JPH09241192A - Production of alcohols - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an alcohol useful as a raw material for medicines, a perfume, etc., under mild conditions in high yield and in high selectivity by a catalytic hydrogenation reduction of a carboxylic acid. SOLUTION: (B) A carboxylic acid is hydrogenated and reduced in a hydrocarbon-based solvent in the presence of (A) a catalyst comprising at least one of elements of the group VIII (preferably rhodium, ruthenium or palladium) of the periodic table and at least one of elements of the group VIb (preferably molybdenum or tungsten) or an element of the group VII (preferably rhenium). The catalyst of the component A may be supported on a carrier. The amount of the catalyst used is preferably 0.01-10mol% based on the component B.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing alcohols by hydrogenation reduction of carboxylic acids. Alcohols are raw materials for pharmaceuticals, fragrances, synthetic intermediates,
It is a useful substance that is widely used as a solvent.

[0002]

2. Description of the Related Art Conventionally, some proposals have been made for a method for producing alcohols by catalytic hydrogenation reduction of carboxylic acid, but the carboxylic acid as a raw material has high polarity and low volatility and solubility. Therefore, it was common knowledge among those skilled in the art that all of them were carried out in an oxygen-containing solvent.

In JP-A-63-301845, a reaction temperature of 225 ° C. and a pressure of 150 kg /
cm ^2, a method for hydrogenating penta decane dicarboxylic acid monomethyl ester in tetrahydrofuran (THF) is described. However, this method uses 5 to 10% by weight of a catalyst, a high temperature of 225 ° C., and a hydrogen pressure of 15%.
It is economically disadvantageous because the reaction requires a high pressure of 0 kg / cm ² .

JP-A-4-99752 discloses that a long-chain diacid monoester is hydrogenated at a reaction temperature of 250 ° C. and a pressure of 60 kg / cm ² in a water solvent using a ruthenium-tin catalyst or a rhenium-tin catalyst. The method of conversion is described. However, in this method, the reaction temperature is as high as 250 ° C., and it takes a long time of 85 hours to obtain the ω-hydroxycarboxylic acid ester with a yield of 72.4%.
Economically inefficient.

As a relatively mild hydrogenation method for compensating for these drawbacks, the present inventors have proposed, as a catalyst, the presence of a binary catalyst containing an element of Group VIII and VIb or VIIb of the Periodic Table. And an ether solvent such as dimethoxyethane (DME) as a solvent at a reaction temperature of 140 to 18
A method for hydrogenating a carboxylic acid at 0 ° C. and a pressure of 100 atm was reported [WO95 / 24371 and Tetrahedron Letters 36, 7, p1059-10.
62 (1995)]. However, in this method using an ether solvent, an expensive solvent must be used in a large amount, and at the reaction temperature used, hydrolysis of the solvent by generated water and hydrogenolysis of the solvent proceed. In addition to the above problem, there was a problem that the reaction temperature was relatively high.

[0006] As described above, there are almost no examples in which a hydrocarbon solvent is used in the hydrogenation reduction of a carboxylic acid using a catalyst, and much less, as in the present invention, a reaction temperature of a hydrocarbon solvent is increased. It has never been known by those skilled in the art that it is possible to reduce

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to provide a method for producing alcohols with high yield and high selectivity under mild conditions by using catalytic hydrogenation reduction of carboxylic acid. .

[0008]

[Means for Solving the Problems] As a result of intensive studies to solve such problems, the present inventors have found that the periodic table VIII
A hydrocarbon-based solvent for the hydrogenation reduction of a carboxylic acid in the presence of a catalyst consisting of at least one element selected from Group VI elements and at least one element selected from Group VIb and Group VIIb of the periodic table It was found that alcohols can be produced in a high yield under mild conditions by using, and the present invention has been completed.

That is, the present invention relates to at least one element selected from Group VIII elements of the Periodic Table and VIb of the Periodic Table.
The present invention relates to a method for producing alcohols, which comprises hydrogenating a carboxylic acid in a hydrocarbon solvent in the presence of a catalyst containing at least one element selected from Group VIIb elements.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, Periodic Table No. VIII
Group elements include iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium,
Platinum, Group VIb elements include chromium, molybdenum, and tungsten, Group VIIb elements include manganese and rhenium, while Group VIII elements of the Periodic Table include ruthenium, rhodium, palladium, and VIb. It is preferable to use molybdenum or tungsten as the group element and rhenium as the group VIIb element in terms of the activity and selectivity of the hydrogenation reaction. These catalysts may be supported on a carrier without any problem.

