CN100556914C - A kind of method that from Fel Sus domestica, prepares the high purity Hyodeoxycholic Acid - Google Patents
A kind of method that from Fel Sus domestica, prepares the high purity Hyodeoxycholic Acid Download PDFInfo
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- CN100556914C CN100556914C CNB2007100214157A CN200710021415A CN100556914C CN 100556914 C CN100556914 C CN 100556914C CN B2007100214157 A CNB2007100214157 A CN B2007100214157A CN 200710021415 A CN200710021415 A CN 200710021415A CN 100556914 C CN100556914 C CN 100556914C
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Abstract
The present invention relates to a kind of method of utilizing Fel Sus domestica or extracting bilirubinic tankage extraction Hyodeoxycholic Acid.With the alkali soap tankage, regulate pH, ethyl acetate extraction, activated carbon decolorizing.Mother liquor is concentrated into proper volume, separates out precipitation, precipitation separation and drying obtain the crude product Hyodeoxycholic Acid.Crude product carries out esterification, carries out addition reaction with benzene then, utilizes different bile acide methyl esters and the different solubilities of benzene affixture in benzene, separates Hyodeoxycholic Acid methyl esters-benzene affixture.Decompose affixture with alkali, regulate pH, obtain the pure product of Hyodeoxycholic Acid.Mother liquid obtainedly also can further extract the high value Chenodiol.Whole technology has abundant raw material and is easy to get, environmental friendliness, and safety non-toxic, cost is low, and the product purity height is easy to advantages such as large-scale industrialization production.
Description
Technical field
The present invention relates to the biochemical pharmacy field, relate in particular to a kind of method of utilizing Fel Sus domestica (or extracting bilirubinic tankage) to prepare the high purity Hyodeoxycholic Acid.
Background technology
Contain bile acide 8.5～12% in the Fel Sus domestica, mainly comprise four kinds of bile acides, wherein Hyodeoxycholic Acid (HDCA) account for TOTAL BILE ACID 40%, 3 Alpha-hydroxies-6-oxo-5 α-ursodeoxycholic acid accounts for 20%, Chenodiol (CDCA) and Iocholic acid (HCA) account for 9%, HDCA and Iocholic acid are the characteristic components of Fel Sus domestica.
HDCA is a hypolipidemic, can suppress the formation and the dissolved fat of cholic acid, reduces blood cholesterol and triglyceride level, is applicable to I
aOr I
bType hyperlipidemia, atherosclerosis.Bordetella pertussis, diphtheria corynebacterium, streptococcus aureus etc. there is certain bacteriostatic action.Can be used as antiphlogistic drug, treatment chronic bronchitis, child virus upper respiratory tract infection etc.HDCA can stimulate choleresis, makes bile thinning and do not increase amount of solid, is applicable to biliary tract inflammation, cholecystitis, cholelithiasis and other nonobstructive cholestasis.HDCA can promote enteron aisle steatolysis and liposoluble vitamin to absorb, and can be used for the maldigestion that hepatobiliary disease causes.HDCA still is the important source material of artificial Calculus Bovis prescription.
About the extraction of HDCA, be raw material generally with the Fel Sus domestica behind Fel Sus domestica or the heating extraction bilirubin, technical hydrochloric acid is acidified to the Congo's red stain indigo plant (the 100L bile about 3L of acid), leaves standstill 12h, and collecting precipitation also washes with water to neutrality, dries, and obtains the Fel Sus domestica total cholic acid.
Get rough Fel Sus domestica acid, add 2 times of amounts (W/W) sodium hydroxide, 8 times of amount distilled water, heating saponification 22h is cooled to room temperature, siphon upper strata weak yellow liquid, abandon it, precipitation makes it dissolving with less water, under agitation uses 1: 1 hydrochloric acid to transfer to congo-red test paper and becomes blue, filter, collecting precipitation also washes with water to neutrality, dries, and promptly gets the HDCA crude product.
