JP2010215604A - Method for producing alcohol - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing an alcohol, comprising reacting an olefinic compound with hydrogen and carbon monoxide in the presence of a catalyst, by which the alcohol having high straight chain selectivity can be produced in one step reaction process. <P>SOLUTION: This method for producing the alcohol is characterized by reacting an olefinic compound with hydrogen and carbon monoxide in the presence of a rhodium compound, a bidentate organophosphorous compound, and a compound containing one or more of the group 8 to 10 transition metals in the periodical table excluding rhodium. The reaction is performed in the coexistence of a hydroformylation reaction catalyst comprising a rhodium-bidentate organophosphorous compound for expressing high straight chain selectivity, with one or more group 8 to 10 transition metals in the periodic table excluding the rhodium as a selective hydrogenation reaction catalyst for an aldehyde produced in the reaction system. Thereby, the alcohol largely improved in straight chain selectivity can be produced in one step reaction process. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a method for producing an alcohol, and more specifically, a method for producing an alcohol having high linear selectivity in a one-step reaction process by reacting an olefinic compound with hydrogen and carbon monoxide in the presence of a catalyst. About.

  A method for producing aldehydes by reacting an olefinic compound with hydrogen and carbon monoxide in the presence of a catalyst comprising a group 8-10 transition metal and an organophosphorus ligand is widely known as a hydroformylation reaction. It has been. In general, aldehydes having higher linearity are useful among the obtained aldehydes, and various organophosphorus ligands have been developed to increase the linearity selectivity. The highly linear aldehyde thus obtained is usually hydrogenated to alcohol, or converted to a higher molecular weight aldehyde by a condensation reaction and then hydrogenated to a higher molecular weight alcohol. It has been converted. These alcohols are used as raw materials for adhesives, paints and plasticizers.

  Of the above reactions, if attention is focused on the production of an alcohol without condensation, if the alcohol can be produced directly from an olefinic compound in a one-step reaction step, the conventional hydroformylation reaction and hydrogenation reaction can be carried out in two stages. Compared with the production in the reaction step, a hydrogenation reaction facility and a hydrogenation reaction catalyst are not required, and the process is economically very advantageous.

  As a catalyst system for obtaining an alcohol from an olefinic compound in a one-step reaction process, a cobalt-based catalyst having a trialkylphosphine as a ligand has long been known. However, a cobalt-based catalyst usually has a reaction temperature. In recent years, attention has been focused on rhodium-based catalysts in which the reaction proceeds under milder conditions, such as 160 to 200 ° C. and a reaction pressure of 5 to 10 MPa.

  Conventionally, as a literature example regarding the production of alcohols in a one-step reaction by a catalyst system composed of a rhodium-organophosphorus compound, as in Non-Patent Document 1, Non-Patent Document 2, and Patent Document 1, A method of reacting an olefinic compound with hydrogen and carbon monoxide in the presence of a catalyst composed of rhodium and a monodentate trialkylphosphine is known.

  However, these methods have low selectivity for the target linear alcohol, and the production ratio of the linear alcohol (L) to the branched alcohol (B) (hereinafter, this ratio is referred to as “L / B ratio”). Is a low value of about 2.5 (linear selectivity = 71%) in a state in which almost all olefinic compound raw materials are converted into products.

As an attempt to improve the low linear selectivity in the alcohol production process by a one-step reaction, as disclosed in Patent Document 2, a bidentate ligand that contributes to the generation of an aldehyde having a high linear selectivity, A method using a rhodium catalyst system in which a monodentate trialkylphosphine ligand contributing to the hydrogenation reaction of the aldehyde is coexisted is disclosed. In this method, the L / B ratio of the alcohol obtained is 7.7 ( Linear selectivity = 89%).
However, in this method, the production of a low linear selectivity aldehyde proceeds concurrently with the coexisting rhodium-monodentate trialkylphosphine catalyst, so the L / B ratio of the alcohol obtained is not always sufficiently high. is not.

  Patent Document 3 discloses a method using a rhodium-trialkyl-type bidentate phosphine catalyst system, but the L / B ratio of the alcohol obtained is 6.3 at maximum (linear selectivity = 86%). Stay on.

As described above, if the method of producing alcohol from an olefin raw material is classified in a one-step reaction process using a rhodium catalyst, it can be roughly classified into two groups.
That is, the first method is a method performed by one type of catalyst system as described in Non-Patent Document 1, Non-Patent Document 2, and Patent Document 1, and the second method is described in Patent Document 2. This is a method in which two types of catalysts, a catalyst for producing a highly linear selective aldehyde as described, and a catalyst for hydrogenating the aldehyde are used in combination.
In the latter method, an efficient hydrogenation reaction of the aldehyde generated in the system becomes an important factor.

  Conventionally, as a catalyst for selectively hydrogenating a substrate having a polar functional group (carbonyl group) such as an aldehyde, there are various catalysts as introduced in the reviews of Non-Patent Document 3 and Non-Patent Document 4. Are known. However, as described in Non-Patent Document 5, such a hydrogenation reaction catalyst is usually used as a hydrogenation reaction catalyst in the presence of carbon monoxide (CO) gas such as a hydroformylation reaction atmosphere. It is known that CO is coordinated strongly and the catalytic activity is greatly reduced due to poisoning.

European Patent No. 0420510 JP 2006-31612 A JP 2009-029712 A

J. et al. Chem. Soc. , Chem. Commun. , 1990, P165 J. et al. Chem. Soc. Dalton Trans. , 1996, p1161 Chem. Soc. Rev. , 2006, 35, p237 Chem. Commun. , 2007, 5134 J. et al. Mol. Catal. A: Chem. 1999, 148, p69

  As described above, if a rhodium-trialkylphosphine catalyst is used, it is possible to produce an alcohol from the raw material olefinic compound in a single reaction step, but the selectivity of the target linear alcohol is low. That remains a big problem.

  For this reason, it is desired to develop a new method capable of directly producing an alcohol having higher straight chain selectivity in one reaction step.

The present invention has been made in view of the above-described problems.
That is, an object of the present invention is to provide an alcohol having a higher linear selectivity than conventional methods in a process for producing an alcohol in a one-step reaction process by reacting an olefinic compound with hydrogen and carbon monoxide in the presence of a catalyst. The invention resides in providing a method of manufacturing.

  As the inventors of the present invention are diligently studying a method for obtaining an alcohol having high linear selectivity from an olefinic compound in a one-step reaction process, the conventionally known high linear selectivity is expressed. Reaction with a hydroformylation reaction catalyst comprising a rhodium-bidentate organophosphorus compound and a group 8-10 transition metal excluding rhodium as a catalyst for selective hydrogenation reaction of aldehydes produced in the reaction system As a result, it was found that alcohol having greatly improved linear chain selectivity can be produced in a one-step reaction process, and the present invention has been achieved.

