JP2000095722A - Production of aldehyde - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce an aldehyde in high yield while suppressing the deactivation of catalyst by reacting an olefinic compound with hydrogen and carbon monoxide in the presence of a liquid phase containing a rare earth element together with a rhodium complex catalyst composed at least of rhodium and an organic phosphite. SOLUTION: The objective compound is produced by reacting (A) an olefinic compound (e.g. propylene) with (B) hydrogen and (C) carbon monoxide preferably at 30-130 deg.C under a pressure of normal pressure to 200 kg/cm2G in the presence of a liquid phase containing (D) a rhodium complex catalyst composed at least of rhodium and an organic phosphite [e.g. tris(2,4-di-t-butylphenyl)phosphite] and (E) a rare earth element (e.g. ytterbium, erbium, dysprosium or lanthanum). In the above reaction, the concentration of the component D is preferably 0.05-5,000 mg in terms of rhodium metal in 1L of the liquid phase and that of the component E in the liquid phase is preferably >=1 ppm.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a method for producing an aldehyde by reacting an olefinic compound with hydrogen and carbon monoxide using a rhodium complex catalyst containing an organic phosphite as a ligand. In particular, the present invention relates to a method for reducing the decomposition of an organic phosphite and preventing a decrease in the activity of the catalyst when the rhodium complex catalyst is recycled.

[0002]

2. Description of the Related Art Rhodium is widely used as a catalyst for a hydroformylation reaction, and the activity and selectivity of the hydroformylation reaction can be improved by modification with a ligand such as a trivalent phosphorus compound. Is well known to those skilled in the art. Therefore, various studies have been made on trivalent phosphorus compounds used as ligands. In particular, many studies have been made in recent years on hydroformylation catalysts using an organic phosphite having high reactivity and selectivity as a ligand.

For example, JP-A-57-123134 discloses that
A method using a triaryl phosphite having a substituent at a specific position of a phenyl ring as a ligand is disclosed. JP-A-59-51228 and JP-A-59-5123
No. 0 discloses a method using a cyclic phosphite containing a phosphorus atom at a bridgehead as a ligand. Tokio Sho 6
1-501268 discloses a method using diorganophosphite having a cyclic structure as a ligand.
JP-A-62-116587 discloses a bidentate phosphite in which one of the two phosphite groups has a cyclic structure, and JP-A-62-116535 discloses that both phosphite groups are cyclic. Bidentate phosphates having the structure are disclosed. JP-A-4-290551 discloses a method using bisphosphite having a cyclic structure as a ligand. Further, Japanese Patent Application Laid-Open No.
39207 discloses a method using bisphosphite or polyphosphite having a substituent at a specific site as a ligand.

However, in order to use an organic phosphite as a ligand industrially, it is desired to improve its stability. That is, as disclosed in JP-A-59-51229, when an open type organic phosphite such as triphenyl phosphite is used as a ligand, the organic phosphite is depleted in a hydroformylation reaction system, and It is known that the catalyst activity is extremely low, and continuous replenishment of the organic phosphite is necessary.

Further, Japanese Patent Application Laid-Open No. 61-501268 discloses that triphenyl phosphite reacts quickly with aldehyde at room temperature even in the absence of rhodium. The reaction product of an organic phosphite and an aldehyde has been shown to readily hydrolyze to the corresponding hydroxyalkyl phosphonic acid. It is disclosed that this hydroxyalkylphosphonic acid promotes the decomposition of organic phosphite, and that it is possible to suppress the decomposition of organic phosphite by removing these acidic components with a weakly basic ion exchange resin. ing. JP-A-6-199728 describes that a new phosphite compound is generated by decomposition of an organic bisphosphite, and this combines with rhodium as a catalyst metal, resulting in a decrease in the activity of the catalyst. A method is disclosed in which a phosphite compound that poisons the catalyst is selectively decomposed by adding a weakly acidic compound to maintain the activity. Further, JP-A-6-199729 discloses that by adding an epoxide compound, a phosphoric acid compound generated by further decomposition of a phosphite compound poisoning a catalyst can be captured. Japanese Patent Application Laid-Open No. 9-59200 describes that Group VIII metals such as ruthenium, cobalt, palladium and platinum have an effect of suppressing decomposition of organic phosphite and insolubilization of rhodium.

[0006]

As described above, rhodium complex catalysts having an organic phosphite as a ligand, as the organic phosphite is decomposed and the catalytic activity tends to decrease, various measures have been studied. But none of them are yet satisfactory. Since rhodium is extremely expensive, when performing a hydroformylation reaction using a rhodium complex catalyst, it is extremely desirable to recover and reuse the rhodium complex catalyst from the reaction mixture without minimizing its activity. Therefore, the present invention provides a hydroformylation reaction,
It is an object of the present invention to provide a method for recycling a rhodium complex catalyst without reducing its activity as much as possible.

