CN103788037B - Method for purifying carabrone - Google Patents
Method for purifying carabrone Download PDFInfo
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- CN103788037B CN103788037B CN201210434466.3A CN201210434466A CN103788037B CN 103788037 B CN103788037 B CN 103788037B CN 201210434466 A CN201210434466 A CN 201210434466A CN 103788037 B CN103788037 B CN 103788037B
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- acetone
- carabrone
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- strong alkali
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
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Abstract
The invention discloses a method for purifying carabrone. The method comprises the following steps: (1) soaking or ultrasonically extracting carpesium abrotanoides in a water solution of inorganic strong base at 0-100 DEG C; then, filtering, adjusting the pH value of filter liquor to be 1-7 by the inorganic strong base to generate deposits; (2) removing the deposits generated in the step (1), and then extracting supernatant liquid by an organic solvent to obtain extracting liquid; and (3) performing silica column chromatography on the extracting liquid obtained from the step (2) to obtain the carabrone. The method is easy to operate; the obtained carabrone is relatively high in purity.
Description
Technical field
The present invention is specifically related to a kind of method of purification of Carabrone.
Background technology
FRUCTUS CARPESII is the dry mature fruit of feverfew root of Common carpesium, has the effect of killing insect and eliminating accumulation, is usually used in treatment roundworm, pinworm, teniasis, abdominal pain due to worm stagnation and infantile malnutrition etc.This field is fewer for the research of FRUCTUS CARPESII chemical composition, current research shows, FRUCTUS CARPESII contains Telekin (Liu Cuizhou, Xu Jing, Gui Liping etc. the chemical constitution study [J] of FRUCTUS CARPESII. drug evaluation is studied, 2010,33 (6): 220-221), Carabrone, carpesia-lactone alcohol and various lipid acid.Research shows, Carabrone belongs to sesquiterpenoids, has sterilization and bacteriostasis effect, in order to realize its good fungistatic effect, needs its separation and purification from FRUCTUS CARPESII.Owing to containing much similar carpesia-lactone compound in FRUCTUS CARPESII, mutual polarity difference is very little, make the segregation ratio of monomeric compound more difficult, if application number is 201010113236, name is called the Chinese invention patent of " a kind of Carpesium abrotanoides total terpene lactones extract ", provides a kind of method extracting Carpesium abrotanoides total terpene lactones compound from root of Common carpesium.What this invention obtained is Carpesium abrotanoides total terpene lactones mixture, and Carabrone wherein, carpesia-lactone alcohol purity are not high, can not meet the demand of real scientific research, production.
Summary of the invention
Technical problem to be solved by this invention is in the method in order to overcome existing purification Carabrone, the defect that Carabrone purity is not high, and provides a kind of Carabrone method of purification.Method of purification of the present invention is simple to operate, and the Carabrone purity obtained is higher.
The invention provides a kind of method of purification of Carabrone, it comprises the following step:
Step 1): in the aqueous solution of inorganic strong alkali, under 0 ~ 100 DEG C of condition, is being undertaken soaking or supersound extraction by FRUCTUS CARPESII; Then filter, filtrate regulates pH to 1 ~ 7 with inorganic acid, produces precipitation;
Step 2): after the precipitation removing that step 1) is produced, supernatant liquor organic solvent is extracted, obtains extraction liquid;
Step 3): by step 2) extraction liquid that obtains carries out silica gel column chromatography, Carabrone.
In step 1), described carrying out is soaked or the temperature of supersound extraction is preferably 30 ~ 70 DEG C.The time of described immersion is preferably 1h ~ 24h.The time of described supersound extraction is preferably 5 ~ 60 minutes, and better is 10 ~ 15 minutes.The number of times of described supersound extraction is preferably 1 ~ 3 time.The pressure of supersound extraction is preferably 0.1 ~ 10.0MPa.In step 1), adopt supersound process, can extraction time be shortened, improve extraction efficiency.
