JP2002047294A - Bidentate phosphorus compound and method of hydroformylation using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a bidentate phosphorus ligand excellent in activity, selectively, thermal stability in a hydroformylation reaction. SOLUTION: This compound is a bidentate phosphorus compound expressed by general formula A-a. [ -Ar1-Ar2- is a bisarylene group expressed by general formulas a-I or a-II; Z1 to Z4 are each a five membered heterocycle or its condensate including one or more nitrogen atoms and having nitrogen atom bonding to phosphorus atom; R4 and R5 are each independently an alkyl group, an alkoxy, a cycloalkyl, a cycloalkoxy, a silyl or siloxy group which may contain a substituent or a halogen; R1 to R3 and R6 to R8 are each independently H, an alkyl, an alkoxy, a cycloaklyl, a cycloalkoxy, a dialkyl amino, an aryl, aryloxy, an alkylaryl, an alkylaryloxy, an alkylaryloxy, arylalkyl, an arylalkoxy, cyano, hydroxy, or a halogen; R14 and R15 are each the same as the above R4 and R5; and R9 to R13 and R16 to R20 are each the same as R1 to R3 and R6 to R8)].

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel bidentate phosphorus compound and a method for hydroformylation of an olefinic compound using the same.

[0002]

2. Description of the Related Art A method for producing an aldehyde or an alcohol which is a hydride thereof by reacting an olefinic compound with carbon monoxide and hydrogen (water gas) in the presence of a catalyst is well known as a hydroformylation method. is there. As a catalyst for the hydroformylation reaction, a soluble complex of a Group VIII metal having an organic phosphorus compound as a ligand is usually used. In general, the ligand used with the metal component of the catalyst has a significant effect on the catalytic reaction. It is widely known that also in the hydroformylation reaction, the ligand greatly changes the activity and selectivity of the reaction. In order to carry out the hydroformylation reaction industrially advantageously, improvement of the reaction activity and selectivity are important issues, and ligands therefor are being actively designed.

[0003] Various phosphite compounds are known as a group of phosphorus compounds used as ligands in hydroformylation reactions, and simple phosphite compounds such as trialkyl phosphites and triaryl phosphites have hitherto been known. In addition to phosphites, various phosphite compounds such as polyphosphites having a plurality of coordinating phosphorus atoms in the molecule have been proposed. For example, Japanese Patent Application Laid-Open No. 62-11658
7, JP-A-6-184036, JP-A-11-130
No. 718 discloses a bisphosphite compound in which at least one of two phosphite groups has a cyclic structure.

On the other hand, JP-A-5-178779, JP-A-10-45776, and JP-A-11-130720 disclose bisphosphite compounds in which two phosphite groups are not both cyclized. In addition, USP5
No. 710344 discloses that bidentate ligands having two phosphorus atoms having at least one PC bond or at least one PN bond can be used for hydroformylation of internal olefins such as pentenoic acid esters. Have been.

As described above, various phosphorus compounds have been proposed as ligands used in hydroformylation reactions.
In the hydroformylation reaction using a bidentate phosphorus compound reported so far, if a high reaction rate is obtained, the selectivity of the target product, a linear aldehyde, is insufficient, and conversely, an extremely high linear When selectivity was obtained, the reaction rate was insufficient. Furthermore, the thermal stability of the ligand itself was insufficient.

[0006]

As described above, various phosphorus compounds have been conventionally proposed as ligands used in hydroformylation reactions. However, in the hydroformylation reaction using these, a high reaction rate and a high purpose are required. Since the selectivity of the product is not satisfied at the same time, there is a fear that commercial production may be reduced in economic efficiency, and there is a problem that it is difficult to use as an industrial catalyst. Therefore, while maintaining a high reaction rate, give excellent selectivity of the target product,
In addition, it has been strongly desired to develop a ligand having high thermal stability.

[0007]

Means for Solving the Problems In the course of hydroponylation, the present inventors have intensively studied a ligand which is effective in improving and maintaining both the reaction activity and the selectivity of a target product. When a novel bidentate phosphorus compound having a specific structure is found and used as a component of the catalyst in the hydroformylation reaction, that is, as a ligand used together with the metal component of the catalyst, the reaction proceeds at a high rate and is extremely excellent. It has been found that the desired product obtained has good selectivity and exhibits excellent performance in thermal stability. That is, a first gist of the present invention is a bidentate phosphorus compound represented by the following general formula (Aa).

[0008]

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[In the formula, the -Ar ₁ -Ar ₂ -group is a bisarylene group represented by the following general formula (a-I) or (a-II), and Z _{1 to} Z ₄ are each a phosphorus atom. The bonding atom is a nitrogen atom and contains at least one nitrogen atom;
It is a membered heterocyclic compound or a condensed cyclic compound thereof.

[0010]

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(Wherein R ₄ and R ₅ each independently represent an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, a silyl group which may have a substituent, Selected from the group consisting of a good siloxy group and a halogen atom, wherein R _{1 to} R ₃ , R _{6 to} R
₈ is each independently a hydrogen atom, an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, a dialkylamino group, an aryl group, an aryloxy group, an alkylaryl group, an alkylaryloxy group, an arylalkyl group, an arylalkoxy group , A cyano group, a hydroxy group and a halogen atom. )

[0012]

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(Wherein R₁₄And R_FifteenAre each independently
R in the general formula (a-I)_FourAnd R_FiveIs synonymous with₉~ R
₁₃, R₁₆~ R₂₀Are each independently in the general formula (a-I)
R₁~ R _Three, R₆~ R₈Is synonymous with )].

A second aspect of the present invention is a bidentate phosphorus compound represented by the following general formula (Ab).

[0015]

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[In the formula, the -Ar ₃ -Ar ₄ -group is a bisarylene group represented by the following general formula (b-I) or (b-II), and Z _{5 to} Z ₈ are a phosphorus atom. The bonding atom is a nitrogen atom and contains at least one nitrogen atom;
It is a membered heterocyclic compound or a condensed cyclic compound thereof.