The ruthenium used in the present invention is a zero-valent metal itself and / or an inorganic compound, organic compound or complex compound of various ruthenium. Specifically, ruthenium black, ruthenium powder, ruthenium oxide, ruthenium nitrate, ruthenium nitrate nitrosyl ruthenium, ruthenium chloride, ruthenium bromide, ruthenium iodide, ammonium oxydecachlorodiruthenate, ammonium pentachloroaquarthenate, oxydecachloro. Potassium diruthenate, sodium oxydecachlorodiruthenate, potassium pentachloroaquarthenate, potassium perruthenate, hexaammineruthenium chloride, pentaamminechlororuthenium chloride, hexaammineruthenium bromide, ruthenium carbonyl, hexacarbonyltetrachloro Diruthenium, tris (acetylacetonato) ruthenium, dichlorotricarbonyl ruthenium dimer, dichlorotris (triphe Le phosphine) ruthenium, dichloro dicarbonyl bis (triphenylphosphine) ruthenium,
Dicarbonyl cyclopentadienyl ruthenium dimer, bis (cyclopentadienyl) ruthenium, etc. can be used.

The rhodium used in the present invention is a zero-valent metal itself, and / or various inorganic compounds of rhodium,
It is an organic compound or a complex compound. In particular,
Rhodium black, rhodium powder, rhodium oxide,
Rhodium nitrate, rhodium acetate, rhodium acetate dimer,
Rhodium chloride, rhodium bromide, rhodium iodide, ammonium hexachlororhodate, ammonium pentachloroacharodiate, potassium pentachloroacharodiate, sodium hexachlororhodate, sodium hexabromorhodate, chloropentaammine rhodium chloride, tetrarhodium Dodecacarbonyl, hexarodium hexadecacarbonyl, tris (acetylacetonato) rhodium, bis (1,3-diphenyl 1,3
-Propanedionato) rhodium acetate, bis (pentamethylcyclopentadienyl) dichlororhodium and the like can be used.

Palladium used in the present invention is a zero-valent metal itself and / or various inorganic compounds, organic compounds or complex compounds of palladium. Specifically, palladium black, palladium powder, palladium oxide, palladium nitrate, palladium acetate, palladium sulfate, palladium chloride, palladium bromide, palladium iodide, ammonium hexachloropalladate, ammonium tetrachloropalladate, dinitrodiamine palladium, hexachloro. Potassium palladate, potassium tetrabromopalladate, sodium hexachloropalladate, bis (acetylacetonato) palladium and the like can be used.

Molybdenum used in the present invention is a zero-valent metal itself and / or an inorganic compound, organic compound or complex compound of various molybdenum. Specifically, molybdenum hexacarbonyl, ammonium molybdate, molybdenum acetate, molybdenum oxide, molybdenum acetylacetonate, or the like can be used.

The tungsten used in the present invention is a zero-valent metal itself, and / or an inorganic compound, organic compound or complex compound of various tungsten. Specifically, tungsten hexacarbonyl, tungsten oxide, tungstic acid, ammonium paratungstate, or the like can be used.

The rhenium used in the present invention is a zero-valent metal itself and / or various inorganic compounds of rhenium,
It is an organic compound or a complex compound. Specifically, rhenium carbonyl, rhenium oxide, perrhenic acid, ammonium perrhenate, rhenium chloride, cyclopentadienyl rhenium tricarbonyl and the like can be used.

VI used for the preparation of supported catalysts
The Group II metal compound is not particularly limited as long as it can be converted to a metallic Group VIII metal during or before the hydrogenation reaction. Also, when preparing a catalyst,
Nitrate, acetate, sulfate of VIb group or VIIb group element,
Inorganic compounds such as chlorides, organic compounds such as acetylacetonate, amine complexes, carbonyl complexes, and the like can be used.

The amount of the Group VIII metal supported in the catalyst supported on the carrier is 0.1 to 60% by weight based on the total amount of the catalyst.
It is preferably 0.5 to 50% by weight. This carrying amount is 6
If it is more than 0%, the activity increase per unit weight of Group VIII metal tends to be small, and if it is less than 0.1% by weight, sufficient activity may not be obtained.

Group VIb in the catalyst supported on the carrier and
The loading amount of the VIIb group element depends on the group VIII metal and the VIb group and VIIb
The atomic ratio of the elements of the group is 100: 1 to 1:50, preferably 50: 1 to 1:20.

