JP2003300989A - Sulfonated bisphosphine, production method thereof and use thereof - Google Patents

Abstract

(57) Abstract: In a hydroformylation reaction of an ethylenically unsaturated compound, a volumetric efficiency is high at a low rhodium concentration, a catalyst recovery efficiency is excellent, economic efficiency is high, and n is high at a high selectivity.
To provide a process for producing aldehydes in an industrially advantageous manner. SOLUTION: General formula (I) (In the formula, each symbol is as defined in the specification.)
Wherein at least one sulfonic acid group or a salt thereof is introduced on the group represented by Ar ¹ and Ar ² in the general formula, a method for producing the same, and the sulfonated bisphosphine Group VIII metal complex comprising:
A method for producing a corresponding n-aldehyde by hydroformylating an ethylenically unsaturated compound with carbon monoxide and hydrogen using a group III metal complex, and a method for efficiently recovering a catalyst component from the hydroformylation reaction mixture.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel sulfonated bisphosphine, a method for producing the same, and uses of the sulfonated bisphosphine. The sulfonated bisphosphine provided by the present invention is useful as a component of a hydroformylation catalyst when hydroformylating an ethylenically unsaturated compound with carbon monoxide and hydrogen to produce a corresponding aldehyde. Accordingly, the above applications include Group VIII metal complexes formed by complexing a sulfonated bisphosphine provided by the present invention with a Group VIII metal compound that acts as a hydroformylation catalyst,
Further, a method for producing an aldehyde using the Group VIII metal complex as a hydroformylation catalyst is included, and a method for recovering a catalyst component from the hydroformylation reaction mixture is also included.

[0002]

2. Description of the Related Art A reaction in which an ethylenically unsaturated compound is reacted with carbon monoxide and hydrogen in the presence of a metal complex of a Group VIII metal compound or a Group VIII metal compound and a phosphorus compound to convert it into an aldehyde. Is called a hydroformylation reaction or an oxo reaction, and the production of an aldehyde using this reaction is industrially extremely valuable.

A rhodium complex formed by complexing a rhodium compound and a phosphorus compound is industrially used as a catalyst in the hydroformylation reaction. This catalyst is extremely expensive, and its recovery in high yield is essential for industrial use. Conventionally, a method has been used in which a lower aldehyde is obtained by a hydroformylation reaction, and the reaction mixture is distilled to separately obtain an aldehyde and an unreacted ethylenically unsaturated compound, and a catalyst is recovered as an evaporation residue (evaporation separation method). It is being appreciated. However, when obtaining a higher aldehyde or an aldehyde having a functional group, the evaporation separation method is not applied. This is because those aldehydes have high boiling points, and it is necessary to raise the distillation temperature.On the other hand, since aldehydes are sensitive to heat, some of the aldehydes are converted into high boiling by-products which are difficult to separate from the catalyst during distillation. The reason is that the yield of aldehyde is reduced, the rhodium complex catalyst is thermally unstable and easily decomposed during distillation, and the catalyst cannot be recovered and reused.

Therefore, as a method for producing a higher aldehyde or an aldehyde having a functional group, a method has been proposed in which a raw material ethylenically unsaturated compound is hydroformylated using a water-soluble catalyst composed of a rhodium compound and a sulfonated phosphine.

For example, (1) 7-octen-1-al is hydroformylated in the presence of a rhodium compound, a sulfonated phosphine and a polyalkylene glycol derivative, water is added to the reaction mixture to extract and separate the catalyst component,
A method for recycling 1,9-polyalkylene glycol derivative containing a catalyst component obtained by removing water from the separated aqueous layer to a reactor and obtaining 1,9-nonanedial from a raffinate layer (organic layer) (See JP-A-7-267890), (2) Method for hydroformylation using a Group VIII noble metal-ligand complex catalyst complexed with a potassium salt of para-diphenylphosphinobenzenesulfonate (Patent Document 8) No. 506110), (3) an aqueous layer containing a catalyst component in the presence of a rhodium compound and a sulfonated sodium salt of 2,2′-bis (diphenylphosphinomethyl) -1,1′-biphenyl. Method for performing hydroformylation in a two-layer system formed from an organic layer containing a substrate [Journal of Molar Catalysis (Journal of Mo lecular Cat
73), pp. 191-201 (1992).
Y.)], (4) Rhodium compounds and sulfonated 4,5-bis (diphenylphosphino) -9,9-
In the presence of the sodium salt of dimethyl-9H-xanthene,
A method for performing hydroformylation in a two-layer system formed of an aqueous layer containing a catalyst component and an organic layer containing a substrate [Journal of Molecular Catalysis (Journal o
f Molecular Catalysis), 13
Vol. 4, pp. 234-249 (1998)], (5)
Aqueous layer containing catalyst component in the presence of rhodium compound, sulfonated sodium salt of 2,2'-bis (diphenylphosphinomethyl) -1,1'-binaphthyl and quaternary ammonium salt as solubilizer There is known a method (see Japanese Patent Laid-Open No. 10-17519) for performing hydroformylation in a two-layer system formed from an organic layer containing a substrate.

[0006]

In the above method (1), meta-diphenylphosphinobenzenesulfonic acid sodium salt is used as the sulfonated phosphine in the embodiment, and it is homogeneous in the presence of polyethylene glycol having a molecular weight of 400. The system is undergoing a 7-octen-1-al hydroformylation reaction. In this method, TOF, which is an index of the catalytic reaction rate (this is calculated as [moles (n-
Aldehyde + iso-aldehyde)] / [representing 1 gram atom (rhodium) × time (h)] is 35,000 at 90 ° C., and practical productivity can be obtained at a low rhodium concentration of 0.04 mmol / L or less. . further,
In this method, the reaction mixture contains only about 10% by volume of polyethylene glycol in addition to the unreacted raw material and the reaction product, and has a high volume efficiency, and as described above, the catalyst component can be recovered and reused. It is economical in that. However, this method has a problem that the selectivity ratio of n-aldehyde to iso-aldehyde (hereinafter, referred to as n / iso ratio) remains high even at 2.5.

In process (2), in that example, para-diphenylphosphinobenzenesulfonic acid potassium salt is used as the sulfonated phosphine, and the presence of lauric acid-dissolved aqueous sodium hydrogen carbonate solution and the auxiliary solvent isopropyl alcohol. Below, the hydroformylation reaction of 1-decene is carried out. In this method, n /
Although the iso ratio is as high as about 13, the reaction mixture contains about 50% by volume of water and a cosolvent in addition to the unreacted raw materials and reaction products, and has a low volumetric efficiency, and the TOF at 80 ° C. is about However, there is a problem that the catalytic reaction rate is low and a high rhodium concentration of about 1.6 mmol / L is required.

In process (3), in that embodiment, the sulfonated 2,2'- as the sulfonated phosphine is used.
The sodium salt of bis (diphenylphosphinomethyl) -1,1'-biphenyl is used, and the hydroformylation reaction of 1-hexene is carried out in a two-layer system in the presence of water. In this method, the selectivity for n-aldehyde is about 95%.
However, the TOF at 123 ° C. is 42, and there is a problem that the catalytic reaction rate is extremely low. Similarly, in method (4), the sodium salt of sulfonated 4,5-bis (diphenylphosphino) -9,9-dimethyl-9H-xanthene is used as the sulfonated phosphine in that example, and water In the presence of, the hydroformylation of 1-hexene is carried out in a two-layer system. In this method,
High n / iso ratio of 35, but TOF at 120 ℃
Is 24, which is a problem that the catalytic reaction rate is extremely low.

In the method (5), in order to improve the catalytic activity which is a problem in the above methods (3) and (4), the use of a solubilizer for improving the solubility of higher olefins in water is proposed. ing. In that example,
Sulfonated 2,2 ′ as sulfonated phosphine
-Bis (diphenylphosphinomethyl) -1,1'-binaphthyl sodium salt is used, and hydroformylation reaction of 1-hexene in a two-layer system in the presence of solubilizing agent tetradecyltrimethylammonium methocarbonate and water Is being done. In this method, the n / iso ratio is as high as 99/1. However, in this method, 122 ° C
Has a TOF of 2400, a low catalytic reaction rate, a high rhodium concentration of 50 ppm, and an organic layer raw material of 16.7-hexene (36.7 g) containing a catalyst-containing aqueous layer (110 g). There is a problem of inefficiency.

