Technical field
[0001]The present invention, cationic ruthenium complex and a manufacturing method thereof, as well as the complex relates to the use as a catalyst.
BACKGROUND
[0002]Today, various transition metal complexes consisting of transition metal and ligand are used in a variety of reactions as catalysts in organic synthesis reactions.
[0003]
　One example, ruthenium catalyst used for hydrogenation reduction such as ketones and esters, have one bis (phosphino alkyl) amine as a tridentate ligand, and carbon monoxide as a monodentate ligand ruthenium complexes having has been reported (see Patent Document 1). Further, this ruthenium complex dehydrogenation oxidation of alcohols as a catalyst, undergo dehydrating condensation of alcohols and amines N- alkylation reaction has also been reported (see Patent Documents 2 and 3). On the other hand, has one bis (phosphino alkyl) amine as a tridentate ligand and ruthenium complexes having two carbon monoxide as monodentate ligands have been reported, this ruthenium complex is used as catalyst are non (see non-Patent Document 1).
CITATION
Patent Document
[0004]
Patent Document 1: WO2011 / 048727 Patent Publication No.
Patent Document 2: WO2012 / 144650 Patent Publication No.
Patent Document 3: WO2014 / 136374 Patent Publication No.
Non-Patent Document 1: Inorg Chem 2012, 51, 9730..
Summary of the Invention
Problems that the Invention is to Solve
[0005]
　An object of the present invention is inexpensive to manufacture can be easy to handle cationic ruthenium complex and a manufacturing method thereof, as well as the ruthenium complex used as a catalyst, the alcohol by hydrogenation reduction of aldehydes or ketones manufacturing method; alcohols, method for producing a carbonyl compound by oxidation of hemiacetals or hemiaminal ethers; alcohols by hydrogenation reduction of esters, aldehydes or manufacturing method of the hemiacetals and N undergoing dehydration condensation of alcohols and amines - to provide a method for producing by alkylation reactions N- alkylamine compound. In these reactions on the industrial field from problems and safety of the cost and residual metal, under milder reaction conditions, it has been demanded new complexes which exhibit high catalytic activity.
Means for Solving the Problems
[0006]
　The present inventors has been made in view of the above circumstances, intensive studies the results of, to have one bis (phosphino alkyl) amine as a tridentate ligand, and two have a carbon monoxide as a monodentate ligand It found cationic ruthenium complex wherein the. On cationic ruthenium complex found by the present invention is inexpensive to manufacture, easy to handle because of the stable powder in air, aldehydes, hydrogenation reduction of ketones and esters, alcohols s and were useful as a catalyst for dehydrogenation oxidation of hemiacetals and hemiaminals acids, and undergoes dehydration condensation of alcohols and amines N- alkylation reaction. Based on these findings, and completed the present invention.
[0007]
　The present invention relates to [17] of the following [1].
[1] the following general formula
　　　(1) [RuX (CO) 2 (PNP)] Y (1)
in (Formula (1), X represents a monovalent anionic monodentate ligand, Y is a counter anion represents .PNP the following general formula (2)
[0008]
[Formula 1]

[0009]
(In the general formula (2), R 1 , R 2 , R 1 'and R 2 ' are each independently an alkyl group, an aryl group, an aralkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an aryloxy group, an aralkyl oxy group, a heterocyclic group or an amino group. alkyl group among these groups, an aryl group, an aralkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an aryloxy group, an aralkyloxy group and the heterocyclic group substituents may have. these R 1 and R 2 and R 1 'R and 2 ' are each independently bonded may .Q also form a ring with the adjacent phosphorus atom together 1 and Q 2 are each independently optionally substituted alkanediyl group, or represents an aralkylene group which may have a substituent.)
represents a tridentate ligand represented by, CO carbon monoxide is A representative. )
Ruthenium complex represented by.
[2] X is characterized in that it is a hydride, ruthenium complex according to [1].
[3] PNP is represented by the following general formula (3)
[0010]
[Formula 2]

[0011]
(In the general formula (3), R 1 , R 2 , R 1 'and R 2 ' is the general formula (.R representing a definition identical groups in 2) 7 , R 7 ', R 8 , R 8 ', R 9 , R 9 ', R 10 and R 10 'each independently represent a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an aryloxy group, aralkyloxy group, a heterocyclic group or an amino group. alkyl group among these groups, an aryl group, an aralkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an aryloxy group, aralkyloxy group and the heterocyclic group optionally having substituent . it may also these R 7 and R 8 or R 9 , or R 10 ; R 7 and 'R 8 'or R 9 ' or R 10 '; R 8 and R 9 or R 10 ; R 8 ' and R 9 'or R 10 '; R 9 and R 10 or R 9 'or R 10 R;' 9 and ' R 10 or R 10 '; and R 10 and R 10 ' may form a ring together with each independently bonded to adjacent carbon atoms together. Characterized in that) is a tridentate ligand shown by the ruthenium complex according to [1] or [2].
[4] PNP is represented by the following general formula (4)
[0012]
[Formula 3]