[0007]

According to the present invention, an olefinic compound is reacted with hydrogen and carbon monoxide at least in the presence of a liquid phase containing a rhodium complex catalyst comprising rhodium and an organic phosphite. In the method for producing an aldehyde for producing an aldehyde, by coexisting a rare earth element with the rhodium complex catalyst, the decomposition of the organic phosphite constituting the rhodium complex catalyst is remarkably reduced, whereby the catalytic activity of the rhodium complex catalyst is reduced. Can be prevented.

[0008]

DETAILED DESCRIPTION OF THE INVENTION The present invention will be described in detail. In the present invention, when performing a hydroformylation reaction in a solution in which at least a rhodium complex having an organic phosphite as a ligand is dissolved, a rare earth element is added to the solution. Make the element exist. As the rare earth element, any of a lanthanoid and an actinoid can be used. Preferably, lanthanoids having an atomic number of 57 to 71, particularly ytterbium, erbium, dysprosium, gatorium, praseodymium, cerium, and lanthanum are used. The rare earth element may be in any form such as an inorganic salt, an organic acid salt, or a complex compound as long as the rare earth element is dissolved in a solution in which the rhodium complex is dissolved. For example, inorganic salts such as carbonates, sulfates, nitrates and halides, organic acid salts such as formate, acetate, oxalate, propionate and 2-ethylhexanoate, as well as hydroxides and oxides Are used. Some examples are lutetium nitrate, ytterbium chloride, thulium oxide, erbium acetate, holmium oxalate, dysprosium carbonate, terbium chloride, gadolinium acetate, tris (dipivaloymethanato) europium, samarium acetate, neodymium carbonate, praseodymium acetate. , Cerium acetylacetonate, lanthanum 2-ethylhexanoate, thorium sulfate and the like. The mechanism by which rare earth elements suppress the decomposition of organic phosphites is unknown, but it may be possible to capture or detoxify compounds that are decomposition products of organic phosphites and have the effect of promoting the decomposition of organic phosphites. Guessed.

The hydroformylation reaction according to the method of the present invention can be carried out according to a conventional method except that the decomposition of organic phosphite which is a ligand of the catalyst is suppressed by using a rare earth element. The rhodium complex catalyst used for the reaction can be prepared according to a known method for preparing a rhodium-organophosphite complex catalyst. The rhodium complex catalyst may be prepared in advance and used in the reaction, or may be formed from a rhodium compound and an organic phosphite in the reaction system. Examples of the rhodium compound used for catalyst preparation include, for example, rhodium chloride, rhodium nitrate, rhodium acetate, rhodium formate, sodium rhodate, inorganic or organic acid salts of rhodium such as potassium rhodate, alumina, silica, activated carbon, and the like. Rhodium metal, rhodium dicarbonyl acetylacetonate, rhodium (1,5-
Rhodium chelating compounds such as cyclooctadiene) acetylacetonate, tetrarhodium dodecacarbonyl, hexarhodium hexadecacarbonyl, μ,
μ′-dichlororhodium tetracarbonyl, [Rh (O
Ac) (COD)] ₂ (COD represents 1,5-cyclooctadiene), [Rh (μ-St-Bu) (C
O) ₂ ] ₂ .

As the organic phosphite of the ligand, any organic phosphite such as triaryl phosphite, trialkyl phosphite and alkylaryl phosphite can be used. Bisphosphite having a plurality of these phosphato structures in the same molecule,
Polyphosphites such as tris phosphite can also be used. Among these organic phosphites, monophosphites can be broadly classified into those having no phosphorus atom-containing cyclic structure and those having such a structure. The former is represented by the following general formula (1).

[0011]

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

Wherein R ^{1 to} R ³ are each independently
A hydrocarbon group having 1 to 30 carbon atoms such as an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group,
Represents a heteroaromatic hydrocarbon group of 0, to which a substituent which does not inhibit the hydroformylation reaction may be bonded. Examples of such a substituent include a halogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group,
Examples include an aryl group, an alkoxy group, an alkylamino group, an acyl group, an acyloxy group, and an alkoxycarbonyl group.

In the organic phosphite represented by the general formula (1), at least ^one of R ^{1 to} R ³ is preferably a substituted aryl group represented by the following general formula (2).