[0017]

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(Wherein, R ₂₃ and R ₂₆ each independently represent an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, a silyl group which may have a substituent, Represents a member selected from the group consisting of a good siloxy group and a halogen atom, and R ₂₁ , R ₂₂ , R ₂₄ ,
R ₂₅ , R ₂₇ and R ₂₈ each independently represent a hydrogen atom, an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, a dialkylamino group, an aryl group, an aryloxy group, an alkylaryl group, an alkylaryloxy group, It represents one selected from the group consisting of an arylalkyl group, an arylalkoxy group, a cyano group, a hydroxy group and a halogen atom. )

[0019]

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[0020] (wherein, R ₃₄ and R ₃₉ have the same meanings as R ₂₃ and R ₂₆ in the general formula (b-I) each independently, R ₃₁ ~
R ₃₃ , R _{35 to} R ₃₈ and R _{40 to} R ₄₂ each independently represent R ₂₁ , R ₂₂ , R ₂₄ , R ₂₅ , R ₂₇ , R ₂₈ in the general formula (b-I).
Is synonymous with )].

A third aspect of the present invention relates to a method for producing a corresponding aldehyde by reacting an olefinic compound with carbon monoxide and hydrogen in the presence of a Group VIII metal compound. 6. A method for hydroformylation, characterized in that the bidentate phosphorus compound according to any one of 6) is present.

[0022]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail. Novel bidentate phosphorus compounds of the present invention (A-a) is, more specifically, the -Ar ₁ -Ar ₂ - group is represented by the following general formula (a
-I) or (a-II).

[0023]

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In the above formula (a-I) or (a-II)
And R_Four, R_Five, R₁₄And R_FifteenIs, for example, a methyl group,
Tyl group, n-propyl group, isopropyl group, t-butyl
Linear or branched alkyl having 1 to 12 carbon atoms such as
Carbon such as a kill group, cyclopropyl group, cyclohexyl group, etc.
Cycloalkyl group of formula 3 to 12, methoxy group, ethoxy
Group, alkoxy having 1 to 12 carbon atoms such as t-butoxy group
Group, silyl group such as trimethylsilyl group, trimethylsilo
Siloxy group such as xyl group, chlorine atom, fluorine atom, bromine atom
And halogen atoms such as iodine atom. this
Among them, lower alkyl groups having 1 to 3 carbon atoms such as methyl group and ethyl group are preferred.
Alkyl group, methoxy group, ethoxy group, etc.
Halogen atoms such as lower alkoxy groups and chlorine atoms are preferred.
And a methyl group and a methoxy group are particularly preferable. Also,
Examples of the substituent for the aryl group or the siloxy group include a group having 1 to 3 carbon atoms.
Or an alkyl group having 1 to 3 carbon atoms is preferred.
No. Further, R in (a-I)₁~ R_Three, R₆~ R₈, And expression
R of (a-II)₉~ R₁₃, R_{1 6}~ R₂₀Is the hydrogen atom
Others, for example, methyl group, ethyl group, n-propyl group, i-
Propyl group, n-butyl group, s-butyl group, t-butyl
Group, n-pentyl group, isopentyl group, neopentyl
Group, t-pentyl group, t-hexyl group, etc.
0 alkyl group, cyclohexyl group, cyclooctyl
, A cycloalkyl having 3 to 20 carbon atoms such as an adamantyl group
And C 6-20 alkyl groups such as phenyl, phenyl and naphthyl groups.
Reel group, methoxy group, ethoxy group, isopropoxy
Group, alkoxy having 1 to 12 carbon atoms such as t-butoxy group
Groups such as dimethylamino, diethylamino, etc.
~ 20 dialkylamino groups, phenoxy groups, naphthoki
An aryloxy group having 6 to 20 carbon atoms such as a silyl group, benzyl
An arylalkyl group having 7 to 20 carbon atoms such as a group, p-tri
Alkyl or C 7-20 alkyl ants such as
And C3 to C2 such as cyclopentyloxy group, etc.
Carbon such as a cycloalkoxy group of 0 or 2,3-xylenoxy
An alkylaryloxy group having a prime number of 7 to 20, 2- (2-
Aryl having 7 to 20 carbon atoms such as naphthyl) ethoxy group
Lucoxy, cyano, hydroxy, fluoro,
A halogen atom such as a loro group and a bromo group;
They may be the same or different. Formula (a-I) and
Preferred as the bisarylene group of (a-II)
Is 3,3'-di-t-butyl-5,5 ', 6,6'-
Tetramethyl-1,1'-biphenyl-2,2'-dii
Group, 3,3 ′, 5,5′-tetra-t-butyl-6,
6'-dimethyl-1,1'-biphenyl-2,2'-di
Yl group, 3,3 ', 5,5'-tetra-t-pentyl-
6,6'-dimethyl-1,1'-biphenyl-2,2 '
-Diyl group, 3,3 ', 5,5'-tetra-t-hexyl
-6,6'-dimethyl-1,1'-biphenyl-2,
2'-diyl group, 3,3'-di-t-butyl-5,5 '
-Dimethoxy-6,6'-dimethyl-1,1'-bife
Nyl-2,2'-diyl group, 3,3'-di-t-butyl
-5,5'-diethoxy-6,6'-dimethyl-1,
1'-biphenyl-2,2'-diyl group, 3,3'-di
-Tert-butyl-5,5'-diethoxy-6,6'-dimethyl
A tyl-1,1′-biphenyl-2,2′-diyl group,
3,3'-di-t-butyl-5,5'-di-t-butoxy
C-6,6'-dimethyl-1,1'-biphenyl-2,
2'-diyl group, 3,3 ', 5,5'-tetra (cyclo
Octyl) -6,6'-dimethyl-1,1'-biphenyl
2,2'-diyl group, 3,3 ', 5,5'-tetra
-T-butyl-6,6'-dichloro-1,1'-biphe
Nyl-2,2'-diyl group and the like.

[0025] Another novel bidentate phosphorus compounds of the present invention (A-b) is more specifically its -Ar ₃ -Ar ₄ -
The group is represented by the following general formula (b-I) or (b-II).

