JP2011178682A - Complex compound of transition metal, catalyst comprising the compound for multimerizing olefin, and method for producing olefin multimer, carried out in the presence of the catalyst - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a complex compound of a transition metal, a catalyst comprising the compound for multimerizing an olefin exhibiting excellent activity, and a method for producing an olefin multimer, carried out in the presence of the catalyst. <P>SOLUTION: The complex compound of a transition metal is represented by the formula of, for example, compound 2. The catalyst for multimerizing an olefin includes a component (A): the complex compound of a transition metal, and a component (B): an organometallic compound or the like. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a transition metal complex compound, an olefin multimerization catalyst containing the compound, and a method for producing an olefin multimer in the presence of the catalyst.

  α-Olefin is an important compound widely used industrially, such as a polyolefin raw material. Among them, 1-hexene is particularly in demand as a polyolefin raw material, and a highly selective production method is desired. However, most of the industrialized production methods of α-olefins are carried out using organoaluminum or a transition metal compound as a catalyst, and a mixture of α-olefins is obtained, which does not satisfy this demand. As the only selective production method of 1-hexene used industrially, an ethylene trimerization reaction using a chromium compound has been carried out (for example, see Patent Document 1), but a transition metal compound other than a chromium compound is used. There are very few techniques which manufacture 1-hexene by the ethylene trimerization reaction to be used (for example, refer patent document 2, 3, nonpatent literature 1, 2).

  In recent years, the present inventors have reported a catalyst for selectively producing 1-hexene by an ethylene trimerization reaction using a transition metal complex compound having a phenoxyimine ligand (see, for example, Patent Document 4). . However, further improvement in catalyst performance has been desired from the viewpoint of production cost and productivity.

US Pat. No. 5,856,257 JP-T-2004-524959 International Publication No. 01/68572 pamphlet International Publication No. 2009/5003 Pamphlet

Journal of American Chemical Society 2001, 123, 7423-7424 Journal of Organometallic Chemistry 2004, 689, 3643-1668.

  The present invention has been made in view of the problems of the prior art, and provides a novel transition metal complex compound and a catalyst for olefin multimerization containing the compound and having excellent activity, and the olefin. It aims at providing the manufacturing method of the olefin multimer performed in the presence of the catalyst for multimerization.

  As a result of intensive studies to solve the above problems, the present inventors have found that an olefin multimerization catalyst containing a transition metal complex compound having a specific structure has an excellent activity, and in the presence of the catalyst, an olefin In particular, when ethylene is used as the olefin, 1-hexene, which is a trimer of ethylene, can be obtained with high selectivity, and the present invention has been completed. It was.

  That is, the present invention relates to the following [1] to [7].

[1]
A transition metal compound represented by the following general formula (1).

[In General Formula (1), M represents an atom of Groups 4-6 of the periodic table,
R ¹ , R ² , R ³ , R ⁷ , R ⁸ , R ¹¹ , R ¹³ and R ¹⁴ may be the same as or different from each other, and are a hydrogen atom, a halogen atom, a hydrocarbon group, a hydrocarbon-substituted silyl group, An atom or group selected from an oxygen-containing group and a nitrogen-containing group;
R ⁴ , R ⁵ , R ⁹ , and R ¹⁰ may be the same or different from each other, and are selected from a hydrogen atom, a halogen atom, a hydrocarbon group, a hydrocarbon-substituted silyl group, an oxygen-containing group, and a nitrogen-containing group. Or R ⁶ and R ^{12, which} may be the same or different from each other, are atoms or groups selected from a hydrogen atom, a hydrocarbon group, a hydrocarbon-substituted silyl group, an oxygen-containing group and a nitrogen-containing group; R ⁴ , R ⁵ , R ⁶ , R ⁹ , R ¹⁰ and R ¹² are not simultaneously hydrogen atoms,
Two adjacent groups out of the groups represented by R ^{1 to} R ¹⁴ may be bonded to form a ring together with the carbon atoms to which they are bonded.

  n represents the valence of M.

X represents a group selected from a hydrogen atom, a halogen atom, a hydrocarbon group, an oxygen-containing group and a nitrogen-containing group, and a plurality of atoms or groups represented by X may be the same or different from each other, and are represented by X A plurality of groups may be bonded to each other, and a plurality of groups represented by X may be bonded to each other to form a ring. ]
[2]
[1] In the general formula (1), at least one of the groups represented by R ⁴ , R ⁵ , R ⁶ , R ⁹ , R ¹⁰ and R ¹² is a hydrocarbon group. Transition metal compounds.

[3]
The transition metal compound according to [1] or [2], wherein in the general formula (1), R ² is a tertiary alkyl group or a hydrocarbon-substituted tertiary silyl group.

[4]
In said general formula (1), M is a titanium atom, The transition metal compound in any one of [1]-[3] characterized by the above-mentioned.

[5]
An olefin multimerization catalyst comprising the following component (A) and component (B):
(A) Transition metal compound according to any one of [1] to [4] (B) (B-1) Organometallic compound (B-2) Organoaluminum oxy compound, and (B-3) Transition metal compound ( At least one compound selected from the group consisting of compounds that react with A) to form ion pairs.

[6]
The olefin multimerization catalyst according to [5], further comprising the following component (C).
Component (C); a carrier for supporting at least one compound selected from component (A) and component (B).

[7]
A method for producing an olefin multimer, wherein the olefin is multimerized using the olefin polymerization catalyst according to [5] or [6].

  According to the present invention, it is possible to provide a specific transition metal complex compound and a highly active olefin multimerization catalyst containing the compound. Furthermore, the manufacturing method of an olefin multimer using this olefin multimerization catalyst can be provided. When the ethylene multimerization reaction is carried out by this production method, 1-hexene can be produced with high activity and selectivity, which is extremely valuable industrially.

  Further, according to the method of the present invention, an olefin multimer can be produced with high activity even at a higher polymerization temperature than in the past. Generally, the higher the polymerization temperature, the easier the heat removal, the smaller the heat removal apparatus, and the same heat removal apparatus can improve the productivity. Furthermore, since the polymerization is performed at a high temperature, even if the polymer concentration is increased, the solution viscosity is not so high and the stirring power can be reduced, so that productivity is improved.

  Hereinafter, the transition metal complex compound of the present invention, an olefin multimerization catalyst, and a method for producing an olefin multimer using the olefin multimerization catalyst will be specifically described.

  In addition, in this invention, the olefin multimerization is making an olefin into a 2-10 mer.

  The olefin multimerization catalyst of the present invention contains a transition metal complex compound (A) described later. In addition to the (A) transition metal complex compound, the olefin multimerization catalyst is usually (B) (b-1) an organometallic compound, (b-2) an organoaluminum oxy compound, and (b-3) (A ) It contains at least one compound selected from the group consisting of compounds that react with transition metal complex compounds to form ion pairs. In addition, the compound which reacts with (b-3) (A) transition metal complex compound to form an ion pair is also referred to as “ionized ionic compound”.

  Further, the olefin multimerization catalyst of the present invention may contain a support (C) for supporting at least one compound selected from the group consisting of component (A) and component (B).

[(A) Transition metal complex compound]
The (A) transition metal complex compound of the present invention is a transition metal complex compound represented by the following general formula (1). The transition metal complex compound has a steric hindrance with an adjacent substituent in the phenoxyimine ligand (R ⁴ , R ⁵ , R ⁶ , R ⁹ , R ^{10 in the following} general formula (1) or By introducing a substituent into R ¹² ), the rotation of a single bond existing between the adjacent substituents is inhibited, and the phenoxyimine ligand is less likely to be detached from the metal, thereby increasing the stability of the compound and increasing the heat resistance. It is characterized by having sex.

In the general formula (1), R ¹ , R ² , R ³ , R ⁷ , R ⁸ , R ¹¹ , R ¹³ and R ¹⁴ may be the same as or different from each other, and are a hydrogen atom, a halogen atom or a hydrocarbon. An atom or group selected from a group, a hydrocarbon-substituted silyl group, an oxygen-containing group and a nitrogen-containing group;

  Here, examples of the halogen atom include fluorine, chlorine, bromine, and iodine.

Specifically, the hydrocarbon group has 1 to 30 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, neopentyl, n-hexyl, preferably 1 to 20, more preferably 1 to 10 linear or branched alkyl group; vinyl, allyl, isopropenyl and the like having 2 to 30, preferably 2 to 20 carbon atoms A branched alkenyl group; a linear or branched alkynyl group having 2 to 30, preferably 2 to 20 carbon atoms such as ethynyl and propargyl; and a carbon atom number such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and adamantyl 3-30, preferably 3-20, cyclic saturated hydrocarbon groups;
A cyclic unsaturated hydrocarbon group having 5 to 30 carbon atoms such as cyclopentadienyl, indenyl, fluorenyl; 6 to 30 carbon atoms such as phenyl, naphthyl, biphenyl, terphenyl, phenanthryl and anthracenyl, preferably 6 to 6 20 aryl groups; alkyl-substituted aryl groups such as tolyl, isopropylphenyl, tert-butylphenyl, dimethylphenyl, and di-tert-butylphenyl; 1 to 30 carbon atoms such as benzylidene, methylidene, and ethylidene, preferably Includes 5 to 10 alkylidene groups.

In the above hydrocarbon group, a hydrogen atom may be substituted with a halogen. For example, a halogenated hydrocarbon group having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms such as trifluoromethyl, pentafluorophenyl, chlorophenyl and the like. Can be mentioned.

  In the hydrocarbon group, a hydrogen atom may be substituted with another hydrocarbon group, and examples thereof include aryl group-substituted alkyl groups such as benzyl, cumyl, diphenylethyl, and trityl.

  Further, the hydrocarbon group includes residues such as nitrogen-containing compounds such as pyrrole, pyridine, pyrimidine, quinoline and triazine, oxygen-containing compounds such as furan and pyran, sulfur-containing compounds such as thiophene, and heterocyclic compounds thereof. A heterocyclic compound residue such as a group further substituted with a substituent such as an alkyl group or alkoxy group having 1 to 30, preferably 1 to 20 carbon atoms in the residue; alkoxy group, aryloxy group, ester group, ether Group, acyl group, carboxyl group, carbonate group, hydroxy group, peroxy group, carboxylic anhydride group and other oxygen-containing groups; amino group, imino group, amide group, imide group, hydrazino group, hydrazono group, nitro group, nitroso Group, cyano group, isocyano group, cyanate ester group, amidino group, diazo group, amino group Nitrogen-containing groups such as those formed into nium salts; Boron-containing groups such as boranediyl group, boranetriyl group, diboranyl group; mercapto group, thioester group, dithioester group, alkylthio group, arylthio group, thioacyl group, thioether group, thiocyanic acid Sulfur-containing groups such as ester groups, isothiocyanate groups, sulfone ester groups, sulfonamido groups, thiocarboxyl groups, dithiocarboxyl groups, sulfo groups, sulfonyl groups, sulfinyl groups, sulfenyl groups; phosphide groups, phosphoryl groups, thiophosphoryls And a phosphorus-containing group such as a phosphato group, a silicon-containing group, a germanium-containing group, or a tin-containing group.

  Among these, in particular, 1 to 30 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, neopentyl, n-hexyl, adamantyl, etc. 20, more preferably 1-10, more preferably 2-10 linear or branched alkyl groups; phenyl, naphthyl, biphenyl, terphenyl, phenanthryl, anthracenyl, etc. 6-30, preferably 6. An aryl group having ˜20; a halogen atom, an alkyl group or alkoxy group having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, an aryl group or aryloxy having 6 to 30 carbon atoms, preferably 6 to 20 carbon atoms; A substituted aryl group substituted with 1 to 5 substituents such as a group is preferred.

  Specific examples of the hydrocarbon-substituted silyl group include methylsilyl, dimethylsilyl, trimethylsilyl, ethylsilyl, diethylsilyl, triethylsilyl, diphenylmethylsilyl, triphenylsilyl, dimethylphenylsilyl, dimethyl-tert-butylsilyl, dimethyl (pentafluorophenyl) Examples include silyl. Among these, methylsilyl, dimethylsilyl, trimethylsilyl, ethylsilyl, diethylsilyl, triethylsilyl, dimethylphenylsilyl, triphenylsilyl and the like are preferable. In particular, trimethylsilyl, triethylsilyl, triphenylsilyl, and dimethylphenylsilyl are preferable.

  Examples of the oxygen-containing group and the nitrogen-containing group include the same groups as those exemplified as the substituent which may be contained in the hydrocarbon group.

R ¹ , R ² , R ³ , R ⁷ , R ⁸ , R ¹¹ , R ^13, and R ¹⁴ are each a hydrogen atom, a halogen atom, or the like because of the catalytic performance and ease of production when used as an olefin multimerization catalyst. An atom, a hydrocarbon group having 1 to 30 carbon atoms, a halogenated hydrocarbon group, or a hydrocarbon-substituted silyl group is preferable, and R ¹ , R ² , R ³ , R ⁷ , R ⁸ , R ¹¹ are more preferable. , R ¹³ and R ¹⁴ are at least R ² selected from a tertiary alkyl group or a hydrocarbon-substituted tertiary silyl group, and a group having 20 or less total carbon atoms.

Among these, preferred groups as R ¹ are hydrocarbon groups having 1 to 20 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, n-hexyl, cyclohexyl, and n-octyl among the above examples. From the viewpoint of catalytic activity and selectivity, methyl, ethyl, n-propyl, and n-butyl are particularly preferable.

Among the above examples, preferred groups as R ² are tertiary alkyl groups having 4 to 20 carbon atoms such as tert-butyl, adamantyl, cumyl, and trityl; carbons such as trimethylsilyl, methyldiphenylsilyl, dimethylphenylsilyl, and triphenylsilyl. It is a hydrocarbon-substituted tertiary silyl group having 1 to 20 atoms.

Preferred examples of R ³ include isopropyl, cyclohexyl, tert, among the above examples.
A hydrocarbon group having 1 to 20 carbon atoms such as butyl, adamantyl, cumyl, trityl, phenyl, tolyl, dimethylphenyl, trimethylphenyl, ethylphenyl, propylphenyl, biphenyl, naphthyl, methylnaphthyl, anthracenyl, phenanthryl; trimethylsilyl, A hydrocarbon-substituted silyl group having 1 to 20 carbon atoms such as methyldiphenylsilyl, dimethylphenylsilyl, triphenylsilyl and the like.

In the general formula (1), R ⁴ , R ⁵ , R ⁹ and R ¹⁰ may be the same or different from each other, and are a hydrogen atom, a halogen atom, a hydrocarbon group, a hydrocarbon-substituted silyl group, an oxygen-containing group and An atom or group selected from a nitrogen-containing group, and in the general formula (1), R ⁶ and R ¹² may be the same or different from each other, and are a hydrogen atom, a hydrocarbon group, a hydrocarbon-substituted silyl group, oxygen An atom or group selected from a containing group and a nitrogen-containing group.

