JP2009096752A - Method for producing alcohol - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing an alcohol in high yield and high catalyst efficiency from an ester or a lactone, under a relatively mild condition and by using an easily synthesized catalyst. <P>SOLUTION: This method for producing the alcohols is provided by hydrogen reduction of the ester or lactone by using the catalyst consisting of a ruthenium (Ru) compound, a monophosphine and an amine. The above reaction is preferably performed in the presence of a base or a reducing agent. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a method for producing an alcohol by reducing an ester or lactone with hydrogen.

  The method of reducing esters and lactones to obtain alcohols is important in chemical synthesis. As a method of obtaining an alcohol by hydrogenating an ester or a lactone, a method for producing an alcohol by hydrogenation of an ester in a liquid phase using a ruthenium complex composed of a ruthenium compound and an organic phosphine compound (for example, a patent Documents 1 to 3 and Non-Patent Documents 1 to 3), a method for producing alcohols by a hydrogenation reaction using a ruthenium compound and a ruthenium complex having a bidentate or tetradentate aminophosphine as a ligand (for example, Patent Document 4) Many methods have been proposed.

JP 2001-247499 A JP 2004-300131 A JP 2005-524704 A WO2006 / 106483 WO2006 / 106484 J. et al. Chem. Soc. Chem. Commun. , 1980, 783 J. et al. Mol. Catal. A, 2002, 178, 105 Angew. Chem. Int. Ed. , 2006, 45, 1113

  However, the hydrogenation reactions described in Patent Documents 1 to 3 and Non-Patent Documents 1 to 3 do not satisfy both yield and catalyst efficiency, and are not economically advantageous. In the ester hydrogenation reactions described in Patent Document 2 and Non-Patent Document 1, a fluorinated alcohol is used as a solvent, and there are problems in terms of economy and environmental burden. In addition, the method described in Non-Patent Document 2 has problems in economic efficiency and operability from an industrial viewpoint because a high temperature of 180 to 200 ° C. is necessary. Furthermore, the method described in Non-Patent Document 3 employs 1,4-dioxane as a reaction solvent, which is economically disadvantageous and is feared to affect the human body. Since the methods described in Patent Documents 4 and 5 use a ruthenium complex having an asymmetric ligand having a phosphorus atom and a nitrogen atom in the same molecule, the synthesis of the ligand may be complicated. .

  Accordingly, an object of the present invention is to provide an ester or lactone that can easily produce an alcohol from an ester or lactone with a high yield and high catalytic efficiency under a relatively mild condition using a catalyst that is easy to produce. Is to provide a method for producing alcohols from

  As a result of intensive studies in view of the above circumstances, the present inventors have used a catalyst comprising a ruthenium compound, a monophosphine compound and an amine compound, thereby producing a corresponding alcohol from an ester or lactone in a high yield and a high catalyst. It discovered that it manufactured with efficiency and came to complete this invention.

That is, this invention relates to the following 1-7.
1. A method for producing an alcohol, characterized in that an ester or lactone is reduced with hydrogen in the presence of a catalyst comprising the following components (i), (ii), and (iii).
(I) ruthenium compound (ii) monophosphine (iii) amines

2. 2. The alcohol according to 1 above, wherein the catalyst comprising (i) a ruthenium compound, (ii) monophosphine, and (iii) an amine is a ruthenium-monophosphine complex represented by the following general formula (1) and an amine. Manufacturing method.

(Wherein, X ¹ and X ² each independently represent a hydrogen atom, a halogen atom, an alkoxy group, a hydroxy group, or an acyloxy group, L _P represents a monophosphine, and m is 3 or 4).

3. 2. The method for producing an alcohol according to 1 above, wherein the catalyst comprising (i) a ruthenium compound, (ii) monophosphine, and (iii) an amine is a ruthenium complex represented by the following general formula (2).

(In the formula, X ¹ and X ² each independently represent a hydrogen atom, a halogen atom, an alkoxy group, a hydroxy group, or an acyloxy group, L _P represents a monophosphine, and L _N represents a bidentate coordination group. Represents amines.)

4). The manufacturing method in any one of said 1-3 whose amine is diamine.
5). The manufacturing method in any one of said 1-4 performed in presence of an additive.
6). 6. The production method according to 5 above, wherein the additive is a base or a reducing agent.
7). 7. The production method according to 5 or 6 above, wherein a mixture obtained by mixing and stirring an additive and a catalyst comprising (i) a ruthenium compound, (ii) monophosphine, and (iii) an amine in advance is used as a catalyst.

  According to the production method of the present invention, it is possible to produce alcohols from esters and lactones with high yield and high catalytic efficiency at industrially advantageous low hydrogen pressure and reaction temperature. Further, by suppressing the pressure and temperature, side reactions such as reduction of the aromatic ring can be suppressed. In addition, when using solvents, there is no need for solvents that are problematic in terms of environment and health, and since the ligands used are relatively inexpensive and easily available reagents, they are economically useful. It is a simple manufacturing method.

Hereinafter, the present invention will be described in detail.
In the present invention, ester or lactone is used as a raw material hydrogenation substrate. Examples of the ester used as the hydrogenation substrate include aliphatic carboxylic acid esters and aromatic carboxylic acid esters. The ester may be derived from a monocarboxylic acid or a polycarboxylic acid. These esters and lactones may be substituted with any substituent that does not adversely affect the hydrogenation method of the present invention.

  Examples of the esters used as the hydrogenation substrate in the present invention include, for example, the following aliphatic carboxylic acid or aromatic carboxylic acid methyl ester, ethyl ester, propyl ester, butyl ester, hexyl ester, octyl ester, etc. -30, preferably 1-20 carbon atoms, more preferably 1-10 carbon atoms, still more preferably alkyl esters composed of linear, branched or cyclic alkyl groups having 1-5 carbon atoms; phenyl esters, biphenyl esters Monocyclic, polycyclic, or condensed cyclic having 6 to 40 carbon atoms, such as naphthyl ester, preferably 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and further preferably 6 to 12 carbon atoms. Aryl ester composed of aryl group; 7 to 40 carbon atoms such as benzyl ester and 1-phenethyl ester Preferably 7 to 20 carbon atoms, more preferably an aralkyl esters consisting of an aralkyl group having 7 to 15 carbon atoms. Preferable esters include alkyl esters having 1 to 5 carbon atoms such as methyl ester and ethyl ester.

