JP5974378B2 - Method for producing alcohol - Google Patents

Description

  The present invention relates to a method for producing an aldehyde by reacting a raw material olefin with hydrogen and carbon monoxide in the presence of a complex containing at least one ligand derived from an organophosphorus compound and a transition metal. The invention also relates to a process for producing alcohol.

Conventionally, a hydroformylation reaction for producing an aldehyde by reacting a raw material olefin with hydrogen and carbon monoxide in the presence of a group 8-10 transition metal and a ligand derived from an organophosphorus compound is widely known. Yes.
For example, as shown in Formula (A), in the hydroformylation reaction of an olefin having 3 or more carbon atoms with hydrogen and carbon monoxide, a linear aldehyde and a branched aldehyde are produced. Since linear aldehydes have a wider range of uses and are generally in high demand, in the reaction system of the following formula (A), aldehyde linear selectivity (hereinafter referred to as “L / B ratio”) Various transition metal-organophosphorus ligand catalysts have been developed for enhancing the above (in formula (A), R represents an aliphatic hydrocarbon group such as an alkyl group).

  Among them, complex catalysts having organophosphorus ligands containing rhodium are mainly used in terms of high activity, but rhodium is very expensive, so the catalyst cost at the start of process operation is very high. If the rhodium is not sufficiently recycled by recovering the catalyst even during the process operation, there is a problem that the catalyst cost is further increased.

  On the other hand, ruthenium and iron are metals that are much cheaper than rhodium, but when used as the metal of the complex catalyst used in the hydroformylation reaction represented by the above formula (A), the organophosphorus coordination containing rhodium. Compared with the complex having a child, the activity and the linear selectivity of the aldehyde were not sufficient. For example, Non-Patent Document 1 and Non-Patent Document 2 describe a hydroformylation reaction of 1-octene using a complex containing ruthenium or iron having a cyclopentadienyl group, but the catalytic activity is low, In addition to the problem that the selectivity of the aldehyde with respect to the conversion of 1-octene is as low as about 20%, the linear selectivity (L / B ratio) of the aldehyde is as low as about 2 to 4.

  Non-Patent Document 3 describes a reaction in which a ruthenium complex having a cyclopentadienyl group coexists in a hydroformylation reaction system using a rhodium-containing complex and a bidentate phosphine to generate an alcohol from a raw material olefin. Has been. However, the ruthenium complex having a cyclopentadienyl group described in Non-Patent Document 3 only contributes to a reaction in which an aldehyde generated in the reaction system is hydrogenated and converted to an alcohol. The reason is that since the abundance ratio of rhodium: bidentate phosphine: ruthenium in the reaction system is 1: 2: 2.5, the bidentate phosphine is preferentially coordinated 1: 1 with respect to rhodium. For ruthenium, only 40% of bidentate phosphine is present.

  Furthermore, Non-Patent Document 3 describes a method for producing an alcohol with high linear selectivity using a ruthenium complex having a cyclopentadienyl group having a hydroxyl group as a substituent. Coexistence is necessary, which is disadvantageous in terms of catalyst cost, and the use of two types of metals, rhodium and ruthenium, may complicate the operation management of industrial processes.

J. et al. Mol. Catal. , 1978, 4, p205-216 J. et al. Mol. Catal. , 1981, 10, p213-221. Angew. Chem. Int. Ed. , 2010, 49, p4488-4490

  As described above, the hydroformylation method using a complex mainly containing rhodium has been known as a conventional method for producing aldehydes, but rhodium is a noble metal, so there are concerns that catalyst costs will increase and price fluctuations due to market fluctuations. There is a concern that is easily affected. For this reason, there has been a demand for an industrially useful method by which an aldehyde can be produced with a L / B ratio equivalent to that when a complex containing rhodium is used, by using a metal much cheaper than rhodium.

  The present invention has been made in view of the above problems, and in producing a corresponding aldehyde by reacting a raw material olefin having 2 or more carbon atoms with hydrogen and carbon monoxide, the catalyst cost is reduced, An object of the present invention is to provide an industrially advantageous method capable of producing an aldehyde with high selectivity at a low cost. Furthermore, it is providing the convenient method which can manufacture alcohol with high linear selectivity by introduce | transducing a specific substituent into a transition metal complex.

  The present inventors pay attention to a complex composed of ruthenium or iron, which is a metal that is much cheaper than rhodium, and in earnestly examining a complex for hydroformylation reaction, a ligand derived from an organophosphorus compound and We have found that the hydroformylation reaction proceeds efficiently by combining a ruthenium complex having a specific cyclic hydrocarbon structure, and further having a ligand derived from an organophosphorus compound in excess of the ruthenium-containing complex. The present invention has been reached. In addition, when a ruthenium or iron catalyst having a cyclopentadienyl group having a substituent having a specific structure is used, it was found that the produced aldehyde can be converted to alcohol in the reaction system, and the present invention has been achieved. .

That is, the gist of the present invention resides in the following (1 ) .

(1) the presence of the ligand and Le ruthenium from organophosphorus compounds of bidentate including complexes, in the absence of a rhodium compound, is reacted with 2 or more feed olefins carbon atoms with hydrogen and carbon monoxide a method for producing an alcohol by having a basic skeleton of the organic phosphorus compound of the bidentate is represented by any one of the following formulas (c-1) ~ (c -3), including the 該Ru ruthenium A method for producing an alcohol, wherein the complex is a complex having a structure represented by the following formula (b).

(In the formula (b), M is Le ^ruthenium, R 1 to R ⁴ are each independently a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a hydroxy group, a cyano group, a nitro A group selected from the group consisting of a group, an amino group, an amide group, a perfluoroalkyl group, a trialkylsilyl group, a formyl group, an acyl group, an acyloxy group, an ester group, a phosphino group, and a carboxy group. which may have a substituent .X represents an oxygen atom. Further, it ^{R 1} and ^R 2, ^{R 2} and ^R 3, and R ³ and ^{R 4} are bonded to each other to form a ring The formed ring may further have a substituent.)

(In the formula (c-1), R ^{11 to} R ¹⁸ are each independently a hydrogen atom, a halogen atom, a hydroxy group, and a chain or cyclic alkyl group, aryl group, alkoxy group, aryloxy group, Represents a group selected from the group consisting of an amino group, an acyl group, an acyloxy group, a carboxy group, and an ester group, and these groups may further have a substituent, and any two substituents may be bonded to each other; It may be formed to form an annular structure.
R ^{21 to} R ²⁴ each independently represents a chain or cyclic alkyl group or aryl group. These groups may further have a substituent, and R ²¹ and R ²² , and R ²³ and R ²⁴ may form a bond with each other to form a cyclic structure. )

(In the above formula (c-2), R ^{31 to} R ³⁶ are each independently a hydrogen atom, a halogen atom, a hydroxy group, and a chain or cyclic alkyl group, aryl group, alkoxy group, aryloxy group, Represents a group selected from the group consisting of an amino group, an acyl group, an acyloxy group, a carboxy group, and an ester group, and these groups may further have a substituent, and any two substituents may be bonded to each other; It may be formed to form an annular structure.
R ^{41 to} R ⁴⁴ each independently represents a chain or cyclic alkyl group or aryl group. These groups may further have a substituent, and R ⁴¹ and R ⁴² and R ⁴³ and R ⁴⁴ may form a bond with each other to form a cyclic structure.
A ¹ and A ² are each independently O, S, SiR ^a R ^b , NR ^c , CR ^d R ^e , where R ^a , R ^b , R ^c , R ^d, and R ^e are Each independently represents a hydrogen atom, a chain or cyclic alkyl group, or an aryl group. )

(In the above formula (c-3), R ^{51 to} R ⁵⁸ are each independently a hydrogen atom, a halogen atom, a hydroxy group, and a chain or cyclic alkyl group, aryl group, alkoxy group, aryloxy group, Represents a group selected from the group consisting of an amino group, an acyl group, an acyloxy group, a carboxy group, and an ester group, and these groups may further have a substituent, and any two substituents may be bonded to each other; It may be formed to form an annular structure.
R ^{61 to} R ⁶⁴ each independently represent a chain or cyclic alkyl group or aryl group. These groups may further have a substituent, and R ⁶¹ and R ⁶² , and R ⁶³ and R ⁶⁴ may form a bond with each other to form a cyclic structure. )

  According to the present invention, in a method for producing an aldehyde or alcohol by reacting a raw material olefin with hydrogen and carbon monoxide, an inexpensive metal complex catalyst such as ruthenium or iron is used, and the catalyst cost is greatly reduced. An aldehyde or alcohol with high chain selectivity can be produced.

  Hereinafter, the present invention will be described in detail.

  The method for producing an aldehyde of the present invention has a structure represented by a ligand derived from a polydentate organophosphorus compound (hereinafter sometimes referred to as “polydentate organophosphorus ligand”) and the following formula (a). An aldehyde is produced by reacting a raw material olefin having 2 or more carbon atoms with hydrogen and carbon monoxide in the presence of a complex containing at least one transition metal (hereinafter sometimes referred to as “transition metal complex (a)”). The molar ratio of the polydentate organophosphorus ligand to the transition metal complex (a) is 1 or more and 20 or less.

(In the above formula (a), M is a group 8-10 transition metal of the periodic table excluding rhodium, and R ^{1 to} R ⁵ are each independently a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an aryl group. From the group consisting of aryloxy group, hydroxy group, cyano group, nitro group, amino group, amide group, perfluoroalkyl group, trialkylsilyl group, formyl group, acyl group, acyloxy group, ester group, phosphino group and carboxy group These groups may be further substituted, and R ¹ and R ² , R ² and R ³ , R ³ and R ⁴ , R ⁴ and R ⁵ , and R ⁵ And R ¹ may combine with each other to form a ring, and the formed ring may further have a substituent.)

