JP2022520575A - Its use as a catalyst for transition metal bis (phenorate) complexes and olefin polymerization - Google Patents

Abstract

The present invention is a transition metal complex of a dianionic tridentate ligand characterized by a central neutral heterocyclic Lewis base and two phenolate donors, the tridentate ligand located at the metal center. It relates to a transition metal complex of a dianionic tridentate ligand that is located to form two 8-membered rings. Preferably, the bis (phenorate) complex is represented by formula (I). JPEG2022520575000170.jpg 3585 (I) (In the formula, M, L, X, m, n, E, E', Q, R1, R2, R3, R4, R1', R2', R3', R4', A1, A1 ', A3-A2 and A2'-A3 are as defined herein, where A1QA1'links A2 to A2' via a triatomic bridge in which the central atom is Q, 4-40. Part of a heterocyclic Lewis base containing a non-hydrogen atom)

Description

Inventor: George P. Goryunov, Michael I. Sharikov, Vladislav A. Popov, Dmitry V. Uborsky, Alexander Z. Voskoboynikov, John R. Hagadorn, Michelle E. et al. Titone, Alex E. Carpenter, Catherine A. Faller, Jo Ann M. Canon

Priority The invention incorporates USSN 62 / 804,372 filed February 12, 2019 and EP Search Report Application No. filed June 12, 2019, which incorporates the entire disclosure. Claim the interests and priority of 19179811.5.

The present invention relates to novel catalytic compounds containing Group 4 bis (phenorate) complexes, catalytic systems containing such compounds and their use.

Olefin polymerization catalysts are very useful in the industry. Therefore, it is of interest to find new catalyst systems that enhance the commercial usefulness of catalysts and enable the production of polymers with improved properties.
The catalyst for olefin polymerization can be based on a bis (phenorate) complex as a catalytic precursor, which is typically activated by an alumoxane, or an activator containing a non-coordinating anion.
KR 2018022137 (LG Chem.) Describes a transition metal complex of bis (methylphenylphenolate) pyridine.
U.S. Pat. No. 7,030,256 (Symyx Technologies, Inc.) describes crosslinked biaromatic ligands, catalysts, processes for polymerization and polymers thereof.
US Pat. No. 6,825,296 (University of Hong Kong) describes a transition metal complex of a bis (phenorate) ligand that coordinates to a metal with two 6-membered rings.
U.S. Pat. No. 7,847,099 (California Institute of Technology) describes a transition metal complex of a bis (phenorate) ligand coordinated to a metal by two 6-membered rings.
International Publication No. 2016/172110 (United Technologies) describes a complex of a tridentate bis (phenorate) ligand characterized by an acyclic ether or thioether donor.
Other interesting references include Baier, MC (2014) “Post-Metallocenes in the Industrial Production of Polyolefins,” Angew. Chem. Int. Ed. 2014, v.53, pp. 9722-9744 and Golisz, S. Et al. (2009) "Synthesis of Early Transition Metal Bisphenolate Complexes and Their Use as Olefin Polymerization Catalysts," Macromolecules, v.42 (22), pp. 8751-8762.
New catalysts capable of polymerizing olefins at high process temperatures to give high molecular weight and / or high tacticity polymers are desirable for the industrial production of polyolefins. New and improved catalytic systems for olefin polymerization, preferably for olefin polymerization at high process temperatures, are available in the art to achieve specific polymer properties such as high molecular weight and / or high tacticity polymers. Still needed.
Therefore, it is an object of the present invention to provide novel catalytic compounds, catalytic systems containing such compounds, and processes for olefin polymerization using such compounds and systems.

The present invention is a transition metal complex of a dianionic tridentate ligand characterized by a central neutral heterocyclic Lewis base and two phenolate donors, the tridentate ligand located at the metal center. It relates to a transition metal complex of a dianionic tridentate ligand that is located to form two 8-membered rings.

(I)
（式中、
Ｍは、３～６族遷移金属またはランタニドであり、
ＥおよびＥ’は、それぞれ独立してＯ、ＳまたはＮＲ⁹（式中、Ｒ⁹は、独立して水素、Ｃ₁－Ｃ₄₀ヒドロカルビル、Ｃ₁－Ｃ₄₀置換ヒドロカルビルまたはヘテロ原子含有基である）であり、
Ｑは、金属Ｍに対して供与結合を形成する１４、１５または１６族原子であり、
Ａ¹ＱＡ^1’は、３原子架橋を介してＡ²をＡ^2’に連結する、４～４０個の非水素原子を含む複素環式ルイス塩基の一部であって、３原子架橋の中心原子はＱであり、Ａ¹およびＡ^1’は、独立してＣ、ＮまたはＣ（Ｒ²²）（式中、Ｒ²²は、水素、Ｃ₁－Ｃ₂₀ヒドロカルビル、Ｃ₁－Ｃ₂₀置換ヒドロカルビルから選択される）であり、 The present invention relates to a bis (phenorate) complex represented by the formula (I).

(I)
(During the ceremony,
M is a Group 3-6 transition metal or lanthanide,
E and E'are independently O, S or NR ⁹ (in the formula, R ⁹ is independently hydrogen, C1 _- C ₄₀ hydrocarbyl, C1 _- C ₄₀ substituted hydrocarbyl or heteroatom-containing group. ) And
Q is a group 14, 15 or 16 atom forming a donor bond to the metal M.
A ¹ QA 1'is part of a heterocyclic Lewis base containing 4-40 non ^- hydrogen atoms that connects A ² to A ^2'via a triatomic bridge and is the center of the triatomic bridge. The atom is Q and A ¹ and A ^1'are independently C, N or C (R ²² ) (in the formula, R ²² is hydrogen, C ₁ -C ₂₀ hydrocarbyl, C ₁ -C ₂₀ substituted hydrocarbyl. (Selected from) and

は、２原子架橋を介してＡ¹をＥ結合アリール基に連結する、２～４０個の非水素原子を含む二価基であり、

は、２原子架橋を介してＡ^1’をＥ’結合アリール基に連結する、２～４０個の非水素原子を含む二価基であり、
Ｌは中性ルイス塩基であり、
Ｘはアニオン性配位子であり、
ｎは、１、２または３であり、
ｍは、０、１または２であり、
ｎ＋ｍは４以下であり、
Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｒ^1’、Ｒ^2’、Ｒ^3’およびＲ^4’のそれぞれは、独立して水素、Ｃ₁－Ｃ₄₀ヒドロカルビル、Ｃ₁－Ｃ₄₀置換ヒドロカルビル、ヘテロ原子もしくはヘテロ原子含有基であり、またはＲ¹およびＲ²、Ｒ²およびＲ³、Ｒ³およびＲ⁴、Ｒ^1’およびＲ^2’、Ｒ^2’およびＲ^3’、Ｒ^3’およびＲ^4’のうちの１つまたは複数が結合されて、５個、６個、７個または８個の環原子をそれぞれ有し、かつ環上の置換基が結合して追加の環を形成することができる１個もしくは複数の置換ヒドロカルビル環、非置換ヒドロカルビル環、置換複素環式環または非置換複素環式環を形成してよく、
任意の２個のＬ基が互いに結合されて二座ルイス塩基を形成してよく、
Ｘ基がＬ基に結合されてモノアニオン性二座基を形成してよく、
任意の２個のＸ基が互いに結合されてジアニオン性配位子基を形成してよい）
本発明は、本明細書に記載の触媒化合物を活性化剤および１種または複数種のモノマーと接触させることを含む、オレフィンを重合する方法にも関する。本発明はさらに、本明細書に記載された方法により生成されたポリマー組成物に関する。

Is a divalent group containing 2 to 40 non-hydrogen atoms that links A ¹ to an E-bonded aryl group via biatomic cross-linking.

Is a divalent group containing 2 to 40 non-hydrogen atoms linking A ^1'to an E'bonded aryl group via biatomic cross-linking.
L is a neutral Lewis base,
X is an anionic ligand
n is 1, 2 or 3
m is 0, 1 or 2,
n + m is 4 or less,
R ¹ , R ² , R ³ , R ⁴ , R ^1' , R ^{2' ,} R ^3'and R 4'are independently hydrogen, C ₁ -C ₄₀ hydrocarbyl, C ₁ -C ₄₀ substituted hydrocarbyl. , Heteroatom or heteroatom-containing group, or R ¹ and R ² , R ² and R ³ , R ³ and R ⁴ , R ^1'and R ^{2 '} , R 2'and R ^3' , R ^3'and One or more of R ^4'are bonded to each other to have 5, 6, 7 or 8 ring atoms, and the substituents on the ring combine to form an additional ring. One or more substituted hydrocarbyl rings, unsubstituted hydrocarbyl rings, substituted heterocyclic rings or unsubstituted heterocyclic rings may be formed.
Any two L groups may be attached to each other to form a bidentate Lewis base.
The X group may be attached to the L group to form a monoanionic bidentate.
Any two X groups may be bonded to each other to form a dianionic ligand group)
The invention also relates to a method of polymerizing an olefin, comprising contacting the catalytic compounds described herein with an activator and one or more monomers. The invention further relates to polymer compositions produced by the methods described herein.

Definitions The following definitions shall be used in the present invention and its claims.
A new numbering system for the Group of Periodic Tables is used as described in Chemical and Engineering News, v.63 (5), pg. 27 (1985). Therefore, the "Group 4 metal" is an element from Group 4 of the Periodic Table, such as Hf, Ti or Zr.

"Catalyst productivity" is a measure of the mass of a polymer produced using a known amount of polymerization catalyst. Typically, "catalyst productivity" is expressed in units of (catalyst g number) / (catalyst g number) or (polymer g number) / (catalyst mmol number) or the like. If no unit is specified, "catalyst productivity" is the unit of (g number of polymer) / (gram number of catalyst). Only the mass of the transition metal component of the catalyst is used to calculate the catalyst productivity (ie, the activator and / or the co-catalyst is excluded). "Catalytic activity" is a measure of the mass of polymer produced using a known amount of polymerization catalyst per unit time for batch and semi-batch polymerization. Only the mass of the transition metal component of the catalyst is used to calculate the catalyst productivity (ie, the activator and / or the co-catalyst is excluded). Typically, "catalytic activity" is expressed in units of (g of polymer) / (mmol of catalyst) / hour or (kg of polymer) / (mmol of catalyst) / hour or the like. To. If no unit is specified, "catalytic activity" is the unit of (g number of polymer) / (mmol number of catalyst) / hour.

"Conversion rate" is the percentage of the monomer converted to the polymer product in the polymerization, reported as%, and calculated based on the polymer yield, the polymer composition, and the amount of the monomer delivered to the reactor.

An "olefin" (also referred to as an "alkene") is a linear, branched or cyclic compound of carbon and hydrogen with at least one double bond. When the polymer or copolymer is expressed as containing an olefin in the present specification and the claims attached thereto, the olefin present in such a polymer or copolymer is an olefin in a polymerized form. For example, when a copolymer is said to have an "ethylene" content of 35% to 55% by weight, the mar units in the copolymer are derived from ethylene in the polymerization reaction and the inductive units are based on the weight of the copolymer. It is understood that it exists in an amount of 35% by mass to 55% by mass. A "polymer" has two or more identical or different mar units. A "homoromer" is a polymer having the same mar units. A "copolymer" is a polymer having two or more different mar units. A "terpolymer" is a polymer having three different mar units. Therefore, the definition of copolymer, as used herein, includes terpolymers and the like. "Different" used to refer to a mer unit indicates that at least one atom of the mer unit is different from each other, or that the mer units are isomerically different. An "ethylene polymer" or "ethylene copolymer" is a polymer or copolymer containing at least 50 mol% of ethylene inducible units, and a "propylene polymer" or "propylene copolymer" is a polymer or copolymer containing at least 50 mol% of propylene inductive units. Yes, and so on.
Ethylene shall be considered an α-olefin.
Unless otherwise specified, the term "C _n " means a hydrocarbon having n carbon atoms per molecule, where n is a positive integer.

The term "hydrocarbon" means a class of compounds containing hydrogen bonded to carbon, having (i) saturated hydrocarbon compounds, (ii) unsaturated hydrocarbon compounds, and (iii) different n values. Includes mixtures of hydrocarbon compounds (saturated and / or unsaturated), including mixtures of hydrocarbon compounds. Similarly, a "C _m -C _y " group or compound refers to a group or compound containing its total number of carbon atoms in the range m-y. Thus, a C ₁ -C ₅₀ alkyl group refers to an alkyl group containing its total number of carbon atoms in the range 1-50.

The terms "group", "radical" and "substituent" can be used interchangeably.

The terms "hydrocarbyl radical", "hydrocarbyl group" or "hydrocarbyl" can be used interchangeably and are defined to mean a group consisting only of hydrogen and carbon atoms. Preferred hydrocarbyls are C1 _{-C 100 groups} , which may be linear, branched or cyclic, and when cyclic, may be aromatic or non-aromatic. Examples of such groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, iso-amyl, hexyl, octyl, cyclopropyl, cyclobutyl, cyclopentyl, etc. Includes, but is not limited to, alkyl groups such as cyclohexyl, cyclooctyl and the like, and aryl groups such as phenyl, benzyl, naphthalenyl and the like.
Unless otherwise stated (eg, the definition of "substituted hydrocarbyl"), the term "substituted" refers to a hydrocarbyl group, a halogen (such as Br, Cl, F or I) or -NR ^* ₂ , -OR. ^* , -SeR ^* , -TeR ^* , -PR ^* ₂ , -AsR ^* ₂ , -SbR ^* ₂ , -SR ^* , -BR ^* ₂ , -SiR ^* ₃ , -GeR ^* ₃ , -SnR ^* ₃ ,- PbR ^* ₃ ,-(CH ₂ ) _q -SiR ^* ₃ and the same kind (in the formula, q is 1 to 10, each R ^* is an independently hydrogen, hydrocarbyl or halocarbyl group, 2 pieces. The above R ^* may be bonded to each other to form a substituted or unsubstituted fully saturated, partially unsaturated, or aromatic ring or polycyclic ring structure, or at least one heteroatom may be contained in the hydrocarbyl ring. It means that at least one hydrogen atom is replaced by at least one non-hydrogen group such as a heteroatom such as at least one functional group or a heteroatom-containing group (inserted in).

