JP6388803B2 - Ruthenium complex - Google Patents

Description

  The present invention relates to a ruthenium complex.

  Ruthenium complexes having various structures have been proposed as catalysts for asymmetric reduction reactions. As one of them, a ruthenium complex having a nitrogen-containing bidentate ligand is known. For example, Patent Document 1 discloses a ruthenium complex (1) represented by the formula (1).

  Non-Patent Document 1 discloses a ruthenium complex represented by the formula (2). The ruthenium complex represented by the formula (2) can complete the hydrogenation reaction of acetophenone in 3 hours under the condition of S / C = 1000 in a hydrogen atmosphere of 1 atm. 82 ° C. on a laboratory scale. It seems.

  Non-Patent Document 2 discloses a ruthenium complex represented by the formula (3). The ruthenium complex represented by the formula (3) is subjected to a hydrogenation reaction of acetophenone in a laboratory scale under a hydrogen atmosphere of 40 atm and 80 ° C. under the condition of S / C = about 4300 in 2 hours. It seems to be able to progress to%.

CN 1020060877 A

M.P.deAraujo, A.L.deFigueiredo, A.L.Bogado, G.VonPoelhsitz, J.Ellena, E.E.Castellano, C.L.Donnici, J.V.Comasseto, A.A.Batista, Organometallics 2005,54,6159-6168. T. Jozak, D. Zabel, A. Schubert, Y. Sun, W. T. Thiel, Eur. J. Inorg. Chem. 2010, 5135-5145.

  An object of the present invention is to provide a ruthenium complex which can be a catalyst applicable to industrial production.

  As a result of repeated studies to achieve the above object, the present inventors have completed the present invention including the following aspects.

[1] A ruthenium complex represented by the formula (I).
Ru (L ¹ ) (L ² ) (Px) _n (Z) (I)
[In Formula (I), L ¹ and L ² each independently represent an anionic ligand. L ¹ and L ² may be combined to form a bidentate or more anionic ligand.
Px represents a phosphine ligand. n represents an integer of 1 or 2.
Z represents a ligand having a structure in which the heterocycle A and the heterocycle B are connected by a single bond.
In the heterocycle A, at least one of the atoms adjacent to the ring constituent atoms connected to the heterocycle B by a single bond is a nitrogen atom, and the heterocycle A does not have an N—H bond.
The heterocycle B is one selected from the formulas b1 to b11.

〔式ｂ１〜ｂ１１中、
Ｙは、Ｏ、Ｓ、またはＮ（Ｒ²）を示す。
Ｒ²は、それぞれ独立に、無置換の若しくは置換基を有するＣ１〜６アルキル基、無置換の若しくは置換基を有するＣ６〜１０アリール基、または無置換の若しくは置換基を有するＣ６〜１０アリールＣ１〜６アルキル基を示す。
Ｒｂは、それぞれ独立に、水素原子、ハロゲノ基、無置換の若しくは置換基を有するＣ１〜６アルキル基、無置換の若しくは置換基を有するＣ１〜６アルコキシ基、無置換の若しくは置換基を有するＣ６〜１０アリール基、無置換の若しくは置換基を有するＣ６〜１０アリールオキシ基、または無置換の若しくは置換基を有するＣ６〜１０アリールＣ１〜６アルキル基を示す。
Ｒｂｂは、それぞれ独立に、無置換の若しくは置換基を有するＣ１〜６アルキル基、無置換の若しくは置換基を有するＣ６〜１０アリール基、または無置換の若しくは置換基を有するＣ６〜１０アリールＣ１〜６アルキル基を示す。
ＲｂとＲｂ、ＲｂとＲ²、またはＲｂｂとＲｂとが一緒になって環を形成していてもよい。
＊はヘテロ環Ａとの結合位置を示す。〕

[In the formulas b1 to b11,
Y represents O, S, or N (R ² ).
Each R ² independently represents an unsubstituted or substituted C 1-6 alkyl group, an unsubstituted or substituted C 6-10 aryl group, or an unsubstituted or substituted C 6-10 aryl C 1 Represents a -6 alkyl group.
Rb each independently represents a hydrogen atom, a halogeno group, an unsubstituted or substituted C1-6 alkyl group, an unsubstituted or substituted C1-6 alkoxy group, an unsubstituted or substituted C6. -10 aryl group, unsubstituted or substituted C6-10 aryloxy group, or unsubstituted or substituted C6-10 aryl C1-6 alkyl group.
Rbb each independently represents an unsubstituted or substituted C1-6 alkyl group, an unsubstituted or substituted C6-10 aryl group, or an unsubstituted or substituted C6-10 aryl C1- 6 represents an alkyl group.
Rb and Rb, Rb and R ² , or Rbb and Rb may be combined to form a ring.
* Shows the bonding position with the heterocycle A. ]

[2] The ruthenium complex according to [1], wherein the heterocycle A is one selected from the formulas a1 to a15.

〔式ａ１〜ａ１５中、
Ｘは、Ｏ、Ｓ、またはＮ（Ｒ¹）を示す。
Ｒ¹は、それぞれ独立に、無置換の若しくは置換基を有するＣ１〜６アルキル基、無置換の若しくは置換基を有するＣ６〜１０アリール基、または無置換の若しくは置換基を有するＣ６〜１０アリールＣ１〜６アルキル基を示す。
Ｒａは、それぞれ独立に、水素原子、ハロゲノ基、無置換の若しくは置換基を有するＣ１〜６アルキル基、無置換の若しくは置換基を有するＣ１〜６アルコキシ基、無置換の若しくは置換基を有するＣ６〜１０アリール基、無置換の若しくは置換基を有するＣ６〜１０アリールオキシ基、または無置換の若しくは置換基を有するＣ６〜１０アリールＣ１〜６アルキル基を示す。 ｍは１または２の整数を示す。
Ｒａａは、それぞれ独立に、無置換の若しくは置換基を有するＣ１〜６アルキル基、無置換の若しくは置換基を有するＣ６〜１０アリール基、または無置換の若しくは置換基を有するＣ６〜１０アリールＣ１〜６アルキル基を示す。
ＲａとＲａ、又は、ＲａとＲ¹とが一緒になって環を形成していてもよい。実線と点線の二重線部分は単結合又は二重結合を表し、＊は環Ｂとの結合位置を示す。〕

[In the formulas a1 to a15,
X represents O, S, or N (R ¹ ).
Each R ¹ is independently an unsubstituted or substituted C 1-6 alkyl group, an unsubstituted or substituted C 6-10 aryl group, or an unsubstituted or substituted C 6-10 aryl C 1 Represents a -6 alkyl group.
Each Ra independently represents a hydrogen atom, a halogeno group, an unsubstituted or substituted C1-6 alkyl group, an unsubstituted or substituted C1-6 alkoxy group, an unsubstituted or substituted C6; -10 aryl group, unsubstituted or substituted C6-10 aryloxy group, or unsubstituted or substituted C6-10 aryl C1-6 alkyl group. m represents an integer of 1 or 2.
Each Raa independently represents an unsubstituted or substituted C1-6 alkyl group, an unsubstituted or substituted C6-10 aryl group, or an unsubstituted or substituted C6-10 aryl C1; 6 represents an alkyl group.
Ra and Ra, or Ra and R ¹ may be combined to form a ring. The solid and dotted double lines represent single bonds or double bonds, and * represents the position of bonding with ring B. ]

[3] A reduction catalyst containing the ruthenium complex according to [1] or [2].
[4] A method for producing an alcohol by hydrogenating a ketone or an aldehyde in the presence of the reduction catalyst according to [3].

  The ruthenium complex according to the present invention is useful as a reduction catalyst. When the reduction catalyst according to the present invention is used, for example, the rate of the reduction reaction from ketones or aldehydes to alcohols can be greatly improved. Since the catalyst according to the present invention has high activity, the reduction reaction rate can be sufficiently improved even with a small amount of use.

First, the meanings of “unsubstituted” and “having a substituent” in the present specification will be described.
The term “unsubstituted” means only the group that is the mother nucleus. When there is no description of “having a substituent” and only the name of the group serving as a mother nucleus is used, it means “unsubstituted” unless otherwise specified.
On the other hand, the term “having a substituent” means that any hydrogen atom of a group serving as a mother nucleus is substituted with a group having the same or different structure as the mother nucleus. Accordingly, the “substituent” is another group bonded to a group serving as a mother nucleus. The number of substituents may be one, or two or more. Two or more substituents may be the same or different.
Terms such as “C1-6” indicate that the number of carbon atoms of the group serving as the mother nucleus is 1-6. This number of carbon atoms does not include the number of carbon atoms present in the substituent. For example, a butyl group having an ethoxy group as a substituent is classified as a C2 alkoxy C4 alkyl group.

