CN105418716B - A kind of method of the duck cholic acid synthesis chenodeoxycholic acid extracted in the bile with duck - Google Patents
A kind of method of the duck cholic acid synthesis chenodeoxycholic acid extracted in the bile with duck Download PDFInfo
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- CN105418716B CN105418716B CN201511000722.8A CN201511000722A CN105418716B CN 105418716 B CN105418716 B CN 105418716B CN 201511000722 A CN201511000722 A CN 201511000722A CN 105418716 B CN105418716 B CN 105418716B
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- C07J9/00—Normal steroids containing carbon, hydrogen, halogen or oxygen substituted in position 17 beta by a chain of more than two carbon atoms, e.g. cholane, cholestane, coprostane
- C07J9/005—Normal steroids containing carbon, hydrogen, halogen or oxygen substituted in position 17 beta by a chain of more than two carbon atoms, e.g. cholane, cholestane, coprostane containing a carboxylic function directly attached or attached by a chain containing only carbon atoms to the cyclopenta[a]hydrophenanthrene skeleton
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Abstract
The invention discloses a kind of method of the duck cholic acid extracted in bile with duck synthesis chenodeoxycholic acid.This method from duck bile by extracting duck cholic acid crude product, then by duck cholic acid crude product after esterification acetylation, is reacted using Huang Min-lon reduction and chenodeoxycholic acid is made.The obtained chenodeoxycholic acid yield of preparation method of the present invention is high, purity is high, basically reaches 95% or so.And using the preparation method of the present invention, it can be salvaged, reduce cost, it is easy and effective, and it is suitable to commercial application.
Description
Technical field
The present invention relates to a kind of preparation method of chenodeoxycholic acid, and in particular to the duck cholic acid extracted in a kind of bile with duck
The method for synthesizing chenodeoxycholic acid.
Background technology
Chenodeoxycholic acid (Chenodeoxycholic acid, abbreviation CDCA), is a kind of natural cholic acid, is 1848
Extract what is obtained from goose bile first.Chenodeoxycholic acid has the ability and other pharmacy functions of dissolving gall stone, is treatment
The natural good medicine of gall stone, while be to synthesize urso and the raw material of other steroidal compounds again.
Because chenodeoxycholic acid is the main component of the poultry bile such as chicken, duck and goose, it can be directly from the bile of birds
Extraction.But by technology restriction, CDCA acid product in the market is substantially to extract what is obtained from chicken bile.
The feeding quantity of goose is less, it is difficult to makees the raw material of extraction chenodeoxycholic acid using its bile.The number of animals raised of duck is huge, with chicken bile
Constituent compare, the composition of duck bile is more complicated, it is impossible to application from chicken bile extract chenodeoxycholic acid method extraction
Chenodeoxycholic acid in duck bile.
Up to the present, it is traditional extracted from the bile of chicken, duck and goose etc. chenodeoxycholic acid technique include bile saponification,
It is acidified, except steps such as alcohol-insoluble substances, grease removal, generation barium salt, de- barium, complex technical process, yield is low, and commercial application is difficult.
Or using calcium salt precipitation method, settling velocity is slow, and efficiency is low, and hydrogen peroxide and activated carbon decolorizing effect are also undesirable.
The content of the invention
[technical problems to be solved]
Present invention aim to address above-mentioned prior art problem, there is provided the duck cholic acid synthesis extracted in a kind of bile with duck
The method of chenodeoxycholic acid.This method from duck bile by extracting duck cholic acid crude product, then by duck cholic acid crude product through esterification
After acetylation, reacted using Huang Min-lon reduction and chenodeoxycholic acid is made, yield is good, purity is high；Suitable for commercial application.
[technical scheme]
In order to reach above-mentioned technique effect, the present invention takes following technical scheme：
A kind of method of the duck cholic acid synthesis chenodeoxycholic acid extracted in bile with duck, it comprises the following steps：
I, the extraction of duck cholic acid
Fresh duck bile, saponification plus salt acid for adjusting pH are taken to obtain black paste after 2~3 acidifyings；Then methanol is added
After being completely dissolved black paste and removing grease using petroleum ether, vacuum concentration methanol layer obtains bile acid crude below 70 DEG C；
Acetonitrile methanol mixed liquor dissolving bile acid crude is subsequently added into, and upper silicagel column adsorbs, it is thick that gradient elution obtains the duck cholic acid
Product；
II, the synthesis of chenodeoxycholic acid
The duck cholic acid crude product that step I obtains is obtained into product A after esterification, acetylation, then reacted through Huang Min-lon reduction
Obtain described chenodeoxycholic acid crude product；
The chenodeoxycholic acid crude product that the step obtains is crystallized through chloroform, obtains the chenodeoxycholic acid.