The term "substituted hydrocarbyl" refers to at least one heteroatom (such as halogen, eg Br, Cl, F or I) or a heteroatom-containing group (such as a functional group, eg-NR ^* ₂ , -OR ^* ,- SeR ^* , -TeR ^* , -PR ^* ₂ , -AsR ^* ₂ , -SbR ^* ₂ , -SR ^* , -BR ^* ₂ , -SiR ^* ₃ , -GeR ^* ₃ , -SnR ^* ₃ , -PbR ^* ₃ ,-(CH ₂ ) _q -SiR ^* ₃ and the same kind (in the formula, q is 1-10, each R ^* is an independently hydrogen, hydrocarbyl or halocarbyl group, and two or more Rs. ^* May be bonded to each other to form a substituted or unsubstituted fully saturated, partially unsaturated, or aromatic or polycyclic ring structure, or at least one heteroatom is inserted into the hydrocarbyl ring. ))) Means a hydrocarbyl group in which at least one hydrogen atom of the hydrocarbyl group is substituted.

The term "aryl" or "aryl group" means an aromatic ring (typically made up of 6 carbon atoms) and its substituted variants such as phenyl, 2-methylphenyl, xylyl, 4-bromoxylyl. Similarly, heteroaryl means an aryl group in which one ring carbon atom (or two or three ring carbon atoms) is replaced with a heteroatom such as N, O or S. As used herein, the term "aromatic" has properties and structures (almost planar) similar to aromatic heterocyclic ligands, but is by definition a non-aromatic heterocyclic substitution. It also refers to the pseudoaromatic heterocycle that is the group.
The term "substituted aromatic" means an aromatic group having one or more hydrogen groups substituted with hydrocarbyl, substituted hydrocarbyl, heteroatoms or heteroatom-containing groups.

"Substituted phenolates" are hydrocarbyl groups, halogens (Br, Cl, F or I, etc.) or -NR ^* ₂ , -OR ^* , -SeR ^* , -TeR ^* , -PR ^* ₂ , -AsR ^* ₂ ,- SbR ^* ₂ , -SR ^* , -BR ^* ₂ , -SiR ^* ₃ , -GeR ^* ₃ , -SnR ^* ₃ , -PbR ^* ₃ ,-(CH ₂ ) _q -SiR ^* ₃ and the same type (in the formula) , Q are 1 to 10, each R ^* is a hydrogen, hydrocarbyl or halocarbyl group independently, and two or more R ^* are bonded to each other, and the substituted or unsubstituted fully saturated, partially unsaturated. , Or at least one non-hydrogen group such as a heteroatom or heteroatom-containing group such as at least one functional group (which may form an aromatic or polycyclic ring structure) at the 2- and 3-positions. At least one, two, three, four or five hydrogen atoms at the 4-position, 5-position and / or 6-position are replaced, and the 1-position is a phenolate group (Ph-O-, Ph-). S- and Ph-N (R ^{^} )-groups (in the formula, R ^ is hydrogen, C1 _- C ₄₀ hydrocarbyl, C1 _- C ₄₀ substituted hydrocarbyl, heteroatom or heteroatom-containing group). It is a phenolate group. Preferably, the "substituted phenolate" group in the catalytic compounds described herein is represented by the following formula.

（式中、Ｒ¹⁸は、水素、Ｃ₁－Ｃ₄₀ヒドロカルビル（Ｃ₁－Ｃ₄₀アルキルなど）またはＣ₁－Ｃ₄₀置換ヒドロカルビル、ヘテロ原子またはヘテロ原子含有基であり、Ｅ¹⁷は、酸素、硫黄またはＮＲ¹⁷であり、Ｒ¹⁷、Ｒ¹⁸、Ｒ¹⁹、Ｒ²⁰およびＲ²¹のそれぞれは、水素、Ｃ₁－Ｃ₄₀ヒドロカルビル（Ｃ₁－Ｃ₄₀アルキルなど）またはＣ₁－Ｃ₄₀置換ヒドロカルビル、ヘテロ原子またはヘテロ原子含有基から独立して選択され、またはＲ¹⁸、Ｒ¹⁹、Ｒ²⁰およびＲ²¹のうちの２個以上が互いに結合されて、Ｃ₄－Ｃ₆₂環式もしくは多環式環構造またはそれらの組合せを形成し、波線は、置換フェノレート基が触媒化合物の残りの部分への結合を形成する位置を示す）

(In the formula, R ¹⁸ is hydrogen, C1 _- C ₄₀ hydrocarbyl (such as C1 _- C ₄₀ alkyl) or C1 _- C ₄₀ substituted hydrocarbyl, heteroatom or heteroatom-containing group, E ¹⁷ is oxygen, Sulfur or NR ¹⁷ , each of R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ and R ²¹ is hydrogen, C1 _- C ₄₀ hydrocarbyl (such as C1 _- C ₄₀ alkyl) or C1 _- C ₄₀ substituted hydrocarbyl. , Heteroatom or heteroatom-containing group, or two or more of ^R18 , ^R19 , ^R20 and ^R21 bonded to each other, _C4 - _C62 ring or polycyclic Forming a ring structure or a combination thereof, the wavy line indicates the position where the substituted phenolate group forms a bond to the rest of the catalytic compound).

"Alkyl-substituted phenolates" include methyl, ethyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, iso-amyl, hexyl, octyl, cyclopropyl, cyclobutyl. , Cyclopentyl, cyclohexyl, cyclooctyl, adamantanyl and the like including their substitution analogs, at least _one such as C1- _C40 , _{C2 - C20} instead, C3- _C12alkyl instead. It is a phenolate group in which at least one, two, three, four or five hydrogen atoms at the 2-position, 3-position, 4-position, 5-position and / or 6-position are replaced with an alkyl group.

"Aryl substituted phenolates" are of the same species including phenyl, 4-fluorophenyl, 2-methylphenyl, 2-propylphenyl, 2,6-dimethylphenyl, mesityl, 2-ethylphenyl, naphthalenyl and their substituted analogs. At least one aryl group, such as C1 _- C ₄₀ , C2-C ₂₀ , instead C _{3 -} C ₁₂ aryl groups, at the 2-position, 3-position, 4-position, 5-position and / or 6 It is a phenolate group in which at least one, two, three, four or five hydrogen atoms are replaced.
The term "ring atom" means an atom that is part of a cyclic ring structure. By this definition, a benzyl group has 6 ring atoms and a tetrahydrofuran has 5 ring atoms.
A heterocyclic ring (also called a heterocyclic) is a ring that has a heteroatom in its ring structure, as opposed to a "heteroatom-substituted ring" in which the hydrogen on the ring atom is replaced by a heteroatom. be. For example, tetrahydrofuran is a heterocyclic ring and 4-N, N-dimethylamino-phenyl is a heteroatom substituted ring. A substituted heterocyclic ring means a heterocyclic ring having one or more hydrogen groups substituted with hydrocarbyl, substituted hydrocarbyl, a heteroatom or a heteroatom-containing group.

A substituted hydrocarbyl ring means a ring consisting of a carbon atom and a hydrogen atom having one or more hydrogen groups substituted with hydrocarbyl, substituted hydrocarbyl, a heteroatom or a heteroatom-containing group.

In the present disclosure, with respect to a catalytic compound (eg, a substituted bis (phenorate) catalytic compound), the term "substitution" refers to a hydrocarbyl group, a halogen (Br, Cl, F or I, etc.) or -NR ^* ₂ , -OR ^*. , -SeR ^* , -TeR ^* , -PR ^* ₂ , -AsR ^* ₂ , -SbR ^* ₂ , -SR ^* , -BR ^* ₂ , -SiR ^* ₃ , -GeR ^* ₃ , -SnR ^* ₃ , -PbR ^* ₃ ,-(CH ₂ ) _q -SiR ^* ₃ and the same kind (in the formula, q is 1 to 10, each R ^* is an independently hydrogen, hydrocarbyl or halocarbyl group, 2 or more. R ^* may combine with each other to form substituted or unsubstituted fully saturated, partially unsaturated, or aromatic or polycyclic ring structures, or at least one heteroatom may be present within the hydrocarbyl ring. It means that the hydrogen group is replaced with a heteroatom or a heteroatom-containing group such as at least one functional group (inserted).
The tertiary hydrocarbyl group has a carbon atom bonded to three other carbon atoms. When this hydrocarbyl group is an alkyl group, the tertiary hydrocarbyl group is also called a tertiary alkyl group. Examples of tertiary hydrocarbyl groups include tert-butyl, 2-methylbutane-2-yl, 2-methylhexane-2-yl, 2-phenylpropane-2-yl, 2-cyclohexylpropane-2-yl, 1-. Includes methylcyclohexyl, 1-adamantyl, bicyclo [2.2.1] heptane-1-yl and the like. The tertiary hydrocarbyl group can be represented by formula A.

（式中、Ｒ^A、Ｒ^BおよびＲ^Cは、互いに結合されてもよいヒドロカルビル基または置換ヒドロカルビル基であり、波線は、三級ヒドロカルビル基が他の基への結合を形成する位置を示す）

(In the formula, ^RA , ^RB and ^RC are hydrocarbyl or substituted hydrocarbyl groups that may be attached to each other and the wavy line indicates the position where the tertiary hydrocarbyl group forms a bond to another group).

A cyclic tertiary hydrocarbyl group is defined as a tertiary hydrocarbyl group that forms at least one alicyclic (non-aromatic) ring. The cyclic tertiary hydrocarbyl group is also called an alicyclic tertiary hydrocarbyl group. When this hydrocarbyl group is an alkyl group, the cyclic tertiary hydrocarbyl group is also referred to as a cyclic tertiary alkyl group or an alicyclic tertiary alkyl group. Examples of cyclic tertiary hydrocarbyl groups include 1-adamantanyl, 1-methylcyclohexyl, 1-methylcyclopentyl, 1-methylcyclooctyl, 1-methylcyclodecyl, 1-methylcyclododecyl, bicyclo [3.3.1]. ] Nonane-1-yl, Bicyclo [2.2.1] Heptane-1-yl, Bicyclo [2.3.3] Hexane-1-yl, Bicyclo (bicycle) [1.1.1] Pentane-1- Il, bicyclo [2.2.2] octane-1-yl and the like are included. The cyclic tertiary hydrocarbyl group can be represented by formula B.

（式中、Ｒ^Aは、ヒドロカルビル基または置換ヒドロカルビル基であり、各Ｒ^Dは、独立して水素またはヒドロカルビル基または置換ヒドロカルビル基であり、ｗは、１～約３０の整数であり、Ｒ^Aおよび１個もしくは複数のＲ^Dおよび／または２個以上のＲ^Dが互いに結合されて追加の環を形成してもよい）
環式三級ヒドロカルビル基が、１個を超える脂環式環を含むとき、これは、多環式三級ヒドロカルビル基と呼ぶことができ、またはこのヒドロカルビル基がアルキル基である場合、これは、多環式三級アルキル基と呼ばれることがある。

(In the formula, ^RA is a hydrocarbyl group or a substituted hydrocarbyl group, each R ^D is an independently hydrogen or hydrocarbyl group or a substituted hydrocarbyl group, w is an integer of 1 to about 30, and ^RA And one or more ^RDs and / or two or more ^RDs may be combined with each other to form an additional ring)
When a cyclic tertiary hydrocarbyl group contains more than one alicyclic ring, it can be referred to as a polycyclic tertiary hydrocarbyl group, or if the hydrocarbyl group is an alkyl group, this can be referred to as a polycyclic tertiary hydrocarbyl group. Sometimes called a polycyclic tertiary alkyl group.

The terms "alkyl group" and "alkyl" are used interchangeably throughout the present disclosure. In the present disclosure, an "alkyl group" is defined as a _{C1-C 100 alkyl} which may be linear, branched or cyclic. Examples of such groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, iso-amyl, hexyl, octyl, cyclopropyl, cyclobutyl, cyclopentyl, etc. Homogeneous ones including cyclohexyl, cyclooctyl and their substitution analogs may be included. Substituent alkyl groups are hydrocarbyl groups, halogens (Br, Cl, F or I, etc.) or -NR ^* ₂ , -OR ^* , -SeR ^* , -TeR ^* , -PR ^* ₂ , -AsR ^* ₂ , -SbR ^*. ₂ , -SR ^* , -BR ^* ₂ , -SiR ^* ₃ , -GeR ^* ₃ , -SnR ^* ₃ , -PbR ^* ₃ ,-(CH ₂ ) q-SiR ^* ₃ and the same type (in the formula, q) Is 1 to 10, each R ^* is an independently hydrogen, hydrocarbyl or halocarbyl group, and two or more R ^* are bonded to each other to be fully saturated, partially unsaturated, or partially unsaturated, substituted or unsubstituted. Heteroatoms or heteroatom-containing groups, such as at least one functional group, which may form an aromatic or polycyclic ring structure, or have at least one heteroatom inserted into the hydrocarbyl ring). It is a group in which at least one hydrogen atom of the alkyl group is substituted with at least one non-hydrogen group such as.

If isomers of the listed alkyl, alkenyl, alkoxide or aryl groups are present (eg n-butyl, iso-butyl, sec-butyl and tert-butyl), to one member of the group (eg n-butyl). Reference is made to explicitly disclose the remaining isomers in the family (eg, iso-butyl, sec-butyl and tert-butyl). Similarly, references to alkyl, alkenyl, alkoxide or aryl groups that do not specify a particular isomer (eg, butyl) refer to all isomers (eg, n-butyl, iso-butyl, sec-butyl and tert-butyl). Explicitly disclose.

