JPS6130651B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention uses primary and secondary alcohols such as
A method for producing tertiary mono- and polyamines by reacting monohydric and polyhydric alcohols, aldehydes, or ketones having hydroxyl groups with ammonia or primary or secondary amines using a special catalyst. It is related to. Depending on their structure, tertiary mono- and polyamines with various substituents can be used as emulsifiers, dispersants, rust preventives, fungicides, textile dyeing aids, and intermediates for fabric softeners. It is a useful substance with many uses. Conventionally, it is well known to react alcohols or aldehydes with ammonia, primary amines, or secondary amines to produce corresponding substituted amines, and the catalysts used for this reaction are generally hydrogenated. This is called a dehydrogenation catalyst. There are patents as shown below as catalysts used in these reactions, all of which are solid catalysts, and are carried out in a heterogeneous reaction system as a catalyst. For the reaction of monohydric alcohols with ammonia or primary or secondary amines, see US Pat.
No., U.S. Patent No. 3223734, German Patent Application No. 1493781, and Japanese Patent Application Laid-open No. 1960-1984, etc. Catalysts include Raney nickel catalyst, supported nickel catalyst, supported cobalt catalyst, and palladium carbon catalyst. , a copper-chromium oxide catalyst, etc. Regarding the reaction of polyhydric alcohols with ammonia or primary or secondary amines, see US Pat.
Specifications of No. 3270059, No. 3847992, and No. 4014933, as well as Japanese Unexamined Patent Application Publication No. 53-59603, etc., include nickel or cobalt catalysts, Raney-nickel catalysts, and copper-nickel-cobalt oxidation as catalysts. For example, in Example 3 of US Pat. No. 3,270,059, 1,6-hexanediol and ammonia are added to a large excess of cobalt catalyst.
℃, under high pressure of 280 atm, and after 72 hours of reaction, the distillation composition shows that the weight percent of the product is 1,6-hexamethylenediamine 29.3%, hexamethyleneimine 46.7%, and residue 24.0% (excluding water). is giving. All of these patents are solid catalyst systems,
As a catalyst, the reaction is carried out in a heterogeneous system. However, since these solid catalysts have low activity, the amount of catalyst used is very large, ranging from 2.5 to 8.5% or more. As a result,
The cost of the catalyst increases, and reaction conditions at high temperature and pressure for a long time are required. Further, it requires equipment for the filtration process, and there are also problems of pollution such as disposal of used catalysts, which is not always satisfactory. Further, the selectivity as well as the catalytic activity is not necessarily satisfactory. That is, in a reaction in which an alcohol or aldehyde is reacted with ammonia, a primary amine, or a secondary amine using a hydrogenation-dehydrogenation catalyst to convert it into a primary, secondary, or tertiary amine, As a living organism, aldol condensation products are produced, which reduces the yield of the desired amine.Also, polyhydric alcohols have a large number of functional groups, which can lead to side reactions such as aldol condensation. There is a tendency for the yield to decrease significantly. In order to solve these problems, the result of intensive research,
He previously discovered an apparently homogeneous colloidal catalyst with high activity and high selectivity, and filed a patent application (patent application filed in 1973).
No. 30149 and No. 54-19580) further,
The present inventors used similar special colloidal catalysts and, as a result of further intensive research, found that not only aliphatic alcohols or aldehydes, but also aromatic alcohols or aldehydes, polyhydric alcohols, ketones, etc., and ammonia or primary or It was discovered that the desired tertiary amine could be obtained in high yield by applying it to a reaction with a secondary amine, allowing the reaction to occur in a rational manner, without reducing catalytic activity and selectivity, and led to the present invention. . That is, the present invention provides a primary alcohol, a secondary alcohol, an aldehyde or a ketone represented by the following general formula () or (), [In the formula, R ₁ and R ₂ are H, a C ₁ to _{C 24} saturated or unsaturated aliphatic hydrocarbon group, an aryl group, or an alkylaryl group, or a carbon atom to which R ₁ and R ₂ are bonded Indicates something that forms a ring with. However, when one of R ₁ and R ₂ is a saturated or unsaturated aliphatic hydrocarbon group, the other is not H. R ₁
The sum of the carbon numbers of and R ₂ is 3 or more. )], ○B Polyether alcohol represented by the following general formula () or (), [In the formula, R ₁ ′ and R ₂ ′ are H or a C ₁ to _{C 24} saturated or unsaturated aliphatic hydrocarbon group, an aryl group, an alkylaryl group, or the carbon to which R ₁ and R ₂ are bonded Indicates something that forms a ring with atoms.
R ₃ represents H or a methyl group, R ₄ represents a C ₈ to _{C 18} saturated or unsaturated aliphatic hydrocarbon group, and n is 1 to 20
indicates an integer. ], ○ C) An alcohol, aldehyde or ketone selected from the group consisting of aliphatic or aromatic polyhydric alcohol or aldehyde, ○ Niamino alcohol or its ethylene oxide adduct, and the general formula

