CN101215265A - Method for integrally extracting and purifying ligustrazine, ferulic acid and volatile oil in ligusticum wallichii - Google Patents
Method for integrally extracting and purifying ligustrazine, ferulic acid and volatile oil in ligusticum wallichii Download PDFInfo
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Abstract
The invention discloses a process for comprehensively extracting ligustrazine, ferulic acid and benzine in purifying ligusticum wallichii, which comprises cutting and disintegrating ligusticum wallichii, stirring raw material powder in acid water solution under 25-40 DEG C, extracting ligustrazine in stirring reflux, stirring herb residue after extracted through adding water under 40-60 DEG C to extract ferulic acid in return flow, finally extracting benzine through adopting steam reflux distillation for herb residues after being extracted ferulic acid under the distillation speed of 3-5ml/min, and purifying extracted ligustrazine extract and ferulic acid extract through the combination way of strong acid cationic ion-exchange resin column and organic solution extraction and the combination way of organic solution deposition, extraction and crystallization. The process which is provides by the invention not only can extract all three effective compositions in ligusticum wallichii, but also has the advantages of larger extraction quantity, high purity, mature technology, easy control and low production cost, which is beneficial for the industrialized production.
Description
Technical field
The invention belongs to the method and technology field of main effective constituent in the comprehensive extraction separation purifying Ligusticum wallichii, be specifically related to main effective constituent---the method for Ligustrazine, forulic acid and volatile oil in a kind of comprehensively extracting and purifying Ligusticum wallichii.
Background technology
Ligusticum wallichii is common Chinese medicinal materials, its property suffering, temperature, return liver, courage, pericardium channel, have blood-activating and qi-promoting, the effect of wind-expelling pain-stopping, can be used for cardiovascular disorder clinically, kidney disease and menoxenia, through close, dysmenorrhoea, postpartum are retarded by silt treatment of diseases such as stomachache.It is the alkaloids of representative that activeconstituents in the Ligusticum wallichii mainly contains with the Ligustrazine, is the organic acid and the volatile oil of representative with the forulic acid.Wherein Ligustrazine is used for the treatment of cerebral thrombosis, migraine and combined external head injuries clinically; Forulic acid is used for clinical as the migrainous medicine of treatment; Lactone composition in the volatile oil has tangible cardiac stimulant, increases the effect of coronary flow.
Sichuan Province is the main milpa of Ligusticum wallichii, Dujiang weir, wherein genuine producing region long-term Ligusticum wallichii cultivated area 700～1000hm
2, export volume accounts for 60% of national export volume, and Pengzhou cultivated area development in nearly 2 years is rapid, and whole city's Ligusticum wallichii output accounts for 90% of national ultimate production.Though the output of the Ligusticum wallichii in Sichuan is very big, be to sell to both at home and abroad mostly with the form of bulk drug, Ligusticum wallichii is not carried out retrofit, the economic benefit of its acquisition is extremely limited.
And at present these domestic Ligusticum wallichii medicinal materials generally are to use as medicine materical crude slice, and instream factor and rate of consumption only have 7%; Other has the more domestic pharmacy producers of minority by extracting the volatile oil in the Ligusticum wallichii, and soft capsule is made in exploitation or hard capsule is used, but this measure has also only utilized in the Ligusticum wallichii 5% resource, and all the other a large amount of useful components such as total alkali, phenolic acid etc. all are dropped in leaching process, have caused a large amount of wastes of herb resource.Thereby, Ligusticum wallichii is carried out retrofit research, satisfy and make the best use of everything, reduce the waste of herb resource, and form Chinese patent medicine production engineeringization, the mass-producing of Ligusticum wallichii, increase economic efficiency, become an urgent demand in this field.
It is reported the retrofit research of relevant Ligusticum wallichii, the i.e. more existing reports of the extraction of its main effective constituent research.As Zhao Lilian (Zhao Lilian, Xiaxin China. Ligusticum wallichii alcohol extraction process research [J]. Chinese patent medicine, 2002,24 (3): 173～174), Ou Yingfu (Ou Yingfu, Yong Hong. the Ligusticum wallichii extraction process of effective component is selected [J]. Shandong medicine, 2007,47 (4): 72～73), Huang Guoxing (Huang Guoxing, Ji Fang, Yang Wendan. the Study on extraction of forulic acid [J] in the Ligusticum wallichii. contemporary Chinese is used pharmaceutical journal, 203～204) etc. 2007,24 (3): the people uses ethanol to extract Ligustrazine or forulic acid separately as solvent.Though less as the water-soluble impurity that extraction agent produced with ethanol, alcohol extraction process can cause the loss of volatile oil, is unfavorable for the extraction of volatile oil; Zhang Hong (Zhang Hong and for example, Liu Zhengliang, Wang Hongquan. supercritical fluid extraction extracts the research [J] of effective constituent in the Ligusticum wallichii. herbal medicine, 2001,32 (12): 1077～1079), originally (Liu originally for Liu, John R Dean, Ligustrazine [J] in Rachel Price. fado rope solvent and the supercritical extraction Ligusticum wallichii. Chinese Journal of Pharmaceuticals, 1999,30 (5): 196～199), Yang Lin (Yang Lin, Luo Xiaoxing, Wang Siwang etc. two kinds of technology comparative studies [J] of extracting the Radix Angelicae Sinensis Rhizoma Chuanxiong volatile oil. Chinese tcm emergency, 1140～1141) etc. 2006,15 (10): the people adopts supercritical fluid extraction to extract Ligustrazine or forulic acid or volatile oil separately.Though supercritical fluid extraction has advantages such as service temperature is low, preservation effective constituent is survivable, this method apparatus expensive, the cost height is not suitable for suitability for industrialized production.
