GB2059792A - Preparation of tertiary amines, and a catalyst for use therein - Google Patents

Preparation of tertiary amines, and a catalyst for use therein Download PDF

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GB2059792A
GB2059792A GB8029402A GB8029402A GB2059792A GB 2059792 A GB2059792 A GB 2059792A GB 8029402 A GB8029402 A GB 8029402A GB 8029402 A GB8029402 A GB 8029402A GB 2059792 A GB2059792 A GB 2059792A
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alcohols
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carboxylic acid
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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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
    • B01J31/2208—Oxygen, e.g. acetylacetonates
    • B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
    • B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
    • B01J31/2234—Beta-dicarbonyl ligands, e.g. acetylacetonates
    • 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/04—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing carboxylic acids or their salts
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/04—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups
    • C07C209/14—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of hydroxy groups or of etherified or esterified hydroxy groups
    • C07C209/16—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of hydroxy groups or of etherified or esterified hydroxy groups with formation of amino groups bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
    • C07C213/02—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups
    • 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
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
    • B01J2231/34—Other additions, e.g. Monsanto-type carbonylations, addition to 1,2-C=X or 1,2-C-X triplebonds, additions to 1,4-C=C-C=X or 1,4-C=-C-X triple bonds with X, e.g. O, S, NH/N
    • B01J2231/341—1,2-additions, e.g. aldol or Knoevenagel condensations
    • 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
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
    • 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
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/10—Complexes comprising metals of Group I (IA or IB) as the central metal
    • B01J2531/16—Copper
    • 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
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/10—Complexes comprising metals of Group I (IA or IB) as the central metal
    • B01J2531/17—Silver
    • 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
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/82—Metals of the platinum group
    • B01J2531/824—Palladium
    • 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
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/84—Metals of the iron group
    • 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
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/84—Metals of the iron group
    • B01J2531/847—Nickel

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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract

Tertiary monoamines and polyamines are prepared by reacting primary aromatic alcohols, aromatic aldehydes, secondary alcohols, ketones, polyether alcohols, aliphatic or aromatic polyhydric alcohols, polyaldehydes, amino alcohols and ethylene oxide adducts thereof with ammonia, a primary aliphatic amine or a secondary aliphatic amine, in the presence of a homogeneous colloidal catalyst prepared by reducing a mixture of components A and B, provided that at least one of A and B is a carboxylate or a mixture of components A, B and C, wherein A is a copper or silver carboxylate or intramolecular complex, component B is a Group VIII, manganese or zinc carboxylate or intramolecular complex, and component C is a fatty acid or alkali metal or alkaline earth metal carboxylate thereof.

Description

SPECIFICATION Preparation of tertiary amines, and a catalyst for use therein This invention relates to a method for the preparation of tertiary monoamines and polyamines, by reacting a monohydric or polyhydric alcohol having hydroxyl groups(s), such as primary and secondary alcohols, an aldhyde or a ketone, with ammonia or a primary or secondary amine, in the presence of a special catalyst. It also relates to a catalyst for use in this reaction.
Tertiary monoamines and polyamines having various substituents are widely useful, for example, as intermediates for emulsifiers, dispersants, rust-preventives, germicides, dyeing auxiliaries for fibers, and softening agents, depending on their specific structures.
A method for the preparation of a corresponding substituted amine by reacting an alcohol or an aldehyde with ammonia or a primary or secondary amine, is well known. Catalysts, generally called hydrogenation-dehydrogenation catalysts, are used in this reaction. These catalysts have been disclosed in patents as described hereunder. They are all solid catalysts and are used in heterogeneous reaction systems. Namely, the reaction between a monohydric alcohol and ammonia or a primary or secondary amine is disclosed in U. S. Patents No. 2 953 601, No.
3223734 and No. 3373204, German Patent Laid-Open No. 1493781, and Japanese Patent Laid-Open No. 52-19604. These patents use, as the catalyst, Raney nickel, supported nickel, supported cobalt, palladium-carbon, copper-chromium oxide and the like. Also, the reaction between a polyhydric alcohol and ammonia or a primary or secondary amine is disclosed in U.
