CN103804453B - The method preparing ursodesoxycholic acid for raw material with Fel Sus domestica - Google Patents
The method preparing ursodesoxycholic acid for raw material with Fel Sus domestica Download PDFInfo
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- CN103804453B CN103804453B CN201310456980.1A CN201310456980A CN103804453B CN 103804453 B CN103804453 B CN 103804453B CN 201310456980 A CN201310456980 A CN 201310456980A CN 103804453 B CN103804453 B CN 103804453B
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Abstract
The invention discloses a kind of method preparing ursodesoxycholic acid for raw material with Fel Sus domestica, including prepare chenodeoxycholic acid, aoxidize, reduce, purification procedures.The present invention is using Fel Sus domestica as extracting raw material, and Fel Sus domestica raw material is extensively easy to get, and reduces preparation cost, and income is higher, and economic benefit is good；When the present invention is with chenodeoxycholic acid synthesis ursodesoxycholic acid, with calcium chloride as precipitant, it is to avoid the environmental pollution that conventional barium salt precipitant causes, also simplify precipitation operation simultaneously.
Description
Technical field
The invention belongs to biomedicine technical field, relate to the preparation method of ursodesoxycholic acid, the method being specifically related to prepare ursodesoxycholic acid with Fel Sus domestica for raw material.
Background technology
The product that bile is human body or vertebrate liver cells is secreted continuously, it is a kind of viscosity color-alkali liquid with bitterness, its composition than water, mainly has bile acid, cholate and bile pigments, in addition with a small amount of cholesterol, fatty acid, lecithin, electrolyte and protein etc..Animal bile the most more typically is generally bird gall, Fel Sus domestica, Fel Bovis seu Bubali, Fel Ursi and Fel Serpentis etc..Bile acid is the main component of bile, account for the 50% ~ 70% of bile total amount, the physiological action of bile is mainly played by bile acid exactly, when as medicine, bile acid can be used to antipyretic, spasmolytic antitussive, regulation blood pressure, heart tonifying function of gallbladder promoting, antibacterial anti-inflammatory and regulation immunity etc., and activity is relatively strong, side effect is the least, cheap, therefore suffers from the welcome of vast medication person.
In various animal biles, Fel Sus domestica is most common and yield is maximum, start just to be widely used in clinic from ancient times, as with Fel Sus domestica treatment acute icteric infectious hepatitis, pertussis, acute enteritis and gastric ulcer etc., good therapeutic effect all can be received.Mainly containing bile acids, bile pigments, mucin, lipid and inorganic matter etc. in Fel Sus domestica, bile acid mainly comprises Hyodeoxycholic Acid, hyocholic acid, chenodeoxycholic acid, 3 Alpha-hydroxy-6-oxygen-5 α-cholanic acid and cholelithiasis acid etc..Wherein Hyodeoxycholic Acid accounts for 40%, and chenodeoxycholic acid accounts for 25%.
Ursodesoxycholic acid entitled 3 α of chemistry, 7 β-dihydroxy-5 β-cholanic acid, molecular formula C24H49O4, molecular weight is 392.58, for white or micro-yellow powder, is soluble in ethanol, glacial acetic acid, is slightly dissolved in chloroform, be practically insoluble in ether and water.Ursodesoxycholic acid is first to find from Fel Ursi for 1920, and Shoda isolated crystal from Fel Ursi in 1927 determines its chemical constitution in 1937.Natural ursodesoxycholic acid derives from Fel Ursi, and along with the demand of clinical practice is continuously increased, natural ursodesoxycholic acid can not meet far away the market demand.Kill Bears to take gallbladder and prohibited by country, therefore, obtain ursodesoxycholic acid by chemical synthesis process and become more and more important.Initially, people's success, with cholic acid, deoxycholic acid etc. as raw material, has synthesized ursodesoxycholic acid, but this kind of method reactions steps is many, and complex process, productivity is low, is difficult to carry out industrialization large-scale production.
In recent years, with chenodeoxycholic acid as raw material, carry out chemosynthesis ursodesoxycholic acid technical process and be greatly simplified.And chenodeoxycholic acid is the Main Ingredients and Appearance of the poultry bile such as chicken, duck and goose, directly can extract from duck, goose and the bile of chicken and obtain, mature production technology, cheap.Therefore, with chenodeoxycholic acid for raw material production ursodesoxycholic acid, Fel Sus domestica particularly extracts from originating after chenodeoxycholic acid chemosynthesis ursodesoxycholic acid widely again, obvious economic benefit and social value can be created.
