CN109468660A - A kind of production technology of Austria's shellfish cholic acid - Google Patents
A kind of production technology of Austria's shellfish cholic acid Download PDFInfo
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- CN109468660A CN109468660A CN201811562602.0A CN201811562602A CN109468660A CN 109468660 A CN109468660 A CN 109468660A CN 201811562602 A CN201811562602 A CN 201811562602A CN 109468660 A CN109468660 A CN 109468660A
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- production technology
- shellfish cholic
- cholic acid
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B3/00—Electrolytic production of organic compounds
- C25B3/20—Processes
- C25B3/25—Reduction
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- Chemical Kinetics & Catalysis (AREA)
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- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
The invention discloses a kind of production technologies of shellfish cholic acid difficult to understand, characterized by the following steps: in diaphragm cell, using cathode as working electrode, using the solution that 6- ethylidene -7- ketone cholelith acid dissolution is formed in conductive solvent as catholyte, anode is auxiliary electrode, using aqueous acid as anolyte, constant-current electrolysis, the current density of the constant current is 10~100A/m2, the temperature of the electrolysis is 10~70 DEG C.Place that purpose of the invention is to overcome the shortcomings in the prior art, provides that a kind of process route is short, and easy to operate, highly-safe, production cost is relatively low, the production technology of the good shellfish cholic acid difficult to understand of the feature of environmental protection.
Description
Technical field
The present invention relates to a kind of production technologies of shellfish cholic acid difficult to understand.
Background technique
Shellfish cholic acid also known as 6- α-ethyl chenodeoxycholic acid difficult to understand, 6- ethyl chenodeoxycholic acid.It is a kind of non-natural Cholic acids
Object is closed, is mainly used for treating primary biliary cirrhosis and non-alcohol fatty liver.
Shellfish cholic acid difficult to understand is the emphasis new drug that disease in the liver and gallbladder therapy field is concerned, it is considered to be future prospect is extremely good
" cookle " type drug.
Lot of domestic and foreign preparation factory adds all in positive research and development using shellfish cholic acid difficult to understand as the drug of effective component, market
Demand to shellfish cholic acid bulk pharmaceutical chemicals difficult to understand is extremely vigorous.Synthesize the basic line of shellfish cholic acid difficult to understand at present substantially with chenodeoxycholic acid or
7- ketone group cholelith acid is starting material, by multistep reaction preparation 6- ethylidene -7- ketone cholelith acid, as preparation shellfish cholic acid difficult to understand
Key intermediate.
Shellfish cholic acid difficult to understand is prepared by this key intermediate, current most important method is first in methanol solvate equal solvent,
Using hydrogen as hydrogen source, using for example activated carbon supported palladium of noble metal catalyst or palladium dydroxide catalytic hydrogenation, 6- ethyl-is obtained
7- ketone group cholelith acid.7- ketone group is reduced to Alpha-hydroxy, obtained by the 6- ethyl 7- ketone cholelith acid of acquisition using sodium borohydride reduction
To purpose product Austria shellfish cholic acid.
The course that shellfish cholic acid difficult to understand is prepared by this sour key intermediate of 6- ethylidene -7- ketone group cholelith, will pass through two steps
Reaction is learned, in some conditions, the 6- ethyl -7- ketone cholelith acid that catalytic hydrogenation obtains is 6- α-ethyls and 6- β-ethyls
Mixture, will also be by an indexable process, and course is longer.Time cost and human cost are bigger.
And catalytic hydrogenation step is needed using hydrogen largely inflammable and explosive using height, and danger of production process is very
Greatly.
In catalytic hydrogenation, the catalyst used, such as activated carbon supported Metal Palladium or activated carbon supported hydrogen-oxygen
Change the material of palladium and highly dangerous, it is careless slightly in last handling process, contact with air and is possible to burn rapidly, initiation
Fire hazard.
The applicable noble metal catalyst price of catalytic hydrogenation is also fairly expensive, and production cost is quite high.
Summary of the invention
Place that purpose of the invention is to overcome the shortcomings in the prior art, it is short to provide a kind of process route, operation letter
Just, highly-safe, production cost is relatively low, the production technology of the good shellfish cholic acid difficult to understand of the feature of environmental protection.