[0013]
(In the general formula (4), R 1 , R 2 , R 1 'and R 2 ' is. Representing a defined and identical radicals in the general formula (2)) is a tridentate ligand represented by characterized in that a ruthenium complex according to [1] to [3].
[5] R 1 , R 2 , R 1 'and R 2 ' are each independently optionally substituted alkyl group, characterized in that an aryl group which may have a substituent to a ruthenium complex according to [4].
[6] the following general formula (5)
[0014]
　［ＲｕＸ １Ｘ ２（ＰＮＰ）］ ｑ　　　　　（５）
[0015]
(In the general formula (5), X 1 and X 2 represent a monovalent anionic monodentate ligands each independently, PNP general formula (2), three expressed by (3) or (4) represents tetradentate ligands, q is characterized by reacting a ruthenium complex and a primary alcohol and / or carbon monoxide represented by the representative.) an integer of 1 or 2, wherein [1] to [5] method for producing a ruthenium complex according to any one of.
[7] the following general formula (6)
[0016]
　　ＲｕＸ ３Ｘ ４（ＣＯ）（ＰＮＰ）　　　（６）
[0017]
(In the general formula (6), X 3 and X 4 represent a monovalent anionic monodentate ligands each independently, PNP general formula (2), three expressed by (3) or (4) represents tetradentate ligands, CO is characterized by reacting a ruthenium complex and a primary alcohol and / or carbon monoxide represented by the representative.) of carbon monoxide, any of [1] to [5] method for producing a ruthenium complex according to one or.
[8] above [1] to the ruthenium complex according to any one of [5] is used as a catalyst, method for producing alcohols by hydrogenation reduction of aldehydes or ketones.
[9] The [1] using a ruthenium complex according to any one of to [5] as a catalyst, an alcohol by hydrogenation reduction of esters, aldehydes, or manufacturing method of hemiacetals.
[10] the use [1] The ruthenium complex according to any one of to [5] as a catalyst, method for producing an alcohol, hemiacetals or dehydrogenative carbonyl compounds by oxidation of hemiaminal ethers.
[11] the production method of [1] to the [5] Any one using ruthenium complex according as a catalyst or, N- alkylamine compounds by undergoing dehydration condensation of alcohols and amines N- alkylation reaction of .
[12] The [8] to the manufacturing method according to any one of [11], the following general formula (5)
[0018]
　　［ＲｕＸ １Ｘ ２（ＰＮＰ）］ ｑ　　　　　（５）
[0019]
(In the general formula (5), X 1 and X 2 represent a monovalent anionic monodentate ligands each independently, PNP general formula (2), tridentate represented by (3) or (4) represents a ligand, q is characterized in that in each added as a catalyst in the reaction system ruthenium complex with primary alcohols and / or carbon monoxide represented by the representative.) an integer of 1 or 2, method for producing alcohols, aldehydes, hemiacetals, carbonyl compounds and N- alkylamine compound.
[13] The [1] ~ characterized by containing a ruthenium complex according to any one of [5], the organic reaction catalyst.
[14] Organic reactions, characterized in that it is a reaction of reducing a functional group having an ester group with a hydrogen donor, an organic reaction catalyst according to [13].
[15] Organic reactions, alcohols, hemiacetals, or wherein the the hemiaminal such dehydrogenated is a reaction for producing a carbonyl compound, an organic reaction catalyst according to [13].
[16] Organic reactions, undergo dehydration condensation of alcohols and amines are N- alkylation reaction, Organic reaction catalyst according to [13].
[17] ruthenium complex is represented by the following general formula (5)
[0020]
［ＲｕＸ １Ｘ ２（ＰＮＰ）］ ｑ　　　　　（５）
[0021]
(In the general formula (5), X 1 and X 2 represent a monovalent anionic monodentate ligands each independently, PNP general formula (2), tridentate represented by (3) or (4) represents a ligand, q is characterized by being formed by each added to the reaction system a ruthenium complex and a primary alcohol and / or carbon monoxide represented by the representative.) an integer of 1 or 2, the [13] to the organic reaction catalyst according to [16].
The invention's effect
[0022]
　Ruthenium complexes of the present invention are ruthenium compounds, tridentate ligand represented by PNP, and can be readily prepared from the primary alcohol (or carbon monoxide), which was suitable for industrial use, the reaction can be carried out under mild reaction conditions and high catalytic activity. Through the dehydration condensation of alcohols and amines; e.g., hydrogen donor presence, aldehydes, ketones and the production of alcohols by hydrogenation reduction of esters; preparation of carbonyl compounds by dehydrogenation oxidation of alcohols such as manufacture, etc. of N- alkyl compounds according N- alkylation reaction is possible.
BRIEF DESCRIPTION OF THE DRAWINGS
[0023]
FIG. 1 is a ORTEP diagram of X-ray structural analysis of the ruthenium complex B (Example 4).
DESCRIPTION OF THE INVENTION
[0024]
　For ruthenium complex described represented by the general formula (1) of the present invention.
　In the general formula (1), PNP represents a tridentate ligand represented by the general formula (2).
[0025]
　In the general formula (2), R 1 , R 2 , R 1 'and R 2 will be described with respect to'.
[0026]
　As the alkyl group, linear, branched, include either alkyl groups of annular. For example, 1 to 50 carbon atoms, preferably 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms. Specific examples include a methyl group, an ethyl group, n- propyl group, an isopropyl group, n- butyl group, isobutyl group, s- butyl group, tert- butyl group, n- pentyl, 2-pentyl, 3-pentyl group, tert- pentyl, 2-methylbutyl group, 3-methylbutyl group, 2,2-dimethylpropyl group, 3-methylbutan-2-yl group, n- hexyl, n- octyl group, a cyclopropyl group, a cyclopentyl group , cyclohexyl group, cyclooctyl group, 1-bicyclo [2.2.1] heptyl, 2-bicyclo [2.2.1] heptyl, 1-bicyclo [2.2.2] octyl group, 2-bicyclo [2.2.2] octyl group, 1-adamantyl group (1-tricyclo [3.3.1.1] decyl group) and 2-adamantyl (1- tricyclo [3.3.1 1] decyl group). Preferably an isopropyl group and cyclohexyl group.
[0027]
　Examples of the aryl group, for example, 6 to 36 carbon atoms, preferably 6 to 18 carbon atoms, or more preferably monocyclic, polycyclic or condensed cyclic aryl group having 6 to 14 carbon atoms. Specific examples include phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl group, 2-anthryl group, 9-anthryl group, 1-phenanthryl group, 2-phenanthryl group, 9-phenanthryl group, 1- biphenyl group, a 2-biphenyl group, and a 3-biphenyl group. With preference given to phenyl group.
[0028]
　The aralkyl group, a group in which at least one hydrogen atom is substituted by an aryl group described above for the alkyl group can be mentioned. For example, 7-37 carbon atoms, preferably 7 to 20 carbon atoms, more preferably an aralkyl group having 7 to 15 carbon atoms. Examples include benzyl, 1-phenylethyl, 2-phenylethyl and 1-phenylpropyl group and the like.
[0029]
　The alkenyl group, a linear, branched, include either an alkenyl group of cyclic. For example, 2 to 20 carbon atoms, preferably 2 to 15 carbon atoms, more preferably an alkenyl group having 2 to 10 carbon atoms. Examples include vinyl, 1-propenyl, 2-propenyl group, 1-cyclohexenyl group, and heptenyl group to 1-cyclopropyl and the like.
[0030]
　The alkynyl group includes alkynyl group which may branched be linear. For example, 2 to 20 carbon atoms, preferably 2 to 15 carbon atoms, more preferably an alkynyl group having 2 to 10 carbon atoms. Examples include ethynyl, 1-propynyl group and 2-propynyl group and the like.
[0031]
　The alkoxy group, a linear, branched, include either an alkoxy group ring. For example, 1 to 20 carbon atoms, preferably 1 to 15 carbon atoms, more preferably an alkoxy group consisting of alkyl groups having 1 to 10 carbon atoms. Specific examples include a methoxy group, an ethoxy group, n- propoxy group, isopropoxy group, n- butoxy group, isobutoxy group, s- butoxy group, tert- butoxy group, n- pentyloxy group, cyclopropyl group, cyclopentyl such group and cyclohexyloxy group.
[0032]
　The aryloxy group includes, for example, 6 to 36 carbon atoms, preferably a monocyclic, polycyclic or fused cyclic aryl group consisting of an aryl group having 6 to 18, more preferably 6 to 14 carbon atoms atoms and the like. Specific examples include a phenoxy group, p- methylphenoxy group, and a 1-naphthyloxy group and the like.
[0033]
　The aralkyloxy group, wherein at least one of the hydrogen atoms of the alkyl group of the alkoxy groups has been substituted with the aryl group, for example, 7 to 20 carbon atoms, an aralkyl group having preferably 7 to 15 and the like. Examples include benzyloxy, 1-phenylethoxy group, 2-phenylethoxy group, 1-phenylpropoxy group, 2-phenylpropoxy group, 3-phenylpropoxy group, 4-phenyl-butoxy group, 1-naphthylmethoxy and 2-naphthylmethoxy group and the like.
[0034]
　Examples of the heterocyclic group include an aliphatic heterocyclic group and an aromatic heterocyclic group. The aliphatic heterocyclic group, for example, at 2 to 14 carbon atoms, at least one as the heteroatom, preferably contains 1 to 3 heteroatoms, 3-8 membered, preferably 4-6 membered aliphatic monocyclic heterocyclic group, aliphatic heterocyclic group of polycyclic or fused and the like. Specific examples of the hetero atom, a nitrogen atom, such as oxygen and / or sulfur atom. Specific examples of the aliphatic heterocyclic group include a 2-pyrrolidyl group, 2-piperidinyl, 2-piperazinyl group, 2-morpholinyl group, 2-tetrahydrofuryl group, 2-tetrahydropyranyl group, and a 2-tetrahydrothienyl group etc. and the like.
[0035]
　The aromatic heterocyclic group, e.g., 2 to 15 carbon atoms, at least one as the heteroatom, preferably contains 1 to 3 heteroatoms, 5 or 6-membered monocyclic heteroaryl group, heteroaryl group polycyclic or condensed cyclic and the like. Specific examples of the hetero atom, a nitrogen atom, such as oxygen and / or sulfur atom. Specific examples of the aromatic heterocyclic group, 2-furyl group, 3-furyl, 2-thienyl, 3-thienyl group, 2-pyridyl, 3-pyridyl, 2-pyrimidyl group, 2-pyrazinyl group , 2-imidazolyl group, 4-imidazolyl group, 2-oxazolyl group, 2-thiazolyl, 2-benzofuryl group, 3-benzofuryl group, 2-benzothienyl group, 3-benzothienyl group, 2-quinolyl group, 3- quinolyl group, 1-isoquinolyl group, 2-benzimidazolyl group, 2-benzoxazolyl group and a 2-benzothiazolyl group and the like.
[0036]
　Amino groups may have a substituent, for example, at least one hydrogen atom of an amino group and an amino group are each independently alkyl groups mentioned above, aryl group, aralkyl group, alkenyl group or alkynyl group substituted amino group. Specific examples, N, N- diethylamino group, N, N- diisopropylamino group, N, N- dicyclohexyl amino group, N, N- diphenylamino group, N- naphthyl -N- phenylamino group and N, N- dibenzylamino group and the like. Also, when having two substituents may be joined to form a ring. Specific examples include a pyrrolidino group, and piperidino group. Further, piperazino group and morpholino group can be mentioned as the amino group.
[0037]
　These alkyl groups, aryl groups, aralkyl group, alkenyl group, alkynyl group, alkoxy group, aryloxy group, aralkyloxy group and the heterocyclic group may have a substituent.
[0038]
　Alkyl group, the substituent of the aralkyl group, an alkenyl group, an alkynyl group, an alkoxy group, and an aralkyloxy group, a hydroxyl group, wherein the alkoxy group, the above-mentioned aryloxy group, the above-mentioned aralkyloxy group, a heterocyclic group mentioned above, the amino groups, halogeno group, a silyl group, and a siloxy group, and an acyloxy group.
[0039]
　Aryl group, the substituents for the aryl group and heterocyclic group, the alkyl group, the above-mentioned aryl group, wherein the aralkyl group, the alkenyl group, the above-mentioned alkynyl group, a heterocyclic group mentioned above, hydroxyl group, wherein the alkoxy group, the above-mentioned aryloxy group, wherein the aralkyloxy group, the amino groups, halogeno group, a halogenoalkyl group, a silyl group, and a siloxy group, and an acyloxy group.
[0040]
　The halogeno group, fluoro group, chloro group, and a bromo group, and iodo group.
[0041]
　The halogenoalkyl group, at least one hydrogen atom on the alkyl group described above can be cited group substituted by a halogen atom. Such as a trifluoromethyl group and n- nonafluorobutyl group can be mentioned as specific examples. With preference given to trifluoromethyl group.
[0042]
　The silyl group, at least one alkyl group having a hydrogen atom the on silyl group, wherein the aryl groups include groups Tsu replace the above-mentioned aralkyl group. Trimethylsilyl group Specific examples, triethylsilyl group, triisopropylsilyl group, t- butyl dimethyl silyl group, etc. t-butyldiphenylsilyl group and triphenylsilyl group.
[0043]
　The siloxy groups include groups wherein the silyl group is bonded to an oxygen atom. Specific examples include trimethylsiloxy group, triethylsiloxy group, triisopropylsiloxy group, t- butyl dimethylsiloxy groups, such as t-butyl diphenyl siloxy group and triphenylsiloxy group.
[0044]
　The acyloxy group, for example, 6 to 36 carbon atoms, preferably 6 to 18 carbon atoms, more preferably acyloxy group having 6 to 14 carbon atoms. Specific examples include such as an acetyl group and benzyloxycarbonyl group.
[0045]
　R 1 and R 2 and R 1 'and R 2 ' may form a ring containing each independently bound adjacent phosphorus atoms with each other. Specific examples of the ring including a phosphorus atom, phosphorane, phosphole, Hosufinan, 2,5-dioxaphospholane and 2,5 Diazaphospholidin phosphorylase gin and the like. These groups may have a substituent such as described above.
[0046]
Q 　in the general formula (2) 1 , Q 2 will be described.
[0047]
　Q 1 and Q 2 denote an aralkylene group which may have a even better alkanediyl group or a substituent substituted.
[0048]
　The alkanediyl group, linear, branched, and good alkanediyl group or cyclic. For example, 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, or more preferably alkanediyl group having 1 to 6 carbon atoms. Specific examples include methylene group, ethylene group, trimethylene group, tetramethylene group, pentamethylene group, cyclopropane-1,2-diyl group, cyclobutane-1,2-diyl group, cyclobutane-1,3-diyl group, cyclopentane-1,2-diyl, cyclopentane-1,3-diyl group, a cyclohexane-1,2-diyl group and a cyclohexane-1,3-diyl group and the like. Preferably include an ethylene group.
[0049]
　The aralkylene group benzyl group, include aralkylene range yl group having 7 to 11 carbon atoms which hydrogen one exception from aryl group on an aralkyl group such as a phenethyl group. Examples include benzylene (-Ph-CH 2 -), 2-phenylethylene group (-Ph-CH 2 CH 2 -), 1-naphthylmethylene group (-Np-CH 2 -) and 2-naphthylmethylene group (-Np-CH 2 -) and the like.
[0050]
　These alkanediyl group, the substituent of the aralkylene group, a hydroxyl group, an alkoxy group, an aryloxy group, an aralkyloxy group, a heterocyclic group, an amino group, a halogeno group, a silyl group, and a siloxy group, and an acyloxy group. These groups include the same groups as described above.
[0051]
　Preferred PNP, general formula (3) with tridentate ligands include, represented, as a more preferred PNP, tridentate ligands and the like represented by the general formula (4).
[0052]
　In the general formula (3), R 7 , R 7 ', R 8 , R 8 ', R 9 , R 9 ', R 10 and R 10 will be described with respect to'. Alkyl group, an aryl group, an aralkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an aryloxy group, aralkyloxy radical, R in the general formula (2) is a heterocyclic group and an amino group 1 , R 2 , R 1 'and R 2 same groups detailed in the description of 'the
[0053]
　Further, these alkyl group, an aryl group, an aralkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an aryloxy group, aralkyloxy group and heterocyclic group may have a substituent.
[0054]
　Alkyl group, an aralkyl group, an alkenyl group, an alkynyl group, the substituent of the alkoxy group and an aralkyloxy group, a hydroxyl group, an alkoxy group, an aryloxy group, an aralkyloxy group, a heterocyclic group, an amino group, a halogeno group, a silyl group, siloxy group and acyloxy group. Alkoxy group Among these groups, an aryloxy group, an aralkyloxy group, a heterocyclic group, an amino group, a halogeno group, a silyl group, a siloxy group and acyloxy group, R in the general formula (2) 1 , R 2 , R 1 'and R 2 ' include the same groups as described in detail in the description of.
[0055]
　Aryl group, the substituents for the aryl group and heterocyclic group, an alkyl group, an aryl group, an aralkyl group, an alkenyl group, an alkynyl group, a hydroxyl group, an alkoxy group, an aryloxy group, an aralkyloxy group, a heterocyclic group, an amino group , a halogeno group, a silyl group, and a siloxy group, and an acyloxy group. Alkyl group Among these groups, an aryl group, an aralkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an aryloxy group, an aralkyloxy group, a heterocyclic group, an amino group, a halogeno group, a silyl group, a siloxy group and acyloxy group , in the general formula (2) R 1 , R 2 , R 1 'and R 2 include the same groups as described in detail in the description of'.
[0056]
　In the general formula (1), X, with respect to Y is described.
　X in the general formula (1) represents a monovalent anionic monodentate ligand. The monoanionic monodentate ligand, has a negative charge monovalent represents a functional group or an anion capable of a single bond to the metal in the metal complex. Specific examples (showing a general formula in parentheses), hydride (-H), a hydroxyl group (-OH), a alkoxy group (-OR), an aryloxy group (-OAr), aralkyloxy group (-OAral), acyloxy group (-OC (= O) R) , a sulfonyloxy group (-OSO 2 R), a halogeno group (-X), bicarbonate ions (HCO 3 - ), tetrahydroborate ion (BH 4 - ), tetrafluoroborate acid ion (BF 4 - ), tetraaryl borate ion (BAr 4 - ), perchlorate ion (ClO 4 - ), hexafluorophosphate ion (PF 6 - ), hexafluoroantimonate ion (SbF 6 - ) , tetrahydrophthalic aluminate ion (AlH 4 - ), tetra hydroxo aluminate ions ([Al (OH) 4 ] - ), bis (2-methoxyethoxy) dihydro aluminate ion (AlH 2 (OCH 2 CH 2 OCH 3 ) 2 - ), trihydrofluoride cyano borate (BH 3 CN - ), triethyl hydro borate ions ( BH (Et) 3 - ) and tris (2-butyl) hydroborate ion (BH (sec-Bu) 3 - ), and the like. Preferably, the hydride (-H), a halogeno group (-X) and tetrahydroborate ion (BH 4 - ) may be mentioned, more preferably, include hydride (-H) it is.
[0057]
　Y in the general formula (1) represents a counter anion. The counter anion, having a negative charge of univalent anion that can function as a counter ion in the metal complex. Examples include hydroxide ion (HO - ), alkoxide ion (RO - ), aryloxides ions (ArO - ), aralkyl oxide ions (AralO - ), carboxylate ions (RCO 2 - ), sulfonate ion ( RSO 3 - ), halide ions (X - ), bicarbonate ions (HCO 3 - ), tetrahydroborate ion (BH 4 - ), tetrafluoroborate ion (BF 4 - ), tetraaryl borate ions (BAr 4 - ), perchlorate ion (ClO 4 - ), hexafluorophosphate ion (PF 6 -), Hexafluoroantimonate ion (SbF 6 - ), tetrahydrophthalic aluminate ion (AlH 4 - ), tetra hydroxo aluminate ions ([Al (OH) 4 ] - ), bis (2-methoxyethoxy) dihydro aluminate ions (AlH 2 (OCH 2 CH 2 OCH 3 ) 2 - ), trihydrofluoride cyano borate (BH 3 CN - ), triethyl hydro borate (BH (Et) 3 - ) and tris (2-butyl) hydroborate ion (BH (sec-Bu) 3 - ) and the like, preferably hydroxide ion (HO - ), halide ions (X - ), tetrafluoroborate ion (BF 4 -), Tetraarylborate ion (BAr 4 - ) and hexafluorophosphate ion (PF 6 - ) and the like. Preferably, the halide ion (X - ) and tetra-aryl borate (BAr 4 - ) and the like.
[0058]
　The alkoxy group / alkoxide ion, for example, alkoxy groups / alkoxide ion having 1 to 10 carbon atoms, preferably an alkoxy group / alkoxide ion having 1 to 4 carbon atoms. Specific examples include methoxy group / methoxide ion, ethoxy / ethoxide ion, 1-propoxy group / 1-propoxide ion, 2-propoxy group / 2-propoxide ion, 1-butoxy group / 1 Butokishidoion , 2-butoxy group / 2 Butokishidoion and tert- butoxy group / tert- Butokishidoion the like.
[0059]
　The aryloxy group / aryloxide ion, e.g., an aryloxy group / aryloxide ion having 6 to 14 carbon atoms, preferably an aryloxy group / aryloxide ion having 6 to 10 carbon atoms. Specific examples include a phenoxy group / phenoxide ion, p- methylphenoxy group / p- methyl phenoxide ion, 2,4,6-methylphenoxy group / 2,4,6 phenoxide ion, p- nitrophenoxy group / p - nitrophenoxide ion, pentafluorophenoxy group / pentafluoro phenoxide ion, 1-naphthyloxy group / 1-naphthyl oxide ions and 2-naphthyloxy group / 2-naphthyl oxide ions, and the like.
[0060]
　The aralkyloxy group / aralkyl oxide ion, for example, aralkyloxy groups / aralkyl oxide ions having 7-20 carbon atoms, preferably an aralkyl group / aralkyl oxide ions having 7 to 15 carbon atoms. Examples include benzyloxy / benzyl oxide ion, 1-phenylethoxy group / 1-phenyl ethoxide ion and 2-phenylethoxy group / 2-phenylethoxy de ions, and the like.
[0061]
　The acyloxy groups / carboxylate ions, for example, 1 to 18 carbon atoms, preferably a carboxyl group / carboxylic acid ion having 1 to 6 carbon atoms, and specific examples, a formyloxy group / formate ion, an acetoxy group / acetate ion, trifluoroacetoxy group / trifluoroacetate ion, propanoyl group / propionate ion, acryloyloxy group / acrylic acid ion, butanoyloxy group / butyrate, pivaloyloxy / pivalic acid ion, pentanoyloxy group / valerate ion, hexanoyloxy group / caproate ion, benzoyloxy group / acid ion and pentafluorobenzoyl group / pentafluoro benzoate ion and the like.
[0062]
　Specific examples of the sulfonyloxy group / sulfonic acid ion, a methanesulfonyloxy group / methanesulfonate ion, a trifluoromethanesulfonyloxy group / trifluoromethanesulfonate ion, n- nonafluorobutanesulfonyloxy group / n-nonafluorobutanesulfonate acid ion, p- toluenesulfonyloxy group / p- toluenesulfonate ion and 10-camphorsulfonyl group / camphorsulfonic acid ion, and the like.
[0063]
　Specific examples of the halogeno group / halide ion, fluoro / fluoride ion, chloro group / chloride ion, bromo group / bromide ion and iodo groups / iodide ions. Preferably, include chloro groups / chloride ions and iodo groups / iodide ions.
[0064]
　Specific examples of the tetraarylborate ion, tetraphenylborate ion, tetrakis (pentafluorophenyl) borate ion and tetrakis [3,5-bis (trifluoromethyl) phenyl] borate ion, and the like.
[0065]
　Ruthenium complexes of the present invention represented by the general formula (1), the ruthenium compound, PNP as a ligand, it can be readily prepared from primary alcohol and / or carbon monoxide.
[0066]
　The ruthenium compound is not particularly limited, for example, a three ruthenium chloride hydrate, tribromide ruthenium hydrate, inorganic ruthenium compounds such as triiodide ruthenium hydrate, tetra (dimethyl sulfoxide) dichloro ruthenium (RuCl 2 (DMSO) 4 ), dichloro (1,5-cyclooctadiene) ruthenium (II) polymer ([Ru (cod) Cl 2 ] n), dichloro (norbornadiene) ruthenium (II) polymer ([Ru (nbd) Cl 2 ] n), bis (2-methallyl) (1,5-cyclooctadiene) ruthenium (II) ((cod) Ru (2-methallyl) 2 ), dichloro (benzene) ruthenium (II) dimer ([Ru ( benzene) Cl 2 ] 2 ), dibromo (benzene) ruthenium (II) dimer ([Ru (benzene) Br 2 ] 2 ), diiodo (benzene) ruthenium (II) dimer ([Ru (benzene) I 2 ] 2 ), dichloro (p- cymene) ruthenium (II) dimer ([Ru (p- Cymene) Cl 2 ] 2), Dibromo (p- cymene) ruthenium (II) dimer ([Ru (p-cymene) Br 2 ] 2 ), diiodo (p- cymene) ruthenium (II) dimer ([Ru (p-cymene) I 2 ] 2 ), dichloro (mesitylene) ruthenium (II) dimer ([Ru (mesitylene) Cl 2 ] 2 ), dibromo (mesitylene) ruthenium (II) dimer ([Ru (mesitylene) Br 2 ] 2 ), diiodo (mesitylene) ruthenium ( II) dimer ([Ru (mesitylene) I 2 ] 2 ), dichloro (hexamethylbenzene) ruthenium (II) dimer ([Ru (hexamethylbenzene) Cl 2 ] 2 ), dibromo (hexamethylbenzene) ruthenium (II) dimer ( [Ru (h Xamethylbenzene) Br 2 ] 2), Diiodo (hexamethylbenzene) ruthenium (II) dimer ([Ru (Hexamethylbenzene) I 2 ] 2 ), dichloro-tris (triphenyl) phosphine (RuCl 2 (PPh 3 ) 3 ), dibromo tris (triphenyl) phosphine ( RuBr 2 (PPh 3 ) 3 ), Jiyodotorisu (triphenyl) phosphine (RuI 2 (PPh 3 ) 3 ), tetrahydropyran tris (triphenylphosphine) ruthenium (IV) (RuH 4 (PPh 3 ) 3 ), hydro-chloro-tris ( triphenylphosphine) ruthenium (II) (RuClH (PPh 3 ) 3 ), Asetatotorisu (triphenylphosphine) ruthenium (II) (RuH (OAc) (PPh 3) 3 ) and dihydro-tetrakis (triphenylphosphine) ruthenium (II) (RuH 2 (PPh 3 ) 4 ), and the like.
[0067]
　The primary alcohol represents a polyhydric alcohol and methanol alcohol hydroxyl group is bonded to a primary carbon hydroxyl group is bonded to a primary carbon. Specific examples include methanol, ethanol, 1-propanol, 2-methyl-1-propanol, 1-butanol, 2-methyl-1-butanol, 3-methyl-1-butanol, 1-pentanol, ethylene glycol, propylene glycol, and the like glycerol and 3-methoxy-1-butanol. Preferably, it includes methanol.
[0068]
　Next, a method for manufacturing a ruthenium complex represented by the general formula (1) of the present invention. Ruthenium complexes of the present invention is represented by the following general formula (5)
[0069]
　［ＲｕＸ １Ｘ ２（ＰＮＰ）］ ｑ　　　　　（５）
[0070]
In ruthenium complex represented, or the following general formula (6)
[0071]
　　ＲｕＸ ３Ｘ ４（ＣＯ）（ＰＮＰ）　　　（６）
[0072]
The in ruthenium complex represented and the primary alcohol and / or carbon monoxide can be obtained by reacting.
[0073]
　Formula (5) and (6) X in the 1 , X 2 , X 3 and X 4 are the general formula (1) monoanionic monodentate ligand synonymous monovalent anionic monodentate detailed in represents the child, the general formula may be the same or different and X in (1).
[0074]
　Ruthenium complexes of the present invention to be produced, resulting in stereoisomers by coordination mode and conformation of the ligand. Stereoisomers such as shown below can be given as specific examples.
[0075]
[Chemical Formula 4]