As used herein, Mn is the number average molecular weight, Mw is the mass average molecular weight, Mz is the z average molecular weight, mass% is mass percent, and mol% is mol percent. The molecular weight distribution (MWD) (also called the polydispersity index (PDI)) is defined as Mw divided by Mn. Unless otherwise stated, all molecular weight units (eg, Mw, Mn, Mz) are g / mol (g mol ^-1 ).
The following abbreviations may be used herein: Me is methyl, Et is ethyl, Pr is propyl, cPr is cyclopropyl, nPr is n-propyl, iPr is isopropyl. , Bu is butyl, nBu is normal butyl, iBu is isobutyl, sBu is sec-butyl, tBu is tert-butyl, Oct is octyl, Ph is phenyl and MAO is Methylarmoxane, dme is 1,2-dimethoxyethane, ptBu is para-tertiary butyl, TMS is trimethylsilyl, TIBAL is triisobutylaluminum, TNOA and TNOAL are tri (n). -Octyl) aluminum, p-Me is para-methyl, Bn is benzyl (ie, CH ₂ Ph), THF (also called thf) is tetrahydrofuran, RT is room temperature (and especially in particular). (Unless otherwise stated, it is 23 ° C.), trol is toluene, EtOAc is ethyl acetate, Cbz is carbazole and Cy is cyclohexyl.

A "catalytic system" is a combination comprising at least one catalytic compound and at least one activator. When a "catalytic system" is used to represent such a pair prior to activation, it is an activator and optionally an inactivated catalytic complex (precatalyst) with a co-activator. means. When "catalytic system" is used to represent such a pair after activation, this means an activated complex and an activator or other charge balancing moiety. The transition metal compound can be neutral, such as in a precatalyst, or a charged species with a counterion, such as in an activation catalytic system. In the present invention and claims thereof, when it is described that the catalyst system contains a component in a neutral stable form, the component in the ionic form may be in a form of reacting with a monomer to form a polymer. Well understood by those skilled in the art. The polymerization catalyst system is a catalyst system capable of polymerizing a monomer into a polymer.
As used herein, catalysts may be described as catalysts, catalyst precursors, precatalytic compounds, catalytic compounds or transition metal compounds, and these terms are used interchangeably.
An "anionic ligand" is a negatively charged ligand that donates one or more electron pairs to a metal ion. The term "anionic donor" is used synonymously with "anionic ligand". Examples of anionic donors in the context of the present invention include methyl, chloride, fluoride, alkoxide, aryloxide, alkyl, alkenyl, thiolate, carboxylate, amide, methyl, benzyl, hydride, amidinate, amidate and phenyl. Included, but not limited to. Two anionic donors may be combined to form a dianionic group.

A "neutral Lewis base" or "neutral donor group" is an uncharged (ie, neutral) group that donates one or more electron pairs to a metal ion. Non-limiting examples of neutral Lewis bases include ethers, thioethers, amines, phosphines, ethyl ethers, tetrahydrofurans, dimethyl sulfides, triethylamines, pyridines, alkenes, alkenes, allenes and carbens. Lewis bases may be combined with each other to form bidentate or tridental Lewis bases.

Within the scope of the present invention and claims relating thereto, the phenolate donors include Ph-O-, Ph-S- and Ph-N (R ^{^} )-groups (in the formula, R ^ is hydrogen, C1 _- C. ₄₀ hydrocarbyls, C1 _- C ₄₀ substituted hydrocarbyls, heteroatoms or heteroatom-containing groups, where Ph is a optionally substituted phenyl).

The present invention is a novel family of catalysts comprising a transitional metal complex of a dianionic tridentate ligand characterized by a central neutral donor group and two phenolate donors, the tridentate ligand being the metal center. With respect to a new family of catalysts coordinated to to form two 8-membered rings. For this type of complex, it is advantageous that the central neutral donor is a heterocyclic group. It is particularly advantageous that the hydrogen at the alpha position is not present in the heterocyclic group with respect to the heteroatom. It is also advantageous for this type of complex that the phenolate is substituted with one or more cyclic tertiary alkyl substituents. The use of cyclic tertiary alkyl substituted phenolates has been shown to improve the ability of this catalyst to produce high molecular weight polymers.
Complexes of substituted bis (phenorate) ligands (such as adamantanyl substituted bis (phenorate) ligands) have been prepared and characterized herein. This complex produces an active olefin polymerization catalyst when combined with an activator such as a non-coordinating anion activator or an alumoxane activator. A useful bis (arylphenolate) pyridine complex comprises a tridentate bis (arylphenorate) pyridine ligand coordinated to a group 4 transition metal with the formation of two 8-membered rings.
The present invention comprises a metal selected from Group 3-6 metals or lanthanide metals and a tridentate dianionic ligand comprising two anionic donor groups and a neutral Lewis base donor, the neutral Lewis base donor. Also relates to metal complexes in which is covalently bonded between two anionic donors and the metal-ligand complex is characterized by a pair of 8-membered metallacycle rings.
The present invention relates to a catalytic system comprising the activator described herein and one or more catalytic compounds.
The present invention uses the catalytic compounds described herein, comprising contacting one or more olefins with a catalytic system comprising an activator described herein and a catalytic compound. It is also involved in the process of polymerizing olefins.

The present disclosure discloses a catalytic system containing the transition metal compound and the activator compound described herein, such an activator compound for activating the transition metal compound in the catalytic system for polymerizing an olefin. And the process for polymerizing olefins, which comprises contacting one or more olefins with a catalytic system containing a transition metal compound and an activator compound under polymerization conditions, such as toluene. The aromatic solvent is absent (eg, present at zero mol% relative to the number of moles of activator, instead less than 1 mol%, preferably catalytic system, polymerization reaction and / or produced polymer. , Does not contain "detectable aromatic hydrocarbon solvents" such as toluene), also involved in the process. In the present disclosure, "detectable aromatic hydrocarbon solvent" means 0.1 mg / m ² or more as measured by gas phase chromatography. In the present disclosure, "detectable toluene" means 0.1 mg / m ² or more as measured by gas phase chromatography.

The polyalpha-olefins produced herein preferably contain 0 ppm (instead less than 1 ppm, instead less than 2 ppm, instead less than 5 ppm) residual aromatic hydrocarbons. Preferably, the polyalpha-olefin produced herein contains 0 ppm (instead less than 1 ppm) of residual toluene.
The catalyst system used herein preferably contains 0 ppm (instead less than 1 ppm) of residual aromatic hydrocarbons. Preferably, the catalytic system used herein comprises 0 ppm (instead less than 1 ppm) of residual toluene.
The polyalpha-olefins produced herein are preferably 5% by weight or less of aromatic hydrocarbons such as toluene (instead of 4% by weight or less, instead of 3% by weight or less, instead of 2% by weight or less). , Instead of 1% by weight or less, instead 0.5% by weight or less, instead less than 50 ppm, instead less than 5 ppm) of residual aromatic hydrocarbons such as toluene.

Catalytic Compounds The terms "catalyst,""compound,""catalyticcompound," and "complex" are synonymous to refer to a transition metal or lanthanide metal complex that produces an olefin polymerization catalyst when combined with a suitable activator. Can be used.

The catalytic complex of the present invention is a trident containing a metal selected from the 3, 4, 5 or 6 group metals or lanthanide metals in the Periodic Table of the Elements, two anionic donor groups and a neutral heterocyclic Lewis base donor. The heterocyclic donor includes a dianionic ligand and is covalently bonded between the two anionic donors. Preferably the dianionic tridentate ligand is characterized by a central heterocyclic donor group and two phenolate donors, which are coordinated to the metal center and have two 8-membered rings. To form.
The metal is preferably selected from Group 3, 4, 5 or 6 elements. Preferably, the metal (M) is a Group 4 metal. Most preferably, the metal (M) is zirconium or hafnium.
Preferably the heterocyclic Lewis base donor is characterized by a nitrogen or oxygen donor atom. Preferred heterocyclic groups include pyridine, pyrazine, pyrimidine, triazine, thiazole, imidazole, thiophene, oxazole, thiazole, furan and derivatives of their substituted variants. Preferably, the hydrogen at the alpha position with respect to the donor atom is absent in the heterocyclic Lewis base. Particularly preferred heterocyclic Lewis base donors include pyridine, 3-substituted pyridine and 4-substituted pyridine.
The anionic donor of the tridentate dianionic ligand may be arylthiolate, phenolate or anilides. The preferred anionic donor is phenolate. It is preferred that the tridentate dianionic ligand coordinates at the center of the metal to form a complex without a mirror plane of symmetry. It is preferred that the tridentate dianionic ligand coordinates to the center of the metal to form a complex with a two-fold axis of symmetry, and when determining the symmetry of the bis (phenorate) complex, the metal and dianionic tridentate. Only the locus ligand is considered (ie, the remaining ligands are ignored).

The bis (phenorate) ligand useful in the present invention is preferably a tridental dianionic ligand that coordinates to the metal M so that a pair of 8-membered metallacycle rings are formed. The bis (phenolate) ligand wraps the metal to form a complex with a double axis of rotation, thus giving the complex C ₂ symmetry. The C ₂ -geometry and 8-membered metallacycle ring are characteristic of this complex, which makes it an effective catalytic component for the formation of polyolefins, especially isotactic polys (alpha olefins). If the ligand is coordinated to the metal so that the complex has mirror plane (C _s ) symmetry, the catalyst is expected to produce only atactic poly (alpha olefin), these symmetries-reactive. The rules are summarized by Bercaw, JE (2009) in Macromolecules, v.42, pp. 8751-8762. The pair of 8-membered metallacycle rings of the complex of the present invention is also a notable feature that favors catalytic activity, temperature stability and iso selectivity of the monomer chain. Related Group 4 complexes characterized by smaller 6-membered metallacycle rings are known to form mixtures of C ₂ symmetric and C _s symmetric complexes when used in olefin polymerization (Macromolecules 2009, 42, 8751-8762), therefore, it is not well suited for the production of high isotactic polys (alpha olefins).

In the present invention, the bis (phenolate) ligand containing the oxygen donor group (ie, in formula (I), E = E'= oxygen) is preferably substituted with an alkyl, substituted alkyl, aryl or other group. ing. It is advantageous that each phenolate group is substituted at a ring position adjacent to the oxygen donor atom. The substituent located adjacent to the oxygen donor atom is preferably an alkyl group containing 1 to 20 carbon atoms. It is preferred that the substituent at the position next to the oxygen donor atom is a non-aromatic cyclic alkyl group having one or more 5- or 6-membered rings. The substituent located next to the oxygen donor atom is preferably a cyclic tertiary alkyl group. It is highly preferred that the substituent at the position next to the oxygen donor atom is adamantane-1-yl or substituted adamantane-1-yl.

The neutral heterocyclic Lewis base donor is covalently bonded between the two anionic donors via a "linker group" that binds the heterocyclic Lewis base to the phenolate group. The "linker group" is represented in formula (I) by (A ³ A ² ) and (A 2'A ^{3' )} . The choice of each linker group can affect the catalytic performance of the poly (alphaolefin) produced, such as tacticity. Each linker group is typically a divalent C2 _- C ₄₀ group that is diatomic in length. One or both linker groups may independently be phenylene, substituted phenylene, heteroaryl, vinylene, or a bicarbon long acyclic linker group. When one or both linker groups are phenylene, the alkyl substituents on the phenylene group may be chosen to optimize catalytic performance. Typically, one or both phenylenes may be unsubstituted, or methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecylic, dodecyl, tridecylic, tetradecyl, pentadecyl, hexadecyl, heptadecyl. , Octadecyl, nonadecil, eicosyl or their isomers (eg, isopropyl, etc.) and the like may be independently substituted with C1-C _{- 20} alkyl.

(I)
（式中、
Ｍは、３、４、５もしくは６族遷移金属またはランタニド（Ｈｆ、ＺｒまたはＴｉなど）であり、
ＥおよびＥ’は、それぞれ独立してＯ、ＳまたはＮＲ⁹（式中、Ｒ⁹は、独立して水素、Ｃ₁－Ｃ₄₀ヒドロカルビル、Ｃ₁－Ｃ₄₀置換ヒドロカルビルまたはヘテロ原子含有基である）、好ましくはＯであり、好ましくはＥおよびＥ’の両方がＯであり、
Ｑは、金属Ｍに対して供与結合を形成する１４、１５または１６族原子であり、好ましくはＱは、Ｃ、Ｏ、ＳまたはＮであり、より好ましくはＱは、Ｃ、ＮまたはＯであり、最も好ましくはＱはＮであり、
Ａ¹ＱＡ^1’は、３原子架橋を介してＡ²をＡ^2’に連結する、４～４０個の非水素原子を含む複素環式ルイス塩基の一部であり（Ａ¹とＡ^1’とを結合する曲線と組み合わさったＡ¹ＱＡ^1’は複素環式ルイス塩基を表す）、３原子架橋の中心原子はＱであり、Ａ¹およびＡ^1’は、独立してＣ、ＮまたはＣ（Ｒ²²）（式中、Ｒ²²は、水素、Ｃ₁－Ｃ₂₀ヒドロカルビルおよびＣ₁－Ｃ₂₀置換ヒドロカルビルから選択される）である。好ましくはＡ¹およびＡ^1’はＣであり、 The present invention further relates to a catalytic compound represented by the formula (I) and a catalytic system containing such a compound.