  In addition, the method for producing an alcohol of the present invention comprises a raw material having 2 or more carbon atoms in the presence of a complex derived from a polydentate organophosphorus compound (polydentate organophosphorus ligand) and one or more transition metals. A method for producing an alcohol by reacting an olefin with hydrogen and carbon monoxide, wherein the complex containing at least one transition metal has a structure represented by the following formula (b) (hereinafter referred to as “transition metal complex ( b) ", which is sometimes referred to as") ".

(In the above formula (b), M is a group 8-10 transition metal of the periodic table excluding rhodium, and R ^{1 to} R ⁴ are each independently a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an aryl group. From the group consisting of aryloxy group, hydroxy group, cyano group, nitro group, amino group, amide group, perfluoroalkyl group, trialkylsilyl group, formyl group, acyl group, acyloxy group, ester group, phosphino group and carboxy group And these groups may further have a substituent, X represents a linking group containing a hetero atom, which is bonded to a hydrogen atom, and R ¹ and R ^2. , R ² and R ³ , R ³ and R ⁴ , R ⁴ and X, and X and R ¹ may be linked to each other to form a ring, and the formed ring may further have a substituent. Good.)

<Transition metal complex (a), transition metal complex (b)>
First, the transition metal complex (a) and the transition metal complex (b) used in the present invention will be described.

  The transition metal contained in the transition metal complex (a) and the transition metal complex (b) according to the present invention is a transition metal of Groups 8 to 10 of the periodic table (according to the revised IUPAC inorganic chemical nomenclature (1998)) excluding rhodium. Specifically, iron, ruthenium, osmium, cobalt, iridium, nickel, palladium and platinum can be mentioned. Among these metals, iron, ruthenium and osmium, which are Group 8 transition metals of the periodic table, are preferable, and because of low toxicity and high reactivity, iron or ruthenium is more preferable, and ruthenium is particularly preferable because of its highest activity. preferable. One type of transition metal may be used, or two or more types may be used in combination.

  When these metals are used as the transition metal complex (a) and the transition metal complex (b) according to the present invention, a compound containing the metal (hereinafter sometimes abbreviated as “metal compound”) is usually used. Specific examples of the metal compound include one or more compounds selected from the group consisting of iron compounds, ruthenium compounds, osmium compounds, cobalt compounds, iridium compounds, nickel compounds, palladium compounds, and platinum compounds. Among these, an iron compound, a ruthenium compound, and an osmium compound are preferable, an iron compound and a ruthenium compound are more preferable, and a ruthenium compound is most preferable.

  In the method for producing an aldehyde of the present invention, the transition metal complex (a) used has a structural feature in which a cyclopentadienyl group is coordinated to the transition metal M as represented by the formula (a). Is provided.

In the formula (a), examples of the halogen atom represented by R ^{1 to} R ⁵ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is preferable.
Examples of the alkyl group for R ^{1 to} R ⁵ include a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms, preferably 1 to 15 carbon atoms. In addition, in an alkyl group, what has a carbon-carbon double bond partially is also included.
Examples of the alkoxy group of R ^{1 to} R ⁵ include linear or branched alkoxy groups having 1 to 30 carbon atoms, preferably 1 to 15 carbon atoms.
As the aryl group for R ^{1 to} R ^5, an aryl group which may have a substituent having 3 to 30 carbon atoms, preferably 5 to 22 carbon atoms, such as a phenyl group, a 4-methylphenyl group, and 4-t-butyl. Phenyl group, 2,4-di-t-butylphenyl group, 2,4,6-trimethylphenyl group, 4-chlorophenyl group, 4-methoxyphenyl group, 1-naphthyl group, 2-naphthyl group, 9-phenanthrenyl group Etc. The aryl group includes a group derived from a heterocyclic aromatic compound (heteroaryl group) containing an atom other than a carbon atom such as a nitrogen atom, an oxygen atom, or a sulfur atom in an aromatic ring-forming atom. Specific examples of heteroaryl groups include pyrrolyl, furanyl, thiophenyl, imidazolyl, oxazolyl, thiazolyl, pyrazolyl, pyrimidyl, pyridyl and the like.
Examples of the aryloxy group for R ^{1 to} R ⁵ include an aryloxy group that may have a substituent having 3 to 30 carbon atoms, preferably 5 to 22 carbon atoms. The aryloxy group also includes a heteroaryl group as the aryl group preceding the oxygen atom.
As the amino group of R ^{1 to} R ⁵ , an amino group having independently a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, and an aryl group having 3 to 30 carbon atoms as two substituents on the nitrogen atom, preferably An amino group independently having an aryl group optionally having a linear or branched or cyclic alkyl group having 1 to 15 carbon atoms and a substituent having 5 to 22 carbon atoms as two substituents on the nitrogen atom; Can be mentioned.
As the amide group of R ^{1 to} R ⁵ , an amide group having independently a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, and an aryl group having 3 to 30 carbon atoms as two substituents on the nitrogen atom, preferably As two substituents on the nitrogen atom, each independently has a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 15 carbon atoms, and an aryl group which may have a substituent having 5 to 22 carbon atoms. An amide group is mentioned.
The perfluoroalkyl group R ¹ to R ^5, perfluoroalkyl group having 1 to 30 carbon atoms, preferably perfluoroalkyl group having 1 to 15 carbon atoms.
The trialkylsilyl group of R ^{1 to} R ⁵ is a silyl group having independently an alkyl group having 1 to 30 carbon atoms as three substituents on the silicon atom, preferably carbon as three substituents on the silicon atom. The linear or branched or cyclic alkyl group of 1-15 is mentioned.
As the acyl group of R ^{1 to} R ⁵ , an acyl group having 1 to 30 carbon atoms or an aryl group having 3 to 30 carbon atoms at the end of the carbonyl group, preferably a straight chain having 1 to 15 carbon atoms or Examples include an acyl group having a branched or cyclic alkyl group or an aryl group which may have a substituent having 5 to 22 carbon atoms at the end of the carbonyl group.
As the acyloxy group of R ^{1 to} R ^5, an acyloxy group having an alkyl group having 1 to 30 carbon atoms or an aryl group having 3 to 30 carbon atoms at the end of the carbonyl group, preferably a straight chain having 1 to 15 carbon atoms or Examples include an acyloxy group having a branched or cyclic alkyl group or an aryl group which may have a substituent having 5 to 22 carbon atoms at the end of the carbonyl group.
As an ester group of R ^{1 to} R ^5, an ester group having an alkyl group having 1 to 30 carbon atoms or an aryl group having 3 to 30 carbon atoms in front of an oxygen atom, preferably a straight chain having 1 to 15 carbon atoms or Examples thereof include a branched or cyclic alkyl group, or an ester group having an aryl group which may have a substituent having 5 to 22 carbon atoms in front of the oxygen atom.
As a phosphino group of R ^{1 to} R ^5, a phosphino group having independently an alkyl group having 1 to 30 carbon atoms or an aryl group having 3 to 30 carbon atoms as two substituents on the phosphorus atom, preferably the carbon number Examples thereof include a phosphino group independently having a linear or branched alkyl group having 1 to 15 carbon atoms, or an aryl group optionally having a substituent having 5 to 22 carbon atoms.

When R ¹ and R ² , R ² and R ³ , R ³ and R ⁴ , R ⁴ and R ⁵ , R ⁵ and R ¹ are connected to each other to form a ring, examples of the ring formed include And C5-C20 aliphatic hydrocarbon rings such as cyclopentene ring and cyclohexene ring, and C6-C20 aromatic hydrocarbon rings such as benzene ring, dimethylbenzene ring, naphthalene ring and phenanthrene ring. .

R ^{1 to} R ⁵ are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 15 carbon atoms, or an aryl group optionally having a substituent having 5 to 22 carbon atoms. It is preferable that

And a ring formed by connecting R ^{1 to} R ⁵ , or R ¹ and R ² , R ² and R ³ , R ³ and R ⁴ , R ⁴ and R ⁵ , and R ⁵ and R ^1. The substituent that may have is not particularly limited as long as it does not adversely affect the reaction system, but is a halogen atom, a hydroxy group, a cyano group, a formyl group, a chain or cyclic alkyl group. , Aryl groups, alkoxy groups, arylalkoxy groups, aryloxy groups, alkylaryloxy groups, alkylthio groups, arylthio groups, amino groups, amide groups, acyl groups, or acyloxy groups.

In addition, when R ^{1 to} R ⁵ have a substituent, each molecular weight including the substituent is 400 or less, particularly 300 or less, especially 200 or less, and a total of 1200 or less, particularly 800 or less. Is preferred. If the molecular weight of R ^{1 to} R ⁵ is too large, it cannot be dissolved in the reaction solvent under the reaction conditions, and the catalytic activity may not be sufficiently exhibited.

  Specific examples of the cyclopentadienyl group constituting the transition metal complex (a) include the following structures of Cp-1 to Cp-45 (in the following, Ph represents a phenyl group). .

Among these, it is preferable that R ^{1 to} R ⁵ are each independently a hydrogen atom, an alkyl group, an aryl group, or a group in which these are connected to each other to form a ring. -1 to Cp-25 is preferable.

On the other hand, the cyclopentadienyl group of the above formula (b) in which R ⁵ is a —X—H group (X represents a linking group containing a hetero atom, and the hetero atom is bonded to a hydrogen atom) The transition metal complex (b) having a coordinated structure functions as an alcohol production catalyst. This is because the hydroformylation reaction proceeds with the catalyst to produce an aldehyde, and the generated aldehyde is efficiently reduced to an alcohol by the selective hydrogenation of the formyl group by the -XH group of the catalyst. It is to be done.

