GB2084145A - Process for preparing 4-aminomethylcyclohexanecarboxylic acid or mineral acid salt thereof - Google Patents
Process for preparing 4-aminomethylcyclohexanecarboxylic acid or mineral acid salt thereof Download PDFInfo
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- GB2084145A GB2084145A GB8128010A GB8128010A GB2084145A GB 2084145 A GB2084145 A GB 2084145A GB 8128010 A GB8128010 A GB 8128010A GB 8128010 A GB8128010 A GB 8128010A GB 2084145 A GB2084145 A GB 2084145A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B61/00—Other general methods
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C227/04—Formation of amino groups in compounds containing carboxyl groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C227/04—Formation of amino groups in compounds containing carboxyl groups
- C07C227/06—Formation of amino groups in compounds containing carboxyl groups by addition or substitution reactions, without increasing the number of carbon atoms in the carbon skeleton of the acid
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C227/14—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton from compounds containing already amino and carboxyl groups or derivatives thereof
- C07C227/16—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton from compounds containing already amino and carboxyl groups or derivatives thereof by reactions not involving the amino or carboxyl groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C229/00—Compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C229/46—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino or carboxyl groups bound to carbon atoms of rings other than six-membered aromatic rings of the same carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C61/00—Compounds having carboxyl groups bound to carbon atoms of rings other than six-membered aromatic rings
- C07C61/08—Saturated compounds having a carboxyl group bound to a six-membered ring
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
prior processes for preparing 4- aminomethylcyclohexanecarboxylic acid or mineral acid salt thereof require extreme conditions or are complicated. These problems are now overcome by preparing 4-ami- nomethylcyclohexanecarboxylic acid or a mineral acid salt thereof by catalytically hydrogenating 4-hydroxyiminomethylbenzoic acid, dispersed in an aqueous medium containing a mineral acid, in the presence of a catalyst of palladium, platinum and rhodium, and if desired converting the resulting mineral acid salt to the free acid. Trans- 4-aminomethylcyclohexanecarboxylic acid, which can be employed as an anti-plasmin agent, can be obtained from the resulting acid.
Description
SPECIFICATION
Process for preparing 4-aminomethylcyclohexanecarboxylic acid or mineral acid salt thereof
The present invention relates to a process for preparing 4-aminomethylcyclohexanecarboxylic acid or a mineral acid salt thereof from 4-hydroxyiminomethylbenzoic acid. More particularly, the present invention relates to a process for preparing 4-aminomethylcyclohexanecarboxylic acid or a mineral acid salt thereof, which is useful as an intermediate in the case of preparing trans-4-aminomethylcyclohexanecarboxylic acid which is useful as a medicine having an antiplasmin function, from 4-hydroxyiminomethylbenzoic acid by catalytic hydrogenation.
Hitherto, as a process for preparing 4-aminomethylcyclohexanecarboxylic acid from 4hydroxyiminomethylbenzoic acid or a derivative thereof, there have been known the following processes (1) and (2):
(1) A process for preparing an acetylated compound or an esterified compound of 4aminomethylcyclohexanecarboxylic acid by catalytically reducing 4-hydroxyiminomethylbenzoic acid or alkyl ester thereof in the presence of palladium catalyst in acetic anhydride (refer to
Japanese Patent Application Laying Open No. 51-52159).
(2) A process of (a) reducing the oxime structure of methyl 4-hydroxyiminomethylbenzoate by a palladium catalyst in a lower alcohol as the solvent, (b) hydrogenating the benzene ring of the thus reduced ester, and (c) deacetylating the ester linkage (hydrolysing the methyl ester) to obtain 4-aminomethylcyclohexanecarboxylic acid (refer to Japanese Patent Application Laying
Open 50-88042).
However, since the process (1) necessitates as the reaction conditions a high temperature such as 1 50 C, a high pressure such as 100 kg/cm2 and an organic solvent such as acetic anhydride or acetic acid as the reaction medium, industrialization of the process (1) is hardly carried out from the viewpoints of economy and safety.
The process (2) is too much complicated in its steps to carry out industrially.
In their studies for finding a new route of preparing 4-aminomethylcyclohexanecarboxylic acid (hereinafter abbreviated as 4-AMCHA) or a mineral acid salt thereof, the present inventors have found a process for simply preparing 4-AMCHA and/or a mineral acid salt thereof in a favorable yield without the demerits of the above-mentioned conventional processes and attained the present invention.