The halogen atom, hydrocarbon group, hydrocarbon-substituted silyl group, oxygen-containing group and nitrogen-containing group selected from R ⁴ , R ⁵ , R ⁶ , R ⁹ , R ¹⁰ and R ¹² are those represented by the general formula (1 ) R ¹
, R ² , R ³ , R ⁷ , R ⁸ , R ¹¹ , R ¹³ and R ¹⁴ are the same.

  Specifically, the halogen atom includes fluorine, chlorine, bromine and iodine.

Specifically, the hydrocarbon group has 1 to 30 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, neopentyl, n-hexyl, preferably 1 to 20, more preferably 1 to 10 linear or branched alkyl group; vinyl, allyl, isopropenyl and the like having 2 to 30, preferably 2 to 20 carbon atoms A branched alkenyl group; a linear or branched alkynyl group having 2 to 30, preferably 2 to 20 carbon atoms such as ethynyl and propargyl; and a carbon atom number such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and adamantyl 3-30, preferably 3-20, cyclic saturated hydrocarbon groups;
A cyclic unsaturated hydrocarbon group having 5 to 30 carbon atoms such as cyclopentadienyl, indenyl, fluorenyl; 6 to 30 carbon atoms such as phenyl, naphthyl, biphenyl, terphenyl, phenanthryl and anthracenyl, preferably 6 to 6 20 aryl groups; alkyl-substituted aryl groups such as tolyl, isopropylphenyl, tert-butylphenyl, dimethylphenyl, and di-tert-butylphenyl; 1 to 30 carbon atoms such as benzylidene, methylidene, and ethylidene, preferably Includes 5 to 10 alkylidene groups.

  In the above hydrocarbon group, a hydrogen atom may be substituted with a halogen. For example, a halogenated hydrocarbon group having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms such as trifluoromethyl, pentafluorophenyl, chlorophenyl and the like. Can be mentioned.

  In the hydrocarbon group, a hydrogen atom may be substituted with another hydrocarbon group, and examples thereof include aryl group-substituted alkyl groups such as benzyl, cumyl, diphenylethyl, and trityl.

  Further, the hydrocarbon group includes residues such as nitrogen-containing compounds such as pyrrole, pyridine, pyrimidine, quinoline and triazine, oxygen-containing compounds such as furan and pyran, sulfur-containing compounds such as thiophene, and heterocyclic compounds thereof. A heterocyclic compound residue such as a group further substituted with a substituent such as an alkyl group or alkoxy group having 1 to 30, preferably 1 to 20 carbon atoms in the residue; alkoxy group, aryloxy group, ester group, ether Group, acyl group, carboxyl group, carbonate group, hydroxy group, peroxy group, carboxylic anhydride group and other oxygen-containing groups; amino group, imino group, amide group, imide group, hydrazino group, hydrazono group, nitro group, nitroso Group, cyano group, isocyano group, cyanate ester group, amidino group, diazo group, amino group Nitrogen-containing groups such as those formed into nium salts; Boron-containing groups such as boranediyl group, boranetriyl group, diboranyl group; mercapto group, thioester group, dithioester group, alkylthio group, arylthio group, thioacyl group, thioether group, thiocyanic acid Sulfur-containing groups such as ester groups, isothiocyanate groups, sulfone ester groups, sulfonamido groups, thiocarboxyl groups, dithiocarboxyl groups, sulfo groups, sulfonyl groups, sulfinyl groups, sulfenyl groups; phosphide groups, phosphoryl groups, thiophosphoryls And a phosphorus-containing group such as a phosphato group, a silicon-containing group, a germanium-containing group, or a tin-containing group.

  Specific examples of the hydrocarbon-substituted silyl group include methylsilyl, dimethylsilyl, trimethylsilyl, ethylsilyl, diethylsilyl, triethylsilyl, diphenylmethylsilyl, triphenylsilyl, dimethylphenylsilyl, dimethyl-tert-butylsilyl, dimethyl (pentafluorophenyl) Examples include silyl. Among these, methylsilyl, dimethylsilyl, trimethylsilyl, ethylsilyl, diethylsilyl, triethylsilyl, dimethylphenylsilyl, triphenylsilyl and the like are preferable. In particular, trimethylsilyl, triethylsilyl, triphenylsilyl, and dimethylphenylsilyl are preferable.

  Examples of the oxygen-containing group and the nitrogen-containing group include the same groups as those exemplified as the substituent which may be contained in the hydrocarbon group.

R ⁴ , R ⁵ , R ⁶ , R ⁹ , R ¹⁰ and R ¹² are not hydrogen atoms at the same time.

The fact that R ⁴ , R ⁵ , R ⁶ , R ⁹ , R ¹⁰ and R ¹² are not hydrogen atoms at the same time means that the phenoxyimine ligand has a steric hindrance with an adjacent substituent that is always 1 One means that a substituent is introduced, which inhibits the rotation of a single bond existing between the adjacent substituents and prevents the phenoxyimine ligand from coming off the metal, thereby stabilizing the compound. The characteristic that it will increase and it will have heat resistance is expressed. As described later, by using such a transition metal compound as an olefin multimerization catalyst, the stability of the catalyst is increased, and favorable results are obtained from the viewpoint of heat resistance and reaction activity of the catalyst.

R ⁴ , R ⁵ , R ⁶ , R ⁹ , R ^10, and R ¹² are R ⁴ , R ⁵ , R ⁶ , R ⁹ , R ⁴ , R ⁵ , R ⁶ , R ⁹ , At least one of R ¹⁰ and R ¹² is an alkyl group such as methyl, ethyl, propyl, butyl, hexyl, cyclohexyl, octyl, nonyl, dodecyl, eicosyl, norbornyl, adamantyl; benzyl, cumyl, phenylethyl, phenylpropyl, diphenylethyl Arylalkyl groups such as phenyl, tolyl, dimethylphenyl, trimethylphenyl, ethylphenyl, propylphenyl, biphenyl, naphthyl, methylnaphthyl, anthracenyl, phenanthryl, etc .; unsubstituted or substituted cyclopentadienyl group, unsubstituted or Contains substituted cyclopentadienyl groups Is preferably a hydrocarbon group having 1 to 30 carbon atoms, such as, in particular, methyl, ethyl, propyl, is preferably a phenyl group.

Furthermore, two or more of the groups represented by R ^{1 to} R ¹⁴ may be linked to each other. Preferably, adjacent groups may be linked to each other to form an alicyclic ring, an aromatic ring, or a hydrocarbon ring containing a different atom such as an oxygen atom or a nitrogen atom, and these rings further have a substituent. May be.

In the general formula (1), R ^{6 to} R ¹³ are preferably not halogen, R ³ , R ⁷ ,
When R ⁸ , R ¹¹ and R ¹³ are hydrocarbon groups, it is preferably 1 or 2 carbon atoms.

  In the general formula (1), M represents a transition metal atom in Groups 4 to 6 of the periodic table, and n represents the valence of M. Preferable examples of M include titanium, zirconium, hafnium, vanadium, tantalum, and chromium. M is more preferably a transition metal atom of Group 4 of the periodic table such as titanium, zirconium, hafnium, etc., and titanium is particularly preferable. n is particularly preferably 4 for Group 4 transition metal atoms such as titanium, zirconium, hafnium, 3-5 for vanadium and tantalum, and 3 for chromium.

  In the general formula (1), X represents a hydrogen atom, a halogen atom, a hydrocarbon group, an oxygen-containing group or a nitrogen-containing group. The atoms and groups represented by X may be the same or different from each other, and the groups represented by X may be bonded to each other to form a ring.

Here, the halogen atom, hydrocarbon group, oxygen-containing group and nitrogen-containing group selected in X are R ¹ , R ² , R ³ , R ⁷ , R ⁸ , R ¹¹ , R in the general formula (1). Examples thereof are the same as those exemplified for ¹³ and R ¹⁴ .

  Specifically, the halogen atom includes fluorine, chlorine, bromine and iodine.

Specifically, the hydrocarbon group has 1 to 30 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, neopentyl, n-hexyl, preferably A linear or branched alkyl group having 1 to 20, more preferably 1 to 10; a linear or branched alkyl group having 2 to 30, preferably 2 to 20 carbon atoms, such as vinyl, allyl, isopropenyl, etc. Is a branched alkenyl group; a linear or branched alkynyl group having 2 to 30, preferably 2 to 20 carbon atoms such as ethynyl, propargyl, etc .; carbon atoms such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl, etc. Is a cyclic saturated hydrocarbon group having 3 to 30, preferably 3 to 20; cyclopentadienyl, indenyl A cyclic unsaturated hydrocarbon group having 5 to 30 carbon atoms such as fluorenyl; aryl having 6 to 30, preferably 6 to 20 carbon atoms such as phenyl, naphthyl, biphenyl, terphenyl, phenanthryl, anthracenyl, etc. Groups; alkyl-substituted aryl groups such as tolyl, isopropylphenyl, tert-butylphenyl, dimethylphenyl, and di-tert-butylphenyl; alkylidene having 1 to 30, preferably 5 to 10 carbon atoms, such as benzylidene, methylidene, and ethylidene Group and the like.

  In the above hydrocarbon group, a hydrogen atom may be substituted with a halogen. For example, a halogenated hydrocarbon group having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms such as trifluoromethyl, pentafluorophenyl, chlorophenyl and the like. Can be mentioned.

In the hydrocarbon group, a hydrogen atom may be substituted with another hydrocarbon group, and examples thereof include aryl group-substituted alkyl groups such as benzyl, cumyl, diphenylethyl, and trityl.

  Further, the hydrocarbon group includes residues such as nitrogen-containing compounds such as pyrrole, pyridine, pyrimidine, quinoline and triazine, oxygen-containing compounds such as furan and pyran, sulfur-containing compounds such as thiophene, and heterocyclic compounds thereof. A heterocyclic compound residue such as a group further substituted with a substituent such as an alkyl group or alkoxy group having 1 to 30, preferably 1 to 20 carbon atoms in the residue; alkoxy group, aryloxy group, ester group, ether Group, acyl group, carboxyl group, carbonate group, hydroxy group, peroxy group, carboxylic anhydride group and other oxygen-containing groups; amino group, imino group, amide group, imide group, hydrazino group, hydrazono group, nitro group, nitroso Group, cyano group, isocyano group, cyanate ester group, amidino group, diazo group, amino group Nitrogen-containing groups such as those formed into nium salts; Boron-containing groups such as boranediyl group, boranetriyl group, diboranyl group; mercapto group, thioester group, dithioester group, alkylthio group, arylthio group, thioacyl group, thioether group, thiocyanic acid Sulfur-containing groups such as ester groups, isothiocyanate groups, sulfone ester groups, sulfonamido groups, thiocarboxyl groups, dithiocarboxyl groups, sulfo groups, sulfonyl groups, sulfinyl groups, sulfenyl groups; phosphide groups, phosphoryl groups, thiophosphoryls And a phosphorus-containing group such as a phosphato group, a silicon-containing group, a germanium-containing group, or a tin-containing group.

  Examples of the oxygen-containing group and the nitrogen-containing group include the same groups as those exemplified as the substituent which may be contained in the hydrocarbon group.

  Among these, X is preferably a halogen atom or an alkyl group, and more preferably a chlorine, bromine or methyl group.

  The synthesis of the transition metal complex compound (A) represented by the general formula (1) of the present invention can be performed in accordance with, for example, the method described in Journal of Organometallic Chemistry 2003, 678, pages 134-141. .

  The reaction product obtained by the method described in the above document can be used as a catalyst for olefin multimerization without any purification operation after the reaction, but it can be used after purification by a purification operation such as recrystallization. It is preferable.

In addition, in this invention, when it describes as (A) transition metal complex compound, said general formula (I)
The transition metal complex compound represented by these is included.

[Olefin multimerization catalyst]
In addition to the above (A) transition metal complex compound, the olefin multimerization catalyst of the present invention is usually
(B) (b-1) an organometallic compound,
It contains at least one compound selected from the group consisting of (b-2) an organoaluminum oxy compound, and (b-3) (A) a compound that reacts with a transition metal complex compound to form an ion pair.

  Hereinafter, (b-1) an organometallic compound, (b-2) an organoaluminum oxy compound, and (b-3) (A) a compound that forms an ion pair by reacting with a transition metal complex compound will be described.

[(B-1) Organometallic compound]
Specific examples of the organometallic compound (b-1) used as necessary in the present invention include the following organometallic compounds of Groups 1, 2 and 12, 13 of the periodic table. Examples thereof include (b-1a), (b-1b), and (b-1c) described below. In the present invention, the (b-1) organometallic compound does not include the (b-2) organoaluminum oxy compound described later.

(B-1a) formula R ^a _m Al (OR ^b) an organic aluminum compound represented by _n H _p X _q.
(In the formula, R ^a and R ^b each represent a hydrocarbon group having 1 to 15, preferably 1 to 4 carbon atoms which may be the same or different from each other, X represents a halogen atom, and m represents 0 < m ≦ 3, n is 0 ≦ n <3, p is 0 ≦ p <3, q is a number of 0 ≦ q <3, and m + n + p + q = 3)
(B-1b) Complex alkylated product of Group 1 metal of the periodic table represented by the general formula M ² AlR ^a ₄ and aluminum.
(Wherein M ² represents Li, Na or K, and R ^a represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms)
(B-1c) A dialkyl compound of Group 2 or Group 12 metal represented by the general formula R ^a R ^b M ³ .
(In the formula, R ^a and R ^b each represent a hydrocarbon group having 1 to 15, preferably 1 to 4 carbon atoms, which may be the same or different from each other, and M ³ is Mg, Zn or Cd)
Examples of the organoaluminum compound belonging to (b-1a) include the following compounds.

General formula R ^a _m Al (OR ^b ) _3-m (wherein R ^a and R ^b represent a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, which may be the same or different from each other. M is preferably a number of 1.5 ≦ m ≦ 3.) An organoaluminum compound represented by the general formula R ^a _m AlX _3-m
(Wherein, R ^a represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, X represents a halogen atom, and m is preferably 0 <m <3). An organoaluminum compound having the general formula R ^a _m AlH _3-m (wherein R ^a represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, and m is preferably 2 ≦ m <3. An organoaluminum compound represented by the general formula R ^a _m Al (OR ^b ) _n X _q (wherein R ^a and R ^b are the same or different and each have 1 to 15 carbon atoms) , Preferably 1 to 4 hydrocarbon groups, X represents a halogen atom, m is a number 0 <m ≦ 3, n is 0 ≦ n <3, q is a number 0 ≦ q <3, and m + n + q = 3).