In the formula (b), an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an amino group, an amide group, a perfluoroalkyl group, a trialkylsilyl group, an acyl group, an acyloxy group, an ester group, of R ^{1 to} R ⁴ , A phosphino group, R ¹ and R ² , R ² and R ³ , R ³ and R ⁴ , R ⁴ and X, X and R ¹ connected to each other to form a ring, , R ^{1 to} R ⁴ groups and the substituents that may be formed by the ring formed by linking these groups are exemplified as the groups R ^{1 to} R ⁵ in formula (a), the rings and the substituents thereof. The same applies to the preferred ones.

In the formula (b), as the linking group X, an oxygen atom, a nitrogen atom having a hydrogen atom, an alkyl group or an aryl group as a substituent (that is, —NH— or —NR— (R is an alkyl group or an aryl group) ), Or a group in which the nitrogen atom is bonded to a cyclopentadienyl group via an alkylene group or a carbonyl group (that is, — (CH ₂ ) _n —NH—, — (CH ₂ ) _n —NR—, — ( C═O) —NH—, or — (C═O) —NR— (n is an integer from 1 to 5, R is an alkyl group or aryl group)), and the alkyl group substituted on the nitrogen atom is preferably Preferably, a linear or branched alkyl group having 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and the aryl group substituted with a nitrogen atom is preferably 3 to 30 carbon atoms, more preferably carbon atoms. Number 5-1 Have a substituent an aryl group which may.

^{Incidentally,} R 1 to R ^4, when having substituents, including substituents thereof, each molecular weight of 400 or less, especially 300 or less, in particularly 200 or ^less, R 1 to R ⁴ and the X-H Is preferably 1200 or less, and particularly preferably 800 or less. If the molecular weights of R ^{1 to} R ⁴ and X—H are too large, they cannot be dissolved in the reaction solvent under the reaction conditions, and the catalytic activity may not be sufficiently exhibited.

  Specific examples of the cyclopentadienyl group constituting the transition metal complex (b) include the following structures of Cp-46 to Cp-75.

  Among these, it is preferable that X in Formula (b) is a nitrogen atom having an oxygen atom, a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 14 carbon atoms as a substituent. That is, a cyclopentadienyl group having a structure in which a hydroxy group or an amino group having at least one hydrogen atom is directly bonded to a cyclopentadienyl ring is preferable. Specifically, Cp-46 to Cp-54, and Cp-59 to Cp-70 are preferred.

  In addition, the transition metal complex (a) and the transition metal complex (b) used in the present invention may be present in the reaction system, and the structure of the complex used in other steps such as the structure of the raw material complex used or the catalyst separation tower is used. Is not dependent.

The following Cp′-1 to Cp′-15 have a structure in which a carbonyl group or an alkenyl group is incorporated in the structure of cyclopentadiene. These complexes are described later. Under the reaction conditions in which a hydrogen donor such as hydrogen gas or alcohol is present as in formula (B) or formula (C), hydrogen is bonded to the oxygen atom of the carbonyl group or the terminal carbon atom of the alkenyl group. It is known that it is converted to a cyclopentadienyl group bonded to a metal (η ⁵ -coordination) at ^five carbon atoms of a five-membered ring. That is, such a cyclopentadiene coordination (coordination to metal at the four carbon atoms of the diene moiety: η ⁴ -coordination) complex can also be preferably used in the present invention. Even if the hydrogen gas concentration is reduced at the place where the hydrogen gas concentration is reduced, such as the bottom of the distillation column, even if the structure returns to the original cyclopentadiene (η ⁴ -coordination), if the catalyst is recycled to the reactor, Since it returns to a cyclopentadienyl coordination complex bonded to a metal with 5 carbon atoms (η ⁵ -coordination), it can be preferably used in the present invention.

  The transition metal complex (a) and the transition metal complex (b) having a cyclopentadienyl group are each an alkali metal-cyclopentadienide salt produced by reacting a corresponding cyclopentadiene with an alkali metal such as sodium, It can be synthesized by reaction with a halide of a transition metal.

  Usually, the transition metal complex having one cyclopentadienyl group has other ligands in addition to the cyclopentadienyl group for stabilization of the complex. The form of the remaining part of the complex excluding the cyclopentadienyl group includes inorganic salts such as halogen compounds, sulfates, nitrates, acetates, acetylcetonate compounds, alkene coordination compounds, amine coordination compounds, Specific examples include pyridine coordination compounds, carbon monoxide coordination compounds, phosphine coordination compounds, and phosphite coordination compounds.

The cyclopentadienyl group or cyclopentadiene ligand represented by the formulas (a) and (b) in the present invention is described in Cp, and then the raw materials for the transition metal complexes (a) and (b) according to the present invention Specific examples of compounds that can be preferably used as compounds include iron compounds such as CpFe (CH ₃ ) (CO) ₂ , CpFeBr (CO) ₂ , CpFeI (CO) ₂ , CpFe (CO) ₃ , [ CpFe (CO) ₂ ] ₂ , CpFe (π-allyl) (CO) ₂ , CpFe (CO) (PPh ₃ ) (Ac) and the like.

Examples of the ruthenium compound include CpRuCl (CO) ₂ , CpRuCl (PPh ₃ ) ₂ , CpRuH (CO) ₂ , CpRu (cod) Cl, CpRu (CO) ₃ , [CpRu (OCH ₃ )] ₂ , [CpRu (acac) _{] 2, [CpRu (CO)} 2] 2, include [CpRuCl _{2] 2} or the like.
Examples of the osmium compound include CpOsCl (PPh ₃ ) ₂ , CpOs (CH ₃ ) (CO) ₂ , and [CpOs (CO)] ₂ .
Examples of the cobalt compound include CpCo (PPh ₃ ) ₂ , CpCo (cod), CpCo (CO) ₂ , and [CpCo (NO)] ₂ .
Examples of the iridium compound include CpIr (cod), CpIr (CH ₃ ) ₃ (Py) Cl, CpIr (CH ₃ ) ₂ (CO), [CpIrCl ₂ ] ₂ , and [CpIrI ₂ ] ₂ .
Examples of the nickel compound include CpNiCl (PPh ₃ ), [CpNi (CO)] ₂ , and CpNi (π-allyl).
Examples of the palladium compound include CpPd (π-allyl), CpPd (CH ₃ ) ₃ , CpPdCl (PPh ₃ ), CpPdCl (CO), CpPd (OAc) (P (i-Pr) ₃ ), and the like.
Examples of the platinum compound include CpPt (CH ₃ ) ₃ , CpPt (CH ₃ ) ₂ Cl, CpPtCl (CO), CpPtI (PPh ₃ ), CpPt (PPh ₃ ) ₂ , and CpPt (CH ₃ ) (cod).
In the above example, π-allyl is a pi-allyl group (that is, CH ₂ ═CH—CH ₂ — group), cod is 1,5-cyclooctadiene, Ac is an acetyl group, and Ph group is a phenyl group. , Acac represents an acetylacetonate group, Py represents pyridine, and i-Pr represents an isopropyl group. The same applies to the embodiments described later.

  In the present invention, the transition metal complex (a) and the transition metal complex (b) are both transition metal complexes having a cyclopentadienyl group represented by the above formula (a) or (b). The form of the complex of the other part is not particularly limited, and the active metal complex species may be a monomer, a dimer and / or a multimer. In addition, when using these transition metal complexes, one kind of specific metal complex is used, the same metal species is used in combination with a plurality of complexes, or two or more different metal species are used. The complex may be used together.

  Although there is no restriction | limiting in particular about the usage-amount of the transition metal complex (a) which concerns on this invention, or a transition metal complex (b), From the viewpoint of catalyst activity and economical efficiency, the transition metal complex in the reaction liquid in a reactor normally The concentration of (a) or the transition metal complex (b) is usually 1 ppm or more, preferably 10 ppm or more, more preferably 100 ppm or more. On the other hand, it is usually 10,000 ppm or less, preferably 5000 ppm or less, more preferably 2000 ppm or less.

<Multidentate organophosphorus ligand>
Next, the ligand derived from the polydentate organophosphorus compound which can be used for this invention is described.

  The polydentate organophosphorus compound used for the polydentate organophosphorus ligand according to the present invention is particularly stable as long as it is stable under hydroformylation reaction conditions and coordinates to a transition metal with a phosphorus atom in the reaction system. It is not limited. The molecular weight of the organophosphorus compound is preferably 3000 or less, preferably 2000 or less, more preferably 1500 or less, and usually 50 or more, preferably 100, because it can be dissolved in the reaction system in order to increase the catalytic activity. Above, more preferably 150 or more.

  Among the multidentate organophosphorus compounds, bidentate organophosphorus compounds that chelate coordinate to transition metals with two phosphorus are preferable. Further, in order to be a phosphorus atom capable of coordinating to a metal, it is necessary to be a trivalent phosphorus atom, but the trivalent phosphorus atom has three covalent bonding sites, each of which is a carbon atom, an oxygen atom, Since there is a possibility of covalent bonding with various atoms such as a nitrogen atom, a wide variety of bidentate organophosphorus compounds are possible. However, considering the ease of synthesis, performance as a ligand, stability, etc., each phosphorus unit of a bidentate organophosphorus compound is composed of a phosphine type in which three carbon atoms are bonded to phosphorus, and two phosphorus units Phosphinite type in which carbon atom and one oxygen atom are bonded, Phosphonite type in which one carbon atom and two oxygen atoms are bonded to phosphorus, Phosphite in which three oxygen atoms are bonded to phosphorus It is preferably one of the types. In that case, the two phosphorus units of the bidentate organophosphorus compound may be of the same type as a phosphine-phosphine compound (bidentate phosphine compound), but different types of phosphine-phosphite compounds. It may be a compound. However, among them, bidentate phosphine compounds and bidentate phosphite compounds are particularly preferable.