[0014]

Embedded image

In the formula, R ⁴ represents an aryl group which may have a substituent which does not inhibit a hydroformylation reaction;
Or -CR ⁹ R ¹⁰ R ¹¹ . Here, R ^{9 to} R ¹¹ each independently represent a hydrogen atom or an optionally fluorinated hydrocarbon group. R ⁴ is preferably a compound having a branch at the 1-position and having a large steric hindrance, such as an isopropyl group and a t-butyl group. R ^{5 to} R ⁸ each independently represent a hydrogen atom or an organic group that does not inhibit the hydroformylation reaction. Adjacent ones of R ^{5 to} R ⁸ may be bonded to each other to form a condensed aromatic ring or condensed heterocyclic ring.

Some examples of such organic phosphites include diphenyl (2,4-di-tert-butylphenyl) phosphite, diphenyl (2-isopropylphenyl) phosphite, and bis (2-tert-butyl).
Butyl-4-methylphenyl) phenyl phosphite,
Diphenyl (3,6-di-tert-butyl-2-naphthyl) phosphite, bis (2-naphthyl) (3,6-
Di-tert-butyl-2-naphthyl) phosphite,
Bis (3,6,8-tri-s-butyl-2-naphthyl) phenyl phosphite, bis (3,6,8-tri-s-butyl-2-naphthyl) (2-naphthyl)
Phosphite and the like.

Organic phosphite represented by the general formula (1)
Is particularly preferred as R¹~ R ^ThreeIs a general formula
It is a substituted aryl group represented by (2). This
Some examples of organic phosphites such as
Lis (2,4-di-tert-butylphenyl) phosph
Aite, tris (2-tert-butyl-4-methyl)
Phenyl) phosphite, tris (2-tert-butyl)
Tyl-4-methoxyphenyl) phosphite, tris
(O-phenylphenyl) phosphite, tris (o-
Methylphenyl) phosphite, bis (3,6-dita-
Shari-butyl-2-naphthyl) (2,4-ditacia)
L-butylphenyl) phosphite, bis (3,6-di
Tert-butyl-2-naphthyl) (2-tert-butyl)
-Butylphenyl) phosphite, tris (3,6-di
Tert-butyl-2-naphthyl) phosphite, g
Squirrel (3,6-dita-shary-amyl-2-naphthyl)
Phosphite and the like. Out of monophosphite
Those having a cyclic structure containing a phosphorus atom are represented by the following general formula
It is represented by (3).

[0018]

Embedded image

In the formula, Z represents a divalent hydrocarbon group which may contain a hetero atom in the carbon chain and may have a substituent which does not inhibit the hydroformylation reaction, and Y represents a hydroformylation group. It represents a hydrocarbon group or a heteroaromatic hydrocarbon group which may have a substituent which does not inhibit the reaction.
In the general formula (3), Y is preferably a substituted aryl group represented by the general formula (2). Further, Z is preferably an alkylene group, an arylene group or a hybrid group of both, which may contain a hetero atom such as an oxygen, nitrogen or sulfur atom in the carbon chain. Examples of such a divalent hydrocarbon group include an alkylene group, an alkyleneoxyalkylene group, an alkyleneaminoalkylene group in which an alkyl group may be bonded to a nitrogen atom, an alkylenethioalkylene group, a cycloalkylene group, an arylene group, and a biarylene. Group, alkylene arylene group, arylene alkylene arylene group, arylene oxyarylene group, arylene oxyalkylene group, arylene thioarylene group, arylene thioalkylene group, or an arylene aminoarylene group or an arylene which may have an alkyl group bonded to a nitrogen atom And an aminoalkylene group. One preferred example of the organic phosphite represented by the general formula (3) is one represented by the following general formula (4).

[0020]

Embedded image

In the formula, R ¹² and R ¹³ each independently represent a hydrogen atom or an alkyl group, a cycloalkyl group or an aryl group which may have a substituent which does not inhibit the hydroformylation reaction, and n is Represents an integer of 0 to 4; Y has the same meaning as in general formula (3), and preferably represents a substituted aryl group represented by general formula (2) described above. In the general formula (4), typical examples of R ¹² and R ¹³ include a methyl group, an ethyl group, a phenyl group, a tolyl group, a benzyl group, a naphthyl group, a hydroxymethyl group, a hydroxyethyl group, and a trifluoromethyl group. And the like. Another preferred example of the organic phosphite represented by the general formula (3) is one represented by the following general formula (5).

[0022]

Embedded image

In the formula, R ¹⁴ is an alkyl group, a cycloalkyl group, an alkoxy group, an acyl group, an acyloxy group, or an aryl group which may have a substituent which does not inhibit a hydroformylation reaction. o-, m-, p-
Any of the positions. R ¹⁴ may be condensed with the benzene ring to which it is bonded to form a condensed aromatic ring such as a naphthalene ring. Y has the same meaning as in general formula (3), and preferably represents a substituted aryl group represented by general formula (2) described above. Another preferable example of the organic phosphite represented by the general formula (3) is represented by the following general formula (6).