Ammonia or a primary or secondary aliphatic amine represented by [Formula] (wherein R ₅ and R ₆ each represent H or a C ₁ to C ₂₄ saturated or unsaturated aliphatic hydrocarbon group) In producing the corresponding tertiary amine by reacting (A) copper acetylacetone complex as a copper carboxylate or copper intramolecular complex, and (B) elements of group group of the periodic table, manganese and zinc. (C) one or more acetylacetone complexes as carboxylates or intramolecular complexes of metals selected from (C) one or more carboxylic acids or alkali metal salts or alkaline earth metal salts of carboxylic acids; Among these, a mixture consisting of (A), (B), and (C), or a mixture consisting of (A) and (B) where (A) and (B) are both carboxylic acid salts, or (A) and
One of (B) is a carboxylate and the other is an intramolecular complex, and either a mixture consisting of (A) and (B) is substituted with hydrogen, a mixture of hydrogen with ammonia or amine of formula (), or other The present invention relates to a method for producing a tertiary amine, which is characterized in that the reaction is carried out at a temperature of 150 to 300°C using a product reduced with a ring agent as a catalyst. The catalyst used in the present invention is dissolved in advance in a reaction medium (for example, an aromatic alcohol or a polyhydric alcohol) or an inert solvent before being used in the reaction, and hydrogen or a mixture of hydrogen and ammonia or amine, or Al ( _C2H5 ) _{3 ,}
It is used after being reduced with a reducing agent such as (C ₂ H ₅ ) ₂ Al (OC ₂ H ₅ ). The catalyst is preferably dissolved in the reaction medium and reduced to use with hydrogen or a mixture of hydrogen and an amine at a temperature of 100 to 200°C. The reduction is very easy and can be completed in a short time during heating to 100-200°C, and the resulting catalyst cannot be separated by normal oral passage, and is apparently a homogeneous colloidal catalyst. After the catalyst becomes a colloid, ammonia, which is the raw material for the desired tertiary amine, and primary
A primary or secondary amine is added to the reaction system. Although the reaction proceeds in the absence of hydrogen, it is preferably carried out in the presence of a small amount of hydrogen. Further, since the catalyst used in the present invention has a reduced catalytic activity due to prolonged contact with water, water produced during the reaction is desirably distilled out of the reaction system continuously. Reaction temperature is 150~
The temperature is preferably 300°C, preferably 170 to 240°C, and the reaction pressure is preferably 0 to 10 atmospheres (gauge pressure), more preferably normal pressure. Among the catalyst components used in the present invention, component (A) is a copper carboxylate or a copper acetylacetone complex. The carboxylic acids that form copper carboxylates may be aromatic or branched as long as they have a carboxyl group in the molecule.
It may have a straight chain alkyl group, or it may have a plurality of carboxyl groups or other substituents. Preferred among these are carboxylic acids having 5 to 36 carbon atoms, which may be natural or synthetic, such as valeric acid, caproic acid, enanthic acid, cabrylic acid, pelargonic acid, capric acid, undecanoic acid, Examples include lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, margaric acid, stearic acid, arachidic acid, pehenic acid, oleic acid, or compounds in which two or more carboxyl groups are introduced into these. . Component (B) used in the present invention is an intramolecular complex or carboxylate of a metal selected from Group Group elements of the periodic table such as nickel, cobalt, iron, and palladium, manganese, and zinc, and is a carboxylic acid salt of a metal selected from manganese and zinc. Examples of the carboxylic acids that form salts include the aforementioned carboxylic acids. Preferred intramolecular complexes and carboxylic acid salts include, for example, nickel acetylacetone complex and nickel stearate. Component (C) used in the present invention is a carboxylic acid or a carboxylate salt of an alkali metal or alkaline earth metal, and the carboxylic acid has 5 to 36 carbon atoms.
Examples of carboxylic acids include capric acid, lauric acid, and stearic acid, and carboxylates include carboxylates of alkali metals or alkaline earth metals such as sodium, potassium, magnesium, calcium, and barium; Examples include barium stearate and barium laurate. The catalysts used for the purpose of the present invention include the above-mentioned catalysts.
