CN109943860A - The synthetic method of homocysteinic acid thiolactone hydrochloride - Google Patents
The synthetic method of homocysteinic acid thiolactone hydrochloride Download PDFInfo
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- CN109943860A CN109943860A CN201910345460.0A CN201910345460A CN109943860A CN 109943860 A CN109943860 A CN 109943860A CN 201910345460 A CN201910345460 A CN 201910345460A CN 109943860 A CN109943860 A CN 109943860A
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- thiolactone hydrochloride
- homocysteinic
- synthetic method
- homocysteinic acid
- acid thiolactone
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Abstract
The invention discloses a kind of synthetic methods of homocysteinic acid thiolactone hydrochloride, DL- homocystine is prepared into catholyte by medium of hydrochloric acid solution, electrolysis obtains homocysteinic acid thiolactone hydrochloride in a cell, wherein, cathode electrode, as substrate, covers lead bismuth alloy in substrate surface using the glassy carbon electrode after roughening.The present invention can be improved the yield of homocysteinic acid thiolactone hydrochloride.
Description
Technical field
The present invention relates to the synthesis fields of compound.It is more particularly related in a kind of homocysteinic acid sulphur
The synthetic method of ester hydrochloride.
Background technique
Homocysteinic acid thiolactone hydrochloride is a kind of biochemical reagents and pharmaceutical intermediate, can be used for preparing west for fertile
Ketone, the drugs such as Erdosteine.In the prior art, synthesize drug Shi Changyong metallic zinc or tin and hydrochloric acid and DL- homocystine into
Row reduction reaction can generate a large amount of hydrogen, zinc salt (pink salt) and a large amount of waste water using this method synthesis, very pollution ring
Border, and operate extremely dangerous.
Summary of the invention
The object of the present invention is to provide the synthetic methods of homocysteinic acid thiolactone hydrochloride, improve synthetic yield.
In order to realize these purposes and other advantages according to the present invention, a kind of homocysteinic acid thiolactone is provided
DL- homocystine is prepared catholyte by medium of hydrochloric acid solution by the synthetic method of hydrochloride, and electrolysis obtains in a cell
Homocysteinic acid thiolactone hydrochloride, wherein cathode electrode uses the glassy carbon electrode after roughening as substrate, in substrate
Surface covers lead bismuth alloy.
Preferably, glassy carbon electrode is roughened specifically: it is that 8-10 is micro- that glass-carbon electrode whole surface, which is roughened to roughness,
Rice.
Preferably, lead bismuth alloy is covered in substrate surface specifically:
Grind the lead bismuth alloy to obtain powder and be placed in CVD burner hearth, argon gas is passed through with the rate of 5sccm, by substrate as
The downstream of argon gas is warming up to 650 DEG C with 20-25 DEG C/min heating rate, keeps the temperature 1 hour, cooling, forms lead bismuth alloy in substrate
Film.
Preferably, the anode of the electrolytic cell is titanium plate, and anolyte is the sulfuric acid solution that mass fraction is 3%, electrolysis
Temperature is 35-45 DEG C, current density 650-700A/m2, electrolysis time is 6-8 hours.
Preferably, the homocysteinic acid thiolactone hydrochloride, crude that electrolysis obtains also be have passed through into decoloration, mistake
Filter, condensing crystallizing, flushing, filtering, drying process.
Preferably, DL- homocystine uses DL- METHIONINE to be prepared for raw material, specifically:
Step 1, the DL- METHIONINE that addition mass ratio is 1:2.5:0.3 into autoclave, mass fraction are 98%
The concentrated sulfuric acid and nickel based metal load type catalyst, are forced into 2Mpa, controlled at 120 DEG C, react 6~8 hours, are hydrolyzed
Liquid；
Step 2, by hydrolyzate with mass fraction be 30%-35% sodium hydroxide solution adjust pH to 5~6, and with work
Property carbon decoloring, filtered after decoloration, obtained filtrate is concentrated and dried, as DL- homocystine.