  That is, the gist of the present invention resides in the following (1) to (7).

(1) An alcohol obtained by reacting an olefinic compound with hydrogen and carbon monoxide in the presence of a rhodium compound, a bidentate organophosphorus compound, and a compound containing at least one group 8-10 transition metal of the periodic table excluding rhodium. A process for producing alcohol, characterized in that

(2) The method for producing an alcohol according to (1), wherein the group 8-10 transition metal excluding the rhodium is a transition metal selected from the group consisting of ruthenium, iridium, palladium, and platinum. .

(3) The compound containing at least one group 8-10 transition metal of the periodic table excluding the rhodium has a ligand containing an organic group represented by the following general formula (I) (1) Or the manufacturing method of alcohol as described in (2).
-XH (I)
(In the formula, X represents a linking group containing a hetero atom, and the hetero atom is bonded to a hydrogen atom.)

(4) The ligand has at least one nitrogen atom and is coordinated to the Group 8-10 transition metal of the periodic table excluding the rhodium with the nitrogen atom, and the nitrogen atom has at least one hydrogen atom. The method for producing alcohol according to (3), wherein atoms are bonded.

(5) In the above (4), the ligand is a multidentate ligand coordinated to a group 8-10 transition metal of the periodic table excluding the rhodium at two or more bonding points. The manufacturing method of alcohol of description.

(6) The method for producing an alcohol according to any one of (1) to (5), wherein the reaction is performed at 80 ° C. or higher.

(7) The method for producing an alcohol according to any one of (2) to (6), wherein the group 8-10 transition metal excluding the rhodium is ruthenium.

  According to the present invention, in a method for producing an alcohol in a one-step reaction process by reacting an olefinic compound with hydrogen and carbon monoxide in the presence of a catalyst, producing an alcohol having higher linear selectivity than conventional. Can do.

  Hereinafter, embodiments of the method for producing alcohol of the present invention will be described in detail.

The method for producing an alcohol of the present invention comprises:
Rhodium compounds,
Bidentate organophosphorus compounds,
And an alcohol is produced by reacting an olefinic compound with hydrogen and carbon monoxide in the presence of a compound containing at least one group 8-10 transition metal of the periodic table excluding rhodium.

  That is, in the present invention, a rhodium compound and a bidentate organophosphorus compound for forming a hydroformylation reaction catalyst comprising a rhodium-bidentate organophosphorus compound that expresses a conventionally known high linear selectivity. And a compound containing a group 8-10 transition metal of the periodic table excluding rhodium for forming a catalyst for selective hydrogenation reaction of aldehyde generated in the reaction system (hereinafter referred to as “transition metal compound for hydrogenation catalyst”) In some cases). It is preferable that the catalyst for selective hydrogenation reaction of aldehyde generated in the reaction system is a transition metal complex compound containing a specific ligand.

[Catalyst for hydroformylation reaction]
<Rhodium compound>
The rhodium compound that can be used as the catalyst for hydroformylation reaction according to the present invention is not particularly limited as long as it exhibits a catalytic action for the hydroformylation reaction. For example, the form thereof includes an acetylacetonate compound, Halides, sulfates, nitrates, organic salts, inorganic salts, alkene coordination compounds, amine coordination compounds, pyridine coordination compounds, carbon monoxide coordination compounds, phosphine coordination compounds, phosphite coordination compounds, etc. it can.

Specifically, RhCl ₃ , RhI ₃ , Rh (NO ₃ ) ₃ , Rh (OAc) ₃ , RhCl (CO) (PPh ₃ ) ₂ , RhH (CO) (PPh ₃ ) ₃ , RhCl (PPh ₃ ) ₃ , Rh (acac) ₃ , Rh (acac) (CO) ₂ , Rh (acac) (cod), [Rh (OAc) ₂ ] ₂ , [Rh (OAc) ₂ ] ₂ , [Rh (OAc) (cod) _{] 2, [RhCl (CO)} ] 2, include _{[RhCl (cod)] 2,} Rh 4 (CO) rhodium compounds such as _12. In the above examples, cod represents 1,5-cyclooctadiene, acac represents acetylacetonate, Ac represents an acetyl group, and Ph represents a phenyl group.

  The type of the rhodium compound is not particularly limited, and may be any of a monomer, a dimer, and a multimer higher than a trimer as long as it is an active rhodium complex species.

  A rhodium compound may be used individually by 1 type, and may use 2 or more types together.

  The amount of rhodium compound used is not particularly limited, but from the viewpoint of catalyst activity and economy, the weight concentration of rhodium atoms in the reaction medium is usually 0.1 ppm or more, preferably 1 ppm or more, more preferably 10 ppm or more. In general, it is 10000 ppm or less, preferably 1000 ppm or less, more preferably 500 ppm or less.

<Bidentate organophosphorus compound>
The bidentate organophosphorus compound that can be used in the present invention is preferably used together with a rhodium compound, when an aldehyde is produced by a reaction of an olefinic compound with hydrogen and carbon monoxide. This is a bidentate organophosphorus compound having a / B ratio of 4.0 or more, that is, a linear selectivity of 80% or more, and there is no particular limitation on its structure.

  That is, the higher the linear selectivity of the resulting alcohol, the higher the linear selectivity of the resulting alcohol. Is preferably used. As a selection criterion for the above-mentioned preferable bidentate organophosphorus compound, a reaction evaluation is performed in advance under the conditions for actually producing alcohol, and the linear selectivity of the aldehyde obtained under the conditions is 80% or more. Those shown are preferred, but more preferably show a straight chain selectivity of 85% or more.

  In general, in order to be a bidentate organophosphorus compound that generates an aldehyde exhibiting high linear selectivity, a structure in which a chelate is coordinated so as to be sandwiched between two phosphorus atoms is preferable. In addition, the phosphorus atom that can be coordinated to the transition metal needs to be a trivalent phosphorus atom, but the trivalent phosphorus atom has three covalent bonding sites, each of which includes a carbon atom, an oxygen atom, a nitrogen atom, etc. Because of the possibility of covalent bonding with various atoms, 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 has a phosphine type in which three carbon atoms are bonded to the phosphorus atom, and a phosphorus atom. A phosphinite type in which two carbon atoms and one oxygen atom are bonded, a phosphonite type in which one carbon atom and two oxygen atoms are bonded to a phosphorus atom, and three oxygen atoms bonded to a phosphorus atom It is preferable that it is either of such phosphite 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 preferable, and bidentate phosphine compounds are particularly preferable.

  In the prior art, as a bidentate phosphine compound and a bidentate phosphite compound that generate an aldehyde having high linear selectivity, those having a basic skeleton represented by the following general formulas (II) to (IV) Such bidentate phosphine compounds and bidentate phosphite compounds are also preferably used in the present invention.

