CN104447428A - Preparation method of etamsylate - Google Patents
Preparation method of etamsylate Download PDFInfo
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- CN104447428A CN104447428A CN201410732806.XA CN201410732806A CN104447428A CN 104447428 A CN104447428 A CN 104447428A CN 201410732806 A CN201410732806 A CN 201410732806A CN 104447428 A CN104447428 A CN 104447428A
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- etamsylate
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- AKRRAYSVNBNHET-UHFFFAOYSA-N CC(CC1)=CC=C1O Chemical compound CC(CC1)=CC=C1O AKRRAYSVNBNHET-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention relates to a preparation method of etamsylate. The etamsylate is prepared by virtue of three steps, namely sulfonating, salifying and refining, and the entire preparation process is free from an organic solvent, so that cost and pollution are reduced; in addition, a crude product is refined by virtue of absolute ethyl alcohol which serves as a solvent; therefore, the entire process is not only lower in cost but also more environment-friendly; the etamsylate prepared by the method is relatively higher in mass percentage; in conclusion, the preparation method disclosed by the invention has the advantages of being simple in design, low in cost, environment-friendly and high in mass percentage.
Description
Technical field
The invention belongs to chemical technology field, be specifically related to a kind of etamsylate, particularly relate to a kind of preparation method of etamsylate.
Background technology
Etamsylate (CAS: 2624-44-4) has another name called etamsylatum, and its chemical name is 2,5-dihydroxybenzenesulfonate
Salt, structural formula is:
, pharmacokinetic studies shows, etamsylate can make platelet counts increase, and strengthen hematoblastic aggegation and bonding strength, promote the release of blood coagulation activity material, thus generation anastalsis, its effect fast, after quiet note, 1h effect is the strongest, generally can maintain 4 to 6 hours, it is hemorrhage that this product is applicable to prevention and therapy surgical operation, it is hemorrhage that thrombopenic purpura or anaphylactoid purpura and other reason cause, as hematencephalon, gastrointestinal hemorrhage, urinary tract is hemorrhage, retinal hemorrhage, gingival hemorrhage, nosebleed epistaxis etc., can with other hemostatic drug as Aminomethylbenzoic Acid, vitamin K is also used, this product toxicity is low, at present domestic be widely used in clinical, now commercially the production method of etamsylate has benzoquinones method method, wherein benzoquinones method is at diethylamine, sulfurous gas is passed in the solution of second alcohol and water, first obtained sulfurous acid diethylamine salt, then at low temperatures para benzoquinone is added in sulfurous acid diethylamine salt solution, react complete underpressure distillation and reclaim ethanol, crude product is separated out after cooling, sodium bisulfite and activated carbon decolorizing is added in water or Diluted Alcohol, refine to obtain product, the shortcoming of this technique is: because para benzoquinone reaction is incomplete, add that the solubleness of etamsylate in water and ethanol is larger, make product yield low, generally be no more than 40%, and para benzoquinone price is higher, sulfurous gas is used to there is the problems such as the absorption of tail gas, in addition market also having adopts chlorsulfonic acid to be sulphonating agent, Resorcinol and organic solvent azeotropic is made to dewater to anhydrous before sulfonation, but this method adopts organic solvent, contaminate environment, the hydrogen chloride gas wherein produced in sulfonation reaction process, contaminate environment.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art and provide that a kind of simplicity of design, cost are low, convenience of drawing materials, protection of the environment, etamsylate that massfraction is high preparation method.
Technical solution of the present invention is: a kind of preparation method of etamsylate, is characterized in that, it comprises the steps:
Step 1: sulfonation: Resorcinol and the vitriol oil are added in same three-necked bottle respectively, then carry out heating in water bath, slowly heat up until Resorcinol melts completely as liquid state, then solution is stirred, after stirring, three-necked bottle is incubated 1 hour, is incubated, after one hour, temperature is reduced to 35-45 DEG C, then add distilled water and gac successively, again temperature is upgraded to 55-65 DEG C, decolouring is filtered after stirring 30min, namely obtains 2,5-dihydroxy benzenes sulfonic acid solution;
Step 2: salify: filtrate step 1 obtained is poured in another three-necked bottle, and filtrate is cooled to 25-35 DEG C, then slowly drips diethylamine, after completion of the reaction, decrease temperature crystalline, then filters, by the crystal washing obtained, dry etamsylate crude product;
Step 3: refining: crude product step 2 obtained is dissolved in dehydrated alcohol, then add a small amount of gac and decolour, after decolorization filtering, frozen water is adopted to lower the temperature again, filter after crystallization, after filtration, filter cake step-down is dried under the environment of 50 DEG C, obtain etamsylate.
