JP2011195583A - Transition metal complex compound, olefin multimerization catalyst containing the same and method for producing olefin multimer carried out in presence of the same catalyst - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a transition metal complex compound, an olefin multimerization catalyst having excellent activity and containing the same and a method for producing an olefin multimer carried out in the presence of the catalyst.SOLUTION: This transition metal complex compound is one having a phenoxyimine ligand and this olefin multimerization catalyst contains following component (A) and component (B). (A) is the transition metal compound and (B) is a compound selected from the group consisting of an organic metal compound (B-1), an organic aluminumoxy compound (B-2) and a compound (B-3) forming an ion pair by reacting with the transition metal compound (A).

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, in the existing technology, the thermal stability and reaction activity of the catalyst are not sufficient from the viewpoints of equipment cost, production cost, and productivity, and further improvement in catalyst performance has been desired. Furthermore, in the existing technology, decenes are produced as a by-product due to the reaction between the produced 1-hexene and the raw material ethylene, and the selectivity of 1-hexene is reduced. The decene produced as a by-product from the viewpoint of production cost and productivity. There has been a demand for a method for suppressing the generation of sucrose.

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 above-described problems of the prior art, and provides a novel transition metal complex compound and an olefin multimerization catalyst containing the compound and having excellent activity and selectivity. Another object of the present invention is to provide a method for producing an olefin multimer carried out in the presence of the olefin multimerization catalyst.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that an olefin multimerization catalyst containing a transition metal complex compound having a specific structure has excellent activity and selectivity, and the presence of the catalyst. Below, the olefin multimerization reaction can be suitably carried out, and particularly when ethylene is used as the olefin, it was found that 1-hexene, which is a trimer of ethylene, can be obtained with high selectivity. Was completed.

That is, the present invention relates to the following [1] to [11].
[1]
A transition metal compound represented by the following general formula (1).

〔一般式（１）中、Ｍは周期律表第４〜６族の原子を表し、
Ｒ¹、Ｒ²、Ｒ⁴〜Ｒ⁶、Ｒ⁹、Ｒ¹⁰、Ｒ¹²およびＲ¹⁴は、互いに同一でも異なっていてもよく、水素原子、ハロゲン原子、炭化水素基、炭化水素置換シリル基、酸素含有基および窒素含有基から選ばれる原子または基であり、
Ｒ³、Ｒ⁷、Ｒ⁸、Ｒ¹¹およびＲ¹³は、互いに同一でも異なっていてもよく、水素原子、ハロゲン原子、炭化水素基、炭化水素置換シリル基、酸素含有基および窒素含有基から選ばれる原子または基であって、少なくとも一つが、炭素数３以上の炭化水素基もしくは炭素数１以上の炭化水素基置換シリル基であり、
Ｒ¹〜Ｒ¹⁴で示される基のうち隣接する２個の基が結合して、それらの結合する炭素原子と一緒に環を形成してもよい。

[In General Formula (1), M represents an atom of Groups 4-6 of the periodic table,
R ¹ , R ² , R ^{4 to} R ⁶ , R ⁹ , R ¹⁰ , R ¹² 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 ³ , R ⁷ , R ⁸ , R ¹¹ and R ¹³ 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. At least one of which is a hydrocarbon group having 3 or more carbon atoms or a hydrocarbon group-substituted silyl group having 1 or more carbon 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 ³ , R ⁷ , R ⁸ , R ¹¹ and R ¹³ is a hydrocarbon group having 3 or more carbon atoms. The transition metal compound described.

[3]
In the general formula (1), at least one of the groups represented by R ³ , R ⁸ and R ¹¹ is a hydrocarbon group having 3 or more carbon atoms, [2], the transition metal compound according to [2].

[4]
In the general formula (1), the group represented by R ¹¹ is a hydrocarbon group having 3 or more carbon atoms, and at least one of the groups represented by R ³ and R ⁸ is a hydrocarbon group having 3 or more carbon atoms. [3] The transition metal compound according to [3].

[5]
The hydrocarbon group having 3 or more carbon atoms is a substituent selected from a secondary alkyl group, a tertiary alkyl group or an aryl group, according to any one of [2] to [4], Transition metal compounds.

[6]
The transition metal compound according to any one of [1] to [5], wherein the groups represented by R ⁶ and R ¹² in the general formula (1) are hydrogen atoms.

[7]
The transition metal compound according to any one of [1] to [6], wherein in the general formula (1), R ² is a tertiary alkyl group or a hydrocarbon-substituted tertiary silyl group.

[8]
In said general formula (1), M is a titanium atom, The transition metal compound of any one of [1]-[7] characterized by the above-mentioned.

[9]
An olefin multimerization catalyst comprising the following component (A) and component (B):
(A) Transition metal compound according to any one of [1] to [8] (B) (B-1) Organometallic compound (B-2) Organoaluminum oxy compound, and (B-3) Transition metal At least one compound selected from the group consisting of compounds that react with compound (A) to form ion pairs.

[10]
The olefin multimerization catalyst according to [9], further comprising the following component (C).
Component (C); a carrier for supporting at least one compound selected from component (A) and component (B).

[11]
[10] A method for producing an olefin multimer, wherein the olefin is multimerized using the olefin multimerization catalyst according to [9] or [10].

  INDUSTRIAL APPLICABILITY According to the present invention, a specific transition metal complex compound and an olefin multimerization catalyst containing the compound and having high activity and selectivity can be provided. 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. Furthermore, according to the present invention, it is possible to suppress the production of decenes by-produced when 1-hexene is produced, and it is possible to improve the selectivity of 1-hexene.

  Hereinafter, the transition metal complex compound of the present invention, the olefin multimerization catalyst, and the method for producing an olefin multimer using the olefin multimerization catalyst will be specifically described, but the present invention is not limited thereto.

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).

前記一般式（１）中、Ｒ¹、Ｒ²、Ｒ⁴〜Ｒ⁶、Ｒ⁹、Ｒ¹⁰、Ｒ¹²およびＲ¹⁴は、互いに同一でも異なっていてもよく、水素原子、ハロゲン原子、炭化水素基、炭化水素置換シリル基、酸素含有基および窒素含有基から選ばれる原子または基を示す。

In the general formula (1), R ¹ , R ² , R ^{4 to} R ⁶ , R ⁹ , R ¹⁰ , R ¹² and R ¹⁴ may be the same 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; 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.

  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 ^{4 to} R ⁶ , R ⁹ , R ¹⁰ , R ^12, and R ¹⁴ are each a hydrogen atom, a halogen atom, or the like, because of catalyst performance and ease of production when used as an olefin multimerization catalyst. It is preferably an atom, a hydrocarbon group having 1 to 30 carbon atoms, or a hydrocarbon-substituted silyl group, and more preferably R ¹ , R ² , R ^{4 to} R ⁶ , R ⁹ , R ¹⁰ , R ¹² and R ^14. In which at least R ² is selected from a tertiary alkyl group or a hydrocarbon-substituted tertiary silyl group, and has a total number of carbon atoms of 20 or less.

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 1-hexene 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 3 to 20 atoms.

Preferred groups as R ⁶ and R ¹² are each simultaneously a hydrogen atom in the above examples. It is particularly preferable that R ⁶ and R ¹² are hydrogen atoms because generation of decenes by-produced when 1-hexene is produced can be suppressed and selectivity of 1-hexene can be improved.

In the general formula (1), R ³ , R ⁷ , R ⁸ , R ¹¹ and R ¹³ 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, oxygen An atom or group selected from a containing group and a nitrogen-containing group, at least one of which is a hydrocarbon group having 3 or more carbon atoms or a hydrocarbon group-substituted silyl group having 1 or more carbon atoms.

The halogen atom, hydrocarbon group, hydrocarbon-substituted silyl group, oxygen-containing group and nitrogen-containing group selected from R ³ , R ⁷ , R ⁸ , R ¹¹ and R ¹³ are the same as R in the general formula (1). Examples thereof include the same as ¹ , R ² , R ^{4 to} R ⁶ , R ⁹ , R ¹⁰ , R ¹² 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 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; 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.

  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.
In the general formula (1), at least one of R ³ , R ⁷ , R ⁸ , R ¹¹ and R ¹³ is a hydrocarbon group having 3 or more carbon atoms or a hydrocarbon group-substituted silyl group having 1 or more carbon atoms, Preferably, at least one of R ³ , R ⁷ , R ⁸ , R ¹¹ and R ¹³ is a hydrocarbon group having 3 or more carbon atoms. Of these substituents, at least one of the groups represented by R ³ , R ⁸ and R ¹¹ is more preferably a hydrocarbon group having 3 or more carbon atoms.

Furthermore, in order to suppress 1-hexene from reacting with ethylene and decenes as a by-product, the group represented by R ¹¹ in the vicinity of the reaction site is a sterically large (bulky) substituent. From the viewpoint of advantageously working from the viewpoint of improving hexene selectivity, the group represented by R ¹¹ is a hydrocarbon group having 3 or more carbon atoms, and at least one of the groups represented by R ³ and R ⁸ is carbon number. Particularly preferred is a hydrocarbon group of 3 or more.

Among the examples of R ³ , R ⁷ , R ⁸ , R ¹¹ and R ¹³ above, the hydrocarbon group having 3 or more carbon atoms from the viewpoint of catalytic activity and heat resistance when used as an olefin multimerization catalyst includes It is preferably a substituent selected from a tertiary alkyl group, a tertiary alkyl group or an aryl group, and more specifically, isopropyl, cyclohexyl, tert-butyl, adamantyl, cumyl, trityl, phenyl, tolyl, dimethylphenyl Hydrocarbon groups having 3 to 20 carbon atoms such as trimethylphenyl, ethylphenyl, propylphenyl, biphenyl, naphthyl, methylnaphthyl, anthracenyl and phenanthryl are particularly preferable examples. Examples of the hydrocarbon-substituted silyl group having 1 or more carbon atoms include hydrocarbon group-substituted silyl groups having 3 to 20 carbon atoms such as trimethylsilyl, methyldiphenylsilyl, dimethylphenylsilyl, and triphenylsilyl.

R ⁴ , R ⁵ , R ⁹ , and R ¹⁰ are preferably hydrogen atoms at the same time, and R ^{6 to} R ¹³ are preferably not halogen atoms.
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), 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 ^{4 to} R ⁶ , R ⁹ , R ¹⁰ , R in the general formula (1). It includes the same as those exemplified in ¹² 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 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; 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 describing as (A) transition metal complex compound, the transition metal complex compound represented by the said general formula (I) 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 is 1 to 1 carbon atoms) 15, preferably 1 to 4 hydrocarbon groups, X represents a halogen atom, and m is preferably 0 <m <3.) An organoaluminum compound represented by 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), a general formula during _{^{R a m Al (oR b)}} n X q ( wherein, R ^a and R ^b are optionally carbon atoms be the same or different from each other 1 15, preferably 1 to 4 hydrocarbon groups, X represents a halogen atom, m is 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 alkylaluminums such as aluminum, tri (3-methylhexyl) aluminum, tri (2-ethylhexyl) aluminum; tricycloalkylaluminums such as tricyclohexylaluminum and tricyclooctylaluminum; triaryl aluminum diethyl hydride, dialkylaluminum hydride such as diisobutylaluminum _{hydride; (iC 4 H 9) x} Al y (C 5 H 10) z ( wherein, x, y, z are each a positive number, z ≧ 2x .iC ₄ H ₉ is represents a isobutyl group) alkenyl aluminum such as isoprenyl aluminum represented by like;. triisobutylaluminum methoxide, isobutyl Arumini Muetokishido, alkylaluminum alkoxides such as isobutylaluminum isopropoxide; alkyl sesquichloride alkoxides such as ethyl aluminum sesqui ethoxide, butyl aluminum sesqui butoxide; dimethyl aluminum methoxide, diethyl aluminum ethoxide, dialkylaluminum alkoxides such as dibutyl aluminum butoxide R ^a _2.5 Al (OR ^b ) _0.5 (wherein, R ^a and R ^b represent a hydrocarbon group having 1 to 15 carbon atoms, which may be the same as or different from each other, preferably 1 to 4). Partially alkoxylated alkylaluminum having an average composition represented; diethylaluminum phenoxide, diethylaluminum (2,6-di-tert-butyl 4-methylpheno) Sid), ethylaluminum bis (2,6-di-tert-butyl 4-methylphenoxide), diisobutylaluminum (2,6-di-tert-butyl 4-methylphenoxide), isobutylaluminum bis (2,6-di-) dialkylaluminum aryloxides such as tert-butyl 4-methylphenoxide); dialkylaluminum halides such as dimethylaluminum chloride, diethylaluminum chloride, dibutylaluminum chloride, diethylaluminum bromide, diisobutylaluminum chloride; ethylaluminum sesquichloride, butylaluminum sesquichloride Alkyl aluminum sesquihalides such as ethyl aluminum sesquibromide; ethyl aluminum dichloride, propyl al Partially halogenated alkylaluminums such as alkylaluminum dihalides such as nium dichloride and butylaluminum dibromide; Dialkylaluminum hydrides such as diethylaluminum hydride and dibutylaluminum hydride; Alkyl such as ethylaluminum dihydride and propylaluminum dihydride Other partially hydrogenated alkylaluminums such as aluminum dihydride; and partially alkoxylated and halogenated alkylaluminums such as ethylaluminum ethoxy chloride, butylaluminum butoxycyclyl, ethylaluminum ethoxybromide and the like.

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).

式中、Ｒ¹⁵は炭素原子数が１〜１０の炭化水素基を示す。Ｒ¹⁶は、互いに同一でも異なっていてもよい水素原子、ハロゲン原子、炭素原子数が１〜１０の炭化水素基を示す。

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).

式中、Ｒ¹⁷⁺としては、Ｈ⁺、カルボニウムカチオン、オキソニウムカチオン、アンモニウムカチオン、ホスホニウムカチオン、シクロヘプチルトリエニルカチオン、遷移金属を有するフェロセニウムカチオンなどが挙げられる。

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).

（式中、Ｅｔはエチル基を示す。）

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

ボラン化合物として具体的には、たとえばデカボラン（１４）； ビス〔トリ（ｎ−ブチル）アンモニウム〕ノナボレート、ビス〔トリ（ｎ−ブチル）アンモニウム〕デカボレート、ビス〔トリ（ｎ−ブチル）アンモニウム〕ウンデカボレート、ビス〔トリ（ｎ−ブチル）アンモニウム〕ドデカボレート、ビス〔トリ（ｎ−ブチル）アンモニウム〕デカクロロデカボレート、ビス〔トリ（ｎ−ブチル）アンモニウム〕ドデカクロロドデカボレートなどのアニオンの塩； トリ（ｎ−ブチル）アンモニウムビス（ドデカハイドライドドデカボレート）コバルト酸塩（ＩＩＩ）、ビス〔トリ（ｎ−ブチル）アンモニウム〕ビス（ドデカハイドライドドデカボレート）ニッケル酸塩（ＩＩＩ）などの金属ボランアニオンの塩などが挙げられる。

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 ) 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-di Methyl-7,8-dicarbaundecaborate) chromate (III), tri (n-butyl) ammonium bis (tribromooctahydride-7,8-dicarboundeborate) 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 borane 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.

As the porous oxide, specifically, SiO ₂ , Al ₂ O ₃ , MgO, ZrO, TiO ₂ , B ₂ O ₃ , CaO, ZnO, BaO, ThO ₂ or the like, or a composite or mixture containing these is used. For example, 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 , SiO ₂ —TiO ₂ —MgO, etc. Can be used. 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 , Na ₂ O, K ₂ O, Li ₂ O and other carbonates, sulfates, nitrates, and oxide components may be contained.

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 not less than 0.1 cc / g and not less than 0.3 cc / g, as measured by mercury porosimetry. Is 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 these compounds were intercalated, they were obtained by hydrolyzing metal alkoxides such as Si (OR) ₄ , Al (OR) ₃ , Ge (OR) ₄ (R is a hydrocarbon group, etc.). A dimerized product, a colloidal inorganic compound 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, and further includes (D) an organic compound component as described later as necessary. You can also.

[(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) and (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.

