CN1912192B - Preparation method of 7-keto lithocholic acid - Google Patents
Preparation method of 7-keto lithocholic acid Download PDFInfo
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Abstract
The invention relates to 7-alkone lithocholic acid preparing method. It includes the following steps: dissolving the compound into the organic solvent to form electrolyte, electrolyzing the electrolyte by constant current at oxidizing medium condition to gain the object. The electrolyzing current density is 47.6A/m<2>-190.4A/m<2>. The invention has the advantages of moderate operation condition, green, simplifying ursodesoxycholic acid preparing steps.
Description
Technical field
The present invention relates to a kind of preparation method of 7-ketone lithocholic acid, particularly adopt electrolytic process to prepare the method for 7-ketone lithocholic acid.
Background technology
7-ketone lithocholic acid [7K-LCA, its structure is suc as formula shown in (1)] is the important intermediate of preparation ursodesoxycholic acid (UDCA).Ursodesoxycholic acid is mainly used in diseases such as treatment various courage diseases (gallbladdergallstonecholetithiasis, cholecystitis), hepatitis and hyperlipidemia, is unique medicine that the FDA approval is used to treat primary biliary cirrhosis (PBC).Ursodesoxycholic acid is the main effective constituent of rare Chinese medicine bear gall, and still, bear gall is very rare resource, is difficult to satisfy the demand of clinical application.
Since the fifties, having occurred with animal cholic acid class material is the chemical synthesis process of raw material.Japanese Patent (JP 0161496) report is a raw material with ox, sheep cholic acid, through 3 hydroxyls of esterification selective protection, uses (NH then
4)
2Ce (NO
3)
3Get the 7-keto cholanic acid with 7 hydroxyls of NaBr oxidation, again with MeSO
2Cl react 12 α-methylsulfonyl ester, at organic amine Me
2Heating was eliminated methylsulfonyl and is got Δ 11-3 α-7-carbonyl ursodeoxycholic acid methyl esters under NPh existed, and got Δ 11-3 α with sodium Metal 99.5 hydrogenolysis in propyl carbinol again, and 7 beta-dihydroxyl ursodeoxycholic acid methyl esters get ursodesoxycholic acid with the Pd/C catalytic hydrogenation.After the sixties, people mainly are devoted to the Stereoselective reduction of 7-ketone lithocholic acid to the study on the synthesis of ursodesoxycholic acid, promptly reduce in lower alcohol with basic metal.1977 (JP 52007950) such as Saito report with potassium metal reduction 7-ketone lithocholic acid, is 7 β hydroxyls with 7 carbonyl reductions in the trimethyl carbinol selectively, thus the preparation ursodesoxycholic acid, yield is 99.9%, and purity is 96.1%, and m.p. is 196 ℃.Japanese Patent (JP 05032692) report 7-ketone lithocholic acid is handled with KOH in propyl alcohol, and backflow 2h uses H
2-Raney Ni is at 80 ℃, and 4.9 * 105Pa reaction 3.5h down gets 99.0% the ursodesoxycholic acid miscellany that contains cholic acid, and the reduction yield is that 97.7%, 7 beta selective is 92.5%.(chemical journal .1998,46 (11): 1150) report is a raw material with the staple Hyodeoxycholic Acid in the Fel Sus domestica to Zhou Weishan in 1988 etc., utilizes 1,2 ketone group sigmatropic reaction to make 6 hydroxyls be converted into 7 hydroxyls.The total recovery of this method is about about 15%.1991; (Chinese science (B collects) .1991, (7): 680) reported to be raw material, synthetic change 1 compound such as Wang Zhongqi with 4-alkene-3-ketone structure with the Hyodeoxycholic Acid; Then through 6; 7 dehydrogenations, epoxidation, catalytic hydrogenations reach the purpose of rebuilding 5 β hydrogen configurations, and have obtained 7 hydroxyls, further synthetic then ursodesoxycholic acid.The key of this method is when 7 α hydroxyls form, has also obtained the configuration of 5 β hydrogen.The total recovery of the synthetic ursodesoxycholic acid of this method is 26%.