[0024]

Embedded image

Wherein Ar inhibits the hydroformylation reaction
Aryl groups which may have unsubstituted substituents,
They may be different. Q is -CR^FifteenR¹⁶-, -O
-, -S-, -NR¹⁷-, -SiR¹⁸R¹⁹-, -CO-
And a divalent cross-linking group. In these crosslinking groups,
R^FifteenAnd R¹⁶Are each independently a hydrogen atom or carbon number
1 to 12 alkyl groups, phenyl groups, tolyl groups or ani groups
Represents a sil group;¹⁷~ R ¹⁹Is, independently of each other, hydrogen
Represents an atom or a methyl group. n is independently 0
Or represents 1. Y has the same meaning as in general formula (3)
You. Preferred examples of Y include a methyl group, an ethyl group, n
-Propyl group, isopropyl group, n-butyl group, sec
-Butyl group, t-butyl group, n-pentyl group, isopene
Tyl group, t-pentyl group, neopentyl group, n-hexyl
Group, t-hexyl group, cyclohexyl group, isooctyl
Group, 2-ethylhexyl group, decyl group, octadecyl
A C1-20 alkyl group such as a group or cycloalkyl
Group and a substituent that does not inhibit the hydroformylation reaction.
Phenyl group, α-naphthyl group, β-naph
And an aryl group such as a tyl group. Aryl group placement
Examples of the substituent include an alkyl group having 1 to 20 carbon atoms and a cycloalkyl group.
Alkyl group, alkoxy group, acyl group, acyloxy group,
Alkoxycarbonyl group, alkylamino group, etc. and halo
Gen atom. Organic phosphite of general formula (6)
Particularly preferred among the compounds are the following general formula (7) or
Is represented by (8).

[0026]

Embedded image

In these formulas, Q, Y and n are the same as in the formula (6), and R ^{20 to} R ²⁵ are each independently an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group,
Represents an alkoxy group, an alkylamino group, an acyl group, an acyloxy group or an alkoxycarbonyl group, or a halogen atom. Some of the above-mentioned organic phosphites having a cyclic structure containing a phosphorus atom are shown in Table 1 below.

[0028]

[Table 1]

[0029]

[Table 2]

In the present invention, as a ligand, 2
The polyphosphite having at least two phosphite structures is represented by the following general formula (9).

[0031]

Embedded image

In the formula, Z has the same meaning as in the formula (3), and R ²⁶ and R ²⁷ each independently represent an alkyl group,
Represents a hydrocarbon group having 1 to 30 carbon atoms such as a cycloalkyl group, an aryl group, or an aralkyl group or a heteroaromatic hydrocarbon group having 5 to 30 carbon atoms, to which a substituent that does not inhibit a hydroformylation reaction is bonded. May be. Examples of such a substituent include a halogen atom and a carbon atom having 1 to 20 carbon atoms.
And alkyl groups, cycloalkyl groups, aryl groups, alkoxy groups, alkylamino groups, acyl groups, acyloxy groups, alkoxycarbonyl groups, and the like.

Some specific examples of R ²⁶ and R ²⁷ are as follows: methyl, ethyl, n-propyl, isopropyl, n-butyl, s-butyl, t-butyl, n-butyl
-Pentyl group, isopentyl group, neopentyl group, t-
A linear or branched alkyl group having 1 to 20 carbon atoms such as a pentyl group and a t-hexyl group; a cycloalkyl group having 3 to 20 carbon atoms such as a cyclopropyl group, a cyclohexyl group, a cyclooctyl group and an adamantyl group; A phenyl group, α
-Naphthyl group, β-naphthyl group, methoxyphenyl group,
Dimethoxyphenyl, cyanophenyl, nitrophenyl, chlorophenyl, dichlorophenyl, pentafluorophenyl, methylphenyl, ethylphenyl, dimethylphenyl, trifluoromethylphenyl, methylnaphthyl, methoxynaphthyl, chloro An aryl group which may have a substituent such as a naphthyl group, a nitronaphthyl group and a tetrahydronaphthyl group; an aralkyl group such as a benzyl group; a pyridyl group, a methylpyridyl group, a nitropyridyl group, a pyrazyl group, a pyrimidyl group, and a benzofuryl group And heteroaromatic groups such as quinolyl group, isoquinolyl group, benzimidazolyl group and indolyl group.

W represents an m-valent hydrocarbon group which may contain a hetero atom such as an oxygen, nitrogen or sulfur atom in the carbon chain and may have a substituent which does not inhibit the hydroformylation reaction. Represent. m ₁ and m ₂ each represent a number of 0 to 6, and m ₁ + m ₂ represents an integer of ₂ to 6. Note that m
_{When 1} or m ₂ represents a number of 2 or more, a plurality of Z, R
²⁶ and R ²⁷ may each be different.

