JP2014019652A - Method of producing primary amine - Google Patents

Abstract

A method for producing a primary amine from a primary or secondary alcohol and ammonia is provided.
A method for producing a primary amine, comprising reacting a primary or secondary alcohol with ammonia in the presence of an alumina-supported metallic nickel catalyst.
[Selection figure] None

Description

  The present invention relates to a method for producing a primary amine.

  Primary amines are fuel additives, surfactants, pharmaceuticals, agricultural chemicals, feed additives, epoxy resin curing agents, polyurethane catalysts, quaternary ammonium compounds, plasticizers, corrosion inhibitors, synthetic resins, ion exchange resins. , Textile aids, dyes, vulcanization accelerators, emulsifiers and the like or intermediates thereof.

  As a method for producing such a primary amine, a method of reacting ammonia with a primary or secondary alcohol is important in that it is inexpensive and has a low environmental impact. Patent Document 1 describes a method for producing a primary amine by bringing a primary alcohol, ammonia and hydrogen into contact with each other in the presence of a zirconia-supported ruthenium catalyst. Patent Document 2 describes a method for producing a primary amine by reacting a primary alcohol and ammonia in the presence of a silica-supported nickel / nickel oxide catalyst or a silica-supported cobalt / cobalt oxide catalyst. However, all have room for improvement in terms of efficiency. Non-Patent Document 1 and Non-Patent Document 2 describe a method for producing a primary amine by reacting a primary or secondary alcohol with ammonia in the presence of a ruthenium complex catalyst. It is expensive, is not easy to recover and reuse, and has room for improvement in terms of economy.

JP 2008-150312 A Japanese Patent Laid-Open No. 9-3011

Angew. Chem. Int. Ed. 47, 8661-8664 (2008) Angew. Chem. Int. Ed. 49, 8126-8129 (2010)

  The object of the present invention is to provide a new process for producing primary amines from primary or secondary alcohols and ammonia.

  The present inventors diligently studied to arrive at the present invention.

（式中、Ｒ^１およびＲ^２は、それぞれ独立して、水素原子、置換基を有していてもよいアルキル基、置換基を有していてもよいシクロアルキル基、置換基を有していてもよい芳香族炭化水素基または置換基を有していてもよい芳香族複素環基を表わし、Ｒ^１とＲ^２とが結合して、それらの結合炭素原子と共に環を形成してもよい。）
で示されるアルコールである［１］〜［４］のいずれかに記載の１級アミンの製造方法；
［６］ニッケル成分中の酸化ニッケルの含量が６０％未満であり、ニッケル成分の平均粒子径が５〜１０ｎｍであり、アルミナがθ−アルミナまたはγ−アルミナであるアルミナ担持金属ニッケル；
［７］１級アミンを製造するための触媒である［６］に記載のアルミナ担持金属ニッケル。 That is, the present invention is as follows.
[1] A method for producing a primary amine, comprising reacting a primary or secondary alcohol with ammonia in the presence of an alumina-supported nickel metal catalyst;
[2] The method for producing a primary amine according to [1], wherein the content of nickel oxide in the nickel component in the alumina-supported metallic nickel catalyst is less than 60%;
[3] The method for producing a primary amine according to [1] or [2], wherein the average particle size of the nickel component in the alumina-supported metallic nickel catalyst is 10 nm or less;
[4] The method for producing a primary amine according to any one of [1] to [3], wherein the alumina in the alumina-supported metallic nickel catalyst is θ-alumina or γ-alumina;
[5] A primary or secondary alcohol is represented by the formula (1)

(In the formula, R ¹ and R ² each independently have a hydrogen atom, an optionally substituted alkyl group, an optionally substituted cycloalkyl group, or a substituent. Represents an optionally substituted aromatic hydrocarbon group or an optionally substituted aromatic heterocyclic group, and R ¹ and R ² may be bonded to form a ring together with their bonded carbon atoms. .)
The method for producing a primary amine according to any one of [1] to [4], which is an alcohol represented by:
[6] Alumina-supported metallic nickel in which the content of nickel oxide in the nickel component is less than 60%, the average particle size of the nickel component is 5 to 10 nm, and the alumina is θ-alumina or γ-alumina;
[7] The alumina-supported metallic nickel according to [6], which is a catalyst for producing a primary amine.