The inventors of the present invention have described the above methods (3) to (5).
The sulfonated phosphine used in the above method (1)
As a result of studying the use in the method (1), it was found that the above-mentioned sulfonated phosphine was hardly soluble in the reaction substrate of the method (1) and was not applicable to the method (1). Furthermore, the inventors of the present invention relate to the sulfonated phosphine used in the above methods (3) and (5) by changing the sulfonation conditions of the raw material phosphine to reduce the number of sulfonic acid groups introduced, thereby improving the solubility. Tried to improve. However, no sulfonated phosphine having an appropriate solubility was obtained, or even if it was obtained, the yield of the sulfonated phosphine was extremely low.

The object of the present invention is to carry out a hydroformylation reaction of an ethylenically unsaturated compound, which can be carried out at a low rhodium concentration, has a high volumetric efficiency, a good catalyst recovery efficiency and an excellent economical efficiency, and It is an object of the present invention to provide a sulfonated bisphosphine, which is a constituent of a hydroformylation catalyst capable of highly selectively producing n-aldehyde, and a method for producing the same. Another object of the present invention is the above sulfonated bisphosphines and VI which act as hydroformylation catalysts.
It is intended to provide a Group VIII metal complex formed by complexing a Group II metal compound. It is a further object of the present invention to provide a method for hydroformylating an ethylenically unsaturated compound with carbon monoxide and hydrogen using the above Group VIII metal complex to produce the corresponding aldehyde.
Still another object of the present invention is to provide a method for efficiently recovering a catalyst component from a reaction mixture obtained by the above-mentioned aldehyde production method.

[0012]

The present invention has the general formula (I)

[0013]

[Chemical 3]

(In the formula, Ar ¹ and Ar ² represent an arylene group which may have a substituent, and R ¹ and R ²
Represents an alkyl group which may have a substituent or an aryl group which may have a substituent, or may form a ring together with the phosphorus atom to which they are bonded, R ³ And R ⁴ represents a hydrogen atom or an alkyl group. However, the carbon atom having R ³ and R ⁴ is Ar
^It binds in the ortho position with respect to the oxygen atom to which it binds ¹ and Ar ² . ) Of bisphosphine [hereinafter, this is abbreviated as bisphosphine (I)] having at least one sulfonic acid group or a salt thereof introduced on the group represented by Ar ¹ and Ar ² in the general formula. Sulfonated bisphosphine (hereinafter referred to as "sulfonated bisphosphine (I ')").

The present invention is a process for producing a sulfonated bisphosphine (I '), which comprises sulfonation of bisphosphine (I) with sulfur trioxide in sulfuric acid.

The present invention also provides a V formed by complexing a Group VIII metal compound with a sulfonated bisphosphine (I ').
It is a Group III metal complex [hereinafter, this is abbreviated as Group VIII metal complex (I ′)].

Further, in the present invention, when a corresponding aldehyde is produced by hydroformylating an ethylenically unsaturated compound with carbon monoxide and hydrogen in the presence of a catalyst, a Group VIII metal complex (I ') is used as a catalyst. A method for producing an aldehyde, which is characterized by being used.

Furthermore, in the present invention, in recovering the catalyst component from the reaction mixture obtained by the above-mentioned aldehyde production method, the reaction mixture is contacted with water to extract the catalyst component into an aqueous layer, A method for recovering the above catalyst component is characterized in that water is removed from the aqueous layer. Here, the catalyst component means a Group VIII metal complex (I ′), VI
It means a sulfonated bisphosphine (I ′) usually used in excess with respect to the Group II metal compound and the Group VIII metal compound.

[0019]

BEST MODE FOR CARRYING OUT THE INVENTION In the above general formula, Ar ¹ and A
Examples of the arylene group represented by r ² include, for example, a phenylene group, a naphthylene group, an anthracylene group, and 1,1 ′.
-Biphenylene group, 1,1'-binaphthylene group and the like. These arylene groups may have a substituent, and as such a substituent, a fluorine atom, a chlorine atom,
Halogen atom such as bromine atom; methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group,
Alkyl group such as s-butyl group, t-butyl group, cyclohexyl group; Fluoro group such as difluoromethyl group, trifluoromethyl group, 1,1-difluoroethyl group, 2,2-difluoroethyl group, 1-fluoropropyl group Alkyl group; methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, isobutoxy group, s-butoxy group, t-butoxy group, and other alkoxy groups; acetyl group, propionyl group, butyryl group, isobutyryl group, and other acyl groups Group: Acyloxy group such as acetyloxy group, propionyloxy group, butyryloxy group, isobutyryloxy group; methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, isopropoxycarbonyl group, butoxycarbonyl group, isobutoxycarbonyl group, s − Butoki Carbonyl group, an alkoxycarbonyl group such as t- butoxycarbonyl group; a carboxylic acid group (hydroxycarbonyl group) or a salt thereof.

The alkyl group represented by R ¹ and R ² is, for example, a methyl group, an ethyl group, a propyl group,
Examples thereof include an isopropyl group, a butyl group, an isobutyl group, a s-butyl group, a t-butyl group and a cyclohexyl group. These alkyl groups may have a substituent,
Examples of the substituent include halogen atoms such as fluorine atom, chlorine atom and bromine atom; alkoxy such as methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, isobutoxy group, s-butoxy group and t-butoxy group. Group: Acyl group such as acetyl group, propionyl group, butyryl group, isobutyryl group; Acyloxy group such as acetyloxy group, propionyloxy group, butyryloxy group, isobutyryloxy group; Methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group , Isopropoxycarbonyl group, butoxycarbonyl group, isobutoxycarbonyl group, s-butoxycarbonyl group, t-
An alkoxycarbonyl group such as butoxycarbonyl group;
Carboxylic acid groups or salts thereof; sulfonic acid groups (hydroxysulfonyl groups) or salts thereof and the like.

Examples of the aryl group represented by R ¹ and R ² include a phenyl group, a naphthyl group and an anthryl group. These aryl groups may have a substituent, and examples of the substituent include halogen atoms such as fluorine atom, chlorine atom and bromine atom; methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group. Group, s-butyl group, t-butyl group, alkyl group such as cyclohexyl group; difluoromethyl group,
Trifluoromethyl group, 1,1-difluoroethyl group,
2,2-difluoroethyl group, fluoroalkyl group such as 1-fluoropropyl group; methoxy group, ethoxy group,
Propoxy group, isopropoxy group, butoxy group, isobutoxy group, s-butoxy group, t-butoxy group and other alkoxy groups; acetyl group, propionyl group, butyryl group,
Acyl group such as isobutyryl group; Acyloxy group such as acetyloxy group, propionyloxy group, butyryloxy group, isobutyryloxy group; methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group,
Isopropoxycarbonyl group, butoxycarbonyl group,
Examples thereof include alkoxycarbonyl groups such as isobutoxycarbonyl group, s-butoxycarbonyl group and t-butoxycarbonyl group; carboxylic acid groups or salts thereof; sulfonic acid groups or salts thereof.

R ¹ and R ² may form a ring together with the phosphorus atom to which they are attached, and examples of the phosphorus-containing heterocycle include 2,5-dimethylphosphorane and 2,5-diethyl. Phosphorane, 2,5-dipropylphosphorane, 2,5-diisopropylphosphorane, 5H-dibenzophosphole, 9,10-dihydro-
9-phosphinetracene, 10H-phenoxaphosphine, 10H-9-thia-10-phosphinetracene and the like can be mentioned. Examples of the alkyl group represented by R ³ and R ⁴ include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group and an isobutyl group.

In the salt of the sulfonic acid group introduced onto the group represented by Ar ¹ and Ar ² in the general formula (I), as long as the sulfonated bisphosphine (I ′) is water-soluble, the salt with the sulfonic acid group The cations forming the are not particularly limited. Examples of the cation include alkali metal ions such as lithium ion, sodium ion and potassium ion; magnesium ion, calcium ion,
Alkaline earth metal ions such as barium ion; ammonium ions; primary ammonium ions such as methylammonium ion, ethylammonium ion, propylammonium ion, butylammonium ion, octylammonium ion; dimethylammonium ion, diethylammonium ion, dipropylammonium ion Ion, secondary ammonium ion such as dibutylammonium ion; trimethylammonium ion, triethylammonium ion, ethyldiisopropylammonium ion, tripropylammonium ion,
Examples thereof include tertiary ammonium ions such as tributylammonium ion; quaternary ammonium ions such as tetramethylammonium ion, tetraethylammonium ion, tetrapropylammonium ion, tetraisopropylammonium ion and tetrabutylammonium ion.

