CN103819353A - Method for preparing tranexamic acid with high productivity through catalyzing and hydrogenating paraaminomethyl benzoic acid - Google Patents
Method for preparing tranexamic acid with high productivity through catalyzing and hydrogenating paraaminomethyl benzoic acid Download PDFInfo
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- CN103819353A CN103819353A CN201410079178.XA CN201410079178A CN103819353A CN 103819353 A CN103819353 A CN 103819353A CN 201410079178 A CN201410079178 A CN 201410079178A CN 103819353 A CN103819353 A CN 103819353A
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Abstract
The invention relates to a method for preparing tranexamic acid through catalyzing and hydrogenating paraaminomethyl benzoic acid. A Pt-M/C catalyst (M refers to Ru, La, Ce, Co and Ni) is used for catalyzing and hydrogenating paraaminomethyl benzoic acid. Through the adoption of the catalyst, the reaction condition is gentle, the reaction temperature is 30-60 DEG C, the hydrogen pressure is 0.3-0.5 MPa, the catalyst activity is high, the conversion rate of paraaminomethyl benzoic acid is 99% after reaction for 2-4 h, the yield of paraaminomethyl cyclohexanecarboxylic acid is 95%, the reaction time is shortened, the unit productivity is improved, and the method has very high industrial application value.
Description
The application is divisional application, the application number of original application: 201110181414.5, and the applying date: 2011-06-30, invention and created name " a kind of method of preparing tranexamic acid from para-aminomethylbenzoic acid by catalytic hydrogenation ".
Technical field
The invention belongs to the applied technical field of shortening, be specially the method that paraaminomethyl benzoic acid shortening is prepared as to tranamic acid under mild conditions.
Background technology
Tranamic acid is trans to aminomethyl hexahydrobenzoic acid, can be by the reversibility blocking-up to being incorporated into Methionin on proplasmin molecule, thereby produce the fibrinogenic effect of resist dissolution, be effective to hemorrhage extensive situation, be generally used for respiratory tract, digestive tract hemorrhage, oozing of blood, surgical operation hemorrhage etc.
The synthetic method of tranamic acid mainly contains two kinds, and one is methyl acrylate method, generates tranamic acid by methyl acrylate and chloro-butadiene through series reaction; Another kind is paraaminomethyl benzoic acid method, generates tranamic acid by paraaminomethyl benzoic acid through catalytic hydrogenation, conversion.Owing to will use hypertoxic prussiate in methyl acrylate method, therefore industrial is mainly to use paraaminomethyl benzoic acid method to produce tranamic acid.
Paraaminomethyl benzoic acid method is produced in tranamic acid process, catalytic hydrogenation is most important step, aminomethyl phenyl first is obtained to cis and trans to aminomethyl hexahydrobenzoic acid through catalytic hydrogenation, again cis is transformed to generation to aminomethyl hexahydrobenzoic acid trans to aminomethyl hexahydrobenzoic acid, i.e. tranamic acid.The normally precious metal such as Pt, Rh, Ru of catalyzer used in catalytic hydrogenation.
US 3932497 uses Ru catalyzer, and Ru is loaded to inert support as on aluminum oxide, diatomite, gac, barium sulfate, calcium carbonate, and the content of Ru in catalyzer is 1～10 wt%.150 ℃ of temperature, under hydrogen pressure 100 kg/cm2, react, the transformation efficiency of paraaminomethyl benzoic acid is 100%, is 97% to the yield of aminomethyl hexahydrobenzoic acid.JP 49062444 uses Ru-C catalyzer, by 45 g paraaminomethyl benzoic acids, and 16.7 g KOH, 100 ml H2O and 25 g 5% Ru-C add in autoclave, 90 ℃ of temperature, under hydrogen pressure 90 kg/cm2, react, product obtains 43.5 g to aminomethyl hexahydrobenzoic acid after processing.
GB 2084145 uses Pd, Pt, Rh mixed catalyst, respectively Pd, Pt, Rh are loaded to and on gac, make 5%Pd-C, 5%Pt-C, 5%Rh-C catalyzer, these three kinds of catalyst mix are added in autoclave, add again paraaminomethyl benzoic acid, water, hydrochloric acid, temperature of reaction 10-60 ℃, hydrogen pressure 1-10 kg/cm2, reaction 6 h, to the yield of aminomethyl hexahydrobenzoic acid in 80% left and right.
JP 58032848 uses Rh catalyzer, and Rh is loaded on gac and makes 5%Rh-C catalyzer, 40 ℃ of temperature of reaction, hydrogen pressure 30 kg/cm2, reaction 3 h, reach 90% to the yield of aminomethyl heptanaphthenic acid.