In step 1), described pH is preferably 1 ~ 3.The mass ratio of described FRUCTUS CARPESII and the aqueous solution of inorganic strong alkali is preferably 1:1 ~ 1:30, and that better is 1:10 ~ 1:15.Described inorganic strong alkali is preferably NaOH and/or KOH.In the aqueous solution of described inorganic strong alkali, the mass concentration of inorganic strong alkali is preferably 0.1% ~ 20%, preferably 0.1% ~ 10%, further preferably 0.5% ~ 1%.Described inorganic acid is preferably one or more in hydrochloric acid, sulfuric acid and nitric acid, and better is hydrochloric acid, and hydrochloric acid preferably exists (preferred hydrochloric acid mass concentration is the aqueous hydrochloric acid of 0.1% ~ 1%) with the form of aqueous hydrochloric acid.During with inorganic acid adjustment pH, the temperature of the solution regulated is preferably room temperature, namely 0 ~ 40 DEG C.In the present invention, step 1) adopts alkali-acid treatment impurity, makes impurity-removing method simple, economical.
Step 2) in, the method for removing precipitation can be centrifugal, or by leaving standstill and filtering.Described supernatant liquor organic solvent is extracted in organic solvent can be conventional extraction, organic solvent immiscible with water, one or more in ethyl acetate, methylene dichloride, carbon trichloride and tetracol phenixin.
In step 3), the method of described silica gel column chromatography and condition all can be ordinary method and the condition of this type of separation method of this area, those skilled in the art (can using existing Carabrone as standard substance in the present invention according to the polarity of target product, by the isolated material of control test), in conjunction with methods such as TLC detections, the condition of being purified by target product Carabrone of the present invention can be selected.The present invention is following method and condition particularly preferably: eluent used is preferably Ether-Acetone, or methylene chloride-methanol; Wherein, elution requirement is Gradient elution, and in described Ether-Acetone, the volume ratio of ether and acetone is preferably the preferred 4:1 ~ 6:1 of 10:0 ~ 0:10().In described methylene chloride-methanol, the volume ratio of methylene dichloride and methyl alcohol is preferably the preferred 95:5 of 100:0 ~ 0:100().Silica gel in silica gel column chromatography used can be macroporous silica gel, silochrom, Type B silica gel or Kiselgel A.Preferably, in elution process, by elutriant point thin-layer silicon offset plate (TLC), developping agent can be Ether-Acetone (2:1 ~ 4:1), and developer can be 5% sulphuric acid soln, can in 105 DEG C of heating 5min colour developing, first round dot occurs starting to collect, merge the elutriant of first round dot, concentrate, fling to organic solvent, Carabrone.
In the present invention, preferably, the following step 4 can also be comprised after step 3)):
Step 4): Carabrone step 3) obtained is dissolved in the mixing solutions of low polar solvent and high polar solvent, be concentrated into clear crystal to separate out, more highly purified Carabrone can be obtained, wherein low polar solvent is ether, hexane, hexanaphthene, methylene dichloride or pentane, and high polar solvent is acetone, ethyl acetate, chloroform, methyl alcohol or ethanol.
In step 4), preferably, the mixing solutions of low polar solvent and high polar solvent is Ether-Acetone mixing solutions, cyclohexane-acetone mixing solutions, or cyclohexane-ethyl acetate mixing solutions.In described Ether-Acetone mixing solutions, the volume ratio of ether and acetone be preferably 4:1 ~ 10:1(better be 8:1).In described cyclohexane-acetone mixing solutions, the volume ratio of hexanaphthene and acetone be preferably 4:1 ~ 10:1(better be 8:1).In described cyclohexane-ethyl acetate mixing solutions, the volume ratio of hexanaphthene and ethyl acetate be preferably 4:1 ~ 10:1(better be 8:1).
Without prejudice to the field on the basis of common sense, above-mentioned each optimum condition, can arbitrary combination, obtains the present invention.
Agents useful for same of the present invention and raw material are all commercially.
Positive progressive effect of the present invention is: method of purification of the present invention is simple to operate, and the Carabrone purity obtained is higher.
Accompanying drawing explanation
Fig. 1 is the schematic flow sheet of the preferred embodiments of the method for purification of Carabrone of the present invention.
Fig. 2 is the obtained final product Carabrone of embodiment 1
1hNMR spectrogram.
