JP2509718B2 - Hydrogenation catalyst - Google Patents

Description

TECHNICAL FIELD The present invention relates to a catalyst useful for hydrogenation reaction.

[Prior art]

Conventionally, many compounds that catalyze hydrogenation reactions are known [New Experimental Science Course 15 Oxidation and Reduction (II) Maruzen (19
77)]. These catalysts are roughly classified into homogeneous catalysts and heterogeneous catalysts according to their operating states.

Among them, the heterogeneous hydrogenation catalyst is generally used in a gaseous state as a reaction substrate, and therefore, the substrate that can be used is limited. Further, since it requires a high reaction temperature, it has a drawback that the reaction substrate is easily decomposed to give a by-product. Further, the heterogeneous hydrogenation catalyst has a drawback that it has lower selectivity than the homogeneous hydrogenation catalyst.

On the other hand, as homogeneous hydrogenation catalysts, Group VIII transition metal catalysts including rhodium, platinum and ruthenium are well known, but these metals are extremely expensive and economically disadvantageous.

Further, the above-mentioned catalyst has a drawback that not only hydrogenation but also hydrogenolysis such as carbon-halogen bond is involved.

In order to solve these drawbacks, Group VIB complexes of chromium, molybdenum, or tungsten, such as arene chromium tricarbonyl and bis (tricarbonylcyclopentadienyl chromium), have been developed. The complex is not only active for hydrogenation of the disene diene or acetylene, but also has the disadvantage that it has a low catalytic activity and requires a large amount of catalyst, and that the reaction must be carried out at high temperature and high pressure, and is adopted industrially. However, there is a great deal of difficulty [see the reference example below].

[Problems to be Solved by the Invention]

An object of the present invention is to provide an inexpensive industrial catalyst that can overcome many of the above-mentioned drawbacks of conventional catalysts.

[Means for solving the problem]

The present invention has the following general formula A ⁺ [M ₂ H (CO) ₁₀ ] ^- (I) (In the formula, A ⁺ represents an alkali metal cation, an ammonium cation, an iminium cation or a phosphonium cation, and M is a chromium atom. , A molybdenum atom or a tungsten atom).

Examples of the compound which can be hydrogenated in the present invention include carbon-oxygen double bonds such as aldehydes and ketones, carbon-carbon double bonds such as alkenes, dienes and polyenes, alkynes,
Carbon-carbon triple bond of diynes and polyynes, carbon-nitrogen double bond of imines and oximes, carbon of nitriles-
The compound which has a nitrogen triple bond etc. can be illustrated. In the present invention, when there are a plurality of unsaturated bonds which may be different in the same molecule, generally some or all of the unsaturated bonds are hydrogenated,
In some cases, these can be controlled by the reaction temperature, the reaction time and the amount of catalyst.

The complex represented by the general formula (I) of the present invention can be produced by a known method [eg, RJ Hayter, JA
m. Chem. Soc., 88 , 4376 (1966)]. From the viewpoint of reaction efficiency and yield, the ammonium cation is preferably a quaternary ammonium cation, the iminium cation is preferably a diphosphine iminium cation, and the phosphonium cation is preferably a quaternary phosphonium cation. . Although the amount of the catalyst used varies depending on the type and number of unsaturated bonds to be hydrogenated, it is usually possible to select a range of 1/5000 to 1/2 equivalent to the unsaturated bonds to be hydrogenated. In addition, a so-called catalytic amount of tertiary phosphine or acid may be added for the purpose of controlling the catalytic activity and asymmetric hydrogenation. It is known that when a tertiary phosphine is added, a part of the ligand is exchanged, and therefore it may be prepared and used separately.

The hydrogenation reaction using the catalyst of the present invention is usually carried out in a solvent, and a solvent that does not participate in the reaction can be preferably used, but ether, tetrahydrofuran, dimethoxyethane, dioxane, etc. can be used in terms of reaction rate and yield. The use of polar solvents of is preferred.