[0026]

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In the above formulas (bI) and (b-II), R ₂₃ , R ₂₆ , R ₃₄ and R ₃₉ are, for example, n-propyl, i-propyl, s-butyl, t-butyl Group, isopentyl group, neopentyl group, t-pentyl group, t-
Represents a linear or branched alkyl group having 1 to 10 carbon atoms such as a hexyl group, among which those having 3 to 10 carbon atoms are preferred, and those having 4 to 10 carbon atoms are particularly preferred. Further, a tertiary carbon atom bonded to the aromatic ring is preferable, and t-
Examples thereof include a butyl group, a t-pentyl group, a t-hexyl group and the like. Further, in addition to the above, C 1-10, preferably C 1-10
C6 to C14, preferably C6, such as an alkoxy group, cyclohexyl group, cyclooctyl group, adamantyl group, etc.
And 10 to 10 silyl groups such as a cycloalkyl group and a trimethylsilyl group, a siloxy group such as a trimethylsiloxy group, and a halogen atom such as a chlorine atom, a fluorine atom, a bromine atom and an iodine atom. The substituent of the silyl group or the siloxy group is preferably an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms. Further, R ₂₁ , R ₂₂ ,
R ₂₄ , R ₂₅ , R ₂₇ , R ₂₈ , and R _{31 to} R of the formula (b-II)
_{33, R 35 ~R 38, R} 40 ~R 42 , in addition to hydrogen atoms, such as methyl group, ethyl group, n- propyl group, i- propyl, n- butyl, s- butyl, t- butyl Group, n-
Pentyl group, isopentyl group, neopentyl group, t-pentyl group, alkyl group having 1 to 20 carbon atoms such as t-hexyl group, cyclohexyl group, cyclooctyl group, cycloalkyl group having 3 to 20 carbon atoms such as adamantyl group, An aryl group having 6 to 20 carbon atoms such as a phenyl group and a naphthyl group, an alkoxy group having 1 to 12 carbon atoms such as a methoxy group, an ethoxy group, an isopropoxy group and a t-butoxy group, a carbon atom such as a dimethylamino group and a diethylamino group. A carbon number of 6 such as a dialkylamino group, a phenoxy group or a naphthoxy group of 2 to 20;
7-20 carbon atoms such as an aryloxy group and a benzyl group;
In addition to an alkylaryl group having 7 to 20 carbon atoms such as an arylalkyl group having 20 carbon atoms, a p-tolyl group and an o-tolyl group, a cycloalkoxy group having 3 to 20 carbon atoms such as a cyclopentyloxy group, 2,3-xylenoxy and the like And a halogen such as an arylalkoxy group having 7 to 20 carbon atoms, such as an alkylaryloxy group having 7 to 20 carbon atoms, a 2- (2-naphthyl) ethoxy group, a cyano group, a hydroxy group, a fluoro group, a chloro group, and a bromo group. Atoms and the like, which may be the same or different.

Suitable bisarylene groups of the formulas (bI) and (b-II) include 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 ',
5,5'-tetra-t-hexyl-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 '
-Diethoxy-1,1'-biphenyl-2,2'-diyl group, 3,3'-di-t-butyl-5,5'-di-t-
Butoxy-1,1'-biphenyl-2,2'-diyl group, 3,3 ', 5,5'-tetra (cyclooctyl)-
1,1'-biphenyl-2,2'-diyl group and the like.

R ₁ and R _{8 in} the general formula (a-I), R ₉ and R ₂₀ in the general formula (a-II), R ₂₁ and R _{28 in} the general formula (b-I), and R ₂₁ and R _{28 in} the general formula (b-I) As R ₃₁ and R _{34 in} II), among the above-mentioned substituents, the bidentate phosphorus compound has high thermal stability, and when used as a ligand for a hydroformylation catalyst, has high activity and high selectivity. In that it has 3 carbon atoms
Preferred are straight-chain or branched-chain alkyl groups of from 20 to 20,
Among them, an alkyl group having 4 to 18 carbon atoms is more preferable, and a branched alkyl group having 4 to 8 carbon atoms is particularly preferable.

In formulas (Aa) and (Ab), Z ₁ to
Z ₈ is a nitrogen atom bonded to a phosphorus atom, and at least one, usually one to four, preferably one to three.
A 5-membered heterocyclic compound containing two nitrogen atoms or a condensed cyclic compound thereof. Among them, Z _{1 to} Z ₈ are preferably a 5-membered heterocyclic compound containing one nitrogen atom, particularly preferably pyrrole. Specific examples of Z _{1 to} Z ₈ include the following.

[0031]

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Z _{1 to} Z ₈ may further have a substituent. Examples of the substituent include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group and an s-butyl group. Group, t-butyl group, n-pentyl group, isopentyl group,
A carbon number of 1 to 12 such as a neopentyl group and a t-pentyl group,
Preferably 1 to 8 carbon atoms having 1 to 12 carbon atoms such as linear or branched alkyl group, methoxy group, ethoxy group and the like, preferably 6 to 6 carbon atoms such as alkoxy group, phenyl group and naphthyl group having 1 to 8 carbon atoms. 18, preferably 6 to 10 aryl groups and the like, and additionally, halogen atoms, cyano groups, nitro groups, trifluoromethyl groups, hydroxyl groups, amino groups, acyl groups, carbonyloxy groups, oxycarbonyl groups, amides Group, sulfonyl group, sulfinyl group, silyl group, thionyl group and the like. One to five of these substituents may be substituted for one Z.

The above general formulas (Aa) and (Ab)
Examples of the bidentate phosphorus compound represented by are shown below.

[0034]

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[0035]

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[0036]

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[0037]

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[0038]

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[0039]

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[0040]

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[0041]

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[0042]

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[0043]

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[0044]

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[0045]

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[0046]

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[0047]

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[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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[0054]

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[0055]

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[0056]

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[0057]

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[0058]

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[0059]

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[0060]

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[0061]

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[0062]

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[0063]

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[0064]

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[0065]

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[0066]

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[0067]

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[0068]

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[0069]

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[0070]

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[0071]

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[0072]

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[0073]

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The general formulas (Aa) and (Ab) of the present invention
As a method for synthesizing the bidentate phosphorus compound represented by the formula (1), there are a method using (1) chlorophosphine and a method (2) via a poly (dihalogenated phosphorous) compound. Hereinafter, for example, -Ar ₁ -Ar _{2 of the} general formula (Aa)
The synthesis method will be described by taking the case where the group is (aI) as an example. As the synthesis method of (1), for example, JP-A-10-45
775, and can be synthesized by the method described in the following general formula (a-I-1) (general formula (a-I-1),
₁ to R ₈ of the general formula have the same meanings as those R ₁ to R ₈ of (a-I) in, M represents an alkali metal or alkaline earth metal salt. 1,1′- each having a substituent represented by
An alkali metal salt or an alkaline earth metal salt of biphenyl-2,2'-diol, and the following general formulas (B) and / or (C) (wherein Z _{1 to} Z ₄ represent the general formula (Aa) Z ₁ ~
Z ₄ and is the same meaning. ) Can be prepared by contacting the compound with the phosphorus compound represented by the formula (1).

