CN103819353B - The method of the preparing tranexamic acid from para-aminomethylbenzoic acid by catalytic hydrogenation that productive rate is high - Google Patents
The method of the preparing tranexamic acid from para-aminomethylbenzoic acid by catalytic hydrogenation that productive rate is high Download PDFInfo
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- CN103819353B CN103819353B CN201410079178.XA CN201410079178A CN103819353B CN 103819353 B CN103819353 B CN 103819353B CN 201410079178 A CN201410079178 A CN 201410079178A CN 103819353 B CN103819353 B CN 103819353B
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Abstract
The present invention relates to a kind of method of preparing tranexamic acid from para-aminomethylbenzoic acid by catalytic hydrogenation, adopt Pt-M/C catalyzer (M=Ru, La, Ce, Co, Ni), for paraaminomethyl benzoic acid shortening, use the reaction conditions of this catalyzer gentle, temperature of reaction 30-60 DEG C, hydrogen pressure 0.3-0.5MPa, catalyst activity is high, reaction 2-4 hour, the transformation efficiency of paraaminomethyl benzoic acid reaches 99%, to aminomethyl cyclohexane carboxylic acid yield 95%, shortens the reaction times, improve specific productivity, there is very high industrial application value.
Description
The application is divisional application, the application number of original application: 201110181414.5, 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 in a mild condition paraaminomethyl benzoic acid shortening being prepared as tranamic acid.
Background technology
Tranamic acid is trans to aminomethyl hexahydrobenzoic acid, by to the reversible being incorporated into Methionin on proplasmin molecule, thus 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 the prussiate of severe toxicity in methyl acrylate method, therefore the industrial paraaminomethyl benzoic acid method that mainly uses produces tranamic acid.
Paraaminomethyl benzoic acid method is produced in tranamic acid process, catalytic hydrogenation is most important step, through catalytic hydrogenation, cis and trans to aminomethyl hexahydrobenzoic acid is obtained to aminomethyl phenyl first, again cis is transformed generation to aminomethyl hexahydrobenzoic acid trans to aminomethyl hexahydrobenzoic acid, i.e. tranamic acid.Catalyzer used in catalytic hydrogenation is the precious metal such as Pt, Rh, Ru normally.
US 3932497 uses Ru catalyzer, and Ru is loaded to inert support as on aluminum oxide, diatomite, gac, barium sulfate, calcium carbonate, Ru content is in the catalyst 1 ~ 10 wt%.Temperature 150 DEG C, react under hydrogen pressure 100 kg/cm2, 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, temperature 90 DEG C, react under hydrogen pressure 90 kg/cm2, obtain 43.5 g after product process to aminomethyl hexahydrobenzoic acid.
GB 2084145 uses Pd, Pt, Rh mixed catalyst, respectively Pd, Pt, Rh are loaded to obtained 5%Pd-C, 5%Pt-C, 5%Rh-C catalyzer on gac, these three kinds of catalyst mix are added in autoclave, add paraaminomethyl benzoic acid, water, hydrochloric acid again, temperature of reaction 10-60 DEG C, hydrogen pressure 1-10 kg/cm2, reacts 6 h, to the yield of aminomethyl hexahydrobenzoic acid about 80%.
JP 58032848 uses Rh catalyzer, and Rh is loaded to obtained 5%Rh-C catalyzer on gac, temperature of reaction 40 DEG C, hydrogen pressure 30 kg/cm2, reacts 3 h, reaches 90% to the yield of aminomethyl heptanaphthenic acid.
Current industrial main use PtO2 makes catalyzer, 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, sulfuric acid is added under stirring, heating makes molten, add platinum dioxide again, eliminate in tank pass into after air hydrogen start reaction.At about 40 DEG C, hydrogen pressure 0.5-1.5 kg/cm2 reaction to suction hydrogen reaches theoretical amount and only no longer inhales hydrogen.Eliminate Yu Qing, extract reaction solution filtration, take out platinum black.Filtrate is heated to 90 DEG C, 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 concentrated, obtain the cis liquid (concentration is that every 10 mol para-amino-methyl-benzoic acid reaction solutions are concentrated into 5 liters) to aminomethyl cyclohexane carboxylic acid.The ratio of components of conversion process is to aminomethyl cyclohexane carboxylic acid cis liquid (v): hydrated barta (w): water (v): ethanol (v)=1: 2.1: 1.6: 6.61.To add in retort to aminomethyl cyclohexane carboxylic acid cis liquid and hydrated barta, airtight, be warming up to 200 DEG C, pressure is 18-20 kg/cm2, reacts 14 hours.Reaction is finished, and is chilled to 60-70 DEG C, adds water and be warming up to 90 DEG C, be 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, filter, crystallization washing with alcohol, is filtered dry, dry, obtains tranamic acid.