Further, hydrogenation is carried out in the presence of hydrogen, and the reaction may be carried out under hydrogen pressure to accelerate the reaction.

The reaction temperature is 0 ° C to 150 ° C, but it is preferably room temperature to 130 ° C from the viewpoint of reaction efficiency, economy, safety and the like.

Hereinafter, the present invention will be described in more detail with reference to Examples, Reference Examples and Comparative Examples.

Reference Example 1 Synthesis of tetraethylammonium μ-hydride-bis (pentacarbonylchromium (0)) Chromium hexacarbonyl (2.0g, 9.08mmol) and sodium borohydride (0.20g, 5.28mmol) in THF (1
(0 ml) was refluxed for 18 hours under an argon atmosphere. The reaction mixture was filtered through Celite, the solvent was evaporated under reduced pressure, and the orange-
A red oily substance was obtained. Ethanol (40 ml) was added, and tetraethylammonium bromide (0.96 g, 4.56 mm) was added.
ol) in ethanol (10 ml) was added. Immediately, yellow crystals began to precipitate. It was left overnight in the refrigerator in order to precipitate crystals completely. The precipitated solid is filtered,
After washing with ethanol and vacuum drying, yellow columnar crystals were obtained (1.6 g, 70%).

Decomposition start temperature 74-76 ℃.

IR (KBr-disk): ν c≡o 2040cm -1 1923cm -1 1865cm -1 1 H-NMR ( acetone _{-d 6): - 19.46 (s} ) Cr-H-Cr
_{1H 1.27 (t) -CH 3 12H} 3.32 (q) -CH 2 - 8H molybdenum complexes also tungsten complex was synthesized in the same manner as described above. However, the reaction time was 4 hours for the molybdenum complex and 18 hours for the tungsten complex. The light green columnar crystals (1.8g, 77%) and the yellow columnar crystals (1.3g, 69%) were used.
%) Was obtained.

Molybdenum complexes decomposition temperature 89-91 ℃ IR (KBr-disk) : ν c≡o 2050cm -1 1922cm -1 1865cm -1 1 H-NMR ( acetone _{-d 6): - 12.15 (S} ) Mo-H-Mo 1
_{H 1.43 (t) -CH 3 12H} 3.52 (q) - CH 2 -8H tungsten complex decomposition temperature 91-93 ℃ IR (KBr-disk) : ν c≡o 2050cm -1 1920cm -1 1865cm -1 1 H- NMR (acetone _{-d 6): - 12.53 (s} ) W-H-W 1H 1.40 (t) -CH 3 12H 3.47 (q) -CH 2 - 8H reference example 2 tetrabutylammonium μ- hydrido - bis (pentacarbonyl Chromium (0)) synthesis It was synthesized in the same manner as in Reference Example 1. A solution of chromium hexacarbonyl (1.0 g, 4.54 mmol) and sodium borohydride (0.10 g, 2.64 mmol) in THF (5.0 ml) was refluxed for 18 hours under an argon atmosphere. The reaction mixture was filtered through Celite, and the solvent was evaporated under reduced pressure to give an orange-red oily substance. Ethanol (20 ml) was added, and further an ethanol solution (5.0 ml) of tetrabutylammonium bromide (0.73 g, 2.27 mmol) was added. After standing overnight, the solvent was distilled off and the residue was purified by column chromatography (filler silica gel, developing solvent chloroform) to give yellow columnar crystals (0.55
g, 42%). This substance gradually decomposes in air at room temperature.

IR (KBr-disk): ν c≡o 1965cm -1 1920cm -1 1875cm -1 1 H-NMR ( chloroform -d): - 19.23 (s) Cr-H
_{-Cr 1H 0.13-2.41 (m) -CH 2} CH 2 CH 3 28H 3.71 (q) N-CH 28H Further, instead bis tetrabutylammonium bromide (triphenylphosphine) iminium chloride (1.30 mg, 2.27 mmol) was used to synthesize a bistriphenylphosphiniminium complex to obtain orange columnar crystals (1.42 g, 75%).