[0075]

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The bisarylene diol salt represented by the general formula (a-I-1) is represented by the following general formula (a-I-2) (R _{1 to} R _{8 in the} general formula (a-I-2)). Is the same as defined for R _{1 to} R _{8 in} formula (a-I), respectively.
1,1′-biphenyl-2, each having a substituent,
2'-diol, n-BuLi, Na, NaH, KH
Such as alkali metal compounds or methyl magnesium bromide,
It can be synthesized by reacting with an alkaline earth metal compound such as ethyl magnesium bromide in a solvent, preferably under an inert gas atmosphere such as nitrogen.

[0077]

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The amount of the metal compound used is determined by the general formula (a-
Usually, 2 moles are sufficient for 1 mole of the bisarylene diol represented by I-2), but more than 2 moles may be used if desired. Examples of the solvent include ethers such as tetrahydrofuran and diethyl ether, hydrocarbons such as hexane and toluene, pyridine, triethylamine, N, N,
Nitrogen-containing compounds such as N ', N'-tetramethylethylenediamine and mixtures thereof are preferably used. The reaction temperature can be appropriately selected from the range of -70 ° C to the boiling point of the solvent.
It is also possible to adopt a method in which the temperature is maintained at a temperature of between 0 ° C. (room temperature) and then gradually raised to the boiling point of the solvent. From the viewpoint of the reaction operation, n-BuLi, Na or N
The reaction is preferably carried out using aH and using tetrahydrofuran as a solvent. The reaction time can be usually selected in the range of 1 minute to 48 hours, but is preferably about 10 minutes to 24 hours.

In the next step, the compound represented by the general formula (a-I-1) may be used as it is without purification, but may be previously isolated by washing with a poor solvent or recrystallization. May be performed. Phosphorus compounds represented by the general formulas (B) and (C) generally contain phosphorus trichloride (PCl ₃ ) and Z ₁ -H, Z ₂ -H, Z ₃ -H or Z ₄ -H (wherein Z ₁ to Z ₄ is Z ₁ in the general formula (a-a)
~Z ₄ synonymous. The heterocyclic compound represented by the formula (1) can be synthesized in the presence or absence of a base, preferably in an atmosphere of an inert gas such as nitrogen, in a solvent or without a solvent. Phosphorus compounds in which Z ₁ and Z ₂ or Z ₃ and Z ₄ are the same are preferred because they can be easily synthesized. Therefore, it is more preferable that both Z ₁ and Z ₂ , and Z ₃ and Z ₄ are the same, and in particular, Z ₁ , Z ₂ , Z
More preferably, ₃ and Z ₄ are the same.

Examples of the base include nitrogen-containing bases such as pyridine, triethylamine and diethylamine, and inorganic bases such as sodium carbonate and potassium carbonate. Nitrogen-containing bases are preferably used because of the ease of reaction operation. The amount of the base used is usually 2 moles per 1 mole of PCl3. If the amount of the base is too large or too small, unnecessary P (Z ₁ ) ₂ (Z ₂ ), P (Z ₁ ) (Z ₂ ) ₂ , P
Phosphorus compounds such as (Z ₁ ) ₃ and P (Z ₂ ) ₃ and Cl ₂ P
This is not preferred because the amount of by-products of dichloro compounds such as (Z ₁ ) increases.

The reaction temperature can be selected arbitrarily. For example, when a nitrogen-containing base is used as the base, the reaction is started at a lower temperature, for example, 0 to 25 ° C. (room temperature). And a method of gradually increasing the reaction temperature. The reaction time can be selected from a range of 1 minute to 48 hours, but a reaction time of about 5 minutes to 10 hours is preferable. When the reaction is carried out in the presence of a base, a salt of hydrogen chloride and a base which is by-produced with the progress of the reaction usually exists in the reaction solution as a solid, but this is preferably an inert gas such as nitrogen. It can be removed from the reaction system by a method such as filtration under an atmosphere. When the reaction is carried out in the absence of a base, a method of removing hydrogen chloride as a by-product from the reaction system by bubbling an inert gas such as nitrogen gas or argon gas into the reaction system is exemplified.

The chlorophosphines represented by the general formulas (B) and (C) may be obtained as a mixture with the above unnecessary phosphorus compounds and dichloro compounds, but without being separated from them. You may proceed to the next step. Examples of a method for separating the phosphorus compounds of the general formulas (B) and (C) from these by-products include a method by recrystallization using an aliphatic hydrocarbon solvent such as hexane and heptane, and a distillation.

The bidentate phosphorus compound of the general formula (AaI) is prepared by mixing the compound of the general formula (a-I-1) and the compound of the general formula (B) and / or (C) in a solvent or 25 without solvent
It can be synthesized by contacting at a temperature of not more than 1 ° C. for 1 minute or more. The contact is preferably performed under an atmosphere of an inert gas such as nitrogen, and the compound of the general formula (a-I-1)
(B) and / or the compound of (C), preferably at 5 ° C.
Or less, more preferably 0 ° C or less, and most preferably -30 ° C.
After mixing at a temperature of not more than ° C and maintaining the temperature for 1 minute or more, preferably 3 minutes to 60 minutes, the target bisphosphite compound can be synthesized by a method of gradually increasing the temperature. The rate of temperature rise can be appropriately selected between 0.1 ° C./min and 20 ° C./min.
A rate of 5 ° C / min to 10 ° C / min is preferred. Examples of the reaction solvent include ethers such as tetrahydrofuran, diethyl ether and dioxane, hydrocarbons such as hexane and toluene, pyridine, triethylamine, N, N, N ', N'.
-Nitrogen-containing compounds such as tetramethylethylenediamine,
And mixtures thereof. It is desirable to use the minimum amount of the solvent necessary for dissolving the target substance to be formed, but it is also possible to use a larger amount.

Next, the method via (2) a poly (dihalogenated phosphorous) compound will be described. As the synthesis method of (2), for example, it can be synthesized by the method described in JP-A-2000-53688, and the following general formula (A)
-A-1) a polydentate organophosphorus compound; Z ₁ -H, Z _2-
H, (wherein, Z ₁ to Z ₄ are the general formula (A-a) is synonymous with Z ₁ to Z ₄ in.) Z ₃ -H or Z ₄ -H and with the heterocyclic compounds represented by By reacting with each other.

[0085]

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(Wherein —Ar ₁ —Ar ₂ — is a group represented by the general formula (A)
-A), and Y represents a halogen atom. ) Z ₁ -H used in the present invention, Z ₂ -H, Z ₃
-H and Z ₄ -H may be used the same as the heterocyclic compounds used in the process of synthesizing a phosphorus compound of the above formula (B) or (C).