式（ＶＩ）中、Ｍ⁴は周期律表第１〜１４族の原子である。Ｒ²⁴は水素、炭素原子数１〜２０の炭化水素基または炭素原子数１〜２０のハロゲン化炭化水素基である。Ｘは水素原子、ハロゲン原子、炭素原子数が１〜２０の炭化水素基、炭素原子数が１〜２０のハロゲン化炭化水素基である。ｍは１〜７の整数であり、ｎはＭの価数であり、１≦ｎ≦７である。

In formula (VI), M ⁴ is an atom of Groups 1-14 of the periodic table. R ²⁴ is hydrogen, a hydrocarbon group having 1 to 20 carbon atoms, or a 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 above olefin multimerization catalyst, component (A) is usually 10 ⁻¹² to 10 ⁻² mol per liter of reaction volume. The amount is 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 (decenes) 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.

[Selectivity of 1-hexene (decenes)]
The selectivity of 1-hexene (decenes) 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 Note that the selectivity for decenes is determined according to the above method. It was.

  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 3)

充分に乾燥した２００ｍＬ三口ナスフラスコ（コンデンサー、三方コック付、磁気攪拌子入り）に２‐ｍｅｔｈｏｘｙｐｈｅｎｙｌｂｏｒｏｎｉｃ ａｃｉｄ（和光純薬工業株式会社製）を３．１９ｇ（１０．５ｍｍｏｌ）、２−ｂｒｏｍｏ−４−ｔｅｒｔ−ｂｕｔｙｌａｎｉｌｉｎｅ２．２８ｇ（１０ｍｍｏｌ）、酢酸パラジウム（和光純薬工業株式会社製）を０．０１１ｇ（０．０５ｍｍｏｌ）、２‐ｄｉｃｙｃｌｏｈｅｘｙｌｐｈｏｓｐｈｉｎｏ‐２’，６’‐ｄｉｍｅｔｈｏｘｙｂｉｐｈｅｎｙｌ（シグマ アルドリッチ ジャパン株式会社製）を０．０４１ｇ（０．１ｍｍｏｌ）、リン酸カリウム一水和物（和光純薬工業株式会社製）６．９ｇ（３０ｍｍｏｌ）加え、トルエン（関東化学株式会社製）２０ｍＬに縣濁させ、１００℃で３時間反応させた。この反応液に水５０ｍＬを加え、トルエンで抽出後、有機層をＭｇＳＯ₄（関東化学株式会社製）で乾燥させ、溶媒を減圧下で留去することにより粗生成物を得た。粗生成物をシリカゲルカラムクロマトグラフ（溶離液；ヘキサン（関東化学株式会社製）／酢酸エチル（関東化学株式会社製）＝９／１）を用いて精製することにより化合物１を２．４０ｇ（９４％、薄黄色液体）を得た。

2.19 g (10.5 mmol) of 2-methoxyphenylboronic acid (manufactured by Wako Pure Chemical Industries, Ltd.), 2-bromo-4-, in a well-dried 200 mL three-necked eggplant flask (condenser, with three-way cock, with magnetic stirrer) tert-butylanline 2.28 g (10 mmol), palladium acetate (manufactured by Wako Pure Chemical Industries, Ltd.) 0.011 g (0.05 mmol), 2-diccyclohexylphosphino-2 ′, 6′-dimethylbiphenyl (manufactured by Sigma Aldrich Japan Co., Ltd.) Add 0.041 g (0.1 mmol), potassium phosphate monohydrate (Wako Pure Chemical Industries, Ltd.) 6.9 g (30 mmol), and suspend in 20 mL of toluene (Kanto Chemical Co., Ltd.) at 100 ° C. 3 It was between reaction. 50 mL of water was added to this reaction liquid, extracted with toluene, the organic layer was dried over MgSO ₄ (manufactured by Kanto Chemical Co., Inc.), 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 (manufactured by Kanto Chemical Co., Inc.) / Ethyl acetate (manufactured by Kanto Chemical Co., Ltd.) = 9/1) to obtain 2.40 g (94 %, Pale yellow liquid).

The result of analyzing the obtained product was as follows.
¹ H NMR (δ, CDCl ₃ ): 7.35-6.99 (m, 6H, Ar—H), 6.72 (d, 1H, J = 8.4 Hz, Ar—H), 3.82 ( s, 3H, OCH ₃ ), 3.61 (br, 2H, NH ₂ ), 1.30 (s, 9H, C (CH ₃ ) ₃ )

充分に乾燥した１００ｍＬナスフラスコ（三方コック、ディーン・スターク管、ジムロート付、磁気攪拌子入り）に化合物１を１．３３ｇ（５．５ｍｍｏｌ）、３‐ａｄａｍａｎｔｙｌ‐２‐ｈｙｄｒｏｘｙ‐５‐ｍｅｔｈｙｌｂｅｎｚａｌｄｅｈｙｄｅ（Ｊｏｕｒｎａｌ ｏｆ Ａｍｅｒｉｃａｎ Ｃｈｅｍｉｃａｌ Ｓｏｃｉｅｔｙ誌２００１年１２３巻６８４７−６８５６頁の記載に従い合成した。）１．３５ｇ（５．０ｍｍｏｌ）、アンバーリスト１５（Ｈ）（和光純薬工業株式会社製）を１３５ｍｇ加えトルエン４０ｍＬ加えた後、還流下で３時間反応させた。この反応液から不溶物をろ過にて取り除いた後、溶媒を減圧下で留去し、エタノール（関東化学株式会社製）から再結晶することにより化合物２を２．１５ｇ（収率 ８９％、黄色固体）得た。

In a well-dried 100 mL eggplant flask (three-way cock, Dean-Stark tube, with Dimroth, with magnetic stirrer), 1.33 g (5.5 mmol), 3-adamantyl-2-hydroxy-5-methylbenzaldehyde (Journal) of American Chemical Society 2001, volume 123, pages 6847-6856.) 1.35 g (5.0 mmol), Amberlyst 15 (H) (manufactured by Wako Pure Chemical Industries, Ltd.) 135 mg and toluene 40 mL added And then 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 (manufactured by Kanto Chemical Co., Inc.) gave 2.15 g (yield 89%, yellow) of compound 2. Solid).

The result of analyzing the obtained product was as follows.
¹ H NMR (δ, CDCl ₃ ): 13.6 (s, 1H, OH), 8.46 (s, 1H, N═CH), 7.45-7.13 (m, 5H, Ar—H) , 7.03-6.92 (m, 4H, Ar -H), 3.75 (s, 3H, OCH 3), 2.26 (s, 3H, CH 3), 2.08 (s, 9H, adamantyl), 1.77 (s, 6H, adamantyl), 1.37 (s, 9H, C (CH ₃ ) ₃ )

充分に乾燥した１００ｍＬシュレンクフラスコ（磁気攪拌子入り）にＴｉＣｌ₄のトルエン溶液（シグマ アルドリッチ ジャパン株式会社製）（１．０ｍｍｏｌ／ｍＬ）を１．１ｍＬ（１．１ｍｍｏｌ）、トルエン２０ｍＬを加え−７８℃に冷却した。この混合液に化合物２を０．５０８ｇ（１．０ｍｍｏｌ）をトルエン５ｍＬに溶かし滴下した後、室温まで昇温させつつ１７時間反応させた。この反応液を減圧下で約２ｍＬまで濃縮した後に、ヘキサン１０ｍＬを加え析出させた。析出物をろ取し、ヘキサン２０ｍＬで洗浄後、乾燥させることにより、化合物３を０．５２７ｇ（収率 ８０％、オレンジ色固体）得た。

To a well-dried 100 mL Schlenk flask (with magnetic stirrer), 1.1 mL (1.1 mmol) of a toluene solution of TiCl ₄ (manufactured by Sigma Aldrich Japan Co., Ltd.) (1.0 mmol / mL) and 20 mL of toluene were added and added to −78. Cooled to ° C. In this mixed solution, 0.508 g (1.0 mmol) of Compound 2 was dissolved in 5 mL of toluene and added dropwise, and then reacted for 17 hours while raising the temperature to room temperature. The reaction solution was concentrated to about 2 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 0.527 g (yield 80%, orange solid) of Compound 3.

The result of analyzing the obtained product was as follows.
¹ H NMR (δ, CDCl ₃ ): 8.10 (s, 1H, N═CH), 7.48-7.26 (m, 6H, Ar—H), 7.08 (d, 1H, J = 1.6 Hz, Ar-H), 7.02 (d, 1 H, J = 8.4 Hz, Ar-H), 4.43 (s, 3 H, OCH ₃ ), 2.32 (s, 3 H, 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), 1.38 (s, 9H, C (CH ₃ ) ₃ )

[Synthesis Example 2]
(Synthesis of Compound 6)

充分に乾燥した２００ｍＬ三口ナスフラスコ（コンデンサー、三方コック付、磁気攪拌子入り）にｐｈｅｎｙｌｂｏｒｏｎｉｃ ａｃｉｄ（シグマ アルドリッチ ジャパン株式会社製）を１．２８ｇ（１０．５ｍｍｏｌ）、４−ｂｒｏｍｏ−２−ｃｈｌｏｒｏａｎｉｌｉｎｅ（東京化成工業株式会社製）を２．０７ｇ（１０ｍｍｏｌ）、酢酸パラジウムを０．０２２ｇ（０．１ｍｍｏｌ）、２‐ｄｉｃｙｃｌｏｈｅｘｙｌｐｈｏｓｐｈｉｎｏ‐２’，６’‐ｄｉｍｅｔｈｏｘｙｂｉｐｈｅｎｙｌを０．０８２ｇ（０．２ｍｍｏｌ）、リン酸カリウム一水和物６．９１ｇ（３０ｍｍｏｌ）加え、ジオキサン（関東化学株式会社製）２０ｍＬに縣濁させ、５０℃で１０時間反応させた。この反応液に２‐ｍｅｔｈｏｘｙｐｈｅｎｙｌｂｏｒｏｎｉｃ ａｃｉｄを１．６０ｇ（１０．５ｍｍｏｌ）を加え１００℃で９時間反応させた。この反応液に水２０ｍＬを加え、トルエンで抽出後、有機層をＭｇＳＯ₄で乾燥させ、溶媒を減圧下で留去することにより粗生成物を得た。粗生成物をシリカゲルカラムクロマトグラフ （溶離液；ヘキサン／酢酸エチル＝９／１）を用いて精製することにより化合物４を１．２２ｇ（４４％、薄黄色液体）を得た。

In a well-dried 200 mL three-necked eggplant flask (condenser, with three-way cock, with magnetic stirrer), 1.28 g (10.5 mmol) of phenylboronic acid (manufactured by Sigma Aldrich Japan Co., Ltd.), 4-bromo-2-chloroaniline (Tokyo) (Made by Kasei Kogyo Co., Ltd.) 2.07 g (10 mmol), 0.022 g (0.1 mmol) of palladium acetate, 0.082 g (0.2 mmol) of 2-diccyclohexylphosphino-2 ′, 6′-dimethylbiphenyl, potassium phosphate 6.91 g (30 mmol) of monohydrate was added, suspended in 20 mL of dioxane (manufactured by Kanto Chemical Co., Inc.), and reacted at 50 ° C. for 10 hours. To this reaction solution, 1.60 g (10.5 mmol) of 2-methoxyphenylboronic acid was added and reacted at 100 ° C. for 9 hours. 20 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 = 9/1) to obtain 1.22 g (44%, light yellow liquid) of Compound 4.

The result of analyzing the obtained product was as follows.
¹ H NMR (δ, CDCl ₃ ): 7.58-7.55 (m, 2H, Ar—H), 7.46-7.26 (m, 7H, Ar—H), 7.09-7. 01 (m, 2H, Ar- H), 6.85 (d, 1H, J = 8.4Hz, Ar-H), 3.83 (s, 3H, OCH 3), 3.80 (br, 2H, NH ₂₎

充分に乾燥した１００ｍＬナスフラスコ（三方コック、ディーン・スターク管、ジムロート付、磁気攪拌子入り）に化合物４を１．１６ｇ（４．２ｍｍｏｌ）、３‐ａｄａｍａｎｔｙｌ‐２‐ｈｙｄｒｏｘｙ‐５‐ｍｅｔｈｙｌｂｅｎｚａｌｄｅｈｙｄｅ１．０８ｇ（４．０ｍｍｏｌ）、アンバーリスト１５（Ｈ）を１０８ｍｇ加えトルエン４０ｍＬ加えた後、還流下で３時間反応させた。この反応液から不溶物をろ過にて取り除いた後、溶媒を減圧下で留去し、エタノールから再結晶することにより化合物５を１．４６ｇ（収率 ６９％、黄色固体）得た。

1.16 g (4.2 mmol), 3-adamantyl-2-hydroxy-5-methylbenzaldehyde 1.08 g in a well-dried 100 mL eggplant flask (three-way cock, Dean-Stark tube, with Dimroth, with magnetic stirrer) (4.0 mmol) and 108 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 1.46 g (yield 69%, yellow solid) of Compound 5.

The result of analyzing the obtained product was as follows.
¹ H NMR (δ, CDCl ₃ ): 13.5 (s, 1H, OH), 8.51 (s, 1H, N═CH), 7.67-7.63 (m, 4H, Ar—H) , 7.47-7.25 (m, 6H, Ar -H), 7.06-6.94 (m, 4H, Ar-H), 3.77 (s, 3H, OCH 3), 2.27 (S, 3H, CH ₃ ), 2.10 (s, 9H, adamantyl), 1.77 (s, 6H, adamantyl)

充分に乾燥した５０ｍＬナスフラスコ（三方コック、磁気攪拌子入り）にＴｉＣｌ₄（ｔｈｆ）₂（シグマ アルドリッチ ジャパン株式会社製）０．５００ｇ（１．５ｍｍｏｌ）、テトラヒドロフラン（関東化学株式会社製）を７．５ｍＬ加え−７８℃に冷却した。この混合液に化合物５を０．６７７ｇ（１．５ｍｍｏｌ）をテトラヒドロフラン１．３ｍＬに溶かし滴下した後、室温まで昇温させつつ２２時間反応させた。この反応液を約３ｍＬまで濃縮した後、ヘキサン１０ｍＬを加え析出させた。析出物をろ取し、ヘキサン２０ｍＬで洗浄後、乾燥させることにより、化合物６のテトラヒドロフラン錯体を０．９０８ｇ（収率 ７９％、赤褐色固体）得た。

To a well-dried 50 mL eggplant flask (with a three-way cock and a magnetic stirrer), 0.500 g (1.5 mmol) of TiCl ₄ (thf) ₂ (manufactured by Sigma Aldrich Japan Co., Ltd.) and 7 of tetrahydrofuran (manufactured by Kanto Chemical Co., Ltd.) .5 mL was added and cooled to -78 ° C. In this mixed solution, 0.677 g (1.5 mmol) of Compound 5 was dissolved in 1.3 mL of tetrahydrofuran and added dropwise, and then reacted for 22 hours while raising the temperature to room temperature. After concentrating the reaction solution to about 3 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 0.908 g (yield 79%, reddish brown solid) of the tetrahydrofuran complex of Compound 6.

The result of analyzing the obtained product was as follows.
¹ H NMR (δ, CDCl ₃ ): 8.09 (s, 1H, N═CH), 7.64-7.04 (m, 14H, Ar—H), 4.39 (s, 3H, OCH ₃₎ ), 3.71 (bs, 4H, thf), 2.26 (s, 3H, CH ₃ ), 2.14 (bs, 6H, adamantyl), 2.10 (bs, 3H, adamantyl), 1.86 (D, 3H, J = 12 Hz, adamantyl), 1.81-1.76 (m, 4H, thf), 1.72 (d, 3H, J = 12 Hz, adamantyl)

[Synthesis Example 3]
(Synthesis of Compound 10)

充分に乾燥した２００ｍＬ三口ナスフラスコ（滴下ロート、三方コック付、磁気攪拌子入り）に４−（２‐ｐｈｅｎｙｌｐｒｏｐａｎ‐２‐ｙｌ）ｐｈｅｎｏｌ（和光純薬工業株式会社製）を５．３１ｇ（２５ｍｍｏｌ）、１−ａｄａｍａｎｔａｎｏｌ（東京化成工業株式会社製）を４．１９ｇ（２７．５ｍｍｏｌ） ジクロロメタン（関東化学株式会社製）１００ｍＬを加え、氷浴にて０℃まで冷却した後、硫酸（関東化学株式会社製）２．７０ｇ（２７．５ｍｍｏｌ）を滴下した後、そのまま１時間反応させた。この反応液を１．０ｍｏｌ／Ｌの水酸化ナトリウム（関東化学株式会社製）水溶液５０ｍＬで二回、純水５０ｍＬで一回洗浄し、有機相をＭｇＳＯ₄（関東化学株式会社製）で乾燥させ、溶媒を減圧下で留去することにより粗生成物を得た。粗生成物をシリカゲルカラムクロマトグラフ （溶離液；ヘキサン／酢酸エチル＝１０／１）を用いて精製することにより化合物７を４．２０ｇ（４８％、白色固体）を得た。

In a well-dried 200 mL three-necked eggplant flask (with dropping funnel, three-way cock, with magnetic stirrer), 5.31 g (25 mmol) of 4- (2-phenylpropan-2-yl) phenol (manufactured by Wako Pure Chemical Industries, Ltd.) , 1.19 g (27.5 mmol) of 1-adamantanol (manufactured by Tokyo Chemical Industry Co., Ltd.) 100 mL of dichloromethane (manufactured by Kanto Chemical Co., Ltd.) was added and cooled to 0 ° C. in an ice bath, and then sulfuric acid (Kanto Chemical Co., Ltd.). (Manufactured) After 2.70 g (27.5 mmol) was added dropwise, the reaction was allowed to proceed for 1 hour. This reaction solution was washed twice with 50 mL of 1.0 mol / L aqueous sodium hydroxide (manufactured by Kanto Chemical Co., Inc.) and once with 50 mL of pure water, and the organic phase was dried with MgSO ₄ (manufactured by Kanto Chemical Co., Ltd.). The crude product was obtained by distilling off the solvent under reduced pressure. The crude product was purified using silica gel column chromatography (eluent: hexane / ethyl acetate = 10/1) to obtain 4.20 g (48%, white solid) of Compound 7.