Sulfonated bisphosphine (I ') is a novel compound that has not been published in the literature, and as will be described later, Group VIII metal complex (I') containing sulfonated bisphosphine (I ') as a constituent is hydroformylated. It gives excellent reaction results as a catalyst. That is, by using the Group VIII metal complex (I ′) as a hydroformylation catalyst,
The Group VIII metal compound exerts a hydroformylation catalyst function at a low concentration, has high volume efficiency, and improves the catalyst recovery rate, so that it is excellent in economic efficiency and can provide n-aldehyde highly selectively.

As a representative example of the sulfonated bisphosphine (I '), 2,2'-bis (diphenylphosphinomethyl) -4,4'-bis (sulfonic acid) -diphenyl ether dilithium salt, 2,2' -Bis (diphenylphosphinomethyl) -4,4'-bis (sulphonic acid) -diphenyl ether disodium salt,
2,2'-bis (diphenylphosphinomethyl) -4,
4'-bis (sulfonic acid) -diphenyl ether dipotassium salt, 2,2'-bis (diphenylphosphinomethyl) -4,4'-bis (sulfonic acid) -6-methoxy-diphenyl ether dilithium salt, 2, 2'-bis (diphenylphosphinomethyl)
-4,4'-bis (sulfonic acid) -6-methoxy-diphenyl ether disodium salt, 2,2'-
Examples thereof include bis (diphenylphosphinomethyl) -4,4′-bis (sulphonic acid) -6-methoxy-diphenyl ether dipotassium salt.

Next, sulfonated bisphosphine (I ')
The manufacturing method of will be described. The sulfonation of bisphosphine (I) with sulfuric trioxide in sulfuric acid is carried out by dissolving bisphosphine (I) in concentrated sulfuric acid and adding fuming sulfuric acid dropwise to the resulting solution, or by adding fuming sulfuric acid to solid It is carried out by a method such as adding bisphosphine (I) in the state. The reaction can be carried out in the presence of a Lewis acid such as boric acid, if necessary.

When introducing two sulfonic acid groups into bisphosphine (I), a method of dissolving bisphosphine (I) in concentrated sulfuric acid and dropping fuming sulfuric acid into the obtained solution is adopted. preferable. The amount of concentrated sulfuric acid that dissolves bisphosphine (I) is 2 to 2 with respect to bisphosphine (I).
It is preferably in the range of 40 times by weight, more preferably in the range of 2 to 10 times by weight. If the amount exceeds the above range, the volume efficiency of sulfonation becomes low, and it becomes difficult to separate the sulfonated bisphosphine (I ′) and the sulfate of an alkali metal by-produced during the post-treatment by filtration, which is not preferable. On the other hand, when it is less than the above range, the solution viscosity is high and stirring becomes difficult, or the bisphosphine (I) tends not to be completely dissolved, which is not preferable.

Sulfur trioxide is used in the reaction in the form of fuming sulfuric acid in which sulfur trioxide is dissolved in concentrated sulfuric acid. The concentration of sulfur trioxide in fuming sulfuric acid is preferably in the range of 1 to 60% by weight, more preferably 5 to 50% by weight, based on concentrated sulfuric acid. When the concentration of sulfur trioxide is too high, it is difficult to handle fuming sulfuric acid, while when the concentration of sulfur trioxide is too low, it is disadvantageous in terms of volume efficiency, which is not preferable.

The amount of sulfur trioxide used is preferably 2 to 20 mol, and more preferably 2 to 5 mol, per 1 mol of bisphosphine (I). When the amount of sulfur trioxide used exceeds the above range, 3
More likely to introduce more than one sulfonic acid group,
On the other hand, if it is less than the above range, the possibility that one sulfonic acid group is introduced tends to increase, and the desired 2
The yield of the sulfonated bisphosphine (I ′) in which one sulfonic acid group is introduced is reduced.

The reaction time is preferably in the range of 2 to 20 hours, more preferably 5 to 14 hours. If the reaction time exceeds the above range, three or more sulfonic acid groups are likely to be introduced, while if less than the above range, one sulfonic acid group is likely to be introduced. And the desired two sulfonic acid groups have been introduced into the sulfonated bisphosphine (I ′)
Yield is reduced.

The reaction temperature is preferably in the range of 0 to 25 ° C., and is preferably in the range of 1 to 15 ° C. because the desired sulfonated bisphosphine (I ′) can be obtained in high yield. preferable. When the temperature is higher than 25 ° C, the sulfonic acid group is excessively introduced, or the oxidation reaction of the phosphorus atom tends to be essentially promoted rather than the sulfonation reaction,
When the temperature is lower than 0 ° C., the sulfonation reaction tends to be slow or the number of introduced sulfonic acid groups tends to be small, and in any case, the desired yield of the sulfonated bisphosphine (I ′) is low. descend.

The reaction mixture obtained by the above operation is
It is treated with ice or water at a temperature in the range 0 to 30 ° C, preferably in the range 0 to 25 ° C. The amount of water used is not particularly limited, but is 5 to 100 relative to the reaction mixture.
It is preferably double weight. By the above operation, a sulfonated bisphosphine (I ′) having a sulfonic acid group introduced
Is obtained.

The sulfonated bisphosphine (I ') in which the alkali metal salt of sulfonic acid group is introduced is the above-mentioned sulfonated bisphosphine (I') in which the sulfonic acid group is introduced.
It can be obtained by reacting with an alkali metal hydroxide such as lithium hydroxide, sodium hydroxide or potassium hydroxide. When an alkali metal hydroxide is added to the reaction mixture of the sulfonated bisphosphine (I ′) into which the sulfonic acid group has been introduced and reacted, the by-produced alkali metal sulfate has low solubility at low temperatures. Low, most of which is removed by filtering the cooled solution. The filtrate is concentrated using a rotary evaporator or the like, and a solvent capable of dissolving only sulfonated bisphosphine (I ′) in the concentrated solution,
For example, an alcohol such as methyl alcohol, ethyl alcohol, propyl alcohol, etc. is added and filtered again to remove the remaining alkali metal sulfate. By drying the filtrate to dryness, sulfonated bisphosphine (I ′) having an alkali metal salt of sulfonic acid group introduced therein can be obtained.

By treating an aqueous solution of a sulfonated bisphosphine (I ') into which an alkali metal salt of a sulfonic acid group has been introduced with a cation exchanger, a sulfonated bisphosphine (I') into which a sulfonic acid group has been introduced is treated. and then, this alkali metal hydroxide, by reacting such with an amine hydroxides, sulfonato (-SO 3 ^_-) and sulfonated bisphosphine salts with various cations capable of forming an ion pair is introduced (I ') can be obtained.

Next, a method for producing bisphosphine (I) will be described. Bisphosphine (I) has the general formula (I
I)

[0036]

[Chemical 4]

(Wherein Ar ¹ , Ar ² , R ³ and R ⁴ are as defined above, and X represents an arylsulfonyloxy group, an alkylsulfonyloxy group or a halogen atom.) Which is abbreviated as compound (II)] is represented by the general formula (III)

[0038]

[Chemical 5]

(In the formula, R ¹ and R ² are as defined above, and M represents a lithium atom, a sodium atom or a potassium atom.) An alkali metal phosphide [hereinafter, referred to as an alkali metal phosphide (III )
Abbreviated].

The reaction for phosphorylating the compound (II) with the alkali metal phosphide (III) is preferably carried out in the presence of a solvent. As the solvent, for example, 1,4
An ether solvent such as dioxane, dibutyl ether, 2-ethoxyethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran or diethyl ether is preferable. Among these, the use of a mixed solvent of tetrahydrofuran and dibutyl ether is suitable as a solvent used when preparing the alkali metal phosphide (III), and moreover, the alkali metal phosphide (III) and the bisphosphine (I) are used. Is particularly preferable because it can be easily separated. The amount of the solvent used is not particularly limited, but the alkali metal phosphide (I
It is preferably in the range of 1 to 1000 times by weight relative to II), and more preferably in the range of 10 to 100 times by weight in view of high volumetric efficiency when separating bisphosphine (I) from the reaction mixture. preferable.