And about the research of Ligusticum wallichii single active ingredient purifying report, mainly be to adopt methods such as macroporous resin column and solvent extraction to separate.As Hong Yanlong (Hong Yanlong, Xu Desheng, Feng Yi etc. contain extraction, the purifying process research [J] of forulic acid active principle in the Ligusticum wallichii. Chinese tcm emergency, 2006,15 (10): 1140～1141), Liu Xu (Liu Xu, Yang Xuemei, Xu Jiang equality. orthogonal test is to the screening study [J] of Ligusticum wallichii extraction process. the Guangdong pharmacy, 3～5) etc. 2003,13 (6): the people uses the macroporous resin purification forulic acid; As Ma Shuancheng (Ma Shuancheng, Deng Shaowei. Ligusticum wallichii extracts, the experimental study [J] of purifying process condition. 215～217) etc. CHINA JOURNAL OF CHINESE MATERIA MEDICA, 1999,24 (4): the people uses the macroporous adsorbent resin separation and purification to obtain the Ligusticum wallichii total extract of Ligustrazine and forulic acid.Because macroporous resin and macroporous adsorbent resin are to utilize the absorption of resin and sieving action principle to carry out separation and purification, thereby less pertinence is strong, alkaloids optionally can not be separated with phenolic acid; Chen Li Na (Chen Lina and for example, Jin Zhexiong, Jiang Jing etc. Ligustrazine Study on extraction process [J]. Heilungkiang medicine, 2000,13 (5): 278-280) wait the people to adopt method purifying Ligustrazines such as crossing macroporous resin column, multiple organic solvent extraction, alkali alumina chromatography, but this purifying process process complexity, the more loss of link is serious, and cost is higher; For another example Zhao Fei (Zhao Fei, Hu Yanyue, Chen Yiping etc. the extraction separation of forulic acid [J] in the Ligusticum wallichii. the Chinese Hospitals pharmaceutical journal, 2005,25 (1): 8～10) etc. the people use ether and yellow soda ash successively abstraction purification obtain forulic acid, but the ether poor stability is unsuitable for suitability for industrialized production.
Because above-mentioned these researchs only relate to a certain effective constituent of independent acquisition, thereby resource utilization is not high, so people begin to pay attention to the comprehensive extraction of Ligusticum wallichii effective constituent, but correlative study is also less.Having of bibliographical information: Wei Yuping (Wei Yuping, Liu Jun, Wang Yongfu, Shi Xingming, old main forces, appoint the Tianchi. extraction of active ingredients technology is set up and multifactorial evaluation [J] in the Ligusticum wallichii. herbal medicine, 2005, (36): 53-54) wait the people to inquire into three kinds of activeconstituentss (Ligustrazine, forulic acid and Z-ligustilide) extraction process and multifactorial evaluation in the Ligusticum wallichii, this article is with 1: 6 solid-liquid ratio with Ligusticum wallichii meal (without sieving), adopt decocting method respectively, return the method for heating up in a steamer, percolation extracts, and as extraction agent, uses single solvent extraction carrying out separation and purification with sherwood oil.The research purpose of this article is to want under same reference condition, by Different Extraction Method gained result is compared, the extraction effect of explanation each effective constituents under different condition has than big-difference, thereby estimate the quality of extraction process with any one index components all can be too biased, and suggestion uses the productive rate of plurality of active ingredients to carry out the conclusion of multifactorial evaluation.This article is not selected optimized extraction conditions and purification condition according to the character that each extracts composition.Luo Huafei (Luo Huafei. comprehensively extract [D] about Ligusticum wallichii in the study on the industrialization of Ligusticum wallichii comprehensive utilization. the master of Chengdu University of Traditional Chinese Medicine Diplomarbeit, 2003) then disclose and adopt percolation, direct distillation and decocting cooking method to extract Rhizoma Chuanxiong total alkaloid, volatile oil and total phenolic acid successively respectively, and use membrane separation technique that extract is carried out purifying, the research of adopting colorimetry to detect.But because this research adopts the decocting cooking method to extract total phenolic acid, and the temperature that the temperature that decocting boils is exactly a water boils, decomposition temperature (because forulic acid will be decomposed rapidly when temperature surpasses 80 ℃) far above forulic acid therefore can do great damage to the main effective constituent forulic acid of treatment headache in total phenolic acid; And the diacolation process of percolation is very slow, and extracting cycle is long; Membrane sepn purification techniques difficulty is bigger, and cost is higher, is unfavorable for fairly large industrialization; And this research is adopted direct distillation to extract volatile oil earlier and is extracted total phenolic acid again, because the temperature of direct distillation is also very high, thereby also can be to some compositions in total phenolic acid, particularly the main effective constituent forulic acid to the treatment headache does great damage.
