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CA1179369A - Process for preparing 4-aminomethylcyclohexane-carboxylic acid or mineral acid salt thereof - Google Patents

Process for preparing 4-aminomethylcyclohexane-carboxylic acid or mineral acid salt thereof

Info

Publication number
CA1179369A
CA1179369A CA000385915A CA385915A CA1179369A CA 1179369 A CA1179369 A CA 1179369A CA 000385915 A CA000385915 A CA 000385915A CA 385915 A CA385915 A CA 385915A CA 1179369 A CA1179369 A CA 1179369A
Authority
CA
Canada
Prior art keywords
acid
process according
mineral acid
hydroxyiminomethylbenzoic
mineral
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.)
Expired
Application number
CA000385915A
Other languages
French (fr)
Inventor
Masaaki Takahashi
Takashi Yamauchi
Akira Iizuka
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Kureha Corp
Original Assignee
Kureha Corp
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Kureha Corp filed Critical Kureha Corp
Application granted granted Critical
Publication of CA1179369A publication Critical patent/CA1179369A/en
Expired legal-status Critical Current

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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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B61/00—Other general methods
    • 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
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • 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

TITLE OF THE INVENTION:

ACID OR MINERAL ACID SALT THEREOF

ABSTRACT OF THE DISCLOSURE:
The present invention relates to a process for preparing 4-aminomethylcyclohexanecarboxylic acid or mineral acid salt thereof from 4-hydroxyiminomethylbenzoic acid by catalytic hydrogenation. The catalytic hydrogenation is carried out in an aqueous medium containing a mineral acid.

Description

117936~

BACK5ROUND AND DE~AILED DESCRIPTION OF THE INVENTIO~:
~he 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-amino-methylcyclohexanecarboxylic acid or a mineral acid salt thereof, which is useful as an intermediate in tne case of preparing trans-4-aminomethylcyclohexanecarboxylic acid which is useful as a medicine having an antiplasmin function, from 4-hydroxyi.lllino-methylben20ic acid by catalytic hydrogenation.
Hitherto, as a process for preparing ~-aminomethyl-cyclohexanecarboxylic acid From 4-hydroxyiminostlethylbenzoic 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 4-aminomethylcyclohexanecarboxylic acid by catalytically reducing 4-hydroxyiminomethylbenzo.ic acid or alkyl ester thereof in the presence of palladium catalyst in acetic anhydride trefer 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-aminomethyl-cyclohexanecarboxylic acid (refer to Japanese Patent Application i 179369 ~aying Open No. 50-88042).
However, since the process (1~ necessitates as the reaction conditions a high temperature such as 150C, a high pressure such as 100 kg/cm 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 g-aminomethylcyclohexanecarboxylic acid (her~inaft~r ~bbrevia~ed as 4-AMCHA) or a mineral acid sal-t thereof, the present inventors have found a process for simply preparing ~-AMCHA
and~or a mineral acid s~lt 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 ~ ~ ~793~g aminomethylation and a reduction of the benzene ring by one step reaction, in which 4-hydroxyiminomethylbenzoic acid (hereinafter abbreviated as 4-EIBA) iS catalytically reduced in an agueous medium by the use of a cat:alyst containing three kinds of the noble metals, namely, palladium, platinum and rhodium, at a relatively low temperature of from room temperature to about 60C in a mineral acidic condition.
The reaction formulae according to the process of the present invention are as follows:

~0-N-C~1~ 3coo~ cata1yst (Pd,~ ~2N C}12 Pt and ~h) ( 4-HBA) min~ral acid ~
3 H2N-CH2-~3 COOH
( 4-AMCHA)
4-HBA, ~le 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-HBA as the starting substance, and a mineral 1 ~7936~
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-HBA, preferably, in an amount of 1 to 3 times thermal equivalent of 4-HBA, 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 in the :Eacts that ~1) the formation of an easily water-soluble mineral acid salt of 4-aminomethylbenzoic acid formed as an intermediate in the reduction of 4-HB~ and its dissolution in the reaction medium to facilitate the hydrogenation of the benzene rin~ a~d (2) the protection of the aminomethyl group by the mineral acid to prevent side reactions such as deamination, thus resultin~3 in yielding 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 reduc~ion of 4-hydroxyimino-methylbenzoic acid is ~-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 of palladium, platinum or rhodium and by the use of a catalyst consisting solely of two 1 ~7g3~;~

metal elements such as palladium and platinum, platinum and rhodium, or further, ruthenium ancl palladium, a salt o~
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, an~
although the catalyst may contain other 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, oxi~e, 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 preEerable being the catalyst carried on activated carbon. The amount of metal carried on t~e carrier is usually 2 to 10~ by weight of the total weight oE 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 60C, the -temperature of higher than 60C being not favorable 11 7~3B~