  The “substituent” is not particularly limited as long as it is chemically acceptable and has the effects of the present invention. Examples of the group that can be a “substituent” include halogeno groups such as fluoro group, chloro group, bromo group, and iodo group; methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, and s-butyl. A C1-8 alkyl group such as a group, i-butyl group, t-butyl group, n-pentyl group, n-hexyl group; a C3-6 cycloalkyl group such as a cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group; Vinyl group, 1-propenyl group, 2-propenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 1-methyl-2-propenyl group, 2-methyl-2-propenyl group, 1-pentenyl group 2-pentenyl group, 3-pentenyl group, 4-pentenyl group, 1-methyl-2-butenyl group, 2-methyl-2-butenyl group, 1-hexenyl group, 2-hexenyl group A C2-6 alkenyl group such as a group, a 3-hexenyl group, a 4-hexenyl group, and a 5-hexenyl group; a C3-6 cycloalkenyl group such as a 2-cyclopropenyl group, a 2-cyclopentenyl group, and a 3-cyclohexenyl group; Ethynyl group, 1-propynyl group, 2-propynyl group, 1-butynyl group, 2-butynyl group, 3-butynyl group, 1-methyl-2-propynyl group, 2-methyl-3-butynyl group, 1-pentynyl group 2-pentynyl group, 3-pentynyl group, 4-pentynyl group, 1-methyl-2-butynyl group, 2-methyl-3-pentynyl group, 1-hexynyl group, 1,1-dimethyl-2-butynyl group, etc. A C2-6 alkynyl group of

  C1-6 alkoxy groups such as methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, s-butoxy group, i-butoxy group, t-butoxy group; vinyloxy group, allyloxy group, propenyl C2-6 alkenyloxy groups such as oxy group and butenyloxy group; C2-6 alkynyloxy groups such as ethynyloxy group and propargyloxy group; C6-10 aryl groups such as phenyl group and naphthyl group; phenoxy group and 1-naphthoxy group A C7-11 aralkyl group such as a benzyl group or a phenethyl group; a C7-11 aralkyloxy group such as a benzyloxy group or a phenethyloxy group; a formyl group, an acetyl group, a propionyl group, a benzoyl group; C1-7 acyl group such as cyclohexylcarbonyl group C1-7 acyloxy groups such as formyloxy group, acetyloxy group, propionyloxy group, benzoyloxy group, cyclohexylcarbonyloxy group; methoxycarbonyl group, ethoxycarbonyl group, n-propoxycarbonyl group, i-propoxycarbonyl group, n- A C1-6 alkoxycarbonyl group such as a butoxycarbonyl group and a t-butoxycarbonyl group; a carboxyl group;

  Hydroxyl group; oxo group; C1-6 haloalkyl such as chloromethyl group, chloroethyl group, trifluoromethyl group, 1,2-dichloro-n-propyl group, 1-fluoro-n-butyl group, perfluoro-n-pentyl group Group; C2-6 haloalkenyl group such as 2-chloro-1-propenyl group and 2-fluoro-1-butenyl group; 4,4-dichloro-1-butynyl group, 4-fluoro-1-pentynyl group, 5- C2-6 haloalkynyl group such as bromo-2-pentynyl group; C1-6 haloalkoxy group such as 2-chloro-n-propoxy group and 2,3-dichlorobutoxy group; 2-chloropropenyloxy group, 3-bromo C2-6 haloalkenyloxy groups such as butenyloxy group; 4-chlorophenyl group, 4-fluorophenyl group, 2,4-dichlorophenyl group, etc. Any C6-10 haloaryl group; C6-10 haloaryloxy group such as 4-fluorophenyloxy group, 4-chloro-1-naphthoxy group; chloroacetyl group, trifluoroacetyl group, trichloroacetyl group, 4-chlorobenzoyl group A cyano group; an isocyano group; a nitro group; an isocyanato group; a cyanato group; an azide group;

  Mercapto group; isothiocyanato group; thiocyanato group; C1-6 alkylthio such as methylthio group, ethylthio group, n-propylthio group, i-propylthio group, n-butylthio group, i-butylthio group, s-butylthio group, t-butylthio group Groups: C2-6 alkenylthio groups such as vinylthio groups and allylthio groups; C2-6 alkynylthio groups such as ethynylthio groups and propargylthio groups; C6-10 arylthio groups such as phenylthio groups and naphthylthio groups; thiazolylthio groups and pyridylthio groups Heteroarylthio group of C7-11 aralkylthio group such as benzylthio group and phenethylthio group; (methylthio) carbonyl group, (ethylthio) carbonyl group, (n-propylthio) carbonyl group, (i-propylthio) carbonyl group, ( n-butyl O) carbonyl group, (i-butylthio) carbonyl group, (s-butylthio) carbonyl group, (t-butylthio) (Cl to 6 alkylthio, such as carbonyl groups) carbonyl group;

  C1-6 alkylsulfinyl groups such as methylsulfinyl group, ethylsulfinyl group, t-butylsulfinyl group; C2-6 alkenylsulfinyl groups such as allylsulfinyl group; C2-6 alkynylsulfinyl groups such as propargylsulfinyl group; phenylsulfinyl group and the like C6-10 arylsulfinyl group; heteroarylsulfinyl group such as thiazolylsulfinyl group, pyridylsulfinyl group; C7-11 aralkylsulfinyl group such as benzylsulfinyl group, phenethylsulfinyl group; methylsulfonyl group, ethylsulfonyl group, t- A C1-6 alkylsulfonyl group such as a butylsulfonyl group; a C2-6 alkenylsulfonyl group such as an allylsulfonyl group; a C2-6 alkyl such as a propargylsulfonyl group; Rusuruhoniru group; C6-10 arylsulfonyl group such as phenylsulfonyl group; thiazolyl sulfonyl group, heteroarylsulfonyl groups such as pyridyl sulfonyl group; benzylsulfonyl group, C7～11 aralkyl sulfonyl group such as a phenethyl sulfonyl group;

  6-membered heteroaryl groups such as pyridyl group, pyrazinyl group, pyrimidinyl group, pyridinyl group, triazinyl group; saturated heterocyclic groups such as aziridinyl group, epoxy group, pyrrolidinyl group, tetrahydrofuranyl group, piperidyl group, piperazinyl group, morpholinyl group; Examples thereof include tri-C1-6 alkylsilyl groups such as trimethylsilyl group, triethylsilyl group and t-butyldimethylsilyl group; triphenylsilyl group.

  These “substituents” may have another “substituent” therein. For example, a butyl group as a substituent and an ethoxy group as another substituent, that is, an ethoxybutyl group may be used.

The ruthenium complex of the present invention is a compound represented by the formula (I).
Ru (L ¹ ) (L ² ) (Px) _n (Z) (I)

In the formula (I), L ¹ and L ² represent anionic ligands. L ¹ and L ² may be the same or different. L ¹ and L ² may be combined to form a bidentate or more anionic ligand.

As an anionic ligand,
CF ₃ SO ₃ ⁻ , BF ₄ ⁻ , PF ₆ ⁻ , ClO ₄ ⁻ ; halogeno group such as fluoro group, chloro group, bromo group and iodo group; hydride group; hydroxyl group; unsubstituted or substituted such as acetylacetonate A diketonate group having a group; an unsubstituted or substituted cyclopentadienyl group; a vinyl group, a 1-propenyl group, a 2-propenyl group, a 1-butenyl group, a 2-butenyl group, a 3-butenyl group, 1- Methyl-2-propenyl group, 2-methyl-2-propenyl group, 1-pentenyl group, 2-pentenyl group, 3-pentenyl group, 4-pentenyl group, 1-methyl-2-butenyl group, 2-methyl-2 -An unsubstituted or substituted group such as a butenyl group, a 1-hexenyl group, a 2-hexenyl group, a 3-hexenyl group, a 4-hexenyl group, and a 5-hexenyl group Lucenyl group; methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, s-butyl group, i-butyl group, t-butyl group, n-pentyl group, n-hexyl group, etc. An unsubstituted or substituted alkyl group; an unsubstituted or substituted aryl group such as a phenyl group or a naphthyl group;

  An unsubstituted or substituted alkoxy group such as a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, an n-butoxy group, an s-butoxy group, an i-butoxy group, or a t-butoxy group; An unsubstituted or substituted aryloxy group such as 1-naphthoxy group; methoxycarbonyl group, ethoxycarbonyl group, n-propoxycarbonyl group, i-propoxycarbonyl group, n-butoxycarbonyl group, t-butoxycarbonyl group An unsubstituted or substituted alkoxycarbonyl group such as a carboxyl group, a methoxycarbonyl group, an ethoxycarbonyl group or an unsubstituted or substituted carboxyl group; a methyl sulfonate group, an ethyl sulfonate group, t -No butyl sulfonate group An unsubstituted or substituted aryl sulfonate group such as a phenyl sulfonate group; a methylthio group, an ethylthio group, an n-propylthio group, an i-propylthio group, an n An unsubstituted or substituted alkylthio group such as a butylthio group, an i-butylthio group, an s-butylthio group or a t-butylthio group; an unsubstituted or substituted alkenylthio group such as a vinylthio group or an allylthio group; An unsubstituted or substituted arylthio group such as a phenylthio group or a naphthylthio group; an unsubstituted or substituted alkylsulfonyl group such as a methylsulfonyl group, an ethylsulfonyl group or a t-butylsulfonyl group; and a methylsulfinyl group; Ethylsulfinyl group, t Examples thereof include an unsubstituted or substituted alkylsulfinyl group such as a butylsulfinyl group. Of these, halogeno groups are preferred.

