JPH0656704A - Method for hydroformylating unsaturated compound - Google Patents

Abstract

PURPOSE:To simplify the separation and recovery of a catalyst and a product and highly selectively obtain an aldehyde which is the objective substance under mild reactional conditions. CONSTITUTION:The method for hydroformylating an unsaturated compound is characterized in that an unsaturated compound, carbon monoxide and hydrogen are used to carry out the hydroformylation in the presence of a catalyst; the catalyst is fixed cluster complex in which an oxide of at least one metal selected from the group consisting of groups II, III and IV of the periodic table is modified with phosphine through ether bond and a cluster complex of at least one metal selected from the group consisting of cobalt and rhodium is chemically fixed at the phosphine site and the unsaturated compound is an olefinic compound having a substituent group, a 11C or more C olefinic compound having no substituent group and an unsaturated compound having a functional group.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for hydroformylating unsaturated compounds.

[0002]

2. Description of the Related Art As a method for synthesizing aldehydes from unsaturated compounds, carbon monoxide and hydrogen (hydroformylation method), for example, the oxo synthesis method described below has been industrialized. (1) Using an organometallic compound composed of an iron carbonyl compound or a cobalt carbonyl compound and a basic compound (for example, an alkylphosphine, an arylphosphine, a nitrogen-containing compound, etc.), about 1
A homogeneous oxo synthesis method in which the reaction is performed at 25 to 200 atm and about 150 to 250 ° C., (2) Rhodium carbonyl complex (general structural formula Rh (CO) _4-x (PR ₃ ) _x , x is an integer of 1 to 4, R is Is an alkyl or aryl group),
It is a homogeneous oxo synthesis method in which the reaction is carried out at about 150 atm and about 50 to 200 ° C.

However, since all of the above methods are homogeneous reactions, it is difficult to separate the catalyst, the product, and the unreacted raw materials from each other, and a high-pressure high-temperature reaction requires an expensive reactor. In addition, there are disadvantages in process operation, such as an increase in power costs for compressing and circulating the reaction gas.

Therefore, in particular, the metal complex catalyst is supported on an inorganic solid, an organic polymer or the like in order to simplify the catalyst separation / recovery process or improve the selectivity of the hydroformylation reaction.
Various attempts have been made to immobilize a heterogeneous catalyst. For example, (1) a heterogeneous hydroformylation method using a catalyst obtained by impregnating a metal oxide in the form of a complex with rhodium or cobalt metal species and then heat-treating the same in an inert atmosphere or a hydrogen gas atmosphere; ) A heterogeneous hydroformylation method using a catalyst obtained by substituting and fixing a rhodium-based organometallic complex on an insoluble polymer having a basic group.

It is clear that the metal species active in the hydroformylation reaction can be immobilized on the carrier by these methods, but all of them still have problems. That is, in the method (1), although a catalyst having an effective hydroformylation activity can be obtained under mild reaction conditions, a hydrogenation reaction of a carbon-carbon double bond portion or a hydrogenation reaction of an aldehyde as a hydroformylation reaction product, etc. Occurs, and the selectivity of the target aldehyde is insufficient. Further, according to the method (2), effective outflow of the metal catalyst can be prevented and the catalyst and the product can be easily separated, but they cannot be sufficiently insolubilized. Further, the catalytic activity is extremely small under the gas phase condition, the activity is lower than that under the homogeneous hydroformylation catalyst even under the liquid phase condition, and the selectivity is not sufficient. Furthermore, the functional polymer is expensive as a carrier, and has the drawbacks of low chemical and thermal stability.

[0006]

An object of the present invention is to solve the problem in hydroformylating an unsaturated compound using the immobilized metal complex catalyst obtained by the above conventional method. That is, the use of a heterogeneous catalyst simplifies the separation and recovery of the catalyst and the product, and is capable of highly selectively obtaining the target aldehyde under mild reaction conditions. It is to provide a hydroformylation method.

In view of the above problems of the prior art, the present inventor has
An intensive study was conducted on the immobilization method of the metal cluster complex in the catalyst used and the hydroformylation reaction conditions. As a result, surprisingly, when the reaction was carried out using a solid catalyst (heterogeneous catalyst) formed by immobilizing a metal cluster complex on a metal oxide carrier through a specific ligand, the above object was achieved. I got the knowledge that I can. The present invention has been completed based on this new finding.

That is, according to the present invention, in the hydroformylation using an unsaturated compound, carbon monoxide and hydrogen in the presence of a catalyst, the catalyst is a group consisting of Group II, Group III and Group IV of the periodic table. An oxide of at least one metal selected from phosphine is modified via an ether bond, and a cluster complex of at least one metal selected from the group consisting of cobalt and rhodium is chemically immobilized on the phosphine site. And the unsaturated compound is an olefinic compound having a substituent, an olefinic compound having a carbon number of 11 or more, which does not have a substituent, and an olefinic compound having a functional group. And a method for hydroformylating the unsaturated compound, wherein

The catalyst used in the present invention is mainly composed of three components which are a support, a metal oxide, a phosphine and a metal cluster complex.