Get crude product and add 6 times of amounts acetone and 0.04 times of carbon content active, heated and stirred backflow 1h is put coldly, filters merging filtrate, add 30% (W/V) anhydrous sodium sulfate dehydration 12h, filter, filtrate is concentrated into 2/5 of original volume, put cold, crystallization, suction filtration, vacuum-drying promptly gets HDCA, 168～179 ℃ of fusing points.
Or after crude product adds the ethyl acetate backflow dissolving of 4 times of amounts, add activated carbon decolorizing (for crude product 5%), continue backflow 10min, be cooled to 30～40 ℃ of suction filtrations; Filter residue adds 3 times of amount ethyl acetate backflow again, filters, and merging filtrate adds 20% anhydrous sodium sulfate dehydration, is concentrated into 1/2～1/3 of original volume after the filtration, and crystallization is separated out in cooling, and yield calculates by the thick Fel Sus domestica acid of air dried and is about 30%, 160～170 ℃ of fusing points.
Defectives such as when producing HDCA in order to overcome existing method, product purity is not high, ethyl acetate and acetone consumption are big the invention provides a kind of with Fel Sus domestica or extract the method that bilirubinic tankage (paste) are production high purity HDCA in the raw material.
Summary of the invention
The technical solution adopted for the present invention to solve the technical problems is: extracting bilirubinic tankage (paste) with fresh pig bile or Fel Sus domestica is raw material, with the alkali soap tankage, and the temperature and the pH of strict control saponification liquor, ethyl acetate extraction, activated carbon decolorizing.Mother liquor is concentrated into proper volume, and precipitation separation obtains the HDCA crude product.Crude product is carried out esterification, carry out addition reaction with benzene then, utilize different bile acide methyl esters and the different solubilities of benzene affixture in benzene, separate Hyodeoxycholic Acid methyl esters-benzene affixture.Decompose affixture with alkali, regulate pH, obtain the pure product of HDCA.The mother liquid obtained CDCA that also can further extract high value.The preparation method may further comprise the steps:
1, the saponification of bile acide
Fel Sus domestica is extracted bilirubinic tankage (paste) dilute with water make suspension, the part by weight that feeds intake is: tankage: water=1: 7～9, this suspension solid content is about 10%～12.5%, and the content of its bile acide is equal to isopyknic fresh pig bile.
Get fresh pig bile or above-mentioned suspension as initial Fel Sus domestica, add the sodium hydroxide or the potassium hydroxide of initial Fel Sus domestica weight 10%～15%, add the defoamer of initial Fel Sus domestica weight 2%, 110～135 ℃ of reflux 16～25h carry out saponification.
2, the separation of total cholic acid
After saponification reaction is finished, when question response liquid is cooled to 50 ℃, under stirring condition, reaction solution is transferred to pH8 with the vitriol oil or hydrochloric acid.The acidizing fluid temperature remains on 55 ± 5 ℃, adds initial Fel Sus domestica weight 3～5%NaHSO
3, stir 15min.The ethyl acetate or the ether that add reaction solution volume 40% then continue to be acidified to pH5 with rare sulfuric acid or hydrochloric acid while stirring, leave standstill 1h behind the stirring 30min, and organic layer is taken out in siphon.
The gac that adds initial Fel Sus domestica weight 5～10%, 50～55 ℃ are stirred 30min, filter, and residue is with the ethyl acetate washing of initial Fel Sus domestica volume 5%, merging filtrate and washings.
3, the separation of HDCA crude product
Above-mentioned amalgamation liquid is evaporated to 1/2～2/3 of ethyl acetate or ether add-on, and following slowly has precipitation to generate after stirring, and places 15～20h under the room temperature then.Suction filtration cleans filter residue with ethyl acetate, is yellow until filtrate.With clear washed precipitate vacuum-drying, obtain canescence HDCA crude product.
4, the esterification of HDCA
Total cholic acid is dissolved in initial Fel Sus domestica volume 30% methyl alcohol or the ethanol, adds an amount of vitriol oil, hydrochloric acid or Phosphation, stirring at room 12～36h.With NaHCO
3Or Na
2CO
3Be neutralized to pH7, mixture filters, and concentrating under reduced pressure gets oily matter.