(I)
(During the ceremony,
M is a Group 3, 4, 5 or 6 transition metal or lanthanide (such as Hf, Zr or Ti).
E and E'are independently O, S or NR ⁹ (in the formula, R ⁹ is independently hydrogen, C1 _- C ₄₀ hydrocarbyl, C1 _- C ₄₀ substituted hydrocarbyl or heteroatom-containing group. ), Preferably O, preferably both E and E'are O,
Q is a Group 14, 15 or 16 atom forming a donor bond to the metal M, preferably Q is C, O, S or N, and more preferably Q is C, N or O. Yes, most preferably Q is N,
A ¹ QA 1'is part of a heterocyclic Lewis base containing 4-40 non-hydrogen atoms that links A ² to A ^2'through a triatomic bridge (A ¹ and A ^{1') .} A ¹ QA ^1'combined with a curve that binds to and represents a heterocyclic Lewis base), the central atom of the triatomic bridge is Q, and A ¹ and A ^1'are C, N or independently. C (R ²² ) (in the formula, R ²² is selected from hydrogen, C1 _- C ₂₀ hydrocarbyl and C1 _- C ₂₀ substituted hydrocarbyl). Preferably A ¹ and A ^1'are C

は、オルト－フェニレン、置換オルト－フェニレン、オルト－アレーン、インドレン、置換インドレン、ベンゾチオフェン、置換ベンゾチオフェン、ピロレン（ｐｙｒｒｏｌｅｎｅ）、置換ピロレン、チオフェン、置換チオフェン、１，２－エチレン（－ＣＨ₂ＣＨ₂－）、置換１，２－エチレン、１，２－ビニレン（－ＨＣ＝ＣＨ－）または置換１，２－ビニレンなど、２原子架橋を介してＡ¹をＥ結合アリール基に連結する、２～４０個の非水素原子を含む二価基であり、好ましくは

Ortho-phenylene, substituted ortho-phenylene, ortho-alene, indren, substituted indrene, benzothiophene, substituted benzothiophene, pyrrolene, substituted pyrrolene, thiophene, substituted thiophene, 1,2-ethylene (-CH ₂ CH). _2- ), substituted 1,2-ethylene, 1,2-vinylene (-HC = CH-) or substituted 1,2-vinylene, etc., which links A ¹ to an E-bonded aryl group via a two-atomic bridge. It is a divalent group containing up to 40 non-hydrogen atoms, preferably

は、二価ヒドロカルビル基であり、

は、オルト－フェニレン、置換オルト－フェニレン、オルト－アレーン、インドレン、置換インドレン、ベンゾチオフェン、置換ベンゾチオフェン、ピロレン、置換ピロレン、チオフェン、置換チオフェン、１，２－エチレン（－ＣＨ₂ＣＨ₂－）、置換１，２－エチレン、１，２－ビニレン（－ＨＣ＝ＣＨ－）または置換１，２－ビニレンなど、２原子架橋を介してＡ^1’をＥ’結合アリール基に連結する、２～４０個の非水素原子を含む二価基であり、好ましくは

Is a divalent hydrocarbyl group,

Ortho-phenylene, substituted ortho-phenylene, ortho-alene, indrene, substituted indrene, benzothiophene, substituted benzothiophene, pyrrolene, substituted pyrrolene, thiophene, substituted thiophene, 1,2-ethylene (-CH ₂ CH _2- ). , Substituent 1,2-ethylene, 1,2-vinylene (-HC = CH-) or substituted 1,2-vinylene, etc., linking A ^1'to an E'bonded aryl group via a diatomic bridge, 2 to It is a divalent group containing 40 non-hydrogen atoms, preferably

は、二価ヒドロカルビル基であり、
各Ｌは、独立してルイス塩基であり、
各Ｘは、独立してアニオン性配位子であり、
ｎは、１、２または３であり、
ｍは、０、１または２であり、
ｎ＋ｍは４以下であり、
Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｒ^1’、Ｒ^2’、Ｒ^3’およびＲ^4’のそれぞれは、独立して水素、Ｃ₁－Ｃ₄₀ヒドロカルビル、Ｃ₁－Ｃ₄₀置換ヒドロカルビル、ヘテロ原子もしくはヘテロ原子含有基であり（好ましくはＲ^1’およびＲ¹は、独立して環式三級アルキル基などの環式基である）、またはＲ¹およびＲ²、Ｒ²およびＲ³、Ｒ³およびＲ⁴、Ｒ^1’およびＲ^2’、Ｒ^2’およびＲ^3’、Ｒ^3’およびＲ^4’のうちの１つまたは複数が結合されて、５個、６個、７個または８個の環原子をそれぞれ有し、かつ環上の置換基が結合して追加の環を形成することができる１個もしくは複数の置換ヒドロカルビル環、非置換ヒドロカルビル環、置換複素環式環または非置換複素環式環を形成してよく、
任意の２個のＬ基が互いに結合されて二座ルイス塩基を形成してよく、
Ｘ基がＬ基に結合されてモノアニオン性二座基を形成してよく、
任意の２個のＸ基が互いに結合されてジアニオン性配位子基を形成してよい）

Is a divalent hydrocarbyl group,
Each L is an independent Lewis base,
Each X is an independent anionic ligand,
n is 1, 2 or 3
m is 0, 1 or 2,
n + m is 4 or less,
R ¹ , R ² , R ³ , R ⁴ , R ^1' , R ^{2' ,} R ^3'and R 4'are independently hydrogen, C ₁ -C ₄₀ hydrocarbyl, C ₁ -C ₄₀ substituted hydrocarbyl. , Heteroatom or heteroatom-containing group (preferably R ^1'and R ¹ are independently cyclic groups such as cyclic tertiary alkyl groups), or R ¹ and R ² , R ² and R. ³ , R ³ and R ⁴ , R ^1'and R ^{2 '} , R 2'and R ^{3 '} , R ^3'and R 4'are combined to form 5, 6, 7 One or more substituted hydrocarbyl rings, unsubstituted hydrocarbyl rings, substituted heterocyclic rings each having one or eight ring atoms and capable of combining substituents on the ring to form an additional ring. Or an unsubstituted heterocyclic ring may be formed,
Any two L groups may be attached to each other to form a bidentate Lewis base.
The X group may be attached to the L group to form a monoanionic bidentate.
Any two X groups may be bonded to each other to form a dianionic ligand group)

(II)
（式中、
Ｍは、３、４、５もしくは６族遷移金属またはランタニド（Ｈｆ、ＺｒまたはＴｉなど）であり、
ＥおよびＥ’は、それぞれ独立してＯ、ＳまたはＮＲ⁹（式中、Ｒ⁹は、独立して水素、Ｃ₁－Ｃ₄₀ヒドロカルビル、Ｃ₁－Ｃ₄₀置換ヒドロカルビルまたはヘテロ原子含有基である）、好ましくはＯであり、好ましくはＥおよびＥ’の両方がＯであり、
各Ｌは、独立してルイス塩基であり、
各Ｘは、独立してアニオン性配位子であり、
ｎは、１、２または３であり、
ｍは、０、１または２であり、
ｎ＋ｍは４以下であり、
Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｒ^1’、Ｒ^2’、Ｒ^3’およびＲ^4’のそれぞれは、独立して水素、Ｃ₁－Ｃ₄₀ヒドロカルビル、Ｃ₁－Ｃ₄₀置換ヒドロカルビル、ヘテロ原子もしくはヘテロ原子含有基であり、またはＲ¹およびＲ²、Ｒ²およびＲ³、Ｒ³およびＲ⁴、Ｒ^1’およびＲ^2’、Ｒ^2’およびＲ^3’、Ｒ^3’およびＲ^4’のうちの１つまたは複数が結合されて、５個、６個、７個または８個の環原子をそれぞれ有し、かつ環上の置換基が結合して追加の環を形成することができる１個もしくは複数の置換ヒドロカルビル環、非置換ヒドロカルビル環、置換複素環式環または非置換複素環式環を形成してよく、
任意の２個のＬ基が互いに結合されて二座ルイス塩基を形成してよく、
Ｘ基がＬ基に結合されてモノアニオン性二座基を形成してよく、
任意の２個のＸ基が互いに結合されてジアニオン性配位子基を形成してよく、
Ｒ⁵、Ｒ⁶、Ｒ⁷、Ｒ⁸、Ｒ^5’、Ｒ^6’、Ｒ^7’、Ｒ^8’、Ｒ¹⁰、Ｒ¹¹およびＲ¹²のそれぞれは、独立して水素、Ｃ₁－Ｃ₄₀ヒドロカルビル、Ｃ₁－Ｃ₄₀置換ヒドロカルビル、ヘテロ原子もしくはヘテロ原子含有基であり、またはＲ⁵およびＲ⁶、Ｒ⁶およびＲ⁷、Ｒ⁷およびＲ⁸、Ｒ^5’およびＲ^6’、Ｒ^6’およびＲ^7’、Ｒ^7’およびＲ^8’、Ｒ¹⁰およびＲ¹¹もしくはＲ¹¹およびＲ¹²のうちの１つまたは複数が結合されて、５個、６個、７個または８個の環原子をそれぞれ有し、かつ環上の置換基が結合して追加の環を形成することができる１個もしくは複数の置換ヒドロカルビル環、非置換ヒドロカルビル環、置換複素環式環または非置換複素環式環を形成してよい）
金属（Ｍ）は、好ましくは、３、４、５または６族元素、より好ましくは４族から選択される。最も好ましくは金属（Ｍ）は、ジルコニウムまたはハフニウムである。 The present invention further relates to a catalytic compound represented by the formula (II) and a catalytic system containing such a compound.

(II)
(During the ceremony,
M is a Group 3, 4, 5 or 6 transition metal or lanthanide (such as Hf, Zr or Ti).
E and E'are independently O, S or NR ⁹ (in the formula, R ⁹ is independently hydrogen, C1 _- C ₄₀ hydrocarbyl, C1 _- C ₄₀ substituted hydrocarbyl or heteroatom-containing group. ), Preferably O, preferably both E and E'are O,
Each L is an independent Lewis base,
Each X is an independent anionic ligand,
n is 1, 2 or 3
m is 0, 1 or 2,
n + m is 4 or less,
R ¹ , R ² , R ³ , R ⁴ , R ^1' , R ^{2' ,} R ^3'and R 4'are independently hydrogen, C ₁ -C ₄₀ hydrocarbyl, C ₁ -C ₄₀ substituted hydrocarbyl. , Heteroatom or heteroatom-containing group, or R ¹ and R ² , R ² and R ³ , R ³ and R ⁴ , R ^1'and R ^{2 '} , R 2'and R ^3' , R ^3'and One or more of R ^4'are bonded to each other to have 5, 6, 7 or 8 ring atoms, and the substituents on the ring combine to form an additional ring. One or more substituted hydrocarbyl rings, unsubstituted hydrocarbyl rings, substituted heterocyclic rings or unsubstituted heterocyclic rings may be formed.
Any two L groups may be attached to each other to form a bidentate Lewis base.
The X group may be attached to the L group to form a monoanionic bidentate.
Any two X groups may be bonded to each other to form a dianionic ligand group.
R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ^5' , R ^6' , R ^7' , R ^8' , R ¹⁰ , R ¹¹ and R ¹² are each independently hydrogen, C ₁ -C ₄₀ . Hydrocarbyl, C1 _{- C40} substituted hydrocarbyl, heteroatom or heteroatom-containing group, or R ⁵ and R ⁶ , R ⁶ and R ⁷ , R ⁷ and R ⁸ , R ^5'and R ^6' , R ^6' And one or more of R ^{7 '} , R 7'and R ^8' , R ¹⁰ and R ¹¹ or R ¹¹ and R ¹² combined to form 5, 6, 7 or 8 ring atoms. One or more substituted hydrocarbyl rings, unsubstituted hydrocarbyl rings, substituted heterocyclic rings or unsubstituted heterocyclic rings, respectively, and the substituents on the ring can be bonded to form an additional ring. May form)
The metal (M) is preferably selected from Group 3, 4, 5 or 6 elements, more preferably Group 4. Most preferably, the metal (M) is zirconium or hafnium.

The donor atom Q of the neutral heterocyclic Lewis base (in formula (I)) is preferably nitrogen, carbon or oxygen. The preferred Q is nitrogen.
Non-limiting examples of neutral heterocyclic Lewis bases include pyridine, pyrazine, pyrimidine, triazine, thiazole, imidazole, thiophene, oxazole, thiazole, furan and derivatives of their substituted variants. Preferred heterocyclic Lewis base groups include derivatives of pyridine, pyrazine, thiazole and imidazole.

Each of the heterocyclic Lewis bases (in formula I) A ¹ and A ^{1'independently} C, N or C (R ²² ) (in formula R ²² is hydrogen, C ₁ -C ₂₀ hydrocarbyl and (Selected from C ₁ -C ₂₀ substituted hydrocarbyls). Preferably A ¹ and A ^1'are carbon. When Q is carbon, it is preferred that A ¹ and A ^1'are selected from nitrogen and C (R ²² ). When Q is nitrogen, it is preferred that A ¹ and A ^1'are carbon. It is preferable that Q = nitrogen and A ¹ = A ^1' = carbon. When Q is nitrogen or oxygen, it is preferred that the heterocyclic Lewis base in formula (I) does not have any hydrogen atom attached to the A ¹ or A ^1'atom . This is preferred because it is believed that hydrogen at those positions may undergo unwanted degradation reactions that reduce the stability of the catalytically active species.
The heterocyclic Lewis base (of formula I) represented by A ¹ QA ^1'combined with a curve connecting A ¹ and A ^1'is preferably selected from the following, with each R ²³ group being hydrogen. , Heteroatom, C ₁ -C ₂₀ alkyl, C ₁ -C ₂₀ alkoxide, C ₁ -C ₂₀ amide and C ₁ -C ₂₀ substituted alkyl.

In some embodiments, the heterocyclic Lewis base (of formula (I)) represented by A ¹ QA ^1'combined with a curve connecting A ¹ and A 1'is ^a ring heteroatom. A 6-membered ring containing a single ring heteroatom with a Q, or a 5-membered ring containing one or two ring heteroatoms but having a Q, which is a ring carbon. Instead, the heterocyclic Lewis base (of formula (I)) represented by A ¹ QA ^1'combined with a curve connecting A ¹ and A 1'has ^a ring heteroatom Q. It is not a 5-membered ring containing one or more ring heteroatoms.