  According to the present invention, a new method for producing a primary amine from alcohol and ammonia can be provided.

It is the figure which showed the behavior in the hydrogen gas temperature-reduction method analysis (H2-TPR) of the alumina carrying metallic nickel catalyst. The ratio of metallic nickel and nickel oxide in the alumina-supported metallic nickel catalyst measured by H2-TPR with respect to the hydrogen reduction temperature and 2 in the reaction of 2-octanol and ammonia (reaction temperature: 160 ° C., reaction time: 4 hours). -It is the figure which showed the relationship with the yield of octylamine. The amount of the primary amine relative to the content of the nickel component of the alumina-supported metal nickel catalyst when the reaction is carried out at 160 ° C. in an o-xylene solvent with a catalyst amount of 1 mol% in terms of nickel. It is the graph which showed the yield. Time course of the yield of the product in the reaction mixture when the reaction was carried out at 160 ° C. in o-xylene in the presence of 1 mol% of an alumina-supported metallic nickel catalyst in terms of nickel with respect to 2-octanol. It is the graph which showed the change.

  The primary amine production method of the present invention is characterized by reacting a primary or secondary alcohol and ammonia in the presence of an alumina-supported metallic nickel catalyst.

（式中、Ｒ^１およびＲ^２は、それぞれ独立して、水素原子、置換基を有していてもよいアルキル基、置換基を有していてもよいシクロアルキル基、置換基を有していてもよい芳香族炭化水素基または置換基を有していてもよい芳香族複素環基を表わし、Ｒ^１とＲ^２とが結合して、それらの結合炭素原子と共に環を形成してもよい。）
で示されるアルコールが挙げられる。 The primary alcohol has an alcoholic hydroxy group (—OH), and the carbon atom to which the alcoholic hydroxy group is bonded has two hydrogen atoms, and the secondary alcohol is an alcoholic hydroxy group. A carbon atom having a group and having the alcoholic hydroxy group bonded thereto means an alcohol having one hydrogen atom. Examples of such alcohol include formula (1)

(In the formula, R ¹ and R ² each independently have a hydrogen atom, an optionally substituted alkyl group, an optionally substituted cycloalkyl group, or a substituent. Represents an optionally substituted aromatic hydrocarbon group or an optionally substituted aromatic heterocyclic group, and R ¹ and R ² may be bonded to form a ring together with their bonded carbon atoms. .)
The alcohol shown by is mentioned.

  Examples of the alkyl group include alkyl groups having 1 to 10 carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a nonyl group, an octyl group, a nonyl group, and a decyl group. Examples of the cycloalkyl group include cycloalkyl groups having 3 to 10 carbon atoms such as a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclononyl group, and a cyclodecyl group.

  As an aromatic hydrocarbon group, C6-C20 aromatic hydrocarbon groups, such as a phenyl group, a naphthyl group, an anthryl group, are mentioned. The aromatic heterocyclic group includes a pyridyl group, a pyrimidyl group, a triazinyl group, a pyrazolyl group, a triazolyl group, an imidazolyl group, an oxazolyl group and the like as ring constituent atoms of 1 to 3 nitrogen atoms, 0 to 1 oxygen atom, and Examples thereof include a 5- to 6-membered aromatic heterocyclic group having 0 to 1 sulfur atom.

  Such an alkyl group, cycloalkyl group, aromatic hydrocarbon group and aromatic heterocyclic group may have a substituent. Examples of the substituent for the alkyl group and cycloalkyl group include a halogen atom, an alkoxy group which may have a substituent, a cycloalkoxy group which may have a substituent, and an alkylthio which may have a substituent. Group, a dialkylamino group, an aromatic hydrocarbon group which may have a substituent, and a heterocyclic group which may have a substituent. Examples of the substituent for the aromatic hydrocarbon group and the aromatic heterocyclic group include a hydroxy group (—OH), a halogen atom, an optionally substituted alkoxy group, and an optionally substituted cycloalkoxy group. Group, an alkylthio group which may have a substituent, an aromatic hydrocarbon group which may have a substituent, and a heterocyclic group which may have a substituent.

  Examples of the halogen atom include a fluorine atom and a chlorine atom.