The reaction equation of above-mentioned synthetic method is as follows:
Described Resorcinol and the mass ratio of the vitriol oil are 1.2:1 ~ 1:1.
2,5-described dihydroxy benzenes sulfonic acids and the mass ratio of diethylamine are 2:1 ~ 1:1.
Described etamsylate crude product and the mass ratio of dehydrated alcohol are 1:2 ~ 1:3.
The mass ratio of described distilled water and gac and Resorcinol is respectively 2:1 and 0.04:1.
The present invention has the following advantages: simplicity of design of the present invention, take Resorcinol as starting raw material, sulphonating agent is made with the vitriol oil, carry out sulfonation, generate diphenol Phenylsulfonic acid, then, namely etamsylate is obtained again with diethylamine salify, refining crude is carried out as solvent in addition with dehydrated alcohol, cost is lower, more environmental protection, at intermediate 2, in the preparation process of the preparation of 5-dihydroxy benzenes sulfonic acid, take Dry synthesis, not with an organic solvent, reduce costs and pollute, whole process not only cost is lower, and more environmental protection, the massfraction being obtained etamsylate by the inventive method is also higher, the present invention has simplicity of design in a word, cost is low, protection of the environment and the high advantage of massfraction.
Embodiment
Below in conjunction with embodiment, the present invention is further illustrated.
Embodiment 1
A preparation method for etamsylate, is characterized in that, it comprises the steps:
Step 1: sulfonation: get Resorcinol 50g and vitriol oil 48g and add in same three-necked bottle respectively, then heating in water bath is carried out, slow intensification, until Resorcinol melts completely as liquid state, is then stirred solution, after stirring, three-necked bottle is incubated 1 hour, be incubated, after one hour, temperature reduced to 40 DEG C, then add distilled water 100g successively and temperature is upgraded to 55 DEG C by 2g gac again, decolouring is filtered after stirring 30min, namely 2,5-dihydroxy benzenes sulfonic acid solution is obtained;
Step 2: salify: filtrate step 1 obtained is poured in another three-necked bottle, filtrate is cooled to 25 DEG C, then slowly 2 are dripped, the mass ratio of 5-dihydroxy benzenes sulfonic acid and diethylamine is the diethylamine of 2:1, after completion of the reaction, decrease temperature crystalline, then filters, by the crystal washing obtained, dry etamsylate crude product;
Step 3: refining: the mass ratio that crude product step 2 obtained is dissolved in etamsylate crude product and dehydrated alcohol is in the dehydrated alcohol of 1:2, add a small amount of gac again to decolour, after decolorization filtering, frozen water is adopted to lower the temperature again, filter after crystallization, after filtration, filter cake step-down is dried under the environment of 50 DEG C, obtain etamsylate 97.5g, yield 92.8%.
This the present invention simplicity of design, with 50g Resorcinol for starting raw material, sulphonating agent is made with the 48g vitriol oil, carry out sulfonation, generate diphenol Phenylsulfonic acid, then, namely etamsylate is obtained again with diethylamine salify, refining crude is carried out as solvent in addition with dehydrated alcohol, cost is lower, more environmental protection, at intermediate 2, in the preparation process of the preparation of 5-dihydroxy benzenes sulfonic acid, take Dry synthesis, not with an organic solvent, reduce costs and pollute, whole process not only cost is lower, and more environmental protection, the massfraction being obtained etamsylate by the inventive method is also higher, the present invention has simplicity of design in a word, cost is low, protection of the environment and the high advantage of massfraction.