because of causing side reactions such as deamination. The pressure of hydrogen used in the reduction of higher than 1 atm may be sufficientr 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 the absorption of hydrogen comes to an end. The reaction period is usually in the extent of 2 to lO hours.
lQ After the reduction is over, the ca-talyst is removed by filtration, and the filtrate (after further neutraliziny the filtrate, in the case where the free acid is the object) is condensed under a reduced pressure and then, if n~cessary, 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 nvention will be explained more in detail while referring to the non-limitative examples as follows:
EXAMP~E 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 ~00 ml of aqueous 3.5% hydrochloric acid ~ l~9~B9 solution, and after adding a mixed catalyst of 5% palladium on activated carbon, 5% platinum on activated carbon ancl 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/cm at a temperature in the range of room temperature to 45C until the absorption of hydrogen came to an end while taking 6 hours. Then the catalyst was removed from the reaction mixture by fil-tration.
After confirming the absence of the specific absorbance oE
4-aminomethylbenzoic acid hydrochloride at 22~ nm in the filtrate, the filtrate was condensed under a reduced press~re and then acetone was added to the condensate.
After leaving the acetonic rnixture 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 177C. By comparing the infrared spectrum of the product with that of the authentic specimen, the product was identified as 4-.~1CHA 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 ~.179369 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 - 177C, 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.
E~AMPLE 4:
In the same manner as in Example 1, except ~or suspendin~
4-hydroxyiminomethyLhenzoic acid in 200 ml of aqueous 5% soluti.on of sulfuric acid, the hydrogenation was carried out a-t a tempera-ture in the range of room temperature to 50C. By treating the reaction mixture in the same manner as in Example 1 15.5 g of white powdery product having m.p. 20~ _o 706C 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 mtil 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 1 ~9369 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 286C
(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-amino-methylbenzoic acid hydrochloride. The yield was 77%.
COMPARATIVE EXAMPLES 2 to 5:
. . . ... .. . . . . _... .. .... .
In the same manner as in Example 1, however, using each one o the mixed catalysts shown in Table, a series of hydrogena-tion was carried out. According to the decrease of pressure of hydrogen in the autoclave, the hydrogenation oE the oxime structure and that of the benzene ring could be traced. Every product of the series of hydrogenation was identified as 4-aminomethylbenzoic 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 4-hydroxyiminomethylbenzoic 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 4-hydroxy-l 1 7~3B~

iminomethylbenzoia 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.

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Claims (9)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE PROPERTY
OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A process for preparing 4-aminomethylcyclohexanecarbo-xylic acid or a mineral acid salt thereof, 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 compound of palladium, a compound of platinum and a compound of rhodium.
2. The process according to claim 1, wherein said mineral acid is a member selected from the group consisting of hydrochloric acid, sulfuric acid and nitric acid.
3. The process according to claim 1 , wherein said mineral acid is contained in said aqueous medium in an amount not less than one equivalent mol per mol of 4-hydroxyiminomethyl-benzoic acid.
4. The process according to claim 3, wherein said mineral acid is contained in said aqueous medium in an amount of 1 to 3 times of mol equivalent of 4-hydroxyiminomethylbenzoic acid.
5. The process according to claim 1, wherein the concentration of said mineral acid is 3 to 5% by weight of said aqueous medium.
6. The process according to claim 1, wherein 4-hydroxyiminomethylbenzoic acid is catalytically hydrogenated at a temperature of 10 to 60°C.
7. The process according to claim 1, wherein 4-hydroxyiminomethylbenzoic acid is catalytically hydrogenated under an initial pressure of hydrogen of 1 to 10 atmospheric pressure.
8. The process according to claim 1, wherein 4-hydroxyiminomethylbenzoic acid is catalytically hydrogenated for 2 to 10 hours.
9. The process according to claim 1, wherein the catalyst is a mixture of palladium on activated carbon, platinum on activated carbon and rhodium on activated carbon.
CA000385915A 1980-09-17 1981-09-15 Process for preparing 4-aminomethylcyclohexane-carboxylic acid or mineral acid salt thereof Expired CA1179369A (en)

Applications Claiming Priority (2)

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
JP128962/80 1980-09-17

Publications (1)

Publication Number Publication Date
CA1179369A true CA1179369A (en) 1984-12-11

Family

ID=14997713

Family Applications (1)

Application Number Title Priority Date Filing Date
CA000385915A Expired CA1179369A (en) 1980-09-17 1981-09-15 Process for preparing 4-aminomethylcyclohexane-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)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105418405A (en) * 2008-07-23 2016-03-23 三菱瓦斯化学株式会社 Production method of hydrogenated compound of aromatic polycarboxylic acid
CN103819353B (en) * 2011-06-30 2015-07-29 常州寅盛药业有限公司 The method of the preparing tranexamic acid from para-aminomethylbenzoic acid by catalytic hydrogenation that productive rate is high
JP7628505B2 (en) * 2019-11-29 2025-02-10 株式会社Ｄｎｐファインケミカル宇都宮 Method for producing 4-(aminomethyl)cyclohexanecarboxylic acid
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

Family Cites Families (2)

* Cited by examiner, † Cited by third party
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

Also Published As

Publication number Publication date
JPS5753440A (en) 1982-03-30
DE3137092C2 (en) 1983-02-03
GB2084145B (en) 1984-07-11
FR2490218B1 (en) 1984-04-20
FR2490218A1 (en) 1982-03-19
JPS5951934B2 (en) 1984-12-17
DE3137092A1 (en) 1982-04-08
GB2084145A (en) 1982-04-07

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