  The aliphatic carboxylic acid constituting the ester of the raw material hydrogenation substrate in the method of the present invention may have a substituent having 2 to 30 carbon atoms, preferably 2 to 20 carbon atoms, more preferably carbon number. 2-15 mono- or polycarboxylic acids may be mentioned, and the aliphatic group in the aliphatic carboxylic acid may be linear or cyclic, and may be either saturated or unsaturated. . Specifically, acetic acid, propionic acid, butyric acid, valeric acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, dodecanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, oxalic acid Propanedicarboxylic acid, butanedicarboxylic acid, hexanedicarboxylic acid, sebacic acid, acrylic acid, cyclopentanecarboxylic acid, cyclohexanecarboxylic acid, cyclopentenecarboxylic acid, cyclohexenecarboxylic acid and the like.

  In addition, these aliphatic carboxylic acids may be substituted with a substituent, such as an alkyl group, an alkoxy group, a halogen atom (fluorine, chlorine, bromine, iodine), an amino group, an aryl group, a heteroaryl group. Aralkyl group, hydroxyl group and the like.

  Examples of the alkyl group as the substituent of the aliphatic carboxylic acid include a linear, branched or cyclic alkyl group, such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and an isobutyl group. Group, s-butyl group, t-butyl group, n-pentyl group, n-hexyl group, n-octyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group and the like.

  In addition, the alkoxy group as the substituent of the aliphatic carboxylic acid may be a linear or branched chain or cyclic (cyclic) having 1 to 20 carbon atoms, preferably 1 to 15 carbon atoms, more preferably 1 to 10 carbon atoms. The number of carbon atoms is 3 or more.), For example, a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, and an s-butoxy group. , T-butoxy group, n-pentyloxy group, n-hexyloxy group, n-octyloxy group, cyclopentyloxy group, cyclohexyloxy group and the like.

  Furthermore, as an amino group as a substituent of the aliphatic carboxylic acid, an amino group; N-methylamino group, N, N-dimethylamino group, N, N-diethylamino group, N, N-diisopropylamino group, N- Mono- or dialkylamino groups such as cyclohexylamino group; mono- or diarylamino groups such as N-phenylamino group, N, N-diphenylamino group, N-naphthylamino group, N-naphthyl-N-phenylamino group; N- Examples thereof include mono- or diaralkylamino groups such as benzylamino group and N, N-dibenzylamino group. In addition, the amino group is Green, Peter G. M.M. Utz, “Protecting Groups in Organic Synthesis 2nd Edition”, John Willie and Sons, 1991 (Theodora W. Greene, Peter GM Wuts, PROTECTING GROUP IN ORGANIC SYNTHE SED, ED ) May be an amino group having a general protecting group described in (4), and examples of the protecting group include t-butoxycarbonyl (Boc), benzyloxycarbonyl (Cbz), acetyl (Ac), and p-toluene. Examples include sulfonyl (Ts) and t-butyldimethylsilyl (TBS).

  In addition, examples of the aryl group as the substituent of the aliphatic carboxylic acid include a phenyl group, a naphthyl group, a biphenyl group, and the like. These aryl groups include an alkyl group, an alkoxy group, a halogen atom, an amino group, and the like as described above. May be substituted.

  Furthermore, the heteroaryl group as a substituent of the aliphatic carboxylic acid has, for example, 2 to 15 carbon atoms and at least one hetero atom, preferably 1 to 3 hetero atoms such as nitrogen atom, oxygen atom and sulfur atom. Examples thereof include a 5- to 8-membered, preferably 5- or 6-membered monocyclic heteroaryl group, polycyclic or condensed ring heteroaryl group containing an atom. Specifically, for example, furyl group, thienyl group, pyridyl group, pyrimidinyl group, pyrazinyl group, pyridazinyl group, pyrazolyl group, imidazolyl group, oxazolyl group, thiazolyl group, benzofuryl group, benzothienyl group, quinolyl group, isoquinolyl group, A quinoxalinyl group, a phthalazinyl group, a quinazolinyl group, a naphthyridinyl group, a cinnolinyl group, a benzoimidazolyl group, a benzoxazolyl group, a benzothiazolyl group, and the like can be given.

  Examples of the aralkyl group as the substituent for the aliphatic carboxylic acid include a benzyl group and a 1-phenethyl group.

  The aromatic carboxylic acid constituting the ester of the raw material hydrogenation substrate in the method of the present invention is monocyclic or polycyclic having 6 to 36 carbon atoms, preferably 6 to 18 carbon atoms, more preferably 6 to 12 carbon atoms. Or an aryl group of the formula or fused ring; or 1 to 4, preferably 1 to 3, more preferably 1 to 2 containing a hetero atom consisting of a nitrogen atom, an oxygen atom or a sulfur atom. Examples thereof include aromatic carboxylic acids having a monocyclic, polycyclic or condensed cyclic heteroaryl group having an 8-membered, preferably 5-8-membered ring. Specific examples thereof include benzoic acid and naphthalene. Examples thereof include carboxylic acid, pyridine carboxylic acid, quinoline carboxylic acid, furan carboxylic acid, and thiophene carboxylic acid.

  These aromatic carboxylic acids may be substituted with an alkyl group, an alkoxy group, a halogen atom, an amino group, an aryl group, a heteroaryl group, an aralkyl group, a hydroxyl group and the like as described above.

  On the other hand, the lactones used in the present invention include β-lactone, γ-lactone, δ-lactone, etc., and these lactones are alkyl groups, alkoxy groups, halogen atoms, amino groups, aryls as described above. It may be substituted with a group, heteroaryl group, aralkyl group, hydroxyl group or the like. Further, it may have a bicyclo ring structure or an aromatic ring and a condensed ring structure.

Next, the catalyst used in the present invention will be described.
The component constituting the catalyst of the present invention comprises (i) a ruthenium compound, (ii) monophosphine, and (iii) amines. These components (i), (ii) and (iii) may consist of (A) a mixture of three compounds, each of which is a simple compound, or (B) components (i) and (ii). ) And amines of component (iii) or (C) complexes of components (i), (ii), and (iii), but (B) and (C ) Is preferred. As the complex composed of the components (i) and (ii), the complex represented by the general formula (1) is preferable, and as the complex composed of the components (i), (ii) and (iii), The complex represented by the general formula (2) is preferable.