Summary of the invention
The objective of the invention is problem at the prior art existence, the method of Ligustrazine, forulic acid and volatile oil in a kind of new comprehensively extracting and purifying Ligusticum wallichii is provided, this method can not damage effective constituent contained in the Ligusticum wallichii on the one hand, the extraction yield height, technology is easy on the other hand, is easy to control, and extracting cycle is short, the product purity height that obtains has better industrial advantages.
Ligustrazine in a kind of comprehensively extracting and purifying Ligusticum wallichii that reaches the object of the invention and provide, the method of forulic acid and volatile oil, this method is earlier Ligusticum wallichii to be cut into slices, pulverize pre-treatment, use aqueous acid under 25～40 ℃ raw material powder then, stirring and refluxing is extracted Ligustrazine, the dregs of a decoction after will extracting again add water and extract forulic acid 40～60 ℃ of following stirring and refluxing, the dregs of a decoction that will extract at last after the forulic acid return the method for heating up in a steamer under distillation speed 3～5ml/min with water vapour, extract volatile oil, and with the Ligustrazine extracting solution that extracts, mode and organic solvent deposit that the forulic acid extracting solution combines with organic solvent extraction with strong acid cation exchange resin column respectively, extraction and crystallization phases bonded mode are purified.
In order to extract and to be unlikely because of particle too carefully influences the solid-liquid separation efficiency the Ligustrazine in the Ligusticum wallichii, forulic acid and volatile oil are as much as possible, the pre-treatment of raw material Ligusticum wallichii should be crushed to 10～50 orders and sieve.
The concrete technology of extracting Ligustrazine in the aforesaid method is to be that 0.05～0.5% aqueous acid is a solvent with concentration of volume percent, and by mass ratio, Szechwan Lovage Rhizome: the proportioning of solvent=1: 3～5, stirring and refluxing is extracted 2～3 times, each 1.5～2.5 hours.Used aqueous acid is hydrochloric acid soln or acetum or sulphuric acid soln.
The concrete technology of extracting forulic acid in the aforesaid method be with extract behind the Ligustrazine the dregs of a decoction by with the condition of mass ratio=1: 4～6 of water under, stirring and refluxing is extracted 2～3 times, each 0.5～1.5 hour.
The concrete technology of extracting volatile oil in the aforesaid method be with extract after the forulic acid the dregs of a decoction by with the condition of mass ratio=1: 4～6 of water under, extracted 8～12 hours.
The Ligustrazine of gained, forulic acid are purified respectively by the following method:
1) purification of Ligustrazine extracting solution specifically be earlier with the Ligustrazine extracting solution through after evaporation concentration, filtration under diminished pressure again, regulating pH value of filtrate with the pH regulator agent then is 1～3, again be filled with on the ion exchange resin column of storng-acid cation exchange resin the adding of this filtrate, with concentration of volume percent 60～80% eluate solution wash-outs, with elutriant after reduction vaporization concentrates, extraction agent with 1～3 times of volume extracts 2～4 times again, merge 2～4 times extract layer, reduction vaporization concentrates, vacuum-drying promptly gets purity and is 79%～83% Ligustrazine;
2) purification of forulic acid extracting solution specifically be earlier with the forulic acid extracting solution after reduction vaporization concentrates, dehydrated alcohol with 1～3 times of volume, staticly settle, the elimination throw out concentrates and removes alcohol, regulating pH value of filtrate with the pH regulator agent then is 2～5, with 1～3 times volumes of acetic acid ethyl ester extraction 2～4 times, merges 2～4 times extract layer again, reduction vaporization is concentrated, vacuum-drying promptly gets purity and is 76%～81% forulic acid.
The used pH regulator agent of the purification process of Ligustrazine extracting solution and forulic acid extracting solution is hydrochloric acid or acetic acid; Wherein the used storng-acid cation exchange resin of the purification process of Ligustrazine extracting solution is 001 * 7 (732) or 001 * 12 strongly acidic styrene type cation exchange resin, elutriant is ammoniacal liquor ethanolic soln or sodium hydroxide ethanolic soln, and extraction agent is chloroform or sherwood oil.
Compared with the prior art the present invention has the following advantages:
1, not only three kinds of main effective constituents in the Ligusticum wallichii all can be extracted owing to integrated extraction technique provided by the invention, and because of the order of its extraction be to extract earlier Ligustrazine and forulic acid at a lower temperature successively, just at high temperature extract volatile oil at last, thereby can avoid prior art to adopt direct distillation at high temperature to extract the destruction that forulic acid is produced behind the volatile oil, and the water decocting method when extracting total phenolic acid to the forulic acid problem that does great damage, to reach the three kinds of effective constituents that extract as much as possible.
2, since the present invention before extraction also with raw material Ligusticum wallichii pre-treatment crushing screening to 10～50 orders, thereby Szechwan Lovage Rhizome is contacted fully with solvent, make as much as possible the extracting of Ligustrazine, forulic acid and volatile oil wherein, being unlikely again because of particle too carefully influences the solid-liquid separation efficiency.
3, because the mode of extraction Ligustrazine that the present invention selects for use and forulic acid is to use sour water and water as solvent and heated and stirred backflow lixiviate, thereby the decocting cooking method condition that adopts than prior art is comparatively gentle, and evaporation and backflow by solvent, the at every turn feasible and contacted solvent of raw material all is a neat solvent, thereby improved extraction power greatly, also have to stir to promote mass transfer in addition, make the easier stripping of extract.