A catalyst that is a combination of specific components among the three components (A), (B), and (C) is effective. In other words, the combination of two of the three components above is a combination of two components (A) and (B), and
When (A) and (B) are both carboxylates and (A) and
It is effective only when one of (B) is a carboxylate and the other is an intramolecular complex, and mixtures of other two components have little or no effect. Furthermore, a third component is added to the two components (A) and (B).
In the case of a mixture of (A), (B), and (C) with (C) added, (A) and (B) may be either carboxylic acid salts or intramolecular complexes, and any combination may be used. It is also effective, and more effective than the combination of the two components (A) and (B). Regarding the mode of use of this catalyst, in the reaction of polyalkylene glycol as a polyhydric alcohol with dimethylamine, for example, copper stearate, nickel stearate,
If a three-way catalyst of barium stearate (copper metal 0.1%, nickel metal 0.02%, barium metal 0.02% relative to alcohol) is reduced with hydrogen and reacted at 190℃, the desired tertiary The diamine is obtained in a yield of nearly 90%, and by distilling it, a tertiary amine with a purity of 99% or more can be obtained. In this reaction, the catalyst according to the present invention has a catalytic activity several tens of times higher than that of conventional solid catalysts, and produces tertiary amines in high yield even with polyhydric alcohol raw materials. That is, even with polyhydric alcohols, side reactions such as polycondensation of aldols such as aldehydes are small, and there is almost no production of monomethylamine and trimethylamine due to disproportionation of dimethylamine. It has also been shown to be a highly selective catalyst for alcohols. In addition, the catalyst used in the reaction of the present invention is extremely stable and remains a homogeneous colloidal catalyst even after the reaction is completed, so it can be distilled as is without passing through the mouth, and the distillation residue containing the catalyst can be directly used in the next reaction. It has the characteristic that it can be used for many purposes and can be reused without decreasing its activity. Alcohols, aldehydes used in the present invention,
Ketones include monohydric alcohols, aldehydes, and ketones represented by the general formula () or (), ○b polyether alcohols represented by the general formula () or (), ○c aliphatic polyhydric alcohols or aldehydes, Examples include aromatic polyhydric alcohols or aldehydes, O-niamino alcohols, and ethylene oxide adducts thereof, and more specifically, for example, those shown below can be used. First, aliphatic secondary alcohols and ketones in which R ₁ and R ₂ are both C ₁ to C ₂₄ alkyl groups in the general formula () or () are mentioned, and specific examples include 2-butanol, 2- Pentanol, 2-octanol, 3-pentanol, 3-
Examples include secondary alcohols such as heptanol and 3-nonanol, and ketones such as methyl butyl ketone, methylhexyl ketone, diethyl ketone, ethyl butyl ketone, dipropyl ketone, butylamyl ketone, dilauryl ketone, and dicetyl ketone. In addition, examples of R ₁ or R ₂ being an aryl group or an alkylaryl group include aromatic alcohols such as benzyl alcohol, xylyl alcohol, and phenylbutyl carbinol, and aromatic aldehydes such as benzaldehyde or butylophenone. Or ketones are mentioned. Examples of the cyclic alcohol or cyclic ketone of formula () or formula () above in which R ₁ and R ₂ form a ring include cyclohexanol, cyclodecanol, cyclododecanol, cyclopentanone, cyclohexanone, cyclooctanone, Examples include cyclododecanone, and further include those forming a heterocycle such as tetrahydrofurfuryl alcohol, furfuryl alcohol, and furfuryl aldehyde. Polyether alcohols of general formulas () and () include polyoxyethylene alkyl ethers, polyoxypropylene alkyl ethers, polyoxyethylene alkyl phenyl ethers having various numbers of carbon atoms and alkyl groups and the number of added moles of oxyalkylene groups; Examples include polyoxypropylene alkyl phenyl ether. As an aliphatic polyhydric alcohol, the formula HO−
It is preferable to use a dihydric alcohol represented by R-OH. Here, R is an alkylene group having 2 to 18 carbon atoms and may have a branched chain, and specific examples include 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.
Examples include 10-decanediol. Also, the expression