  In the formula (I), Px represents a phosphine ligand. The phosphine ligand is not particularly limited as long as it can stably form a ruthenium complex. Examples of Px include a monodentate phosphine ligand represented by the formula (II) and a bidentate phosphine ligand represented by the formula (III).

PR _A R _B R _C (II)

R _D R _E P-W-PR _F R _G (III)

In the formula (II), R _A , R _B and R _C are each independently methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, isobutyl group, t-butyl group. An unsubstituted or substituted C1-20 alkyl group such as a group, a pentyl group, a hexyl group, a heptyl group, a nonyl group, a dodecyl group; an unsubstituted or substituted phenyl group; a cyclopropyl group, a cyclopentyl group, An unsubstituted or substituted C3-8 cycloalkyl group such as a cyclohexyl group and a cyclooctyl group; an unsubstituted or substituted C7 such as a benzyl group, an α-methylbenzyl group, an α, α-dimethylbenzyl group; To 20 aralkyl groups; Further, two of R _A , R _B and R _C may be bonded to form an unsubstituted or substituted heterocycle.

Examples of the monodentate phosphine ligand represented by the formula (II) preferably used in the present invention include trimethylphosphine, triethylphosphine, tributylphosphine, triphenylphosphine, tricyclohexylphosphine, tri (p-tolyl) phosphine, and diphenylmethylphosphine. Tertiary phosphine such as dimethylphenylphosphine, diisopropylmethylphosphine, 1- [2- (diphenylphosphino) ferrocenyl] ethyl methyl ether, 2- (diphenylphosphino) -2′-methoxy-1,1′-binaphthyl Can be mentioned. Further, a phosphine ligand composed of three different groups of R _A , R _B, and R _C such as ethylmethylbutylphosphine, ethylmethylphenylphosphine, isopropylethylmethylphosphine, and cyclohexyl (O-anisyl) methylphosphine is used. You can also.

In the formula (III), R _D , R _E , R _F and R _G are each independently methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, t-butyl. Group, pentyl group and its isomer, hexyl group and its isomer, heptyl group and its isomer, nonyl group and its isomer, dodecyl group and its isomer, etc., unsubstituted or substituted C1-20 alkyl An unsubstituted or substituted phenyl group; an unsubstituted or substituted C3-8 cycloalkyl group such as a cyclopropyl group, a cyclopentyl group, and a cyclohexyl group; R _D and R _E and / or R _F and R _G may be combined to form an unsubstituted or substituted heterocycle.

  W is an unsubstituted or substituted C1-5 alkanediyl group such as methanediyl group, ethanediyl group, propanediyl group, butanediyl group, pentanediyl group; cyclopropanediyl group, cyclobutanediyl group, cyclopentanediyl group, cyclohexane Unsubstituted or substituted C3-6 cycloalkanediyl group such as diyl group; phenylene group, naphthylene group, 1,1'-biphenyl-2,2'-diyl group, 1,1'-binaphthyl-2, Unsubstituted or substituted arylene group such as 2′-diyl group, 1,1′-binaphthyl-7,7′-diyl group; unsubstituted such as ethenediyl group, propenediyl group, isopropenediyl group, butenediyl group Or a C2-20 alkenediyl group having a substituent, or ethynediyl Shows a C2~20 alkynediyl group having unsubstituted or substituted group such as Puropinjiiru group.

  Examples of the bidentate phosphine ligand represented by the formula (III) include bis (diphenylphosphino) methane, 1,2-bis (diphenylphosphino) ethane, 1,3-bis (diphenylphosphino) propane, , 4-bis (diphenylphosphino) butane, 1,2-bis (dimethylphosphino) ethane, 1,3-bis (dimethylphosphino) propane, 1,1′-bis (diphenylphosphino) ferrocene, etc. be able to.

  Further, in the present invention, 2,2′-bis- (diphenylphosphino) -1,1′-binaphthyl (hereinafter referred to as BINAP) and a naphthyl ring of BINAP have a substituent such as an alkyl group or an aryl group. Asymmetric ligands such as BINAP derivatives, BINAP derivatives having a fluorine substituent, and BINAP derivatives having 1 to 5 substituents such as alkyl groups and alkoxy groups on two benzene rings on the phosphorus atom are also suitable. It can be illustrated as a bidentate phosphine ligand. More specifically, 2,2′-bis- (di-p-tolylphosphino) -1,1′-binaphthyl (Tol-BINAP), 2,2′-bis [bis (3,5-dimethylphenyl) phosphino ] -1,1'-binaphthyl (Xylyl-BINAP), 1- [1 ', 2-bis (diphenylphosphino) ferrocenyl] ethyldiamine, 2,2'-bis- (dicyclohexylphosphino) -6,6' -Dimethyl-1,1'-biphenyl, 2,3-bis- (diphenylphosphino) butane, 1-cyclohexyl-1,2-bis- (diphenylphosphino) ethane, 1-substituted-3,4-bis- (Diphenylphosphino) pyrrolidine, 2,3-O-isopropylidene-2,3-dihydroxy-1,4-bis- (diphenylphosphino) butane, 1,2-bis [(O-me Xylphenyl) phenylphosphino] ethane, substituted-1,2-bis (phosphorano) benzene, 5,6-bis- (diphenylphosphino) -2-norbornene, N, N′-bis- (diphenylphosphino) -N , N′-bis (1-phenylethyl) ethylenediamine, 1,2-bis- (diphenylphosphino) propane, 2,4-bis- (diphenylphosphino) pentane, [(5,6), (5 ′, 6 ′)-bis (methylenedioxy) biphenyl-2,2′-diyl] bis (diphenylphosphine), 1,2-bis (t-butylmethylphosphino) ethane, 2,4-bis- (diphenylphosphino) ) Pentane can be mentioned.

  Many of the phosphine ligands (Px) are known substances and can be produced and obtained by known methods. Moreover, what is marketed can be used as it is or after purification if desired.

  In the formula (I), n represents an integer of 1 or 2.

  In the formula (I), Z represents a ligand having a structure in which the heterocycle A and the heterocycle B are connected by a single bond.

In the heterocycle A, at least one of the atoms adjacent to the ring constituent atom connected to the heterocycle B by a single bond is a nitrogen atom. Heterocycle A does not have an N—H bond.
The heterocycle A is preferably one selected from the formulas a1 to a15.

In the formulas a1 to a15, X represents O, S, or N (R ¹ ).

In formulas a1 to a15, each R ¹ independently represents a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an s-butyl group, an i-butyl group, a t-butyl group, an unsubstituted or substituted C1-6 alkyl group such as an n-pentyl group or an n-hexyl group; an unsubstituted or substituted C6-10 aryl group such as a phenyl group or a naphthyl group; a benzyl group or a phenethyl group An unsubstituted or substituted C6-10 aryl C1-6 alkyl group such as a group is shown.

  In formulas a1 to a15, each Ra is independently a hydrogen atom; a halogeno group; a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an s-butyl group, an i-butyl group, unsubstituted or substituted C1-6 alkyl group such as t-butyl group, n-pentyl group, n-hexyl group; methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group , S-butoxy group, i-butoxy group, t-butoxy group and the like unsubstituted or substituted C1-6 alkoxy group; phenyl group, naphthyl group and the like unsubstituted or substituted C6-10 aryl A group: an unsubstituted or substituted C6-10 aryloxy group such as a phenoxy group or a 1-naphthoxy group; an unsubstituted group such as a benzyl group or a phenethyl group; It shows a C6~10 aryl C1~6 alkyl group having substituent. m represents an integer of 1 or 2.

  In formulas a1 to a15, Raa is each independently a methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, s-butyl group, i-butyl group, t-butyl group, n -Unsubstituted or substituted C1-6 alkyl group such as pentyl group and n-hexyl group; unsubstituted or substituted C6-10 aryl group such as phenyl group, naphthyl group; benzyl group, phenethyl group An unsubstituted or substituted C6-10 aryl C1-6 alkyl group such as

Ra and Ra, or Ra and R ¹ may be combined to form a ring.
In the formula A1 to A15, C6～ ring Ra and Ra, or, and the Ra and R ¹ are formed together is not particularly limited, having a phenyl group, an unsubstituted or substituted group such as a naphthyl group A 10 aryl ring, an unsubstituted or substituted 5-10 membered hetero ring is preferred.
Examples of the unsubstituted or substituted 5- to 10-membered heterocycle include unsubstituted or substituted 5-membered heteroaryl ring, unsubstituted or substituted 6-membered heteroaryl ring, Examples thereof include a saturated or unsaturated hetero 5-membered ring having a substituent or a substituent, and a saturated or unsaturated hetero 6-membered ring having an unsubstituted or a substituent.
The solid and dotted double lines represent single bonds or double bonds, and * represents the position of bonding with ring B.