(Wherein R ^{11 to} R ¹⁸ are each independently a hydrogen atom, a halogen atom, a hydroxy group, a chain or cyclic alkyl group, an aryl group, an alkoxy group, an aryloxy group, an amino group, an acyl group, an acyloxy group, A carboxy group or an ester group, which may further have a substituent, R ¹¹ and R ¹² , R ¹² and R ¹³ , R ¹³ and R ¹⁴ , R ¹⁵ and R ¹⁶ , R ¹⁶ and R ¹⁷ , R ¹⁷ and R ¹⁸ , or any two of these substituents may form a bond with each other to form a cyclic structure.
R ^{21 to} R ²⁴ each independently represents a chain or cyclic alkyl group or an 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. )

(Wherein R ^{31 to} R ³⁶ each independently represents a hydrogen atom, a halogen atom, a hydroxy group, a chain or cyclic alkyl group, an aryl group, an alkoxy group, an aryloxy group, an amino group, an acyl group, an acyloxy group, A carboxy group or an ester group, which may further have a substituent, R ³¹ and R ³² , R ³² and R ³³ , R ³⁴ and R ³⁵ , R ³⁵ and R ³⁶ , or Any two substituents possessed by them may form a bond with each other to form a cyclic structure.
R ^{41 to} R ⁴⁴ each independently represents a chain or cyclic alkyl group or an 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 each independently represent O, S, SiR ^a R ^b , NR ^c , or 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 formula, R ^{51 to} R ⁵⁸ are each independently a hydrogen atom, a halogen atom, a hydroxy group, a chain or cyclic alkyl group, an aryl group, an alkoxy group, an aryloxy group, an amino group, an acyl group, an acyloxy group, A carboxy group or an ester group, which may further have a substituent, R ⁵¹ and R ⁵² , R ⁵² and R ⁵³ , R ⁵³ and R ⁵⁴ , R ⁵⁵ and R ⁵⁶ , R ⁵⁶ and R ⁵⁷ , R ⁵⁷ and R ⁵⁸ , or any two of these substituents may form a bond with each other to form a cyclic structure.
R ^{61 to} R ⁶⁴ each independently represents a chain or cyclic alkyl group or an 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. )

Among the bidentate organophosphorus compounds represented by the above general formulas (II) to (IV), more preferably, R of the general formula (II) is used from the viewpoint of generating an aldehyde having high linear selectivity. The terminal substituent of the bidentate organophosphorus compound represented by ^{21 to} R ²⁴ , R ^{41 to} R ⁴⁴ of the general formula (III), and R ^{61 to} R ⁶⁴ of the general formula (IV) has a substituent. An aryl group that may be present. Specific examples of such a bidentate organophosphorus compound having a preferred structure are shown below. Among the following exemplary compounds, 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 “ ^t Bu” represents a ^t -butyl group.

  These bidentate organophosphorus compounds may be used alone or in combination of two or more.

  In the present invention, by using a rhodium complex compound composed of the aforementioned rhodium compound and the above bidentate organophosphorus compound, the hydroformylation reaction proceeds, and an aldehyde having high linear selectivity is introduced into the reaction system. Can be generated.

  The amount of the bidentate organophosphorus compound is not particularly limited, and can be arbitrarily set so as to obtain desirable results for reaction results, catalyst activity, catalyst stability, etc. Is 0.1 mol or more, preferably 0.5 mol or more, more preferably 1 mol or more, usually 500 mol or less, preferably 100 mol or less, more preferably 50 mol or less per mol of rhodium compound. .

[Catalyst for selective hydrogenation reaction of aldehyde]
<Transition metal compounds for hydrogenation catalysts>
In the present invention, together with the rhodium compound and the bidentate organophosphorus compound, as a catalyst for selective hydrogenation reaction of aldehyde, groups 8 to 10 of the periodic table other than rhodium (according to IUPAC inorganic chemical nomenclature revised version (1998)) And a compound containing one or more transition metals selected from the group consisting of transition metals belonging to).

  Specific examples of the transition metal compound for the hydrogenation catalyst include iron compounds, ruthenium compounds, osmium compounds, cobalt compounds, iridium compounds, nickel compounds, palladium compounds, and platinum compounds, among which ruthenium compounds and iridium compounds. Compounds, palladium compounds and platinum compounds are preferred, and ruthenium compounds are particularly preferred.

  The form of these compounds is arbitrary, but specific examples include acetates of the above transition metals, acetylacetonate compounds, halides, sulfates, nitrates, organic salts, inorganic salts, alkene coordination compounds, amine coordination compounds. Pyridine coordination compounds, carbon monoxide coordination compounds, phosphine coordination compounds, phosphite coordination compounds, and the like.

Specific examples of transition metal compounds for hydrogenation catalysts are listed as iron compounds such as Fe (OAc) ₂ , Fe (acac) ₃ , FeCl ₂ , Fe (NO ₃ ) _{3 and the} like. Ruthenium compounds include RuCl ₃ , RuBr ₃ , RuI ₃ , Ru (OAc) ₃ , Ru (acac) ₃ , RuCl ₂ (PPh ₃ ) ₃ , RuCl ₂ (CO) ₂ (PPh ₃ ) ₂ , RuH ₂ (CO ) (PPh ₃ ) ₃ etc., CpRuCl (PPh ₃ ) ₂ , Cp ^* RuCl ₂ polynuclear, Cp ^* Ru (cod) Cl, Ru (cod) Cl ₂ polynuclear, Ru (benzene) Cl ₂ binuclear, Ru (P-cymene) Cl ₂ dinuclear body and the like. Examples of the osmium compound include OsCl ₃ and Os (OAc) ₃ . Examples of the cobalt compound include Co (OAc) ₂ , Co (acac) ₂ , CoBr ₂ , and Co (NO ₃ ) ₂ . Examples of the iridium compound include IrCl ₃ , Ir (OAc) ₃ , and [IrCl (cod)] ₂ . Examples of the nickel compound include NiCl ₂ , NiBr ₂ , Ni (NO ₃ ) ₂ , NiSO ₄ , Ni (cod) ₂ , NiCl ₂ (PPh ₃ ) _{3 and the} like. Examples of the palladium compound include PdCl ₂ , PdCl ₂ (cod), PdCl ₂ (PPh ₃ ) ₂ , Pd (PPh ₃ ) ₄ , Pd ₂ (dba) ₃ , K ₂ PdCl ₄ , PdCl ₂ (CH ₃ CN) ₂ , Pd (NO ₃ ) ₂ , Pd (OAc) ₂ , PdSO ₄ , Pd (acac) _{2 and the} like can be mentioned. Platinum compounds include Pt (acac) ₂ , PtCl ₂ (cod), PtCl ₂ (CH ₃ CN) ₂ , PtCl ₂ (PhCN) ₂ , Pt (PPh ₃ ) ₄ , K ₂ PtCl ₄ , Na ₂ PtCl ₆ , H ₂ PtCl ₆ is mentioned. In the above examples, cod is 1,5-cyclooctadiene, dba is dibenzylideneacetone, acac is acetylacetonate, Ac is an acetyl group, Ph is a phenyl group, and Cp is cyclopentadienyl. Cp ^* represents a pentamethylcyclopentadienyl group.

