JPH07101910A - Production of amines - Google Patents

Abstract

PURPOSE:To efficiently obtain an amine with a small amount of a highly active catalyst by using a specific cobalt-based catalyst, reduction-aminating a cyclic ketone or reducing an imino compound of a cyclic ketone. CONSTITUTION:A cyclic ketone is reduction-aminated or an imino compound of a cyclic ketone is reduced to give a corresponding amine. In the reaction, a cobalt-based catalyst containing an alkaline earth metal carbonate (preferably calcium carbonate) and/or a lanthanum oxide is used as the catalyst. Further the cobaltbased catalyst preferably contains copper and/or ruthenium. Forther, the cobalt-based catalyst preferably contains an alkali metal compound. The catalyst used in the reaction is obtained by precipitation method or co- precipitation method. Amines are useful as intermediates for fine chemicals or raw materials for resins.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing amines, and more specifically, in producing a corresponding amine from a cyclic ketone or an imino derivative thereof, a carbonate of an alkaline earth metal and / or a catalyst. The present invention relates to a method for producing amines, which comprises using a cobalt-based catalyst containing lanthanum oxide.

[0002]

2. Description of the Related Art Amines are useful as an intermediate for fine chemicals, as a raw material for resins and the like, and it is well known to produce cyclic ketones by reductive amination or by reducing imino compounds of cyclic ketones. For example, 3-cyano-
As a method for producing 3-aminomethyl-3,5,5-trimethylcyclohexylamine (IPDA) by reductive amination of 3,5,5-trimethylcyclohexanone (IPCN), a method using a silicic acid-supported cobalt catalyst (special (Publication No. 39-10923)
, Method using Raney cobalt catalyst (JP-A-62-1231)
No. 54) is known. Further, as a method for producing IPDA by reducing the imino form of IPCN, a method using a cobalt catalyst (Japanese Patent Publication No. 2-15530), a method using a ruthenium catalyst supported on alumina (Japanese Patent Application Laid-Open No. 4-221350) and the like are available. Are known.

[0003]

However, in any of the methods, the yield of the target amines is not sufficient, and improvement of this point has been desired. The present inventors have conducted extensive studies on the catalyst in order to find a better method for producing amines. As a result, a specific cobalt-based catalyst called a cobalt-based catalyst containing a carbonate of an alkaline earth metal and / or lanthanum oxide has been obtained. It was found that the catalyst not only improves the yield of amines but also exhibits high catalytic activity and efficiently gives amines with a small amount of catalyst, and further various studies were conducted to complete the present invention.

[0004]

[Means for Solving the Problems] That is, the present invention provides a method for producing a corresponding amine by reductive amination of a cyclic ketone or reduction of an imino derivative of a cyclic ketone, and a catalyst of alkaline earth metal. The present invention provides a method for industrially producing amines, which is characterized by using a cobalt-based catalyst containing the carbonate and / or lanthanum oxide.

Next, the present invention will be described in more detail. The present invention is characterized in that a cobalt-based catalyst containing an alkaline earth metal carbonate and / or lanthanum oxide is used as the catalyst. Examples of the alkaline earth metal carbonate include magnesium. , Carbonates such as calcium, strontium, and barium. Preferred is calcium carbonate. The weight ratio of alkaline earth metal carbonate and / or lanthanum oxide to cobalt metal is usually 10/90 to 98/2. Further, the cobalt-based catalyst in the present invention preferably contains copper, ruthenium, an alkali metal compound, etc. in addition to the alkaline earth metal carbonate, and contains copper and / or ruthenium and an alkali metal compound. More preferable.

The catalyst used in the present invention can be easily produced by, for example, a precipitation method, a coprecipitation method, a mixing method, an impregnation supporting method, etc., but the precipitation method and the coprecipitation method are preferable. As a typical example, a method for producing a cobalt-based catalyst containing an alkaline earth metal carbonate, copper and / or ruthenium, and an alkali metal compound will be described. As the precipitation method, for example, an alkaline earth metal carbonate is suspended in a solution in which a cobalt salt and a copper salt and / or a ruthenium salt are dissolved, and then an alkali solution is added to the solution to add cobalt, copper and / or A method in which ruthenium is precipitated and supported on a carbonate of an alkaline earth metal, filtered, washed, and then mixed with a solution of an alkali metal compound, and then the solvent is evaporated, dried, calcined, and reduced by hydrogen. Is mentioned. Here, when the alkali solution is an alkali metal compound solution, the alkali metal compound may be left by adjusting the washing after filtration and the like, and the alkali metal compound may be dried, calcined, or hydrogen-reduced. . Examples of the cobalt salt, copper salt and ruthenium salt include water-soluble salts such as nitrates, sulfates, halides and organic acid salts thereof. When using an organic solvent such as methanol, a complex compound such as cobalt carbonyl or ruthenium carbonyl can also be used.

Examples of alkalis include alkali metal carbonates, hydroxides, hydrogen carbonates, organic acid salts, ammonium carbonate and ammonia. Examples of the alkali metal compound include alkali metal carbonates, nitrates, hydroxides, hydrogen carbonates and the like. Examples of the alkali metal include lithium, sodium, potassium, rubidium, cesium and the like. These alkalis are usually used as an aqueous solution, a solution of an organic solvent such as methanol, or a mixed solution thereof. The temperature at which cobalt and copper and / or ruthenium are carried on the carbonate of an alkaline earth metal by precipitation is usually in the range of room temperature to 100 ° C. The precipitate-supported product should be calcined under a nitrogen stream at 300-500 ° C for 30
It is usually about 5 to 5 hours, and hydrogen reduction is 200 to 500
It is usually about 30 minutes to 20 hours at ℃.