IR (KBr-disk): ν c≡o 1970cm -1 1940cm -1 1880cm -1 1 H-NMR ( chloroform -d): - 19.37 (S) Cr-H
-Cr 1H 7.01-7.91 (m) -C ₆ H ₅ 20H Example 1 PhCHO → PhCH ₂ OH Benzaldehyde (1.0 mmol), tetraethylammonium μ-hydrido-bis (pentacarbonylchromium (0)) (0.01 mmol) and dimethoxy. Ethane (DME)
(1.0 ml) in an autoclave under hydrogen pressure (50 at)
m), heated and stirred at 100 ° C. for 5 hours. GL of reaction mixture
As a result of C analysis, benzyl alcohol was produced in a yield of 98%.

Example 2-18 In the same manner as in Example 1, the reaction was carried out using various benzaldehydes and catalysts. Table 1 shows the type and amount of benzaldehydes, the type and amount of catalysts, the reaction temperature, the reaction time, and the yield in each reaction.

Comparative Example 1 Benzaldehyde (1.0 mmol), chromium hexacarbonyl (0.02 mmol) and dimethoxyethane (DME) (1.
0 ml) in an autoclave under hydrogen pressure (50 atm),
The mixture was heated and stirred at 100 ° C for 13 hours. As a result of GLC analysis of the reaction mixture, formation of benzyl alcohol was not observed.

Comparative Example 2 Benzaldehyde (1.0 mmol), benzenechromium tricarbonyl (0.02 mmol) and dimethoxyethane (DM
E) (1.0 ml) in an autoclave under hydrogen pressure (50
The mixture was heated and stirred at 100 ° C. for 13 hours. GLC of reaction mixture
As a result of the analysis, formation of benzyl alcohol was not observed.

Example 19 nC ₇ H ₁₅ CHO → nC ₇ H ₁₅ OH n-octyl aldehyde (1.0 mmol) and tetraethylammonium μ-hydridobis (pentacarbonylchromium (0)) (0.01 mmol) in DME (1.0 ml) with hydrogen. The mixture was heated and stirred at 100 ° C. for 13 hours under pressure (50 atm). GLC analysis of the reaction mixture showed that n-octyl alcohol was 100%.
It was produced in a yield of%.

Example 20 PhCH ₂ CH ₂ CHO → PhCH ₂ CH ₂ CH ₂ OH 3-phenylpropanal (1.0 mmol) and tetraethylammonium μ-hydridobisbis (pentacarbonylchromium (0)) (0.01 mmol) in DME (1.0 ml). so,
The mixture was heated and stirred at 100 ° C. for 13 hours under hydrogen pressure (50 atm). As a result of GLC analysis of the reaction mixture, 3-phenylpropanol was produced in a yield of 100%.

Example 21 PhCH = CHCHO → PhCH = CHCH ₂ OH + PhCH ₂ CH ₂ CH ₂ OH Cinnamic aldehyde (1.0 mmol) and tetraethylammonium μ-hydridobis (pentacarbonylchromium (0)) (0.02 mmol) in DME (1.0 ml). Then, the mixture was heated and stirred at 100 ° C. for 13 hours under hydrogen pressure (50 atm). As a result of GLC analysis of the reaction mixture, cinnamic alcohol was produced in a yield of 87% and 3-phenylpropanol was produced in a yield of 13%.

Comparative Example 3 Cinnamaldehyde (1.0 mmol) and benzenechromium tricarbonyl (0.02 mmol) were heated and stirred in DME (1.0 ml) under hydrogen pressure (50 atm) at 100 ° C. for 13 hours. As a result of GLC analysis of the reaction mixture, formation of cinnamic alcohol and 3-phenylpropanol was not observed.

