JP2000351746A - Production of aldehyydes - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce the subject compounds without accompanying the deposition of rhodium by carrying out a hydroformylating reaction of an olefinically unsaturated compound with a rhodium-phosphite-based complex catalyst and then converting the rhodium into a stable enolate complex. SOLUTION: An olefinically unsaturated compound (e.g. an α-olefin, an internal olefin or an alkyl alkenoate) is reacted with carbon monoxide and hydrogen in the presence of a rhodium-phosphite-based complex catalyst (a triaryl phosphite, a trialkyl phosphite, an aryl alkyl phosphite or the like is cited as the phosphite compound) in the liquid phase and hydroformylated. When at least one component is separated from a reactional liquid after completing the hydroformylating reaction, the rhodium in the reactional liquid is made to exist as an enolate complex represented by the formula (R1 to R3 are each H, an alkyl, an alkoxy or the like or two or more of R1 to R3 may be bound to form a ring; L1 and L2 are each carbonyl or a phosphite ligand) to thereby produce the objective compounds.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing aldehydes by subjecting an olefinically unsaturated compound to a hydroformylation reaction in the presence of a rhodium-phosphite complex catalyst.

[0002]

2. Description of the Related Art Processes for producing aldehydes by reacting an olefinically unsaturated compound with carbon monoxide and hydrogen in the presence of a Group VIII metal complex catalyst of the periodic table have been widely industrialized. As a catalyst in this hydroformylation reaction, a complex catalyst obtained by modifying a Group VIII metal such as rhodium with a ligand such as a trivalent phosphorus compound is used, and the activity and selectivity of the hydroformylation reaction are improved. For this reason, various ligands have been studied. For example, Japanese Patent Publication No. 45-10730 discloses that a rhodium catalyst modified with a trivalent phosphorus ligand such as triarylphosphine or triarylphosphite is effective. Among them, a catalyst modified with a phosphite ligand is known to exhibit high activity and excellent selectivity in a hydroformylation reaction.

[0003] However, as disclosed in JP-A-59-51229, in a phosphite ligand such as triphenyl phosphite, the ligand is relatively quickly decomposed in a hydroformylation reaction system, It is known that the catalytic activity decreases with this, and it is necessary to continuously replenish the phosphite ligand. Therefore, various phosphite ligands have been proposed not only to improve the activity and selectivity of the catalyst but also to reduce the decrease in catalyst activity due to the loss of the phosphite ligand. For example, JP-A-59-51228 and JP-A-59-51228.
No. 5,512,230 discloses a method using a cyclic phosphite ligand containing a phosphorus atom at the bridgehead. JP-A-57-123134 discloses a method using a triaryl phosphite ligand having a substituent at a specific site of a benzene ring.
No. 88033 discloses a method using a triaryl phosphite ligand having a substituent at a specific site of a naphthyl ring. JP-T-61-501268 discloses a method using a diorganophosphite ligand having a cyclic structure containing a phosphorus atom in the molecule.
Further, as examples of bisphosphite ligands and polyphosphite ligands, JP-A-62-116535 and JP-A-62-116587 disclose a method using a diorganophosphite ligand. JP-A-4-2905
No. 51 discloses a method using a bisphosphite ligand having a cyclic structure. Japanese Patent Application Laid-Open No. 5-178779 by the present applicant discloses a method using bisphosphite ligands and polyphosphite ligands having no cyclic structure.

In an oxo process for producing the corresponding aldehyde from a polysubstituted olefin compound which is considered to have relatively low reaction activity by an oxo reaction, a benzene ring or a naphthalene ring is considered from the viewpoint of ligand stability and activity during the oxo reaction. It is known that it is advantageous to use a rhodium complex catalyst having a ligand of a triaryl phosphite having a substituent at a specific site and a diorgano phosphite having a cyclic structure containing a phosphorus atom in the molecule. I have. In the oxo reaction using a phosphite having a bulky substituent at a specific aromatic site as a ligand, it is known that a rhodium complex having an average of one phosphite coordinated per rhodium is an active species (Journal of Organometallic Chem
istry, 421 (1991) 121-128), and the ease of coordination of olefins with large steric hindrance to rhodium atoms is considered as a reason for particularly high activity.

On the other hand, in an industrial process, it is essential to recycle expensive rhodium-complex catalysts, and it is necessary to separate the rhodium catalyst from the reaction solution in an active or easily reactivated form. . Therefore, stability of phosphite ligand and rhodium in catalyst separation is also a serious problem. Techniques for separating the catalyst include an adsorption method (Japanese Patent Application Laid-Open No. 50-49190) and a crystallization method (Japanese Patent Application Laid-Open No. 57-12 / 1982).
2948), a membrane separation method (JP-A-2-231435).
And various extraction techniques such as an extraction method (Japanese Patent Application Laid-Open No. 56-2994) can be applied. However, industrially, separation is often performed by distillation or evaporation.

However, the rhodium-phosphite complex is easily decomposed by heating, and carbon monoxide and hydrogen, which contribute to stabilization of rhodium, are released from the system when the formed aldehydes and the catalyst are separated. This causes an unstable situation in which rhodium itself tends to precipitate. Particularly, in the hydroformylation reaction of an olefin compound having a large number of carbon atoms, since the generated aldehydes have a high boiling point, high temperature conditions are required when separating the generated aldehydes and the catalyst by distillation, and rhodium is remarkably destabilized. Is done. Japanese Patent Publication No. 5-48215 discloses that when a circulating liquid for a hydroformylation reaction is heated in the absence of carbon monoxide and hydrogen, a phenomenon of depletion of rhodium occurs.

As a distillation separation method for reducing the loss of the phosphite ligand, the present applicant has previously adopted a method in which specific distillation conditions are employed (Japanese Patent Application Laid-Open No. 8-165266) or a method in which a specific amine is used during distillation. Method to make it exist
No. 68947). In addition, for example,
No. 8215 states that in order to suppress metallization of rhodium,
To perform distillation in the presence of an organic polymer having a specific polar functional group, and to distill and separate an aldehyde product from a product solution containing a rhodium-phosphite-based complex catalyst, the distillation is performed at a temperature lower than 150 ° C., preferably It is disclosed that it is better to carry out at a temperature below 140 ° C.

[0008]

DISCLOSURE OF THE INVENTION The present invention relates to a hydroformylation of an olefinically unsaturated compound using a rhodium catalyst having a phosphite as a ligand exhibiting high activity and excellent selectivity in the hydroformylation reaction. An object of the present invention is to establish an industrially advantageous method in which the loss of rhodium is suppressed in the reaction, and particularly to provide a method of suppressing the precipitation of rhodium during a separation operation.

