CA1207341A - Diamines and a process for their preparation - Google Patents
Diamines and a process for their preparationInfo
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- CA1207341A CA1207341A CA000434223A CA434223A CA1207341A CA 1207341 A CA1207341 A CA 1207341A CA 000434223 A CA000434223 A CA 000434223A CA 434223 A CA434223 A CA 434223A CA 1207341 A CA1207341 A CA 1207341A
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- diamines
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3225—Polyamines
- C08G18/3234—Polyamines cycloaliphatic
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
DIAMINES AND A PROCESS FOR THEIR PREPARATION
ABSTRACT OF THE DISCLOSURE
Diamines corresponding to the general formula
ABSTRACT OF THE DISCLOSURE
Diamines corresponding to the general formula
Description
~L2~
Mo-2503 LeA 21,940 DIAMINES AND A PROCESS FOR THEIR PREPARATION
.
Thls invention relates to new dip~imary amino cyclohexyl methyl anilines which are mono- or di-sub-stituted on the aromatic ring and may be present as isomeric mixtures and/or as mixtures with minor quanti-ties of the corresponding unhydrogenated or perhYdro-genated diamines, and to a process for the preparation of the new compounds by catalytic partial hydrogenation of the underlying aromatic diamines.
BACKGROUND OE` THE INVENTIO~
Ami~ocyclohexyl-alkyl-anilines which are either unsubstituted or substituted on both rings have already been disclosed in U.S. Patent 2, 511, 028. They may be used~ for example, as intermediate products for the production of dyes, rubber auxiliaries, surface active substances, polyamides or polyester polyamides or as corrosion protecting agents. According to the teaching of this reference, the compounds are prepared by catalytic partial hydrogenation of the underlying aromatic diamines. This process has, however, the dis-ad~antage that the asymmetric hydrogenation of diamino-diphenyl alkanes cannot be caxried out selectively, with the result that the ~ield of the aforesaid partially-hydrogenated diamines is, at most, only slightly above 50~ of the theoretical yield, as may be seen from the examples of practical application given in the reference.
Primary aminocyclohexyl-methyl-anilines are not only valuable intermediate products for the fields of application mentioned above, however, but are, in particular, also interesting chain-lengthening agents for polyurethane chemistry, having amino groups of Mo-2503 ~eA 21,940 73~
graded reactivity. The present invention was, therefore, based on the problem of finding new compounds of this type in which the amino groups would show a more marked differentiation of their reactivities due to the additional substitution on the aromatic ring and which would be able to be prepared more selectively due to the asymmetric substitution.
This problem was solved by th~ preparation of the diamines and diamine mixtures according to the inven-tion and by a process suitable for their preparation.
DESCRIPTION OF THE INVENTION
The present invention relates to diaminescorresponding to the formula, Rl (H2N)m - ~ CH2 ~ NH2 (NH2)n R
wherein R1 and R may be identical or di~erentt one o~
which represents a straight-chained or branched-chained alkyl group having 1 to 12 carbon atoms, and the other o which may represent hydrogen or such an alkyl group, and m and n each represent 0 or 1 provided that the sum of m ~ n = 1 and where m or n = 0 the free valency is saturated by hydrogen.
These diamines are optionally in the form o~ isomeric mixtures and optionally contain up to 35%, by weight, based on the total mixture, of the corresponding perhydrogenated diamines, and/or optionally mi~ed with up to 10%, by weight, based on the total mixture, of the corresponding unhydrogenated aromatic diamines.
Mo-2503 ~ Z~7~
This invention also relates to a process for the preparation of these diamines or diamine mixtures, which is characterized in that aromatic diamines corre-sponding to the formula:
Rl (H2N)m ~ CH2 ~ NH2 (NH2)n R
optionally present as isomeric mixtures, in which formula Rl, R , m and n have the meaning indicated above, are catalytically-hydrogenated with the addition o~ 3 mols of hydrogen per mol of diamine.
Aromatic diamines corresponding to the general formula above, which are suitable as starting materials for the process according to the invention, may be either pure substances or isomeric mixtures. Particularly suitable are those diamines corresponding to thls ormula in which either Rl and R2, ~hich may be identical or diferent, denote branched or unbranchecl alkyl groups having 1 to 4 carbon atoms, in particular methyl groups or 20 R denotes an alkyl group having 1 to 4 carbon atoms, in particular a methyl group, and R denotes hydrogen.
Examples o~ aromatic diamines suitable as starting material according to the invention include the diamines corresponding to the general formula Rl (H2N)m ~ CH2 ~ - NH2 (NH2)n R
Mo-2503 73~1 which are produced by arylamine/formaldehyde conden-sation using a mixture of aniline and substituted anilines correspondin~ to the formula:
Rl 2 R2 as the "arylamine" according to German Offenlegungs-schriften 2,133,870; 29149,998; and 2,700,185; or, by the reaction of o-nitrobenzyl halides with substituted anilines of the above formula, reduction of the nitro group and molecular rearrangement according to Belgium Patent 864,533 or British Patent 1,567,114.