The result of analyzing the obtained product was as follows.
¹ H NMR (δ, CDCl ₃ ): 7.29-7.11 (m, 6H, Ar—H), 6.86 (dd, 1H, J = 8.3, 2.3 Hz, Ar—H), 6.52 (d, 1H, J = 8.3 Hz, Ar-H), 4.61 (s, 1H, OH), 2.07 (bs, 9H, adamantyl), 1.75 (bs, 6H, adamantyl) ), 1.65 (s, 6H, CH ₃ )

充分に乾燥した２００ｍＬ三口ナスフラスコ（滴下ロート、三方コック付、磁気攪拌子入り）に化合物７ ４．１６ｇ（１２ｍｍｏｌ）、テトラヒドロフラン２５ｍＬを加え氷浴にて０℃まで冷却した後、ＥｔＭｇＢｒのテトラヒドロフラン溶液（関東化学株式会社製）（１．０ｍｍｏｌ／ｍＬ）１３．２ｍＬ（１３．２ｍｍｏｌ）を滴下し、そのまま室温まで昇温させつつ１時間反応させた。この反応液に、パラホルムアルデヒド（和光純薬工業株式会社製）０．９１０ｇ（３０ｍｍｏｌ）、トリエチルアミン（東京化成工業株式会社製）２．５０ｍＬ（１８ｍｍｏｌ）を加え、６０℃にて５時間反応させた。この反応液にトルエン５０ｍＬを加えた後、１０ｗｔ％塩酸水（関東化学株式会社製）１０ｍＬを加え、分液した後、有機相を純水５０ｍＬで二回洗浄しＭｇＳＯ₄で乾燥させ、溶媒を減圧下で留去することにより粗生成物を得た。粗生成物をエタノールから再結晶することにより目的物を３．９０ｇ（８７％、白色固体）を得た。

To a well-dried 200 mL three-necked eggplant flask (with a dropping funnel, with a three-way cock, with a magnetic stirrer), 4.16 g (12 mmol) of Compound 7 and 25 mL of tetrahydrofuran were added and cooled to 0 ° C. in an ice bath, followed by a tetrahydrofuran solution of EtMgBr. (Manufactured by Kanto Chemical Co., Inc.) (1.0 mmol / mL) 13.2 mL (13.2 mmol) was added dropwise, and the mixture was allowed to react for 1 hour while raising the temperature to room temperature. To this reaction solution, paraformaldehyde (manufactured by Wako Pure Chemical Industries, Ltd.) 0.910 g (30 mmol) and triethylamine (manufactured by Tokyo Chemical Industry Co., Ltd.) 2.50 mL (18 mmol) were added and reacted at 60 ° C. for 5 hours. . After adding 50 mL of toluene to this reaction solution, 10 mL of 10 wt% aqueous hydrochloric acid (manufactured by Kanto Chemical Co., Inc.) is added and separated, and the organic phase is washed twice with 50 mL of pure water and dried over MgSO _4. The crude product was obtained by distilling off under reduced pressure. The crude product was recrystallized from ethanol to obtain 3.90 g (87%, white solid) of the target product.

The result of analyzing the obtained product was as follows.
¹ H NMR (δ, CDCl ₃ ): 11.7 (s, 1H, OH), 9.79 (s, 1H, O═CH), 7.36-7.16 (m, 7H, Ar—H) 2.06 (bs, 6H, adamantyl), 2.07 (s, 3H, adamantyl), 1.75 (s, 6H, adamantyl), 1.69 (s, 6H, CH ₃ )

充分に乾燥した１００ｍＬナスフラスコ（三方コック、ディーン・スターク管、ジムロート付、磁気攪拌子入り）に２’−ｍｅｔｈｏｘｙｂｉｐｈｅｎｙｌ−２−ａｍｉｎｅ（国際公開第２００９／５００３号パンフレットの記載に従い合成した。）を０．６２８ｇ（３．１５ｍｍｏｌ）、化合物８を１．１２３ｇ（３．０ｍｍｏｌ）、アンバーリスト１５（Ｈ）を５０ｍｇ加えトルエン２０ｍＬ加えた後、還流下で４時間反応させた。この反応液から不溶物をろ過にて取り除いた後、溶媒を減圧下で留去し、エタノールから再結晶することにより化合物９を０．５９７ｇ（収率 ３６％、黄色固体）得た。

2′-methoxybiphenyl-2-amine (synthesized as described in International Publication No. 2009/5003 pamphlet) was added to a well-dried 100 mL eggplant flask (three-way cock, Dean-Stark tube, with Dimroth, magnetic stirrer). 0.628 g (3.15 mmol), 1.123 g (3.0 mmol) of Compound 8 and 50 mg of Amberlyst 15 (H) were added, and 20 mL of toluene was added, followed by reaction 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 0.597 g of Compound 9 (yield 36%, yellow solid).

The result of analyzing the obtained product was as follows.
¹ H NMR (δ, CDCl ₃ ): 13.6 (s, 1H, OH), 8.44 (s, 1H, N═CH), 7.43-7.12 (m, 11H, Ar—H) , 7.01-6.93 (m, 3H, Ar -H), 6.68 (s, 1H, Ar-H), 3.77 (s, 3H, OCH 3), 2.10 (bs, 9H , Adamantyl), 1.74 (s, 6H, adamantyl), 1.65 (s, 6H, CH ₃ )

充分に乾燥した１００ｍＬシュレンクフラスコ（磁気攪拌子入り）にＴｉＣｌ₄のトルエン溶液（１．０ｍｍｏｌ／ｍＬ）を０．８８ｍＬ（０．８８ｍｍｏｌ）、トルエンを２０ｍＬ加え−７８℃に冷却した。この混合液に化合物９を０．４４５ｇ（０．８ｍｍｏｌ）をトルエン５ｍＬに溶かし滴下した後、室温まで昇温させつつ１８時間反応させた。この反応液を減圧下で約５ｍＬまで濃縮した後、ヘキサン２０ｍＬを加え析出させ、析出物をろ取し、ヘキサン２０ｍＬで洗浄後、乾燥させることにより、化合物１０を０．２９４ｇ（収率 ５２％、オレンジ色固体）得た。

To a sufficiently dried 100 mL Schlenk flask (with magnetic stirrer), 0.88 mL (0.88 mmol) of a toluene solution of TiCl ₄ (1.0 mmol / mL) and 20 mL of toluene were added and cooled to −78 ° C. To this mixed solution, 0.445 g (0.8 mmol) of Compound 9 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, 20 mL of hexane was added for precipitation, the precipitate was collected by filtration, washed with 20 mL of hexane, and dried to give 0.294 g of Compound 10 (yield 52%). Orange solid).

The result of analyzing the obtained product was as follows.
¹ H NMR (δ, CDCl ₃ ): 8.09 (s, 1H, N═CH), 7.47-7.07 (m, 15H, Ar—H), 4.43 (s, 3H, OCH ₃₎ ), 2.13 (bs, 6H, adamantyl), 2.12 (bs, 3H, adamantyl), 1.90 (d, 3H, J = 12 Hz, adamantyl), 1.81 (d, 3H, J = 12 Hz) , Adamantyl), 1.64 (s, 6H, CH ₃ )

[Synthesis Example 4]
(Synthesis of Compound 14)

充分に乾燥した２００ｍＬ三口ナスフラスコ（滴下ロート、三方コック付、磁気攪拌子入り）に４−ｉｓｏｐｒｏｐｙｌｐｈｅｎｏｌ（和光純薬工業株式会社製）３．４１ｇ（２５ｍｍｏｌ）、１−ａｄａｍａｎｔａｎｏｌを４．１９ｇ（２７．５ｍｍｏｌ） ジクロロメタン５０ｍＬを加え、氷浴にて０℃まで冷却した後、硫酸２．７０ｇ（２７．５ｍｍｏｌ）を滴下した後、そのまま１時間反応させた。この反応液を１．０ｍｏｌ／Ｌの水酸化ナトリウム水溶液５０ｍＬで二回、純水５０ｍＬで一回洗浄し、有機相をＭｇＳＯ₄で乾燥させ、溶媒を減圧下で留去することにより粗生成物を得た。粗生成物をメタノールから再結晶することにより化合物１１を６．３０ｇ（９３％、白色固体）を得た。

In a well-dried 200 mL three-necked eggplant flask (with dropping funnel, three-way cock, with magnetic stirrer), 4-isopropylphenol (manufactured by Wako Pure Chemical Industries, Ltd.) 3.41 g (25 mmol), 4.19 g of 1-adamantanol (27) 0.5 mmol) After adding 50 mL of dichloromethane and cooling to 0 ° C. in an ice bath, 2.70 g (27.5 mmol) of sulfuric acid was added dropwise, and the reaction was allowed to proceed for 1 hour. This reaction solution was washed twice with 50 mL of 1.0 mol / L aqueous sodium hydroxide solution and once with 50 mL of pure water, the organic phase was dried over MgSO ₄ , and the solvent was distilled off under reduced pressure to obtain a crude product. Got. The crude product was recrystallized from methanol to obtain 6.30 g (93%, white solid) of Compound 11.

The result of analyzing the obtained product was as follows.
¹ H NMR (δ, CDCl ₃ ): 7.06 (d, 1H, J = 2.3 Hz, Ar—H), 6.91 (d, 1H, J = 2.3, 8.3 Hz, Ar—H) ), 6.57 (d, 1H, J = 8.3 Hz, Ar-H), 4.59 (s, 1H, OH), 2.83 (sept, 1H, J = 6.9 Hz, CH), 2 .13 (bs, 6H, adamantyl), 2.08 (bs, 3H, adamantyl), 1.78 (bs, 6H, adamantyl), 1.22 (d, 6H, J = 6.9 Hz, CH ₃ )

充分に乾燥した２００ｍＬ三口ナスフラスコ（滴下ロート、三方コック付、磁気攪拌子入り）に化合物１１ ５．４１ｇ（２０ｍｍｏｌ）、テトラヒドロフラン４０ｍＬを加え氷浴にて０℃まで冷却した後、ＥｔＭｇＢｒのテトラヒドロフラン溶液（１．０ｍｍｏｌ／ｍＬ）２２ｍＬ（２２ｍｍｏｌ）を滴下し、そのまま室温まで昇温させつつ１時間反応させた。この反応液に、パラホルムアルデヒド１．５２ｇ（５０ｍｍｏｌ）、トリエチルアミン３．０４ｍＬ（３０ｍｍｏｌ）を加え、６０℃にて４時間反応させた。この反応液にトルエン１００ｍＬを加えた後、１０ｗｔ％塩酸水２０ｍＬを加え、分液した後、有機相を純水５０ｍＬで二回洗浄しＭｇＳＯ₄で乾燥させ、溶媒を減圧下で留去することにより粗生成物を得た。粗生成物をエタノールから再結晶することにより目的物を３．９０ｇ（６０％、白色固体）を得た。

A well-dried 200 mL three-necked eggplant flask (with a dropping funnel, with a three-way cock, with a magnetic stirrer) was added 5.41 g (20 mmol) of Compound 11 and 40 mL of tetrahydrofuran, cooled to 0 ° C. in an ice bath, and then a tetrahydrofuran solution of EtMgBr. (1.0 mmol / mL) 22 mL (22 mmol) was added dropwise, and the reaction was allowed to proceed to room temperature for 1 hour. To this reaction solution, 1.52 g (50 mmol) of paraformaldehyde and 3.04 mL (30 mmol) of triethylamine were added and reacted at 60 ° C. for 4 hours. To this reaction solution is added 100 mL of toluene, 20 mL of 10 wt% hydrochloric acid is added, and the mixture is separated. The organic phase 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 crude product was recrystallized from ethanol to obtain 3.90 g (60%, white solid) of the target product.

The result of analyzing the obtained product was as follows.
¹ H NMR (δ, CDCl ₃ ): 11.6 (s, 1H, OH), 9.85 (s, 1H, O═CH), 7.34 (d, 1H, J = 2.3, Ar— H), 7.20 (d, 1H, J = 2.3 Hz, Ar-H), 2.83 (sept, 1H, J = 6.9 Hz, CH), 2.15 (bs, 6H, adamantyl), 2.09 (bs, 3H, adamantyl), 1.78 (bs, 6H, adamantyl), 1.25 (d, 6H, J = 6.9 Hz, CH ₃ )

充分に乾燥した１００ｍＬナスフラスコ（三方コック、ディーン・スターク管、ジムロート付、磁気攪拌子入り）に２’−ｍｅｔｈｏｘｙｂｉｐｈｅｎｙｌ−２−ａｍｉｎｅを０．８７７ｇ（４．４ｍｍｏｌ）、化合物１２を１．１９ｇ（４．０ｍｍｏｌ）、アンバーリスト１５（Ｈ）を１２０ｍｇ加えトルエン２０ｍＬ加えた後、還流下で３時間反応させた。この反応液から不溶物をろ過にて取り除いた後、溶媒を減圧下で留去し、エタノールから再結晶することにより化合物１３を１．５５ｇ（収率 ３２％、黄色固体）得た。

In a well-dried 100 mL eggplant flask (three-way cock, Dean-Stark tube, with Dimroth, with magnetic stirrer), 0.877 g (4.4 mmol) of 2′-methoxybiphenyl-2-amine and 1.19 g of Compound 12 ( 4.0 mmol), 120 mg of Amberlyst 15 (H) was added, and 20 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 1.55 g of Compound 13 (yield 32%, yellow solid).

The result of analyzing the obtained product was as follows.
¹ H NMR (δ, CDCl ₃ ): 13.5 (s, 1H, OH), 8.50 (s, 1H, N═CH), 7.45-7.10 (m, 7H, Ar—H) 7.01-6.92 (m, 3H, Ar-H), 3.77 (s, 3H, OCH ₃ ), 2.83 (sept, 1H, J = 6.9 Hz, CH) 2.11. bs, 6H, adamantyl), 2.07 (bs, 3H, adamantyl), 1.77 (bs, 6H, adamantyl), 1.25 (d, 6H, J = 6.9 Hz, CH ₃ )

充分に乾燥した１００ｍＬシュレンクフラスコ（磁気攪拌子入り）にＴｉＣｌ₄のトルエン溶液（１．０ｍｍｏｌ／ｍＬ）を１．１０ｍＬ（１．１０ｍｍｏｌ）、トルエンを２０ｍＬ加え−７８℃に冷却した。この混合液に化合物１３を０．４８０ｇ（１．０ｍｍｏｌ）をトルエン５ｍＬに溶かし滴下した後、室温まで昇温させつつ１６時間反応させた。この反応液を減圧下で約２ｍＬまで濃縮した後、ヘキサン１０ｍＬを加え析出させ、析出物をろ取し、ヘキサン２０ｍＬで洗浄後、乾燥させることにより、化合物１４を０．５１４ｇ（収率 ８１％、赤褐色固体）得た。

To a well-dried 100 mL Schlenk flask (with a magnetic stirrer), 1.10 mL (1.10 mmol) of a toluene solution of TiCl ₄ (1.0 mmol / mL) and 20 mL of toluene were added and cooled to −78 ° C. In this mixed solution, 0.480 g (1.0 mmol) of Compound 13 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 2 mL under reduced pressure, 10 mL of hexane was added for precipitation, the precipitate was collected by filtration, washed with 20 mL of hexane, and dried to obtain 0.514 g of Compound 14 (yield 81%) A reddish brown solid).