[0076]
(Wherein, R 1 , R 2 , R 1 ', R 2 ', Q 1 , Q 2 , X, Y are the same as defined in the general formula (1), the broken line coordination bonds between each symbol represents,.) solid line represents a covalent bond between the symbols
　in the notation of the stereoisomers of the complex, ent-[D] enantiomers of [D], Racemi- [D] is [D] and ent- It represents a racemic mixture of [D]. Ruthenium complexes of the present invention to be used for the reaction of the present invention is may be a isomeric mixture is an even pure One of these stereoisomers include [B] More preferred stereoisomer. For example, a manufacturing method for obtaining a pure [B], the general formula (5) or the general formula (6) with a ruthenium complex and a manufacturing method of reacting a primary alcohol and / or carbon monoxide represented the like.
[0077]
　In the production of the ruthenium complex represented by the general formula (1), it is preferable to use a solvent. Specific examples of the solvent used, hexane and aliphatic hydrocarbons such as hexane and heptane, aromatic hydrocarbons such as toluene and xylene, halogenated hydrocarbons such as diethyl ether methylene chloride and chlorobenzene, tetrahydrofuran, methyl tert- butyl ether and cyclopentyl ethers such as methyl ether, methanol, ethanol, isopropyl alcohol, n- butyl alcohol, and 2-butanol and tert- butyl alcohol, ethylene glycol, propylene glycol, 1,2-propanediol and multivalent such as glycerin alcohols, dimethyl formamide, amides such as dimethylacetamide and nitriles such as acetonitrile, sulfoxides such as dimethyl sulfoxide and water and the like, preferably Aliphatic hydrocarbons, aromatic hydrocarbons, ethers, alcohols, polyhydric alcohols, amides, nitriles and sulfoxides and the like. Specific examples include tetrahydrofuran, methanol, ethanol, isopropyl alcohol, dimethylformamide, acetonitrile and dimethyl sulfoxide. Preferably, it includes methanol. These solvents may be used in combination as appropriate of two or more with either singly.
[0078]
　Production method of the present invention is an inert gas, carbon monoxide gas, or be carried out in an air atmosphere desirable. As the inert gas, argon gas and nitrogen gas, etc. Specific examples. These gases and the atmosphere may be used as a mixed gas be used either singly. The reaction temperature is usually -50 ° C. ~ 300 ° C., it is suitably selected preferably from -20 ° C. ~ 250 ° C., more preferably in the range of 30 ℃ ~ 200 ℃. The reaction time base, naturally differs depending on the solvent and reaction temperature and other conditions, usually 1 minute to 72 hours, preferably from 1 minute to 24 hours, more preferably selected from a range of 5 minutes to 12 hours.
[0079]
　Further, in the production method of the present invention may be appropriately added additives. Specific examples of the additive, Bronsted acids, salts of Bronsted acids, basic compounds and the like. Specific examples of Bronsted acids, hydrofluoric acid, hydrochloric acid, hydrobromic acid, hydroiodic acid, acetic acid, benzoic acid, trifluoromethanesulfonic acid, etc. tetrafluoroborate and hexafluorophosphate and the like. Specific examples of salts of Bronsted acids, metal salts consisting of Bronsted acid. As more preferred examples include metal halides. Further preferred specific examples, lithium chloride, lithium bromide, lithium iodide, sodium fluoride, sodium bromide, sodium iodide, potassium fluoride and potassium bromide and the like. Specific examples of the basic compounds include lithium hydroxide, sodium hydroxide, metal hydroxides such as potassium hydroxide and cesium hydroxide, lithium hydride, sodium hydride, potassium hydride, lithium borohydride, borohydride sodium, potassium borohydride, lithium aluminum hydride, and metal hydride such as diisobutylaluminum hydride, lithium methoxide, lithium isopropoxide, lithium tert- butoxide, sodium methoxide, sodium ethoxide, sodium isopropoxide, sodium tert- butoxide, potassium methoxide, potassium ethoxide, and metal alkoxides such as potassium isopropoxide and potassium tert- butoxide. More preferably, sodium borohydride, sodium methoxide and potassium tert- butoxide.
[0080]
　Ruthenium complexes of the present invention produced by the production method of the present invention can be carried out post-treatment, isolation and purification as required. Examples of post-processing method, concentration, solvent substitution, washed, extracted, back extraction, crystallization, etc. can be mentioned by filtration and the addition of the poor solvent. These can be used alone or in combination thereof. Specific examples of methods of isolation and purification, dryness of the reaction solution, column chromatography, crystallization cleaning and the like by recrystallization and antisolvent. These can be used alone or in combination thereof.
[0081]
　Ruthenium complex represented by the general formula (1) of the present invention are useful as catalysts in the hydrogenation reduction of aldehydes, ketones and esters. Moreover, the ruthenium complex represented by the general formula (1) of the present invention, alcohols, dehydrogenation oxidation of hemiacetals and hemiaminals acids, as well as through the dehydration condensation of alcohols and amines in N- alkylation reaction it is useful as a catalyst.
[0082]
　Accordingly, the present invention contains a ruthenium complex represented by the general formula (1), provides a ruthenium catalyst for organic reactions.
[0083]
　A method for producing aldehydes or ketones alcohols by hydrogenation reduction.
[0084]
　Method for producing alcohols by hydrogenation reduction of aldehydes or ketones in the present invention, a method of using a ruthenium complex and a hydrogen donor represented by the general formula (1) the production of alcohols from aldehydes or ketones , and the following scheme (1)
[0085]
[Formula 5]

[0086]
In (Scheme (1), R 10 is an alkyl group, an aryl group, an aralkyl group, an alkenyl group, an alkynyl group, a carbonyl group having one heterocyclic group, or a monovalent group, preferably an alkyl group, an aryl group represented. Further, these alkyl group, aryl group, aralkyl group, alkenyl group, alkynyl group and heterocyclic group may have a substituent.)
method represented by, or the following scheme (2)
[0087]
[Formula 6]