Namely, it is an object of the present invention to provide a process for preparing 4-AMCHA and/or a mineral acid salt thereof, the process comprising the step of catalytically hydrogenating 4-hydroxyiminomethylbenzoic acid dispersed in an aqueous medium containing a mineral acid in the presence of a catalyst obtained from a palladium compound, a platinum compound and a rhodium compound. Other objects will appear hereinafter.
The present invention relates to a process for preparing 4-AMCHA and/or a mineral acid salt thereof, which comprises an aminomethylation and a reduction of the benzene ring by one step reaction, in which 4-hydroxyiminomethylbenzoic acid (hereinafter abbreviated as 4-H BA) is catalytically reduced in an aqueous medium by the use of a catalyst containing three kinds of the noble metals, namely, palladium, platinum and rhodium, at a relatively low temperature of from room temperature to about 60"C in a mineral acidic condition.
The reaction formulae according to the process of the present invention are as follows:
H2 t a l / S F H 2 N - C H 2 m / R - COCH P .d, 2' 2 rr.ineral aces ; > E ^ 1- C A u;l-C'i~- 4 - fl:CHA ) 4-H BA, the starting substance of the present invention, is easily available at a low price as an industrial raw material by, for instance, bringing p-formylbenzoic acid available as a by-product in the case of preparing terephthalic acid into reaction with hydroxylamine hydrochloride.
The amount of water used as the reaction medium of the process according to the present invention (hereinafter referred to as the present process) is suitably 10 to 20 times of the weight of 4-H BA as the starting substance, and a mineral acid which forms a water-soluble salt with the product (4-AMCHA), for instance, hydrochloric acid, sulfuric acid and nitric acid is added to water in an amount of not less than one equivalent mol per mol of 4-H BA, preferably in an amount of 1 to 3 times of mol equivalent of 4-H BA, the concentration of the mineral acid in water being suitably about 3 to 5% by weight.
The effects of addition of the mineral acid to water as the reaction medium reside are in the facts of (1) the formation of an easily water-soluble mineral acid salt of 4-aminomethylbenzoic acid formed as an intermediate in the reduction of 4-H BA and its dissolution in the reaction medium to facilitate the hydrogenation of the benzene ring and (2) the protection of the aminomethyl group by the mineral acid to prevent the side reactions such as deamination, thus resulting in giving the mineral acid salt of 4-AMCHA in a favorable yield.
In cases where the mineral acid is not present in the reaction medium, the product of reduction of 4-hydroxyiminomethylbenzoic acid is 4-aminomethylbenzoic acid, the 4-AMCHA not being producible.
Namely, the addition of the mineral acid is one of the indispensable conditions of the present process.
Another indispensable condition of the present process is the use of a catalyst comprising the three metals, palladium, platinum and rhodium. Namely, by the use of a catalyst of single metal element or paradium, platinum or rhodium and by the use of a catalyst consisting solely of two metal elements such as palladium and platinum, platinum and rhodium, or further, ruthenium and palladium, a salt of 4-aminomethylbenzoic acid is formed by the reduction of the oxime structure, however, the hydrogenation of the benzene ring does not proceed at all.
The catalyst used in the present process comprises three novel metals of palladium, platinum and rhodium, and although the catalyst may contain other metals suitabley than these three metals, it is uneconomical. The state of the above-mentioned three kinds of metals may be metal itself, compounds of the metal, for instance, oxide, and alloy of two or three kinds of the metal.
It is preferable to use the catalyst carried on a carrier such as activated carbon or diatomaceous earth, the particularly preferable being the catalyst carried on activated carbon. The amount of metal carried on the carrier is usually 2 to 10% by weight of the total weight of the catalyst.
The amount of each of the three active components of the catalyst used in the present process may be more than about 0.25% by weight as a metal to the weight of the starting substance, 4
HBA, and although the ratio of palladium, platinum and rhodium may be optionally decided, in consideration of the activity and economics of the catalyst, the ratio, Pd:Pt:Rh, is preferably, around 1:1:1.
Of the reaction conditions in the catalytic hydrogenation of the present process, the temperature is relatively low as 10 to 60"C, the temperature of higher than 60"C being not favorable because of causing side reactions such as deamination. The pressure of hydrogen used in the reduction of higher than 1 atm may be sufficient, and generally, the reaction proceeds easily under the low pressure of 1 to 10 atm. The reaction period depends on the amount of catalyst, the reaction temperature and the pressure of hydrogen in the reaction system. Anyhow, the reaction is continued until absorption of hydrogen comes to an end. The reaction period is usually in the extent of 2 to 10 hours.