The coprecipitation method is carried out, for example, by adding an alkali metal carbonate, ammonium carbonate or another alkali solution to a mixed solution of a cobalt salt and a copper salt and / or a ruthenium salt and an alkaline earth metal salt, A method in which a precipitate is formed, filtered, washed, then mixed with a solution of an alkali metal compound, the solvent is evaporated, dried, calcined, and hydrogen reduced is used. Here, when the alkali solution is an alkali metal compound solution, the alkali metal compound may be left by adjusting the washing after filtration and the like, and the alkali metal compound may be dried, calcined, or hydrogen-reduced. . Examples of the cobalt salt, copper salt, and ruthenium salt include the same salts and complex compounds as described above, and examples of the alkaline earth metal salt include nitrates and chlorides of alkaline earth metals. The same alkali and alkali metal compounds as mentioned above can be used. The conditions for producing a precipitate, the conditions for calcination, hydrogen reduction and the like are usually the same as the above method.

As a mixing method, for example, a solution of an alkali is added to a solution of a cobalt salt and a copper salt and / or a ruthenium salt to form a precipitate, and then a carbonate of an alkaline earth metal is added to and mixed with the solution. The method may be a method in which it is produced by filtering, washing, mixing with a solution of an alkali metal compound, evaporating the solvent, drying, firing, and hydrogen reduction. Here, when the alkali solution is an alkali metal compound solution, the alkali metal compound may be left by adjusting the washing after filtration and the like, and the alkali metal compound may be dried, calcined, or hydrogen-reduced. . Examples of the cobalt salt, copper salt and ruthenium salt include the same salts and complex compounds as described above, and examples of the alkali and alkali metal compounds include the same as above.
The conditions for forming a precipitate and the conditions for reducing hydrogen by calcination are usually the same as those in the above method.

As the impregnating and supporting method, for example, a carbonate of an alkaline earth metal is impregnated with a solution in which a cobalt salt and a copper salt and / or a ruthenium salt are dissolved, and then dried,
Examples include a method in which the salt is pyrolyzed at a temperature equal to or higher than the pyrolysis temperature, then mixed with a solution of an alkali metal compound, and the solvent is evaporated, followed by drying, firing, and hydrogen reduction. Examples of the cobalt salt, copper salt and ruthenium salt include the same salts as described above. Also, as the alkali metal compound, the same ones as described above can be mentioned. The impregnated and supported product is usually calcined at 200 to 800 ° C. for about 30 minutes to 5 hours, and the hydrogen reduction is usually carried out under the same conditions as above.

The content ratio of copper, ruthenium or the like to cobalt metal is usually 0.1 to 30% in weight conversion. In addition to copper and ruthenium, compounds such as chromium, manganese and aluminum can be contained. The amount is usually 10 wt% or less with respect to cobalt. The content ratio of the alkali metal compound is, in terms of alkali metal, based on the total amount of the catalyst,
It is usually 0.01 to 10 wt%, preferably 0.03 to 5 wt%. Further, the catalyst used in the present invention may also use a lubricant such as graphite, which is used when forming the catalyst.

The present invention is to produce the corresponding amines by reductive amination of cyclic ketones or reduction of the imino form of cyclic ketones using the above-mentioned specific cobalt-based catalyst. . The cyclic ketones and their imino compounds used in the present invention may be cyclic compounds containing a hetero atom, and may have a substituent such as a nitrile group and an amino group. Specific compounds include, for example, cyclopentanone, cyclohexanone, cycloheptanone, isophorone, 3-cyano-3,5,5-trimethylcyclohexanone (IPCN) and other alicyclic ketones having 5 to 20 carbon atoms, piperidone, 2 Cyclic ketones such as heteroalicyclic ketones having 4 to 20 carbon atoms such as 2,2,6,6-tetramethyl-4-piperidone and 5-benzyl-7-oxo-5-azaspiro [2.4] heptane; Examples thereof include, but are not limited to, imino forms. Among them, nitrile group, those having a substituent such as amino group are preferably used, for example, IPCN, when producing 3-aminomethyl-3,5,5-trimethylcyclohexylamine (IPDA) from its imino form, an intermediate -Iminomethyl-3,5,5-trimethylcyclohexylamine, 3-aminomethyl-3,5,5-trimethylcyclohexylimine etc -It can also suppress by-products such as azabicyclo [3.2.1] octane (TMAB).

In the reductive amination of cyclic ketones and the reduction of the imino form of cyclic ketones, the reaction system may be either batch system or flow system, but the latter is preferred.
When the flow system is adopted, a fixed bed liquid phase flow system is usually adopted, and either an up-flow system or a down-flow system can be used. The reaction temperature is generally 0 to 200 ° C, preferably 30 to 150 ° C. The reaction pressure is usually from the pressure at which ammonia liquefies at the reaction temperature to about 300 atm.
Ammonia is usually used in an amount of about 1.5 to 60 times, preferably about 60 to 60 times the molar amount of the cyclic ketones to be reduced, or the imino form of the cyclic ketones, in order to iminoize the cyclic ketones and prevent the formation of by-products. Is used about 10 to 50 mole times.