  As the alkoxy group, a chain alkoxy group having 1 to 10 carbon atoms such as methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group, nonyloxy group, decyloxy group, etc. And a cyclic alkoxy group having 3 to 10 carbon atoms such as a cyclopropyloxy group, a cyclopentyloxy group, a cyclohexyloxy group, a cycloheptyloxy group, a cyclooctyloxy group, a cyclononyloxy group, and a cyclodecyloxy group. As the alkylthio group, a chain alkylthio group having 1 to 10 carbon atoms such as methylthio group, ethylthio group, propylthio group, butylthio group, pentylthio group, hexylthio group, heptylthio group, octylthio group, nonylthio group, decylthio group, and the like, and cyclo Examples thereof include cyclic alkylthio groups having 3 to 10 carbon atoms such as propylthio group, cyclopentylthio group, cyclohexylthio group, cycloheptylthio group, cyclooctylthio group, cyclononylthio group, and cyclodecylthio group. Examples of the substituent that the alkoxy group and the alkylthio group may have include a hydroxy group, a fluorine atom, an alkoxy group that may be substituted with an alkoxy group, an alkylthio group that may have a substituent, and a substituent. An aromatic hydrocarbon group which may have a heterocyclic group, a heterocyclic group which may have a substituent, and the like. Examples of the alkoxy group and the alkylthio group include the same groups as those described above. The aromatic hydrocarbon group which may have a substituent and the heterocyclic group which may have a substituent may be The thing similar to what is mentioned later is mentioned. As an aromatic hydrocarbon group, a C6-C20 aromatic hydrocarbon group of a phenyl group, a naphthyl group, and an anthranyl group is mentioned. Examples of the heterocyclic group include a furyl group, a thienyl group, a pyrrolyl group, an imidazolyl group, a pyrazolyl group, a triazolyl group, an oxazolyl group, a thiazolyl group, a pyridyl group, a pyrazinyl group, a pyridazinyl group, a pyrimidinyl group, and a triazinyl group. 10 aromatic heterocyclic groups and 4 to 10 carbon atoms such as oxolanyl group, thiolanyl group, 1,3-dioxolanyl group, oxanyl group, 1,3-dioxanyl group, thianyl group, 1,3-dithianyl group, etc. Examples thereof include a saturated heterocyclic group and a group in which the aromatic heterocyclic group or the saturated heterocyclic group and a benzene ring are condensed. Examples of the dialkylamino group include amino groups substituted with two alkyl groups having 1 to 6 carbon atoms such as a dimethylamino group, a diethylamino group, and a methylethylamino group.

  Examples of the primary or secondary alcohol include methanol, ethanol, propanol, isopropanol, butanol, sec-butanol, 1-pentanol, 2-pentanol, 3-pentanol, 1-hexanol, 2-hexanol, 3-hexanol, 1-heptanol, 1-octanol, 1-nonanol, 1-decanol, 1-dodecanol, stearyl alcohol, 2-hexyl-1-decanol, 2-octyl-1-decanol, 2-dodecyl-1-tetradecanol, 1 -Diethylaminopentan-4-ol, cyclopentanol, cyclohexanol, cycloheptanol, cyclooctanol, benzyl alcohol, 2-phenyl-1-ethanol, 1-phenyl-1-ethanol, 2-pyridylmethanol and 2-c An example is rolo-3-thiazolyl methanol.

  The reaction between the primary or secondary alcohol and ammonia is carried out in the presence of an alumina-supported metallic nickel catalyst.

  The alumina-supported metal nickel catalyst can be prepared by preparing alumina-supported nickel oxide by a known impregnation method and reducing the prepared alumina-supported nickel oxide.

  Specifically, the alumina-supported nickel oxide can be prepared by impregnating a powdery alumina in a nickel compound solution, removing the solvent, and firing the obtained solid in air. A calcination temperature is 100-800 degreeC normally, and 100-500 degreeC is preferable. Examples of the nickel compound include nickel salts such as nickel chloride, nickel nitrate, nickel sulfate, nickel acetate, nickel acetyl acetate, and nickel nitrate is preferable. The solvent of the nickel compound solution may be any solvent that can dissolve the nickel compound, such as alcohol solvents such as methanol, ethanol, and propanol, nitrile solvents such as acetonitrile, ketone solvents such as acetone and methyl ethyl ketone, ethyl acetate, and butyl acetate. And ether solvents such as tert-butyl methyl ether and tetrahydrofuran. These solvents may be used in combination of two or more.