When the catalyst supported on the carrier is used, the method for producing the catalyst is not particularly limited, and those produced by known methods can be used. For example, it can be prepared by an impregnation method, an ion exchange method, a physical mixing method, or the like.

When prepared by the impregnation method, in the group VIII metal compound, at least one metal compound selected from the group VIb and the group VIIb is further dissolved in a suitable solvent, and a carrier is added thereto, if necessary. For example, after leaving it to stand for a predetermined time, it is dried. The reduction may be performed immediately after drying, or in some cases, reduction may be performed after firing. Of course, it may be reduced in the reaction system. The reduction method is not particularly limited, and if a Group VIII zero-valent metal is obtained, it may be reduced in the gas phase using, for example, hydrogen or in the liquid phase using hydrazine. . The reduction temperature is not particularly limited as long as at least the Group VIII metal compound is reduced to a zero-valent metal. There is no particular limitation on the valence of the VIb group or VIIb group element after the reduction operation, and it may be a zero-valent metal or in an oxidized state. Generally 60
Temperatures up to 0 ° C are sufficient. Needless to say, it is not always necessary to carry all of the catalyst components at once, and it is possible to carry one of them first and then carry the remaining components.

When the catalyst is supported on the carrier in the present invention, the carrier used may be a porous substance, and examples thereof include metal oxides or composite oxides, layered clay compounds, activated carbon and the like. Of these, silica, alumina and activated carbon are preferable. Further, the shape of the catalyst is not particularly limited, and it can be used as a powder or after being molded. In addition, in the method of the present invention, the reaction suitably proceeds using ordinary activated carbon without using as the carrier graphitized carbon having a particularly high surface area. Alumina or zeolite usually used as the second component of the catalyst may not be particularly added.

The amount of the catalyst used is not particularly limited, but it is preferably 0.01 to 10 mol% and more preferably 0.1 to 3 mol% with respect to the carboxylic acid.

The carboxylic acid as the raw material of the present invention may be any one as long as it has a carboxyl group in the molecule. Specifically, it may have a substituent, acetic acid, propionic acid, acrylic acid, butyric acid, crotonic acid, valeric acid, lauric acid, myristic acid, palmitic acid, stearic acid,
Aliphatic carboxylic acids such as cyclopropanecarboxylic acid, cyclopentanecarboxylic acid, cyclohexanecarboxylic acid, cycloheptanecarboxylic acid and adamantanecarboxylic acid;
Benzoic acid, 1-naphthoic acid, which may have a substituent, 2
-Aromatic carboxylic acids such as naphthoic acid, 9-anthracenecarboxylic acid, nicotinic acid, and furan-2-carboxylic acid are included, but are not limited thereto. As the substituent, an alkyl group having 1 to 10 carbon atoms, which may be branched, an alkenyl group, an alkynyl group, an aromatic group, a halogen atom, a hydroxyl group, an alkoxy group, an acyl group, an ester group, an amino group, an alkylamino group, Examples thereof include a nitro group and a cyano group. Further, in a molecule having an unsaturated bond or the like in the molecule, the unsaturated bond or the like may be reduced depending on the conditions used.

In the present invention, the use of a hydrocarbon solvent is an essential requirement. As hydrocarbon solvents,
There is no particular limitation as long as it is a compound composed of carbon atoms and hydrogen atoms, 2,2-dimethylbutane, 2,3-dimethylbutane, pentane, 2-methylpentane, 3-methylpentane, hexane, 2-methylhexane, 3-methylhexane, heptane, octane, isooctane, nonane,
Hydrocarbon-based solvents having no unsaturated bond such as decane, cyclopentane, cyclohexane, methylcyclohexane, ethylcyclohexane, propylcyclohexane, isopropylcyclohexane, butylcyclohexane and t-butylcyclohexane are economically preferable. Moreover, you may use the mixed solvent which has a hydrocarbon compound as a main component, such as petroleum ether, kerosene, and gasoline. The amount of the solvent used is not particularly limited as long as it can dissolve some or all of the raw materials at the reaction temperature.

In the method of the present invention, the reaction is carried out under heating and hydrogen pressure. The reaction method is not particularly limited, and may be, for example, a batch type or semi-batch type reaction method.

The reaction temperature is usually 50 to 250 ° C, preferably 100 to 200 ° C. If the temperature is higher than this, side reaction products tend to increase, and conversely, if the temperature is lower than this, there is a disadvantage in the reaction rate. The pressure of hydrogen is usually selected from 10 to 150 kg / cm ² G, preferably 20 to 120 kg / cm ² G. Higher pressures are disadvantageous in terms of safety and economy, and lower pressures are disadvantageous because of slow reaction rate.