In the case of a batch type, the amount of the catalyst used is
It is usually 0.01 to 5 times the weight of the substance to be reduced, and the reaction time is usually about 30 minutes to 10 hours. The feed speed of the reduction product solution in the case of flow system is usually 0.05～10H ^-1 approximately at LHSV, preferably about 0.1 to 5 h ^-1. The reaction can also be carried out in the presence of a solvent. Examples of the solvent include alcohols such as methanol, ethanol, propanol, ethylene glycol and ethylene glycol monomethyl ether, ethers such as diethyl ether, tetrahydrofuran, dioxane and ethylene glycol dimethyl ether, hydrocarbons such as hexane and heptane, and mixtures thereof. A solvent and the like can be mentioned, but methanol is preferable. When a solvent is used, the amount used is usually 0.5 to 10 times the weight of the substance to be reduced. The amount of hydrogen used is
In the case of the batch system, the reaction pressure is regulated and the pressure is usually 300 atm or less. In the case of the flow system, the amount of the product to be reduced is usually 1 to 30 times the theoretical amount.

In the case of producing amines from cyclic ketones, it is preferable from the viewpoint of the yield of the desired product that the cyclic ketones are reacted with ammonia to form an imino compound and then reduced. The imino form is usually produced in the presence of a catalyst. Examples of such a catalyst include ion exchangers such as sulfonated polystyrene (Japanese Patent Publication No.
2-15530), acidic metal oxides such as alumina (Japanese Patent Publication No. 4-221350), metal composite oxides such as silica-alumina, and activated carbon. Of these, activated carbon is preferable, and activated carbon may be produced from any of plants, coal, petroleum, etc., and one having a large surface area is preferably used. Further, both activated carbon treated with acid and treated activated carbon may be used.

In the iminoization, a batch method,
Any distribution method can be adopted, but the latter is preferable. When the flow system is adopted, a fixed bed liquid phase flow system is usually adopted, and either an up-flow system or a down-flow system can be used. The reaction temperature is usually 0 to 100 ° C. The reaction pressure is usually from the pressure at which ammonia liquefies at the reaction temperature to about 300 atm. A particularly high pressure is not required, but the same pressure as in the next hydrogenation step can be used. The amount of ammonia used for cyclic ketones is usually 1 to 60.
It is about mole times. Considering the case where the reaction mass is directly subjected to the hydrogenation step which is the next step, 2 to 50 mole times is preferably adopted.

In the case of the batch type, the amount of the imination catalyst used is usually 1 to 25% by weight based on the cyclic ketones, and the reaction time is usually 5 minutes to 3 hours. The feed rate of the raw material ketone solution in the case of the flow type is usually 0 in LHSV.
It is about 1 to 10 h ^-1 , preferably about 0.2 to 5 h ^-1 . The iminoization step can be carried out in the presence of a solvent.
Such solvents include methanol, ethanol, propanol, ethylene glycol, alcohols such as ethylene glycol monomethyl ether, diethyl ether,
Examples include ethers such as tetrahydrofuran, dioxane, and ethylene glycol dimethyl ether, hydrocarbons such as hexane and heptane, and mixed solvents thereof, with preference given to methanol. When a solvent is used, the amount used is usually 0.5 to 10 times the weight of the cyclic ketones. In this way, an imino form is produced, and the imino form is usually supplied to the hydrogenation step which is the next step without isolation after separating the catalyst from the reaction mass, but it may also be supplied after isolation. it can.

[0018]

According to the method of the present invention, by using a cobalt-based catalyst containing a carbonate of an alkaline earth metal as a catalyst, cyclic ketones, their imino bodies, etc.
The corresponding amines can be produced in good yield and efficiently.

[0019]

The present invention will be described in more detail based on the following examples, but the invention is not intended to be limited thereto.

Catalyst Preparation Example 1 After dissolving 72.9 g of cobalt nitrate hexahydrate and 2.9 g of copper nitrate trihydrate in 300 ml of water, 18.8 g of calcium carbonate was suspended and the temperature was raised to 80 ° C. Then, with stirring, a solution of sodium carbonate (49.3 g) and water (300 ml) was added dropwise over 2 hours, and the stirring was continued at the same temperature for 2 hours. The formed precipitate was separated by filtration and then washed 5 times with 500 ml of warm water at 80 ° C. Then add 250 ml of water and 1.
After adding to 9 g of the mixed solution, it was concentrated by a rotary evaporator, dried at 60 ° C., and ground to obtain 48.7 g of a purple solid. 45 g of this product was heated under a nitrogen stream at 320 ° C. for 1 hour, cooled to room temperature and taken out into the air to obtain 37.0 g of a black solid. The Na content was 1.9 wt%. Next, this was molded into 10 to 22 mesh (filling specific gravity = 1.1) and then heated at 280 ° C. for 5 hours in a hydrogen stream to obtain a cobalt-based catalyst A.

Catalyst preparation example 2 Catalyst preparation example 1 was carried out in the same manner as in catalyst preparation example 1 except that the precipitate was washed with warm water and then 1.9 g of sodium carbonate used was changed to 0.76 g. A cobalt-based catalyst B of 1.1 was obtained. The Na content was 0.9 wt%.

Catalyst preparation example 3 Catalyst preparation example 1 was carried out in the same manner as in catalyst preparation example 1 except that the precipitate was washed with warm water and then the sodium carbonate used was changed from 1.9 g to 0.19 g. A cobalt-based catalyst C of No. 1 was obtained. The Na content was 0.25 wt%.