Use Ru catalyzer in catalytic hydrogenation, 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 is gentle, 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 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 successively, is airtightly 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 DEG C, reaction 2-4 h generates aminomethyl cyclohexane carboxylic acid;
C), to aminomethyl cyclohexane carboxylic acid through under alkaline-earth metal catalysis, 220 DEG C, under 2.0-2.5MPa condition, configuration conversion obtains tranamic acid.
The principal reaction equation that 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 the H2PtCl6 of 0.01-1 times amount and contain in the mixing solutions of 0.01-1 M ion (M=Ru, La, Ce, Co or Ni) doubly, after abundant infiltration, dipping, use reductive agent reduces, and reduce rear cooling, filtration, washing, obtained Pt-M/C catalyzer, wherein in Pt-M/C catalyzer, the charge capacity of Pt is the charge capacity of 1-5%, 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 hydrazine hydrate, a kind of in KBH4, CH3COONa or their mixture.
The invention has the beneficial effects as follows:
1. method for preparing catalyst is simple, by dipping, to reduce active constituent loading on gac, decreases the usage quantity of precious metal, improve the utilization ratio of precious metal.
2. because catalyst activity is high, only need react 2-4 hour, the transformation efficiency of paraaminomethyl benzoic acid just can reach more than 98%, and can reach more than 95% to aminomethyl cyclohexane carboxylic acid yield, shortens the reaction times, improves specific productivity.
3. the reaction conditions adopted in paraaminomethyl benzoic acid catalytic hydrogenation is gentleer, temperature of reaction
30-60 DEG C, 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
For 1 gram of catalyst preparing: 0.135g H2PtCl6 and 0.05g La (NO3) 3 is dissolved in 30ml water, 1g gac be impregnated in this solution, flood 12 h, be heated to 100 DEG C, drip hydrazine hydrate reduction, reduce rear cooling, filtration, washing, obtained 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, hydrogen exchange nitrogen 2 times, reacting by heating temperature to 60 DEG C, 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 cyclohexane carboxylic acid, and 220 DEG C, under 2.0MPa condition, configuration conversion obtains tranamic acid.
Embodiment 2
Catalyst preparing: 0.135g H2PtCl6 and 0.4g Ni (NO3) 2 is dissolved in 30ml water, 1g gac is impregnated in this solution, flood 12 h, be heated to 100 DEG C, drip KBH4 solution reduction, reduce rear cooling, filter, washing, obtained 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, hydrogen exchange nitrogen 2 times, reacting by heating temperature to 50 DEG C, 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 cyclohexane carboxylic acid, and 220 DEG C, under 2.5MPa condition, configuration conversion obtains tranamic acid.
Embodiment 3
Catalyst preparing: 0.135g H2PtCl6 and 0.4g Co (NO3) 2 is dissolved in 30ml water, 1g gac is impregnated in this solution, flood 12 h, be heated to 100 DEG C, drip CH3COONa solution, reduce rear cooling, filter, washing, obtained 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, hydrogen exchange nitrogen 2 times, reacting by heating temperature to 40 DEG C, 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 cyclohexane carboxylic acid, and 220 DEG C, under 2.2MPa condition, configuration conversion obtains tranamic acid.
Embodiment 4
Catalyst preparing: 0.135g H2PtCl6 and 0.03g RuCl3 is dissolved in 30ml water, 1g gac be impregnated in this solution, flood 13 h, be heated to 95 DEG C, drip NaOH solution and Glacial acetic acid, reduce rear cooling, filter, washing, obtained 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, temperature of reaction 30 DEG C, hydrogen pressure 0.4 MPa, reaction times 4 h, paraaminomethyl benzoic acid transformation efficiency is 99.5%.