S. Patents No. 3219707, No. 3223734, No. 3270059, No. 3847992 and No. 4014933, and Japanese Patent Laid-Open No. 53-59603. These patents use, as the catalyst, nickel or cobalt, Raney nickel, copper-nickel-cobalt oxides, copper-zinc-chromium and the like. For instance, in Example 3 of U. S. Patent No. 3270059, 1,6-hexanediol was reacted with ammonia, in the presence of a large excess of a cobalt catalyst, at 205"C and at a high pressure of 280 atm., and a distillate obtained after 72 hours of reaction comprised 29.3 wt % of 1,6hexamethylenediamine, 46.7 wt % of hexamethyleneimine and 24.0 wt % of residue (excluding water).
All of these patents use solid catalysts and these catalysts are used in heterogeneous reaction systems.
However, these solid catalysts have low activities and consequently have to be used in large quantities, i.e. in a range of 2.5 to 8.5 % or even higher. As a result, the catalyst costs are high and the reactions have to be carried out at high temperatures and high pressures and for a long time. Furthermore, such catalysts require filtration facilities, and moreover, public nuisance problems, such as disposal of used catalysts, arise. Thus, these solid catalysts are not satisfactory in catalyst activity. They are not satisfactory in selectivity, either.As an example, in a reaction of an alcohol or an aldehyde with ammonia or a primary or secondary amine, in the presence of a hydrogenation-dehydrogenation catalyst, for preparing a primary, secondary or tertiary amine, aldol condensation products and the like are formed as by-products and thereby the yield of the desired amine is reduced. In the case of a polyhydric alcohol which possesses many functional groups, side reactions, such as aldol condensation, tend to cause a sharp reduction in the amine yield.
Our research efforts to solve these problems previously led to the findings of apparently homogeneous and colloidal catalysts having high activity and selectivity, and patent applications were filed (Japanese Patent Application No. 53-30149, corresponding to U. S. Patent No.
4210605, and Application No. 54-19580, corresponding to U. S. Serial No. 122405). Our continued research efforts with similar, but special, colloidal catalysts have succeeded in obtaining the desired tertiary amines at high yields, without reducing the activity and the selectivity of the catalysts used, by reacting not only an aliphatic alcohol or aldehyde, but also an aromatic alcohol or aldehyde or a polyhydric alcohol or a ketone and the like, with ammonia or a primary or secondary amine, and thereby this invention has been achieved.
This invention provides a process for the preparation of tertiary amines by reacting: (1.) an alcohol, an aldehyde, or a ketone selected from: (a) a primary alcohols, secondary alcohols, aldehydes, or ketones represented by the following general formulas (I) or (II),
wherein R, and R2 are independantly hydrogen, C, to C24 saturated or unsaturated aliphatic hydrocarbon, aryl, or alkylaryl groups, or R, and R2 together form an alicyclic (C5-C,2) ring, or one of them is a heterocyclic ring containing oxygen and the other is hydrogen, and in the case where either of R, and R2 is an alkyl group, the other is other than hydrogen and the sum of the number of carbon atoms of R, and R2 is 3 or more, (b) polyether alcohols represented by the following general formulas (Ill) or (lV)
wherein R,' and R2' are independently hydrogen, C, to C24 saturated or unsaturated aliphatic hydrocarbon, aryl, or alkylaryl groups, or R,' and R21 together form a ring, R3 is hydrogen or methyl group, R4 is C8 to C,8 saturated or unsaturated aliphatic hydrocarbon group, and n is an integer from 1 to 20, (c) aliphatic or aromatic polyhydric alcohols or dialdehydes, and (d) amino alcohols or ethylene oxide or propylene oxide adducts thereof, with:: (2.) ammonia or a primary or secondary aliphatic amine represented by the following general formula (V)
wherein R8 and R6 are independently hydrogen, or C, to C24 saturated or unsaturated aliphatic hydrocarbon groups, characterized in that the reaction is carried out at a temperature of 150 to 300"C in the presence of a catalyst which is prepared by the reduction of a mixture consisting of (A), (B) and (C), or a mixture consisting of (A) and (B) provided that both (A) and (B) are salts of carboxylic acids, or a mixture consisting of (A) and (B) provided that one of (A) and (B) is a salt of a carboxylic acid and the other is an intramolecular complex, wherein (A) is at least one copper or silver salt of a carboxylic acid or at least one intramolecular complex of copper or silver, (B) is at least one carboxylic acid salt or at least one intramolecular complex of a metal of Group VIII in the Mendeleev Periodic Table, manganese and zinc, and (C) is at least one carboxylic acid or alkali metal or alkaline earth metal salt thereof.