Preferably, Z is the above formula (4) to (8)
R is represented by²⁶And R ²⁷Is hydroformyl
That may be substituted with a substituent that does not inhibit the
A group. Some examples of such aryl groups
Then, a phenyl group, a 2-methylphenyl group, a 3-methyl
Ruphenyl group, 4-methylphenyl group, 2,4-dimethyl
Phenyl group, 2,5-dimethylphenyl group, 2,6-
Dimethylphenyl group, 2-methoxyphenyl group,
Toxiphenyl 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
And a 3-methyl-β-naphthyl group.

W is preferably an alkylene group, or a general formula
-Ar- (CH in (6)_Two) _n-(Q)_n− (C
H_Two)_nIt is a divalent group represented by -Ar-. like this
Examples of such a divalent group include a 1,2-ethylene group and a 1,3-propylene group.
Ropylene group, 1,3-dimethyl-1,3-propylene
Group, 1,4-butylene group, 1,5-pentylene, 1,6
-Hexylene group, 1,8-octylene group, 1,2-fe
Nylene group, 1,3-phenylene group, 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.
You.

More preferred examples of the polyorganophosphite represented by the general formula (9) are those wherein Z is -Ar- (CH ₂ ) _n -Q _n- (CH ₂ ) _n -Ar- in the general formula (6).
And m ₁ is at least 1;
And W is represented by the following general formula (10).

[0038]

Embedded image

In the formula, Q and n are as follows in the general formula (6).
Synonymous with R³²And R³³Are each independently carbon
Number 1 to 12 alkyl groups, cycloalkyl groups, alcohols
A xy, silyl or siloxy group, or a halogen atom
Represents a hydrogen atom or a hydrogen atom. Some examples
And methyl, ethyl, n-propyl, isopropyl
Group, n-butyl group, methoxy group, ethoxy group, n-propyl
Loxy group, hydrogen atom, fluorine atom, chlorine atom, bromine atom
And an iodine atom. Also, R²⁸~ R ³¹Is
Each independently represents an alkyl group having 1 to 20 carbon atoms,
Chloroalkyl, alkoxy, silyl or silo
A xy group, a halogen atom or a hydrogen atom,
Examples of these include methyl, ethyl, n-propyl
Group, isopropyl group, n-butyl group, t-butyl group,
An opentyl group, a 2,2-dimethylbutyl group, a nonyl group,
Decyl group, methoxy group, ethoxy group, t-butoxy group, etc.
Is mentioned. Also, R³⁰And R³²Or R³¹And R³³And
1,1'-binaphthyl-2,2'-diyl
And a condensed ring such as a phenyl group may be formed.

In the general formula (10), R ²⁸ and R ²⁹ are preferably an alkyl group having 3 to 20 carbon atoms and branched at the 1-position. R ³⁰ and R ³¹ are an alkyl group or an alkoxy group having 1 to 20 carbon atoms, or R ³⁰ and R ³² , or R ³¹ and R ³³ are bonded to form an alkyl group or an alkoxy group as a substituent; It preferably forms part of a naphthalene ring that may be present. Some examples of W represented by the general formula (10) include: 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.

Of the W represented by the general formula (10),
One of the preferred is R³²And R ³³But independent
A methyl group, an ethyl group, an n-propyl group,
Pill group, methoxy group, ethoxy group, n-propoxy group,
Isopropoxy group, fluorine atom, chlorine atom, bromine atom,
Alkyl groups having 1 to 3 carbon atoms, such as iodine atom, alkoxy
It is a group or a halogen atom. Such a W
Examples of 3,3'-di-t-butyl-5,5 ',
6,6'-tetramethyl-1,1'-biphenyl-2,
2'-diyl group, 3,3 ', 5,5'-tetra-t-butyl
Tyl-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'-biphe
Nyl-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
-1,1'-biphenyl-2,2'-diyl group and the like.
Can be Polyphosphite represented by the general formula (9)
Some are illustrated in Table-2.

[0042]

[Table 3]

[0043]

[Table 4]

[0044]

[Table 5]

[0045]

[Table 6]

[0046]

[Table 7]

[0047]

[Table 8]

[0048]

[Table 9]

[0049]

[Table 10]

[0050]

[Table 11]

[0051]

[Table 12]

[0052]

[Table 13]

[0053]

[Table 14]

[0054]

[Table 15]

[0055]

[Table 16]

[0056]

[Table 17]

[0057]

[Table 18]

[0058]

[Table 19]

[0059]

[Table 20]

[0060]

[Table 21]

[0061]

[Table 22]

[0062]

[Table 23]