Specific examples of the ruthenium compound of the catalyst component (i) used in the present invention include RuCl ₂ (DMSO) ₄ , RuCl ₃ .nH ₂ O, (cod) ₂ Ru (μ-OAc), (cod) ₂ Ru ( μ-O ₂ CCF ₃ ), (cod) Ru (η ² -O ₂ CCF ₃ ) ₂ , (cod) Ru (η ³ -methallyl) ₂ , Ru ₂ (CO) ₆ (C ₈ H ₈ ) , RuCl (CO) ₃ (C ₃ H ₅ ), Ru (C ₅ H ₅ ) ₂ , Ru (C ₅ H ₅ ) (CH ₃ COC ₅ H ₄ ), Ru (C ₅ H ₅ ) (C ₅ H _{4 CH 3), [Ru (cod} ) Cl 2] n, [Ru ( _{benzene) Cl 2] 2, [Ru} ( _{benzene) Br 2] 2, [Ru} ( _{benzene) I 2] 2, [Ru} (p- cymene _{) Cl 2] 2, [Ru} (p- _{cymene) Br 2] 2, [Ru} (p- _{cymene) I 2] 2, [Ru} ( mesitylene Cl _{2] 2,} [Ru (mesitylene) Br _{2] 2,} include [Ru (mesitylene) I _{2] 2} and the like. In the examples, DMSO represents dimethyl sulfoxide, cod represents 1,5-cyclooctadiene, and Ac represents acetyl (hereinafter the same).

Subsequently, the monophosphine component (ii) of the catalyst used in the present invention will be described.
Examples of the monophosphine used in the present invention include monodentate monophosphines represented by the following general formula (3).

Wherein R ¹ , R ² and R ³ are each independently an alkyl group, an alkoxy group, an aryl group which may have a substituent, an aryloxy group which may have a substituent, or a substituent Represents an optionally substituted cycloalkyl group.)

In the above formula, the alkyl group represented by R ¹ , R ² and R ³ is a linear or branched alkyl having 1 to 20 carbon atoms, preferably 1 to 15 carbon atoms, more preferably 1 to 10 carbon atoms. Specific examples of preferred alkyl groups include, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, n- A pentyl group, n-hexyl group, n-octyl group, etc. are mentioned.

In the above formula, the alkoxy group represented by R ¹ , R ² and R ³ is a linear or branched chain having 1 to 20 carbon atoms, preferably 1 to 15 carbon atoms, more preferably 1 to 10 carbon atoms, or An alkoxy group composed of a cyclic alkyl group (having 3 or more carbon atoms in the case of a cyclic group) or an aryl group is exemplified. Preferred specific examples of the alkoxy group include, for example, a methoxy group, an ethoxy group, and an n-propoxy group. , Isopropoxy group, n-butoxy group, isobutoxy group, s-butoxy group, t-butoxy group, n-pentyloxy group, n-hexyloxy group, n-octyloxy group, cyclopentyloxy group, cyclohexyloxy group, etc. Can be mentioned.

In the above formula, the aryl group of the aryl group which may have a substituent represented by R ¹ , R ² and R ³ includes, for example, an aryl group having 6 to 14 carbon atoms, specifically, Examples thereof include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a biphenyl group, and a furyl group. Examples of the substituent for these aryl groups include alkyl groups, alkoxy groups, halogen atoms (fluorine, chlorine, bromine, iodine), aryl groups, and the like.

  Examples of the alkyl group as a substituent of the aryl group include linear or branched alkyl groups having 1 to 15 carbon atoms, preferably 1 to 10 carbon atoms, and more preferably 1 to 6 carbon atoms. Specific examples include, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, s-butyl group, isobutyl group, t-butyl group, n-pentyl group, neopentyl group, n-hexyl. Groups and the like.

  Examples of the alkoxy group as a substituent of the aryl group include linear or branched alkoxy groups having 1 to 6 carbon atoms, specifically methoxy group, ethoxy group, and n-propoxy group. , Isopropoxy group, n-butoxy group, s-butoxy group, isobutoxy group and t-butoxy group, n-pentyloxy group, neopentyloxy group, n-hexyloxy group and the like.

  Examples of the aryl group as a substituent for the aryl group include aryl groups having 6 to 14 carbon atoms, and specific examples include phenyl, naphthyl, anthryl, phenanthryl, biphenyl, and furyl groups. It is done.

In the above formula, the aryloxy group of the aryloxy group which may have a substituent represented by R ¹ , R ² and R ³ includes, for example, an aryloxy group having 6 to 14 carbon atoms. Specific examples include a phenoxy group, a naphthyloxy group, an anthryloxy group, a phenanthryloxy group, and a biphenyl group. Examples of the substituent for these aryloxy groups include alkyl groups, alkoxy groups, halogen atoms and the like as described above.

Examples of the cycloalkyl group represented by R ¹ , R ² and R ³ which may have a substituent include a 5-membered or 6-membered cycloalkyl group, which is preferable. Examples of the cycloalkyl group include a cyclopentyl group and a cyclohexyl group. These cycloalkyl groups may be substituted with one or two or more substituents such as alkyl groups or alkoxy groups mentioned as substituents for the aryl group.

Specific examples of the monophosphine represented by the general formula (3) include triphenylphosphine [PPh ₃ ], tri (4-methylphenyl) phosphine, tri (3-methylphenyl) phosphine, and tri (2 -Methylphenyl) phosphine, tris (4-trifluoromethylphenyl) phosphine, tri (4-methoxyphenyl) phosphine, tri (3-methoxyphenyl) phosphine, tri (2-methoxyphenyl) phosphine, tris (3,5- Dimethylphenyl) phosphine, tris (3,5-dimethoxyphenyl) phosphine, tris (3,5-dimethyl-4-methoxyphenyl) phosphine, tris [3,5-bis (1,1-dimethylethyl) -4-methoxy Phenyl] phosphine, tri (4-fluorophenyl) phosphine Tris (3,5-difluorophenyl) phosphine, tri (4-chlorophenyl) phosphine, tris (3,5-dichlorophenyl) phosphine, tri (1-naphthyl) phosphine, trimethylphosphine [PMe _3], tris (trifluoromethyl) Phosphine, triethylphosphine, tri-n-propylphosphine, triisopropylphosphine, tri-n-butylphosphine, tri-t-butylphosphine, tripentylphosphine, tri-n-hexylphosphine, tri-n-heptylphosphine, trioctyl Examples include phosphine, tricyclopentylphosphine, tricyclohexylphosphine, methyldiphenylphosphine, cyclohexylmethylphenylphosphine, and dicyclohexylphenylphosphine.

Subsequently, the amines of the component (iii) of the catalyst used in the present invention will be described.
Examples of amines used in the present invention include monodentate amines (monoamine, monoimine) and bidentate amines (diamine, diimine, iminoamine). Among them, bidentate coordination is used. Amines are preferred. Examples of the monodentate amine and bidentate amine (diimine, iminoamine) include amines represented by the following formulas (A) to (F).

(Wherein, R ^{a to} R ^s each independently represents an alkyl group which may have a substituent, an aryl group which may have a substituent, or an aralkyl which may have a substituent. Q ^a , Q ^b , and Q ^c each independently represent an alkylene chain that may have a substituent, a cycloalkylene group that may have a substituent, or a substituent. R ^a and R ^b , R ^c and R ^d , R ^c and R ^f , R ^h and R ⁱ , R ^j and R ^k , R ^p and R ^q are each independently To form an alicyclic ring.)