In formula (I) or (II), E and E'are oxygen or NR ⁹ (where R ⁹ is independently hydrogen, C1 _- C ₄₀ hydrocarbyl, C1 _- C ₄₀ substituted hydrocarbyl or heteroatom). It is selected from each of the contained groups). It is preferred that E and E'are oxygen. When E and / or E'is NR ⁹ , R ⁹ is preferably selected from C1 _- C ₂₀ hydrocarbyl, alkyl or aryl. In one embodiment, E and E'are O, S or N (alkyl) or N (aryl) (in the formula, alkyl is preferably methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, nonyl). , Decyl, undecyl, dodecyl and the like, and the aryl is a C _{6 -} C ₄₀ aryl group, such as phenyl, naphthalenyl, benzyl, methylphenyl and the like _. ) Are selected from each.

は、独立してＣ₁－Ｃ₁₂ヒドロカルビル基などの二価ヒドロカルビル基である。
式（Ｉ）または（ＩＩ）の錯体では、ＥおよびＥ’が酸素であるとき、酸素原子の隣の位置（すなわち、式（Ｉ）または（ＩＩ）中、Ｒ¹およびＲ^1’）で各フェノレート基が置換されていることが有利である。したがって、ＥおよびＥ’が酸素であるとき、Ｒ¹およびＲ^1’のそれぞれが、独立してＣ₁－Ｃ₄₀ヒドロカルビル、Ｃ₁－Ｃ₄₀置換ヒドロカルビル、ヘテロ原子またはヘテロ原子含有基であることが好ましく、より好ましくは、Ｒ¹およびＲ^1’のそれぞれは、独立して１個もしくは複数の５または６員環を有する非芳香族環式アルキル基（シクロヘキシル、シクロオクチル、アダマンタニルまたは１－メチルシクロヘキシルまたは置換アダマンタニルなど）、最も好ましくは非芳香族環式三級アルキル基（１－メチルシクロヘキシル、アダマンタニルまたは置換アダマンタニルなど）である。
式（Ｉ）または（ＩＩ）の本発明のいくつかの実施形態において、Ｒ¹およびＲ^1’のそれぞれは、独立して三級ヒドロカルビル基である。式（Ｉ）または（ＩＩ）の本発明の他の実施形態において、Ｒ¹およびＲ^1’のそれぞれは、独立して環式三級ヒドロカルビル基である。式（Ｉ）または（ＩＩ）の本発明の他の実施形態において、Ｒ¹およびＲ^1’のそれぞれは、独立して多環式三級ヒドロカルビル基である。
式（Ｉ）または（ＩＩ）の本発明のいくつかの実施形態において、Ｒ¹およびＲ^1’のそれぞれは、独立して三級ヒドロカルビル基である。式（Ｉ）または（ＩＩ）の本発明の他の実施形態において、Ｒ¹およびＲ^1’のそれぞれは、独立して環式三級ヒドロカルビル基である。式（Ｉ）または（ＩＩ）の本発明の他の実施形態において、Ｒ¹およびＲ^1’のそれぞれは、独立して多環式三級ヒドロカルビル基である。 In embodiments,

Is independently a divalent hydrocarbyl group such as _a C1- _C12 hydrocarbyl group.
In the complex of formula (I) or (II), when E and E'are oxygen, each at the position next to the oxygen atom (ie, in formula (I) or (II), R ¹ and R ^1' ). It is advantageous that the phenolate group is substituted. Therefore, when E and E'are oxygen, each of R ¹ and R ^1'is independently a C1 _- C ₄₀ hydrocarbyl, _a C1-C ₄₀ substituted hydrocarbyl, a heteroatom or a heteroatom-containing group. Preferably, more preferably, each of R ¹ and R ^1'is a non-aromatic cyclic alkyl group (cyclohexyl, cyclooctyl, adamantanyl or 1-methyl) having one or more independent 5- or 6-membered rings. Cyclohexyl or substituted adamantanyl, etc.), most preferably a non-aromatic cyclic tertiary alkyl group (1-methylcyclohexyl, adamantanyl, substituted adamantanyl, etc.).
In some embodiments of the invention of formula (I) or (II), each of R ¹ and R ^1'is an independent tertiary hydrocarbyl group. In another embodiment of the invention of formula (I) or (II), each of R ¹ and R ^1'is an independently cyclic tertiary hydrocarbyl group. In another embodiment of the invention of formula (I) or (II), each of R ¹ and R ^1'is an independently polycyclic tertiary hydrocarbyl group.
In some embodiments of the invention of formula (I) or (II), each of R ¹ and R ^1'is an independent tertiary hydrocarbyl group. In another embodiment of the invention of formula (I) or (II), each of R ¹ and R ^1'is an independently cyclic tertiary hydrocarbyl group. In another embodiment of the invention of formula (I) or (II), each of R ¹ and R ^1'is an independently polycyclic tertiary hydrocarbyl group.

）は、それぞれ好ましくはオルト－フェニレン基の一部、好ましくは置換オルト－フェニレン基の一部である。式（ＩＩ）のＲ⁷位およびＲ^7’位が水素、またはメチル、エチル、プロピル、ブチル、ペンチル、ヘキシル、ヘプチル、オクチル、ノニル、デシル、ウンデシル、ドデシル、トリデシル、テトラデシル、ペンタデシル、ヘキサデシル、ヘプタデシル、オクタデシル、ノナデシル、エイコシルもしくはそれらの異性体（例えばイソプロピル（ｉｏｓｐｒｏｐｙｌ）など）などのＣ₁－Ｃ₂₀アルキルであることが好ましい。高タクチシチーを有するポリマーを目標とする適用については、式（ＩＩ）のＲ⁷位およびＲ^7’位がＣ₁－Ｃ₂₀アルキルであることが好ましく、Ｒ⁷およびＲ^7’の両方がＣ₁－Ｃ₃アルキルであることが最も好ましい。 Linker group (ie, in formula (I))

) Are preferably a part of an ortho-phenylene group, preferably a part of a substituted ortho-phenylene group. The ^R7 and ^R7'positions of formula (II) are hydrogen, or methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecylic, dodecyl, tridecylic, tetradecyl, pentadecyl, hexadecyl, heptadecyl. , Octadecyl, nonadecyl, eicosyl or isomers thereof (eg, isopropyl, etc.) and the like, preferably C1 _- C ₂₀ alkyl. For applications targeting polymers with high tacticity, the R ⁷ and R 7'positions of formula (II) are preferably C ₁ -C ₂₀ alkyl, with both R ⁷ and R ^7'being C ₁ ^' . -C ₃ alkyl is most preferred.

In the embodiment of formula (I) herein, Q is C, N or O, preferably Q is N.
In an embodiment of formula (I) herein, A ¹ and A ^1'are independently carbon, nitrogen or C (R ²² ), where R ²² is hydrogen, C ₁ -C ₂₀ hydrocarbyl, C. Selected from ₁ -C ₂₀ substituted hydrocarbyls. Preferably A ¹ and A ^1'are carbon.
In embodiments of formula (I) herein, A ¹ QA ^1'in formula (I) is pyridine, pyrazine, pyrimidine, triazine, thiazole, imidazole, thiophene, oxazole, thiazole, furan or a substituted variant thereof. It is a part of the heterocyclic Lewis base such as.
In an embodiment of formula (I) herein, A ¹ QA ^1'contains a heterocyclic Lewis containing 2 to 20 non-hydrogen atoms linking A ² to A ^2'through a triatomic bridge. It is part of the base and the central atom of the triatomic bridge is Q. Preferably each A ¹ and A ^1'is a carbon atom and the A ¹ QA ^1'fragment is a pyridine, pyrazine, pyrimidine, triazine, thiazole, imidazole, thiophene, oxazole, thiazole, furan or a substituted variant group thereof or theirs. Form some of the substitutional variants of.
In one embodiment of formula (I) herein, Q is carbon, each A ¹ and A ^1'is N or C (R ²² ) (in the formula, R ²² is hydrogen, C ₁ −. C ₂₀ hydrocarbyl, C1 _- C ₂₀ substituted hydrocarbyl, heteroatom or heteroatom-containing group). In this embodiment, the A ¹ QA ^1'fragment forms part of a cyclic carbene, an N-heterocyclic carbene, a cyclic aminoalkyl carbene or a substituted variant group thereof or a substituted variant thereof.

は、２原子架橋を介してＡ¹をＥ結合アリール基に連結する、２～２０個の非水素原子を含む二価基であり、ここで

は直鎖状アルキルであり、または環式基（置換されてもよいオルト－フェニレン基、またはオルト－アリーレン基など）もしくはその置換変種の一部を形成する。 In the embodiment of formula (I) of the present specification.

Is a divalent group containing 2 to 20 non-hydrogen atoms linking A ¹ to an E-bonded aryl group via biatomic cross-linking, where

Is a linear alkyl or forms part of a cyclic group (such as an ortho-phenylene group which may be substituted, or an ortho-allylene group) or a substituted variant thereof.

は、２原子架橋を介してＡ^1’をＥ’結合アリール基に連結する、２～２０個の非水素原子を含む二価基であり、ここで

は直鎖状アルキルであり、または環式基（置換されてもよいオルト－フェニレン基、またはオルト－アリーレン基など）もしくはその置換変種の一部を形成する。

Is a divalent group containing 2 to 20 non-hydrogen atoms linking A ^1'to an E'bonded aryl group via biatomic cross-linking, where

Is a linear alkyl or forms part of a cyclic group (such as an ortho-phenylene group which may be substituted, or an ortho-allylene group) or a substituted variant thereof.

In embodiments of the invention herein, in formulas (I) and (II), M is a Group 4 metal such as Hf or Zr.
In embodiments of the invention herein, E and E'in formulas (I) and (II) are O.
In embodiments of the invention herein, in formulas (I) and (II), R ¹ , R ² , R ³ , R ⁴ , R ^1' , R ^{2' ,} R ^3'and R 4'are independent. And hydrogen, C1 _- C ₄₀ hydrocarbyl, C1 _- C ₄₀ substituted hydrocarbyl, heteroatom or heteroatom-containing group, or R ¹ and R ² , R ² and R ³ , R ³ and R ⁴ , R ¹ One or more of'and R ^{2' ,} R ^2'and R ^{3 '} , R ^3'and R 4'are bonded and have 5, 6, 7 or 8 ring atoms, respectively. And to form one or more substituted hydrocarbyl rings, unsubstituted hydrocarbyl rings, substituted heterocyclic rings or unsubstituted heterocyclic rings on which the substituents on the ring can be bonded to form additional rings. It may be hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl or an isomer thereof.

In embodiments of the invention herein, in formulas (I) and (II), R ¹ , R ² , R ³ , R ⁴ , R ^1' , R ^2' , R ^3' , R ^4'and R ⁹ Methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecil, eikosyl, heneikosyl, docosyl, trichosyl, tetracosyl, From pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl, triacontyl, phenyl, substituted phenyl (such as methylphenyl and dimethylphenyl), benzyl, substituted benzyl (such as methylbenzyl), naphthalenyl, cyclohexyl, cyclohexenyl, methylcyclohexyl and their isomers. Selected independently.
In embodiments of the invention herein, in formulas (I) and (II), R ⁴ and R ^4'are independently hydrogen or C1 _{-C 3 hydrocarbyls} such as methyl, ethyl or propyl.
In embodiments of the invention herein, in formulas (I) and (II), R ⁹ is hydrogen, C1 _- C ₄₀ hydrocarbyl, C1 _- C ₄₀ substituted hydrocarbyl or heteroatomic group, preferably hydrogen. Methyl, ethyl, propyl, butyl, pentyl, hexyl or isomers thereof. Preferably R ⁹ is methyl, ethyl, propyl, butyl, C1 _{-C 6 alkyl} , phenyl, 2-methylphenyl, 2,6-dimethylphenyl or 2,4,6-trimethylphenyl.

In embodiments of the invention herein, in formulas (I) and (II), each X is an independently hydrocarbyl group having 1 to 20 carbon atoms (such as alkyl or aryl), hydrides, amides, and the like. Selected from the group consisting of alkoxides, sulfides, phosphides, halides, alkylsulfonates and combinations thereof (two or more Xs may form a fused ring or part of the ring system), preferably each X is a halide. , Aryl and C ₁ -C ₅ alkyl groups independently selected, preferably each X is independently hydride, dimethylamide, diethylamide, methyltrimethylsilyl, neopentyl, phenyl, benzyl, methyl, ethyl, propyl, butyl, It is a pentyl, fluoro, iodo, bromo or chloro group.
Alternatively, each X may independently be a halide, hydride, alkyl group, alkenyl group or arylalkyl group.

In embodiments of the invention herein, in formulas (I) and (II), each L is independently an ether, thioether, amine, nitrile, imine, pyridine, halocarbon and phosphine, preferably ether and thioether. , And a Lewis base selected from the group consisting of combinations thereof, optionally two or more Ls may form a fused ring or part of the ring system, preferably each L is an ether and a thioether group. Each L is preferably an ethyl ether, tetrahydrofuran, dibutyl ether or dimethyl sulfide group.

In embodiments of the invention herein, in formulas (I) and (II), R1 and R1'are independently cyclic tertiary alkyl groups.
In embodiments of the invention herein, n in formulas (I) and (II) is 1, 2 or 3, typically 2.
In embodiments of the invention herein, in formulas (I) and (II), m is 0, 1 or 2, typically 0.
In embodiments of the invention herein, in formulas (I) and (II), R ¹ and R ^1'are not hydrogen.

