CN103193681A - Clean preparation method of guanidinoacetic acid - Google Patents
Clean preparation method of guanidinoacetic acid Download PDFInfo
- Publication number
- CN103193681A CN103193681A CN2013101332940A CN201310133294A CN103193681A CN 103193681 A CN103193681 A CN 103193681A CN 2013101332940 A CN2013101332940 A CN 2013101332940A CN 201310133294 A CN201310133294 A CN 201310133294A CN 103193681 A CN103193681 A CN 103193681A
- Authority
- CN
- China
- Prior art keywords
- reaction
- preparation
- solvent
- cyanamide
- glycine
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a preparation method of guanidinoacetic acid. The method comprises the following steps: performing reaction on glycine and hydrogen cyanamide under the alkaline condition; and performing centrifugal separation on the reaction system after reacting, thereby obtaining a solid phase and a liquid phase, wherein the solid phase is guanidinoacetic acid while the liquid phase is a solvent. The method has the advantages that (1) the clean solvent is adopted, and solvent resulting in environmental pollution is not utilized; (2) the raw material matched with hydrogen cyanamide is excessive properly, so that hydrogen cyanamide can react fully and completely; (3) based on the characteristics of hydrogen cyanamide, the reaction solution is concentrated, so that possible trace waste gases can be removed; and (4) a centrifugation mother solution is recycled totally, so that the zero discharge is achieved. Therefore, the environmental protection requirement is satisfied while ammonia and guanidine acetic acid in the mother solution are recycled. As a result, the yield is improved; and the consumption is lowered.
Description
Technical field
The present invention relates to a kind of preparation method that cleans of guanidoacetic acid, belong to technical field of organic synthesis.
Background technology
Guanidoacetic acid is white crystalline powder, mainly contains five kinds of preparation methods at present: 1, generate S-ethyl thiourea hydrobromate by thiocarbamide and monobromethane reaction, make guanidoacetic acid with glycine reactant again.Thiocarbamide, monobromethane and dehydrated alcohol are mixed, in the warm 3h of water-bath, thiocarbamide is all dissolved.Decompression steams ethanol and excessive monobromethane then, makes the residue crystallization, and drying gets S-ethyl thiourea hydrobromate.Sodium hydroxide solution is added in the S-ethyl thiourea hydrobromate of gained, cooling adds the hot solution that glycine and water are made into rapidly again.Add ether after the crystallization, placement is spent the night, and mixture is cooled off 2h in ice bath, tells ether layer.Suction strainer washs with frozen water, ethanol, ether successively, dries to get product.2, generate free guanidine with Guanidinium hydrochloride and alkali substance reaction, generate guanidoacetic acid with chloroacetate reaction again, through filtration and dry finished product.3, with cyanamide and alkaline matter and glycine reactant, the cooling, centrifugal dry finished product.4, dissolve glycine with Virahol as solvent, drip cyanamide again.Generate crude product again with water dissolution refining finished product.5, be starting raw material with thanomin, generate guanidine radicals ethanol with the reaction of O-methyl-isourea, generate guanidoacetic acid with the Manganse Dioxide reaction again.In above-mentioned each method, exist synthetic route length, product purity to hang down and be difficult to purify, use the shortcomings such as solvent that are easy to generate pollution, and increased the workload that reclaims solvent.
Summary of the invention
The preparation method that cleans who the purpose of this invention is to provide a kind of guanidoacetic acid, method technology of the present invention is simple, the nothing discharging, and the yield height of guanidoacetic acid, and the purity of product is good.
The preparation method of a kind of guanidoacetic acid provided by the present invention comprises the steps:
Under alkaline condition, glycine and cyanamide react; After reaction finishes, the system of described reaction is carried out centrifugation, obtain solid phase and liquid phase, described solid phase is described guanidoacetic acid, and described liquid phase is as the solvent of described reaction.
Among the above-mentioned preparation method, the mol ratio of described glycine and described cyanamide can be 1.0～1.1:1, specifically can be 1.02～1.05:1,1.02:1 or 1.05:1.
Among the above-mentioned preparation method, the pH value of described alkaline condition can be 7.1～10.0, specifically can be 8.5.
Among the above-mentioned preparation method, described method also comprises the step that water washs described solid phase; The mother liquor that described washing obtains and described liquid-phase mixing are as the solvent of described reaction.