When a bidentate phosphorus compound represented by the general formula (Aa) is produced from a poly (dihalogenated phosphorous) compound represented by the general formula (Aa-1), coexistence of a base is essential. However, it is advantageous because the reaction easily proceeds in the coexistence thereof. As the base,
Examples of the alkali metal include lithium, sodium, and potassium. Examples of the alkaline earth metal include magnesium and calcium. Examples of the secondary amine having a hydrocarbon group having 1 to 22 carbon atoms include diethylamine and diisopropylamine. Is a tertiary amine having a hydrocarbon group having 1 to 22 carbon atoms, triethylamine,
Tripropylamine, triisopropylamine, tributylamine, triisobutylamine, trioctylamine, N, N-dimethylaniline, 1-methylpyrrolidine, 1-methylpiperidine, 1-methyl-2-pyrrolidone, 1-methyl-2-piperidone, heterocyclic aromatic Pyridine, 2-picoline, 3-picoline, 3-
Picoline and 1-methylpyrrole, among which alkali metals and tertiary amines are preferred.

A poly (dihalogenated phosphorous) compound,
Z₁H ~ Z_FourH, and mixing of each component when reacting a base
There are no restrictions on the order in which they may be used.
When using earth metal, Z₁H ~ Z_FourH and base
Followed by poly (dihalogenated phosphorous)
Reaction of the compound gives a better yield.
When a secondary amine is used as the base, Z₁
H ~ Z_FourH and a poly (dihalogenated phosphorous) compound
Or reacting a base after mixing ₁H ~
Z_FourAfter mixing H and the base, the poly (dihalogen)
Phosphoryl) compound gives better yield
It is advantageous in that it can be obtained. Tertiary amine or active
When using a heterocyclic aromatic compound having no hydrogen atom
In this case, the mixing order is not limited.₁H ~ Z_FourH
Or Z₁H ~ Z_FourH and the base are mixed and then
(Halogenated phosphorous) compound is more advantageous
is there.

The amount of the base used in carrying out the reaction of the present invention is not particularly limited, and is usually 0.01 mole times the number of halogen atoms bonded to the phosphorus atoms of the poly (dihalogenated phosphorous) compound. To 100,000 mole times, preferably 0.1 to 100 mole times, particularly preferably 1 to 10 mole times.

In carrying out the reaction of the present invention, the use of a reaction solvent is not essential, but if necessary, an inert solvent can be present in the reaction. Specific examples of preferred solvents include aliphatic hydrocarbons such as hexane, heptane and octane; aromatic hydrocarbons such as toluene, xylene and dodecylbenzene; ketones such as acetone, diethyl ketone and methyl ethyl ketone; diethyl ether, dibutyl ether and tetrahydrofuran. , Dioxane and other ethers, ethyl acetate and other esters, triethylamine, tripropylamine, 1-methyl-2-pyrrolidone, 1-methyl-2
Tertiary amines such as -piperidone, heterocyclic aromatic compounds such as pyridine and 2-picoline, and mixtures produced as by-products when producing poly (dihalogenated phosphorous) compounds;
The poly (dihalogenated phosphorous) compound itself, Z ₁ H
Z ₄ H can be used as a solvent.

The Z ₁ H to Z ₄ used in carrying out the reaction of the present invention
The amount of H used is not particularly limited, and is usually selected in the range of 0.01 to 10,000 times the number of halogen atoms bonded to the phosphorus atom of the poly (dihalogenated phosphorous) compound, preferably The molar ratio is selected in the range of 0.1 to 100 times, particularly preferably 1 to 10 times.

The reaction temperature for carrying out the reaction of the present invention is -78 ° C.
To 80 ° C, preferably from -50 ° C to 30 ° C,
Particularly preferably, it is selected in the range of -30 ° C to 10 ° C, most preferably in the range of -15 ° C to 5 ° C.

Although it is not essential to remove impurities active in the reaction which may be mixed in the solvent and all chemicals used in the present invention, the removal improves the yield and is economically advantageous. Is preferable.

The method for synthesizing the bidentate phosphorus compound to which the present invention can be applied is not limited, but Z ₁ H to Z ₄ H are simultaneously present with the poly (dihalogenated phosphorous) compound of the general formula (A-a-1). The reaction may be carried out or stepwise.
A stepwise synthesis method is suitable for the purpose of more advantageously synthesizing a bidentate phosphorus compound in which Z ₁ and Z ₂ on the (Z ₁ ) and (Z ₂ ) groups are different. That is, when a poly (dihalogenated phosphorous) compound represented by the general formula (A-a-1) is reacted with a heterocyclic compound, one halogen atom of each dihalogenated phosphorous group is preferentially substituted. You. Therefore, after reacting the same number of Z ₁ Hs as the number of phosphorus atoms, the same number of Z ₂ Hs as the number of phosphorus atoms are also reacted, whereby Z _{2 on the} —P (Z ₁ ) (Z ₂ ) group is _It is possible to synthesize bidentate phosphorus compounds in which ₁ and Z ₂ are different. The bidentate phosphorus compound synthesized by this method is used as a ligand in a catalytic reaction, and each phosphorus atom has chirality. Suitable for use in optical resolution of compounds. It is also suitable for use as an additive to polymer materials.

The poly (dihalogenated phosphorous) compound represented by the general formula (A-a-1) can be synthesized by various reactions. For example, in DE19513541,
It is described that the compound is obtained by a reaction between a corresponding polyhydroxy compound and phosphorus trichloride, such as bisphenols. AA Kutyrev et al. Also reported that the reaction of 1,4-benzoquinone with phosphorus trichloride afforded the corresponding dichlorophosphite (Zh.
Obshch. Khim. 62 (8), 1768
-1771 (1992)). Further, JP-A-2000-53
688, a poly (bis (dihydrocarbylamino) phosphorus) compound is reacted with a hydrogen halide represented by HY to obtain a poly (dihalogenated phosphorous) compound in good yield. And at the same time, an intramolecular cyclization reaction which is a side reaction can be suppressed.

According to the synthesis method described above, the compound represented by the general formula (A-
In the case where the -Ar ₁ -Ar ₂ -group of a) is the bidentate phosphorus compound of (a-II) or the -Ar ₃ -Ar ₄ -group of the general formula (Ab) is (b-I) Alternatively, in the case of the bidentate phosphorus compound (b-II), it can be synthesized in the same manner. Among the above methods (1) and (2), the synthesis method (1) is more preferable. Examples of the method for purifying the bidentate phosphorus compounds of the general formulas (Aa) and (Ab) include a method by column development (chromatography), a method by hanging washing, and a method by recrystallization. Examples of the method using column development include a method using silica gel, alumina oxide, or the like as a filler. Examples of the column developing solution include ethers such as tetrahydrofuran and dioxane, aliphatic hydrocarbons such as hexane and heptane, aromatic hydrocarbons such as toluene and xylene, esters such as ethyl acetate and methyl acetate, chloroform, and dichloromethane. These solutions are used as a single solvent or as a mixture of two or more solvents so as to be suitable for the purification of the target substance.