Oily matter is dissolved in initial Fel Sus domestica volume 30～40% hot benzene, and filtrate decompression is concentrated to about 1/2 o'clock of original volume, places refrigerator overnight, separates out dope.Filter, with a little washing leaching cake of benzene, be Hyodeoxycholic Acid methyl esters-benzene affixture.
5, the separation of the pure product of HDCA
Hyodeoxycholic Acid methyl esters-benzene affixture adds the NaOH of initial Fel Sus domestica weight 4～6% or KOH, initial Fel Sus domestica volume 10～12% water, and steam distillation all steams until benzene and to remove, add 1N HCl and transfer pH to 4～5, separate out precipitation, be washed to neutrality, vacuum-drying.Obtain the pure product of HDCA.
Wherein the purification process of the 4th and the 5th step HDCA also can adopt the acetoneand ethyl acetate recrystallization method of existing production method, yet the purity of products obtained therefrom can significantly improve.
The present invention is in the sepn process of total cholic acid, control the temperature of rational pH and feed liquid by strictness, the acid of selective precipitation Fel Sus domestica makes that the Fel Sus domestica acid in the saponification resultant can fully be separated out, reduce foreign matter content wherein simultaneously, alleviated the purifying difficulty of follow-up HDCA.
The present invention utilizes this characteristic of the different solubilities of bile acide methyl esters benzene affixture in benzene, selective precipitation Hyodeoxycholic Acid methyl esters-benzene affixture in the purge process of HDCA.It is big to have overcome this traditional method solvent consumption of organic solvent recrystallization on the one hand, and the defective of complex operation makes finished product purity significantly improve on the other hand.
HDCA production method cost of the present invention is lower, can form large-scale industrialization production, products obtained therefrom purity height (HPLC＞98%), total recovery reach more than 20% of the tankage that drop into; Defective such as this invention has overcome that existing method products obtained therefrom purity is not high, ethyl acetate and acetone consumption are big; The raw materials used CDCA product that behind output HDCA, also can therefrom further extract high value of this invention.
Embodiment
Below in conjunction with embodiment the present invention is further elaborated.
Embodiment 1
Get Fel Sus domestica and extract bilirubinic tankage (paste) 125g, with sodium hydroxide saponification tankage, the part by weight that feeds intake is: tankage: water: sodium hydroxide=1: 7: 1.2, blanking by weight proportion, prior to the 875ml of intaking in the 2L three-necked flask, 150g sodium hydroxide is dropped in the water stir again, treat to dissolve fully the back and drop into tankage, before being warmed up to 80 ℃, adding defoamer and prevent to produce too much bubble.Carefully be warming up to 110 ℃ then, back flow reaction 25h.
After saponification reaction is finished, when question response liquid is cooled to 50 ℃, with the vitriol oil reaction solution is transferred to pH8 while stirring, and make temperature maintenance at 55～60 ℃.Add 5g NaHSO then
3, stir 15min.Add the 400ml ethyl acetate, further be acidified to pH 5.0 with dilute sulphuric acid while stirring, temperature remains on 55 ℃, leaves standstill 1h behind the stirring 30min, and solution is divided into two-layer, and lower floor is the xanchromatic water, and the upper strata is henna ethyl acetate phase, and organic layer is taken out in siphon.
Add each 10g of diatomite and gac, stir 30min, filter, residue is with the washing of 50mL ethyl acetate, merging filtrate and washings.Above-mentioned amalgamation liquid is evaporated to 285ml, and following slowly has precipitation to generate after stirring, and leaves standstill 15h under the room temperature then.Suction filtration cleans filter cake with ethyl acetate, is faint yellow until filtrate.The vacuum-drying of gained solid obtains the canescence HDCA crude product of 30.5g.Fusing point is 187.5～190.2 ℃, and yield accounts for 24.4% of the tankage that drop into.
Embodiment 2
30g HDCA with embodiment 1 obtains is dissolved in the 300ml methyl alcohol, adds the esterification of the 4.0ml vitriol oil, stirring at room 24h.Use NaHCO
3Be neutralized to pH7, mixture filters, and concentrating under reduced pressure gets oily matter.
