JPH11246464A - Production of aldehydes - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for further improving reactive activity of catalyst reaction system containing an organic polydentate phosphite in hydroformylation reaction. SOLUTION: In this method for producing the corresponding aldehydes by subjecting an olefinic compound to hydroformylation reaction with carbon monoxide and hydrogen in the presence of a catalyst containing a metal of the group 8 and a organic polydentate phosphite compound, the reaction is carried out in the presence of a cyclic single-seated phosphite compound represented by the general, formula [either one of Ar1 and Ar2 is a divalent aromatic organic group substituted with at least one branched hydrocarbon group and Ar3 is an aromatic organic group not having bulky substituent group at ortho position of phosphite-based oxygen atom] in the reaction system.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a method for producing aldehydes. More specifically, the present invention relates to a method for producing a corresponding aldehyde by subjecting an olefinic compound to a hydroformylation reaction.

[0002]

2. Description of the Related Art The reaction of reacting an olefinic compound with carbon monoxide and hydrogen in the presence of a catalyst to produce aldehydes or their hydrogenated alcohols is known as a hydroformylation reaction. ing. As the catalyst for the hydroformylation reaction, a Group VIII metal such as rhodium modified with a phosphorus-containing ligand is usually used, and the activity and product of the reaction are determined by the ligand used together with the metal component of the catalyst. It has been known that the selectivity of the compound greatly changes. Therefore, in order to carry out the hydroformylation reaction industrially advantageously, it is important to improve the reaction activity and the selectivity of the product and to suppress the olefin reduction product by a side reaction. The design is active. As such a method, a hydroformylation method using various phosphine compounds or various phosphite compounds has been reported.

[0003] Examples of using a monodentate phosphine compound as a ligand in a hydroformylation reaction have been reported for a long time, and are widely used industrially. In addition, in the reaction, a monodentate phosphite compound is often used, for example, Japanese Patent Application Laid-Open No. 62-116587 and JP-A-5-15-1.
78779 have been reported. In many cases, a polydentate phosphite compound is used. In general, monodentate ligands have been known to have lower selectivity in their catalytic function than polydentate ligands. Therefore, in recent years, multidentate ligands expressing high selectivity have been actively developed, for example, US Pat. No. 5,332,846 (Eastman).
Chemical) has been reported. Similarly, an example in which a polydentate phosphite compound is used is disclosed in
116587 (UCC), JP-A-5-178779 (M
CC) etc. have been reported.

[0004]

In such a conventional flow, instead of using a single organophosphorus compound, the behavior of the hydroformylation reaction under the condition that organophosphorus compounds having different structures coexist is considered. Are very few examples analyzed. For example, in WO97 / 20795, it is reported that a bidentate phosphite catalyst system having a cyclic structure at both terminals can prevent Rh precipitation in the presence of a monodentate ligand such as a monodentate phosphite compound or a monodentate phosphine compound. Have been. Also, JP-A-6-19
9728 states that in a hydroformylation reaction of a rhodium-bidentate phosphite catalyst system, monodentate phosphite is generally produced as a decomposition product in the reaction system, and this acts as a catalyst poison, so that the catalytic activity is reduced. Is described.

That is, in the prior art, when an oxo reaction is industrially carried out using a bidentate phosphite ligand, particularly when the reaction is carried out continuously for a long period of time, the reaction system It was expected that the presence of a monodentate phosphite compound, even if it was a decomposition product of a ligand, would not have a favorable effect on the activity of the reaction. Furthermore, in the hydroformylation reaction of an olefinic compound, the activity when a polydentate phosphorus ligand such as various bidentate phosphines or bidentate phosphites conventionally disclosed is used is not always satisfactory, Also, the formation of by-products has led to reduced economics in commercial production. For example, as a by-product, a branched product is of low industrial value, and it has been strongly desired to develop a ligand capable of maintaining high activity even in continuous operation without causing such a side reaction. . The present invention provides a hydroformylation reaction system capable of further improving the reaction activity of a catalyst reaction system containing an organic polydentate phosphite.