The above reaction is carried out by dropping the alkali metal phosphide (III) into the solution containing the compound (II) or dropping the compound (II) into the solution containing the alkali metal phosphide (III).

The amount of alkali metal phosphide (III) used is preferably in the range of 2 to 4 mol, and in the range of 2 to 2.2 mol unreacted, per 1 mol of compound (II). It is more preferable because the alkali metal phosphide (III) and the bisphosphine (I) can be easily separated. The reaction temperature is preferably in the range of −75 ° C. to the reflux temperature of the solvent, and more preferably in the range of −75 ° C. to room temperature because the production of by-products can be suppressed. The reaction time is preferably in the range of 0.5 to 10 hours,
The range of 0.5 to 3 hours is more preferable because generation of by-products can be suppressed.

After completion of the reaction, the reaction mixture containing bisphosphine (I) or the reaction mixture is concentrated, and the concentrate is added with toluene, pentane, hexane, diethyl ether, dipropyl ether, butyl methyl ether, tetrahydrofuran, methyl acetate. , A solvent suitable for water extraction, such as ethyl acetate or propyl acetate, is added, the mixture is washed with water, and bisphosphine (I) can be isolated and purified from the resulting organic layer by an operation such as recrystallization.

The compound (II) is generally called a sulfonic acid ester in which X is an arylsulfonyloxy group or an alkylsulfonyloxy group in the general formula (II) [hereinafter, abbreviated as sulfonic acid ester (II-a)]. In formula (II), X is a halogen atom [hereinafter, this is abbreviated as halide (II-b)].

The sulfonic acid ester (II-a) can be produced by a known method. For example, 2,2'-bis (p- included in sulfonic acid ester (II-a).
Tolylsulfonyloxymethyl) -di (substituted) phenyl ether [hereinafter, referred to as sulfonic acid ester (II-
a ') is abbreviated] can be manufactured by the following method.

[0046]

[Chemical 6]

In the above formula, R ^a and R ^b are halogen atoms such as fluorine atom, chlorine atom and bromine atom; methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, s-butyl group, alkyl groups such as t-butyl group and cyclohexyl group; difluoromethyl group,
Trifluoromethyl group, 1,1-difluoroethyl group,
2,2-difluoroethyl group, fluoroalkyl group such as 1-fluoropropyl group; methoxy group, ethoxy group,
Propoxy group, isopropoxy group, butoxy group, isobutoxy group, s-butoxy group, t-butoxy group and other alkoxy groups; acetyl group, propionyl group, butyryl group,
Acyl group such as isobutyryl group; Acyloxy group such as acetyloxy group, propionyloxy group, butyryloxy group, isobutyryloxy group; methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group,
Isopropoxycarbonyl group, butoxycarbonyl group,
An alkoxycarbonyl group such as an isobutoxycarbonyl group, an s-butoxycarbonyl group, and a t-butoxycarbonyl group; a substituent on the benzene ring such as a carboxylic acid group; Hal represents a chlorine atom or a bromine atom;
Cl represents p-tolyl sulfonyl chloride.

(Reaction II-a-1) 1 mole or more of arene (V) halide is reacted with 1 mole of hydroxyarene potassium salt (IV) in the presence of activated copper powder to produce diarene ether ( VI) is obtained. The reaction is preferably carried out at the reflux temperature of the arene (V) halide. After the reaction, an organic solvent such as ether and water are added to the reaction mixture to carry out an extraction operation, and diarene ether (VI) is isolated and purified from the organic layer by an operation such as vacuum distillation. [Organic Syntheses (Org
anic Syntheses, Volume 2, 446 pages (1
943)]

(Regarding Reaction II-a-2) Dithiolated diarene ether (VII) is obtained by reacting 2 mol of a lithiating agent with 1 mol of diarene ether (VI) in the presence of a solvent. As a lithiation agent,
For example, methyl lithium, butyl lithium, phenyl lithium, etc. are used. As the solvent, for example, diethyl ether, tetrahydrofuran or the like is used. The reaction temperature is selected from temperatures below room temperature. [The Journal of Organic Chemistry (The Jou
rnal of Organic Chemistr
y), Vol. 23, No. 10, pp. 1476-1479 (1958).
Year)]

(Regarding Reaction II-a-3) Reaction II-
a dithiolated diarene ether (VI
The reaction mixture containing I) is reacted with 2 mol or more of carbon dioxide with respect to 1 mol of dilithiated diarene ether (VII) to obtain dicarboxy diarene ether (VIII). The reaction temperature is selected from temperatures below room temperature. After the reaction, the reaction mixture is concentrated, an organic solvent such as ethyl acetate and water are added to the concentrated solution for extraction,
Dicarboxy diarene ether (VIII) is isolated and purified from the organic layer by an operation such as recrystallization. [The Journal of Organic Chemistry (The Journal of Organic Chemistry
Journal of Organic Chemis
try), Vol. 55, No. 2, 438-441 (1990).
Year)]

(Reaction II-a-4) Dicarboxy diarene ether (VIII) 1 was added to Soxhlet extractor by allowing solid state dicarboxy diarene ether (VIII) to exist and solvent extraction intermittently.
The dihydroxyalkyl diarene ether (IX) is obtained by reacting 1 mol or more of lithium aluminum hydride with respect to mol. As the solvent, for example, diethyl ether or the like is used. From the viewpoint of high extraction efficiency, the reaction is preferably carried out at the reflux temperature of the solvent. After the reaction, the reaction mixture is concentrated, water is added to the concentrate, extraction is performed, and dihydroxyalkyl diarene ether (IX) is isolated and purified from the organic layer by an operation such as recrystallization. [The Journal of Organic Chemistry (The Journal of Organic Chemistry
Chemistry), Vol. 34, No. 4, 1165-11
See page 68 (1969)]

(Reaction II-a-5) Sulfonic acid was obtained by reacting 2 mol of p-toluenesulfonyl chloride with 1 mol of dihydroxyalkyl diarene ether (IX) in the presence of 2 mol or more of amines. The ester (II-a ') is obtained. As the amine, for example, pyridine or the like is used. The reaction temperature is selected from temperatures below room temperature. After the reaction, the reaction mixture is concentrated, and the sulfonate (I
Ia ') is isolated and purified. [The Journal of the
American Chemical Society (The Jura
nal of the American Chemica
l Society), Vol. 74, No. 2, 425-428 (1952), etc.]

The halide (II-b) can be produced by a known method. For example, halide (I
2,2'-bis (bromomethyl)-included in Ib)
Di (substituted) phenyl ether [hereinafter, abbreviated as halide (II-b ')] and 2,2'-bis (fluoromethyl) -di (substituted) phenyl ether [hereinafter, referred to as halide (II-b')]. -B '')
Can be produced by the following method.

[0054]

[Chemical 7]

In the above formula, R ^c and R ^d are halogen atoms such as fluorine atom, chlorine atom and bromine atom; methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, s-butyl group, alkyl groups such as t-butyl group and cyclohexyl group; difluoromethyl group,
Trifluoromethyl group, 1,1-difluoroethyl group,
2,2-difluoroethyl group, fluoroalkyl group such as 1-fluoropropyl group; methoxy group, ethoxy group,
Propoxy group, isopropoxy group, butoxy group, isobutoxy group, s-butoxy group, t-butoxy group and other alkoxy groups; acetyl group, propionyl group, butyryl group,
Acyl group such as isobutyryl group; Acyloxy group such as acetyloxy group, propionyloxy group, butyryloxy group, isobutyryloxy group; methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group,
Isopropoxycarbonyl group, butoxycarbonyl group,
An alkoxycarbonyl group such as an isobutoxycarbonyl group, an s-butoxycarbonyl group, and a t-butoxycarbonyl group; a substituent on the benzene ring such as a carboxylic acid group, NBS represents N-bromosuccinimide, and Hal represents chlorine. Represents an atom or a bromine atom, and Tos-Cl represents p-tolylsulfonyl chloride.