  Furthermore, as a diamine which is a bidentate amine preferably used in the present invention, a diamine which may be substituted, for example, a compound represented by the following general formula (4) is preferable.

(In the formula, R ⁴ , R ⁵ , R ⁶ and R ⁷ are each independently a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, or a substituent. Represents an optionally substituted cycloalkyl group, or an optionally substituted alkane or arenesulfonyl group, and Q ¹ has an optionally substituted alkylene chain and a substituent. A cycloalkylene group which may be substituted, or an arylene group which may have a substituent.

In the diamine represented by the general formula (4), a diamine in which at least one of R ⁴ , R ⁵ , R ⁶ and R ⁷ is a hydrogen atom is preferable.

Moreover, it has the alkyl group which may have a substituent in R < ⁴ >, R < ⁵ >, R < ⁶ > and R < ⁷ > of General formula (4), the aryl group which may have a substituent, and a substituent. Examples of the cycloalkyl group which may be mentioned include groups exemplified in the description of R ¹ , R ² and R ³ described above.

The alkane or arenesulfonyl group which may have a substituent in R ⁴ , R ⁵ , R ⁶ and R ⁷ in the general formula (4) has 1 to 20 carbon atoms, preferably 1 to 15 carbon atoms. Preferably a linear or branched alkane having 1 to 10 carbon atoms, or a monocyclic, polycyclic, or 6 to 36 carbon atoms, preferably 6 to 18 carbon atoms, more preferably 6 to 12 carbon atoms, or Examples thereof include a sulfonyl group bonded to a condensed cyclic arene, and examples thereof include a methanesulfonyl group, a trifluoromethanesulfonyl group, a benzenesulfonyl group, and a p-toluenesulfonyl group.

The alkylene chain which may have a substituent represented by Q ¹ is a chain or branched chain having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms. An alkylene group is mentioned, Specifically, a methylene group, ethylene group, trimethylene group, tetramethylene group, pentamethylene group etc. are mentioned, for example. Examples of the substituent substituted on the alkylene chain include alkyl groups having 1 to 4 carbon atoms such as methyl group, ethyl group, isopropyl group and t-butyl group, cycloalkyl groups such as cyclopentyl group and cyclohexyl group, phenyl group, 4 Examples thereof include aryl groups such as methoxyphenyl group and naphthyl group, but are not limited thereto.

Examples of the cycloalkylene group optionally having a substituent represented by Q ¹ include a divalent group consisting of a cycloalkyl group having 3 to 15 carbon atoms, preferably 4 to 6 carbon atoms. , Cyclobutylene group, cyclopentylene group, cyclohexylene group and the like. Examples of the substituent for these cycloalkylene groups include, but are not limited to, alkyl groups having 1 to 4 carbon atoms such as a methyl group, an ethyl group, an isopropyl group, and a t-butyl group.

The arylene group which may have a substituent represented by Q ¹ is monocyclic or polycyclic having 6 to 36 carbon atoms, preferably 6 to 18 carbon atoms, more preferably 6 to 12 carbon atoms. And an arylene group having a formula or a condensed cyclic group include, for example, a phenylene group, a biphenyldiyl group, a binaphthalenediyl group, and the like. Examples of the phenylene group include o or m-phenylene group, and examples of the substituent in these arylene groups include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, s-butyl group, isobutyl group. Groups and alkyl groups such as t-butyl group; alkoxy groups such as methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, s-butoxy group, isobutoxy group and t-butoxy group; Examples of the substituent include an amino group and a substituted amino group, but are not limited thereto.

  As the biphenyldiyl group and binaphthalenediyl group which may have a substituent, those having a 1,1′-biaryl-2,2′-diyl type structure are preferable, and the biphenyldiyl group and binaphthalene are preferred. Examples of the substituent for the diyl group include alkyl groups and alkoxy groups as described above, for example, alkylenedioxy groups such as methylenedioxy group, ethylenedioxy group, and trimethylenedioxy group, hydroxyl groups, amino groups, and substituted amino groups. However, it is not limited to these.

  Specific examples of the diamine used in the present invention include, for example, ethylenediamine, 1,2-diaminopropane, 1,3-diaminopropane, 2-methyl-1,3-diaminobutane, 1,4-diaminobutane, 2,3. -Diaminobutane, 1,2-diaminopentane, 1,3-diaminopentane, 1,2-cyclopentanediamine, 1,2-cyclohexanediamine, 1,2-cycloheptanediamine, N-methylethylenediamine, N, N- Dimethylethylenediamine, N, N-diethylethylenediamine, N, N-diisopropylethylenediamine, N, N′-dimethylethylenediamine, N, N′-diethylethylenediamine, N, N′-diisopropylethylenediamine, 2,3-dimethyl-2,3 -Diaminobutane, o-phenylenediamine 2- (aminomethyl) pyridine, 2-dimethylamino-1-phenylethylamine, 2-diethylamino-1-phenylethylamine, 2-diisopropylamino-1-phenylethylamine, 1,2-diphenylethylenediamine, 1,2-bis ( 4-methoxyphenyl) ethylenediamine, 1,2-dicyclohexylethylenediamine, 1,2-bis (4-N, N-dimethylaminophenyl) ethylenediamine, 1,2-bis (4-N, N-diethylaminophenyl) ethylenediamine, 1 , 2-bis (4-N, N-dipropylaminophenyl) ethylenediamine, (N-benzenesulfonyl) -1,2-bis (4-N, N-dimethylaminophenyl) ethylenediamine, (Np-toluenesulfonyl) ) -1,2-bis (4-N, N-di) Methylaminophenyl) ethylenediamine, (N-methanesulfonyl) -1,2-bis (4-N, N-dimethylaminophenyl) ethylenediamine, (N-trifluoromethanesulfonyl) -1,2-bis (4-N, N -Dimethylaminophenyl) ethylenediamine, (N-benzenesulfonyl) -1,2-bis (4-N, N-diethylaminophenyl) ethylenediamine, (N-benzenesulfonyl) -1,2-bis (4-N, N- Dipropylaminophenyl) ethylenediamine, 2,3-dimethyl-1,4-diaminobutane, 1-methyl-2,2-diphenylethylenediamine, 1-isobutyl-2,2-diphenylethylenediamine, 1-isopropyl-2,2- Diphenylethylenediamine, 1-methyl-2,2-di (p-methoxy Phenyl) ethylenediamine, 1-isobutyl-2,2-di (p-methoxyphenyl) ethylenediamine, 1-isopropyl-2,2-di (p-methoxyphenyl) ethylenediamine, 1-benzyl-2,2-di (p- Methoxyphenyl) ethylenediamine, 1-methyl-2,2-dinaphthylethylenediamine, 1-isobutyl-2,2-dinaphthylethylenediamine, 1-isopropyl-2,2-dinaphthylethylenediamine, N, N′-bis (phenylmethyl) ) -1,2-diphenyl-1,2-ethylenediamine, N, N′-bis (mesitylmethyl) -1,2-diphenyl-1,2-ethylenediamine, N, N′-bis (naphthylmethyl) -1,2 -Diphenyl-1, 2-ethylenediamine etc. are mentioned. In addition, the following diamines are also included. However, the diamine used in the present invention is not limited to those specifically exemplified.