Summary of the invention
The technical problem to be solved is to provide a kind of method preparing ursodesoxycholic acid for raw material with Fel Sus domestica, and the method extraction process is simple, and raw material sources are extensively easy to get, and environmental pollution is little, and product purity is high.
For solving above-mentioned technical problem, the technical scheme that the present invention takes is as follows:
The method preparing ursodesoxycholic acid for raw material with Fel Sus domestica, comprises the steps:
(1) chenodeoxycholic acid is prepared: with Fel Sus domestica as raw material, extract the mother solution after bilirubin and prepare TOTAL BILE ACID TBA, add and adjust pH to 7.2～7.5 with sodium hydroxide after ethanol dissolves, add calcium chloride solution to precipitation completely, water washing and precipitating obtains CDCA acid calcium salt, adding 50% propanoic acid or 60% acetic acid, at a temperature of 40～50 DEG C, heating makes it be completely dissolved, and adds and i.e. separates out chenodeoxycholic acid in water；
(2) oxidation: chenodeoxycholic acid is dissolved in the mixed solution of acetone and water, adds weak oxidant, make chenodeoxycholic acid be converted into 7-O-lithocholic acid；
(3) reduction: with sec-butyl alcohol as solvent, metallic sodium is reducing agent, at reflux, the 7-O-lithocholic acid of step (2) is reduced to ursodesoxycholic acid and chenodeoxycholic acid mixture；
(4) purification: the ursodesoxycholic acid of step (3) and chenodeoxycholic acid mixture are placed in organic solvent, react with silication agent at a temperature of 75～85 DEG C, generate ursodesoxycholic acid silicon ether solid precipitation, then by this solid at a temperature of 40～50 DEG C with acid reaction, obtain ursodesoxycholic acid sterling.
As the improvement of the present invention, the weak oxidant of above-mentioned steps (2) is N-bromo-succinimide, and its consumption is 1～5wt%.
Further improve as the present invention, above-mentioned steps (4) organic solvent is benzene, toluene, Nitrobenzol, chloroform, dichloromethane, carbon tetrachloride and oxolane one or more.
Further, the acid of above-mentioned steps (4) is 5～10% sulphuric acid or 5～10% hydrochloric acid.
The silication agent of above-mentioned steps (4) is two replacements or trisubstituted alkyl silicon halogenide, two replacements or trisubstituted silicon urea or dialkyl group silicon amide, preferably dimethyl-silicon amide.
Compared with prior art, the invention have the benefit that
The present invention is using Fel Sus domestica as extracting raw material, and Fel Sus domestica raw material is extensively easy to get, and reduces preparation cost, and income is higher, and economic benefit is good；When the present invention is with chenodeoxycholic acid synthesis ursodesoxycholic acid, with calcium chloride as precipitant, it is to avoid the environmental pollution that conventional barium salt precipitant causes, also simplify precipitation operation simultaneously.
Accompanying drawing explanation
Fig. 1 is the process chart of the present invention.
Detailed description of the invention
For ease of understanding the present invention, it is as follows that the present invention enumerates embodiment.Those skilled in the art understand the present invention it will be clearly understood that described embodiment is used only for help, are not construed as the concrete restriction to the present invention.
In the following example, the same meaning that all specialties used are familiar with scientific words and those skilled in the art.
Embodiment 1
As it is shown in figure 1, the method preparing ursodesoxycholic acid for raw material with Fel Sus domestica, comprise the steps:
(1) chenodeoxycholic acid is prepared: with Fel Sus domestica as raw material, extract the mother solution after bilirubin and prepare TOTAL BILE ACID TBA, add and adjust pH to 7.2～7.5 with sodium hydroxide after ethanol dissolves, add calcium chloride solution to precipitation completely, water washing and precipitating obtains CDCA acid calcium salt, adding 50% propanoic acid, at a temperature of 40～50 DEG C, heating makes it be completely dissolved, and adds and i.e. separates out chenodeoxycholic acid in water；
(2) oxidation: chenodeoxycholic acid is dissolved in the mixed solution of acetone and water, adds the N-bromo-succinimide of 3wt%, make chenodeoxycholic acid be converted into 7-O-lithocholic acid；
(3) reduction: with sec-butyl alcohol as solvent, metallic sodium is reducing agent, at reflux, the 7-O-lithocholic acid of step (2) is reduced to ursodesoxycholic acid and chenodeoxycholic acid mixture；
(4) purification: the ursodesoxycholic acid of step (3) and chenodeoxycholic acid mixture are placed in oxolane, react with dimethyl-silicon amide at a temperature of 75～85 DEG C, generate ursodesoxycholic acid silicon ether solid precipitation, again by this solid at a temperature of 40～50 DEG C with 8% hydrochloric acid reaction, obtain ursodesoxycholic acid sterling.