(Regarding Reaction II-b-1) The diarene ether (XII) is obtained by reacting 1 mol or more of the halogenated arene (XI) with 1 mol of the hydroxyarene potassium salt (X). The reaction is preferably carried out at the reflux temperature of the arene halide (XI). After the reaction, the reaction mixture is concentrated, an organic solvent such as hexane and water are added to the concentrated solution for extraction, and diarene ether (XII) is isolated and purified from the organic layer by an operation such as vacuum distillation. [The Journal of Organic Chemistry (The Journal of Or
ganic Chemistry), Vol. 34, No. 4, 11
65 to 1168 (1969)]

(Reaction II-b-2) The halide (II-b ′) was prepared by reacting 2 moles or more of N-bromosuccinimide with 1 mole of diarene ether (XII) in the presence of a solvent. ) Get. Benzoyl peroxide or the like is used as the radical reaction initiator. As the solvent, for example, carbon tetrachloride or the like is used. The reaction is preferably carried out at the reflux temperature of the solvent. After the reaction, the reaction mixture is filtered, the filtrate is concentrated, and then the halide (II-b ′) is isolated and purified from the concentrated solution by an operation such as recrystallization. [The Journal of Organic
Chemistry (The Journal of Org
anic Chemistry), Vol. 34, No. 4, 116
See pages 5-1168 (1969)]

(Reaction II-b-3) Halide (II-b ') is obtained by reacting 1 mol of dihydroxyalkyl diarene ether (XIII) with 2 mol or more of hydrogen bromide in the presence of a solvent. To get For example, benzene is used as the solvent. The reaction temperature is selected from temperatures below room temperature. After the reaction, the reaction mixture is concentrated, and the halide (II-b ′) is isolated and purified from the concentrated solution by an operation such as recrystallization. [The Journal of Organic Chemistry (The Journal
l of Organic Chemistry), 3
Vol. 4, No. 4, pp. 1165 to 1168 (1969)]

(Regarding Reaction II-b-4) The halide (II-b ″) is converted to 1 mol of the sulfonic acid ester (XIV) by reacting 2 mol or more of potassium fluoride in the presence of a solvent. obtain. As the solvent, for example, diethylene glycol or the like is used. Reaction temperature is 1
It is selected from temperatures of 30 ° C. or lower. After the reaction, the halide (II-
b ″) is isolated and purified. [Chemistry Letters, No. 3, 26
See pages 5-268 (1982)]

The alkali metal phosphide (III) can be produced by a known method. For example, an alkali metal phosphide in which M is a lithium atom in the general formula (III) is produced by reacting a corresponding phosphine with a lithiating agent. The alkali metal phosphide in which M is a sodium atom or a potassium atom in the general formula (III) is produced by reacting a corresponding phosphine halide with metal sodium or metal potassium [Chemiche Berichte (Chem
ische Berichte), vol. 92, 1118-
See page 1126 (1959)].

Sulfonated bisphosphine (I ') and VI
The Group VIII metal complex (I ′) formed by forming a complex with a Group II metal compound is a novel compound that has not been published in the literature and gives excellent reaction results as a hydroformylation catalyst. That is,
By using the Group VIII metal complex (I ′) as the hydroformylation catalyst, the Group VIII metal compound exerts a hydroformylation catalytic function at a low concentration, the volume efficiency is increased, and the catalyst recovery rate is improved, which is economical. It is possible to give n-aldehyde with excellent and high selectivity. Further, when recovering the catalyst component from the hydroformylation reaction mixture, the reaction mixture is contacted with water, the catalyst component is extracted into an aqueous layer, and water is removed from the aqueous layer to easily recover the catalyst component. be able to.

As the Group VIII metal compound, ethylene
To accelerate the hydroformylation reaction of unsaturated compounds
Possibly having a capacity from the beginning, or a hydroformylation reaction
A compound that acquires the catalytic ability under the conditions
Used as catalyst in Droformylation reaction
Rhodium compound, cobalt compound, ruthenium compound,
Examples include iron compounds. As a rhodium compound,
For example, RhO, RhO_Two , Rh_Two O, Rh_Two O_Three 
Rhodium oxides such as; rhodium nitrate, rhodium sulfate, salts
Rhodium iodide, rhodium iodide, rhodium acetate, etc.
Um salt; Rh (acac) (CO)_Two , RhCl (C
O) (PPh_Three )_Two , RhCl (CO) (AsPh_Three
 )_Two , RhCl (PPh_Three )_Three , RhBr (CO)
(PPh _Three )_Two , Rh_Four (CO)₁₂, Rh₆ (C
O)₁₆Rhodium complex compounds and the like.

As the cobalt compound, for example, HCo
(CO)_Three , HCo (CO)_Four , Co _Two (CO)
₈ , HCo_Three (CO)₉ Such as a cobalt complex compound
Which can be mentioned. Examples of the ruthenium compound include R
u (CO)_Three (PPh_Three )_Two , RuCl_Two (PPh
_Three )_Three, RuCl_Three (PPh_Three )_Three , Ru_Three (C
O)_{1 Two}And ruthenium complex compounds such as.
Further, as the iron compound, for example, Fe (CO)₅ , F
e (CO)_Four PPh_Three , Fe (CO)_Four (PP
h_Three)_Two And iron complex compounds such as. these
Among the above compounds, mild in the hydroformylation reaction
Rhodium compounds are used because various reaction conditions can be selected.
Preferably Rh (acac) (CO)_Two use
It is particularly preferable to use.

The sulfonated bisphosphine (I ') may be used alone or in combination of two or more kinds.
It can also be used in combination with other phosphorus compounds. As other phosphorus compounds, for example, triethylphosphine, triisopropylphosphine, tributylphosphine, tricyclohexylphosphine, tribenzylphosphine, dimethylphenylphosphine, diethylphenylphosphine, methyldiphenylphosphine, ethyldiphenylphosphine, butyldiphenylphosphine,
Cyclohexyldiphenylphosphine, 2-furyldiphenylphosphine, 2-pyridyldiphenylphosphine, 4-pyridyldiphenylphosphine, triphenylphosphine, o-toluyldiphenylphosphine, diphenyl (pentafluorophenyl) phosphine, m-diphenylphosphinobenzenesulfonic acid or its A metal salt, p-diphenylphosphinobenzoic acid or a metal salt thereof, p-diphenylphosphinophenylphosphonic acid or a metal salt thereof, p-diphenylphosphinobenzenesulfonic acid or a metal salt thereof,

Bis (pentafluorophenyl) phenylphosphine, tris (p-fluorophenyl) phosphine, tris (pentafluorophenyl) phosphine, tris (p-chlorophenyl) phosphine, tri-o-toluylphosphine, tri-m-toluylphosphine. , Phosphines such as tri-p-toluylphosphine, tris (p-methoxyphenyl) phosphine, tris (pN, N-dimethylaminophenyl) phosphine; triethylphosphite, triphenylphosphite, tris (p-methylphenyl) Phosphite, tris (p-trifluoromethylphenyl) phosphite, tris (p
-Methoxyphenyl) phosphite, tris (2,4-
Di-methylphenyl) phosphite, tris (2,4-
And phosphites such as di-t-butylphenyl) phosphite.

The amount of the sulfonated bisphosphine (I ') used is preferably in the range of 2 to 10000 mol in terms of phosphorus atom, based on 1 mol of the group VIII metal compound in terms of group VIII metal atom, and 2 to More preferably, it is in the range of 1000 moles. When the amount of the sulfonated bisphosphine (I ′) used is less than the above range, the stability of the catalyst is impaired, and when it exceeds the above range, the catalyst cost increases, which is not preferable.

The method for preparing the Group VIII metal complex is not particularly limited, but for example, a Group VIII metal compound solution and a sulfonated bisphosphine (I ′) solution separately prepared using a solvent that does not affect the hydroformylation reaction. Can be prepared by separately introducing the compound into a hydroformylation reaction system, and reacting both in the system to form a complex. Alternatively, it can be prepared by adding sulfonated bisphosphine (I ′) to the above-mentioned Group VIII metal compound solution and then adding a solvent that does not affect the hydroformylation reaction to form a uniform solution.

Next, the ethylenically unsaturated compound was added to VIII.
A method for producing a corresponding aldehyde by hydroformylation with carbon monoxide and hydrogen in the presence of the group metal complex (I ′) will be described.