Dihydric alcohols represented by [Formula] (in which m is 2 to 10 and R ₃ is the same as above) can also be used, and specific examples thereof include diethylene glycol, triethylene glycol, tetraethylene glycol, and alcohols with increased condensation degrees. Examples include polyethylene glycol, dipropylene glycol, tripropylene glycol, and likewise polypropylene glycol. In addition to these, polyhydric alcohols having three or more hydroxyl groups such as glycerin, trimethylolpropane, pentaerythritol, and sorbitol can also be used. Examples of the aliphatic polyaldehyde include glutaraldehyde, adipine aldehyde, pimeline dialdehyde, spering dialdehyde, and sebacine dialdehyde. Examples of aromatic polyhydric alcohols include bisphenol and xylylene diol. As the amino alcohol, any compound having one or more hydroxyl group and one or more amino group in one molecule and having a molecular weight of 60 to 1000 can be used, and those with a molecular weight of 60 to 600 are more preferable. . Examples of preferred amino alcohols include diethylethanolamine, dimethylethanolamine, diisopropylethanolamine, monoethanolamine, diethanolamine, dibutylethanolamine, methyldiethanolamine,
Examples include methylethanolamine and the like, and adducts of long-chain alkylamine with ethylene oxide and propylene oxide. The aliphatic amines to be reacted with these alcohols, aldehydes or ketones include methylamine,
Primary amines such as ethylamine, dodecylamine, and octadecylamine, secondary amines such as dimethylamine, diethylamine, didodecylamine, and dioctadecylamine, and ammonia can be used. In carrying out the present invention, depending on the type of raw material monohydric alcohol and polyhydric alcohol, an inert solvent may be used, and in particular, an inert solvent may be used that is generally used as a support or carrier for a catalyst. , silica gel, colloidal silica, ultrafine anhydrous silica, alumina, diatomaceous earth, activated carbon, etc. may be used in combination to improve the catalytic activity. Preferred examples of the inert solvent include liquid paraffin, paraffin wax, silicone oil, long-chain dialkyl ether, and diphenyl ether. Next, the present invention will be specifically explained using examples. Examples using solid catalysts such as a copper-chromite catalyst and a stabilized nickel catalyst are also shown as comparative examples. Example 1 Benzyl alcohol was added to a 1000 ml flask equipped with a condenser and a separator to separate the reaction water.
150g and 150g of liquid paraffin as a solvent, and 60g of copper stearate, nickel stearate, and barium stearate, respectively (metallic copper 0.4% to alcohol), 1.2g (metallic nickel to alcohol 0.08%), 1.2g (metallic to alcohol) Barium (0.08%) was charged, the stirrer was rotated, the inside of the system was purged with nitrogen, and the temperature was raised. After slowing the temperature to 100°C, hydrogen gas was bubbled into the system at a flow rate of 30/Hr through a flow meter. At 160°C to 170°C, the catalyst was reduced to an apparently homogeneous colloidal catalyst. It takes about 40 minutes to raise the temperature to 170℃, after which the reaction temperature is kept at 170℃ and hydrogen is added at 30/Hr and dimethylamine is added at 30/Hr (dimethylamine concentration is 50/Hr).
%) was bubbled into the system as a mixed gas. After 4 hours of reaction, the reaction product was distilled and analyzed from the amine value and gas chromatography.
It was as follows. Dimethylbenzylamine 82.1% Unreacted alcohol 13.4%* High boilers (aldol condensate) 4.5% (% is weight%) * Unreacted alcohol is distilled out of the system by the hydrogen gas flow and does not participate in the reaction. It is something that As a result, both (A) and (B) are carboxylate salts, and the catalyst, which is a mixture of (A), (B), and (C), can be used sufficiently for the reaction between aromatic alcohol and amine. I found out that it can be done. Example 2 The reaction between benzyl alcohol and dimethylamine was investigated using the apparatus of Example 1 with different catalyst compositions (A) and (B). benzyl alcohol 150
g, 150g of liquid paraffin was added as a solvent,
The catalyst was reduced in the same manner as in Example 1, and the reaction temperature was
At 170℃, hydrogen 30/Hr, dimethylamine 30/Hr
(Dimethylamine concentration 50%) mixed gas was bubbled into the system. The results of distillation and analysis of the reaction product after 4 hours of reaction are shown in Table 1 along with the catalyst compositions of (A) and (B).