In the present embodiment, 20 grams of chenodeoxycholic acid, behind step (2), (3), (4), can synthesize and obtain 18～20 grams of (mp.191～193 DEG C) ursodesoxycholic acid dry products, then with alcohol crystal (mp.198～203 DEG C), purity is up to 98%.
Embodiment 2
The method preparing ursodesoxycholic acid for raw material with Fel Sus domestica, comprises the steps:
(1) chenodeoxycholic acid is prepared: with Fel Sus domestica as raw material, extract the mother solution after bilirubin and prepare TOTAL BILE ACID TBA, add and adjust pH to 7.2～7.5 with sodium hydroxide after ethanol dissolves, add calcium chloride solution to precipitation completely, water washing and precipitating obtains CDCA acid calcium salt, adding 60% acetic acid, at a temperature of 40～50 DEG C, heating makes it be completely dissolved, and adds and i.e. separates out chenodeoxycholic acid in water；
(2) oxidation: chenodeoxycholic acid is dissolved in the mixed solution of acetone and water, adds the N-bromo-succinimide of 3wt%, make chenodeoxycholic acid be converted into 7-O-lithocholic acid；
(3) reduction: with sec-butyl alcohol as solvent, metallic sodium is reducing agent, at reflux, the 7-O-lithocholic acid of step (2) is reduced to ursodesoxycholic acid and chenodeoxycholic acid mixture；
(4) purification: the ursodesoxycholic acid of step (3) and chenodeoxycholic acid mixture are placed in carbon tetrachloride, react with dimethyl-silicon amide at a temperature of 75～85 DEG C, generate ursodesoxycholic acid silicon ether solid precipitation, again by this solid at a temperature of 40～50 DEG C with 8% hydrochloric acid reaction, obtain ursodesoxycholic acid sterling.
In the present embodiment, 20 grams of chenodeoxycholic acid, behind step (2), (3), (4), can synthesize and obtain 15～18 grams of (mp.191～193 DEG C) ursodesoxycholic acid dry products, then with alcohol crystal (mp.198～203 DEG C), purity is up to 95%.
Embodiment 3
The method preparing ursodesoxycholic acid for raw material with Fel Sus domestica, comprises the steps:
(1) chenodeoxycholic acid is prepared: with Fel Sus domestica as raw material, extract the mother solution after bilirubin and prepare TOTAL BILE ACID TBA, add and adjust pH to 7.2～7.5 with sodium hydroxide after ethanol dissolves, add calcium chloride solution to precipitation completely, water washing and precipitating obtains CDCA acid calcium salt, adding 60% acetic acid, at a temperature of 40～50 DEG C, heating makes it be completely dissolved, and adds and i.e. separates out chenodeoxycholic acid in water；
(2) oxidation: chenodeoxycholic acid is dissolved in the mixed solution of acetone and water, adds the N-bromo-succinimide of 2wt%, make chenodeoxycholic acid be converted into 7-O-lithocholic acid；
(3) reduction: with sec-butyl alcohol as solvent, metallic sodium is reducing agent, at reflux, the 7-O-lithocholic acid of step (2) is reduced to ursodesoxycholic acid and chenodeoxycholic acid mixture；
(4) purification: the ursodesoxycholic acid of step (3) and chenodeoxycholic acid mixture are placed in chloroform, react with trimethyl silicane urea at a temperature of 75～85 DEG C, generate ursodesoxycholic acid silicon ether solid precipitation, again by this solid at a temperature of 40～50 DEG C with 8% hydrochloric acid reaction, obtain ursodesoxycholic acid sterling.
In the present embodiment, 20 grams of chenodeoxycholic acid, behind step (2), (3), (4), can synthesize and obtain 15～16 grams of (mp.191～193 DEG C) ursodesoxycholic acid dry products, then with alcohol crystal (mp.198～203 DEG C), purity is up to 92%.