  Examples of the heterocyclic ring A represented by the formula a1 include 1-methyl-1H-benzoimidazol-2-yl group, benzoxazol-2-yl group, benzothiazol-2-yl group, 1-methyl-1H-imidazole- 2-yl group, oxazol-2-yl group, thiazol-2-yl group, 1,4-dimethyl-1H-imidazol-2-yl group, 4,5-dihydrooxazol-2-yl group, imidazo [1, 5-a] pyridin-3-yl group, 1-benzyl-1H-imidazol-2-yl group and the like can be mentioned.

  The heterocyclic ring A represented by the formula a2 includes 1-methyl-1H-imidazol-4-yl group, 1,2-dimethyl-1H-imidazol-4-yl group, thiazol-4-yl group, 2-methyl Thiazol-4-yl group, oxazol-4-yl group, 2-methyloxazol-4-yl group, 4,5-dihydrooxazol-4-yl group, 1,5-dimethyl-1H-imidazol-4-yl group And imidazo [1,2-a] pyridin-2-yl group, imidazo [1,5-a] pyridin-1-yl group, and the like.

  Examples of the heterocyclic ring A represented by the formula a3 include isoxazol-3-yl group, isothiazol-3-yl group, 1-methyl-1H-pyrazol-3-yl group, and 4,5-dihydroisoxazole-3. -Yl group, 1,5-dimethyl-1H-pyrazol-3-yl group, 1,4-dimethyl-1H-pyrazol-3-yl group, 1-benzyl-1H-pyrazol-3-yl group, benzoisoxazole Examples include a -3-yl group, a 1-methyl-1H-indazol-3-yl group, and a pyrazolo [1,5-a] pyridin-2-yl group.

  The heterocyclic ring A represented by the formula a4 includes 1,3,4-oxadiazol-2-yl group, 1,3,4-thiadiazol-2-yl group, 4-methyl-4H-1,2, 4-triazol-3-yl group, 5-methyl-1,3,4-oxadiazol-2-yl group, 5-methyl-1,3,4-thiadiazol-2-yl group, 4,5-dimethyl -4H-1,2,4-triazol-3-yl group, [1,2,4] triazolo [4,3-a] pyridin-3-yl group, 4-benzyl-4H-1,2,4- Triazol-3-yl group, [1,2,4] triazolo [1,5-a] pyridin-2-yl group, 5-tert-butyl-4-methyl-4H-1,2,4-triazole-3 -An yl group etc. can be mentioned.

  The heterocyclic ring A represented by the formula a5 includes 1,2,4-oxadiazol-3-yl group, 1,2,4-thiadiazol-3-yl group, 1-methyl-1H-1,2, 4-triazol-3-yl group, 5-methyl-1,2,4-oxadiazol-3-yl group, 5-methyl-1,2,4-thiadiazol-3-yl group, 1,5-dimethyl -1H-1,2,4-triazol-3-yl group, [1,2,4] triazolo [1,5-a] pyridin-2-yl group, 5-phenyl-1,2,4-thiadiazole- 3-yl group, 5-phenyl-1,2,4-oxadiazol-3-yl group, 5-tert-butyl-1-methyl-1H-1,2,4-triazol-3-yl group, etc. Can be mentioned.

  The heterocyclic ring A represented by the formula a6 includes 1,2,4-oxadiazol-5-yl group, 1,2,4-thiadiazol-5-yl group, 1-methyl-1H-1,2, 4-triazol-5-yl group, 3-methyl-1,2,4-oxadiazol-5-yl group, 3-methyl-1,2,4-thiadiazol-5-yl group, 1,3-dimethyl -1H-1,2,4-triazol-5-yl group, 3-phenyl-1,2,4-thiadiazol-5-yl group, 3-phenyl-1,2,4-oxadiazol-5-yl Examples include groups.

  Examples of the heterocyclic ring A represented by the formula a7 include 1-methyl-1H-1,2,3-triazolo-4-yl group, 1,2,3-oxadiazol-4-yl group, 1,2, 3-thiadiazol-4-yl group, 1,5-dimethyl-1H-1,2,3-triazol-4-yl group, 5-methyl-1,2,3-oxadiazol-4-yl group, 5 -Methyl-1,2,3-thiadiazol-4-yl group, 1-benzyl-1H-1,2,3-triazol-4-yl group, 1-methyl-5-phenyl-1H-1,2,3 -Triazol-4-yl group, 1-ethyl-1H-1,2,3-triazol-4-yl group, 1-propyl-1H-1,2,3-triazol-4-yl group it can.

  Examples of the heterocycle A represented by the formula a8 include 2-methyl-2H-1,2,3-triazol-4-yl group, 1,2,5-thiadiazol-3-yl group, 1,2,5- Oxadiazol-3-yl group, 2,5-dimethyl-2H-1,2,3-triazol-4-yl group, 4-methyl-1,2,5-thiadiazol-3-yl group, 4-methyl -1,2,5-oxadiazol-3-yl group, 2-ethyl-2H-1,2,3-triazol-4-yl group, 2-benzyl-2H-1,2,3-triazole-4 -Yl group, 2-propyl-2H-1,2,3-triazol-4-yl group, 2-methyl-5-phenyl-2H-1,2,3-triazol-4-yl group, and the like. it can.

  The heterocyclic ring A represented by the formula a9 includes 1-methyl-1H-tetrazol-5-yl group, 1-ethyl-1H-tetrazol-5-yl group, 1-propyl-1H-tetrazol-5-yl group 1-benzyl-1H-tetrazol-5-yl group, 1-phenyl-1H-tetrazol-5-yl group, and the like.

  The heterocyclic ring A represented by the formula a10 includes a 2-methyl-2H-tetrazol-5-yl group, a 2-ethyl-2H-tetrazol-5-yl group, and a 2-propyl-2H-tetrazol-5-yl group. 2-benzyl-2H-tetrazol-5-yl group, 2-phenyl-2H-tetrazol-5-yl group, and the like.

  Examples of the heterocyclic ring A represented by the formula a11 include pyridin-2-yl group, isoquinolin-1-yl group, isoquinolin-3-yl group, quinolin-2-yl group, 3-methylpyridin-2-yl group, 4-methylpyridin-2-yl group, 5-methylpyridin-2-yl group, 6-methylpyridin-2-yl group, 3-chloropyridin-2-yl group, 4-chloropyridin-2-yl group, 5-chloropyridin-2-yl group, 6-chloropyridin-2-yl group, 3-phenylpyridin-2-yl group, 4-phenylpyridin-2-yl group, 5-phenylpyridin-2-yl group, A 6-phenylpyridin-2-yl group can be exemplified.

  The heterocyclic ring A represented by the formula a12 includes pyrimidin-4-yl group, quinazolin-4-yl group, 5-methylpyrimidin-4-yl group, 6-methylpyrimidin-4-yl group, and 2-methylpyrimidine. -4-yl group, 5-chloropyrimidin-4-yl group, 6-chloropyrimidin-4-yl group, 2-chloropyrimidin-4-yl group, 5-phenylpyrimidin-4-yl group, 6-phenylpyrimidine Examples thereof include a -4-yl group and a 2-phenylpyrimidin-4-yl group.

  The heterocyclic ring A represented by the formula a13 includes pyrimidin-2-yl group, quinazolin-2-yl group, 4-phenylpyrimidin-2-yl group, 4-methylpyrimidin-2-yl group, and 4-chloropyrimidine. Examples include 2-yl group, 4,6-dimethylpyrimidin-2-yl group, 4,6-dichloropyrimidin-2-yl group, and 5-phenylpyrimidin-2-yl group.

  The heterocyclic ring A represented by the formula a14 includes pyrazin-2-yl group, 3-methylpyrazin-2-yl group, 5-methylpyrazin-2-yl group, 6-methylpyrazin-2-yl group, 3 -Chloropyrazin-2-yl group, 5-chloropyrazin-2-yl group, 6-chloropyrazin-2-yl group, 3,6-dichloropyrazin-2-yl group, 3,5-dichloropyrazin-2- Il group can be mentioned.

  Examples of the heterocyclic ring A represented by the formula a15 include 1,3,5-triazin-2-yl group, 4-methyl-1,3,5-triazin-2-yl group, 4,6-dimethyl-1, 3,5-triazin-2-yl group, 4-chloro-1,3,5-triazin-2-yl group, 4,6-dichloro-1,3,5-triazin-2-yl group, 4-phenyl Examples include a -1,3,5-triazin-2-yl group and a 4,6-diphenyl-1,3,5-triazin-2-yl group.

  The heterocycle B is one selected from the formulas b1 to b11.

In the formulas b1 to b11, Y represents O, S, or N (R ² ).

In formulas b1 to b11, each R ² independently represents a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an s-butyl group, an i-butyl group, a t-butyl group, an unsubstituted or substituted C1-6 alkyl group such as an n-pentyl group or an n-hexyl group; an unsubstituted or substituted C6-10 aryl group such as a phenyl group or a naphthyl group; a benzyl group or a phenethyl group An unsubstituted or substituted C6-10 aryl C1-6 alkyl group such as a group is shown.