In the present invention, a hydroformylation reaction can be carried out according to a conventional method, except that the above-mentioned rhodium complex catalyst having an organic phosphate as a ligand is used and a rare earth element is coexisted in the catalyst. The reaction can be carried out using the olefinic compound as a raw material as a main solvent, but it is usually preferable to use a solvent inert to the reaction.
Examples of such a solvent include aromatic hydrocarbons such as toluene, xylene and dodecylbenzene; ketones such as acetone, diethyl ketone and methyl ethyl ketone; ethers such as tetrahydrofuran and dioxane; ethyl acetate;
Esters such as n-octyl phthalate; and high-boiling component mixtures which are by-produced during the hydroformylation reaction of aldehyde condensates and the like. Among them, it is preferable to use an aromatic hydrocarbon such as toluene or xylene, a high-boiling component mixture by-produced in the reaction, or a combination of these.

The concentration of the rhodium complex catalyst in the reaction zone is usually 0.00 as rhodium metal per liter of liquid phase.
5 to 5000 mg. It is preferably from 0.5 to 1000 mg, particularly preferably from 10 to 500 mg. The organic phosphite is usually used in an amount of about 0.1 to 500 moles relative to rhodium. It is preferably used in an amount of 0.1 to 100 times, particularly 1 to 30 times the mole of rhodium. In addition, several types of organic phosphites may be used as a mixture. The rare earth element is used so as to be 1 ppm or more, usually 1 to 10000 ppm in the liquid phase. 10
It is preferable to use it so as to be from 1 to 10,000 ppm, especially from 50 to 5000 ppm.

As the olefinic compound as a raw material, any compound can be used as long as it has at least one olefinic double bond in the molecule. The olefinic double bond may be at the terminal or inside the molecular chain. The carbon chain constituting the molecule may be linear, branched or cyclic. Further, in the molecule, a carbonyl group which is substantially inert to the hydroformylation reaction in the reaction,
It may contain a hydroxy group, an alkoxy group, an alkoxycarbonyl group, an acyl group, an acyloxy group, a halogen atom and the like. Representative olefinically unsaturated compounds are α-olefins, internal olefins, alkyl alkenoates, alkenyl alkanoates, alkenyl alkyl ethers, alkenols and the like. Some examples of olefinically unsaturated compounds include ethylene, propylene, butene, butadiene, pentene, hexene, hexadiene, octene, octadiene, nonene, decene,
Hexadecene, octadecene, eicosene, docosene,
Styrene, α-methylstyrene, cyclohexene, and lower olefin mixtures such as propylene-butene mixture, 1-butene-2-butene-isobutylene mixture, 1-butene-2-butene-isobutylene-butadiene mixture, propylene, n-butene Olefins such as a mixture of olefin oligomer isomers such as dimer to tetramer of lower olefin such as isobutylene, 3-phenyl-1-
Hydrocarbon olefins such as propene, 1,4-hexadiene, 1,7-octadiene, 3-cyclohexyl-1-butene, acrylonitrile, allyl alcohol, 1-hydroxy-2,7-octadiene, 3-hydroxy-
1,7-octadiene, oleyl alcohol, 1-methoxy-2,7-octadiene, methyl acrylate, methyl methacrylate, methyl oleate, oct-1-en-4-ol, vinyl acetate, allyl acetate, acetic acid 3 -Butenyl, allyl propionate, vinyl ethyl ether,
Vinyl methyl ether, allyl ethyl ether, n-propyl-7-octenoate, 3-butenenitrile, 5
And olefins substituted with a polar group such as -hexenamide. Preferably, a monoolefinic unsaturated compound having only one olefinic double bond in the molecule is used. Particularly preferred are olefins having 2 to 20 carbon atoms, especially propylene, or 1-butene, 2-butene, isobutene, and mixtures thereof, 1-octene, and mixed octene.

The reaction temperature of the hydroformylation reaction is usually 1
5 to 150C, but 30 to 130C, especially 50 to 1C.
A range of 10 ° C. is preferred. The reaction pressure is from normal atmospheric pressure to 20
0 kg / cm ² G, but 1-100 kg / cm
² G, especially 3 to 50 kg / cm ² G, is preferred. The molar ratio of hydrogen to carbon monoxide (H ₂ / CO) of the oxo gas supplied to the reaction zone is usually 10/1 to 1/10,
/ 1 to 6/1 are preferred.

