CA1129428A

CA1129428A - Preparation of tertiary amines

Info

Publication number: CA1129428A
Application number: CA360,415A
Authority: CA
Inventors: Yukinaga Yokota; Fumiro Hoshino; Youzi Sawamoto
Original assignee: Kao Soap Co Ltd
Current assignee: Kao Corp
Priority date: 1979-09-17
Filing date: 1980-09-17
Publication date: 1982-08-10
Also published as: FR2464940B1; JPS6130651B2; DE3034433A1; BR8005955A; IT8024709A0; GB2059792A; ES495138A0; ES8200325A1; JPS5643246A; GB2059792B; FR2464940A1

Abstract

ABSTRACT OF THE DISCLOSURE
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 com-ponents A, B and C, wherein A is a copper or solver carboxylate or intra-molocular 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. The colloidal catalyst permit tertiary amine to be prepared at high yields, without reducing the activity and selectivity of the catalysts.

Description

~129428 PREPARATION OF TERTIARY AMINES

This invention relates to a method for the prepara-tion of tertiary monoamines and polyamines, by reacting a monohydric or polyhydric alcohol having hydroxyl groups(s), such as primary and secondary alcohols, an aldehyde or a ketone, with ammonia or a primary or secondary amine, in the presence of a special catalyst.
Tertiary monoamines and polyamines having various substituents are widely useful, for example, as inter-mediates for emulsi~iers, 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 byreacting 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 de-scribed hereunder. They are all solid catalysts and are used in heterogeneo;ls reaction systems. Namely, the reaction between a monohydric alcohol and ammonia or a primary or secondary amine is disclosed in U. S.
PatentsNo. 2 953 601, No. 3 223 734 and No. 3 373 204, German Patent Laid-Open No. 1 493 781, and Japanese Patent Laid-Open No. 52-19604. These patents use, as ~1294Z8 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 dis-closed in U. S. Patents No. 3 219 707, No. 3 223 734, No. 3 270 059, No. 3 847 992 and No. 4 014 933, 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 ~o. 3 270 059, 1,6-hexanediol was reacted with ammonia, in the presence of a large excess of a cobalt catalyst, at 205C and at a high pressure of 280 atm., and a distillate obtained after 72 hours of reaction comprised 29.3 wt % of 1,6-hexamethylenediamine; 46.7 wt % o~
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 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 re-quire filtration facilities, and moreover, public nui-sance 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 ?42~

yield of the desired amine is reduced. In the case of a polyhydric alcohol which possesses many functional groups, side reactions, such as aldol condensa-tion, 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 United States Patent No. 4,210,605, and Applica-tion No. 54-19580. 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 arom-atic 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 relates to a method for the preparation of tertiary amines by reacting ~1.) an alcohol, an aldehyde, or a ketone selected from the group consisting of:
(a) primary alcohols, secondary alcohols, aldehydes, or ketones represented by the following general formulas (I) or (II), l > CH-OH (1), 1 > C = (Il) wherein Rl and R2 are hydrogcn, Cl to C24 saturated or unsaturated aliphatic hy-drocarbon group, aryl group, or alkylaryl group, or Rl and R2 together form an alicyclic (C5-C12) ring, or one of them is a heterocyclic ring containing oxygen and the other is hydrogen, and l~Z942~