The reaction time varies depending on how to set the temperature, the pressure, the amount of the catalyst, etc., so that it is difficult to determine the range unconditionally, but in the batch system and the semi-batch system, it is usually 1 to 30 hours, preferably. Is good for 2 to 20 hours. The reaction time may be longer than 30 hours, but within the range, the reaction proceeds sufficiently. On the other hand, if it is less than 1 hour, a high conversion rate may not be obtained.

[0029]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples and Comparative Examples. Example 1

[0030]

Embedded image

In a 10 ml autoclave made of stainless steel, 242 mg (1.00 mmol) of pentadecanoic acid and 1.8 mg (0.00 of hexarodium hexadecacarbonyl) were added.
17 mmol), 3.3 mg of rhenium carbonyl (0.
005 mmol) and 1.0 ml of hexane were charged, and after fully replacing the system with hydrogen, 100 kg / cm ²
Hydrogen was injected under pressure so as to be G. While stirring with heating 14
The temperature was raised to 0 ° C. and the hydrogenation reaction was carried out for 16 hours. After the completion of the reaction, the autoclave was cooled to room temperature, subsequently purged with hydrogen, and the reaction solution was taken out. As a result of analyzing the reaction liquid by gas chromatography, the yield of pentadecanol was 66% based on pentadecanoic acid as a raw material. The results are shown in Table 1.

Example 2 242 mg of pentadecanoic acid (1.00 mmo as a substrate)
l), Example 1 except that 1.8 mg (0.0017 mmol) of hexalodium hexadecacarbonyl as a catalyst, 2.6 mg (0.010 mmol) of molybdenum hexacarbonyl and 1.0 ml of hexane as a solvent were used.
The hydrogenation reaction and analysis were performed in the same manner as in. The results are shown in Table 1.

Example 3 As a substrate, 242 mg of pentadecanoic acid (1.00 mmo)
l), 5% ruthenium / Al ₂ O ₃ 20.2m as catalyst
Hydrogenation reaction and analysis were performed in the same manner as in Example 1 except that g (0.010 mmol), molybdenum hexacarbonyl 2.6 mg (0.010 mmol), and hexane 2.0 ml were used as the solvent. The results are shown in Table 1.

Example 4 242 mg of pentadecanoic acid (1.00 mmo as a substrate)
l), 5% ruthenium / Al ₂ O ₃ 20.2m as catalyst
Hydrogenation reaction and analysis were performed in the same manner as in Example 1 except that g (0.010 mmol), molybdenum hexacarbonyl 2.6 mg (0.010 mmol) and heptane 2.0 ml were used as the solvent. The results are shown in Table 1.

Example 5 Pentadecanoic acid 242 mg (1.00 mmo) as a substrate
l), 5% ruthenium / Al ₂ O ₃ 20.2m as catalyst
Hydrogenation reaction and analysis were performed in the same manner as in Example 1 except that g (0.010 mmol), molybdenum hexacarbonyl 2.6 mg (0.010 mmol), and cyclohexane 2.0 ml were used as the solvent. The results are shown in Table 1.

Comparative Example 1 As a substrate, 242 mg of pentadecanoic acid (1.00 mmo)
l), 1.8 mg (0.0017 mmol) of hexalodium hexadecacarbonyl as a catalyst, 3.3 mg (0.005 mmol) of rhenium carbonyl, and D as a solvent.
The hydrogenation reaction and analysis were performed in the same manner as in Example 1 except that 1.0 ml of ME was used. The results are shown in Table 1.

Comparative Example 2 Pentadecanoic acid 242 mg (1.00 mmo) as a substrate
l), 1.8 mg (0.0017 mmol) of hexalodium hexadecacarbonyl as a catalyst, 2.6 mg (0.010 mmol) of molybdenum hexacarbonyl, and 1.0 ml of DME as a solvent, except that the reaction temperature was 150 ° C. The hydrogenation reaction and analysis were carried out in the same manner as in Example 1. The results are shown in Table 1.

Comparative Example 3 Pentadecanoic acid 242 mg (1.00 mmo) as a substrate
l), 5% ruthenium / Al ₂ O ₃ 20.2m as catalyst
g (0.010 mmol), molybdenum hexacarbonyl 2.6 mg (0.010 mmol), DM as a solvent
The hydrogenation reaction and analysis were performed in the same manner as in Example 1 except that E1.0 ml was used. The results are shown in Table 1.