[0009]

DISCLOSURE OF THE INVENTION The present inventors have developed an oxo process for producing a corresponding aldehyde from a olefinically unsaturated compound by a hydroformylation reaction.
As a result of intensive studies on a versatile separation method that does not involve the precipitation of rhodium, the conversion of rhodium in the catalyst separation step to a thermally stable rhodium-β-carbonylenolate complex has led to the precipitation of rhodium. It has been found that the produced aldehydes and high-boiling substances can be separated without accompanying the present invention, leading to the present invention.

That is, the gist of the present invention is to react an olefinic unsaturated compound with carbon monoxide and hydrogen in a liquid phase in the presence of a rhodium-phosphite complex catalyst to hydroformylate the olefinic unsaturated compound. In the method for producing an aldehyde, when at least one component is separated from the reaction solution after the completion of the hydroformylation reaction, rhodium in the reaction solution is converted into the following general formula (1)

[0011]

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(Wherein R ₁ , R ₂ and R ₃ represent a hydrogen atom, an alkyl group, an alkoxy group, a substituted amino group, an aryl group,
Represents an aryloxy group, an arylamino group, or a heteroaryl group, and these groups may further have a substituent that does not inhibit a hydroformylation reaction. Also, at least two of R ₁ , R ₂ and R ₃ may combine to form a ring. L ₁ and L ₂ represent carbonyl or a phosphite ligand. ), Wherein the compound is present as a rhodium-β-carbonyl enolate complex.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
As described above, a reaction of hydroformylating an olefinically unsaturated compound by reacting an olefinically unsaturated compound with carbon monoxide and hydrogen using a rhodium complex catalyst having phosphite as a ligand is well known. As described later, any of these known hydroformylation reaction methods can be applied to the method of the present invention. In particular, a liquid catalyst circulation process in which a rhodium catalyst solution containing a phosphite ligand is separated from a reaction product solution, and continuously circulated and reused is preferable.

After the completion of the reaction, the hydroformylation reaction product solution contains at least 1) a complex catalyst containing rhodium and a phosphite compound, 2) aldehydes formed, and an unreacted olefinic unsaturated compound, carbon monoxide and Hydrogen, reaction solvents or high-boiling by-products of the produced aldehyde in the recycle process may be included in the reaction form.
The present invention is represented by the above general formula (1), which is a rhodium species capable of stably and reactivating rhodium species in a liquid when at least one of the above components is separated from the reaction mixture after the hydroformylation reaction. The presence of a rhodium-β-carbonylenolate complex suppresses rhodium precipitation during the separation operation.

The rhodium-β-carbonyl enolate complex of the general formula (1) will be specifically described. R ₁ , R ₂
And R ₃ are hydrogen atoms; methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, t-butyl, n-amyl, sec- Amyl group, t-amyl group, hexyl group, cyclohexyl group, heptyl group,
Linear, branched or cyclic alkyl groups such as octyl group, nonyl group and decyl group; alkoxy groups such as methoxy group, ethoxy group, propoxy group, butoxy group, pentoxy group and heptoxy group; phenoxy group and naphthoxy group Aryloxy group; dimethylamino group, diethylamino group,
Substituted amino groups such as alkylamino group such as dipropylamino group, diphenylamino group, dibenzylamino group, methylphenylamino group, ethylphenylamino group, methylbenzylamino group, ethylbenzylamino group; phenyl group, naphthyl group, 2-tolyl group, 3-tolyl group, 4-tolyl group, 2,4-dimethylphenyl group, 2,6-dimethylphenyl group, 2,4,6-trimethylphenyl group, 2-t-butylphenyl group, 4 -t-butylphenyl group, 2-t-butyl-4-methylphenyl group, 2,6-dimethyl-4-t-butylphenyl group, 2,4-di-
aryl groups such as t-phenyl group; and heteroaryl groups such as 2-pyridyl group, 3-pyridyl group and 4-pyridyl group.

These groups may further have a substituent which does not inhibit the hydroformylation reaction. Examples of such a substituent include a linear or cyclic alkyl group having 1 to 20 carbon atoms, an alkoxy group, a halogen atom, an alkylamino group, an acyl group, a carboalkoxy group, and an oxycarbonyl group. At least two of R ₁ , R ₂ and R ₃ may combine to form a cyclic group. L ₁ and L ₂ are carbonyl or various phosphite ligands described below.

In the general formula (1), preferably, R ₁
And R ₂ is a methyl group, R ₃ is a hydrogen atom, _one of L ₁ and L ₂ is carbonyl, and the other is tris (2,4-di-t-butylphenyl) phosphite. The method for converting rhodium in the hydroformylation reaction solution after the reaction to the rhodium-β-carbonylenolate complex of the general formula (1) is not particularly limited, but for example, a simple preparation method is as follows. After the reaction is completed, rhodium in the reaction solution is brought into contact with a β-dicarbonyl compound having at least one active proton. The contact between the β-dicarbonyl compound and rhodium is preferably in a state where carbon monoxide and hydrogen have been reduced and rhodium has been destabilized, and more preferably in a heated state. The method of the heat treatment is not particularly limited, but it is preferable to heat to 110 ° C. or higher. Since the reaction between the β-dicarbonyl compound and the destabilized rhodium complex is faster than the precipitation phenomenon of rhodium due to the heat treatment, the desired reaction substantially proceeds only by the coexistence of the β-dicarbonyl compound, A rhodium-β-carbonyl enolate complex is prepared. As a specific contact method, a β-dicarbonyl compound is added to a reaction solution of a batch reaction or a flow reaction after releasing carbon monoxide and hydrogen after the reaction, and heated, and then a separation operation is performed. Or a method of adding a β-dicarbonyl compound when performing an operation involving a heat treatment such as distillation.

All rhodium in the reaction solution is represented by the general formula (1)
The amount of the β-dicarbonyl compound to be supplied is preferably at least equimolar to the rhodium present in the hydroformylation reaction product, but the amount of rhodium in the reaction The effect of the present invention can be exhibited only by converting the moiety into the form of the general formula (1). The β-dicarbonyl compound can be previously made to coexist in a series of catalyst liquid recirculation oxo processes including a hydroformylation reaction, a separation operation, and recycle. Therefore, at the time of the separation operation, the β-dicarbonyl compound may be added in consideration of the amount existing in the reaction solution in advance.