Among the above-mentioned preparation method, described method also comprises the step that feeds liquefied ammonia in the system of described reaction.
Among the above-mentioned preparation method, the temperature of described reaction can be 95～98 ℃, specifically can be 95 ℃, 96 ℃ or 98 ℃, and the time can be 4～8 hours, specifically can be 6 hours.
Among the above-mentioned preparation method, when described glycine and described cyanamide carry out the prepared in reaction guanidoacetic acid first, with water as solvent; The mother liquor that this reaction obtains in step is namely as the solvent of next step reaction.
Preparation method provided by the invention has following advantage:
(1) use cleans solvent, avoids using environment is produced the solvent that pollutes;
(2) suitably excessive with the raw material of cyanamide compatibility, the bonding cyanamide thoroughly reacts completely;
(3) consider from the characteristic of cyanamide, reaction solution is carried out concentrate, removes possible micro-waste gas;
(4) thus realizing that centrifuge mother liquor all reclaims realizes zero release, not only guaranteed environmental requirement but also reclaimed that ammonia and the guanidoacetic acid in the mother liquor makes yield improve, consume and reduce.
Embodiment
Employed experimental technique is ordinary method if no special instructions among the following embodiment.
Used material, reagent etc. if no special instructions, all can obtain from commercial channels among the following embodiment.
Embodiment 1, preparation guanidoacetic acid
In the 500mL of the dried and clean that reflux condensing tube, dropping funnel and thermometer are housed four-hole boiling flask, the mother liquor 150mL(that contains cyanamide and guanidoacetic acid that add to reclaim wherein when glycine and cyanamide carry out the prepared in reaction guanidoacetic acid first, with water as solvent; The mother liquor that this step reaction obtains is namely as next step solvent that reacts), add the 51.02g glycine again, stirring heating, drip the 28g cyanamide (in this reaction system, the mol ratio of glycine and cyanamide is 1.02:1.00), temperature is controlled to be 98 ℃, lead to liquefied ammonia control pH value slightly 8.5 reactions 6 hours this moment in reactor, stop then refluxing, and opens the concentrate steam discharge and collect mouth, stopped reaction after 1 hour, begin to cool down, when treating that temperature arrives 20 ℃, the beginning centrifugation, with 15ml deionized water rinsing centrifugal material, washing gained liquid is as the solvent of next still reaction.
Wet feed after centrifugal goes drying, and mother liquor is put into the mother liquor pond and prepared the use that feeds intake of next still.
The dry guanidoacetic acid that gets of wet feed, content (being purity) is 98.5%, yield is 90%.
Embodiment 2, preparation guanidoacetic acid
In the 500mL of the dried and clean that reflux condensing tube, dropping funnel and thermometer are housed four-hole boiling flask, the mother liquor 150mL(that contains cyanamide and guanidoacetic acid that add to reclaim wherein when glycine and cyanamide carry out the prepared in reaction guanidoacetic acid first, with water as solvent; The mother liquor that this step reaction obtains is namely as next step solvent that reacts), add the 52.52g glycine again, stirring heating, drip the 28g cyanamide (in this reaction system, the mol ratio of glycine and cyanamide is 1.05:1.00), temperature control is at 95 ℃, lead to liquefied ammonia control pH value slightly 8.5 reactions 6 hours this moment in reactor, stop then refluxing, open the concentrate steam discharge and collect mouth, stopped reaction after a hour, begin to cool down, when treating that temperature arrives below 25 ℃, the beginning centrifugation is with 15ml deionized water rinsing centrifugal material.
Wet feed goes drying, and mother liquor is put into the mother liquor pond and prepared the use that feeds intake of next still, and washing gained liquid is as the solvent of next still reaction.
The dry guanidoacetic acid that gets, content (being purity) is 98.5%, yield is 91%.
Embodiment 3, preparation guanidoacetic acid
In the 500mL of the dried and clean that reflux condensing tube, dropping funnel and thermometer are housed four-hole boiling flask, the mother liquor 150mL(that contains cyanamide and guanidoacetic acid that add to reclaim wherein when glycine and cyanamide carry out the prepared in reaction guanidoacetic acid first, with water as solvent; The mother liquor that this step reaction obtains is namely as next step solvent that reacts), add the 54.02g glycine again, stirring heating, drip the 28g cyanamide (in this reaction system, the mol ratio of glycine and cyanamide is 1.05:1.00), temperature is controlled to be 96 ℃, lead to liquefied ammonia control pH value slightly 8.5 reactions 6 hours this moment in reactor, stop then refluxing, and opens the concentrate steam discharge and collect mouth, stopped reaction after 1 hour, begin to cool down, when treating that temperature arrives below 25 ℃, the beginning centrifugation, with 15ml deionized water rinsing centrifugal material, washing gained liquid is as the solvent of next still reaction.