Example 22 PhCH = CHCHO → PhCH = CHCH ₂ OH + PhCH ₂ CH ₂ CH ₂ OH Cinnamaldehyde (1.0 mmol), tetraethylammonium μ-hydride-bis (pentacarbonylchromium (0)) (0.02 mmol), and cinnamic acid (0.03 mmol)
The mixture was heated and stirred in DME (1.0 ml) under hydrogen pressure (50 atm) at 100 ° C. for 13 hours.

GLC analysis of the reaction mixture showed that cinnamon alcohol was 65%.
% And 3-phenylpropanol were produced in a yield of 35%.

Example 23 1,4-Cyclohexanedione (1.0 mmol) and tetraethylammonium μ-hydrido-bis (pentacarbonylchromium (0)) (0.01 mmol) in DME (1.0 ml) under hydrogen pressure (50 atm) at 100 ° C. Stirred for hours. As a result of GLC analysis of the reaction mixture, 1,4-cyclohexanediol was produced in a yield of 100%.

Comparative Example 4 1,4-cyclohexanedione (1.0 mmol) and benzenerochromium tricarbonyl (0.02 mmol) were added to DME (1.0
ml) under hydrogen pressure (50 atm) at 100 ° C. for 60 hours with stirring. As a result of GLC analysis of the reaction mixture, 1,4-cyclohexanediol was produced in a yield of 100%.

Example 24 Methylbenzoyl formate (1.0 mmol) and tetraethylammonium μ-hydrido-bis (pentacarbonylchromium (0)) (0.01 mmol) were heated in DME (1.0 ml) under hydrogen pressure (50 atm) at 100 ° C for 60 hours. I stirred it. As a result of GLC analysis of the reaction mixture, methyl 1-hydroxy-1-phenylate was produced in a yield of 91%.

Example 25 Methyl pyruvate (0.1 mmol) and tetraethylammonium μ-hydrido-bis (pentacarbonylchromium (0)) (0.01 mmol) were heated and stirred in DME (1.0 ml) under hydrogen pressure (50 atm) at 100 ° C. for 60 hours. did. As a result of GLC analysis of the reaction mixture, methyl butyrate was produced in a yield of 82%.

Example 26 Ketopantoyl lactone (1.0 mmol) and tetraethylammonium μ-hydrido-bis (pentacarbonylchromium (0)) (0.01 mmol) were heated in DME (1.0 ml) under hydrogen pressure (50 atm) at 100 ° C for 13 hours. I stirred it.
As a result of GLC analysis of the reaction mixture, pantolactone was produced in a yield of 52%.

Comparative Example 5 Ketopantoyl lactone (1.0 mmol) and benzenechromium tricarbonyl (0.02 mmol) were heated and stirred in DME (1.0 ml) under hydrogen pressure (50 atm) at 100 ° C. for 13 hours. As a result of GLC analysis of the reaction mixture, formation of pantolactone was not observed.

Example 27 Ketopantoyl lactone (1.0 mmol) and tetraethylammonium μ-hydridobis (pentacarbonylchromium (0)) (0.01 mmol) were heated and stirred in DME (1.0 ml) under hydrogen pressure (50 atm) at 100 ° C. for 60 hours. .
As a result of GLC analysis of the reaction mixture, pantolactone was produced in a yield of 99%.

Example 28 Ketopantoyl lactone (1.0 mmol), tetraethylammonium μ-hydrido-bis (pentacarbonylchromium (0)) (0.01 mmol), and (−)-2,3-
O-isopropylidene-2,3-dihydroxy-1,4
-Bis (diphenylphosphino) butane [(-)-DIO
P)] (0.01 mmol) in DME (1.0 ml) under hydrogen pressure (5
The mixture was heated and stirred at 100 ° C. for 60 hours. As a result of GLC analysis of the reaction mixture, pantolactone was produced in a yield of 99%.