Preferred starting materials for the process according to the invention include: 4,2'-diamino-3,5-dimethyl-diphenyl methane 9 4,2'-diamino-3,5-diethyl-di-phenyl methane, 4,2'-diamino-3,~-diisopropyl-diphenyl methane, and 4,2'-diamino-3-ethyl-5-Tne~hyl-diphenyl methane; isomeric mixtures containing, a~ their main component: 4,4'-diamino-3,5-dimethyl-diphenyl methane, 4,4'-diamino-3,5-diethyl-diphenyl methane, 4,4'-di-amino-3,5-diisopropyl-diphenyl methane, and 4,4'-di-amino-3-methyl-5-ethyl-diphenyl methane; and isomeric mixtures containing, as their main components: 4,2l-di-amino-3-methyl-diphenyl methane, 4,2'-diamino-3-ethyl-diphenyl methane, and 4,2'-diamino-3-isopropyl-diphenyl methane. Other preferred starting materials for the process include mixtures of the above-identified compounds with correspondîng 4,4'-diamino-3-alkyl- or ~,4'-diamino-3-alkyl-diphenyl methanes, including:
4,4'-diamino-3-methyl-diphenyl methane, 4,4'-diamino-3-ethyl-diphenyl methane, and 4,4'-diamino-3-isopropyl-di-phenyl methane; and mixtures of the above-identlfied :1~073~:~
disubstituted compounds with other position isomers, including, for example: 4,2'-diamino-3-alkyl-diphenyl methanes and/or 2,4'-diamino 3-alkyl-diphenyl methanes.
When carrying out the process according ~o the invention, the aromatic diamines to be used as s~arting material are catalytically-hydrogenated with the ad-dition of 3 mols of hydrogen per mol of diamine. This means that the hydrogenation reaction is preferably stopped when 3 mols of hydrogen per mol of starting compound have been used up. Hydrogenation is carried out at 20 to 300C, preferably 70 to 300C and, in particular, at 120 to 250C, using a pressure of 20 to 300 bar, preferably 70 ~o 300 bar and, in particular, 120 to 250 bar. As to be seen from NMR-spectroscopic investigations of the products of the hydrogenation the partially hydrated "H 6"-diamines consist almost ex clusively of diamines whose alkyl substituents are linked to the aromatic ring.
The hydrogenation reaction according to the invention is carried out in the presence of from 0.1 to 10%9 preferably from 0.1 to 1~ by weight, based on catalytically~active me~al on the one hand and diamino compound on the other hand, of a hydrogenation catalyst.
The hydrogenation reaction according to the invention i~ carried out in the presence of from 0.1 to 10~, preferably from 0.1 to 1%, by weight, based on the diamino compound, of a hydrogenation catalyst.
Suitable ca~alysts inclu~e, for example, elements of the eight subgroup of ~he periodic table of the elements, optionally supported on inert carriers, such as active charcoal, silica gel and, in particular, aluminum oxide 9 or catalytically-active inorganic compounds of these elements. Examples of particularly suitable substances include ruthenium~ platinum, -~r ~2~?7;~
rhodium, nickel and/or cobalt catalysts either in the elementary form or in a chemically-bound form.
Ruthenium or catalytically-active ruthenium compounds are particularly preferred. Examples of suitable ruthenium compounds include ruthenium dioxide, ruthenium tetraoxide, barium perruthenite, sodium, potassium, silver, calcium and magnesium ruthenate, sodium per-ruthenate, ruthenium pentafluoride, ruthenium tetra-fluoride hydrate and ruthenium trichloride. If carrier substances are used for the catalysts, the metal content of the carrier catalyst is generally rom 1 to 10~, preferably from 1 to 5~, by weight. The nature and quantity of catalyst to be used is, of course, in other respects not an essential part of the invention, since the hydrogenation reaction is carried out by methods known in the art.
It is oten useul to carry out the hydrogen-ation reaction according to the invention in the prasence of ammonia, since ammonia suppresses undesirable 20 deamination reactions and the formation of secondary amines as by-products. I ammonia is used, the quantities are from 0.1 to 30~, preferably from 5 to 10%, by weight, based on the starting materials which are to be hydrogenated.
The process according to the invention may be carried out solvent~free or in the presence of inert solvents. Low melting or li~uid diamines are generally hydrogenated solvent-free whereas high melting diamines are hydrogenated in the form of solutions. Suitable solvents include organic compounds of low boiling point which are inert undeL the reaction conditions, partic-ularly alcohols, such as methanol, ethanol, n-propanol or i-propanol, or ethers such as, for example, dioxane, tetrahydrouran or diethyl ether or hydrocarbons, such as cyclohexane. The process according to the invention may be carried out continuously in a reaction tube or a cascade of pressure vessels, but is preferably carried 7~4~
out batch-wise, in a stirrer autoclave, in which the autoclave is charged with catalyst, the substance to be hydrogenated, and optionally a solvent, and is flushed several times with inert gas, and ammonia is optionally added. Hydrogen is then -forced in and the mixture is heated to the reaction temperature and hydrogenated until the theoretically-required quantity of hydrogen has been absorbed. After cooling of the reaction mixture and separation of the catalyst, the end product may be worked up by distillation.
As already mentioned above, the main advantage of the process according to the invention compared with the process according to U.S. Patent 2,511,028 is in the fact that partial hydrogenation takes place with greater selectivity, so that aminocyclohexyl-methyl-anilines corresponding to the starting materials in the process are obtained in substantially higher yields.
Based on the total quantity of diamines, the reaction mixtures obtained rom the process according to the invention generally CQntain less than 35%, preferably less than 20~, by weight, of perhydrogenated cyclo-aliphatic diamines and less than 10~, preerably less than 5%, b~ weight, of unhydrogenated aromatic diamines.
The main product generally consists of the partially hydrogenated, cycloaliphatic-aromatic diamine required.