Wet feed goes drying, and mother liquor is put into the mother liquor pond and prepared the use that feeds intake of next still.
The dry guanidoacetic acid that gets, content (being purity) is 98.5%, yield is 93%.
Claims (6)
1. the preparation method of a guanidoacetic acid comprises the steps:
Under alkaline condition, glycine and cyanamide react; After reaction finishes, the system of described reaction is carried out centrifugation, obtain solid phase and liquid phase, described solid phase is described guanidoacetic acid, and described liquid phase is as the solvent of described reaction.
2. preparation method according to claim 1, it is characterized in that: the mol ratio of described glycine and described cyanamide is 1.0～1.1:1.
3. preparation method according to claim 1 and 2, it is characterized in that: the pH value of described alkaline condition is 7.1～10.0.
4. according to each described preparation method among the claim 1-3, it is characterized in that: described method also comprises the step that water washs described solid phase; The mother liquor that described washing obtains and described liquid-phase mixing are as the solvent of described reaction.
5. according to each described preparation method among the claim 1-4, it is characterized in that: described method also comprises the step that feeds liquefied ammonia in the system of described reaction.
6. according to each described preparation method among the claim 1-5, it is characterized in that: the temperature of described reaction is 95～98 ℃, and the time is 4～8 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2013101332940A CN103193681A (en) | 2013-04-17 | 2013-04-17 | Clean preparation method of guanidinoacetic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2013101332940A CN103193681A (en) | 2013-04-17 | 2013-04-17 | Clean preparation method of guanidinoacetic acid |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103193681A true CN103193681A (en) | 2013-07-10 |
Family
ID=48716518
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2013101332940A Withdrawn CN103193681A (en) | 2013-04-17 | 2013-04-17 | Clean preparation method of guanidinoacetic acid |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103193681A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103936633A (en) * | 2014-05-13 | 2014-07-23 | 宁夏宝马药业有限公司 | Preparation method of gugnidotaurine |
| CN105503659A (en) * | 2016-01-29 | 2016-04-20 | 浙江汇能生物股份有限公司 | Synthesis method for glycocyamine with high purity and high yield |
| CN111393330A (en) * | 2019-01-02 | 2020-07-10 | 赢创运营有限公司 | Process for preparing guanidinoacetic acid |
| CN111393331A (en) * | 2020-05-14 | 2020-07-10 | 内蒙古天翊生物科技有限公司 | Preparation method of glycocyamine |
| CN113651726A (en) * | 2021-08-18 | 2021-11-16 | 成都迪欣动物保健有限公司 | Preparation method of guanidinoacetic acid |
| CN114702410A (en) * | 2022-03-23 | 2022-07-05 | 杭州丰禾生物技术有限公司 | Preparation method of glycocyamine |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB747668A (en) * | 1952-04-07 | 1956-04-11 | Int Minerals & Chem Corp | Improvements in or relating to process for the preparation of guanidino substituted fatty acids |
| JP2001174459A (en) * | 1999-12-17 | 2001-06-29 | Nippon Zoki Pharmaceut Co Ltd | Renal function examination method |
| CN101462983A (en) * | 2007-12-21 | 2009-06-24 | 上海浩洲化工有限公司 | Preparation of glycocyamine |
| CN101525305A (en) * | 2009-04-17 | 2009-09-09 | 北京君德同创农牧科技有限公司 | Method for synthesizing glycocyamine and salt thereof |
| CN102329250A (en) * | 2011-07-22 | 2012-01-25 | 周彬 | Chemical synthesis method of glycocyamine |
-
2013
- 2013-04-17 CN CN2013101332940A patent/CN103193681A/en not_active Withdrawn
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB747668A (en) * | 1952-04-07 | 1956-04-11 | Int Minerals & Chem Corp | Improvements in or relating to process for the preparation of guanidino substituted fatty acids |