More specifically, as the organoaluminum compound belonging to (b-1a), trimethylaluminum, triethylaluminum, tri (n-butyl) aluminum, tripropylaluminum, tripentylaluminum, trihexylaluminum, trioctylaluminum, tridecyl Tri (n-alkyl) aluminum such as aluminum; triisopropylaluminum, triisobutylaluminum, tri (sec-butyl) aluminum, tri (tert-butyl) aluminum, tri (2-methylbutyl) aluminum, tri (3-methylbutyl) aluminum , Tri (2-methylpentyl) aluminum, tri (3-methylpentyl) aluminum, tri (4-methylpentyl) aluminum, tri (2-methylhexyl) Tri-branched alkyl aluminums such as aluminum, tri (3-methylhexyl) aluminum, tri (2-ethylhexyl) aluminum;
Tricyclohexyl aluminum, tri-cycloalkyl aluminum such as tri-cyclooctyl aluminum; triphenyl aluminum, triaryl aluminum such as tri-tolyl aluminum, diethyl aluminum hydride, dialkylaluminum hydride such as diisobutylaluminum _{hydride; (iC 4 H 9) x} Al y (C ₅ H ₁₀ ) _z (wherein x, y and z are positive numbers and z ≧ 2x. IC ₄ H ₉ represents an isobutyl group) Alkenyl aluminum;
Alkyl aluminum alkoxides such as isobutylaluminum methoxide, isobutylaluminum ethoxide and isobutylaluminum isopropoxide; Dialkylaluminum alkoxides such as dimethylaluminum methoxide, diethylaluminum ethoxide and dibutylaluminum butoxide; Ethylaluminum sesquiethoxide and butylaluminum sesquibutoxide R ^a _2.5 Al (OR ^b ) _0.5 (wherein R ^a and R ^b are carbon atoms having 1 to 15 carbon atoms, which may be the same as or different from each other, preferably 1 to 4 carbon atoms). A partially alkoxylated alkylaluminum having an average composition represented by, for example: diethylaluminum phenoxide, diethylal Ni (2,6-di-tert-butyl 4-methylphenoxide), ethylaluminum bis (2,6-di-tert-butyl 4-methylphenoxide), diisobutylaluminum (2,6-di-tert-butyl 4- Dialkylaluminum aryloxides such as methylphenoxide) and isobutylaluminum bis (2,6-di-tert-butyl4-methylphenoxide); dimethylaluminum chloride, diethylaluminum chloride, dibutylaluminum chloride, diethylaluminum bromide, diisobutylaluminum chloride, etc. Dialkylaluminum halides such as ethylaluminum sesquichloride, butylaluminum sesquichloride, and ethylaluminum sesquibromide Halides; partially halogenated alkylaluminums such as alkylaluminum dihalides such as ethylaluminum dichloride, propylaluminum dichloride and butylaluminum dibromide; dialkylaluminum hydrides such as diethylaluminum hydride and dibutylaluminum hydride; ethylaluminum dihydride; Other partially hydrogenated alkylaluminums such as alkylaluminum dihydrides such as propylaluminum dihydride; partially alkoxylated and halogenated alkyls such as ethylaluminum ethoxychloride, butylaluminum butoxycycloride, ethylaluminum ethoxybromide Aluminum etc. are mentioned.

Moreover, the compound similar to (b-1a) can also be used, for example, the organoaluminum compound which two or more aluminum compounds couple | bonded through the nitrogen atom is mentioned. Specific examples of such a compound include (C ₂ H ₅ ) ₂ AlN (C ₂ H ₅ ) Al (C ₂ H ₅ ) ₂ .

Examples of the compound belonging to (b-1b) include LiAl (C ₂ H ₅ ) ₄ and LiAl (C ₇ H ₁₅ ) ₄ .

  Examples of the compound belonging to (b-1c) include dimethylmagnesium, diethylmagnesium, dibutylmagnesium, and butylethylmagnesium.

  As (b-1) organometallic compounds other than the above (b-1a) to (b-1c), methyllithium, ethyllithium, propyllithium, butyllithium, methylmagnesium bromide, methylmagnesium chloride, ethylmagnesium bromide, ethyl Magnesium chloride, propylmagnesium bromide, propylmagnesium chloride, butylmagnesium bromide, butylmagnesium chloride and the like can also be used.

  A compound that can form the organoaluminum compound in the multimerization reaction system, such as a combination of an aluminum halide and an alkyl lithium, or a combination of an aluminum halide and an alkyl magnesium, can also be used.

  (B-1) Among organometallic compounds, organoaluminum compounds are preferred. The above (b-1) organometallic compounds are used singly or in combination of two or more.

[(B-2) Organoaluminum oxy compound]
The (b-2) organoaluminum oxy compound used as necessary in the present invention may be a conventionally known aluminoxane, or a benzene insoluble organoaluminum as exemplified in JP-A-2-78687. It may be an oxy compound.

  A conventionally well-known aluminoxane can be manufactured, for example with the following method, and is normally obtained as a solution of a hydrocarbon solvent. (1) Compounds containing adsorbed water or salts containing water of crystallization, such as magnesium chloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate, nickel sulfate hydrate, first cerium chloride hydrate, etc. A method of reacting adsorbed water or crystal water with an organoaluminum compound by adding an organoaluminum compound such as trialkylaluminum to the suspension of the hydrocarbon. (2) A method of allowing water, ice or water vapor to act directly on an organoaluminum compound such as trialkylaluminum in a medium such as benzene, toluene, ethyl ether or tetrahydrofuran. (3) A method in which an organotin oxide such as dimethyltin oxide or dibutyltin oxide is reacted with an organoaluminum compound such as trialkylaluminum in a medium such as decane, benzene, or toluene.

  The aluminoxane may contain a small amount of an organometallic component. Further, after removing the solvent or the unreacted organoaluminum compound from the recovered aluminoxane solution by distillation, it may be redissolved in a solvent or suspended in a poor aluminoxane solvent.

  Specific examples of the organoaluminum compound used when preparing the aluminoxane include the same organoaluminum compounds as those exemplified as the organoaluminum compound belonging to (b-1a).

  Of these, trialkylaluminum and tricycloalkylaluminum are preferable, and trimethylaluminum is particularly preferable.

  The organoaluminum compounds as described above are used singly or in combination of two or more.

  Solvents used for the preparation of aluminoxane include aromatic hydrocarbons such as benzene, toluene, xylene, cumene, and cymene, aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, hexadecane, and octadecane, and cyclopentane. , Cycloaliphatic hydrocarbons such as cyclohexane, cyclooctane and methylcyclopentane, petroleum fractions such as gasoline, kerosene and light oil, or halides of the above aromatic hydrocarbons, aliphatic hydrocarbons and alicyclic hydrocarbons, especially chlorine And hydrocarbon solvents such as bromide and bromide. Furthermore, ethers such as ethyl ether and tetrahydrofuran can also be used. Of these solvents, aromatic hydrocarbons or aliphatic hydrocarbons are particularly preferable.

  The benzene-insoluble organoaluminum oxy compound used in the present invention has an Al component dissolved in benzene at 60 ° C. of usually 10% or less, preferably 5% or less, particularly preferably 2% or less in terms of Al atom, That is, those which are insoluble or hardly soluble in benzene are preferred.

  Examples of the organoaluminum oxy compound used in the present invention also include an organoaluminum oxy compound containing boron represented by the following general formula (i).

In the formula, R ¹⁵ represents a hydrocarbon group having 1 to 10 carbon atoms. R ¹⁶ represents a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 10 carbon atoms, which may be the same as or different from each other.

  The organoaluminum oxy compound containing boron represented by the general formula (i) includes an alkyl boronic acid represented by the following general formula (ii) and an organoaluminum compound in an inert solvent under an inert gas atmosphere. It can be produced by reacting at a temperature of -80 ° C to room temperature for 1 minute to 24 hours.

R ¹⁵ -B (OH) ₂ (ii)
(Wherein R ¹⁵ represents the same group as described above)
Specific examples of the alkyl boronic acid represented by the general formula (ii) include methyl boronic acid, ethyl boronic acid, isopropyl boronic acid, n-propyl boronic acid, n-butyl boronic acid, isobutyl boronic acid, and n-hexyl boron. Examples include acid, cyclohexyl boronic acid, phenyl boronic acid, 3,5-difluorophenyl boronic acid, pentafluorophenyl boronic acid, 3,5-bis (trifluoromethyl) phenyl boronic acid, and the like. Among these, methyl boronic acid, n-butyl boronic acid, isobutyl boronic acid, 3,5-difluorophenyl boronic acid, and pentafluorophenyl boronic acid are preferable.

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

  Specific examples of the organoaluminum compound to be reacted with the alkylboronic acid include the same organoaluminum compounds as those exemplified as the organoaluminum compound belonging to (b-1a). Of these, trialkylaluminum and tricycloalkylaluminum are preferable, and trimethylaluminum, triethylaluminum, and triisobutylaluminum are particularly preferable. These may be used alone or in combination of two or more.

  The above (b-2) organoaluminum oxy compounds are used singly or in combination of two or more.

[(B-3) Ionized ionic compound]
(B-3) (A) A compound that reacts with a transition metal complex compound to form an ion pair, which is used as necessary in the present invention, reacts with (A) a transition metal complex compound to form an ion pair. A compound. Therefore, what forms an ion pair by making it contact with at least (A) transition metal complex compound is contained in this compound.

  Examples of such compounds include JP-A-1-501950, JP-A-1-502036, JP-A-3-179905, JP-A-3-179006, JP-A-3-207703, and JP-A-3. And Lewis acids, ionic compounds, borane compounds and carborane compounds described in US Pat. No. 207704 and US Pat. No. 5,321,106. Furthermore, heteropoly compounds and isopoly compounds can also be mentioned.

Specifically, as the Lewis acid, a compound represented by BR ₃ (R is a phenyl group or fluorine which may have a substituent such as fluorine, methyl group or trifluoromethyl group) can be mentioned. For example, trifluoroboron, triphenylboron, tris (4-fluorophenyl) boron, tris (3,5-difluorophenyl) boron, tris (4-fluoromethylphenyl) boron, tris (pentafluorophenyl) boron, tris (P-Tolyl) boron, tris (o-tolyl) boron, tris (3,5-dimethylphenyl) boron and the like can be mentioned.

Examples of the ionic compound include compounds represented by the following general formula (III).

In the formula, ^examples of R ¹⁷⁺ include H ⁺ , carbonium cation, oxonium cation, ammonium cation, phosphonium cation, cycloheptyltrienyl cation, and ferrocenium cation having a transition metal.

R ^{18 to} R ²¹ are organic groups which may be the same as or different from each other, preferably an aryl group or a substituted aryl group.

  Specific examples of the carbonium cation include trisubstituted carbonium cations such as triphenylcarbonium cation, tri (methylphenyl) carbonium cation, and tri (dimethylphenyl) carbonium cation.

  Specific examples of the ammonium cation include trialkylammonium cations such as trimethylammonium cation, triethylammonium cation, tri (n-propyl) ammonium cation, and tri (n-butyl) ammonium cation; N, N-dimethylanilinium cation, N, N-diethylanilinium cation, N, N-diphenylanilinium cation such as N, N, 2,4,6-pentamethylanilinium cation; dialkylammonium cation such as di (isopropyl) ammonium cation and dicyclohexylammonium cation Etc.

  Specific examples of the phosphonium cation include triarylphosphonium cations such as triphenylphosphonium cation, tri (methylphenyl) phosphonium cation, and tri (dimethylphenyl) phosphonium cation.

R ¹⁷⁺ is preferably a carbonium cation, an ammonium cation or the like, and particularly preferably a triphenylcarbonium cation, an N, N-dimethylanilinium cation or an N, N-diethylanilinium cation.

Examples of the ionic compound include trialkyl-substituted ammonium salts, N, N-dialkylanilinium salts, dialkylammonium salts, and triarylphosphonium salts.

  Specific examples of the trialkyl-substituted ammonium salt include triethylammonium tetraphenylborate, tri (n-propyl) ammonium tetraphenylborate, tri (n-butyl) ammonium tetraphenylborate, trimethylammonium tetra (p-tolyl) borate, Trimethylammonium tetra (o-tolyl) borate, tri (n-butyl) ammonium tetra (pentafluorophenyl) borate, tri (n-propyl) ammonium tetra (o, p-dimethylphenyl) borate, tri (n-butyl) ammonium Tetra (m, m-dimethylphenyl) borate, tri (n-butyl) ammonium tetra (p-trifluoromethylphenyl) borate, tri (n-butyl) ammonium tetra (3,5-di Trifluoromethyl phenyl) borate, tri (n- butyl) ammonium tetra (o-tolyl) borate.

  Specific examples of the N, N-dialkylanilinium salt include, for example, N, N-dimethylanilinium tetraphenylborate, N, N-diethylanilinium tetraphenylborate, N, N, 2,4,6-pentamethylaniline. Examples thereof include nium tetraphenylborate.

  Specific examples of the dialkylammonium salt include di (n-propyl) ammonium tetra (pentafluorophenyl) borate and dicyclohexylammonium tetraphenylborate.

  Further, as ionic compounds, triphenylcarbenium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, ferrocenium tetra (pentafluorophenyl) borate, triphenylcarbenium pentaphenyl Examples thereof include cyclopentadienyl complexes, N, N-diethylanilinium pentaphenylcyclopentadienyl complexes, and boron compounds represented by the following formula (IV) or (V).

(In the formula, Et represents an ethyl group.)

  Specific examples of the borane compound include decaborane (14); bis [tri (n-butyl) ammonium] nonaborate, bis [tri (n-butyl) ammonium] decaborate, bis [tri (n-butyl) ammonium] undeca. Salts of anions such as borate, bis [tri (n-butyl) ammonium] dodecaborate, bis [tri (n-butyl) ammonium] decachlorodecaborate, bis [tri (n-butyl) ammonium] dodecachlorododecaborate; Of metal borane anions such as tri (n-butyl) ammonium bis (dodecahydridododecaborate) cobaltate (III), bis [tri (n-butyl) ammonium] bis (dodecahydridododecaborate) nickate (III) Examples include salt.