These diamines according to the invention are generally isomeric mixtures, substantially corre-sponding to the starting materials in their position isomerism, but the reaction mixture obtained generally also contains stereo isomeric compounds. For the purpose o~ technical utilization of the products pro-duced by the process according to the invention, Mo~2503 ~:e 0~3~
separation into the individual position isomers and stereo isomers is generally not necessary, however. When the products according to the invention are used for their preferred purpose as chain-lengthening agents in poly-urethane chemistry with graded reactivity, the positionisomerism and stereo isomerism are not important, the essential factor being only that the main component of the diamine mixture should consist of partially-hydrogenated aminocyclo hexyl-methyl anilines.
The following examples serve to illustrate the invention. Percentages are by weight unless other-wise indicated.
EXAMPLES
Example 1 250 g (1.18 mol) of 4,4'-diamino-3-methyl-5-ethyl-diphenyl methane and 25 g o ruthenium carrier catalyst (5~ Ru on A1203) are introduced into a 0.7 liter stirrer autoclave, and 25 g of ammonia are added after repeated rinsing with nitrogen and hydrogen. The reaction mixture is heated to 14()C with stirring and hydrogenated at 200 bar until 3.5 mol of hydrogen have been absorbed. The mixture is then left to cool, the autoclave is depressuriæed and the crude product is dissolved in methanol. The cata:Lyst is filtered off and washed with methanol and the organic solutions are combined. After evaporation of the solvent, the product is subjected to flash distillation at 100C to 190C/0.1 mbar and analyzed by gas chromatography.
The yields shown in Table 1 were found.
Examples 2-4 Examples 2-4 followed the same method in Ex-ample 1, starting with 1.18 mol of 4,4'-diamino-3,5 dialkyl-diphenyl methane, with the alkyl groups as Mo-2503 ~7;3 ~
g defined in Table 1, and maintaining the same ratio of weight of catalyst and ammonia and mol amount of hydrogen absorbed as in Example 1.
Mo-2503 312~73~
--1 o--o .~ o ~ ~ ~ o ~ ~ X ~ ~ ~ U~
0 ~ 0 _~. rl^i 0 N O r i O ~i 0 ~ d.
o ,_ W
O ~ ~rl . . I I I N 11~
~ ~ N I ~i m o r~
NO t) ~11 ~ ~~r O N N
~ dP ~J ~~iIr) ~i IS~ N Ll~ 00 N N N N m C) .
.,1 o ~ m ~
0 o w ~ I I o ~ o ~ ~ In d t~ ~ ~i o ._i o :~''~ O
Ul '~1 ~ C
O U ~It` ~ N N10 tr~ ~
C rl ~ d~ -L) C~ i 1~ ~ ~ N
pql~~ O
'C ~
C ~ u~
~ ~J ~ X ~ ~ N N I , r~ ~ 11 r:C V ~1~ N~ r~ N~; r~ N~; r~ N~
rl (L) , ~ ~ ~I N
Mo- 2 5 0 3 ~73~1 Legend of Table l R
1) Hl2 = H2N _ ~ 2 \~ ~ -NH2, "H12-dialkyl-MDA~
~2
Mo-2503 LeA 21,940 DIAMINES AND A PROCESS FOR THEIR PREPARATION
.
Thls invention relates to new dip~imary amino cyclohexyl methyl anilines which are mono- or di-sub-stituted on the aromatic ring and may be present as isomeric mixtures and/or as mixtures with minor quanti-ties of the corresponding unhydrogenated or perhYdro-genated diamines, and to a process for the preparation of the new compounds by catalytic partial hydrogenation of the underlying aromatic diamines.
BACKGROUND OE` THE INVENTIO~
Ami~ocyclohexyl-alkyl-anilines which are either unsubstituted or substituted on both rings have already been disclosed in U.S. Patent 2, 511, 028. They may be used~ for example, as intermediate products for the production of dyes, rubber auxiliaries, surface active substances, polyamides or polyester polyamides or as corrosion protecting agents. According to the teaching of this reference, the compounds are prepared by catalytic partial hydrogenation of the underlying aromatic diamines. This process has, however, the dis-ad~antage that the asymmetric hydrogenation of diamino-diphenyl alkanes cannot be caxried out selectively, with the result that the ~ield of the aforesaid partially-hydrogenated diamines is, at most, only slightly above 50~ of the theoretical yield, as may be seen from the examples of practical application given in the reference.
Primary aminocyclohexyl-methyl-anilines are not only valuable intermediate products for the fields of application mentioned above, however, but are, in particular, also interesting chain-lengthening agents for polyurethane chemistry, having amino groups of Mo-2503 ~eA 21,940 73~
graded reactivity. The present invention was, therefore, based on the problem of finding new compounds of this type in which the amino groups would show a more marked differentiation of their reactivities due to the additional substitution on the aromatic ring and which would be able to be prepared more selectively due to the asymmetric substitution.
This problem was solved by th~ preparation of the diamines and diamine mixtures according to the inven-tion and by a process suitable for their preparation.
DESCRIPTION OF THE INVENTION
The present invention relates to diaminescorresponding to the formula, Rl (H2N)m - ~ CH2 ~ NH2 (NH2)n R
wherein R1 and R may be identical or di~erentt one o~
which represents a straight-chained or branched-chained alkyl group having 1 to 12 carbon atoms, and the other o which may represent hydrogen or such an alkyl group, and m and n each represent 0 or 1 provided that the sum of m ~ n = 1 and where m or n = 0 the free valency is saturated by hydrogen.