Among the above components, the metal oxides include Group II metal oxides such as zinc oxide and magnesium oxide; Group II metal oxides such as aluminum oxide, lanthanum oxide and cerium oxide.
Examples thereof include Group I metal oxides and Group IV metal oxides such as titanium oxide, zirconium oxide, thorium oxide and silica. The physical and chemical properties of the oxide are not particularly limited, but from the viewpoint of catalytic performance, it is sufficient that the oxide has a surface area and a pore volume that are similar to those of a generally used ordinary catalyst carrier. . For example, the surface area is preferably about 5 to 1000 m ² / g, and the pore volume is preferably about 0 to 5 cc / g. Further, the oxide preferably has a surface hydroxyl group effective for phosphine modification. The shape of the oxide may be a usual one such as powder, pellet, sphere, and extrusion molded product, and the size of the carrier is preferably about 0.1 μm to 6 mm, but is not particularly limited. It is desirable that the oxide as a carrier be heated and exhausted to remove water and adsorbed gas adsorbed on the surface of the oxide before being modified with phosphine. The heating temperature is not particularly limited, but is generally between about 100 ° C and about 800 ° C. If the temperature is lower than 100 ° C, dehydration tends to be insufficient, and if the temperature is higher than 800 ° C, the amount of hydroxyl groups on the oxide surface decreases, and the number of reactive surface hydroxyl groups involved in the subsequent phosphine immobilization reaction decreases. Both of them are not preferable because they tend to occur. It is generally said that the water physically adsorbed on the oxide can be removed by heating at 200 ° C. or higher.

The phosphine used in the present invention is not particularly limited, but it is required that the oxide surface can be modified by an ether bond. More specifically, it is necessary to have at least one hydroxyl group in the phosphine molecule from the viewpoint of forming an ether bond by a dehydration condensation reaction with the hydroxyl group on the surface of the carrier oxide to be immobilized. Specific examples of such a phosphine include, for example, tris (hydroxymethyl) phosphine [P (CH ₂ OH)
₃ , hereinafter referred to as THP], tris (hydroxyphenyl) phosphine [P (C ₆ H ₄ OH) ₃ ] and the like.

The amount of phosphine added to the carrier oxide is not particularly limited, but is usually about 0.01-40% by weight, preferably about 0.1-2, relative to the total weight of the catalyst.
It is set to 0% by weight. If it is less than 0.01% by weight, the effect of adding phosphine is not sufficiently exhibited, which is not preferable. That is, the metal cluster complex described below directly reacts with the surface of the carrier oxide, and the cluster structure is likely to change, which is not preferable. On the other hand, if it exceeds 40% by weight, the reaction between the phosphine and the oxide surface becomes insufficient and immobilization of phosphine may not be completed, which is not preferable.

The method for immobilizing the phosphine on the surface of the oxide carrier is not particularly limited. For example, it can be carried out by impregnating or adsorbing phosphine on an oxide carrier in the presence of an organic solvent, and then performing heat treatment to ether bond the phosphine on the oxide carrier. More specifically, phosphine is dissolved in an anhydrous organic solvent, stirred with an oxide carrier at room temperature, and then the solvent is distilled off or filtered to impregnate or adsorb the phosphine, and then usually heated and exhausted to form an oxide carrier surface. It is preferably achieved by dehydrating and condensing the hydroxyl group of 1 and the hydroxyl group of phosphine to form an ether bond. The organic solvent used satisfies the two requirements of dissolving phosphine having a hydroxyl group and not reacting with the hydroxyl group on the oxide surface, such as methanol, ethanol, propanol, isopropanol, butanol, acetone, tetrahydrofuran and benzene. In general, the above anhydrous solvent is suitable, and anhydrous solvents such as ethanol, propanol, and isopropanol are preferable from the aspect of the embodiment. When an organic solvent mixed with water is used, water reacts with the oxide surface hydroxyl group before phosphine, and the dehydration condensation reaction between phosphine and the oxide surface hydroxyl group is substantially inhibited and immobilization is sufficient. Is not achieved.
In addition, since phosphine having a hydroxyl group generally has high hygroscopicity in the immobilization reaction, it is desirable to handle it in sufficiently dry air or an inert gas such as nitrogen.

In the above-mentioned immobilization reaction, heat treatment is performed because the dehydration condensation reaction between the hydroxyl group on the oxide surface and the hydroxyl group on phosphine proceeds, and the reaction product water is distilled out of the system to react chemically equilibrium. This is because it is possible to promote the adsorption and to prevent the generated water from being adsorbed on the oxide surface. Here, the heating temperature is usually preferably about 200 ° C. or lower, and 70 to 15
About 0 ° C. is more preferable. This is because if heating is performed at more than 200 ° C, decomposition of phosphine tends to start to occur. The heat treatment time is not particularly limited, but it is good enough to complete the reaction between the hydroxyl group on the oxide surface and the hydroxyl group on the phosphine, and usually about 1 to 5 hours is appropriate. . The end point of the reaction can be determined by IR spectrum. That is, when the phosphine is stirred with an oxide carrier in an organic solvent at room temperature and then the solvent is distilled off, stretching vibration absorption of the hydroxyl groups present in the phosphine and the oxide is largely observed at 3000 to 3800 cm ^-1 , This is because the dehydration condensation reaction between the hydroxyl groups progresses by the heat treatment and this absorption intensity decreases, and the reaction end point can be easily recognized as the time when this IR absorption change disappears. By this immobilization reaction, a phosphine-modified metal oxide in which the oxide support is modified with phosphine through an ether bond is prepared.