  Specific examples of the bidentate phosphine compound include 1,2-bis (di-t-butylphosphino) ethane, 1,3-bis (diethylphosphino) propane, 1,4-bis (dimethylphosphino). -1,1,4,4-tetramethylbutane, 1,2-bis (diphenylphosphino) ethane, 1,3-bis (diphenylphosphino) propane, 1,4-bis (diphenylphosphino) butane, , 5-bis (diphenylphosphino) pentane, 1,6-bis (diphenylphosphino) hexane and the like. Specific examples of bidentate phosphites include bidentate phosphites described in Japanese Patent No. 3416956. Etc.

However, in order to produce linear aldehydes and alcohols useful in industry, bidentate phosphines and bidentate phosphites that exhibit high linear selectivity in hydroformylation reactions using conventional rhodium catalysts are used. It is preferable.
Specifically, it is preferable to use a bidentate phosphine or a bidentate phosphite having a basic skeleton represented by the following formulas (c-1) to (c-3).

(In the formula (c-1), R ^{11 to} R ¹⁸ are each independently a hydrogen atom, a halogen atom, a hydroxy group, and a chain or cyclic alkyl group, aryl group, alkoxy group, aryloxy group, Represents a group selected from the group consisting of an amino group, an acyl group, an acyloxy group, a carboxy group, and an ester group, and these groups may further have a substituent, and any two substituents may be bonded to each other; It may be formed to form an annular structure.
R ^{21 to} R ²⁴ each independently represents a chain or cyclic alkyl group or aryl group. These groups may further have a substituent, and R ²¹ and R ²² , and R ²³ and R ²⁴ may form a bond with each other to form a cyclic structure. )

(In the above formula (c-2), R ^{31 to} R ³⁶ are each independently a hydrogen atom, a halogen atom, a hydroxy group, and a chain or cyclic alkyl group, aryl group, alkoxy group, aryloxy group, Represents a group selected from the group consisting of an amino group, an acyl group, an acyloxy group, a carboxy group, and an ester group, and these groups may further have a substituent, and any two substituents may be bonded to each other; It may be formed to form an annular structure.
R ^{41 to} R ⁴⁴ each independently represents a chain or cyclic alkyl group or aryl group. These groups may further have a substituent, and R ⁴¹ and R ⁴² and R ⁴³ and R ⁴⁴ may form a bond with each other to form a cyclic structure.
A ¹ and A ² are each independently O, S, SiR ^a R ^b , NR ^c , CR ^d R ^e , where R ^a , R ^b , R ^c , R ^d, and R ^e are Each independently represents a hydrogen atom, a chain or cyclic alkyl group, or an aryl group. )

(In the above formula (c-3), R ^{51 to} R ⁵⁸ are each independently a hydrogen atom, a halogen atom, a hydroxy group, and a chain or cyclic alkyl group, aryl group, alkoxy group, aryloxy group, Represents a group selected from the group consisting of an amino group, an acyl group, an acyloxy group, a carboxy group, and an ester group, and these groups may further have a substituent, and any two substituents may be bonded to each other; It may be formed to form an annular structure.
R ^{61 to} R ⁶⁴ each independently represent a chain or cyclic alkyl group or aryl group. These groups may further have a substituent, and R ⁶¹ and R ⁶² , and R ⁶³ and R ⁶⁴ may form a bond with each other to form a cyclic structure. )

Of the three types of bidentate organophosphorus compounds represented by the above formulas (c-1) to (c-3), those more preferable from the viewpoint of generating an aldehyde exhibiting high linear selectivity. , R ^{21 to} R ²⁴ , R ^{41 to} R ⁴⁴ , and the terminal substituent of the bidentate organophosphorus compound represented by R ^{61 to} R ⁶⁴ are aryl groups that may have a substituent. It is. Specific examples of such a bidentate organophosphorus compound having a preferred structure are shown below. In the following examples, L-1 to L-20 are preferred bidentate phosphine compounds, and L-21 to L-30 are preferred bidentate phosphite compounds. In the following, Me represents a methyl group, and tBu represents a t-butyl group.

  These organic phosphorus compounds may be reacted using only one type of organic phosphorus compound or may be reacted using any combination of two or more types of organic phosphorus compounds.

  The amount of the organophosphorus compound used is usually 1 or more, preferably 1.5 or more, particularly preferably 2 or more, as a ratio (molar ratio) to the transition metal complex (a) or the transition metal complex (b). Usually, it is 20 or less, preferably 15 or less, particularly preferably 10 or less. When the amount of the organophosphorus compound used is within the above range, good reaction activity and straight chain selectivity can be obtained.

<Catalyst supply method>
In the present invention, the transition metal complex (a) or transition metal complex (b) having a polydentate organophosphorus ligand is present in the reactor to carry out the hydroformylation reaction. The transition metal complex (a) or Even if the transition metal compound and the organophosphorus compound, which are raw materials for the transition metal complex (b), are independently supplied to the reactor to form a complex in the reactor, before the hydroformylation reaction, A complex may be formed and supplied to the reactor. Alternatively, an organic phosphorus compound bonded to an insoluble resin carrier may be supplied to the reactor as an insoluble solid catalyst in which the above-described transition metal compound is supported.

  Further, when a compound having a halogen atom bonded thereto is used as the transition metal compound, it is usually preferable to prepare an active species by adding a basic compound and removing halide (halide ion) from the transition metal compound. . This is because halides can often be a source of catalyst poisoning in hydroformylation reactions.

In this case, as the basic compound, a base such as an inorganic base, an organic base, or a Lewis base can be used. Specifically, examples of the inorganic base include alkali metal hydroxides such as LiOH, NaOH, KOH, and CsOH, and alkalis such as Li ₂ CO ₃ , Na ₂ CO ₃ , K ₂ CO ₃ , and Cs ₂ CO _3. Metal carbonate, alkaline metal hydrogen carbonate such as LiHCO ₃ , NaHCO ₃ , KHCO ₃ , CsHCO ₃ , alkaline earth metal water such as Mg (OH) ₂ , Ca (OH) ₂ , Ba (OH) ₂ Examples thereof include carbonates of alkaline earth metals such as oxides, MgCO ₃ , CaCO ₃ and BaCO ₃ . Examples of organic bases include alkali metal alkoxide compounds such as methoxy sodium, ethoxy sodium, t-butoxy sodium, methoxy potassium, ethoxy potassium, and t-butoxy potassium, sodium acetate, sodium butyrate, potassium acetate, potassium butyrate, etc. Alkali metal carboxylates, pyridines such as pyridine and 4-methylpyridine, tertiary amines such as triethylamine, triisopropylamine, tri-n-octylamine and 1,5-diazabicyclo [2.2.2] octane , Piperidine, N-methylpiperidine, other amines such as morpholine, 1,8-diazabicyclo [5.4.0] undecene-7 (abbreviation: DBU), 1,5-diazabicyclo [4.3.0] nonene-5 (abbreviation) : DBN) cyclic amidine derivatives such as, t- butyl imino-tris (dimethylamino phosphorane) (abbreviation: P ₁ -t-Bu , 1-t-butyl-4,4,4-tris (dimethylamino) -2,2-bis [tris (dimethylamino) phosphoranylidene two isopropylidene amino] -2Λ ^5, 4Λ ⁵ - Katenaji (phosphazene) (abbreviation: P Phosphazene bases such as _4- t-Bu), 2,8,9-triisopropyl-2,5,8,9-tetraaza-1-phosphabicyclo [3.3.3] undecane, 2,8,9-trimethyl- And proazaphosphatran base such as 2,5,8,9-tetraaza-1-phosphabicyclo [3.3.3] undecane.

Among these bases, relatively strong basic compounds that reliably pull out halides from transition metal compounds are preferred, and alkali metal hydroxides such as LiOH, NaOH, KOH, and CsOH, Li ₂ CO ₃ , Na ₂ CO ₃ , Alkali metal carbonates such as alkali metal carbonates such as K ₂ CO ₃ and Cs ₂ CO ₃ and methoxy sodium, ethoxy sodium, t-butoxy sodium, methoxy potassium, ethoxy potassium, and t-butoxy potassium are preferred.

  These basic compounds may be used individually by 1 type, and may be used in combination of 2 or more type.

  Although there is no restriction | limiting in particular about the usage-amount in the case of using a basic compound, It is 0.1 mol times or more normally with respect to the use mole number of a transition metal compound, Preferably it is 0.5 mol times or more, More preferably, it is 1 The molar ratio is usually 10 times or more, preferably 5 times or less, more preferably 2 times or less.

  In addition, when preparing a catalyst when using a basic compound, each catalyst component (raw material transition metal compound, organophosphorus compound, and basic compound) is individually added to the reaction system to prepare the catalyst in the reaction system. It is preferable to prepare the catalyst in a separate catalyst preparation tank and add the catalyst to the reaction system. This is because if the basic compound is added to the reaction system more than necessary, the aldehyde produced by the catalytic reaction may undergo aldol condensation and partially disappear. In order to maintain high hydroformylation reaction activity, halides dissociated from transition metal compounds by reaction with basic compounds should be removed in advance by filtration, washing with water, decantation, etc., and not brought into the reaction system. Is preferred.

  As can be said in general catalyst preparation, it is preferable that the catalyst is led to the reaction system in a dissolved state so that the catalyst reaction can be quickly started in the reaction system. In some cases, before the catalyst is prepared and introduced into the reaction system, gas treatment necessary for heat treatment or conversion to a catalytically active species, for example, pressure contact with a gas such as hydrogen or carbon monoxide is performed in advance. The catalyst may be introduced into the reaction system after it has been carried out.

<Raw material olefin>
Subsequently, the raw material olefin applicable to the present invention will be described. The raw material olefin applied to the method for producing an aldehyde or alcohol of the present invention is an olefin having 2 or more carbon atoms, particularly if it is a compound having at least one olefinic double bond in the molecule. It is not limited, either an olefin substituted only by a saturated hydrocarbon group, an olefin substituted by a hydrocarbon group containing an unsaturated hydrocarbon group, or an olefin substituted by a functional group containing a hetero atom, etc. It can also be applied to other olefins.