[0006]

Means for Solving the Problems In the course of diligently studying a ligand effective for improving the reaction activity and the selectivity of a target product, the present inventors have studied a group VIII metal and a polydentate phosphine. When olefinic compounds undergo a hydroformylation reaction in the presence of a catalyst containing phyte, the presence of a monodentate phosphite having a specific structure improves the activity of the reaction and suppresses the generation of by-products. The inventors have found what can be done and arrived at the present invention. That is, the gist of the present invention is to produce a corresponding aldehyde by hydroformylating an olefinic compound with carbon monoxide and hydrogen in the presence of a catalyst containing a Group VIII metal and an organic polydentate phosphite compound. A method for producing aldehydes, wherein the reaction is carried out in the presence of a cyclic monodentate phosphite compound represented by the following general formula (I) in the reaction system.

[0007]

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(Wherein, _one of Ar ₁ and Ar ₂ is a divalent aromatic organic group each substituted with at least one branched hydrocarbon group, and Ar ₃ is a phosphite oxygen atom Is an aromatic organic group having no bulky substituent at the ortho position.)

[0009]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. In the present invention, the reaction is carried out in the presence of an organic polydentate phosphite compound and a cyclic monodentate phosphite compound having a specific structure in a hydroformylation reaction system. The organic polydentate phosphite compound used in the present invention comprises 2
A compound having at least two phosphite structures, such as bidentate phosphite, tridentate phosphite, and tetradentate phosphite. A typical polydentate phosphite is represented, for example, by the following general formula (II).

[0010]

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In the general formula (I), m is an integer of 2 or more, and W represents an optionally substituted aliphatic group, aromatic group or bisaromatic group. When W represents an aliphatic group, W is preferably an alkylene group having 2 to 4 carbon atoms. When W has an aromatic group, W is preferably an arylene group such as a phenylene group, a naphthylene group, an anthrylene group, a phenanthrylene group, and among them, an o-arylene group is preferable. Further, when W represents a bisaromatic group, the o-positions of the oxygen atoms bonded to the arylene group are directly linked to each other, or a hydrocarbon group, an oxygen atom,
A bisarylene group bonded via a bonding group such as a sulfur atom is preferable, and a group in which the o-positions of oxygen atoms bonded to a phenyl group or a naphthyl group are directly bonded to each other is preferable. Further, R ¹ and R ² are optionally substituted alkyl group, an aryl group, R ¹ and R
² may independently form a ring structure containing a -OPO- bond. When R ¹ and R ² represent an alkyl group, they are preferably linear or cyclic and have 1 to 20 carbon atoms. When R ¹ and R ² represent an aryl group,
Examples include a phenyl group and a naphthyl group. When R ¹ and R ² form a ring structure, the formed R ¹ -R
^{The two} groups represent an optionally substituted alkylene group, an arylene group or a bisarylene group, and when representing an alkylene group, the alkylene chain preferably has 2 to 4 carbon atoms, and when representing an arylene group, Is usually a phenylene group, a naphthylene group, an anthrylene group, a phenanthrylene group, and among them, an o-arylene group is preferable.When representing a bisarylene group, the o-position of the oxygen atom bonded to the aryl group is preferred. It is preferable that they are directly bonded to each other or via a bonding group such as a hydrocarbon group, an oxygen atom and a sulfur atom.

Among the polydentate phosphite compounds represented by the general formula (II), it is preferable to use a bidentate phosphite compound wherein m = 2. Specific examples of the bidentate phosphite compound include, for example, the following compounds. Among them, it is preferable to use a bidentate phosphite having no cyclic structure in the molecule. (In each formula, Me is a methyl group, t-Bu and

[0013]

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Represents a t-butyl group. )

[0015]

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[0020]

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[0021]

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[0022]

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[0023]

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[0024]

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[0025]

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[0026]

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[0027]

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[0028]

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[0029]

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[0030]

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[0031]

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[0032]

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[0033]

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[0034]

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[0035]

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[0036]

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[0037]

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The monodentate phosphite used in the present invention is a cyclic monodentate phosphite compound represented by the following general formula (I).

