JP2000351748A - Method for producing aldehydes - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for hydroformylating an olefinically unsaturated compound using a rhodium-phosphite complex catalyst exhibiting high activity and excellent selectivity, in which rhodium is removed during the separation operation of the formed aldehyde. A method for suppressing loss due to precipitation. SOLUTION: In a liquid phase in the presence of a rhodium-phosphite complex catalyst, an olefinic unsaturated compound is reacted with carbon monoxide and hydrogen to hydroformylate the olefinic unsaturated compound to produce an aldehyde. When at least one component is separated from the reaction product solution after the reaction is completed, the reaction product solution contains at least 1.01 mole times the amount of rhodium in the solution of the following general formula (1): (Wherein R ₁ , R ₂ , R ₃ Are each independently a hydrogen atom, an alkyl group which may have a substituent, an alkoxy group, a substituted amino group, an aryl group, an aryloxy group,
Represents a heteroaryl group. Also, R ₁ , R ₂ , R ₃ May combine to form a ring. A process for producing aldehydes, characterized by the presence of a β-dicarbonyl compound having at least one active proton represented by the formula (1).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

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

[0002]

2. Description of the Related Art Processes for producing aldehydes by reacting an olefinic unsaturated compound with carbon monoxide and hydrogen in the presence of a metal complex catalyst of Group VIII of the Periodic Table have been widely industrialized. As a catalyst in the hydroformylation reaction, a Group VIII metal such as rhodium is used.
A complex catalyst modified with a ligand such as a valent phosphorus compound is used, and various ligands have been studied in order to improve the activity and selectivity of the hydroformylation reaction. 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 indispensable to separate and recover an expensive rhodium-complex catalyst from a reaction solution, circulate and reuse it. Therefore, stability of the phosphite ligand and rhodium during catalyst separation is also important. As a method for separating the catalyst, an adsorption method (JP-A-50-49190)
), Crystallization method (JP-A-57-122948), membrane separation method (JP-A-2-23143), and extraction method (JP-A-56-122).
Various types of separation techniques such as No. 2994, JP-A-56-5372) can be applied, but industrially, separation is often performed by distillation.

However, it is known that a rhodium-phosphite complex is easily decomposed at a high temperature, and is more easily decomposed in a system in which carbon monoxide and hydrogen are absent. The present applicant first employs specific distillation conditions (Japanese Unexamined Patent Publication No.
165266) or the presence of a specific amine at the time of distillation (JP-A-8-268947) to suppress the decomposition of phosphite. In particular, in the hydroformylation reaction of an olefinically unsaturated compound having a large number of carbon atoms, the generated aldehydes have a high boiling point, so when the formed aldehyde and the catalyst are separated by distillation,
High temperature conditions are required and rhodium is significantly destabilized. For example, Japanese Patent Publication No. 5-48215 describes that when a hydroformylation circulating liquid is heated in the absence of carbon monoxide and hydrogen, a phenomenon of depletion of rhodium occurs. The publication proposes heating in the presence of an organic polymer having a specific polar functional group in order to suppress metallization of rhodium, and also discloses a reaction product containing a rhodium-phosphite complex catalyst. It is proposed to carry out the distillation of the formed aldehyde from the liquor at a temperature below 150 ° C., preferably below 140 ° C.

[0007]

DISCLOSURE OF THE INVENTION The present invention suppresses rhodium loss in a hydroformylation reaction process of an olefinically unsaturated compound using a rhodium-phosphite complex catalyst exhibiting high activity and excellent selectivity. It is an object of the present invention to establish an industrially advantageous method, and in particular, to provide a method for suppressing the precipitation of rhodium during a separation operation.

[0008]

DISCLOSURE OF THE INVENTION The present inventors have developed a versatile separation method which does not involve the precipitation of rhodium in a process for producing the corresponding aldehydes by a hydroformylation reaction of an olefinically unsaturated compound. As a result of intensive studies, the separation reaction was carried out in the presence of a β-dicarbonyl compound having at least one active proton in the hydroformylation reaction product liquid, whereby the aldehydes and high boiling points formed without the precipitation of rhodium were obtained. It has been found that a substance can be separated, and the present invention has been achieved. That is, the gist of the present invention is to produce aldehydes 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 aldehydes. When at least one component is separated from the reaction product solution after the completion of the reaction, the reaction product solution contains 1.01 mol times or more of the amount of rhodium in the solution in the following general formula (1)

[0009]

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(Wherein R ₁ , R ₂ , R ₃ Each independently represents a hydrogen atom, an alkyl group which may have a substituent, an alkoxy group, a substituted amino group, an aryl group, an aryloxy group, or a heteroaryl group. Also, R ₁ , R
_Two , R ₃ May combine to form a ring. ), Wherein the β-dicarbonyl compound is present.