| JP2001174459A (en) * | 1999-12-17 | 2001-06-29 | Nippon Zoki Pharmaceut Co Ltd | Renal function examination method |
| CN101462983A (en) * | 2007-12-21 | 2009-06-24 | 上海浩洲化工有限公司 | Preparation of glycocyamine |
| CN101525305A (en) * | 2009-04-17 | 2009-09-09 | 北京君德同创农牧科技有限公司 | Method for synthesizing glycocyamine and salt thereof |
| CN102329250A (en) * | 2011-07-22 | 2012-01-25 | 周彬 | Chemical synthesis method of glycocyamine |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103936633A (en) * | 2014-05-13 | 2014-07-23 | 宁夏宝马药业有限公司 | Preparation method of gugnidotaurine |
| CN105503659A (en) * | 2016-01-29 | 2016-04-20 | 浙江汇能生物股份有限公司 | Synthesis method for glycocyamine with high purity and high yield |
| CN111393330A (en) * | 2019-01-02 | 2020-07-10 | 赢创运营有限公司 | Process for preparing guanidinoacetic acid |
| CN111393330B (en) * | 2019-01-02 | 2023-05-26 | 赢创运营有限公司 | Process for preparing guanidinoacetic acid |
| CN111393331A (en) * | 2020-05-14 | 2020-07-10 | 内蒙古天翊生物科技有限公司 | Preparation method of glycocyamine |
| CN111393331B (en) * | 2020-05-14 | 2022-05-31 | 内蒙古天翊生物科技有限公司 | Preparation method of glycocyamine |
| CN113651726A (en) * | 2021-08-18 | 2021-11-16 | 成都迪欣动物保健有限公司 | Preparation method of guanidinoacetic acid |
| CN114702410A (en) * | 2022-03-23 | 2022-07-05 | 杭州丰禾生物技术有限公司 | Preparation method of glycocyamine |
| CN114702410B (en) * | 2022-03-23 | 2024-04-12 | 杭州丰禾生物技术有限公司 | Preparation method of guanidinoacetic acid |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103193681A (en) | Clean preparation method of guanidinoacetic acid | |
| CN101891649B (en) | Novel 3-cyano methyl benzoate preparing method | |
| CN103570568A (en) | Clean production process of glycine in coproduction with ammonium chloride | |
| CN102329250A (en) | Chemical synthesis method of glycocyamine | |
| CN105503659A (en) | Synthesis method for glycocyamine with high purity and high yield | |
| CN104817443B (en) | Benzoin dimethyl ether synthesis process | |
| CN101880270B (en) | Method for preparing 1,1-cyclopropanedimethyl cyclicsulfite | |
| CN102030669A (en) | Clean production method for glycine | |
| CN103408427A (en) | 9-fluorenylmethyl chloroformate preparation method | |
| CN103396318A (en) | Synthetic process for 2,4-dinitroanisole | |
| CN103450080B (en) | A kind of preparation method of 3,3-pentamethylene glutarimide | |
| CN104610095A (en) | Preparation method of o-hydroxybenzonitrile | |
| CN104387301B (en) | The synthetic method of the fluoro-4-Methyl benzenesulfonyl of a kind of 2-methyl isonitrile | |
| CN105585539A (en) | One-pot ceftazidime side-chain acid ethyl ester synthesis method | |
| CN103242186B (en) | Combined production method of methacrylamide and methyl methacrylate | |
| CN104557685A (en) | Method for producing nicotinic acid by using nicotinamide mother solution | |
| CN102126970A (en) | Methods for separating leucine and arginine by selective precipitation | |
| CN101967081B (en) | Process for recovering water-containing methanol solution produced in production of antioxygen 1010 | |
| CN103951596A (en) | Preparation method of medicinal D, L-alpha-hydroxymethionine calcium | |
| CN103739580B (en) | The treatment process of palmitinic acid residue | |
| CN103626768B (en) | Moxifloxacin hydrochloride new preparation process | |
| CN112778112A (en) | Method and device for synthesizing vitamin K3 | |
| CN103351314A (en) | Cleaner production process for combined glycine and calcium sulfate | |
| CN101696021A (en) | Method for separating ammonium chloride and methanol from mother liquor subjected to alcohol precipitation and separation of glycine | |
| CN108892619A (en) | A kind of separation method of nitro neighbour acetophenone admixture of isomeric compound |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C04 | Withdrawal of patent application after publication (patent law 2001) | ||
| WW01 | Invention patent application withdrawn after publication |
Application publication date: 20130710 |