These diamines are optionally in the form o~ isomeric mixtures and optionally contain up to 35%, by weight, based on the total mixture, of the corresponding perhydrogenated diamines, and/or optionally mi~ed with up to 10%, by weight, based on the total mixture, of the corresponding unhydrogenated aromatic diamines.
Mo-2503 ~ Z~7~
This invention also relates to a process for the preparation of these diamines or diamine mixtures, which is characterized in that aromatic diamines corre-sponding to the formula:
Rl (H2N)m ~ CH2 ~ NH2 (NH2)n R
optionally present as isomeric mixtures, in which formula Rl, R , m and n have the meaning indicated above, are catalytically-hydrogenated with the addition o~ 3 mols of hydrogen per mol of diamine.
Aromatic diamines corresponding to the general formula above, which are suitable as starting materials for the process according to the invention, may be either pure substances or isomeric mixtures. Particularly suitable are those diamines corresponding to thls ormula in which either Rl and R2, ~hich may be identical or diferent, denote branched or unbranchecl alkyl groups having 1 to 4 carbon atoms, in particular methyl groups or 20 R denotes an alkyl group having 1 to 4 carbon atoms, in particular a methyl group, and R denotes hydrogen.
Examples o~ aromatic diamines suitable as starting material according to the invention include the diamines corresponding to the general formula Rl (H2N)m ~ CH2 ~ - NH2 (NH2)n R
Mo-2503 73~1 which are produced by arylamine/formaldehyde conden-sation using a mixture of aniline and substituted anilines correspondin~ to the formula:
Rl 2 R2 as the "arylamine" according to German Offenlegungs-schriften 2,133,870; 29149,998; and 2,700,185; or, by the reaction of o-nitrobenzyl halides with substituted anilines of the above formula, reduction of the nitro group and molecular rearrangement according to Belgium Patent 864,533 or British Patent 1,567,114.
Preferred starting materials for the process according to the invention include: 4,2'-diamino-3,5-dimethyl-diphenyl methane 9 4,2'-diamino-3,5-diethyl-di-phenyl methane, 4,2'-diamino-3,~-diisopropyl-diphenyl methane, and 4,2'-diamino-3-ethyl-5-Tne~hyl-diphenyl methane; isomeric mixtures containing, a~ their main component: 4,4'-diamino-3,5-dimethyl-diphenyl methane, 4,4'-diamino-3,5-diethyl-diphenyl methane, 4,4'-di-amino-3,5-diisopropyl-diphenyl methane, and 4,4'-di-amino-3-methyl-5-ethyl-diphenyl methane; and isomeric mixtures containing, as their main components: 4,2l-di-amino-3-methyl-diphenyl methane, 4,2'-diamino-3-ethyl-diphenyl methane, and 4,2'-diamino-3-isopropyl-diphenyl methane. Other preferred starting materials for the process include mixtures of the above-identified compounds with correspondîng 4,4'-diamino-3-alkyl- or ~,4'-diamino-3-alkyl-diphenyl methanes, including:
4,4'-diamino-3-methyl-diphenyl methane, 4,4'-diamino-3-ethyl-diphenyl methane, and 4,4'-diamino-3-isopropyl-di-phenyl methane; and mixtures of the above-identlfied :1~073~:~
disubstituted compounds with other position isomers, including, for example: 4,2'-diamino-3-alkyl-diphenyl methanes and/or 2,4'-diamino 3-alkyl-diphenyl methanes.
When carrying out the process according ~o the invention, the aromatic diamines to be used as s~arting material are catalytically-hydrogenated with the ad-dition of 3 mols of hydrogen per mol of diamine. This means that the hydrogenation reaction is preferably stopped when 3 mols of hydrogen per mol of starting compound have been used up. Hydrogenation is carried out at 20 to 300C, preferably 70 to 300C and, in particular, at 120 to 250C, using a pressure of 20 to 300 bar, preferably 70 ~o 300 bar and, in particular, 120 to 250 bar. As to be seen from NMR-spectroscopic investigations of the products of the hydrogenation the partially hydrated "H 6"-diamines consist almost ex clusively of diamines whose alkyl substituents are linked to the aromatic ring.
The hydrogenation reaction according to the invention is carried out in the presence of from 0.1 to 10%9 preferably from 0.1 to 1~ by weight, based on catalytically~active me~al on the one hand and diamino compound on the other hand, of a hydrogenation catalyst.
The hydrogenation reaction according to the invention i~ carried out in the presence of from 0.1 to 10~, preferably from 0.1 to 1%, by weight, based on the diamino compound, of a hydrogenation catalyst.
Suitable ca~alysts inclu~e, for example, elements of the eight subgroup of ~he periodic table of the elements, optionally supported on inert carriers, such as active charcoal, silica gel and, in particular, aluminum oxide 9 or catalytically-active inorganic compounds of these elements. Examples of particularly suitable substances include ruthenium~ platinum, -~r ~2~?7;~
rhodium, nickel and/or cobalt catalysts either in the elementary form or in a chemically-bound form.
Ruthenium or catalytically-active ruthenium compounds are particularly preferred. Examples of suitable ruthenium compounds include ruthenium dioxide, ruthenium tetraoxide, barium perruthenite, sodium, potassium, silver, calcium and magnesium ruthenate, sodium per-ruthenate, ruthenium pentafluoride, ruthenium tetra-fluoride hydrate and ruthenium trichloride. If carrier substances are used for the catalysts, the metal content of the carrier catalyst is generally rom 1 to 10~, preferably from 1 to 5~, by weight. The nature and quantity of catalyst to be used is, of course, in other respects not an essential part of the invention, since the hydrogenation reaction is carried out by methods known in the art.