  In formulas b1 to b11, each Rb independently represents a hydrogen atom; a halogeno group; a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an s-butyl group, an i-butyl group, unsubstituted or substituted C1-6 alkyl group such as t-butyl group, n-pentyl group, n-hexyl group; methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group , S-butoxy group, i-butoxy group, t-butoxy group and the like unsubstituted or substituted C1-6 alkoxy group; phenyl group, naphthyl group and the like unsubstituted or substituted C6-10 aryl A group: an unsubstituted or substituted C6-10 aryloxy group such as a phenoxy group or a 1-naphthoxy group; an unsubstituted group such as a benzyl group or a phenethyl group; It shows a C6~10 aryl C1~6 alkyl group having substituent.

  In formulas b1 to b11, Rbb independently represents a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an s-butyl group, an i-butyl group, a t-butyl group, n -Unsubstituted or substituted C1-6 alkyl group such as pentyl group and n-hexyl group; unsubstituted or substituted C6-10 aryl group such as phenyl group, naphthyl group; benzyl group, phenethyl group An unsubstituted or substituted C6-10 aryl C1-6 alkyl group such as

Rb and Rb, Rb and R ² , or Rbb and Rb may be combined to form a ring.
The ring formed by combining Rb and Rb, Rb and R ² , or Rbb and Rb is not particularly limited, but is an unsubstituted or substituted C6-10 aryl ring, unsubstituted or substituted It is preferably a 5-10 membered heterocyclic ring having a group. The unsubstituted or substituted 5- to 10-membered heterocycle includes an unsubstituted or substituted 5-membered heteroaryl ring, an unsubstituted or substituted 6-membered heteroaryl ring, saturated -An unsaturated hetero 5-membered ring, a saturated / unsaturated hetero 6-membered ring, etc. can be mentioned.
In the formulas b1 to b11, * represents a bonding position with the ring A.

  The heterocycle B represented by the formula b1 includes oxazol-2-yl group, benzoxazol-2-yl group, 5-methyloxazol-2-yl group, 5-ethyloxazol-2-yl group, and 5-phenyl. Examples thereof include an oxazol-2-yl group, a 4-methyloxazol-2-yl group, a 4-ethyloxazol-2-yl group, and a 4-phenyloxazol-2-yl group.

  Examples of the heterocyclic ring B represented by the formula b2 include 1-methyl-1H-imidazol-2-yl group, 1-methyl-1H-benzimidazol-2-yl group, and imidazo [1,5-a] pyridine-3. -Yl group, 1,5-dimethyl-1H-imidazol-2-yl group, 5-ethyl-1-methyl-1H-imidazol-2-yl group, 1-methyl-5-phenyl-1H-imidazol-2-yl Yl group, 1,4-dimethyl-1H-imidazol-2-yl group, 4-ethyl-1-methyl-1H-imidazol-2-yl group, 1-methyl-4-phenyl-1H-imidazol-2-yl Examples include groups.

  The heterocyclic ring B represented by the formula b3 includes oxazol-4-yl group, thiazol-4-yl group, 1-methyl-1H-imidazol-4-yl group, 1-ethyl-1H-imidazol-4-yl Group, 1-benzyl-1H-imidazol-4-yl group, 1-phenyl-1H-imidazol-4-yl group, 1,2-dimethyl-1H-imidazol-4-yl group, 5-methyloxazol-4- Yl group, 5-methylthiazol-4-yl group, and the like.

  The heterocyclic ring B represented by the formula b4 includes isoxazol-3-yl group, isothiazol-3-yl group, 1-methyl-1H-pyrazol-3-yl group, 4-methylisothiazol-3-yl Group, 4-methylisoxazol-3-yl group, 1,4-dimethyl-1H-pyrazol-3-yl group, 1,5-dimethyl-1H-pyrazol-3-yl group, 5-methylisoxazole-3 -Yl group, 5-methylisothiazol-3-yl group, benzoisoxazol-3-yl group, 1-methyl-1H-indazol-3-yl group, benzoisothiazol-3-yl group, 1-phenyl- A 1H-pyrazol-3-yl group and the like can be mentioned.

  As the heterocyclic ring B represented by the formula b5, 1,3,4-oxadiazol-2-yl group, 1,3,4-thiadiazol-2-yl group, 4-methyl-4H-1,2, 4-triazol-3-yl group, 4,5-dimethyl-4H-1,2,4-triazol-3-yl group, 4-benzyl-5-methyl-4H-1,2,4-triazole-3- Yl group, [1,2,4] triazolo [4,3-a] pyridin-3-yl group, 5-methyl-1,3,4-oxadiazol-2-yl group, 5-methyl-1, Examples include 3,4-thiadiazol-2-yl group.

  The heterocyclic ring B represented by the formula b6 includes 1,2,4-oxadiazol-3-yl group, 1,2,4-thiadiazol-3-yl group, 1-methyl-1H-1,2, 4-triazol-3-yl group, 5-methyl-1,2,4-oxadiazol-3-yl group, 5-methyl-1,2,4-thiadiazol-3-yl group, 5-phenyl-1 , 2,4-thiadiazol-3-yl group, 1,5-dimethyl-1H-1,2,4-triazol-3-yl group, 5-phenyl-1,2,4-oxazol-3-yl group, Examples thereof include a 1-methyl-5-phenyl-1H-1,2,4-triazol-3-yl group and a 1-phenyl-1H-1,2,4-triazol-3-yl group.

  As the heterocyclic ring B represented by the formula b7, 1,2,4-oxadiazol-5-yl group, 1,2,4-thiadiazol-5-yl group, 1-methyl-1H-1,2, 4-triazol-5-yl group, 3-methyl-1,2,4-oxadiazol-5-yl group, 3-methyl-1,2,4-thiadiazol-5-yl group, 3-phenyl-1 , 2,4-thiadiazol-5-yl group, 1,3-dimethyl-1H-1,2,4-triazol-5-yl group, 3-phenyl-1,2,4-oxadiazol-5-yl Group, 1-methyl-3-phenyl-1H-1,2,4-triazol-5-yl group, 1,3-diphenyl-1H-1,2,4-triazol-5-yl group, etc. it can.

  As the heterocyclic ring B represented by the formula b8, 1,2,3-oxadiazol-4-yl group, 1,2,3-thiadiazol-4-yl group, 1-methyl-1H-1,2, 3-triazol-4-yl group, 5-methyl-1,2,3-oxadiazol-4-yl group, 5-methyl-1,2,3-oxadiazol-4-yl group, 5-methyl -1,2,3-thiadiazol-4-yl group, 1,5-dimethyl-1H-1,2,3-triazol-4-yl group, 1-benzyl-1H-1,2,3-triazole-4 -An yl group etc. can be mentioned.

  As the heterocyclic ring B represented by the formula b9, 1,2,5-oxadiazol-3-yl group, 1,2,5-thiadiazol-3-yl group, 2-methyl-2H-1,2, 3-triazol-4-yl group, 2-ethyl-2H-1,2,3-triazol-4-yl group, 2-benzyl-2H-1,2,3-triazol-4-yl group, 4-methyl -1,2,5-oxadiazol-3-yl group, 4-methyl-1,2,5-thiadiazol-3-yl group, 2,5-dimethyl-2H-1,2,3-triazole-4 -Yl group, 2-ethyl-5-methyl-2H-1,2,3-triazol-4-yl group, 2-benzyl-5-methyl-2H-1,2,3-triazol-4-yl group, etc. Can be mentioned.

  The heterocycle B represented by the formula b10 includes a 1-methyl-1H-tetrazol-5-yl group, a 1-ethyl-1H-tetrazol-5-yl group, and a 1-benzyl-1H-tetrazol-5-yl group. 1-phenyl-1H-tetrazol-5-yl group and the like.

  Examples of the heterocycle B represented by the formula b11 include 2-methyl-2H-tetrazol-5-yl group, 2-ethyl-2H-tetrazol-5-yl group, and 2-benzyl-2H-tetrazol-5-yl group. And 2-phenyl-2H-tetrazol-5-yl group.

  Specific examples of Z include 2- (1-methyl-1H-benzoimidazol-2-yl) -4,5-dihydrooxazole, 1-methyl-2- (pyridin-2-yl) -1H-benzimidazole, 2- (1-methyl-1H-imidazol-2-yl) pyridine, 2- (1-methyl-1H-pyrazol-3-yl) pyridine, 2- (1,5-dimethyl-1H-1,2,4 -Triazol-3-yl) pyridine and the like. Z can be produced by a known method, for example, a method as shown in Reference Examples.

  The ruthenium complex of the present invention can be produced by reacting a ruthenium simple substance or a ruthenium complex with a phosphine ligand (Px) and a nitrogen-containing bidentate ligand (Z). Ruthenium, which is the central element, may have a valence of 0, 1, 2, 3, or higher. The ruthenium simple substance or ruthenium complex may be reacted with the phosphine ligand (Px) and the nitrogen-containing bidentate ligand (Z) at the same time, or one of the ruthenium simple substance or ruthenium complex is reacted first. The other may then be reacted. In the present invention, it is preferable to react a divalent ruthenium-halide complex with a phosphine ligand (Px) and then react with a nitrogen-containing bidentate ligand (Z).