  Specific examples of the olefin substituted only with a hydrogen atom or a saturated hydrocarbon group include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-nonene, 1-nonene, Linear terminal olefinic hydrocarbons such as decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicocene, 1-docosene, etc., branched ends such as isobutene and 2-methyl-1-butene Olefinic hydrocarbons, cis and trans-2-butene, cis and trans-2-hexene, cis and trans-3-hexene, cis and trans-2-octene, cis and trans-3-octene, cis and trans-4 -Linear internal olefinic hydrocarbons such as octene, octene obtained by dimerization of butenes, propylene, - dimer-terminal olefinic hydrocarbon or internal olefinic hydrocarbon mixtures olefin oligomer isomer mixtures such as tetramer of lower olefins such as butene and isobutene and the like.

  Examples of olefins substituted with hydrocarbon groups containing unsaturated hydrocarbon groups include olefins having aromatic groups such as styrene, α-methylstyrene, allylbenzene, 1,3-butadiene, 1,5-hexadiene. And diene compounds such as 1,7-octadiene. Other examples of the olefin substituted with a functional group containing a hetero atom include ethers having an olefinic double bond such as vinyl ethyl ether, allyl-n-propyl ether, 1-methoxy-2,7-octadiene, Olefinic double bonds such as allyl alcohol, 1-hexen-4-ol, 3-methyl-3-buten-1-ol, 3-hydroxy-1,7-octadiene, 1-hydroxy-2,7-octadiene In addition to esters having an olefinic double bond such as alcohols having vinyl acetate, methyl acrylate, methyl methacrylate, 1-acetoxy-2,7-octadiene, 3,4-diacetoxy-1-butene, Examples include octen-1-al and acrylonitrile.

Among the above olefins, a linear olefin having 3 or more carbon atoms is preferable, and a linear terminal olefinic hydrocarbon having 3 or more carbon atoms is particularly preferable.
In addition, although there is no restriction | limiting in particular about the upper limit of the carbon number of an olefinic compound, Usually, it is 30 or less in consideration of the problem of solubility, the problem of viscosity, the ease of securing a raw material, etc.

<Aldehyde>
The aldehyde produced by the aldehyde production method of the present invention is an aldehyde having 3 or more carbon atoms, and a hydrogen atom and a formyl group (aldehyde group: —CHO group) with respect to the olefinic double bond of the raw material olefin described above. The structure is not particularly limited as long as it is an aldehyde having a structure added thereto. However, since the hydrogen atom and formyl group are added to the olefinic double bond, the raw material olefin having 2 or more carbon atoms has two types of bonds as described in the above formula (A). A linear aldehyde and a branched aldehyde are produced. In order to increase the yield of linear aldehyde, as described above, an organic phosphorus compound that exhibits high linear selectivity such as L-1 to L-30 may be used as a ligand.

  Specifically, the aldehyde produced by the method for producing an aldehyde of the present invention is substituted with an aldehyde produced from an olefin substituted with only a hydrogen atom or a saturated hydrocarbon group, or a hydrocarbon group containing an unsaturated hydrocarbon group. Examples include aldehydes generated from olefins, aldehydes generated from olefins substituted with functional groups containing heteroatoms, and the like.

  As specific examples for each, aldehydes generated from olefins substituted only with hydrogen atoms or saturated hydrocarbon groups include n-propyl aldehyde, n-butyraldehyde, n-pentyl aldehyde, n-hexyl. Aldehyde, n-heptylaldehyde, n-nonylaldehyde, n-decylaldehyde, n-undecylaldehyde, n-tridecylaldehyde, n-pentadecylaldehyde, n-heptadecylaldehyde, n-nonadecylaldehyde, n-hen Linear aldehydes such as eicosyl aldehyde, n-tricosyl aldehyde, i-butyraldehyde, 2-methylbutyraldehyde, 2-methylpentylaldehyde, 2-methylhexylaldehyde, 2-methyloctylaldehyde, 2-methylnonyl aldehyde 2-methyldecylaldehyde, 2-methyldodecylaldehyde, 2-methyltetradecylaldehyde, 2-methylhexadecylaldehyde, 2-methyloctadecylaldehyde, 2-methyleicosylaldehyde, 2-methyldocosylaldehyde, 3-methylbutyl In addition to branched aldehydes such as aldehyde, 3-methylpentylaldehyde, 2-ethylpentylaldehyde, 2-ethylheptylaldehyde, 2-propylhexylaldehyde, 2,3-dimethylheptylaldehyde, 2,5-dimethylheptyl Examples include octene obtained by dimerization of butenes such as aldehyde, aldehydes produced from a mixture of olefin oligomer isomers such as dimers to tetramers of lower olefins such as propylene, 1-butene and isobutene. It is.

  Examples of aldehydes generated from olefins substituted with hydrocarbon groups containing unsaturated hydrocarbon groups include 2-phenylpropylaldehyde, 3-phenylpropylaldehyde, 3-phenylbutyraldehyde, 4-phenylbutyraldehyde, Aldehyde having an aromatic group such as 3-phenyl-2-methylpropylaldehyde, 2-pentenylaldehyde, 3-pentenylaldehyde, 4-pentenylaldehyde, 2-methyl-2-butenylaldehyde, 2-methyl-3- Examples thereof include aldehydes having an unsaturated aliphatic group such as butenyl aldehyde, 6-heptenyl aldehyde, 2-methyl-5-hexenyl aldehyde, 8-nonenyl aldehyde, and 2-methyl-7-octenyl aldehyde.

  Other examples of aldehydes generated from olefins substituted with functional groups containing heteroatoms include 2-ethoxypropyl aldehyde, 3-ethoxypropyl aldehyde, 2- (n-propoxymethyl) propyl aldehyde, 4- (n- Propoxy) butyraldehyde, 2-methoxymethyl-7-octenylaldehyde, 2- (2′-methoxyethyl) -6-heptenylaldehyde, 8-methoxy-2-methyl-6-heptenylaldehyde, 9-methoxy- Aldehydes containing ether groups such as 7-nonenylaldehyde, 4-hydroxybutyraldehyde, 3-hydroxy-2-methylpropylaldehyde, 5-hydroxyheptylaldehyde, 4-hydroxy-2-methylhexylaldehyde, 5-hydroxy -3-Methylpentylua Dehydr, 4-hydroxy-8-nonenyl aldehyde, 3-hydroxy-2-methyl-7-octenyl aldehyde, 9-hydroxy-7-nonenyl aldehyde, 8-hydroxy-2-methyl-6-octenyl aldehyde, etc. Aldehydes containing 2-hydroxyl group, 2-acetoxypropylaldehyde, 3-acetoxypropylaldehyde, 3-methoxycarbonylbutyraldehyde, 2-methoxycarbonylpropylaldehyde, 3-methoxycarbonylpropylaldehyde, 2-acetoxymethyl-7-octenyl In addition to aldehydes containing ester groups such as aldehyde, 2- (2′-acetoxyethyl) -6-heptenylaldehyde, 4,5-diacetoxypentylaldehyde, 3,4-diacetoxy-2-methylbutyraldehyde, Nonane 1,9 Other and aldehydes containing a formyl group such as-dial, aldehydes containing cyano group such as 2-cyanopropyl aldehyde and the like.

<Alcohol>
The alcohol produced by the method for producing an alcohol of the present invention is an alcohol having 3 or more carbon atoms and having a structure in which the above-mentioned formyl group (aldehyde group: —CHO group) of the aldehyde is hydrogenated. The structure is not particularly limited. When it is desired to efficiently produce a linear alcohol useful in the industry in one reactor, an organophosphorus compound exhibiting high linear selectivity such as L-1 to L-30 is used as a ligand. And a compound having hydrogenation ability of the formyl group of the produced aldehyde such as Cp-46 to Cp-75 as the cyclopentadienyl group of the transition metal complex may be used.

  Specific examples of the alcohol produced by the method for producing an alcohol of the present invention include an alcohol produced from an olefin substituted only with a hydrogen atom or a saturated hydrocarbon group, and a hydrocarbon group containing an unsaturated hydrocarbon group. Examples thereof include alcohols produced from olefins, alcohols produced from olefins substituted with functional groups containing heteroatoms, and the like.

  As specific examples for each, alcohols generated from olefins substituted only with hydrogen atoms or saturated hydrocarbon groups include n-propyl alcohol, n-butyl alcohol, n-pentyl alcohol, n-hexyl. Alcohol, n-heptyl alcohol, n-nonyl alcohol, n-decyl alcohol, n-undecyl alcohol, n-tridecyl alcohol, n-pentadecyl alcohol, n-heptadecyl alcohol, n-nonadecyl alcohol, n-hen Linear alcohols such as eicosyl alcohol and n-tricosyl alcohol, i-butyl alcohol, 2-methylbutyl alcohol, 2-methylpentyl alcohol, 2-methylhexyl alcohol, 2-methyloctyl alcohol, 2-methylnonyl alcohol 2-methyldecyl alcohol, 2-methyldodecyl alcohol, 2-methyltetradecyl alcohol, 2-methylhexadecyl alcohol, 2-methyloctadecyl alcohol, 2-methyleicosyl alcohol, 2-methyldocosyl alcohol, 3-methylbutyl In addition to branched alcohols such as alcohol, 3-methylpentyl alcohol, 2-ethylpentyl alcohol, 2-ethylheptyl alcohol, 2-propylhexyl alcohol, 2,3-dimethylheptyl alcohol, 2,5-dimethylheptyl Examples include octene obtained by dimerization of butenes such as alcohol, alcohol produced from a mixture of olefin oligomer isomers such as dimers to tetramers of lower olefins such as propylene, 1-butene and isobutene. It is.