After the reduction is over, the catalyst is removed by filtration, and the filtrate (after further neutralizing the filtrate, in the case where the free acid is the object) is condensed under a reduced pressure and then, if necessary, acetone is added to the condensed filtrate followed with standing the mixture to cool. The thus separated and sedimented substance is collected by filtration, washed with a suitable solvent and dried to obtain 4-AMCHA or a mineral acid salt thereof.
As has been described, the present process is excellent in usefulness as an industrial method for preparing 4-AMCHA and a mineral acid salt.
The present invention will be explained more in detail while referring to the non-limitative examples as follows:
EXAMPLE 1:
In an autoclave of capacity of 500 ml made of pressure-resistance glass, 16.5 g (0.1 mol) of 4-hydroxyiminomethylbenzoic acid was suspended into 200 ml of aqueous 3.5% hydrochloric acid solution, and after adding a mixed catalyst of 5% palladium on activated carbon, 5% platinum on activated carbon and 5% rhodium on activated carbon in respective amounts shown in Table to the suspension, hydrogenation was carried out under the initial pressure of hydrogen of 5 kg/cm2 at a temperature in the range of room temperature to 45"C until the absorption of hydrogen came to an end while taking 6 hours. Then the catalyst was removed from the reaction mixture by filtration. After confirming the absence of the specific absorbance of 4-aminomethylbenzoic acid hydrochloride at 228 nm in the filtrate, the filtrate was condensed under a reduced pressure and then acetone was added to the condensate.
After leaving the acetonic mixture to cool, the thus sedimented crystals were collected by filtration and dried to obtain 15.9 g of white powdery product having a melting point of 175 to 1 77 C. By comparing the infrared spectrum of the product with that of the authentic specimen, the product was identified as 4-AMCHA hydrochloride, the yield being 82% of the theoretical.
As a result of esterifying the product to N-acetyl ester and n-butyl ester and analysing the ester by gas-chromatography to find the formation ratio of cis-trans isomers, the product was composed of 62 to 66% of cis-isomer and 34 to 38% of trans-isomer.
EXAMPLES 2 and 3:
In the same manner as in Example 1, however, using each of the mixed catalysts shown in
Table, the hydrogenation of 4-hydroxyiminomethylbenzoic acid was carried out. The product of
Example 2 and the product of Example 3 showed the same melting point as that of the product of Example 1, namely, 175-177"C, and both of them were identified as 4-AMCHA hydrochloride by infrared spectrum. The ratio of cis-trans isomers in each of the products of Examples 2 and 3 was in the same range as in the product of Example 1.
EXAMPLE 4:
In the same manner as in Example 1, except for suspending 4-hydroxyiminomethylbenzoic acid in 200 ml of aqueous 5% solution of sulfuric acid, the hydrogenation was carried out at a temperature in the range of room temperature to 50"C. By treating the reaction mixture in the same manner as in Example 1, 1 5.5 g of white powdery product having m.p. 205 to 206"C was obtained. The product was identified as 4-AMCHA sulfate by the same method as in
Example 1. The ratio of cis-trans isomers in the product was 68:32.
COMPARATIVE EXAMPLE 1:
In the same manner as in Example 1 except for suspending 4-hydroxyiminomethylbenzoic acid in 200 ml of water without containing 3.5% of aqueous hydrochloric acid in Example 1, the hydrogenation was carried out until the absorption of hydrogen came to an end after 4 hours. After the absorption of hydrogen came to an end, 20 ml of conc. hydrochloric acid was added to the mixture to dissolve the crystal because of sedimenting a part of crystals in the reaction mixture and the mixture was filtered to remove the catalyst. After condensing the filtrate and adding acetone to the condensate, the thus sedimented crystals were collected by filtration, and dried to obtain 14.5 g of white powdery product having melting point of 284 to 286"C (decomp.).The product was identified as 4-aminomethylbenzoic acid hydrochloride by comparison of its infrared absorption spectrum with that of the authentic specimen of 4-aminomethylbenzoic acid hydrochloride. The yield was 77%.