A kind of production technology of Austria's shellfish cholic acid, it is characterised in that the following steps are included:
In diaphragm cell, using cathode as working electrode, with 6- ethylidene -7- ketone cholelith acid dissolution in conductive solvent
For the solution of formation as catholyte, anode is auxiliary electrode, using aqueous acid as anolyte, constant-current electrolysis, and institute
The current density for stating constant current is 10~100A/m2, the temperature of the electrolysis is 10~70 DEG C.
The production technology of a kind of shellfish cholic acid difficult to understand as described above, it is characterised in that the conductive solvent is electric containing supporting
Solve the water-containing organic solvent of matter.
The production technology of a kind of shellfish cholic acid difficult to understand as described above, it is characterised in that aqueous containing supporting electrolyte has
Solvent is the mixed solvent that lower alcohol and water are formed, and wherein the volume content of water is 5~50%.
The production technology of a kind of shellfish cholic acid difficult to understand as described above, it is characterised in that the lower alcohol is methanol, ethyl alcohol, third
The mixture of one or more of alcohol, isopropanol, ethylene glycol.
The production technology of a kind of shellfish cholic acid difficult to understand as described above, it is characterised in that the supporting electrolyte is salt electrolysis
Matter, the additional amount of the supporting electrolyte is in 0.01~0.1mol/L.
The production technology of a kind of shellfish cholic acid difficult to understand as described above, it is characterised in that the salt electrolyte is potassium bromide, four
One or both of butyl amine bromide.
The production technology of a kind of shellfish cholic acid difficult to understand as described above, it is characterised in that the cathode of the diaphragm cell is nickel plate
Electrode or sheet tin electrode or stereotype electrode, the anode of the diaphragm cell be platinum electrode, graphite electrode, titanium ruthenium mesh electrode or
One of ti-supported lead dioxide electric mesh electrode.
A kind of production technology of shellfish cholic acid difficult to understand as described above, it is characterised in that the diaphragm be HF-101 strong-acid type sun from
Proton exchange or Du Pont's N-117 proton exchange membrane.
A kind of production technology of shellfish cholic acid difficult to understand as described above, it is characterised in that the aqueous acid be concentration be 1%~
20% aqueous sulfuric acid.
A kind of production technology of shellfish cholic acid difficult to understand as described above, it is characterised in that effective electrode area 5-15cm2。
In the present invention, the compound structure of the formula 6- ethylidene -7- ketone cholelith sour (I) is as follows:
By the electrolyte current density be 10~100A/m2Constant current restore lower acquisition shellfish cholic acid difficult to understand
(II) solution, shellfish cholic acid (II) structural formula difficult to understand are as follows:
In conclusion the present invention compared with the existing technology the beneficial effect is that:
One, the present invention uses the method for electroreduction, and in a cell, reduction 6- ethylidene -7- ketone cholelith acid a, step obtains
To shellfish cholic acid difficult to understand.Process route is short, easy to operate.
Two, the invention avoids the large-scale uses of the hydrogen of highly dangerous, enhance the safety of production process.
Three, the invention avoids the use of expensive noble metal catalyst, production cost is reduced.
Four, the invention avoids the use of chemical reducing agent, pollutant emission is reduced, significantly reduces environmental protection pressure.
Specific embodiment
The invention will be further described With reference to embodiment:
Embodiment 1
A kind of production technology of Austria's shellfish cholic acid, comprising the following steps:
In diaphragm cell, using cathode as working electrode, with 6- ethylidene -7- ketone cholelith acid dissolution in conductive solvent
For the solution of formation as catholyte, anode is auxiliary electrode, using aqueous acid as anolyte, constant-current electrolysis, and institute
The current density for stating constant current is 10A/m2, the temperature of the electrolysis is 10 DEG C.
Wherein the conductive solvent is the mixed solvent that methanol and water are formed, and wherein the volume content of water is 5%.
Wherein the supporting electrolyte is potassium bromide, and the additional amount of the supporting electrolyte is in 0.01mol/L.
The cathode of the diaphragm cell is nickel plate electrode, and the anode of the diaphragm cell is platinum electrode.
The diaphragm is HF-101 Strong acid cation exchange membrane.
The aqueous acid is the aqueous sulfuric acid that concentration is 1%.
Embodiment 2
A kind of production technology of Austria's shellfish cholic acid, comprising the following steps:
In diaphragm cell, using cathode as working electrode, with 6- ethylidene -7- ketone cholelith acid dissolution in conductive solvent
For the solution of formation as catholyte, anode is auxiliary electrode, using aqueous acid as anolyte, constant-current electrolysis, and institute
The current density for stating constant current is 100A/m2, the temperature of the electrolysis is 70 DEG C.
