CN109943860B - Synthesis method of DL-homocysteine thiolactone hydrochloride - Google Patents
Synthesis method of DL-homocysteine thiolactone hydrochloride Download PDFInfo
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- CN109943860B CN109943860B CN201910345460.0A CN201910345460A CN109943860B CN 109943860 B CN109943860 B CN 109943860B CN 201910345460 A CN201910345460 A CN 201910345460A CN 109943860 B CN109943860 B CN 109943860B
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- homocysteine thiolactone
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Abstract
The invention discloses a method for synthesizing DL-homocysteine thiolactone hydrochloride, which comprises the steps of preparing catholyte by using a hydrochloric acid solution as a medium for DL-homocysteine, and electrolyzing in an electrolytic bath to obtain the DL-homocysteine thiolactone hydrochloride, wherein a roughened glassy carbon electrode is used as a base material for a cathode electrode, and a lead-bismuth alloy covers the surface of the base material. The invention can improve the yield of DL-homocysteine thiolactone hydrochloride.
Description
Technical Field
The present invention relates to the field of synthesis of compounds. More specifically, the invention relates to a method for synthesizing DL-homocysteine thiolactone hydrochloride.
Background
DL-homocysteine thiolactone hydrochloride is a biochemical reagent and a drug intermediate, and can be used for preparing medicines such as cetivone, erdosteine and the like. In the prior art, metal zinc or tin and hydrochloric acid are commonly used for carrying out reduction reaction with DL-homocystine when the medicine is synthesized, and the method can generate a large amount of hydrogen, zinc salt (tin salt) and a large amount of waste water, so that the environment is polluted and the operation is dangerous.
Disclosure of Invention
The invention aims to provide a method for synthesizing DL-homocysteine thiolactone hydrochloride, which improves the synthesis yield.
In order to achieve these objects and other advantages and in accordance with the purpose of the invention, a method for synthesizing DL-homocysteine thiolactone hydrochloride is provided, wherein DL-homocysteine is used as a cathode solution prepared by taking a hydrochloric acid solution as a medium, and is electrolyzed in an electrolytic bath to obtain DL-homocysteine thiolactone hydrochloride, wherein the cathode electrode adopts a roughened glassy carbon electrode as a base material, and the surface of the base material is covered with a lead-bismuth alloy.
Preferably, the glassy carbon electrode coarsening specifically comprises: and coarsening the whole surface of the glassy carbon electrode to the roughness of 8-10 microns.
Preferably, the covering of the surface of the base material with the lead-bismuth alloy specifically comprises:
grinding the lead-bismuth alloy to obtain powder, placing the powder into a CVD furnace, introducing argon at the rate of 5sccm, placing the substrate at the downstream of the argon, heating to 650 ℃ at the heating rate of 20-25 ℃/min, preserving the heat for 1 hour, cooling, and forming a lead-bismuth alloy film on the substrate.
Preferably, the anode of the electrolytic cell is a titanium plate, the anolyte is a sulfuric acid solution with the mass fraction of 3%, the electrolysis temperature is 35-45 ℃, and the current density is 650-700A/m2The electrolysis time is 6-8 hours.
Preferably, the crude DL-homocysteine thiolactone hydrochloride obtained by electrolysis is further subjected to decolorization, filtration, concentration and crystallization, washing, filtration and drying.
Preferably, the DL-homocystine is prepared by taking DL-methionine as a raw material, and specifically comprises the following steps:
step 1, adding DL-methionine, concentrated sulfuric acid with the mass fraction of 98% and a nickel-based metal supported catalyst into a high-pressure reaction kettle in a mass ratio of 1:2.5:0.3, pressurizing to 2Mpa, controlling the temperature to be 120 ℃, and reacting for 6-8 hours to obtain hydrolysate;
and 2, adjusting the pH of the hydrolysate to 5-6 by using a sodium hydroxide solution with the mass fraction of 30% -35%, decoloring by using activated carbon, filtering after decoloring, and concentrating and drying the obtained filtrate to obtain the DL-homocystine.