[0039]

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In the general formula (I), Ar ₁ and Ar ₂
Is a divalent aromatic organic group substituted with at least one, preferably two or more branched hydrocarbon groups, which may be different from each other. Examples of the divalent aromatic organic groups Ar ₁ and Ar ₂ include a phenylene group, a naphthylene group, an anthranylene group and the like. Among them, a phenylene group and a naphthylene group are preferable in that the activity of the reaction can be improved. . Ar ₁ and / or Ar
_The at least one branched hydrocarbon group substituted by ₂ includes a hydrocarbon group having 3 or more carbon atoms such as an i-propyl group, an i-butyl group, a sec-butyl group, a t-butyl group, and a t-amyl group. Among them, a hydrocarbon group having 4 or more carbon atoms is preferable, and a t-butyl group is particularly preferably used.

At least one branched hydrocarbon group substituted by Ar ₁ and Ar ₂ is preferably a steric group which is preferably substituted ortho to the carbon atom to which the phosphite oxygen atom is bonded. In the case of a substituted benzene ring, it is preferable that a hydrocarbon group or an alkoxy group is further substituted at the para position. Also, A
r ₃ is a monovalent aromatic organic group having no bulky substituent at both ortho positions of the phosphite oxygen atom. Here, having no bulky substituent means having no tertiary hydrocarbon group or condensed ring. That is,
A substituent such as a hydrogen atom, a methyl group, an ethyl group, a propyl group, an n-butyl group, a methoxy group, an ethoxy group, a halogen atom, among others, a methyl group or a hydrogen atom; And among them, it is preferable to have a hydrogen atom at the ortho-position of the phosphite oxygen atom.

Specific examples of the aromatic organic group Ar ₃ include a phenyl group, a 2-toluyl group, a 3-toluyl group, a 4-toluyl group, a 2,5-dimethylphenyl group, a 2-methoxyphenyl group, Examples thereof include a 2-methoxy-4-t-butylphenyl group, a 2-naphthyl group, and a 2-chlorophenyl group. Among them, a phenyl group and a 2-naphthyl group are preferable. Ar ₁ , Ar ₂ and Ar ₃ which are aromatic organic groups may further have another substituent as long as the above-mentioned requirements are satisfied, and the substituent has 1 to 30 carbon atoms, preferably Is an alkyl group of 1 to 8, a cycloalkyl group, having 6 to 22 carbon atoms, preferably 6
To 14 aryl groups, having 6 to 22 carbon atoms, preferably 6 to
14 aryloxy groups, an alkoxy group having 1 to 30 carbon atoms, preferably 1 to 8 carbon atoms, an alkyl aryl group having 7 to 30 carbon atoms, an arylalkyl group, an acyl group, a carbonyloxy group, an oxycarbonyl group, Examples thereof include a sulfonyl group, a sulfinyl group, a silyl group, an alkylamino group, a hydroxyl group, an amino group, a cyano group, a nitro group, and a halogen atom.

Examples of the alkyl group as a substituent include a methyl group, an ethyl group, a propyl group, a butyl group and an octyl group. Examples of the cycloalkyl group include a cyclopropyl group, a cyclopentyl group and a cyclohexyl group. Examples of the alkenyl group include a vinyl group, an allyl group, and 2-
Examples thereof include a cyclohexenyl group. Examples of the aryl group include a phenyl group, a 1-naphthyl group, and a 2-naphthyl group. Examples of the aryloxy group include a phenoxy group, a 1-naphthoxy group, and a 2-naphthoxy group. A plurality of these substituents may be substituted on each of the hydrocarbon groups Ar ₁ , Ar ₂ and Ar ₃ , and the respective substituents may be the same or different. Further, the aryl group as a substituent may be further substituted with the above-mentioned substituent.