Catalyst Preparation Example 4 By carrying out according to Catalyst Preparation Example 1 except that the precipitate was washed with warm water, dried and pulverized without being treated with an aqueous solution of sodium carbonate in Catalyst Preparation Example 1, A cobalt-based catalyst D having a packing specific gravity of 1.1 was obtained. Na content is 0.
It was 06 wt%.

Catalyst Preparation Example 5 In Catalyst Preparation Example 1, 0.55 g of ruthenium chloride was used in place of copper nitrate, the precipitate was washed with warm water, dried and pulverized without treatment with an aqueous solution of sodium carbonate, and then under a stream of hydrogen. Was carried out in accordance with Catalyst Preparation Example 1 except that the heating was carried out at 380 ° C. for 5 hours to obtain a cobalt-based catalyst E having a packing density of 1.1. The Na content was 0.045 wt%.

Catalyst Preparation Example 6 In Catalyst Preparation Example 1, except that the precipitate was washed with warm water and then a solution consisting of 1.9 g of sodium hydroxide and 250 ml of water was used in place of the solution consisting of 1.9 g of sodium carbonate and 250 ml of water. By carrying out according to Catalyst Preparation Example 1, a cobalt-based catalyst F having a packing specific gravity of 1.1 was obtained. Na content is 2.63wt
%Met.

Catalyst Preparation Example 7 In Catalyst Preparation Example 1, 49.3 g of sodium carbonate and 300 parts of water were added.
In accordance with Catalyst Preparation Example 1 except that a solution of 51.7 g of ammonium carbonate and 300 ml of water was used in place of the solution of ammonium carbonate to form a precipitate, and the precipitate was dried and crushed without treatment with an aqueous solution of sodium carbonate. As a result, a cobalt-based catalyst G having a packing specific gravity of 1.1 was obtained. The Na content was below the detection limit.

Catalyst Preparation Example 8 After dissolving 145.5 g of cobalt nitrate hexahydrate in 600 ml of water,
37.5 g of calcium carbonate was suspended in this, and the temperature was raised to 80 ° C. Then, under stirring, a solution of 93.8 g of sodium carbonate and 600 ml of water was added dropwise over 2 hours, and then stirring was continued for 2 hours at the same temperature. The formed precipitate was separated by filtration and then washed 5 times with 500 ml of warm water at 80 ° C. Then add this to a mixed solution of 500 ml of water and 3.75 g of sodium carbonate, concentrate on a rotary evaporator and dry at 60 ° C.
Trituration gave 94.7 g of a purple solid. After heating 45 g of this product at 320 ° C. for 1 hour under a nitrogen stream, it was cooled to room temperature and taken out into the air to obtain 36.8 g of a black solid. The Na content was 1.7 wt%. Then this
After being formed into 10 to 22 mesh (filling specific gravity = 1.1), it was fired at 380 ° C. for 5 hours in a hydrogen stream to obtain a cobalt-based catalyst H.

Catalyst Preparation Example 9 Catalyst Preparation Example 8 was carried out in the same manner as in Catalyst Preparation Example 8 except that the precipitate was washed with warm water and then dried and crushed without treatment with an aqueous solution of sodium carbonate. A cobalt-based catalyst I having a filling specific gravity of 1 was obtained. Na content is 0.06wt
%Met.

Catalyst Preparation Example 10 In Catalyst Preparation Example 8, the heating temperature under nitrogen flow was
A cobalt-based catalyst J having a packing specific gravity of 1.1 was obtained by carrying out the procedure of Catalyst Preparation Example 8 except that the temperature was changed from 320 ° C to 420 ° C. The Na content was 0.06 wt%.

Catalyst Preparation Example 11 Catalyst preparation example 8 was repeated except that after washing the precipitate with warm water, a solution consisting of 3.75 g of sodium nitrate and 500 ml of water was used in place of the solution consisting of 3.75 g of sodium carbonate and 500 ml of water. By carrying out according to Preparation Example 9, a cobalt-based catalyst K having a filling specific gravity of 1 was obtained. Na content is 1.17 wt%
Met.

Catalyst Preparation Example 12 In Catalyst Preparation Example 8, basic magnesium carbonate (37.5 g) was used instead of calcium carbonate, and the precipitate was dried and crushed without treatment with an aqueous sodium carbonate solution after washing with warm water. By carrying out according to Catalyst Preparation Example 8, a cobalt-based catalyst L having a packing specific gravity of 0.7 was obtained.

Catalyst Preparation Example 13 Catalyst Preparation Example 8 was repeated except that 37.5 g of strontium carbonate was used instead of calcium carbonate, and the precipitate was dried and crushed without treatment with an aqueous solution of sodium carbonate after washing with warm water. By carrying out according to Example 8, a cobalt-based catalyst M having a filling specific gravity of 1.1 was obtained.

Catalyst Preparation Example 14 Catalyst Preparation Example 8 was repeated except that 37.5 g of barium carbonate was used in place of calcium carbonate, and the precipitate was dried and crushed without treatment with an aqueous sodium carbonate solution after washing with warm water. By carrying out according to Example 8, a cobalt-based catalyst N having a filling specific gravity of 1.1 was obtained.

Catalyst Preparation Example 15 Catalyst Preparation Example 8 was repeated except that 37.5 g of lanthanum oxide was used in place of calcium carbonate and the precipitate was dried and crushed without treatment with an aqueous sodium carbonate solution after washing with warm water. By carrying out according to Example 8, a cobalt-based catalyst O having a filling specific gravity of 1.1 was obtained.