The catalyst system used in this invention is preferably reduced, prior to its use in the reaction, by means of hydrogen, or a mixture of hydrogen and ammonia or an amine, or an aluminium alkyl derivative such as Al (C2H5)3 and (C2H5)2Al (OC2H8), in a reaction rnediunn such as a secondary aliphatic alcohol, aromatic alcohol or polyhydric alcohol, or in an inert solvent.
Preferably, the catalyst system is dissolved in the reaction medium, reduced at a temperature of 100 to 200"C by means of hydrogen or a mixture of hydrogen and an amine, and then used for the reaction. The reduction is very easily conducted and completes in a short period of time at a temperature of a 1(10 to 200"C. The catalyst system thus prepared cannot be separated by means of normal filtration and it is superficially homogeneous and colloidal. Once the catalyst system has become colloidal, ammonia, or a primary or secondary amine, which is a starting material for preparing the desired tertiary amine, is added into the reaction system. The reaction proceeds in the absence of hydrogen, but preferably it is carried out in the presence of a small quantity of hydrogen.The activity of the catalyst used in this invention is reduced by long contact with water, and therefore the water formed during the reaction is preferably continuously distilled out of the reaction system. The reaction temperature employed is 150 to 300 C, preferably 170 to 240 C. The reaction pressure can be a reduced pressure, but preferably it is from 0 to 10 atm. (gauge pressure) and more preferably, it is atmospheric pressure.
Among the catalyst components used in this invention, the component (A) is (are) intrarnolec- ular complex(es) or carboxylic acid salts of copper or silver. Ligands which can form intramolecular complex salts used in this invention can be ssåiketone compounds, glyoxime compounds, glycine, salicylaldehyde, cz-picolinic acid, oz-benzoinoxime, etc. ll However, the ligands which contain bydrogenation poisons, such as halogens and sulfur, cannot be used. As an example, metal complexes of dimethyldithiocarbamic acid cannot be used because sulfur acts as a catalyst poison. Preferable ligands are ss-d ketone compounds and glyoxime compounds.
Preferable intramolecular complexes are, for instance, copper-acetylacetone complex and silveracetylacetone complex.
Carboxylic acids which form salts thereof can be aromatic type, branched-chain alkyl type, straight alkyl-chain type, or a type having more than one carboxyl group or other substituents, so long as they have at least one carboxyl group in their molecules. Among these, carboxylic acids of C8 to C36 are preferable, and both natural and synthetic products can be used. Included in this category are valeric acid, caproic acid, enanthic acid, caprylic acid, perlargonic acid, capric acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, margaric acid, stearic acid, arachic acid, behenic acid, oleic acid, or derivatives of these acids containing more than one carboxyl group.
The component (B) used in this invention is (are) intramolecular complex(es) or carboxylic acid salt(s) of a metal selected from the Group VIII elements in the Periodic Table of The Elements, such as nickel, cobalt, iron and palladium, and also manganese and zinc. Ligands and carboxylic acids which form these intramolecular complexes and carboxylic acid salts can be the same as those described previously. Examples of preferable intramolecular complexes and carboxylic acid salts are nickel-acetylacetone complexes, nickel stearate and the like.
The component (C) used in this invention is (are) carboxylic acid(s) or carboxylic acid salt(s) of alkali metal(s) or alkaline earth metal(s). Carboxylic acids can be those of C5 to C35, such as capric acid, lauric acid, and stearic acid. Carboxylic acid salts can be those of alkali metals or alkaline earth metals, such as sodium, potassium, magnesium, calcium and barium, and for instance, barium stearate, barium laurate, and the like, can be used.
Catalysts used in this invention are effective in particular combinations of components (A), (B) and (c) as described above.
As combinations of two components, combinations of (A) and (B) are effective. More specifically, only the combinations wherein both (A) and (B) are carboxylic acid salts and wherein either one of (A) and (B) is a carboxylic acid salt and the other is an intramolecular complex, are effective, and all other combinations of (A) and (B) have small or little effects. In combinations of three components (A), (B) and (C), (A) and (B) can be carboxylic acid salts or intramolecular complexes. Any combination of (A), (B) and (C) is effective and the threecomponent combinations of (A), (B) and (C) are more effective than two-component combinations of (A) and (B).