Specific examples of the aromatic organic group Ar ₁ -Ar ₂ of the monodentate phosphite compound represented by the general formula (I) include those in which both Ar ₁ and Ar ₂ are substituted or unsubstituted phenylene groups. , 3-t-butyl-
2,2′-biphenylene group, 3-t-amyl-2,2 ′
-Biphenylene group, 3,5-di-t-butyl-2,2 '
-Biphenylene group, 3,5-di-t-amyl-2,2 '
-Biphenylene group, 3,3'-di-t-butyl-2,
2'-biphenylene group, 3,3'-di-t-amyl-
2,2′-biphenylene group, 3,3 ′, 5,5′-tetra-t-butyl-2,2′-biphenylene group, 3,
3 ′, 5,5′-tetra-t-amyl-2,2′-biphenylene group, 3,3′-di-t-butyl-5,5′-dimethoxy-2,2′-biphenylene group, 3, 3'-di-
t-amyl-5,5'-dimethoxy-2,2'-biphenylene group, 6-methyl-3,3 ', 5,5'-tetra-
t-butyl-2,2'-biphenylene group, 6-methyl-
3,3 ', 5,5'-tetra-t-amyl-2,2'-
Biphenylene group, 6,6′-dimethyl-3,3 ′, 5
5′-tetra-t-butyl-2,2′-biphenylene group, 6,6′-dimethyl-3,3 ′, 5,5′-tetra-t-amyl-2,2′-biphenylene group, 6, 6'-
Dimethyl-3,3'-di-t-butyl-5,5'-dimethoxy-2,2'-biphenylene group, 6,6'-dimethyl-3,3'-di-t-amyl-5,5 '-Dimethoxy-2,2'-biphenylene group and the like.

Examples of a substituted or unsubstituted naphthylene group for both Ar ₁ and Ar ₂ include 3-t
-Butyl-2,2 ′-(1,1′-binaphthylene group),
3-t-amyl-2,2 '-(1,1'-binaphthylene group), 3,6-di-t-butyl-2,2'-(1,1 '
-Binaphthylene group), 3,6-di-t-amyl-2,
2 ′-(1,1′-binaphthylene group), 3,3′-di-
t-butyl-2,2 ′-(1,1′-binaphthylene group), 3,3′-di-t-amyl-2,2 ′-(1,
1′-binaphthylene group), 3,3,6,6′-tetra-
t-butyl-2,2 '-(1,1'-binaphthylene group), 3,3,6,6'-tetra-di-t-amyl-
2,2 ′-(1,1′-binaphthylene group) and the like.

In addition, _one of Ar ₁ having a substituted or unsubstituted phenylene group and the other being a substituted or unsubstituted naphthylene group includes (3,5-di-t-
Butyl-2phenylene) -1- (2-naphthylene) group,
(3,5-di-t-amyl-2phenylene) -1- (2
-Naphthylene) group, (3,5-di-t-butyl-6-methyl-2-phenylene) -1- (2naphthylene) group,
(3,5-di-t-amyl-6-methyl-2-phenylene) -1- (2naphthylene) group, (3,5-di-t-
Butyl-2phenylene) -2- (1-naphthylene) group,
(3,5-di-t-amyl-2phenylene) -2- (1
Naphthylene) group, (3,5-di-t-butyl-6-methyl-2phenylene) -2- (1-naphthylene) group,
(3,5-di-t-amyl-6-methyl-2phenylene) -2- (1-naphthylene) group, (3,5-di-t-
Butyl-2phenylene) -3,6-di-t-butyl-2
-(1-naphthylene) group, (3,5-di-t-butyl-
6-methyl-2phenylene) -3,6-di-t-butyl-2- (1-naphthylene) group, (3,5-di-t-butyl-2phenylene) -3- (2-naphthylene) group ,
(3,5-di-t-amyl-2phenylene) -3- (2
-Naphthylene) group, (3,5-di-t-butyl-6-methyl-2-phenylene) -3- (2-naphthylene) group,
And a (3,5-di-t-amyl-6-methyl-2-phenylene) -3- (2-naphthylene) group.