In embodiments of the invention herein, in formulas (I) and (II), M is Hf or Zr, E and E'are O, and R ¹ and R ^1'are independent of each other. C ₁ -C ₄₀ hydrocarbyl, C1 _- C ₄₀ substituted hydrocarbyl, heteroatom or heteroatom-containing group, each R ² , R ³ , R ⁴ , R ^{2' ,} R ^3'and R 4'is independent. And hydrogen, C1 _- C ₂₀ hydrocarbyl, C1 _- C ₂₀ substituted hydrocarbyl, heteroatom or heteroatom-containing group, or R ¹ and R ² , R ² and R ³ , R ³ and R ⁴ , R ¹ One or more of'and R ^{2' ,} R ^2'and R ^{3 '} , R ^3'and R 4'are bonded and have 5, 6, 7 or 8 ring atoms, respectively. And to form one or more substituted hydrocarbyl rings, unsubstituted hydrocarbyl rings, substituted heterocyclic rings or unsubstituted heterocyclic rings on which the substituents on the ring can be bonded to form additional rings. Typically, each X is independently selected from the group consisting of hydrocarbyl groups (such as alkyl or aryl) having 1 to 20 carbon atoms, hydrides, amides, alkoxides, sulfides, phosphides, halides and combinations thereof. , (Two or more Xs may form part of a fused ring or ring system), each L is independently selected from the group consisting of ethers, thioethers and halocarbons (two or more Ls). May form a fused ring or part of the ring system).

In embodiments of the invention herein, in formula (II), R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ^5' , R ^6' , R ^7' , R ^8' , R ¹⁰ , R ¹¹ and Each of R ¹² is independently hydrogen, C1 _- C ₄₀ hydrocarbyl, C1 _- C ₄₀ substituted hydrocarbyl, heteroatom or heteroatom-containing group, or one or more adjacent R groups are attached. One or more substituted hydrocarbyl rings, each having 5, 6, 7 or 8 ring atoms and capable of bonding substituents on the ring to form additional rings. A substituted hydrocarbyl ring, a substituted heterocyclic ring or an unsubstituted heterocyclic ring may be formed.

In embodiments of the invention herein, in formula (II), R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ^5' , R ^6' , R ^7' , R ^8' , R ¹⁰ , R ¹¹ and Each of R ¹² is independently hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl or an isomer thereof.
In embodiments of the invention herein, in formula (II), R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ^5' , R ^6' , R ^7' , R ^8' , R ¹⁰ , R ¹¹ and Each of R ¹² is methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecil, eikosyl, heneikosyl, docosyl, Tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl, triacontyl, phenyl, substituted phenyl (such as methylphenyl and dimethylphenyl), benzyl, substituted benzyl (such as methylbenzyl), naphthalenyl, cyclohexyl, cyclohexenyl, methylcyclohexyl and theirs. Selected independently of the isomers of.

In embodiments of the invention herein, in formula (II), M is Hf or Zr, E and E'are O, and R ¹ and R ^1'are independently C _1- . C ₄₀ hydrocarbyl, C1 _- C ₄₀ substituted hydrocarbyl, heteroatom or heteroatom-containing group,
Each R ¹ , R ² , R ³ , R ⁴ , R ^1' , R ^{2' ,} R ^3'and R 4'are independently hydrogen, C ₁ -C ₂₀ hydrocarbyl, C ₁ -C ₂₀ substituted hydrocarbyl, Heteroatom or heteroatom-containing group, or R ¹ and R ² , R ² and R ³ , R ³ and R ⁴ , R ^1'and R ^{2 '} , R 2'and R ^3' , R ^3'and R One or more of the ^4'is bonded to have 5, 6, 7 or 8 ring atoms, respectively, and the substituents on the ring are bonded to form an additional ring. Can form one or more substituted hydrocarbyl rings, unsubstituted hydrocarbyl rings, substituted heterocyclic rings or unsubstituted heterocyclic rings, where R ⁹ is hydrogen, methyl, ethyl, propyl, butyl, pentyl, Hydrogen, C1 _- C ₂₀ hydrocarbyl, C1 _- C ₂₀ -substituted hydrocarbyl or heteroatom-containing groups, such as hexyls or isomers thereof,

Each X is independently derived from hydrocarbyl groups (such as alkyl or aryl) having 1 to 20 carbon atoms, hydrides, amides, alkoxides, sulfides, phosphides, halides, dienes, amines, phosphines, ethers and combinations thereof. Selected from the group of (two or more Xs may form a fused ring or part of the ring system), n is 2 and m is 0, R ⁵ , R ⁶ , R ⁷ , R. ⁸ , R ^5' , R ^6' , R ^7' , R ^8' , R ¹⁰ , R ¹¹ and R ¹² , respectively, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, Undecyl, Dodecyl, Tridecyl, Tetradecyl, Pentadecyl, Hexadecyl, Heptadecyl, Octadecyl, Nonadecil, Eikosyl, Heneikosyl, Dococil, Tricosyl, Tetracosyl, Pentacosyl, Hexacosyl, Heptacosyl, Octacosyl, Nonacosyl, Triacontyl, Phenyl, Substituted phenyl (Methylphenyl and dimethylphenyl) Etc.), benzyl, substituted benzyl (such as methylbenzyl), naphthyl, cyclohexyl, cyclohexenyl, methylcyclohexyl and their isomers independently selected, such as R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ^{5 '} , R ^6' , R ^7' , R ^8' , R ¹⁰ , R ¹¹ and R ¹² are each independently hydrogen, C1 _- C ₂₀ hydrocarbyl, C1 _- C ₂₀ substituted hydrocarbyl, heteroatomic or hetero. It is an atomic-containing group, or one or more adjacent R groups are bonded to each other to have 5, 6, 7 or 8 ring atoms, respectively, and the substituents on the ring are bonded. One or more substituted hydrocarbyl rings, unsubstituted hydrocarbyl rings, substituted heterocyclic rings or unsubstituted heterocyclic rings may be formed, which can form additional rings.

In a preferred embodiment of formula (I), M is Zr or Hf, Q is nitrogen, both A ¹ and A ^1'are carbon, both E and ^E'are oxygen, and R. Both ¹ and R ^1'are C ₄ -C ₂₀ cyclic tertiary alkyls.
In a preferred embodiment of formula (I), M is Zr or Hf, Q is nitrogen, both A ¹ and A ^1'are carbon, both E and ^E'are oxygen, and R. Both ¹ and R ^1'are adamantane-1-yl or substituted adamantane-1-yl.
In a preferred embodiment of formula (I), M is Zr or Hf, Q is nitrogen, both A ¹ and A ^1'are carbon, both E and ^E'are oxygen, and R. Both ¹ and R ^1'are C ₆ -C ₂₀ aryl.

In a preferred embodiment of formula (II), M is Zr or Hf, both E and ^E'are oxygen, and both R ¹ and R ^1'are C ₄ -C ₂₀ cyclic tertiary alkyls. There is.
In a preferred embodiment of formula (II), M is Zr or Hf, both E and ^E'are oxygen, and both R ¹ and R ^1'are adamantane-1-yl or substituted adamantane-1-. It is to be Il.
In a preferred embodiment of formula (II), M is Zr or Hf, both E and ^E'are oxygen, and R ¹ , R ^1' , R ³ and R ^3'are each Adamantane-1-. It is ill or substituted adamantane-1-yl.
In a preferred embodiment of formula (II), M is Zr or Hf, both E and ^E'are oxygen, and both R ¹ and R ^1'are C ₄ -C ₂₀ cyclic tertiary alkyls. Yes, both R ⁷ and R ^7'are C ₁ -C ₂₀ alkyl.

Catalyst compounds that are particularly useful in the present invention include dimethylzirconium [2', 2'''-(pyridine-2,6-diyl) bis (3-adamantane-1-yl) -5- (tert-butyl). -[1,1'-biphenyl] -2-olate)], dimethylhafnium [2', 2'''-(pyridine-2,6-diyl) bis (3-adamantane-1-yl) -5- ( tert-butyl)-[1,1'-biphenyl] -2-oleate)], dimethylzirconium [6,6'-(pyridine-2,6-diylbis (benzo [b] thiophene-3,2-diyl))) Bis (2-adamantane-1-yl) -4-methylphenolate)], dimethylhafnium [6,6'-(pyridine-2,6-diylbis (benzo [b] thiophen-3,2-diyl)) bis (2-adamantane-1-yl) -4-methylphenolate)], dimethylzirconium [2', 2'''-(pyridine-2,6-diyl) bis (3-((3r, 5r, 7r)) -Adamantane-1-yl) -5-methyl- [1,1'-biphenyl] -2-olate)], dimethylhafnium [2', 2'''-(pyridine-2,6-diyl) bis (3) -((3r, 5r, 7r) -adamantane-1-yl) -5-methyl- [1,1'-biphenyl] -2-olate)], dimethylzirconium [2', 2'''-(pyridine-) 2,6-diyl) bis (3-((3r, 5r, 7r) -adamantane-1-yl) -4', 5-dimethyl- [1,1'-biphenyl] -2-oleate)], dimethylhafnium [2', 2'''-(pyridine-2,6-diyl) bis (3-((3r, 5r, 7r) -adamantan-1-yl) -4', 5-dimethyl- [1,1' -Biphenyl] -2-olate)], one or more of them are included.

The catalytic compound particularly useful in the present invention includes a catalytic compound represented by one or more of the following formulas.

In some embodiments, two or more different catalytic compounds are present in the catalytic system used herein. In some embodiments, two or more different catalytic compounds are present within the reaction zone where the processes described herein occur. When two transition metal compound-based catalysts are used as a mixed catalyst system in one reactor, the two transition metal compounds are preferably selected so that the two are compatible. A simple screening method known to those of skill in the art, such as ¹ H or ¹³ C NMR, can be used to determine which transition metal compound is compatible. It is preferred to use the same activator for the transition metal compound, but two different activators such as non-coordinating anion activators and alumoxane can be used in combination. If the transition metal compound of one or more contains an X group that is not hydride, hydrocarbyl or substituted hydrocarbyl, the alumoxane can be contacted with the transition metal compound prior to the addition of the non-coordinating anion activator.

Two transition metal compounds (precatalysts) may be used in any ratio. The preferred molar ratio of (A) transition metal compound to (B) transition metal compound is (A: B) 1: 1000 to 1000: 1, or 1: 100 to 500: 1, or 1:10 to 200: 1. Alternatively, it falls within the range of 1: 1 to 100: 1, or 1: 1 to 75: 1, or 5: 1 to 50: 1. The particular ratio chosen will depend on the exact precatalyst chosen, the method of activation and the desired final product. In certain embodiments, when two precatalysts, both activated by the same activator, are used, a useful mole percent based on the molecular weight of the precatalyst is 10-99.9% A vs. 0.1. ~ 90% B, or 25 ~ 99% A vs 0.5-50% B, or 50 ~ 99% A vs 1-25% B, or 75 ~ 99% A vs 1-10% B.

Methods for Preparing Catalytic Compounds Ligand Synthesis Bis (phenol) ligands may be prepared using the general method shown in Scheme 1. The formation of a bis (phenol) ligand by coupling of compound A with compound B (method 1) may be achieved by known Pd and Ni catalytic couplings such as Negishi, Suzuki or Kumada couplings. The formation of a bis (phenol) ligand by coupling of compound C with compound D (method 2) may be achieved by known Pd and Ni catalytic couplings such as Negishi, Suzuki or Kumada couplings. Compound D is a reaction of compound E from compound E with either an organolithium reagent or a magnesium metal, followed by a main metal halide (eg ZnCl ₂ ) or a boron-based reagent (eg B (O ⁱ Pr) ₃ ). , ^I PrOB (pin)) may be prepared by an optional reaction. Compound E may be prepared by reaction with an aryllithium or aryl Grignard reagent (Compound F) with a dihalogenated allene (Compound G) such as 1-bromo-2-chlorobenzene in a non-catalytic reaction. Compound E may be prepared by the reaction of an arylzinc or aryl-boron reagent (Compound F) with a dihalogenated arene (Compound G) in a Pd or Ni-catalyzed reaction.
Scheme 1

（式中、Ｍ’は、１、２、１２もしくは１３族元素またはＬｉ、ＭｇＣｌ、ＭｇＢｒ、ＺｎＣｌ、Ｂ（ＯＨ）₂、Ｂ（ピナコレート）などの置換元素であり、Ｐは、メトキシメチル（ＭＯＭ）、テトラヒドロピラニル（ＴＨＰ）、ｔ－ブチル、アリル、エトキシメチル、トリアルキルシリル、ｔ－ブチルジメチルシリルまたはベンジルなどの保護基であり、Ｒは、Ｃ₁－Ｃ₄₀アルキル、置換アルキル、アリール、三級アルキル、環式三級アルキル、アダマンタニルまたは置換アダマンタニルであり、各Ｘ’およびＸは、Ｃｌ、Ｂｒ、ＦまたはＩなどのハロゲンである）。ビス（フェノール）配位子の調製のために使用されるビス（フェノール）配位子および中間体が、カラムクロマトグラフィーを使用せずに調製および精製されることが好ましい。これは、蒸留、沈殿および洗浄、不溶性塩の生成（有機酸とのピリジン誘導体の反応などによる）および液－液抽出を含む様々な方法により達成されてよい。好ましい方法には、Neal C. AndersonによるPractical Process Research and Development - A Guide for Organic Chemists(ISBN:1493300125X)に記載された方法が含まれる。

(In the formula, M'is a group 1, 2, 12 or 13 element or a substituent such as Li, MgCl, MgBr, ZnCl, B (OH) ₂ , B (pinacholate), and P is methoxymethyl (MOM). ), Tetrahydropyranyl (THP), t-butyl, allyl, ethoxymethyl, trialkylsilyl, t-butyldimethylsilyl or benzyl, etc., where R is C1 _- C ₄₀ alkyl, substituted alkyl, aryl , Tertiary alkyl, cyclic tertiary alkyl, adamantanyl or substituted adamantanyl, where each X'and X is a halogen such as Cl, Br, F or I). It is preferred that the bis (phenol) ligands and intermediates used for the preparation of bis (phenol) ligands are prepared and purified without the use of column chromatography. This may be achieved by a variety of methods including distillation, precipitation and washing, insoluble salt formation (such as by reaction of a pyridine derivative with an organic acid) and liquid-liquid extraction. Preferred methods include those described in Practical Process Research and Development-A Guide for Organic Chemists (ISBN: 1493300125X) by Neal C. Anderson.