  The alumina as the carrier is preferably alumina having high heat resistance and a large specific surface area, and more preferably θ-alumina or γ-alumina.

Specific surface area of the alumina is preferably 30~3000m ² / g, and more preferably 50 to 300 m ² / g. If the specific surface area value is too small, sintering may easily occur during the production or regeneration of the catalyst, and a catalyst exhibiting good activity may not be obtained. If the specific surface area value is too large, the nickel component may not be sufficiently reduced in the reduction treatment, and a catalyst exhibiting good activity may not be obtained.

  The average particle size of the nickel component in the alumina-supported metallic nickel catalyst is preferably 0.5 to 10 nm, more preferably 5 to 10 nm, and particularly preferably 2 to 10 nm. Such an alumina-supported metal nickel catalyst is prepared by setting the average particle size of the nickel component in the alumina-supported nickel oxide to preferably 0.5 to 10 nm, more preferably 5 to 10 nm, and particularly preferably 2 to 10 nm. can do. Moreover, this average particle diameter can be calculated by observation with a transmission electron microscope or the result of X-ray diffraction.

  The nickel component in the alumina-supported metallic nickel catalyst may be metallic nickel alone, or may contain nickel oxide in addition to metallic nickel. From the viewpoint of reaction results, the proportion of nickel oxide contained in the nickel component is preferably less than 60%.

  The content of the nickel component in the alumina-supported metallic nickel catalyst is preferably in the range of 3 to 15% by weight, and more preferably in the range of 5 to 10% by weight from the viewpoint of reaction yield. Such an alumina-supported metallic nickel catalyst is prepared by adjusting the content of the nickel component in the alumina-supported nickel oxide, preferably in the range of 3 to 15% by weight, more preferably in the range of 5 to 10% by weight. be able to. When the content of the nickel component is small, the particle size of the nickel component can be made relatively small, and when the amount of nickel supported is large, the particle size of the nickel component can be made relatively large.

  By reducing the alumina-supported nickel oxide obtained by calcination, an alumina-supported metal nickel catalyst in which the nickel component containing metal nickel is highly dispersed is obtained. The reduction treatment may be performed wet or dry, but is preferably performed dry. In the case of dry reduction, a gaseous reducing agent such as gaseous hydrogen is usually used. A gaseous reducing agent such as gaseous hydrogen may be diluted with an inert gas such as nitrogen. Gaseous hydrogen is preferred as the gaseous reducing agent, and a catalyst having a high content of metallic nickel in the nickel component can be obtained by reduction with gaseous hydrogen. In the case of wet reduction, a liquid reducing agent such as methanol, formaldehyde or formic acid is used as the reducing agent.

  The reduction temperature in the reduction treatment is preferably 300 to 900 ° C, and more preferably 400 to 800 ° C. If the reduction temperature is too low, the reduction may not proceed sufficiently. If the reduction temperature is too high, the nickel component may sinter, the specific surface area value per mass will be small, and the activity may be reduced.

  When the reduction temperature is low, a catalyst having a relatively high nickel oxide content in the nickel component is usually obtained, and when the reduction temperature is high, a catalyst having a relatively low nickel oxide content in the nickel component is usually obtained.

  The alumina-supported metallic nickel catalyst is preferably stored so as not to come into contact with oxygen. In view of avoiding contact between the alumina-supported metal nickel catalyst and oxygen, it is preferable to reduce the prepared alumina-supported nickel oxide immediately before the catalyst is subjected to the reaction between the primary or secondary alcohol and ammonia.

  The reaction between the primary or secondary alcohol and ammonia may be performed in the absence of a solvent, or may be performed in the presence of a solvent. Solvents include aromatic hydrocarbon solvents such as toluene, ethylbenzene and xylene, halogenated hydrocarbon solvents such as benzotrifluoride, aliphatic hydrocarbon solvents such as cyclohexane, heptane, nonane and decane, tetrahydrofuran, tert-butyl methyl ether , Ether solvents such as dibutyl ether, diethylene glycol dimethyl ether, and diethylene glycol dibutyl ether. Its usage is not limited.