The present invention is include at least the following beneficial effects:
1, the synthetic method of homocysteinic acid thiolactone hydrochloride provided by the invention, on the basis of existing technology
By change cathode material and structure, the mechanical strength of cathode construction is improved, the service life of electrode is significantly extended, it can
Cathode activity suitable for industrial amplification production, while after improvement is high, can further increase homocysteinic acid thiolactone
The yield of hydrochloride.
2, the present invention is when preparing homocysteinic acid thiolactone hydrochloride as raw material using DL- METHIONINE, intermediate product
The yield of DL- homocystine is an important factor for directly affecting target product homocysteinic acid thiolactone hydrochloride yield, originally
Application is shortening the same of reaction time by the way that nickel based metal load type catalyst is added in hydrolysis and carries out compressive reaction
When can significantly improve the yield of DL- homocystine, this is an important breakthrough.
Further advantage, target and feature of the invention will be partially reflected by the following instructions, and part will also be by this
The research and practice of invention and be understood by the person skilled in the art.
Detailed description of the invention
Fig. 1 is the nuclear magnetic resonance figures of homocysteinic acid thiolactone hydrochloride in embodiment 1；
Fig. 2 is the Purity figure of homocysteinic acid thiolactone hydrochloride in embodiment 1.
Specific embodiment
The present invention will be further described in detail below with reference to the embodiments, to enable those skilled in the art referring to specification
Text can be implemented accordingly.It should be noted that experimental method described in following embodiments is unless otherwise specified normal
Rule method, the reagent and material commercially obtain unless otherwise specified.
Synthetic line of the invention are as follows:
Embodiment 1
The preparation of cathode electrode in electrolytic cell: glass-carbon electrode whole surface is roughened to roughness and obtains base for 10 microns
Material, surface roughness are measured using contact pin type roughness measuring gauge, are calculated using the standard of JIS B0601:2001 average thick
Rugosity.It grinds the lead bismuth alloy to obtain powder and be placed in CVD burner hearth, argon gas is passed through with the rate of 5sccm, by substrate as argon gas
Downstream, be warming up to 650 DEG C with 25 DEG C/min heating rate, keep the temperature 1 hour, cooling forms lead bismuth alloy film in substrate, i.e.,
Cathode electrode is obtained, anode uses titanium plate, and cathode electrode and anode electrode are applied in ion diaphragm electrolytic cell.
200kg DL- homocystine is dissolved completely in the hydrochloric acid solution that mass fraction is 8%, amounts to the yin of about 373L
Pole liquid, anolyte use mass fraction for 3% sulfuric acid solution, and using above-mentioned ion diaphragm electrolytic tank electrolysis, electrolytic condition is
Electrolysis temperature is 35 DEG C, current density 650A/m2, electrolysis time is 8 hours, at this time without DL- homocystine in catholyte,
The active carbon decoloring for the homocysteinic acid thiolactone hydrochloride, crude 3kg that electrolysis is obtained, filtering, condensing crystallizing, then
It rinses, filtration drying, obtains 221.7Kg homocysteinic acid thiolactone hydrochloride, product yield is 96.8% (with DL- high
On the basis of cystine), purity 100%.
Comparative example 1
Cathode electrode in electrolytic cell uses lead electrode, and anode electrode uses titanium plate, cathode electrode and anode electrode are answered
For in ion diaphragm electrolytic cell.200kg DL- homocystine is dissolved completely in the hydrochloric acid solution that mass fraction is 8%,
The catholyte of total about 373L, anolyte use mass fraction for 3% sulfuric acid solution, using above-mentioned ion diaphragm electrolyzer electric
Solution, electrolytic condition is that electrolysis temperature is 35 DEG C, current density 650A/m2, electrolysis time is 12 hours, in catholyte at this time
Without DL- homocystine, the active carbon decoloring for the homocysteinic acid thiolactone hydrochloride, crude 3kg that electrolysis is obtained, mistake
Filter refilters drying after condensing crystallizing, obtains 209Kg homocysteinic acid thiolactone hydrochloride, product yield 91.3%,
Its purity is 99.8%.