To sum up, chemical synthesis exists synthesis step many, and operational condition is harsh, and yield is low, and shortcoming such as easy contaminate environment.
After the eighties, methods such as microbe fermentation method, enzyme chemical method, electrochemical synthesis also grow up.Sawada in 1980 (Appl.Environ.Microbial.1982,44 (6): 1249-1252) wait and reported and a kind ofly prepare the method for ursodesoxycholic acid from lithocholic acid that yield is 50% through Fusarium scouring rush sickle spore Fusarium equiseti M-41.(J.Lipid.Res.1981,22 (7): 1060-1068) reported the method for utilizing the human intestinal flora to transform to ursodesoxycholic acid at external realization Chenodiol (CDCA), total conversion rate is 80～90% to Hirano in 1981.Kole in 1985 etc. (FEMS Microbiol.Lett., 1985,28 (1), 69-72) utilize the immobilized cell of C.absonum to carry out the exploration that ursodesoxycholic acid transforms first, on the whole, transformation efficiency is too low, is merely about 20%.
Microbe fermentation method subject matter is that screening is stable, bacterial strain is relatively more difficult efficiently, and tunning is complicated, separation difficulty.
The research direction of electrochemical method for synthesizing is mainly being sought suitable Stereoselective reduction catalyzer.Japanese Patent (JP06002184) report 7-ketone lithocholic acid can be converted into ursodesoxycholic acid with electrochemical reduction in lower alcohol, studied the influence to the ursodesoxycholic acid productive rate of different electric flow density and conduction time.(US 4 for USP; 547; 271) be reported in the electrolytic solution that contains lower alcohol; Adding weak acid bipolarity compound such as DMSO 99.8MIN., tetramethyl-urea etc., is that electrode electro Chemical reduction 7-ketone lithocholic acid is a ursodesoxycholic acid with ruthenium coating-Ti alloy and mercury, selects suitable electrolyte system can obtain the higher ursodesoxycholic acid of productive rate.This method is relatively simple, safety.
In sum, the electrochemical synthesis method has special advantages in the preparation of ursodesoxycholic acid (UDCA).Given this, if can realize adopting the electrochemical synthesis method to prepare 7-ketone lithocholic acid, then will overcome shortcomings such as having preparation process is long, efficient is low, product separation difficulty, the harsh and easy contaminate environment of operational condition among the existing ursodesoxycholic acid preparation method.
Summary of the invention
The object of the invention is, a kind of method that adopts electrolytic process to prepare 7-ketone lithocholic acid is provided.
The present invention adopts electrolytic process, and oxidizing medium indirect oxidation Chenodiol [CDCA, its structure is suc as formula shown in (2)] inexpensive relatively, that be easy to get makes 7-ketone lithocholic acid (important intermediate of synthetic ursodesoxycholic acid).
(2)
The said method for preparing 7-ketone lithocholic acid of the present invention; It is characterized in that; Said preparing method's key step is: structure is dissolved in organic solvent suc as formula the compound shown in (2) constitutes electrolytic solution; Under the condition that has oxidizing medium to exist, the said electrolytic solution of constant-current electrolysis obtains target compound [structure is suc as formula shown in (1)], and wherein: electrolytic current density is 47.6A/m
2～190.4A/m
2(preferred electrolytic current density is 95.2A/m
2).
In the present invention, the organic solvent of recommending to use is C
1～C
3Monohydroxy-alcohol or acetonitrile, best be acetonitrile, methyl alcohol or ethanol: the oxidizing medium of recommending to use is a water-soluble bromide, and the best is a Potassium Bromide.
With the oxidizing medium is that Potassium Bromide is an example, and principal reaction equation of the present invention is following:
Anodic electrode reaction: 2Br
--2e → Br
2
Can know that by technique scheme the present invention has operational condition gentleness, environmentally friendly and simplified the advantages such as preparation process of ursodesoxycholic acid (UDCA).