4, because the present invention selects for use the water vapour direct distillation to extract volatile oil, thereby adopt supercritical carbon dioxide extraction method to compare with prior art, material fatty acids that the water vapour direct distillation is extracted and fatty acid ester seldom, therefore the lactone material relative content that obtains is higher.Like this, the relative content that not only obtains Z-ligustilide in the product is than the supercritical carbon dioxide extraction method height, and equipment is very cheap, simple to operate, is easy to industrialization.
5, because the present invention selects the storng-acid cation exchange resin purifying Ligustrazine that combines with organic solvent extraction for use, thereby with extraction phase ratio with an organic solvent merely, emulsion and the more situation of impurity of not only having avoided simple solvent extraction to produce, make product purity higher, and the storng-acid cation exchange resin selective adsorption, make its specific aim stronger, cheap more a lot of than silica gel and aluminum oxide etc. in addition, and can use repeatedly, make cost lower.
6, because the present invention in the purge process of forulic acid, adopts solvent extraction technology to replace column chromatography and membrane sepn is purified, thereby technical difficulty is little, cost is lower, be more conducive to fairly large industrialization, and select for use ethyl acetate as extraction agent, higher than ether security.
7, because extracting or the purifying mode all is comparatively ripe of adopting of the present invention no matter be, whole in addition technological process mild condition, each process procedure solvent for use is recyclable, thereby it is simple to operate, be easy to control, production cost is low, not only meets the resource that makes full use of that country vigorously advocates, reduce the recycling economy requirement of environmental pollution, and help realizing suitability for industrialized production.
Embodiment
Below by embodiment the present invention is specifically described; be necessary to be pointed out that at this following examples only are used for that the invention will be further described; can not be interpreted as limiting the scope of the invention; the person skilled in the art in this field makes some nonessential improvement and adjustment according to the invention described above content to the present invention, still belongs to protection domain of the present invention.
Embodiment 1
Commercial Ligusticum wallichii crude drug section back is pulverized it with pulverizer, and gained Ligusticum wallichii meal is crossed 20 mesh sieves, get Szechwan Lovage Rhizome.
Take by weighing Szechwan Lovage Rhizome 100g, add 0.1% the hydrochloric acid soln of 500ml, extract 2 times in 40 ℃ of following stirring and refluxing of temperature, each 2.5 hours, filtration under diminished pressure merged secondary filtrate, the Ligustrazine extracting solution.With the Ligustrazine extracting solution after evaporation concentration, filtration under diminished pressure again, regulating filtrate pH value with the acetic acid of 1mol/L is 2.5; Filtrate being added to is filled with on the ion exchange resin column of strongly acidic styrene type cation exchange resin 001 * 7 (732), uses ethanol: the eluant solution of 10mol/L ammoniacal liquor=7: 3 (volume ratio), collect elutriant; Elutriant after reduction vaporization is concentrated into 50ml, is used the chloroform extraction 3 times of 2 times of volumes again.Merge three times the chloroform extraction layer, reduction vaporization concentrates, and vacuum-drying promptly gets the Ligustrazine colourless acicular crystal.This crystal calculates acquisition Ligustrazine amount and counts 0.81mg/g with the Ligusticum wallichii crude drug through high-performance liquid chromatogram determination, and purity is 83%.
The dregs of a decoction with behind the extraction Ligustrazine add 600ml water, extract 3 times in 50 ℃ of following stirring and refluxing of temperature, and each 0.5 hour, filtration under diminished pressure merged No. 3 times extracting solution, got the forulic acid extracting solution.After reduction vaporization concentrated, the dehydrated alcohol that adds 3 times of volumes staticly settled 10h with the forulic acid extracting solution; Elimination precipitation concentrates and removes alcohol, is 4 with the hydrochloric acid adjusting filtrate pH value of 1mol/L, with the ethyl acetate extraction of 3 times of volumes 2 times.The ethyl acetate layer that merges 2 extractions, reduction vaporization concentrate, and vacuum-drying promptly gets the forulic acid of faint yellow oily thing.The forulic acid of this oily matter is calculated acquisition forulic acid amount and is counted 0.44mg/g with the Ligusticum wallichii crude drug through high-performance liquid chromatogram determination, and purity is 80%.
With the dregs of a decoction after the extraction forulic acid, add 500ml water, under distillation speed 5ml/min condition, according to pharmacopeia (2000 editions one [S] .2000 of Chinese Pharmacopoeia, appendix XD) method that provides is used volatile oil extractor, is adopted steam distillation to carry out the extraction of volatile oil, extraction time is 9 hours, obtains the volatilization oil mass and counts 0.70ml/100g with the Ligusticum wallichii crude drug.
Embodiment 2
Commercial Ligusticum wallichii crude drug section back is pulverized it with pulverizer, and gained Ligusticum wallichii meal is crossed 50 mesh sieves, get Szechwan Lovage Rhizome.