The result of analyzing the obtained product was as follows.
¹ H NMR (δ, CDCl ₃ ): 8.16 (s, 1H, N═CH), 7.49-7.26 (m, 8H, Ar—H), 7.15-7.10 (m, 2H, Ar-H), 4.43 (s, 3H, OCH 3), 2.88 (sept, 1H, J = 6.8Hz, CH), 2.22 (bs, 6H, adamantyl), 2.16 (Bs, 3H, adamantyl), 1.93 (d, 3H, J = 12 Hz, adamantyl), 1.79 (d, 3H, J = 12 Hz, adamantyl), 1.21 (dd, 6H, J = 2. 2,6.8 Hz, CH ₃ )

[Synthesis Example 5]
(Synthesis of Compound 19)

充分に乾燥した１００ｍＬ三口ナスフラスコ（滴下ロート、三方コック付、磁気攪拌子入り）に４−ｂｒｏｍｏｐｈｅｎｏｌ（東京化成工業株式会社製）を３．４６ｇ（２０ｍｍｏｌ）、１−ａｄａｍａｎｔａｎｏｌを３．０４ｇ（２０ｍｍｏｌ） ジクロロメタン３０ｍＬを加え、氷浴にて０℃まで冷却した後、硫酸１．０７ｍＬ（２０ｍｍｏｌ）を滴下した後、そのまま１時間反応させた。この反応液を飽和炭酸水素ナトリウム水溶液１００ｍＬで中和し、ジクロロメタン５０ｍＬ×２で抽出したのち、有機相を純水５０ｍＬで二回洗浄し、ＭｇＳＯ₄で乾燥させ、溶媒を減圧下で留去することにより粗生成物を得た。粗生成物をヘキサンを用いて再沈殿することにより化合物１５を４．６１ｇ（７５％、白色固体）得た。

In a well-dried 100 mL three-necked eggplant flask (with dropping funnel, with three-way cock, with magnetic stirrer), 3.46 g (20 mmol) of 4-bromophenol (manufactured by Tokyo Chemical Industry Co., Ltd.) and 3.04 g (20 mmol) of 1-adamantanol After adding 30 mL of dichloromethane and cooling to 0 ° C. in an ice bath, 1.07 mL (20 mmol) of sulfuric acid was added dropwise, and the reaction was allowed to proceed for 1 hour. The reaction solution is neutralized with 100 mL of saturated aqueous sodium hydrogen carbonate solution and extracted with 50 mL × 2 of dichloromethane. The organic phase is washed twice with 50 mL of pure water, dried over MgSO ₄ , and the solvent is distilled off under reduced pressure. This gave a crude product. The crude product was reprecipitated with hexane to obtain 4.61 g (75%, white solid) of Compound 15.

The result of analyzing the obtained product was as follows.
¹ H NMR (δ, CDCl ₃ ): 7.29 (d, 1H, J = 2.3 Hz, Ar—H), 7.15 (dd, 1H, J = 8.6 Hz, 2.3 Hz, Ar—H) ), 6.53 (d, 1H, J = 8.6 Hz, Ar-H), 2.08 (bs, 9H, adamantyl), 1.77 (s, 6H, adamantyl)

充分に乾燥した１００ｍＬ三口ナスフラスコ（滴下ロート、三方コック付、磁気攪拌子入り）に化合物１５を１．０ｇ（３．２５ｍｍｏｌ）、テトラヒドロフラン１５ｍＬを加え、−７８℃まで冷却した後、ノルマルブチルリチウムのヘキサン溶液（関東化学株式会社製）（１．６ｍｏｌ／Ｌ）２．０ｍＬ（３．２０ｍｍｏｌ）、塩化トリイソプロピルシリル（東京化成工業株式会社製）１．０２ｍＬ（８．１２ｍｍｏｌ）をテトラヒドロフラン１０ｍＬに溶解させたものを順に滴下し、温度を保ったまま３０分間反応させた。そののちさらにノルマルブチルリチウムのヘキサン溶液（１．６ｍｏｌ／Ｌ）２．１ｍＬ（３．３６ｍｍｏｌ）を滴下し、ゆっくり室温まで昇温してそのまま３時間反応させた。この反応液に１０ｗｔ％塩酸水５０ｍＬを加えた後、酢酸エチル５０ｍＬ×３で抽出後、有機層を飽和塩化アンモニウム（関東化学株式会社製）水溶液５０ｍＬ×２で洗浄し、ＭｇＳＯ₄で乾燥させ、溶媒を減圧下で留去することにより、粗生成物を得た。得られた粗生成物をシリカゲルカラムクロマトグラフ （溶離液；ヘキサン／酢酸エチル＝５０／１）を用いて精製することにより、化合物１６を０．６０ｇ（４８％、無色粘性液体）得た。

1.0 g (3.25 mmol) of Compound 15 and 15 mL of tetrahydrofuran were added to a well-dried 100 mL three-necked eggplant flask (with a dropping funnel, with a three-way cock, and a magnetic stirrer), and cooled to −78 ° C. Hexane solution (manufactured by Kanto Chemical Co., Ltd.) (1.6 mol / L) 2.0 mL (3.20 mmol) and triisopropylsilyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) 1.02 mL (8.12 mmol) in 10 mL of tetrahydrofuran The dissolved ones were dropped in order and reacted for 30 minutes while maintaining the temperature. Thereafter, 2.1 mL (3.36 mmol) of a normal butyllithium hexane solution (1.6 mol / L) was added dropwise, and the mixture was slowly warmed to room temperature and allowed to react for 3 hours. 50 mL of 10 wt% hydrochloric acid was added to the reaction solution, and the mixture was extracted with 50 mL × 3 of ethyl acetate, and the organic layer was washed with 50 mL × 2 of saturated aqueous ammonium chloride (manufactured by Kanto Chemical Co., Ltd.) and dried over MgSO ₄ . The solvent was distilled off under reduced pressure to obtain a crude product. The obtained crude product was purified using silica gel column chromatography (eluent: hexane / ethyl acetate = 50/1) to obtain 0.60 g (48%, colorless viscous liquid) of Compound 16.

The result of analyzing the obtained product was as follows.
¹ H NMR (δ, CDCl ₃ ): 7.31 (d, 1H, J = 1.6 Hz, Ar—H), 7.18 (dd, 1H, J = 7.6, 1.6 Hz, Ar—H) ), 6.64 (d, 1H, J = 7.6 Hz, Ar-H), 4.75 (s, 1H, OH), 2.12 (s, 6H, adamantyl), 2.08 (s, 3H) , Adamantyl), 1.79 (s, 6H, adamantyl), 1.33 (sep, 3H, J = 7.3 Hz, CH), 1.06 (d, 18H, J = 7.3 Hz, CH ₃ )

充分に乾燥した１００ｍＬ三口ナスフラスコ（滴下ロート、三方コック付、磁気攪拌子入り）に化合物１６を０．６０ｇ（１．５６ｍｍｏｌ）、テトラヒドロフラン１５ｍＬを加え氷浴にて０℃まで冷却した後、ＥｔＭｇＢｒのテトラヒドロフラン溶液（１．０ｍｍｏｌ／ｍＬ）１．７２ｍＬ（１．７２ｍｍｏｌ）を滴下し、そのまま室温まで昇温させつつ１時間反応させた。この反応液に、パラホルムアルデヒド０．１１７ｇ（３．９ｍｍｏｌ）、トリエチルアミン０．３２ｍＬ（２．３４ｍｍｏｌ）を加え、５０℃にて３時間反応させた。この反応液に１０ｗｔ％塩酸水３０ｍＬを加え、分液した後、有機相を飽和塩化アンモニウム水溶液３０ｍＬで二回洗浄しＭｇＳＯ₄で乾燥させ、溶媒を減圧下で留去することにより粗生成物を得た。粗生成物をシリカゲルカラムクロマトグラフ （溶離液；ヘキサン／酢酸エチル＝５０／１）を用いて精製することにより、目的物を０．４４６ｇ（６９％、淡桃色粘性液体）を得た。

After adding 0.60 g (1.56 mmol) of Compound 16 and 15 mL of tetrahydrofuran to a well-dried 100 mL three-necked eggplant flask (with a dropping funnel, with a three-way cock, and a magnetic stirrer), the mixture was cooled to 0 ° C. in an ice bath, and then EtMgBr. Solution (1.0 mmol / mL) of 1.72 mL (1.72 mmol) was added dropwise and reacted for 1 hour while raising the temperature to room temperature. To this reaction solution, 0.117 g (3.9 mmol) of paraformaldehyde and 0.32 mL (2.34 mmol) of triethylamine were added and reacted at 50 ° C. for 3 hours. To this reaction liquid was added 30 mL of 10 wt% hydrochloric acid and the phases were separated. The organic phase was washed twice with 30 mL of saturated aqueous ammonium chloride solution and dried over MgSO ₄ , and the solvent was distilled off under reduced pressure to obtain a crude product. Obtained. The crude product was purified using silica gel column chromatography (eluent: hexane / ethyl acetate = 50/1) to obtain 0.446 g (69%, pale pink viscous liquid) of the target product.

The result of analyzing the obtained product was as follows.
¹ H NMR (δ, CDCl ₃ ): 11.86 (s, 1H, OH), 9.89 (s, 1H, CHO), 7.56 (d, 1H, J = 1.6 Hz, Ar—H) 7.47 (d, 1H, J = 1.6 Hz, Ar-H), 2.13 (s, 6H, adamantyl), 2.10 (s, 3H, adamantyl), 1.79 (s, 6H, adamantyl), 1.39 (sep, 3H, J = 7.3 Hz, CH), 1.08 (d, 18H, J = 7.3 Hz, CH ₃ )

充分に乾燥した１００ｍＬナスフラスコ（三方コック、ディーン・スターク管、ジムロート付、磁気攪拌子入り）に２’−ｍｅｔｈｏｘｙｂｉｐｈｅｎｙｌ−２−ａｍｉｎｅを０．２３０ｇ（１．１３ｍｍｏｌ）、化合物１７を０．４４６ｇ（１．０８ｍｍｏｌ）、アンバーリスト１５（Ｈ）を１００ｍｇ加えトルエン４０ｍＬ加えた後、還流下で５時間反応させた。この反応液から不溶物をろ過にて取り除いた後、溶媒を減圧下で留去し、エタノールから再結晶することにより化合物１８を０．２９３ｇ（収率 ４５％、黄色固体）得た。

In a well-dried 100 mL eggplant flask (three-way cock, Dean-Stark tube, with Dimroth, with magnetic stirrer), 0.230 g (1.13 mmol) of 2′-methoxybiphenyl-2-amine and 0.446 g of compound 17 ( 1.08 mmol), 100 mg of Amberlyst 15 (H) was added, and 40 mL of toluene was added, followed by reaction under reflux for 5 hours. After removing insolubles from the reaction solution by filtration, the solvent was distilled off under reduced pressure, and recrystallization from ethanol gave 0.293 g (yield 45%, yellow solid) of Compound 18.

The result of analyzing the obtained product was as follows.
¹ H NMR (δ, CDCl ₃ ): 13.83 (s, 1H, OH), 8.53 (s, 1H, C═NH), 7.19-7.48 (m, 8H, Ar—H) 7.01 (d, 1H, J = 7.6 Hz, Ar—H), 6.94 (d, 1H, J = 8.2 Hz, Ar—H), 3.77 (s, 3H, OCH ₃ ). , 2.06-2.14 (m, 9H, adamantyl), 1.78 (m, 6H, adamantyl), 1.35 (sep, 3H, J = 7.3 Hz, CH), 1.05 (d, 18H, J = 7.3 Hz, CH ₃ )

充分に乾燥した５０ｍＬナスフラスコ（三方コック、磁気攪拌子入り）にＴｉＣｌ₄（１．０ｍｏｌ／Ｌトルエン溶液）０．４０ｍＬ（０．４０ｍｍｏｌ）、トルエンを５．０ｍＬ加え−７８℃に冷却した。この混合液に化合物１８を０．２６１ｇ（０．４４ｍｍｏｌ）をトルエン１０ｍＬに溶かし滴下した後、室温まで昇温させつつ１６時間反応させた。この反応液にヘキサン１０ｍＬを加え析出させた後、析出物をろ取し、ヘキサン１０ｍＬで洗浄後、乾燥させることにより、化合物１９を０．０５ｇ（収率 １８％、橙褐色固体）得た。

TiCl ₄ (1.0 mol / L toluene solution) 0.40 mL (0.40 mmol) and toluene 5.0 mL were added to a well-dried 50 mL eggplant flask (with three-way cock and magnetic stirrer), and cooled to −78 ° C. To this mixed solution, 0.261 g (0.44 mmol) of Compound 18 was dissolved and added dropwise in 10 mL of toluene, and then reacted for 16 hours while raising the temperature to room temperature. After adding 10 mL of hexane to this reaction solution to precipitate, the precipitate was collected by filtration, washed with 10 mL of hexane and dried to obtain 0.05 g of Compound 19 (yield 18%, orange brown solid).

The result of analyzing the obtained product was as follows.
¹ H NMR (δ, CDCl ₃ ): 8.19 (s, 1H, C═NH), 7.68 (d, 1H, J = 1.3 Hz, Ar—H), 7.13-7.50 ( m, 9H, Ar-H) , 4.44 (s, 3H, OCH 3), 2.15-2.27 (m, 9H, adamantyl), 1.94 (d, 3H, J = 11.9Hz, adamantyl), 1.79 (d, 3H, J = 11.9 Hz, adamantyl), 1.33 (sep, 3H, J = 7.6 Hz, CH), 1.05 (d, 18H, J = 7.6 Hz) , CH ₃ )

[Synthesis Example 6]
(Synthesis of Compound 21)

充分に乾燥し窒素置換した１００ｍＬナスフラスコ（三方コック、磁気攪拌子入り）に２’‐ｍｅｔｈｏｘｙｂｉｐｈｅｎｙｌ‐２‐ａｍｉｎｅを０．６４ｇ（３．２２ｍｍｏｌ）、３−ａｄａｍａｎｔｙｌ−２−ｈｙｄｒｏｘｙ−５−ｐｈｅｎｙｌｂｅｎｚａｌｄｅｈｙｄｅを１．０６ｇ（３．２０ｍｍｏｌ）加えトルエン２０ｍＬに溶解させ、アンバーリスト１５（Ｈ）を１．１ｇ加え、加熱還流下８時間反応させた。反応液を濃縮し、ヘキサンを２０ｍＬ加え静置すると結晶が析出した。結晶をろ過し、ヘキサンで洗浄した後、減圧乾燥することにより化合物２０を１．３９ｇ（収率 ８４％、黄色固体）得た。

In a 100 mL eggplant flask (three-way cock, with magnetic stirrer) thoroughly dried and purged with nitrogen, 0.64 g (3.22 mmol) of 2′-methoxybiphenyl-2-amine and 3-adamantyl-2-hydroxy-5-phenylbenzaldehyde were added. 1.06 g (3.20 mmol) was added and dissolved in 20 mL of toluene, 1.1 g of Amberlyst 15 (H) was added, and the mixture was reacted for 8 hours under heating and reflux. The reaction solution was concentrated, 20 mL of hexane was added, and the mixture was allowed to stand to precipitate crystals. The crystals were filtered, washed with hexane, and dried under reduced pressure to obtain 1.39 g of Compound 20 (yield 84%, yellow solid).