i.n the case where either one of Rl and R2 is an alkyl group, the other is other than hydrogen and the sum of the number of carbon atoms of Rl and R2 is 3 or more, (b) polyether alcohols represented by the following general formulas (III) or (IV), > CH-O ~ CH2 CHO ~nH ( I I I ), \~ ~ CH2c~o ~nH ( IV) wherein Rl' and R2' are hydrogen, Cl to C24 saturated or unsaturated aliphatic hydrocarbon group, aryl group, or alkylaryl group, or Rl' and R2' together form'a ring, R3 is hydrogen or methyl group, R4 is C8 to C18 saturated or unsaturated aliphatic hydrocarbon group, and n is an integer of 1 to 20, (c) aliphatic or aromatic polyhydr.ic alcohols or di-aldehydes, and (d) amino alcohols or ethylene oxide or propylene oxide adducts thereof, with (~.) ammonia or a primary or secondary aliphatic amine represented by the general formula 20 H- ~ (V) wherein R5 and R6 are hydrogen, or Cl to C24saturated or unsaturated aliphatic hydrocarbon group, characterized in ~hat the reaction is carried out at a temperature of 150 to 300C, in the presence of a catalyst which is prepared by reduction, with hydrogen, or a mixture of hydrogen and ammonia or an amine repre-sented by the formu~.a (V), or another reducing agent, 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 one or more of copper or silver salts of carboxylic acids or intramolecular complexes of copper or silver, (B) is one or more of carboxylic acid salts or intramolecular complexes of a metal se lected from the Group VIII elements in the Periodic Table of The Elements, manganese and zinc, and (C) is one or more of carboxylic acids or alkali metal or alkaline earth metal salts thereof.
The catalyst system used in this invention is reduced, prior to its use in the reaction; by means of hydrogen, or a mixture of hydrogen and ammonia or an amine, or a reducing agent such as AQ(C2H5)3 and (C2H5)2AQ(OC2H5), in a reaction medium such as a secondary aliphatic alcohol, aromatic alcohol or poly-hydric alcohol, or in an inert solvent. Preferably,the catalyst system is dissolved in the reaction medium, reduced at a temperature of 100 to 200C by means of hydrogen or a mixture of hydrogen and an amine, and then used for the reaction. The reduc~ion is very easily conducted and completes in a short period of time at a temperature oE 100 to 200C. 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 reac-tion is preferably continuously distilled out of the reaction system. The reaction temperature employed is 150 to 300C, preferably 170~ to 240C. The reaction pressure can be a reduced pressure, but preferably it is ~rom 0 to 10 atm. (gauge pressure) and more prefer-ably, it is atmospheric pressure.
Among the catalyst components used in this inven-tion, the component (A) is (are) intramolecular com-plex(es) or carboxylic acid salt(s) o~ copper or silver.
Ligands which can form intramolecular complex salts used in this invention can be ~-diketone compounds, glyoxime compounds, glycine, salicylaldehyde, -picolinic acid, a-bènzoinoxime, etc~
However, the ligands which contain hydrogenation poisons, such as halogens and sulfur, CannQt be used.
As an example, metal complexes of dimethyldithiocar-bamic acid cannot be used because sulfur acts as a catalyst poison. Preferable ligands are ~-diketone compounds and glyoxime compounds. Preferable intra-molecular complexes are, for instànce, copper-acetylacetone complex and silver-acetylacetone 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 substit~lents, so long as they have at least one carboxyl group in their moLecules. Among these, carboxylic acids of C5 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 t arachic acid, behenic , 42~

acid, oleic acid, or derivatives of these acids con-taining 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 C36, 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 o (A) and (B) are eEfective. 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 combina-tions of three components (A), (B) and (C), (A) and (B) can be carboxylic acid salts or intramolecular com-plexes. Any combination of (A), (B) and (C) is effect-4~E~

ive and the three-component combinations of (A), (B) and (C) are more effective than two-component combina-tions of (A) and (B).
A mode of using the catalyst system of this in-vention 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 190C, 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 con-ventional 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 re-actions such as aldol polycondensations of aldehyde, etc. at low levels and scarcely allows the formation of monomethylamine and trimethylamine by the dispro-portionation of dimethylamine. These facts indicate that the catalyst of this invention also has a very high selectivity even when polyhydric alcohols are used.
E`urther, the catalysts used in this invention are characterized in that they are very stable, main-tain a homogeneous colloidal state even after the reaction, and the reaction product can be distilled without filtration. The distillation residue con-tainin~ the catalyst can be reused as such in the reaction without reduction of its activity.

1~294~8 The alcohols, 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 al cohols or aldehydes, or aromatic polyhydric alcohols or aldehydes, and (d) amino alcohols or ethylene oxide adducts thereof. More specifically, the following com-pounds can be used.
Firstly cited are aliphatic secondary alcohols and ketones represented by the general ~ormula (I) or (II) wherein Rl and R2 are both Cl 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, diethyi ke~one, ethyl butyl ketone, dipropyl ketone, butyl amyl ketone, dilauryl ketone and dicetyl ketone. Next, cited as compounds wherein either of Rl and R2 is an aryl group or 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 Rl 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 HO-R-OH are preferable. Here, R is a C2 to C18 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, l,9-nonanediol, 1,10-decanediol, etc. Also dihydric alcohols represented by the formula HO -~ CH2CHO ~-mH 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 in-creased degrees of polycondensation. Besides, poly-hydric alcohols having three or more hydroxyl groups such as glycerol, trimethylolpropane, pentaerythrito], and sorbitol can also be used.
As aliphatic dialdehydes, glutaraldehyde, adip-aldehyde, pimelaldehyde, suberaldehyde, and sebacal-dehyde are cited.
As aromatic polyhydric alcohols, especially dihydric olles such as bi,sphenols a~d xylylenediols are cit~d.
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 30 from 60 to 1,000, can be used. Molecular weights of 60 to 600 are more preferable. Preferable examples of amino alcohols are diethylethanolamine, dimethyl-ethanolamine~ diisopropylethanolamine, monoethanolamine, 112g428 ~