It is oten useul to carry out the hydrogen-ation reaction according to the invention in the prasence of ammonia, since ammonia suppresses undesirable 20 deamination reactions and the formation of secondary amines as by-products. I ammonia is used, the quantities are from 0.1 to 30~, preferably from 5 to 10%, by weight, based on the starting materials which are to be hydrogenated.
The process according to the invention may be carried out solvent~free or in the presence of inert solvents. Low melting or li~uid diamines are generally hydrogenated solvent-free whereas high melting diamines are hydrogenated in the form of solutions. Suitable solvents include organic compounds of low boiling point which are inert undeL the reaction conditions, partic-ularly alcohols, such as methanol, ethanol, n-propanol or i-propanol, or ethers such as, for example, dioxane, tetrahydrouran or diethyl ether or hydrocarbons, such as cyclohexane. The process according to the invention may be carried out continuously in a reaction tube or a cascade of pressure vessels, but is preferably carried 7~4~
out batch-wise, in a stirrer autoclave, in which the autoclave is charged with catalyst, the substance to be hydrogenated, and optionally a solvent, and is flushed several times with inert gas, and ammonia is optionally added. Hydrogen is then -forced in and the mixture is heated to the reaction temperature and hydrogenated until the theoretically-required quantity of hydrogen has been absorbed. After cooling of the reaction mixture and separation of the catalyst, the end product may be worked up by distillation.
As already mentioned above, the main advantage of the process according to the invention compared with the process according to U.S. Patent 2,511,028 is in the fact that partial hydrogenation takes place with greater selectivity, so that aminocyclohexyl-methyl-anilines corresponding to the starting materials in the process are obtained in substantially higher yields.
Based on the total quantity of diamines, the reaction mixtures obtained rom the process according to the invention generally CQntain less than 35%, preferably less than 20~, by weight, of perhydrogenated cyclo-aliphatic diamines and less than 10~, preerably less than 5%, b~ weight, of unhydrogenated aromatic diamines.
The main product generally consists of the partially hydrogenated, cycloaliphatic-aromatic diamine required.
These diamines according to the invention are generally isomeric mixtures, substantially corre-sponding to the starting materials in their position isomerism, but the reaction mixture obtained generally also contains stereo isomeric compounds. For the purpose o~ technical utilization of the products pro-duced by the process according to the invention, Mo~2503 ~:e 0~3~
separation into the individual position isomers and stereo isomers is generally not necessary, however. When the products according to the invention are used for their preferred purpose as chain-lengthening agents in poly-urethane chemistry with graded reactivity, the positionisomerism and stereo isomerism are not important, the essential factor being only that the main component of the diamine mixture should consist of partially-hydrogenated aminocyclo hexyl-methyl anilines.
The following examples serve to illustrate the invention. Percentages are by weight unless other-wise indicated.
EXAMPLES
Example 1 250 g (1.18 mol) of 4,4'-diamino-3-methyl-5-ethyl-diphenyl methane and 25 g o ruthenium carrier catalyst (5~ Ru on A1203) are introduced into a 0.7 liter stirrer autoclave, and 25 g of ammonia are added after repeated rinsing with nitrogen and hydrogen. The reaction mixture is heated to 14()C with stirring and hydrogenated at 200 bar until 3.5 mol of hydrogen have been absorbed. The mixture is then left to cool, the autoclave is depressuriæed and the crude product is dissolved in methanol. The cata:Lyst is filtered off and washed with methanol and the organic solutions are combined. After evaporation of the solvent, the product is subjected to flash distillation at 100C to 190C/0.1 mbar and analyzed by gas chromatography.
The yields shown in Table 1 were found.
Examples 2-4 Examples 2-4 followed the same method in Ex-ample 1, starting with 1.18 mol of 4,4'-diamino-3,5 dialkyl-diphenyl methane, with the alkyl groups as Mo-2503 ~7;3 ~
g defined in Table 1, and maintaining the same ratio of weight of catalyst and ammonia and mol amount of hydrogen absorbed as in Example 1.
Mo-2503 312~73~
--1 o--o .~ o ~ ~ ~ o ~ ~ X ~ ~ ~ U~
0 ~ 0 _~. rl^i 0 N O r i O ~i 0 ~ d.
o ,_ W
O ~ ~rl . . I I I N 11~
~ ~ N I ~i m o r~
NO t) ~11 ~ ~~r O N N
~ dP ~J ~~iIr) ~i IS~ N Ll~ 00 N N N N m C) .