The ethylenically unsaturated compound may be a linear, branched or cyclic terminal olefin or an internal olefin. As the ethylenically unsaturated compound,
For example, ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1
-Nonene, 2-butene, isobutene, 2-octene,
Unsaturated aliphatic hydrocarbons such as 1,7-octadiene, vinylcyclohexene, cyclooctadiene, dicyclopentadiene, butadiene polymer and isoprene polymer;
Styrene, α-methylstyrene, β-methylstyrene,
Styrenes such as alkyl group nucleus-substituted styrene and divinylbenzene; alicyclic olefinic hydrocarbons such as cyclopentene, cyclohexene, 1-methylcyclohexene, cyclooctene and limonene; allyl alcohol, crotyl alcohol, 3-methyl-3- Butene-1-ol, 7-octen-1-ol, 2,7-octadienol, vinyl acetate, allyl acetate, methyl acrylate, ethyl acrylate, methyl methacrylate, allyl acrylate, vinyl methyl ether, allyl ethyl ether, 5- Examples thereof include olefins containing a functional group such as hexenamide, acrylonitrile, and 7-octen-1-al.

The amount of the Group VIII metal complex (I ') used is
It is preferable to select an amount in the range of 0.0001 to 1000 mg atom, in terms of Group VIII metal atom, and an amount in the range of 0.005 to 10 mg atom, per liter of the reaction mixture. More preferably. When the amount of the Group VIII metal complex (I ′) used is less than the above range, the reaction rate is too slow, and when it exceeds the above range, the catalyst cost increases, which is not preferable.

The hydroformylation reaction is carried out in the presence or absence of a solvent. Examples of the solvent include dimethyl sulfoxide, N-methylpyrrolidone, sulfolane,
Aprotic polar solvents such as dimethylformamide, acetonitrile, acetone, dioxane, tetrahydrofuran; alcohols such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, s-butyl alcohol, t-butyl alcohol. Kinds; glycol derivatives such as ethylene glycol, propylene glycol, diethylene glycol, ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, diethylene glycol diethyl ether, triethylene glycol, triethylene glycol dimethyl ether, tetraethylene glycol and tetraethylene glycol dimethyl ether;

Examples thereof include polyalkylene glycol derivatives such as polyethylene glycol, polypropylene glycol, polyethylene glycol monomethyl ether, polyethylene glycol dimethyl ether and polyethylene glycol dimethyl ether. These solvents may be used alone or in combination of two or more. Among these, it is preferable to use the polyalkylene glycol derivative from the viewpoints of preventing precipitation of the catalyst component during catalyst extraction and improving recovery efficiency of the catalyst component. In particular, polyethylene glycol, polyethylene glycol dimethyl ether and the like are preferably used. The amount of these solvents to be used is preferably selected so as to be in the range of 2 to 50% by volume in the hydroformylation reaction mixture, and is preferably selected to be in the range of 5 to 20% by volume. More preferable.

The mixed gas of hydrogen and carbon monoxide used in the hydroformylation reaction contains a H ₂ / CO molar ratio and preferably has a gas composition in the range of 0.1 to 10, preferably 0.5 to 10. The range of 2 is more preferable from the viewpoint of easy maintenance of the mixed gas composition. The reaction pressure is 0.1
It is preferably in the range of 10 MPa to 0.5 M
The range of Pa is preferable from the viewpoint of reaction rate. The reaction temperature is appropriately selected depending on the kind of the ethylenically unsaturated compound used and the time required for the reaction, but is 40 to 1
The range of 50 ° C. is preferable because the reaction rate is high and the deactivation of the catalyst can be suppressed, and the range of 60 to 100 ° C. is slow in the formation of a high boiling by-product during the hydroformylation reaction. Therefore, it is more preferable in that the decrease in the yield of aldehyde can be suppressed. The reaction can be carried out using a stirring reaction tank, a liquid circulation reaction tank, a gas circulation reaction tank, a bubble column reaction tank, or the like. Further, the reaction can be carried out in a continuous system or a batch system.

The method for charging the raw materials is not particularly limited, but an ethylenically unsaturated compound, a separately prepared Group VIII metal complex (I ') solution and, if necessary, a solvent are charged, and then hydrogen and carbon monoxide are added. It is preferable to introduce the mixed gas of 2) at a predetermined pressure and stir at a predetermined temperature to carry out the reaction.

The aldehyde obtained by the above method is
It can be isolated / purified by a method generally used for isolation / purification of organic compounds. For example, distillation, recrystallization from the organic layer obtained through the catalyst component recovery step described below,
Isolate and purify by column chromatography.

Next, a method for recovering the catalyst component from the reaction mixture obtained by the above-mentioned aldehyde production method will be described. In recovering the catalyst component from the hydroformylation reaction mixture, first, the reaction mixture after the hydroformylation reaction is brought into contact with water. The amount of water used with respect to the reaction mixture is not particularly limited, but in consideration of operability and solubility of the catalyst component in water, etc., it is 1 to 200 with respect to the reaction mixture.
It is preferable to select an amount such that the range is% by volume,
It is more preferable to select an amount in the range of 5 to 50% by volume.

The reaction mixture and water are thoroughly contacted by stirring, and the catalyst component is extracted with water. At this time, the temperature is 2
The temperature is preferably in the range of 0 to 90 ° C., and the operation is preferably carried out in an atmosphere of an inert gas such as nitrogen, helium or argon or a mixed gas of hydrogen and carbon monoxide.

Next, the organic layer containing the hydroformylation reaction product and the aqueous layer containing the catalyst component are separated. In the extraction operation, when the organic layer and the aqueous layer are not sufficiently separated by standing, a centrifugal separation operation or the like can be used together to accelerate the layer separation. Further, layer separation can be promoted by adding a hydrocarbon such as hexane or cyclohexane having a specific gravity smaller than that of water.

In addition to the reaction product, the organic layer contains unreacted ethylenically unsaturated compound and a small amount of catalyst component,
In order to increase the recovery rate of the catalyst component, it is preferable to wash the organic layer with water and combine the washing solution with the aqueous layer.

The catalyst component can be recovered by removing water from the obtained aqueous layer. Water is removed by a conventional method such as distillation under reduced pressure. When depressurizing distillation is performed, VI
In order to prevent thermal deterioration of the Group II metal complex (I ′) and the like, it is preferable to carry out at a low temperature, and 30 to 100 is preferable.
It is preferable to carry out at a temperature of ° C under a pressure condition of 10 to 300 mmHg. The water is preferably distilled off to such an extent that when the concentrate containing the catalyst component is reused in the hydroformylation reaction, separated water does not exist in the reaction system. The catalyst component obtained can be reused in the hydroformylation reaction.

[0081]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. In the following examples, unless otherwise specified, the synthesis operation of the phosphorus compound is performed under a nitrogen or argon atmosphere, and the hydroformylation reaction and the water extraction operation are all performed with carbon monoxide and hydrogen, and H ₂ / CO It was performed in a mixed gas atmosphere with a molar ratio of 1.

Bisphosphine (I), sulfonated bisphosphine (I ') and their precursors are ¹ H-NMR spectroscope (Lambda 270 type manufactured by JEOL Ltd.) and / or ³¹ P-NMR spectroscope (Japan). It was identified by using a Lambda 500 manufactured by Denshi Co., Ltd.). The ³¹ P-NMR chemical shift described in the examples is a value when the heavy water containing 20% by weight of phosphoric acid was previously measured and the chemical shift of phosphoric acid was set to 0 ppm. Recovery of the aqueous layer extracted sulfonated bisphosphine by the operation (I ') is the ³¹
It quantified using the P-NMR spectrometer. Recovery of the sulfonated bisphosphine (I ′) into the aqueous layer by the extraction operation is
Quantification was performed using a CID plasma emission spectrophotometer (IRIS / AP manufactured by Nippon Jarrell Ash Co., Ltd.). Recovery of the rhodium compound to the aqueous layer by extraction operation,
Quantification was performed using a polarized Zeeman atomic absorption spectrophotometer (Z-5300 manufactured by Hitachi, Ltd.).