[0011]

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 methods can be applied to the method of the present invention. In particular, the present invention can be advantageously applied to a liquid catalyst circulation process in which a rhodium catalyst solution containing a phosphite ligand is separated from a reaction solution and continuously circulated.

After the reaction, the hydroformylation reaction product solution contains at least 1) a complex catalyst containing rhodium and phosphite, 2) aldehydes formed, and other unreacted olefinic unsaturated compounds, reaction solvent, It contains carbon oxides and hydrogen, by-products, and the like. At least 1) and 2) are separated from the reaction product liquid, 1) is circulated and used as a catalyst liquid, and 2) is further purified if necessary to obtain a product. Other components are separated if necessary.
In the method of the present invention, when one or more of the above components are separated from the hydroformylation reaction solution or beforehand, the reaction product solution has at least one active proton represented by the general formula (1). By the presence of the β-dicarbonyl compound, rhodium in the liquid can be stabilized, and the separation operation can be performed without precipitation of rhodium.

The separation operation employed in the method of the present invention is not particularly limited, and any separation method can be employed. Specifically, 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, and other separation operations. Is also good. Each separation operation may be performed in an independent step, or two or more components may be separated simultaneously. The method of the present invention is particularly preferably applied to a separation operation involving a heat treatment.
Distillation and evaporation. Although these operations are not particularly limited, it is well known that rhodium precipitation loss generally becomes remarkable at a high temperature operation of 50 ° C. or higher, and the present invention is particularly effective for a separation operation at a higher temperature. Specifically, 7
It can be applied to a separation operation at 0 ° C. or higher, more preferably a separation operation at 110 ° C. or higher. On the other hand, a high temperature of 200 ° C. or higher is not preferable. Even at such a high temperature, although the effect of adding the β-carbonyl compound is effective, the precipitation of rhodium cannot be completely suppressed.

The β-dicarbonyl compound used in the method of the present invention is represented by the general formula (1). In the general formula (1), R ₁ , R ₂ , R ₃ Specifically, specifically, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, t-butyl, n-amyl, sec-amyl, t-amyl, hexyl, Linear, branched and cyclic alkyl groups such as cyclohexyl, heptyl, octyl, nonyl, and decyl; alkoxy groups corresponding to the above alkyl groups; phenyl, naphthyl, 2-tolyl, 3-tolyl, 4-tolyl, 2,4 -Dimethylphenyl, 2,6-dimethylphenyl, 2,4,6-trimethylphenyl, 2-t-butylphenyl, 4-t-butylphenyl, 2-t-butyl-4-methylphenyl, 2,
6-dimethyl-4-t-butylphenyl, 2,4-di-
aryl groups such as t-butylphenyl; aryloxy groups such as phenoxy and naphthoxy; dialkylamino groups such as dimethylamino, diethylamino and dipropylamino or diphenylamino, dibenzylamino, methylphenylamino, ethylphenylamino and methylbenzyl Substituted amino groups such as amino and ethylbenzylamino; 2
And heteroaryl groups such as -pyridyl, 3-pyridyl and 4-pyridyl. These groups may be further substituted by a substituent that does not inhibit the hydroformylation reaction. Examples of the substituent include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, an alkoxy group, a halogen atom, an alkylamino group, an acyl group, a carboalkoxy group, and an oxycarbonyl group. Β represented by the general formula (1)
Specific examples of dicarbonyl compounds include, for example, 2,
4-pentanedione, 2,4-hexanedione, 3,5
Diketones such as heptanedione, 3-methyl-2,4-pentanedione, 1,3-diphenyl-1,3-propanedione; methyl-3-oxo-butyrate, ethyl-3-oxo-butyrate, propyl- Ketoesters such as 3-oxo-butyrate and phenyl-3-oxo-butyrate; dimethyl-3-oxo-butylamide, diethyl-3-oxo-butylamide, dipropyl-3-
Ketoamides such as oxo-butylamide and diphenyl-3-oxo-butylamide; diesters such as dimethyl malonate and diethyl malonate;