Industrial main use PtO2 makes catalyzer at present, ratio of components is paraaminomethyl benzoic acid: platinum dioxide: sulfuric acid: water=1: 0.05: 0.56: 33, paraaminomethyl benzoic acid and water are added in retort, under stirring, add sulfuric acid, heating makes molten, add again platinum dioxide, eliminate and after air, pass into hydrogen in tank and start reaction.40 ℃ of left and right, hydrogen pressure 0.5-1.5 kg/cm2 reaction reaches theoretical amount and only no longer inhales hydrogen to inhaling hydrogen.Eliminate Yu Qing, extract reaction solution filtration, take out platinum black.Filtrate is heated to 90 ℃, is neutralized to pH=7-7.5 with hydrated barta.After leaving standstill, filtering barium sulfate.Wash filter residue with water, merge filter, washing lotion, after concentrating, obtain the cis liquid (concentration is that every 10 mol para-amino-methyl-benzoic acid reaction solutions are concentrated into 5 liters) to aminomethyl hexahydrobenzoic acid.The ratio of components of conversion process is to aminomethyl hexahydrobenzoic acid cis liquid (v): hydrated barta (w): water (v): ethanol (v)=1: 2.1: 1.6: 6.61.To add in retort aminomethyl hexahydrobenzoic acid cis liquid and hydrated barta, airtight, be warming up to 200 ℃, pressure is 18-20 kg/cm2, reacts 14 hours.Reaction is finished, and is chilled to 60-70 ℃, adds water and is warming up to 90 ℃, is neutralized to pH=5.52-5.56 with sulfuric acid (30%).Place more than 2 hours, filter, filter cake washes with water.Merge diafiltration liquid, add gac appropriate, boiling decoloring.Filter, it is 6 liters that filtrate is concentrated into every 10 mol para-amino-methyl-benzoic acids, adds ethanol crystallization.Cooling, to filter, crystallization washing with alcohol, is filtered dry, dry, obtains tranamic acid.
In shortening process, use Ru catalyzer, reaction conditions is harsher, and High Temperature High Pressure is high to equipment requirements, is unsuitable for industrial production; Use Rh catalyzer, because Rh price is high, production cost is increased; Use Pt catalyzer, reaction conditions gentleness, but the reaction times is longer.
Summary of the invention
The object of this invention is to provide a kind of reaction times short, the method of the preparing tranexamic acid from para-aminomethylbenzoic acid by catalytic hydrogenation that productive rate is high, adopt high-activity hydrogenation catalyst, the shortening that paraaminomethyl benzoic acid is prepared in tranamic acid process can carry out under relatively mild reaction conditions simultaneously.
For achieving the above object, technical solution of the present invention is, adopt Pt-M/C catalyzer (M=Ru, La, Ce, Co, Ni), for paraaminomethyl benzoic acid shortening, its method is specially: a), in autoclave, add successively 0.3 times of Pt-M/C catalyzer (M=Ru, La, Ce, Co, Ni), 1 times of paraaminomethyl benzoic acid, 30 times of deionized waters and 0.6 times of H2SO4 solubility promoter, airtight being evacuated to-0.08 ~-0.06Mpa;
B), with air in nitrogen replacement autoclave 2 times, with hydrogen exchange nitrogen 2 times, and hydrogen pressure is adjusted to 0.3-0.5MPa, be warming up to 30-60 ℃, reaction 2-4 h generates aminomethyl hexahydrobenzoic acid;
C), to aminomethyl hexahydrobenzoic acid through under alkaline-earth metal catalysis, 220 ℃, under 2.0-2.5MPa condition, configuration conversion obtains tranamic acid.
The principal reaction equation the present invention relates to is:
In the present invention, the preparation method of Pt-M/C catalyzer is: 1 part of gac be impregnated in H2PtCl6 that 0.01-1 doubly measures and the mixing solutions containing 0.01-1 M ion (M=Ru, La, Ce, Co or Ni) doubly, after fully infiltrating, flooding, use reductive agent reduction, reduce rear cooling, filtration, washing, make Pt-M/C catalyzer, wherein in Pt-M/C catalyzer, the charge capacity of Pt is 1-5%, and the charge capacity of M is 0.1-5%.
As the preferred embodiments of the present invention: the reductive agent that described Pt-M/C catalyzer uses in preparation process is a kind of in hydrazine hydrate, KBH4, CH3COONa or their mixture.
The invention has the beneficial effects as follows:
1. method for preparing catalyst is simple, by dipping, reduction, active constituent loading, to gac, has been reduced to the usage quantity of precious metal, has improved the utilization ratio of precious metal.
2. because catalyst activity is high, only need reaction 2-4 hour, the transformation efficiency of paraaminomethyl benzoic acid just can reach more than 98%, and can reach more than 95% aminomethyl hexahydrobenzoic acid yield, has shortened the reaction times, improves unit productive rate.