  The amount of ammonia used is usually 1 mol or more per 1 mol of the primary or secondary alcohol. The upper limit is not limited.

  The reaction is usually performed in an atmosphere of an inert gas such as nitrogen.

  The reaction pressure is not limited, and the reaction may be performed at normal pressure or the reaction may be performed under pressure.

  The reaction temperature is usually 120 to 200 ° C.

  The amount of the alumina-supported metallic nickel catalyst used is usually 0.01 to 20 mol%, preferably 0.1 to 10 mol%, in terms of nickel, with respect to 1 mol of the primary or secondary alcohol.

  The reaction time is usually 0.1 to 100 hours, preferably 0.5 to 24 hours.

  After completion of the reaction, the intended reaction is achieved by removing excess ammonia, unreacted primary or secondary alcohol, solvent and catalyst from the resulting reaction mixture by a conventional separation method such as distillation, filtration or centrifugation. Primary amine can be removed. The separation of the catalyst is preferably carried out so that the catalyst does not come into contact with oxygen. The separated catalyst can be reused in the reaction between the primary or secondary alcohol and ammonia as it is or after being subjected to a reduction treatment. The separated catalyst may have a reduced activity. In such a case, it is preferable to regenerate the catalyst by reduction treatment and reuse it in the reaction. Such a reduction treatment may be carried out in the same manner as the above-described reduction treatment of alumina-supported nickel oxide.

  Examples of the primary amine obtained include methylamine, ethylamine, propylamine, isopropylamine, butylamine, sec-butylamine, 1-pentylamine, 2-pentylamine, 3-pentylamine, 1-hexylamine, 2-hexylamine, 3-hexylamine, 1-heptylamine, 1-octylamine, 1-nonylamine, 1-decylamine, 1-dodecylamine, stearylamine, 2-hexyl-1-decylamine, 2-octyl-1-decylamine, 2-dodecyl -1-tetradecylamine, 1-diethylaminopentyl-4-amine, cyclopentylamine, cyclohexylamine, cycloheptylamine, cyclooctylamine, benzylamine, 2-phenyl-1-ethylamine, 1-phenyl-1-ethylamine Down, 2-pyridyl methyl amine, 2-chloro-3-thiazolyl methyl amine.

（式中、Ｒ^１およびＲ^２は上記と同一の意味を表わす。）
で示される一級アミンが得られる。 When the alcohol represented by the formula (1) is used as the alcohol, the formula (2)

(In the formula, R ¹ and R ² have the same meaning as described above.)
A primary amine represented by is obtained.

  Hereinafter, the present invention will be described in detail by way of examples.

The analysis was performed by GC (GC-14B manufactured by Shimadzu Corporation) and GC-MS (GCMS-QP2010 manufactured by Shimadzu Corporation). As the column, an Ultra ALLOY capillary column UA ⁺ -5 (manufactured by Frontier Laboratories) was used, and nitrogen was used as a carrier gas.

¹ H-NMR spectrum was measured by JEOL JNM-ECX400 (400 MHz) (internal standard: tetramethylsilane, solvent: CDCl ₃ ).
Ra-Ni (B113W, Ni> 90%) used was provided by Evonik.

Titania (JRC-TIO4, 50 m ² g ⁻¹ ), ceria (JRC-CEO ^3, 81.4 m ² g ⁻¹ ) and silica-alumina (JRC-SAL-2, alumina 13.75 wt%, 560 m ² g ⁻¹ ) The one provided by the Japan Catalytic Society was used. Silica (Q-10,300 m ² g ⁻¹ ) used was provided by Fuji Silysia Chemical.

Zirconia (60 m ² g ⁻¹ ) was obtained by performing hydrolysis by gradually adding ammonia water (1.0 mol · dm ⁻¹ ) to zirconium oxynitrate dihydrate in distilled water. The precipitate was taken out by filtration, washed 3 times with distilled water, dried at 100 ° C., and further baked at 500 ° C.

Activated carbon (296 m ² g ⁻¹ ) was purchased from Kishida Chemical.