In the method of the present invention, the β-dicarbonyl compound may be present in the hydroformylation reaction product solution before the separation operation, and the β-dicarbonyl compound may be directly added to the reaction solution, or the β-dicarbonyl compound may be added to the reaction solution. A dicarbonyl compound may be formed. After completion of the reaction, the β-dicarbonyl compound is purged with carbon monoxide and hydrogen, and then converted into a stable and re-activatable rhodium complex before rhodium deposition by contacting the destabilized rhodium complex with heating conditions. . There is no particular limitation on the method of contacting the β-dicarbonyl compound with the rhodium complex as long as the heat treatment step is such that carbon monoxide and hydrogen are reduced, and the β-dicarbonyl compound is more destabilized than the precipitation phenomenon of rhodium due to the heat treatment. Since the reaction with the rhodium complex is fast, a desired effect can be substantially achieved only by the coexistence of the β-dicarbonyl compound. As a specific operation, there is a method in which a β-dicarbonyl compound is added and heated during a batch reaction, a flow reaction, or a distillation operation after releasing carbon monoxide and hydrogen out of the system. Therefore, the heat treatment and the separation operation such as distillation can be performed simultaneously.

The amount of the β-dicarbonyl compound represented by the general formula (1) is at least 1.01 mol times, preferably 1.05 mol times or more, more preferably 1.1 mol times or more with respect to rhodium present in the reaction product solution. The molar ratio is not less than 1000 times, preferably not more than 100 times, more preferably not more than 100 times. The β-dicarbonyl compound represented by the general formula (1) is not limited to the above-mentioned method in which the β-dicarbonyl compound is present in the hydroformylation reaction solution after the completion of the reaction. It may be made to coexist in the reaction solution through the formula reaction process.

In this case, in the hydroformylation reaction process, the β-dicarbonyl compound is depleted by a condensation reaction with the formed aldehydes or a self-condensation reaction. Therefore, it is necessary to continuously or intermittently replenish the β-dicarbonyl compound in order to maintain the amount of the β-dicarbonyl compound in the liquid in which the catalyst is present. The method for replenishing the β-dicarbonyl compound is not particularly limited, and it may be added in a preferable manner in terms of the process.However, in order to prevent rhodium precipitation in a step where carbon monoxide and hydrogen are reduced, a hydroformylation reaction is performed. Is preferably added before and after.

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. Raw material rhodium species that can be used in the present invention include organic acid salts such as rhodium acetate and rhodium formate, Rh
₄ (CO) ₁₂ , Rh ₆ (CO) ₁₆ , Rh (CO) ₂ (acac), (Rh (cod) C
l] ₂ , carbonyl complex compounds such as [Rh (OAc) (cod)] ₂ and [Rh (OAc) (CO) ₂ ] ₂ , and inorganic basic acid salts such as sodium rhodate, potassium rhodate, etc. acac represents an acetylacetonate group, Ac represents an acetyl group, and cod represents cyclooctadiene). The rhodium-phosphite complex catalyst may be prepared by supplying rhodium and a phosphite compound directly to a 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 a pressure of normal pressure to 100 kg / cm ² G and a temperature of 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).

[0020]

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

(Wherein R ¹ , R ² and R ^{3 each} have 1 carbon atom)
Represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or a heteroaryl group which may have a substituent of from 1 to 20. ). 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 these, preferred compounds include
At least one of R ¹ , R ² and R ³ in the general formula (2) is a phosphite which is a substituted aryl group represented by the following general formula (3).

[0022]

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(Wherein R ⁴ is —C (R ⁹ ) (R ¹⁰ ) R ¹¹
Represents an aryl group which may have a group or a substituent;
^9, respectively R ¹⁰ and R ¹¹ represents a hydrogen atom, a fluorinated hydrocarbon group or a hydrocarbon group, 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.

A more preferred phosphite is an organic phosphite compound in which R ¹ , R ² and R ³ in the general formula (2) are all substituted aryl groups represented by the general formula (3). Specific examples include tris (2,4-di-tert-butylphenyl) phosphite, tris (2-tert-butyl-4-methylphenyl) phosphite, tris (2-tert-butyl-4-methoxyphenyl) phosphite, tris (o −
Phenylphenyl) phosphite, tris (o-methylphenyl) phosphite, bis (3,6-di-tert-butyl-2-naphthyl) (2,4-di-tert-butylphenyl) phosphite, bis (3,6-di-tert-butyl) L-butyl-2-naphthyl) (2-tert-butylphenyl) phosphite, tris (3,6-di-tert-butyl-2naphthyl) phosphite, tris (3,6-di-tert-amylyl 2-naphthyl) phosphite, and the like. . Another group of monophosphite compounds, that is, phosphite compounds having a cyclic structure and a phosphorus atom contained in the cyclic structure include compounds represented by the following general formula (4).