In addition, as the bidentate coordinating imine, diimine represented by the above formula (C) prepared from diamine and ketone or aldehyde, diketone, ketoaldehyde, or the above formula (D) prepared from dialdehyde and amine. And the imine (iminoamine) represented by the above formula (E) or formula (F) prepared from an amine and a ketone or aldehyde.
Specific examples of diimine or iminoamine include the following.

Subsequently, the general formula (1) used in the production method of the present invention:

(Wherein, X ¹ and X ² each independently represent a hydrogen atom, a halogen atom, an alkoxy group, a hydroxy group, or an acyloxy group, L _P represents a monophosphine, and m is 3 or 4).
The ruthenium complex represented by the formula will be described.

In the general formula (1), the mono-phosphine represented by L _P, include monophosphine described in component (ii).

In the general formula (1), examples of the halogen atom represented by X ¹ and X ² include a chlorine atom, a bromine atom, and an iodine atom, and the alkoxy group includes a linear or branched carbon number of 1 to 8 carbon atoms. Alkoxy groups such as methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, s-butoxy group, t-butoxy group, n-pentyloxy group, neopentyloxy group, n -Hexyloxy group, n-heptyloxy group, n-octyloxy group, etc. are mentioned.

In the general formula (1), examples of the acyloxy group represented by X ¹ and X ² include those represented by (R ^a CO ₂ ). Acyloxy group: The R ^a in R ^a CO _2, hydrogen atom, an optionally substituted alkyl group having 1 to 3 carbon atoms, include a phenyl group or a naphthyl group which may have a substituent, Examples of the substituent of the alkyl group having 1 to 3 carbon atoms which may have the substituent include an alkyl group having 1 to 4 carbon atoms and a halogen atom. Specific examples of the alkyl group having 1 to 3 carbon atoms which may have a substituent include a methyl group, an ethyl group, a propyl group, a t-butyl group, and a trifluoromethyl group. In the phenyl group or naphthyl group which may have a substituent, examples of the substituent include alkyl groups such as a methyl group, an ethyl group and an n-propyl group, such as a methoxy group, an ethoxy group and a propoxy group. An alkoxy group, for example, a halogen atom such as chlorine and bromine is exemplified.

As the ruthenium complex represented by the general formula (1), for example, when triphenylphosphine is used as the monophosphine, RuCl ₂ (PPh ₃ ) ₃ , RuBr ₂ (PPh ₃ ) ₃ , RuI ₂ (PPh ₃ ) ₃ , RuH ₄ (PPh ₃ ) ₃ , RuClH (PPh ₃ ) _{3 and the} like, and when trimethylphosphine is used as the monophosphine, for example, RuCl ₂ (PMe ₃ ) ₃ and others, for example, RuCl ₂ (PCy) _{3) 3, RuCl 2 (P} (n-Bu) 3) 3, RuCl 2 (P (t-Bu) 3) 3, RuCl 2 (P (4-MeO-C 6 H 4) 3) 3 or the like is exemplified Is done. However, it is needless to say that the monophosphine is not limited to those exemplified. In the examples, Ph represents phenyl, Cy represents cyclohexyl, Bu represents butyl, and Me represents methyl (the same shall apply hereinafter).

When the catalyst of the present invention is composed of the ruthenium complex represented by the general formula (1) and the amine of the component (iii), the amine is preferably a bidentate amine, and the general formula ( 4) Among them, a diamine having an ethylenediamine skeleton such as ethylenediamine or (1R, 2R) -1,2-diphenylethylenediamine, in which Q ¹ is ethylene, is preferable.

Subsequently, the general formula (2) used in the production method of the present invention:

(In the formula, X ¹ and X ² each independently represent a hydrogen atom, a halogen atom, an alkoxy group, a hydroxy group, or an acyloxy group, L _P represents a monophosphine, and L _N represents a bidentate coordination group. Represents amines.)
The ruthenium complex represented by the formula will be described.

In the general formula (2), the halogen atom represented by X ¹ and X ² , the alkoxy group, the acyloxy group, and the monophosphine represented by Lp are specifically the same as described in the general formula (1). Specific examples of the bidentate amines represented by L _N include the same as those described for the component (iii).

Examples of the ruthenium compound used as a starting material for the synthesis of the ruthenium complex represented by the general formulas (1) and (2) used in the present invention include ruthenium halides such as RuCl ₃ hydrate and RuBr ₃ water. hydrate, inorganic ruthenium compounds such as RuI _{3 hydrate, RuCl 2 (DMSO) 4,} [Ru (cod) Cl 2] n, [Ru (nbd) Cl 2] n, [Ru ( benzene) Cl _{2] 2} , [Ru (benzene) Br ₂ ] ₂ , [Ru (benzene) I ₂ ] ₂ , [Ru (p-cymene) Cl ₂ ] ₂ , [Ru (p-cymene) Br ₂ ] ₂ , [Ru (p- Cymene) I ₂ ] ₂ , [Ru (mesitylene) Cl ₂ ] ₂ , [Ru (mesitylene) Br ₂ ] ₂ , [Ru (mesitylene) I ₂ ] ₂ , [Ru (hexamethylbenzene) Cl ₂ ] ₂ , [ ru (hexamethylbenzene) Br _{2] 2} [Ru (hexamethylbenzene) I _{2] 2} and the like, as further starting materials for the ruthenium complex synthesis represented by the general formula (2), complexes represented by the general formula (1). Nbd represents norbornadiene.

Ruthenium complexes represented by the general formula (1) are described in, for example, Inorg. synth. , 1972, 12, 238 and J.A. Organometal. Chem. , 1973, 54, 259, and the like. For example, RuCl ₂ (PPh ₃ ) ₃ can be obtained by refluxing RuCl ₃ .3H ₂ O and excess triphenylphosphine in methanol. In addition, RuCl ₃ .3H ₂ O and triphenylphosphine and NaBH ₄ are refluxed in ethanol, or RuCl ₂ (PPh ₃ ) ₃ and triphenylphosphine and NaBH ₄ are refluxed in ethanol, whereby RuH ₂ (PPh ₃ ) ₄ is obtained.