The invention at least comprises the following beneficial effects:
1. according to the synthesis method of DL-homocysteine thiolactone hydrochloride provided by the invention, on the basis of the prior art, by changing the cathode material and structure, the mechanical strength of the cathode structure is improved, the service life of the electrode is obviously prolonged, the method can be suitable for industrial amplification production, and meanwhile, the improved cathode has high activity, and the yield of DL-homocysteine thiolactone hydrochloride can be further improved.
2. When the DL-homocysteine thiolactone hydrochloride is prepared by taking DL-methionine as a raw material, the yield of the intermediate product DL-homocysteine is an important factor which directly influences the yield of the target product DL-homocysteine thiolactone hydrochloride.
Additional advantages, objects, and features of the invention will be set forth in part in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from practice of the invention.
Drawings
FIG. 1 is a nuclear magnetic resonance image of DL-homocysteine thiolactone hydrochloride in example 1;
FIG. 2 is a graph showing the purity of DL-homocysteine thiolactone hydrochloride in example 1.
Detailed Description
The present invention is further described in detail below with reference to examples so that those skilled in the art can practice the invention with reference to the description. It is to be noted that the experimental methods described in the following embodiments are all conventional methods unless otherwise specified, and the reagents and materials are commercially available unless otherwise specified.
The synthesis circuit of the invention is as follows:
example 1
Preparation of cathode electrode in electrolytic cell: the entire surface of the glassy carbon electrode was roughened to a roughness of 10 μm to obtain a substrate, and the surface roughness was measured by a stylus type roughness meter, and the average roughness was calculated by the standard of JIS B0601: 2001. Grinding a lead-bismuth alloy to obtain powder, placing the powder in a CVD furnace, introducing argon at the rate of 5sccm, placing a substrate at the downstream of the argon, heating to 650 ℃ at the heating rate of 25 ℃/min, preserving heat for 1 hour, cooling, forming a lead-bismuth alloy film on the substrate to obtain a cathode electrode, adopting a titanium plate as an anode, and applying the cathode electrode and the anode electrode in an ion diaphragm electrolytic cell.
Completely dissolving 200kg DL-homocystine in 8% hydrochloric acid solution to obtain about 373L catholyte, and 3% sulfuric acid solution as anolyte, and electrolyzing with the above ion diaphragm electrolyzer at 35 deg.C and 650A/m current density2And the electrolysis time is 8 hours, at the moment, DL-homocystine does not exist in the catholyte, the crude product of DL-homocysteine thiolactone hydrochloride obtained by electrolysis is decolorized by 3Kg of activated carbon, filtered, concentrated and crystallized, washed, filtered and dried to obtain 221.7Kg of DL-homocysteine thiolactone hydrochloride, the product yield is 96.8 percent (based on DL-homocystine), and the purity is 100 percent.
Comparative example 1
The cathode electrode in the electrolytic cell adopts a lead electrode, the anode electrode adopts a titanium plate, and the cathode electrode and the anode electrode are applied to the ion diaphragm electrolytic cell. Completely dissolving 200kg DL-homocystine in 8% hydrochloric acid solution to obtain about 373L catholyte, and 3% sulfuric acid solution as anolyte, and electrolyzing with the above ion diaphragm electrolyzer at 35 deg.C and 650A/m current density2And the electrolysis time is 12 hours, at the moment, DL-homocysteine does not exist in the catholyte, the DL-homocysteine thiolactone hydrochloride crude product obtained by electrolysis is decolorized by 3Kg of activated carbon, filtered, concentrated, crystallized, filtered and dried to obtain 209Kg of DL-homocysteine thiolactone hydrochloride, the product yield is 91.3 percent, and the purity is 99.8 percent.
Example 2
Adding 300kg of DL-methionine, 750kg of concentrated sulfuric acid with the mass fraction of 98% and 90kg of nickel-based metal supported catalyst into a high-pressure reaction kettle, pressurizing to 2Mpa, controlling the temperature to be 120 ℃, and reacting for 7 hours to obtain hydrolysate; adjusting pH of the hydrolysate to 5 with 30% sodium hydroxide solution, decolorizing with 4kg active carbon, filtering, concentrating the filtrate, crystallizing, washing with ethanol for 2 times, and oven drying to obtain 196.1kg DL-homocystine with a product yield of 72.7% (based on DL-methionine) and a purity of 99.9%.