Catalyst Preparation Example 16 After dissolving 72.9 g of cobalt nitrate hexahydrate and 44.4 g of calcium nitrate in 300 ml of water, the temperature was raised to 80 ° C. Then, with stirring, a solution of 66.8 g of sodium carbonate and 300 ml of water was added dropwise thereto over 2 hours, and then stirring was continued at the same temperature for 2 hours. The formed precipitate was separated by filtration and then washed 5 times with 500 ml of warm water at 80 ° C. Then, this was dried at 60 ° C., pulverized, heated in a nitrogen stream and calcined in a hydrogen stream in accordance with Catalyst Preparation Example 8 to obtain a cobalt-based catalyst P having a filling specific gravity of 1. The Na content was 0.09 wt%.

Catalyst Preparation Example 17 In Catalyst Preparation Example 8, 93.8 g of sodium carbonate and 600 g of water were added.
In accordance with Catalyst Preparation Example 8 except that instead of a solution consisting of 10 ml, a solution consisting of 100.3 g of ammonium carbonate and 600 ml of water was used to form a precipitate, which was dried and ground without treatment with an aqueous solution of sodium carbonate. As a result, a cobalt-based catalyst Q having a filling specific gravity of 1.3 was obtained. The Na content was below the detection limit.

Catalyst Preparation Example 18 After dissolving 58.3 g of cobalt nitrate hexahydrate in 300 ml of water,
The temperature was raised to 80 ° C. Then, with stirring, a solution of sodium carbonate (37.5 g) and water (300 ml) was added dropwise over 2 hours, and the stirring was continued at the same temperature for 2 hours. The precipitate formed was filtered off and washed 4 times with 500 ml of warm water at 80 ° C. to obtain a purple solid. Then add 500g of hot water at 80 ℃
Silica gel (manufactured by Nippon Aerosil Co., Ltd.) 15 g
Was added, and the mixture was stirred and mixed, filtered, dried at 60 ° C., and pulverized to obtain 36.2 g of a purple solid. After heating 24.1 g of this product at 330 ° C. for 1 hour under a nitrogen stream, it was cooled to room temperature and taken out into the air to obtain 20.6 g of a black solid. Then, this was molded into 10 to 22 mesh (filling specific gravity = 0.
After that, the cobalt-based catalyst R was obtained by baking at 380 ° C. for 5 hours in a hydrogen stream.

Catalyst Preparation Example 19 Same as Catalyst Preparation Example 18 except that 58.3 g of cobalt nitrate hexahydrate and 3 g of manganese nitrate hexahydrate were used in place of cobalt nitrate hexahydrate in Catalyst Preparation Example 18. Then, a cobalt-based catalyst S having a filling specific gravity of 0.45 was obtained.

Catalyst preparation example 20 15.2 g of β-alumina and 0.92 g of ruthenium chloride were suspended in 150 ml of methanol, stirred at room temperature for 1 hour and then concentrated using a rotary evaporator to obtain 17.3 g of a tan solid. 14g of this product was baked at 120 ° C in a nitrogen atmosphere.
2.9 g of a tan solid was obtained. Next, after molding this into 10-22 mesh (filling specific gravity = 0.4), 230
A cobalt-based catalyst T was obtained by baking at 5 ° C. for 5 hours.

Example 1 (1) Activated carbon (24-48 mesh, GVA-S manufactured by Tsurumi Coal) 16.9
Stainless steel reaction tube filled with g (length 80 cm, inner diameter 9 mm)
And (2) Cobalt-based catalyst A 2 previously reduced with hydrogen
Stainless steel reaction tube filled with 0 ml (length 55 cm, inner diameter 9 mm)
Was installed vertically, and the upper part of the reaction tube of (1) and the lower part of the reaction tube of (2) were connected. Then, a mixture of 3-cyano-3,5,5-trimethylcyclohexanone (IPCN) and methanol in a ratio of 1: 1.5 (weight ratio) was added to 34.7
Liquefied ammonia was supplied at 38.4 g / h from the bottom of the reaction tube of (1) at g / h. Hydrogen was supplied at 23.2 l / h from below the reaction tube of (2). The internal temperatures of the reaction tubes of (1) and (2) were 24 ° C and 121 ° C, respectively. The pressure is 15 each
It was carried out while maintaining a pressure of 0 kg / cm ² G.

After 300 minutes from the start of supply, sampling was carried out from the outlets of the reaction tubes of (1) and (2) and analyzed by gas chromatography. The yield of the IPCN imino derivative at the outlet of the reaction tube of (1) was 97.7%. 3-aminomethyl-3,5,5-trimethylcyclohexylamine (IPDA) was 99.4 wt% in the reaction solution at the reaction tube outlet of (2).
%, 3-aminomethyl-3,5,5-trimethylcyclohexyl alcohol (IPAA) is 0.2w
t%, IPCN, IPCN imino body was not detected, and 1,3,3-trimethyl-6-azabicyclo [3.2.1] octane (TMAB) was 0.1wt%.
%, Others 0.3 wt%, and the yield of IPDA was 99.4%.

Example 2 In Example 1, a mixture of IPCN and methanol at a ratio of 1: 1.5 (weight ratio) was 23.3 g / h and liquefied ammonia was 25.0 g / h.
Example 1 was repeated except that hydrogen was supplied at 15.1 l / h. The yield of the IPCN imino derivative at the outlet of the reaction tube of (1) was 97.7%. In the reaction solution at the outlet of the reaction tube of (2), IPDA is 99.3 wt%, IPAA is 0.5 wt%, IPCN, IP
No CN imino form was detected, TMAB was 0.2 wt%, and IPDA yield was 99.3%.