Example 29 2,3-Dimethylbutadiene (1.0 mmol) and tetraethylammonium μ-hydridobis (pentacarbonylchromium (0)) (0.01 mmol) were heated in DME (1.0 ml) under hydrogen pressure (50 atm) at 100 ° C. for 60 hours. I stirred it. As a result of GLC analysis of the reaction mixture, 2,3-dimethyl-2-butene was produced in a yield of 60%.

Example 30 Myrcene (1.0 mmol) and tetraethylammonium μ
-Hydride-bis (pentacarbonylchromium (0)) (0.01 mmol) was heated and stirred in DME (1.0 ml) under hydrogen pressure (50 atm) at 100 ° C for 60 hours. As a result of GLC analysis of the reaction mixture, 2,6-dimethyl-2,6-octadiene was produced in a yield of 100%.

Comparative Example 6 Myrcene (1.0 mmol) and benzenechromium tricarbonyl (0.01 mmol) were heated and stirred in DME (1.0 ml) under hydrogen pressure (50 atm) at 100 ° C. for 60 hours. As a result of GLC analysis of the reaction mixture, formation of 2,6-dimethyl-2,6-octadiene was not observed.

Example 31 Styrene (1.0 mmol) and tetraethylammonium μ
-Hydride-bis (pentacarbonylchromium (0)) (0.01 mmol) was heated and stirred in DME (1.0 ml) under hydrogen pressure (50 atm) at 100 ° C for 84 hours. As a result of GLC analysis of the reaction mixture, ethylbenzene was produced in a yield of 80%.

Example 32 Styrene (1.0 mmol) and tetraethylammonium μ
-Hydride-bis (pentacarbonylchromium (0)) (0.01 mmol) was heated and stirred in DME (1.0 ml) under hydrogen pressure (50 atm) at 100 ° C for 13 hours. As a result of GLC analysis of the reaction mixture, ethylbenzene was produced in a yield of 29%.

Example 33 Styrene (1.0 mmol) and tetrabutylammonium μ
-Hydride-bis (pentacarbonylchromium (0)) (0.01 mmol) was heated and stirred in DME (1.0 ml) under hydrogen pressure (50 atm) at 100 ° C for 13 hours. As a result of GLC analysis of the reaction mixture, ethylbenzene was produced in a yield of 44%.

Example 34 Styrene (1.0 mmol) and bis (triphenylphosphine) iminium μ-hydrido-bis (pentacarbonylchromium (0)) (0.01 mmol) in DME (1.0 ml)
The mixture was heated and stirred at 100 ° C. for 13 hours under hydrogen pressure (50 atm). GLC analysis of the reaction mixture showed 42% ethylbenzene.
It was produced in a yield of%.

Comparative Example 7 Styrene (1.0 mmol) and benzenechromium tricarbonyl (0.01 mmol) were heated and stirred in DME (1.0 ml) under hydrogen pressure (50 atm) at 100 ° C. for 13 hours. As a result of GLC analysis of the reaction mixture, production of ethylbenzene was not observed.

Example 35 2-Cyclohexen-1-one (1.0 mmol) and tetraethylammonium μ-hydridobis (pentalbornylchromium (0)) (0.01 mmol) in DME (1.0 ml) under hydrogen pressure (50 atm) at 100 ° C. for 13 hours. Heated and stirred. As a result of GLC analysis of the reaction mixture, cyclohexanone was produced in a yield of 75%.

Example 36 Citric acid alcohol (1.0 mmol) and tetraethylammonium μ-hydrido-bis (pentacarbonylchromium (0)) (0.01 mmol) in DME (1.0 ml) under hydrogen pressure (50 atm) and stirring at 100 ° C. for 60 hours. did. GLC analysis of the reaction mixture showed that 3-phenylpropanol was 100%.
It was produced in a yield of%.