Take by weighing Szechwan Lovage Rhizome 100g, add 0.4% the acetum of 450ml, extract 2 times in 25 ℃ of following stirring and refluxing of temperature, each 2.0 hours, filtration under diminished pressure merged secondary filtrate, the Ligustrazine extracting solution.With the Ligustrazine extracting solution after evaporation concentration, filtration under diminished pressure again, regulating filtrate pH value with the hydrochloric acid of 1mol/L is 1.5; Filtrate being added to is filled with on the ion exchange resin column of strongly acidic styrene type cation exchange resin 001 * 7 (732), uses ethanol: 10mol/L sodium hydroxide=6.5: 3.5 (volume ratio) eluant solution, collect elutriant; Elutriant after reduction vaporization is concentrated into 50ml, is used the chloroform extraction 4 times of 1 times of volume again.Merge four times the chloroform extraction layer, reduction vaporization concentrates, and vacuum-drying promptly gets the Ligustrazine colourless acicular crystal.This crystal calculates acquisition Ligustrazine amount and counts 0.79mg/g with the Ligusticum wallichii crude drug through high-performance liquid chromatogram determination, and purity is 80.5%.
The dregs of a decoction with behind the extraction Ligustrazine add 500ml water, extract 2 times in 55 ℃ of following stirring and refluxing of temperature, and each 1.0 hours, filtration under diminished pressure merged No. 2 times extracting solution, got the forulic acid extracting solution.After reduction vaporization concentrated, the dehydrated alcohol that adds 2 times of volumes staticly settled 13h with the forulic acid extracting solution; Elimination precipitation concentrates and removes alcohol, is 3.5 with the acetic acid adjusting filtrate pH value of 1mol/L, with the ethyl acetate extraction of 1 times of volume 3 times.The ethyl acetate layer that merges 3 extractions, reduction vaporization concentrate, and vacuum-drying promptly gets the forulic acid of faint yellow oily thing.The forulic acid of this oily matter is calculated acquisition forulic acid amount and is counted 0.43mg/g with the Ligusticum wallichii crude drug through high-performance liquid chromatogram determination, and purity is 76%.
With the dregs of a decoction after the extraction forulic acid, add 600ml water, under distillation speed 4ml/min condition, according to pharmacopeia (2000 editions one [S] .2000 of Chinese Pharmacopoeia, appendix XD) method that provides is used volatile oil extractor, is adopted steam distillation to carry out the extraction of volatile oil, extraction time is 10 hours, obtains the volatilization oil mass and counts 0.70ml/100g with the Ligusticum wallichii crude drug.
Embodiment 3
Commercial Ligusticum wallichii crude drug section back is pulverized it with pulverizer, and gained Ligusticum wallichii meal is crossed 30 mesh sieves, get Szechwan Lovage Rhizome.
Take by weighing Szechwan Lovage Rhizome 100 g, add 0.05% the acetum of 300ml, extract 3 times in 40 ℃ of following stirring and refluxing of temperature, each 1.5 hours, filtration under diminished pressure merged three times filtrate, must the Ligustrazine extracting solution.With the Ligustrazine extracting solution after evaporation concentration, filtration under diminished pressure again, regulating filtrate pH value with the acetic acid of 1mol/L is 3.0; Filtrate being added to is filled with on the ion exchange resin column of strongly acidic styrene type cation exchange resin 001 * 12, uses ethanol: 10mol/L ammoniacal liquor=8: 2 (volume ratio) eluant solution, collect elutriant; Elutriant after reduction vaporization is concentrated into 50ml, is used the petroleum ether extraction 2 times of 3 times of volumes again.Merge secondary petroleum ether extraction layer, reduction vaporization concentrates, and vacuum-drying promptly gets the Ligustrazine colourless acicular crystal.This crystal calculates acquisition Ligustrazine amount and counts 0.80mg/g with the Ligusticum wallichii crude drug through high-performance liquid chromatogram determination, and purity is 81%.
The dregs of a decoction with behind the extraction Ligustrazine add 400ml water, extract 3 times in 50 ℃ of following stirring and refluxing of temperature, and each 1.0 hours, filtration under diminished pressure merged No. 3 times extracting solution, got the forulic acid extracting solution.After reduction vaporization concentrated, the dehydrated alcohol that adds 2 times of volumes staticly settled 11h with the forulic acid extracting solution; Elimination precipitation concentrates and removes alcohol, is 5.0 with the acetic acid adjusting filtrate pH value of 1mol/L, with the ethyl acetate extraction of 1 times of volume 4 times.The ethyl acetate layer that merges 4 extractions, reduction vaporization concentrate, and vacuum-drying promptly gets the forulic acid of faint yellow oily thing.The forulic acid of this oily matter is calculated acquisition forulic acid amount and is counted 0.43mg/g with the Ligusticum wallichii crude drug through high-performance liquid chromatogram determination, and purity is 78%.
With the dregs of a decoction after the extraction forulic acid, add 400ml water, under distillation speed 3ml/min condition, according to pharmacopeia (2000 editions one [S] .2000 of Chinese Pharmacopoeia, appendix XD) method that provides is used volatile oil extractor, is adopted steam distillation to carry out the extraction of volatile oil, extraction time is 11 hours, obtains the volatilization oil mass and counts 0.68ml/100g with the Ligusticum wallichii crude drug.
Embodiment 4
Commercial Ligusticum wallichii crude drug section back is pulverized it with pulverizer, and gained Ligusticum wallichii meal is crossed 10 mesh sieves, get Szechwan Lovage Rhizome.