The result of analyzing the obtained product was as follows.
¹ H NMR (δ, CDCl ₃ ): 13.81 (s, 1H, OH), 8.58 (s, 1H, N═CH), 7.55-7.21 (m, 13H, Ar—H) 7.03 (dd, 1H, J = 7.42, 0.99 Hz, Ar-H), 699-6.94 (m, 1H, Ar-H), 3.77 (s, 3H, OCH) ₃ ), 2.16 (bs, 6H, adamantyl), 2.09 (bs, 3H, adamantyl), 1.79 (bs, 6H, adamantyl)

充分に乾燥し窒素置換した１００ｍＬ二口ナスフラスコ（三方コック付、磁気攪拌子入り）に四塩化チタン ２．６０ｍＬ（２．６０ｍｍｏｌ、１Ｍトルエン溶液）を加えさらにトルエン２０ｍＬを加えた。この溶液を−７８℃まで冷却した後に、化合物２０ １．３４ｇ（２．６１ｍｍｏｌ）を含むトルエン溶液２０ｍＬを１５分間かけて滴下した。この反応液を徐々に室温まで昇温させつつ１５時間反応させた。反応溶媒を全て留去した後、ジエチルエーテル３０ｍＬを加え、不溶の固体をろ取しジエチルエーテル（関東化学株式会社製）で洗浄し、減圧乾燥することにより化合物２１を１．１０ｇ（６３％、赤褐色固体）得た。

2. 100 mL of titanium tetrachloride (2.60 mmol, 1M toluene solution) was added to a 100 mL two-necked eggplant flask (with a three-way cock, with a magnetic stirrer) that had been thoroughly dried and purged with nitrogen, and 20 mL of toluene was further added. After this solution was cooled to −78 ° C., 20 mL of a toluene solution containing 1.34 g (2.61 mmol) of Compound 20 was added dropwise over 15 minutes. The reaction was allowed to react for 15 hours while gradually warming to room temperature. After all the reaction solvent was distilled off, 30 mL of diethyl ether was added, the insoluble solid was collected by filtration, washed with diethyl ether (manufactured by Kanto Chemical Co., Inc.), and dried under reduced pressure to give 1.10 g (63%, 63%, A reddish brown solid) was obtained.

The result of analyzing the obtained product was as follows.
¹ H NMR (δ, CDCl ₃ ): 8.24 (s, 1H, N═CH), 7.79 (d, 1H, J = 2.23 Hz, Ar—H), 7.54-7.26 ( m, 13H, Ar-H) , 7.20-7.17 (m, 1H, Ar-H), 4.43 (s, 3H, OCH 3), 2.28 (bs, 6H, adamantyl), 2 .18 (bs, 3H, adamantyl), 1.95 (d, 3H, J = 12 Hz, adamantyl), 1.81 (d, 3H, J = 12 Hz, adamantyl)
FD-MS: m / z = 667 (M ⁺ ), 615 (M ⁺ —CH ₃ Cl) C ₃₆ H ₃₄ Cl ₃ NO ₂ Ti

[Synthesis Example 7]
(Synthesis of Compound 23)

充分に乾燥した１００ｍＬナスフラスコ（三方コック、ディーン・スターク管、ジムロート付、磁気攪拌子入り）に２’−ｅｔｈｏｘｙｂｉｐｈｅｎｙｌ−２−ａｍｉｎｅ（国際公開第２００９／５００３号パンフレットの記載に従い合成した。）を０．４４８ｇ（２．１ｍｍｏｌ）、３‐ａｄａｍａｎｔｙｌ‐５‐ｔｅｒｔ−ｂｕｔｙｌ‐２‐ｈｙｄｒｏｘｙｂｅｎｚａｌｄｅｈｙｄｅを０．６２５ｇ（２．０ｍｍｏｌ）、アンバーリスト１５（Ｈ）を６３ｍｇ加えトルエン２０ｍＬ加えた後、還流下で３時間反応させた。この反応液から不溶物をろ過にて取り除いた後、溶媒を減圧下で留去し、エタノールから再結晶することにより化合物２２を０．５２５ｇ（収率 ５２％、黄色固体）得た。

2′-ethoxybiphenyl-2-amine (synthesized as described in International Publication No. 2009/5003 pamphlet) was placed in a well-dried 100 mL eggplant flask (three-way cock, Dean-Stark tube, fitted with a Dimroth, with magnetic stirrer). 0.448 g (2.1 mmol), 3-adamantyl-5-tert-2-butyl-2-hydroxybenzaldehyde (0.625 g (2.0 mmol)), Amberlyst 15 (H) (63 mg) and toluene (20 mL) were added. The reaction was performed 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 0.525 g (yield 52%, yellow solid) of Compound 22.

The result of analyzing the obtained product was as follows.
¹ H NMR (δ, CDCl ₃ ): 13.6 (s, 1H, OH), 8.50 (s, 1H, N═CH), 7.44-7.10 (m, 8H, Ar—H) , 6.99-6.89 (m, 2H, Ar -H), 4.01 (q, 2H, J = 6.8Hz, OCH 2), 2.11 (s, 6H, adamantyl), 2.07 (S, 3H, adamantyl), 1.77 (s, 6H, adamantyl), 1.29 (s, 9H, C (CH ₃ ) ₃ ), 1.26 (t, 3H, J = 6.8 Hz, CH ₃ )

充分に乾燥した１００ｍＬシュレンクフラスコ（磁気攪拌子入り）にＴｉＣｌ₄のトルエン溶液（１．０ｍｍｏｌ／ｍＬ）を１．１ｍＬ（１．１ｍｍｏｌ）、トルエン２０ｍＬを加え−７８℃にドライアイス−メタノールバスにて冷却した。この混合液に化合物２２を０．５０８ｇ（１．０ｍｍｏｌ）トルエン５ｍＬに溶かし滴下した後、室温まで昇温させつつ１４時間反応させた。この反応液を減圧下で約５ｍＬまで濃縮した後に、ヘキサン１０ｍＬを加え析出させた。析出物をろ取し、ヘキサン２０ｍＬで洗浄後、乾燥させることにより、化合物２３を０．４９３ｇ（収率 ７５％、赤紫色固体）得た。

To a well-dried 100 mL Schlenk flask (with magnetic stirrer), add 1.1 mL (1.1 mmol) of a toluene solution of TiCl ₄ (1.0 mmol / mL) and 20 mL of toluene to a dry ice-methanol bath at −78 ° C. And cooled. Compound 22 was dissolved in 0.508 g (1.0 mmol) of toluene (5 mL) and added dropwise to this mixed solution, and then reacted for 14 hours while raising the temperature to room temperature. The reaction solution was concentrated to about 5 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 0.493 g of Compound 23 (yield 75%, red purple solid).

The result of analyzing the obtained product was as follows.
¹ H NMR (δ, CDCl ₃ ): 8.17 (s, 1H, N═CH), 7.61 (s, 1H, Ar—H), 7.61-7.09 (m, 9H, Ar— H), 5.49-5.42 (m, 1H , OCH 2), 4.85-4.78 (m, 1H, OCH 2), 2.24-2.16 (m, 9H, adamantyl), 1.93 (d, 3H, J = 12 Hz, adamantyl), 1.79 (d, 3H, J = 12 Hz, adamantyl), 1.28 (s, 9H, C (CH ₃ ) ₃ ), 0.95 ( t, 3H, J = 7.0 Hz, CH ₃ )

[Synthesis Example 8]
(Synthesis of Compound 25)

充分に乾燥した１００ｍＬナスフラスコ（三方コック、ディーン・スターク管、ジムロート付、磁気攪拌子入り）に２’−ｍｅｔｈｏｘｙ−５−ｍｅｔｈｙｌｂｉｐｈｅｎｙｌ−２−ａｍｉｎｅ（国際公開第２００９／５００３号パンフレットの記載に従い合成した。）を０．４４８ｇ（２．１ｍｍｏｌ）、３‐ａｄａｍａｎｔｙｌ‐５‐ｔｅｒｔ−ｂｕｔｙｌ‐２‐ｈｙｄｒｏｘｙｂｅｎｚａｌｄｅｈｙｄｅを０．６２５ｇ（２．０ｍｍｏｌ）、アンバーリスト１５（Ｈ）を６３ｍｇ加えトルエン２０ｍＬ加えた後、還流下で３時間反応させた。この反応液から不溶物をろ過にて取り除いた後、溶媒を減圧下で留去し、エタノールから再結晶することにより化合物２４を０．２８４ｇ（収率 ２８％、黄色固体）得た。

2′-methoxy-5-methylbiphenyl-2-amine (synthesized as described in 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) 0.448 g (2.1 mmol), 3-adamantyl-5-tert-2-butyl-2-hydroxybenzaldehyde (0.625 g (2.0 mmol)), Amberlyst 15 (H) (63 mg) and toluene (20 mL) were added. And 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 0.284 g (yield 28%, yellow solid) of Compound 24.

The result of analyzing the obtained product was as follows.
¹ H NMR (δ, CDCl ₃ ): 13.6 (s, 1H, OH), 8.51 (s, 1H, N═CH), 7.35-7.7.09 (m, 7H, Ar— H), 7.00-6.92 (m, 2H , Ar-H), 3.78 (s, 3H, OCH 3), 2.38 (s, 3H, CH 3), 2.11 (s, 6H, adamantyl), 2.07 (s, 3H, adamantyl), 1.77 (s, 6H, adamantyl), 1.28 (s, 9H, C (CH ₃ ) ₃ )

充分に乾燥した１００ｍＬシュレンクフラスコ（磁気攪拌子入り）にＴｉＣｌ₄のトルエン溶液（１．０ｍｍｏｌ／ｍＬ）を０．５５ｍＬ（０．５５ｍｍｏｌ）、トルエン２０ｍＬを加え−７８℃にドライアイス−メタノールバスにて冷却した。この混合液に化合物２４を０．２５４ｇ（０．５ｍｍｏｌ）トルエン５ｍＬに溶かし滴下した後、室温まで昇温させつつ１４時間反応させた。この反応液を減圧下で約５ｍＬまで濃縮した後に、ヘキサン１０ｍＬを加え析出させた。析出物をろ取し、ヘキサン２０ｍＬで洗浄後、乾燥させることにより、化合物２５を０．２２６ｇ（収率 ６８％、赤褐色固体）得た。

To a well-dried 100 mL Schlenk flask (with magnetic stirrer), add 0.55 mL (0.55 mmol) of a TiCl ₄ toluene solution (1.0 mmol / mL) and 20 mL of toluene to −78 ° C. in a dry ice-methanol bath. And cooled. Compound 24 was dissolved in 5 mL of 0.254 g (0.5 mmol) of toluene in this mixed solution and dropped, and then reacted for 14 hours while raising the temperature to room temperature. The reaction solution was concentrated to about 5 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 0.226 g of Compound 25 (yield 68%, reddish brown solid).

The result of analyzing the obtained product was as follows.
¹ H NMR (δ, CDCl ₃ ): 8.16 (s, 1H, N═CH), 7.61 (s, 1H, Ar—H), 7.48-7.12 (m, 7H, Ar— H), 6.98 (d, 1H , J = 7.8Hz, Ar-H), 4.45 (s, 3H, OCH 3), 2.44 (s, 3H, CH 3), 2.21 ( s, 6H, adamantyl), 2.16 (s, 3H, adamantyl), 1.93 (d, 3H, J = 12 Hz, adamantyl), 1.79 (d, 3H, J = 12 Hz, adamantyl), 1. 28 (s, 9H, C (CH ₃ ) ₃ )

[Synthesis Example 9]
(Synthesis of Compound 29)

充分に乾燥した３００ｍＬ三口ナスフラスコ（滴下ロート、三方コック付、磁気攪拌子入り）に４−ｔｒｉｍｅｔｈｙｌｓｉｌｙｌａｎｉｓｏｌｅを１．０ｇ（５．６ｍｍｏｌ）、ヘキサン３０ｍＬを加え、氷浴にて０℃まで冷却した後、Ｎ，Ｎ，Ｎ’，Ｎ’−テトラメチルエチレンジアミン（東京化成工業株式会社製）０．８８ｍＬ（５．８３ｍｍｏｌ）を加え、ノルマルブチルリチウムのヘキサン溶液（１．６ｍｏｌ／Ｌ）３．６４ｍＬ（５．８３ｍｍｏｌ）を滴下した後、１６時間反応させた。５００ｍＬ三口ナスフラスコ（三方コック付、磁気攪拌子入り）にヘキサン４０ｍＬ、ホウ酸トリメチル（シグマ アルドリッチ ジャパン 株式会社製）１．８６ｍＬ（１６．７ｍｍｏｌ）を加えた後、−７８℃に冷却した後に、先ほど調製した反応液を滴下し、そのまま室温まで昇温させつつ３時間反応させた。この反応液に飽和塩化アンモニウム水溶液５０ｍＬを加えた後、酢酸エチル５０ｍＬ×３で抽出後、有機層を純水５０ｍＬ×２で洗浄し、ＭｇＳＯ₄で乾燥させ、溶媒を減圧下で留去することにより、粗生成物を得た。得られた粗生成物をヘキサンから再沈殿することにより、化合物２６を０．７１５ｇ（６０％、白色固体）得た。

After adding 1.0 g (5.6 mmol) of 4-trimethylsilylanisole and 30 mL of hexane to a well-dried 300 mL three-necked eggplant flask (with a dropping funnel, with a three-way cock, and a magnetic stirrer), the mixture was cooled to 0 ° C. in an ice bath. , N, N, N ′, N′-tetramethylethylenediamine (manufactured by Tokyo Chemical Industry Co., Ltd.) 0.88 mL (5.83 mmol) was added, and hexane solution of normal butyl lithium (1.6 mol / L) 3.64 mL ( 5.83 mmol) was added dropwise, followed by reaction for 16 hours. After adding 40 mL of hexane and trimethyl borate (manufactured by Sigma Aldrich Japan Co., Ltd.) 1.86 mL (16.7 mmol) to a 500 mL three-necked eggplant flask (with a three-way cock, with a magnetic stirrer), cooling to −78 ° C. The reaction solution prepared earlier was added dropwise and reacted for 3 hours while raising the temperature to room temperature. After adding 50 mL of saturated aqueous ammonium chloride solution to this reaction solution, and extracting with 50 mL × 3 ethyl acetate, the organic layer is washed with 50 mL × 2 pure water, dried over MgSO ₄ , and the solvent is distilled off under reduced pressure. Gave a crude product. The obtained crude product was reprecipitated from hexane to obtain 0.715 g (60%, white solid) of Compound 26.

The result of analyzing the obtained product was as follows.
¹ H NMR (δ, CDCl ₃ ): 8.00 (d, 1H, J = 2.0 Hz, Ar—H), 7.61 (dd, 1H, J = 8.2, 2.0 Hz, Ar—H) ), 6.92 (d, 1H, J = 8.2 Hz, Ar-H), 5.95 (s, 2H, B (OH) ₂ ), 3.92 (s, 3H, OCH ₃ ), 0. 26 (s, 9H, Si (CH ₃ ) ₃ )

充分に乾燥した１００ｍＬ三口ナスフラスコ（コンデンサー、三方コック付、磁気攪拌子入り）に化合物２６を０．６ｇ（２．７ｍｍｏｌ）、２−ｃｈｌｏｒｏａｎｉｌｉｎｅ（東京化成工業株式会社製）を０．２９ｍＬ（２．８４ｍｍｏｌ）、１，３−ｂｉｓ−（２，６−ｄｉｉｓｏｐｒｏｐｙｌｐｈｅｎｙｌ）ｉｍｉｄａｚｏｌｉｕｍ−（ａｌｌｙｌ）−ｐａｌｌａｄｉｕｍ（ＩＩ）−ｃｈｌｏｒｉｄｅ（シグマ アルドリッチ ジャパン 株式会社製）を０．００８ｇ（０．００２ｍｍｏｌ）、水酸化バリウム八水和物（和光純薬工業株式会社製）０．９ｇ（２．８４ｍｍｏｌ）加え、イソプロピルアルコール（関東化学株式会社製）３０ｍＬに溶解させ、８０℃で３時間反応させた。反応後固体残さをろ過によって取り除き、溶媒を減圧下で留去することにより粗生成物を得た。粗生成物をシリカゲルカラムクロマトグラフ（溶離液；ヘキサン／酢酸エチル＝１０／１）を用いて精製することにより化合物２７を０．６０６ｇ（８３％、淡褐色液体）得た。

In a well-dried 100 mL three-necked eggplant flask (condenser, with a three-way cock, with a magnetic stirrer), 0.6 g (2.7 mmol) of compound 26 and 0.29 mL (2) of 2-chloroaniline (Tokyo Chemical Industry Co., Ltd.) .84 mmol), 1,3-bis- (2,6-diisopropylphenyl) imidazolium- (allyl) -palladium (II) -chloride (manufactured by Sigma Aldrich Japan Co., Ltd.), 0.008 g (0.002 mmol), barium hydroxide 0.9 g (2.84 mmol) of octahydrate (Wako Pure Chemical Industries, Ltd.) was added, dissolved in 30 mL of isopropyl alcohol (Kanto Chemical Co., Ltd.), and reacted at 80 ° C. for 3 hours. After the reaction, 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 0.606 g (83%, light brown liquid) of Compound 27.