According to the further technical scheme of the present invention, in step I, the saponification is by fresh duck bile and hydroxide
The mass ratio of sodium is 1：0.3~0.4 adds sodium hydroxide into fresh duck bile, and then sealing is warming up to 110~125 DEG C, stirs
Mix 12~14h of reaction.
It is described to remove grease process repetition 2 using petroleum ether in step I according to the further technical scheme of the present invention
~3 times.
According to the further technical scheme of the present invention, in step I, the acetonitrile methanol mixed solution be by acetonitrile and
Methanol by volume 72：25 is well mixed；The gradient elution is to use acetonitrile and methanol volume range as 72：25~60：40
Acetonitrile methanol mixed solution gradient elution.
According to the further technical scheme of the present invention, in step I, thin-layered chromatography is used after the gradient elution
(TLC) point sample confirms that Fractional Collections eluent obtains duck cholic acid crude product.
According to the further technical scheme of the present invention, in step II, the esterification is to add duck cholic acid crude product
After methanol dissolving, the mass fraction that is slowly added to 0.11~0.13 times of duck cholic acid crude product quality is 98% sulfuric acid, first under normal temperature
4~5h of esterification；Then it is 6~8 to add sodium hydroxide to reaction solution pH, terminates esterification reaction of organic acid；Filter off except neutralization production
Thing sodium sulphate, concentration filtrate obtain duck Methyl cholate compound.
According to the further technical scheme of the present invention, in step II, the acetylation is to the duck Methyl cholate
After adding acetic anhydride in compound, 4~5h of acetylization reaction at 135~145 DEG C, after reaction completely, vacuum is dense below 120 DEG C
Contracting obtains product A.
According to the further technical scheme of the present invention, in step II, the Huang Min-lon reduction reaction is into product A
Add ethylene glycol, the hydrazine hydrate solution and potassium hydroxide that mass fraction is 85%, be then heated to reflux 4~5h, obtain the goose
Deoxycholic aicd crude product.
According to the further technical scheme of the present invention, the product A, ethylene glycol, hydrazine hydrate solution and potassium hydroxide
Mass ratio is 1：3：1：5.
In step I, during bile acid crude is through upper silicagel column gradient elution, it is thick also to elute chenodeoxycholic acid
Product, the part crude product can crystallize to obtain chenodeoxycholic acid fine work by chloroform.
The present invention is will be described in detail below.
After the present invention is by saponification, acidifying, grease removal reaction, the bile acid crude that will be obtained using acetonitrile methanol mixed solution
Silica gel column separating purification is crossed, confirms that Fractional Collections eluent obtains duck cholic acid crude product by thin-layered chromatography (TLC) point sample.Due to
After silica gel column separating purification, obtained duck cholic acid crude product purity is higher, so as to ensure that the chenodeoxycholic acid that subsequent reactions obtain produces
The high-purity of thing.When addition petroleum ether removes grease, petroleum ether layer is gone by siphon point, can inspissated oil ether layer recovery oil
Ether, concentrate are grease, are abandoned.
Described concentration methanol layer refers to remove the reacted methanol solution of grease, and methanol need to be concentrated in vacuo below 70 DEG C
Layer because methanol is difficult to that concentration is complete under normal pressure, and the temperature concentrated be not easy it is too high, in order to avoid destroy reaction product.Utilize acetonitrile
Methyl alcohol mixed liquor gradient elution bile acid crude, is the material chemical polarity difference in its crude product and gradient elution obtains duck
Cholic acid crude product and chenodeoxycholic acid crude product.The duck cholic acid crude product obtained after elution is added into the sulfuric acid first that mass fraction is 98%
3.8~4.2h of esterification, reaction time can not be long or too short, and the reaction time is too short, and duck cholic acid crude product can not complete methyl esters
Change, it is long and may cause to produce excessive impurity, subsequent operation is influenceed so as to finally influence the purity of chenodeoxycholic acid.
[beneficial effect]
The present invention compared with prior art, has following beneficial effect：
The obtained chenodeoxycholic acid yield of preparation method of the present invention is high, purity is high, basically reaches 95% or so.And profit
With the preparation method of the present invention, it can be salvaged, reduce cost, it is easy and effective, and it is suitable to commercial application.