Take by weighing Szechwan Lovage Rhizome 100g, add 0.5% the sulphuric acid soln of 500ml, extract 3 times in 25 ℃ of following stirring and refluxing of temperature, each 1.5 hours, filtration under diminished pressure merged three times filtrate, must the Ligustrazine extracting solution.With the Ligustrazine extracting solution after evaporation concentration, filtration under diminished pressure again, regulating filtrate pH value with the hydrochloric acid of 1mol/L is 1.0; Filtrate being added to is filled with on the ion exchange resin column of strongly acidic styrene type cation exchange resin 001 * 12, uses ethanol: 10mol/L ammoniacal liquor=6: 4 (volume ratio) eluant solution, collect elutriant; Elutriant after reduction vaporization is concentrated into 50ml, is used the petroleum ether extraction 4 times of 1 times of volume again.Merge four times the petroleum ether extraction layer, reduction vaporization concentrates, and vacuum-drying promptly gets the Ligustrazine colourless acicular crystal.This crystal calculates acquisition Ligustrazine amount and counts 0.80mg/g with the Ligusticum wallichii crude drug through high-performance liquid chromatogram determination, and purity is 79%.
The dregs of a decoction with behind the extraction Ligustrazine add 600ml water, extract 2 times in 45 ℃ of following stirring and refluxing of temperature, and each 1.5 hours, filtration under diminished pressure merged No. 2 times extracting solution, got the forulic acid extracting solution.After reduction vaporization concentrated, the dehydrated alcohol that adds 1 times of volume staticly settled 16h with the forulic acid extracting solution; Elimination precipitation concentrates and removes alcohol, is 2.5 with the acetic acid adjusting filtrate pH value of 1mol/L, with the ethyl acetate extraction of 2 times of volumes 4 times.The ethyl acetate layer that merges 4 extractions, reduction vaporization concentrate, and vacuum-drying promptly gets the forulic acid of faint yellow oily thing.The forulic acid of this oily matter is calculated acquisition forulic acid amount and is counted 0.45mg/g with the Ligusticum wallichii crude drug through high-performance liquid chromatogram determination, and purity is 79%.
With the dregs of a decoction after the extraction forulic acid, add 600ml water, under distillation speed 5ml/min condition, according to pharmacopeia (2000 editions one [s] .2000 of Chinese Pharmacopoeia, appendix XD) method that provides is used volatile oil extractor, is adopted steam distillation to carry out the extraction of volatile oil, extraction time is 8 hours, obtains the volatilization oil mass and counts 0.69ml/100g with the Ligusticum wallichii crude drug.
Embodiment 5
Commercial Ligusticum wallichii crude drug section back is pulverized it with pulverizer, and gained Ligusticum wallichii meal is crossed 40 mesh sieves, get Szechwan Lovage Rhizome.
Take by weighing Szechwan Lovage Rhizome 100 g, add 0.2% the sulphuric acid soln of 350ml, extract 2 times in 35 ℃ of following stirring and refluxing of temperature, each 2.5 hours, filtration under diminished pressure merged secondary filtrate, the Ligustrazine extracting solution.With the Ligustrazine extracting solution after evaporation concentration, filtration under diminished pressure again, regulating filtrate pH value with the hydrochloric acid of 1mol/L is 2.0; Filtrate being added to is filled with on the ion exchange resin column of strongly acidic styrene type cation exchange resin 001 * 7 (732), uses ethanol: 10mol/L sodium hydroxide=7: 3 (volume ratio) eluant solution, collect elutriant; Elutriant after reduction vaporization is concentrated into 50ml, is used the petroleum ether extraction 3 times of 2 times of volumes again.Merge three times the petroleum ether extraction layer, reduction vaporization concentrates, and vacuum-drying promptly gets the Ligustrazine colourless acicular crystal.This crystal calculates acquisition Ligustrazine amount and counts 0.78mg/g with the Ligusticum wallichii crude drug through high-performance liquid chromatogram determination, and purity is 81.5%.
The dregs of a decoction with behind the extraction Ligustrazine add 400ml water, extract 3 times in 40 ℃ of following stirring and refluxing of temperature, and each 1.5 hours, filtration under diminished pressure merged No. 3 times extracting solution, got the forulic acid extracting solution.After reduction vaporization concentrated, the dehydrated alcohol that adds 1 times of volume staticly settled 15h with the forulic acid extracting solution; Elimination precipitation concentrates and removes alcohol, is 3.0 with the hydrochloric acid adjusting filtrate pH value of 1mol/L, with the ethyl acetate extraction of 3 times of volumes 2 times.The ethyl acetate layer that merges 2 extractions, reduction vaporization concentrate, and vacuum-drying promptly gets the forulic acid of faint yellow oily thing.The forulic acid of this oily matter is calculated acquisition forulic acid amount and is counted 0.44mg/g with the Ligusticum wallichii crude drug through high-performance liquid chromatogram determination, and purity is 77%.
With the dregs of a decoction after the extraction forulic acid, add 400ml water, under distillation speed 4ml/min condition, according to pharmacopeia (2000 editions one [S] .2000 of Chinese Pharmacopoeia, appendix XD) method that provides is used volatile oil extractor, is adopted steam distillation to carry out the extraction of volatile oil, extraction time is 9 hours, obtains the volatilization oil mass and counts 0.68ml/100g with the Ligusticum wallichii crude drug.