Specific examples of the carborane compound include 4-carbanonaborane (14), 1,3-dicarbanonaborane (13), 6,9-dicarbadecarborane (14), dodecahydride-1-phenyl-1, 3-dicarbanonaborane, dodecahydride-1-methyl-1,3-dicarbanonaborane, undecahydride-1,3-dimethyl-1,3-dicarbanonaborane, 7,8-dicarbaundecaborane (13), 2,7-dicarboundecarborane (13), undecahydride-7,8-dimethyl-7,8-dicarboundecarborane, dodecahydride-11-methyl-2,7-dicarboundecarborane Tri (n-butyl) ammonium 1-carbadecaborate, tri (n-butyl) ammonium 1-carbaundecaborate, (N-butyl) ammonium 1-carbadodecaborate, tri (n-butyl) ammonium 1-trimethylsilyl-1-carbadecaborate, tri (n-butyl) ammonium bromo-1-carbadodecaborate, tri (n-butyl) Ammonium 6-carbadecaborate (14), tri (n-butyl) ammonium 6-carbadecaborate (12), tri (n-butyl) ammonium 7 carbaundecaborate (13), tri (n-butyl) ammonium 7 , 8-dicarbaundecaborate (12), tri (n-butyl) ammonium 2,9-dicarbaundecaborate (12), tri (n-butyl) ammonium dodecahydride-8-methyl-7,9-dicarbaun Decaborate, tri (n-butyl) ammonium undecahydrate Id-8-ethyl-7,9-dicarbaundecaborate, tri (n-butyl) ammonium undecahydride-8-butyl-7,9-dicarbaundecaborate, tri (n-butyl) ammonium undecahydride 8-allyl-7,9-dicarbaundecaborate, tri (n-butyl) ammonium undecahydride-9-trimethylsilyl-7,8-dicarbaundecaborate, tri (n-butyl) ammonium undecahydride-4, Salts of anions such as 6-dibromo-7-carbaundecaborate; tri (n-butyl) ammonium bis (nonahydride-1,3-dicarbanonaborate) cobaltate (III), tri (n-butyl) Ammonium bis (undecahydride-7,8-dicarbaoundecabo Acid) ferrate (III), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarbaundecaborate) cobaltate (III), tri (n-butyl) ammonium bis (undeca) Hydride-7,8-dicarbaundecaborate) nickelate (III), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarbaundecaborate) cuprate (III), tri (n -Butyl) ammonium bis (undecahydride-7,8-dicarbaundecaborate) aurate (III), tri (n-butyl) ammonium bis (nonahydride-7,8-dimethyl-7,8-dicarbaun) Decaborate) ferrate (III), tri (n-butyl) ammonium bis (nonahydride-7,8-dimethyl) Til-7,8-dicarbaundecaborate) chromate (III), tri (n-butyl) ammonium bis (tribromooctahydride-7,8-dicarbundecaborate) cobaltate (III), tris [ Tri (n-butyl) ammonium] bis (undecahydride-7-carbaundecaborate) chromate (III), bis [tri (n-butyl) ammonium] bis (undecahydride-7-carbaundecaborate ) Manganate (IV), bis [tri (n-butyl) ammonium] bis (undecahydride-7-carbaundecaborate) cobaltate (III), bis [tri (n-butyl) ammonium] bis ( Metal carbonates such as undecahydride-7-carbaundecaborate) nickelate (IV) Such as the salt of the run-anion, and the like.

  The heteropoly compound is composed of atoms composed of silicon, phosphorus, titanium, germanium, arsenic or tin and one or more atoms selected from vanadium, niobium, molybdenum and tungsten. Specifically, phosphovanadic acid, germanovanadic acid, arsenic vanadic acid, phosphoniobic acid, germanoniobic acid, siliconomolybdic acid, phosphomolybdic acid, titanium molybdic acid, germanomolybdic acid, arsenic molybdic acid, tin molybdic acid, phosphorus Tungstic acid, germanotungstic acid, tin tungstic acid, phosphomolybdovanadic acid, lintongost vanadic acid, germanotangostovanadic acid, phosphomolybdotangostobanamic acid, germanomolybdo tungstovanadate, phosphomolybdo Tungstic acid, phosphomolybniobic acid, salts of these acids, such as metals of Group 1 or 2 of the periodic table, specifically lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium , With barium etc. Salts, and organic salts such as triphenylethyl salt, and isopoly compound can be used but not limited thereto.

  The heteropoly compound and the isopoly compound are not limited to one of the above compounds, and two or more of them can be used.

  The above (b-3) ionized ionic compounds are used singly or in combination of two or more.

  When the olefin multimerization catalyst of the present invention is used, an olefin multimer can be obtained with high activity, and particularly when ethylene is used as the olefin, the selectivity of 1-hexene is high.

  For example, when an organoaluminum oxy compound (b-2) such as methylaluminoxane is used in combination as a promoter component, 1-hexene can be produced by showing very high trimerization activity with respect to ethylene. Even if an ionized ionic compound (b-3) such as triphenylcarbonium tetrakis (pentafluorophenyl) borate is used as a promoter component, 1-hexene can be obtained from ethylene with good activity and very high selectivity. .

  The olefin multimerization catalyst according to the present invention includes (A) a transition metal complex compound, and if necessary, (B) (b-1) an organometallic compound, (b-2) an organoaluminum oxy compound, and (B-3) It contains at least one compound selected from ionized ionic compounds, and may further contain (C) a carrier as described later, if necessary.

[(C) Carrier]
The carrier (C) used as necessary in the present invention is an inorganic or organic compound and is a granular or fine particle solid. In the present invention, the (C) carrier is a carrier for carrying the (A) and / or (B). Among these, as the inorganic compound, a porous oxide, an inorganic halide, clay, clay mineral, or an ion-exchange layered compound is preferable.

Specific examples of the porous oxide include SiO ₂ , Al ₂ O ₃ , MgO, ZrO, TiO ₂ and B _2.
O ₃ , CaO, ZnO, BaO, ThO ₂ etc., or composites or mixtures containing these are used, eg natural or synthetic zeolite, SiO ₂ —MgO, SiO ₂ —Al ₂ O ₃ , SiO ₂ —TiO ₂ , SiO _{2 -V 2 O 5, SiO 2} -Cr 2 O 3, etc. can be used SiO ₂ -TiO ₂ -MgO. Of these, those containing SiO ₂ and / or Al ₂ O ₃ as main components are preferred.

Note that the inorganic oxide includes a small amount of Na ₂ CO ₃ , K ₂ CO ₃ , CaCO ₃ , MgCO ₃ , Na ₂ SO ₄ , Al ₂ (SO ₄ ) ₃ , BaSO ₄ , KNO ₃ , Mg (NO ₃ ). ₂ , Al (NO ₃ ) ₃ , N
It may contain carbonates, sulfates, nitrates and oxide components such as a ₂ O, K ₂ O and Li ₂ O.

Such porous oxides have different properties depending on the type and production method, but the carrier preferably used in the present invention has a particle size of 0.5 to 300 μm and a specific surface area of 50 to 1000 m ² / g. It is desirable that the pore volume be in the range of 0.3 to 3.0 cm ³ / g. Such a carrier is used after being calcined at 100 to 1000 ° C. as necessary.

As the inorganic halide, MgCl ₂ , MgBr ₂ , MnCl ₂ , MnBr ₂ or the like is used. The inorganic halide may be used as it is or after being pulverized by a ball mill or a vibration mill. Further, it is also possible to use a material in which an inorganic halide is dissolved in a solvent such as alcohol and then precipitated into fine particles with a precipitating agent.

  The clay used as a carrier in the present invention is usually composed mainly of a clay mineral. Further, the ion-exchangeable layered compound used as a carrier in the present invention is a compound having a crystal structure in which the surfaces constituted by ionic bonds and the like are stacked in parallel with a weak binding force, and the ions contained can be exchanged It is. Most clay minerals are ion-exchangeable layered compounds. In addition, these clays, clay minerals, and ion-exchange layered compounds are not limited to natural products, and artificial synthetic products can also be used.

Further, as clay, clay mineral or ion-exchangeable layered compound, clay, clay mineral, ionic crystalline compound having a layered crystal structure such as hexagonal fine packing type, antimony type, CdCl ₂ type, CdI ₂ type, etc. It can be illustrated.

Examples of such clays and clay minerals include kaolin, bentonite, kibushi clay, gyrome clay, allophane, hysinger gel, pyrophyllite, ummo group, montmorillonite group, vermiculite, ryokdeite group, palygorskite, kaolinite, nacrite, dickite And halloysite, and the ion-exchangeable layered compounds include α-Zr (HAsO ₄ ) ₂ .H ₂ O, α-Zr (KPO ₄ ) ₂ .3H ₂ O, α-Ti (HPO ₄ ) ₂ , α-Ti (HAsO ₄ ) ₂ .H ₂ O, α-Sn (HPO ₄ ) ₂ .H ₂ O, γ-Zr (HPO ₄ ) ₂ , γ-Ti (HPO ₄ ) ₂ , γ-Ti (NH ₄ Examples thereof include crystalline acidic salts of polyvalent metals such as PO ₄ ) ₂ .H ₂ O.

Such a clay, clay mineral or ion-exchange layered compound preferably has a pore volume of 0.1 cc / g or more with a radius of 20 angstroms or more measured by mercury porosimetry.
Those of ˜5 cc / g are particularly preferred. Here, the pore volume is measured in a pore radius range of 20 to ³ × 10 ⁴ angstroms by mercury porosimetry using a mercury porosimeter. When a carrier having a pore volume with a radius of 20 angstroms or more and smaller than 0.1 cc / g is used as a carrier, high multimerization activity tends to be difficult to obtain.

  The clay and clay mineral used in the present invention are preferably subjected to chemical treatment. As the chemical treatment, any of a surface treatment that removes impurities adhering to the surface and a treatment that affects the crystal structure of clay can be used. Specific examples of the chemical treatment include acid treatment, alkali treatment, salt treatment, and organic matter treatment. In addition to removing impurities on the surface, the acid treatment increases the surface area by eluting cations such as Al, Fe, and Mg in the crystal structure. Alkali treatment destroys the crystal structure of the clay, resulting in a change in the structure of the clay. In the salt treatment and the organic matter treatment, an ion complex, a molecular complex, an organic derivative, and the like can be formed, and the surface area and interlayer distance can be changed.

The ion-exchangeable layered compound used in the present invention may be a layered compound in a state where the layers are expanded by exchanging the exchangeable ions between the layers with other large and bulky ions using the ion-exchange property. . Such bulky ions play a role of supporting pillars to support the layered structure and are usually called pillars. Moreover, introducing another substance between the layers of the layered compound in this way is called intercalation. Examples of guest compounds to be intercalated include cationic inorganic compounds such as TiCl ₄ and ZrCl ₄ , metal alkoxides such as Ti (OR) ₄ , Zr (OR) ₄ , PO (OR) ₃ , and B (OR) ₃ ( R is a hydrocarbon group), metal hydroxide ions such as [Al ₁₃ O ₄ (OH) ₂₄ ] ⁷⁺ , [Zr ₄ (OH) ₁₄ ] ²⁺ , [Fe ₃ O (OCOCH ₃ ) ₆ ] ⁺ Etc.

  These compounds are used alone or in combination of two or more.

Further, when intercalating these compounds, Si (OR) ₄ , Al (OR
) ₃ , Ge (OR) ₄ and other metal alkoxides (R is a hydrocarbon group and the like), dimerization products obtained by hydrolysis, colloidal inorganic compounds such as SiO _2, and the like can also coexist. Examples of the pillar include oxides generated by heat dehydration after intercalation of the metal hydroxide ions between layers.

  The clay, clay mineral, and ion-exchangeable layered compound used in the present invention may be used as they are, or may be used after a treatment such as ball milling or sieving. Further, it may be used after newly adsorbing and adsorbing water or after heat dehydration treatment. Furthermore, you may use individually or in combination of 2 or more types.

  Among these, preferred are clays or clay minerals, and particularly preferred are montmorillonite, vermiculite, hectorite, teniolite and synthetic mica.

  Examples of the organic compound include granular or fine particle solids having a particle size in the range of 10 to 300 μm. Specifically, a (co) dimer or vinylcyclohexane produced mainly from an α-olefin having 2 to 14 carbon atoms such as ethylene, propylene, 1-butene and 4-methyl-1-pentene, Examples thereof include (co) dimers produced with styrene as a main component, and modified products thereof.

The olefin multimerization catalyst according to the present invention includes the (A) transition metal complex compound, and if necessary, the (B) (b-1) organometallic compound, (b-2) the organoaluminum oxy compound, and (B-3) includes at least one compound selected from ionized ionic compounds, and further includes a carrier (C) as necessary.
An organic compound component can also be included.

[(D) Organic compound component]
In the present invention, the organic compound component (D) is used for the purpose of improving the multimerization performance, if necessary. Examples of such organic compounds include, but are not limited to, alcohols, phenolic compounds, carboxylic acids, phosphorus compounds, and sulfonates.

As alcohols and phenolic compounds, those represented by R ²² —OH are usually used (where R ²² is a hydrocarbon group having 1 to 50 carbon atoms or a halogenated group having 1 to 50 carbon atoms). As the alcohol, R ²² is preferably a halogenated hydrocarbon.

  Moreover, as a phenolic compound, what substituted the (alpha), (alpha) '-position of the hydroxyl group with the C1-C20 hydrocarbon is preferable.

As the carboxylic acid, one represented by R ²³ —COOH is usually used. R ²³ represents a hydrocarbon group having 1 to 50 carbon atoms or a halogenated hydrocarbon group having 1 to 50 carbon atoms, and a halogenated hydrocarbon group having 1 to 50 carbon atoms is particularly preferable.

  As the phosphorus compound, phosphoric acid having P—O—H bond, P—OR, phosphate having P═O bond, and phosphine oxide compound are preferably used.

  As the sulfonate, those represented by the following general formula (VI) are used.

In formula (VI), M ⁴ is an atom of Groups 1-14 of the periodic table. R ²⁴ is hydrogen, 1 carbon atom
-20 hydrocarbon group or halogenated hydrocarbon group having 1 to 20 carbon atoms. X is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a halogenated hydrocarbon group having 1 to 20 carbon atoms. m is an integer of 1 to 7, n is the valence of M, and 1 ≦ n ≦ 7.

  The olefin multimerization catalyst of the present invention can be used for olefin multimerization. Examples of olefins include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, vinylcyclohexene, vinyl compounds such as styrene, 1-octene, 1-decene, 2-butene, cyclopentene, Preferred examples include internal olefins such as cyclohexene and norbornene, with ethylene being particularly preferred. A plurality of the olefins described above may be co-multiplied.

  Hereinafter, a method for producing an olefin multimer in which an olefin multimerization reaction is performed in the presence of the olefin multimerization catalyst will be described.

[Olefin multimer production method]
A method for producing the olefin multimer will be described.

  In the method for producing an olefin multimer according to the present invention, an olefin multimerization reaction, preferably a trimerization reaction, is performed in the presence of the olefin multimerization catalyst.

  Preferred is an ethylene multimerization reaction using ethylene as an olefin, and particularly preferred is a method for producing 1-hexene by an ethylene trimerization reaction.

  In the multimerization reaction, the method of adding the transition metal complex compound (A) (hereinafter simply referred to as “component (A)”) to the reactor, the method of using each component, the method of addition, and the order of addition are arbitrarily selected. The following method is exemplified.

  (1) Component (A) and at least one component (B) selected from (b-1) an organometallic compound, (b-2) an organoaluminum oxy compound, and (b-3) an ionized ionic compound (below) And simply adding “component (B)” to the reactor in any order.

  (2) A method in which a catalyst in which the component (A) and the component (B) are contacted in advance is added to the reactor.