  The ruthenium complex represented by the general formula (2) can be obtained by, for example, the method described in JP-A-11-189600. For example, a method in which a ruthenium compound is first reacted with a monophosphine ligand in a solvent, and then the resulting compound is reacted with an amine ligand. More specifically, for example, when ruthenium halide is used as the ruthenium compound, the reaction between the ruthenium halide and the phosphine ligand is performed by using an aromatic hydrocarbon solvent such as toluene or xylene, or an aliphatic hydrocarbon such as pentane or hexane. Solvents, halogen-containing hydrocarbon solvents such as methylene chloride, ether solvents such as ether and tetrahydrofuran, alcohol solvents such as methanol, ethanol, 2-propanol, butanol and benzyl alcohol, acetonitrile, DMF (N, N-dimethylformamide) , N-methylpyrrolidone, DMSO and the like in an organic solvent containing a hetero atom at an appropriate reaction temperature to obtain a phosphine-ruthenium halide complex. Next, the reaction of the obtained phosphine-ruthenium halide complex with an amine ligand is carried out by using an aromatic hydrocarbon solvent such as toluene or xylene, an aliphatic hydrocarbon solvent such as pentane or hexane, or a halogen-containing hydrocarbon such as methylene chloride. Solvent, ether solvents such as ether and tetrahydrofuran, alcohol solvents such as methanol, ethanol, 2-propanol, butanol and benzyl alcohol, and organic solvents containing heteroatoms such as acetonitrile, DMF, N-methylpyrrolidone and DMSO are suitable. It is carried out at the reaction temperature, and a ruthenium complex represented by the general formula (2) can be obtained. However, the method for producing the ruthenium complex represented by the general formula (2) of the present invention is not limited to the above.

  In addition, the ruthenium complex represented by the general formula (2) is not limited to one diastereomer, and may be any of a cis body, a trans body, or a mixture of a cis body and a trans body.

  The method for producing alcohols of the present invention can be preferably carried out without a solvent or in a solvent, but it is preferable to use a solvent. The solvent used is preferably a solvent capable of dissolving the hydrogenation substrate and the Ru complex as the catalyst, and a single solvent or a mixed solvent is used. Specifically, water, aromatic hydrocarbons such as toluene and xylene, aliphatic hydrocarbons such as hexane and heptane, halogenated hydrocarbons such as methylene chloride and chlorobenzene, diethyl ether, tetrahydrofuran, methyl t-butyl ether, cyclopentyl methyl ether Ethers such as methanol, ethanol, isopropanol, n-butanol, 2-butanol, t-butanol, etc., polyhydric alcohols such as ethylene glycol, propylene glycol, 1,2-propanediol and glycerin, acetonitrile, etc. Nitriles, N, N-dimethylformamide, amides such as N-methylpyrrolidone, and amines such as pyridine and triethylamine. Of these, ethers are preferred. Particularly preferred is tetrahydrofuran. Although the usage-amount of a solvent can be suitably selected according to reaction conditions etc., it is 0.5 mol / L-8.0 mol / L with respect to a raw material, Preferably it is 0.8 mol / L-2.0 mol / L. The reaction is carried out with stirring as necessary.

  In a preferred embodiment of the production method of the present invention, a base can be further added to the reaction system, and the reaction can be carried out in the presence of a base, whereby hydrogen reduction proceeds smoothly. Examples of the base used for adding to the reaction system include organic base compounds and inorganic base compounds.

  Examples of the organic base compound include the following phosphazene compounds.

  Examples of the inorganic base compound used in the present invention include alkali metal carbonates such as potassium carbonate, sodium carbonate, lithium carbonate and cesium carbonate, alkaline earth metal carbonates such as magnesium carbonate and calcium carbonate, sodium hydrogen carbonate, hydrogen carbonate Alkali metal hydrogen carbonates such as potassium, alkali metal hydroxides such as sodium hydroxide, potassium hydroxide and lithium hydroxide, alkaline earth metal hydroxides such as magnesium hydroxide and calcium hydroxide, sodium methoxide, sodium Alkalis such as ethoxide, sodium isopropoxide, sodium t-butoxide, potassium methoxide, potassium ethoxide, potassium isopropoxide, potassium t-butoxide, lithium methoxide, lithium isopropoxide, lithium t-butoxide Genus alkoxides, magnesium methoxide, an alkaline earth metal alkoxides such as magnesium ethoxide, sodium hydride, and metal hydride such as calcium hydride. Of these, potassium t-butoxide and sodium methoxide are particularly preferable.

  The amount of the base compound used in the present invention can be appropriately selected depending on the ruthenium compound and ruthenium complex to be used, reaction conditions, etc., but usually 2 equivalents to 100,000 equivalents, preferably based on the ruthenium compound and ruthenium complex. Is 5 equivalents to 10,000 equivalents. The base compound can be added to the reaction system as it is, or can be added to the reaction system as a solution dissolved in a reaction solvent or the like.

  As described above, the base may be added directly or as a dissolved solution to a reaction system comprising a mixture of a ruthenium compound, a monophosphine and an amine, and a hydrogenated substrate and a solvent used if necessary. A catalyst comprising a ruthenium compound, a monophosphine compound and an amine compound and a base are mixed in advance, and this mixture can be used as a catalyst. Specifically, a catalyst comprising a ruthenium compound, a monophosphine compound, and an amine compound and a base are mixed and stirred in advance in a solvent, and the mixed solution is added to the reaction system as it is, or a residue obtained by distilling off the solvent is used as a catalyst in the reaction system. Or the residue is dissolved in the reaction solvent, and the resulting solution is added to the reaction system as a catalyst. Thereby, the conversion rate of the hydrogenated substrate into alcohol and the selectivity which is the conversion rate into the target alcohol may be improved.

In the present invention, a reducing agent can be used as an additive. Examples of the reducing agent that can be used in the present invention include Zn, Zn (BH ₄ ) ₂ , LiAlH ₄ , LiAlH (OBu-t) ₃ , NaAlH ₄ , LiAlHEt ₃ , (i-Bu) ₂ AlH, NaBH _{4 and the} like. Can be mentioned. The amount of the reducing agent used can be appropriately selected depending on the ruthenium compound and ruthenium complex to be used, reaction conditions, etc., but is usually 1 to 50 equivalents, preferably 1 to 10 equivalents, relative to the ruthenium compound and ruthenium complex. It is. The reducing agent can be added to the reaction system as it is, or can be added to the reaction system as a solution dissolved in a reaction solvent or the like.