Embodiment 6
Commercial Ligusticum wallichii crude drug section back is pulverized it with pulverizer, and gained Ligusticum wallichii meal is crossed 20 mesh sieves, get Szechwan Lovage Rhizome.
Take by weighing Szechwan Lovage Rhizome 100g, add 0.3% the hydrochloric acid soln of 400ml, extract 3 times in 30 ℃ of following stirring and refluxing of temperature, each 2.0 hours, filtration under diminished pressure merged 3 times filtrate, must the Ligustrazine extracting solution.With the Ligustrazine extracting solution after evaporation concentration, filtration under diminished pressure again, regulating filtrate pH value with the acetic acid of 1mol/L is 1.5; Filtrate being added to is filled with on the ion exchange resin column of strongly acidic styrene type cation exchange resin 001 * 12, uses ethanol: 10mol/L sodium hydroxide=7.5: 2.5 (volume ratio) eluant solution, collect elutriant; Elutriant after reduction vaporization is concentrated into 50ml, is used the chloroform extraction 2 times of 3 times of volumes again.Merge secondary chloroform extraction layer, reduction vaporization concentrates, and vacuum-drying promptly gets the Ligustrazine colourless acicular crystal.This crystal calculates acquisition Ligustrazine amount and counts 0.79mg/g with the Ligusticum wallichii crude drug through high-performance liquid chromatogram determination, and purity is 82%.
The dregs of a decoction with behind the extraction Ligustrazine add 500ml water, extract 2 times in 60 ℃ of following stirring and refluxing of temperature, and each 0.5 hour, filtration under diminished pressure merged No. 2 times extracting solution, got the forulic acid extracting solution.After reduction vaporization concentrated, the dehydrated alcohol that adds 3 times of volumes staticly settled 12h with the forulic acid extracting solution; Elimination precipitation concentrates and removes alcohol, is 2.0 with the hydrochloric acid adjusting filtrate pH value of 1mol/L, with the ethyl acetate extraction of 2 times of volumes 3 times.The ethyl acetate layer that merges 3 extractions, reduction vaporization concentrate, and vacuum-drying promptly gets the forulic acid of faint yellow oily thing.The forulic acid of this oily matter is calculated acquisition forulic acid amount and is counted 0.42mg/g with the Ligusticum wallichii crude drug through high-performance liquid chromatogram determination, and purity is 81%.
With the dregs of a decoction after the extraction forulic acid, add 500ml water, under distillation speed 3ml/min condition, according to pharmacopeia (2000 editions one [S] .2000 of Chinese Pharmacopoeia, appendix XD) method that provides is used volatile oil extractor, is adopted steam distillation to carry out the extraction of volatile oil, extraction time is 12 hours, obtains the volatilization oil mass and counts 0.69ml/100g with the Ligusticum wallichii crude drug.
Claims (10)
1. Ligustrazine in the comprehensively extracting and purifying Ligusticum wallichii, the method of forulic acid and volatile oil, this method is earlier Ligusticum wallichii to be cut into slices, pulverize pre-treatment, use aqueous acid under 25～40 ℃ raw material powder then, stirring and refluxing is extracted Ligustrazine, the dregs of a decoction after will extracting again add water and extract forulic acid 40～60 ℃ of following stirring and refluxing, the dregs of a decoction that will extract at last after the forulic acid return the method for heating up in a steamer under distillation speed 3～5ml/min with water vapour, extract volatile oil, and with the Ligustrazine extracting solution that extracts, mode and organic solvent deposit that the forulic acid extracting solution combines with organic solvent extraction with strong acid cation exchange resin column respectively, extraction and crystallization phases bonded mode are purified.
2. the method for Ligustrazine, forulic acid and volatile oil in the comprehensively extracting and purifying Ligusticum wallichii according to claim 1 is characterized in that the pre-treatment of raw material Ligusticum wallichii should be crushed to 10～50 orders in this method to sieve.
3. the method for Ligustrazine, forulic acid and volatile oil in the comprehensively extracting and purifying Ligusticum wallichii according to claim 1 and 2, it is characterized in that in this method extracting Ligustrazine and be with concentration of volume percent is that 0.05～0.5% aqueous acid is a solvent, by mass ratio, Szechwan Lovage Rhizome: the proportioning of solvent=1: 3～5, stirring and refluxing is extracted 2～3 times, each 1.5～2.5 hours.
4. the method for Ligustrazine, forulic acid and volatile oil in the comprehensively extracting and purifying Ligusticum wallichii according to claim 3 is characterized in that extracting the used aqueous acid of Ligustrazine in this method is hydrochloric acid soln or acetum or sulphuric acid soln.
5. the method for Ligustrazine, forulic acid and volatile oil in the comprehensive extraction Ligusticum wallichii according to claim 1 and 2, it is characterized in that in this method extracting forulic acid and be with extract behind the Ligustrazine the dregs of a decoction by with the condition of mass ratio=1: 4～6 of water under, stirring and refluxing is extracted 2～3 times, each 0.5～1.5 hour.