Embodiment
With reference to embodiments of the invention, the invention will be further elaborated.
Measure for N times in following embodiments and refer to N times of quality, wherein N represents ＞ 0 natural number.
Embodiment 1：
I, the extraction of duck cholic acid
1000g fresh ducks bile is taken to put into reactor first, 0.35 times of amount sodium hydroxide continues to put into, and sealing keeps pressure
120 DEG C are warming up to, stirring reaction 12 hours, standing is down to room temperature, adds watery hydrochloric acid and adjusts pH value to obtain black paste 200g for 3；
3 times of amount methanol are added into black paste, are heated to 50 DEG C, stirring is complete to dissolving；Continuously add 3 times of amount petroleum ether and stirrings
30 minutes, stand, petroleum ether layer is removed in siphon point；After repeating to add petroleum ether except grease process 3 times, methanol layer is collected, and 70
Methanol layer is concentrated in vacuo below DEG C and obtains bile acid crude 70g, adds 2 times of amount acetonitriles, methanol volume ratio is 75：25 acetonitrile methanol
Mixed solution, upper silicagel column absorption after normal-temperature dissolution；It is 75 followed by acetonitrile, methanol volume ratio：25~60：40 acetonitrile first
Mixed alkoxide solution gradient elution, confirm that Fractional Collections eluent obtains duck cholic acid crude product 32g by TLC；
II, the synthesis of chenodeoxycholic acid
Obtain adding 2 times of amount methanol in duck cholic acid crude product to step I, stirring at normal temperature is complete to dissolving, and is slowly added to 0.12
98% sulfuric acid is measured again, and esterification reaction of organic acid is carried out 4 hours under normal temperature；Appropriate solid sodium hydroxide neutralisation of sulphuric acid is added, it is 6 to make pH value
~8, neutralized reaction product sodium sulphate is filtered to remove, less than 70 DEG C vacuum concentration filtrates, obtains duck Methyl cholate compound；It is thick to add duck cholic acid
1.5 times of product amount acetic anhydride carry out acetylization reaction 4 hours at 140 DEG C, after reaction is complete, less than 120 DEG C be concentrated in vacuo it is above-mentioned
Solution obtains the common 39g of product A, and 3 times of amount ethylene glycol, 1 times of 85% hydrazine hydrate solution of amount, 5 times of amount hydroxides are then added into product A
Potassium；It is heated to reflux 4 hours, generation chenodeoxycholic acid crude product 31.4g；
Finally by chenodeoxycholic acid crude product with obtained after chloroform crystal refining purity be 95.4% chenodeoxycholic acid 27g.
Embodiment 2：
I, the extraction of duck cholic acid
Fresh duck bile is taken to put into reactor first, 0.3 times of amount sodium hydroxide continues to put into, and sealing keeps pressure to be warming up to
115 DEG C, stirring reaction 13 hours, standing is down to room temperature, adds watery hydrochloric acid and adjusts pH value to obtain black paste for 3；To black paste
3 times of amount methanol are added in thing, are heated to 50 DEG C, stirring is complete to dissolving；Continuously add 3 times and measure petroleum ether and stirring 30 minutes, it is quiet
Put, petroleum ether layer is removed in siphon point；After repeating to add petroleum ether except grease process 2 times, methanol layer, and the vacuum below 70 DEG C are collected
Concentration methanol layer obtains bile acid crude, adds 2 times of amount acetonitriles, methanol volume ratio is 75：25 acetonitrile methanol mixed solution, normal temperature
Upper silicagel column absorption after dissolving；It is 75 followed by acetonitrile, methanol volume ratio：25~60：40 acetonitrile methanol mixed solution ladder
Degree elution, confirm that Fractional Collections eluent obtains duck cholic acid crude product by TLC；
II, the synthesis of chenodeoxycholic acid
Obtain adding 2 times of amount methanol in duck cholic acid crude product to step I, stirring at normal temperature is complete to dissolving, and is slowly added to 0.12
98% sulfuric acid is measured again, and esterification reaction of organic acid is carried out 3.8 hours under normal temperature；Appropriate solid sodium hydroxide neutralisation of sulphuric acid is added, makes pH value
For 6~8, neutralized reaction product sodium sulphate is filtered to remove, less than 70 DEG C vacuum concentration filtrates, obtains duck Methyl cholate compound；Add duck courage
1.5 times of amount acetic anhydride of acid crude carry out acetylization reaction 4 hours at 140 DEG C, after reaction completely, less than 120 DEG C vacuum concentrations
Above-mentioned solution obtains product A, and 3 times of amount ethylene glycol, 1 times of 85% hydrazine hydrate solution of amount, 5 times of amount hydroxides are then added into product A
Potassium；It is heated to reflux 4 hours, generates chenodeoxycholic acid crude product；
Finally by chenodeoxycholic acid crude product with obtained after chloroform crystal refining purity be 94.9% chenodeoxycholic acid.