  The type of the transition metal compound for the hydrogenation catalyst is not particularly limited, and may be any of a monomer, a dimer, and a multimer higher than a trimer as long as it is an active metal complex type. Examples of the transition metal compound for the hydrogenation catalyst include a halide compound, and particularly preferably a chloride compound.

  The amount of the transition metal compound for the hydrogenation catalyst is not particularly limited, but the relationship between the rate of aldehyde formation by the hydroformylation reaction catalyst described above and the rate of aldehyde hydrogenation reaction by the selective hydrogenation reaction catalyst, It is selected from the viewpoint of economy. Considering the instability of the aldehyde, it is preferable that the aldehyde generated in the reaction system is hydrogenated relatively quickly. From this viewpoint, the transition for the hydrogenation catalyst relative to the amount of rhodium used as the catalyst for the hydroformylation reaction The use ratio of the metal compound in terms of transition metal is usually 0.01 mol times or more, preferably 0.1 mol times or more, more preferably 1 mol times or more, and usually 1000 mol times or less, preferably 100 mol times or less. More preferably, it is 10 mole times or less.

<Ligand>
In the present invention, the above-mentioned various transition metal compounds for hydrogenation catalysts can be arbitrarily used as the catalyst for selective hydrogenation reaction of aldehyde, but the reaction system can be used without hydrogenating the olefinic compound as a raw material. In order to selectively hydrogenate only the aldehyde produced in step 1, the central metal of the selective hydrogenation reaction catalyst contains a ligand containing an organic group represented by the following general formula (I) during the reaction Is preferably coordinated.

-XH (I)
(In the formula, X represents a divalent linking group containing a hetero atom and bonded to a hydrogen atom at the hetero atom.)

  The hetero atom of X in the general formula (I) is not particularly limited as long as it is an atom other than a carbon atom and a hydrogen atom and can form two or more chemically stable bonds. Or an oxygen atom is preferable, and a nitrogen atom is particularly preferable.

  Moreover, as a structural characteristic of the ligand containing the organic group represented by the general formula (I), the ligand is a periodic table group 8-10 transition metal other than rhodium of the transition metal compound for hydrogenation catalyst. When coordinated to, it is preferred that the heteroatom is or can be located within 4 cm, preferably within 3 mm from the center of the transition metal. This is due to the following reasons.

  Usually, the carbon atom of the carbonyl group of the aldehyde has a weak positive charge and the oxygen atom has a weak negative charge, but a catalytically constructed state in which a negatively charged hydrogen atom and a positively charged hydrogen atom are close to each other. Then, the carbonyl group can be selectively hydrogenated by electrostatic affinity. That is, when the hydrogenation reaction proceeds in a periodic table group 8-10 transition metal complex having a ligand containing an organic group represented by the general formula (I), rhodium is excluded as shown below. The hydrogen atom bonded to the group 8-10 transition metal M of the periodic table is negatively charged, and the hydrogen atom bonded to the heteroatom Q contained in the ligand forms a positively charged active species. Thus, the carbonyl group of the aldehyde approaches as it is attracted by electrostatic force, and selective hydrogenation proceeds. In this case, if the distance between the metal center M and the heteroatom Q is closer, the carbonyl group C═O can be more efficiently attracted, and more selective hydrogenation of the aldehyde RC (═O) H proceeds. It becomes.

(In the above formula, M represents a group 8-10 transition metal in the periodic table excluding rhodium, Q represents a hetero atom in a ligand such as a nitrogen atom or an oxygen atom. R represents a monovalent organic group. .)

Incidentally, after passing the hydrogen atom bonded to the heteroatom Q to the aldehyde RC (═O) H, an unshared electron pair remains on the heteroatom Q. Usually, the unshared electron pair is represented by the metal center M or It stabilizes by bonding to adjacent carbon, or it is stabilized in a state where it is held on the heteroatom Q as it is. When the hydrogen molecule is coordinated to the metal center M again, the active species is regenerated through hetero-cleavage of hydrogen-hydrogen bonds (cleavage to proton: H ⁺ and hydride: H ⁻ ).

  The following A-1 to A-68 and the like can be mentioned as specific structures of the ligand containing the organic group represented by the general formula (I) suitable for the present invention.

  Among the ligands described above, in particular, it has at least one nitrogen atom as a hetero atom, and the nitrogen atom coordinates to Group 8-10 transition metal of the periodic table excluding rhodium of the transition metal compound for hydrogenation catalyst. A ligand having a structure in which at least one hydrogen atom is bonded to the nitrogen atom is preferable. That is, the ligand is an amine ligand having at least one N—H bond, and is preferably represented by the following general formula (i).

NHR ^A R ^B (i)
(In the formula, R ^A represents a hydrogen atom or a monovalent organic group which may have a substituent, and R ^B represents a monovalent organic group which may have a substituent.)

  Specific examples of such an amine ligand include A-9 to A-68 of the exemplified ligand.

  Among these ligands, in addition to coordinating to the Group 8-10 transition metal of the periodic table excluding rhodium of the transition metal compound for hydrogenation catalyst with a nitrogen atom, the ligand is further bonded to the transition metal at one or more bonding points. It further has a structure of a so-called bidentate or more multidentate ligand that coordinates, that is, coordinates at two or more bonding points to the transition metal of the transition metal compound for a hydrogenation catalyst. preferable.

  In general, ligands that bind by coordinating an unshared electron pair to a metal center, such as amine ligands and organophosphorus ligands, have a dissociation equilibrium, and have a high temperature under reaction conditions. Under the conditions, ligand coordination and dissociation occur at a high rate. As in the present invention, an organophosphorus compound is used as a rhodium ligand for a hydroformylation reaction, and an amine compound is used as a ligand for a Group 8-10 transition metal excluding rhodium for a hydrogenation reaction. When used, the ligand may be dissociated from each metal, and ligand exchange may occur. Such ligand exchange causes a decrease in the desired reactivity of each metal, and therefore ligand exchange should be suppressed as much as possible. Therefore, it is desirable that the amine ligand has a multidentate structure and is strongly coordinated to the metal center of the hydrogenation reaction catalyst.

  Examples of the bonding point other than the nitrogen atom of the amine ligand include a phosphorus atom, an oxygen atom, a sulfur atom, a carbon atom, a silicon atom, and other nitrogen atoms. Specific examples of the amine ligand having such a preferred multidentate ligand structure include A-26 to A-68 of the exemplified ligand.