The result of analyzing the obtained product was as follows.
¹ H NMR (δ, CDCl ₃ ): 7.50 (dd, 1H, J = 8.2, 1.6 Hz, Ar—H), 7.39 (d, 1H, J = 1.6 Hz, Ar—H) ), 7.18 (td, 1H, J = 7.9, 1.3 Hz, Ar-H), 7.12 (dd, 1H, J = 7.6, 1.6 Hz, Ar-H), 7. 00 (d, 1H, J = 8.2 Hz, Ar-H), 6.84 (td, 1H, J = 7.6, 1.3 Hz, Ar-H), 6.78 (dd, 1H, J = 7.9,1.3Hz, Ar-H), 3.81 (s, 3H, OCH 3), 3.69 (bs, 2H, NH 2).

充分に乾燥した１００ｍＬナスフラスコ（三方コック、ディーン・スターク管、ジムロート付、磁気攪拌子入り）に化合物２７を０．３７ｇ（１．４ｍｍｏｌ）、３‐ａｄａｍａｎｔｙｌ‐２‐ｈｙｄｒｏｘｙ‐５‐ｍｅｔｙｌｂｅｎｚａｌｄｅｈｙｄｅ０．３９ｇ（１．４７ｍｍｏｌ）、エタノール２５ｍＬを加えた後、還流下で６時間反応させた。この反応液から不溶物をろ過にて取り除いた後、溶媒を減圧下で留去し、エタノールから再結晶することにより化合物２８を０．４４２ｇ（収率 ６２％、橙色固体）得た。

0.37 g (1.4 mmol) of compound 27 in a well-dried 100 mL eggplant flask (three-way cock, Dean-Stark tube, with Dimroth, with magnetic stirrer), 0.39 g of 3-adamantyl-2-hydroxy-5-methylbenzaldehyde 0.39 g (1.47 mmol) and ethanol (25 mL) were added, followed by reaction under reflux for 6 hours. After removing insolubles from the reaction solution by filtration, the solvent was distilled off under reduced pressure, and recrystallization from ethanol gave 0.442 g (yield 62%, orange solid) of Compound 28.

The result of analyzing the obtained product was as follows.
¹ H NMR (δ, CDCl ₃ ): 13.4 (s, 1H, OH), 8.44 (s, 1H, N═CH), 7.46-7.33 (m, 5H, Ar—H) 7.18 (d, 1H, J = 7.9 Hz, Ar-H), 7.05 (d, 1H, J = 2.3 Hz, Ar-H), 6.93 (m, 2H, Ar-H) ), 3.76 (s, 3H, OCH ₃ ), 2.26 (s, 3H, CH ₃ ), 2.09-2.06 (m, 9H, adamantyl), 1.77 (s, 6H, adamantyl) ), 0.23 (s, 9H, Si (CH ₃ ) ₃ )

充分に乾燥した１００ｍＬシュレンクフラスコ（磁気攪拌子入り）に四塩化チタンの１．０Ｍトルエン溶液を０．３ｍＬ（０．３ｍｍｏｌ）、トルエンを１０ｍＬ加え、ドライアイス−アセトンバスで−７８℃に冷却した。これに、化合物２８を０．１７３ｇ（０．３３ｍｍｏｌ）トルエン５ｍＬに溶かしたものを滴下した後、室温まで昇温させつつ１５時間反応させた。反応液を３ｍＬまで減圧下で濃縮しヘキサン２０ｍＬを加えた後、析出物をろ取、ヘキサン２０ｍＬで洗浄後、乾燥させることにより、化合物２９を０．０６４ｇ（収率 ３２％、赤褐色固体）得た。

To a well-dried 100 mL Schlenk flask (with magnetic stirrer), 0.3 mL (0.3 mmol) of 1.0 M toluene solution of titanium tetrachloride and 10 mL of toluene were added, and cooled to −78 ° C. with a dry ice-acetone bath. . To this was added dropwise a solution of compound 28 dissolved in 0.173 g (0.33 mmol) of toluene 5 mL, and then allowed to react for 15 hours while raising the temperature to room temperature. The reaction solution was concentrated to 3 mL under reduced pressure, 20 mL of hexane was added, and the precipitate was collected by filtration, washed with 20 mL of hexane, and dried to obtain 0.064 g of Compound 29 (yield 32%, reddish brown solid). It was.

The result of analyzing the obtained product was as follows.
¹ H NMR (δ, CDCl ₃ ): 8.13 (s, 1H, HC = N), 7.52-7.33 (m, 8H, Ar—H), 7.11 (m, 1H, Ar— H), 4.42 (s, 3H , OCH 3), 2.33 (s, 3H, CH 3), 2.33-2.14 (m, 9H, adamantyl), 1.92 (d, 3H, J = 12 Hz, adamantyl), 1.79 (d, 3 H, J = 12 Hz, adamantyl), 0.26 (s, 9 H, Si (CH ₃ ) ₃ )

[Synthesis Example 10]
(Synthesis of Compound 33)

充分に乾燥した３００ｍＬ三口ナスフラスコ（滴下ロート、三方コック付、磁気攪拌子入り）に４−ｐｈｅｎｙｌａｎｉｓｏｌｅ（東京化成工業株式会社製）を２．９５ｇ（１６．０ｍｍｏｌ）、ヘキサン３０ｍＬを加え、氷浴にて０℃まで冷却した後、Ｎ，Ｎ，Ｎ’，Ｎ’−テトラメチルエチレンジアミン（東京化成工業株式会社製）２．６ｍＬ（１６．８ｍｍｏｌ）を加え、ノルマルブチルリチウムのヘキサン溶液（１．６ｍｏｌ／Ｌ）１０．５ｍＬ（１６．８ｍｍｏｌ）を滴下した後、１６時間反応させた。５００ｍＬ三口ナスフラスコ（三方コック付、磁気攪拌子入り）にヘキサン４０ｍＬ、ホウ酸トリメチル（シグマ アルドリッチ ジャパン 株式会社製）５．４ｍＬ（４８．０ｍｍｏｌ）を加えた後、−７８℃に冷却した後に、先ほど調製した反応液を滴下し、そのまま室温まで昇温させつつ３時間反応させた。この反応液に飽和塩化アンモニウム水溶液５０ｍＬを加えた後、酢酸エチル５０ｍＬ×３で抽出後、有機層を純水５０ｍＬ×２で洗浄し、ＭｇＳＯ₄で乾燥させ、溶媒を減圧下で留去することにより、粗生成物を得た。得られた粗生成物をヘキサンから再沈殿することにより、化合物３０を１．９３ｇ（５４％、白色固体）得た。

To a well-dried 300 mL three-necked eggplant flask (with dropping funnel, three-way cock, with magnetic stirrer), 2.95 g (16.0 mmol) of 4-phenylanisole (manufactured by Tokyo Chemical Industry Co., Ltd.) and 30 mL of hexane are added, and an ice bath is added. After cooling to 0 ° C., 2.6 mL (16.8 mmol) of N, N, N ′, N′-tetramethylethylenediamine (manufactured by Tokyo Chemical Industry Co., Ltd.) was added, and a hexane solution of normal butyl lithium (1. 6 mol / L) 10.5 mL (16.8 mmol) was added dropwise, followed by reaction for 16 hours. After adding 40 mL of hexane and 5.4 mL (48.0 mmol) of trimethyl borate (manufactured by Sigma-Aldrich Japan Co., Ltd.) to a 500 mL three-necked eggplant flask (with a three-way cock, with a magnetic stirrer), the mixture was cooled to −78 ° C. The reaction solution prepared earlier was added dropwise and reacted for 3 hours while raising the temperature to room temperature. After adding 50 mL of saturated aqueous ammonium chloride solution to this reaction solution, and extracting with 50 mL × 3 ethyl acetate, the organic layer is washed with 50 mL × 2 pure water, dried over MgSO ₄ , and the solvent is distilled off under reduced pressure. Gave a crude product. The obtained crude product was reprecipitated from hexane to obtain 1.93 g (54%, white solid) of Compound 30.

The result of analyzing the obtained product was as follows.
¹ H NMR (δ, CDCl ₃ ): 8.10 (d, 1H, J = 2.6 Hz, Ar—H), 7.68 (dd, 1H, J = 8.6, 2.6 Hz, Ar—H) ), 7.59 (m, 2H, Ar-H), 7.42 (m, 2H, Ar-H), 7.31 (m, 1H, Ar-H), 7.00 (d, 1H, J = 8.6Hz, Ar-H), 6.04 (s, 2H, B (OH) 2), 3.96 (s, 3H, CH 3)

充分に乾燥した１００ｍＬ三口ナスフラスコ（コンデンサー、三方コック付、磁気攪拌子入り）に化合物３０を０．８ｇ（３．５ｍｍｏｌ）、２−ｃｈｌｏｒｏａｎｉｌｉｎｅ（東京化成工業株式会社製）を０．３９ｍＬ（３．６８ｍｍｏｌ）、１，３−ｂｉｓ−（２，６−ｄｉｉｓｏｐｒｏｐｙｌｐｈｅｎｙｌ）ｉｍｉｄａｚｏｌｉｕｍ−（ａｌｌｙｌ）−ｐａｌｌａｄｉｕｍ（ＩＩ）−ｃｈｌｏｒｉｄｅ（シグマ アルドリッチ ジャパン 株式会社製）を０．０１０ｇ（０．０１８ｍｍｏｌ）、水酸化バリウム八水和物（和光純薬工業株式会社製）１．２ｇ（３．６８ｍｍｏｌ）加え、イソプロピルアルコール（関東化学株式会社製）３０ｍＬに溶解させ、８０℃で３時間反応させた。反応後固体残さをろ過によって取り除き、溶媒を減圧下で留去することにより粗生成物を得た。粗生成物をシリカゲルカラムクロマトグラフ（溶離液；ヘキサン／酢酸エチル＝１０／１）を用いて精製することにより化合物３１を０．７３３ｇ（７６％、淡褐色液体）得た。

In a well-dried 100 mL three-necked eggplant flask (condenser, with a three-way cock, with magnetic stirrer), 0.8 g (3.5 mmol) of compound 30 and 2-chloroaniline (manufactured by Tokyo Chemical Industry Co., Ltd.) 0.39 mL (3 .68 mmol), 1,3-bis- (2,6-diisopropylphenyl) imidazolium- (allyl) -palladium (II) -chloride (manufactured by Sigma Aldrich Japan Co., Ltd.), 0.010 g (0.018 mmol), barium hydroxide 1.2 g (3.68 mmol) of octahydrate (manufactured by Wako Pure Chemical Industries, Ltd.) was added, dissolved in 30 mL of isopropyl alcohol (manufactured by Kanto Chemical Co., Ltd.), and reacted at 80 ° C for 3 hours. After the reaction, 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 0.733 g (76%, light brown liquid) of Compound 31.

The result of analyzing the obtained product was as follows.
¹ H NMR (δ, CDCl ₃ ): 7.61-7.52 (m, 4H, Ar—H), 7.44-7.38 (m, 2H, Ar—H), 7.33-7. 27 (s, 1H, Ar-H), 7.22-7.14 (m, 2H, Ar-H), 7.07 (d, 1H, J = 8.2 Hz, Ar-H), 6.85. (td, 1H, J = 7.6,1.3Hz , Ar-H), 6.80 (d, 1H, J = 8.2Hz, Ar-H), 3.85 (s, 3H, OCH 3) , 3.70 (bs, 2H, NH ₂ )

充分に乾燥した１００ｍＬナスフラスコ（三方コック、ディーン・スターク管、ジムロート付、磁気攪拌子入り）に化合物３１を０．４０ｇ（１．５ｍｍｏｌ）、３‐ａｄａｍａｎｔｙｌ‐２‐ｈｙｄｒｏｘｙ‐５‐ｍｅｔｙｌｂｅｎｚａｌｄｅｈｙｄｅを０．４１ｇ（１．５８ｍｍｏｌ）、エタノール２０ｍＬを加えた後、還流下で６時間反応させた。この反応液から不溶物をろ過にて取り除いた後、溶媒を減圧下で留去し、エタノールから再結晶することにより化合物３２を０．５３１ｇ（収率 ６９％、橙色固体）得た。

In a well-dried 100 mL eggplant flask (three-way cock, Dean Stark tube, with Dimroth, with magnetic stirrer), 0.40 g (1.5 mmol) of compound 31 and 3-adamantyl-2-hydroxy-5-methylbenzaldehyde were 0. .41 g (1.58 mmol) and 20 mL of ethanol were added, and the mixture was reacted for 6 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 0.531 g (yield 69%, orange solid) of Compound 32.

The result of analyzing the obtained product was as follows.
¹ H NMR (δ, CDCl ₃ ): 13.5 (s, 1H, OH), 8.48 (s, 1H, N═CH), 7.60-7.21 (m, 11H, Ar—H) , 7.05-6.94 (m, 3H, Ar -H), 3.79 (s, 3H, OCH 3), 2.26 (s, 3H, CH 3), 2.09-2.06 ( m, 6H, adamantyl), 2.04 (m, 3H, adamantyl), 1.74 (s, 6H, adamantyl)

充分に乾燥した１００ｍＬシュレンクフラスコ（磁気攪拌子入り）に四塩化チタンの１．０Ｍトルエン溶液を０．４ｍＬ（０．４ｍｍｏｌ）、トルエンを１０ｍＬ加え、ドライアイス−アセトンバスで−７８℃に冷却した。これに、化合物３２を０．２３２ｇ（０．４４ｍｍｏｌ）トルエン５ｍＬに溶かしたものを滴下した後、室温まで昇温させつつ１５時間反応させた。反応液を３ｍＬまで減圧下で濃縮しヘキサン２０ｍＬを加えた後、析出物をろ取、ヘキサン２０ｍＬで洗浄後、乾燥させることにより、化合物３３を０．２１３ｇ（収率 ７８％、赤褐色固体）得た。

To a well-dried 100 mL Schlenk flask (with magnetic stirrer), 0.4 mL (0.4 mmol) of 1.0 M toluene solution of titanium tetrachloride and 10 mL of toluene were added, and cooled to -78 ° C with a dry ice-acetone bath. . To this was added dropwise a solution of Compound 32 in 0.232 g (0.44 mmol) of toluene (5 mL), followed by reaction for 15 hours while raising the temperature to room temperature. The reaction solution was concentrated to 3 mL under reduced pressure, 20 mL of hexane was added, and the precipitate was collected by filtration, washed with 20 mL of hexane, and dried to obtain 0.213 g of Compound 33 (yield 78%, reddish brown solid). It was.

The result of analyzing the obtained product was as follows.
¹ H NMR (δ, CDCl ₃ ): 8.15 (s, 1H, HC═N), 7.62-7.12 (m, 14H, Ar—H), 4.45 (s, 3H, OCH ₃₎ ), 2.32 (s, 3H, CH ₃ ), 2.22-2.16 (m, 9H, adamantyl), 1.93 (d, 3H, J = 12 Hz, adamantyl), 1.79 (d, 3H, J = 12Hz, adamantyl)

[Synthesis Example 11]
(Synthesis of Compound 37)

充分に乾燥した３００ｍＬ三口ナスフラスコ（滴下ロート、三方コック付、磁気攪拌子入り）に４−ｔｅｒｔ−ｂｕｔｙｌａｎｉｓｏｌｅを２．８０ｍＬ（１６．０ｍｍｏｌ）、ヘキサン３０ｍＬを加え、氷浴にて０℃まで冷却した後、Ｎ，Ｎ，Ｎ’，Ｎ’−テトラメチルエチレンジアミン（東京化成工業株式会社製）２．６ｍＬ（１６．８ｍｍｏｌ）を加え、ノルマルブチルリチウムのヘキサン溶液（１．６ｍｏｌ／Ｌ）１０．５ｍＬ（１６．８ｍｍｏｌ）を滴下した後、１６時間反応させた。５００ｍＬ三口ナスフラスコ（三方コック付、磁気攪拌子入り）にヘキサン４０ｍＬ、ホウ酸トリメチル（シグマ アルドリッチ ジャパン 株式会社製）５．４ｍＬ（４８．０ｍｍｏｌ）を加えた後、−７８℃に冷却した後に、先ほど調製した反応液を滴下し、そのまま室温まで昇温させつつ３時間反応させた。この反応液に飽和塩化アンモニウム水溶液５０ｍＬを加えた後、酢酸エチル５０ｍＬ×３で抽出後、有機層を純水５０ｍＬ×２で洗浄し、ＭｇＳＯ₄で乾燥させ、溶媒を減圧下で留去することにより、粗生成物を得た。得られた粗生成物をヘキサンから再沈殿することにより、化合物３４を１．７６ｇ（５３％、白色固体）得た。

Add 2.80 mL (16.0 mmol) of 4-tert-butylanisole and 30 mL of hexane to a well-dried 300 mL three-necked eggplant flask (with a dropping funnel, with a three-way cock, and a magnetic stir bar), and cool to 0 ° C. in an ice bath. Then, 2.6 mL (16.8 mmol) of N, N, N ′, N′-tetramethylethylenediamine (manufactured by Tokyo Chemical Industry Co., Ltd.) was added, and a hexane solution of normal butyl lithium (1.6 mol / L) was added. After adding 5 mL (16.8 mmol) dropwise, the reaction was allowed to proceed for 16 hours. After adding 40 mL of hexane and 5.4 mL (48.0 mmol) of trimethyl borate (manufactured by Sigma-Aldrich Japan Co., Ltd.) to a 500 mL three-necked eggplant flask (with a three-way cock, with a magnetic stirrer), the mixture was cooled to −78 ° C. The reaction solution prepared earlier was added dropwise and reacted for 3 hours while raising the temperature to room temperature. After adding 50 mL of saturated aqueous ammonium chloride solution to this reaction solution, and extracting with 50 mL × 3 ethyl acetate, the organic layer is washed with 50 mL × 2 pure water, dried over MgSO ₄ , and the solvent is distilled off under reduced pressure. Gave a crude product. The obtained crude product was reprecipitated from hexane to obtain 1.76 g (53%, white solid) of Compound 34.