Oily matter is dissolved in the hot benzene of 350ml, and filtrate decompression is concentrated to about 1/2 o'clock of original volume, places refrigerator overnight, separates out dope.Filter, with a little washing leaching cake of benzene (Hyodeoxycholic Acid methyl esters-benzene affixture).
Hyodeoxycholic Acid methyl esters-benzene affixture adds 5.5gNaOH and 100ml water, and steam distillation after whole steaming of benzene removed, added 145ml 1N HCl, is separated out precipitation, is washed to neutrality, vacuum-drying.Obtain the HDCA of 197～198.2 ℃ of 27.07g fusing points, this step yield is 90.2%, total recovery by the input tankage 22%, HPLC detects, purity＞99%.
Embodiment 3
The HDCA crude product that embodiment 1 is obtained carries out recrystallization with acetone.Get the gac that 20g HDCA crude product adds 500ml acetone and liquor capacity 5%, mixed dissolution, backflow 0.5h.Filtered while hot is used the washing with acetone residue, and merging filtrate and washing lotion are evaporated to 200ml, at 0～5 ℃ of refrigeration 15h, separates out crystal.Fractional crystallization, vacuum-drying obtains the white HDCA of 13.6g fusing point more than 196.7 ℃, yield 68%, HPLC detects, purity＞98%.
Embodiment 4
The HDCA crude product that embodiment 1 is obtained carries out recrystallization with ethyl acetate.Get 20g HDCA crude product, add ethyl acetate 200ml, mixed dissolution, backflow 0.5h.Be evaporated to solution and just begun muddiness (volume is about 110ml).In 0～5 ℃ of refrigeration 5h, crystallization.Fractional crystallization, vacuum-drying obtains the white HDCA of 16.6g fusing point more than 190.5 ℃, yield 83%.
Embodiment 5
Get 1000g fresh pig bile and 120g KOH, join in the three-necked flask of 2L, stir and heat up, be warming up to 135 ℃, back flow reaction 20h.
After saponification reaction is finished, when question response liquid is cooled to 50 ℃, with concentrated hydrochloric acid reaction solution is transferred to pH8 while stirring, and make temperature maintenance at 50～63 ℃.Add 5.3g NaHSO then
3, stir 15min.Add the 400ml ether, continue to be acidified to pH 4.75 while stir with dilute sulphuric acid, temperature remains on 50 ℃, leaves standstill 1h behind the stirring 30min, and solution is divided into two-layer, and lower floor is yellowish water, and the upper strata is henna ether phase, and organic layer is taken out in siphon.
Add each 10g of diatomite and gac, stir 30min, filter, residue is with the washing of 50ml ether, merging filtrate and washings.Above-mentioned amalgamation liquid is evaporated to 250ml, and following slowly has precipitation to generate after stirring, and places 20h under the room temperature then.Filter,, be faint yellow until filtrate with the ether washing leaching cake.The vacuum-drying of gained solid obtains the canescence HDCA crude product of 46g.Yield is 4.6% of a former bile weight.
Embodiment 6
Get Fel Sus domestica and extract bilirubinic tankage (paste) 125g, with sodium hydroxide saponification tankage, the part by weight that feeds intake is: tankage: water: sodium hydroxide=1: 7: 1.0, blanking by weight proportion, prior to the 875ml of intaking in the 2L three-necked flask, 125g sodium hydroxide is dropped in the water stir again, treat to dissolve fully the back and drop into tankage, before being warmed up to 80 ℃, adding defoamer and prevent to produce too much bubble.Carefully be warming up to 110 ℃ then, back flow reaction 22h.
After saponification reaction is finished, when question response liquid is cooled to 50 ℃, with the vitriol oil reaction solution is transferred to pH8 under stirring condition, temperature maintenance is at 55 ± 3 ℃.Above-mentioned acidizing fluid temperature remains on 55 ℃, adds NaHSO
34.5g, stir 15min.Add the 500mL ether then, continue to be acidified to pH 4.75 with dilute sulphuric acid while stirring, leave standstill 1h behind the stirring 30min, organic layer is taken out in siphon.