  Examples of alcohols generated from olefins substituted with hydrocarbon groups containing unsaturated hydrocarbon groups include 2-phenylpropyl alcohol, 3-phenylpropyl alcohol, 3-phenylbutyl alcohol, 4-phenylbutyl alcohol, Alcohol having an aromatic group such as 3-phenyl-2-methylpropyl alcohol, 2-pentenyl alcohol, 3-pentenyl alcohol, 4-pentenyl alcohol, 2-methyl-2-butenyl alcohol, 2-methyl-3- Examples thereof include alcohols having an unsaturated aliphatic group such as butenyl alcohol, 6-heptenyl alcohol, 2-methyl-5-hexenyl alcohol, 8-nonenyl alcohol and 2-methyl-7-octenyl alcohol.

  Other examples of alcohols formed from olefins substituted with functional groups containing heteroatoms include 2-ethoxypropyl alcohol, 3-ethoxypropyl alcohol, 2- (n-propoxymethyl) propyl alcohol, 4- (n- Propoxy) butyl alcohol, 2-methoxymethyl-7-octenyl alcohol, 2- (2′-methoxyethyl) -6-heptenyl alcohol, 8-methoxy-2-methyl-6-heptenyl alcohol, 9-methoxy- Alcohols containing an ether group such as 7-nonenyl alcohol, 4-hydroxybutyl alcohol, 3-hydroxy-2-methylpropyl alcohol, 5-hydroxyheptyl alcohol, 4-hydroxy-2-methylhexyl alcohol, 5-hydroxy -3-Methylpentylua Cole, 4-hydroxy-8-nonenyl alcohol, 3-hydroxy-2-methyl-7-octenyl alcohol, 9-hydroxy-7-nonenyl alcohol, 8-hydroxy-2-methyl-6-octenyl alcohol, etc. Alcohols containing 2-hydroxyl group, 2-acetoxypropyl alcohol, 3-acetoxypropyl alcohol, 3-methoxycarbonylbutyl alcohol, 2-methoxycarbonylpropyl alcohol, 3-methoxycarbonylpropyl alcohol, 2-acetoxymethyl-7-octenyl In addition to alcohols containing 2- (2′-acetoxyethyl) -6-heptenyl alcohol, 4,5-diacetoxypentyl alcohol, and 3,4-diacetoxy-2-methylbutyl alcohol ester groups, 2 -Shea Alcohol containing a cyano group such as propyl alcohol.

<Solvent>
The aldehyde production method and alcohol production method of the present invention can be reacted in the presence or absence of a solvent. If a solvent is used, it should dissolve at least a part of the transition metal compound, organophosphorus compound, and raw material olefin described above, and does not adversely affect the reaction activity of the hydroformylation reaction or the selectivity of the reaction. It can be used and is not particularly limited.

  Specific examples of the solvent when using the solvent include water, for example, diglyme (diethylene glycol dimethyl ether), triglyme (triethylene glycol dimethyl ether), diphenyl ether, dibenzyl ether, diallyl ether, tetrahydrofuran (THF), dioxane, and the like. Amides such as ethers, N-methyl-2-pyrrolidone, dimethylformamide, N, N-dimethylacetamide, ethyl acetate, butyl acetate, ethyl butyrate, butyl butyrate, γ-butyrolactone, di (n-octyl) phthalate, etc. Esters, aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, dodecylbenzene, aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, chloroform, dichloro Tan, halogenated hydrocarbons such as carbon tetrachloride, nitriles such as acetonitrile, propionitrile, benzonitrile, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, t-butyl alcohol, n-pen Examples include alcohols such as butanol, neopentyl alcohol, n-hexanol, 2-ethylhexanol, n-octanol, n-nonanol, and n-decanol.

  In addition, a compound having a higher boiling point than the target product aldehyde or alcohol, such as an acetal reactant of an aldehyde produced as a by-product of the aldehyde production reaction or alcohol production reaction of the present invention, an ester or an aldol condensate, etc. Can also be used as a solvent.

The amount of the solvent when using the solvent is usually 5% by weight or more, preferably 10% by weight or more, and usually 95% by weight or less, preferably 90% by weight with respect to the total weight of the reaction liquid in the reactor. % Or less.
Note that one type of solvent may be used, or a plurality of solvents may be mixed and used.

<Reaction conditions>
Next, reaction conditions for carrying out the aldehyde production reaction and alcohol production reaction of the present invention will be described.

  Reaction pressure in the reactor, that is, partial pressure of hydrogen, partial pressure of carbon monoxide, partial pressure of inert gas, partial pressure of raw material olefin, and hydroformylation reaction or aldehyde hydrogenation reaction in the reactor The sum of the vapor pressures of the reaction mixture containing aldehydes and alcohols produced by this method (and the value obtained by adding the vapor pressure of the solvent to the reaction pressure when a solvent is used if necessary) is not particularly limited. However, it is usually 0.01 MPa or more, preferably 0.10 MPa or more, more preferably 0.50 MPa or more, and usually 30.00 MPa or less, preferably 20.00 MPa or less, more preferably 10.00 MPa or less. If the reaction pressure is too low, the transition metal complex of the transition metal complex used in the reaction may be metallized and deactivated, and the hydroformylation reaction or aldehyde hydrogenation reaction activity is not fully expressed. Aldehyde and alcohol yield may be reduced. On the other hand, if the reaction pressure, particularly hydrogen partial pressure and carbon monoxide partial pressure, are too high, the loss of raw olefins due to hydrogenation of raw olefins increases, or the aldehydes and alcohols of the target products obtained directly increase. There is a risk that the chain selectivity may decrease. In particular, the partial pressure of hydrogen is preferably 0.005 MPa or more, more preferably 0.01 MPa or more, and preferably 20 MPa or less, more preferably 10 MPa or less. If the partial pressure of hydrogen is too low, the reaction activity may be lowered, and if the partial pressure of hydrogen is too high, the raw material olefin may be wasted due to the progress of the hydrogenation reaction of the raw material olefin. The partial pressure of carbon monoxide is preferably 0.005 MPa or more, more preferably 0.01 MPa or more, while it is preferably 15 MPa or less, more preferably 8 MPa or less. If the partial pressure of carbon monoxide is too low, there is a concern about a decrease in reaction activity, particularly metalation of a transition metal, and if it is too high, a decrease in linear selectivity of the aldehyde or alcohol obtained is expected.

  In the present invention, the molar ratio of hydrogen to carbon monoxide supplied to the reactor is 1:10 to 10: 1, more preferably 1: 5 to 5: 1, and still more preferably 1: 2 to 2. 2: 1. In particular, when alcohol is produced, 2 moles of hydrogen and 1 mole of carbon monoxide are theoretically consumed for 1 mole of raw material olefin, so the molar ratio of hydrogen to oxygen monoxide in the reactor is, for example, 3: 1. It is preferable that hydrogen has a higher pressure, such as ˜1.1: 1.

  The reaction temperature in the reactor is usually 25 ° C. or higher, preferably 50 ° C. or higher, more preferably 70 ° C. or higher, and is usually 200 ° C. or lower, preferably 180 ° C. or lower, more preferably 160 ° C. or lower. It is. If the reaction temperature is too low, the reaction activity itself may not be sufficiently obtained. If the reaction temperature is too high, the linear selectivity of the target product aldehyde or alcohol obtained may be reduced or the alcohol of the aldehyde produced The product yield may be reduced due to the progress of side reactions (eg, aldol condensation). Furthermore, there is a possibility that the organophosphorus compound may disappear due to thermal decomposition, or the deactivation associated with the decomposition of the transition metal complex itself may occur.

<Reaction process>
The reaction processes that can be used in the present invention are described below.

  As a reaction method, any of continuous, semi-continuous, and batch operations can be easily carried out in a stirring reaction vessel or a bubble column reaction vessel.

  Separation of unreacted raw olefins and products from the catalyst is usually performed by distillation such as simple distillation, vacuum distillation, thin film distillation, steam distillation, etc., gas-liquid separation, evaporation (evaporation), gas stripping, gas It can be performed by a known method such as absorption and extraction. Distillation conditions are not particularly limited and are arbitrarily set so as to obtain desirable results in consideration of the volatility of the product, thermal stability, volatility of the catalyst components, thermal stability, etc. Usually, it selects from the range of the temperature conditions of 50-300 degreeC, and the pressure conditions of 760-0.01 mmHg.

In the separation operation, when unreacted raw materials (unreacted aldehydes when producing olefin, hydrogen, carbon monoxide, alcohol) are obtained, they can be recycled to the reaction process and reused. Economical and desirable.
In performing the distillation, the use of a solvent is not essential, but an inert solvent can be present in the products and catalyst components as necessary. The transition metal can be recovered from the remaining liquid containing the separated catalyst by a known method, or the catalyst can be reused by recycling the entire amount or a part of the residual liquid to the reaction step.

  EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further in detail, this invention is not limited to a following example, unless the summary is exceeded.

<Example 1>
[Cp ^* Ru (acac)] ₂ (8.4 mg, 0.025 mmol in terms of Ru) and a bidentate phosphite ligand ( In the specification, the compound of formula L-22) (26.8 mg, 0.025 mmol, 1 equivalent to Ru) was weighed, toluene (2.0 ml) was added and stirred for several minutes to dissolve the complex and the ligand. It was. Thereafter, 210 mg (1-decene: 1.0 mmol) of a mixture of 1-decene as a reaction raw material and dodecane as an internal standard substance for gas chromatography analysis (molar ratio = 2/1) was added, and the autoclave was sealed, A mixed gas of hydrogen and carbon monoxide (mixing ratio: hydrogen / carbon monoxide = 1/1 (molar ratio)) was fed so that the internal pressure (gauge pressure) became 2.0 MPa, and the stirring speed was 800 rpm. The reaction was performed at 100 ° C. for about 18 hours.
Here, Cp ^* represents a pentamethylcyclopentadienyl group of the formula Cp-12 in the specification.