Embodiment 2
A preparation method for etamsylate, is characterized in that, it comprises the steps:
Step 1: sulfonation: get Resorcinol 60g and vitriol oil 60g and add in same three-necked bottle respectively, then heating in water bath is carried out, slow intensification, until Resorcinol melts completely as liquid state, is then stirred solution, after stirring, three-necked bottle is incubated 1 hour, be incubated, after one hour, temperature reduced to 40 DEG C, then add distilled water 120g successively and temperature is upgraded to 55 DEG C by 2.4g gac again, decolouring is filtered after stirring 30min, namely 2,5-dihydroxy benzenes sulfonic acid solution is obtained;
Step 2: salify: filtrate step 1 obtained is poured in another three-necked bottle, filtrate is cooled to 25 DEG C, then slowly 2 are dripped, the mass ratio of 5-dihydroxy benzenes sulfonic acid and diethylamine is the diethylamine of 1:1, after completion of the reaction, decrease temperature crystalline, then filters, by the crystal washing obtained, dry etamsylate crude product;
Step 3: refining: the mass ratio that crude product step 2 obtained is dissolved in etamsylate crude product and dehydrated alcohol is in the dehydrated alcohol of 1:2, add a small amount of gac again to decolour, after decolorization filtering, frozen water is adopted to lower the temperature again, filter after crystallization, after filtration, filter cake step-down is dried under the environment of 50 DEG C, obtain etamsylate 118.0g, yield 93.2%.
This the present invention simplicity of design, with 60g Resorcinol for starting raw material, sulphonating agent is made with the 60g vitriol oil, carry out sulfonation, generate diphenol Phenylsulfonic acid, then, namely etamsylate is obtained again with diethylamine salify, refining crude is carried out as solvent in addition with dehydrated alcohol, cost is lower, more environmental protection, at intermediate 2, in the preparation process of the preparation of 5-dihydroxy benzenes sulfonic acid, take Dry synthesis, not with an organic solvent, reduce costs and pollute, whole process not only cost is lower, and more environmental protection, the massfraction being obtained etamsylate by the inventive method is also higher, the present invention has simplicity of design in a word, cost is low, protection of the environment and the high advantage of massfraction.
Embodiment 3
A preparation method for etamsylate, is characterized in that, it comprises the steps:
Step 1: sulfonation: get Resorcinol 80g and vitriol oil 70g and add in same three-necked bottle respectively, then heating in water bath is carried out, slow intensification, until Resorcinol melts completely as liquid state, is then stirred solution, after stirring, three-necked bottle is incubated 1 hour, be incubated, after one hour, temperature reduced to 40 DEG C, then add distilled water 160g successively and temperature is upgraded to 55 DEG C by 3.2g gac again, decolouring is filtered after stirring 30min, namely 2,5-dihydroxy benzenes sulfonic acid solution is obtained;
Step 2: salify: filtrate step 1 obtained is poured in another three-necked bottle, filtrate is cooled to 25 DEG C, then slowly 2 are dripped, the mass ratio of 5-dihydroxy benzenes sulfonic acid and diethylamine is the diethylamine of 2:1, after completion of the reaction, decrease temperature crystalline, then filters, by the crystal washing obtained, dry etamsylate crude product;
Step 3: refining: the mass ratio that crude product step 2 obtained is dissolved in etamsylate crude product and dehydrated alcohol is in the dehydrated alcohol of 1:3, add a small amount of gac again to decolour, after decolorization filtering, frozen water is adopted to lower the temperature again, filter after crystallization, after filtration, filter cake step-down is dried under the environment of 50 DEG C, obtain etamsylate 158.4g, yield 94.6%.
This the present invention simplicity of design, with 80g Resorcinol for starting raw material, sulphonating agent is made with the 70g vitriol oil, carry out sulfonation, generate diphenol Phenylsulfonic acid, then, namely etamsylate is obtained again with diethylamine salify, refining crude is carried out as solvent in addition with dehydrated alcohol, cost is lower, more environmental protection, at intermediate 2, in the preparation process of the preparation of 5-dihydroxy benzenes sulfonic acid, take Dry synthesis, not with an organic solvent, reduce costs and pollute, whole process not only cost is lower, and more environmental protection, the massfraction being obtained etamsylate by the inventive method is also higher, the present invention has simplicity of design in a word, cost is low, protection of the environment and the high advantage of massfraction.