Embodiment 5
Catalyst preparing: 0.135g H2PtCl6 and 0.4g Ce (NO3) 3 is dissolved in 30ml water, 1g gac be impregnated in this solution, flood 11 h, be heated to 105 DEG C, drip the mixing solutions of hydrazine hydrate, KBH4, reduce rear cooling, filtration, washing, obtained 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, temperature of reaction 60 DEG C, 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 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 successively, be airtightly evacuated to-0.08 ~-0.06Mpa, wherein, M is La, one in Ce, Co, 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 DEG C, and reaction 2-4 h generates aminomethyl cyclohexane carboxylic acid;
C), to aminomethyl cyclohexane carboxylic acid through under alkaline-earth metal catalysis, 220 DEG C, 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 the H2PtCl6 of 0.01-1 times amount and contain in the mixing solutions of 0.01-1 M ion doubly, after abundant infiltration, dipping, use reductive agent heat reduction, reduce rear cooling, filter, washing, obtained Pt-M/C catalyzer;
In described Pt-M/C catalyzer, the charge capacity of Pt is the charge capacity of 1-5%, M is 0.1-5%;
The reductive agent that described Pt-M/C catalyzer uses in preparation process is hydrazine hydrate, a kind of in KBH4, CH3COONa or their mixture.
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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 |
| CN104151183B (en) * | 2014-07-29 | 2016-04-13 | 浙江工业大学 | A kind of preparation method of 4-acetyl aminomethyl methyl cyclohexanecarboxylaand |
| CN106816606B (en) * | 2017-01-19 | 2019-06-07 | 广西师范大学 | A kind of preparation and application of recessed cube PtLa alloy nanometer crystals catalyst |
| CN107954887B (en) * | 2017-11-27 | 2020-02-21 | 常州寅盛药业有限公司 | Method for preparing tranexamic acid |
| CN108689870B (en) * | 2018-07-30 | 2020-12-18 | 周道平 | Preparation method of tranexamic acid |
| CN109713323B (en) * | 2018-11-27 | 2021-02-09 | 浙江大学 | Preparation method of PtNi/C alloy catalyst |
| CN111574388A (en) * | 2020-06-18 | 2020-08-25 | 安徽鼎旺医药有限公司 | Tranexamic acid and preparation method thereof |
| 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 |
| 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 |
| 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 |
| 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 |
| CN115778896B (en) * | 2022-12-01 | 2024-04-02 | 湖南洞庭药业股份有限公司 | Tranexamic acid injection and its preparation method and use |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3932497A (en) * | 1972-10-02 | 1976-01-13 | Asahi Kasei Kogyo Kabushiki Kaisha | Process for preparing 4-aminomethyl cyclohexane carboxylic acid-1 |
| US4048222A (en) * | 1974-03-04 | 1977-09-13 | Kureha Kagaku Kogyo Kabushiki Kaisha | Process for preparing trans-4-aminomethyl-cyclohexane-1-carboxylic acid |
| CN101069850A (en) * | 2006-05-12 | 2007-11-14 | 中国科学院大连化学物理研究所 | Loaded and non-loaded catalyst and preparing method |
Family Cites Families (2)
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| JPS5951934B2 (en) * | 1980-09-17 | 1984-12-17 | 呉羽化学工業株式会社 | Method for producing 4-aminomethylcyclohexanecarboxylic acid and its mineral acid salt |
| CN100336799C (en) * | 2003-02-28 | 2007-09-12 | 湖南洞庭药业股份有限公司 | Producing method of of tranexamic acid |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3932497A (en) * | 1972-10-02 | 1976-01-13 | Asahi Kasei Kogyo Kabushiki Kaisha | Process for preparing 4-aminomethyl cyclohexane carboxylic acid-1 |
| US4048222A (en) * | 1974-03-04 | 1977-09-13 | Kureha Kagaku Kogyo Kabushiki Kaisha | Process for preparing trans-4-aminomethyl-cyclohexane-1-carboxylic acid |
| CN101069850A (en) * | 2006-05-12 | 2007-11-14 | 中国科学院大连化学物理研究所 | Loaded and non-loaded catalyst and preparing method |
Non-Patent Citations (1)
| Title |
|---|
| 氨甲环酸原料药合成工艺研究;孙加亮;《中国实用医药》;20110620;第6卷(第17期);第160-161页 * |
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