Add each 10g of diatomite and gac, stir 30min, filter, residue is with the washing of 50mL ether, and merging filtrate and washings steam and remove ether to doing, and obtain the HDCA crude product oily matter of 72g.
Embodiment 7
Get embodiment 6 gained oily matter and be dissolved in the 300ml dehydrated alcohol, add 4.0ml 72% Phosphation, stirring at room 32h.Use Na
2CO
3Be neutralized to pH7, mixture filters, and concentrating under reduced pressure gets oily matter.
Oily matter is dissolved in the hot benzene of 320ml, and filtrate decompression is concentrated to about 1/2 o'clock of original volume, places refrigerator overnight, separates out dope.Filter, with a little washing leaching cake of benzene, i.e. Hyodeoxycholic Acid methyl esters-benzene affixture.
Hyodeoxycholic Acid methyl esters-benzene affixture adds 5.5gKOH and 120ml water, and steam distillation after whole steaming of benzene removed, added 150ml 1N HCl, is separated out precipitation, is washed to neutrality, vacuum-drying.Obtain 25.23gHDCA, fusing point is more than 197 ℃, and total recovery accounts for and drops into 20.18% of tankage, and HPLC detects, purity＞98.5%.
Claims (3)
1. method that from Fel Sus domestica, prepares the high purity Hyodeoxycholic Acid, it is characterized in that: extracting bilirubinic tankage with fresh pig bile or Fel Sus domestica is raw material, with the alkali soap tankage, and the temperature and the pH of control saponification liquor, ethyl acetate extraction, activated carbon decolorizing; Mother liquor is concentrated into proper volume, and precipitation separation obtains the HDCA crude product; Crude product is carried out purifying, obtain the pure product of HDCA; The method that wherein prepares the HDCA crude product may further comprise the steps:
(1) saponification of bile acide
Fel Sus domestica is extracted bilirubinic tankage dilute with water make suspension, the part by weight that feeds intake is: tankage: water=1: 7～9, and this suspension solid content is about 10%～12.5%, and the content of its bile acide is equal to isopyknic fresh pig bile;
Get fresh pig bile or above-mentioned suspension as initial Fel Sus domestica, add the sodium hydroxide or the potassium hydroxide of initial Fel Sus domestica weight 10%～15%, add the defoamer of initial Fel Sus domestica weight 2%, 110～135 ℃ of reflux 16～25h carry out saponification;
(2) separation of total cholic acid
After saponification reaction is finished, when question response liquid is cooled to 50 ℃, under stirring condition, reaction solution is transferred to pH8 with the vitriol oil or hydrochloric acid; The acidizing fluid temperature remains on 55 ± 5 ℃, adds initial Fel Sus domestica weight 3～5%NaHSO
3, stir 15min; The ethyl acetate or the ether that add reaction solution volume 40% then continue to be acidified to pH5 with rare sulfuric acid or hydrochloric acid while stirring, leave standstill 1h behind the stirring 30min, and organic layer is taken out in siphon;
The gac that adds initial Fel Sus domestica weight 5～10%, 50～55 ℃ are stirred 30min, filter, and residue is with the ethyl acetate washing of initial Fel Sus domestica volume 5%, merging filtrate and washings;
(3) separation of HDCA crude product
Above-mentioned amalgamation liquid is evaporated to 1/2～2/3 of ethyl acetate or ether add-on, and following slowly has precipitation to generate after stirring, and places 15～20h under the room temperature then; Suction filtration cleans filter residue with ethyl acetate, is yellow until filtrate; With clear washed precipitate vacuum-drying, obtain canescence HDCA crude product.
