dissolved among the 40mL DMF (DMF), magnetic agitation is combined at microwave solid-liquid/react in the abstraction instrument, passes into Ar before the reaction
2, drain the air in the reaction flask.It is 145 ℃ that temperature of reaction is set, and reaction power is 450W, and the reaction times is 40mim, begins reaction.Treat its cool to room temperature after having reacted, add deionized water.Add 2mol hydrochloric acid, regulator solution pH value is 2, filters with Büchner funnel, and precipitation is extremely neutral with cold wash, vacuum-drying.Wash-out on the silica gel column chromatography post, elutriant (sherwood oil: ethyl acetate: methyl alcohol=4: 8: 0.9), obtain former hypericin 0.544mg, yield 53.9%
(3) former hypericin is converted into hypericin
After former hypericin 170mg (0.33mmol) is dissolved in 500mL acetone, Ar
2Protection, irradiation is 24 hours under 500 watts halogen lamp.After reaction was finished, the rotary evaporation solvent was to 5mL.Weigh after the vacuum-drying and obtain product.With above-mentioned products therefrom wash-out on the silica gel column chromatography post, elutriant (sherwood oil: ethyl acetate: methyl alcohol=4: 8: 0.5), obtain hypericin 150mg, yield 95%.(content is 〉=98.5%).
Claims (3)
1. method for synthesizing hypericin, comprise that step (1) is converted into emodin anthrone with Schuttgelb, (2) emodin anthrone is converted into former hypericin, (3) former hypericin is converted into hypericin, it is characterized in that: described step (2) is under the condition of microwave, carries out the reaction of emodin anthrone catalyzing and condensing with potassium tert.-butoxide as catalyzer; Described step (2) is that emodin anthrone and potassium tert.-butoxide are dissolved among the DMF, is combined at microwave solid-liquid/react in the abstraction instrument, and cooling separates obtaining former hypericin, and wherein the mol ratio of emodin anthrone and potassium tert.-butoxide is 3-5:0.5-0.7; The reaction of emodin anthrone catalyzing and condensing is with the Ar protection in the described step (2), and microwave reaction power remains on 250-550W, and temperature of reaction is 130-150 ℃, and the reaction times is 30-90 minute; The product that the reaction of described step (2) catalyzing and condensing obtains is through purification by silica gel column chromatography, and elutriant is that volume ratio is the sherwood oil of 4:8:2-0.3: ethyl acetate: methyl alcohol; Described step (1) is with Schuttgelb and SnCl
22H
2O is dissolved in the glacial acetic acid, is warming up to 100-125 ℃, then adds concentrated hydrochloric acid in batches, keeps 100-125 ℃ of temperature of reaction, reaction 1-3 hour, and cooling separates obtaining emodin anthrone; Wherein Schuttgelb and SnCl
22H
2The mol ratio of O is 1:3.5-5, and glacial acetic acid and concentrated hydrochloric acid volume ratio are 5:1-3; With Ar protection, reach 100-125 ℃ in temperature of reaction in the reaction process of described step (1), and slowly add concentrated hydrochloric acid when backflow phenomenon occurring in batches.
2. method for synthesizing hypericin as claimed in claim 1, it is characterized in that: described step (3) is after former hypericin is dissolved in acetone, halogen lamp irradiation 15-24 hour is concentrated, obtains hypericin; Wherein said former hypericin and acetone mol ratio are 0.5-0.7:3-10.
3. method for synthesizing hypericin as claimed in claim 2 is characterized in that: after former hypericin is dissolved in acetone, and the Ar protection, and Ar passed into below the liquid level.
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| CN 201010600246 CN102126942B (en) | 2010-12-22 | 2010-12-22 | Method for synthesizing hypericin |
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| CN102126942B true CN102126942B (en) | 2013-10-23 |
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| CN103274920B (en) * | 2013-06-14 | 2014-12-17 | 西北农林科技大学 | Efficient hypericin synthesizing method initiated by monochromatic light |
| CN108863741A (en) * | 2017-05-11 | 2018-11-23 | 上海凯伟化工科技有限公司 | A kind of synthetic method of hypericin |
| CN108084065B (en) * | 2017-11-21 | 2020-06-16 | 中国农业科学院兰州畜牧与兽药研究所 | Hypericin derivative and preparation method and application thereof |
| CN111138262A (en) * | 2020-01-13 | 2020-05-12 | 成都金石缘科技有限公司 | Hypericin synthesis method |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1827574A (en) * | 2006-04-19 | 2006-09-06 | 中国农业科学院兰州畜牧与兽药研究所 | Chemical synthesis process for hypericin and derivatives thereof |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1827574A (en) * | 2006-04-19 | 2006-09-06 | 中国农业科学院兰州畜牧与兽药研究所 | Chemical synthesis process for hypericin and derivatives thereof |
Non-Patent Citations (6)
| Title |
|---|
| A microwave-assisted synthesis of phenanthroperylene quinones as exemplified with hypericin;Stefan Aigner et al.;《Monatshefte für Chemie》;20080218;第139卷;第991-993页 * |
| Stefan Aigner et al..A microwave-assisted synthesis of phenanthroperylene quinones as exemplified with hypericin.《Monatshefte für Chemie》.2008,第139卷第991-993页. |
| 汤媛 等.金丝桃素的合成工艺改进.《合成化学》.2009,第17卷(第4期),第498-499、502页. |
| 汤媛 等.金丝桃素研究进展.《医药导报》.2009,第28卷第65-67页. |
| 金丝桃素的合成工艺改进;汤媛 等;《合成化学》;20090820;第17卷(第4期);第498-499、502页 * |
| 金丝桃素研究进展;汤媛 等;《医药导报》;20090518;第28卷;第65-67页 * |
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