  (3) A method in which the catalyst component in which the component (A) and the component (B) are contacted in advance, and the component (B) are added to the reactor in an arbitrary order. In this case, the component (B) may be the same or different.

  (4) A method in which the catalyst component having component (A) supported on carrier (C) and component (B) are added to the reactor in any order.

  (5) A method in which a catalyst in which component (A) and component (B) are supported on a carrier (C) is added to a reactor.

  (6) A method in which the catalyst component in which the component (A) and the component (B) are supported on the carrier (C), and the component (B) are added to the reactor in an arbitrary order. In this case, the component (B) may be the same or different.

  (7) A method in which the catalyst component having component (B) supported on support (C) and component (A) are added to the reactor in any order.

  (8) A method in which the catalyst component having component (B) supported on carrier (C), component (A), and component (B) are added to the reactor in any order. In this case, the component (B) may be the same or different.

  (9) A method in which a component carrying component (A) on carrier (C) and a component carrying component (B) on carrier (C) are added to the reactor in any order.

  (10) A method in which component (A) is supported on carrier (C), component (B) is supported on carrier (C), and component (B) is added to the reactor in any order. In this case, the component (B) may be the same or different.

  (11) A method in which component (A), component (B), and component (D) are added to the reactor in any order.

  (12) A method in which component (B) and component (D) are contacted in advance, and component (A) are added to the reactor in any order.

  (13) A method in which the component (B) and the component (D) supported on the carrier (C) and the component (A) are added to the reactor in any order.

  (14) A method in which the catalyst component obtained by previously contacting the component (A) and the component (B), and the component (D) are added to the reactor in an arbitrary order.

  (15) A method in which the catalyst component in which the component (A) and the component (B) are previously contacted, and the component (B) and the component (D) are added to the reactor in an arbitrary order. In this case, the component (B) may be the same or different.

  (16) A method in which a catalyst component in which the component (A) and the component (B) are previously contacted and a component in which the component (B) and the component (D) are previously contacted are added to the reactor in an arbitrary order. In this case, the component (B) may be the same or different.

  (17) A method in which the component (A) supported on the carrier (C), the component (B), and the component (D) are added to the reactor in any order.

  (18) A method in which a component having component (A) supported on carrier (C) and a component in which component (B) and component (D) are contacted in advance are added to the reactor in any order.

  (19) A method in which a catalyst obtained by bringing the component (A), the component (B), and the component (D) into contact in advance in an arbitrary order is added to the reactor.

  (20) A method in which the catalyst component obtained by bringing the component (A), the component (B) and the component (D) into contact in advance in an arbitrary order and the component (B) are added to the reactor in an arbitrary order. In this case, the component (B) may be the same or different.

  (21) A method in which a catalyst having components (A), (B) and (D) supported on a carrier (C) is added to a reactor.

  (22) A method in which component (A), component (B) and component (D) are supported on a carrier (C) and a catalyst component and component (B) are added to the reactor in any order. In this case, the component (B) may be the same or different.

  In the method for producing an olefin multimer according to the present invention, the olefin multimer is obtained by multimerizing the olefin in the presence of the olefin multimerization catalyst as described above. In the present invention, multimerization can be carried out by any of liquid phase reaction methods such as dissolution reaction and suspension reaction, or gas phase reaction methods.

  In the liquid phase reaction method, an inert hydrocarbon medium is used. Specific examples of the inert hydrocarbon medium used include propane, butane, isobutane, pentane, isopentane, hexane, heptane, octane, decane, dodecane, Aliphatic hydrocarbons such as kerosene; Alicyclic hydrocarbons such as cyclopentane, cyclohexane, and methylcyclopentane; Aromatic hydrocarbons such as benzene, toluene, xylene, trimethylbenzene, and tetralin; Ethylene chloride, chlorobenzene, and dichloromethane And halogenated hydrocarbons or a mixture thereof. As the reaction solvent, pentane, n-hexane and n-heptane are particularly preferable.

When 1-hexene is produced by trimerization of ethylene using the olefin multimerization catalyst as described above, component (A) is usually 10 ⁻¹² to 10 ⁻² per liter of reaction volume.
It is used in such an amount that it becomes a mol, preferably 10 ⁻¹⁰ to 10 ⁻³ mol. In the present invention, an olefin multimer can be obtained with high multimerization activity even when component (A) is used at a relatively low concentration.

  Moreover, when using a component (B), a component (b-1) is a molar ratio [(b-1) / M of a component (b-1) and the transition metal atom (M) in a component (A). ] Is usually used in an amount of 0.01 to 100,000, preferably 0.05 to 50,000.

  Component (b-2) has a molar ratio [(b-2) / M] of the aluminum atom in component (b-2) and the transition metal atom (M) in component (A) usually 10 to 10. The amount used is 500,000, preferably 20 to 100,000.

  Component (b-3) has a molar ratio [(b-3) / M] of component (b-3) to transition metal atom (M) in component (A) usually from 1 to 10, preferably It is used in such an amount as to be 1-5.

  In the component (C), the ratio (g / mol) of the mass (g) of the component (C) to the moles of the transition metal atom (M) in the component (A) is usually 100 to 10,000, preferably 1000 to 5000. Is used in such an amount.

  When component (D) is component (b-1) with respect to component (B), the molar ratio [(D) / (b-1)] is usually 0.01 to 10, preferably 0.1 to 0.1. In the case of component (b-2), the molar ratio [(D) / (b-2)] between component (D) and aluminum atom in component (b-2) is usually 0. 0.001 to 2, preferably 0.005 to 1 and in the case of component (b-3), the molar ratio [(D) / (b-3)] is usually 0.01 to 10, preferably Is used in an amount of 0.1-5.

  The reaction temperature of olefin multimerization using such an olefin multimerization catalyst is usually in the range of −50 to 200 ° C., preferably 0 to 170 ° C. The reaction pressure is usually from normal pressure to 10 MPa, preferably from normal pressure to 5 MPa, and the multimerization reaction can be carried out by any of batch, semi-continuous and continuous methods.

  The reaction of olefin multimerization using such an olefin multimerization catalyst may be carried out by adding an antistatic agent. Antistatic agents include polypropylene glycol, polypropylene glycol distearate, ethylenediamine-PEG-PPG-block copolymer, stearyl diethanolamine, lauryl diethanolamine, alkyl diethanolamide, polyoxyalkylene (eg, polyethylene glycol / polypropylene glycol / polyethylene glycol block copolymer) (PEG-PPG-PEG)) and the like are preferable, and polyoxyalkylene (PEG-PPG-PEG) is particularly preferable. These antistatic agents are used in such an amount that the ratio (g / mol) of mass (g) to mol of transition metal atom (M) in component (A) is usually 100 to 10,000, preferably 100 to 1,000. Used.

  The reaction of olefin multimerization using such an olefin multimerization catalyst may be performed by adding hydrogen. The hydrogen pressure in the reaction is 0.01 MPa to 5 MPa, preferably 0.01 MPa to 1 MPa.

  EXAMPLES Hereinafter, although this invention is demonstrated concretely based on an Example, this invention is not limited to these Examples.

  The yield of the reaction product and the selectivity of 1-hexene were analyzed using gas chromatography (Shimadzu GC-14A, J & W Scientific DB-5 column).

[Catalytic activity]
The mass of the reaction product obtained per unit time was obtained by dividing the mass of the transition metal atom (mmol) in the transition metal catalyst component used for the multimerization.

[Selection rate of 1-hexene]
The selectivity for 1-hexene was determined according to the following formula.

S (%) = Wp / Wr × 100
S (%): 1-hexene selectivity (weight fraction)
Wr (weight): total weight of products having 4 or more carbon atoms produced by the reaction Wp (weight): weight of 1-hexene produced by the reaction 1-decene selectivity was determined according to the above method. .

  In the following, specific examples of synthesis of the transition metal compound (A) of the present invention are shown, and specific examples and comparative examples of ethylene multimerization are shown.

[Synthesis Example 1]
(Synthesis of Compound 2)

  0.63 g (3) of 2′-methoxybiphenyl-2-amine (synthesized as described in International Publication No. 2009/5003 pamphlet) in a 100 mL eggplant flask (three-way cock, with magnetic stirrer) thoroughly dried and purged with nitrogen. .16 mmol), 1.05 g (3.16 mmol) of 3-adamantyl-2-hydroxy-6-phenylbenzaldehyde is added, dissolved in 20 mL of toluene (manufactured by Kanto Chemical Co., Inc.), and Amberlyst 15 (H) (Wako Pure Chemical Industries, Ltd.) 0.2 g) was added and reacted for 8 hours under heating and reflux. The reaction solution was concentrated, and 30 mL of hexane (manufactured by Kanto Chemical Co., Inc.) was added and allowed to stand to precipitate crystals. The crystals were filtered, washed with hexane, and then dried under reduced pressure to obtain 0.73 g (yield 45%, yellow solid) of Compound 1.

The result of analyzing the obtained product was as follows.
¹ H NMR (δ, CDCl ₃ ): 14.72 (s, 1H, OH), 8.47 (s, 1H, N═CH), 7.41-6.67 (m, 15H, Ar—H) , 3.75 (s, 3H, OCH ₃ ), 2.15-1.74 (m, 15H, adamantyl)

  Add 1.27 mL (1.27 mmol, 1 M toluene solution) of titanium tetrachloride (Sigma Aldrich Japan Co., Ltd.) to a 100 mL two-necked eggplant flask (with a three-way cock, with a magnetic stirrer) that is thoroughly dried and purged with nitrogen. Toluene 10 mL was added. After cooling this solution to −78 ° C., 10 mL of a toluene solution containing 0.65 g (1.27 mmol) of Compound 1 was added dropwise over 5 minutes. The reaction was allowed to react for 15 hours while gradually warming to room temperature. After distilling off the reaction solvent, 20 mL of diethyl ether (manufactured by Kanto Chemical Co., Inc.) was added, the insoluble solid was collected by filtration, washed with diethyl ether, and dried under reduced pressure to give 0.67 g (79%, reddish brown) of Compound 2. Solid).

The result of analyzing the obtained product was as follows.
¹ H NMR (δ, CDCl ₃ ): 7.90 (s, 1H, N═CH), 7.59 (d, J = 8.12 Hz, 1H, Ar—H), 7.45-7.08 ( m, 14H, Ar-H) , 4.33 (s, 3H, OCH 3), 2.24 (bs, 6H, adamantyl), 2.19
(Bs, 3H, adamantyl), 1.96 (d, J = 12 Hz, 3H, adamantyl), 1.82 (d, J = 12 Hz, 3H, adamantyl)
FD-MS: m / z = 667 (M ⁺ ), 615 (M ⁺ —CH ₃ Cl) C ₃₆ H ₃₄ Cl ₃ NO ₂ T
i
[Synthesis Example 2]
(Synthesis of Compound 6)

  In a well-dried 300 mL three-necked eggplant flask (with dropping funnel, three-way cock, with magnetic stirrer), 6.11-g (50 mmol) of 3,4-dimethylphenol (manufactured by Tokyo Chemical Industry Co., Ltd.), 1-Adamantanol (Tokyo Chemical Industry) 8.37 g (50 mmol) manufactured by Co., Ltd., 0.611 g of Amberlyst 15 (H) and 200 mL of toluene were added and reacted at 100 ° C. for 3 hours. This reaction solution was obtained by removing insolubles by filtration and then concentrating. The crude product was purified using a silica gel column chromatograph (eluent: hexane / ethyl acetate (manufactured by Kanto Chemical Co., Ltd.) = 20/1) to obtain 10.99 g (86%, white solid) of Compound 3. It was.

The result of analyzing the obtained product was as follows.
¹ H NMR (δ, CDCl ₃ ): 6.95 (s, 1H, Ar—H), 6.45 (s, 1H, Ar—H), 4.52 (s, 1H, OH), 2.18 (S, 3H, CH ₃ ), 2.16
(S, 3H, CH ₃ ), 2.10 (s, 6H, adamantyl), 2.07 (s, 3
H, adamantyl), 1.77 (s, 6H, adamantyl)

To a well-dried 200 mL three-necked eggplant flask (with a dropping funnel, with a three-way cock, containing a magnetic stirrer) was added 9.95 g (35 mmol) of Compound 3 and 70 mL of tetrahydrofuran, and the mixture was cooled to 0 ° C. in an ice bath, and then EtMgBr in tetrahydrofuran. 38.5 mL (38.5 mmol) of a solution (manufactured by Kanto Chemical Co., Inc.) (1.0 mmol / mL) was added dropwise, and the mixture was allowed to react for 1 hour while being heated to room temperature. To this reaction solution, 2.65 g (87.5 mmol) of paraformaldehyde (manufactured by Tokyo Chemical Industry Co., Ltd.) and 7.28 mL (52.5 mmol) of triethylamine (manufactured by Tokyo Chemical Industry Co., Ltd.) were added, and the mixture was heated at 60 ° C. for 3 hours. Reacted. After adding 100 mL of toluene to this reaction solution, 20 mL of 10 wt% hydrochloric acid water (manufactured by Kanto Chemical Co., Ltd.) is added and separated, and then the organic phase is washed twice with 100 mL of pure water and MgSO ₄ (manufactured by Kanto Chemical Co., Ltd.). ) And the solvent was distilled off under reduced pressure to obtain a crude product. The crude product was recrystallized from ethanol (manufactured by Kanto Chemical Co., Inc.) to obtain 7.37 g (74%, white solid) of Compound 4.

The result of analyzing the obtained product was as follows.
¹ H NMR (δ, CDCl ₃ ): 12.76 (s, 1H, OH), 10.38 (s, 1H, O═CH), 7.22 (s, 1H, Ar—H), 2.45. (S, 3H, CH ₃ ), 2.
23 (s, 3H, CH ₃ ), 2.12 (s, 6H, adamantyl), 2.07 (s
, 3H, adamantyl), 1.77 (s, 6H, adamantyl)

  In a well-dried 100 mL eggplant flask (three-way cock, Dean-Stark tube, with Dimroth, with magnetic stirrer), 2'-methoxybiphenyl-2-amine (1.10 g, 5.5 mmol) and compound 4 (1.42 g) 5.0 mmol) and 0.142 g of Amberlyst 15 (H) were added, and 40 mL of toluene was added, followed by reaction under reflux for 3 hours. After removing insolubles from the reaction solution by filtration, the solvent was distilled off under reduced pressure and recrystallized from ethanol to obtain 1.24 g of Compound 5 (yield 53%, orange solid).