[0097] Further, as a purification method by hanging washing, after completion of the bidentate phosphorus synthesis reaction, a salt produced by filtration or by-produced with a polar solvent such as water, for example, metal chloride (MCl) or hydrochloric acid of a nitrogen-containing compound is used. After the salts are removed from the reaction solution, the solution is evaporated to dryness, and the residue is subjected to a solvent such as aliphatic hydrocarbons such as acetonitrile, hexane, heptane, ketones such as acetone and diethyl ketone, and alcohols such as methanol and ethanol. By stirring in the solvent, the target substance can be purified by a method of dissolving unnecessary substances in the solvent without dissolving the target substance in these solvents.

As a purification method by recrystallization, after completion of the synthesis reaction of the bidentate phosphorus compound, a salt produced by filtration or a by-product of a polar solvent such as water, for example, a metal chloride or a hydrochloride of a nitrogen-containing compound is used. After removing from the reaction solution, evaporating the solution to dryness, dissolving the residue in the minimum amount of solvent capable of dissolving, and then cooling, and dissolving the residue in a solvent capable of dissolving, The solvent is added by adding a solvent insoluble or hardly soluble in the bidentate phosphorus compound of the product, and cooling if necessary, separating the solid by a method such as filtration, and washing the solid with a solvent in which the solid is insoluble. Method and the like. Examples of the solvent in which the bidentate phosphorus compound is soluble include aromatic hydrocarbons such as benzene, toluene, and xylene, and ethers such as tetrahydrofuran and dioxane.As the hardly soluble solvent, in addition to acetonitrile,
Aliphatic hydrocarbons such as hexane and heptane, acetone,
Examples thereof include ketones such as diethyl ketone and alcohols such as methanol and ethanol.

In the present invention, the hydroformylation reaction is carried out using the above-mentioned novel bidentate phosphorus compound,
It is possible to simultaneously satisfy a high reaction rate and excellent selectivity of the target product. In the hydroformylation method 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. Specifically, ethylene, propylene, butene, butadiene, pentene, hexene, hexadiene, octene, octadiene, decene, hexadecene, octadecene, icosene, dococene, styrene, α-methylstyrene, cyclohexene, and a mixture of propylene and butene, 1 -Butene to 2-butene-isobutylene mixture, 1-butene to
Olefins such as a mixture of lower olefins such as a mixture of 2-butene-isobutylene-butadiene, a mixture of olefin oligomers such as a dimer to a tetramer of a lower olefin such as propylene, n-butene, and isobutylene; acrylonitrile, allyl alcohol , 1-hydroxy-
2,7-octadiene, 3-hydroxy-1,7-octadiene, oleyl alcohol, 1-methoxy-2,7
Polar olefins such as octadiene, methyl acrylate, methyl methacrylate and methyl oleate; In the present invention, among the above, olefinic compounds having no polar functional group are preferable, and α
-Olefins are more preferred, and propylene is most preferred.

Catalyst for hydroformylation reaction or precursor thereof
The Group 8 metal compound used as the compound is a Group 8 metal
Hydride, halide, organic acid salt, inorganic acid salt, oxidation
Compounds, carbonyl compounds, amine compounds, olefin coordination
Compound, phosphine coordination compound or phosphite coordination
Compounds and the like can be used, for example, ruthenium trichloride,
Tolamine hydroxochlororuthenium chloride, di
Chlorotris (triphenylphosphine) ruthenium, etc.
Ruthenium compounds, palladium acetate, palladium chloride
Osmium such as palladium compounds, osmium trichloride
Compounds, iridium trichloride, iridium carbonyl, etc.
Compounds of iridium, platinum acid, sodium hexachloroplatinate
Platinum compounds such as lithium and potassium diplatinate, Zicobar
Kovar such as tooctacarbonyl and cobalt stearate
Compound, rhodium trichloride, rhodium nitrate, rhodium acetate
, Rh (acac) (CO)_Two , [Rh (OAc)
(COD)]_Two , Rh_Four (CO)₁₂, Rh₆ (C
O)₁₆, HRh (CO) (PPh_Three)_Three , [Rh (OA
c) (CO)_Two ]_Two , [Rh (μ-S (t-Bu))
(CO _Two ]_Two , [RhCl (COD)]_Two (Acac is
Acetylacetonate group, OAc is acetyl group, CO
D is 1,5-cyclooctadiene, Ph is a phenyl group
And t-Bu represents a tertiary butyl group).
Compounds, but are not necessarily limited to these.
Not something. In the present invention, among them, cobalt,
Rhodium and ruthenium are preferred, and rhodium is most preferred.
New

In the method of the present invention, the bidentate phosphorus compound can be used after forming a complex with the above-mentioned Group 8 metal compound in advance. Group 8 metal complexes containing bidentate phosphorus compounds are
It can be easily prepared from a Group 8 metal compound and the bidentate phosphorus compound by a known complex forming method. In some cases, the Group 8 metal compound and the bidentate phosphorus compound can be supplied to a hydroformylation reaction zone to form a complex there and used. The amount of the Group VIII metal compound used is not particularly limited, and may be limited in view of catalytic activity and economic efficiency. However, in the present invention, the concentration in the hydroformylation reaction zone is usually expressed in terms of metal atoms. 0.05 mg to 5 g, preferably 0.5 m, per liter of olefinic compound or reaction solvent
g to 1 g.

In the present invention, the use amount of the bidentate phosphorus compound is not particularly limited, and is appropriately set so as to obtain a desired result with respect to the activity and selectivity of the catalyst.
Usually, it is selected from the range of about 0.001 to 500 mol, preferably 0.1 to 100 mol, per mol of the eighth metal. In conducting the hydroformylation reaction, the use of a reaction solvent is not essential, but if necessary, a solvent inert to the hydroformylation reaction can be present. Specific examples of preferred solvents include aromatic hydrocarbons such as toluene, xylene and todecylbenzene, ketones such as acetone, diethyl ketone and methyl ethyl ketone, ethers such as tetrahydrofuran and dioxane, ethyl acetate and di-n-octyl phthalate. And high-boiling components by-produced during the hydroformylation reaction of aldehyde condensates and the like, and olefinic compounds as reaction raw materials.