[0026]

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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).

[0028]

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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).

[0030]

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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. Y represents the general formula (4) 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).

[0032]

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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);

[0035]

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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.

[0037]

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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. , Cyclopropyl group, cyclohexyl group, cyclooctyl group, cycloalkyl group having 3 to 20 carbon atoms such as adamantyl group, phenyl group, α-naphthyl group, β-naphthyl group, methoxyphenyl group, dimethoxyphenyl group, carboxy group Methoxyphenyl, cyanophenyl, nitrophenyl, chlorophenyl, dichlorophenyl, pentafluorophenyl, methylphenyl, ethylphenyl, dimethylphenyl, trifluoromethylphenyl, methylnaphthyl, methoxynaphthyl, chloro Naphthyl group, nitronaphthyl group, tetrahydronaph Aryl group which may have a substituent such as benzyl group, aralkyl group such as benzyl group, pyridyl group, methylpyridyl group, nitropyridyl group, pyrazyl group, pyrimidyl group, benzofuryl group, quinolyl group, isoquinolyl group, benz Examples include an aromatic group containing a hetero element such as an imidazolyl group and an indolyl group.

As a more preferred phosphite compound, Z in the general formula (10) is represented by 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, 2-
Methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 2,4-dimethylphenyl group, 2,5-dimethylphenyl group, 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-
Examples include a naphthyl group, a β-naphthyl group, a 1-methyl-β-naphthyl group, and a 3-methyl-β-naphthyl group.

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, 1,5-pentylene, 1,6-hexylene, 1, 8-
Octylene, 1,2-phenylene, 1,3-phenylene, 2,3-naphthylene, 1,8-naphthylene, 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, Z in the general formula (10) is the same as Z defined in the general formula (7).
And W is a compound of the general formula (11)

[0043]

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(Where 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. R ³⁶ from a certain .R ³³
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 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 thereof. 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, about 0.1 to 500 moles, preferably 0.1 to 100 moles, per mole of rhodium compound,
More preferably, the amount is selected from the range of 1 to 30 mol.

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. The reaction can be carried out usually at a temperature of normal temperature to 150 ° C., and the rhodium concentration is 1 to 1000 ppm, preferably 10 to 1000 ppm.
To 500 ppm, more preferably 25 to 350 ppm.

[0052]

EXAMPLES Hereinafter, the present invention will be described specifically with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples unless it exceeds the gist thereof. In the following examples, in a hydroformylation process using a rhodium-phosphite-based complex catalyst, as a method for suppressing loss of rhodium, a β-dicarbonyl compound is present in a reaction product liquid subjected to a separation step. To clearly demonstrate the efficacy of Rhodium, a rhodium impairment test was employed. This method comprises placing a rhodium-phosphite complex catalyst solution under severe conditions,
In general, the purpose of the present invention is to avoid the problem of rhodium analysis accuracy that may cause an analysis error of about ± 3%, and to clarify the degree of rhodium loss.

Example 1 In a 200 cc stainless steel autoclave, 93.58 g of an octene mixture, 18.44 g of an oxo-reaction high-boiling by-product, and Rh (CO) ₂ (acac) 18. And 455.2 mg of tris (2,4-di-t-butylphenyl) phosphite (hereinafter DBPO) were charged under nitrogen. The autoclave was heated to 150 ° C. with stirring, and then a mixed gas of hydrogen and carbon monoxide (mixing ratio 1:
1) was introduced into an autoclave, and 15 MPa at 5.0 MPa.
The stirring operation was continued at 0 ° C. for 2 hours. After cooling, a mixed gas of hydrogen and carbon monoxide was purged, a part of the liquid after the hydroformylation reaction was withdrawn from the autoclave, and quantitative analysis of rhodium was performed by Zeeman atomic absorption method. Next, 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 solution after the hydroformylation reaction in the autoclave, and 11
The mixture was heated and stirred at 0 ° C. for 1 hour, and cooled to room temperature again. Then, the mixture was fitted with a cooling tube and a thermometer 3
Transfer to a 00 ml three-necked flask,
Heating and stirring were performed for 0 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 100%.