6. the method for Ligustrazine, forulic acid and volatile oil in the comprehensively extracting and purifying Ligusticum wallichii according to claim 4, it is characterized in that in this method extracting forulic acid and be with extract behind the Ligustrazine the dregs of a decoction by with the condition of mass ratio=1: 4～6 of water under, stirring and refluxing is extracted 2～3 times, each 0.5～1.5 hour.
7. the method for Ligustrazine, forulic acid and volatile oil in the comprehensively extracting and purifying Ligusticum wallichii according to claim 1 and 2, it is characterized in that in this method extracting volatile oil and be with extract after the forulic acid the dregs of a decoction by with the condition of mass ratio=1: 4～6 of water under, extracted 8～12 hours.
8. the method for Ligustrazine, forulic acid and volatile oil in the comprehensively extracting and purifying Ligusticum wallichii according to claim 6, it is characterized in that in this method extracting volatile oil and be with extract after the forulic acid the dregs of a decoction by with the condition of mass ratio=1: 4～6 of water under, extracted 8～12 hours.
9. the method for Ligustrazine, forulic acid and volatile oil in the comprehensively extracting and purifying Ligusticum wallichii according to claim 1 and 2 is characterized in that:
1) purification of Ligustrazine extracting solution specifically be earlier with the Ligustrazine extracting solution after evaporation concentration, filtration under diminished pressure again, regulating pH value of filtrate with the pH regulator agent then is 1～3, again be filled with on the ion exchange resin column of storng-acid cation exchange resin the adding of this filtrate, with concentration of volume percent 60～80% eluate solution wash-outs, with elutriant after reduction vaporization concentrates, extraction agent with 1～3 times of volume extracts 2～4 times again, merge 2～4 times extract layer, reduction vaporization concentrates, vacuum-drying promptly gets purity and is 79%～83% Ligustrazine;
2) purification of forulic acid extracting solution specifically be earlier with the forulic acid extracting solution after reduction vaporization concentrates, dehydrated alcohol with 1～3 times of volume, staticly settle, the elimination throw out concentrates and removes alcohol, regulating pH value of filtrate with the pH regulator agent then is 2～5, use the ethyl acetate extraction 2～4 times of 1～3 times of volume again, merge 2～4 times extract layer, reduction vaporization concentrates, vacuum-drying promptly gets purity and is 76%～81% forulic acid.
10. the method for Ligustrazine, forulic acid and volatile oil in the comprehensively extracting and purifying Ligusticum wallichii according to claim 9 is characterized in that the used pH regulator agent of purification process of Ligustrazine extracting solution and forulic acid extracting solution is hydrochloric acid or acetic acid; Wherein the used storng-acid cation exchange resin of the purification process of Ligustrazine extracting solution is 001 * 7 (732) or 001 * 12 strongly acidic styrene type cation exchange resin, elutriant is ammoniacal liquor ethanolic soln or sodium hydroxide ethanolic soln, and extraction agent is chloroform or sherwood oil.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101978980A (en) * | 2010-11-04 | 2011-02-23 | 深圳市泰康制药有限公司 | Szechuan lovage rhizome total phthalide extract |
| CN102266364A (en) * | 2011-08-17 | 2011-12-07 | 华南理工大学 | Traditional Chinese medicine effective part for treating cardiovascular and cerebrovascular diseases and preparation method thereof |
| CN106977465A (en) * | 2017-04-06 | 2017-07-25 | 成都众宜坊农业开发有限公司 | A kind of method that ligustrazine is extracted in cauline leaf from Ligusticum wallichii |
| CN107011158A (en) * | 2017-04-06 | 2017-08-04 | 成都众宜坊农业开发有限公司 | A kind of method of extraction purification forulic acid in cauline leaf from Ligusticum wallichii |
| CN114989006A (en) * | 2022-06-23 | 2022-09-02 | 安徽雷允上药业有限公司 | Method for separating ferulic acid from volatile oil of ligusticum wallichii and angelica sinensis |
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2008
- 2008-01-15 CN CNB2008100451941A patent/CN100564364C/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101978980A (en) * | 2010-11-04 | 2011-02-23 | 深圳市泰康制药有限公司 | Szechuan lovage rhizome total phthalide extract |
| CN101978980B (en) * | 2010-11-04 | 2012-07-25 | 深圳市泰康制药有限公司 | Szechuan lovage rhizome total phthalide extract |
| CN102266364A (en) * | 2011-08-17 | 2011-12-07 | 华南理工大学 | Traditional Chinese medicine effective part for treating cardiovascular and cerebrovascular diseases and preparation method thereof |
| CN102266364B (en) * | 2011-08-17 | 2013-03-20 | 华南理工大学 | Traditional Chinese medicine effective part for treating cardiovascular and cerebrovascular diseases and preparation method thereof |
| CN106977465A (en) * | 2017-04-06 | 2017-07-25 | 成都众宜坊农业开发有限公司 | A kind of method that ligustrazine is extracted in cauline leaf from Ligusticum wallichii |
| CN107011158A (en) * | 2017-04-06 | 2017-08-04 | 成都众宜坊农业开发有限公司 | A kind of method of extraction purification forulic acid in cauline leaf from Ligusticum wallichii |
| CN114989006A (en) * | 2022-06-23 | 2022-09-02 | 安徽雷允上药业有限公司 | Method for separating ferulic acid from volatile oil of ligusticum wallichii and angelica sinensis |
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