diethanolamine, dibutylethanolamine, methyldiethanol-amine, methylethanolamine, as well as ethylene oxide or propylene oxide adducts o~ 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~to-géther 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 specifical-ly 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 mQ flask fitted with a stirrer, a condenser and a separator to remove reaction water, 3 there were fed 150 g of benzyl alcohol, 150 g of liquid parain solvent, 6.0 g of copper s-tearate (copper 0.4 wt. %, based on the alcohol), 1.2 g of nickel stearate (nickel 0.08 wt. %, based on the alco-hol) and 1.2 g of barium stearate (bariumO.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 42~3 100C, hydrogen gas was bubbledinto thesystem at a rate of 30 Q per hour through a flowmeter. At 160 to 170C~
the catalyst was reduced and became apparently homo- -geneous and colloidal. About 40 minutes were required to reach 170C. Then, the reaction temperature was kept at 170C and a mixed gas consisting of hydrogen (30 Q per hour) and dimethylamine (30 Q per hour) (dimethylamine concentration in the mixed gas of 50 vol. %) was bubbled into the system.
Reaction products formed after 4 hoursof reaction were distilled. Analyses of the reaction products by amine values and gas chromatography gave the following results.
Dimethylbenzylamine 82.1 %
Unreacted alcohol 13.4 ~ *
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 satisfac-torily used in a reaction between an aromatic alcohol and an amine.
Example 2 The reaction between benzyl alcohol and dimethylamine was examined, using a two-component catalyst system with various compositions of (A) and (B), and using the same apparatus as described in Example 1. 150 g of benzyl alcohol and 150 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 170C, a mixed gas consisting of hydrogen (30 Q per hour) and di~
methylamine (30 Q per hour) ~dimethylamine concentration in the mixed ~as of S0 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 Run Catalyst Composition Product Composition (wt~%) No. (A) (B) Dimethyl- Unre- By-benzyl- acted products 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 satis-factory reactivity is attained also in a two-component catalyst system consisting of (A) and (B) wherein both (A) and ~B) are carboxylic acid salts or either one o (A) and ~B) is an intramolecular complex.
Example 3 The catalyst of this invention was used in a re-action of a polyhydric alcohol. Namely, into the same apparatus as described in Example 1, 150 g of 1,6--hexanediol, 150 g of liquid paraffin solvent, 1.5 g of copper stearate ~copper 0.1 wt. %, based on the alcohol)d 0.3 g of nickel stearate (nickel 0.02 wt. %, based on the alcohol) and 0.3 g of barium stearate ~barium 0O02 ~2~4~

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 190C and a mixed gas consisting of hydrogen (30 Q per hour) and dimethylamine (30 Q per hour) (dimethylamine concentration in the mixed gas of 50 vol. %) was bubbled into the system. ~he composition of the reaction products after 6 hours of reaction was as follows.
N,N,N',N'-tetramethylhexamethylenediamine ~3~ %
10N,N-dimethylaminohexanol (reaction in-termediate) 6.8 %
Unreacted 1,6-hexanediol 0.1 %
Higher boiling products (aldol condensate) 6O0 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 poly-hydric 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 alkyl-polyoxyalkylene alcohol or amino alcohol, and mono-methylamine as primary amine or dimethylamine as secondary amine. 150 g of alcohol were fed, and copper stearate (copper 0.1 wt. %, based on the alcohol) as (A), nickel stearate (nickel 0.02 wt. %, based on the alcohol) as (B) and barium stearate (barium 0.02 wto %~
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 con--ducted by bubbling a mixed gas consisting of hydrogen (30 Q per hour) and an amine (30 Q 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 Q per hour of hydrogen and 5 Q per hour of monomethylamine.

Table 2 Run Alcohol Amine Reaction Conver-No. Tempera- sionRatio ture ofAlcohol CH
16 33(0cH2cH2)3oH > NH 210C 76.8 %

16 33(CH2cH2)3HCH3-NH2 210C 75.0 %

(CH3)2N(CH2)60H3~ NH 190C 96.0 ~

Thus it was found that the catalyst of this inven-tion shows satisfactory reactivity also for other al-cohols as shown above.
Reference Example 1 Copper chromite catalyst, which is a solid catalyst, was compared with the colloidal catalyst of this inven~
tion .
Into the same apparatus as described in Example 1, 150 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 (30Qper hour) and diméthylamine ~30 Q per hour~ (dimethylamine concentration in the mixed gas of 50 vol. ~) was bubbled into the systemO

The results of Reference Examples 1 and 2 are shown to--gether in Table 3.
Reference Example 2 As catalyst, stabilized nickel catalyst was usedO
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 hy--drogen (30 Q per hour) and dimethylamine (30 Q per hour)(.dimethylamine concentration ln 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 in-'ferior to the catalyst of this invention in react,ivi.tyeven when the former are employed in large excess.
Also, the catalyst of this invention is far superior in selectivity.