COMPARATIVE EXAMPLES 2 to 5:
In the same manner as in Example 1, however, using each one of the mixed catalysts shown in Table, a series of hydrogenation was carried out. According to the decrease of pressure of hydrogen in the autoclave, the hydrogenation of the oxime structure and thatof the benzene ring could be traced. Every product of the series of hydrogenation was identified as 4aminomethylbenzoic acid hydrochloride by the ultraviolet absorption spectrum at 228 nm and by the infrared absorption spectrum. The conditions and the results of Comparative Examples 2 to 5 are also shown in Table.
As are understood from Comparative Examples 1 and 2 to 5, (a) even in the presence of a ternary metal element catalyst of palladium, platinum and rhodium, the hydrogenation of 4hydroxyiminomethylbenzoic acid stops at the stage of 4-aminomethylbenzoic acid and (b) even in the presence of a mineral acid in aqueous reaction medium, the hydrogenation of 4hydroxyiminomethylbenzoic acid stops at the stage of 4-aminomethylbenzoic acid in the case where the catalyst system does not fulfil the conditions of the present invention.
Table: Reaction Conditions and Results of Hydrogenation in Examples 1 to 4 and in
Comparative Examples 1 to 5 Table: Reaction Conditions and Results of Hydrogenation in
Examples 1 to 4 and in Comparative Examples 1 to 5
Composition of catalyst (g) Period of Product absorp- Amount (g) 5%Pd-C*1) 5%Pt-C*2) 5%Rh-C*3) Mineral acid tion of Melting Mineral acid salt (or hydrogen point 5%Ru-C*4) (hours) ( C) acid of 4-aminomethyl- Yield salt of benzoic acid 4-AMCHA Example 1 1.6 1.6 1.6 hydrochloric acid 6 175-177 15.9 0 82 2 1.6 1.6 8.0 " 8.5 175-177 15.3 0 79 3 4.8 1.6 1.8 " 6 175-177 16.3 0 84 4 1.6 1.6 1.6 sulfuric acid 6 205-206 15.5 0 80 Comparative Example 1 1.6 1.6 1.6 - 4 284-286*5) 0 14.5 2 3.3 - - hydrochloric acid 3 - 0 16.7 3 1.6 1.6 - " 2.5 - 0 13.7 4 - 1.6 1.6 " 5 - 0 13.1 5 1.6 - 1.6 " 2.5 - 0 13.5 (5%Ru-C) Notes: *1) 5% palladium on activated carbon.
*2) 5% platinum on activated carbon.
*3) 5% rhodium on activated carbon.
*4) 5% ruhenium on activated carbon.
*5) The compound was decomposed at a temperature of 284 to 286 C.
Claims (14)
1. A process for preparing 4-aminomethylcyclohexanecarboxylic acid or a mineral acid salt thereof, which process comprises catalytically hydrogenating 4-hydroxyiminomethylbenzoic acid, dispersed in an aqueous medium containing a mineral acid, in the presence of a catalyst of palladium, platinum and rhodium, and if desired converting the resulting mineral acid salt to the free acid.
2. A process according to claim 1, wherein said mineral acid is hydrochloric acid, sulfuric acid or nitric acid.
3. A process according to claim 1 or 2, wherein said mineral acid is present in said aqueous medium in an amount not less than one molar equivalent per mol of 4-hydroxyiminomethylbenzoic acid.
4. A process according to claim 3, wherein said mineral acid is present in said aqueous medium in an amount of 1 to 3 molar equivalents per molar equivalent of 4-hydroxyiminomethylbenzoic acid.
5. A process according to any one of the preceding claims, wherein the concentration of said mineral acid is 3 to 5% by weight of said aqueous medium.
6. A process according to any one of the preceding claims, wherein 4-hydroxyiminomethylbenzoic acid is catalytically hydrogenated at a temperature of 10 to 60"C.
7. A process according to any one of the preceding claims, wherein 4-hydroxyiminomethylbenzoic acid is catalytically hydrogenated under an initial pressure of hydrogen of 1 to 10 atmospheres.
8. A process according to any one of the preceding claims, wherein 4-hydroxyiminomethylbenzoic acid is catalytically hydrogenated for 2 to 10 hours.
9. A process according to any one of the preceding claims, wherein the catalyst is composed of palladium metal, platinum metal and rhodium metal.
10. A process according to claim 9, wherein the catalyst is a mixture of palladium on activated carbon, platinum on activated carbon and rhodium on activated carbon.