[0088]
In (Scheme (2), R 11 and R 12 represent each independently an alkyl group, an aryl group, an aralkyl group, an alkenyl group, an alkynyl group, a carbonyl group having one heterocyclic group, or a monovalent group, preferably represents an alkyl group or an aryl group. Further, R 11 and R 12 may form a ring together with the bonded adjacent atoms together. also, these alkyl groups, an aryl group, an aralkyl group, an alkenyl group, an alkynyl group and heterocyclic group may have a substituent.)
and a method represented by.
[0089]
R 　in Scheme (1) and Scheme (2) 10 , R 11 and R 12 will be described.
[0090]
　As the alkyl group, linear, branched, include either alkyl groups of annular. For example, 1 to 50 carbon atoms, preferably 1 to 30 carbon atoms, more preferably an alkyl group having 1 to 20 carbon atoms. Specific examples include a methyl group, an ethyl group, n- propyl group, an isopropyl group, n- butyl group, isobutyl group, s- butyl group, tert- butyl group, n- pentyl, 2-pentyl, 3-pentyl group, tert- pentyl, 2-methylbutyl group, 3-methylbutyl group, 2,2-dimethylpropyl group, 3-methylbutan-2-yl group, n- hexyl, n- octyl, n- nonyl radical, n - decyl, n- undecyl, n- dodecyl group, n- tridecyl, n- tetradecyl, n- pentadecyl, n- hexadecyl group, n- heptadecyl group, n- octadecyl, n- nonadecyl radical, n - eicosyl group, a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, cyclooctyl group, 1-bicyclo [2.2.1] heptyl, 2-bicyclo 2.2.1] heptyl, 1-bicyclo [2.2.2] octyl group, 2-bicyclo [2.2.2] octyl group, 1-adamantyl group (1-tricyclo [3.3.1. 1] decyl group) and 2-adamantyl (1- tricyclo [3.3.1.1] decyl group). Preferably, a methyl group, an ethyl group, an isopropyl group and a cyclohexyl group. More preferably, methyl group.
[0091]
　Examples of the aryl group, for example, 6 to 36 carbon atoms, preferably 6 to 18 carbon atoms, or more preferably monocyclic, polycyclic or condensed cyclic aryl group having 6 to 14 carbon atoms. Specific examples include phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl group, 2-anthryl group, 9-anthryl group, 1-phenanthryl group, 2-phenanthryl group, 9-phenanthryl group, 1- biphenyl group, a 2-biphenyl group, and a 3-biphenyl group. Preferably, phenyl group.
[0092]
　The aralkyl group, a group in which at least one hydrogen atom is substituted by an aryl group described above for the alkyl group can be mentioned. For example, having 7 to 50 carbon atoms, preferably from 7 to 30 carbon atoms, more preferably an aralkyl group having 7 to 20 carbon atoms. Examples include benzyl, 1-phenylethyl, 2-phenylethyl, 1-phenylpropyl group, 1-phenylbutyl group, 1-phenyl-pentyl group, 1-phenyl-hexyl group, 1-phenyl-heptyl group, 1-phenyl-octyl group, 1-phenyl-nonyl group, 1-phenyl-decyl group, 1-undecyl group, 1-phenyl-dodecyl group, 1-phenyl-tridecyl group, and a 1-phenyl-tetradecyl group and the like.
[0093]
　The alkenyl group, a linear, branched, include either an alkenyl group of cyclic. For example, 2 to 50 carbon atoms, preferably 2 to 30 carbon atoms, more preferably an alkenyl group having 2 to 20 carbon atoms. Examples include vinyl, 1-propenyl, 2-propenyl, 2-butenyl, 2-pentenyl group, 2-hexenyl, 2-heptenyl group, 2-octenyl, 2-nonenyl, 2- icosenyl group, a 1-cyclohexenyl group, and heptenyl group to 1-cyclopropyl and the like.
[0094]
　The alkynyl group includes alkynyl group which may branched be linear, e.g., 2 to 50 carbon atoms, preferably 2 to 30 carbon atoms, more preferably an alkynyl group having 2 to 20 carbon atoms. Examples include ethynyl, 1-propynyl, 2-propynyl, 2-butynyl group, 2-pentynyl group, 2-hexynyl, 2-heptynyl group, 2-octynyl, 2-nonynyl group and 2 Ikoshiniru group, and the like.
[0095]
　Examples of the heterocyclic group include an aliphatic heterocyclic group and an aromatic heterocyclic group. The aliphatic heterocyclic group, for example, at 2 to 14 carbon atoms, at least one as the heteroatom, preferably contains 1 to 3 heteroatoms, 3-8 membered, preferably 4-6 membered aliphatic monocyclic heterocyclic group, aliphatic heterocyclic group of polycyclic or fused and the like. Specific examples of the hetero atom, a nitrogen atom, such as oxygen and / or sulfur atom. Specific examples of the aliphatic heterocyclic group include a 2-pyrrolidyl group, 2-piperidinyl, 2-piperazinyl group, 2-morpholinyl group, 2-tetrahydrofuryl group, 2-tetrahydropyranyl group, and a 2-tetrahydrothienyl group etc. and the like.
[0096]
　The aromatic heterocyclic group, e.g., 2 to 15 carbon atoms, at least one as the heteroatom, preferably contains 1 to 3 heteroatoms, 5 or 6-membered monocyclic heteroaryl group, heteroaryl group polycyclic or condensed cyclic and the like. Specific examples of the hetero atom, a nitrogen atom, such as oxygen and / or sulfur atom. Specific examples of the aromatic heterocyclic group, 2-furyl group, 3-furyl, 2-thienyl, 3-thienyl group, 2-pyridyl, 3-pyridyl, 2-pyrimidyl group, 2-pyrazyl group, 2-imidazolyl group, 4-imidazolyl group, 2-oxazolyl group, 2-thiazolyl, 2-benzofuryl group, 3-benzofuryl group, 2-benzothienyl group, 3-benzothienyl group, 2-quinolyl group, 3-quinolyl group, 1-isoquinolyl group, 2-benzimidazolyl group, 2-benzoxazolyl group and a 2-benzothiazolyl group and the like.
[0097]
　Examples of the carbonyl group having one univalent group represented by the following general formula (A)
[0098]
[Chemical Formula 7]

[0099]
(In the general formula (A), R P represents a monovalent group, a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, an alkenyl group, an alkynyl group, a heterocyclic group, an alkoxy group, an aryloxy group, aralkyloxy group, amino group, and a halogeno group or halogenoalkyl group. alkyl group among these groups, an aryl group, an aralkyl group, an alkenyl group, an alkynyl group, a heterocyclic group, an alkoxy group, an aryloxy group, aralkyloxy group, and halogenoalkyl group may have a substituent)
include those represented by.
[0100]
R 　in the general formula (A) P will be described. Alkyl group, the aryl group, an aralkyl group, an alkenyl group, an alkynyl group and the heterocyclic group include the same groups as described above.
[0101]
　The alkoxy group, a linear, branched, include either an alkoxy group ring. For example, 1 to 50 carbon atoms, preferably 1 to 30 carbon atoms, more preferably an alkoxy group consisting of alkyl groups having 1 to 20 carbon atoms. Specific examples include a methoxy group, an ethoxy group, n- propoxy group, isopropoxy group, n- butoxy group, isobutoxy group, s- butoxy group, tert- butoxy group, n- pentyloxy group, n- hexyl radical, n - heptyloxy group, n- octyl group, n- nonyloxy group, n- decyloxy group, n- undecyl group, n- dodecyloxy group, n- tridecyl group, n- tetradecyl group, n- pentadecyl group, n- hexadecyl group, n- heptadecyl group, n- octadecyl group, n- nonadecyloxy group, n- icosyloxy group, include cyclopropyloxy group, cyclopentyloxy group and cyclohexyloxy group and the like It is.
[0102]
　The aryloxy group includes, for example, 6 to 36 carbon atoms, preferably a monocyclic, polycyclic or fused cyclic aryl group consisting of an aryl group having 6 to 18, more preferably 6 to 14 carbon atoms atoms and the like. Specific examples thereof include a phenoxy group, p- methylphenoxy group, and a 1-naphthyloxy group and the like.
[0103]
　The aralkyloxy group include groups in which at least one hydrogen atom is substituted by the aryl group of the alkyl group of the alkoxy group. For example, aralkyloxy groups having 7 to 15 carbon atoms. As a specific example, benzyloxy group, 1-phenylethoxy group, 2-phenylethoxy group, 1-phenylpropoxy group, 2-phenylpropoxy group, 3-phenylpropoxy group, 4-phenyl-butoxy group, 1-naphthylmethoxy and 2-naphthylmethoxy group and the like.
[0104]
　Amino groups may have a substituent. For example, at least one hydrogen atom of the amino group are each independently alkyl groups mentioned above, aryl group, alkenyl group, alkynyl group or and amino groups substituted with an aralkyl group. Specific examples, N, N-diethylamino group, N, N-diisopropylamino group, N, N-dibutylamino group, N, N-dipentylamino group, N, N-didecylamino group, N, N-dicyclohexyl amino group, N, N- diphenylamino group, N- naphthyl -N- phenylamino group and N, N- dibenzylamino group and the like. Also, when having two substituents may be joined to form a ring. Specific examples include a pyrrolidino group, and piperidino group. Further, piperazino group and morpholino group can be mentioned as examples of the amino group.
[0105]
　The halogeno group, fluoro group, chloro group, and a bromo group, and iodo group.
[0106]
　The halogenoalkyl group, at least one hydrogen atom on the alkyl group described above can be cited group substituted by a halogen atom. As a specific example, a trifluoromethyl group, and n- nonafluorobutyl group, and the like. Preferably, it includes trifluoromethyl group.
[0107]
　R P is the alkyl group, an aryl group, an aralkyl group, an alkenyl group, an alkynyl group, a heterocyclic group, an alkoxy group, an aryloxy group, if an aralkyl group or a halogenoalkyl group may have a substituent . R P is an alkyl group, an aralkyl group, the alkenyl group, the substituent that may have in the case of an alkynyl group or halogenoalkyl group, a heterocyclic group, a hydroxyl group, an oxo group, an alkoxy group, an aryloxy group, aralkyloxy group, an amino group, a halogeno group, a silyl group, and a siloxy group, and an acyloxy group. Heterocyclic group Among these groups, an alkoxy group, an aryloxy group, an aralkyloxy group, an amino group and a halogeno group include the same groups described above
　as the silyl group, at least one hydrogen on the silyl group alkyl group in which atoms are the include groups Tsu replace an aryl group or an aralkyl group. Specific examples thereof include trimethylsilyl group, triethylsilyl group, triisopropylsilyl group, t- butyl dimethyl silyl group, etc. t-butyldiphenylsilyl group and triphenylsilyl group.
[0108]
　The siloxy groups include groups wherein the silyl group is bonded to an oxygen atom. As a specific example, trimethylsiloxy group, triethylsiloxy group, triisopropylsiloxy group, t- butyl dimethylsiloxy groups, such as t-butyl diphenyl siloxy group and triphenylsiloxy group.
[0109]
　The acyloxy group, a linear, branched, include either good acyloxy group ring. For example, 1 to 50 carbon atoms, preferably 1 to 30 carbon atoms, more preferably acyloxy group having 2 to 20 carbon atoms. Specific examples thereof include acetoxy group, benzoyloxy group, pivaloyloxy group (2,2-dimethyl propanoyl group), n- butanoyl group, n- pentanoyloxy group, n- hexanoyl group, n- heptanoyl oxy group, n- octanoyl group, n- nonanoyloxy group, n- decanoyloxy group, n- undecanoyl group and n- dodecanoyloxy group, and the like.
[0110]
　R P is an aryl group, a heterocyclic group, an alkoxy group, as the substituent which may have in the case of an aryloxy group or an aralkyloxy group, an alkyl group, an aryl group, an aralkyl group, an alkenyl group, an alkynyl group, a heterocyclic group, a hydroxyl group, an alkoxy group, an aryloxy group, an aralkyloxy group, an amino group, a halogeno group, a halogenoalkyl group, a silyl group, and a siloxy group, and an acyloxy group. Alkyl group Among these groups, an aryl group, an aralkyl group, an alkenyl group, an alkynyl group, a heterocyclic group, an alkoxy group, an aryloxy group, an aralkyloxy group, an amino group, a halogeno group, a halogenoalkyl group, a silyl group, a siloxy group and acyloxy groups include the same groups as described above.
[0111]
　In Scheme (1) and Scheme (2), the alkyl group, aryl group, aralkyl group, alkenyl group, alkynyl group and the heterocyclic group may have a substituent.
[0112]
　Alkyl group, an aralkyl group, examples of the substituent of the alkenyl group and alkynyl group, a heterocyclic group, a hydroxyl group, an alkoxy group, an aryloxy group, an aralkyloxy group, an amino group, a halogeno group, a silyl group, a siloxy group, an acyloxy group and a carbonyl group, and the like. Heterocyclic group Among these groups, an alkoxy group, an aryloxy group, an aralkyloxy group, an amino group, a halogeno group, a silyl group, a siloxy group, an acyloxy group and a carbonyl group include the same groups as described above.
[0113]
　Examples of the substituent of the aryl group and the heterocyclic group, an alkyl group, an aryl group, an aralkyl group, an alkenyl group, an alkynyl group, a heterocyclic group, a hydroxyl group, an alkoxy group, an aryloxy group, an aralkyloxy group, an amino group, a halogeno group, halogenoalkyl group, a silyl group, siloxy group, acyloxy group and a carbonyl group. Alkyl group Among these groups, an aryl group, an aralkyl group, an alkenyl group, an alkynyl group, a heterocyclic group, an alkoxy group, an aryloxy group, an aralkyloxy group, an amino group, a halogeno group, a halogenoalkyl group, a silyl group, a siloxy group , an acyloxy group and a carbonyl group include the same groups as described above.
[0114]
　In Scheme (2), R 11 and R 12 when they form a ring together with the atoms to which are bonded to adjacent to each other, ketones becomes cyclic ketone.
[0115]
　Scheme (1) and Scheme (2) in R 10 , R 11 and R 12 when a carbonyl group having one each independently a monovalent group, an alkenyl group or an alkynyl group and, R 10 , R 11 and R 12 is a carbonyl group having one each independently a monovalent group, if having an alkenyl group, an alkynyl group and / or an acyloxy group as a substituent, these groups may be reduced in the course of the reaction.
[0116]
　R 10 , R 11 and R 12 when the independently each have a aralkyloxy group as a substituent, an aralkyloxy group may be reduced in the course of the reaction.
[0117]
　If PNP is an optically active compound represented by the general formula (2), as a product in Scheme (2) it may be mirror images of one obtain excessive alcohol.
[0118]
　Hydrogenation from aldehydes or ketones in the present invention to alcohols, which can be suitably carried out without a solvent or in a solvent, it is desirable to use a solvent. Preferred solvents toluene, xylene and like aromatic hydrocarbons, hexane, heptane and the like aliphatic hydrocarbons, methylene chloride, halogenated hydrocarbons, diethyl ether chlorobenzene, tetrahydrofuran, methyl tert- butyl ether, such as cyclopentyl methyl ether ethers, methanol, ethanol, isopropyl alcohol, n- butyl alcohol, 2-butanol, alcohols such as tert- butyl alcohol, ethylene glycol, propylene glycol, 1,2-propane diol, polyhydric alcohols and water as glycerin etc. the. More preferably, toluene, tetrahydrofuran and methanol. These solvents may be used in combination as appropriate of two or more with either singly.
[0119]
　The hydrogen donor used in the method of the present invention, hydrogen gas, formic acid, and a primary alcohol and secondary alcohols or the like. As a specific example, hydrogen gas, methanol, ethanol, 1-butanol and isopropanol, and the like. More preferably include hydrogen gas.
[0120]
　The amount of the catalyst, the substrate varies depending on the type of the reaction conditions and catalyst, usually 0.0001mol% ~ 20mol% (amount of substance of the ruthenium complex to a substance amount of substrate), preferably from 0.002 mol% ~ 10 mol%, more preferably in the range of 0.005mol% ~ 5mol%.
[0121]
　The hydrogenation reduction of aldehydes or ketones of the present invention may be appropriately added additives. As the additive, for example, salts and basic compound such as Bronsted acid. Specific examples of salts of Bronsted acids, metal salts consisting of Bronsted acid. Metal halide or the like as a more specific example. More preferably, lithium chloride, lithium bromide, lithium iodide, sodium fluoride, sodium bromide, sodium iodide, potassium fluoride and potassium bromide and the like. Specific examples of the basic compound, triethylamine, diisopropylethylamine, N, N-dimethylaniline, piperidine, pyridine, 4-dimethylaminopyridine, 1,5-diazabicyclo [4.3.0] non-5-ene, 1, 8-diazabicyclo [5.4.0] undec-7-ene, amines such as tri -n- butylamine and N- methylmorpholine, potassium carbonate, sodium carbonate, lithium carbonate, alkali metal carbonates such as cesium carbonate magnesium and alkaline earth metal carbonates such as calcium carbonate, alkali metal hydrogen carbonates such as sodium hydrogen carbonate and potassium hydrogen carbonate, alkali metal hydroxides, magnesium hydroxide such as sodium hydroxide and potassium hydroxide and lithium hydroxide and alkaline earth metal hydrosulfide acids such as calcium hydroxide Things, sodium methoxide, sodium ethoxide, sodium isopropoxide, sodium tert- butoxide, potassium methoxide, potassium ethoxide, potassium isopropoxide, potassium tert- butoxide, lithium methoxide, tert- lithium isopropoxide and lithium alkali metal alkoxides butoxide, magnesium methoxide and alkaline earth metal alkoxides such as magnesium ethoxide, sodium hydride, calcium hydride, lithium borohydride, sodium borohydride, potassium borohydride and lithium aluminum hydride or the like include metal hydride. Preferably, sodium methoxide, potassium tert- butoxide Kishido and sodium borohydride, and the like. The amount of these additives is not particularly limited as long as the reaction proceeds, making it possible also by using the following 10 mol% of the substrate to obtain a sufficiently high conversion.
[0122]
　The pressure at the time of performing hydrogenation reduction with a hydrogen donor hydrogen gas is usually atmospheric pressure ~ 20 MPa, preferably normal pressure ~ 10 MPa, more preferably atmospheric pressure ~ 5 MPa. Incidentally, do not require pressurization of the hydrogen to the atmospheric pressure is meant the pressure under a hydrogen atmosphere.
[0123]
　The reaction temperature is usually -50 ° C. ~ 250 ° C., it is suitably selected preferably from -20 ° C. ~ 200 ° C., more preferably in the range of 0 ℃ ~ 150 ℃.
[0124]
　The reaction time, solvent, reaction temperature, and naturally differs but other conditions, usually 1 minute to 72 hours, preferably from 1 minute to 24 hours, more preferably selected from a range of 5 minutes to 12 hours.
[0125]
　The product can be carried out post-treatment, isolation and purification as required. Examples of post-processing method, concentration, washing, extraction, crystallization, etc. can be mentioned by stripping and the addition of the poor solvent. These can be used alone or in combination thereof. Specific examples of the isolation and purification, dryness of the reaction solution, various chromatography, distillation, crystallization cleaning and the like by recrystallization and antisolvent, they may be used alone or in combination thereof.
[0126]
　Subsequently, alcohol by hydrogenation reduction of esters, process for producing aldehydes and hemiacetals be described.
[0127]
　Method for producing alcohols, aldehydes and hemiacetals by hydrogenation reduction of esters in the present invention, the following scheme (3)
[0128]
[Formula 8]