Embodiment 4
A preparation method for etamsylate, is characterized in that, it comprises the steps:
Step 1: sulfonation: get Resorcinol 90g and vitriol oil 85g and add in same three-necked bottle respectively, then heating in water bath is carried out, slow intensification, until Resorcinol melts completely as liquid state, is then stirred solution, after stirring, three-necked bottle is incubated 1 hour, be incubated, after one hour, temperature reduced to 40 DEG C, then add distilled water 180g successively and temperature is upgraded to 55 DEG C by 3.6g gac again, decolouring is filtered after stirring 30min, namely 2,5-dihydroxy benzenes sulfonic acid solution is obtained;
Step 2: salify: filtrate step 1 obtained is poured in another three-necked bottle, filtrate is cooled to 25 DEG C, then slowly 2 are dripped, the mass ratio of 5-dihydroxy benzenes sulfonic acid and diethylamine is the diethylamine of 1:1, after completion of the reaction, decrease temperature crystalline, then filters, by the crystal washing obtained, dry etamsylate crude product;
Step 3: refining: the mass ratio that crude product step 2 obtained is dissolved in etamsylate crude product and dehydrated alcohol is in the dehydrated alcohol of 1:2, add a small amount of gac again to decolour, after decolorization filtering, frozen water is adopted to lower the temperature again, filter after crystallization, after filtration, filter cake step-down is dried under the environment of 50 DEG C, obtain etamsylate 173.1g, yield 93.6%.
This the present invention simplicity of design, with 90g Resorcinol for starting raw material, sulphonating agent is made with the 80g vitriol oil, carry out sulfonation, generate diphenol Phenylsulfonic acid, then, namely etamsylate is obtained again with diethylamine salify, refining crude is carried out as solvent in addition with dehydrated alcohol, cost is lower, more environmental protection, at intermediate 2, in the preparation process of the preparation of 5-dihydroxy benzenes sulfonic acid, take Dry synthesis, not with an organic solvent, reduce costs and pollute, whole process not only cost is lower, and more environmental protection, the massfraction being obtained etamsylate by the inventive method is also higher, the present invention has simplicity of design in a word, cost is low, protection of the environment and the high advantage of massfraction.
Embodiment 5
A preparation method for etamsylate, is characterized in that, it comprises the steps:
Step 1: sulfonation: get Resorcinol 100g and vitriol oil 95g and add in same three-necked bottle respectively, then heating in water bath is carried out, slow intensification, until Resorcinol melts completely as liquid state, is then stirred solution, after stirring, three-necked bottle is incubated 1 hour, be incubated, after one hour, temperature reduced to 40 DEG C, then add distilled water 200g successively and temperature is upgraded to 55 DEG C by 4.0g gac again, decolouring is filtered after stirring 30min, namely 2,5-dihydroxy benzenes sulfonic acid solution is obtained;
Step 2: salify: filtrate step 1 obtained is poured in another three-necked bottle, filtrate is cooled to 25 DEG C, then slowly 2 are dripped, the mass ratio of 5-dihydroxy benzenes sulfonic acid and diethylamine is the diethylamine of 2:1, after completion of the reaction, decrease temperature crystalline, then filters, by the crystal washing obtained, dry etamsylate crude product;
Step 3: refining: the mass ratio that crude product step 2 obtained is dissolved in etamsylate crude product and dehydrated alcohol is in the dehydrated alcohol of 1:2, add a small amount of gac again to decolour, after decolorization filtering, frozen water is adopted to lower the temperature again, filter after crystallization, after filtration, filter cake step-down is dried under the environment of 50 DEG C, obtain etamsylate 197.4g, yield 92.5%.
This the present invention simplicity of design, with 100g Resorcinol for starting raw material, sulphonating agent is made with the 95g vitriol oil, carry out sulfonation, generate diphenol Phenylsulfonic acid, then, namely etamsylate is obtained again with diethylamine salify, refining crude is carried out as solvent in addition with dehydrated alcohol, cost is lower, more environmental protection, at intermediate 2, in the preparation process of the preparation of 5-dihydroxy benzenes sulfonic acid, take Dry synthesis, not with an organic solvent, reduce costs and pollute, whole process not only cost is lower, and more environmental protection, the massfraction being obtained etamsylate by the inventive method is also higher, the present invention has simplicity of design in a word, cost is low, protection of the environment and the high advantage of massfraction.