The rhodium-β-carbonyl enolate complex of the general formula (1) exists stably without depositing rhodium in the subsequent separation operation. In particular, it is stable even in a heated state, and is suitable for a separation operation involving heat treatment. The temperature range of the heat treatment in this case is 50 to 200C, preferably 70 to 180C. At low temperatures, substantially no destabilization of the rhodium species occurs, and at high temperatures exceeding 200 ° C., the rhodium-β-carbonylenolate complex itself also destabilizes, which may cause a decrease in rhodium loss, which is not preferable.

The separation method employed in the method of the present invention is not particularly limited, and any method can be employed. Specifically, separation operations such as distillation (simple distillation, vacuum distillation, thin film distillation, steam distillation, etc.), evaporation (evaporation), gas stripping, gas-liquid separation, gas absorption, extraction, crystallization, adsorption, membrane separation, etc. And an operation involving a heat treatment is particularly preferable. Each separation operation may be performed in an independent step, or two or more components may be separated simultaneously.

Representative of these separation operations are distillation and evaporation (evaporation). First, an example of distillation separation in the liquid catalyst recycle process will be described. Generally, a reaction solvent having a boiling point higher than that of the aldehyde product is used, and a catalyst and a ligand are dissolved in this solvent and used as a catalyst solution. The catalyst solution, the olefinically unsaturated compound, carbon monoxide and hydrogen are supplied to a usual continuous reactor, and a hydroformylation reaction is performed at a predetermined temperature and a predetermined pressure. The reaction product liquid taken out of the reactor is converted into rhodium into the form of the general formula (1), and then heated and distilled to separate unreacted olefin-based unsaturated compounds and aldehyde products from the catalyst solution and the catalyst solution. The liquid is recycled to the reaction liquid. A part of the catalyst solution is continuously or intermittently purged from the reaction system as a waste catalyst solution in order to prevent accumulation of the deactivated catalyst and high-boiling by-products. Corresponding amounts of fresh catalyst and ligand are supplied to the reaction system.

Next, an example of evaporation will be described. The recovery of the produced aldehyde is performed by evaporation. As the reaction solvent, a high-boiling organic compound composed of a polymer or a condensate of an aldehyde product is generally used. A catalyst and a ligand are dissolved in this solvent and used as a catalyst solution. An olefin, carbon monoxide and hydrogen are supplied to a reactor containing the catalyst solution, and a hydroformylation reaction is performed at a predetermined temperature and a predetermined pressure. Rhodium in the reaction solution is converted to the general formula (1)
After conversion to the form of
It is removed from the reactor by stripping with an unreacted gas containing unreacted olefin, carbon monoxide and hydrogen. At the same time, a part of the high-boiling by-product generated is taken out of the reactor together with the unreacted gas. Preferably, the entire amount of high-boiling by-products is removed from the reactor, in which case the amount of high-boiling by-products purged from the reaction system with the spent catalyst is approximately equal to the amount produced. If much higher boiler by-products are removed from the reactor with unreacted gas than are produced, some of the higher boiler by-products is recycled to the reactor to maintain a constant volume of catalyst liquid. You.

In this method by evaporation, the amount of the catalyst in the hydroformylation reactor is kept constant. Liquid substances (mainly aldehydes) in the gas mixture withdrawn from the reactor are separated from unreacted gases by cooling or condensation. Some of the unreacted gas is purged, mainly to prevent accumulation of hydrogenated by-products such as paraffin, and the rest is recycled to the reactor. In addition, part of the catalyst solution in the reactor is continuously or intermittently purged as spent catalyst to prevent accumulation of deactivated catalyst and high-boiling by-products, and the amount of fresh catalyst required to compensate for those losses And the ligand are supplied to the reaction system.

The hydroformylation reaction method to which the method of the present invention is applied will be described below. Various rhodium compounds and phosphite compounds can be used as the rhodium-phosphite complex catalyst used in the hydroformylation reaction of the present invention. The form of rhodium fed to the reaction system is not particularly limited, and can be supplied to the reaction system in any form. Examples of the raw material rhodium species that can be used in the present invention include organic acid salts such as rhodium acetate and rhodium formate, and Rh ₄ (C
O) ₁₂ , Rh ₆ (CO) ₁₆ , Rh (CO) ₂ (acac), [Rh (cod) Cl] ₂ , [Rh
(OAc) (cod)] ₂ , carbonyl complex compounds such as [Rh (OAc) (CO) ₂ ] ₂ , sodium rhodate, potassium chloride rhodate and other inorganic basic acid salts (where acac is an acetylacetonate group) , Ac represents an acetyl group, and cod represents cyclooctadiene). The rhodium-phosphite-based complex catalyst may be formed by supplying the rhodium and the phosphite compound directly to the hydroformylation reactor and forming the same in the hydroformylation reaction system.However, carbon monoxide, hydrogen and phosphite are formed outside the reactor. The complex catalyst can be prepared in advance by reacting with the compound in a solvent under high temperature and pressure conditions. The preparation conditions are usually from normal pressure to 10
0 Kg / cm ² G, temperature is from normal temperature to 150 ° C.

The phosphite compound used in the method of the present invention is not particularly limited, and any phosphite compound such as triaryl phosphite, trialkyl phosphite, and arylalkyl phosphite is used. Bisphosphite and polyphosphite compounds having these combinations in the same molecule are also included. More specifically, monophosphite compounds can be classified into the following two compound groups. That is, one group of these compounds is a phosphite compound having a cyclic structure and a phosphorus atom contained in the cyclic structure, and another group of compounds is a phosphite compound having a cyclic structure containing a phosphorus atom. There are no phosphite compounds.
Among the first group of phosphites, that is, phosphite compounds having no phosphorus atom-containing cyclic structure, preferred examples include phosphite compounds represented by the following general formula (2).

[0026]

Embedded image P (OR ¹ ) (OR ² ) (OR ³ ) (2)

(Wherein, R ¹ , R ² and R ³ represent an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or a heteroaryl group which may have a substituent having 1 to 20 carbon atoms). ). The substituent is not limited as long as it does not inhibit the hydroformylation reaction, but may be an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, an alkoxy group, a halogen, an alkylamino group, an acyl group, Carboalkoxy group, oxycarbonyl group and the like. Among them, a preferred compound is a phosphite in which at least one of R ¹ , R ² and R ^{3 in} the general formula (2) is a substituted aryl group represented by the following general formula (3).