  After completion of the reaction, the reaction vessel was cooled and purged with gas, and then the product was analyzed by gas chromatography. As a result, the conversion rate of 1-decene was 29.4%, the yield of undecanal (n-undecylaldehyde) was 4.4%, linear undecanal (L-form) and branched undecanal. The ratio of (B-form) is L / B = ∞ (no branched undecanal is produced), the yield of undecanol (n-undecyl alcohol) is 0%, decane (raw material 1-decene hydrogenated product) ) Was 0%, and the yield of the internal isomer of the starting material 1-decene was 22.3%.

<Examples 2 to 4, Comparative Example 1>
In Example 1, the amount of bidentate phosphite ligand (compound of formula L-22 in the specification) added to Ru was 2 equivalents (Example 2), 5 equivalents (Example 3), 10 equivalents (Example 4). ) And 0.4 equivalents (Comparative Example 1), except that the reaction was performed in the same manner, and analysis was performed. The results are shown in Table 1 together with the results of Example 1.

  From the results of Examples 1 to 4 and Comparative Example 1, the target aldehyde (in the range where the amount of bidentate phosphite ligand is 1 equivalent or more and 10 equivalents or less with respect to the Ru catalyst having a cyclopentadienyl group) It can be seen that the yield of undecanal is increased, the linear selectivity (L / B ratio) is high, and the ratio of the internal isomer to the conversion of the raw material 1-decene is low.

<Comparative example 2>
In Example 2, the reaction was performed in the same manner except that Ru ₃ (CO) ₁₂ (5.3 mg, 0.025 mmol in terms of Ru) was used as the Ru catalyst, and the analysis was performed. The results are shown in Table 1.

<Comparative Example 3>
In Example 2, the reaction was performed in the same manner except that [RuCl ₂ (p-cymene)] ₂ (7.7 mg, 0.025 mmol in terms of Ru) was used as the Ru catalyst, and the analysis was performed. The results are shown in Table 1.

  From the comparison between Example 2 and Comparative Examples 2 and 3, when a ruthenium compound having no cyclopentadienyl group was used as a catalyst, the target aldehyde was obtained even when a bidentate phosphite ligand was used. It can be seen that the yield of (undecanal) is low and that many by-products such as decane and internal isomers are produced.

<Example 5>
In Example 1, a bidentate phosphine ligand (a compound of formula L-11 in the specification, 14.5 mg, 0.025 mmol, 1 equivalent to Ru) was used instead of the bidentate phosphite ligand, and the reaction The reaction was conducted in the same manner except that the temperature was 160 ° C., and the analysis was performed. The results are shown in Table 1.

<Example 6>
In Example 5, the reaction was conducted in the same manner except that the amount of bidentate phosphine ligand (compound of formula L-11 in the specification) added to Ru was changed to 2 equivalents, and the analysis was conducted. The results are shown in Table 1.

<Example 7>
In Example 5, the reaction was performed in the same manner except that [Cp ^* Ru (OCH ₃ )] ₂ (6.7 mg, 0.025 mmol in terms of Ru) was used as the Ru catalyst, and analysis was performed. The results are shown in Table 1.

<Example 8>
In Example 5, Cp ^* Ru (cod) Cl (9.5 mg, 0.025 mmol) was used as the Ru catalyst, and t-BuOK (2.8 mg, 0.025 mmol, 1 equivalent to Ru) was used as the basic compound. Was added and the reaction was carried out in the same manner except that the reaction time was 20 hours, and the analysis was carried out. The results are shown in Table 1.

<Example 9>
In Example 6, a bidentate phosphine ligand was used from the compound of formula L-11 in the specification using 1,3-bis (diphenylphosphino) propane (20.6 mg, 0.025 mmol, 2 equivalents to Ru). The reaction was conducted in the same manner except that the analysis was performed. The results are shown in Table 1. In addition, 1,3-bis (diphenylphosphino) propane is described as DPPP in Table 1.

<Comparative example 4>
The reaction was conducted in the same manner as in Example 5 except that the ligand was not used and the reaction time was 12 hours. The results are shown in Table 1.

<Comparative Example 5>
The reaction was conducted in the same manner as in Example 8 except that the ligand was not used and the reaction time was 18 hours. The results are shown in Table 1.

  From the results of Examples 5 to 9 and Comparative Examples 4 and 5, the following can be understood. When 1 equivalent or 2 equivalents of a bidentate phosphine ligand is used relative to a Ru catalyst having a cyclopentadienyl group, the yield of the target aldehyde (undecanal) increases. In particular, when the more preferred bidentate phosphine ligand (L-11) that can give high linear selectivity as in Examples 5 to 8, the DPPP ligand of Example 9 Compared to the case, an aldehyde having a high linear selectivity (L / B ratio) is produced. For comparison, an example of a system without addition of a ligand (Comparative Example 4 as a comparative example of Example 5 and Comparative Example 5 as a comparative example of Example 8) is shown, but the yield of aldehyde (undecanal) is low. Many internal isomers are produced.

<Example 10>
In Example 5, Ru compound (I) (13.6 mg, 0.025 mmol in terms of Ru) having the following structure was used as the Ru catalyst, and the reaction was performed in the same manner except that the reaction time was 23 hours, and analysis was performed. . The results are shown in Table 1. The Ru compound (I) is a binuclear complex. In terms of form, the Ru complex on the right side has a structure in which a cyclopentadiene ligand is coordinated. As described in the specification, The cyclopentadiene ligand changes to a cyclopentadienyl group having a hydroxyl group like the Ru complex on the left side in an atmosphere where hydrogen gas is present.

<Example 11>
In Example 10, the reaction was carried out in the same manner except that Ru compound (II) (14.2 mg, 0.025 mmol) having the following structure was used as the Ru catalyst, and analysis was performed. The results are shown in Table 1. The Ru compound (II) has a structure in which a cyclopentadiene ligand is coordinated. As described in Example 10, the Ru compound (II) changes to a cyclopentadienyl group having a hydroxyl group in the presence of hydrogen gas. .

<Example 12>
In Example 10, the reaction was performed in the same manner except that Fe compound (III) (10.5 mg, 0.025 mmol) having the following structure was used as the Fe catalyst, and analysis was performed. The results are shown in Table 1. The Fe compound (III) has a structure in which a cyclopentadiene ligand is coordinated. As described in Example 10, the Fe compound (III) changes to a cyclopentadienyl group having a hydroxyl group in the presence of hydrogen gas. .

<Comparative Example 6>
In Example 11, the same procedure except that triphenylphosphine (26.2 mg, 0.100 mmol, 4 equivalents to Ru), which is a monodentate phosphine, was used instead of the bidentate phosphine ligand, and the reaction time was 18 hours. The reaction was performed and the analysis was performed. The results are shown in Table 1.

  The following can be seen from the results of Examples 10 to 12 and Comparative Example 6. In Ru catalysts having a cyclopentadienyl group having a hydroxyl group as a substituent (Examples 10 and 11), the yield of alcohol (undecanol) is high and the linear selectivity (L / B ratio) is high. In addition, in the Fe catalyst having a cyclopentadienyl group having a hydroxyl group as a substituent (Example 12), the yield of aldehyde (undecanal) is high and the linear selectivity (L / B ratio) is high. . On the other hand, even when the Ru catalyst has a cyclopentadienyl group having a hydroxyl group as a substituent, when monodentate phosphine is used as a ligand (Comparative Example 6), both the yield of aldehyde and the yield of alcohol are both. Low, and many internal isomers are produced.

<Example 13>
[Cp ^* Ru (acac)] ₂ (8.4 mg, 0.025 mmol in terms of Ru) and bidentate phosphine ligand (specification) in a magnetic induction stirring type stainless steel autoclave having a dry content of 50 ml under an argon gas atmosphere Compound of formula L-11) (28.9 mg, 0.050 mmol, 2 equivalents to Ru), 1,4-dioxane (2.0 ml) was added, and the mixture was stirred for several minutes. Was dissolved. Then, after introducing propylene gas into the autoclave and applying 0.8 MPa as the gas pressure of propylene, a mixed gas of hydrogen and carbon monoxide (mixing ratio: hydrogen / carbon monoxide = 1/1 (molar ratio)) system Feeding was performed so that the internal pressure (gauge pressure) became 2.0 MPa, and the reaction was performed at 160 ° C. for 24 hours under a stirring speed of 800 rpm.

After completion of the reaction, the reaction vessel was cooled and purged with gas. Then, dodecane, an internal standard substance for gas chromatography analysis, was added, and the product was analyzed by gas chromatography. As a result, butanal was obtained at TON = 37.9, and the ratio of branched butanal (I-isomer) to linear butanal (N-isomer) was N / I = 13.0. Butanol was obtained with TON = 1.1, and the ratio of branched butanol (I-isomer) to linear butanol (N-isomer) was N / I = ∞ (branched butanol was not produced). )Met.
Here, TON indicates the molar ratio of the target product to the Ru compound used in the reaction. The results are shown in Table 2.

<Example 14>
In Example 13, the reaction was carried out in the same manner except that the reaction was carried out using Ru compound (III) (11.3 mg, 0.025 mmol) having the following structure instead of [Cp ^* Ru (acac)] _2. Carried out. The results are shown in Table 2.

<Example 15>
In Example 14, the reaction was performed in the same manner except that the solvent was changed from 1,4-dioxane to toluene, and analysis was performed. The results are shown in Table 2.