  Hereafter, the manufacturing method at the time of using a bivalent ruthenium-halide complex as a starting material is shown as an example, and the manufacturing method of the ruthenium complex of this invention is demonstrated in detail.

  a) A phosphine ligand (Px) is reacted with a divalent ruthenium-halide complex. This reaction produces a phosphine-ruthenium-halide complex. The produced phosphine-ruthenium-halide complex may be isolated by a known purification method.

The divalent ruthenium-halide complex is not particularly limited as long as it is a ruthenium complex having a ligand that can be substituted with a phosphine ligand (Px) and a nitrogen-containing bidentate ligand (Z). Examples of the divalent ruthenium-halide complex include [ruthenium dichloride (norbornadiene)] multinuclear complex, [ruthenium dichloride (cyclooctadiene)] multinuclear complex, and [bis (methylallyl) ruthenium (cyclooctadiene)]. Diene-coordinated ruthenium halide complex; [ruthenium dichloride (benzene)] binuclear complex, [ruthenium dichloride (p-cymene)] binuclear complex, [ruthenium dichloride (trimethylbenzene)] binuclear complex, [ And ruthenium halides coordinated with an aromatic compound such as ruthenium dichloride (hexamethylbenzene)] binuclear complex.
When the phosphine ligand (Px) is a monodentate ligand, the amount of the phosphine ligand (Px) used is preferably 2 to 3 mol, more preferably 1 mol with respect to 1 mol of the divalent ruthenium-halide complex. Is 2 mol, and when the phosphine ligand (Px) is a bidentate ligand, it is preferably 1 to 2 mol, more preferably 1 mol.

Examples of the solvent used in this reaction include aromatic hydrocarbons such as benzene, toluene and xylene; aliphatic hydrocarbons such as pentane and hexane; dichloromethane, chloroform, trichloromethane, carbon tetrachloride, and 1,2-dichloroethane. Halogen hydrocarbons such as: ethers such as diethyl ether, tetrahydrofuran (THF), 1,2-dimethoxyethane, 1,4-dioxane; alcohols such as methanol, ethanol, n-propanol, isopropanol, butanol, benzyl alcohol N, N-dimethylformamide (DMF), N, N-dimethylacetamide, 1,3-dimethylimidazolidine, 1,3-dimethyl-2-imidazolidinone, N-methylpyrrolidone, hexamethylphosphoric triamide (HMPT) etc. Amides; acetonitrile, nitriles such as benzonitrile; and the like dimethyl sulfoxide (DMSO). These solvents can be used alone or in admixture of two or more.
The amount of the solvent used is preferably 1 ml to 100 ml, more preferably 1 ml to 10 ml, with respect to 1 g of the reactant. The reaction temperature is preferably 0 to 200 ° C, more preferably room temperature to 120 ° C.

  b) A nitrogen-containing bidentate ligand (Z) is reacted with a phosphine-ruthenium-halide complex. This reaction produces a nitrogen-containing bidentate ligand-phosphine-ruthenium-halide complex.

  The amount of the nitrogen-containing bidentate ligand (Z) used for this reaction is preferably 1 to 2 mol, more preferably 1 mol, per 1 mol of the phosphine-ruthenium-halide complex.

Examples of the solvent used for this reaction include the same solvents as those exemplified for the reaction of the phosphine ligand (Px).
The amount of the solvent used is preferably 1 ml to 100 ml, more preferably 1 ml to 10 ml, with respect to 1 g of the reactant. The reaction temperature is preferably −100 to + 200 ° C., more preferably −10 to + 120 ° C.

c) When a nitrogen-containing bidentate ligand-phosphine-ruthenium-halide complex is reacted with a base in a solvent, the nitrogen-containing bidentate ligand-phosphine-ruthenium hydride complex (represented by the formula (I)) Among the complexes, L ¹ = L ² = H.).

Examples of the base used include triethylamine, diisopropylethylamine, pyridine, 1,4-diazabicyclo [2,2,2] octane (DABCO), 1,4-diazabicyclo [5,4,0] unde-7-ene (DBU). Organic bases such as sodium methoxide, sodium ethoxide, potassium t-butoxide, magnesium ethoxide; organolithium complexes such as n-butyllithium and lithium diisopropylamide (LDA); sodium hydroxide, water Alkali metal hydroxides such as potassium oxide; carbonates such as potassium carbonate and sodium carbonate; metal hydrides such as sodium hydride;
The amount of the base used is preferably 2 to 10000 mol, more preferably 2 to 40 mol, per 1 mol of the nitrogen-containing bidentate ligand-phosphine-ruthenium-halide complex.

  Examples of the solvent used in this reaction include aromatic hydrocarbons such as benzene, toluene and xylene; aliphatic hydrocarbons such as pentane and hexane; dichloromethane, chloroform, trichloromethane, carbon tetrachloride, and 1,2-dichloroethane. Halogen ethers such as; ethers such as diethyl ether, THF, 1,2-dimethoxyethane, 1,4-dioxane; alcohols such as methanol, ethanol, n-propanol, isopropanol, butanol, benzyl alcohol; acetonitrile, Nitriles such as benzonitrile; Amides such as DMF, N, N-dimethylacetamide, 1,3-dimethylimidazolidine, 1,3-dimethyl-2-imidazolidinone, N-methylpyrrolidone; Can be mentioned. These solvents can be used alone or in admixture of two or more.

  The amount of the solvent used is preferably 1 mL to 10 L, more preferably 1 mL to 1 L, with respect to 1 g of the nitrogen-containing bidentate ligand-phosphine-ruthenium-halide complex. The reaction temperature is preferably −100 to + 200 ° C., more preferably −10 to + 50 ° C.

d) When RCOONa or RONa (R represents an alkyl group) is reacted with a nitrogen-containing bidentate ligand-phosphine-ruthenium-halide complex, in formula (I), X and / or Y is a carboxyl group, A ruthenium complex that is a hydroxyl group or an alkoxy group is produced.
The amount of RCOONa or RONa (R represents an alkyl group) used for this reaction is preferably 1 to 2 mol, more preferably 1 mol, per 1 mol of the phosphine-ruthenium-halide complex.

Examples of the solvent used for this reaction include the same solvents as those exemplified for the reaction of the phosphine ligand (Px).
The amount of the solvent used is preferably 1 ml to 100 ml, more preferably 1 ml to 10 ml, with respect to 1 g of the reactant. The reaction temperature is preferably −100 to + 200 ° C., more preferably −10 to + 120 ° C.

  The ruthenium complex of the present invention is useful as a catalyst for a reduction reaction or the like. For example, it can be used as a catalyst in a reaction in which a carbonyl group is converted to a hydroxyl group using an inexpensive hydrogen source such as hydrogen gas.

  Next, an Example is shown and this invention is demonstrated in detail. However, the present invention is not limited to these examples.

In this example, the apparatus used for measuring physical properties is as follows.
NMR spectrum: JNM-ECS400, manufactured by JEOL Ltd. Gas chromatography: GC-17A, C-R7A Plus, manufactured by Shimadzu Corporation The abbreviations shown below represent the following meanings.
DPPP: 1,3-bis (diphenylphosphino) propane BINAP: 2,2′-bis (diphenylphosphino) -1,1′-binaphthyl

Reference example 1
Nitrogen-containing bidentate ligands (z5), (z10), (z11), (z12) and (z13) were produced by the following scheme. In addition, other mentors were produced by known methods.

Example 1
Complex 1: Preparation of RuCl ₂ (DPPP) (1-methyl-2- (pyridin-2-yl) -1H-benzimidazole) To 1 mL of dimethylformamide, 206 mg of DPPP and dichloro (1,5-cyclooctadiene) ruthenium (II 140 mg was added, and the mixture was stirred at 120 ° C. for 1 hour under an argon atmosphere. To this, 110 mg of 1-methyl-2- (pyridin-2-yl) -1H-benzimidazole (formula (z1)) was added and stirred at 120 ° C. for 10 minutes. After cooling to room temperature, dimethylformamide was distilled off under reduced pressure. Next, ethyl acetate was added to the residue, and the precipitated crystals were filtered and dried to obtain 380 mg of Complex 1 (yield 96%).

錯体１のＮＭＲは以下のとおりであった。
³¹P-NMR(160MHz、CDCL₃):δ=36.46(s、isomer a)、34.60(d、J=45.1Hz、isomer b)、31.64(d、J=45.1Hz、isomer b)

NMR of complex 1 was as follows.
³¹ P-NMR (160 MHz, CDCL ₃ ): δ = 36.46 (s, isomer a), 34.60 (d, J = 45.1 Hz, isomer b), 31.64 (d, J = 45.1 Hz, isomer b)

Example 2
Complex 2: Production of RuCl ₂ ((R) BINAP) (1-methyl-2- (pyridin-2-yl) -1H-benzimidazole In the same manner as in Example 1 except that 206 mg of DPPP was changed to 311 mg of (R) BINAP. Complex 2 was prepared.

Example 3
Complex 3: RuCl ₂ (DPPP) (1-methyl-2- (oxazolin-2-yl) -1H-benzimidazole)
Except for changing 110 mg of 1-methyl-2- (pyridin-2-yl) -1H-benzimidazole to 105 mg of 1-methyl-2- (oxazolin-2-yl) -1H-benzimidazole (formula (z2)) Complex 3 was produced in the same manner as in Example 1.