Embodiment
The said electrolysis of the present invention can be carried out in diaphragm type or non-diaphragm electrolytic cell, and division is following:
I. in diaphragm electrolytic cell, the present invention includes following steps:
(1) respectively 0.4g KBr is dissolved in the 13ml deionized water, (preferred 2.0～2.5g) Chenodiols (CDCA) are dissolved in 50ml acetonitrile, methyl alcohol or the ethanol 1.0～2.5g, put into the anolyte compartment as anolyte after then two solution being mixed; Dilute sulphuric acid with 63ml 20% is a catholyte; With PbO
2/ Ti mesh electrode, titanium ruthenium mesh electrode or graphite plate electrode are anode, and stainless steel plate is a negative electrode; HF-101 strong-acid type cation exchange membrane (Shanghai Huakai Technology & Trade Co., Ltd.) is a barrier film, and the electric current during with dc current regulator power supply control electrolysis carries out constant-current electrolysis, and electrolytic current density is 47.6 A/m
2～190.4A/m
2, adopt thin layer chromatography (TLC) to judge that (used developing agent is trichloromethane/methyl alcohol/glacial acetic acid to reaction end, and its volume ratio is 40: 2: 1; Developer is 20% phosphomolybdic acid ethanol solution, and colour temp is about 100 ℃), behind thin-layer chromatography; When raw material point disappears, stop electrolysis;
(2) will carry out suction filtration through the anolyte after step (1) electrolysis, filtrating under agitation slowly joins in the deionized water about 700ml, leaves standstill, and has deposition to separate out, and filters, and filter cake is target compound (7-ketone lithocholic acid) after drying.
II. in non-diaphragm electrolytic cell, the present invention includes following steps:
(1) respectively 0.4g KBr is dissolved in the 13ml deionized water, (preferred 2.0～2.5g) CDCA are dissolved in 50ml acetonitrile, methyl alcohol or the ethanol 1.0～2.5g, put into electrolyzer as electrolytic solution after then two solution being mixed; With PbO
2/ Ti mesh electrode, titanium ruthenium mesh electrode or graphite plate electrode are anode, and stainless steel plate is a negative electrode; Electric current during with dc current regulator power supply control electrolysis carries out constant-current electrolysis, and electrolytic current density is 47.6A/m
2～190.4A/m
2, adopt TLC to judge reaction end (used developing agent and ratio thereof and developer and colour temp are the same), when raw material point disappears, stop electrolysis;
(2) will carry out suction filtration through the electrolytic solution after step (1) electrolysis, filtrating under agitation slowly joins in the deionized water about 700ml, leaves standstill, and has deposition to separate out, and filters, and filter cake is target compound (7-ketone lithocholic acid) after drying.
Through instance the present invention is described further below, its purpose only is better to understand content of the present invention and unrestricted protection scope of the present invention:
Among the embodiment, adopt performance liquid chromatography (HPLC) that product (7-ketone lithocholic acid) is carried out quantitative analysis below.Except that specifying, the testing conditions of HPLC is: chromatographic column is a RP C18 reversed-phase column, and moving phase is that volume ratio is 70: 30 acetonitrile and the phosphoric acid buffer of pH=3.0, and flow velocity is 1.0ml/min, and column temperature is a room temperature, and the outer survey of purple inspection wavelength is 208nm.
Embodiment 1
0.4g KBr is dissolved in the 13ml secondary deionized water, takes by weighing 2.0gCDCA and be dissolved in the 50ml acetonitrile, the anolyte compartment that puts into H type diaphragm sell after two solution are mixed is as anolyte.Dilute sulphuric acid with 63ml 20% is a catholyte.HF-101 strong-acid type cation exchange membrane is a barrier film.With PbO
2/ Ti mesh electrode is an anode, and stainless steel plate is a negative electrode.Used current density is 95.2A/m
2, detect through TLC, when the CDCA primitive reaction is finished, stop electrolysis, be 2.5h conduction time.Obtain 7K-LCA bullion 1.697g, HPLC content is 90.4%.Calculate productive rate and current efficiency and be respectively 77.1% and 84.2%.Product records fusing point behind column chromatography, recrystallization purifying: m.p.200～203 ℃ (literature value: 201～203 ℃).1H nuclear magnetic resonance spectroscopy result: δ 0.5～1.8,2.1,2.2 (33H, m ,-CH
2-,-CH
2CH
3,-CH
2CH
2-) δ 1.9 (1H, d ,-CH-), δ 2.4 (1H, t ,-COCH), δ 2.8 (1H, q ,-CHCHCH
2-), δ 4.5 (1H, s ,-OH), δ 11.4 (1H, s ,-COOH).