Example 37 4-Methyl-3-penten-2-one (1.0 mmol) and tetraethylammonium μ-hydrido-bis (pentacarbonylchromium (0)) (0.01 mmol) were added to DME (1.0 mmol).
ml) under hydrogen pressure (50 atm) at 100 ° C. for 13 hours. As a result of GLC analysis of the reaction mixture, 4-methyl-2-pentanone was produced in a yield of 60%.

Example 38 Benzalacetone (1.0 mmol) and tetraethylammonium μ-hydrido-bis (pentacarbonylchromium (0)) (0.01 mmol) were heated and stirred in DME (1.0 ml) under hydrogen pressure (50 atm) at 100 ° C. for 13 hours. did. As a result of GLC analysis of the reaction mixture, 4-phenyl-2-butanone was found to be 8
It was produced in a yield of 2%.

Example 39 β-phenyl-α-acetylaminoacrylic acid (1.0m
mol) and tetraethylammonium μ-hydrido-bis (pentacarbonylchromium (0)) (0.01 mmol)
The mixture was heated and stirred in DME (1.0 ml) under hydrogen pressure (50 atm) at 100 ° C. for 60 hours. As a result of ¹ H-NMR measurement after treating the reaction mixture with an ion exchange resin, N-acetylphenylalanine was produced in a yield of 50%.

Example 40 α-Acetylaminoacrylic acid (1.0 mmol) and tetraethylammonium μ-hydrido-bis (pentacarbonylchromium (0)) (0.01 mmol) in DME (1.0 ml) under hydrogen pressure (50 atm) at 100 ° C. Stirred for hours. ¹ HN after treating the reaction mixture with ion exchange resin
As a result of MR measurement, N-acetylalanine was produced in a yield of 100%.

Example 41 β-phenyl-α-acetylaminoacrylic acid (1.0m
mol), tetraethylammonium μ-hydride-bis (pentacarbonylchromium (0)) (0.01 mmol),
And (-)-2,3-O-isopropylidene-2,3-
Dihydroxy-1,4-bis (diphenylphosphino)
Butane [(−)-DIOP) (0.01 mmol) was heated and stirred in DME (1.0 ml) under hydrogen pressure (50 atm) at 100 ° C. for 72 hours. ¹ H NMR after treating the reaction mixture with an ion exchange resin
As a result of the measurement, N-acetylphenylalanine was produced in a yield of 57%. Optical purity 13.0% ee Example 42 α-Acetylaminoacrylic acid (1.0 mmol), tetraethylammonium μ-hydrido-bis (pentacarbonylchromium (0)) (0.01 mmol), and (−)-
2,3-O-isopropylidene-2,3-dihydroxy-1,4-bis (diphenylphosphino) butane [(-)-DIOP) (0.01 mmol) in DME (1.0 ml) under hydrogen pressure ( The mixture was heated and stirred at 100 ° C. for 72 hours.
As a result of ¹ H NMR measurement after treating the reaction mixture with an ion exchange resin, N-acetylalanine was produced in a yield of 96%. Optical purity 6.8% ee Example 43 Vinyldiphenylphosphine oxide (1.0 mmol) and tetraethylammonium μ-hydrido-bis (pentacarbonylchromium (0)) (0.01 mmol) were added to DME (1.0 mmol).
ml) under hydrogen pressure (50 atm) at 100 ° C. for 13 hours. As a result of GLC analysis of the reaction mixture, ethyldiphenylphosphine oxide was produced in a yield of 100%.

Example 44 2-octyne (1.0 mmol) and tetraethylammonium μ-hydrido-bis (pentacarbonylchromium (0)) (0.01 mmol) were heated and stirred in DME (1.0 ml) under hydrogen pressure (50 atm) at 100 ° C for 48 hours. did. As a result of GLC analysis of the reaction mixture, octane was produced in a yield of 100%.