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Claims

The embodiments of the invention in which an ex-clusive property or privilege is claimed are defined as follows:

1. In a process for preparing a tertiary amine which comprises reacting (1.) an alcohol, an aldehyde, or a ketone selected from the group consisting of:
(a) primary alcohols, secondary alcohols, aldehydes and ketones having the formulas (I) or (II), (I), (II) wherein R1 and R2 are hydrogen, C1 to C24 saturated or unsaturated aliphatic hydrocarbon group, aryl group, or alkylaryl group, or R1 and R2 together with the carbon atom to which they are attached form an alicyclic, or either of R1 and R2 is a heterocyclic group and the other is hydrogen, and the sum of the number of carbon atoms of R1 and R2 is 3 or more, (b) polyether alcohols having the general formulas (III) or (IV), (III), (IV), wherein Rl' and R2' are hydrogen, C1 to C24 saturated or unsaturated aliphatic hydrocarbon group, aryl group, or alkylaryl group, or R1' and R2' together with the carbon atom to which they are attached form a ring, R3 is hydrogen or methyl group, R4 is C8 to C18 saturated or unsaturated aliphatic hydrocarbon group, and n is an integer of 1 to 20, (c) aliphatic or aromatic polyhydric alcohols and dialdehydes, and (d) amino alcohols and ethylene oxide or propylene oxide adducts thereof, with (2.) ammonia, or a primary or secondary aliphatic amine represented by a general formula (V), wherein R5 and R6 are hydrogen, or C1 to C24 saturated or unsaturated aliphatic hydrocarbon group, the im-provement which comprises: the reaction is carried out at a temperature of 150°to 300°C, in the presence of a homogeneous colloidal catalyst prepared by reducing with hydrogen, or a mixture of hydrogen and ammonia or an amine having the formula (V), or another reducing agent, a catalyst material selected from the group con-sisting of (1) a mixture consisting essentially of component A, component B and component C, (2) a mixture consisting essentially of component A and component B, with the proviso that both of components A and B are salts of carboxylic acids, and (3) a mixture consisting essentially of component A and component B, with the proviso that one of said compo-nents A and B is salt of carboxylic acid and the other thereof is an intramolecular complex, wherein component A is one or a mixture of two or more materials selected from the group consisting of car-boxylic acid salts and intramolecular complexes of one or more elements selected from the group consisting of copper and silver, and component B is one or a mixture of two or more materials selected from the group con-sisting of carboxylic acid salts and intramolecular complexes of one or more elements selected from the group consisting of the elements of Group VIII of the Periodic Table of The Elements, manganese and zinc, and component C is one or a mixture of two or more of carboxylic acids and salts of carboxylic acids with one or more elements selected from the group consisting of alkali metals and alkaline earth metals.

2. Process for preparing a tertiary amine accord-ing to Claim 1, wherein reactant (1) is an alcohol selected from the group consisting of:
(a) secondary aliphatic alcohols having the formula (I), wherein both of R1 and R2 are C1 to C18 alkyl groups and the sum of the number of carbon atoms in R1 plus R2 is 3 or more, (b) aromatic alcohols having the formula (I), wherein R1 is a C6 to C18 aryl or alkylaryl group and R2 is hydrogen, (c) polyether alcohols having the formula (III), (d) dihydric alcohols having the formula HO-R-OH wherein R is a C2 to C18 straight chain or branched chain alkylene group, or (e) dihydric alcohols having the formula wherein m is an integer of to 10.

3. A process according to Claim 1 or 2 wherein the ligand material forming said intramolecular complex is a .beta.-diketone compound or a glyoxime compound.

4. A process according to Claim 1 or 2 wherein said carboxylic acid has 5 to 36 carbon atoms.

5. A process according to Claim 1 or 2 wherein the ligand material forming said intramolecular complex is a .beta.-diketone compound or a glyoxime compound and said carboxylic acid is an aliphatic carboxylic acid having 5 to 22 carbon atoms.

6. A process according to Claim 1 or 2 wherein the ligand material forming said intramolecular complex is acetylacetone.

7. A process according to Claim 1 wherein said elements of Group VIII
of the Periodic Table of The Elements are nickel, cobalt, iron or palladium.

8. A process according to Claim 1 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).

9. A process according to Claim 1 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).

10. A process according to Claim 1 wherein said catalyst material is dissolved in said reactant (1) in the liquid phase, then hydrogen gas is flowed through said solution of said catalyst material in said reactant (1), at a temperature of from about 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.