  In the present invention, the reaction temperature at the time of hydrogen reduction is preferably 10 ° C to 200 ° C, more preferably 50 ° C to 120 ° C. If the reaction temperature is too low, a large amount of unreacted raw material may remain. If the reaction temperature is too high, decomposition of the raw material, catalyst, etc. may occur, which is not preferable.

  In the present invention, the hydrogen pressure at the time of hydrogen reduction is preferably 0.5 MPa to 10 MPa, more preferably 3 MPa to 6 MPa.

  In the present invention, the amount of the catalyst used varies depending on the raw material hydride substrate, reaction conditions, type of catalyst, etc., and also economically, but is usually 0.0001 mol in terms of a molar ratio of ruthenium metal to hydride substrate. % To 10 mol%, preferably 0.01 mol% to 5 mol%, more preferably 0.1 mol% to 5 mol%.

  The reaction time is about 8 to 24 hours, and a sufficiently high raw material conversion can be obtained. After completion of the reaction, the desired alcohols can be obtained by combining commonly used purification methods such as extraction, filtration, crystallization, distillation, various chromatography, etc., alone or in appropriate combination.

  EXAMPLES The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples. The conversion and selectivity were measured by gas chromatography (GC). The equipment used is as follows.

GC: Agilent Technologies 6850 Series GC System
Column: HP-INNO WAX 0.25 mm (ID) × 30 m (length), 0.250 μm (thickness) (manufactured by Hewlett-Packard Company)
Conditions: injection 250 ° C, detector 250 ° C
80 ° C. (1 min.) − 10 ° C./min. −250 ° C. (12 min.)

In addition, the ¹ H-NMR spectrum and ³¹ P-NMR spectrum of the complex obtained by the synthesis were measured using Mercury plus 300 4N type ( ¹ H-NMR 300 MHz, ³¹ P-NMR 121 MHz) manufactured by Varian Technology Japan Limited. went.

Example 1 (Synthesis of RuCl ₂ [PPh ₃ ] ₂ [(1R, 2R) -1,2-diphenylethylenediamine] (1))
RuCl ₂ (PPh ₃ ) ₃ (800 mg, 0.83 mmol) and (1R, 2R) -1,2-diphenylethylenediamine (195 mg, 0.92 mmol) are weighed into a 20 mL Schlenk type reaction tube, and the inside of the container is depressurized. After removing the air, nitrogen was introduced. Dichloromethane (8 mL) was added with a syringe, followed by stirring at room temperature for 3 hours under a nitrogen atmosphere. Subsequently, the reaction solution was filtered through Celite and further washed with dichloromethane (2 mL). The obtained mother liquor was concentrated to about 2 mL under reduced pressure, hexane (16 mL) was added, and the mixture was stirred at room temperature for 1 hour. The precipitate was collected by filtration under a nitrogen atmosphere, and the obtained powder was dried under reduced pressure (1 mmHg) to obtain 531 mg of the desired product. (Yield 70%)

¹ H-NMR (CDCl ₃ ): δ (ppm) 7.52 (d, J = 9.6 Hz, 12H), 7.21 (t, J = 9.6 Hz, 6H), 7.09 (m, 18H) ), 6.83 (m, 4H), 4.25 (m, 2H), 3.75 (m, 2H), 3.35 (m, 2H).
³¹ P-NMR (CDCl ₃ ): δ (ppm) 43.76.

Example 2 (Reduction of methyl benzoate)
In a 100 ml autoclave containing a stir bar, the catalyst (1) (0.02 mmol) obtained in Example 1 and potassium t-butoxide (0.4 mmol) were weighed, tetrahydrofuran (3 mL) and methyl benzoate (4 0.0 mmol) was added with a syringe, and the mixture was stirred at a hydrogen pressure of 5 MPa and 100 ° C. for 15 hours. As a result, the conversion rate of methyl benzoate was 88.9%, and the selectivity to benzyl alcohol was 93.2%.

Example 3 (Reduction of phthalide)
In a 100 ml autoclave containing a stir bar, phthalide (3.73 mmol), catalyst (1) (0.0373 mmol) obtained in Example 1 and potassium t-butoxide (0.373 mmol) were weighed and tetrahydrofuran (3 mL) was added. ) Was added with a syringe, followed by stirring at a hydrogen pressure of 5 MPa and 100 ° C. for 16 hours. As a result, the conversion of phthalide was 84.8%, and the selectivity to o-xylylene glycol was 97.1%.

Example 4 (Reduction of methyl benzoate)
In a 100 ml autoclave containing a stir bar, RuCl ₂ (PPh ₃ ) ₃ (0.02 mmol), (1R, 2R) -1,2-diphenylethylenediamine (0.02 mmol), and potassium t-butoxide (0.4 mmol) ) And tetrahydrofuran (3 mL) and methyl benzoate (4.0 mmol) were added by a syringe, followed by stirring at a hydrogen pressure of 5 MPa and 100 ° C. for 15 hours. As a result, the conversion rate of methyl benzoate was 81.7%, and the selectivity to benzyl alcohol was 89.0%.

Example 5 (Reduction of methyl hexanoate)
In a 100 ml autoclave containing a stir bar, RuCl ₂ (PPh ₃ ) ₃ (0.017 mmol), (1R, 2R) -1,2-diphenylethylenediamine (0.017 mmol) and potassium t-butoxide (0.34 mmol) After adding tetrahydrofuran (3 mL) and methyl hexanoate (3.4 mmol) with a syringe, the mixture was stirred at a hydrogen pressure of 5 MPa and 100 ° C. for 15 hours. As a result, the conversion of methyl hexanoate was 48.7%, and the selectivity to 1-hexanol was 43.1%.

Example 6 (Reduction of methyl benzoate)
RuCl ₂ (PPh ₃ ) ₃ (0.02 mmol) and potassium t-butoxide (0.4 mmol) are weighed into a 100 ml autoclave containing a stir bar, ethylenediamine (0.02 mmol), tetrahydrofuran (3 mL), and benzoic acid. After adding methyl acid (4.0 mmol) with a syringe, the mixture was stirred at a hydrogen pressure of 5 MPa and 100 ° C. for 15 hours. As a result, the conversion rate of methyl benzoate was 18.0%, and the selectivity to benzyl alcohol was 35.3%.

Example 7 (Reduction of methyl benzoate)
In a 100 ml autoclave containing a stir bar, RuCl ₂ (PPh ₃ ) ₃ (0.02 mmol) and potassium t-butoxide (0.4 mmol) were weighed, trans-1,2-diaminocyclohexane (0.02 mmol), Tetrahydrofuran (3 mL) and methyl benzoate (4.0 mmol) were added with a syringe, and the mixture was stirred at a hydrogen pressure of 5 MPa and 100 ° C. for 15 hours. As a result, the conversion rate of methyl benzoate was 26.6%, and the selectivity to benzyl alcohol was 52.5%.