[0028]

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(Wherein, R ⁴ represents a —C (R ⁹ ) (R ¹⁰ ) R ¹¹ group or an aryl group which may have a substituent;
R ⁹ , R ¹⁰ and R ¹¹ each represent a hydrogen atom, a fluorinated hydrocarbon group or a hydrocarbon group, and may be different from each other. Preferably, R ⁴ is a group having steric hindrance as a whole, which is equal to or more than an isopropyl group, that is, at least two of R ⁹ , R ¹⁰ and R ¹¹ are fluorinated hydrocarbon groups or hydrocarbon groups.
R ⁵ , R ⁶ , R ⁷ and R ⁸ may be different from each other and are each a hydrogen atom or an organic group, and adjacent substituents, for example, R ⁶ and R ⁷ are bonded to each other and condensed with a benzene ring. To form an aromatic ring or a heterocyclic ring.

Specific examples of these compounds include diphenyl (2,4-di-tert-butylphenyl) phosphite, diphenyl (2-isopropylphenyl) phosphite, bis (2-tert-butyl-4-methylphenyl) phenyl phosphite, Diphenyl (3, 6
Ditertiary butyl-2-naphthyl) phosphite, bis (2naphthyl) (3,6 ditertiarybutyl-2-naphthyl) phosphite, bis (3,6,8)
And tris-tert-butyl-2-naphthyl) phenyl phosphite, and bis (3,6,8-tritertiary-butyl-2-naphthyl) (2-naphthyl) phosphite.

As more preferred phosphites,
R in equation (2)¹, R^TwoAnd R ^ThreeAll of the above
Organic phos which is a substituted aryl group represented by the general formula (3)
It is a phyto compound. A specific example is Tris (2,
4-di-tert-butylphenyl) phosphite,
Squirrel (2-tert-butyl-4-methylphenyl)
Phosphite, Tris (2-tert-butyl-4-
Methoxyphenyl) phosphite, tris (o-phenyl)
Ruphenyl) phosphite, tris (o-methylphenyl)
Le) phosphite, bis (3,6 tertiary buchi)
Lou 2 Naphthyl) (2, 4 tertiary butyl fu
Phenyl) phosphite, bis (3,6 ditertiary)
Butyl-2-naphthyl) (2-tert-butyl-fe)
Nyl) phosphite, Tris (3,6 ditertiary)
Butyl-2-naphthyl) phosphite, Tris (3,6)
Jittery Amilou 2 naphthyl) phosphite
And the like. Another group of monophosphite compounds,
That is, it has a cyclic structure, and a phosphorus atom is contained in the cyclic structure.
As the phosphite compound to be used, the following general formula (4)
The compound shown by these is mentioned.

[0032]

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(Where Z represents a divalent organic group and Y represents a substituted or unsubstituted monovalent organic group). General formula (4)
In the formula, a representative divalent group represented by Z is a divalent aliphatic group or a divalent aromatic group. Examples of divalent aliphatic radicals are, for example alkylene, alkyleneoxy alkylene, alkylene -NR ¹² - alkylene (R ¹² is a hydrogen atom or a monovalent hydrocarbon group), an alkylene -S- alkylene and cycloalkylene groups and similar groups is there. Examples of the divalent aromatic group include arylene, biarylene, arylenealkylene, arylenealkylenearylene, aryleneoxyarylene, aryleneoxyalkylene, arylene-N
R ¹² -arylene and arylene-NR ¹² -alkylene (R ¹² is hydrogen or a monovalent hydrocarbon group), arylene-
S-alkylene and arylene-S-arylene groups. Preferred examples of the phosphite compound represented by the general formula (4) include a phosphite compound represented by the following general formula (5).

[0034]

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(Wherein, R ¹³ and R ^{13 ′} each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, a cycloalkyl group, or an aryl group, and n represents a number from 0 to 4. Represents a substituted or unsubstituted monovalent organic group.) In the general formula (5), typical examples of R ¹³ and R ^{13 ′} include a methyl group, an ethyl group, a phenyl group, a tolyl group, a benzyl group and a naphthyl group. , A hydroxymethyl group, a hydroxyethyl group, a trifluoromethyl group and the like. More preferably, Y in the general formula (5) is an aryl group having a substituent at a carbon atom adjacent to a carbon atom bonded to an oxygen atom as represented by the general formula (3). . Another preferred example of the phosphite compound represented by the general formula (4) is a phosphite compound represented by the following general formula (6).

[0036]

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(Where R ¹⁴ represents an arbitrary substituent at the o, m and p positions, or R ¹⁴ represents a condensed aromatic ring such as a naphthyl ring condensed with the original benzene ring. Has the same meaning as that of the general formula (6). Representative R ^{14 in} the general formula (6) is an alkyl group, a cycloalkyl group, an alkoxy group, an acyl group, an acyloxy group,
And an aryl group which may have a substituent,
Examples of the condensed aromatic ring include a naphthyl group. More preferably, Y in the general formula (6) is an aryl group having a substituent at a carbon atom adjacent to a carbon atom bonded to an oxygen atom as a substituent as represented by the general formula (3). desirable. Another example of a preferred phosphite compound is diorganophosphite represented by the general formula (7).

[0038]

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Wherein Ar is the same or different, and
Or each unsubstituted aryl group, wherein each y is independently 0 or
1 represents a number, and Q represents -CR¹⁵R¹⁶-, -O-, -S-,
-NR ¹⁷-, -SiR¹⁸R¹⁹-And -CO- (R¹⁵You
And R¹⁶Each represents a hydrogen atom, an alkyl having 1 to 12 carbons
A phenyl, tolyl, or acyl group. R¹⁷, R
¹⁸And R¹⁹Indicates a hydrogen atom or a methyl group
You. ) Is a divalent bridge group selected from the group consisting of
And n represents a number of 0 or 1, and Y represents the same as in the general formula (4).
It has one significance. ｝.