.,1 o ~ m ~
0 o w ~ I I o ~ o ~ ~ In d t~ ~ ~i o ._i o :~''~ O
Ul '~1 ~ C
O U ~It` ~ N N10 tr~ ~
C rl ~ d~ -L) C~ i 1~ ~ ~ N
pql~~ O
'C ~
C ~ u~
~ ~J ~ X ~ ~ N N I , r~ ~ 11 r:C V ~1~ N~ r~ N~; r~ N~; r~ N~
rl (L) , ~ ~ ~I N
Mo- 2 5 0 3 ~73~1 Legend of Table l R
1) Hl2 = H2N _ ~ 2 \~ ~ -NH2, "H12-dialkyl-MDA~
~2
2) H6 = H2N ~ ~_ CE ~ NH2, llH6-dialk
3) Ho ~ H2N-- ~ ~ CH2 ~ H2, "Dialkyl-MDA"
Example 5 (Comparison Exam~
721.7 g (3.65 mol~ of 4,4'-diamino-diphenyl methane and 72.2 g of ruthenium catalyst ~5% Ru on A1203) are introduced into a 1.3 liter stirrer autoclave. The autoclave is rinsed several times with nitrogen and hydrogen, and 72.2 g of ammonia are introduced. The mixture is then heated to 125C with vigorous stirring and hydrogenated at 200 bar until, after about 10 hours, 10.95 mol of hydrogen have been absorbed. The auto-cla~e is le~t to cool~ the pressure is released, andthe autoclave cont~nts are taken up with methanol;
The catalyst is filtered ofE and washed, and the crude product is subjected to fractional distillation. 332.6 g distil over at 120 to 135C/0.1 mbar tfraction l) and 380.6 g at 135 to 150C/Ool mbar (fraction 2) while 20.6 g are l~ft in the sump as distillation residue.
According to the gas chromatographic finding, fraction l contains 72.4% of 4,4'-diamino-dicyclohexyl methane and 25. 5% Of 4-(4-aminobenzyl)-cyclohexylamine, and fraction 2 contains 9.0% of 4,4'-diamino-dicyclo-hexyl methane and 85. 3% of 4-(4-aminobenzyl)-cyclo-hexylamine, so that the total yield of the required semi-hydrogenated diamine amounts to 55. 6% o the theoretical yield.
Mo-2503 .
~ 20'~3~
:
Example 6 250 g (1.18 mol) of 4,4'-diamino-3-me~hyl-diphenyl methane are hydrogenated for 12.5 hours in a manner analogous to Example 1. The ~ollowing yields were determined gas-chromatographically:
49.4 g (18.7~ o~ theoretical yield) of 4,4'-diamino-3-methyl-dicyclohexyl methane, 198.7 g (77.3~ o~ theoretical yield) of 4-(4-amino-3-methylbenzyl)-cyclohe~ylamine and 7O7 g t3.1~ o theoretical yield) of 4,4'-diamino-3-methyl diphenyl methane.
Z.l g (0.8~ of theoretical amount) of distillation residue remain in the sump.
Although the invention has been described in detail in the oregoing for the purpose of lllustration, it is to be understood that such detail is solely for that purpose and that variations can be made therein by those skilled in the art without departing rom the spirit and scope of the i~ventiorl e~cept as it may be limited by the clai~s.
Example 7 226 9 ( 1 Mol) of 4,2'-diamino-3,5~di7~thyldiphenylmethane and 22,6 9 of ruthenium carrier catalyst ( 5~!7 Ru on A1203) are introduced into a 0,7 liter stirrer autoclave. The autoclave is rinsed several times with nitrogen and hydrogen and 22,6 9 of ammonia are introduced. The mixture is then heated to 14~C with vigorous stirring and hydrogenated at 200 bar until, after about 4 hours, 3 mol of hydrogen have been absorbed. The content of the autoclave is worked up as described in 30 example 1. Upon flash distillaticn at 114C to 152C /0,015 mbar 228,6 9 Mo-2503 ., of a diamine mixture i9 obtained consisting of 93 ~O oF 2-(4-amino-3,5-dimethylbenzyl)-cyclohexylamine, 6.3 ,~ of 4,2'-diamino-3,5-dlmethyldicyclohexyl methane and 0,6 O oF unreacted starting rnaterial.
Example 8 Following the procedure of Example 7 212 9 (1 mol) of 4,2'-diamino-3-methyl-diphenylmethane are hydrogenated in the presence of 21,2 9 of said ruthenium carrier catalyst. After working up of the reaction mixture 153,4 9 of 2-(4-amino-3-methylbenzyl)-cyclohexylamine are obtained as distillate at 145-149C/0,018 mbar. According to gas chromatography ~he purity of the product is 98~4~o.
Example 5 (Comparison Exam~
721.7 g (3.65 mol~ of 4,4'-diamino-diphenyl methane and 72.2 g of ruthenium catalyst ~5% Ru on A1203) are introduced into a 1.3 liter stirrer autoclave. The autoclave is rinsed several times with nitrogen and hydrogen, and 72.2 g of ammonia are introduced. The mixture is then heated to 125C with vigorous stirring and hydrogenated at 200 bar until, after about 10 hours, 10.95 mol of hydrogen have been absorbed. The auto-cla~e is le~t to cool~ the pressure is released, andthe autoclave cont~nts are taken up with methanol;
The catalyst is filtered ofE and washed, and the crude product is subjected to fractional distillation. 332.6 g distil over at 120 to 135C/0.1 mbar tfraction l) and 380.6 g at 135 to 150C/Ool mbar (fraction 2) while 20.6 g are l~ft in the sump as distillation residue.
According to the gas chromatographic finding, fraction l contains 72.4% of 4,4'-diamino-dicyclohexyl methane and 25. 5% Of 4-(4-aminobenzyl)-cyclohexylamine, and fraction 2 contains 9.0% of 4,4'-diamino-dicyclo-hexyl methane and 85. 3% of 4-(4-aminobenzyl)-cyclo-hexylamine, so that the total yield of the required semi-hydrogenated diamine amounts to 55. 6% o the theoretical yield.
Mo-2503 .