A mode of using the catalyst system of this invention will now be described. In a reaction between a polyalkylene glycol (as polyhydric alcohol) and dimethylamine, a catalyst system is used, for example, which is prepared by reducing a three-component catalyst comprising copper stearate, nickel stearate and barium stearate (copper 0.1 wt. %, nickel 0.02 wt. %, barium 0.02 wt. %, based on the alcohol) with hydrogen. When the reaction is conducted at 190"C, the desired tertiary diamine is obtained with a yield close to 90 %. Through distillation, a tertiary diamine having a purity higher than 99 % is obtained. In this reaction, the catalyst of this invention has an activity several tens of times as high as conventional solid catalysts and a tertiary amine is produced at a high yield, even when a polyhydric alcohol is used.Namely, even in the case of a polyhydric alcohol, the catalyst suppresses side reactions such as aldol polycondensations of aldehyde, etc. at low levels and scarcely allows the formation of monomethylamine and trimethylamine by the disproportionation of dimethylamine. These facts indicate that the catalyst of this invention also has a very high selectivity even when polyhydric alcohols are used.
Further, the catalysts used in this invention are characterized in that they are very stable, maintain a homogeneous colloidal state even after the reaction, and the reaction product can be distilled without filtration. The distillation residue containing the catalyst can be reused as such in the reaction without reduction of its activity.
The alchols, aldehydes and ketones used in this invention can be (a) monohydric alcohols, aldehydes and ketones represented by the general formulas (I) or (II), (b) polyether alcohols represented by the general formulas (III) or (IV), (c) aliphatic polyhydric alcohols or aldehydes, or aromatic polyhydric alcohols or aldehydes, and (d) amino alcohols or ethylene oxide adducts thereof. More specifically, the following compounds can be used.
Firstly cited are aliphatic secondary alcohols and ketones represented by the general formula (I) or (II) wherein R, and R2 are both C, to C24 alkyl groups. Specifically, they are secondary alcohols such as 2-butanol, 2-pentanol, 2-octanol, 3-pentanol, 3-heptanol, 3-nonanol; and ketones such as methyl butyl ketone, methyl hexyl ketone, diethyl ketone, ethyl butyl ketone, dipropyl ketone, butyl amyl ketone, dilauryl ketone and dicetyl ketone. Next, cited as compounds wherein either of R1 and R2 is an aryl group of alkylaryl group, are aromatic alcohols such as benzyl alcohol, xylyl alcohol and phenylbutylcarbinol and aromatic aldehydes or ketones such as benzaldehyde and butyrophenone.
Cyclic alcohols or cyclic ketones represented by the formula (I) or (II) wherein R, and R2 form a ring, include cyclohexanol, cyclodecanol, cyclododecanol, cyclopentanone, cyclohexanone, cyclooctanone and cyclododecanone and one of them is heterocyclic compounds such as tetrahydrofurfuryl alcohol, furfuryl alcohol and furfural.
Polyether alcohols represented by the general formulae (III) and (IV) include polyoxyethylene alkyl ethers, polyoxypropylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyoxypropylene alkylphenyl ethers, etc. which have alkyl groups and oxyalkylene groups of various carbon numbers and various values for "n".
As aliphatic polyhydric alcohols, dihydric alcohols represented by the formula I HO-R-OH are preferable. Here, R is a C2 to C,8 alkylene group which can have a branched chain. Specific examples are ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, 1 , 5-pentanediol, 1 6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1 ,9-nonanediol, 1 , 10- decanediol, etc. Also dihydric alcohols represented by the formula
wherein m is 2 to 10 and R3 is the same as described previously, can be used.Specific examples are diethylene glycol, triethylene glycol, tetraethylene glycol and polyethylene glycols with increased degrees of polycondensation, as well as dipropylene glycol, tripropylene glycol and polypropylene glycols with increased degrees of polycondensation. Besides, polyhydric alcohols having three or more hydroxyl groups such as glycerol, trimethylolpropane, pentaerythritol, and sorbitol can also be used.
As aliphatic dialdehydes, glutaraldehyde, adipaldehyde, pimelaldehyde, suberaldehyde, and sebacaldehyde are cited.
As aromatic polyhydric alcohols, especially dihydric ones such as bisphenols and xylylenediols are cited.
As amino alcohols, those which have one to three hydroxyl groups as well as one to three amino groups in each molecule and which have molecular weights of from 60 to 1,000, can be used. Molecular weights of 60 to 600 are more preferable. Preferable examples of amino alcohols are diethylethanolamine, dimethylethanolamine, diisopropylethanolamine, monoethanolamine, diethanolamine, dibutylethanolamine, methyldiethanolamine, methylethanolamine, as well as ethylene oxide or propylene oxide adducts of long chain alkylamines. Besides, there are used ethylene diamine, diethylene triamine and ethylene oxide or propylene oxide adducts thereof.