Embodiment
Mode below by embodiment further illustrates the present invention, but does not therefore limit the present invention among described scope of embodiments.The experimental technique of unreceipted actual conditions in the following example, conventionally and condition, or selects according to catalogue.
Embodiment 1
The preparation technology of Carabrone, take namely FRUCTUS CARPESII as raw material, 0.5%NaOH solution is the technique of extraction agent, extraction and isolation Carabrone, and concrete steps are as follows:
(1) 1kg FRUCTUS CARPESII is got, use 5L 0.5%(w/w) NaOH solution, 30 DEG C of supersound process 30min, separate FRUCTUS CARPESII with 200 object filter clothes, use 4L 0.5%(w/w again) NaOH solution at 30 DEG C of supersound process 30min, with 200 object filter clothes, FRUCTUS CARPESII is separated; Use 3L 0.5%(w/w again) NaOH solution at 30 DEG C of supersound process 30min, with 200 order filter clothes, FRUCTUS CARPESII is separated; Merge the extracting solution extracted for three times.
(2) in extracting solution, 1%(w/w is added) hydrochloric acid soln neutralizes under room temperature (25 DEG C) condition, adjusts about pH to 3, produces precipitation, leave standstill.
(3) sinking to the bottom of generation is separated with supernatant liquor, precipitates heavy multiple (1), (2) step; Supernatant liquor adds 1L ethyl acetate and extracts, and extracts three times, merges the extraction liquid of three times, concentrated.
(4) by silicagel column on the ethyl acetate extract after concentrated, carry out Gradient elution with Ether-Acetone mixed solution, wherein, Ether-Acetone volume ratio is 4:1.In elution process, adopt stepwise elution, launch with silica gel thin-layer plate with Ether-Acetone developping agent, carry out qualitative test, elutriant will be obtained containing same compound point and merge.Wherein, will only containing first point elutriant concentrated, reclaim eluent, obtain Carabrone 3.75g, purity more than 90%.
(5) Carabrone of acquisition is dissolved in Ether-Acetone (V/V, volume ratio 8:1), is concentrated into and occurs white opacity, have colourless crystallization, dry, obtain the Carabrone of 3.65g purity more than 99.5%.
The nuclear magnetic spectrogram of product Carabrone is as Fig. 1, and concrete data are as follows:
1HNMR（CDCl
3）δH：6.23(1H，d，J=2.8Hz，H-13)，5.56(1H，d，J=2.4Hz，H-13')，4.79（1H，ddd，J=6，g，11，11.4Hz，H-8)，3.15(1H，ddddd，J=7，9，13Hz，H-7)，2.16(3H，s，H-15)，1.08(3H，s，H-1.4)，0.45(1H，m，H-5)，0.37(1H，m，H-1)。
Embodiment 2
(1) 5kg FRUCTUS CARPESII is got, use 20L 1%(w/w) NaOH solution, 30 DEG C of supersound process 30min, separate FRUCTUS CARPESII with 200 object filter clothes, use 15L 1%(w/w again) NaOH solution at 30 DEG C of supersound process 30min, with 200 object filter clothes, FRUCTUS CARPESII is separated; Use 10L 1%(w/w again) NaOH solution at 30 DEG C of supersound process 30min, with 200 order filter clothes, FRUCTUS CARPESII is separated; Merge the extracting solution extracted for three times.
(2) in extracting solution, 3%(w/w is added) hydrochloric acid soln neutralizes under room temperature (25 DEG C) condition, adjusts about pH to 2, produces precipitation, leave standstill.
(3) sinking to the bottom of generation is separated with supernatant liquor, precipitates heavy answering (1), (2) step; Supernatant liquor adds 2.5L ethyl acetate and extracts, and extracts three times, merges the extraction liquid of three times, concentrated.
(4) by silicagel column on the ethyl acetate extract after concentrated, carry out Gradient elution with methylene chloride-methanol mixed solution, wherein, methylene chloride-methanol volume ratio is 95:5.In elution process, adopting stepwise elution, is that developping agent launches, qualitative test with Ether-Acetone with silica gel thin-layer plate, by the elutriant merging containing same compound.By concentrated for the elutriant only containing first compound, recovery eluent, obtain Carabrone 16.35g, purity more than 90%.