Cobalt used in the catalyst of the present invention
And at least one selected from the group consisting of rhodium
The metal cluster complex is not particularly limited,
For example Rh_Four(CO)₁₂, Rh₆(CO)₁₆, Rh₃C
P₂(CO)₃, Rh₃CP₃(CO)₃(In each formula, C
P is a cyclopentadienyl group), Co₂(CO)
₈, Co_Four(CO)₁₂, Co₆(CO)₁₆Represented by
Rhodium or cobalt carbonyl cluster complex, R
h₆(CO)₁₅2M⁺, Rh₆(CO)₁₄4M⁺, Rh
₇(CO)₁₆3M⁺, Rh₁₂(CO)₃₀2M⁺, Co₆
(CO)₁₅2M ⁺, Co₃(CO)₁₁2M⁺(In each formula,
M is an alkali metal or quaternary alkyl ammonium
Rhodium or cobalt clusters represented by
A complex salt, and a rhodium-cobalt mixed cluster
-RhCo as a complex₃(CO)₁₂, Rh₂Co
₂(CO)₁₂And Rh_FourCo₂(CO)₁₆Etc.
It A catalyst derived from these complexes by the method described below
If used, all of them have mild reaction conditions and high selectivity.
Moreover, it is easy to separate and collect the catalyst and the product. In particular
Touch derived from Rh-Co bimetal cluster complex
If a medium is used, the formation of by-product hydrocarbons will be completed.
It can be completely suppressed and the selectivity of linear aldehyde (n-form) can be reduced.
Can be improved.

The method of chemically immobilizing the metal cluster complex on the phosphine-modified metal oxide is not particularly limited, but the following method can be adopted, for example.

(1) Coordination bond is formed between the metal cluster complex and the modified phosphine by a ligand exchange reaction between CO which is a ligand of the metal cluster complex and P atom on the phosphine modified oxide. A method of generating and chemically immobilizing.

The above-mentioned immobilization method will be described in detail below.
After dissolving the metal cluster complex in a solvent capable of dissolving the cluster complex under an inert gas stream (eg, tetrahydrofuran, hexane, chloroform, etc.), the phosphine-modified metal oxide is usually added at room temperature and mixed by stirring. Then, the complex is immobilized on a phosphine-modified metal oxide, and then the solvent in the system is distilled off under an inert gas or under vacuum, followed by drying to obtain the target immobilized metal cluster complex catalyst. As for the temperature condition for immobilization, heating can be performed to a relatively low temperature of about 100 ° C. or less, if necessary. This is because the metal cluster complex is generally thermally unstable.

(2) With respect to the phosphine-modified metal oxide obtained above, the metal cluster complex is evaporated under vacuum,
A method of depositing and fixing on a phosphine-modified metal oxide.

Unlike the above methods (1) and (2), first, a ligand exchange reaction between CO, which is a ligand of the metal cluster complex, and a P atom of phosphine is carried out to give a phosphine of the metal cluster. It is also possible to employ a method in which after the complex is obtained, a dehydration reaction is caused between the hydroxyl group at the phosphine site of the phosphine complex and the hydroxyl group at the surface of the oxide carrier to form an ether bond. In the former step, various conditions in a usual method for synthesizing a phosphine complex can be applied. That is, a solution of the metal cluster complex (solvent is a solvent capable of dissolving the metal cluster complex, such as tetrahydrofuran, hexane, chloroform, etc.) and a solution of the phosphine (solvent dissolves the phosphine in an inert gas atmosphere. Solvent, for example, water, methanol, ethanol, isopropanol, tetrahydrofuran, benzene, etc.) are mixed and stirred to obtain a metal cluster phosphine complex, and then the solvent in the system is added under an inert gas or vacuum. The target complex can be obtained by distilling off and drying. The latter step is preferably carried out in an inert dry gas atmosphere for the same reason as explained in the production of the phosphine-modified metal oxide.

The lower limit of the amount of the metal cluster complex supported is not particularly limited, but considering the catalytic activity, it is preferably 0.001% by weight or more in terms of metal weight. On the other hand, the upper limit of the addition amount is preferably an equimolar amount or less of the addition amount of the metal cluster complex with respect to the molar amount of the phosphine used as described above. It is preferably about 50% by weight or less.

As the unsaturated compound which is a raw material for the production of the method of the present invention, an olefinic compound having a substituent, an olefinic compound having a carbon number of 11 or more, which does not have a substituent, and an unsaturated compound having a functional group. Is applicable.

More specifically, examples of the unsaturated compound include the following.

Examples of the olefin compound having a substituent include aromatic hydrocarbon groups such as phenyl group, lower alkyl-substituted phenyl group, p-phenylene group and naphthyl group; furyl group, furfuryl group, thienyl group, pyridyl group and piperidyl group. A heterocyclic group such as a group; a mono-, di-, or triolefin substituted with at least one selected from the group consisting of halogen atoms, and may be linear, branched or cyclic. Of the above-mentioned substituents and substituent atoms, preferred are phenyl group, lower alkyl-substituted phenyl group, p
-Phenylene group, naphthyl group, pyridyl group, piperidyl group and halogen atom can be mentioned. Examples of the olefinic compound substituted with an aromatic hydrocarbon group include styrene, α-methylstyrene, vinyltoluene, divinylbenzene, indene, α-methylstyrene dimer, styrene oligomer, vinylbiphenyl, vinylanthracene and the like. Examples of the olefinic compound substituted with a heterocyclic group include vinyl pyridine, vinyl carbazole, vinyl imidazole, vinyl furan and the like. Further, as the olefinic compound substituted with a halogen atom, vinyl chloride, vinyl bromide, methallyl chloride,
Examples include allyl chloride, allyl bromide, chloroprene and the like.