Wherein the conductive solvent is the mixed solvent that ethyl alcohol and water are formed, and wherein the volume content of water is 50%.
Wherein the supporting electrolyte is four butyl bromation amine, and the additional amount of the supporting electrolyte is in 0.1mol/L.
The cathode of the diaphragm cell is sheet tin electrode, and the anode of the diaphragm cell is graphite electrode.
The diaphragm is Du Pont N-117 proton exchange membrane.
The aqueous acid is the aqueous sulfuric acid that concentration is 20%.
Embodiment 3
A kind of production technology of Austria's shellfish cholic acid, comprising the following steps:
In diaphragm cell, using cathode as working electrode, with 6- ethylidene -7- ketone cholelith acid dissolution in conductive solvent
For the solution of formation as catholyte, anode is auxiliary electrode, using aqueous acid as anolyte, constant-current electrolysis, and institute
The current density for stating constant current is 50A/m2, the temperature of the electrolysis is 40 DEG C.
Wherein the conductive solvent is the mixed solvent that propyl alcohol and water are formed, and wherein the volume content of water is 30%.
Wherein the supporting electrolyte is potassium bromide, and the additional amount of the supporting electrolyte is in 0.05mol/L.
The cathode of the diaphragm cell is stereotype electrode, and the anode of the diaphragm cell is titanium ruthenium mesh electrode.
The diaphragm is HF-101 Strong acid cation exchange membrane.
The aqueous acid is the aqueous sulfuric acid that concentration is 10%.
Wherein effective electrode area is 10cm2。
Embodiment 4
A kind of production technology of Austria's shellfish cholic acid, comprising the following steps:
In diaphragm cell, using cathode as working electrode, with 6- ethylidene -7- ketone cholelith acid dissolution in conductive solvent
For the solution of formation as catholyte, anode is auxiliary electrode, using aqueous acid as anolyte, constant-current electrolysis, and institute
The current density for stating constant current is 20A/m2, the temperature of the electrolysis is 60 DEG C.
Wherein the conductive solvent is the mixed solvent that isopropanol and water are formed, and wherein the volume content of water is 40%.
Wherein the supporting electrolyte is four butyl bromation amine, and the additional amount of the supporting electrolyte is in 0.02mol/L.
The cathode of the diaphragm cell is stereotype electrode, and the anode of the diaphragm cell is that ti-supported lead dioxide electric is netted
Electrode.
The diaphragm is Du Pont N-117 proton exchange membrane.
The aqueous acid is the aqueous sulfuric acid that concentration is 15%.
Wherein effective electrode area is 10cm2。
Embodiment 5
A kind of production technology of Austria's shellfish cholic acid, comprising the following steps:
In diaphragm cell, using cathode as working electrode, with 6- ethylidene -7- ketone cholelith acid dissolution in conductive solvent
For the solution of formation as catholyte, anode is auxiliary electrode, using aqueous acid as anolyte, constant-current electrolysis, and institute
The current density for stating constant current is 80A/m2, the temperature of the electrolysis is 40 DEG C.
Wherein the conductive solvent is the mixed solvent that methanol, ethyl alcohol and water are formed, and wherein the volume content of water is 10%.
Wherein the supporting electrolyte is potassium bromide, and the additional amount of the supporting electrolyte is in 0.08mol/L.
The cathode of the diaphragm cell is sheet tin electrode, and the anode of the diaphragm cell is platinum electrode.
The diaphragm is HF-101 Strong acid cation exchange membrane.
The aqueous acid is the aqueous sulfuric acid that concentration is 5%.
Wherein effective electrode area is 10cm2。
Basic principles and main features and advantages of the present invention of the invention have been shown and described above.The skill of the industry
Art personnel it should be appreciated that the present invention is not limited to the above embodiments, the above embodiments and description only describe
The principle of the present invention, without departing from the spirit and scope of the present invention, various changes and improvements may be made to the invention, these
Changes and improvements all fall within the protetion scope of the claimed invention.The claimed scope of the invention by appended claims and
Its equivalent thereof.