The result of analyzing the obtained product was as follows.
¹ H NMR (δ, CDCl ₃ ): 14.48 (s, 1H, OH), 8.87 (s, 1H,
N = CH), 7.42-7.19 (m, 6H, Ar-H), 7.01-6.90 (m, 3H, Ar-H), 3.75 (s, 3H, OMe), 2.23 (s, 3H, CH ₃ ), 2.
19 (s, 3H, CH ₃ ), 2.09 (s, 6H, adamantyl), 2.05 (s
, 3H, adamantyl), 1.77 (s, 6H, adamantyl)

To a well-dried 100 mL Schlenk flask (with magnetic stirrer), 1.1 mL (1.1 mmol) of a toluene solution (1.0 mmol / mL) of TiCl ₄ and 10 mL of toluene were added and cooled to −78 ° C. To this mixed solution, 0.466 g (1.0 mmol) of Compound 5 was dissolved in 5 mL of toluene and dropped, and then reacted for 18 hours while raising the temperature to room temperature. The reaction solution was concentrated to about 5 mL under reduced pressure, and then 15 mL of hexane was added for precipitation. The precipitate was collected by filtration, washed with 20 mL of hexane, and dried to obtain 0.521 g (yield 84%, orange solid) of Compound 6.

The result of analyzing the obtained product was as follows.
¹ H NMR (δ, CDCl ₃ ): 8.43 (s, 1H, N═CH), 7.51 to 7.23 (m, 9H, Ar—H), 4.37 (s, 3H, OMe) , 2.26 (s, 3H, CH ₃
), 2.25 (s, 3H, CH ₃ ), 2.18 (bs, 6H, adamantyl), 2
. 15 (bs, 3H, adamantyl), 1.93 (d, 3H, J = 12 Hz, adamantyl), 1.79 (d, 3H, J = 12 Hz, adamantyl)
[Synthesis Example 3]
(Synthesis of Compound 9)

In a well-dried 200 mL three-necked eggplant flask (condenser, with three-way cock, with magnetic stirrer), 3.19 g (21 mmol) of 2-methoxyphenylboronic acid and 3 of 3-bromo-3-methylalanine (manufactured by Sigma Aldrich Japan Co., Ltd.) .72 g (20 mmol), 0.022 g (0.1 mmol) of palladium acetate, 0.082 g (0.2 mmol) of 2-Diccyclohexylphosphino-2 ′, 6′-dimethylbiphenyl, 13.8 g of potassium phosphate monohydrate ( 60 mmol), suspended in 40 mL of toluene, and reacted at 100 ° C. for 3 hours. 100 mL of water was added to the reaction solution, and extracted with toluene. The organic layer was dried over MgSO ₄ and the solvent was distilled off under reduced pressure to obtain a crude product. The crude product was purified using silica gel column chromatography (eluent: hexane / ethyl acetate = 19/1) to obtain 3.75 g (88%, light yellow liquid) of Compound 7.

The result of analyzing the obtained product was as follows.
¹ H NMR (δ, CDCl ₃ ): 7.36 (t, d, 1H, J = 8.1, 2.1 Hz, Ar—H), 7.17-7.00 (m, 4H, Ar—H) ), 6.72-6.62 (m, 2H, Ar-H), 3.76 (s, 3H, OCH 3), 3.40 (br, 2H, NH 2), 1.97 (s, 3H , CH ₃ )

  1.17 g (5.5 mmol), 3-adamantyl-2-hydroxy-5-methylbenzaldehyde 1.35 g in a well-dried 100 mL eggplant flask (three-way cock, Dean-Stark tube, with Dimroth, with magnetic stirrer) (5.0 mmol) and 135 mg of Amberlyst 15 (H) were added, and 40 mL of toluene was added, followed by reaction for 3 hours under reflux. After removing insolubles from the reaction solution by filtration, the solvent was distilled off under reduced pressure, and recrystallization from ethanol gave 1.40 g (yield 62%, orange solid) of Compound 8.

The result of analyzing the obtained product was as follows.
¹ H NMR (δ, CDCl ₃ ): 13.2 (s, 1H, OH), 8.45 (s, 1H, N═CH), 7.34-7.19 (m, 3H, Ar—H) , 7.09-6.91 (m, 6H, Ar -H), 3.71 (s, 3H, OCH 3), 2.25 (s, 3H, CH 3), 2.16 (s, 3H, _{CH 3), 2.09 (s,} 9H, adamantyl), 1.76 (s, 6
H, adamantyl)

A well-dried 50 mL eggplant flask (three-way cock with magnetic stirrer) was placed in TiCl ₄ (
thf) ₂ 0.500 g (1.5 mmol) and 7.5 mL of tetrahydrofuran were added.
Cool to 8 ° C. In this mixed solution, 0.677 g (1.5 mmol) of Compound 8 was dissolved in 1.3 mL of tetrahydrofuran and added dropwise, and then reacted for 17 hours while raising the temperature to room temperature. After concentrating the reaction solution to about 2 mL, 10 mL of hexane was added for precipitation. The precipitate was collected by filtration, washed with 20 mL of hexane, and dried to obtain 0.778 g of Compound 9 (yield 83%, orange solid).

The result of analyzing the obtained product was as follows.
¹ H NMR (δ, CDCl ₃ ): 8.02 (s, 1H, N═CH), 7.34-6.95 (m, 9H, Ar—H), 4.23 (s, 3H, OCH ₃₎ ), 2.23 (s, 3H, CH ₃ ), 2.20 (s, 3H, CH ₃ ), 2.11 (bs, 6H, adamantyl), 2
. 08 (bs, 3H, adamantyl), 1.86 (d, 3H, J = 12 Hz, adamantyl), 1.72 (d, 3H, J = 12 Hz, adamantyl)
[Synthesis Example 4]
(Synthesis of Compound 12)

To a well-dried 100 mL three-necked eggplant flask (condenser, with three-way cock, with magnetic stirrer), 1.83 g (11 mmol) of 2-Ethoxyphenylboronic acid (manufactured by Wako Pure Chemical Industries, Ltd.), 2-bromo-3-methylalanine 1.86 g (10 mmol), 0.011 g (0.05 mmol) of palladium acetate, 0.041 g (0.1 mmol) of 2-Diccyclohexylphosphino-2 ′, 6′-dimethylbiphenyl, 6.91 g of potassium phosphate monohydrate (30 mmol) was added, suspended in 30 mL of toluene, and reacted at 100 ° C. for 3 hours. 20 mL of water was added to the reaction solution, and after extraction with toluene, the organic layer was dried over MgSO ₄ .
The solvent was distilled off under reduced pressure to obtain a crude product. The crude product was purified using silica gel column chromatography (eluent: hexane / ethyl acetate = 95/5) to obtain 2.05 g (90%, light yellow liquid) of Compound 10.

The result of analyzing the obtained product was as follows.
¹ H NMR (δ, CDCl ₃ ): 7.36-7.30 (m, 1H, Ar—H), 7.17-7.16 (m, 1H, Ar—H), 7.14-6. 99 (m, 3H, Ar- H), 6.71-6.61 (m, 2H, Ar-H), 4.01 (q, 2H, J = 7.0Hz, OCH 2), 3.43 ( _{br, 2H, NH 2),} 1.99 (s, 3H, CH 3), 1.24 (t,
_{3H, J = 7.0Hz, CH 3} )

In a fully dried 100 mL eggplant flask (three-way cock, Dean-Stark tube, with Dimroth, with magnetic stirrer), 0.718 g (3.15 mmol), 3-adamantyl-2-hydroxy-5-methylbenzaldehyde 0.811 g (3.0 mmol) and 81 mg of Amberlyst 15 (H) were added, and 30 mL of toluene was added, followed by reaction under reflux for 3 hours. After removing insolubles from this reaction solution by filtration, the solvent was distilled off under reduced pressure, and recrystallization from ethanol gave 0.458 g (yield 32%, yellow solid) of Compound 11.

The result of analyzing the obtained product was as follows.
¹ H NMR (δ, CDCl ₃ ): 13.3 (s, 1H, OH), 8.44 (s, 1H, N═CH), 7.33-7.05 (m, 3H, Ar—H) , 7.01-6.91 (m, 6H, Ar -H), 3.96 (q, 2H, J = 7.0Hz, OCH 2), 2.25 (s, 3H
, CH ₃ ), 2.16 (s, 3H, CH ₃ ), 2.05 (s, 9H, adamantyl), 1.76 (s, 6H, adamantyl), 1.16 (t, 3H, J = 7 .0Hz, CH ₃₎

To a well-dried 100 mL Schlenk flask (with magnetic stirrer), 0.55 mL (0.55 mmol) of a toluene solution of TiCl ₄ (1.0 mmol / mL) and 10 mL of toluene were added and cooled to −78 ° C. In this mixed solution, 0.234 g (0.5 mmol) of Compound 11 was dissolved in 5 mL of toluene and dropped, and then reacted for 14 hours while raising the temperature to room temperature. After concentrating the reaction solution to about 5 mL under reduced pressure, 10 mL of hexane was added for precipitation, and the precipitate was collected by filtration, washed with 10 mL of hexane, and dried to obtain 0.0.225 g (yield). 71%, reddish brown solid).

The result of analyzing the obtained product was as follows.
¹ H NMR (δ, CDCl ₃ ): 8.08 (s, 1H, N═CH), 7.39-7.03 (m, 9H, Ar—H), 5.23-5.11 (m, 1H, OCH _2), 4.90-4.
78 (m, 1H, OCH ₂ ), 2.31 (s, 3H, CH ₃ ), 2.26 (s, 3H, CH ₃ ), 2.18 (bs, 6H, adamantyl), 2.15 (bs) , 3H, adam
antyl), 1.93 (d, 3H, J = 12 Hz, adamantyl), 1.79 (d, 3H, J = 12 Hz, adamantyl), 1.07 (t, 3H, J = 7.0 Hz, CH ₃ )
[Synthesis Example 5]
(Synthesis of Compound 16)

8.17 g (60 mmol) of 1-methoxy-3,5-dimethylbenzene (manufactured by Tokyo Chemical Industry Co., Ltd.), 120 mL of diethyl ether in a well-dried 300 mL three-necked eggplant flask (with dropping funnel, with three-way cock, with magnetic stirrer) After cooling to 0 ° C. in an ice bath, 7.67 g (66 mmol) of N, N, N ′, N′-tetramethylethylenediamine (manufactured by Tokyo Chemical Industry Co., Ltd.) is added, and a hexane solution of normal butyl lithium (Manufactured by Kanto Chemical Co., Inc.) (1.6 mol / L) 39.8 mL (66 mmol) was added dropwise, followed by reaction for 5 hours. After adding 60 mL of diethyl ether and 12.47 g (120 mmol) of trimethyl borate (manufactured by Sigma Aldrich Japan Co., Ltd.) to a 500 mL three-necked eggplant flask (with a three-way cock and containing a magnetic stirrer), the mixture was cooled to −78 ° C. The prepared reaction solution was added dropwise and reacted for 18 hours while raising the temperature to room temperature. 100 mL of 10 wt% hydrochloric acid solution was added to the reaction solution, followed by extraction three times with 50 mL of ethyl acetate, and then the organic layer was washed twice with 50 mL of pure water and dried over MgSO ₄ , and the solvent was distilled off under reduced pressure. Gave a crude product. The obtained crude product was recrystallized from toluene to obtain 6.67 g (62%, white solid) of Compound 13.

The result of analyzing the obtained product was as follows.
¹ H NMR (δ, CDCl ₃ ): 6.97 (s, 1H, Ar—H), 6.58 (s, 1H, Ar—H), 6.29 (s, 2H, B (OH) ₂ ) , 3.86 (s, 3H, OCH ₃ ), 2.53 (s, 3H, CH ₃ ), 2.32 (s, 3H, CH ₃ )

In a well-dried 100 mL three-necked eggplant flask (condenser, with three-way cock, with magnetic stirrer), 1.30 g (7.2 mmol) of compound 13 and 1.03 g (6 mmol) of 2-bromoaniline (manufactured by Tokyo Chemical Industry Co., Ltd.) ), 0.07 g (0.03 mmol) of palladium acetate, 0.025 g (0.06 mmol) of 2-Dicyclohexylphosphino-2 ′, 6′-dimethylbiphenyl, 4.15 g (18 mmol) of potassium phosphate monohydrate, The mixture was suspended in 18 mL of toluene and reacted at 100 ° C. for 3 hours. 10 mL of water was added to this reaction liquid, extracted with toluene, the organic layer was dried over MgSO ₄ , and the solvent was distilled off under reduced pressure to obtain a crude product. The crude product was purified using silica gel column chromatography (eluent: hexane / ethyl acetate = 95/5) to obtain 0.390 g (29%, light yellow liquid) of Compound 14.

The result of analyzing the obtained product was as follows.
¹ H NMR (δ, CDCl ₃ ): 7.19-7.13 (m, 1H, Ar—H), 6.98-6.94 (m, 1H, Ar—H), 6.84-6. 76 (m, 3H, Ar- H), 6.66 (s, 1H, Ar-H), 3.71 (s, 3H, OCH 3), 3.45 (br, 2H
, NH ₂ ), 2.37 (s, 3H, CH ₃ ), 2.05 (s, 3H, CH ₃ )

  0.358 g (1.58 mmol) of compound 14 in a well-dried 100 mL eggplant flask (three-way cock, Dean-Stark tube, with Dimroth, magnetic stir bar), 3-adamantyl-2-hydroxy-5-methylbenzaldehyde 0.406 g (1.5 mmol) and 41 mg of Amberlyst 15 (H) were added, 30 mL of toluene was added, and the mixture was reacted for 3 hours under reflux. After removing insolubles from the reaction solution by filtration, the solvent was distilled off under reduced pressure, and recrystallization from ethanol gave 0.404 g (yield 56%, yellow solid) of Compound 15.

The result of analyzing the obtained product was as follows.
¹ H NMR (δ, CDCl ₃ ): 13.3 (s, 1H, OH), 8.45 (s, 1H, N═CH), 7.43-7.25 (m, 4H, Ar—H) 7.02 (s, 1H, Ar—H), 6.91 (s, 1H, Ar—H), 6.70 (s, 1H, Ar—H), 6.61 (s, 1H, Ar—) H), 3.66 (s, 3H, OCH ₃ ), 2.33 (s, 3H, CH ₃ ), 2.26 (s, 3H, CH ₃ ), 2.07 (bs, 9H, adamantyl), 1.9
7 (s, 3H, CH ₃ ), 1.77 (s, 6H, adamantyl)

To a well-dried 100 mL Schlenk flask (with magnetic stirrer), 0.55 mL (0.55 mmol) of a toluene solution of TiCl ₄ (1.0 mmol / mL) and 10 mL of toluene were added and cooled to −78 ° C. In this mixed solution, 0.240 g (0.5 mmol) of Compound 15 was dissolved in 5 mL of toluene and dropped, and then reacted for 16 hours while raising the temperature to room temperature. After concentrating the reaction solution to about 5 mL under reduced pressure, 15 mL of hexane was added for precipitation, and the precipitate was collected by filtration, washed with 20 mL of hexane, and dried to give 0.123 g of Compound 16 (yield 39%). A reddish brown solid).