[Table] The result is that both (A) and (B) are carboxylates (A)
It is possible to have sufficient reactivity even in a catalyst system consisting of a mixture of I understand. Example 3 The catalyst of the present invention was used in the reaction of polyhydric alcohols. That is, using the same apparatus as in Example 1, 1.
150 g of 6-hexanediol, 150 g of liquid paraffin as a solvent, 1.5 g each of copper stearate, nickel stearate, and barium stearate (0.1% copper metal relative to alcohol), 0.3
g (nickel metal 0.02% relative to alcohol),
0.3g (metal barium 0.02 to alcohol
%), the catalyst was reduced under the same conditions as in Example 1, the temperature was raised to 190°C, and a mixed gas of hydrogen 30/Hr and dimethylamine 30/Hr (dimethylamine concentration 50%) was bubbled into the system. Ta. The composition of the reaction product after 6 hours was as follows. N・N・N′・N′-tetramethylhexamethylenediamine 83.4% N・N-dimethylaminohexanol* 6.8% Unreacted 1,6-hexanediol 0.1% High boilers (aldol condensate) 6.0% Others 3.7% * Reaction intermediate As a result, the catalyst is a three-way catalyst system consisting of a mixture of (A), (B), and (C), which has sufficient activity and high selectivity even with a small amount of catalyst against polyhydric alcohols. I understood. (See Comparative Example) Example 4 Using a catalyst mixture of (A), (B), and (C) of the present invention, a reaction was carried out by changing other alcohols and amines. That is, an alkyl polyoxyalkylene alcohol and an amino alcohol were reacted with monomethylamine and dimethylamine as primary and secondary amines. Alcohol is 150 each
The catalysts were copper stearate as (A), nickel stearate as (B), and barium stearate as (C) at a metal weight of 0.1%, 0.02%, and 0.02% relative to the alcohol, respectively. The catalyst reduction conditions were as per Example 1, hydrogen 30/H
r, amine 30/Hr mixed gas (amine concentration 50
%) was bubbled into the system to carry out the reaction. The alcohol conversion rates after 6 hours of reaction were as shown in Table 2. For Run-4, the reaction was carried out by bubbling a mixed gas of hydrogen 30/Hr and monomethylamine 5/Hr. The results are shown in Table-2.