[0129]
(In the scheme (3), R 13 represents a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, an alkenyl group, an alkynyl group, one having a carbonyl group a heterocyclic group, or a monovalent group, preferably an alkyl group, It represents an aryl group or a heterocyclic group. the alkyl group among these groups, an aryl group, an aralkyl group, an alkenyl group, an alkynyl group and the heterocyclic group may have a substituent .R 14 is alkyl group, an aryl group, an aralkyl group, an alkenyl group, an alkynyl group or a heterocyclic group, preferably an alkyl group. Furthermore, these alkyl groups, an aryl group, an aralkyl group, an alkenyl group, an alkynyl group and the heterocyclic group may have a substituent. Further, R 13 and R 14 may be bonded to each other.)
and a method represented by.
[0130]
R 　in Scheme (3) 13 and R 14 will be described.
　Scheme (3) R in 13 alkyl group in an aryl group, an aralkyl group, an alkenyl group, an alkynyl group, a carbonyl group having one heterocyclic group and monovalent group Scheme (1) and R in (2) 10 , R 11 and R 12 include the same groups as described in detail in the description of.
[0131]
　The alkyl groups of these groups, an aryl group, an aralkyl group, an alkenyl group, an alkynyl group and heterocyclic group may have a substituent.
[0132]
　Alkyl group, an aralkyl group, an alkenyl group or heterocyclic group as the substituent that may be possessed by an alkynyl group, a hydroxyl group, an alkoxy group, an aryloxy group, an aralkyloxy group, an amino group, a halogeno group, a silyl group, siloxy group, It includes a carbonyl group having one acyloxy group and monovalent group. Heterocyclic group, an alkoxy group Among these groups, an aryloxy group, an aralkyloxy group, an amino group, a halogeno group, a silyl group, a siloxy group, a carbonyl group having one acyloxy group and monovalent group Scheme (1) and R in (2) 10 , R 11 and R 12 include the same groups as described in detail in the description of.
[0133]
　The aryl group or a heterocyclic group substituent that may have, an alkyl group, an aryl group, an aralkyl group, an alkenyl group, an alkynyl group, a heterocyclic group, a hydroxyl group, an alkoxy group, an aryloxy group, an aralkyloxy group, an amino group, a halogeno group, a halogenoalkyl group, a silyl group, siloxy group, and a carbonyl group having one acyloxy group and monovalent group. Alkyl group Among these groups, an aryl group, an aralkyl group, an alkenyl group, an alkynyl group, a heterocyclic group, an alkoxy group, an aryloxy group, an aralkyloxy group, an amino group, a halogeno group, a halogenoalkyl group, a silyl group, a siloxy group , a carbonyl group having one acyloxy group and monovalent radicals R in the scheme (1) and (2) 10 , R 11 and R 12 include the same groups as described in detail in the description of.
[0134]
R 　in the scheme (3) 14 alkyl group in an aryl group, an aralkyl group, an alkenyl group, R in the alkynyl group and the heterocyclic group Scheme (1) and (2) 10 , R 11 and R 12 more in the description of It includes the same groups as mentioned with the group.
　These groups may have a substituent.
[0135]
　Alkyl group, an aralkyl group, the alkenyl group or substituent that may be possessed by an alkynyl group, a heterocyclic group, a hydroxyl group, an alkoxy group, an aryloxy group, an aralkyloxy group, an amino group, a halogeno group, a silyl group, a siloxy group , and a carbonyl group having one acyloxy group and monovalent group. Heterocyclic group, an alkoxy group Among these groups, an aryloxy group, an aralkyloxy group, an amino group, a halogeno group, a silyl group, a siloxy group, a carbonyl group having one acyloxy group and monovalent group Scheme (1) and R in (2) 10 , R 11 and R 12 include the same groups as described in detail in the description of.
[0136]
　The aryl group or a heterocyclic group substituent that may have, an alkyl group, an aryl group, an aralkyl group, an alkenyl group, an alkynyl group, a heterocyclic group, a hydroxyl group, an alkoxy group, an aryloxy group, an aralkyloxy group, an amino group, a halogeno group, a halogenoalkyl group, a silyl group, siloxy group, and a carbonyl group having one acyloxy group and monovalent group. Alkyl group Among these groups, an aryl group, an aralkyl group, an alkenyl group, an alkynyl group, a heterocyclic group, an alkoxy group, an aryloxy group, an aralkyloxy group, an amino group, a halogeno group, a halogenoalkyl group, a silyl group, a siloxy group , a carbonyl group having one acyloxy group and monovalent radicals R in the scheme (1) and (2) 10 , R 11 and R 12 include the same groups as described in detail in the description of.
[0137]
　R 13 and R 14 if are bonded to each other, esters is a cyclic compound of a lactone such.
[0138]
　R 13 and when is a carbonyl group having one univalent radical, R 13 and R 14 when having a carbonyl group which has one each independently a monovalent group as a substituent, for one have a monovalent group carbonyl group may be reduced in the course of the reaction.
[0139]
　R 13 and R 14 are, when an alkenyl group or an alkynyl group or each independently, R 13 and R 14 if has each independently an alkenyl group, an alkynyl group and / or an acyloxy group as a substituent, these the group may be reduced in the course of the reaction.
[0140]
　R 13 and R 14 are, if they have as a substituent an aralkyloxy group each independently, an aralkyloxy group may be reduced in the course of the reaction.
[0141]
　Hydride reducing esters of the present invention can be suitably carried out without a solvent or in a solvent, it is desirable to use a solvent. The solvent includes the same solvents as described in detail in the hydrogenation reduction of aldehydes or ketones.
[0142]
　Hydrogen donor used in the hydrogenation reduction of esters of the present invention, a hydrogen donor and a similar hydrogen donor detailed in the hydrogenation reduction of aldehydes or ketones.
[0143]
　The amount of the catalyst, the substrate varies depending on the type of the reaction conditions and catalyst, usually 0.0001mol% ~ 20mol% (amount of substance of the ruthenium complex to a substance amount of substrate), preferably from 0.002 mol% ~ 10 mol%, more preferably in the range of 0.005mol% ~ 5mol%.
[0144]
　Further, in the hydrogenation reduction of esters of the present invention may be appropriately added additives. The additives include additives and similar additives as detailed in the hydrogenation reduction of aldehydes or ketones.
[0145]
　The pressure at the time of performing hydrogenation reduction with a hydrogen donor hydrogen gas is usually atmospheric pressure ~ 20 MPa, preferably normal pressure ~ 10 MPa, more preferably atmospheric pressure ~ 5 MPa. Incidentally, do not require pressurization of the hydrogen to the atmospheric pressure is meant the pressure under a hydrogen atmosphere.
[0146]
　The reaction temperature is usually -50 ° C. ~ 250 ° C., it is suitably selected preferably from -20 ° C. ~ 200 ° C., more preferably in the range of 0 ℃ ~ 150 ℃.
[0147]
　The reaction time, solvent, reaction temperature, and naturally differs but other conditions, usually 1 minute to 72 hours, preferably from 1 minute to 24 hours, more preferably selected from a range of 5 minutes to 12 hours.
[0148]
　The product can be carried out post-treatment, isolation and purification as required. Examples of post-processing method, concentration, washing, extraction, crystallization, etc. can be mentioned by stripping and the addition of the poor solvent. These can be used alone or in combination thereof. Specific examples of methods of isolation and purification, dryness of the reaction solution, various chromatography, distillation, crystallization cleaning and the like by recrystallization and antisolvent, these can be used alone or in combination with .
[0149]
　Next, alcohols, will be described a manufacturing method of the carbonyl compound to oxidize the hemiacetals and hemiaminals acids.
[0150]
　Method for producing an alcohol, hemiacetals and dehydrogenatively carbonyl compounds by oxidation of the hemiaminal compounds of the present invention, for example following Scheme (4), (5) and (6)
[0151]
[Formula 9]