As aliphatic amines to be reacted with these alcohols, aldehydes or ketones, primary amines such as methylamine, ethylamine, dodecylamine and octadecylamine, or secondary amines such as dimethylamine, diethylamine, didodecylamine and dioctadecylamine, or ammonia can be used.
In the practice of this invention, dependent on the kind of monohydric and polyhydric alcohols used, an inert solvent can be used and also a catalyst support or carrier, specifically, silica gel, colloidal silica, superfine particles of anhydrous silica, alumina, diatomaceous earth, or active carbon can be used together with the active catalyst, to enhance the catalyst activity. As inert solvents, liquid paraffin, paraffin wax, silicone oil, dialkyl ethers with long chains, or diphenyl ether are preferable.
The following illustrative examples more specifically explain the present invention.
Two reference examples of solid catalysts, i.e., one using copper-chromite catalyst and the other using stabilized nickel catalyst are also described.
Example 1 Into a 1,000 ml flask fitted with a stirrer, a condenser and a separator to remove reaction water, there were fed 150 g of benzyl alcohol, 150 g of liquid paraffin solvent, 6.0 g of copper stearate (copper 0.4 wt. %, based on the alcohol), 1.2 g of nickel stearate (nickel 0.08 wt. %, based on the alcohol) and 1.2 g of barium stearate (barium 0.08 wt. %, based on the alcohol).
While the stirrer was rotated, all gases in the system were replaced with nitrogen and the system was heated. When the temperature reached 100"C, hydrogen gas was bubbled into the system at a rate of 30 I per hour through a flowmeter. At 160 to 170"C, the catalyst was reduced and became apparently homogeneous and colloidal. About 40 minutes were required to reach 170"C. Then, the reaction temperature was kept at 170"C and a mixed gas consisting of hydrogen (30 I per hour) and dimethylamine (30 I per hour) (dimethylamine concentration in the mixed gas of 50 vol. %) was bubbled into the system.
Reaction products formed after 4 years of reaction where distilled. Analyses of the reaction products by amine values and gas chromatography gave the following results.
Dimethylbenzylamine 82.1 % Unreacted alcohol 1 3.4 % * Higher boiling products 4.5 % (aldol condensate) (% by weight) *This is the unreacted alcohol which was taken out of the reaction system by the hydrogen gas stream and did not react.
It was found from this experiment that a catalyst in which both (A) and (B) are carboxylic acid salts and which is a mixture of (A), (B) and (C) can be satisfactorily used in a reaction between an aromatic alcohol and an amine.
Example 2 The reaction between benzyl alcohol and dimethylamine was examined, using a twocomponent catalyst system with various compositions of (A) and (B), and using the same apparatus as described, in Example 1. 1 50 g of benzyl alcohol and 1 50 g of liquid paraffin solvent were fed. The catalyst was reduced by a procedure similar to that in Example 1, and at a reaction temperature of 170"C, a mixed gas consisting of hydrogen (30 I per hour) and dimethylamine (30 I per hour) (dimethylamine concentration in the mixed gas of 50 vol. %) was bubbled into the system. Reaction products formed after 4 hours of reaction were distilled and their analysis results are shown in Table 1, together with catalyst compositions of (A) and (B).
Table 1 Catalyst Composition Product Composition (wt.%) Dimethyl- Unre- By Run benzyl- acted products No. (A) (B) amine alcohol and others 1 Copper Nickel 77.8 16.5** 5.7 stearate stearate "1 *2 2 Copper Nickel 81.5 14.4" 4.1 stearate acetyl "1 acetone "2 *1 Cu 0.4 % "2 Ni 0.08 % *,This is the unreacted alcohol which was taken out of the reaction system by the hydrogen gas stream and did not react.
It was found from this experiment that a satisfactory reactivity is attained also in a twocomponent catalyst system consisting of (A) and (B) wherein both (A) and (B) are carboxylic acid salts or either one of (A) and (B) is an intramolecular complex.