Among these phosphorus compounds, 3,3′-
Di-t-butyl-2,2′-biphenylene group, 3,
3 ′, 5,5′-tetra-t-butyl-2,2′-biphenylene group, 3,3′-di-t-butyl-5,5′-dimethoxy-2,2′-biphenylene group, 6- Methyl-
3,3 ′, 5,5′-tetra-t-butyl-2,2′-
Biphenylene group, 6,6′-dimethyl-3,3 ′, 5
5'-tetra-t-butyl-2,2'-biphenylene group, 6,6'-dimethyl-3,3'-di-t-butyl-
5,5′-dimethoxy-2,2′-biphenylene group,
3,3′-di-t-butyl-2,2 ′-(1,1′-binaphthylene group), 3,3,6,6′-tetra-t-butyl-2,2 ′-(1,1 '-Binaphthylene group), (3
5-di-t-butyl-2phenylene) -3,6-di-t
-Butyl-2- (1-naphthylene) group, (3,5-di-
A t-butyl-6-methyl-2-phenylene) -3,6-di-t-butyl-2- (1-naphthylene) group is preferred. More preferred phosphorus compounds include 3,
3 ', 5,5'-tetra-t-butyl-2,2'-biphenylene group, 3,3'-di-t-butyl-5,5'-dimethoxy-2,2'-biphenylene group, 6, 6'-dimethyl-3,3 ', 5,5'-tetra-t-butyl-2,
A 2'-biphenylene group. Representative examples of the cyclic monodentate phosphite compound represented by the general formula (I) are shown below.

[0048]

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[0049]

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[0050]

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[0051]

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[0052]

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[0053]

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The monodentate phosphite represented by the above general formula (I) of the present invention may be newly supplied to the reaction system or may be a by-product decomposed in the reaction system. Although the detailed reaction mechanism in the reaction system of the present invention is not clear,
Since the specific monodentate phosphite of the present invention has a rigid structure, it is easily affected sterically by the ortho-position substituent of the phosphite oxygen atom of Ar _{1 to} Ar ₃ , and as a result, the reaction activity is affected. It is presumed to have given. In the hydroformylation reaction of the present invention, the olefinic compound used as a reaction raw material is not particularly limited as long as it is an organic compound having at least one olefinic double bond in the molecule, and specifically, ethylene, propylene , Butene, butadiene, pentene, hexene, hexadiene,
Octene, octadiene, decene, hexadecene, octadecene, icosene, dococene, styrene, α-methylstyrene, cyclohexene, propylene-butene mixture, n-butene-2-butene-isobutylene mixture, n-butene-2-butene-isobutylene A lower olefin mixture such as a butadiene mixture, propylene, n-
Olefinic hydrocarbons such as olefinic oligomer-isomer mixtures such as dimers to tetramers of lower olefins such as butene and isobutylene, acrylonitrile, allyl alcohol, 1-hydroxy-2,7-octadiene, 3-
Hydroxy-1,7-octadiene, oleylalco-
And heteroatom-substituted olefins such as 1-methoxy-2,7-octadiene, methyl acrylate, methyl methacrylate, and methyl oleate. Among them,
It is preferable to use an olefin having 3 to 8 carbon atoms, and particularly preferable to use propylene.

The Group VIII metal compound used in the present invention includes a Group VIII metal selected from the group consisting of rhodium, cobalt, platinum, iridium, palladium, ruthenium, and mixtures thereof. Rhodium, cobalt, platinum are listed as types of metals,
Particularly preferred is rhodium. As the Group VIII metal compound, for example, a carrier such as an inorganic or organic acid salt of rhodium such as rhodium chloride, rhodium nitrate, rhodium acetate, rhodium formate, sodium rhodate and potassium rhodate, alumina, silica, activated carbon and the like Metal supported on a metal, a chelating compound of rhodium such as rhodium dicarbonyl acetylacetonate, tetrarhodium dodecacarbonyl, hexarhodium hexadecacarbonyl, μ, μ′-dichlororhodium tetracarbonyl, [Rh (OAc) (COD)] 2 (COD is 1,
Represents 5-cyclooctadiene. ), [Rh (μ-S
-T-Bu) (CO) 2] 2. Other Group VIII metal compounds include, for example, cobalt compounds such as dicobalt octacarbonyl and cobalt stearate, platinum compounds such as platinum acid, sodium hexachloroplatinate and potassium diplatinate, iridium trichloride, iridium carbonyl and the like. And ruthenium compounds such as ruthenium trichloride and tetraamine hydroxochlororuthenium chloride. The addition form of the Group VIII metal compound is not particularly limited. The amount of the Group VIII metal compound is not particularly limited, and there is a limit to be taken into consideration from the viewpoint of catalytic activity and economical efficiency. 0.05 mg to 5 g, preferably 0.5 mg to 1
g is selected from the range.