Example _{45 PhC≡CCH 3 → PhCH 2 CH 2} CH 3 + PhCH = CHCH 3 1- phenyl-1-propyne (1.0 mmol) and tetraethylammonium μ- hydride - bis (pentacarbonyl chromium (0)) (0.01 mmol) The mixture was heated and stirred in DME (1.0 ml) under hydrogen pressure (50 atm) at 100 ° C. for 18 hours. As a result of GLC analysis of the reaction mixture, propylbenzene was produced in a yield of 79% and β-methylstyrene was produced in a yield of 19%.

Comparative Example 8 1-Phenyl-1-propyne (1.0 mmol) and benzenechromium tricarbonyl (0.02 mmol) were added to DME (1.0 ml).
Then, the mixture was heated and stirred at 100 ° C. for 60 hours under hydrogen pressure (50 atm). As a result of GLC analysis of the reaction mixture, β-methylstyrene was produced in a yield of 27%.

Example _{46 PhC≡CCH 3 → PhCH 2 CH 2} CH 3 + PhCH = CHCH 3 1- phenyl-1-propyne (1.0 mmol) and tetraethylammonium μ- hydride - bis (pentacarbonyl chromium (0)) (0.01 mmol) The mixture was heated and stirred in DME (1.0 ml) under hydrogen pressure (5 atm) at 100 ° C for 13 hours. As a result of GLC analysis of the reaction mixture, 46% of propylbenzene and 10% of β-methylstyrene were formed.

Example _{47 PhC≡CCH 3 → PhCH 2 CH 2} CH 3 + PhCH = CHCH 3 1- phenyl-1-propyne (1.0 mmol) and tetraethylammonium μ- hydride - bis (pentacarbonyl chromium (0)) (0.01 mmol) The mixture was heated and stirred in DME (1.0 ml) under hydrogen pressure (15 atm) at 100 ° C for 13 hours. As a result of GLC analysis of the reaction mixture, 82% of propylbenzene and 11% of β-methylstyrene were formed.

Example 48 Benzylideneaniline (1.0 mmol) and tetraethylammonium μ-hydrido-bis (pentacarbonylchromium (0)) (0.01 mmol) were heated and stirred in DME (1.0 ml) under hydrogen pressure (50 atm) at 100 ° C. for 60 hours. . GLC analysis of the reaction mixture showed 5 phenylbenzylamine.
It was produced in a yield of 8%.

Example 49 PhCN → PhCH ₂ NH ₂ benzonitrile (1.0 mmol) and tetraethylammonium μ-hydrido-bis (pentacarbonylchromium (0)) (0.05 mmol) in DME (1.0 ml) under hydrogen pressure (50 atm). The mixture was heated and stirred at 120 ° C for 60 hours. As a result of GLC analysis of the reaction mixture, benzylamine was produced in a yield of 10%.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location C07C 5/13 9546-4H C07C 5/13 9/00 9/00 11/02 11/02 15 / 02 15/02 29/141 9155-4H 29/141 31/125 9155-4H 31/125 31/20 9155-4H 31/20 33/22 9155-4H 33/22 33/32 9155-4H 33/32 35 / 08 9155-4H 35/08 45/61 9049-4H 45/61 49/04 9049-4H 49/04 E 49/213 9049-4H 49/213 49/403 9049-4H 49/403 E 69/732 9546 -4H 69/732 Z 233/47 9547-4H 233/47 C07F 9/53 9450-4H C07F 9/53 11/00 9450-4H 11/00 // C07B 61/00 300 C07B 61/00 300 C07C 211 / 62 8517-4H C07C 211/62

Claims (1)

(57) [Claims] 1. A hydrogenation catalyst comprising a complex represented by the general formula A ⁺ [M ₂ H (CO) ₁₀ ] ^- (wherein A ⁺ is an alkali metal cation, ammonium cation, iminium cation or phosphor). Represents a aluminum cation, and M represents a chromium atom, a molybdenum atom or a tungsten atom).