Example 3 The catalyst of this invention was used in a reaction of a polyhydric alcohol. Namely, into the same apparatus as described in Example 1, 1 50 g of 1,6-hexanediol, 1 50 g of liquid paraffin solvent, 1.5 g of copper stearate (copper 0.1 wt. %, based on the alcohol), 0.3 g of nickel stearate (nickel 0.02 wt. %, based on the alcohol) and 0.3 g of barium stearate (barium 0.02 wt. %, based on the alcohol) were fed, and the catalyst was reduced in the same manner as described in Example 1. The system was heated up to 190"C and a mixed gas consisting of hydrogen (30 I per hour) and dimethylamine (30 I per hour) (dimethylamine concentration in the mixed gas of 50 vol. %) was bubbled into the system. The composition of the reaction products after 6 hours of reaction was as follows.
N,N, N', N'-tetramethylhexamethylenediamine 83.4 % N,N-dimethylaminohexanol (reaction in termediate) 6.8 % Unreacted 1,6-hexanediol 0.1 % Higher boiling products (aldol condensate) 6.0 % Others 3.7 % It was found from this experiment that a three-component catalyst system consisting of (A), (B) and (C) has satisfactory activity and high selectivity for polyhydric alcohols, even in very small amounts.
Example 4 Using three-component catalyst systems consisting of (A), (B) and (C), reactions were conducted for various combinations of other alcohols and amines.
Namely, reactions were conducted between alkylpolyoxyalkylene alcohol or amino alcohol, and monomethylamine as primary amine or dimethylamine as secondary amine. 1 50 g of alcohol were fed, and copper stearate (copper 0.1 wt. %, based on the alcohol) as (A), nickel stearate (nickei 0.02 wt. %, based on the alcohol) as (B) and barium stearate (barium 0.02 wt.
%, based on the alcohol) as (C) were added. The apparatus and the reduction conditions for the catalyst system were as described in Example 1. Reactions were conducted by bubbling a mixed gas consisting of hydrogen (30 I per hour) and an amine (30 I per hour) (amine concentration in the mixed gas of 50 vol. %) into the reaction system. Conversion ratios of alcohols after 6 hours of reaction were as shown in Table 2. The reaction of Run No. 4 was exceptional in that the mixed gas consisted of 30 I per hour of hydrogen and 5 I per hour of monomethylamine.
Table 2
Reaction Conver Run Tempera- sion Ratio No. Alcohol Amine ture of Alcohol CH3 3 C,6H33(OCH2CH2)3OH NH 210"C 76.8 % CH3 4 C,6H33(OCH2CH2)3OH CH3-NH2 210C 75.0 % CH3 5 (CH3)2N(CH2)6OH NH 190"C 96.0 % CH3 Thus it was found that the catalyst of this invention shows satisfactory reactivity also for other alcohols as shown above.
Reference Example 1 Copper chromite catalyst, which is a solid catalyst, was compared with the colloidal catalyst of this invention.
Into the same apparatus as described in Example 1, 1 50 g of 1,6-hexanediol and 15.0 g of copper chromite catalyst (copper 4.8 wt. %, based on the alcohol) were fed, and the catalyst was reduced by hydrogen while the temperature was being increased. Then, a mixed gas consisting of hydrogen (30 I per hour) and dimethylamine (30 I per hour) (dirnethylamine concentration in the mixed gas of 50 vol. %) was bubbled into the system. The results of Reference Examples 1 and 2 are shown together in Table 3.
Reference Example 2 As catalyst, stabilized nickel catalyst was used. Into the same apparatus as described in Example 1, 150 g of 1,6-hexanediol and 11.1 g of stabilized nickel (nickel 3.7 wt. %, based on the alcohol) were fed and, after reduction with hydrogen, reaction was carried out by bubbling into the system a mixed gas consisting of hydrogen (30 1 per hour) and dimethylamine (30 I per hour) (dimethylamine concentration in the mixed gas of vol. 50 %). The results were compared with those of the catalyst of this invention (Example 3).
Table 3 shows that solid catalysts of the copper chromite type and the stabilized nickel type are inferior to the catalyst of this invention in reactivity even when the former are employed in large excess. Also, the catalyst of this invention is far superior in selectivity.
Table 3 Catalyst Reaction Condition N,N,N',N'- N,N-Di- Higher Tempera- tetramethyl- methyl- Unre- boiling ture Time hexamethyl- amino- acted products, Kind * % ("C) (Hr) enediamine hexanol alcohol etc.