More preferably, Y in the general formula (7)
Is an alkyl group having 1 to 20 carbon atoms (primary, secondary and tertiary alkyl groups such as methyl, ethyl, n-propyl,
Isopropyl, butyl, sec-butyl, t-butyl,
t-butylethyl, t-butylpropyl, n-hexyl, amyl, sec-amyl, t-amyl, isooctyl, 2-ethylhexyl, decyl, octadecyl, etc.),
An unsubstituted or substituted monovalent hydrocarbon group selected from the group consisting of an aralkyl group such as a benzyl group, an o-tolyl group, and a p-tolyl group, and an optionally substituted aryl group (for example, α-naphthyl, β-naphthyl, etc.). Examples of the substituent of the aryl group include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, an alkoxy group, a halogen atom,
Examples thereof include an alkylamino group, an acyl group, a carboalkoxy group, and an oxycarbonyl group. Among the diorganophosphites represented by the general formula (7), more preferably,
A phosphite compound represented by the general formula (8) or (9);

[0041]

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(Wherein Q and Y are the same as defined in the above formula (7). R ²⁰ , R ²¹ , R ²² , R ²³ , R ²⁴
And R ²⁵ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, an alkoxy group,
It represents a halogen atom, an alkylamino group, an acyl group, a carboalkoxy group, an oxycarbonyl group or the like. Further, as the phosphite of the present invention, the following bisphosphites and polyphosphites can also be used.

[0043]

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(Where Z represents the same divalent organic group as defined in the above general formula (4), and R ²⁶ and R ²⁷ may have a substituent having 1 to 30 carbon atoms.) Alkyl group,
Represents a cycloalkyl group, an aryl group, an aralkyl group, or a heteroaryl group. W represents a substituted or unsubstituted m-valent hydrocarbon group. Each Z and R ²⁶ and R ²⁷ may be the same or different from each other. m ₁ and m ₂ each have a value of 0 to 6, and m = m ₁ + m ₂ has a value of 2 to 6).

The substituent such as an alkyl group is not particularly limited as long as it does not inhibit the hydroformylation reaction, and specific examples thereof include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group and an alkoxy group. , A halogen atom, an alkylamino group, an acyl group, a carbalkoxy group,
An oxycarbonyl group; Examples of the terminal organic group represented by R ²⁶ and R ²⁷ include, for example, methyl, ethyl, n-propyl, isopropyl, n
A straight-chain or branched alkyl group having 1 to 20 carbon atoms such as -butyl group, s-butyl group, t-butyl group, n-pentyl group, isopentyl group, neopentyl group, t-pentyl group, t-hexyl group, etc. , A cycloalkyl group having 3 to 20 carbon atoms such as a cyclopropyl group, a cyclohexyl group, a cyclooctyl group, an adamantyl group, a phenyl group, an α-naphthyl group, a β-naphthyl group, a methoxyphenyl group, a dimethoxyphenyl group, and a carboxy group. Methoxyphenyl, cyanophenyl, nitrophenyl, chlorophenyl, dichlorophenyl, pentafluorophenyl, methylphenyl, ethylphenyl, dimethylphenyl, trifluoromethylphenyl, methylnaphthyl, methoxynaphthyl, chloro Naphthyl group, nitronaphthyl group, tetrahydronaphthyl Aryl group which may have a substituent such as a group, aralkyl group such as benzyl group, pyridyl group, methylpyridyl group, nitropyridyl group, pyrazyl group, pyrimidyl group, benzofuryl group, quinolyl group, isoquinolyl group, benzimidazolyl And a hetero element-containing aromatic group such as an indolyl group.

As a more preferred phosphite compound, Z in the general formula (10) is the same as in the above formula (5),
A group corresponding to Z in (6) or (7), and each Z
Is a phosphite compound represented by a combination of the above formulas. Further, it is preferable that R ²⁶ and R ²⁷ are the same or different and are aryl groups which may have a substituent. Specific examples include a phenyl group, a 2-methylphenyl group, a 3-methylphenyl group, a 4-methylphenyl group, a 2,4-dimethylphenyl group, a 2,5-dimethylphenyl group, a 2,6-dimethylphenyl group, 2-methoxyphenyl group, 3-methoxyphenyl group, 4-methoxyphenyl group, 2,
4-dimethoxyphenyl group, 2,5-dimethoxyphenyl group, 2,6-dimethoxyphenyl group, α-naphthyl group, 3-methyl-α-naphthyl group, 3,6-dimethyl-α-naphthyl group,
β-naphthyl group, 1-methyl-β-naphthyl group, 3-methyl-β
-Naphthyl group and the like.

W is a substituted or unsubstituted m-valent hydrocarbon group. For example, when m = 2, alkylene;
Arylene and arylene _{- (CH 2) y- (Q} ) n
- (CH ₂₎ y- arylene - {each arylene radical is the same or different, a substituted or unsubstituted arylene group, Q is individually ^{-CR 28 R 29 -, - O} -, - S -, - N
^{R 30 -, - SiR 31 R} 32 - and -CO- (R ²⁸ and R ²⁹ individually represent a hydrogen atom or an alkyl group, R ^30, R
³¹ and R ³² are each independently a hydrogen atom or a methyl group)
And y and n each independently represent a group having a value of 0 or 1. ｝ Group.

Specific examples of the divalent organic group represented by W include, for example, 1,2-ethylene group, 1,3-propylene group,
1,3-dimethyl-1,3-propylene group, 1,4-butylene group, 1,
5-pentylene, 1,6-hexylene, 1,8-octylene, 1,2-phenylene, 1,3-phenylene, 2,3-
Naphthylene group, 1,8-naphthylene group, 1,1'-biphenyl-
2, 2'-diyl group, 1, 1'-binaphthyl-7, 7'-diyl group,
1, 1'-binaphthyl-2,2'-diyl group, 2,2'-binaphthyl-
1,1'-diyl group, 2,2'-binaphthyl-3,3'-diyl group and the like are included. More preferably, it is a compound in which Z in the general formula (10) is Z defined in the general formula (7), and W is a compound in which the general formula (11).

[0049]

Embedded image

(Wherein R ³⁷ and R ³⁸ are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, an alkoxy group, a silyl group, a siloxy group, or a halogen atom or a hydrogen atom. from .R ³³ R ³⁶
Each independently represents an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, an alkoxy group, a silyl group, a siloxy group,
Or a halogen atom or a hydrogen atom. )

R³⁷And R³⁸Examples of a hydrogen atom,
Methyl group, ethyl group, n-propyl group, isopropyl group,
n-butyl group, methoxy group, ethoxy group, n-propoxy
Group, fluorine atom, chlorine atom, bromine atom, iodine atom, etc.
No. Also, R³³To R ³⁶Examples of hydrogen sources
Child, methyl group, ethyl group, n-propyl group, isopropyl
Group, n-butyl group, t-butyl group, t-pentyl group, neopen
Tyl, t-hexyl, nonyl, decyl, methoxy
Examples thereof include a silyl group, an ethoxy group, and a t-butoxy group. Ma
As a special example of the group represented by the general formula (11), R
³⁵And R³⁷And / or R³⁶And R³⁸But each is independent
And a cyclic structure having 3 to 40 carbon atoms bonded to each other.
And a group that forms a part of, specifically, 1, 1'-
And a binaphthyl-2,2'-diyl group.