The olefinic compound having no substituent and having 11 or more carbon atoms has no substituent and has 1 carbon atom.
It is not particularly limited as long as it is 1 or more, and various linear, branched or cyclic mono-, di- or triolefins are applicable. Specific examples thereof include linear monoolefins such as dodecene, tridecene, tetradecene, hexadecene, octadecene, and eicosene, and branched chain monoolefins corresponding to these; cazinene, caryophyllene, santalen,
Suitable are linear diolefins such as tetradeca 1,13-diene, the corresponding branched chain diolefins; cyclic mono-, di- or triolefins such as cyclododeca-1,5,9-triene.

Examples of the unsaturated compound having a functional group include unsaturated alcohols, unsaturated aldehydes, unsaturated ketones, unsaturated carboxylic acids, unsaturated acid anhydrides, unsaturated acid halides, unsaturated amines, unsaturated amides, Unsaturated nitrile,
Examples include unsaturated ethers, unsaturated isocyanates, unsaturated thioalcohols, and the like.

The unsaturated alcohol may be linear, branched or cyclic, and the carbon number thereof is not particularly limited. For example, allyl alcohol, trans-2-
Hexen 1-ol, oleyl alcohol, cyclo-2
-Hexen-1-ol, cinnamic alcohol, citronellol, farnesol, nerolidol, geranylgeraniol and the like can be exemplified.

The unsaturated aldehyde may be linear, branched or cyclic, and the number of carbon atoms is not particularly limited. For example, acrolein, crotonaldehyde, 1-formylcyclo-2-hexene, citral,
Examples thereof include cinnamaldehyde, 3-cyclohexene-1-carboxaldehyde, safranal, and perillaaldehyde.

The unsaturated ketone may be linear, branched or cyclic, and the number of carbon atoms is not particularly limited. For example, 5-hexene-2-one, mesityl oxide, 2-cyclohexen-1-one, isophorone, civetone, α-ionone, β-ionone, cholesterol and the like can be exemplified.

The unsaturated carboxylic acid may be linear, branched or cyclic, and the carbon number thereof is not particularly limited. For example, acrylic acid, methacrylic acid, tetrahydrophthalic acid, oleic acid, allyl acetic acid, abietic acid, itaconic acid, maleic acid, fumaric acid, citraconic acid, 12,13-epoxyoleic acid, linoleic acid, linolenic acid and the like can be exemplified. . As the acid anhydride, acid halide and ester corresponding to these unsaturated carboxylic acids,
For example, unsaturated acid anhydrides such as cis-4-cyclohexene-1,2-dicarboxylic acid anhydride and citraconic acid anhydride; unsaturated acid halides such as acrylic chloride; methyl acrylate;
Examples of unsaturated acid esters such as methyl methacrylate, methyl tetrahydrophthalate, methyl oleate, methyl linoleate, methyl linolenate, methyl abietate, allyl acetate, vinyl acetate, vinyl acrylate, dimethyl fumarate, and dimethyl maleate. be able to.

The unsaturated amine may be linear, branched or cyclic, and the number of carbon atoms is not particularly limited. For example, allylamine, camphoramine, etc. can be illustrated.

The unsaturated amide may be linear, branched or cyclic, and the carbon number thereof is not particularly limited. For example, acrylamide, methacrylamide, etc. can be mentioned.

The unsaturated nitrile may be linear, branched or cyclic, and the number of carbon atoms is not particularly limited. For example, acrylonitrile, methacrylonitrile, allyl cyanide, etc. can be mentioned.

The unsaturated ether may be linear, branched or cyclic, and its carbon number is not particularly limited. For example, allyl ether, allyl ethyl ether, allyl glycidyl ether, etc. can be mentioned.

The unsaturated isocyanate may be linear, branched or cyclic, and the carbon number thereof is not particularly limited, and examples thereof include allyl isocyanate. The unsaturated thioalcohol may be linear, branched or cyclic, and the carbon number thereof is not particularly limited, and examples thereof include allyl mercaptan.

The mode of the hydroformylation reaction method of the present invention is not particularly limited, and for example, a batch reaction system or a flow reaction system under normal pressure or increased pressure can be adopted, and it is carried out in a gas phase or a liquid phase. The catalyst may be used in either a fixed bed or a fluidized bed. When the unsaturated compound is fed into the reactor, the feeding mode can be appropriately determined in consideration of the properties of the compound, and it may be introduced after diluting with a solvent as necessary.