Reference Example 1 Synthesis of 2,2′-dimethyldiphenyl ether In a three-necked flask having an internal volume of 1 L equipped with a reflux tube, a Dean Stark apparatus, a dropping funnel, a thermometer and a mechanical stirrer, 40 g of potassium hydroxide (0 0.71 mol), 77 g (0.71 mol) of o-cresol, 100 g (0.79 mol) of 2-chlorotoluene and 400 g (2.34 mol) of 2-bromotoluene, while heating a three-necked flask at 150 ° C. The resulting water was continuously removed from the reaction using a Dean Stark apparatus. Activated copper powder (3 g) was added, and water and 2-chlorotoluene contained in the activated copper were continuously removed from the reaction solution using a Dean-Stark apparatus, and heated until the solution temperature reached 190 ° C.
The mixture was stirred for 0 hours at the same temperature. After the reaction was completed, the reaction solution was allowed to cool to room temperature, 400 ml of diethyl ether was added,
The resulting solution was filtered through Celite. The filtrate was washed 5 times with 200 ml of a 5 wt% potassium hydroxide aqueous solution,
The obtained organic layer was distilled under reduced pressure at 0.3 mmHg to 93 ° C.
84 g of distillate was obtained. This fraction is a colorless oil,
It was 2,2'-dimethyldiphenyl ether having the following physical properties. The yield was 60% based on o-cresol.

¹ H-NMR (270 MHz, deuterated benzene, TMS, ppm) δ: 2.18 (s, 6 H, Ar-
_{C H 3), 6.67 (d} , 2H), 6.80~7.0
0 (m, 4H), 7.05 (d, 2H)

Reference Example 2 Synthesis of 2,2′-bis (bromomethyl) diphenyl ether Internal volume 500 equipped with reflux tube, thermometer and mechanical stirrer
In a 3-mL 3-neck flask, 250 ml of carbon tetrachloride, N
58 g (0.33 mol) of -bromosuccinimide and 32 g (0.16 mol) of 2,2'-dimethyldiphenyl ether synthesized in Reference Example 1 were added, and the solution was refluxed at 70 ° C. 1g of benzoyl peroxide divided into 3 times
It took 0 minutes and was stirred for another 30 minutes. The obtained reaction mixture was filtered, the filtrate was concentrated to dryness, and recrystallized with hexane as a solvent to obtain 20 g of 2,2′-bis (bromomethyl) diphenyl ether having the following physical properties as colorless crystals. . The yield was 35% based on 2,2′-dimethyldiphenyl ether.

¹ H-NMR (270 MHz, deuterated benzene, TMS, ppm) δ: 4.30 (s, 4 H, Ar-
_{C H 2 -Br), 6.58 (} d, 2H), 6.73
(T, 2H), 6.83 (t, 2H), 7.04 (d,
2H)

Reference Example 3 Synthesis of 2,2'-bis (diphenylphosphinomethyl) diphenyl ether 250 ml of tetrahydrofuran was placed in a three-necked flask having an inner volume of 500 ml equipped with a reflux tube, a dropping funnel, a thermometer and a magnetic rotor. After adding 20 g (0.11 mol) of diphenylphosphine, the liquid temperature was cooled to -75 ° C. Next, 69 ml of hexane solution of butyl lithium (1.56 mol / L)
(0.11 mol) was added dropwise over 2 hours at such a rate that the liquid temperature was maintained at -75 to -65 ° C, and then 1
The mixture was stirred for the same time at the same liquid temperature to obtain lithium diphenylphosphide. Then, 19 g (0.05 g of 2,2′-bis (bromomethyl) diphenyl ether synthesized in Reference Example 3)
4 mol) of tetrahydrofuran (100 ml) at a rate such that the solution temperature is maintained at -75 to -65 ° C.
After adding dropwise to the above solution over a period of time, the mixture was returned to room temperature and stirred for 1 hour. After completion of the reaction, 250 ml of tetrahydrofuran was distilled off from the obtained reaction mixture, and 200 ml of diethyl ether was added. The obtained solution was washed with 150 ml of a saturated aqueous solution of ammonium chloride three times and with 150 ml of water three times. The organic layer thus obtained was dehydrated with anhydrous magnesium sulfate, filtered, and the filtrate was concentrated to an oil. 200m of methyl alcohol in the concentrate
1, 2'-bis (diphenylphosphinomethyl) diphenyl ether 2 having the following physical properties as a white powder was obtained by adding 1 and boiling for 10 minutes at the solvent reflux temperature.
6 g was obtained. The yield was 85% based on 2,2′-bis (bromomethyl) diphenyl ether.

¹ H-NMR (270 MHz, deuterated benzene, TMS, ppm) δ: 3.60 (s, 4 H, Ar-
_{C H 2 -P), 6.67~6.78 (} m, 4H),
6.85 (t, 2H), 6.95 to 7.10 (m, 14)
H, of which 12H are _{P (C 6 H 5) 2} ), 7.36~
^{_{7.50 (m, 8H, P (}} C 6 H 5) 2) 31 P-NMR (500MHz, heavy benzene, phosphoric acid weight aqueous, ppm) δ: -11.2 (s )

Example 1 2,2'-bis (diphenylphosphinomethyl) -4,
Synthesis of 4'-bis (sulphonic acid) -diphenyl ether dipotassium salt 3 with an internal volume of 100 ml equipped with a thermometer and a magnetic rotor
In a two-necked flask, 50 ml of sulfuric acid and a sulfur trioxide content of 3
10 ml of 0% fuming sulfuric acid was added, and 18 g (0.03) of solid 2,2'-bis (diphenylphosphinomethyl) diphenyl ether was added so that the liquid temperature became 25 ° C or lower.
2 mol) was added over 2 hours. Then, the mixture was stirred at room temperature for 15 hours. The reaction solution was added to 100 ml of water containing 100 g of ice and neutralized with potassium hydroxide. The obtained aqueous solution was dried using a rotary evaporator, and then 50 ml of ethanol was added and filtered. The filtrate was dried, 50 ml of ethanol was added, and filtration was performed. By drying the filtrate to dryness, 2,2′-bis (diphenylphosphinomethyl) -4, which has the following physical properties as a white powder,
24 g of 4'-bis (sulphonic acid) -diphenyl ether dipotassium salt was obtained. The yield was 93% based on 2,2'-bis (diphenylphosphinomethyl) diphenyl ether.

Compounds in which the number of sulfonic acid groups introduced into 2,2'-bis (diphenylphosphinomethyl) diphenyl ether is 1 or 3 or more are estimated to be ¹ H.
-NMR and ³¹ P-NMR could not observe.

[0091]¹H-NMR (270 MHz, heavy water, TS
P, ppm) δ: 3.24 (s, 4H, Ar-CH _Two 
-P), 6.51 (d, 2H), 6.82 to 7.02
(M, 12H, P (C₆ H ₅ )_Two ), 7.02 ~
7.18 (m, 8H, P (C₆ H ₅ )_Two ), 7.2
8 (s, 2H), 7.39 (d, 2H)³¹ P-NMR (500 MHz, heavy benzene, phosphoric acid
Aqueous solution, ppm) δ: -10.9 (s)

Example 2 2,2'-bis (diphenylphosphinomethyl) -4,
Hydroformylation reaction using 4'-bis (sulfonic acid) -diphenyl ether dipotassium salt-rhodium complex catalyst Internal volume 10 equipped with a magnetic rotor made of Teflon (registered trademark)
Add Rh (acac) (CO) to a 0 ml 3-neck flask.
₂ 3.9 mg (0.015 mmol) and 30.1 mg of 2,2'-bis (diphenylphosphinomethyl) -4,4'-bis (sulphonic acid) -diphenyl ether dipotassium salt synthesized in Example 1 (0. 037
5 mmol) (5 mole times as a phosphorus atom relative to the rhodium compound), and further 4.5 ml of polyethylene glycol dimethyl ether and butyl alcohol 4.5
After adding ml, the mixture was stirred at 50 ° C. for 30 minutes to prepare a uniform catalyst solution. In a three-necked flask having an internal volume of 50 ml equipped with a magnetic rotor made of Teflon (registered trademark), 6 ml of the above catalyst solution and 34 ml of 7-octen-1-al were added.
(0.21 mol, purity 93%) was added, and the resulting mixed solution was added with a gas inlet port and a sampling port to have an internal volume of 1
It was charged into a 00 ml autoclave. Total pressure 1.0M
After setting to Pa and raising the internal temperature to 85 ° C. with stirring, 1
After reacting for 5 hours, 27.6 g of 1,9-nonane dial
(0.176 mol, yield 84%) and 4.2 g of 2-methyloctanal (0.014 mol, yield 6%) were obtained. The conversion of 7-octen-1-al is 95% and the selectivity to n-aldehyde is 88%.
The selectivity to aldehyde was 7%. The selectivity to hydrogenation and isomerization was 5%.