  Such a ligand may be used individually by 1 type, and may use 2 or more types together.

  The amount of the above-mentioned ligand used is not particularly limited, but is usually 0.1 mol times or more, preferably 0.5 mol times or more, more preferably as a ratio to the above-mentioned transition metal compound for hydrogenation catalyst. Is 1 mol times or more, usually 100 mol times or less, preferably 10 mol times or less, more preferably 5 mol times or less.

<Method for preparing catalyst>
The catalyst for selective hydrogenation reaction of aldehyde can be prepared in advance in a separately prepared catalyst preparation tank and then added to the reaction system, or the transition for hydrogenation catalyst which is the raw material for hydrogenation reaction. The catalyst may be prepared in the reaction system by individually adding the metal compound and the ligand to the reaction system. Further, after the reaction, the product system and the catalyst system may be separated, and the catalyst may be recycled to the reaction system again. In this case, depending on the degree of deterioration or disappearance of the catalyst, a transition metal compound for a hydrogenation catalyst, a ligand, and, if necessary, any or all of basic compounds described later are supplemented. It is desirable to do.

  In the preparation of a catalyst for selective hydrogenation reaction of aldehyde, when a halide compound which is a preferred transition metal compound for hydrogenation catalyst described above is used, the organic group represented by the general formula (I) is usually included. In the presence of a ligand, it is preferable to prepare an active species by adding a basic compound and removing a halide from the transition metal compound for a hydrogenation catalyst.

Here, 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 carbonates, alkaline metal bicarbonates such as LiHCO ₃ , NaHCO ₃ , KHCO ₃ , CsHCO ₃ , alkaline earth metal waters 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 groups such as triethylamine, triisopropylamine, tri-n-octylamine and 1,5-diazabicyclo [2.2.2] octane Other amines such as amines, piperidine, N-methylpiperidine, morpholine, 1,8-diazabicyclo [5.4.0] undecene-7 (abbreviation: DBU), 1,5-diazabicyclo [4.3.0 ] Cyclic amidine derivatives such as nonene-5 (abbreviation: DBN) Body, t- butyl imino-tris (dimethylamino phosphorane) _{(abbreviation: P 1 -t-Bu),} 1-t- butyl-4,4,4-tris (dimethylamino) -2,2-bis [tris ( Dimethylamino) phosphoranylideneamino] -2Λ ⁵ , 4Λ ⁵ -catenadi (phosphazene) (abbreviation: P ₄ -t-Bu) and the like, 2,8,9-triisopropyl-2,5,8,9 -Tetraaza-1-phosphabicyclo [3.3.3] undecane, 2,8,9-trimethyl-2,5,8,9-tetraaza-1-phosphabicyclo [3.3.3] undecane, etc. And proazaphosphatran base.

Among these bases, a relatively strong basic compound that reliably pulls out the halide from the transition metal compound for the hydrogenation catalyst is preferable. Alkali metal hydroxides such as LiOH, NaOH, KOH, and CsOH, Li ₂ CO ₃ Alkali metal carbonates such as Na ₂ CO ₃ , K ₂ CO ₃ , and Cs ₂ CO ₃ , alkali metal alkoxides such as methoxy sodium, ethoxy sodium, t-butoxy sodium, methoxy potassium, ethoxy potassium, and t-butoxy potassium Compounds are preferred.

  These basic compounds may be used individually by 1 type, and may use 2 or more types together.

  When these basic compounds are used, the amount of the basic compound used is not particularly limited, but is usually 0.1 mol times or more, preferably 0.5 mol relative to the transition metal compound for a hydrogenation catalyst. It is 1 time or more, more preferably 1 time or more, and usually 100 times or less, preferably 10 times or less, more preferably 5 times or less.

  When preparing a hydrogenation reaction catalyst using a halide compound as the transition metal compound for the hydrogenation catalyst and adding a basic compound to remove the halide, add each catalyst component individually to the reaction system. Rather than preparing the catalyst in the reaction system, it is preferable to prepare the catalyst in a separate catalyst preparation tank and then 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 hydroformylation reaction catalyst may undergo aldol condensation and partially disappear. Moreover, it is because the halide of a transition metal halide compound can often be a poisoning source of a catalyst for hydroformylation reaction.

  In addition, the method for contacting the hydroformylation reaction catalyst and the selective hydrogenation reaction catalyst described above is not particularly limited, but the rhodium compound and the bidentate organophosphorus compound are first mixed to obtain the catalyst precursor component for the hydroformylation reaction. Then, the catalyst component may be prepared by adding a hydrogenation reaction catalyst component, and includes a hydrogenation catalyst transition metal compound of the hydrogenation reaction catalyst and an organic group represented by the general formula (I). It is also possible to prepare a catalyst precursor component for a hydrogenation reaction by first mixing a ligand and optionally a basic compound first, and then add a catalyst component for a hydroformylation reaction to prepare a catalyst. Or you may prepare by mixing both catalyst components simultaneously.

  However, as described above, the hydroformylation reaction catalyst is preferably prepared in advance in a separately prepared catalyst preparation tank and then brought into contact with the hydroformylation reaction catalyst. At this time, as described above, when a halide compound is used as the transition metal compound for the hydrogenation catalyst, in order to prevent the halide from poisoning the hydroformylation reaction catalyst, a halide is prepared in advance in a separately prepared catalyst preparation tank. Is preferably removed. Specifically, as described above, a method of withdrawing a halide from a catalyst material for hydrogenation reaction in the form of a salt by reaction with a basic compound and removing it by a technique such as filtration, washing, decantation, etc. may be mentioned. It is done.

In addition, as can be said in general catalyst preparation, it is preferable that the catalyst is led to the reaction system in a dissolved state in order to quickly start the catalyst reaction in the reaction system. In this case, as a solvent for dissolving the catalyst, those described later can be used.
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.

[Olefinic compound]
The raw material olefinic compound applied to the method for producing an alcohol of the present invention is not particularly limited as long as it is a compound having 3 or more carbon atoms and a compound having at least one olefinic double bond in the molecule. Olefinic compounds substituted only by saturated hydrocarbon groups, olefinic compounds substituted by hydrocarbon groups containing unsaturated hydrocarbon groups, or olefinic compounds substituted by functional groups containing heteroatoms It can be applied to any olefinic compound such as a compound.

  Specific examples include olefinic compounds substituted only with saturated hydrocarbon groups: propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-nonene, 1-decene, 1 -Linear terminal olefinic hydrocarbons such as dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicocene, 1-docosene, etc., branched terminal olefinic carbons such as isobutene and 2-methyl-1-butene Hydrogen, 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-octene, etc. Linear internal olefinic hydrocarbons, octene obtained by dimerization of butenes, propylene, 1-butene and Terminal olefinic hydrocarbon or internal olefinic hydrocarbon mixtures olefin oligomer isomer mixtures, such as dimers - tetramers of lower olefins such as butene, and the like.