The reaction conditions for carrying out the hydroformylation method of the present invention are the same as those conventionally used conventionally, and the reaction temperature is usually 15 to 200 ° C., preferably 5 to 200 ° C.
The partial pressure of CO and the partial pressure of H2 are usually from 0.001 to 200 atm, preferably from 0.1 to 150 atm.
The pressure is selected from the range of 100 atm, particularly preferably 1 to 50 atm. The molar ratio of hydrogen to carbon monoxide (H ₂ / CO) is usually 10/1 to 1/10, preferably 1/1 to 1/6.
Is selected from the range. As a system of the hydroformylation reaction, either a continuous system or a batch system can be carried out in a stirred type reaction vessel or a bubble column type reaction vessel.

In the present invention, general formula (Aa) or (A-
In the hydroformylation reaction system using the novel bidentate phosphorus compound shown in b), after the formed aldehyde is separated by a method such as distillation, the recovered liquid containing the Group VIII metal and the bidentate phosphorus compound is used. The hydroformylation reaction of the olefinic compound can be performed again. Further, when continuously converting olefinic compounds to aldehydes,
The remaining reaction solution from which a part or all of the generated aldehyde is separated can be continuously circulated as a catalyst solution to the hydroformylation reaction tank. Aldehydes obtained by the method of the present invention can be obtained by known methods, for example, USP 555.
According to US Pat. No. 5,030,644 or US Pat. No. 5,667,644, it is possible to produce alcohols suitable for plasticizers such as normal butanol, 2-ethylhexanol and nonyl alcohol by subjecting them to a hydrogenation reaction as they are, or subjecting them to a hydrogenation reaction after dimerization. It becomes possible.

[0105]

EXAMPLES Next, specific 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 of the present invention.

[0106] Example 1 (Synthesis of tetra pylori bis phosphite (Ligand _{1)) PCl 3 (3.99g,} 29mmol) in toluene (1
00 ml) solution into freshly distilled pyrrole (3.89).
g, 58 mmol) and triethylamine (8.82 g,
87 mmol) in toluene (80 ml) was added dropwise at 0 ° C. After heating at 60 ° C. for 2 hours, ³¹ P-NMR confirmed that dipyrrolylchlorophosphine was formed with a selectivity of 83% (δ104.4). The filtrate from which the salt was filtered was concentrated to 50 ml. Separately, 3,
3 ', 5,5'-tetra-tert-butyl-6,6'
-Dimethyl-2,2-biphenol (6.37 g, 1
4.5 mmol) of a THF solution (40 ml) was added to n-Bu.
A hexane solution of Li (29 mmol) was mixed at 0 ° C., and then heated and refluxed for 1.2 hours.
Salt was obtained. An Li salt of biphenol was added dropwise to a toluene solution of dipyrrolylchlorophosphine at 0 ° C. After the reaction, the salt was filtered off, and the filtrate was concentrated. The remaining residue was isolated and purified by silica gel column chromatography (developing solution: toluene: hexane = 1: 5), and as a result, 2.13 g (19%) of ligand 1 having the following structure was obtained. mp 215.6-216.3 ° C. ³¹ P-NMR (CDCl ₃ ) δ 99.78 ¹ H-NMR (CDCl ₃ ) δ 7.37 (s, 2H),
6.81 (m, 4H), 6.68 (m, 4H), 6.2
0 (m, 4H), 6.15 (m, 4H), 1.94
(S, 6H), 1.29 (s, 18H), 1.06
(S, 18H)

[0107]

Embedded image

The structure of the above-mentioned ligand 1 was confirmed using phosphorus 31-nuclear magnetic resonance spectrophotometry, proton nuclear magnetic resonance spectrophotometry (apparatus: Unity 300, manufactured by Varian) or elemental analysis.

Reaction Example-1 (Hydroformylation Reaction Using Ligand 2) Under a dried nitrogen atmosphere, 19.7 mg of [Rh
(cod) (OAc)] ₂ , the following bidentate phosphorus ligand 2 214.4m
g, 55 ml of degassed and dehydrated toluene, and 5 ml of degassed and dehydrated heptane (an internal standard for gas chromatography analysis after the reaction) were added to prepare a homogeneous solution. Subsequently, the well-dried stainless steel vertical stirring autoclave having an inner volume of 200 ml was replaced with dry nitrogen three times, and the above solution was pressed into the autoclave under a nitrogen atmosphere by a nitrogen pressure and sealed. After 4.5 g of propylene was further pressed into the autoclave and hermetically sealed, the autolab was heated to 70 ° C. At this time, the internal pressure was 4 kg / cm ² . After that, the synthesis gas (H ₂ : CO = 1: 1) was introduced into the auto-reave to start the propylene hydroformylation reaction, but the synthesis gas was introduced from the accumulator through the secondary pressure regulator and reacted. At all times, the total pressure in the autoclave was adjusted to 9 kg / cm ² . 5.0
After an hour, the pressure in the accumulator almost disappeared, and the reaction was completed. After the reaction, cool the autoclave to room temperature,
The gas phase and the liquid phase in the autoclave were collected, and each was subjected to component analysis using gas chromatography. As a result, the conversion of propylene was 93.7% and the yield of C ₄ -aldehyde was
91.9%, the ratio of n-butyraldehyde as a target product and i-butyraldehyde as a by-product in C ₄ -aldehyde (n / i
Ratio) was 25.5. The reaction rate constant determined from the pressure reduction rate of the accumulator was 0.53 h ⁻¹ . Further, as a result of performing ³¹ P-NMR measurement of the reaction solution, a signal based on a free ligand was observed at 100.8 ppm, and a signal based on a Rh-P complex was observed at 138 to 142 ppm. No signal based on ligand degradation was observed.

[0110]

Embedded image

Reaction Example-2 (Hydroform using ligand 1)
Milling reaction) Instead of 214.4 mg of ligand 2 used in Reaction Example-1
222.6 mg of the bidentate phosphorus ligand synthesized in Example 1 above
1 in the same manner, but otherwise
A formylation reaction was performed. The reaction time was 2.0 hours
Was. A similar analysis showed that the conversion of propylene was 9
6.6%, C_Four-The aldehyde yield is 94.8%, C _Four-Aldehi
The n / i ratio in C was 100.9. Also, the reaction rate constant
The number is 2.16h^{- 1}Met. In addition, the reaction solution³¹P-NMR measurement
As a result, a signal based on a free ligand was found at 99.5 ppm.
But also 137.7 ppm (d,^TwoJ_Rh-P= 209.8Hz) Rh-P complex
Was observed, but other than that,
No signal due to degradation was observed.