The result of analyzing the obtained product was as follows.
¹ H NMR (δ, CDCl ₃ ): 7.67 (d, 1H, J = 2.6 Hz, Ar—H), 7.47 (dd, 1H, J = 8.6, 2.6 Hz, Ar—H) ), 6.86 (d, 1H, J = 8.6 Hz, Ar—H), 5.90 (s, 2H, B (OH) ₂ ), 3.90 (s, 3H, OMe ₃ ), 1. 32 (s, 9H, C (CH ₃ ) ₃ )

充分に乾燥した１００ｍＬ三口ナスフラスコ（コンデンサー、三方コック付、磁気攪拌子入り）に化合物３４を０．８ｇ（３．８ｍｍｏｌ）、２−ｃｈｌｏｒｏａｎｉｌｉｎｅ（東京化成工業株式会社製）を０．４２ｍＬ（３．９９ｍｍｏｌ）、１，３−ｂｉｓ−（２，６−ｄｉｉｓｏｐｒｏｐｙｌｐｈｅｎｙｌ）ｉｍｉｄａｚｏｌｉｕｍ−（ａｌｌｙｌ）−ｐａｌｌａｄｉｕｍ（ＩＩ）−ｃｈｌｏｒｉｄｅ（シグマ アルドリッチ ジャパン 株式会社製）を０．０１１ｇ（０．０１９ｍｍｏｌ）、水酸化バリウム八水和物（和光純薬工業株式会社製）１．３ｇ（３．９９ｍｍｏｌ）加え、イソプロピルアルコール（関東化学株式会社製）３０ｍＬに溶解させ、８０℃で３時間反応させた。反応後固体残さをろ過によって取り除き、溶媒を減圧下で留去することにより粗生成物を得た。粗生成物をシリカゲルカラムクロマトグラフ（溶離液；ヘキサン／酢酸エチル＝１０／１）を用いて精製することにより化合物３５を１．００ｇ（＞９９％、淡褐色液体）得た。

In a well-dried 100 mL three-necked eggplant flask (condenser, with three-way cock, with magnetic stirrer), 0.8 g (3.8 mmol) of compound 34, and 0.42 mL (3) of 2-chloroaniline (manufactured by Tokyo Chemical Industry Co., Ltd.) .99 mmol), 1,3-bis- (2,6-diisopropylphenyl) imidazolium- (allyl) -palladium (II) -chloride (manufactured by Sigma Aldrich Japan Co., Ltd.), 0.011 g (0.019 mmol), barium hydroxide Octahydrate (manufactured by Wako Pure Chemical Industries, Ltd.) 1.3 g (3.99 mmol) was added, dissolved in 30 mL of isopropyl alcohol (manufactured by Kanto Chemical Co., Ltd.), and reacted at 80 ° C. for 3 hours. After the reaction, 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 1.00 g of compound 35 (> 99%, light brown liquid).

The result of analyzing the obtained product was as follows.
¹ H NMR (δ, CDCl ₃ ): 7.35 (dd, 1H, J = 8.6, 2.6 Hz, Ar—H), 7.28 (d, 1H, J = 2.6 Hz, Ar—H) ), 7.21-7.11 (m, 2H, Ar-H), 6.93 (d, 1H, J = 8.6 Hz, Ar-H), 6.84 (td, 1H, J = 7. 6, 1.3 Hz, Ar—H), 6.78 (dd, 1 H, J = 7.9, 1.0 Hz, Ar—H), 3.79 (s, 3 H, CH ₃ ), 1.32 ( s, 9H, C (CH ₃ ) ₃ )

充分に乾燥した１００ｍＬナスフラスコ（三方コック、ディーン・スターク管、ジムロート付、磁気攪拌子入り）に化合物３５を０．４０ｇ（１．６ｍｍｏｌ）、３‐ａｄａｍａｎｔｙｌ‐２‐ｈｙｄｒｏｘｙ‐５‐ｍｅｔｙｌｂｅｎｚａｌｄｅｈｙｄｅ０．４４ｇ（１．６８ｍｍｏｌ）、エタノール１５ｍＬを加えた後、還流下で６時間反応させた。この反応液から不溶物をろ過にて取り除いた後、溶媒を減圧下で留去し、エタノールから再結晶することにより化合物３６を０．５２０ｇ（収率 ６５％、橙色固体）得た。

0.40 g (1.6 mmol) of compound 35 in a well-dried 100 mL eggplant flask (three-way cock, Dean-Stark tube, with Dimroth, with magnetic stirrer), 0.44 g of 3-adamantyl-2-hydroxy-5-methylbenzaldehyde 0.44 g (1.68 mmol) and ethanol (15 mL) were added, and the mixture was reacted under reflux for 6 hours. After removing insolubles from the reaction solution by filtration, the solvent was distilled off under reduced pressure, and recrystallization from ethanol gave 0.520 g (yield 65%, orange solid) of Compound 36.

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), 7.44-7.24 (m, 5H, Ar—H) 7.18 (m, 1H, Ar-H), 7.04 (d, 1H, J = 2.0 Hz, Ar-H), 6.92 (d, 1H, J = 2.0 Hz, Ar-H) ), 6.86 (d, 1H, J = 8.2Hz, Ar-H), 3.71 (s, 3H, OCH 3), 2.26 (s, 3H, CH 3), 2.09-2 .05 (m, 9H, adamantyl), 1.76 (s, 6H, adamantyl), 1.30 (s, 9H, C (CH ₃ ) ₃ )

充分に乾燥した１００ｍＬシュレンクフラスコ（磁気攪拌子入り）に四塩化チタンの１．０Ｍトルエン溶液を０．４ｍＬ（０．４ｍｍｏｌ）、トルエンを１０ｍＬ加え、ドライアイス−アセトンバスで−７８℃に冷却した。これに、化合物３６を０．２２３ｇ（０．４４ｍｍｏｌ）トルエン５ｍＬに溶かしたものを滴下した後、室温まで昇温させつつ１５時間反応させた。反応液を３ｍＬまで減圧下で濃縮しヘキサン２０ｍＬを加えた後、析出物をろ取、ヘキサン２０ｍＬで洗浄後、乾燥させることにより、化合物３７を０．１８５ｇ（収率 ７０％、赤褐色固体）得た。

To a well-dried 100 mL Schlenk flask (with magnetic stirrer), 0.4 mL (0.4 mmol) of 1.0 M toluene solution of titanium tetrachloride and 10 mL of toluene were added, and cooled to -78 ° C with a dry ice-acetone bath. . To this was added dropwise a solution of compound 36 in 0.223 g (0.44 mmol) of toluene (5 mL), and the mixture was reacted for 15 hours while raising the temperature to room temperature. The reaction solution was concentrated to 3 mL under reduced pressure, 20 mL of hexane was added, the precipitate was collected by filtration, washed with 20 mL of hexane, and dried to obtain 0.185 g (yield 70%, reddish brown solid) of Compound 37. It was.

The result of analyzing the obtained product was as follows.
¹ H NMR (δ, CDCl ₃ ): 8.12 (s, 1H, HC = N), 7.45-7.12 (m, 9H, Ar—H), 4.40 (s, 3H, OCH ₃₎ ), 2.33 (s, 3H, CH ₃ ), 2.22-2.15 (m, 9H, adamantyl), 1.93 (d, 3H, J = 12 Hz, adamantyl), 1.76 (d, 3H, J = 12 Hz, adamantyl), 1.31 (s, 9H, C (CH ₃ ) ₃ )

[Synthesis Example 12]
(Synthesis of Compound 42)

充分に乾燥した２００ｍＬ二口ナスフラスコ（三方コック付、磁気攪拌子入り）に４−ｃｕｍｙｌｐｈｅｎｏｌ（和光純薬工業株式会社製）を５．０ｇ（２３．５ｍｍｏｌ）、炭酸カリウムを４．９ｇ（３５．３ｍｍｏｌ）加え、アセトン８０ｍＬに溶解させた。溶液を４５℃に昇温した後、ヨウ化メチル（和光純薬工業株式会社製）２．１９ｍＬ（３５．３ｍｍｏｌ）をゆっくり滴下したのち、４５℃に保って３時間反応させた。反応終了後、反応液から不溶分をろ別し、飽和塩化アンモニウム水溶液を加えて酢酸エチルで抽出し、有機層を水で洗浄、無水硫酸ナトリウムで乾燥した。溶媒を減圧下で留去、得られた粗生成物をシリカゲルカラムクロマトグラフィー（溶離液：ヘキサン）で精製することにより、化合物３８を３．８８ｇ（７３％、無色液体）得た。

In a well-dried 200 mL two-necked eggplant flask (with a three-way cock, with a magnetic stirrer), 5.0 g (23.5 mmol) of 4-cumylphenol (manufactured by Wako Pure Chemical Industries, Ltd.) and 4.9 g of potassium carbonate (35 .3 mmol) and dissolved in 80 mL of acetone. After the temperature of the solution was raised to 45 ° C., 2.19 mL (35.3 mmol) of methyl iodide (manufactured by Wako Pure Chemical Industries, Ltd.) was slowly added dropwise, and the reaction was carried out for 3 hours while maintaining the temperature at 45 ° C. After completion of the reaction, insoluble matter was filtered off from the reaction solution, a saturated aqueous ammonium chloride solution was added, and the mixture was extracted with ethyl acetate. The solvent was distilled off under reduced pressure, and the resulting crude product was purified by silica gel column chromatography (eluent: hexane) to obtain 3.88 g (73%, colorless liquid) of Compound 38.

The result of analyzing the obtained product was as follows.
¹ H NMR (δ, CDCl ₃ ): 7.29-7.12 (m, 7H, Ar—H), 6.80 (d, 2H, J = 8.9 Hz, Ar—H), 3.78 ( s, 3H, OCH ₃ ), 1.66 (s, 6H, C (CH ₃ ) ₂ )

充分に乾燥した３００ｍＬ三口ナスフラスコ（滴下ロート、三方コック付、磁気攪拌子入り）に化合物３８を２．６ｇ（１１．５ｍｍｏｌ）、ヘキサン３０ｍＬを加え、氷浴にて０℃まで冷却した後、Ｎ，Ｎ，Ｎ’，Ｎ’−テトラメチルエチレンジアミン（東京化成工業株式会社製）１．８２ｍＬ（１２．１ｍｍｏｌ）を加え、ノルマルブチルリチウムのヘキサン溶液（１．６ｍｏｌ／Ｌ）７．５５ｍＬ（１２．１ｍｍｏｌ）を滴下した後、１６時間反応させた。５００ｍＬ三口ナスフラスコ（三方コック付、磁気攪拌子入り）にヘキサン４０ｍＬ、ホウ酸トリメチル（シグマ アルドリッチ ジャパン 株式会社製）３．８５ｍＬ（３４．５ｍｍｏｌ）を加えた後、−７８℃に冷却した後に、先ほど調製した反応液を滴下し、そのまま室温まで昇温させつつ３時間反応させた。この反応液に飽和塩化アンモニウム水溶液５０ｍＬを加えた後、酢酸エチル５０ｍＬ×３で抽出後、有機層を純水５０ｍＬ×２で洗浄し、ＭｇＳＯ₄で乾燥させ、溶媒を減圧下で留去することにより、粗生成物を得た。得られた粗生成物をヘキサンから再沈殿することにより、化合物３９を２．２ｇ（７１％、白色固体）得た。

2.6 g (11.5 mmol) of compound 38 and 30 mL of hexane were added to a well-dried 300 mL three-necked eggplant flask (with a dropping funnel, with a three-way cock, and a magnetic stirrer), and cooled to 0 ° C. in an ice bath. N, N, N ′, N′-tetramethylethylenediamine (manufactured by Tokyo Chemical Industry Co., Ltd.) 1.82 mL (12.1 mmol) was added, and hexane solution of normal butyl lithium (1.6 mol / L) 7.55 mL (12 0.1 mmol) was added dropwise, followed by reaction for 16 hours. After adding 40 mL of hexane and 3.85 mL (34.5 mmol) of trimethyl borate (manufactured by Sigma Aldrich Japan Co., Ltd.) to a 500 mL three-necked eggplant flask (with a three-way cock, containing a magnetic stirrer), the mixture was cooled to −78 ° C. The reaction solution prepared earlier was added dropwise and reacted for 3 hours while raising the temperature to room temperature. After adding 50 mL of saturated aqueous ammonium chloride solution to this reaction solution, and extracting with 50 mL × 3 ethyl acetate, the organic layer is washed with 50 mL × 2 pure water, dried over MgSO ₄ , and the solvent is distilled off under reduced pressure. Gave a crude product. The obtained crude product was reprecipitated from hexane to obtain 2.2 g (71%, white solid) of Compound 39.

The result of analyzing the obtained product was as follows.
¹ H NMR (δ, CDCl ₃ ): 7.80 (d, 1H, 2.6 Hz, Ar—H), 7.29-7.13 (m, 6H, Ar—H), 6.81 (d, 1H, J = 8.6Hz, Ar- H), 5.95 (s, 2H, B (OH) 2), 3.88 (s, 3H, OCH 3), 1.69 (s, 6H, C ( CH ₃ ) ₂ )

充分に乾燥した１００ｍＬ三口ナスフラスコ（コンデンサー、三方コック付、磁気攪拌子入り）に化合物３９を１．０ｇ（３．７ｍｍｏｌ）、２−ｃｈｌｏｒｏａｎｉｌｉｎｅ（東京化成工業株式会社製）を０．３９ｍＬ（３．９ｍｍｏｌ）、１，３−ｂｉｓ−（２，６−ｄｉｉｓｏｐｒｏｐｙｌｐｈｅｎｙｌ）ｉｍｉｄａｚｏｌｉｕｍ−（ａｌｌｙｌ）−ｐａｌｌａｄｉｕｍ（ＩＩ）−ｃｈｌｏｒｉｄｅ（シグマ アルドリッチ ジャパン 株式会社製）を０．０１１ｇ（０．０１９ｍｍｏｌ）、水酸化バリウム八水和物（和光純薬工業株式会社製）１．２ｇ（３．９ｍｍｏｌ）加え、イソプロピルアルコール（関東化学株式会社製）３０ｍＬに溶解させ、８０℃で３時間反応させた。反応後固体残さをろ過によって取り除き、溶媒を減圧下で留去することにより粗生成物を得た。粗生成物をシリカゲルカラムクロマトグラフ（溶離液；ヘキサン／酢酸エチル＝１０／１）を用いて精製することにより化合物４０を０．９１ｇ（７７％、淡褐色液体）得た。

In a well-dried 100 mL three-necked eggplant flask (condenser, with three-way cock, with magnetic stirrer), 1.0 g (3.7 mmol) of compound 39 and 0.39 mL of 3-chloroaniline (manufactured by Tokyo Chemical Industry Co., Ltd.) (3 .9 mmol), 1,3-bis- (2,6-diisopropylphenyl) imidazolium- (allyl) -palladium (II) -chloride (manufactured by Sigma Aldrich Japan Co., Ltd.), 0.011 g (0.019 mmol), barium hydroxide 1.2 g (3.9 mmol) of octahydrate (manufactured by Wako Pure Chemical Industries, Ltd.) was added, dissolved in 30 mL of isopropyl alcohol (manufactured by Kanto Chemical Co., Ltd.) and reacted at 80 ° C. for 3 hours. After the reaction, 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 0.91 g (77%, light brown liquid) of Compound 40.