The organic polydentate phosphite compound of the present invention comprises
A complex can be formed in advance with the above Group 8 metal compound and used. Eighth containing organic polydentate phosphite compound
A Group 8 metal complex can be easily prepared from a Group 8 metal compound and an organic polydentate polyphosphite compound by a known complex forming method. In some cases, a Group VIII metal compound and an organic polydentate phosphite compound may be supplied to a hydroformylation reaction zone where a complex is formed and used. Further, the coordination state of the monodentate phosphite to the Group VIII metal compound to be present in the present invention may be in any form. In the present invention, the monodentate phosphite is present even in a very small amount in the system. Just do it.

The amount of the organic polydentate phosphite compound of the present invention is not particularly limited, and is usually about 0.001 to 1000 mol, preferably 0.01 to 200 mol, per 1 mol of Group 8 metal. Selected from a range. The amount of the monodentate phosphite of the present invention is not particularly limited, and is usually about 0.001 to 10 per mol of the Group 8 metal.
00 mol, preferably in the range of 0.01 to 200 mol. In the reaction system, the molar ratio of monodentate phosphite to organic polydentate phosphite compound is:
It is good to be 0.01 to 100, preferably 0.01 to 20, and more preferably 0.05 to 2. Here, the above molar ratio is defined as the total amount of both phosphite coordinated to the complex and phosphite existing in a free state. The use of a reaction solvent is not essential for performing the hydroformylation reaction, but if necessary, a solvent inert to the hydroformylation reaction can be present. Specific examples of preferred solvents include toluene, xylene, aromatic hydrocarbons such as dodecylbenzene, acetone, diethyl ketone, ketones such as methyl ethyl ketone, tetrahydrofuran,
Examples include ethers such as dioxane, esters such as ethyl acetate and di-n-octyl phthalate, and high-boiling components which are by-produced during the hydroformylation reaction of aldehyde condensates and the like. It can also be used.

As the reaction conditions for performing the hydroformylation reaction of the present invention, conventionally used conditions can be used, and the reaction temperature is usually 15 to 200 ° C., preferably 50 to 200 ° C.
~ 150 ° C, the reaction pressure is usually normal pressure ~
The pressure is selected from the range of 200 atm, preferably 5 to 100 atm, particularly preferably 5 to 50 atm. The molar ratio of hydrogen to carbon monoxide (H ₂ / CO) is generally selected from the range of 10/1 to 1/10, preferably 1/1 to 6/1. As a method of the hydroformylation reaction, for example, either a continuous method or a batch method can be carried out in a stirred type reaction vessel or a bubble column type reaction vessel. In addition, as a method for separating the aldehydes and the catalyst to be generated, a known method such as distillation or extraction can be used. Using the separated catalyst solution, the hydroformylation reaction of the olefinic compound is further repeated. be able to. Further, when the olefinic compound is continuously converted into the aldehyde, the remaining reaction liquid obtained by separating a part or all of the aldehyde to be produced can be continuously circulated to the hydroformylation reaction tank for use.

[0059]

EXAMPLES The embodiments of the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples unless it exceeds the gist thereof. Example 1 Toluene as a solvent was placed in a stainless steel vertical stirring type autoclave having an internal volume of 200 ml under a nitrogen atmosphere.
5 ml of heptane as an internal standard, [Rh (OA
c) (COD)] 2, 1 mol of the following bidentate phosphite compound 27, 2.0 mol per gram atom of rhodium, and 4.0 mol of the following monodentate phosphite (6) per mol of rhodium. The charging and the autoclave were sealed. After the inside of the autoclave was sufficiently replaced with nitrogen gas, the pressure was released, and propylene 4.50 was obtained.
g. Next, after the temperature was raised to 70 ° C., water gas (H 2 / CO) was injected into the autoclave to bring the total pressure to 10.0 atm, and the reaction was started. The pressure in the autoclave used for the reaction was maintained at a constant pressure until the end of the reaction by supplying water gas through an automatic pressure regulator, and the reaction was carried out for 0.85 to 1.10 hours. After the completion of the reaction, the reactor was cooled to room temperature. The gas phase and the liquid phase in the autoclave are subjected to component analysis by gas chromatography, quantitative analysis of aldehydes generated, unreacted propylene, propane as a reduction reaction product, and the like are performed. The selectivity of the body product was determined. The results are shown in Table 1.