Embodiment 2
300kg DL- METHIONINE is added into autoclave, the concentrated sulfuric acid that 750kg mass fraction is 98%, 90kg nickel
Base Metal loaded catalyst, is forced into 2Mpa, controlled at 120 DEG C, reacts 7 hours, obtains hydrolyzate；Hydrolyzate is used
The sodium hydroxide solution that mass fraction is 30% adjusts pH to 5, and with 4kg activity carbon decoloring, filters after decoloration, filtrate is concentrated
It crystallizes, then with alcohol rinse 2 times, the DL- homocystine obtained by drying to 196.1kg, the product yield of DL- homocystine is
72.7% (on the basis of DL- METHIONINE), purity 99.9%.
The preparation of cathode electrode in electrolytic cell: glass-carbon electrode whole surface is roughened to roughness and obtains base for 10 microns
Material, surface roughness are measured using contact pin type roughness measuring gauge, are calculated using the standard of JIS B0601:2001 average thick
Rugosity.It grinds the lead bismuth alloy to obtain powder and be placed in CVD burner hearth, argon gas is passed through with the rate of 5sccm, by substrate as argon gas
Downstream, be warming up to 650 DEG C with 25 DEG C/min heating rate, keep the temperature 1 hour, cooling forms lead bismuth alloy film in substrate, i.e.,
Cathode electrode is obtained, anode uses titanium plate, and cathode electrode and anode electrode are applied in ion diaphragm electrolytic cell.
196.1kg DL- homocystine is dissolved completely in the hydrochloric acid solution that mass fraction is 8%, amounts to about 365L's
Catholyte, anolyte use mass fraction for 3% sulfuric acid solution, using above-mentioned ion diaphragm electrolytic tank electrolysis, electrolytic condition
It is 35 DEG C for electrolysis temperature, current density 650A/m2, electrolysis time is 8 hours, at this time without DL- high Guang ammonia in catholyte
Acid, the active carbon decoloring for the homocysteinic acid thiolactone hydrochloride, crude 3kg that electrolysis is obtained, filtering, condensing crystallizing
Afterwards, then washing and filtering is dry, obtains 214.9Kg homocysteinic acid thiolactone hydrochloride, product yield is respectively 95.7%
(on the basis of DL- homocystine), 69.6% (on the basis of DL- METHIONINE), purity 100%.
Comparative example 2
300kg DL- METHIONINE is added into reaction kettle, the concentrated sulfuric acid that 750kg mass fraction is 98%, controlled at
It 120 DEG C, reacts 12 hours, obtains hydrolyzate；The sodium hydroxide solution that hydrolyzate mass fraction is 30% is adjusted into pH to 5,
And with 4kg activity carbon decoloring, filtered after decoloration, it is obtained by drying to arrive 121.9kg by filtrate condensing crystallizing, then with alcohol rinse 2 times
DL- homocystine, the product yield of DL- homocystine is 45.2% (on the basis of DL- METHIONINE), and purity is
99.9%.
The preparation of cathode electrode in electrolytic cell: glass-carbon electrode whole surface is roughened to roughness and obtains base for 10 microns
Material, surface roughness are measured using contact pin type roughness measuring gauge, are calculated using the standard of JIS B0601:2001 average thick
Rugosity.It grinds the lead bismuth alloy to obtain powder and be placed in CVD burner hearth, argon gas is passed through with the rate of 5sccm, by substrate as argon gas
Downstream, be warming up to 650 DEG C with 25 DEG C/min heating rate, keep the temperature 1 hour, cooling forms lead bismuth alloy film in substrate, i.e.,
Cathode electrode is obtained, anode uses titanium plate, and cathode electrode and anode electrode are applied in ion diaphragm electrolytic cell.