[0152]
(Scheme (4), (5) and (6), R 15 , R 16 , R 17 , R 19 are each independently hydrogen atom, an alkyl group, an aryl group, an aralkyl group, an alkenyl group, an alkynyl group, a heterocyclic ring group, an alkoxy group, an aryloxy group, a carbonyl group having one aralkyloxy group or a monovalent group. preferably, an alkyl group, an aryl group, an aralkyl group, an alkenyl group, an alkynyl group, or a heterocyclic group . more preferably an alkyl group, an aryl group. these alkyl group, an aryl group, an aralkyl group, an alkenyl group, an alkynyl group, a heterocyclic group, an alkoxy group, an aryloxy group and aralkyloxy group optionally having substituent good .R even 18 represents an alkyl group, an aryl group, an aralkyl group, an alkenyl group, an alkynyl group or a heterocyclic group. this Et alkyl group, aryl group, aralkyl air, alkenyl group, alkynyl group and the heterocyclic group may .R have a substituent 20 and R 21 are independently each a hydrogen atom, an alkyl group, an aryl group , an aralkyl group, an alkenyl group, an alkynyl group, or a heterocyclic group. these alkyl group, an aryl group, an aralkyl group, an alkenyl group, an alkynyl group and heterocyclic group may have a substituent. also, scheme R in (4) 15 and R 16May be binding to each other, Scheme (5) R in the 17 and R 18 may be bonded to each other, R in Scheme (6) 19 and R 20 and / or R 21 , or R 21 and R 20 are each bonds may be. )
Represented by.
[0153]
　Scheme (4), (5) and in (6) 17 , R 18 , R 19 , R 20 and R 21 will be described.
[0154]
　Scheme (4), (5) and (6) R in 15 , R 16 , R 17 and R 19 alkyl group in an aryl group, an aralkyl group, an alkenyl group, an alkynyl group, a heterocyclic group, an alkoxy group, an aryloxy group, a carbonyl group having one aralkyloxy group and monovalent radicals R in the scheme (1) and (2) 10 , R 11 and R 12 include the same groups as described in detail in the description of.
[0155]
　The alkyl groups of these groups, an aryl group, an aralkyl group, an alkenyl group, an alkynyl group, a heterocyclic group, an alkoxy group, an aryloxy group and aralkyloxy group may have a substituent.
[0156]
　Alkyl group, an aralkyl group, an alkenyl group or heterocyclic group as the substituent that may be possessed by an alkynyl group, a hydroxyl group, an alkoxy group, an aryloxy group, an aralkyloxy group, an amino group, a halogeno group, a silyl group, siloxy group, It includes a carbonyl group having one acyloxy group and monovalent group. Heterocyclic group, an alkoxy group Among these groups, an aryloxy group, an aralkyloxy group, an amino group, a halogeno group, a silyl group, a siloxy group, a carbonyl group having one acyloxy group and monovalent group Scheme (1) and R in (2) 10 , R 11 and R 12 include the same groups as described in detail in the description of.
[0157]
　Aryl group, a heterocyclic group, an alkoxy group, aryloxy group or a substituent that may be possessed by aralkyloxy group, an alkyl group, an aryl group, an aralkyl group, an alkenyl group, an alkynyl group, a heterocyclic group, a hydroxyl group, an alkoxy group, an aryloxy group, an aralkyloxy group, an amino group, a halogeno group, a halogenoalkyl group, a silyl group, siloxy group, and a carbonyl group having one acyloxy group and monovalent group. Alkyl group Among these groups, an aryl group, an aralkyl group, an alkenyl group, an alkynyl group, a heterocyclic group, an alkoxy group, an aryloxy group, an aralkyloxy group, an amino group, a halogeno group, a halogenoalkyl group, a silyl group, a siloxy group , a carbonyl group having one acyloxy group and monovalent radicals R in the scheme (1) and (2) 10 , R 11 and R 12 include the same groups as described in detail in the description of.
[0158]
R 　in Scheme (5) 18 will be described.
　Alkyl group, an aryl group, an aralkyl group, an alkenyl group, an alkynyl group and heterocyclic group for R in the scheme (1) and (2) 10 , R 11 and R 12 include the same groups as described in detail in the description of It is. These groups may have a substituent.
[0159]
　Alkyl group, an aralkyl group, an alkenyl group or heterocyclic group as the substituent that may be possessed by an alkynyl group, a hydroxyl group, an alkoxy group, an aryloxy group, an aralkyloxy group, an amino group, a halogeno group, a silyl group, siloxy group, It includes a carbonyl group having one acyloxy group and monovalent group. Heterocyclic group, an alkoxy group Among these groups, an aryloxy group, an aralkyloxy group, an amino group, a halogeno group, a silyl group, a siloxy group, a carbonyl group having one acyloxy group and monovalent group Scheme (1) and R in (2) 10 , R 11 and R 12 include the same groups as described in detail in the description of.
[0160]
　The aryl group or a heterocyclic group substituent that may have, an alkyl group, an aryl group, an aralkyl group, an alkenyl group, an alkynyl group, a heterocyclic group, a hydroxyl group, an alkoxy group, an aryloxy group, an aralkyloxy group, an amino group, a halogeno group, a halogenoalkyl group, a silyl group, siloxy group, and a carbonyl group having one acyloxy group and monovalent group. Alkyl group Among these groups, an aryl group, an aralkyl group, an alkenyl group, an alkynyl group, a heterocyclic group, an alkoxy group, an aryloxy group, an aralkyloxy group, an amino group, a halogeno group, a halogenoalkyl group, a silyl group, a siloxy group , a carbonyl group having one acyloxy group and monovalent radicals R in the scheme (1) and (2) 10 , R 11 and R 12 include the same groups as described in detail in the description of.
[0161]
　R in Scheme (4) 15 and R 16 if are bonded to each other, alcohol is a cyclic compound such as cyclic alcohol. R in Scheme (5) 17 and R 18 if are bonded to each other, hemiacetals is a cyclic compound. R in Scheme (6) 19 and R 20 and / or R 21 if are bonded to each other, hemiaminal such is the cyclic compound.
Also, R 20 and R 21 if are bonded to each other, hemiaminal such is the cyclic compound.
[0162]
　Scheme (4) - in the scheme (6), R 15 - R 21 are each optionally having independently hydroxyl group as a substituent, a hydroxyl group may be oxidized in the course of the reaction.
[0163]
　Further, Scheme hemiacetals in (5) may also be formed in the reaction system, for example, the following scheme (7)
[0164]
[Formula 10]

[0165]
(In the scheme (7), R 17 and R 18 Scheme (representing definitions the same group in 5).), And a technique represented by.
[0166]
　Scheme hemiaminal rocks in (6) may be formed in the reaction system, for example, the following scheme (8)
[0167]
[Of 11]

[0168]
(In the scheme (8), R 19 , R 20 and R 21 Scheme (. Representing a definition identical groups in 6)), and a technique represented by.
[0169]
　Alcohols of the present invention, the dehydrogenation oxidation of hemiacetals and hemiaminals include, but can be suitably carried out without a solvent or in a solvent, it is desirable to use a solvent. Preferred solvents toluene, xylene and like aromatic hydrocarbons, hexane, heptane and the like aliphatic hydrocarbons, methylene chloride, halogenated hydrocarbons, diethyl ether chlorobenzene, tetrahydrofuran, methyl tert- butyl ether, such as cyclopentyl methyl ether ethers, ketones such as 1-phenyl-ethanone and benzophenones. More preferably, toluene and xylene.
[0170]
　The amount of the catalyst, the substrate varies depending on the type of the reaction conditions and catalyst, usually 0.0001mol% ~ 20mol% (amount of substance of the ruthenium complex to a substance amount of substrate), preferably from 0.002 mol% ~ 10 mol%, more preferably in the range of 0.005mol% ~ 5mol%.
[0171]
　Further, alcohols of the present invention, the dehydrogenation oxidation of hemiacetals and hemiaminals acids, may be added as appropriate additive. The additives include additives and similar additives as detailed in the hydrogenation reduction of ketones and aldehydes.
[0172]
　This reaction is preferably carried out in an inert gas or air atmosphere. As the inert gas, argon gas and nitrogen gas, etc. Specific examples. Be used These inert gases and air are each independently, it may be used as mixed gas.
[0173]
　The reaction temperature is usually -50 ° C. ~ 300 ° C., preferably from 0 ° C. ~ 200 ° C., more preferably selected from a range of 20 ℃ ~ 150 ℃.
The reaction time, solvent, reaction temperature, and naturally differs but other conditions, usually 1 minute to 72 hours, preferably from 1 minute to 24 hours, more preferably selected from a range of 5 minutes to 12 hours.
[0174]
　The product can be carried out post-treatment, isolation and purification as required. Examples of post-processing method, concentration, washing, extraction, crystallization, etc. can be mentioned by stripping and the addition of the poor solvent. These can be used alone or in combination thereof. Specific examples of methods of isolation and purification, dryness of the reaction solution, various chromatography, distillation, crystallization cleaning and the like by recrystallization and antisolvent. These can be used alone or in combination thereof.
[0175]
　Next, will be described a method of manufacturing due to the fact that through the dehydration condensation of alcohols and amines N- alkylamine compound.
[0176]
　Method for producing an alcohol and by going through dehydration condensation of amines N- alkylamine compound in the present invention, for example, the following scheme (9) and (10)
[0177]
[Chem. 12]