Example 3 In Example 1, a 1: 1.5 (weight ratio) mixture of IPCN and methanol was supplied at 10 g / h, liquefied ammonia at 10 g / h and hydrogen at 6 l / h, and the pressure was 70 kg. Example 1 was repeated except that the pressure was held at / cm ² G. The yield of the IPCN imino derivative at the outlet of the reaction tube of (1) was 98.3%. In the reaction solution at the reaction tube outlet of (2), IPDA is 97.6 wt% and IPAA is
1.6wt%, IPCN, IPCN imino body was not detected, TMAB0.8w
The yield of IPDA was 97.6%.

Example 4 The procedure of Example 1 was repeated except that the cobalt catalyst A was replaced by the cobalt catalyst B. The yield of the IPCN imino derivative at the outlet of the reaction tube of (1) was 97.7%, and in the reaction liquid at the outlet of the reaction tube of (2),
IPDA was 99.3 wt%, IPAA was 0.4 wt%, IPCN and IPCN imino form were not detected, TMAB was 0.2 wt% and other was 0.1 wt%.
The yield of IPDA was 99.2%.

Example 5 The procedure of Example 1 was repeated except that the cobalt catalyst A was replaced by the cobalt catalyst C. The yield of the IPCN imino derivative at the outlet of the reaction tube of (1) was 97.8%, and in the reaction liquid at the outlet of the reaction tube of (2),
IPDA was 98.7 wt%, IPAA was 0.4 wt%, IPCN and IPCN imino compounds were not detected, and TMAB was 0.4 wt% and others were 0.5 wt%.
The yield of IPDA was 98.7%.

Example 6 The procedure of Example 1 was repeated except that the cobalt catalyst D was used in place of the cobalt catalyst A. The yield of the IPCN imino derivative at the outlet of the reaction tube of (1) was 98.9%, and in the reaction liquid at the outlet of the reaction tube of (2),
IPDA was 98.5wt%, IPAA was 0.5wt%, IPCN and IPCN imino body were not detected, TMAB was 1.0wt%, and IPDA yield was 98.4wt%.
%Met.

Example 7 In Example 1, cobalt-based catalyst D was used in place of cobalt-based catalyst A, a mixture of IPCN and methanol at a ratio of 1: 1.5 (weight ratio) was 23.3 g / h, and liquefied ammonia was 25 g. / h
It carried out based on Example 1 except supplying hydrogen at 15 l / h. The yield of the IPCN imino derivative at the outlet of the reaction tube of (1) was 99%, and in the reaction liquid at the outlet of the reaction tube of (2),
IPDA is 99wt%, IPAA is 0.1wt%, IPCN and IPCN imino body are not detected, TMAB is 0.9wt%, IPDA yield is 98.9%
Met.

Example 8 The procedure of Example 1 was repeated, except that the cobalt catalyst A was replaced by the cobalt catalyst E. The yield of the IPCN imino derivative at the outlet of the reaction tube of (1) was 98.8%, and in the reaction liquid at the outlet of the reaction tube of (2),
IPDA was 97.7 wt%, IPAA was 1.5 wt%, IPCN and IPCN imino form were not detected, TMAB was 0.5 wt% and other was 0.3 wt%,
The yield of IPDA was 97.6%.

Example 9 The procedure of Example 1 was repeated except that the cobalt catalyst A was replaced by the cobalt catalyst F. The yield of the IPCN imino derivative at the outlet of the reaction tube of (1) was 98.2%, and in the reaction liquid at the outlet of the reaction tube of (2),
IPDA was 97.2 wt%, IPAA was 2.6 wt%, IPCN and IPCN imino form were not detected, TMAB was 0.1 wt%, other was 0.1 wt%,
The yield of IPDA was 97.1%.

Example 10 The procedure of Example 1 was repeated except that the cobalt catalyst G was used in place of the cobalt catalyst A. The yield of the IPCN imino derivative at the outlet of the reaction tube of (1) was 97.6%, and in the reaction liquid at the outlet of the reaction tube of (2),
IPDA was 95.8 wt%, IPAA was 2.8 wt%, IPCN and IPCN imino form were not detected, TMAB was 0.6 wt% and other was 0.8 wt%.
The yield of IPDA was 95.7%.

Example 11 In Example 1, cobalt-based catalyst H was used in place of cobalt-based catalyst A, a mixture of IPCN and methanol at a ratio of 1: 1.5 (weight ratio) was 33.7 g / h, and liquefied ammonia was 38.4 g. g / h
Then, the procedure of Example 1 was repeated except that hydrogen was supplied at 23.2 l / h. The yield of the IPCN imino compound at the outlet of the reaction tube of (1) was 97.8%, and in the reaction solution at the outlet of the reaction tube of (2), IPDA was 98.6 wt%, IPAA was 0.8 wt%, IPCN, IPCN
No imino form was detected, TMAB 0.1wt%, other 0.5wt%
And the yield of IPDA was 98.6%.

Example 12 In Example 1, cobalt cobalt catalyst H was used instead of cobalt catalyst A, a mixture of IPCN and methanol at a ratio of 1: 1.5 (weight ratio) was 23.7 g / h, and liquefied ammonia was 25.6 g. g / h
Then, the procedure was carried out in accordance with Example 1 except that hydrogen was supplied at 16.1 l / h. The yield of the IPCN imino compound at the outlet of the reaction tube of (1) was 97.8%, and in the reaction solution at the outlet of the reaction tube of (2), IPDA was 99.3 wt%, IPAA was 0.6 wt%, IPCN, IPCN
No imino form was detected, TMAB was 0.1 wt%, and IPDA yield was 99.3%.