3. the reaction conditions adopting in paraaminomethyl benzoic acid shortening process is gentleer, temperature of reaction
30-60 ℃, hydrogen pressure 0.3-0.6 MPa, is applicable to suitability for industrialized production.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail.
Embodiment 1
Be prepared as example with 1 gram of catalyzer: 0.135g H2PtCl6 and 0.05g La (NO3) 3 are dissolved in 30ml water, 1g gac be impregnated in this solution, flood 12 h, be heated to 100 ℃, drip hydrazine hydrate reduction, reduce rear cooling, filtration, washing, makes Pt-La/C catalyzer.
Shortening: add 0.3 gPt-La/C catalyzer in autoclave, 1 g paraaminomethyl benzoic acid, 30 ml deionized waters, 0.6 g H2SO4, airtight, be evacuated to-0.08 Mpa, rear nitrogen replacement air 2 times, the hydrogen exchange nitrogen 2 times used, reacting by heating temperature to 60 ℃, hydrogen pressure 0.5 MPa, reaction times 4 h, paraaminomethyl benzoic acid transformation efficiency is 99.3%; That makes passes through under alkaline-earth metal catalysis aminomethyl hexahydrobenzoic acid, and 220 ℃, under 2.0MPa condition, configuration conversion obtains tranamic acid.
Embodiment 2
Catalyzer preparation: 0.135g H2PtCl6 and 0.4g Ni (NO3) 2 are dissolved in 30ml water, 1g gac be impregnated in this solution, dipping 12 h, be heated to 100 ℃, drip KBH4 solution reduction, reduced rear cooling, filter, washing, makes Pt-Ni/C catalyzer.
Shortening: add 0.3 above-mentioned catalyzer in autoclave, 1 g paraaminomethyl benzoic acid, 30 ml deionized waters, 0.6 g H2SO4, airtight, be evacuated to-0.06 Mpa, rear nitrogen replacement air 2 times, the hydrogen exchange nitrogen 2 times used, reacting by heating temperature to 50 ℃, hydrogen pressure 0.6 MPa, reaction times 3 h, paraaminomethyl benzoic acid transformation efficiency is 98.6%; That makes passes through under alkaline-earth metal catalysis aminomethyl hexahydrobenzoic acid, and 220 ℃, under 2.5MPa condition, configuration conversion obtains tranamic acid.
Embodiment 3
Catalyzer preparation: 0.135g H2PtCl6 and 0.4g Co (NO3) 2 are dissolved in 30ml water, 1g gac be impregnated in this solution, dipping 12 h, be heated to 100 ℃, drip CH3COONa solution, reduced rear cooling, filter, washing, makes Pt-Co/C catalyzer.
Shortening: add 0.3 above-mentioned catalyzer in autoclave, 1 g paraaminomethyl benzoic acid, 30 ml deionized waters, 0.6 g H2SO4, airtight, be evacuated to-0.07 Mpa, rear nitrogen replacement air 2 times, the hydrogen exchange nitrogen 2 times used, reacting by heating temperature to 40 ℃, hydrogen pressure 0.5 MPa, reaction times 4 h, paraaminomethyl benzoic acid transformation efficiency is 97.6%; That makes passes through under alkaline-earth metal catalysis aminomethyl hexahydrobenzoic acid, and 220 ℃, under 2.2MPa condition, configuration conversion obtains tranamic acid.
Embodiment 4
Catalyzer preparation: 0.135g H2PtCl6 and 0.03g RuCl3 are dissolved in 30ml water, 1g gac be impregnated in this solution, dipping 13 h, be heated to 95 ℃, drip NaOH solution and Glacial acetic acid, reduced rear cooling, filter, washing, makes Pt-Ru/C catalyzer.
Shortening: add 0.3 g catalyzer in autoclave, 1 g paraaminomethyl benzoic acid, 30 ml deionized waters, 0.6 g H2SO4, airtight, vacuumize displaced air, 30 ℃ of temperature of reaction, hydrogen pressure 0.4 MPa, reaction times 4 h, paraaminomethyl benzoic acid transformation efficiency is 99.5%.
Embodiment 5
Catalyzer preparation: 0.135g H2PtCl6 and 0.4g Ce (NO3) 3 are dissolved in 30ml water, 1g gac be impregnated in this solution, flood 11 h, be heated to 105 ℃, drip the mixing solutions of hydrazine hydrate, KBH4, reduce rear cooling, filtration, washing, makes Pt-Ce/C catalyzer.