~ 20'~3~
:
Example 6 250 g (1.18 mol) of 4,4'-diamino-3-me~hyl-diphenyl methane are hydrogenated for 12.5 hours in a manner analogous to Example 1. The ~ollowing yields were determined gas-chromatographically:
49.4 g (18.7~ o~ theoretical yield) of 4,4'-diamino-3-methyl-dicyclohexyl methane, 198.7 g (77.3~ o~ theoretical yield) of 4-(4-amino-3-methylbenzyl)-cyclohe~ylamine and 7O7 g t3.1~ o theoretical yield) of 4,4'-diamino-3-methyl diphenyl methane.
Z.l g (0.8~ of theoretical amount) of distillation residue remain in the sump.
Although the invention has been described in detail in the oregoing for the purpose of lllustration, it is to be understood that such detail is solely for that purpose and that variations can be made therein by those skilled in the art without departing rom the spirit and scope of the i~ventiorl e~cept as it may be limited by the clai~s.
Example 7 226 9 ( 1 Mol) of 4,2'-diamino-3,5~di7~thyldiphenylmethane and 22,6 9 of ruthenium carrier catalyst ( 5~!7 Ru on A1203) are introduced into a 0,7 liter stirrer autoclave. The autoclave is rinsed several times with nitrogen and hydrogen and 22,6 9 of ammonia are introduced. The mixture is then heated to 14~C with vigorous stirring and hydrogenated at 200 bar until, after about 4 hours, 3 mol of hydrogen have been absorbed. The content of the autoclave is worked up as described in 30 example 1. Upon flash distillaticn at 114C to 152C /0,015 mbar 228,6 9 Mo-2503 ., of a diamine mixture i9 obtained consisting of 93 ~O oF 2-(4-amino-3,5-dimethylbenzyl)-cyclohexylamine, 6.3 ,~ of 4,2'-diamino-3,5-dlmethyldicyclohexyl methane and 0,6 O oF unreacted starting rnaterial.
Example 8 Following the procedure of Example 7 212 9 (1 mol) of 4,2'-diamino-3-methyl-diphenylmethane are hydrogenated in the presence of 21,2 9 of said ruthenium carrier catalyst. After working up of the reaction mixture 153,4 9 of 2-(4-amino-3-methylbenzyl)-cyclohexylamine are obtained as distillate at 145-149C/0,018 mbar. According to gas chromatography ~he purity of the product is 98~4~o.
Claims (15)
OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. Diamines corresponding to the general formula, wherein, R1 and R2, which may be identical or different, denote hydrogen ox branched or straight-chain alkyl groups having 1 to 12 carbon atoms, provided that at least one of the groups R1 and R2 is an alkyl group, and m and n each represents 0 or 1, provided that the sum of m + n = 1, the free valency being saturated by hydrogen where m or n = 0.
2. Diamines according to Claim 1, characterized in that said diamines are in the form of isomeric mixtures.
3. Diamines according to Claim 1, characterized in that said diamines are present with up to 35%, by weight, based on the total mixture, of the corresponding perhydrogenated diamines.
4. Diamines according to Claims 1 or 3, characterized in that said diamines are present with up to 10%, by weight, based on the total mixture, of the corresponding unhydrogenated diamines.
5. Diamines according to Claim 1, characterized in that said diamines correspond to the general formula:
wherein R1 and R2 may be identical or different and denote branched-chain or unbranched alkyl groups having 1 to 4 carbon atoms.
wherein R1 and R2 may be identical or different and denote branched-chain or unbranched alkyl groups having 1 to 4 carbon atoms.
6. Diamines according to Claim 2, characterized in that diamines wherein n = 0, and R1 and R2 may be identical or different and denote branched-chain or unbranched alkyl groups having 1 to 4 carbon atoms, amount to more than 70%, by weight, of the total mixture.
7. Diamines according to Claim 1, characterized in that said diamines correspond to the general formula:
wherein R1 and R2, may be identical or different and denote branched-chain or unbranched alkyl groups having 1 to 4 carbon atoms.
wherein R1 and R2, may be identical or different and denote branched-chain or unbranched alkyl groups having 1 to 4 carbon atoms.
8. Diamines according to Claim 2, characterized in that diamines wherein m = 0, and R1 and R2 may be identical or different and denote branched-chain or unbranched alkyl groups having 1 to 4 carbon atoms, represent the main component in the diamine mixture.
9. Diamines according to Claim 1, characterized in that said diamines correspond to the general formula:
wherein R1 denotes a branched-chain or unbranched alkyl group having 1 to 4 carbon atoms, and R2 denotes hydrogen.
wherein R1 denotes a branched-chain or unbranched alkyl group having 1 to 4 carbon atoms, and R2 denotes hydrogen.
10. Diamines according to Claim 2, character-ized in that m=0, R1 denotes a branched-chain or unbranched alkyl group having 1 to 4 carbon atoms, and R2 denotes hydrogen.
11. Diamines according to Claim 1, character-ized in that said diamines correspond to the general formula:
wherein R1 denotes a branched-chain or unbranched alkyl group having 1 to 4 carbon atoms, and R2 denotes hydrogen.
wherein R1 denotes a branched-chain or unbranched alkyl group having 1 to 4 carbon atoms, and R2 denotes hydrogen.
12. Diamines corresponding to Claim 2, characterized in that n = 0, R1 denotes a branched-chain or unbranched alkyl group having 1 to 4 carbon atoms, and R2 denotes hydrogen.