[Table] Therefore, it was found that this catalyst has sufficient reactivity with the alcohols mentioned above. Example 5 Into the same reactor as in Example 1, 150 g of each alcohol, aldehyde or ketone was charged. 0.08 to alcohol by preparing acid nickel as metal
(C) Barium stearate as a catalyst was charged at 0.08% as a metal, and hydrogen 30% was charged at a reaction temperature of 190°C.
A mixed gas of /H and dimethylamine 30/H was blown into the system to carry out the reaction. The results are shown in Table-3.

[Table] As a result, since aldehydes and ketones are produced as intermediates even when starting from alcohol, tertiary amines can be obtained by this reaction even when these intermediate aldehydes and ketones are used as starting materials. Example 6 Regarding a reaction example of an amino alcohol and its ethylene oxide adduct with an amine In the same reaction vessel as in Example-1, 150 g each of amino alcohol and its ethylene oxide adduct were charged (A) copper stearate as a catalyst, (B) Nickel stearate as a catalyst;
(C) As a catalyst, barium stearate was charged as a catalyst metal, respectively, 0.4% and 0.08% relative to alcohol.
%, 0.08% preparation reaction was performed. Reaction temperature 190℃
Then, a mixed gas of hydrogen 30/H and dimethylamine 30/H was blown into the system to carry out a reaction. The results are shown in Table 4.

[Table] As a result, it is clear that when the catalyst of the present invention is used, the same reactivity is obtained even when amino alcohol and an ethylene oxide adduct of amino alcohol are used as starting materials. Example 7 150 g of benzyl alcohol was charged in the same reactor as in Example 1, (A) copper stearate or copper acetylacetone was used as a catalyst at 0.4% of the alcohol as copper metal, and (B) nickel acetylacetone or stearic acid was used as a catalyst. The reaction was carried out using 0.08% nickel as metal in alcohol. Furthermore, in the case of combinations in which both (A) and (B) form an intramolecular complex (acetylacetone complex), the activity was investigated using 0.08% barium stearate as the metal as component (C). The reaction was conducted at 190℃, hydrogen 30/H, and dimethylamine.
/H mixed gas was blown into the system. The results are shown in Table-5.

[Table] From this result, as a combination of (A) and (B), (A),
(B) When both carboxylates or either one of the carboxylates and one is an acetylacetone complex as an intramolecular complex, the original activity is exhibited, but the combination (A) and (B) do not have fatty acid groups. ) It is clear that both of them show no activity at all in the case of molecular complexes. However, even when both (A) and (B) are intramolecular complexes, it is clear that the original activity can be exhibited by introducing a fatty acid group using a carboxylic acid salt as the catalyst component (C). Therefore, as the catalyst (A), a copper carboxylate or acetylacetone complex can be used, and as the catalyst (B), a nickel carboxylate or acetylacetone complex can be used. (A) and (B) are two components that form an intramolecular complex. In the case of a catalyst, it does not show catalytic activity, but if a third component (C) catalyst is added and a fatty acid group is introduced in a three-component system (A), (B), and (C), the original activity can be maintained even in this case. can be obtained. Example 8 Regarding the activity of a catalyst consisting of a combination of (A), (B), and (C), (A) using a copper acetylacetone complex or a copper carboxylate as a catalyst component, and (B) using a copper acetylacetone complex or a copper carboxylate as a catalyst component.
A carboxylate of a metal other than Ni or an acetylacetone complex was used, and the catalyst component (C) was investigated using barium stearate as a carboxylate of an alkaline earth metal. The same reaction as in Example 1 was carried out using the catalyst (A) in an amount of 0.4% as a metal based on the alcohol, and the catalysts (B) and (C) as a metal in an amount of 0.08% based on the alcohol. The results are shown in Table-6.

【table】

[Table] As a result, in the combination consisting of (A), (B), and (C), (A) is copper stearate or copper acetylacetone, (B) is cobalt, palladium from the group elements of the periodic table, and It has been found that iron is effective, and that manganese and zinc also act effectively as catalysts (B), whether they are carboxylic acids or acetylacetone complexes. Example 9 (A) using copper stearate as a catalyst, (B) using nickel stearate as a catalyst, (C) using potassium stearate or sodium stearate, which is an alkali metal carboxylate, as a catalyst, Example 3
A similar reaction was carried out. The amount of catalytic metal to alcohol is
0.1%, 0.02%, 0.02% were used. Table this result.
7. Note that the results of Example 3 are also shown.