Still more preferably, R ²⁶ and R ²⁷ in the general formula (10) are the same or different from each other and are an optionally substituted aryl group,
And W is a branched alkyl group having 3 to 20 carbon atoms, wherein R ³³ and R ³⁴ in the general formula (11) are each independently;
And R ³⁵ and R ³⁶ each independently have 1 to 20 carbon atoms
1, 1'- which is a branched alkyl group or an alkoxy group of
It is a substituted arylene-arylene group having a biphenyl-2,2'-diyl skeleton or a 1,1'-binaphthyl-2,2'-diyl skeleton. As a specific example, 3,3′-di-t
-Butyl-1,1'-binaphthyl-2,2'-diyl group, 3,3 ', 6,6'-tetra-t-butyl-1,
1'-binaphthyl-2,2'-diyl group, 3,3'-di-t-butyl-6,6'-di-t-butoxy-1,1'-
Binaphthyl-2,2'-diyl group, 3,3'-di-t-
Pentyl-1,1'-binaphthyl-2,2'-diyl group, 3,3 ', 6,6'-tetra-t-pentyl-1,
1'-binaphthyl-2,2'-diyl group, 3,3'-di-t-butyl-5,5'-dimethyl-1,1'-biphenyl-2,2'-diyl group, 3,3 ' , 5,5'-Tetra-t-butyl-1,1'-biphenyl-2,2'-diyl group, 3,3 ', 5,5'-tetra-t-pentyl-
1,1'-biphenyl-2,2'-diyl group, 3,3 '
-Di-t-butyl-5,5'-dimethoxy-1,1'-
Biphenyl-2,2'-diyl group, 3,3'-di-t-
Butyl-5,5 ', 6,6'-tetramethyl-1,1'
-Biphenyl-2,2'-diyl group, 3,3 ', 5
5'-tetra-t-butyl-6,6'-dimethyl-1,
1'-biphenyl-2,2'-diyl group, 3,3 ',
5,5'-tetra-t-pentyl-6,6'-dimethyl-1,1'-biphenyl-2,2'-diyl group, 3,
3'-di-t-butyl-5,5'-dimethoxy-6
6'-dimethyl-1,1'-biphenyl-2,2'-diyl group, 3,3 ', 5,5'-tetra-t-butyl-
6,6'-dichloro-1,1'-biphenyl-2,2 '
-Diyl group and the like.

Most preferably, W is in addition to the above-mentioned restrictions, and R ³⁷ and R ³⁸ are each independently an alkyl group, an alkoxy group, or a halogen atom having 1 to 3 carbon atoms. , Methyl group, ethyl group, n-propyl group, isopropyl group, methoxy group, ethoxy group,
In this case, it is an n-propoxy group, an isopropoxy group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or the like. Therefore, examples of the most preferred divalent organic group of the cross-linking part include:
3,3'-di-t-butyl-5,5 ', 6,6'-tetramethyl-1,1'-biphenyl-2,2'-diyl group, 3,3', 5,5'-tetra -T-butyl-6,
6'-dimethyl-1,1'-biphenyl-2,2'-diyl group, 3,3 ', 5,5'-tetra-t-butyl-
6,6'-diethyl-1,1'-biphenyl-2,2 '
-Diyl group, 3,3 ', 5,5'-tetra-t-butyl-6,6'-dimethoxy-1,1'-biphenyl-2,
2'-diyl group, 3,3'-di-t-butyl-5,5 '
-Dimethoxy-6,6'-dichloro-1,1'-biphenyl-2,2'-diyl group, 3,3 ', 5,5'-tetra-t-butyl-6,6'-difluoro-1, And a 1'-biphenyl-2,2'-diyl group.

These phosphite ligands may be used alone or as a mixture of each. For example, a system in which a monophosphite and a bisphosphite or polyphosphite compound coexist may be used. The amount of the phosphite compound used is not particularly limited, but is preferably set so as to obtain a desired result with respect to the activity and selectivity of the catalyst. Generally, it is an amount selected from the range of about 0.1 to 500 mol, preferably 0.1 to 100 mol, more preferably 1 to 30 mol per mol of the rhodium compound.

The olefinically unsaturated compound used in the present invention may be used alone or as a mixture, and may have a linear, branched or cyclic structure. Suitable olefinically unsaturated compounds are olefins having 2 to 20 carbon atoms and may contain two or more ethylenically unsaturated groups. A carbonyl group that does not substantially adversely affect the hydroformylation reaction, a carbonyloxy group, an alkoxy group,
It may be substituted with a hydroxy group, oxycarbonyl group, halogen atom, aryl group, alkyl group, haloalkyl group and the like. Examples of olefinically unsaturated compounds include:
α-olefins, internal olefins, alkyl alkenoates, alkenyl alkanoates, alkenyl alkyl ethers, alkenols and the like, specifically, ethylene, propylene, butene, pentene, hexene, octene, nonene, decene, dodecene, octadecene, Cyclohexene, propylene dimer mixture, propylene trimer mixture, propylene tetramer mixture, butene dimer mixture, butene trimer mixture, styrene, 3-phenyl-1
-Propene, 1,4-hexadiene, 1,7-octadiene, 3-cyclohexyl-1-butene, allyl alcohol, 1-hexen-4-ol, 1-octene-4-
All, vinyl acetate, allyl acetate, 3-butenyl acetate, allyl propionate, methyl methacrylate, acetic acid
Examples thereof include 3-butenyl, vinyl ethyl ether, vinyl methyl ether, allyl ethyl ether, n-propyl-7-octenoate, 3-butennitrile, and 5-hexenamide.

Examples of the solvent for the hydroformylation reaction include aromatic hydrocarbons such as benzene, toluene and xylene; aliphatic hydrocarbons such as hexane and octane; esters such as butyl acetate; ketones; May be used, or a mixture of two or more kinds may be used. In general, it is preferable to use an aldehyde product and / or a high-boiling aldehyde liquid condensation by-product produced in the reaction system. For example, even if any primary solvent is used at the beginning of the continuous process, the primary solvent will usually ultimately consist of an aldehyde product and a high boiling aldehyde liquid condensation by-product due to the nature of the continuous process. If desired, the aldehyde condensation by-product may be preformed. The amount of solvent used is not critical to the present invention and may be any amount sufficient to maintain the particular rhodium concentration desired for a given process and to serve as a reaction medium. Generally, the amount of solvent is from about 5% to about 95% by weight based on the total weight of the reaction medium.