121.9kg DL- homocystine is dissolved completely in the hydrochloric acid solution that mass fraction is 8%, amounts to about 227L's
Catholyte, anolyte use mass fraction for 3% sulfuric acid solution, using above-mentioned ion diaphragm electrolytic tank electrolysis, electrolytic condition
It is 35 DEG C for electrolysis temperature, current density 650A/m2, electrolysis time is 8 hours, at this time without DL- high Guang ammonia in catholyte
Acid, the active carbon decoloring for the homocysteinic acid thiolactone hydrochloride, crude 3kg that electrolysis is obtained, filtering, condensing crystallizing
Afterwards, then washing and filtering is dry, obtains 134.2Kg homocysteinic acid thiolactone hydrochloride, product yield is respectively 96.1%
(on the basis of DL- homocystine), 43.4% (on the basis of DL- METHIONINE), purity 100%.
Although the embodiments of the present invention have been disclosed as above, but its is not only in the description and the implementation listed
With it can be fully applied to various fields suitable for the present invention, for those skilled in the art, can be easily
Realize other modification, therefore without departing from the general concept defined in the claims and the equivalent scope, the present invention is simultaneously unlimited
In specific details and embodiment shown and described herein.
Claims (6)
1. a kind of synthetic method of homocysteinic acid thiolactone hydrochloride, which is characterized in that by DL- homocystine with hydrochloric acid
Solution is that medium prepares catholyte, and electrolysis obtains homocysteinic acid thiolactone hydrochloride in a cell, wherein cathode electricity
Pole, as substrate, covers lead bismuth alloy in substrate surface using the glassy carbon electrode after roughening.
2. the synthetic method of homocysteinic acid thiolactone hydrochloride as described in claim 1, which is characterized in that vitreous carbon
Electrode roughening specifically: it is 8-10 microns that glass-carbon electrode whole surface, which is roughened to roughness,.
3. the synthetic method of homocysteinic acid thiolactone hydrochloride as claimed in claim 2, which is characterized in that in substrate
Surface covers lead bismuth alloy specifically:
It grinds the lead bismuth alloy to obtain powder and be placed in CVD burner hearth, argon gas is passed through with the rate of 5sccm, by substrate as argon gas
Downstream, be warming up to 650 DEG C with 20-25 DEG C/min heating rate, keep the temperature 1 hour, it is thin to form lead bismuth alloy in substrate for cooling
Film.
4. the synthetic method of homocysteinic acid thiolactone hydrochloride as claimed in claim 1 or 3, which is characterized in that described
The anode of electrolytic cell is titanium plate, and anolyte is the sulfuric acid solution that mass fraction is 3%, and electrolysis temperature is 35-45 DEG C, current density
For 650-700A/m2, electrolysis time is 6-8 hours.
5. the synthetic method of homocysteinic acid thiolactone hydrochloride as described in claim 1, which is characterized in that will be electrolysed
Obtained homocysteinic acid thiolactone hydrochloride, crude also have passed through decoloration, filtering, condensing crystallizing, flushing, filtering, do
Dry processing.
6. the synthetic method of homocysteinic acid thiolactone hydrochloride as described in claim 1, which is characterized in that DL- high Guang
Propylhomoserin uses DL- METHIONINE to be prepared for raw material, specifically:
The dense sulphur that step 1, the DL- METHIONINE that addition mass ratio is 1:2.5:0.3 into autoclave, mass fraction are 98%
Acid and nickel based metal load type catalyst, are forced into 2Mpa, controlled at 120 DEG C, react 6~8 hours, obtain hydrolyzate；
Hydrolyzate is adjusted pH to 5~6 with the sodium hydroxide solution that mass fraction is 30%-35%, and uses active carbon by step 2
Decoloration, is filtered after decoloration, and obtained filtrate is concentrated and dried, as DL- homocystine.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111004209A (en) * | 2019-12-24 | 2020-04-14 | 浙江工业大学 | Continuous production method of DL-homocysteine thiolactone hydrochloride |
| CN113430546A (en) * | 2021-06-09 | 2021-09-24 | 苏州至善化学有限公司 | Preparation method of homocysteine thiolactone hydrochloride |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111004209A (en) * | 2019-12-24 | 2020-04-14 | 浙江工业大学 | Continuous production method of DL-homocysteine thiolactone hydrochloride |
| CN113430546A (en) * | 2021-06-09 | 2021-09-24 | 苏州至善化学有限公司 | Preparation method of homocysteine thiolactone hydrochloride |
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