Synthesis of Calbenbis (Phenol) Ligand A general synthetic method for producing a carbenbis (phenol) ligand is shown in Scheme 2. The substituted phenol can be orthobrominated and then protected by known phenol protecting groups such as MOM, THP, t-butyldimethylsilyl (TBDMS), benzyl (Bn) and the like. The bromide is then converted to a boronic acid ester (Compound I) or boronic acid, which can be used in Suzuki coupling with bromoaniline. Biphenylaniline (Compound J) can be crosslinked by reaction with dibromoethane or condensation with oxalaldehyde and then deprotected (Compound K). Reaction with triethyl orthoformate produces an iminium salt, which is deprotonated to carbene.
Scheme 2

Equivalent N-bromosuccinimide and 0.1 equivalent diisopropylamine are added to the substituted phenol (Compound H) dissolved in methylene chloride. After stirring at ambient temperature until completion, the reaction is quenched with a 10% solution of HCl. The organic moieties are washed with brine, dried over magnesium sulphate, filtered and concentrated under reduced pressure to give bromophenol typically as a solid. Substituted bromophenol, methoxymethyl chloride and potassium carbonate are dissolved in dry acetone and stirred at ambient temperature until the reaction is complete. The solution is filtered and the filtrate is concentrated to give the protected phenol (Compound I). Alternatively, substituted bromophenol and an equivalent amount of dihydropyran are dissolved in methylene chloride and cooled to 0 ° C. A catalytic amount of para-toluenesulfonic acid is added and the reaction is stirred for 10 minutes and then quenched with trimethylamine. The mixture is washed with water and brine, then dried over magnesium sulphate, filtered and concentrated under reduced pressure to give tetrahydropyran-protected phenol.

Aryl bromide (Compound I) is dissolved in THF and cooled to −78 ° C. n-Butyllithium is added slowly, followed by trimethoxyborate. The reaction is stirred at ambient temperature until completion. The solvent is removed and the solid boronic acid ester is washed with pentane. Boronic acid can be prepared from the boronic acid ester by treatment with HCl. The boronic acid ester or boronic acid is dissolved in toluene containing an equivalent amount of ortho-bromoaniline and a catalytic amount of palladium tetrakistriphenylphosphine. An aqueous solution of sodium carbonate is added and the reaction is reflux heated overnight. Upon cooling, the layers are separated and the aqueous layer is extracted with ethyl acetate. The combined organic moieties are washed with brine, dried (00544), filtered and concentrated under reduced pressure. Column chromatography is typically used to purify the coupled product (Compound J).
Aniline (Compound J) and dibromoethane (0.5 eq) are dissolved in acetonitrile and heated at 60 ° C. overnight. The reaction is filtered and concentrated to give ethylene crosslinked dianiline. The protected phenol is deprotected by reaction with HCl to give crosslinked bisamino (biphenyl) all (Compound K).
Diamine (Compound K) is dissolved in triethyl orthoformate. Ammonium chloride is added and the reaction is reflux heated overnight. A precipitate is formed, which is collected by filtration and washed with ether to give an iminium salt. Iminium chloride is suspended in THF and treated with lithium or sodium hexamethyldisilylamide. When complete, the reactants are filtered and the filtrate is concentrated to give the carbene ligand.

Preparation of Bis (Phonolate) Complexs Transition metal or lanthanide metal bis (phenorate) complexes are used as catalytic components for olefin polymerization in the present invention. The terms "catalyst" and "catalytic complex" are used interchangeably. Preparation of a transition metal or lanthanide metal bis (phenorate) complex may be accomplished by the reaction of a bis (phenol) ligand with a metal reactant containing an anionic basic leaving group. Typical anionic basic leaving groups include dialkylamides, benzyls, phenyls, hydrides and methyls. In this reaction, the role of the basic leaving group is to deprotonate the bis (phenol) ligand. Metal reactants suitable for this type of reaction include HfBn ₄ (Bn = CH ₂ Ph), ZrBn ₄ , TiBn ₄ , ZrBn ₂ Cl ₂ (OEt ₂ ), HfBn ₂ Cl ₂ (OEt ₂ ) ₂ , Zr ( NMe ₂ ) ₂ Cl ₂ (dimethoxyethane), Hf (NMe ₂ ) ₂ Cl ₂ (dimethoxy ethane), Hf (NMe ₂ ) ₄ , Zr (NMe ₂ ) ₄ and Hf (NEt ₂ ) ₄ are included. Not limited to. Suitable metal reagents also include ZrMe ₄ , HfMe ₄ , and other Group 4 alkyls that are produced in situ and may be used without isolation.

A second method for the preparation of transition metals or lanthanidobis (phenorate) complexes is an alkali metal or alkaline earth metal base (eg, Na, BuLi, ⁱ ) for producing deprotonated ligands. It is based on the reaction of a bis (phenol) ligand with PrMgBr) and the subsequent reaction with a metal halide (eg, HfCl ₄ , ZrCl ₄ ) for forming a bis (phenorate) complex. A bis (phenorate) metal complex containing a metal halide, an alkoxide or an amide leaving group may be alkylated by reaction with an organic lithium reagent, a Grignard reagent and an organic aluminum reagent. In the alkylation reaction, the alkyl group is transferred to the bis (phenolate) metal center and the leaving group is removed. Reagents typically used for alkylation reactions include, but are not limited to, MeLi, MeMgBr, AlMe ₃ , Al (iBu) ₃ , ^AlOct ₃ and PhCH ₂ MgCl. Typically 2-20 molar equivalents of alkylating reagent are added to the bis (phenorate) complex. Alkylation is generally carried out in ethereal solvents or hydrocarbon solvents or solvent mixtures at temperatures typically in the range of −80 ° C. to 120 ° C.

Activators The terms "cocatalyst" and "activator" are used interchangeably herein.
The catalytic system described herein typically comprises a catalytic complex such as the transition metal or lanthanidobis (phenolate) complex described above and an activator such as alumoxane or a non-coordinating anion. This catalyst system may be produced by combining the catalyst components described herein with an activator by any method known in the literature. The catalytic system may be added to or produced in solution polymerization or bulk polymerization (in the monomer). The catalyst system of the present disclosure may have one or more activators and one, two or more catalyst components. The activator is defined as any compound capable of activating any one of the above catalytic compounds by converting the neutral metal compound into a catalytically active metal compound cation. For example, non-limiting activators include alumoxane, ionizing activators that may be neutral or ionic, and conventional types of cocatalysts. Preferred activators typically include alumoxane compounds, modified alumoxane compounds, and reactive metal ligands to remove the metal compounds to make them cationic, charge-balanced non-coordinating or weakly coordinating anions. For example, ionized anion precursor compounds that provide non-coordinating anions.

Armoxan Activator The Armoxan activator is utilized as the activator in the catalytic system described herein. Aluminum is generally an oligomer compound containing the -Al (R ¹ ) -O- subunit (where R ¹ is an alkyl group in the formula). Examples of alumoxane include methylalmoxane (MAO), denatured methylalmoxane (MMAO), ethylalmoxane and isobutylarmoxane. Alkyl armoxane and modified alkyl armoxane are suitable as catalytic activators, especially when the removable ligand is an alkyl, halide, alkoxide or amide. Mixtures of different alumoxane and modified alumoxane may be used. It would be preferable to use a visually transparent methylarmoxane. The turbid or gelled alumoxane can be filtered to produce a clear solution, or the clear alumoxane can be decanted from the turbid solution. Useful alumoxane is protected under modified methylaluminoxane (MMAO) cocatalyst type 3A (patent number US Pat. No. 5,041,584) and is commercially available from Akzo Chemicals, Inc. under the trade name Modified Methylaluminoxane type 3A. Is). Another useful alumoxane is the solid polymethylaluminoxane described in US Pat. No. 9,340,630, US Pat. No. 8,404,880 and US Pat. No. 8,975,209.

When the activator is alumoxane (modified or non-denatured), typically the maximum amount of activator is up to 5,000-fold molar excess of Al / M (per metal catalyst site) with respect to the catalytic compound. be. The smallest activator vs. catalytic compound has a molar ratio of 1: 1. Preferred ranges of alternatives include 1: 1 to 500: 1, alternatives 1: 1 to 200: 1, alternatives 1: 1 to 100: 1, or alternatives 1: 1 to 50: 1.
In an alternative embodiment, alumoxane is used little or no in the polymerization process described herein. Preferably, the alumoxane is present in zero mol%, instead the alumoxane is less than 500: 1, preferably less than 300: 1, preferably less than 100: 1, preferably less than 1: 1 aluminum vs. catalytic compound transition metal. It exists in the molar ratio of.

Ionization / Non-coordinating anion activator The term "non-coordinating anion" (NCA) is not cation-coordinated or only weakly-coordinated to a cation, thereby sufficient with a neutral Lewis base. Means anions that remain prone to replacement. Moreover, the anion does not transfer anionic substituents or fragments to the cation so as to form a neutral transition metal compound and a neutral by-product from this anion. The useful non-coordinating anions according to the invention are compatible, stabilizing transition metal cations in the sense of balancing their ionic charges by +1 and retaining sufficient instability to allow substitution during polymerization. It is a non-coordinating anion. The term NCA is also defined to include a multi-component NCA-containing activator such as N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, which comprises an acidic cationic group and a non-coordinating anion. The term NCA is also defined to include neutral Lewis acids such as tris (pentafluorophenyl) boron, which can react with catalysts to produce activated species by removal of anionic groups. Any metal or metalloid capable of forming a compatible weakly coordinating complex may be used or may be included in a noncoordinating anion. Suitable metals include, but are not limited to, aluminum, gold and platinum. Suitable metalloids include, but are not limited to, boron, aluminum, phosphorus and silicon.

The use of neutral or ionic ionization activators is within the scope of the invention. It is also within the scope of the invention to use the neutral or ionic activator alone or in combination with the alumoxane or modified alumoxane activator.

In the embodiment of the present invention, the activator is represented by the formula (III).
(Z) _d ⁺ (A ^d- ) (III)
(In the formula, Z is (L—H), that is, a reducible Lewis acid, L is a neutral Lewis base, H is hydrogen, and (L—H) ⁺ is a Bronsted acid. A ^d- is a non-coordinating anion having a charge d-, d is an integer of 1 to 3 (such as 1, 2 or 3), and Z is preferably (Ar ₃ C ⁺ ) (in the equation). , Ar is an aryl, or an aryl substituted with a heteroatom, C1 _- C ₄₀ hydrocarbyl or substituted C1 _- C ₄₀ hydrocarbyl)). The anion component A ^d- is of the formula [M ^{k +} Q _n ] ^d- (where k is 1, 2 or 3 and n is 1, 2, 3, 4, 5 or 6 (preferably 1, 1,). 2, 3 or 4), nk = d, M is an element selected from Group 13 of the Periodic Table of the Elements, preferably boron or aluminum, and Q is independently hydride, crosslinked or Non-bridged dialkylamides, halides, alkoxides, aryl oxides, hydrocarbyls, substituted hydrocarbyls, halocarbyls, substituted halocarbyls and halo-substituted hydrocarbyl groups, wherein the Q is (optionally, the condition that Q is a halide in the presence of one or less). Includes those with (with a maximum of 40 carbon atoms). Preferably, each Q is a fluorinated hydrocarbyl group having 1 to 40 (1 to 20, etc.) carbon atoms, and more preferably each Q is a fluorinated aryl group such as a perfluorinated aryl group. Most preferably, each Q is a pentafluoryl aryl group or a perfluoronaphthalenyl group. Suitable examples of Ad- also include the diboron compounds disclosed in US Pat. No. ^5,447,895 , which is incorporated herein by reference in its entirety.

When Z is the activating cation (LH), it is methylamine, aniline, dimethylamine, diethylamine, N-methylaniline, N-methyl-4-nonadecil-N-octadecylaniline, N-methyl-4. -Octadecyl-N-octadecylaniline, diphenylamine, trimethylamine, triethylamine, N, N-dimethylaniline, methyldiphenylamine, pyridine, p-bromo-N, N-dimethylaniline, p-nitro-N, N-dimethylaniline, dioctadecyl Aniline from ammonium, triethylphosphine, triphenylphosphine and diphenylphosphine of methylamine, oxonium from ethers such as dimethylether, diethylether, tetrahydrofuran and dioxane, sulfonium from thioethers such as diethylthioether, tetrahydrothiophene and mixtures thereof, etc. It can be a Bronsted acid that can donate protons to a transition metal catalyst precursor to give a transition metal cation, including ammonium, oxonium, phosphonium, sulfonium and mixtures thereof.

In a particularly useful embodiment of the invention, the activator is soluble in a non-aromatic hydrocarbon solvent such as an aliphatic solvent.
In one or more embodiments, a 20% by mass mixture of activator compounds in n-hexane, isohexane, cyclohexane, methylcyclohexane or a combination thereof produces a clear homogeneous solution at 25 ° C., preferably n. -A 30% by mass mixture of activator compounds in hexane, isohexane, cyclohexane, methylcyclohexane or a combination thereof produces a clear homogeneous solution at 25 ° C.

In embodiments of the invention, the activators described herein have a solubility of greater than 10 mM (or greater than 20 mM, or greater than 50 mM) in methylcyclohexane at 25 ° C. (stirring for 2 hours).
In embodiments of the invention, the activators described herein have a solubility of greater than 1 mM (or greater than 10 mM, or greater than 20 mM) in isohexane at 25 ° C. (stirring for 2 hours).
In embodiments of the invention, the activators described herein have a solubility of greater than 10 mM (or greater than 20 mM, or greater than 50 mM) in methylcyclohexane at 25 ° C. (stirring for 2 hours) and 25 ° C. (2) in isohexane. It has a solubility of more than 1 mM (or more than 10 mM, or more than 20 mM) with time stirring).
In a preferred embodiment, the activator is a non-aromatic hydrocarbon soluble activator compound.