Embodiment 3：
I, the extraction of duck cholic acid
Fresh duck bile is taken to put into reactor first, 0.4 times of amount sodium hydroxide continues to put into, and sealing keeps pressure to be warming up to
125 DEG C, stirring reaction 12 hours, standing is down to room temperature, adds watery hydrochloric acid and adjusts pH value to obtain black paste for 2.5；To black cream
3 times of amount methanol are added in shape thing, are heated to 50 DEG C, stirring is complete to dissolving；Continuously add 3 times and measure petroleum ether and stirring 30 minutes,
Stand, petroleum ether layer is removed in siphon point；After repeating to add petroleum ether except grease process 3 times, methanol layer is collected, and it is true below 70 DEG C
Sky concentration methanol layer obtains bile acid crude, adds 2 times of amount acetonitriles, methanol volume ratio is 75：25 acetonitrile methanol mixed solution, often
Upper silicagel column absorption after temperature dissolving；It is 75 followed by acetonitrile, methanol volume ratio：25~60：40 acetonitrile methanol mixed solution
Gradient elution, confirm that Fractional Collections eluent obtains duck cholic acid crude product by TLC；
II, the synthesis of chenodeoxycholic acid
Obtain adding 2 times of amount methanol in duck cholic acid crude product to step I, stirring at normal temperature is complete to dissolving, and is slowly added to 0.12
98% sulfuric acid is measured again, and esterification reaction of organic acid is carried out 4.2 hours under normal temperature；Appropriate solid sodium hydroxide neutralisation of sulphuric acid is added, makes pH value
For 6~8, neutralized reaction product sodium sulphate is filtered to remove, less than 70 DEG C vacuum concentration filtrates, obtains duck Methyl cholate compound；Add duck courage
1.5 times of amount acetic anhydride of acid crude carry out acetylization reaction 4 hours at 140 DEG C, after reaction completely, less than 120 DEG C vacuum concentrations
Above-mentioned solution obtains product A, and 3 times of amount ethylene glycol, 1 times of 85% hydrazine hydrate solution of amount, 5 times of amount hydroxides are then added into product A
Potassium；It is heated to reflux 4 hours, generates chenodeoxycholic acid crude product；
Finally by chenodeoxycholic acid crude product with obtained after chloroform crystal refining purity be 95% chenodeoxycholic acid.
In summary, chenodeoxycholic acid preparation method cost of the invention is low, purity is high, simple to operate, may be adapted to industry
Change application.
Although reference be made herein to invention has been described for explanatory embodiment of the invention, and above-described embodiment is only this hair
Bright preferable embodiment, embodiments of the present invention are simultaneously not restricted to the described embodiments, it should be appreciated that people in the art
Member can be designed that a lot of other modifications and embodiment, and these modifications and embodiment will fall in principle disclosed in the present application
Within scope and spirit.