[0039]

[Table 1]

Example 6

[0041]

Embedded image

In a 10 ml autoclave made of stainless steel, 180 mg of adamantanecarboxylic acid (1.00 mmo)
l), 5% ruthenium / Al ₂ O ₃ 20.2m as catalyst
g (0.010 mmol), molybdenum hexacarbonyl 2.6 mg (0.010 mmol) and hexane 2.0 ml were charged, the system was sufficiently replaced with hydrogen, and then 1
Hydrogen was injected under pressure so that the pressure would be 00 kg / cm ² G. The temperature was raised to 160 ° C. with heating and stirring, and a hydrogenation reaction was carried out for 16 hours. After the completion of the reaction, the autoclave was cooled to room temperature, subsequently purged with hydrogen, and the reaction solution was taken out. As a result of analyzing the reaction liquid by gas chromatography, the yield of adamantanol was 92% based on the adamantanecarboxylic acid as a raw material.

Comparative Example 4 Adamantanecarboxylic acid 180 mg (1.0
0 mmol), ruthenium carbonyl as a catalyst 2.1
mg (0.0033 mmol), molybdenum hexacarbonyl 2.6 mg (0.010 mmol), DME 2.0 ml was used as the solvent, and the hydrogenation reaction and analysis were performed in the same manner as in Example 4 except that the reaction temperature was 170 ° C. went. Table 2 shows the results.

[0044]

[Table 2]

Example 7

[0046]

Embedded image

158 mg of 4-methoxycyclohexanecarboxylic acid was added to a 10 ml stainless steel autoclave.
(1.00 mmol), as a catalyst hexarodium hexadecacarbonyl 1.8 mg (0.0017 mmo
l), rhenium carbonyl 3.3 mg (0.005 mm
Ol) and 2.0 ml of hexane were charged, the system was sufficiently replaced with hydrogen, and then hydrogen was injected under pressure to 100 kg / cm ² G. While heating and stirring, raise the temperature to 150 ° C,
The hydrogenation reaction was carried out for 16 hours. After the completion of the reaction, the autoclave was cooled to room temperature, subsequently purged with hydrogen, and the reaction solution was taken out. As a result of analyzing the reaction liquid by gas chromatography, the yield of (4-methoxycyclohexyl) methanol was 71% based on 4-methoxycyclohexanecarboxylic acid as a raw material.

[0048]

According to the present invention, it has become possible to catalytically hydrogenate carboxylic acids under extremely mild conditions. Therefore, the catalytic hydrogenation reaction can be applied to a thermally unstable substrate, and the usefulness of hydrogenation reduction as an industrial alcohol synthesis method is enhanced.

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[Procedure amendment]

[Submission date] May 22, 1997

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0042

[Correction method] Change

[Correction contents]

In a 10 ml autoclave made of stainless steel, 180 mg of adamantanecarboxylic acid (1.00 mmo)
l), 5% ruthenium / Al ₂ O ₃ 20.2m as catalyst
g (0.010 mmol), molybdenum hexacarbonyl 2.6 mg (0.010 mmol) and hexane 2.0 ml were charged, the system was sufficiently replaced with hydrogen, and then 1
Hydrogen was injected under pressure so that the pressure would be 00 kg / cm ² G. The temperature was raised to 160 ° C. with heating and stirring, and a hydrogenation reaction was carried out for 16 hours. After the completion of the reaction, the autoclave was cooled to room temperature, subsequently purged with hydrogen, and the reaction solution was taken out. The reaction gas chromatography - was analyzed by the yield rate of Ada <br/> manta Nmeta Nord was 92% relative to adamantane carboxylic acid of the raw material.

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0044

[Correction method] Change

[Correction contents]

[0044]

[Table 2]

Claims (4)

[Claims] 1. Hydrogenation of a carboxylic acid in a hydrocarbon solvent in the presence of a catalyst comprising at least one element selected from Group VIII elements of the periodic table and at least one element selected from Group VIb or Group VIIb. A method for producing alcohols, which comprises redox. 2. The method according to claim 1, wherein the elements of Group VIII of the periodic table are rhodium, ruthenium and palladium. 3. The element of Group VIb of the periodic table is molybdenum,
The manufacturing method according to claim 1, wherein the manufacturing method is tungsten. 4. The method according to claim 1, wherein the element of Group VIIb of the periodic table is rhenium.