The reaction can be carried out in either a continuous mode or a batch mode, but is usually carried out in a continuous mode. As a reaction mode, the raw material olefinic compound and oxo gas are continuously supplied to a reaction zone containing a liquid phase containing a commonly used rhodium complex catalyst, and the generated aldehyde is mixed with unreacted oxo gas. A stripping method of flowing out of the reaction zone, and a reaction solvent containing a catalyst, a raw material olefinic compound and oxo gas containing a catalyst are continuously supplied to the reaction zone, and a reaction product liquid containing an aldehyde generated from the reaction zone is continuously withdrawn. Any of a liquid circulation system in which a reaction solvent containing a catalyst remaining after separating at least the aldehyde formed therefrom can be circulated to the reaction zone can be used. Separation of the produced aldehyde in the liquid circulation system may be performed by any method, and is usually performed by distillation.
When the aldehyde is separated from the reaction product solution by distillation, the rhodium complex catalyst is generally easily deactivated. In particular, since the rhodium complex catalyst having an organic phosphite as a ligand as in the present invention has high activity, the hydroformylation reaction is often performed at a relatively low temperature as described above, and the aldehyde is separated from the reaction product by distillation. In some cases, the distillation temperature may be higher. In this case, it is considered that the deactivation of the rhodium complex catalyst mainly occurs in the distillation step. The deactivation of the rhodium complex catalyst during distillation is
During the distillation, there is no carbon monoxide or hydrogen that is easily coordinated to rhodium in the system, so that the rhodium complex becomes coordinatively unsaturated and easily decomposes, resulting in deactivation of the rhodium complex catalyst. it is conceivable that. However,
When the catalyst and the rare earth element coexist according to the method of the present invention, that is, when the reaction product solution contains the rare earth element together with the catalyst, the deactivation of the catalyst in this distillation step can be reduced. In order to prevent the deactivation of the rhodium complex catalyst in the distillation step, the concentration of the rare earth element in the reaction solvent containing the rhodium complex catalyst circulated from the distillation step to the reaction zone is preferably set to 1 to 10000 ppm. 10
More preferably, it is 10,000 ppm, especially 50 to 5000 ppm. However, even if rare earth elements coexist, decomposition of the rhodium complex catalyst is unavoidable at high temperatures,
The distillation temperature is preferably 150 ° C. or lower, particularly preferably 130 ° C. or lower. Most preferably, it is distilled at 50 to 120 ° C. Therefore, when the boiling point of the aldehyde is high, it is preferable to perform distillation under reduced pressure. The reaction solvent containing the rhodium complex catalyst obtained by separating the aldehyde by distillation is present in the reaction solvent by an appropriate means such as extraction, washing, crystallization, or adsorption before being circulated to the reaction zone. The decomposition products of the organic phosphite may be removed.

[0068]

The present invention will be further described below with reference to Examples and Comparative Examples.
Although described in detail, the present invention does not depart from the gist of the invention without departing from the gist thereof.
The present invention is not limited to the examples below. Example 1 SUS-304 stainless steel with a magnetic stirrer and an inner volume of 70 mL
The di-μ-acetato-bis (1,5-
Cyclooctadiene) rhodium ([Rh (C ₈H₁₂)
(Μ-CH_ThreeCO_Two)]_Two) Complex 33 mg, (0.06
1 mmol), a bidentate phosphite 52 represented by the following formula:
0.2 mg (0.486 mmol) and Erbium acetate
504.8 mg (Er / Rh = 10 (mo
12.5 mL of toluene and n-butyl
12.5 mL of aldehyde was charged under a nitrogen atmosphere. This
Oxo gas (H_Two/ CO = 1 (molar ratio))
9kg / cm^TwoPress in to G and stir at room temperature for 15 minutes
This activated the catalyst. Then oxo gas
After discharging and purging with nitrogen gas again,
The tube was heated at 130 ° C. for 135 hours under a nitrogen atmosphere. Heat treatment
Decomposition products generated by decomposition of the ligand in the solution after processing
It was quantified by high performance liquid chromatography. The result
As a result, the detected decomposition product was 7 mol% of the original ligand.
there were. In addition, by the above-mentioned catalyst activation treatment, rhodium
Hydrogen, carbon monoxide and phosphite coordinate to the
Didium hydride dicarbonyl (phosphite)
And was confirmed separately.

[0069]

Embedded image

Example 2 Activation and heat treatment were carried out in exactly the same manner as in Example 1 except that 494.5 mg of gadolinium acetate tetrahydrate (Gd / Rh = 10 (molar ratio)) was used instead of erbium acetate. went. As a result, the decomposition product detected in the solution after the heat treatment was 9 mol% of the original ligand.

Comparative Example 1 SUS-316 having a magnetic stirrer and having an internal volume of 100 mL
Di-μ-acetato-bis (1,5-cyclooctadiene) dirhodium ([Rh
_{(C 8 H 12) (μ} -CH 3 CO 2)] 2) complexes 66.3
mg, (0.123 mmol), 1047.1 mg (0.977 mm) of the same bidentate phosphite used in Example 1.
ol), and 25 mL of toluene and 25 mL of n-butyraldehyde were charged under a nitrogen atmosphere. Next, activation and heat treatment were performed in exactly the same manner as in Example 1 except that the heat treatment time was changed to 90 hours. As a result, the phosphite was decomposed 100%. The decomposition product is one of the original ligands.
It was 00 mol%.