Preparation of cathode electrode in electrolytic cell: the entire surface of the glassy carbon electrode was roughened to a roughness of 10 μm to obtain a substrate, and the surface roughness was measured by a stylus type roughness meter, and the average roughness was calculated by the standard of JIS B0601: 2001. Grinding a lead-bismuth alloy to obtain powder, placing the powder in a CVD furnace, introducing argon at the rate of 5sccm, placing a substrate at the downstream of the argon, heating to 650 ℃ at the heating rate of 25 ℃/min, preserving heat for 1 hour, cooling, forming a lead-bismuth alloy film on the substrate to obtain a cathode electrode, adopting a titanium plate as an anode, and applying the cathode electrode and the anode electrode in an ion diaphragm electrolytic cell.
196.1kg of DL-homocystine is completely dissolved in 8% hydrochloric acid solution, the total amount of catholyte is 365L, the anolyte is 3% sulfuric acid solution, and the above ion diaphragm electrolyzer is adopted for electrolysis under the conditions of 35 deg.C of electrolysis temperature and 650A/m of current density2And the electrolysis time is 8 hours, at the moment, DL-homocystine does not exist in the catholyte, the crude product of DL-homocysteine thiolactone hydrochloride obtained by electrolysis is decolorized by 3Kg of activated carbon, filtered, concentrated and crystallized, and then washed, filtered and dried to obtain 214.9Kg of DL-homocysteine thiolactone hydrochloride, the product yield is 95.7 percent (based on DL-homocystine) and 69.6 percent (based on DL-methionine) respectively, and the purity is 100 percent.
Comparative example 2
Adding 300kg of DL-methionine and 750kg of concentrated sulfuric acid with the mass fraction of 98% into a reaction kettle, controlling the temperature to be 120 ℃, and reacting for 12 hours to obtain hydrolysate; adjusting the pH of the hydrolysate to 5 by using 30% by mass of sodium hydroxide solution, decoloring by using 4kg of activated carbon, filtering, concentrating and crystallizing the filtrate, washing for 2 times by using alcohol, and drying to obtain 121.9kg of DL-homocystine with the product yield of 45.2% (based on DL-methionine) and the purity of 99.9%.
Preparation of cathode electrode in electrolytic cell: the entire surface of the glassy carbon electrode was roughened to a roughness of 10 μm to obtain a substrate, and the surface roughness was measured by a stylus type roughness meter, and the average roughness was calculated by the standard of JIS B0601: 2001. Grinding a lead-bismuth alloy to obtain powder, placing the powder in a CVD furnace, introducing argon at the rate of 5sccm, placing a substrate at the downstream of the argon, heating to 650 ℃ at the heating rate of 25 ℃/min, preserving heat for 1 hour, cooling, forming a lead-bismuth alloy film on the substrate to obtain a cathode electrode, adopting a titanium plate as an anode, and applying the cathode electrode and the anode electrode in an ion diaphragm electrolytic cell.
Dissolving 121.9kg DL-homocystine completely in 8% hydrochloric acid solution to obtain about 227L catholyte, and 3% sulfuric acid solution as anolyte, and electrolyzing in the above ion diaphragm electrolyzer at 35 deg.C and 650A/m current density2And the electrolysis time is 8 hours, at the moment, DL-homocystine does not exist in the catholyte, the DL-homocystine thiolactone hydrochloride crude product obtained by electrolysis is decolorized by 3Kg of activated carbon, filtered, concentrated and crystallized, and then washed, filtered and dried to obtain 134.2Kg of DL-homocystein thiolactone hydrochloride, the product yield is 96.1 percent (based on DL-homocystine) and 43.4 percent (based on DL-methionine) respectively, and the purity is 100 percent.