The result of analyzing the obtained product was as follows.
¹ H NMR (δ, CDCl ₃ ): 7.27-7.06 (m, 9H, Ar—H), 6.90-6.73 (m, 3H, Ar—H), 3.78 (s, 3H, OCH ₃ ), 3.68 (bs, 2H, NH ₂ ), 1.68 (s, 6H, C (CH ₃ ) ₂ )

充分に乾燥した１００ｍＬナスフラスコ（三方コック、ディーン・スターク管、ジムロート付、磁気攪拌子入り）に化合物４０を０．５０ｇ（１．６ｍｍｏｌ）、３‐ａｄａｍａｎｔｙｌ‐２‐ｈｙｄｒｏｘｙ‐５‐ｍｅｔｙｌｂｅｎｚａｌｄｅｈｙｄｅを０．４５ｇ（１．６８ｍｍｏｌ）、エタノール１５ｍＬを加えた後、還流下で６時間反応させた。この反応液から不溶物をろ過にて取り除いた後、溶媒を減圧下で留去し、エタノールから再結晶することにより化合物４１を０．６６ｇ（収率 ７３％、橙色固体）得た。

In a well-dried 100 mL eggplant flask (three-way cock, Dean-Stark tube, with Dimroth, with magnetic stirrer), compound 40 was added at 0.50 g (1.6 mmol), 3-adamantyl-2-hydroxy-5-methylbenzaldehyde 0 .45 g (1.68 mmol) and 15 mL of ethanol were added, and the mixture was reacted for 6 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 0.66 g of Compound 41 (yield 73%, orange solid).

The result of analyzing the obtained product was as follows.
¹ H NMR (δ, CDCl ₃ ): 13.3 (s, 1H, OH), 8.41 (s, 1H, N═CH), 7.41-7.07 (m, 12H, Ar—H) 6.92 (d, 1H, J = 1.6 Hz, Ar-H), 6.81 (d, 1H, J = 8.6 Hz, Ar-H), 3.68 (s, 3H, OCH ₃ ) , 2.28 (s, 3H, CH ₃ ), 2.13-2.05 (m, 9H, adamantyl), 1.76 (s, 6H, adamantyl), 1.66 (s, 6H, C (CH ₃ ) ₂ )

充分に乾燥した１００ｍＬシュレンクフラスコ（磁気攪拌子入り）に四塩化チタンの１．０Ｍトルエン溶液を０．５ｍＬ（０．５ｍｍｏｌ）、トルエンを１０ｍＬ加え、ドライアイス−アセトンバスで−７８℃に冷却した。これに、化合物４１を０．３１３ｇ（０．５５ｍｍｏｌ）トルエン５ｍＬに溶かしたものを滴下した後、室温まで昇温させつつ１５時間反応させた。反応液を３ｍＬまで減圧下で濃縮しヘキサン２０ｍＬを加えた後、析出物をろ取、ヘキサン２０ｍＬで洗浄後、乾燥させることにより、化合物４２を０．２２４ｇ（収率 ６２％、赤褐色固体）得た。

To a well-dried 100 mL Schlenk flask (with magnetic stirrer), 0.5 mL (0.5 mmol) of a 1.0 M solution of titanium tetrachloride in toluene and 10 mL of toluene were added and cooled to −78 ° C. in a dry ice-acetone bath. . To this was added dropwise a solution of compound 41 in 0.313 g (0.55 mmol) of toluene (5 mL), followed by reaction for 15 hours while raising the temperature to room temperature. The reaction solution was concentrated to 3 mL under reduced pressure, 20 mL of hexane was added, and the precipitate was collected by filtration, washed with 20 mL of hexane, and dried to obtain 0.224 g of Compound 42 (yield 62%, reddish brown solid). It was.

The result of analyzing the obtained product was as follows.
¹ H NMR (δ, CDCl ₃ ): 8.06 (s, 1H, HC = N), 7.45-7.06 (m, 14H, Ar—H), 4.37 (s, 3H, OCH ₃ ), 2.35 (s, 3H, CH 3), 2.20-2.09 (m, 9H, adamantyl), 1.93 (d, 3H, J = 11Hz, adamantyl), 1.78 (d, 3H, J = 11 Hz, adamantyl), 1.65 (s, 6H, C (CH ₃ ) ₂ )

[Synthesis Example 13]
(Synthesis of Compound 44)

充分に乾燥した１００ｍＬナスフラスコ（三方コック、ディーン・スターク管、ジムロート付、磁気攪拌子入り）に化合物３１を０．６０ｇ（２．２ｍｍｏｌ）、３‐ａｄａｍａｎｔｙｌ‐２‐ｈｙｄｒｏｘｙ‐５‐ｐｈｅｎｙｌｂｅｎｚａｌｄｅｈｙｄｅを０．７２ｇ（２．２ｍｍｏｌ）、エタノール１５ｍＬを加えた後、還流下で６時間反応させた。この反応液から不溶物をろ過にて取り除いた後、溶媒を減圧下で留去し、エタノールから再結晶することにより化合物４３を１．１７ｇ（収率 ９６％、黄色固体）得た。

In a well-dried 100 mL eggplant flask (three-way cock, Dean-Stark tube, with Dimroth, with magnetic stirrer), compound 31 (0.60 g, 2.2 mmol), 3-adamantyl-2-hydroxy-5-phenylbenzaldehyde is 0 .72 g (2.2 mmol) and 15 mL of ethanol were added, and the mixture was reacted for 6 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 1.17 g of Compound 43 (yield 96%, yellow solid).

The result of analyzing the obtained product was as follows.
¹ H NMR (δ, CDCl ₃ ): 13.8 (s, 1H, OH), 8.62 (s, 1H, N═CH), 7.61-7.27 (m, 18H, Ar—H) 7.03 (d, 1H, J = 8.6 Hz, Ar—H), 3.82 (s, 3H, OCH ₃ ), 2.14 (m, 6H, adamantyl), 2.06 (m, 3H) , Adamantyl), 1.76 (s, 6H, adamantyl)

充分に乾燥した１００ｍＬシュレンクフラスコ（磁気攪拌子入り）に四塩化チタンの１．０Ｍトルエン溶液を０．３ｍＬ（０．３ｍｍｏｌ）、ヘキサンを２０ｍＬ加え、ドライアイス−アセトンバスで−７８℃に冷却した。これに、化合物４３を０．１９５ｇ（０．３３ｍｍｏｌ）トルエン１ｍＬ／ヘキサン１０ｍＬに溶かしたものを滴下した後、室温まで昇温させつつ２時間反応させた。析出物をろ取し、ヘキサン２０ｍＬで洗浄後、乾燥させることにより、化合物４４を０．１７０ｇ（収率 ８６％、赤褐色固体）得た。

To a well-dried 100 mL Schlenk flask (with magnetic stirrer), 0.3 mL (0.3 mmol) of 1.0 M toluene solution of titanium tetrachloride and 20 mL of hexane were added, and cooled to −78 ° C. with a dry ice-acetone bath. . A solution prepared by dissolving 0.143 g (0.33 mmol) of toluene in 1 mL of toluene / 10 mL of hexane was added dropwise thereto, and then reacted for 2 hours while raising the temperature to room temperature. The precipitate was collected by filtration, washed with 20 mL of hexane, and dried to obtain 0.170 g of Compound 44 (yield 86%, reddish brown solid).

The result of analyzing the obtained product was as follows.
¹ H NMR (δ, CDCl ₃ ): 8.28 (s, 1H, HC = N), 7.80 (d, 1H, J = 2.3 Hz, Ar—H), 7.63-7.30 ( m, 17H, Ar-H) , 7.19 (m, 1H, Ar-H), 4.47 (s, 3H, OCH 3), 2.28 (m, 6H, adamantyl), 2.19 (m , 3H, adamantyl), 1.95 (d, 3H, J = 13 Hz, adamantyl), 1.81 (d, 3H, J = 13 Hz, adamantyl)

[Synthesis Example 14]
(Synthesis of Compound 46)

充分に乾燥した１００ｍＬナスフラスコ（三方コック、ディーン・スターク管、ジムロート付、磁気攪拌子入り）に化合物４０を０．４０ｇ（１．２８ｍｍｏｌ）、３‐ａｄａｍａｎｔｙｌ‐２‐ｈｙｄｒｏｘｙ‐５‐ｐｈｅｎｙｌｂｅｎｚａｌｄｅｈｙｄｅを０．４２ｇ（１．２８ｍｍｏｌ）、エタノール１５ｍＬを加えた後、還流下で５時間反応させた。この反応液から不溶物をろ過にて取り除いた後、溶媒を減圧下で留去し、エタノールから再結晶することにより化合物４５を０．６３９ｇ（収率 ６７％、橙色固体）得た。

In a well-dried 100 mL eggplant flask (three-way cock, Dean-Stark tube, with Dimroth, with magnetic stirrer), compound 40 (0.40 g, 1.28 mmol), 3-adamantyl-2-hydroxy-5-phenylbenzaldehyde 0 .42 g (1.28 mmol) and 15 mL of ethanol were added, followed by reaction for 5 hours under reflux. After removing insolubles from this reaction solution by filtration, the solvent was distilled off under reduced pressure, and recrystallization from ethanol gave 0.639 g (yield 67%, orange solid) of Compound 45.

The result of analyzing the obtained product was as follows.
¹ H NMR (δ, CDCl ₃ ): 13.7 (s, 1H, OH), 8.54 (d, 1H, J = 2.0 Hz, N = CH), 7.57-7.30 (m, 10H), 7.23-7.08 (m, 8H , Ar-H), 6.84 (d, 1H, J = 9.2Hz, Ar-H), 3.70 (s, 3H, OCH 3) 2.18 (s, 6H, adamantyl), 2.08 (s, 3H, adamantyl), 1.78 (s, 6H, adamantyl), 1.70 (s, 6H, C (CH ₃ ) ₂ )

充分に乾燥した１００ｍＬシュレンクフラスコ（磁気攪拌子入り）に四塩化チタンの１．０Ｍトルエン溶液を０．８ｍＬ（０．８ｍｍｏｌ）、トルエンを１５ｍＬ加え、ドライアイス−アセトンバスで−７８℃に冷却した。これに、化合物４５を０．５５６ｇ（０．８８ｍｍｏｌ）トルエン１０ｍＬに溶かしたものを滴下した後、室温まで昇温させつつ１６時間反応させた。反応液を３ｍＬ程度まで濃縮した後ヘキサン２０ｍＬを加え、沈殿物をろ取、乾燥させることにより、化合物４６を０．５５５ｇ（収率 ８７％、赤褐色固体）得た。

To a well-dried 100 mL Schlenk flask (with magnetic stirrer), 0.8 mL (0.8 mmol) of 1.0 M toluene solution of titanium tetrachloride and 15 mL of toluene were added, and cooled to -78 ° C with a dry ice-acetone bath. . To this was added dropwise a solution of compound 45 in 0.556 g (0.88 mmol) of toluene (10 mL), and the mixture was reacted for 16 hours while raising the temperature to room temperature. The reaction solution was concentrated to about 3 mL, 20 mL of hexane was added, and the precipitate was collected by filtration and dried to obtain 0.555 g of Compound 46 (yield 87%, reddish brown solid).

The result of analyzing the obtained product was as follows.
¹ H NMR (δ, CDCl ₃ ): 8.20 (s, 1H, HC = N), 7.81 (d, 1H, J = 2.3 Hz, Ar—H), 7.53-7.04 ( m, 18H, Ar-H) , 4.39 (s, 3H, OCH 3), 2.28-2.18 (m, 9H, adamantyl), 1.95 (d, 3H, J = 11Hz, adamantyl) , 1.81 (d, 3H, J = 11 Hz, adamantyl), 1.64 (s, 6H, C (CH ₃ ) ₂ )

[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 3 (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 93.3%. As other products, the selectivity of decenes was 5.9%, the selectivity of polyethylene was 0.8%, and the catalytic activity calculated from the total amount of these products was 18.0 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.) / (Activity at reaction temperature 25 ° C.)

[Examples 2 to 14]
The reaction temperature was 25 ° C. in the same manner as in Example 1 except that the compounds 6, 10, 14, 19, 21, 23, 25, 29, 33, 37, 42, 44, 46 were used instead of the compound 3. And the reaction was carried out at 40 ° C. 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 9 (compound 47 below) described in WO2009 / 5003 pamphlet [0225] was used instead of compound 3. went. The results are shown in Table 1.

［比較例２］
化合物３に代えて国際公開第２００９／５００３号パンフレット［０２７３］に記載の化合物３１（下記化合物４８）を用いた以外は、実施例１と同様にして、反応温度２５℃および４０℃で反応を行った。結果を表１に記す。

[Comparative Example 2]
The reaction was conducted at reaction temperatures of 25 ° C. and 40 ° C. in the same manner as in Example 1 except that compound 31 (the following compound 48) described in WO2009 / 5003 pamphlet [0273] was used instead of compound 3. went. The results are shown in Table 1.

上記実施例・比較例の結果から、本発明にかかる遷移金属化合物を用いたオレフィンの多量化反応では、従来公知の遷移金属化合物を用いた場合と比べ、高温での活性が高い（比活性が高い）ことが明確になった。これは、前記したとおり本発明にかかる一般式（１）で表される遷移金属化合物のフェノキシイミン配位子の特定の位置に置換基を導入したことにより、化合物の安定性が増し、耐熱性を有することに起因すると想定できる。

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

Furthermore, in the olefin multimerization reaction using a transition metal compound having a substituent at a specific position (specifically, R ¹¹ ) according to the present invention, compared with the case of using a conventionally known transition metal compound, 1- It is mentioned as a preferred embodiment because of its high hexene selectivity. As described above, this is because the substituent at the position indicated by R ¹¹ in the vicinity of the reaction site of the phenoxyimine ligand of the transition metal compound represented by the general formula (1) according to the present invention is sterically large (bulk). It can be assumed that the generation of decenes by-produced due to the high (substituent) is suppressed.

  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 (11)

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 ^{4 to} R ⁶ , R ⁹ , R ¹⁰ , R ¹² 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 ³ , R ⁷ , R ⁸ , R ¹¹ and R ¹³ 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. At least one of which is a hydrocarbon group having 3 or more carbon atoms or a hydrocarbon group-substituted silyl group having 1 or more carbon 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. ] In the general formula (1), at least one of the groups represented by R ³ , R ⁷ , R ⁸ , R ¹¹ and R ¹³ is a hydrocarbon group having 3 or more carbon atoms. The transition metal compound described. The transition metal compound according to claim 2, wherein at least one of the groups represented by R ³ , R ⁸ and R ¹¹ in the general formula (1) is a hydrocarbon group having 3 or more carbon atoms. In the general formula (1), the group represented by R ¹¹ is a hydrocarbon group having 3 or more carbon atoms, and at least one of the groups represented by R ³ and R ⁸ is a hydrocarbon group having 3 or more carbon atoms. The transition metal compound according to claim 3.   5. The hydrocarbon group according to claim 2, wherein the hydrocarbon group having 3 or more carbon atoms is a substituent selected from a secondary alkyl group, a tertiary alkyl group, or an aryl group. Transition metal compounds. 6. The transition metal compound according to claim 1, wherein the group represented by R ¹² and R ¹⁴ in the general formula (1) is a hydrogen atom. The transition metal compound according to any one of claims 1 to 6, wherein R ² in the general formula (1) is a tertiary alkyl group or a hydrocarbon-substituted tertiary silyl group.   In the said General formula (1), M is a titanium atom, The transition metal compound of any one of Claims 1-7 characterized by the above-mentioned. An olefin multimerization catalyst comprising the following component (A) and component (B):
(A) Transition metal compound according to any one of claims 1 to 8 (B) (B-1) Organometallic compound (B-2) Organoaluminum oxy compound, and (B-3) Transition metal At least one compound selected from the group consisting of compounds that react with compound (A) to form ion pairs. The olefin multimerization catalyst according to claim 9, 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 multimerization catalyst according to claim 9 or 10.