Comparative Example 1 In a 200 cc stainless steel autoclave, 93.71 g of an octene mixture, 18.35 g of an oxo-reaction high-boiling by-product, 18.1 mg of Rh (CO) ₂ (acac), and DB
457.8 mg of PO 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, a part of the liquid after the hydroformylation reaction was withdrawn from the autoclave, and quantitative analysis of rhodium was performed by Zeeman atomic absorption method. Thereafter, the mixture was transferred to a 300 ml three-necked flask equipped with a cooling tube and a thermometer, and heated at 150 ° C.
Heating and stirring were performed at (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%.

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 at 0.0
301 g (0.465 mmol), 5.12 mg (0.0512 mmol) of 2,4-pentadione (acetylacetone) and 120 ml of o-xylene were charged, and the contents were dissolved at room temperature. The dissolved contents were subjected to quantitative analysis of rhodium by Zeeman atomic absorption spectrometry. Thereafter, this mixture was subjected to a reflux treatment (internal temperature: 144 ° C.) for 3 hours under nitrogen.
After filtration through a μm filter, Zeeman atomic absorption analysis was performed. The residual rhodium ratio before and after the heating and stirring treatment was 98%.

Comparative Example 2 Under a nitrogen atmosphere, a tetrarhodium dodecacarbonyl (Rh ₄ (C
O) ₁₂ ) 6.60 mg (0.0116 mmol), DBPO at 0.0
301 g (0.465 mmol) and 120 ml of o-xylene were charged, and the contents were dissolved at room temperature. The dissolved contents were subjected to quantitative analysis of rhodium by Zeeman atomic absorption spectrometry. Then, the mixture was heated under reflux (internal temperature: 144 ° C.) under nitrogen for 3 hours, cooled, and the content was filtered through a 0.2 μm filter, and quantitative analysis of rhodium by Zeeman atomic absorption method was performed. The residual ratio of rhodium after heat treatment by Zeeman atomic absorption method was 13%.

[0057]

As is clear from the examples, according to the method of the present invention, the loss of the hydroformylation reaction solution in which the β-dicarbonyl compound is present due to the precipitation of rhodium when heated is greatly suppressed. Therefore, according to the method of the present invention, it is possible to greatly reduce the loss of rhodium generated when separating the produced aldehyde from the hydroformylation reaction solution.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C07C 47/06 C07C 47/06 D // C07B 61/00 300 C07B 61/00 300 (72) Inventor Nakanishi Akio 3-10, Ushidori, Kurashiki-shi, Okayama Prefecture Mitsubishi Chemical Corporation Mizushima Plant F-term (reference) 4H006 AA02 AC45 AD16 BA24 BA48 BC14 BD20 BD36 BD52 BE20 BE40 4H039 CA62 CF10 CL45

Claims (7)

[Claims] 1. A method for producing aldehydes 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 aldehydes. In the above, when at least one component is separated from the reaction product liquid after the completion of the reaction, the reaction product solution contains 1.01 mol times or more of the amount of rhodium in the liquid in the following general formula (1). 1) (Wherein R ₁ , R ₂ , R ₃ Are each independently a hydrogen atom, an alkyl group which may have a substituent, an alkoxy group, a substituted amino group, an aryl group, an aryloxy group,
Represents a heteroaryl group. Also, R ₁ , R ₂ , R ₃ May combine to form a ring. A process for producing aldehydes, characterized by the presence of a β-dicarbonyl compound represented by the formula 2. After completion of the hydroformylation reaction, carbon monoxide and hydrogen are removed out of the system, and the reaction solution in which the β-dicarbonyl compound is present is heated to carry out an operation of separating at least one component in the reaction solution. The method for producing aldehydes according to claim 1, wherein 3. The method for producing an aldehyde according to claim 1, wherein the amount of the β-dicarbonyl compound is in a range of 1.05 to 100 mol times the amount of rhodium in the solution. 4. The method according to claim 1, wherein the catalyst is separated from the hydroformylation reaction liquid and recycled.
The method for producing an aldehyde according to any one of the above. 5. The method for producing aldehydes according to claim 4, wherein the separation of the catalyst from the hydroformylation reaction solution is carried out at 110 ° C. or higher. 6. The method for producing aldehydes according to claim 1, wherein the β-dicarbonyl compound is 2,4-pentanedione. 7. During the hydroformylation reaction, the β-carbonyl compound is present continuously or intermittently so that the β-dicarbonyl compound is present in the reaction solution in an amount of 1.01 mol times or more of the rhodium amount.
The method for producing aldehydes according to any one of claims 1 to 6, wherein a dicarbonyl compound is added to the reaction solution.