Embodiment 2
0.4g KBr is dissolved in the 13ml secondary deionized water, takes by weighing 2.0gCDCA and be dissolved in the 50ml ethanol, the anolyte compartment that puts into H type diaphragm sell after two solution are mixed is as anolyte.Dilute sulphuric acid with 63ml 20% is a catholyte.HF-101 strong-acid type cation exchange membrane is a barrier film.With PbO
2/ Ti mesh electrode is an anode, and stainless steel plate is a negative electrode.Used current density is 95.2A/m
2, detect through TLC, when the CDCA primitive reaction is finished, stop electrolysis, be about 4.5h conduction time.Obtain 7K-LCA bullion 1.652g, HPLC content is 89.5%.Calculate productive rate and current efficiency and be respectively 74.3% and 45.5%.After product is purified, record fusing point: m.p.200～203 ℃ (literature value: 201～203 ℃).
Embodiment 3
0.4g KBr is dissolved in the 13ml secondary deionized water, takes by weighing 2.0gCDCA and be dissolved in the 50ml acetonitrile, the anolyte compartment that puts into H type diaphragm sell after two solution are mixed is as anolyte.Dilute sulphuric acid with 63ml 20% is a catholyte.HF-101 strong-acid type cation exchange membrane is a barrier film.With PbO
2/ Ti mesh electrode is an anode, and stainless steel plate is a negative electrode.Used current density is 190.4A/m
2, detect through TLC, when the CDCA primitive reaction is finished, stop electrolysis, be 2.25h conduction time.Obtain 7K-LCA bullion 1.423g, HPLC content is 87.9%.Calculate product productive rate and current efficiency and be respectively 62.8% and 38.1%.After product is purified, record fusing point: m.p.200～203 ℃ (literature value: 201～203 ℃).
Embodiment 4
0.4g KBr is dissolved in the 13ml secondary deionized water, takes by weighing 2.0gCDCA and be dissolved in the 50ml acetonitrile, the anolyte compartment that puts into H type diaphragm sell after two solution are mixed is as anolyte.Dilute sulphuric acid with 63ml 20% is a catholyte.HF-101 strong-acid type cation exchange membrane is a barrier film.With PbO
2/ Ti mesh electrode is an anode, and stainless steel plate is a negative electrode.Used current density is 47.6A/m
2, detect through TLC, when the CDCA primitive reaction is finished, stop electrolysis, be 4.5h conduction time.Obtain 7K-LCA bullion 1.589g, HPLC content is 86.7%.Calculate product productive rate and current efficiency and be respectively 69.2% and 84.0%.After product is purified, record fusing point: m.p.200～203 ℃ (literature value: 201～203 ℃).
Embodiment 5
0.4g KBr is dissolved in the 13ml secondary deionized water, takes by weighing 2.5gCDCA and be dissolved in the 50ml acetonitrile, the anolyte compartment that puts into H type diaphragm sell after two solution are mixed is as anolyte.Dilute sulphuric acid with 63ml 20% is a catholyte.HF-101 strong-acid type cation exchange membrane is a barrier film.With PbO
2/ Ti mesh electrode is an anode, and stainless steel plate is a negative electrode.Used current density is 95.2A/m
2, detect through TLC, when the CDCA primitive reaction is finished, stop electrolysis, be 3.5h conduction time.Obtain 7K-LCA bullion 1.678g, HPLC content is 86.4%.Calculate product productive rate and current efficiency and be respectively 58.3% and 56.9%.After product is purified, record fusing point: m.p.200～203 ℃ (literature value: 201～203 ℃).