More specifically, the reaction apparatus is charged with the prepared catalyst, a mixed gas of an unsaturated compound, carbon monoxide and hydrogen is introduced under normal pressure or pressure, and the reaction is carried out under suitable reaction conditions. To be achieved. The suitable reaction conditions depend on the physical and chemical properties of the raw material unsaturated compound and cannot be described in a general way, but in the intended hydroformylation reaction, a sufficient reaction rate is obtained and side reactions are sufficiently suppressed. It is preferable to carry out the reaction at such a reaction temperature, reaction pressure and gas partial pressure.

Usually, the reaction temperature is room temperature to about 200 ° C.,
The reaction pressure is about 1 to 200 Kg / cm ² . Regarding the mixing ratio of the unsaturated compound, carbon monoxide and hydrogen,
It is not particularly limited, but is usually an unsaturated compound: carbon monoxide =
It is preferably in the range of 1:50 to 10: 1 (molar ratio) and in the range of carbon monoxide: hydrogen = 1: 30 to 10: 1 (molar ratio).

In order to separate the solidified cluster catalyst and the reaction product, if the reaction product is a gas, it may be extracted from the reaction apparatus as it is, and if it is a liquid or a solid, it may be filtered while hot or by a suitable method. Operations such as filtration of the solution after dilution with a solvent may be performed. The immobilized cluster catalyst separated after the reaction can be subjected to the reaction again as long as it retains the catalytic activity.

[0040]

EXAMPLES The present invention will be described in detail below with reference to Reference Examples, Examples and Comparative Examples, but the present invention is not limited to these Examples. In the examples, all parts and% are by weight unless otherwise specified.

Reference Example 1 Preparation of Rh ₄ (CO) ₁₂ / THP / SiO ₂ catalyst Silica powder dried under vacuum (1 Torr or less) at 200 ° C. for 4 hours (manufactured by Nippon Aerosil Industry Co., Ltd., trade name Aerosil-300, ratio) 4.56 g (surface area 280 m ^{2 /} g) was weighed in a Schlenk tube having a volume of 150 ml under a nitrogen gas atmosphere, and 90 ml of an absolute ethanol solution in which 439 mg of THP was dissolved was added thereto under a nitrogen gas atmosphere. After stirring at room temperature for about 8 hours, anhydrous ethanol was distilled off under reduced pressure with a vacuum pump, and the solvent was dried under reduced pressure at room temperature until the solvent was completely evaporated.

Then, the temperature is raised to 130 ° C. in about 1 hour,
Finally under reduced pressure (1 Torr or less) at 130 ° C for 2 hours.
By vacuum heating in, THP-modified silica was obtained.

Rh ₄ (CO) was added to this THP-modified silica.
About 60 ml of anhydrous hexane solution in which 182 mg of Rh cluster complex ₁₂ was dissolved was added under N ₂ gas atmosphere, and the mixture was stirred at room temperature for about 30 minutes. At this stage, the hexane solution, which initially had an orange color, became colorless, and all the Rh cluster complexes were immobilized on the THP-modified silica. Anhydrous hexane was distilled off under reduced pressure with a vacuum pump, and further dried under reduced pressure (1 Torr or less) at room temperature until the solvent was completely evaporated to obtain the title Rh ₄ (CO) ₁₂ / THP / SiO ₂ catalyst.

Reference Example 2 Preparation of Rh ₂ Co ₂ (CO) ₁₂ / THP / SiO ₂ Catalyst 4.33 g of silica powder (Aerosil-300) vacuum dried (1 Torr or less) at 200 ° C. for 4 hours had a volume of 150.
A Schlenk tube of ml was weighed under a nitrogen gas atmosphere, and THP417 mg was dissolved in this anhydrous ethanol solution 9
0 ml was added under a nitrogen gas atmosphere. After stirring at room temperature for about 8 hours, anhydrous ethanol was distilled off under reduced pressure with a vacuum pump, and the solvent was dried under reduced pressure at room temperature until the solvent was completely evaporated.

Then, the temperature is raised to 130 ° C. in about 1 hour,
Further, by vacuum heating at 130 ° C. for 2 hours under reduced pressure (1 Torr or less), THP-modified silica was obtained.

Rh ₂ Co was added to this THP-modified silica.
About 60 ml of anhydrous hexane solution in which 255 mg of Rh-Co bimetal cluster complex which is ₂ (CO) ₁₂ is dissolved
Was added under an inert gas atmosphere, and the mixture was stirred at room temperature for about 30 minutes. At this stage, the hexane solution, which initially had a dark brown color, became colorless and all the Rh-Co bimetal cluster complexes were immobilized on the THP-modified silica. Anhydrous hexane was distilled off under reduced pressure with a vacuum pump, and further dried under reduced pressure (1 Torr or less) at room temperature until the solvent was completely evaporated to obtain the title Rh ₂ Co ₂ (CO) ₁₂ / THP / SiO ₂ catalyst.

Examples 1 to 10 In a shaking autoclave having an internal volume of 300 ml, 5.0 g of various unsaturated compounds exemplified in Table 1 and 25 m of toluene
1 was charged, and about 250 mg of the catalyst obtained in Reference Example 1 was added,
The reaction was performed for 5.0 to 6.5 hours under the reaction conditions of hydrogen and carbon monoxide mixed gas (H ₂ : CO = 1: 1 (molar ratio)) pressure of 50 kg / cm ² and temperature of 70 ° C. After the reaction, the mixture was allowed to cool to room temperature, the reaction solution was taken out, and the catalyst was filtered off. The filtrate was analyzed by gas chromatography. The results are shown in Table 1 below.