[0060]

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Example 2 Example 1 was repeated except that the monodentate phosphite compound (16) shown below was used as the monodentate phosphite compound.
The reaction was carried out in the same manner as described above. The results are shown in Table 1.

[0062]

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Comparative Example 1 Example 1 except that no monodentate phosphite was used.
The reaction was carried out in the same manner as described above. The results are shown in Table 1. Comparative Example 2 A reaction was carried out in the same manner as in Example 1 except that the following phosphite compound (ratio 1) was used as a monodentate phosphite. The results are shown in Table 1.

[0064]

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[0065]

[Table 1]

In the table, k / k ₀ represents the ratio of the reaction rate k in the presence of a monodentate phosphite to the reaction rate k ₀ in the presence of only a bidentate phosphite compound A as a phosphite compound. From Table 1 As is apparent, Ar ₃ structures such as 1-naphthyl group, as compared with monodentate phosphite compound having a steric hindrance in the ortho position of the phosphite oxygen atom (Comparative Example 2), Example It can be seen that a monodentate phosphite compound such as 1 or 2 improves the reaction activity when coexisting with an organic polydentate phosphite compound. Further, by allowing the polydentate phosphite and the monodentate phosphite of the present invention to coexist in the hydroformylation reaction system, it is possible to keep the selectivity of the n-form product constant regardless of the type of the monodentate phosphite. I understand.

[0067]

Industrial Applicability Since the specific monodentate phosphite compound of the present invention is allowed to coexist with a catalyst system containing a Group VIII metal and an organic polydentate phosphite, a high reaction activity can be achieved. It is possible to stably produce useful linear aldehydes. Further, reduction of the olefinic compound which is a side reaction can be suppressed.

Claims (8)

[Claims] 1. A process for producing a corresponding aldehyde by hydroformylating an olefinic compound with carbon monoxide and hydrogen in the presence of a catalyst containing a Group VIII metal and an organic polydentate phosphite compound. A method for producing aldehydes, wherein the reaction is carried out in the presence of a cyclic monodentate phosphite compound represented by the following general formula (I) in a reaction system. Embedded image (In the formula, _one of Ar ₁ and Ar ₂ is a divalent aromatic organic group substituted with at least one branched hydrocarbon group, and Ar ₃ is located ortho to the phosphite oxygen atom. It is an aromatic organic group having no bulky substituent.) 2. The monodentate phosphite compound represented by the general formula (I), wherein Ar ₁ and Ar ₂ are each an aromatic organic group substituted with at least one branched hydrocarbon group. A method for producing the aldehyde described in the above. 3. A monodentate phosphite compound represented by the general formula (I), wherein Ar ₁ and Ar ₂ are aromatic organic groups each substituted by at least one branched hydrocarbon group having 4 or more carbon atoms. The method for producing an aldehyde according to claim 1 or 2. 4. The monodentate phosphite compound represented by the general formula (I), wherein at least one substituent substituted on Ar ₁ and / or Ar ₂ is substituted on the ortho position of the phosphite oxygen atom. The method for producing an aldehyde according to any one of claims 1 to 3, wherein the aldehyde is used. 5. The monodentate phosphite compound represented by the general formula (I), wherein Ar ₃ is an aromatic organic group having a hydrogen atom at an ortho position to a phosphite oxygen atom.
5. The method for producing an aldehyde according to any one of 4. 6. The monodentate phosphite compound represented by the general formula (I), wherein Ar ₃ is a 2-naphthyl group.
5. The method for producing an aldehyde according to any one of 5. 7. The method for producing an aldehyde according to claim 1, wherein the organic polydentate phosphite is a bidentate phosphite compound. 8. The method for producing an aldehyde according to claim 7, wherein the organic polydentate phosphite is an acyclic bidentate phosphite compound.