[0178]
(In the scheme (9) and (10), R 22 , R 25 and R 26 each independently represents a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, an alkenyl group, an alkynyl group or a heterocyclic group. Preferably represents an alkyl group, more preferably. to an aryl group, an aryl group. alkyl group among these groups, an aryl group, an aralkyl group, an alkenyl group, an alkynyl group and heterocyclic group have substituents which may .R 23 and R 24 are each independently a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, an alkenyl group, an alkynyl group, a heterocyclic group, a halogeno group, preferably from. representing a halogenoalkyl group or a silyl group represents an alkyl group or an aralkyl group. alkyl group among these groups, an aryl group, an aralkyl group, an alkenyl group, an alkynyl group, double Ring group and a halogenoalkyl group may have a substituent. In addition, R in the scheme (9) 22 and R 23 , R 22 and R 24 , R 22 and R 23 and R 24 , or R 23 and R 24 may be bonded to each other, R in Scheme (10) 23 and R 24 , R 26 and R 25 , R 26 and R 24 and / or R 23 , R 26 and R 25 and R 24 and / or R 23 , or R 25 and R 24 and / or R 23 may be bonded to each other. )
Represented by.
[0179]
　In Scheme (9) and (10), R 22 , R 25 and R 26 will be described.
[0180]
　Scheme (9) and R in (10) 22 , R 25 and R 26 alkyl group in an aryl group, an aralkyl group, an alkenyl group, R in the alkynyl group and the heterocyclic group Scheme (1) and (2) 10 , R 11 and R 12 include the same groups as described in detail in the description of. The alkyl groups of these groups, an aryl group, an aralkyl group, an alkenyl group, an alkynyl group and heterocyclic group may have a substituent.
[0181]
　Alkyl group, an aralkyl group, an alkenyl group or heterocyclic group as the substituent that may be possessed by an alkynyl group, a hydroxyl group, an alkoxy group, an aryloxy group, an aralkyloxy group, an amino group, a halogeno group, a silyl group, siloxy group, It includes a carbonyl group having one acyloxy group and monovalent group. Heterocyclic group Among these groups, an alkoxy group, an aryloxy group, an aralkyloxy group, an amino group, a halogeno group, a silyl group, a siloxy group, a carbonyl group having one acyloxy group and monovalent radicals, the scheme (1 ) and R in (2) 10 , R 11 and R 12 include the same groups as described in detail in the description of.
[0182]
　The aryl group or a heterocyclic group substituent that may have, an alkyl group, an aryl group, an aralkyl group, an alkenyl group, an alkynyl group, a heterocyclic group, a hydroxyl group, an alkoxy group, an aryloxy group, an aralkyloxy group, an amino group, a halogeno group, a halogenoalkyl group, a silyl group, siloxy group, and a carbonyl group having one acyloxy group and monovalent group. Alkyl group Among these groups, an aryl group, an aralkyl group, an alkenyl group, an alkynyl group, a heterocyclic group, an alkoxy group, an aryloxy group, an aralkyloxy group, an amino group, a halogeno group, a halogenoalkyl group, a silyl group, a siloxy group , a carbonyl group having one acyloxy group and monovalent radicals R in the scheme (1) and (2) 10 , R 11 and R 12 include the same groups as described in detail in the description of.
[0183]
　Scheme (9) and (10) R in 23 and R 24 alkyl group in an aryl group, an aralkyl group, an alkenyl group, an alkynyl group, a heterocyclic group, a halogeno group, a halogenoalkyl group and silyl group, the scheme (1 ) and R in (2) 10 , R 11 and R 12 include the same groups as described in detail in the description of. The alkyl groups of these groups, an aryl group, an aralkyl group, an alkenyl group, an alkynyl group, a heterocyclic group, and the halogenoalkyl group may have a substituent.
[0184]
　Alkyl group, an aralkyl group, an alkenyl group, an alkynyl group or halogenoalkyl heterocyclic group group as the substituent that may be possessed by a hydroxyl group, an alkoxy group, an aryloxy group, an aralkyloxy group, an amino group, a halogeno group, a silyl group , siloxy group, and a carbonyl group having one acyloxy group and monovalent group. Heterocyclic group, an alkoxy group Among these groups, an aryloxy group, an aralkyloxy group, an amino group, a halogeno group, a silyl group, a siloxy group, a carbonyl group having one acyloxy group and monovalent group Scheme (1) and R in (2) 10 , R 11 and R 12 include the same groups as described in detail in the description of.
[0185]
　The aryl group or a heterocyclic group substituent that may have, an alkyl group, an aryl group, an aralkyl group, an alkenyl group, an alkynyl group, a heterocyclic group, a hydroxyl group, an alkoxy group, an aryloxy group, an aralkyloxy group, an amino group, a halogeno group, a halogenoalkyl group, a silyl group, siloxy group, and a carbonyl group having one acyloxy group and monovalent group. Alkyl group Among these groups, an aryl group, an aralkyl group, an alkenyl group, an alkynyl group, a heterocyclic group, an alkoxy group, an aryloxy group, an aralkyloxy group, an amino group, a halogeno group, a halogenoalkyl group, a silyl group, a siloxy group , a carbonyl group having one acyloxy group and monovalent radicals R in the scheme (1) and (2) 10 , R 11 and R 12 include the same groups as described in detail in the description of.
[0186]
R 　in Scheme (9) 22 and R 23 , R 22 and R 24 and R 22 and R 23 and R 24 if are bonded to each other, the reaction becomes intramolecular reaction, the reaction product is a cyclic compound such as cyclic amines to become. Also, R 23 and R 24 when are bonded to each other, alcohol is a cyclic compound such as cyclic alcohol. R in Scheme (10) 23 and R 24 when are bonded to each other, alcohol is a cyclic compound such as cyclic alcohol. Also, R 26 and R 25 when are bonded to each other, amines will cyclic compound such as cyclic amines. Also, R 26 and R 24 and / or R 23 , R 26 and R 25And R 24 and / or R 23 and R 25 and R 24 and / or R 23 if are bonded to each other, the reaction becomes intramolecular reaction, the reaction product is a cyclic compound such as cyclic amines.
[0187]
　In the scheme (9) and (10), R 22 ~ R 26 are each optionally independently an alkenyl group or an alkynyl group and, R 22 ~ R 26 are each independently an alkenyl group, an alkynyl group, an acyloxy group and optionally having as a substituent a carbonyl group having one / or monovalent group, these groups may be reduced in the course of the reaction.
[0188]
　In the scheme (9) and (10), R 22 ~ R 26 is, if having as a substituent an aralkyloxy group each independently, an aralkyloxy group may be reduced in the course of the reaction.
[0189]
　In the scheme (9) and (10), R 22 ~ R 26 is, if each independently having a hydroxyl group as a substituent group, a hydroxyl group may be oxidized in the course of the reaction.
[0190]
　Dehydration condensation of alcohols and amines of the present invention can be suitably carried out without a solvent or in a solvent, it is desirable to use a solvent. Solvents, alcohols, include the same solvents as described in detail in the dehydrogenation oxidation of hemiacetals and hemiaminal.
[0191]
　The amount of the catalyst, the substrate varies depending on the type of the reaction conditions and catalyst, usually 0.0001mol% ~ 20mol% (amount of substance of the ruthenium complex to a substance amount of substrate), preferably from 0.002 mol% ~ 10 mol%, more preferably in the range of 0.005mol% ~ 5mol%.
[0192]
　It may also be appropriately added additives with N- alkylation reaction of the present invention. The additives include additives and similar additives as detailed in the hydrogenation reduction of aldehydes or ketones.
[0193]
　This reaction is an inert gas, hydrogen gas, carbon monoxide gas, or be carried out in an air atmosphere desirable. As the inert gas, argon gas and nitrogen gas, etc. Specific examples. These gases and the atmosphere may be used as a mixed gas be used either singly.
[0194]
　Since this reaction is capable of performing the dehydrogenation oxidation and hydrogenation reduction in the same system, but the hydrogen donor is not necessarily required, hydrogen gas may be used hydrogen donor such as formic acid. The pressure at which hydrogen gas is used as the hydrogen donor is usually normal pressure ~ 10 MPa, preferably normal pressure ~ 5 MPa, more preferably atmospheric pressure ~ 2 MPa. Incidentally, do not require pressurization of the hydrogen to the atmospheric pressure is meant the pressure under a hydrogen atmosphere.
[0195]
　The reaction temperature is usually -50 ° C. ~ 300 ° C., preferably from 0 ° C. ~ 200 ° C., more preferably selected from a range of 20 ℃ ~ 150 ℃.
[0196]
　The reaction time, solvent, reaction temperature, and naturally differs but other conditions, usually 1 minute to 72 hours, preferably from 1 minute to 24 hours, more preferably selected from a range of 5 minutes to 12 hours.
[0197]
　The product can be carried out post-treatment, isolation and purification as required. Examples of post-processing method, concentration, washing, extraction, crystallization, etc. can be mentioned by stripping and the addition of the poor solvent. These can be used alone or in combination thereof. Specific examples of methods of isolation and purification, dryness of the reaction solution, various chromatography, distillation, crystallization cleaning and the like by recrystallization and antisolvent. These can be used alone or in combination thereof.
[0198]
　Represented the reaction using ruthenium complex is in the general formula (1) can be performed while both to form a complex (in situ method). For example, ruthenium complex represented by the general formula (5), encapsulated primary alcohol and / or carbon monoxide, substrates, additives according to the solvent and optionally in the same container, aldehydes in the presence of a hydrogen donor, ketone it is possible to carry out the hydrogenation reduction classes and esters. Solvent, a hydrogen donor, a catalyst amount, additives, reaction temperature, pressure in the case of using hydrogen gas, post-treatment, for isolation and purification, the scheme (1) and aldehydes and ketones in (2) solvents described in the hydrogenation reduction, a hydrogen donor, a catalyst amount, additives, reaction temperature, pressure in the case of using hydrogen gas, post-treatment, the same conditions as isolation and purification thereof.
[0199]
　Similarly, the ruthenium complex represented by the general formula (5), alcohols by encapsulating primary alcohol and / or carbon monoxide, substrates, additives according to the solvent and optionally in the same container, hemiacetals and hemiaminals it is possible to carry out dehydrogenating oxidation classes. The solvent in this reaction, a catalytic amount of additives, reaction temperature, workup, with respect to isolation and purification, Scheme (4), (5) and an alcohol in (6), dehydrogenatively of hemiacetals and hemiaminals acids It detailed the solvent, a catalytic amount in the oxidation, additives, reaction temperature, pressure in the case of using hydrogen gas, post-treatment, the same conditions as isolation and purification thereof.
[0200]
　Moreover, the ruthenium complex represented by the general formula (5), primary alcohol and / or carbon monoxide, substrate (amines and alcohols), solvents, hydrogen donor if necessary, and an additive if necessary it is also possible to carry out through the dehydration condensation of alcohols and amines N- alkylation reaction by encapsulating the same container. The solvent in this reaction, a hydrogen donor, a catalyst amount, additives, reaction temperature, pressure in the case of using hydrogen gas, post-treatment, with respect to isolation and purification, Scheme (9), and N- alkylated in (10) solvents described in the reaction, a hydrogen donor, a catalyst amount, additives, reaction temperature, pressure in the case of using hydrogen gas, post-treatment, the same conditions as isolation and purification thereof.
Example
[0201]
　EXAMPLES Hereinafter, the present invention will be described in detail, but the present invention should not be construed by these examples in any way limiting.
[0202]
　Furthermore, the structural formula in the examples, facial / meridional isomers having a metal complex having a tridentate ligand and geometric isomers of cis / trans isomers or the like having a metal complex having a plurality of monodentate ligands It does not take into account.
[0203]
　Incidentally, GC yield was carried out by gas chromatography (hereinafter abbreviated as GC). Apparatus used is as follows.
Proton nuclear magnetic resonance spectrum (hereinafter, 1 abbreviated as H
NMR) ; 400MR / DD2 (resonance frequency: 400 MHz, Agilent)
Phosphorus 31 nuclear magnetic resonance spectrum (hereinafter 31 referred to as P
NMR) ; 400MR / DD2 (resonance frequency : 161 MHz, Agilent)
carbon 13 nuclear magnetic resonance spectrum (hereinafter 13 referred to as C
NMR) : Avance III 500 (125-MHz, Bruker Inc.)
gas chromatography
(GC) ; GC-4000 (GL-SCIENCES Inc.
　Ltd.) DB-WAX (30M, 0.25MmID, 0.25Myuemu Df)
　Inj. Temp. ; 200 ℃, Det. Temp. ; 230 ° C.
　Temp. 80 ℃ (0min.) - 5 ℃ / min. ℃ -250
(1Min.)
HRMS ; LCMS-IT-TOF (Ionization: ESI, manufactured by Shimadzu Corp.)
[0204]
(Example 1) ruthenium complex manufacturing
　was prepared ruthenium complex A by following scheme.
[0205]
[Formula 13]

[0206]
　In 100mL stainless steel autoclave [RuCl 2 (PNP)] 2 and 100 mg (0.16 mmol), KO t of Bu added 915 mg (8.2 mmol), after nitrogen substitution, methanol was added 10 mL. It was stirred for 5 hours at 0.99 ° C. bath after sealed, and cooled to room temperature. It was added to the reaction until a 0.5 N HCl / MeOH to pH 3-5, and the filtrate was concentrated under reduced pressure after removal of the precipitated solid by filtration to give a pale yellow solid. The resulting solid was washed with toluene 5 mL, water 5 mL, to give a ruthenium complex A. Further washing solution was separated, ruthenium complex A was obtained by adding by the organic layer is concentrated under reduced pressure. Together, these complexes, to obtain a ruthenium complex A total of 92.1mg as a pale yellow solid (89% yield).
1 H NMR (400 MHz, CD 2 Cl 2 )
[delta] = 8.70-8.80 (m, IH), 8.70 (s, IH) 7.86-7.96 (m, 4H), 7.60 -7.70 (m, 4H), 7.40-7.58 (m, 12H), 3.35-3.60 (m, 2H), 3.18-3.40 (m, 2H), 2 .80-2.90 (m, 2H), 2.20-2.40 (m, 2H), -
6.27 (t, J = 16.4 Hz) 31 P NMR (161 MHz, CD 2 Cl 2 ): δ = 57.80
13 C NMR (125 MHz, CD 2 Cl 2 )
[delta] = 168.42 (S), 138.26 (S), 135.76 (t, J = 23.8Hz), 133.55 (t, J = 23. 8Hz), 133.80 (t, J = 6.3Hz), 131.57 (t, J = 6.3Hz), 131.47 (S), 130.85 (S), 129.26 (t, J 5.0 Hz =), 129.13 (t, J = 5.0 Hz), 33.13,33.02,32.91,21.43
HRMS (ESI, m / z)
calcd C 30 H 30 NO 2 P 2 Ru ([M-Cl] + as), 600.078978
Found 600.078160
[0207]
(Example 2) ruthenium complex manufacturing
　was prepared ruthenium complex A by following scheme.
[0208]
[Formula 14]

[0209]
　200 mg (0.33 mmol) of Ru-MACHO in 100mL stainless steel autoclave, KO t of Bu added 2.02 g (18.0 mmol), after nitrogen substitution, methanol was added 20 mL. It was stirred for 5 hours at 0.99 ° C. bath after sealed, and cooled to room temperature. It was added to the reaction until a 0.5 N HCl / MeOH to pH 3-5, and the filtrate was concentrated under reduced pressure after removal of the precipitated solid by filtration to give a pale yellow solid. The resulting solid was washed with toluene 5 mL, water 5 mL, to give a ruthenium complex A. Further washing solution was separated, ruthenium complex A was obtained by adding by the organic layer is concentrated under reduced pressure. Together, these complexes was obtained quantitatively as a pale yellow solid ruthenium complex A.
[0210]
(Example 3) ruthenium complex manufacturing
　was prepared ruthenium complex A by following scheme.
[0211]
[Formula 15]

[0212]
　The Ru-MACHO added 6.1 mg (0.01 mmol) in a Schlenk tube 20 mL, after nitrogen substitution, 1M NaOMe and (MeOH solution) 1.0mL (1.0mmol), methanol was added 8.0 mL, 10 min at room temperature and the mixture was stirred. After replacing with carbon monoxide gas and stirred at room temperature for one hour, added until the 0.5 N HCl / MeOH to pH3-5 the reaction, and concentrated under reduced pressure. Was added 2mL heavy methylene chloride precipitated solid, where the filtered solution was analyzed by IH NMR, it was confirmed that by converting the ruthenium complex A.
[0213]
(Example 4) ruthenium complex manufacturing
　was prepared ruthenium complex B by the following scheme.
[0214]
[Chemical Formula 16]