Refer- copper ence chro Example mite 4.8 190 8 34.1 35.8 2.8 27.3 1-1 ditto copper 1-2 chro mite 4.8 210 8 58.1 10.1 1.1 30.5 ditto stabil2 ized nickel 3.7 190 8 17.2 5.8 1.0 75.0 Exam- catalyst ple 3 of this inven tion 0.1 190 6 83.4 6.8 0.1 9.7 * Percentage refers to copper wt. %, based on alcohol (in Reference Example 2, nickel wt. %)

Claims (11)

1. A process for the preparation of tertiary amines by reacting: (1.) an alcohol, an aldehyde, or a ketone selected from: (a) a primary alcohols, secondary alcohols, aldehydes, or ketones represented by the following general formulas (I) or (Il),
wherein R1 and R2 are independantly of hydrogen, C, to C24 saturated or unsaturated aliphatic hydrocarbon, aryl, or alkylaryl groups, or R1 and R2 together form an alicyclic (C5-C,2) ring, or one of them is a heterocyclic ring containing oxygen and the other is hydrogen, and in the case where either of R, and R2 is an alkyl group, the other is other than hydrogen and the sum of the number of carbon atoms of R1 and R2 is 3 or more, (b) polyether alcohols represented by the following general formulas (III) or (IV)
wherein R1' and R2' are independently hydrogen, C, to C24 saturated or unsaturated aliphatic hydrocarbon, aryl, or alkylaryl groups, or R,' and R2' together form a ring, R3 is hydrogen or methyl group, R4 is C6 to C,8 saturated or unsaturated aliphatic hydrocarbon group, and n is an integer from 1 to 20, (c) aliphatic or aromatic polyhydric alcohols or dialdehydes, and (d) amino alcohols or ethylene oxide or propylene oxide adducts thereof, with:: (2.) ammonia or a primary or secondary aliphatic amine represented by the following general formula (V)
wherein R6 and R6 are independently hydrogen, or C, to C24 saturated or unsaturated aliphatic hydrocarbon groups, characterized in that the reaction is carried out at a temperature of 150 to 300'C in the presence of a catalyst which is prepared by the reduction of a mixture consisting of (A), (B) and (C), or a mixture consisting of (A) and (B) provided that both (A) and (B) are salts of carboxylic acids, or a mixture consisting of (A) and (B) provided that one of (A) and (B) is a salt of a carboxylic acid and the other is an intramolecular complex, wherein (A) is at least one copper or silver salt of a carboxylic acid or at least one intramolecular complex of copper or silver, (B) is at least one carboxylic acid salt or at least one intramolecular complex of a metal of Group VIII in the Mendeleev Periodic Table, manganese and zinc, and (C) is at least one carboxylic acid or alkali metal or alkaline earth metal salt thereof.
2. A process according to Claim 1 wherein the reduction is carried out by using hydrogen, or a mixture of hydrogen and ammonia, or an amine of formula (V), or an aluminium alkyl derivative.
3. Process according to Claim 1 or Claim 2, wherein reactant (1) is an alcohol selected from: (a) secondary aliphatic alcohols having the formula (I), wherein both of R, and R2 are C, to C,8 alkyl groups and the sum of the number of carbon atoms in R, plus R2 is 3 or more, (b) aromatic alcohols having the formula (I), wherein R, is a C6 to C,8 aryl or alkylaryl group and R2 is hydrogen, (c) polyether alcohols having the formula (III), (d) dihydric alcohols having the formula HO-R-OH wherin R is a C2 to C,8 straight chain or branched chain alkylene group, or (e) dihydric alcohols having the formula
wherein m is an integer of 2 to 10.
4. A process according to any preceding claim wherein the ligand material forming said intramolecular complex is a P-diketone compound or a glyoxime compound.
5. A process according to any of Claims 1 to 3 wherein said carboxylic acid has 5 to 36 carbon atoms.
6. A process according to Claim 5 wherein said carboxylic acid is an aliphatic carboxylic acid having 5 to 22 carbon atoms.
7. A process according to Claim 4 wherein ligand material forming said intramolecular complex is acetyl-acetone.
8. A process according ta any preceding claim wherein said Group VIII element is nickel, colbalt, iron or palladium.
9. A process according to any preceding claim wherein the amount of said catalyst is from 0.001 to 5 wt. %, calculated as the metals, based on the weight of the starting reactant (1).
1 0. A process according to Claim 9 wherein the amount of said catalyst is from 0.01 to 1.0 wt. %, calculated as the metals, based on the weight of the starting reactant (1).