[0112]

Industrial Applicability The bidentate phosphorus compound of the present invention forms a homogeneous metal catalyst in various organic reactions such as hydrogenation, hydroformylation, hydrocyanation, hydrocarboxylation, hydroamidation, hydroesterification, and aldol condensation. It is a novel compound that can be used as an element. In the method of the present invention, by using a bidentate phosphorus compound having a specific structure as a catalyst component in the hydroformylation reaction, not only high reaction activity but also extremely high aldehyde isomer selectivity can be obtained. It can be carried out advantageously.

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (reference) C07F 9/6506 C07F 9/6506 9/6524 9/6524 // C07B 61/00 300 C07B 61/00 300 (72) Invention Person Nao Urata 3-1, Chuo, Ami-cho, Inashiki-gun, Ibaraki Pref. F-term in the Tsukuba Research Laboratory, Mitsubishi Chemical Corporation 4H006 AA02 AC45 BA24 BA48 BE20 BE40 4H039 CA62 CL45 4H050 AB40

Claims (14)

[Claims] 1. A bidentate resin represented by the following general formula (Aa)
Compound. Embedded image[Wherein, -Ar₁-Ar_TwoThe group is represented by the following general formula (a-I)
Or a bisarylene group represented by (a-II),₁
 ~ Z_Four Is a nitrogen atom bonded to the phosphorus atom,
And a 5-membered heterocyclic ring containing at least one nitrogen atom
It is a formula compound or its fused cyclic compound. Embedded image(Where R_FourAnd R_FiveAre each independently an alkyl group,
Alkoxy group, cycloalkyl group, cycloalkoxy group,
Silyl group which may have a substituent,
Selected from the group consisting of a siloxy group and a halogen atom.
R₁~ R_Three, R₆~ R₈Is German
Hydrogen, alkyl, alkoxy, cycloal
Kill group, cycloalkoxy group, dialkylamino group,
Reel group, aryloxy group, alkylaryl group,
Alkylaryloxy, arylalkyl, aryl
Alkoxy, cyano, hydroxy and halogen
Represents a member selected from the group consisting of atoms. )(Where R₁₄And R_FifteenAre each independently of the general formula (a-
R in I)_FourAnd R_FiveIs synonymous with₉~ R₁₃, R₁₆~
R₂₀Are each independently R in formula (a-I)₁~ R _Three,
R₆~ R₈Is synonymous with )] 2. The compound represented by the formula (Aa), wherein: —Ar ₁ —Ar ₂ —
The group is represented by the general formula (a-I), and in the general formula (a-I), R ₄ and R ₅ are an alkyl group having 1 to 3 carbon atoms, and an alkoxy group having 1 to 3 carbon atoms. 2. The bidentate phosphorus compound according to claim 1, which is a group selected from halogen atoms. 3. A bidentate phosphorus compound represented by the following general formula (Ab). Embedded image [Wherein the -Ar ₃ -Ar ₄ -group is represented by the following general formula (b-I)
Or (b-II) a bisarylene group represented by, Z ₅
~ Z ₈ is a nitrogen atom bonded to a phosphorus atom,
In addition, it is a 5-membered heterocyclic compound containing at least one nitrogen atom or a condensed cyclic compound thereof. Embedded image (Wherein R ₂₃ and R ₂₆ are each independently an alkyl group,
Alkoxy group, a cycloalkyl group, cycloalkoxy group, which may have a substituent silyl group, those selected from the group consisting of optionally substituted siloxy group and a halogen atom, R _21, R ₂₂ , R ₂₄ , R ₂₅ ,
R ₂₇ and R ₂₈ each independently represent a hydrogen atom, an alkyl group,
Alkoxy group, cycloalkyl group, cycloalkoxy group, dialkylamino group, aryl group, aryloxy group, alkylaryl group, alkylaryloxy group,
It represents one selected from the group consisting of an arylalkyl group, an arylalkoxy group, a cyano group, a hydroxy group and a halogen atom. ) (Wherein, R ₃₄ and R ₃₉ are each independently a group represented by the general formula (b-
Have the same meaning as R ₂₃ and R ₂₆ in _{I), R 31 ~R 33,} R 35
To R ₃₈ and R _{40 to} R ₄₂ each independently represent a group represented by the general formula (b-I)
It has the same meaning as R ₂₁ , R ₂₂ , R ₂₄ , R ₂₅ , R ₂₇ , and R ₂₈ . )] 4. The compound represented by the formula (Ab), wherein: —Ar ₃ —Ar ₄ —
The group is represented by the general formula (b-I), and in the general formula (b-I), R ₂₃ and R ₂₆ are an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms. The bidentate phosphorus compound according to claim 3, which is a group selected from: 5. Z in the general formulas (Aa) and (Ab)
_{1 to} Z ₈ each may have a substituent; a pyrrolyl group (pyrrory 1), an indolyl group (indory group)
The bidentate phosphorus compound according to any one of claims 1 to 4, which is l) or an imidazolyl group (imidazolyl). 6. A compound represented by the general formula (a-I), (a-II) or (b-
In I) and (b-II), R ₁ , R ₈ , R ₉ , R ₂₀ ,
R ₂₁ , R ₂₈ , R ₃₁ and R ₄₂ are each independently selected from an alkyl group having 3 to 20 carbon atoms which may have a substituent. Bidentate phosphorus compound. 7. The method according to claim 1, wherein the olefinic compound is reacted with carbon monoxide and hydrogen in the presence of a Group VIII metal compound to produce a corresponding aldehyde. A hydroformylation method characterized by the presence of a phosphorus compound. 8. The hydroformylation method according to claim 7, wherein the bidentate phosphorus compound according to claim 1 is present. 9. The hydroformylation method according to claim 7, wherein the bidentate phosphorus compound according to claim 3 is present. 10. The hydroformylation method according to claim 7, wherein the olefinic compound is a compound having no polar functional group. 11. The hydroformylation method according to claim 7, wherein the olefinic compound is an α-olefin. 12. The hydroformylation method according to claim 7, wherein the olefinic compound is propylene. 13. The hydroformylation method according to claim 7, wherein the Group VIII metal compound is rhodium. 14. A method for producing an alcohol by directly subjecting an aldehyde obtained by the method according to any one of claims 7 to 13 to a hydrogenation reaction, or dimerizing the aldehyde and then supplying it to the hydrogenation reaction.