Embodiment 4
The method preparing ursodesoxycholic acid for raw material with Fel Sus domestica, comprises the steps:
(1) chenodeoxycholic acid is prepared: with Fel Sus domestica as raw material, extract the mother solution after bilirubin and prepare TOTAL BILE ACID TBA, add and adjust pH to 7.2～7.5 with sodium hydroxide after ethanol dissolves, add calcium chloride solution to precipitation completely, water washing and precipitating obtains CDCA acid calcium salt, adding 60% acetic acid, at a temperature of 40～50 DEG C, heating makes it be completely dissolved, and adds and i.e. separates out chenodeoxycholic acid in water；
(2) oxidation: chenodeoxycholic acid is dissolved in the mixed solution of acetone and water, adds the N-bromo-succinimide of 5wt%, make chenodeoxycholic acid be converted into 7-O-lithocholic acid；
(3) reduction: with sec-butyl alcohol as solvent, metallic sodium is reducing agent, at reflux, the 7-O-lithocholic acid of step (2) is reduced to ursodesoxycholic acid and chenodeoxycholic acid mixture；
(4) purification: the ursodesoxycholic acid of step (3) and chenodeoxycholic acid mixture are placed in Nitrobenzol, react with trimethyl silicane urea at a temperature of 75～85 DEG C, generate ursodesoxycholic acid silicon ether solid precipitation, again by this solid at a temperature of 40～50 DEG C with 8% hydrochloric acid reaction, obtain ursodesoxycholic acid sterling.
In the present embodiment, 20 grams of chenodeoxycholic acid, behind step (2), (3), (4), can synthesize and obtain 15～18 grams of (mp.191～193 DEG C) ursodesoxycholic acid dry products, then with alcohol crystal (mp.198～203 DEG C), purity is up to 93%.
Embodiment 5
The method preparing ursodesoxycholic acid for raw material with Fel Sus domestica, comprises the steps:
(1) chenodeoxycholic acid is prepared: with Fel Sus domestica as raw material, extract the mother solution after bilirubin and prepare TOTAL BILE ACID TBA, add and adjust pH to 7.2～7.5 with sodium hydroxide after ethanol dissolves, add calcium chloride solution to precipitation completely, water washing and precipitating obtains CDCA acid calcium salt, adding 60% acetic acid, at a temperature of 40～50 DEG C, heating makes it be completely dissolved, and adds and i.e. separates out chenodeoxycholic acid in water；
(2) oxidation: chenodeoxycholic acid is dissolved in the mixed solution of acetone and water, adds the N-bromo-succinimide of 3wt%, make chenodeoxycholic acid be converted into 7-O-lithocholic acid；
(3) reduction: with sec-butyl alcohol as solvent, metallic sodium is reducing agent, at reflux, the 7-O-lithocholic acid of step (2) is reduced to ursodesoxycholic acid and chenodeoxycholic acid mixture；
(4) purification: the ursodesoxycholic acid of step (3) and chenodeoxycholic acid mixture are placed in toluene, react with trimethyl silicane urea at a temperature of 75～85 DEG C, generate ursodesoxycholic acid silicon ether solid precipitation, again by this solid at a temperature of 40～50 DEG C with 8% sulfuric acid reaction, obtain ursodesoxycholic acid sterling.
In the present embodiment, 20 grams of chenodeoxycholic acid, behind step (2), (3), (4), can synthesize and obtain 15～18 grams of (mp.191～193 DEG C) ursodesoxycholic acid dry products, then with alcohol crystal (mp.198～203 DEG C), purity is up to 91%.
Embodiment 6
The method preparing ursodesoxycholic acid for raw material with Fel Sus domestica, comprises the steps:
(1) chenodeoxycholic acid is prepared: with Fel Sus domestica as raw material, extract the mother solution after bilirubin and prepare TOTAL BILE ACID TBA, add and adjust pH to 7.2～7.5 with sodium hydroxide after ethanol dissolves, add calcium chloride solution to precipitation completely, water washing and precipitating obtains CDCA acid calcium salt, adding 60% acetic acid, at a temperature of 40～50 DEG C, heating makes it be completely dissolved, and adds and i.e. separates out chenodeoxycholic acid in water；
(2) oxidation: chenodeoxycholic acid is dissolved in the mixed solution of acetone and water, adds the N-bromo-succinimide of 3wt%, make chenodeoxycholic acid be converted into 7-O-lithocholic acid；
(3) reduction: with sec-butyl alcohol as solvent, metallic sodium is reducing agent, at reflux, the 7-O-lithocholic acid of step (2) is reduced to ursodesoxycholic acid and chenodeoxycholic acid mixture；
(4) purification: the ursodesoxycholic acid of step (3) and chenodeoxycholic acid mixture are placed in benzene, react with dimethyl-silicon amide at a temperature of 75～85 DEG C, generate ursodesoxycholic acid silicon ether solid precipitation, again by this solid at a temperature of 40～50 DEG C with 8% sulfuric acid reaction, obtain ursodesoxycholic acid sterling.