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

Of the above olefinic compounds, linear olefinic compounds having 3 or more carbon atoms are preferable, and linear terminal olefinic hydrocarbons having 3 or more carbon atoms are 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.

[solvent]
In the present invention, the reaction can be carried out in the presence or absence of a solvent. When a solvent is used, a preferable solvent is a hydroformylation catalyst component, a catalyst component for selective hydrogenation reaction of an aldehyde, and in some cases, at least a part of the above-mentioned basic compound and a raw material olefin compound. There is no particular limitation as long as it does not adversely affect the reaction activity or the selectivity of the reaction, but it is weak as a suitable ligand for the catalyst for selective hydrogenation reaction in the present invention. Since amine-based compounds exhibiting basicity are often used, it is preferable to use a neutral or alkaline solvent that can maintain the coordination power of the amine.

  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 Halogenated hydrocarbons such as methane and carbon tetrachloride, nitriles such as acetonitrile, propionitrile, and benzonitrile, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, t-butyl alcohol, n- Examples include alcohols such as pentanol, neopentyl alcohol, n-hexanol, 2-ethylhexanol, n-octanol, n-nonanol, and n-decanol. In addition, high boiling substances having a boiling point higher than that of the target alcohol, such as an acetal reactant or aldol condensate of an aldehyde generated as a by-product of this reaction, can be mentioned. These solvents may be used alone or in combination of two or more.

  In the reaction of the present invention, the target product is an alcohol, and a basic compound is often used in the preparation of a selective hydrogenation reaction catalyst. Therefore, a preferable solvent is an alcohol solvent from the viewpoint of solubility. it can. In particular, when the alcohol which is the object of this reaction is used as it is as an alcohol solvent, it can be an economically advantageous process.

  The amount of the solvent used is usually 5% by weight or more, preferably 10% by weight or more, usually 95% by weight or less, preferably 90% by weight or less, based on the total weight of the reaction medium.

[Reaction conditions]
Suitable reaction conditions in the alcohol production method of the present invention are as follows.

<Reaction pressure>
The reaction pressure formed by the sum of the vapor pressures of hydrogen partial pressure, carbon monoxide partial pressure, raw material, product, solvent, etc. is usually 0.01 MPa or more, preferably 0.1 MPa or more, more preferably 0.5 MPa or more. Usually, it is 30 MPa or less, preferably 20 MPa or less, more preferably 10 MPa or less.
If the reaction pressure is too low, there is a concern that the catalyst metal compound of the hydroformylation reaction catalyst and the selective hydrogenation reaction catalyst of the aldehyde may be deactivated and metallized, and the hydroformylation reaction catalyst and the selective hydrogen of the aldehyde It is expected that the catalytic activity of the oxidization reaction catalyst is not sufficiently expressed and the alcohol yield is lowered. On the other hand, if it is too high, it is not preferable because the linear selectivity of the resulting alcohol tends to decrease.

  In particular, the hydrogen partial pressure is preferably 0.005 MPa or more, more preferably 0.01 MPa or more, preferably 20 MPa or less, more preferably 10 MPa or less. If the hydrogen partial pressure is too low, there is a concern about a decrease in reaction activity, and if it is too high, waste associated with the progress of the hydrogenation reaction of the raw material olefinic compound is expected.

  The carbon monoxide partial pressure is preferably 0.005 MPa or more, more preferably 0.01 MPa or more, preferably 15 MPa or less, more preferably 8 MPa or less. If the partial pressure of carbon monoxide is too low, there is concern about reduction of reaction activity, especially metalization of the catalyst for hydroformylation reaction. If it is too high, reduction of the linear selectivity of the resulting alcohol is expected. A significant decrease in activity of the catalyst is expected.

<Hydrogen / carbon monoxide molar ratio>
The molar ratio of hydrogen to carbon monoxide is 1:10 to 10: 1, more preferably 1: 2 to 8: 1, and still more preferably 1: 1 to 5: 1.

<Reaction temperature>
The reaction temperature is usually 80 ° C or higher, preferably 100 ° C or higher, more preferably 120 ° C or higher, and usually 300 ° C or lower, preferably 250 ° C or lower, more preferably 200 ° C or lower. That is, the reaction of the present invention is preferably carried out at a reaction temperature of 80 ° C. or higher. This is because carbon monoxide is strongly coordinated to the selective hydrogenation reaction catalyst under a low temperature condition, and the catalytic activity of the hydrogenation reaction is greatly reduced. By increasing the reaction temperature, the catalyst for selective hydrogenation reaction This is because it is necessary to make the conditions under which carbon monoxide can be dissociated by thermal energy. On the other hand, if the reaction temperature is too high, the linear selectivity of the resulting alcohol decreases, the disappearance of the ligand due to thermal decomposition, or the decomposition of the hydroformylation reaction catalyst or aldehyde selective hydrogenation reaction catalyst occurs. Deactivation is expected.

<Reaction method>
There is no restriction | limiting in particular as a reaction system of this invention, Any of a continuous type, a semi-continuous type, or a batch type operation can be easily implemented in a stirring type reaction vessel or a bubble column type reaction vessel.

<Product separation and recovery>
Separation of unreacted raw material olefinic compounds 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. Further, it can be carried out by a known method such as gas 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 or alcohol precursor aldehydes are obtained, it is more economical and desirable to recycle and reuse them in the reaction step. 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.
From the remaining liquid containing the separated catalyst, the group 8-10 transition metal of the periodic table excluding rhodium and rhodium which are catalyst components can be recovered by a known method. Alternatively, the catalyst can be reused by recycling the entire amount or a part of the residual liquid to the reaction step.

[Yield of alcohol]
Since the target product in the reaction of the present invention is alcohol, the yield of alcohol is preferably 60% or more, more preferably 70% or more.
In order to achieve an alcohol yield of 60% or more, basically, the conditions for sufficiently pushing out the reaction (that is, the conditions for converting almost all olefinic compound raw materials into products) can be achieved. For example, techniques such as increasing the catalyst concentration and increasing the residence time in the reaction zone can be mentioned. In addition, if reaction conditions suitable for alcohol production such as increasing a relatively high reaction temperature (for example, about 120 to 160 ° C.) or increasing a hydrogen partial pressure (for example, about 120 to 160 ° C./0.5 to 5 MPa) are adopted, The yield can be increased.