[Table] From this result, it is clear that (C) an alkali metal carboxylate acts as effectively as an alkaline earth metal in the catalyst composition. Comparative Example 1 Using a solid catalyst copper-chromato catalyst,
A comparison was made with the colloidal catalyst of the present invention. Into the same apparatus as in Example 1, 150 g of 1,6-hexanediol was charged, and 15.0 g of copper-chromato catalyst was charged (4.8% as metallic copper to alcohol), and after reducing the catalyst with hydrogen while increasing the temperature, hydrogen was heated at 30/Hr. , dimethylamine/Hr (dimethylamine concentration 50
%) was bubbled into the system. This result and the result of Comparative Example 2 are shown in Table-8. Comparative Example 2 A reaction was carried out using a stabilized nickel catalyst as a catalyst. 150g of 1,6-hexanediol was charged into the same equipment as in Example 1, and 11.1g of stabilized nickel was obtained.
(nickel metal 3.7% based on alcohol) and reduced with hydrogen, hydrogen 30/Hr, dimethylamine 30
A mixed gas of /Hr (dimethylamine concentration 50%) was bubbled into the system and compared with the catalyst of the present invention (Example 3) in which no reaction occurred.

[Table] As a result, the copper-chromite and stabilized nickel-based solid catalysts had poor reactivity even though the amount of catalyst added was in large excess compared to the catalyst of the present invention, and the catalyst of the present invention also had a higher selectivity. Turns out it's much better.

Claims (1)

[Claims] 1 ○a A primary alcohol, secondary alcohol, aldehyde or ketone represented by the following general formula () or (), [Formula] [Formula] [In the formula, R ₁ , R ₂ is H, a C ₁ to _{C 24} saturated or unsaturated aliphatic hydrocarbon group, an aryl group, or an alkylaryl group, or one in which R ₁ and R ₂ form a ring together with the carbon atom to which they are bonded shows. However, when one of R ₁ and R ₂ is a saturated or unsaturated aliphatic hydrocarbon group, the other is not H. The sum of the carbon numbers of R ₁ and R ₂ is 3 or more. ], ○B Polyether alcohol represented by the following general formula () or (), [In the formula, R ₁ ′ and R ₂ ′ are H, a C ₁ to _{C 24} saturated or unsaturated aliphatic hydrocarbon group, an aryl group, or an alkylaryl group, or the carbon to which R ₁ and R ₂ are bonded Indicates something that forms a ring with atoms. R ₃ represents H or a methyl group, R ₄ is C ₈
~ _C18 saturated or unsaturated aliphatic hydrocarbon group, and n represents an integer of 1 to 20. ], ○C Aliphatic or aromatic polyhydric alcohol or aldehyde, ○D An alcohol, aldehyde or ketone selected from the group consisting of amino alcohol or its ethylene oxide adduct, and the general formula (In the formula, R ₅ and R ₆ each represent H or a C ₁ to _{C 24} saturated or unsaturated aliphatic hydrocarbon group.) Reaction with ammonia or a primary or secondary aliphatic amine In producing the corresponding tertiary amine by One or more acetylacetone complexes as metal carboxylates or intramolecular complexes, and (C) one or more carboxylic acids or alkali metal salts or alkaline earth metal salts of carboxylic acids, ( a mixture consisting of A), (B) and (C), or (A) and
A mixture of (A) and (B) where both (B) are carboxylates, or a mixture of (A) and (B) where one of (A) and (B) is a carboxylate and the other is an intramolecular complex. B) The reaction is carried out at a temperature of 150 to 300°C using hydrogen, a mixture of hydrogen and ammonia or amine of formula (), or a product treated with other cyclizing agent as a catalyst. A method for producing a tertiary amine, characterized by: 2 Alcohol is the formula () in which R ₁ and R ₂ are
A secondary aliphatic alcohol that is a C ₁ to C ₁₈ saturated or unsaturated aliphatic hydrocarbon group (however, the sum of the carbon numbers of R ₁ and R ₂ is 3 or more), R ₁ is a C ₆ to C ₁₈ aryl or alkylaryl groups, aromatic alcohols in which R ₂ is H, polyether alcohols of the formula (), polyether alcohols of the formula HO-R-OH (wherein R is C ₂ to C ₁₈
2 represented by a linear or branched alkylene group)
alcohol or formula The method for producing a tertiary amine according to claim 1, which is an alcohol selected from the group consisting of dihydric alcohols represented by the formula (where m is an integer of 2 to 10 and R ₃ is the same as above) .