<Preparation of catalyst>
(1) θ-alumina (specific surface area 112 m ² g ⁻¹ ) was prepared by heating γ-AlOOH (Catapal B alumina; purchased from Sasol) at 1000 ° C. for 3 hours.
(2) γ-AlOOH (Catapal B alumina; purchased from Sasol) was heated at 900 ° C. for 3 hours to prepare γ-alumina.
(3) 9.0 g of θ-alumina was impregnated with 100 mL of 0.17M aqueous solution of nickel (II) nitrate hexahydrate. Water was distilled off from the resulting mixture under reduced pressure at 50 ° C., followed by drying at 90 ° C. for 12 hours. The obtained solid was fired in air at 300 ° C. for 1 hour to obtain alumina-supported nickel oxide. The obtained catalyst was placed in a Pyrex (registered trademark) or quartz glass test tube for 20 cm ³ min. ^The alumina-supported metal nickel catalyst (the content of nickel component: 10% by weight) subjected to the reduction treatment was prepared by reduction at 500 ° C. for 0.5 hours in a hydrogen stream of ⁻¹ .
(4) Alumina-supported metal nickel catalyst having a nickel component content of 5% by weight and 20% by weight, a catalyst in which metal nickel is supported on various supports (nickel component content: 10% by weight), and cobalt or copper as θ A catalyst supported on alumina (cobalt or copper component content: 10% by weight) was prepared by an impregnation method using each metal nitrate aqueous solution.

<Analysis of catalyst>
Powder X-ray diffraction (XRD) was performed with Cu-Kα radiation using a MiniFlex II / AP diffractometer manufactured by Rigaku Corporation.

  The average particle diameter of the nickel component of the alumina-supported nickel oxide was calculated by calculating the volume average from 100-point nickel particle images measured with a transmission electron microscope (TEM; JEM-2100F TEM, manufactured by JEOL, acceleration voltage: 200 kV). However, the average particle diameter of the nickel component of the alumina-supported nickel catalyst having a nickel component content of 20% by weight was calculated according to the Scherer equation from the half width of the Ni (200) peak at 51.8 ° of XRD.

  Table 1 shows the content of the nickel component of the alumina-supported nickel oxide and the average particle diameter D of the nickel component.

FIG. 1 shows the behavior of the alumina-supported metallic nickel catalyst in the hydrogen gas temperature programmed reduction method analysis (H2-TPR). The hydrogen gas temperature reduction method analysis (H2-TPR) was performed under the following conditions.
Device: Nippon Bell BELCAT-A
Circulating gas: 5% hydrogen / air Temperature rising rate: 10 ° C / min Temperature range: 50 ° C to 850 ° C

  FIG. 2 shows the ratio of metallic nickel and nickel oxide in the alumina-supported metallic nickel catalyst measured by H2-TPR with respect to the hydrogen reduction temperature, and the reaction of 2-octanol and ammonia (reaction temperature: 160 ° C., reaction time: 4). The graph which showed the relationship with the yield of 2-octylamine in (time) is shown.

<Examples 1-2 and Comparative Examples 1-12>
Alumina-supported nickel oxide (nickel content: 10% by weight) corresponding to 0.03 mmol of nickel was placed in a glass test tube, covered with a rubber cap, and then 20 cm ³ min. ^{-1 in} a hydrogen gas stream at 500 ° C. for 0.5 hour to obtain an alumina-supported metal nickel catalyst (Ni / Al ₂ O ₃ ). After the test tube was cooled to room temperature, o-xylene (4.0 g), 2-octanol (3.0 mmol) and n-dodecane (0.5 mmol) as an internal standard were injected with a syringe. The rubber cap was removed, a magnetic stirring bar was inserted, and the test tube was placed in a stainless steel autoclave (30 cm ² ). After replacing the gas in the autoclave with ammonia, ammonia was introduced under pressure up to 0.4 MPa at room temperature and then sealed. While stirring at 150 rpm, the reaction was carried out at 160 ° C. for 4 hours. Conversion and yield were measured by GC analysis using n-dodecane as an internal standard. The product was identified by GC-MS using the same column as GC analysis.