The hydroformylation reaction is carried out by charging a rhodium-phosphite complex catalyst and an olefinically unsaturated compound in a solvent and passing through carbon monoxide and hydrogen. The hydroformylation reaction conditions are such that the total gas pressure of hydrogen, carbon monoxide and olefinically unsaturated compounds is 500 kg
/ Cm is preferable to operate the hydroformylation process in less than ² G, less than 200 Kg / cm ² G are preferred. The minimum total gas pressure is limited by the amount of reactants required to achieve the initial rate of the reaction. Further, the carbon monoxide partial pressure in the hydroformylation reaction of the present invention is:
It is preferably 0.1 to 100 kg / cm ² G, more preferably 1 to 50 kg / cm ² G, and the hydrogen partial pressure is preferably 0.1 to 100 kg / cm ² G, more preferably 1 to 50 kg / cm 2. is a ² G. Generally, the molar ratio of hydrogen to carbon monoxide gas (H ₂ : CO) is 1:10 to 10
0: 1, more preferably 1: 1 to 10: 1. Further, the reaction can be usually carried out at a temperature of normal temperature to 150 ° C, and the rhodium concentration is 1 to 1000 ppm, preferably 10
To 500 ppm, more preferably 25 to 350 ppm.

[0058]

EXAMPLES Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples unless it exceeds the gist of the invention. In the following example, in a hydroformylation process using a rhodium-phosphite-based complex catalyst, as a method of suppressing loss of rhodium, a rhodium species to be subjected to a separation step is present as a rhodium-β-carbonyl enolate complex. Rhodium impairment tests were employed to clearly demonstrate that this was effective. This method uses rhodium
-The phosphite-based complex catalyst solution is subjected to severe conditions, avoiding the problem of rhodium analysis accuracy, which generally results in an analysis error of about ± 3%, and clarifying the degree of rhodium depletion. Is what you do.

Example 1 In a 300 ml three-necked flask equipped with a condenser and a thermometer under nitrogen, 12.0 mg (0.0465 mmol) of rhodium dicarbonyl acetylacetonate (hereinafter referred to as Rh (CO) ₂ (acac)) and tris ( 0.0301 g (0.465 mmol) of 2,4-di-t-butylphenyl) phosphite (hereinafter referred to as DBPO) and o-xylene 12
0 ml was charged and the contents were dissolved at room temperature. The dissolved contents were subjected to ³¹ P-NMR (toluene d ₆ , reference substance: triphenyl phosphate (-18.0 ppm)) measurement and IR measurement.
^{In the 31} P-NMR measurement, the uncoordinated DBP was found at 131.4 ppm.
O and DB coordinated to rhodium at 117.4ppm (J = 299Hz)
PO appeared at an integral ratio of 9: 1. In IR measurement, 2
At 008 cm ^-1 , CO coordinated to rhodium was observed. From this measurement, the rhodium species in the mixture was
Rh in which one CO of Rh (CO) ₂ (acac) is replaced by DBPO
(CO) (DBPO) (acac).

After the mixture was quantitatively analyzed for rhodium by Zeeman atomic absorption spectrometry, the mixture was heated to reflux (internal temperature: 144 ° C.) under nitrogen for 3 hours.
After filtration through a μm filter, the filtrate was subjected to quantitative analysis of rhodium by Zeeman atomic absorption spectrometry and ³¹ P-NMR measurement. The rhodium residual ratio after heat treatment by Zeeman atomic absorption method was 100%. ^{In the 31} P-NMR measurement, 1
Uncoordinated DBPO at 31.4 ppm, DBPO coordinated to rhodium at 117.4 ppm (J = 299 Hz), and a new peak generated by heat treatment at 141.5 ppm appeared at an integration ratio of 6: 1: 3.
It can be said that the compound of 117.4 ppm (J = 299 Hz) is a rhodium compound which is stable against heat treatment.

COMPARATIVE EXAMPLE 1 In a 300 ml three-necked flask equipped with a condenser and a thermometer under nitrogen, tetrarhodium dodecacarbonyl (Rh ₄ (C
O) ₁₂ ) 6.60 mg (0.0116 mmol), DBPO 0.0301 g (0.465 m
mol) and 120 ml of o-xylene, and the contents were dissolved at room temperature. The dissolved content was subjected to quantitative analysis of rhodium by Zeeman atomic absorption spectrometry and ³¹ P-NMR (toluene d ₆ , reference substance: triphenyl phosphate (-18.0 ppm)) measurement. ^{In 31} P-NMR measurement, uncoordinated DB at 131.4 ppm
PO and D coordinated to rhodium at 132.9 ppm (J = 249 Hz)
BPO appeared at an integral ratio of 9: 1. Put the above mixture under nitrogen 3
After heating and refluxing (internal temperature: 144 ° C.) for an hour, the content was cooled, the content was filtered through a 0.2 μm filter, and quantitative analysis of rhodium by Zeeman atomic absorption spectrometry and ³¹ P-NMR measurement were performed. The residual ratio of rhodium after heat treatment by Zeeman atomic absorption method was 13%. ^{In the 31} P-NMR measurement, 13
An uncoordinated DBPO at 1.4 ppm and a number of complex new peaks from the heat treatment at 120-170 ppm appeared.
A compound at 132.9 ppm (J = 249 Hz) can be said to be a rhodium compound that is unstable to heat treatment.

Example 2 In a 300 ml three-necked flask equipped with a condenser and a thermometer under nitrogen, tetrarhodium dodecacarbonyl (Rh ₄ (C
O) ₁₂ ) 6.60 mg (0.0116 mmol), DBPO 0.0301 g (0.465 mmo
l), 5.12-mg of 2,4-pentadione (acetylacetone)
(0.0512 mmol) and 120 ml of o-xylene were charged, and the contents were dissolved at room temperature. The dissolved content was subjected to quantitative analysis of rhodium by Zeeman atomic absorption spectrometry and ³¹ P-NMR (toluene d ₆ , reference substance: triphenyl phosphate (-18.0 ppm)) measurement. ^{In 31} P-NMR measurement, uncoordinated DBPO at 131.4 ppm and rhodium-coordinated DBPO at 132.9 ppm (J = 249 Hz) appeared at an integration ratio of 9: 1. The mixture was heated and stirred at 110 ° C. for 3 hours under nitrogen, cooled, partially extracted, filtered through a 0.2 μm filter, and subjected to ³¹ P-NMR measurement. ^{In 31-} PNMR measurement, 131.4 ppm of uncoordinated DBPO, 117.4 ppm (J = 299 Hz)
In addition, DBPO coordinated with rhodium, and a very small amount of a complex peak appeared between 120 and 170 ppm. Thereafter, the mixture was further subjected to a reflux treatment (internal temperature: 144 ° C.) for 3 hours under nitrogen, and after cooling,
The contents were filtered through a 0.2 μm filter, and Zeeman atomic absorption analysis was performed. The rhodium residual ratio was 98%. 132.9ppm unstable to rhodium deposition (J = 249Hz)
Rhodium compound in the presence of 2,4-pentadione,
117.4ppm stable to heat treatment by heat treatment under nitrogen
It is evident that it was converted to a rhodium compound (J = 299 Hz).