The result of analyzing the obtained product was as follows.
¹ H NMR (δ, CDCl ₃ ): 8.13 (s, 1H, N═CH), 7.49-7.35 (m, 3H, Ar—H), 7.27-7.09 (m, 4H, Ar-H), 6.95 (s, 1H, Ar-H), 4.33 (s, 3H, OCH 3), 2.33 (s, 3H, CH 3), 2.27 (s, 3H, CH ₃ ), 2.26 (s, 3H, CH ₃ ), 2.18 (bs, 6H, adamantyl), 2.12 (bs, 3H, adamantyl), 1.92 (d, 3H, J = 12Hz, adamantyl), 1.79 (d, 3H, J = 12Hz, adamantyl)
[Synthesis Example 6]
(Synthesis of Compound 20)

To a well-dried 100 mL three-necked eggplant flask (with a dropping funnel, with a three-way cock, with a magnetic stirrer), 1.5 g (6.3 mmol) of 1-bromo-2-methoxynaphthalene and 20 mL of tetrahydrofuran (manufactured by Kanto Chemical Co., Inc.) are added. After cooling to −78 ° C., 4.8 mL (7.6 mmol) of a normal butyl lithium hexane solution (1.6 mol / L) was added dropwise, and the mixture was slowly warmed to room temperature and allowed to react for 1 hour. After adding tetrahydrofuran 50mL and trimethyl borate 2.1mL (19.0mmol) to a 300mL three-necked eggplant flask (with a three-way cock, with magnetic stirrer), the mixture was cooled to -78 ° C, and then the reaction solution was added dropwise. The reaction was carried out for 3 hours while raising the temperature to room temperature. After adding 50 mL of 10 wt% aqueous hydrochloric acid to the reaction solution and extracting 3 times with 50 mL of ethyl acetate, the organic layer is washed twice with 50 mL of pure water and dried over MgSO ₄ , and the solvent is distilled off under reduced pressure. Gave a crude product. The obtained crude product was reprecipitated from a hexane / ethyl acetate mixed solvent to obtain 0.33 g (43%, light pink solid) of Compound 17.

The result of analyzing the obtained product was as follows.
¹ H NMR (δ, CDCl ₃ ): 8.83 (d, J = 8.6 Hz, 1H, Ar—H), 7.94 (d, J = 8.9 Hz, 1H, Ar—H), 7. 78 (d, J = 8.2 Hz, 1H, Ar-H), 7.51 (ddd, J = 8.6 Hz, 6.9 Hz, 1.6 Hz, 1H, Ar-H), 7.37 (ddd, J = 8.2 Hz, 6.9 Hz, 1.3 Hz, 1H, Ar—H), 7.28 (d, J = 8.9 Hz, 1H, Ar—H), 6.06 (s, 2H, OH) , 4.03 (s, 3H, OCH ₃ )

In a well-dried 100 mL three-necked eggplant flask (condenser, with three-way cock, with magnetic stirrer), 0.3 g (1.5 mmol) of compound 17 and 2-Chloroaniline
0.17 mL (1.8 mmol) (manufactured by Tokyo Chemical Industry Co., Ltd.), 1,3-bis- (2,6-diisopropylphenyl) imidazolium- (allyl) -palladium (II) -chloride (manufactured by Sigma Aldrich Japan Co., Ltd.) ) 0.004 mg (0.008 mmol), barium hydroxide octahydrate (Wako Pure Chemical Industries, Ltd.) 0.5 g (1.6 mmol), and dissolved in isopropyl alcohol (Kanto Chemical Co., Ltd.) 15 mL. And reacted at 80 ° C. for 3 hours. After cooling the reaction solution to room temperature, the solid residue was removed by filtration, and the solvent was distilled off under reduced pressure to obtain a crude product. The crude product was purified using silica gel column chromatography (eluent: hexane / ethyl acetate = 10/1) to obtain 0.28 g (76%, light brown liquid) of Compound 18.

The result of analyzing the obtained product was as follows.
¹ H NMR (δ, CDCl ₃ ): 7.91 (d, J = 9.2 Hz, 1H, Ar—H), 7.83 (m, 1H, Ar—H), 7.23-7.46 ( m, 5H, Ar-H), 7.10 (td, J = 7.6 Hz, 1.6 Hz, 1H, Ar-H), 6.90 (td, J = 7.6 Hz, 1.3 Hz, 1H, Ar-H), 6.87 (dd , J = 7.9Hz, 1.0Hz, 1H, Ar-H), 3.87 (s, 3H, OCH 3), 1.61 (bs, 2H, NH 2 )

  In a well-dried 100 mL eggplant flask (three-way cock, Dean-Stark tube, with Dimroth, with magnetic stirrer), 0.28 g (1.12 mmol) of compound 18 and 3-adamantyl-2-hydroxy-5-methylbenzaldehyde 0 .32 g (1.18 mmol), 100 mg of Amberlyst 15 (H) and 30 mL of toluene were added, and the mixture was reacted under reflux for 3 hours. After removing insolubles from the reaction solution by filtration, the solvent was distilled off under reduced pressure, and recrystallization from ethanol gave 0.25 g (yield 48%, yellow solid) of Compound 19.

The result of analyzing the obtained product was as follows.
¹ H NMR (δ, CDCl ₃ ): 13.09 (s, 1H, OH), 8.44 (s, 1H, C═NH), 7.88 (d, J = 9.2 Hz, 1H, Ar— H), 7.81 (m, 1H, Ar-H), 7.51 (m, 1H, Ar-H), 7.29-7.43 (m, 7H, Ar-H), 6.95 ( d, J = 2.0 Hz, 1H, Ar—H), 6.83 (d, J = 2.0 Hz, 1H, Ar—H), 3.84 (s, 3H, OCH ₃ ), 2.20 ( _{s, 3H, CH 3),} 2.01 (bs, 3H, adamantyl), 1.95 (bs, 6H, adamantyl), 1.73 (bs, 6H, adamantyl)

A well-dried 50 mL eggplant flask (three-way cock with magnetic stirrer) was placed in TiCl ₄ (
1.0 mol / L toluene solution) 0.35 mL (0.35 mmol) and 5.0 mL toluene were added and cooled to -78 ° C. To this mixed solution, 0.181 g (0.39 mmol) of Compound 19 was dissolved in 10 mL of toluene and dropped, and then reacted for 16 hours while raising the temperature to room temperature. After adding 10 mL of hexane to the reaction solution to precipitate, the precipitate was collected by filtration, washed with 10 mL of hexane, and dried to obtain 0.164 g (yield 72%, orange brown solid) of Compound 20.

The result of analyzing the obtained product was as follows.
¹ H NMR (δ, CDCl ₃ ): 8.18 (s, 1H, C═NH), 7.89 (d, J = 9.2 Hz, 1H, Ar—H), 7.86 (d, J = 8.9 Hz, 1H, Ar-H), 7.38-7.56 (m, 5H, Ar-H), 7.62 (d, J = 8.9 Hz, 1H, Ar-H), 7.66. (D, J = 7.9 Hz, 1H, Ar—H), 7.34 (d, J = 1.6 Hz, 1H, Ar—H), 7.20 (m, 1H, Ar—H), 7. 07 (s, 1H, Ar- H), 4.49 (s, 3H, OCH 3), 2.29 (s, 3H, CH 3), 2.13-2.21 (m, 9H.Adamantyl), 1.91 (d, J = 12.2 Hz, 3H, adamantyl), 1.78 (d, J = 12.2 Hz, 3H, adamantyl)
[Synthesis Example 7]
(Synthesis of Compound 22)

2'-methoxy-3 ', 5'-dimethylbiphenyl-2-amine (International Publication No. 2009/5003 pamphlet) in a well-dried 100 mL eggplant flask (three-way cock, Dean-Stark tube, with Dimroth, with magnetic stirrer) 0.716 g (3.15 mmol), 3-adamantyl-2-hydroxy-5-methylbenzaldehyde 0.811 g (3.0 mm)
ol), 80 mg of Amberlyst 15 (H) was added, and 15 mL of toluene was added, followed by reaction under reflux for 3 hours. After removing insolubles from the reaction solution by filtration, the solvent was distilled off under reduced pressure, and recrystallization from ethanol gave 0.997 g of Compound 21 (yield 69%, yellow solid).

The result of analyzing the obtained product was as follows.
¹ H NMR (δ, CDCl ₃ ): 13.2 (s, 1H, OH), 8.51 (s, 1H, N═CH), 7.48-7.24 (m, 4H, Ar—H) , 7.04-6.91 (m, 4H, Ar -H), 3.32 (s, 3H, OCH 3), 2.32 (s, 3H, CH 3), 2.30 (s, 3H, _{CH 3), 2.26 (s,} 3H, CH 3), 2.10 (s, 6H, adamantyl), 2.06 (s, 3H, adamantyl), 1.77 (s, 6H, adamantyl)

To a well-dried 100 mL Schlenk flask (with magnetic stirrer), 1.1 mL (1.1 mmol) of a toluene solution (1.0 mmol / mL) of TiCl ₄ and 20 mL of toluene were added and cooled to −78 ° C. In this mixed solution, 0.478 g (1.0 mmol) of Compound 21 was dissolved in 5 mL of toluene and dropped, and then reacted for 16 hours while raising the temperature to room temperature. The reaction solution was concentrated to about 3 mL under reduced pressure, and 10 mL of hexane was added for precipitation. The precipitate was collected by filtration, washed with 20 mL of hexane, and dried to obtain 0.357 g (yield 56%, orange solid) of Compound 22.

The result of analyzing the obtained product was as follows.
¹ H NMR (δ, CDCl ₃ ): 8.13 (bs, 1H, N═CH), 7.46-6.91 (m, 8H, Ar—H), 4.27 (s, 3H, OCH ₃₎ ), 2.57 (s, 3H, C
_{H 3), 2.35 (s,} 3H, CH 3), 2.33 (s, 3H, CH 3), 2.19 (bs
, 6H, adamantyl), 2.15 (bs, 3H, adamantyl), 1.92 (d, 3H, J = 12 Hz, adamantyl), 1.78 (d, 3H, J = 12 Hz, adamantyl)
[Synthesis Example 8]
(Synthesis of Compound 26)

4.51 g (30 mmol) of 1-ethoxy-2,4-dimethylbenzene and 50 mL of diethyl ether are added to a well-dried 300 mL three-necked eggplant flask (with a dropping funnel, with a three-way cock, and a magnetic stirrer). After cooling to ° C., 4.92 g (33 mmol) of N, N, N ′, N′-tetramethylethylenediamine was added, and 20.6 mL (33 mmol) of hexane solution of normal butyl lithium (1.6 mol / L) was added dropwise. Thereafter, the reaction was allowed to proceed for 5 hours. After adding 50 mL of diethyl ether and 6.23 g (60 mmol) of trimethyl borate to a 500 mL three-necked eggplant flask (with a three-way cock, containing a magnetic stirrer), the mixture was cooled to −78 ° C., and then the reaction solution was added dropwise to the room temperature. The reaction was allowed to proceed for 16 hours while raising the temperature. 100 mL of 10 wt% hydrochloric acid solution was added to the reaction solution, followed by extraction three times with 50 mL of ethyl acetate, and then the organic layer was washed twice with 50 mL of pure water and dried over MgSO ₄ , and the solvent was distilled off under reduced pressure. Gave a crude product. The obtained crude product was recrystallized from hexane to obtain 2.53 g (43%, white solid) of Compound 23.

The result of analyzing the obtained product was as follows.
¹ H NMR (δ, CDCl ₃ ): 7.46 (s, 1H, Ar—H), 7.11 (s, 1H, Ar—H), 6.13 (s, 2H, B (OH) ₂ ) , 3.90 (q, 2H, J = 7.0
Hz, OCH ₂ ), 2.29 (s, 3H, CH ₃ ), 2.26 (s, 3H, CH ₃ ), 1.
43 (t, 3H, J = 7.0 Hz, CH ₃ )

  In a well-dried 100 mL three-necked eggplant flask (condenser, with three-way cock, with magnetic stirrer), 0.8 g (4.1 mmol) of compound 23, 0.53 mL (4.31 mmol) of 2-Chloro-4-methylalanine, 0.012 mg (0.021 mmol) of 1,3-bis- (2,6-diisopropylphenyl) imidazolium- (allyl) -palladium (II) -chloride, 1.39 g (4.42 mmol) of barium hydroxide octahydrate In addition, it was dissolved in 30 mL of isopropyl alcohol and reacted at 80 ° C. for 5 hours. After cooling the reaction solution to room temperature, the solid residue was removed by filtration, and the solvent was distilled off under reduced pressure to obtain a crude product. The crude product was purified using silica gel column chromatography (eluent: hexane / ethyl acetate = 10/1) to obtain 0.76 g (72%, light brown liquid) of Compound 24.

The result of analyzing the obtained product was as follows.
¹ H NMR (δ, CDCl ₃ ): 7.06 (d, J = 2.0 Hz, 1H, Ar—H), 6.90-6.99 (m, 2H, Ar—H), 6.86 ( dd, J = 8.2 Hz, 2.0 Hz, 1H, Ar—H), 6.67 (d, J = 8.2 Hz, 1H, Ar—H), 3.85 (bs, 2H, NH ₂ ), 3.56 (m, 2H, OCH ₂ ), 2.29 (s, 3H, CH ₃ )
, 2.27 (s, 3H, CH ₃ ), 2.22 (s, 3H, CH ₃ ), 1.07 (t, J = 7.3 Hz, 3H, CH ₃ )

  In a well-dried 100 mL eggplant flask (three-way cock, Dean-Stark tube, with Dimroth, with magnetic stirrer), 0.50 g (1.96 mmol) of compound 24, 3-adamantyl-2-hydroxy-5-methylbenzaldehyde 0 .56 g (2.07 mmol), 150 mg of Amberlyst 15 (H) and 40 mL of toluene were added, and the mixture was reacted for 4 hours under reflux. After removing insolubles from the reaction solution by filtration, the solvent was distilled off under reduced pressure, and recrystallization from ethanol gave 0.235 g (yield 24%, orange-yellow solid) of Compound 25.

The result of analyzing the obtained product was as follows.
¹ H NMR (δ, CDCl ₃ ): 13.24 (s, 1H, OH), 8.50 (s, 1H, C═NH), 7.14-7.30 (m, 4H, Ar—H) 7.03 (s, 1H, Ar—H), 6.93-6.97 (m, 2H, Ar—H), 3.46 (q, 2H, OCH ₂ ),
2.40 (s, 3H, CH ₃ ), 2.29 (s, 3H, CH ₃ ), 2.28 (s, 3H, CH ₃ ), 2.26 (s, 3H, CH ₃ ), 2. 04-2.14 (m, 9H, adamantyl), 1.77 (m, 6H, adamantyl), 0.98 (t, 3H, J = 7.3 Hz, CH ₃ )

A well-dried 50 mL eggplant flask (three-way cock with magnetic stirrer) was placed in TiCl ₄ (
1.0 mol / L toluene solution) 0.3 mL (0.3 mmol) and 5.0 mL toluene were added and cooled to -78 ° C. 0.168 g (0.33 mmol) of Compound 25 was dissolved in 10 mL of toluene and added dropwise to this mixed solution, and then reacted for 16 hours while raising the temperature to room temperature. The reaction solution was precipitated by adding 10 mL of hexane, and then the precipitate was collected by filtration, washed with 10 mL of hexane, and dried to obtain 0.053 g (yield 28%, reddish brown solid) of Compound 26.