Examples 11 to 12 In a shaking autoclave having an internal volume of 300 ml, 5.0 g of various unsaturated compounds exemplified in Table 1 and 25 m of toluene
1 was charged, and about 250 mg of the catalyst obtained in Reference Example 2 was added,
The reaction was carried out for 6.5 hours under the reaction conditions of hydrogen and carbon monoxide mixed gas (H ₂ : CO = 1: 1 (molar ratio)) pressure of 50 kg / cm ² and temperature of 70 ° C. After the reaction, the mixture was allowed to cool to room temperature, the reaction solution was taken out, and the catalyst was filtered off. The filtrate was analyzed by gas chromatography. The results are shown in Table 1 below.

[0049]

[Table 1]

[0050]

[Table 2]

Reference Example 3 Preparation of Rh ₄ (CO) ₁₂ / THP / SiO ₂ Catalyst Reference Example 1 was the same as Reference Example 1 except that the addition amount of Rh ₄ (CO) ₁₂ Rh cluster complex was 329 mg. A catalyst was similarly prepared.

Example 13 A shaking autoclave having an internal volume of 300 ml was charged with 5.0 g of styrene and 25 ml of hexane, about 250 mg of the catalyst obtained in Reference Example 3 was added, and a mixed gas of hydrogen and carbon monoxide (H ₂ : CO = 1: 1 (molar ratio)) pressure 50 kg / cm
^{2. The} reaction was carried out for 5 hours at a temperature of 70 ° C. After the reaction, the mixture was allowed to cool to room temperature, the reaction solution was taken out, and the catalyst was filtered off.
The filtrate was analyzed by gas chromatography. The results are shown in Table 2 below.

Example 14 5.0 g of styrene and 25 ml of hexane were charged into a shaking autoclave having an internal volume of 300 ml, and about 250 mg of the catalyst obtained in Reference Example 3 was added, followed by hydrogen, carbon monoxide and helium at 10 kg / each. cm ² , 10 kg / c
m ^{2 at} a pressure ratio of 30 kg / cm ² , total pressure of 50 kg / c
m ² was added. Then, at a reaction temperature of 70 ° C, 5
Reacted for hours. After the reaction, the mixture was allowed to cool to room temperature, the reaction solution was taken out, and the catalyst was filtered off. The filtrate was analyzed by gas chromatography. The results are shown in Table 2 below.

Example 15 5.0 g of styrene and 25 ml of hexane were charged into a shaking autoclave having an internal volume of 300 ml, and about 250 mg of the catalyst obtained in Reference Example 3 was added, followed by hydrogen and carbon monoxide at 42 kg / cm ² respectively. , At a pressure ratio of 8 kg / cm ² ,
A total pressure of 50 kg / cm ² was applied. Then, the reaction was carried out at a reaction temperature of 70 ° C. for 5 hours. After the reaction, the mixture was allowed to cool to room temperature, the reaction solution was taken out, and the catalyst was filtered off. The filtrate was analyzed by gas chromatography. The results are shown in Table 2 below.

Example 16 To a shaking autoclave having an internal volume of 300 ml, 5.0 g of styrene and 25 ml of hexane were charged, and about 250 mg of the catalyst obtained in Reference Example 3 was added, followed by hydrogen, carbon monoxide and helium at 25 kg / each. cm ² , 5 kg / cm ² ,
A pressure ratio of 20 kg / cm ² was applied to give a total pressure of 50 kg / cm ² . Then, the reaction was carried out at a reaction temperature of 70 ° C. for 5 hours. After the reaction, the mixture was allowed to cool to room temperature, the reaction solution was taken out, and the catalyst was filtered off. The filtrate was analyzed by gas chromatography. The results are shown in Table 2 below.

Example 17 A shaking autoclave having an internal volume of 300 ml was charged with 13.5 g of styrene, and about 250 mg of the catalyst obtained in Reference Example 3 was added without using a solvent, and a mixed gas of hydrogen and carbon monoxide (H ₂ : CO = 1: 1 (molar ratio)) pressure 50 kg
The reaction was performed for 7.5 hours under the reaction conditions of / cm ² and a temperature of 70 ° C. After the reaction, the mixture was allowed to cool to room temperature, the reaction solution was taken out, and the catalyst was filtered off. The filtrate was analyzed by gas chromatography. The results are shown in Table 2 below.

Reference Example 4 Preparation of Rh ₄ (CO) ₁₂ / THP / SiO ₂ Catalyst 4.56 g of silica powder (Aerosil-300) vacuum dried (1 Torr or less) at 200 ° C. for 4 hours had a volume of 150.
A Schlenk tube of ml was weighed under a nitrogen gas atmosphere, and 310 mg of THP was dissolved in this absolute ethanol solution 9
0 ml was added under a nitrogen gas atmosphere. After stirring at room temperature for about 8 hours, anhydrous ethanol was distilled off under reduced pressure with a vacuum pump, and the solvent was dried under reduced pressure at room temperature until the solvent was completely evaporated.

Then, the temperature is raised to 130 ° C. in about 1 hour,
Finally under reduced pressure (1 Torr or less) at 130 ° C for 2 hours.
By vacuum heating in, THP-modified silica was obtained.