Claims (4)
1. the method for the duck cholic acid synthesis chenodeoxycholic acid extracted in a kind of bile with duck, it is characterised in that it includes following step
Suddenly：
I, the extraction of duck cholic acid
Fresh duck bile, saponification plus salt acid for adjusting pH are taken to obtain black paste after 2~3 acidifyings；Then it is complete to add methanol
After dissolving black paste and removing grease using petroleum ether, vacuum concentration methanol layer obtains bile acid crude below 70 DEG C；Then
Acetonitrile methanol mixed liquor dissolving bile acid crude is added, and upper silicagel column adsorbs, gradient elution obtains the duck cholic acid crude product；
II, the synthesis of chenodeoxycholic acid
The duck cholic acid crude product that step I obtains is obtained into product A after esterification, acetylation, then reacts to obtain through Huang Min-lon reduction
Described chenodeoxycholic acid crude product；
The chenodeoxycholic acid crude product that the step obtains is crystallized through chloroform, obtains the chenodeoxycholic acid；
In step I, the acetonitrile methanol mixed solution is by acetonitrile and methanol by volume 72：25 is well mixed；The ladder
Degree elution is to use acetonitrile and methanol volume range as 72：25~60：40 acetonitrile methanol mixed solution gradient elution；
In step II, the esterification is after duck cholic acid crude product is added into methanol dissolving, to be slowly added to duck cholic acid crude product quality
0.11~0.13 times of mass fraction is 98% sulfuric acid, 3.8~4.2h of esterification reaction of organic acid under normal temperature；Then sodium hydroxide is added
It is 6~8 to reaction solution pH, terminates esterification reaction of organic acid；Filter off and remove neutralized reaction product sodium sulphate, concentration filtrate obtains duck Methyl cholate
Compound；
In step II, the acetylation is after adding acetic anhydride into the duck Methyl cholate compound, at 135~145 DEG C
4~5h of acetylization reaction, after reaction completely, it is concentrated in vacuo below 120 DEG C and obtains product A；
In step II, the Huang Min-lon reduction reaction is addition ethylene glycol, the hydrazine hydrate that mass fraction is 85% into product A
Solution and potassium hydroxide, are then heated to reflux 4~5h, obtain the chenodeoxycholic acid crude product.
2. the method for the duck cholic acid synthesis chenodeoxycholic acid extracted in the bile according to claim 1 with duck, its feature exist
In in step I, the utilization petroleum ether repeats 2~3 times except grease process.
3. the method for the duck cholic acid synthesis chenodeoxycholic acid extracted in the bile according to claim 1 with duck, its feature exist
In in step I, confirm that Fractional Collections eluent obtains duck cholic acid crude product with thin-layered chromatography point sample after the gradient elution.
4. the method for the duck cholic acid synthesis chenodeoxycholic acid extracted in the bile according to claim 1 with duck, its feature exist
In the product A, ethylene glycol, hydrazine hydrate solution and potassium hydroxide mass ratio be 1：3：1：5.
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106883281B (en) * | 2017-03-08 | 2017-12-22 | 眉山市新功生物科技有限公司 | The method that chenodeoxycholic acid is extracted from duck bile |
| CN109825547A (en) * | 2019-03-18 | 2019-05-31 | 常德云港生物科技有限公司 | A method of passing through half enzymatic clarification ursodesoxycholic acid by raw material of cholic acid |
| CN112300237A (en) * | 2020-04-13 | 2021-02-02 | 苏州恩泰新材料科技有限公司 | Preparation method and application of seal cholic acid |
| CN112341512A (en) * | 2020-04-13 | 2021-02-09 | 苏州恩泰新材料科技有限公司 | Method for preparing chenodeoxycholic acid from seal cholic acid |
| CN111995652B (en) * | 2020-08-12 | 2023-06-27 | 山东省药学科学院 | Method for separating chenodeoxycholic acid from duck bile |
| CN112321665A (en) * | 2020-12-01 | 2021-02-05 | 江西邦泰绿色生物合成生态产业园发展有限公司 | Method for synthesizing 3 alpha, 7 alpha-dihydroxy-5-beta-cholanic acid from duck cholic acid |
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| CN103113447A (en) * | 2013-03-21 | 2013-05-22 | 天津纽伟仕生物医药技术有限公司 | Method for extracting chenodeoxycholic acid in duck bile by adopting calcium salt process |
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| CN100484952C (en) * | 2005-12-13 | 2009-05-06 | 山东博尔德生物科技有限公司 | Method for producing high-purity chenodeoxy cholic acid from poultry and livestock bile |
| CN102453069A (en) * | 2010-10-20 | 2012-05-16 | 曾科 | Method for extracting chenodeoxycholic acid from goose and duck bile |
| CN102372757B (en) * | 2011-10-31 | 2013-01-16 | 安徽科宝生物工程有限公司 | Method for preparing chenodeoxycholic acid in pig bile by esterification method |
| CN102827234B (en) * | 2012-08-30 | 2014-07-16 | 苏州天绿生物制药有限公司 | Method for separating and purifying chenodeoxycholic acid from duck gall |
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| CN103113447A (en) * | 2013-03-21 | 2013-05-22 | 天津纽伟仕生物医药技术有限公司 | Method for extracting chenodeoxycholic acid in duck bile by adopting calcium salt process |
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