11. A process according to Claim 1 wherein said catalyst material is dissolved in said reactant (1) in the liquid phase, then hydrogen is passed through said solution of said catalyst material in said reactant (1), at a temperature of from 100" to 200"C until said catalyst material is reduced and is transformed to a homogeneous colloidal state in said reactant (1), and then said ammonia or said primary or secondary aliphatic amine in a gaseous state is bubbled through said solution in the liquid phase.
1 2. A method of preparing a catalyst, comprising reducing a mixture of (A), (B) and (C), or a mixture consisting of (A) and (B) provided that both (A) and (B) are salts of carboxylic acids, or a mixture consisting of (A) and (B) provided that one of (A) and (B) is a salt of a carboxylic acid and the other is an intramolecular complex, wherein (A) is at least one copper or silver salt of a carboxylic acid or at least one intramolecular complex of copper or silver, (B) is at least one carboxylic acid salt or at least one intramolecular complex of a metal of Group VIII in the Mendeleev Periodic Table, manganese and zind, and (C) is at least one carboxylic acid or alkali metal or alkaline earth metal salt thereof.
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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0141328A2 (en) * 1983-10-22 1985-05-15 Hoechst Aktiengesellschaft Process for the preparation of tertiary amines
EP0356046A2 (en) * 1988-08-18 1990-02-28 BP Chemicals Limited The reductive amination of hydroxy-containing compounds
US5266730A (en) * 1987-10-16 1993-11-30 Kao Corporation Process for preparing N-substituted amine
WO2012031884A1 (en) * 2010-09-10 2012-03-15 Evonik Degussa Gmbh Process for the direct amination of secondary alcohols with ammonia to give primary amines
US8486183B2 (en) 2005-08-09 2013-07-16 Exxonmobil Research And Engineering Company Alkylamino alkyloxy (alcohol) monoalkyl ether for acid gas scrubbing process

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0485371B1 (en) * 1987-10-16 1995-06-14 Kao Corporation Process for preparing N-substituted amine
CA2032449A1 (en) * 1990-01-24 1991-07-25 John F. Knifton "twin-tailed" polyoxyalkylene tertiary amines
CN110407706A (en) * 2019-07-22 2019-11-05 中国日用化学研究院有限公司 A kind of homogeneous catalyst system preparing fat tertiary amine and application

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS54125603A (en) * 1978-03-16 1979-09-29 Kao Corp Preparation of aliphatic amine

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0141328A2 (en) * 1983-10-22 1985-05-15 Hoechst Aktiengesellschaft Process for the preparation of tertiary amines
EP0141328A3 (en) * 1983-10-22 1986-03-26 Hoechst Aktiengesellschaft Process for the preparation of tertiary amines
US5266730A (en) * 1987-10-16 1993-11-30 Kao Corporation Process for preparing N-substituted amine
EP0356046A2 (en) * 1988-08-18 1990-02-28 BP Chemicals Limited The reductive amination of hydroxy-containing compounds
EP0356046A3 (en) * 1988-08-18 1990-10-03 BP Chemicals Limited The reductive amination of hydroxy-containing compounds
US5015773A (en) * 1988-08-18 1991-05-14 Bp Chemicals Limited Reductive amination of hydroxy-containing compounds
US8486183B2 (en) 2005-08-09 2013-07-16 Exxonmobil Research And Engineering Company Alkylamino alkyloxy (alcohol) monoalkyl ether for acid gas scrubbing process
WO2012031884A1 (en) * 2010-09-10 2012-03-15 Evonik Degussa Gmbh Process for the direct amination of secondary alcohols with ammonia to give primary amines
CN103097324A (en) * 2010-09-10 2013-05-08 赢创德固赛有限公司 Process for the direct amination of secondary alcohols with ammonia to give primary amines
US8927773B2 (en) 2010-09-10 2015-01-06 Evonik Degussa Gmbh Process for the direct amination of secondary alcohols with ammonia to give primary amines
RU2593994C2 (en) * 2010-09-10 2016-08-10 Эвоник Дегусса Гмбх Method for direct amination of secondary alcohols using ammonia to primary amines

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IT8024709A0 (en) 1980-09-17
ES8200325A1 (en) 1981-11-01
BR8005955A (en) 1981-03-31
JPS5643246A (en) 1981-04-21
FR2464940A1 (en) 1981-03-20
ES495138A0 (en) 1981-11-01
DE3034433A1 (en) 1981-04-02

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