  Instead of the alumina-supported metal nickel catalyst, the reaction shown in Table 2 was used and the reaction was performed in the same manner as described above. The results are shown in Table 2. The conversion rate and yield in Table 2 were calculated by GC analysis on the basis of 2-octylamine. Moreover, the usage-amount of the alumina in the comparative example 4 was 0.1 g, and the usage-amount of the nickel conversion catalyst in the comparative examples 11 and 12 was 10 mol%.

Examples 3-17

  Using a primary or secondary alcohol (3.0 mmol) shown in Table 3, the reaction was carried out in the presence of a reduction-treated alumina-supported metal nickel catalyst. In Example 4, the test tube after the reaction in Example 3 was sealed with a rubber cap and replaced with hydrogen (1 atm). The reaction solution was collected with a syringe and 1 g of o-xylene was injected into the test tube. . Again, the solution in the test tube was collected with a syringe, and 1 g of o-xylene was injected into the test tube. Thereafter, a predetermined amount of primary or secondary alcohol was injected to react. In Example 5, the tester after the reaction in Example 4 was sealed with a rubber cap and replaced with hydrogen (1 atm). The reaction solution was collected with a syringe, and 1 g of o-xylene was injected into the test tube. Again, the solution in the test tube was collected with a syringe, and 1 g of o-xylene was injected into the test tube. Thereafter, a predetermined amount of primary or secondary alcohol was injected to react. In Example 6, the catalyst after the reaction in Example 5 was obtained by centrifugation, air-dried at 120 ° C. for 12 hours, and then reduced at 800 ° C. for 0.5 hour under a hydrogen stream (1 atm, 20 ml / min). The obtained catalyst was used for the reaction without being exposed to the atmosphere. In Example 7, the catalyst after the reaction in Example 6 was obtained by centrifugation, air-dried at 120 ° C. for 12 hours, and then reduced at 800 ° C. for 0.5 hour in a hydrogen stream (1 atm, 20 ml / min). The obtained catalyst was used for the reaction without being exposed to the atmosphere. The results are shown in Table 3 and Table 4.

(#) 生成物は、

であった。

(#) The product is

Met.

  FIG. 3 shows the nickel content of the alumina-supported nickel metal catalyst when the reaction is carried out at 160 ° C. in an o-xylene solvent at a catalyst amount of 1 mol% in terms of nickel and based on 2-octanol. The graph which showed the yield of the primary amine was shown.

  FIG. 4 shows the yield of the product in the reaction mixture when the reaction was carried out at 160 ° C. in o-xylene in the presence of 1 mol% alumina-supported metallic nickel catalyst with respect to 2-octanol. The graph which showed the time-dependent change of the rate was shown. In the graph, 1 (●) is 2-octanol, 2 (◯) is 2-octylamine produced, 3 (▽) is di- (2-octyl) amine produced, 4 (▲) is The yields of 2-octanone produced are shown.

  According to the present invention, a primary amine can be produced from a primary or secondary alcohol.

Claims (7)

  A method for producing a primary amine, comprising reacting a primary or secondary alcohol and ammonia in the presence of an alumina-supported metallic nickel catalyst.   The method for producing a primary amine according to claim 1, wherein the content of nickel oxide in the nickel component in the alumina-supported metallic nickel catalyst is less than 60%.   The method for producing a primary amine according to claim 1 or 2, wherein an average particle diameter of a nickel component in the alumina-supported metallic nickel catalyst is 10 nm or less.   The method for producing a primary amine according to any one of claims 1 to 3, wherein the alumina in the alumina-supported metallic nickel catalyst is θ-alumina or γ-alumina. A primary or secondary alcohol is of formula (1)

(In the formula, R ¹ and R ² each independently have a hydrogen atom, an optionally substituted alkyl group, an optionally substituted cycloalkyl group, or a substituent. Represents an optionally substituted aromatic hydrocarbon group or an optionally substituted aromatic heterocyclic group, and R ¹ and R ² may be bonded to form a ring together with their bonded carbon atoms. .)
The method for producing a primary amine according to any one of claims 1 to 4, wherein the alcohol is represented by the formula:   Alumina-supported metallic nickel in which the content of nickel oxide in the nickel component is less than 60%, the average particle size of the nickel component is 5 to 10 nm, and the alumina is θ-alumina or γ-alumina.   The alumina-supported metallic nickel according to claim 6, which is a catalyst for producing a primary amine.

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