The reaction mixture obtained above was obtained by pressure-feeding from the autoclave to a 50 ml three-necked flask, which had been sufficiently replaced with a mixed gas of hydrogen / carbon monoxide, without touching air. 20 ml of the reaction mixture, 20 g of water and 6 ml of hexane were added to a Schlenk having an inner volume of 50 ml, and the mixture was stirred for 20 minutes under a mixed gas atmosphere of the above composition while keeping the internal temperature at 20 ° C. After stopping stirring, the mixture was allowed to stand for 12 hours at the same temperature to obtain an aqueous layer (19.0 g). As a result of the high frequency inductively coupled plasma optical emission spectrometry analysis, the recovery rate of sulfonated bisphosphine (I ′) in the aqueous layer was 7
It was 1.2%. As a result of atomic absorption analysis, the recovery rate of rhodium was 66.7%. 20 g of water was added again to the organic layer and the same operation was performed to obtain 21.2 g of an aqueous layer. As a result of the high frequency inductively coupled plasma optical emission spectroscopy, the recovery rate of the sulfonated bisphosphine (I ′) in the aqueous layer was 26.5%. As a result of atomic absorption analysis, the recovery rate of rhodium in the aqueous layer was 32.3%. From this, the recovery of sulfonated bisphosphine (I ′) in the aqueous layer was 97.7% and the recovery of rhodium was 99.0% by repeating the water extraction operation twice.

Comparative Example 1 Hydroformylation reaction using meta-diphenylphosphinobenzenesulfonic acid sodium salt-rhodium complex catalyst In Example 2, 2,2'-bis (diphenylphosphinomethyl) -4,4'-bis (Sulfonic acid) -diphenyl ether dipotassium salt 30.1 mg
440 mg of meta-diphenylphosphinobenzenesulfonic acid sodium salt instead of (0.0375 mmol)
The same operation was performed except that (1.2 mmol) (80 mol times as a phosphorus atom relative to the rhodium compound) was used and the reaction time was 8 hours.
0.1 g (0.129 mol, 73% yield) and 2-
7.0 g (0.045 mol, yield 27%) of methyl octanal was obtained. The conversion of 7-octen-1-al was 100%, the selectivity to n-aldehyde was 73%, and the selectivity to iso-aldehyde was 27%. No hydrogenation or isomerization was observed.

Then, the reaction mixture was obtained by pressure-feeding from the autoclave into a three-necked flask having an internal volume of 50 ml, which had been sufficiently replaced with a mixed gas of hydrogen / carbon monoxide, in such a manner as not to come in contact with air. 20 ml of the reaction mixture, 20 g of water and 6 ml of hexane were added to a Schlenk having an inner volume of 50 ml, and the mixture was stirred for 20 minutes under a mixed gas atmosphere of the above composition while keeping the internal temperature at 20 ° C. After stopping the stirring, the mixture was allowed to stand for 12 hours at the same temperature to obtain 18.5 g of an aqueous layer. As a result of the high frequency inductively coupled plasma optical emission spectroscopy, the recovery of sulfonated monophosphine in the aqueous layer was 70.3%. As a result of atomic absorption analysis, the recovery rate of rhodium is 7
It was 0.0%. 20 g of water was added again to the organic layer and the same operation was performed to obtain 21.2 g of an aqueous layer. As a result of the high frequency inductively coupled plasma optical emission spectroscopy, the recovery rate of the sulfonated monophosphine in the aqueous layer was 22.5%. As a result of atomic absorption analysis, the recovery rate of rhodium in the aqueous layer was 24.2%. From this, the recovery rate of the sulfonated monophosphine in the aqueous layer was 9 by repeating the water extraction operation twice.
It was 2.8% and the recovery rate of rhodium was 94.2%.

Comparing Example 2 and Comparative Example 1 above,
When the sulfonated bisphosphine (I ′) is used, the VI
Even under the condition that the amount of the phosphorus atom converted to the group II metal complex (I ′) is small, n- can be obtained by the hydroformylation reaction.
A high selectivity to aldehydes can be achieved. In addition, when the catalyst is recovered by adding water to the reaction mixture, the sulfonated phosphine compound and rhodium can be recovered at a higher recovery rate when using the sulfonated bisphosphine (I ′) than when using a conventional sulfonated monophosphine. The compound is obtained.

[0097]

According to the present invention, the hydroformylation reaction of an ethylenically unsaturated compound can be carried out at a low rhodium concentration, the volume efficiency is high, the catalyst recovery efficiency is good, and the economy is excellent. Also provided is a Group VIII metal complex (I ′) which is a hydroformylation catalyst capable of highly selectively producing n-aldehyde, and a sulfonated bisphosphine (I ′) which is a constituent component of the complex and a production method thereof are provided. Provided. By hydroformylating an ethylenically unsaturated compound with carbon monoxide and hydrogen using the Group VIII metal complex (I ′), the reaction can be performed at a low rhodium concentration, the volume efficiency is high, and the catalyst recovery efficiency is high. The n-aldehyde can be obtained with high efficiency and excellent economy. Furthermore, the catalyst component can be efficiently recovered from the reaction mixture obtained by the above-mentioned aldehyde production method.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C07F 15/00 C07F 15/00 B // C07B 61/00 300 C07B 61/00 300 F term (reference) 4G069 AA06 AA10 BA27A BA27B BC65A BC66A BC67A BC69A BC70A BC71A BC71B BE22A BE22B BE26A BE27A BE27B CB51 CB52 CB72 GA01 GA09 4H006 AA02 AC21 AC45 AD16 BA17 BA24 BA81 BA40 BA60 BA62 BA60 BA62 BA40 BA60 BA62 BA40 BA62 BA40 BA62 BA40 BA62 BA40 BA62 BA40 BA62 BA40 BA62 BA40 BA62 BA40 BA62 BA40 WB15 WB16 WB21

Claims (5)

[Claims] 1. A compound represented by the general formula (I): (In the formula, Ar ¹ and Ar ² represent an arylene group which may have a substituent, and R ¹ and R ² may have an alkyl group which may have a substituent or a substituent which may have a substituent. It may represent a good aryl group or may form a ring together with the phosphorus atom to which it is attached, and R ³ and R ⁴ represent a hydrogen atom or an alkyl group, provided that
The carbon atoms having R ³ and R ⁴ are Ar ¹ and A
Attaches in the ortho position to the oxygen atom to which they bind in r ² . ) A sulfonated bisphosphine obtained by introducing at least one sulfonic acid group or a salt thereof onto the group represented by Ar ¹ and Ar ² in the general formula of the bisphosphine represented by the formula (1). 2. A compound represented by the general formula (I): (In the formula, Ar ¹ and Ar ² represent an arylene group which may have a substituent, and R ¹ and R ² may have an alkyl group which may have a substituent or a substituent which may have a substituent. It may represent a good aryl group or may form a ring together with the phosphorus atom to which it is attached, and R ³ and R ⁴ represent a hydrogen atom or an alkyl group, provided that
The carbon atoms having R ³ and R ⁴ are Ar ¹ and A
Attaches in the ortho position to the oxygen atom to which they bind in r ² . The method for producing a sulfonated bisphosphine according to claim 1, wherein the bisphosphine represented by 1) is sulfonated with sulfur trioxide in sulfuric acid. 3. A Group VIII metal complex formed by complexing the Group VIII metal compound with the sulfonated bisphosphine according to claim 1. 4. Use of a Group VIII metal complex according to claim 3 as a catalyst in the preparation of the corresponding aldehyde by hydroformylating an ethylenically unsaturated compound with carbon monoxide and hydrogen in the presence of a catalyst. A method for producing an aldehyde, which comprises: 5. When recovering the catalyst component from the reaction mixture obtained by the method for producing an aldehyde according to claim 4, the reaction mixture is contacted with water to extract the catalyst component into an aqueous layer, and then the aqueous layer. The method for recovering a catalyst component as described above, characterized in that water is removed from the catalyst.