11. A process according to any one of claims 1 to 8, wherein the catalyst is composed of a palladium compound, a platinum compound and a rhodium compound.
1 2. A process according to any one of claims 1 to 8, wherein the catalyst is composed of either palladium metal or a palladium compound, either platinum metal or a platinum compound, and either rhodium metal or a rhodium compound.
1 3. A process for preparing 4-aminomethylcyclohexanecarboxylic acid or a mineral salt thereof substantially as hereinbefore described in any one of Examples 1 to 4.
14. Trans-4-aminomethylcyclohexanecarboxylic acid obtained from 4-aminomethylcyclohexanecarboxylic acid or a mineral salt thereof prepared by a process as claimed in any one of the preceding claims.
1 5. Cis-4-aminomethylcyclohexanecarboxylic acid obtained from 4-aminomethylcyclohexanecarboxylic acid or a mineral salt thereof prepared by a process as claimed in any one of claims 1 to 13.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP55128962A JPS5951934B2 (en) | 1980-09-17 | 1980-09-17 | Method for producing 4-aminomethylcyclohexanecarboxylic acid and its mineral acid salt |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| GB2084145A true GB2084145A (en) | 1982-04-07 |
| GB2084145B GB2084145B (en) | 1984-07-11 |
Family
ID=14997713
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB8128010A Expired GB2084145B (en) | 1980-09-17 | 1981-09-16 | Process for preparing 4-aminomethycyclohexane-carboxylic acid or mineral acid salt thereof |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JPS5951934B2 (en) |
| CA (1) | CA1179369A (en) |
| DE (1) | DE3137092C2 (en) |
| FR (1) | FR2490218A1 (en) |
| GB (1) | GB2084145B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102276490A (en) * | 2011-06-30 | 2011-12-14 | 常州寅盛药业有限公司 | Method for preparing tranexamic acid from para-aminomethylbenzoic acid by catalytic hydrogenation |
| US8846973B2 (en) | 2008-07-23 | 2014-09-30 | Mitsubishi Gas Chemical Company, Inc. | Process for producing hydrogenated aromatic polycarboxylic 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 |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021107047A1 (en) * | 2019-11-29 | 2021-06-03 | 株式会社Ｄｎｐファインケミカル | Method for producing 4-(aminomethyl)cyclohexane carboxylic acid |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2265725A1 (en) * | 1974-03-27 | 1975-10-24 | Asahi Chemical Ind | 4-Aminomethyl-cyclohexane carboxylic acid prepn. - by hydrogenating para-aminomethyl benzoic acid in presence of ruthenium catalysts and alkal-ine hydroxides |
| JPS5152159A (en) * | 1974-10-31 | 1976-05-08 | Toray Industries | 44 asechiruaminomechirushikurohekisankarubonsan mataha sonojudotaino seizoho |
-
1980
- 1980-09-17 JP JP55128962A patent/JPS5951934B2/en not_active Expired
-
1981
- 1981-09-15 CA CA000385915A patent/CA1179369A/en not_active Expired
- 1981-09-16 FR FR8117501A patent/FR2490218A1/en active Granted
- 1981-09-16 GB GB8128010A patent/GB2084145B/en not_active Expired
- 1981-09-17 DE DE3137092A patent/DE3137092C2/en not_active Expired
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8846973B2 (en) | 2008-07-23 | 2014-09-30 | Mitsubishi Gas Chemical Company, Inc. | Process for producing hydrogenated aromatic polycarboxylic acid |
| CN102276490A (en) * | 2011-06-30 | 2011-12-14 | 常州寅盛药业有限公司 | Method for preparing tranexamic acid from para-aminomethylbenzoic acid by catalytic hydrogenation |
| CN102276490B (en) * | 2011-06-30 | 2014-03-19 | 常州寅盛药业有限公司 | Method for preparing tranexamic acid from para-aminomethylbenzoic acid by catalytic hydrogenation |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| GB2084145B (en) | 1984-07-11 |
| CA1179369A (en) | 1984-12-11 |
| FR2490218A1 (en) | 1982-03-19 |
| DE3137092C2 (en) | 1983-02-03 |
| JPS5753440A (en) | 1982-03-30 |
| FR2490218B1 (en) | 1984-04-20 |
| DE3137092A1 (en) | 1982-04-08 |
| JPS5951934B2 (en) | 1984-12-17 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PCNP | Patent ceased through non-payment of renewal fee |