Example 4
Complex 4: RuCl ₂ (DPPP) (1-methyl-3- (pyridin-2-yl) -pyrazole)
Example 1 except that 110 mg of 1-methyl-2- (pyridin-2-yl) -1H-benzimidazole was changed to 100 mg of 1-methyl-3- (pyridin-2-yl) -pyrazole (formula (z3)) Complex 4 was produced in the same manner as described above.

Example 5
Complex 5: RuCl ₂ (DPPP) (1-methyl-2- (pyridin-2-yl) -imidazole)
Example 1 except that 110 mg of 1-methyl-2- (pyridin-2-yl) -1H-benzimidazole was changed to 160 mg of 1-methyl-2- (pyridin-2-yl) -imidazole (formula (z4)) Complex 5 was produced in the same manner as described above.

Example 6
Complex 6: RuCl ₂ (DPPP) (1,5-dimethyl-3- (pyridin-2-yl) -1,2,4-triazole)
110 mg of 1-methyl-2- (pyridin-2-yl) -1H-benzimidazole was converted to 100 mg of 1,5-dimethyl-3- (pyridin-2-yl) -1,2,4-triazole (formula (z5)). Complex 6 was produced in the same manner as in Example 1 except that

錯体６のＮＭＲは以下のとおりであった。
³¹P-NMR (ppm) 39.42, 35.24(isomer 1); 36.77, 30.90(isomer 2)

The NMR of complex 6 was as follows.
³¹ P-NMR (ppm) 39.42, 35.24 (isomer 1); 36.77, 30.90 (isomer 2)

Example 7
Complex 7: RuCl ₂ ((R) BINAP) (5-methyl-3- (pyridin-2-yl) -1,2,4-oxadiazole)
110 mg of 1-methyl-2- (pyridin-2-yl) -1H-benzimidazole and 90 mg of 5-methyl-3- (pyridin-2-yl) -1,2,4-oxadiazole (formula (z10)) Complex 7 was produced in the same manner as in Example 2 except that

錯体７のＮＭＲは以下のとおりであった。
³¹P-NMR (ppm) 47~51(b); 29.03(s)

NMR of Complex 7 was as follows.
³¹ P-NMR (ppm) 47-51 (b); 29.03 (s)

Example 8
Complex 8: RuCl ₂ ((R) BINAP) (2-benzyl-5- (pyridin-2-yl) -tetrazole)
Example 2 except that 110 mg of 1-methyl-2- (pyridin-2-yl) -1H-benzimidazole was changed to 130 mg of 2-benzyl-5- (pyridin-2-yl) -tetrazole (formula (z11)) Complex 8 was produced in the same manner as described above.

錯体８のＮＭＲは以下のとおりであった。
³¹P-NMR (ppm) 53.64, 44.06(isomer 1); 49.94, 46.94(isomer 2)

The NMR of Complex 8 was as follows.
³¹ P-NMR (ppm) 53.64, 44.06 (isomer 1); 49.94, 46.94 (isomer 2)

Example 9
Complex 9: RuCl ₂ (DPPP) (1-benzyl-5- (pyridin-2-yl) -tetrazole)
Example 1 except that 110 mg of 1-methyl-2- (pyridin-2-yl) -1H-benzimidazole was changed to 130 mg of 1-benzyl-5- (pyridin-2-yl) -tetrazole (formula (z12)) The complex 9 was produced by the same method.

錯体９のＮＭＲは以下のとおりであった。
³¹P-NMR (ppm) 47.07, 35.14

NMR of complex 9 was as follows.
³¹ P-NMR (ppm) 47.07, 35.14

Example 10
Complex 10: RuCl ₂ (DPPP) (1- (pyridin-2-yl) -3-phenylimidazo [1,5-a] pyridine)
110 mg of 1-methyl-2- (pyridin-2-yl) -1H-benzimidazole was converted to 140 mg of 1- (pyridin-2-yl) -3-phenylimidazo [1,5-a] pyridine (formula (z13)). A complex 10 was produced in the same manner as in Example 1 except for the change.

錯体１０のＮＭＲは以下のとおりであった。
³¹P-NMR (ppm) 40.14, 34.25(isomer 1); 39.00, 32.79(isomer 2)

NMR of complex 10 was as follows.
³¹ P-NMR (ppm) 40.14, 34.25 (isomer 1); 39.00, 32.79 (isomer 2)

Comparative Example 1
Complex 11: RuCl ₂ (DPPP) (2- (pyridin-2-yl) -1H-benzimidazole)
Example 1 except that 110 mg of 1-methyl-2- (pyridin-2-yl) -1H-benzimidazole was changed to 110 mg of 2- (pyridin-2-yl) -1H-benzimidazole (formula (z6)). Complex 11 was prepared in the same manner.

Comparative Example 2
Complex 12: RuCl ₂ (DPPP) (2- (oxazolin-2-yl) -1H-benzimidazole)
Example 1 except that 110 mg of 1-methyl-2- (pyridin-2-yl) -1H-benzimidazole was changed to 100 mg of 2- (oxazolin-2-yl) -1H-benzimidazole (formula (z7)). Complex 12 was prepared in the same manner.

Comparative Example 3
Complex 13: RuCl ₂ (DPPP) (3- (pyridin-2-yl) -pyrazole)
The same procedure as in Example 1 except that 110 mg of 1-methyl-2- (pyridin-2-yl) -1H-benzimidazole was changed to 90 mg of 3- (pyridin-2-yl) -pyrazole (formula (z8)). Complex 13 was prepared.

Comparative Example 4
Complex 14: RuCl ₂ (DPPP) (2- (pyridin-2-yl) -imidazole)
The same as Example 1 except that 110 mg of (1-methyl-2- (pyridin-2-yl) -1H-benzimidazole) was changed to 80 mg of 2- (pyridin-2-yl) -imidazole (formula (z9)). Complex 14 was prepared by the procedure.

Example 11 (hydrogenation reaction)
In a glass autoclave, 8 mg of complex 1 obtained in Example 1 and 11 mg of potassium t-butoxide were placed, and the atmosphere was replaced with an argon atmosphere. Subsequently, 1.20 g of acetophenone was added to 5 mL of isopropanol (hereinafter sometimes referred to as IPA), and the deaerated solution was transferred to the autoclave. The operation of injecting 1 MPa of hydrogen into the autoclave and immediately releasing it to 2 atm was repeated 5 times. Thereafter, hydrogen of 1 MPa was injected and stirred at room temperature for 20 minutes to perform a hydrogenation reaction. The residual pressure was then released.
When the reaction solution was measured by gas chromatography (mobile phase: helium, capillary column: TC-WAX (length 30 m, inner diameter 0.25 mm), manufactured by GL Sciences), the conversion rate was 99% or more. This means that the reaction time for 99% conversion is less than 20 minutes.

Examples 12 to 15 (hydrogenation reaction)
The hydrogenation reaction was performed in the same manner as in Example 11 except that Complex 1 was changed to Complexes 2-5. In all cases, the conversion rate was 99% or more. This means that the reaction time for achieving a conversion rate of 99% is less than 20 minutes.

Example 16 (hydrogenation reaction)
A hydrogenation reaction was performed in the same manner as in Example 11 except that Complex 1 was changed to Complex 6. Hydrogen absorption stopped after 15 minutes from the start of the reaction. The conversion rate was 99% or more. This means that the reaction time for 99% conversion is less than 20 minutes.

Example 17 (hydrogenation reaction)
A hydrogenation reaction was performed in the same manner as in Example 11 except that Complex 1 was changed to Complex 10. Hydrogen absorption stopped after 5 minutes from the start of the reaction. The conversion rate was 99% or more. This means that the reaction time for 99% conversion is less than 20 minutes.

Comparative Example 5 (hydrogenation reaction)
A hydrogenation reaction was performed in the same manner as in Example 11 except that Complex 1 was changed to Complex 11. The reaction time was 60 minutes, and the conversion rate was 98%.

Comparative Example 6 (hydrogenation reaction)
A hydrogenation reaction was performed in the same manner as in Example 11 except that Complex 1 was changed to Complex 12. The reaction time was 120 minutes, and the conversion rate was 99% or more.

Comparative Example 7 (hydrogenation reaction)
A hydrogenation reaction was attempted in the same manner as in Example 11 except that Complex 1 was changed to Complex 13. The reaction time was 120 minutes and almost no reaction.

Comparative Example 8 (hydrogenation reaction)
A hydrogenation reaction was performed in the same manner as in Example 11 except that Complex 1 was changed to Complex 14. The reaction time was 120 minutes, and the conversion rate was 51%.