Rh ₄ (CO) was added to this THP-modified silica.
About 60 ml of anhydrous hexane solution in which 43 mg of Rh cluster complex of ₁₂ was dissolved was added under N ₂ gas atmosphere,
Stir for about 30 minutes at room temperature. At this stage, the hexane solution, which initially had an orange color, became colorless, and all the Rh cluster complexes were immobilized on the THP-modified silica. Anhydrous hexane was distilled off under reduced pressure with a vacuum pump, and further dried under reduced pressure (1 Torr or less) at room temperature until the solvent was completely evaporated to obtain the title Rh ₄ (CO) ₁₂ / THP / SiO ₂ catalyst.

Example 18 To a shaking autoclave having an internal volume of 300 ml, 5.0 g of styrene and 25 ml of hexane were charged, and about 250 mg of the catalyst obtained in Reference Example 4 was added, followed by hydrogen and carbon monoxide at 42 kg / cm ² respectively. , At a pressure ratio of 8 kg / cm ² ,
A total pressure of 50 kg / cm ² was applied. Then, the reaction was carried out at a reaction temperature of 70 ° C. for 5 hours. After the reaction, the mixture was allowed to cool to room temperature, the reaction solution was taken out, and the catalyst was filtered off. The filtrate was analyzed by gas chromatography. The results are shown in Table 2 below.

Reference Example 5 Preparation of Rh ₄ (CO) ₁₂ / THP / SiO ₂ Catalyst 4.56 g of silica powder (Aerosil-300) vacuum dried (1 Torr or less) at 200 ° C. for 4 hours had a volume of 150.
A Schlenk tube of ml was weighed under a nitrogen gas atmosphere, and 66 mg of THP was dissolved in this absolute ethanol solution 90
ml was added under a nitrogen gas atmosphere. After stirring at room temperature for about 8 hours, anhydrous ethanol was distilled off under reduced pressure with a vacuum pump, and the solvent was dried under reduced pressure at room temperature until the solvent was completely evaporated.

Then, the temperature is raised to 130 ° C. in about 1 hour,
Finally under reduced pressure (1 Torr or less) at 130 ° C for 2 hours.
By vacuum heating in, THP-modified silica was obtained.

Rh ₄ (CO) was added to this THP-modified silica.
About 60 ml of anhydrous hexane solution in which 43 mg of Rh cluster complex of ₁₂ was dissolved was added under N ₂ gas atmosphere,
Stir for about 30 minutes at room temperature. At this stage, the hexane solution, which initially had an orange color, became colorless, and all the Rh cluster complexes were immobilized on the THP-modified silica. Anhydrous hexane was distilled off under reduced pressure with a vacuum pump, and further dried under reduced pressure (1 Torr or less) at room temperature until the solvent was completely evaporated to obtain the title Rh ₄ (CO) ₁₂ / THP / SiO ₂ catalyst.

Example 19 5.0 g of styrene and 25 ml of hexane were charged into a shaking autoclave having an internal volume of 300 ml, and about 250 mg of the catalyst obtained in Reference Example 5 was added, followed by hydrogen and carbon monoxide at 42 kg / cm ² respectively. , At a pressure ratio of 8 kg / cm ² ,
A total pressure of 50 kg / cm ² was applied. Then, the reaction was carried out at a reaction temperature of 70 ° C. for 5 hours. After the reaction, the mixture was allowed to cool to room temperature, the reaction solution was taken out, and the catalyst was filtered off. The filtrate was analyzed by gas chromatography. The results are shown in Table 2 below.

Reference Example 6 Preparation of Rh ₄ (CO) ₁₂ / THP / SiO ₂ Catalyst Silica powder vacuum-dried (1 Torr or less) at 200 ° C. for 4 hours (trade name: Caractact 5 manufactured by Fuji Silysia Chemical Ltd.)
0, specific surface area 79 m ^{2 /} g) 4.56 g, volume 150 m
1 in a Schlenk tube of 1 under a nitrogen gas atmosphere, and THP 294 mg was dissolved in this absolute ethanol solution 90
ml was added under a nitrogen gas atmosphere. After stirring at room temperature for about 8 hours, anhydrous ethanol was distilled off under reduced pressure with a vacuum pump, and the solvent was dried under reduced pressure at room temperature until the solvent was completely evaporated.

Then, the temperature is raised to 130 ° C. in about 1 hour,
Finally under reduced pressure (1 Torr or less) at 130 ° C for 2 hours.
By vacuum heating in, THP-modified silica was obtained.

Rh ₄ (CO) was added to this THP-modified silica.
About 60 ml of anhydrous hexane solution in which 46 mg of Rh cluster complex of ₁₂ was dissolved was added under N ₂ gas atmosphere,
Stir for about 30 minutes at room temperature. At this stage, the hexane solution, which initially had an orange color, became colorless, and all the Rh cluster complexes were immobilized on the THP-modified silica. Anhydrous hexane was distilled off under reduced pressure with a vacuum pump, and further dried under reduced pressure (1 Torr or less) at room temperature until the solvent was completely evaporated to obtain the title Rh ₄ (CO) ₁₂ / THP / SiO ₂ catalyst.