Example 13 In Example 1, cobalt-based catalyst I was used in place of cobalt-based catalyst A, a mixture of IPCN and methanol at a ratio of 1: 1.5 (weight ratio) was 24.4 g / h, and liquefied ammonia was 26.5 g. g / h
Then, the procedure was carried out in accordance with Example 1 except that hydrogen was supplied at 15 l / h. The yield of IPCN imino compound at the outlet of the reaction tube of (1) was 99.2%, and in the reaction solution at the outlet of the reaction tube of (2), IPDA was 98.6 wt%, IPAA was 0.7 wt%, IPCN, IPCN imino compound. Was not detected, TMAB was 0.6 wt%, other was 0.1 wt%, and the yield of IPDA was 98.5%.

Example 14 In Example 1, cobalt-based catalyst I was used in place of cobalt-based catalyst A, and 2,2,6,6-tetramethyl-4-piperidone ( TMP) and methanol at a ratio of 1: 1.5 (weight ratio) was carried out according to Example 1 except that 10 g / h of a mixed solution, 10 g / h of liquefied ammonia and 6 l / h of hydrogen were supplied. The yield of TMP imino form at the outlet of the reaction tube of (1) was 94.9%, and TMP imino form and TMP were not detected in the reaction solution at the outlet of the reaction tube of (2), and the yield of TMP imino form was It was 94.7%.

Example 15 In Example 1, the cobalt catalyst A was used in place of the cobalt catalyst A, the mixture of IPCN and methanol at a ratio of 1: 1.5 (weight ratio) was 23.3 g / h, and liquefied ammonia was 25 g. / h
It carried out based on Example 1 except supplying hydrogen at 15 l / h. The yield of IPCN imino compound at the outlet of the reaction tube of (1) was 98.6%, and in the reaction solution at the outlet of the reaction tube of (2), IPDA was 98.1 wt%, IPAA was 1.2 wt%, IPCN, IPCN imino compound. Was not detected, TMAB was 0.7 wt%, and the yield of IPDA was
It was 98%.

Example 16 The procedure of Example 1 was repeated except that the cobalt catalyst K was used in place of the cobalt catalyst A. The yield of the IPCN imino derivative at the outlet of the reaction tube of (1) was 97.6%, and in the reaction liquid at the outlet of the reaction tube of (2),
IPDA was 96.1% by weight, IPAA was 3.1% by weight, IPCN and IPCN imino form were not detected, and TMAB was 0.4% by weight and other 0.4% by weight.
The yield of IPDA was 96.1%.

Example 17 The procedure of Example 1 was repeated except that the cobalt catalyst A was replaced by the cobalt catalyst L. The yield of the IPCN imino derivative at the outlet of the reaction tube of (1) was 97.5%, and in the reaction liquid at the outlet of the reaction tube of (2),
IPDA was 95.6wt%, IPAA was 1.6wt%, IPCN and IPCN imino body were not detected, and TMAB was 2.8wt%, and the yield of IPDA was 95.2wt%.
%Met.

Example 18 The procedure of Example 1 was repeated except that the cobalt catalyst M was used in place of the cobalt catalyst A. The yield of the IPCN imino derivative at the outlet of the reaction tube of (1) was 97.4%, and in the reaction liquid at the outlet of the reaction tube of (2),
IPDA was 98.5 wt%, IPAA was 0.2 wt%, IPCN and IPCN imino compounds were not detected, TMAB was 0.2 wt%, and others were 1.1 wt%.
The yield of IPDA was 98.5%.

Example 19 The procedure of Example 1 was repeated except that the cobalt catalyst A was replaced by the cobalt catalyst N. The yield of the IPCN imino derivative at the outlet of the reaction tube of (1) was 97.8%, and in the reaction liquid at the outlet of the reaction tube of (2),
IPDA was 97.6 wt%, IPAA was 0.3 wt%, IPCN and IPCN imino compounds were not detected, TMAB was 0.6 wt%, and others were 1.5 wt%.
The yield of IPDA was 97.5%.

Example 20 In Example 1, cobalt-based catalyst O was used instead of cobalt-based catalyst A, and the mixture of IPCN and methanol at a ratio of 1: 1.5 (weight ratio) was 23.3 g / h and liquefied ammonia was 25 g. / h
It carried out based on Example 1 except supplying hydrogen at 15 l / h. The yield of the IPCN imino derivative at the outlet of the reaction tube of (1) was 98%, and in the reaction liquid at the outlet of the reaction tube of (2),
IPDA was 95.5 wt%, IPAA was 3.4 wt%, IPCN and IPCN imino form were not detected, TMAB was 1.1 wt%, and IPDA yield was 95.4 wt%.
%Met.

Example 21 In Example 1, a cobalt-based catalyst P was used in place of the cobalt-based catalyst A, a mixture of IPCN and methanol at a ratio of 1: 1.5 (weight ratio) was 23.3 g / h, and liquefied ammonia was 25 g. / h
It carried out based on Example 1 except supplying hydrogen at 15 l / h. The yield of IPCN imino compound at the outlet of the reaction tube of (1) was 98.4%, and in the reaction solution at the outlet of the reaction tube of (2), IPDA was 97.2 wt%, IPAA was 1.7 wt%, IPCN, IPCN imino compound. Was not detected, TMAB was 0.9 wt%, other was 0.2 wt%, and the yield of IPDA was 97.2%.