Claims (5)
1. a preparation method for etamsylate, is characterized in that, it comprises the steps:
Step 1: sulfonation: Resorcinol and the vitriol oil are added in same three-necked bottle respectively, then carry out heating in water bath, slowly heat up until Resorcinol melts completely as liquid state, then solution is stirred, after stirring, three-necked bottle is incubated 1 hour, is incubated, after one hour, temperature is reduced to 35-45 DEG C, then add distilled water and gac successively, again temperature is upgraded to 55-65 DEG C, decolouring is filtered after stirring 30min, namely obtains 2,5-dihydroxy benzenes sulfonic acid solution;
Step 2: salify: filtrate step 1 obtained is poured in another three-necked bottle, and filtrate is cooled to 25-35 DEG C, then slowly drips diethylamine, after completion of the reaction, decrease temperature crystalline, then filters, by the crystal washing obtained, dry etamsylate crude product;
Step 3: refining: crude product step 2 obtained is dissolved in dehydrated alcohol, then add a small amount of gac and decolour, after decolorization filtering, frozen water is adopted to lower the temperature again, filter after crystallization, after filtration, filter cake step-down is dried under the environment of 50 DEG C, obtain etamsylate;
The reaction equation of above-mentioned synthetic method is as follows:
。
2. the preparation method of a kind of etamsylate as claimed in claim 1, is characterized in that: described Resorcinol and the mass ratio of the vitriol oil are 1.2:1 ~ 1:1.
3. the preparation method of a kind of etamsylate as claimed in claim 1, is characterized in that: 2,5-described dihydroxy benzenes sulfonic acids and the mass ratio of diethylamine are 2:1 ~ 1:1.
4. the preparation method of a kind of etamsylate as claimed in claim 1, is characterized in that: described etamsylate crude product and the mass ratio of dehydrated alcohol are 1:2 ~ 1:3.
5. the preparation method of a kind of etamsylate as claimed in claim 1, is characterized in that: the mass ratio of described distilled water and gac and Resorcinol is respectively 2:1 and 0.04:1.
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| CN201410732806.XA CN104447428A (en) | 2014-12-07 | 2014-12-07 | Preparation method of etamsylate |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109467522A (en) * | 2018-11-27 | 2019-03-15 | 成都平和安康医药科技有限公司 | A method of producing high-purity etamsylate |
| CN110642756A (en) * | 2019-10-18 | 2020-01-03 | 海南顿斯医药科技有限公司 | A kind of1/20Hydrophenol sulfoethylamine compounds |
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| CN1359897A (en) * | 2001-12-11 | 2002-07-24 | 西安利君制药股份有限公司 | Process for synthesizing hydrate of calcium phenolsulfonate |
| CN102942509A (en) * | 2012-10-17 | 2013-02-27 | 山东方明药业集团股份有限公司 | Synthetic method of etamsylate |
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2014
- 2014-12-07 CN CN201410732806.XA patent/CN104447428A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| PL122497B1 (en) * | 1979-07-16 | 1982-07-31 | Farmaceutyczna Spoldzielnia Pr | Process for preparing 2,5-dihydroxybenzenesulfonic acid and process for preparing salt of 2,5-dihydroxybenzenesulfonic acid with diethylamine |
| CN1359897A (en) * | 2001-12-11 | 2002-07-24 | 西安利君制药股份有限公司 | Process for synthesizing hydrate of calcium phenolsulfonate |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109467522A (en) * | 2018-11-27 | 2019-03-15 | 成都平和安康医药科技有限公司 | A method of producing high-purity etamsylate |
| CN109467522B (en) * | 2018-11-27 | 2021-01-22 | 成都平和安康医药科技有限公司 | Method for producing high-purity etamsylate |
| CN110642756A (en) * | 2019-10-18 | 2020-01-03 | 海南顿斯医药科技有限公司 | A kind of1/20Hydrophenol sulfoethylamine compounds |
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Application publication date: 20150325 |