Claims (10)

[Claims] 1. A method for producing an aldehyde, comprising reacting an olefinic compound with hydrogen and carbon monoxide to form an aldehyde in the presence of a liquid phase containing at least a rhodium complex catalyst comprising rhodium and an organic phosphite, A method characterized by causing a rare earth element to coexist in a rhodium complex catalyst. 2. The method according to claim 1, wherein the rare earth element is present in an amount of 1 ppm or more in the liquid phase containing the rhodium complex catalyst. 3. A reaction step of reacting an olefinic compound with hydrogen and carbon monoxide in the reaction zone in the presence of a liquid phase containing at least a rhodium complex catalyst comprising rhodium and an organic phosphite to form an aldehyde. In a method for producing aldehydes, the separation step of separating the aldehyde from the reaction mixture taken out from the reaction zone to obtain a catalyst solution containing a rhodium complex catalyst, and the circulation step of circulating the catalyst solution to the reaction zone, A method wherein the separation step is performed in the presence of a rhodium complex catalyst and a rare earth element in a liquid phase. 4. The method according to claim 3, wherein the separation step is performed so that the concentration of the rare earth element in the obtained catalyst solution is 1 to 10 ⁴ ppm. 5. The method according to claim 1, wherein the organic phosphite constituting the rhodium complex catalyst is represented by the general formula (1). [Image Omitted] P (OR ¹ ) (OR ² ) (OR ³ ) (1) (wherein, R ¹ to R ³ are each independently a carbon number which may have a substituent. Represents a hydrocarbon group having 1 to 30 or a heteroaromatic hydrocarbon group having 5 to 30 carbon atoms) 6. In the general formula (1), R ¹ to R ³
Are each independently a substituted aryl group represented by the general formula (2). Embedded image (Wherein R ⁴ is —CR ⁹ R ¹⁰ R ¹¹ (R ⁹ , R ¹⁰ and R ¹¹
Each independently represents a hydrogen atom or a hydrocarbon group which may be fluorinated) or an aryl group which may have a substituent. R ⁵ to R ⁸ each independently represent a hydrogen atom or an organic group. Note that adjacent ones of R ⁵ to R ⁸ may combine with each other to form a condensed aromatic ring or a condensed heterocyclic ring. 7. The method according to claim 1, wherein the organic phosphite constituting the rhodium complex catalyst is represented by the general formula (3). Embedded image (In the formula, Z represents a divalent hydrocarbon group which may contain a hetero atom in the carbon chain and may have a substituent, and Y represents a carbon atom which may have a substituent. Represents a hydrogen group or a heteroaromatic hydrocarbon group.) 8. The method according to claim 1, wherein the organic phosphite constituting the rhodium complex catalyst is represented by the general formula (9). Embedded image (In the formula, Z represents a divalent hydrocarbon group which may contain a hetero atom in the carbon chain and may have a substituent. R ²⁶ and R ²⁷ each independently represent Represents an optionally substituted hydrocarbon group having 1 to 30 carbon atoms or a heteroaromatic hydrocarbon group having 5 to 30 carbon atoms, W may include a hetero atom in the carbon chain, and Represents an m-valent hydrocarbon group which may have a substituent, m ₁ and m
₂ represents an integer of 0 to 6, and m ₁ + m ₂ =
2-6) 9. In the general formula (9), R ²⁶ and R ²⁷ are each independently an aryl group which may have a substituent, and W is represented by the general formula (10). 9. The method of claim 8, wherein the method comprises: Embedded image (Wherein, R ²⁸ and R ²⁹ each independently represent a group having 3 carbon atoms)
~ 20 branched alkyl groups. R ³⁰ and R ³¹ are each independently an alkyl group or an alkoxy group having 1 to 20 carbon atoms. R ³² and R ³³ are each independently a hydrogen atom, a halogen atom, a silyl group, siloxy group, or an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group or an alkoxy group. Q is -CR ¹⁵ R ^16- , -O-,-
^{S -, - NR 17 -,} - SiR 18 R 19 - is a bridging group which is, or -CO-. In this bridging group, R ¹⁵ and R
¹⁶ each independently represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a phenyl group, a tolyl group or an anisyl group, and R ^{17 to} R ¹⁹ each independently represent a hydrogen atom or a methyl group. n represents 0 or 1. ) 10. The olefinic compound is propylene,
1-butene, 2-butene, isobutene, mixed butene, 1
10. The method according to claim 1, wherein the method is selected from the group consisting of octene and mixed octene.