Embodiment 6
0.4g KBr is dissolved in the 13ml secondary deionized water, takes by weighing 2.0gCDCA and be dissolved in the 50ml acetonitrile, the anolyte compartment that puts into H type diaphragm sell after two solution are mixed is as anolyte.Dilute sulphuric acid with 63ml 20% is a catholyte.HF-101 strong-acid type cation exchange membrane is a barrier film.With the graphite plate electrode is anode, and stainless steel plate is a negative electrode.Used current density is 95.2A/m
2, detect through TLC, when the CDCA primitive reaction is finished, stop electrolysis, be about 3.3h conduction time.Obtain 7K-LCA bullion 1.597g, HPLC content is 88.7%.Calculate product productive rate and current efficiency and be respectively 71.2% and 58.6%.
Embodiment 17
0.4g KBr is dissolved in the 13ml secondary deionized water, takes by weighing 2.0gCDCA and be dissolved in the 50ml acetonitrile, put into undivided cell as electrolytic solution after two solution are mixed.With PbO
2/ Ti mesh electrode is an anode, and stainless steel plate is a negative electrode.Used current density is 95.2A/m
2, detect through TLC, when the CDCA primitive reaction is finished, stop electrolysis, be about 3.8h conduction time.Obtain 7K-LCA bullion 1.519g, HPLC content is 89.7%.Calculate product productive rate and current efficiency and be respectively 68.4% and 48.8%.After product is purified, record fusing point: m.p.200～203 ℃ (literature value: 201～203 ℃).
Embodiment 8
0.4g KBr is dissolved in the 13ml secondary deionized water, takes by weighing 2.0gCDCA and be dissolved in the 50ml ethanol, put into undivided cell as electrolytic solution after two solution are mixed.With PbO
2/ Ti mesh electrode is an anode, and stainless steel plate is a negative electrode.Used current density is 95.2A/m
2, detect through TLC, when the CDCA primitive reaction is finished, stop electrolysis, be about 8.4h conduction time.Obtain 7K-LCA bullion 1.627g, HPLC content is 88.4%.Calculate product productive rate and current efficiency and be respectively 72.3% and 23.4%.After product is purified, record fusing point: m.p.200～203 ℃ (literature value: 201～203 ℃).
Claims (8)
1. the preparation method of a 7-ketone lithocholic acid is characterized in that, said preparing method's key step is: structure is dissolved in organic solvent suc as formula the compound shown in (2) constitutes electrolytic solution,
Under the condition that has oxidizing medium to exist, the said electrolytic solution of constant-current electrolysis obtains target compound,
Wherein: electrolytic current density is 47.6A/m
2～190.4A/m
2, described oxidizing medium is a water-soluble bromide.
2. preparation method as claimed in claim 1 is characterized in that, wherein said organic solvent is C
1～C
3Monohydroxy-alcohol or acetonitrile.
3. preparation method as claimed in claim 2 is characterized in that, wherein said organic solvent is acetonitrile, methyl alcohol or ethanol.
4. preparation method as claimed in claim 1 is characterized in that, wherein said oxidizing medium is a Potassium Bromide.
5. like any described preparation method in the claim 1～4, it is characterized in that said preparation method comprises the steps:
(1) respectively 0.4g KBr is dissolved in the 13ml deionized water, 1.0～2.5g Chenodiol is dissolved in 50ml acetonitrile, methyl alcohol or the ethanol, puts into the anolyte compartment as anolyte after then two solution being mixed; Dilute sulphuric acid with 63ml 20% is a catholyte; With PbO
2/ Ti mesh electrode, titanium ruthenium mesh electrode or graphite plate electrode are anode, and stainless steel plate is a negative electrode; HF-101 strong-acid type cation exchange membrane is a barrier film, and the electric current during with dc current regulator power supply control electrolysis carries out constant-current electrolysis, and electrolytic current density is 47.6A/m
2～190.4A/m
2, behind thin-layer chromatography, when raw material point disappears, stop electrolysis;
(2) will carry out suction filtration through the anolyte after step (1) electrolysis, filtrating under agitation slowly joins in the 700ml deionized water, leaves standstill, and has deposition to separate out, and filters, and filter cake is target compound after drying.