In the present embodiment, 20 grams of chenodeoxycholic acid, behind step (2), (3), (4), can synthesize and obtain 12～16 grams of (mp.191～193 DEG C) ursodesoxycholic acid dry products, then with alcohol crystal (mp.198～203 DEG C), purity is up to 90%.
Applicant states, person of ordinary skill in the field is on the basis of above-described embodiment, by the concrete content point value of above-described embodiment component, combined with the technical scheme of Summary, thus the new numerical range produced, also being one of the record scope of the present invention, the application, for making description simple and clear, no longer enumerates these numerical rangies.
Claims (2)
1. the method preparing ursodesoxycholic acid with Fel Sus domestica for raw material, it is characterised in that comprise the steps:
(1) prepare chenodeoxycholic acid: with Fel Sus domestica as raw material, extract the mother solution after bilirubin and prepare TOTAL BILE ACID TBA, add ethanol molten
Adjusting pH to 7.2～7.5 with sodium hydroxide after solution, add calcium chloride solution to precipitation completely, water washing and precipitating obtains chenodeoxycholic acid calcium
Salt, adds 50% propanoic acid or 60% acetic acid, and at a temperature of 40～50 DEG C, heating makes it be completely dissolved, and adds and i.e. separates out goose deoxidation in water
Cholic acid；
(2) oxidation: chenodeoxycholic acid is dissolved in the mixed solution of acetone and water, adds weak oxidant, make chenodeoxycholic acid
It is converted into 7-O-lithocholic acid；
(3) reduction: with sec-butyl alcohol as solvent, metallic sodium is reducing agent, at reflux, by the 7-O-lithocholic acid of step (2)
It is reduced to ursodesoxycholic acid and chenodeoxycholic acid mixture；
(4) purification: the ursodesoxycholic acid of step (3) and chenodeoxycholic acid mixture are placed in organic solvent, in 75～85 DEG C
At a temperature of react with silication agent, generate ursodesoxycholic acid silicon ether solid precipitation, then by this solid at a temperature of 40～50 DEG C with acid
Reaction, obtains ursodesoxycholic acid sterling；
The weak oxidant of described step (2) is N-bromo-succinimide, and its consumption is 1～5wt%；
The organic solvent of described step (4) is benzene, toluene, Nitrobenzol, chloroform, dichloromethane, carbon tetrachloride and oxolane
One or more；
The silication agent of described step (4) be two replacements or trisubstituted alkyl silicon halogenide, two replacements or trisubstituted silicon urea or
Dialkyl group silicon amide.
2. the method preparing ursodesoxycholic acid with Fel Sus domestica for raw material as claimed in claim 1, it is characterised in that: described step
(4) acid is 5～10% sulphuric acid or 5～10% hydrochloric acid.
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| CN104017043A (en) * | 2014-06-20 | 2014-09-03 | 华东理工大学 | Method for purifying ursodesoxycholic acid by adopting silanization technology |
| CN107226832A (en) * | 2017-06-15 | 2017-10-03 | 马鞍山汇智生物技术有限公司 | A kind of new method that chenodeoxycholic acid is prepared by raw material of chicken courage |
| CN108218942A (en) * | 2017-12-18 | 2018-06-29 | 南京科技职业学院 | A kind of preparation method of 3-5 β of Alpha-hydroxy-7- oxos of high-purity-cholanic acid |
| CN108218943B (en) * | 2018-03-05 | 2020-06-05 | 常德云港生物科技有限公司 | Method for synthesizing ursodesoxycholic acid from chenodeoxycholic acid and cholic acid in chicken gall |
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| CN101215308A (en) * | 2007-01-04 | 2008-07-09 | 苏州天绿生物制药有限公司 | Method for producing ursodeoxycholic acid by using swine bladder as raw material |
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| CN101215308A (en) * | 2007-01-04 | 2008-07-09 | 苏州天绿生物制药有限公司 | Method for producing ursodeoxycholic acid by using swine bladder as raw material |
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| 鹅去氧胆酸制备新工艺;高玉琼;《中国生化药物杂志》;19961231;第17卷(第1期);第16-17页 * |
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