While embodiments of the invention have been described above, it is not limited to the applications set forth in the description and the embodiments, which are fully applicable to various fields of endeavor for which the invention may be embodied with additional modifications as would be readily apparent to those skilled in the art, and the invention is therefore not limited to the details given herein and to the embodiments shown and described without departing from the generic concept as defined by the claims and their equivalents.
Claims (5)
1. A synthetic method of DL-homocysteine thiolactone hydrochloride is characterized in that DL-homocysteine is used for preparing catholyte by taking a hydrochloric acid solution as a medium, and the DL-homocysteine thiolactone hydrochloride is obtained by electrolysis in an electrolytic bath, wherein a roughened glassy carbon electrode is used as a base material for a cathode electrode, and a lead-bismuth alloy covers the surface of the base material;
the DL-homocystine is prepared by taking DL-methionine as a raw material, and specifically comprises the following steps:
step 1, adding DL-methionine, concentrated sulfuric acid with the mass fraction of 98% and a nickel-based metal supported catalyst into a high-pressure reaction kettle in a mass ratio of 1:2.5:0.3, pressurizing to 2Mpa, controlling the temperature to be 120 ℃, and reacting for 6-8 hours to obtain hydrolysate;
and 2, adjusting the pH of the hydrolysate to 5-6 by using a sodium hydroxide solution with the mass fraction of 30% -35%, decoloring by using activated carbon, filtering after decoloring, and concentrating and drying the obtained filtrate to obtain the DL-homocystine.
2. The method for synthesizing DL-homocysteine thiolactone hydrochloride according to claim 1 wherein the coarsening of the glassy carbon electrode is specifically: and coarsening the whole surface of the glassy carbon electrode to the roughness of 8-10 microns.
3. The method for synthesizing DL-homocysteine thiolactone hydrochloride according to claim 2, wherein the covering of the surface of the base material with the lead-bismuth alloy is specifically:
grinding the lead-bismuth alloy to obtain powder, placing the powder into a CVD furnace, introducing argon at the rate of 5sccm, placing the substrate at the downstream of the argon, heating to 650 ℃ at the heating rate of 20-25 ℃/min, preserving the heat for 1 hour, cooling, and forming a lead-bismuth alloy film on the substrate.
4. The method for synthesizing DL-homocysteine thiolactone hydrochloride as claimed in claim 1 or 3, wherein the anode of the electrolytic cell is a titanium plate, the anolyte is a 3% sulfuric acid solution, the electrolysis temperature is 35-45 ℃, the current density is 650-700A/m2The electrolysis time is 6-8 hours.
5. The method for synthesizing DL-homocysteine thiolactone hydrochloride according to claim 1 wherein the crude DL-homocysteine thiolactone hydrochloride obtained by electrolysis is further subjected to decolorization, filtration, concentration crystallization, washing, filtration and drying.
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| EP0618312A1 (en) * | 1993-03-02 | 1994-10-05 | Prodesfarma, S.A. | Process for obtaining n-acetyl homocysteine thiolactone from DL-homocystine by electrochemical methods |
| CN1268193A (en) * | 1997-09-05 | 2000-09-27 | 巴斯福股份公司 | Electrochemical reduction of organic compounds |
| CN101144169A (en) * | 2007-08-24 | 2008-03-19 | 湖北新生源生物工程股份有限公司 | Method for producing DL-homocysteine lactone hydrochlorate |
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| CN1089000A (en) * | 1992-12-31 | 1994-07-06 | 福建师范大学 | The electrode special that is used for preparing L-semicystine by electrolytic reduction |
| EP0618312A1 (en) * | 1993-03-02 | 1994-10-05 | Prodesfarma, S.A. | Process for obtaining n-acetyl homocysteine thiolactone from DL-homocystine by electrochemical methods |
| CN1268193A (en) * | 1997-09-05 | 2000-09-27 | 巴斯福股份公司 | Electrochemical reduction of organic compounds |
| CN101144169A (en) * | 2007-08-24 | 2008-03-19 | 湖北新生源生物工程股份有限公司 | Method for producing DL-homocysteine lactone hydrochlorate |
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