(5) Carabrone of acquisition is dissolved in cyclohexane-acetone (V/V, volume ratio 8:1), is concentrated into and occurs white opacity, leave standstill, have crystallization, dry, obtain the Carabrone that 15.95g purity reaches more than 99.5%.
The nuclear magnetic data of product Carabrone is as follows:
1HNMR（CDCl
3）δH：6.23(1H，d，J=2.8Hz，H-13)，5.56(1H，d，J=2.4Hz，H-13')，4.79（1H，ddd，J=6，g，11，11.4Hz，H-8)，3.15(1H，ddddd，J=7，9，13Hz，H-7)，2.16(3H，s，H-15)，1.08(3H，s，H-1.4)，0.45(1H，m，H-5)，0.37(1H，m，H-1)。
Embodiment 3
(1) 10kg FRUCTUS CARPESII is got, use 25L 2%(w/w) NaOH solution, 30 DEG C of supersound process 30min, separate FRUCTUS CARPESII with 200 object filter clothes, use 20L 2%(w/w again) NaOH solution at 30 DEG C of supersound process 30min, with 200 object filter clothes, FRUCTUS CARPESII is separated; Use 15L 2%(w/w again) NaOH solution at 30 DEG C of supersound process 30min, with 200 order filter clothes, FRUCTUS CARPESII is separated; Merge the extracting solution extracted for three times.
(2) 6%(w/w is added in Fructus Carpesii extract filtrate northwards) hydrochloric acid soln neutralizes, adjusts about pH to 1, produce precipitation, leave standstill under room temperature (25 DEG C) condition.
(3) sinking to the bottom of generation be separated with supernatant liquor, precipitation repeats (1) (2) step; Supernatant liquor adds 4L ethyl acetate and extracts, and extracts three times, merges the extraction liquid of three times, concentrated.
(4) by silicagel column on the ethyl acetate extract after concentrated, carry out Gradient elution with Ether-Acetone mixed solution, wherein, Ether-Acetone volume ratio is 4:1.In elution process, adopting stepwise elution, is that developping agent launches, qualitative test with Ether-Acetone with silica gel thin-layer plate, by the elutriant merging containing same compound.Wherein, by concentrated for the elutriant only containing first compound, recovery eluent, Carabrone 29.6g is obtained, purity more than 90%.
(5) Carabrone of acquisition is dissolved in hexanaphthene and ethyl acetate (V/V, volume ratio 4:1), is concentrated into and occurs white opacity, leave standstill, have crystallization, dry gained crystallization, obtain the Carabrone that 28.56g purity reaches more than 99.5%.
The nuclear magnetic data of product Carabrone is as follows:
1HNMR（CDCl
3）δH：6.23(1H，d，J=2.8Hz，H-13)，5.56(1H，d，J=2.4Hz，H-13')，4.79（1H，ddd，J=6，g，11，11.4Hz，H-8)，3.15(1H，ddddd，J=7，9，13Hz，H-7)，2.16(3H，s，H-15)，1.08(3H，s，H-1.4)，0.45(1H，m，H-5)，0.37(1H，m，H-1)。
Claims (5)
1. a method of purification for Carabrone, is characterized in that comprising the following step:
Step 1): in the aqueous solution of inorganic strong alkali, under 0 ~ 100 DEG C of condition, FRUCTUS CARPESII is being carried out soaking or supersound extraction; Then filter, filtrate regulates pH to 1 ~ 3 with inorganic acid, produces precipitation; Described inorganic strong alkali is NaOH and/or KOH; Described inorganic acid is one or more in hydrochloric acid, sulfuric acid and nitric acid;
Step 2): by step 1) after the removing of the precipitation that produces, supernatant liquor organic solvent is extracted, obtains extraction liquid;
Step 3): by step 2) extraction liquid that obtains carries out silica gel column chromatography, Carabrone; Step 2) in, described supernatant liquor organic solvent is extracted in organic solvent be one or more in ethyl acetate, methylene dichloride, carbon trichloride and tetracol phenixin; Step 3) in, in described silica gel column chromatography, eluent used is Ether-Acetone, or methylene chloride-methanol; Wherein, elution requirement is Gradient elution, and in described Ether-Acetone, the volume ratio of ether and acetone is 10:0 ~ 0:10; In described methylene chloride-methanol, the volume ratio of methylene dichloride and methyl alcohol is 100:0 ~ 0:100;
In step 3) after also comprise the following step 4):
Step 4): by step 3) obtained Carabrone is dissolved in the mixing solutions of low polar solvent and high polar solvent, is concentrated into clear crystal precipitation; Wherein the mixing solutions of low polar solvent and high polar solvent is Ether-Acetone mixing solutions, cyclohexane-acetone mixing solutions, or cyclohexane-ethyl acetate mixing solutions, in described Ether-Acetone mixing solutions, the volume ratio of ether and acetone is 4:1 ~ 10:1; In described cyclohexane-acetone mixing solutions, the volume ratio of hexanaphthene and acetone is 4:1 ~ 10:1; In described cyclohexane-ethyl acetate mixing solutions, the volume ratio of hexanaphthene and ethyl acetate is 4:1 ~ 10:1.