[Linear selectivity]
The object of the present invention is to produce an alcohol having a high linear selectivity. For this reason, the L / B ratio in the method for producing an alcohol of the present invention is not less than 5.7 (linear selectivity = 85%). In particular, it is preferably 9.0 (linear selectivity = 90%) or more. In order to realize such an L / B ratio, in the present invention, the hydroformylation reaction catalyst and the selective hydrogenation reaction catalyst for aldehyde are used in combination, for example, the carbon monoxide partial pressure is further hydroformylated. It is preferable to make it as low as possible within a range that does not adversely affect the catalytic activity of the reaction.

  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>
Three glass containers for catalyst preparation are prepared, and Cp ^* Ru (cod) Cl (19.) is used as a transition metal compound for hydrogenation catalyst as a catalyst raw material for selective hydrogenation reaction of aldehyde under nitrogen atmosphere in each glass container. 0 mg, 0.050 mmol), the ligand A-46 (11.5 mg, 0.050 mmol) as the ligand of the hydrogenation reaction catalyst, and t-butoxypotassium (5.6 mg, 0.050 mmol) as the basic compound ) Were added, and these were sequentially used as a glass container A (transition metal compound for hydrogenation catalyst), B (ligand), and C (basic compound).
Separately, Rh (acac) (CO) ₂ (5.2 mg, 0.020 mmol) as a rhodium compound for the hydroformylation reaction and hydroformylation were added to a 50 ml stainless steel autoclave containing a magnetic stirrer in a container. The bidentate organophosphorus compound L-11 (23.1 mg, 0.040 mmol) was weighed out as a ligand for the reaction catalyst.

  Next, isopropyl alcohol (0.5 ml) as a solvent is added to each of the glass containers A, B, and C in a nitrogen atmosphere to dissolve each component, and then the solution in the glass container A is added to the glass container B with a cannula. The solution was transferred to a glass container C with a cannula and stirred for 5 minutes. Further, isopropyl alcohol (0.5 ml) as a solvent was added to the autoclave under a nitrogen atmosphere, and the mixture was stirred for 5 minutes.

  Subsequently, the solution in the glass container C was transferred to an autoclave by a cannula, the inside of the glass container C was washed with isopropyl alcohol (2.0 ml), and the washing liquid was also transferred to the autoclave. Furthermore, 450.0 mg (1-decene: 2.06 mmol, n-dodecane) of a mixed solution (2/1 mol / mol) of 1-decene (reaction raw material) and n-dodecane (internal standard substance for GC analysis) was added to the autoclave. 1.03 mmol) was added. After sealing the autoclave, a hydrogen / carbon monoxide mixed gas (mixing ratio: 3/1) is rapidly introduced to 4.0 MPa from the gas introduction valve, and the temperature is increased to 160 ° C. in an electric furnace with stirring at 800 rpm with a magnetic stirrer. The reaction was allowed to proceed for 12.5 hours while heating.

After completion of the reaction, the reaction mixture was cooled to room temperature, the residual gas was released, and the reaction results were analyzed by NMR and gas chromatography.
As a result, the undecanal yield was 0% and the undecanol yield was 61.1%. The ratio (L / B ratio) of linear alcohol (1-undecanol) to branched alcohol (2-methyl-1-decanol etc.) in undecanol is 12.6 (linear selectivity = 92.6%). Met.

<Example 2>
The reaction was carried out in the same manner except that the reaction time in Example 1 was changed to 24 hours.
As a result, the undecanal yield was 0% and the undecanol yield was 80.3%. In addition, the ratio (L / B ratio) of linear alcohol (1-undecanol) to branched alcohol (2-methyl-1-decanol etc.) in undecanol is 11.2 (linear selectivity = 91.8%) Met.

<Example 3>
The reaction was carried out in the same manner except that the reaction time in Example 1 was changed to 24 hours and the solvent was changed from isopropyl alcohol to toluene.
As a result, the undecanal yield was 2.7% and the undecanol yield was 35.6%. Further, the ratio (L / B ratio) of the linear alcohol (1-undecanol) to the branched alcohol (such as 2-methyl-1-decanol) in undecanol is 17.7 (linear selectivity = 94.7%). Met.

<Example 4>
The reaction was carried out in the same manner except that the reaction temperature in Example 1 was changed to 120 ° C.
As a result, the undecanal yield was 25.7% and the undecanol yield was 42.8%. In addition, the ratio (L / B ratio) of linear alcohol (1-undecanol) to branched alcohol (2-methyl-1-decanol etc.) in undecanol is 21.2 (linear selectivity = 95.5%). Met.

<Example 5>
The reaction was conducted in the same manner except that the reaction temperature in Example 1 was changed to 70 ° C.
As a result, the undecanal yield was 30.5% and the undecanol yield was 2.5%. The ratio (L / B ratio) of linear alcohol (1-undecanol) to branched alcohol (2-methyl-1-decanol, etc.) in undecanol is 24.0 (linear selectivity = 96.0%). Met.

<Example 6>
An aldehyde selective hydrogenation reaction catalyst (27.3 mg, 0.025 mmol) having the above-described ligand A-2 as a ligand is weighed into a glass container under a nitrogen atmosphere, and isopropyl alcohol as a solvent. (1.0 ml) was added under a nitrogen atmosphere and stirred for 5 minutes.

Separately, Rh (acac) (CO) ₂ (5.2 mg, 0.020 mmol) as a rhodium compound for the hydroformylation reaction and hydroformylation were added to a 50 ml stainless steel autoclave containing a magnetic stirrer in a container. The bidentate organophosphorus compound L-11 (23.1 mg, 0.040 mmol) was weighed as a ligand for the reaction catalyst, and isopropyl alcohol (1.0 ml) as a solvent was added under a nitrogen atmosphere and stirred for 5 minutes. did.

  The solution in the glass container was transferred to an autoclave with a cannula, the inside of the glass container was washed with isopropyl alcohol (0.2 ml), and the washing was also transferred to the autoclave. Furthermore, 450.0 mg (1-decene: 2.06 mmol, n-dodecane) of a mixed solution (2/1 mol / mol) of 1-decene (reaction raw material) and n-dodecane (internal standard substance for GC analysis) was added to the autoclave. 1.03 mmol) was added. After sealing the autoclave, a hydrogen / carbon monoxide mixed gas (mixing ratio: 1/1) is rapidly introduced to 2.0 MPa from the gas introduction valve, and the temperature is increased to 160 ° C. in an electric furnace while stirring at 800 rpm with a magnetic stirrer. The reaction was carried out for 1.0 hour while heating.

After completion of the reaction, the reaction mixture was cooled to room temperature, the residual gas was released, and the reaction results were analyzed by NMR and gas chromatography.
As a result, the undecanal yield was 0% and the undecanol yield was 87.3%. In addition, the ratio (L / B ratio) of the linear alcohol (1-undecanol) to the branched alcohol (such as 2-methyl-1-decanol) in undecanol was 17 (linear selectivity = 94.4%). It was.