<Example 16>
In Example 13, the reaction was performed in the same manner except that the reaction was performed using Ru compound (IV) (6.8 mg, 0.025 mmol in terms of Ru) having the following structure instead of [Cp ^* Ru (acac)] _2. Conducted and analyzed. The results are shown in Table 2.

<Example 17>
In Example 13, the reaction was performed in the same manner except that the reaction was performed using Ru compound (V) (15.1 mg, 0.025 mmol in terms of Ru) having the following structure instead of [Cp ^* Ru (acac)] _2. Conducted and analyzed. The results are shown in Table 2.

<Comparative Example 7>
Example 13 was carried out in the same manner except that the reaction was carried out using [RuCl ₂ (p-cymene)] ₂ (7.7 mg, 0.025 mmol in terms of Ru) instead of [Cp ^* Ru (acac)] _2. Reaction was performed and analysis was performed. The results are shown in Table 2.

  From the comparison between Examples 13 to 17 and Comparative Example 7, when a Ru complex having no cyclopentadienyl group as in Comparative Example 7 was used, linear selectivity of the resulting aldehyde (butanal) was obtained. It can be seen that the (N / I ratio) is low.

<Example 18>
In Example 13, the ligand was changed from the bidentate phosphine of formula L-11 in the specification to the bidentate phosphine of formula L-1 in the specification (27.5 mg, 0.050 mmol, 2 equivalents to Ru). Reacted in the same way and analyzed. The results are shown in Table 2.

<Example 19>
In Example 18, the reaction was carried out in the same manner except that the reaction was carried out using the above-described Ru compound (III) (11.3 mg, 0.025 mmol) instead of [Cp ^* Ru (acac)] _2. Carried out. The results are shown in Table 2.

<Example 20>
In Example 13, the ligand was changed from a bidentate phosphite of formula L-11 in the specification to a bidentate phosphite of formula L-22 in the specification (53.6 mg, 0.050 mmol, 2 equivalents to Ru). The reaction was conducted in the same manner except that the reaction temperature was changed from 160 ° C. to 120 ° C., and the analysis was performed. The results are shown in Table 2.

<Example 21>
In Example 20, the reaction was performed in the same manner except that the solvent was changed from 1,4-dioxane to toluene, and the reaction temperature was changed from 120 ° C to 160 ° C, and the analysis was performed. The results are shown in Table 2.

<Example 22>
In Example 14, the reaction was performed in the same manner except that the reaction temperature was changed from 160 ° C to 120 ° C, and the analysis was performed. The results are shown in Table 2.

<Example 23>
In Example 14, the reaction was performed in the same manner except that the reaction temperature was changed from 160 ° C to 140 ° C, and the analysis was performed. The results are shown in Table 2.

<Example 24>
In Example 14, the reaction was conducted in the same manner except that the internal pressure (gauge pressure) at the start of the reaction was changed from 2.0 MPa to 0.5 MPa, and the analysis was performed. The results are shown in Table 2.

<Example 25>
In Example 14, the reaction was performed in the same manner except that the internal pressure (gauge pressure) at the start of the reaction was changed from 2.0 MPa to 1.0 MPa, and the analysis was performed. The results are shown in Table 2.

<Example 26>
In Example 14, the reaction was performed in the same manner except that the internal pressure (gauge pressure) at the start of the reaction was changed from 2.0 MPa to 1.5 MPa, and the analysis was performed. The results are shown in Table 2.

<Example 27>
In Example 14, the reaction was performed in the same manner except that the internal pressure (gauge pressure) at the start of the reaction was changed from 2.0 MPa to 3.0 MPa, and analysis was performed. The results are shown in Table 2.

<Example 28>
In Example 14, the reaction was performed in the same manner except that the internal pressure (gauge pressure) at the start of the reaction was changed from 2.0 MPa to 4.0 MPa, and the analysis was performed. The results are shown in Table 2.

<Example 29>
[Cp ^* Ru (acac)] ₂ (8.4 mg, 0.025 mmol in terms of Ru) and bidentate phosphine ligand (specification) in a magnetic induction stirring type stainless steel autoclave having a dry content of 50 ml under an argon gas atmosphere The compound of formula L-22 in the text) (53.6 mg, 0.050 mmol, 2 equivalents to Ru) was weighed, toluene (2.0 ml) was added and stirred for several minutes to dissolve the complex and ligand. Then, propene gas was introduced into the autoclave, and after applying 0.8 MPa as the gas pressure of propene, a mixed gas of hydrogen and carbon monoxide (mixing ratio: hydrogen / carbon monoxide = 1/1 (molar ratio)) was used. Feeding was performed so that the internal pressure (gauge pressure) was 2.0 MPa, and the reaction was performed at 120 ° C. for 24 hours under a stirring speed of 800 rpm.

After completion of the reaction, the reaction vessel was cooled and purged with gas. Then, dodecane, an internal standard substance for gas chromatography analysis, was added, and the product was analyzed by gas chromatography. As a result, butanal was obtained with TON = 13, and the ratio of branched butanal (I-form) to linear butanal (N-form) was N / I = 40.0. Butanol was obtained with TON = 0.9, and the ratio of branched butanol (I-isomer) to linear butanol (N-isomer) was N / I = 2.9.
Here, TON indicates the molar ratio of the target product to the Ru compound used in the reaction.

<Example 30>
The same reaction as in Example 29 except that the reaction was carried out using the Ru compound (IV) (6.8 mg, 0.025 mmol) used in Example 16 instead of [Cp ^* Ru (acac)] ₂ The analysis was conducted.

As a result, butanal was obtained with TON = 51, and the ratio of branched butanal (I-form) to linear butanal (N-form) was N / I = 32. Butanol was obtained with TON = 3.3, and the ratio of branched butanol (I-isomer) to linear butanol (N-isomer) was N / I = 12.
Here, TON indicates the molar ratio of the target product to the Ru compound used in the reaction.

<Example 31>
In Example 29, instead of [Cp ^* Ru (acac)] ₂ , the same reaction was carried out except that the following Ru compound (VI) (7.9 mg, 0.025 mmol) was used. Carried out.

As a result, butanal was obtained with TON = 102, and the ratio of branched butanal (I-form) to linear butanal (N-form) was N / I = 41. In addition, n-butanol was obtained with TON = 3.3, and the ratio of branched butanol (I-isomer) to linear butanol (N-isomer) was N / I = ∞ (branched butanol was detected) Not).
Here, TON indicates the molar ratio of the target product to the Ru compound used in the reaction.

  Table 2 shows the results of Examples 13 to 28 including the results of Examples 29 to 31 described above.

Claims (1)

Presence of including complex ligand and Le ruthenium from organophosphorus compounds of bidentate, in the absence of a rhodium compound, an alcohol by reacting two or more feed olefins carbon atoms with hydrogen and carbon monoxide A method of manufacturing
The bidentate organophosphorus compound has a basic skeleton represented by any of the following formulas (c-1) to (c-3),
Method for producing an alcohol, characterized in that the 該Ru ruthenium including complex is a complex having a structure represented by the following formula (b).

(In the formula (b), M is Le ^ruthenium, R 1 to R ⁴ are each independently a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a hydroxy group, a cyano group, a nitro A group selected from the group consisting of a group, an amino group, an amide group, a perfluoroalkyl group, a trialkylsilyl group, a formyl group, an acyl group, an acyloxy group, an ester group, a phosphino group, and a carboxy group. which may have a substituent .X represents an oxygen atom. Further, it ^{R 1} and ^R 2, ^{R 2} and ^R 3, and R ³ and ^{R 4} are bonded to each other to form a ring The formed ring may further have a substituent.)

(In the formula (c-1), R ^{11 to} R ¹⁸ are each independently a hydrogen atom, a halogen atom, a hydroxy group, and a chain or cyclic alkyl group, aryl group, alkoxy group, aryloxy group, Represents a group selected from the group consisting of an amino group, an acyl group, an acyloxy group, a carboxy group, and an ester group, and these groups may further have a substituent, and any two substituents may be bonded to each other; It may be formed to form an annular structure.
R ^{21 to} R ²⁴ each independently represents a chain or cyclic alkyl group or aryl group. These groups may further have a substituent, and R ²¹ and R ²² , and R ²³ and R ²⁴ may form a bond with each other to form a cyclic structure. )

(In the above formula (c-2), R ^{31 to} R ³⁶ are each independently a hydrogen atom, a halogen atom, a hydroxy group, and a chain or cyclic alkyl group, aryl group, alkoxy group, aryloxy group, Represents a group selected from the group consisting of an amino group, an acyl group, an acyloxy group, a carboxy group, and an ester group, and these groups may further have a substituent, and any two substituents may be bonded to each other; It may be formed to form an annular structure.
R ^{41 to} R ⁴⁴ each independently represents a chain or cyclic alkyl group or aryl group. These groups may further have a substituent, and R ⁴¹ and R ⁴² and R ⁴³ and R ⁴⁴ may form a bond with each other to form a cyclic structure.
A ¹ and A ² are each independently O, S, SiR ^a R ^b , NR ^c , CR ^d R ^e , where R ^a , R ^b , R ^c , R ^d, and R ^e are Each independently represents a hydrogen atom, a chain or cyclic alkyl group, or an aryl group. )

(In the above formula (c-3), R ^{51 to} R ⁵⁸ are each independently a hydrogen atom, a halogen atom, a hydroxy group, and a chain or cyclic alkyl group, aryl group, alkoxy group, aryloxy group, Represents a group selected from the group consisting of an amino group, an acyl group, an acyloxy group, a carboxy group, and an ester group, and these groups may further have a substituent, and any two substituents may be bonded to each other; It may be formed to form an annular structure.
R ^{61 to} R ⁶⁴ each independently represent a chain or cyclic alkyl group or aryl group. These groups may further have a substituent, and R ⁶¹ and R ⁶² , and R ⁶³ and R ⁶⁴ may form a bond with each other to form a cyclic structure. )