Reference example 2
Synthesis of 1-methyl-2- (pyrimidin-2-yl) imidazole (z14)

２-（ピリミジン−２−イル）イミダゾール０．８６ｇをジメチルホルムアミド２ｍＬに溶解し、水素化ナトリウム（６０％）０．２６ｇを加えて攪拌した。ｐ−トルエンスルホン酸メチルエステル１．１０ｇを加えて１時間攪拌した。ジメチルホルムアミドを留去し、残渣に３Ｍ塩酸１ｍＬを加え、ヘキサンで洗浄した。３Ｍ水酸化ナトリウム溶液で中和し、その後、クロロホルムで抽出して、目的物を０．９８ｇ（純度８１％）得た。
目的物のＮＭＲによる測定結果は以下のとおりであった。
¹H-NMR(400MHz, CDCl₃)：δ 8.81(d, 2H), 7.22(d, 1H), 7.20(d, 1H), 7.03(d, 1H), 4.14 (s, 3H).

0.86 g of 2- (pyrimidin-2-yl) imidazole was dissolved in 2 mL of dimethylformamide, and 0.26 g of sodium hydride (60%) was added and stirred. 1.10 g of p-toluenesulfonic acid methyl ester was added and stirred for 1 hour. Dimethylformamide was distilled off, and 1 mL of 3M hydrochloric acid was added to the residue, followed by washing with hexane. Neutralization with 3M sodium hydroxide solution followed by extraction with chloroform gave 0.98 g (purity 81%) of the desired product.
The measurement results of the target product by NMR were as follows.
¹ H-NMR (400 MHz, CDCl ₃ ): δ 8.81 (d, 2H), 7.22 (d, 1H), 7.20 (d, 1H), 7.03 (d, 1H), 4.14 (s, 3H).

Example 18
Complex 15: Preparation of RuCl ₂ (DPPP) (1-methyl-2- (pyrimidin-2-yl) imidazole) To 1 mL of dimethylformamide, 275 mg of DPPP and 187 mg of dichloro (1,5-cyclooctadiene) ruthenium (II) were added. The mixture was stirred at 120 ° C. for 1 hour in an argon atmosphere. To this, 150 mg (purity 81%) of 1-methyl-2- (pyrimidin-2-yl) imidazole (formula (z14)) was added and stirred at 120 ° C. for 10 minutes. After cooling to room temperature, dimethylformamide was distilled off under reduced pressure. Next, ethyl acetate was added to the residue, and the precipitated solid was filtered and dried to obtain 470 mg (yield 95%) of Complex 15.
The measurement result of the complex 15 by NMR was as follows.
³¹ P-NMR (160 MHz, CDCl ₃ ): δ = 47.27, 35.46

Example 19
Complex 16: Preparation of RuCl ₂ (DPPP) (1-methyl-2- (thiazol-4-yl) benzimidazole) The amount of DPPP was changed to 206 mg, and 1-methyl-2- (pyrimidin-2-yl) imidazole ( The complex 16 was prepared in the same manner as in Example 18 except that 150 mg (formula (81%)) (formula (z14)) was changed to 110 mg (formula (z15)) of 1-methyl-2- (thiazol-4-yl) benzimidazole. Manufactured.

錯体１６のＮＭＲによる測定結果は以下のとおりであった。
³¹P-NMR(160MHz、CDCl₃):δ=42.17、33.93

The measurement result of the complex 16 by NMR was as follows.
³¹ P-NMR (160 MHz, CDCl ₃ ): δ = 42.17, 33.93

Reference example 3
Synthesis of 1-methyl-2- (4-methoxypyridin-2-yl) benzimidazole (z16)

２−（４−メトキシピリジン−２−イル）ベンズイミダゾール０．５０ｇをジメチルホルムアミド２ｍＬに溶解し、水素化ナトリウム（６０％）０．１０ｇを加えて攪拌した。ｐ−トルエンスルホン酸メチルエステル０．４３ｇを加えて１時間攪拌した。ジメチルホルムアミドを留去し、残渣に３Ｍ塩酸１ｍＬを加え、ヘキサンで洗浄した。３Ｍ水酸化ナトリウム溶液で中和した後、酢酸エチル抽出して目的物を０．４８ｇ得た。
目的物のＮＭＲの測定結果は以下のとおりであった。
¹H-NMR(400MHz, CDCl₃)：δ 8.50(d, 1H), 7.92(d, 1H), 7.84(m, 1H), 7.44(m, 1H), 7.33(m, 2H), 6.89(dd, 1H), 4.27(s, 3H), 3.96 (s, 3H).

0.50 g of 2- (4-methoxypyridin-2-yl) benzimidazole was dissolved in 2 mL of dimethylformamide, and 0.10 g of sodium hydride (60%) was added and stirred. 0.43 g of p-toluenesulfonic acid methyl ester was added and stirred for 1 hour. Dimethylformamide was distilled off, and 1 mL of 3M hydrochloric acid was added to the residue, followed by washing with hexane. After neutralizing with 3M sodium hydroxide solution, extraction with ethyl acetate yielded 0.48 g of the desired product.
The NMR measurement results of the target product were as follows.
¹ H-NMR (400 MHz, CDCl ₃ ): δ 8.50 (d, 1H), 7.92 (d, 1H), 7.84 (m, 1H), 7.44 (m, 1H), 7.33 (m, 2H), 6.89 (dd , 1H), 4.27 (s, 3H), 3.96 (s, 3H).

Example 20
Complex 17: Preparation of RuCl ₂ (DPPP) (1-methyl-2- (4-methoxypyridin-2-yl) benzimidazole) The amount of DPPP was changed to 206 mg, and 1-methyl-2- (pyrimidin-2-yl) was prepared. ) Same as Example 18 except that 150 mg (purity 81%) of imidazole (formula (z14)) was changed to 120 mg of 1-methyl-2- (4-methoxypyridin-2-yl) benzimidazole (formula (z16)) Complex 17 was prepared by the procedure.
The measurement result of the complex 17 by NMR was as follows.
³¹ P-NMR (160 MHz, CDCL ₃ ): δ = 40.37, 31.51 (isomer 1); 37.77, 29.86 (isomer 2)

Examples 15 and 16 (hydrogenation reaction)
A hydrogenation reaction was performed in the same manner as in Example 11 except that Complex 1 was changed to Complexes 15 and 16, respectively. In all cases, the conversion rate was 99% or more. This means that the reaction time for achieving a conversion rate of 99% is less than 20 minutes.

Example 17 (hydrogenation reaction)
The hydrogenation reaction was performed in the same manner as in Example 11 except that Complex 1 was changed to Complex 17 and S / C was changed to 10,000. The reaction time was 110 minutes, and the conversion rate was 99% or more.

Claims (4)

A ruthenium complex represented by the formula (I).

Ru (L ¹ ) (L ² ) (Px) _n (Z) (I)

Wherein (I), L ¹ and L ² are each independently an anionic ligand indicates,
L ¹ and L ² is rather good also form an anionic ligand of more than 2 seats together,
Px is shows the phosphine ligand,
n is it indicates an integer of 1 or 2,
Z is indicates a ligand having a structure in which the heterocycle A and heterocycle B is linked by a single bond,
The heterocycle A is one selected from the formulas a1, a2, a11, and a13, and the heterocycle B is one selected from the formulas b2, b3, b4, b6, b10, and b11 .

(In the formulas a1, a2, a11, and a13,
X represents O, S, or N (R ¹ );
Each R ¹ is independently an unsubstituted or substituted C 1-6 alkyl group, an unsubstituted or substituted C 6-10 aryl group, or an unsubstituted or substituted C 6-10 aryl C 1 ~ 6 alkyl groups,
Each Ra independently represents a hydrogen atom, a halogeno group, an unsubstituted or substituted C1-6 alkyl group, an unsubstituted or substituted C1-6 alkoxy group, an unsubstituted or substituted C6; -10 aryl group, unsubstituted or substituted C6-10 aryloxy group, or unsubstituted or substituted C6-10 aryl C1-6 alkyl group,
m represents an integer of 1 or 2,
Ra and R ¹ may be combined to form a ring,
The solid and dotted double lines represent single bonds or double bonds, and
* Indicates a bonding position with the heterocycle B. ]

(In the formulas b2, b3, b4, b6, b10 and b11 ,
Y is, O, S or N and (R ^2), shows,
Each R ² independently represents an unsubstituted or substituted C 1-6 alkyl group, an unsubstituted or substituted C 6-10 aryl group, or an unsubstituted or substituted C 6-10 aryl C 1 It shows the 6 alkyl group,
Rb each independently represents a hydrogen atom, a halogeno group, an unsubstituted or substituted C1-6 alkyl group, an unsubstituted or substituted C1-6 alkoxy group, an unsubstituted or substituted C6. 10 aryl group, a unsubstituted or C6~10 aryloxy group having a substituent or unsubstituted or C6~10 aryl C1~6 alkyl group having a substituent, shows,
Rbb each independently represents an unsubstituted or substituted C1-6 alkyl group, an unsubstituted or substituted C6-10 aryl group, or an unsubstituted or substituted C6-10 aryl C1- 6 alkyl group shows,
Rb and Rb, rather good even if Rb and R ^2, or Rbb and the Rb together form a ring, and * represents a bonding position of the heterocycle A. ] Z is the formula Z1 through Z5, which is one selected from Z10～z16, ruthenium complex according to claim 1.

  A reduction catalyst containing the ruthenium complex according to claim 1.   A method for producing alcohols by hydrogenating ketones or aldehydes in the presence of the reduction catalyst according to claim 3.