13. A process for the preparation of diamines or isomeric diamine mixtures, characterized in that pure or isomeric aromatic diamines are catalytically hydrogenated with the addition of 3 mols of hydrogen per mol of diamine, said pure or isomeric aromatic diamine corresponding to the formula:
wherein R1 and R2 , which may be identical or different, denote hydrogen or branched or straight-chain alkyl groups having 1 to 12 carbon atoms, provided that at least one of the groups R1 and R2 is an alkyl group, and m and n each represents 0 or 1, provided that the sum of m + n = 1, the free valency being saturated by hydrogen where m or n = 0.
wherein R1 and R2 , which may be identical or different, denote hydrogen or branched or straight-chain alkyl groups having 1 to 12 carbon atoms, provided that at least one of the groups R1 and R2 is an alkyl group, and m and n each represents 0 or 1, provided that the sum of m + n = 1, the free valency being saturated by hydrogen where m or n = 0.
14. A process according to Claim 13, characterized in that the hydrogenation reaction is carried out at a temperature of from 20° to 300°C under a pressure of from 20 to 300 bar.
15. A process according to Claim 13, characterized in that hydrogenation is carried out in the presence of a total of from 0.1 to 10% by weight, based on the aromatic diamine, of at least one catalyst selected from the group consisting of elements of the eighth sub-group of the periodic table of the elements and catalytically-active inorganic compounds of these elements, the catalyst being optionally present on inert carriers.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP3231911.8 | 1982-08-27 | ||
| DE19823231911 DE3231911A1 (en) | 1982-08-27 | 1982-08-27 | DIAMINES OR DIAMINE MIXTURES, AND A METHOD FOR THE PRODUCTION THEREOF |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1207341A true CA1207341A (en) | 1986-07-08 |
Family
ID=6171853
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000434223A Expired CA1207341A (en) | 1982-08-27 | 1983-08-09 | Diamines and a process for their preparation |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP0105146B1 (en) |
| JP (1) | JPS5965048A (en) |
| CA (1) | CA1207341A (en) |
| DE (2) | DE3231911A1 (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3401753A1 (en) * | 1984-01-19 | 1985-08-01 | Bayer Ag, 5090 Leverkusen | METHOD FOR THE PRODUCTION OF POLYURETHANES, POLYURETHANES WITH AROMATIC AMINO END GROUPS AND THE USE THEREOF |
| DE3414803A1 (en) * | 1984-04-19 | 1985-10-24 | Bayer Ag, 5090 Leverkusen | NEW TRIAMINE, A METHOD FOR THE PRODUCTION THEREOF AND THEIR USE AS A NETWORKER OR. HARDENER FOR EPOXY GROUPS OR ISOCYANATE GROUPS OF PLASTICS OR PLASTIC LEADER |
| DE3414804A1 (en) * | 1984-04-19 | 1985-10-24 | Bayer Ag, 5090 Leverkusen | NEW TRIAMINE, A METHOD FOR THE PRODUCTION THEREOF AND THEIR USE AS A NETWORKER OR. HARDENER FOR EPOXY GROUPS OR ISOCYANATE GROUPS OF PLASTICS OR PLASTIC LEADER |
| DE4008074A1 (en) * | 1990-03-14 | 1991-09-19 | Basf Ag | METHOD FOR IMPROVING THE QUALITY OF RAW DIAMINODIPHENYLMETHANES |
| JPH07109337B2 (en) * | 1992-02-26 | 1995-11-22 | 池永鉄工株式会社 | De-icing / crushing machine |
| IL112569A (en) * | 1994-02-10 | 1999-12-22 | Wyeth John & Brother Ltd | Pharmaceutical compositions comprising cyclohexylamine derivatives certain such novel compounds and their preparation |
| US20100048832A1 (en) * | 2008-08-22 | 2010-02-25 | Air Products And Chemicals, Inc. | Alkylated 4-Aminobenzyl-4-Aminocyclohexane |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2511028A (en) * | 1947-12-04 | 1950-06-13 | Du Pont | 4-[(para-aminophenyl) alkyl] cyclo-hexylamine |
| GB1550051A (en) * | 1976-07-22 | 1979-08-08 | Bayer Ag | Tetraalkylated biscyclohexylamine derivatives |
| DE2935318A1 (en) * | 1979-08-31 | 1981-03-26 | Bayer Ag, 51373 Leverkusen | NEW DIISOCYANATES OR DIISOCYANATE MIXTURES OF THE DIPHENYLMETHANE SERIES, METHOD FOR THE PRODUCTION THEREOF, AND THEIR USE AS CONSTRUCTION COMPONENT IN THE PRODUCTION OF POLYURETHANE PLASTICS BY THE ISOCYANATE POLYADDITION METHOD |
-
1982
- 1982-08-27 DE DE19823231911 patent/DE3231911A1/en not_active Withdrawn
-
1983
- 1983-08-09 CA CA000434223A patent/CA1207341A/en not_active Expired
- 1983-08-13 DE DE8383108026T patent/DE3361566D1/en not_active Expired
- 1983-08-13 EP EP83108026A patent/EP0105146B1/en not_active Expired
- 1983-08-26 JP JP58155116A patent/JPS5965048A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| EP0105146A1 (en) | 1984-04-11 |
| DE3361566D1 (en) | 1986-01-30 |
| JPS5965048A (en) | 1984-04-13 |
| DE3231911A1 (en) | 1984-03-01 |
| EP0105146B1 (en) | 1985-12-18 |
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