<Example 7>
The reaction was performed in the same manner except that the reaction temperature in Example 6 was changed to 120 ° C., the reaction time was changed to 12.5 hours, and the solvent was changed from isopropyl alcohol to N, N-dimethylacetamide.
As a result, the undecanal yield was 1.0% and the undecanol yield was 92.7%. In addition, the ratio (L / B ratio) of linear alcohol (1-undecanol) to branched alcohol (2-methyl-1-decanol etc.) in undecanol was 19 (linear selectivity = 95.0%). It was.

<Example 8>
In Example 6, a catalyst for selective hydrogenation reaction of an aldehyde having the following structure (31.0 mg, 0.050 mmol) having the ligand A-7 as a ligand was used, and as a basic compound The reaction was carried out in the same manner except that potassium t-butoxy (5.6 mg, 0.050 mmol) was added to the glass container.

  As a result, the undecanal yield was 30.0% and the undecanol yield was 31.7%. Moreover, the ratio (L / B ratio) of the linear alcohol (1-undecanol) to the branched alcohol (2-methyl-1-decanol etc.) in undecanol was 18 (linear selectivity = 94.7%). It was.

<Example 9>
In Example 6, a catalyst for selective hydrogenation reaction of aldehyde having the following structure (27.5 mg, 0.050 mmol) having the ligand A-68 as a ligand was used, and as a basic compound The reaction was carried out in the same manner except that potassium t-butoxy (5.6 mg, 0.050 mmol) was added to the glass container.

  As a result, the undecanal yield was 4.2% and the undecanol yield was 40.6%. In addition, the ratio (L / B ratio) of linear alcohol (1-undecanol) to branched alcohol (2-methyl-1-decanol, etc.) in undecanol was 25 (linear selectivity = 96.2%). It was.

<Example 10>
The catalyst for selective hydrogenation reaction of aldehyde used in Example 6 (152.6 mg, 0.141 mmol) was weighed into a glass container under a nitrogen atmosphere, and N, N-dimethylacetamide (8.9 ml) as a solvent was nitrogen. Added under atmosphere and stirred for 5 minutes.
Also, in a separate glass container, Rh (acac) (CO) ₂ (29.0 mg, 0.112 mmol) as a rhodium compound for the hydroformylation reaction catalyst and the bidentate organic as a ligand for the hydroformylation reaction catalyst. Phosphorus compound L-11 (130.3 mg, 0.225 mmol) was weighed, N, N-dimethylacetamide (8.9 ml) as a solvent was added under a nitrogen atmosphere, and the mixture was stirred for 5 minutes.

  Using a syringe, the solution containing the hydrogenation reaction catalyst is transferred to a glass container containing the hydroformylation reaction catalyst, and n-dodecane (0.607 g, 3.565 mmol), which is an internal standard substance for GC analysis. Was added. The obtained solution was charged in a separately prepared 50 ml stainless steel autoclave in a nitrogen atmosphere, and propylene (1.17 g, 27.804 mmol) as a reaction raw material was injected under pressure, and then the autoclave was sealed.

  After raising the temperature of the autoclave to 140 ° C., the reaction was carried out by injecting a mixed gas of hydrogen and carbon monoxide (mixing ratio: hydrogen / carbon monoxide = 1/1) so that the system pressure was 4.0 MPa. Started. The mixed gas was introduced through the feed tube attached in the autoclave while being bubbled into the reaction solution, and the reaction solution was stirred with a magnetic stirrer in advance in the autoclave. . Further, when the gas is consumed in the reactor and the internal pressure decreases, the mixed gas is automatically supplied from the accumulator through the secondary pressure regulator so that the system internal pressure can be constantly maintained at 4.0 MPa. did. After the reaction for 3.5 hours, the autoclave was cooled to room temperature, the residual gas was released, and the reaction results were analyzed by gas chromatography.

  As a result, the butanal yield was 60.4% and the butanol yield was 28.7%. The ratio of linear alcohol (n-butanol) to branched alcohol (isobutanol) in butanol (L / B ratio) was 7.1 (linear selectivity = 87.7%).

<Example 11>
In Example 10, the reaction was performed in the same manner except that the reaction temperature was changed to 160 ° C.
As a result, the butanal yield was 1.6% and the butanol yield was 82.4%. Further, the ratio (L / B ratio) of the linear alcohol (n-butanol) to the branched alcohol (isobutanol) in butanol was 10.4 (linear selectivity = 91.2%).

<Comparative Example 1>
The reaction was conducted in the same manner as in Example 4 except that the catalyst component for aldehyde hydrogenation reaction, that is, Cp ^* Ru (cod) Cl, ligand A-46, and potassium t-butoxy were not used.
As a result, the undecanal yield was 54.0% and the undecanol yield was 7.6%. The ratio (L / B ratio) of linear alcohol (1-undecanol) to branched alcohol (such as 2-methyl-1-decanol) in undecanol is 8.5 (linear selectivity = 89.5%). Met.

  From the above results, rhodium compounds and bidentate organophosphorus compounds as hydroformylation reaction catalysts, transition metal compounds for hydrogenation catalysts as selective hydrogenation reaction catalysts for aldehydes, more preferably specific ligands It can be seen that according to the method for producing an alcohol of the present invention using an alcohol, the alcohol can be produced with high linear selectivity.

Claims (7)

  An alcohol is produced by reacting an olefinic compound with hydrogen and carbon monoxide in the presence of a rhodium compound, a bidentate organophosphorus compound, and a compound containing at least one group 8-10 transition metal of the periodic table excluding rhodium. A method for producing alcohol characterized by the above.   The method for producing an alcohol according to claim 1, wherein the Group 8-10 transition metal in the periodic table excluding the rhodium is a transition metal selected from the group consisting of ruthenium, iridium, palladium, and platinum. The compound containing at least one group 8-10 transition metal of the periodic table excluding the rhodium has a ligand containing an organic group represented by the following general formula (I). The manufacturing method of alcohol of description.
-XH (I)
(In the formula, X represents a linking group containing a hetero atom, and the hetero atom is bonded to a hydrogen atom.)   The ligand has at least one nitrogen atom, and the nitrogen atom is coordinated to a Group 8-10 transition metal excluding the rhodium, and at least one hydrogen atom is bonded to the nitrogen atom. The method for producing alcohol according to claim 3, wherein the alcohol is produced.   The alcohol according to claim 4, wherein the ligand is a multidentate ligand coordinated to a group 8-10 transition metal of the periodic table excluding the rhodium at two or more bonding points. Manufacturing method.   The method for producing an alcohol according to any one of claims 1 to 5, wherein the reaction is carried out at 80 ° C or higher.   The method for producing an alcohol according to claim 2, wherein the Group 8-10 transition metal in the periodic table excluding the rhodium is ruthenium.