2. method of purification as claimed in claim 1, is characterized in that: step 1) in, described carrying out is soaked or the temperature of supersound extraction is 30 ~ 70 DEG C; The time of described immersion is 1h ~ 24h; The time of described supersound extraction is 5 ~ 60 minutes; The number of times of described supersound extraction is 1 ~ 3 time.
3. method of purification as claimed in claim 1, is characterized in that: step 1) in, the mass ratio of described FRUCTUS CARPESII and the aqueous solution of inorganic strong alkali is 1:1 ~ 1:30; In the aqueous solution of described inorganic strong alkali, the mass concentration of inorganic strong alkali is 0.1% ~ 20%.
4. method of purification as claimed in claim 3, is characterized in that: step 1) in, in the aqueous solution of described inorganic strong alkali, the mass concentration of inorganic strong alkali is 0.1% ~ 10%.
5. method of purification as claimed in claim 1, is characterized in that: step 1) in, during with inorganic acid adjustment pH, the temperature of the solution regulated is 0 ~ 40 DEG C.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105900994A (en) * | 2016-05-21 | 2016-08-31 | 泉州绿邦贸易有限公司 | Sterilization composition containing carabrone and prothioconazole |
| CN105994342A (en) * | 2016-05-21 | 2016-10-12 | 泉州绿邦贸易有限公司 | Sterilization composition containing botanical bactericide |
| CN106138079B (en) * | 2016-07-29 | 2018-08-24 | 甘肃新天马制药股份有限公司 | A kind of liniment and preparation method thereof for treating animal body surface parasitic disease |
| CN111574353B (en) * | 2020-05-22 | 2022-10-25 | 丽水市中心医院 | Phenolic compound |
| CN112263600B (en) * | 2020-10-27 | 2022-07-05 | 湖南省中医药研究院 | Carpesium abrotanoides extract, preparation method and application thereof in anti-liver cancer active drugs passing through JAK2/STAT3 channel |
| CN112402412B (en) * | 2020-11-18 | 2022-03-18 | 中国医学科学院药用植物研究所 | Application of inner ester compound of jingdao in preparing medicine for treating inflammation-caused diseases |
| CN113288893B (en) * | 2021-07-02 | 2023-05-05 | 中国科学院兰州化学物理研究所 | Application of sesquiterpene lactone compound in preparation of medicine for treating renal anemia |
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| CN1970550A (en) * | 2006-11-07 | 2007-05-30 | 西北农林科技大学无公害农药研究服务中心 | Carrageenan sesquiterpene lactone compound separated from Carpesium macrocephalum with bactericidal activity and application thereof |
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| CN1970550A (en) * | 2006-11-07 | 2007-05-30 | 西北农林科技大学无公害农药研究服务中心 | Carrageenan sesquiterpene lactone compound separated from Carpesium macrocephalum with bactericidal activity and application thereof |
| CN101050209A (en) * | 2006-11-10 | 2007-10-10 | 西北农林科技大学无公害农药研究服务中心 | Eudesmane type sesquiterpene lactone compound extracted from Carpesium macrocephalum and having antibacterial activity, and its application |
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