Example 8 (Synthesis of RuCl ₂ [PMe ₃ ] ₂ [ethylenediamine] (2))
In a 100 ml autoclave containing a stir bar, (cod) Ru (η ³ -methallyl) ₂ (150 mg, 0.47 mmol) was weighed, heptane (3 mL), 1.0 M PMe ₃ toluene solution (1 mL) under a nitrogen atmosphere. , 1.0 mmol) was added with a syringe, followed by stirring at 80 ° C. for 5 hours. The reaction solution was transferred to a 20 mL Schlenk-type reaction tube, and the solvent was distilled off under reduced pressure. The obtained powder was dried under reduced pressure to obtain 132 mg of (PMe ₃ ) ₂ Ru (η ³ -methallyl) ₂ . Obtained. (Yield 77%).

In a 20 mL Schlenk-type reaction tube, (PMe ₃ ) ₂ Ru (η ³ -methallyl) ₂ (123.6 mg, 0.34 mmol) obtained above was weighed and acetone (3 mL), 1. A 25 M HCl ethanol solution (0.6 mL, 0.75 mmol) was added by syringe, followed by stirring at room temperature for 2 hours. After the solvent was distilled off under reduced pressure, dimethylformamide (3 mL) and ethylenediamine (60 μL, 0.90 mmol) were added with a syringe, and the mixture was stirred at room temperature for 3 hours. After the solvent was distilled off under reduced pressure, the obtained powder was dried under reduced pressure to obtain 123 mg of the desired product. (Yield 94%)

¹ H-NMR (C ₆ D ₆ ): δ (ppm) 2.69 (s, 4H), 2.30 (s, 4H), 1.28 (t, J = 4.2 Hz, 18H).
³¹ P-NMR (C ₆ D ₆ ): δ (ppm) 19.94.

Example 9 (Reduction of methyl benzoate)
In a 100 ml autoclave containing a stir bar, the catalyst (2) (0.02 mmol) obtained in Example 8 and potassium t-butoxide (0.4 mmol) were weighed, tetrahydrofuran (3 mL) and methyl benzoate (4 0.0 mmol) was added with a syringe, and the mixture was stirred at a hydrogen pressure of 5 MPa and 100 ° C. for 15 hours. As a result, the conversion rate of methyl benzoate was 49.0%, and the selectivity to benzyl alcohol was 76.1%.

Example 10 (Synthesis of RuCl ₂ [PMe ₃ ] ₂ [(1R, 2R) -1,2-diphenylethylenediamine] (3))
In a 100 ml autoclave containing a stir bar, (cod) Ru (η ³ -methallyl) ₂ (150 mg, 0.47 mmol) was weighed, heptane (3 mL), 1.0 M PMe ₃ toluene solution (1 mL) under a nitrogen atmosphere. , 1.0 mmol) was added with a syringe, followed by stirring at 80 ° C. for 6.5 hours. The reaction solution was transferred to a 20 mL Schlenk-type reaction tube, and the solvent was distilled off under reduced pressure. The obtained powder was dried under reduced pressure, and 144 mg of (PMe ₃ ) ₂ Ru (η ³ -methallyl) ₂ (Yield 84%). Subsequently, acetone (3 mL) and a 1.25 M HCl ethanol solution (0.7 mL, 0.88 mmol) were added by a syringe, followed by stirring at room temperature for 2 hours under a nitrogen atmosphere. After the solvent was distilled off under reduced pressure, dimethylformamide (3 mL), (1R, 2R) -1,2-diphenylethylenediamine (84.1 mg, 0.40 mmol) and triethylamine (0.07 mL, 0.50 mmol) were added. And stirred at room temperature for 3 hours. After the solvent was distilled off under reduced pressure, toluene (4 mL) was added and stirred at room temperature for 5 minutes. The reaction solution was filtered through Celite, and the solvent was distilled off from the mother liquor under reduced pressure. The resulting powder was dried under reduced pressure to obtain 196 mg of the desired product. (Yield 92%)

¹ H-NMR (C ₆ D ₆ ): δ (ppm) 7.00 (m, 4H), 6.84 (m, 6H), 4.53 (m, 2H), 3.90 (m, 4H) , 1.25 (t, J = 4.2 Hz, 18H).
³¹ P-NMR (C ₆ D ₆ ): δ (ppm) 19.78.

Example 11 (Reduction of methyl benzoate)
In a 100 ml autoclave containing a stir bar, the catalyst (3) (0.02 mmol) and potassium t-butoxide (0.4 mmol) obtained in Example 10 were weighed, tetrahydrofuran (3 mL) and methyl benzoate (4 0.0 mmol) was added with a syringe, and the mixture was stirred at a hydrogen pressure of 5 MPa and 100 ° C. for 15 hours. As a result, the conversion rate of methyl benzoate was 55.9%, and the selectivity to benzyl alcohol was 70.1%.

Claims (7)

A method for producing an alcohol, characterized in that an ester or a lactone is reduced with hydrogen in the presence of a catalyst comprising the following components (i), (ii) and (iii).
(I) ruthenium compound (ii) monophosphine (iii) amines The alcohol according to claim 1, wherein the catalyst comprising (i) a ruthenium compound, (ii) a monophosphine, and (iii) an amine is a ruthenium-monophosphine complex represented by the following general formula (1) and an amine. Manufacturing method.

(Wherein, X ¹ and X ² each independently represent a hydrogen atom, a halogen atom, an alkoxy group, a hydroxy group, or an acyloxy group, L _P represents a monophosphine, and m is 3 or 4). The method for producing an alcohol according to claim 1, wherein the catalyst comprising (i) a ruthenium compound, (ii) monophosphine, and (iii) an amine is present as a ruthenium complex represented by the following general formula (2).

(In the formula, X ¹ and X ² each independently represent a hydrogen atom, a halogen atom, an alkoxy group, a hydroxy group, or an acyloxy group, L _P represents a monophosphine, and L _N represents a bidentate coordination group. Represents amines.)   The method for producing an alcohol according to any one of claims 1 to 3, wherein the amine is a diamine.   The method for producing an alcohol according to any one of claims 1 to 4, which is carried out in the presence of an additive.   The method for producing an alcohol according to claim 5, wherein the additive is a base or a reducing agent.   The method for producing an alcohol according to claim 5 or 6, wherein a mixture obtained by mixing and stirring an additive and a catalyst comprising (i) a ruthenium compound, (ii) a monophosphine, and (iii) an amine in advance is used as a catalyst.