The result of analyzing the obtained product was as follows.
¹ H NMR (δ, CDCl ₃ ): 8.06 (s, 1H, C═NH), 7.36 (d, J = 2.0 Hz, 1H, Ar—H), 7.22 (m, 1H, Ar-H), 6.91-7.10 (m , 5H, Ar-H), 5.39 (m, 1H, OCH 2), 4.60 (m, 1H, OC
_{H 2), 2.58 (s,} 3H, CH 3), 2.42 (s, 3H, CH 3), 2.33 (s,
_{3Hx2, CH 3), 2.13-2.26 (} m, 9H, adamantyl), 1.92
(D, J = 11.5 Hz, 3H, adamantyl), 1.77 (d, J = 11.5 Hz, 3H, adamantyl), 0.89 (t, J = 6.9 Hz, 3H, CH ₃ )
[Synthesis Example 9]
(Synthesis of Compound 30)

11.27 g (75 mmol) of 1-ethoxy-3,5-dimethylbenzene and 100 mL of diethyl ether are added to a well-dried 300 mL three-necked eggplant flask (with a dropping funnel, with a three-way cock, and a magnetic stirrer). After cooling to ° C., 9.59 g (83 mmol) of N, N, N ′, N′-tetramethylethylenediamine was added, and 51.6 mL (82.5 mmol) of hexane solution of normal butyl lithium (1.6 mol / L) was added. After dripping, it was made to react for 5 hours. After adding 50 mL of diethyl ether and 15.59 g (150 mmol) of trimethyl borate to a 500 mL three-necked eggplant flask (with a three-way cock, with a magnetic stirrer), after cooling to −78 ° C., the reaction solution prepared above was added dropwise, The reaction was allowed to proceed for 18 hours while raising the temperature to room temperature. 100 mL of 10 wt% hydrochloric acid solution was added to the reaction solution, followed by extraction three times with 50 mL of ethyl acetate, and then the organic layer was washed twice with 50 mL of pure water and dried over MgSO ₄ , and the solvent was distilled off under reduced pressure. Gave a crude product. The obtained crude product was recrystallized from toluene to obtain 1.56 g (11%, white solid) of Compound 27.

The result of analyzing the obtained product was as follows.
¹ H NMR (δ, CDCl ₃ ): 6.69 (s, 1H, Ar—H), 6.56 (s, 1H, Ar—H), 6.32 (s, 2H, B (OH) ₂ ) , 4.10 (q, 2H, J = 6.9
Hz, OCH ₂ ), 2.53 (s, 3H, CH ₃ ), 2.30 (s, 3H, CH ₃ ), 1.
46 (t, 3H, J = 6.9 Hz, CH ₃ )

In a well-dried 100 mL three-necked eggplant flask (condenser with three-way cock, with magnetic stirrer), 1.07 g (5.5 mmol) of compound 27, 0.860 g (5.5 mmol) of 2-bromoaniline, 0 of palladium acetate 0.011 g (0.05 mmol), 2-Dicyclohexylphosphino-2 ′, 6′-dimethylbiphenyl 0.041 g (0.1 mmol), potassium phosphate monohydrate 3.4
5 g (15 mmol) was added, suspended in 10 mL of toluene, and reacted at 100 ° C. for 1.5 hours. 10 mL of water was added to this reaction liquid, extracted with toluene, the organic layer was dried over MgSO ₄ , and the solvent was distilled off under reduced pressure to obtain a crude product. The crude product was purified using silica gel column chromatography (eluent: hexane / ethyl acetate = 96/4) to obtain 0.321 g (27%, colorless liquid) of Compound 28.

The result of analyzing the obtained product was as follows.
¹ H NMR (δ, CDCl ₃ ): 7.14 (dt, J = 1.6, 7.6 Hz, 1H, Ar—H), 6.95 (dd, J = 1.6, 7.3 Hz, 1H , Ar-H), 6.82-6.75 (m, 3H, Ar-H), 6.66 (s, 1H, Ar-H), 3.96 (q, 2H, J = 7.0 Hz, OCH ₂ ), 3.45 (br, 2H, NH ₂ ), 2.35 (s, 3H, CH ₃ ), 2.04 (s, 3H, CH ₃ ), 1.19 (t, 3H, J = 7.0Hz, CH ₃₎

  0.319 g (1.32 mmol), 3-adamantyl-2-hydroxy-5-methylbenzaldehyde 0.324 g in a well-dried 100 mL eggplant flask (three-way cock, Dean-Stark tube with Dimroth, with magnetic stirrer) (1.2 mmol) and 32 mg of Amberlyst 15 (H) were added, and 30 mL of toluene was added, followed by reaction under reflux for 3 hours. After removing insolubles from this reaction solution by filtration, the solvent was distilled off under reduced pressure, and recrystallization from ethanol gave 0.320 g of Compound 29 (yield 54%, yellow solid).

The result of analyzing the obtained product was as follows.
¹ H NMR (δ, CDCl ₃ ): 13.3 (s, 1H, OH), 8.44 (s, 1H, N═CH), 7.42-7.23 (m, 4H, Ar—H) 7.02 (s, 1H, Ar—H), 6.90 (s, 1H, Ar—H), 6.69 (s, 1H, Ar—H), 6.59 (s, 1H, Ar—) H), 3.88 (q, 2H, J = 6.9 Hz, OCH ₂ ), 2.31 (s
, 3H, CH ₃ ), 2.25 (s, 3H, CH ₃ ), 2.07 (bs, 9H, adamantyl), 1.97 (s, 3H, CH ₃ ), 1.77 (bs, 6H, adamantyl)
1.12 (t, 3H, J = 6.9 Hz, CH ₃ )

To a well-dried 100 mL Schlenk flask (with magnetic stirrer), 0.55 mL (0.55 mmol) of a toluene solution of TiCl ₄ (1.0 mmol / mL) and 10 mL of toluene are added and cooled to −78 ° C. In this mixed solution, 0.247 g (0.5 mmol) of Compound 29 was dissolved in 5 mL of toluene and added dropwise, and then reacted for 18 hours while raising the temperature to room temperature. After concentrating the reaction solution to about 2 mL under reduced pressure, 30 mL of hexane was added for precipitation, and the precipitate was collected by filtration, washed with 20 mL of hexane, and dried to give 0.47 g of Compound 30 (yield 14%). Orange solid).

The result of analyzing the obtained product was as follows.
¹ H NMR (δ, CDCl ₃ ): 8.13 (s, 1H, N═CH), 7.46-7.35 (m, 3H, Ar—H), 7.23-7.15 (m, 2H, Ar-H), 7.12 (s, 1H, Ar-H), 7.07 (s, 1H, Ar-H), 6.96 (s, 1H, Ar-H), 5.37-. 5.28 (m, 1H, OCH ₂ ), 4.82-4.73 (m, 1H, OCH ₂ ), 2.33 (s, 3H, CH ₃ ), 2.29 (s, 3H, CH ₃₎ ), 2.19 (bs, 9H, adamantyl), 2.14 (s, 3H, CH ₃ ), 1.92 (d, 3H, J =
12 Hz, adamantyl), 1.78 (d, 3H, J = 12 Hz, adamantyl), 0.96 (t, 3H, J = 6.9 Hz, CH ₃ )
[Example 1]
To an autoclave with an internal volume of 100 mL sufficiently purged with nitrogen, 28 mL of toluene was added, and then 0.5 mmol of methylaluminoxane (Tosoh Finechem MMAO-3A, 10 wt% hexane solution) was added in terms of aluminum atoms. Subsequently, 0.25 μmol of the compound 2 (1 mM toluene solution) was added, and the reaction was started by pressurizing with ethylene (0.8 MPa-G). The reaction was stopped at 25 ° C. for 60 minutes while supplying ethylene at the same pressure, and then the reaction was stopped by adding a small amount of isopropanol. After completion of the reaction, the reaction solution is washed with 0.1 N hydrochloric acid and pure water, and a low-boiling component (10 or less carbon atoms) is separated from the high-boiling component and polyethylene using a liquid nitrogen trap under reduced pressure. Analysis was performed using chromatography. Among the products, the selectivity for 1-hexene was 79.9%. As other products, the selectivity of decenes was 18.8%, the selectivity of polyethylene was 1.2%, and the catalytic activity calculated from the total amount of these products was 11.7 kg-product / (mmol-Ti -H). In addition, the same reaction as described above was performed even at a reaction temperature of 40 ° C. The results are shown in Table 1.

  Here, the specific activity is defined as follows.

Specific activity = (activity at reaction temperature (40 ° C. or 50 ° C.)) / (Activity at reaction temperature of 25 ° C.)
[Example 2]
The reaction was carried out at reaction temperatures of 25 ° C. and 40 ° C. in the same manner as in Example 1 except that compound 6 was used instead of compound 2. The results are shown in Table 1.

[Examples 3 to 5]
The reaction was carried out at reaction temperatures of 25 ° C., 40 ° C. and 50 ° C. in the same manner as in Example 1 except that compounds 9, 12, and 16 were used instead of compound 2, respectively. The results are shown in Table 1.

[Examples 6 to 9]
The reaction was conducted at reaction temperatures of 25 ° C. and 40 ° C. in the same manner as in Example 1 except that compounds 20, 22, 26, and 30 were used instead of compound 2, respectively. The results are shown in Table 1.

[Comparative Example 1]
The reaction was carried out at reaction temperatures of 25 ° C. and 40 ° C. in the same manner as in Example 1 except that Compound 31 described in International Publication No. 2009/5003 pamphlet was used instead of Compound 2. The results are shown in Table 1.

[Example 10]
144 mL of n-heptane was put into an autoclave having an internal volume of 500 mL that was sufficiently purged with nitrogen, and then 1.0 mmol of methylaluminoxane (Tosoh Finechem MMAO-3A, 1M hexane solution) was added in terms of aluminum atom. Subsequently, 0.5 μmol of the above compound 12 (1.0 mM toluene solution) was added, and the reaction was started by pressurizing with ethylene (3.5 MPa-G) and hydrogen (0.1 MPa-G). After reacting at 50 ° C. for 60 minutes while supplying ethylene at the same pressure, the reaction was stopped by adding a small amount of methanol. After completion of the reaction, the reaction solution is washed with 0.1 N hydrochloric acid and pure water, and a low-boiling component (10 or less carbon atoms) is separated from the high-boiling component and polyethylene using a liquid nitrogen trap under reduced pressure. Analysis was performed using chromatography. The selectivity of 1-hexene among the products was 89.6%. As other products, the selectivity of decenes was 9.7%, the selectivity of polyethylene was 0.7%, and the catalytic activity calculated from the total amount of these products was 93 kg-product / (mmol-Ti · h). )Met.

[Examples 11 and 12]
The reaction was performed in the same manner as in Example 10 except that the compounds 16 and 22 were used instead of the compound 12, respectively. The results are shown in Table 2.

[Comparative Example 2]
The reaction was conducted in the same manner as in Example 10 except that compound 31 was used instead of compound 12. The results are shown in Table 2.

  From the results of the above Examples and Comparative Examples, the olefin multimerization reaction using the transition metal compound according to the present invention has a higher activity at a higher temperature (specific activity is higher than that in the case of using a conventionally known transition metal compound). It became clear. This is because, as described above, by introducing a substituent at a specific position of the phenoxyimine ligand of the transition metal compound represented by the general formula (1) according to the present invention, the stability of the compound is increased and the heat resistance is increased. It can be assumed that it is caused by having

  When the olefin multimerization reaction is carried out using the transition metal compound according to the present invention, an olefin multimer can be obtained at a higher catalyst activity and higher reaction temperature than in the prior art, which is extremely valuable industrially.

Claims (7)

A transition metal compound represented by the following general formula (1).

[In General Formula (1), M represents an atom of Groups 4-6 of the periodic table,
R ¹ , R ² , R ³ , R ⁷ , R ⁸ , R ¹¹ , R ¹³ and R ¹⁴ may be the same as or different from each other, and are a hydrogen atom, a halogen atom, a hydrocarbon group, a hydrocarbon-substituted silyl group, An atom or group selected from an oxygen-containing group and a nitrogen-containing group;
R ⁴ , R ⁵ , R ⁹ , and R ¹⁰ may be the same or different from each other, and are selected from a hydrogen atom, a halogen atom, a hydrocarbon group, a hydrocarbon-substituted silyl group, an oxygen-containing group, and a nitrogen-containing group. Or a group,
R ⁶ and R ^{12, which} may be the same or different from each other, are atoms or groups selected from a hydrogen atom, a hydrocarbon group, a hydrocarbon-substituted silyl group, an oxygen-containing group and a nitrogen-containing group;
R ⁴ , R ⁵ , R ⁶ , R ⁹ , R ¹⁰ and R ¹² are not simultaneously hydrogen atoms,
Two adjacent groups out of the groups represented by R ^{1 to} R ¹⁴ may be bonded to form a ring together with the carbon atoms to which they are bonded.
n represents the valence of M.
X represents a group selected from a hydrogen atom, a halogen atom, a hydrocarbon group, an oxygen-containing group and a nitrogen-containing group, and a plurality of atoms or groups represented by X may be the same or different from each other, and are represented by X A plurality of groups may be bonded to each other, and a plurality of groups represented by X may be bonded to each other to form a ring. ] The general formula (1), wherein at least one of the groups represented by R ⁴ , R ⁵ , R ⁶ , R ⁹ , R ¹⁰ and R ¹² is a hydrocarbon group. Transition metal compounds. The transition metal compound according to claim 1 or 2, wherein R ² in the general formula (1) is a tertiary alkyl group or a hydrocarbon-substituted tertiary silyl group.   The transition metal compound according to any one of claims 1 to 3, wherein in the general formula (1), M is a titanium atom. An olefin multimerization catalyst comprising the following component (A) and component (B):
(A) Transition metal compound according to any one of claims 1 to 4 (B) (B-1) Organometallic compound (B-2) Organoaluminum oxy compound, and (B-3) Transition metal compound ( At least one compound selected from the group consisting of compounds that react with A) to form ion pairs. The olefin multimerization catalyst according to claim 5, further comprising the following component (C).
Component (C); a carrier for supporting at least one compound selected from component (A) and component (B).   A method for producing an olefin multimer, wherein the olefin is multimerized using the olefin polymerization catalyst according to claim 5 or 6.