Claims (10)
1. a kind of production technology of Austria's shellfish cholic acid, it is characterised in that the following steps are included:
In diaphragm cell, using cathode as working electrode, formed in conductive solvent with 6- ethylidene -7- ketone cholelith acid dissolution
Solution as catholyte, anode is auxiliary electrode, using aqueous acid as anolyte, constant-current electrolysis, the perseverance
The current density of electric current is 10~100A/m2, the temperature of the electrolysis is 10~70 DEG C.
2. a kind of production technology of shellfish cholic acid difficult to understand according to claim 1, it is characterised in that the conductive solvent be containing
There is the water-containing organic solvent of supporting electrolyte.
3. a kind of production technology of shellfish cholic acid difficult to understand according to claim 2, it is characterised in that described to contain supporting electrolyte
Water-containing organic solvent be mixed solvent that lower alcohol and water are formed, wherein the volume content of water is 5~50%.
4. a kind of production technology of shellfish cholic acid difficult to understand according to claim 2, it is characterised in that the lower alcohol is methanol, second
The mixture of one or more of alcohol, propyl alcohol, isopropanol, ethylene glycol.
5. a kind of production technology of shellfish cholic acid difficult to understand according to claim 2, it is characterised in that the supporting electrolyte is salt
Class electrolyte, the additional amount of the supporting electrolyte is in 0.01~0.1mol/L.
6. a kind of production technology of shellfish cholic acid difficult to understand according to claim 2, it is characterised in that the salt electrolyte is bromine
Change one or both of potassium, four butyl bromation amine.
7. a kind of production technology of shellfish cholic acid difficult to understand according to claim 1, it is characterised in that the yin of the diaphragm cell
Extremely nickel plate electrode or sheet tin electrode or stereotype electrode, the anode of the diaphragm cell are platinum electrode, graphite electrode, titanium ruthenium net
One of shape electrode or ti-supported lead dioxide electric mesh electrode.
8. a kind of production technology of shellfish cholic acid difficult to understand according to claim 1, it is characterised in that the diaphragm is that HF-101 is strong
Acid type cation-exchange membrane or Du Pont's N-117 proton exchange membrane.
9. a kind of production technology of shellfish cholic acid difficult to understand according to claim 1, it is characterised in that the aqueous acid is concentration
For 1%~20% aqueous sulfuric acid.
10. a kind of production technology of shellfish cholic acid difficult to understand according to claim 1, it is characterised in that effective electrode area 5-
15cm2。
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811562602.0A CN109468660A (en) | 2018-12-20 | 2018-12-20 | A kind of production technology of Austria's shellfish cholic acid |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811562602.0A CN109468660A (en) | 2018-12-20 | 2018-12-20 | A kind of production technology of Austria's shellfish cholic acid |
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| Publication Number | Publication Date |
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| CN109468660A true CN109468660A (en) | 2019-03-15 |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102660755A (en) * | 2012-06-04 | 2012-09-12 | 华东理工大学 | Method for preparing ursodesoxycholic acid by electro-reduction |
| WO2016080817A1 (en) * | 2014-11-21 | 2016-05-26 | 재단법인 철원플라즈마 산업기술연구원 | Organic light-emitting device |
| CN105669815A (en) * | 2016-03-21 | 2016-06-15 | 苏州敬业医药化工有限公司 | Preparation method of 3Alpha-hydrol-7-oxo-5Beta-cholanic acid |
| CN108676049A (en) * | 2017-11-02 | 2018-10-19 | 华东师范大学 | A kind of preparation method of Austria's shellfish cholic acid, ursodesoxycholic acid and 7- Ketocholic acid |
-
2018
- 2018-12-20 CN CN201811562602.0A patent/CN109468660A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102660755A (en) * | 2012-06-04 | 2012-09-12 | 华东理工大学 | Method for preparing ursodesoxycholic acid by electro-reduction |
| WO2016080817A1 (en) * | 2014-11-21 | 2016-05-26 | 재단법인 철원플라즈마 산업기술연구원 | Organic light-emitting device |
| CN105669815A (en) * | 2016-03-21 | 2016-06-15 | 苏州敬业医药化工有限公司 | Preparation method of 3Alpha-hydrol-7-oxo-5Beta-cholanic acid |
| CN108676049A (en) * | 2017-11-02 | 2018-10-19 | 华东师范大学 | A kind of preparation method of Austria's shellfish cholic acid, ursodesoxycholic acid and 7- Ketocholic acid |
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