Example 3 In a 200 cc stainless steel autoclave, 93.58 g of the octene mixture and the oxo-reaction high-boiling by-product of octene were 18.44.
g, 18.0 mg of Rh (CO) ₂ (acac) and 455.2 mg of DBPO were charged under nitrogen. The temperature of the autoclave was raised to 150 ° C. while stirring, then a mixed gas of hydrogen and carbon monoxide (mixing ratio 1: 1) was introduced into the autoclave, and the stirring operation was continued at 150 ° C. and 5.0 MPa for 2 hours. After cooling, a mixed gas of hydrogen and carbon monoxide was purged, and quantitative analysis of rhodium by Zeeman atomic absorption spectrometry and ³¹ P-NMR (toluene d _6, reference substance: triphenyl phosphate (-18.0 ppm)) measurement were performed.
^{In the 31} P-NMR measurement, 131.4 ppm and 132.9 ppm (J = 249H
In z), a peak having an integral ratio of about 9: 1 and a very small peak at 117.4 ppm (J = 299 Hz) were confirmed. After the hydroformylation reaction in the autoclave, 10 g of the oxo-reaction high-boiling by-product of octene and 7.72 mg of 2,4-pentadione (acetylacetone) were injected into the autoclave, and the mixture was heated and stirred at 110 ° C. for 1 hour and cooled again to room temperature did. Thereafter, the mixture was transferred to a 300 ml three-necked flask equipped with a cooling tube and a thermometer, and heated and stirred at 150 ° C. (internal temperature) for 40 minutes. After cooling to room temperature, ³¹ P-NMR (toluene d ₆ , reference substance: triphenyl phosphate (-18.0 ppm)) measurement and quantitative analysis of rhodium by Zeeman atomic absorption method were performed. ^{In 31} P-NMR measurement, DBPO uncoordinated to 131.4 ppm, 117.4 ppm (J = 299 Hz)
In addition, DBPO coordinated with rhodium, and a very small amount of a complex peak appeared between 120 and 170 ppm. 15 after the end of the reaction
Rhodium remaining rate after completion of heating and stirring at 0 ° C is 100%
Met.

Comparative Example 2 In a 200 cc stainless steel autoclave, 93.71 g of the octene mixture and the oxo-reaction high-boiling by-product of octene, 18.3, were added.
5 g, 18.1 mg of Rh (CO) ₂ (acac) and 457.8 mg of DBPO were charged under nitrogen. Autoclave at 150 ° C with stirring
Temperature, and then a mixed gas of hydrogen and carbon monoxide (mixing ratio 1: 1) was introduced into the autoclave, and 5.0 MPa
At 150 ° C. for 2 hours. After cooling, the mixed gas of hydrogen and carbon monoxide was purged, and quantitative analysis of rhodium by Zeeman atomic absorption spectrometry and ³¹ P-NMR (toluene d ₆ ,
Reference substance: triphenyl phosphate (-18.0 ppm)) was measured. ^{In the 31} P-NMR measurement, 131.4 ppm and 132.9 ppm
(J = 249 Hz) and a peak with an integration ratio of about 9: 1 and 117.4 ppm (J = 299H
An extremely small peak was confirmed in z). Thereafter, the mixture was transferred to a 300 ml three-necked flask equipped with a cooling tube and a thermometer, and heated and stirred at 150 ° C. (internal temperature) for 40 minutes. After cooling to room temperature, rhodium was quantitatively analyzed by Zeeman atomic absorption spectrometry. The rhodium residual ratio from the end of the reaction to the end of the heating and stirring at 150 ° C. was 76%.

[0065]

As is clear from the examples, the general formula (1)
Is stable even under severe heating conditions. Therefore, according to the method of the present invention, when the separation operation is performed after the hydroformylation reaction, rhodium in the reaction solution is present as the enolate complex of the general formula (1), thereby greatly suppressing the loss of rhodium during the separation operation. You can do it.

Continued on the front page (72) Inventor Akio Nakanishi 3-10 Ushidori, Kurashiki-shi, Okayama Prefecture F-term (reference) 4H006 AA02 AC21 AC45 BA24 BA45 BA48 BA83 BC14 BD36 BD52 BE20 BE40 4H039 CA62 CL45

Claims (4)

[Claims] 1. A process for producing an aldehyde by reacting an olefinically unsaturated compound with carbon monoxide and hydrogen in a liquid phase in the presence of a rhodium-phosphite complex catalyst to hydroformylate the olefinically unsaturated compound to produce an aldehyde. ,
After the completion of the hydroformylation reaction, at least 1
When the two components are separated, rhodium in the reaction solution is converted into the following general formula (1): (Wherein R ₁ , R ₂ and R ₃ represent a hydrogen atom, an alkyl group, an alkoxy group, a substituted amino group, an aryl group, an aryloxy group, an arylamino group, a heteroaryl group, and these groups further include hydroformyl And at least two of R ₁ , R ₂ and R ₃ may combine to form a ring.
₁ , L ₂ represents carbonyl or a phosphite ligand. ). A process for producing aldehydes, wherein the aldehyde is present as an enolate complex. 2. The process for producing an aldehyde according to claim 1, wherein the catalyst solution is separated from the hydroformylation reaction solution and recycled. 3. The method for producing aldehydes according to claim 1, wherein the separation operation is an operation involving heating of the reaction solution. 4. In the general formula (1), R ₁ and R ₂ are a methyl group, R ₃ is a hydrogen atom, _one of L ₁ and L ₂ is a carbonyl group and the other is a phosphite. Item 4. The method for producing an aldehyde according to any one of Items 1 to 3.