Shortening: add 0.3 g catalyzer in autoclave, 1 g paraaminomethyl benzoic acid, 30 ml deionized waters, 0.6 g H2SO4, it is airtight,, vacuumize displaced air, 60 ℃ of temperature of reaction, hydrogen pressure 0.5 MPa, reaction times 2 h, paraaminomethyl benzoic acid transformation efficiency is 99.6%.
Claims (1)
1. a method for preparing tranexamic acid from para-aminomethylbenzoic acid by catalytic hydrogenation, is characterized in that comprising the following steps:
A), in autoclave, add successively 0.3 times of Pt-M/C catalyzer, 1 times of paraaminomethyl benzoic acid, 30 times of deionized waters and 0.6 times of H2SO4 solubility promoter, airtight being evacuated to-0.08 ~-0.06Mpa, wherein, M is Ru, La, Ce, Co, the one in Ni element;
B), with air in nitrogen replacement autoclave 2 times, with hydrogen exchange nitrogen 2 times, and hydrogen pressure is adjusted to 0.3-0.6
MPa, is warming up to 30-60 ℃, and reaction 2-4 h generates aminomethyl hexahydrobenzoic acid;
C), to aminomethyl hexahydrobenzoic acid through under alkaline-earth metal catalysis, 220 ℃, under 2.0-2.5MPa condition, configuration conversion obtains tranamic acid;
Described Pt-M/C catalyzer is prepared by the following method: 1 part of gac be impregnated in H2PtCl6 that 0.01-1 doubly measures and the mixing solutions containing 0.01-1 M ion doubly, after fully infiltrating, flooding, use reductive agent heat reduction, reduce rear cooling, filter, washing, makes Pt-M/C catalyzer;
In described Pt-M/C catalyzer, the charge capacity of Pt is 1-5%, and the charge capacity of M is 0.1-5%;
The reductive agent that described Pt-M/C catalyzer uses in preparation process is a kind of in hydrazine hydrate, KBH4, CH3COONa or their mixture.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108689870A (en) * | 2018-07-30 | 2018-10-23 | 周道平 | A kind of preparation method of tranexamic acid |
| CN113042040A (en) * | 2021-03-26 | 2021-06-29 | 白云山东泰商丘药业有限公司 | Platinum-carbon catalyst and method for preparing tranexamic acid by using platinum-carbon catalyst |
| CN114380707A (en) * | 2022-01-20 | 2022-04-22 | 南京科瑞健医药科技有限公司 | Preparation method of trans-tranexamic acid |
| CN115445665A (en) * | 2022-08-29 | 2022-12-09 | 江西师范大学 | Composite nano catalyst for decomposing hydrazine hydrate to produce hydrogen and preparation method and application thereof |
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| CN103172528B (en) * | 2011-12-23 | 2014-10-08 | 烟台万润精细化工股份有限公司 | Tranexamic acid preparation method |
| CN104086452B (en) * | 2014-07-23 | 2016-04-06 | 常州齐晖药业有限公司 | A kind of shortening prepares the method for high purity (3,4-diamino-phenyl) (4-fluorophenyl) ketone |
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| CN111574388A (en) * | 2020-06-18 | 2020-08-25 | 安徽鼎旺医药有限公司 | Tranexamic acid and preparation method thereof |
| CN114014768A (en) * | 2021-12-03 | 2022-02-08 | 南京科瑞健医药科技有限公司 | Tranexamic acid without barium salt impurity and preparation method and preparation composition thereof |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108689870A (en) * | 2018-07-30 | 2018-10-23 | 周道平 | A kind of preparation method of tranexamic acid |
| CN108689870B (en) * | 2018-07-30 | 2020-12-18 | 周道平 | Preparation method of tranexamic acid |
| CN113042040A (en) * | 2021-03-26 | 2021-06-29 | 白云山东泰商丘药业有限公司 | Platinum-carbon catalyst and method for preparing tranexamic acid by using platinum-carbon catalyst |
| CN113042040B (en) * | 2021-03-26 | 2023-07-28 | 白云山东泰商丘药业有限公司 | Method for preparing tranexamic acid by using platinum-carbon catalyst |
| CN114380707A (en) * | 2022-01-20 | 2022-04-22 | 南京科瑞健医药科技有限公司 | Preparation method of trans-tranexamic acid |
| CN115445665A (en) * | 2022-08-29 | 2022-12-09 | 江西师范大学 | Composite nano catalyst for decomposing hydrazine hydrate to produce hydrogen and preparation method and application thereof |
| CN115445665B (en) * | 2022-08-29 | 2023-10-13 | 江西师范大学 | Composite nano catalyst for decomposing hydrazine hydrate to produce hydrogen and preparation method and application thereof |
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| CN103819353B (en) | 2015-07-29 |
| CN102276490B (en) | 2014-03-19 |
| CN102276490A (en) | 2011-12-14 |
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