6. preparation method as claimed in claim 5 is characterized in that, wherein electrolytic current density is 95.2A/m
2
7. like any described preparation method in the claim 1～4, it is characterized in that said preparation method comprises the steps:
(1) respectively 0.4g KBr is dissolved in the 13ml deionized water, 1.0～2.5g Chenodiol is dissolved in 50ml acetonitrile, methyl alcohol or the ethanol, puts into electrolyzer as electrolytic solution after then two solution being mixed; With PbO
2/ Ti mesh electrode, titanium ruthenium mesh electrode or graphite plate electrode are anode, and stainless steel plate is a negative electrode; Electric current during with dc current regulator power supply control electrolysis carries out constant-current electrolysis, and electrolytic current density is 47.6A/m
2～190.4A/m
2, behind thin-layer chromatography, when raw material point disappears, stop electrolysis;
(2) will carry out suction filtration through the electrolytic solution after step (1) electrolysis, filtrating under agitation slowly joins in the 700ml deionized water, leaves standstill, and has deposition to separate out, and filters, and filter cake is target compound after drying.
8. preparation method as claimed in claim 7 is characterized in that, wherein electrolytic current density is 95.2A/m
2
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107200763A (en) * | 2017-06-01 | 2017-09-26 | 江苏佳尔科药业集团有限公司 | A kind of method using chenodeoxycholic acid as Material synthesis lithocholic acid |
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| CN102660755B (en) * | 2012-06-04 | 2016-08-03 | 华东理工大学 | Electroreduction prepares the method for ursodesoxycholic acid |
| CN104328454B (en) * | 2014-09-29 | 2017-11-28 | 华东理工大学 | The method that stereoselectivity prepares urso |
| CN106868534B (en) * | 2016-11-16 | 2018-05-25 | 成都市新功生物科技有限公司 | The method that Technique of Nano Pd electro-catalysis chenodeoxycholic acid synthesizes ursodesoxycholic acid |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1391735A (en) * | 1963-10-17 | 1965-03-12 | Tetsuo Sato | Process for preparing ursodesoxycholic acid |
| US4147601A (en) * | 1977-07-28 | 1979-04-03 | Ppg Industries, Inc. | Electrolytic production of hydrobromic acid |
| FR2653126A1 (en) * | 1989-10-17 | 1991-04-19 | Sanofi Sa | Process for the preparation of diacetoxycholanates |
| US6811679B2 (en) * | 2003-03-28 | 2004-11-02 | Council Of Scientific & Industrial Research | Process for electrochemical oxidation of bromide to bromine |
| CN1771353A (en) * | 2003-03-31 | 2006-05-10 | 科学和工业研究委员会 | A process for electrochemical oxidation of bromide to bromine |
-
2006
- 2006-07-27 CN CN200610029416A patent/CN1912192B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1391735A (en) * | 1963-10-17 | 1965-03-12 | Tetsuo Sato | Process for preparing ursodesoxycholic acid |
| US4147601A (en) * | 1977-07-28 | 1979-04-03 | Ppg Industries, Inc. | Electrolytic production of hydrobromic acid |
| FR2653126A1 (en) * | 1989-10-17 | 1991-04-19 | Sanofi Sa | Process for the preparation of diacetoxycholanates |
| US6811679B2 (en) * | 2003-03-28 | 2004-11-02 | Council Of Scientific & Industrial Research | Process for electrochemical oxidation of bromide to bromine |
| CN1771353A (en) * | 2003-03-31 | 2006-05-10 | 科学和工业研究委员会 | A process for electrochemical oxidation of bromide to bromine |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107200763A (en) * | 2017-06-01 | 2017-09-26 | 江苏佳尔科药业集团有限公司 | A kind of method using chenodeoxycholic acid as Material synthesis lithocholic acid |
| CN107200763B (en) * | 2017-06-01 | 2019-05-03 | 江苏佳尔科药业集团有限公司 | A method of using chenodeoxycholic acid as Material synthesis lithocholic acid |
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| CN1912192A (en) | 2007-02-14 |
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