2. a kind of method for preparing the high purity Hyodeoxycholic Acid from Fel Sus domestica according to claim 1 is characterized in that: comprise in the purification process of the described HDCA of preparing crude product:
(1) esterification of HDCA:
Total cholic acid is dissolved in initial Fel Sus domestica volume 30% methyl alcohol or the ethanol, adds an amount of vitriol oil, hydrochloric acid or Phosphation, stirring at room 12～36h.Be neutralized to pH7 with NaHCO3 or Na2CO3, mixture filters, and concentrating under reduced pressure gets oily matter;
Oily matter is dissolved in initial Fel Sus domestica volume 30～40% hot benzene, and filtrate decompression is concentrated to about 1/2 o'clock of original volume, places refrigerator overnight, separates out dope; Filter, with a little washing leaching cake of benzene, be Hyodeoxycholic Acid methyl esters-benzene affixture;
(2) separation of the pure product of described HDCA:
Hyodeoxycholic Acid methyl esters-benzene affixture adds the NaOH of initial Fel Sus domestica weight 4～6% or KOH, initial Fel Sus domestica volume 10～12% water, and steam distillation all steams until benzene and to remove, add 1N HCl and transfer pH to 4～5, separate out precipitation, be washed to neutrality, vacuum-drying obtains the pure product of HDCA.
3. a kind of method for preparing the high purity Hyodeoxycholic Acid from Fel Sus domestica according to claim 1 is characterized in that: the purification process of the described HDCA of preparing crude product adopts existing acetoneand ethyl acetate recrystallization method.
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| CNB2007100214157A CN100556914C (en) | 2007-04-11 | 2007-04-11 | A kind of method that from Fel Sus domestica, prepares the high purity Hyodeoxycholic Acid |
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| CNB2007100214157A CN100556914C (en) | 2007-04-11 | 2007-04-11 | A kind of method that from Fel Sus domestica, prepares the high purity Hyodeoxycholic Acid |
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Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102443033A (en) * | 2010-10-08 | 2012-05-09 | 娄倩倩 | Method for extracting bile acid from bilirubin leftovers |
| CN102838647A (en) * | 2011-06-23 | 2012-12-26 | 福建省仙游县南丰生化有限公司 | Hyodeoxycholic acid |
| CN102617689B (en) * | 2012-03-14 | 2013-11-06 | 江苏正大清江制药有限公司 | Purification method of hyodeoxycholic acid |
| CN102775459B (en) * | 2012-07-30 | 2014-12-10 | 南京新百药业有限公司 | Process for preparing hyodeoxycholic acid |
| CN103012534B (en) * | 2012-12-19 | 2015-03-18 | 四川大熊生物技术有限公司 | Method for extracting hyodeoxycholic acid from pig bile |
| CN104257691A (en) * | 2014-09-01 | 2015-01-07 | 安徽科宝生物工程有限公司 | Preparation method of ox-gall powder |
| CN106866771A (en) * | 2017-04-14 | 2017-06-20 | 赵厚发 | A kind of preparation method of bile acid |
| CN107312054A (en) * | 2017-07-25 | 2017-11-03 | 贵州慧静生物科技有限公司 | A kind of method that urso and Tauro ursodesoxy cholic acid are synthesized from pig's bile |
| CN107549123A (en) * | 2017-10-18 | 2018-01-09 | 湖北聚注通用技术研究有限公司 | A kind of scorpion breeding method |
| CN111961105A (en) * | 2020-09-23 | 2020-11-20 | 安徽科宝生物工程有限公司 | Method for separating hyodeoxycholic acid from pig bile paste by extraction method |
| CN112094883A (en) * | 2020-09-28 | 2020-12-18 | 常德云港生物科技有限公司 | Method for preparing beta-hyodeoxycholic acid by microbial transformation |
| CN114085263A (en) * | 2021-12-27 | 2022-02-25 | 安徽科宝生物工程有限公司 | Synthesis process of ursodeoxycholic acid |
| CN115850362A (en) * | 2022-12-30 | 2023-03-28 | 上海雷允上药业有限公司 | Method for preparing hyodeoxycholic acid extract |
-
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Non-Patent Citations (1)
| Title |
|---|
| 猪胆汁、鸡胆汁研制鹅脱氧胆酸比较. 张传慧等.安徽大学学报，第23卷第3期. 1999 * |
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