[0215]
　20mL of Schlenk tube ruthenium complex 150 mg A (0.24 mmol), NaBPh 4 was added 81 mg (0.24 mmol), after nitrogen substitution, methanol was added 3.0 mL. After the reaction solution was stirred at room temperature for 2 hours, water was added 2 mL, the precipitated solid was filtered off. The resulting solid was washed with methanol and hexane, subjected to vacuum concentration to obtain a ruthenium complex B of 169.9mg as a white solid (77% yield). Create a single crystal of ruthenium complex B using heavy methylene chloride / hexane to determine the structure by X-ray structural analysis.
1 H NMR (400 MHz, CD 2 Cl 2 )
[delta] = 7.62-7.74 (m, 2H), 7.30-7.60 (m, 26H), 6.98-7.10 (m, 8H ), 6.80-6.90 (m, 4H) , 2.20-2.70 (m, 5H), 1.60-2.10 (m, 4H), - 6.24 (t, J = 16.2
Hz) 31 P NMR (161 MHz, CD 2 Cl 2 ): [delta] =
54.87 13 C NMR (125 MHz, CD 2 Cl 2 )
δ＝１９８．７２（Ｓ）、１９２．５３（Ｓ）、１６７．９９（Ｓ）、１６４．５９（Ｓ）、１６４．２０（Ｓ）、１６３．８１（Ｓ）、１３６．３３（Ｓ）、１３４．４１（ｔ、Ｊ＝２３．８Ｈｚ）、１３３．０４（ｔ、Ｊ＝６．３Ｈｚ）、１３２．６９（ｔ、Ｊ＝２３．８Ｈｚ）、１３１．４５（ｔ、Ｊ＝６．３Ｈｚ）、１２９．６８（ｔ、Ｊ＝５．０Ｈｚ）、１２９．３５（ｔ、Ｊ＝５．０Ｈｚ）、５４．１６（Ｓ）、３３．１４（ｔ、Ｊ＝１３．８Ｈｚ）
計算値　Ｃ ３０Ｈ ３０ＮＯ ２Ｐ ２Ｒｕ([Ｍ－ＢＰｈ ４] ＋)として、６００．０７８９７８
実測値　６００．０７８０８６
[0216]
(Example 5) acetophenone hydrogenation reduction with ruthenium complex A
[0217]
[Chemical Formula 17]

[0218]
　The ruthenium complex A obtained in 100mL stainless autoclave in Example 2 was added 1.6 mg (0.0025), after nitrogen substitution, 1 M KO t Bu and (THF solution) 0.25mL (0.25mmol), toluene 2 mL, was added to a substrate 0.29 mL (2.5 mmol), and stirred for 5 hours at a hydrogen pressure 1 MPa, 80 ° C.. After cooling, the reaction with GC 94% yield was analyzed by GC 1-phenyl-1-ethanol was obtained.
[0219]
(Example 6) Hydrogenation reduction of methyl benzoate using ruthenium complex A
[0220]
[Chem. 18]

[0221]
　The ruthenium complex A obtained in 100mL stainless autoclave in Example 2 was added 1.6 mg (0.0025), after nitrogen substitution, 1 M KO t Bu and (THF solution) 0.25mL (0.25mmol), toluene 2 mL, was added to the substrate 0.3 mL (2.5 mmol), and stirred for 6 hours at a hydrogen pressure of 1 MPa, 80 ° C.. After cooling, the reaction of benzyl alcohol was obtained by GC 37% yield was analyzed by GC.
[0222]
(Example 7) was used ruthenium complex A 1-phenyl-1-dehydrogenation type oxidation reaction of ethanol
[0223]
[Of 19]

[0224]
　The ruthenium complex A obtained in 100mL stainless autoclave in Example 2 was added 1.6 mg (0.0025), after nitrogen substitution, 1 M KO t Bu and (THF solution) 0.25mL (0.25mmol), toluene 2 mL, was added to a substrate 0.31 mL (2.5 mmol), and stirred for 5 hours at 80 ° C.. After cooling, the reaction acetophenone was obtained by GC yield 67% was analyzed by GC.
[0225]
(Example 8) according to aniline and methanol using ruthenium complex A N-methylation reaction
[0226]
[Of 20]

[0227]
　The ruthenium complex A obtained in 100mL stainless autoclave in Example 2 was added 1.3 mg (0.002 mmol), after nitrogen substitution, 1 M KO t Bu (THF solution) 0.4 mL (0.4 mmol), methanol 3.6 mL, was added to the substrate 169.5mg (1.82mmol), was sealed and stirred for 5 hours at 0.99 ° C.. After cooling, the reaction with 95% GC yield was analyzed N- methylaniline obtained in GC.
[0228]
(Example 9) aniline and ethanol by N- ethylation reaction using a ruthenium complex A
[0229]
[Of 21]

[0230]
　The ruthenium complex A obtained in 100mL stainless autoclave in Example 2 was added 1.3 mg (0.002 mmol), after nitrogen substitution, 1 M KO t Bu (THF solution) 0.4 mL (0.4 mmol), ethanol 3.6mL, substrate 183.5mg a (1.97mmol) was added. After the reaction vessel with hydrogen gas replacement, the mixture was stirred for 5 hours at a hydrogen pressure of 1 MPa, 0.99 ° C.. After cooling, the reaction by GC yield 71% was analyzed N- ethylaniline obtained in GC.
[0231]
(Example 10) N-benzylation reaction according aniline with benzyl alcohol using the ruthenium complex A
[0232]
[Formula 22]

[0233]
　The ruthenium complex A obtained in 100mL stainless autoclave in Example 2 was added 1.3 mg (0.002 mmol), after nitrogen substitution, 1 M KO t Bu (THF solution) 0.8 mL (0.8 mmol), tetrahydrofuran 2.8 mL, substrate 191.0mg a (2.05 mmol) was added, after sealing, the mixture was stirred for 5 hours at 0.99 ° C.. After cooling, the reaction with GC 92% yield was analyzed N- benzyl aniline obtained in GC.
Industrial Applicability
[0234]
　The present invention provides a novel cationic ruthenium complex wherein having one bis (phosphino alkyl) amine as a tridentate ligand, and carbon monoxide that has two-fold as monodentate ligands is there. Ruthenium complexes of the present invention can be conveniently prepared from inexpensive and readily available inorganic ruthenium compounds. Ruthenium complexes of the present invention, a hydrogen donor presence, aldehydes, hydrogenation reduction of ketones and esters to catalyze. The alcohols, dehydrogenation oxidation of hemiacetals and hemiaminals acids, catalyzes the N- alkylation reaction undergo dehydration condensation of alcohols and amines. Further, the ruthenium complexes of the present invention is a stable powder in air, is suitable for industrial use for handling even easier. Further, the ruthenium complexes of the present invention, since it is also possible to carry out while forming a complex, to allow a variety of reaction conditions according to the situation. Furthermore, therefore, the reaction using ruthenium complex and the same of the present invention is useful in the field of organic industrial chemistry.

The scope of the claims

[Requested item 1]Following general formula
　　　(1) [RuX (CO) 2 (PNP)] Y (1)
in (Formula (1), X represents a monovalent anionic monodentate ligand, Y represents a counter anion .PNP the following general formula (2)

in (formula (2), R 1 , R 2 , R 1 'and R 2 ' are each independently an alkyl group, an aryl group, an aralkyl group, an alkenyl group, an alkynyl group, an alkoxy represents group, an aryloxy group, an aralkyloxy group, a heterocyclic group or an amino group. alkyl group among these groups, an aryl group, an aralkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an aryloxy group, aralkyloxy group and heterocyclic group may have a substituent. in addition, these R 1 and R 2 and R 1 'R and 2 ' are to form a ring with each independently bound adjacent phosphorus atoms with each other even if There .Q 1 and Q 2 represent each independently an optionally substituted alkanediyl group, or may have a substituent group aralkylene group.)
In represents the tridentate ligand represented, CO represents carbon monoxide. )
Ruthenium complex represented by.
[Requested item 2]
And wherein X is hydride, ruthenium complex according to claim 1.
[Requested item 3]
PNP the following general formula (3)

in (Formula (3), R 1 , R 2 , R 1 'and R 2 ' are, .R representing a defined and identical radicals in the general formula (2) 7 , R 7 ', R 8 , R 8 ', R 9 , R 9 ', R 10 and R 10 ' each independently represent a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an aryloxy group, an aralkyloxy group, a heterocyclic group or an amino group. alkyl group among these groups, an aryl group, an aralkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an aryloxy group, aralkyloxy group and the heterocyclic . group may have a substituent these R 7 and R 8 or R 9 , or R 10 ; R 7'And R 8 ' or R 9 'or R 10 '; R 8 and R 9 or R 10 ; R 8 'and R 9 ' or R 10 '; R 9 and R 10 or R 9 ' or R 10 '; R 9 'and R 10 or R 10 '; and R 10 and R 10 'may form a ring together with each independently bonded to adjacent carbon atoms together. )
Characterized in that it is a tridentate ligand represented by a ruthenium complex according to claim 1 or 2.
[Requested item 4]
PNP the following general formula (4)

(In the general formula (4), R 1 , R 2 , R 1 'and R 2 ' is. Representing a defined and identical radicals in the general formula (2))
represented by characterized in that it is a that tridentate ligand, a ruthenium complex according to claim 1-3.
[Requested item 5]
R 1 , R 2 , R 1 'and R 2 are' are each independently, and wherein the optionally substituted alkyl group, an aryl group which may have a substituent, ruthenium complex according to claim 4.
[Requested item 6]
　Following general formula (5)
[RuX 1 X 2 (PNP)]　　　　　q (5) in (formula (5), X 1 and X 2 represent a monovalent anionic monodentate ligands each independently, PNP the formula (2), (3) or (4) represents a tridentate ligand represented by, q is 1 or 2 represents an integer.) ruthenium complex with primary alcohols and / or represented characterized in that the reaction of carbon monoxide, a manufacturing method of a ruthenium complex according to any one of claims 1-5.

[Requested item 7]
　Following general formula (6)
RuX 3 X 4 (CO) (PNP) (6) in (formula (6), X 3 and X 4 represent a monovalent anionic monodentate ligands each independently, PNP the general formula (2), (3) or (4) represents a tridentate ligand represented by, CO represents carbon monoxide.) ruthenium complex with primary alcohols and expressed / or carbon monoxide and wherein the reacting carbon manufacturing method of a ruthenium complex according to any one of claims 1-5.
[Requested item 8]
Ruthenium complexes according to any one of claims 1 to 5, used as a catalyst, method for producing alcohols by hydrogenation reduction of aldehydes or ketones.
[Requested item 9]
Using ruthenium complex according to any one of claims 1 to 5 as a catalyst, an alcohol by hydrogenation reduction of esters, method for producing aldehydes or hemiacetals.
[Requested item 10]
Using ruthenium complex according to any one of claims 1 to 5 as a catalyst, method for producing an alcohol, hemiacetals or dehydrogenative carbonyl compounds by oxidation of hemiaminal ethers.
[Requested item 11]
Method of manufacturing according to claim 1 using a ruthenium complex according to any one of the 5 as a catalyst, the alcohol and undergoes dehydration condensation of amines N- alkylation with N- alkylamine compound.
[Requested item 12]
The method of manufacture according to any one of claims 8-11, the following general formula (5)
[RuX 1 X 2 (PNP)]　　　　　q (5) in (formula (5), X 1 and X 2 are each independently represents a monovalent anionic monodentate ligands, PNP is the general formula (2) represents a tridentate ligand represented by (3) or (4), q is an integer of 1 or 2 the expressed.) , characterized in that each added to a catalyst represented by the ruthenium complex and the primary alcohol and / or the carbon monoxide reaction at, alcohols, aldehydes, hemiacetals, carbonyl compounds and method for producing N- alkylamine compound.

[Requested item 13]
Characterized by containing a ruthenium complex according to any one of claims 1 to 5, the organic reaction catalyst.
[Requested item 14]
Organic reactions, aldehyde groups with hydrogen donor, characterized in that it is a reaction of reducing a functional group having a ketone group and an ester group, a catalyst for organic reactions according to claim 13.
[Requested item 15]
Organic reaction, alcohols, hemiacetals, or wherein the the hemiaminal compound is a reaction to dehydrogenation catalyst for organic reactions according to claim 13.
[Requested item 16]
Organic reactions, characterized in that through the dehydration condensation of alcohols and amines are N- alkylation reaction catalyst for organic reactions according to claim 13.
[Requested item 17]
Ruthenium complex represented by the following general formula (5)
[RuX 1 X 2 (PNP)]　　　　　q (5) in (formula (5), X 1 and X 2 a are each independently a monovalent anionic monodentate ligand represents, PNP general formula (2), (3) or (4) represents a tridentate ligand represented by, q represents.) an integer of 1 or 2 ruthenium complex and a primary alcohol and represented by / or characterized in that it is formed by respectively adding carbon monoxide in the reaction system, a catalyst for organic reactions according to claim 13 to 16.