Example 22 In Example 1, a cobalt-based catalyst Q was used instead of the cobalt-based catalyst A, a mixture of IPCN and methanol at a ratio of 1: 1.5 (weight ratio) was 23.3 g / h, and liquefied ammonia was 25 g. / h
It carried out based on Example 1 except supplying hydrogen at 15 l / h. The yield of IPCN imino compound at the outlet of the reaction tube of (1) was 98.4%, and in the reaction solution at the outlet of the reaction tube of (2), IPDA was 95.5 wt%, IPAA was 2.9 wt%, IPCN, IPCN imino compound. Was not detected, TMAB was 1.4 wt%, other was 0.2 wt%, and the yield of IPDA was 95.4%.

Example 23 20 ml of cobalt-based catalyst I previously reduced with hydrogen was charged.
The filled stainless reaction tube (length 55 cm, inner diameter 9 mm) is vertically
Installed, IPCN and methanol and ammonia 1: 1.5: 2.5
(Weight ratio) 51.2 g / h of the mixed solution is supplied from below the reaction tube
did. Hydrogen was supplied at 15.1 l / h from below. Reaction tube
Has an internal temperature of 121 ° C and a pressure of 150 kg / cm ²Hold the pressure on G and actually
gave. Reaction liquid at the reaction tube outlet 300 minutes after the start of supply
Medium, IPDA 84.8wt%, IPAA 14wt%, IPCN, IPCN imino
No body detected, TMAB 1.2 wt%, IPDA yield 8
It was 4.8%.

Comparative Example 1 In Example 1, a cobalt-based catalyst R was used instead of the cobalt-based catalyst A, a mixture of IPCN and methanol at a ratio of 1: 1.5 (weight ratio) was 24.5 g / h, and liquefied ammonia was 25.3. g / h
Then, the procedure was carried out in accordance with Example 1 except that hydrogen was supplied at 15 l / h. The yield of the IPCN imino derivative at the outlet of the reaction tube of (1) was 99.2%. In the reaction liquid at the reaction tube outlet of (2), IPDA is 91.0 wt%, IPAA is 5.8 wt%, IPCN, IPCN
No imino form was detected, TMAB was 3.2 wt%, and IPDA yield was 90.7%.

Comparative Example 2 In Example 1, a cobalt-based catalyst S was used in place of the cobalt-based catalyst A, a mixture of IPCN and methanol at a ratio of 1: 1.5 (weight ratio) was 24.5 g / h, and liquefied ammonia was 25.3. g / h
Then, the procedure was carried out in accordance with Example 1 except that hydrogen was supplied at 15 l / h. The yield of the IPCN imino derivative at the outlet of the reaction tube of (1) was 97.9%. In the reaction solution at the outlet of the reaction tube of (2), IPDA is 89.9 wt%, IPAA is 6.3 wt%, IPCN, IPCN
No imino form was detected, TMAB was 3.8 wt%, and IPDA yield was 89.6%.

Comparative Example 3 The procedure of Example 1 was repeated except that the cobalt catalyst A was replaced by the cobalt catalyst T. The yield of the IPCN imino derivative at the outlet of the reaction tube of (1) was 99.2%. In the reaction liquid at the outlet of the reaction tube of (2), IPDA was 71.8 wt%, IPAA was 9.4 wt%, IPCN and IPCN imino compounds were not detected, and TMAB was 10.8 wt% and other 7 wt%, and the yield of IPDA was It was 71.8%.

Comparative Example 4 The procedure of Example 23 was repeated, except that the cobalt catalyst I was replaced by the cobalt catalyst R. 76.5 wt% of IPDA in the reaction solution at the outlet of the reaction tube,
IPAA is 19.5 wt%, IPCN, IPCN imino body is not detected, TM
AB was 4 wt% and the yield of IPDA was 76.3%.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Reference number within the agency FI technical indication C07C 209/48 209/52 // C07B 61/00 300 C07C 251/20 (31) Priority claim number Japanese Patent Application No. 5-196041 (32) Priority Date 5 (1993) August 6 (33) Country of priority claim Japan (JP) (31) Priority claim number Japanese Patent Application No. 5-197339 (32) Priority Day 5 (1993) August 9 (33) Priority claiming country Japan (JP) (72) Inventor Kazuyuki Tanaka 2-10-1 Tsukahara, Takatsuki City, Osaka Prefecture Sumitomo Chemical Co., Ltd. (72) Inventor Tada Kazuhiro 2-10-1, Tsukahara, Takatsuki-shi, Osaka Prefecture Sumitomo Kagaku Kogyo Co., Ltd. (72) Inventor Masami Fukao 2-10-1, Tsukahara, Takatsuki-shi Osaka Prefecture (72) Inventor Suzu Takeo Kamo 2-10-1 Tsukahara, Takatsuki City, Osaka Sumitomo In Manabu Industrial Co., Ltd.

Claims (3)

[Claims] 1. An alkaline earth metal carbonate and / or lanthanum oxide is used as a catalyst for producing a corresponding amine by reductive amination of a cyclic ketone or reduction of an imino derivative of a cyclic ketone. A method for producing an amine, which comprises using a cobalt-based catalyst contained therein. 2. The method according to claim 1, wherein the cobalt-based catalyst is a catalyst further containing copper and / or ruthenium. 3. The method according to claim 1, wherein the cobalt-based catalyst is a catalyst further containing an alkali metal compound.