Example 20 A shaking autoclave having an internal volume of 300 ml was charged with 5.0 g of styrene and 25 ml of hexane, and after adding about 500 mg of the catalyst obtained in Reference Example 6, hydrogen and carbon monoxide were respectively added at 42 kg / cm ^2. , At a pressure ratio of 8 kg / cm ² ,
A total pressure of 50 kg / cm ² was applied. Then, the reaction was carried out at a reaction temperature of 70 ° C. for 5 hours. After the reaction, the mixture was allowed to cool to room temperature, the reaction solution was taken out, and the catalyst was filtered off. The filtrate was analyzed by gas chromatography. The results are shown in Table 2 below.

Reference Example 7 Preparation of Rh ₄ (CO) ₁₂ / THP / SiO ₂ Catalyst 4.56 g of silica powder (Carriact 50) dried under vacuum (1 Torr or less) at 200 ° C. for 4 hours has a volume of 150 m.
1 in a Schlenk tube of 1 under a nitrogen gas atmosphere, and THP 294 mg was dissolved in this absolute ethanol solution 90
ml was added under a nitrogen gas atmosphere. After stirring at room temperature for about 8 hours, the ethanol solution was filtered off. The residual silica was vacuum dried at room temperature.

Then, the temperature is raised to 130 ° C. in about 1 hour,
Finally under reduced pressure (1 Torr or less) at 130 ° C for 2 hours.
By vacuum heating in, THP-modified silica was obtained.

Rh ₄ (CO) was added to this THP-modified silica.
About 60 ml of anhydrous hexane solution in which 46 mg of Rh cluster complex of ₁₂ was dissolved was added under N ₂ gas atmosphere,
It was left at room temperature for about 30 minutes. At this stage, the hexane solution, which initially had an orange color, became colorless, and all the Rh cluster complexes were immobilized on the THP-modified silica. Anhydrous hexane was distilled off under reduced pressure with a vacuum pump, and further dried under reduced pressure (1 Torr or less) at room temperature until the solvent was completely evaporated to obtain the title Rh ₄ (CO) ₁₂ / THP / SiO ₂ catalyst.

Example 21 5.0 g of styrene and 25 ml of hexane were charged into a shaking autoclave having an internal volume of 300 ml, and about 500 mg of the catalyst obtained in Reference Example 7 was added, and then 42 kg / cm ^{2 of} hydrogen and carbon monoxide, respectively. , At a pressure ratio of 8 kg / cm ² ,
A total pressure of 50 kg / cm ² was applied. Then, the reaction was carried out at a reaction temperature of 70 ° C. for 5 hours. After the reaction, the mixture was allowed to cool to room temperature, the reaction solution was taken out, and the catalyst was filtered off. The filtrate was analyzed by gas chromatography. The results are shown in Table 2 below.

[0073]

[Table 3]

[0074]

[Table 4]

[0075]

According to the present invention, there is provided a method for hydroformylation of an unsaturated compound which can easily separate and recover a catalyst and a product and can highly selectively obtain an objective aldehyde under mild reaction conditions. Can be provided.

Continuation of the front page (51) Int.Cl. ⁵ Identification number Office reference number FI technical display location C07C 45/50 7457-4H 47/02 7457-4H 47/12 7457-4H 47/19 7457-4H 47/228 7457-4H 67/29 67/313 69/67 9279-4H 69/73 9279-4H 69/84 9279-4H // C07B 61/00 300 (72) Inventor Masaru Ichikawa Hachiken 3 west, Nishi-ku, Sapporo, Hokkaido 4 chome 4-22 -22

Claims (7)

[Claims] 1. In the hydroformylation using an unsaturated compound, carbon monoxide and hydrogen in the presence of a catalyst, the catalyst is selected from the group consisting of groups II, III and IV of the periodic table. In addition, at least one metal oxide is modified with phosphine through an ether bond, and at least one metal cluster complex selected from the group consisting of cobalt and rhodium is chemically immobilized on the phosphine site. It is an immobilized cluster complex, and the unsaturated compound is an olefinic compound having a substituent, an olefinic compound having no carbon atoms of 11 or more, and an unsaturated compound having a functional group. A method for hydroformylating the unsaturated compound, wherein 2. The metal oxide is silica.
The method described. 3. The method according to claim 1, wherein the phosphine is a phosphine having at least one hydroxyl group in its molecule. 4. The method according to claim 3, wherein the phosphine is tris (hydroxymethyl) phosphine. 5. The supported amount of the phosphine is 0.01 to 40% by weight based on the total weight of the catalyst, and the supported amount of the cluster complex is 0.001 in terms of metal weight based on the total weight of the catalyst. 2. The method according to claim 1, which is ˜50% by weight. 6. An olefinic compound having a substituent,
A monoolefin, diolefin or triolefin substituted with at least one selected from the group consisting of a phenyl group, a lower alkyl-substituted phenyl group, a p-phenylene group, a naphthyl group, a pyridyl group, a piperidyl group and a halogen atom. The method described in 1. 7. The unsaturated compound having a functional group is an unsaturated alcohol, an unsaturated aldehyde, an unsaturated ketone, an unsaturated carboxylic acid, an unsaturated acid anhydride, an unsaturated acid halide, an unsaturated amine, an unsaturated amide, The process according to claim 1, which is an unsaturated nitrile, an unsaturated ether, an unsaturated isocyanate or an unsaturated thioalcohol.