Non-aromatic hydrocarbon soluble activator compounds useful herein include activator compounds represented by formula (V).
[R ^{1'R 2'R 3'EH} ] _{d +} [Mt ^{k +} Q _n ] ^d- (V)
(During the ceremony,
E is nitrogen or phosphorus,
d is 1, 2 or 3, k is 1, 2 or 3, n is 1, 2, 3, 4, 5 or 6, and n−k = d (preferably d). Is 1, 2 or 3, k is 3, and n is 4, 5 or 6),
R ^{1' ,} R ^2'and R 3'are independently C ₁ -C ₅₀ hydrocarbyl groups which may be substituted with one or more alkoxy groups, silyl groups, halogen atoms or halogen-containing groups.
R ^{1' ,} R ^2'and R 3'contain more than 15 carbon atoms in total.
Mt is an element selected from Group 13 of the Periodic Table of the Elements, such as B or Al.
Each Q is an independently hydride, crosslinked or non-crosslinked dialkylamide, halide, alkoxide, aryloxide, hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl or halo-substituted hydrocarbyl group).

Non-aromatic hydrocarbon soluble activator compounds useful herein include activator compounds represented by formula (VI).
[R ^{1'R 2'R 3'EH} ] ⁺ [BR ^4'R 5'R 6'R ^{7' ] -} ( ^VI )
(In the formula, E is nitrogen or phosphorus, R ^1'is a methyl group, and R ^2'and R ^3'are independently one or more alkoxy groups, silyl groups, halogen atoms or halogens. It is a C ₄ -C ₅₀ hydroxy group which may be substituted with a containing group, R 2'and R 3'contain a total of 14 or more carbon atoms, B is boron, and R ^{4 '} , R ^{5' .} , R ^6'and R ^7'are independently hydrides, crosslinked or non-bridged dialkylamides, halides, alkoxides, aryloxides, hydrocarbyls, substituted hydrocarbyls, halocarbyls, substituted halocarbyls or halo-substituted hydrocarbyl groups).

（式中、
Ｎは窒素であり、
Ｒ^2’およびＲ^3’は、独立して、１個もしくは複数のアルコキシ基、シリル基、ハロゲン原子またはハロゲン含有基で置換されてもよいＣ₆－Ｃ₄₀ヒドロカルビル基であり、Ｒ^2’およびＲ^3’（存在する場合）は合わせて１４個以上の炭素原子を含み、
Ｒ^8’、Ｒ^9’およびＲ^10’は、独立してＣ₄－Ｃ₃₀ヒドロカルビルまたは置換Ｃ₄－Ｃ₃₀ヒドロカルビル基であり、
Ｂはホウ素であり、
Ｒ^4’、Ｒ^5’、Ｒ^6’およびＲ^7’は、独立してヒドリド、架橋もしくは非架橋ジアルキルアミド、ハライド、アルコキシド、アリールオキシド、ヒドロカルビル、置換ヒドロカルビル、ハロカルビル、置換ハロカルビルまたはハロ置換ヒドロカルビル基である） Non-aromatic hydrocarbon soluble activator compounds useful herein include activator compounds represented by formula (VII) or formula (VIII).

(During the ceremony,
N is nitrogen,
R ^2'and R ^3'are independently C ₆ -C ₄₀ hydrocarbyl groups optionally substituted with one or more alkoxy groups, silyl groups, halogen atoms or halogen-containing groups, R ^2'and R 2'and. R ^3' (if present) contains a total of 14 or more carbon atoms and contains
R ^{8' ,} R ^9'and R 10'are independent C4-C ₃₀ hydrocarbyl or substituted C _{4 -} C ₃₀ hydrocarbyl groups.
B is boron,
R ^4' , R ^{5' ,} R ^6'and R 7'independently hydride, crosslinked or non-crosslinked dialkylamides, halides, alkoxides, aryloxides, hydrocarbyls, substituted hydrocarbyls, halocarbyls, substituted halocarbyls or halo-substituted hydrocarbyl groups. Is)

Optionally, in any of the formulas (V), (VI), (VII) or (VIII) herein, R ^4' , R ^{5' ,} R ^6'and R 7'are pentafluorophenyls.
Optionally, in any of the formulas (V), (VI), (VII) or (VIII) herein, R ^4' , R ^{5' ,} R ^6'and R 7'are pentafluoronaphthalenyl. be.
Optionally, in any embodiment of formula (VIII) herein, R ^8'and R ^10'are hydrogen atoms and R ^9'is one or more alkoxy groups, silyl groups, halogen atoms or It is a C ₄ -C ₃₀ hydrocarbyl group that may be substituted with a halogen-containing group.
Optionally, in any embodiment of formula (VIII) herein, R ^9'may be substituted with one or more alkoxy groups, silyl groups, halogen atoms or halogen-containing groups C ₈ -C. ₂₂ Hydrocarbyl groups.
Optionally, in any embodiment of formula (VII) or (VIII) herein, R ^2'and R ^3'are independently C ₁₂ -C ₂₂ hydrocarbyl groups.
Optionally, R ^{1' ,} R 2'and R ^3'have a total of 15 or more carbon atoms (18 or more carbon atoms, 20 or more carbon atoms, 22 or more carbon atoms, etc., 25). More than 30 carbon atoms, more than 30 carbon atoms, 35 or more carbon atoms, 38 or more carbon atoms, 40 or more carbon atoms, 15 to 100 carbon atoms, 25 to 75 Includes carbon atoms, etc.).

Optionally, R ^2'and R ^3'have a total of 15 or more carbon atoms (18 or more carbon atoms, 20 or more carbon atoms, 22 or more carbon atoms, 25 or more carbon atoms, etc.) 25-75 carbon atoms such as 15-100 carbon atoms such as 30 or more carbon atoms, 35 or more carbon atoms, 38 or more carbon atoms, 40 or more carbon atoms, etc. Etc.).
Optionally, R ^8' , R ^9'and R ^10' have a total of 15 or more carbon atoms (18 or more carbon atoms, 20 or more carbon atoms, 22 or more carbon atoms, etc., 25). More than 30 carbon atoms, more than 30 carbon atoms, 35 or more carbon atoms, 38 or more carbon atoms, 40 or more carbon atoms, 15 to 100 carbon atoms, 25 to 75 Includes carbon atoms, etc.).
Optionally, when Q is a fluorophenyl group, R ^2'is not a C ₁ -C ₄₀ linear alkyl group (instead, R ^2'may be substituted C ₁ -C ₄₀ linear). Not an alkyl group).

Optionally, each of R ^{4' ,} R ^{5' ,} R 6'and R 7'is an aryl group (such as phenyl or naphthalenyl) and of R ^4' , R ^{5' ,} R 6'and R ^7' . At least one is substituted with at least one fluorine atom, preferably each of R ^{4' ,} R ^{5' ,} R 6'and R 7'is a perfluoroaryl group (such as perfluorophenyl or perfluoronaphthalenyl). Is.

Optionally, each Q is an aryl group (such as phenyl or naphthalenyl) and at least one Q is substituted with at least one fluorine atom, preferably each Q is a perfluoroaryl group (perfluorophenyl or perfluoronaphthal). Renil etc.).
Optionally, R ^1'is a methyl group, R ^2'is a C ₆ -C ₅₀ aryl group, and R ^3'is independently a C ₁ -C ₄₀ linear alkyl or C ₅ -C _50- . It is an aryl group.
Optionally, each of R ^2'and R ^3'is independently unsubstituted or halide, C ₁ -C ₃₅ alkyl, C ₅ -C ₁₅ aryl, C ₆ -C ₃₅ aryl alkyl, C _6- . Substituted with at least one of the C ₃₅ alkylaryls, R ² and R ³ contain a total of 20 or more carbon atoms.

Optionally, when Q is a fluorophenyl group, R ^2'is not a C ₁ -C ₄₀ linear alkyl group, preferably R ^2'is a C ₁ -C ₄₀ linear alkyl group which may be substituted. Not an alkyl group (instead, when Q is a substituted phenyl group, R ^2'is not a C ₁ -C ₄₀ linear alkyl group, preferably R ^2'is optionally substituted C ₁ -C. Each Q is independently hydride, crosslinked or non-bridged dialkylamide, halide, alkoxide, _aryloxide , hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl or halo-substituted hydrocarbyl group. Is. Optionally, when Q is a fluorophenyl group (instead, when Q is a substituted phenyl group), R ^2'is a meta-and / or para-substituted phenyl group, and the meta and para-substituted groups are Independently optionally substituted C ₁ -C ₄₀ hydrocarbyl group (C ₆ -C ₄₀ aryl group or linear alkyl group, C ₁₂ -C ₃₀ aryl group or linear alkyl group, or C ₁₀ -C ₂₀ aryl groups or linear alkyl groups, etc.), optionally substituted alkoxy groups or optionally substituted silyl groups. Optionally, each Q is a fluorinated hydrocarbyl group having 1 to 30 carbon atoms, more preferably each Q is an aryl fluorinated (such as phenyl or naphthalenyl) group, and most preferably each Q is a perfluorinated group. Perfluinated aryl (such as phenyl or naphthalenyl) groups. Suitable examples of [Mt ^{k +} Q _n ] ^d- also include the diboron compounds disclosed in US Pat. No. 5,447,895, which is incorporated herein by reference in its entirety. Optionally, at least one Q is not substituted phenyl. Optionally, not all Qs are substituted phenyls. Optionally, at least one Q is not perfluorophenyl. Optionally, not all Q's are perfluorophenyl.

In some embodiments of the invention, R ^1'is not methyl, R 2'is not C ₁₈ alkyl, R ^3'is not C ₁₈ alkyl, and instead R ^{1'is not methyl and R 2 ' . '} Is not C ₁₈ alkyl, R ^3'is not C ₁₈ alkyl, at least one Q is not substituted phenyl, and optionally all Qs are not substituted phenyl.

Useful cation components in formulas (III) and (V) to (VIII) include cation components represented by the following formulas.

Useful cation components in formulas (III) and (V) to (VIII) include cation components represented by the following formulas.

The anionic component of the activator described herein includes the formula [Mt ^{k +} Q _n ] ^- (where k is 1, 2 or 3 and n is 1, 2, 3, 4, 5 or 6 (preferably 1, 2, 3 or 4) (preferably k is 3 and n is 4, 5 or 6 and preferably n is 4 when M is B). ), Mt is an element selected from Group 13 of the Periodic Table of the Elements, preferably boron or aluminum, and Q is independently hydride, crosslinked or non-bridged dialkylamide, halide, alkoxide, aryloxide, hydrocarbyl, substituted. It is a hydrocarbyl, halocarbyl, substituted halocarbyl and halo-substituted hydrocarbyl group, wherein the Q has a maximum of 20 carbon atoms in the presence of one or less, provided that Q is a halide). .. Preferably, each Q is a fluorinated hydrocarbyl group which may have 1 to 20 carbon atoms, more preferably each Q is a fluorinated aryl group, and most preferably each Q is a perfluorinated aryl. It is the basis. Preferably at least one Q is not a substituted phenyl such as perfluorophenyl, and preferably all Qs are not substituted phenyls such as perfluorophenyl.

In one embodiment, the borate activator comprises tetrakis (heptafluoronaphth-2-yl) borate.
In one embodiment, the borate activator comprises tetrakis (pentafluorophenyl) borate.

（式中、
Ｍ^*は、１３族原子、好ましくはＢまたはＡｌ、好ましくはＢであり、
各Ｒ¹¹は、独立して、ハライド、好ましくはフルオリドであり、
各Ｒ¹²は、独立して、ハライド、Ｃ₆－Ｃ₂₀置換芳香族ヒドロカルビル基または式－Ｏ－Ｓｉ－Ｒ^a（式中、Ｒ^aは、Ｃ₁－Ｃ₂₀ヒドロカルビルまたはヒドロカルビルシリル基である）のシロキシ基であり、好ましくはＲ¹²は、フルオリドまたは過フッ素化フェニル基であり、
各Ｒ¹³は、ハライド、Ｃ₆－Ｃ₂₀置換芳香族ヒドロカルビル基または式－Ｏ－Ｓｉ－Ｒ^a（式中、Ｒ^aは、Ｃ₁－Ｃ₂₀ヒドロカルビルまたはヒドロカルビルシリル基である）のシロキシ基であり、好ましくはＲ¹³は、フルオリドまたはＣ₆過フッ素化芳香族ヒドロカルビル基であり、
Ｒ¹²およびＲ¹³は、１個もしくは複数の飽和または不飽和の、置換または非置換環を形成することができ、好ましくはＲ¹²およびＲ¹³は過フッ素化フェニル環を形成する）。好ましくはアニオンは、７００ｇ／ｍｏｌ超の分子量を有し、好ましくは、Ｍ^*原子上の置換基のうちの少なくとも３個それぞれが、１８０立方Å超の分子体積を有する。 The anions for use in the non-coordinating anion activators described herein also include anions represented by the following formula 7.

(During the ceremony,
M ^* is a Group 13 atom, preferably B or Al, preferably B.
Each R ¹¹ is independently a halide, preferably a fluoride,
Each R ¹² is independently a halide, C ₆ -C ₂₀ substituted aromatic hydrocarbyl group or formula-O-Si-R ^a (where R ^a is a C1 _- C ₂₀ hydrocarbyl or hydrocarbylsilyl group. ) Syloxy group, preferably R ¹² is a fluoride or perfluorinated phenyl group.
Each R ¹³ is a halide, a siroxy group of a C ₆ -C ₂₀ substituted aromatic hydrocarbyl group or a formula-O-Si-R ^a (where R ^a is a C1 _- C ₂₀ hydrocarbyl or hydrocarbylsilyl group). R ¹³ is preferably a fluoride or C ₆ perfluorinated aromatic hydrocarbyl group.
R ¹² and R ¹³ can form one or more saturated or unsaturated, substituted or unsubstituted rings, preferably R ¹² and R ¹³ form a perfluorinated phenyl ring). Preferably the anion has a molecular weight of greater than 700 g / mol, preferably each of at least three of the substituents on the M ^* atom has a molecular volume of greater than 180 cubic Å.

"Molecular volume" is used herein as an approximation of the spatial three-dimensional volume of the activator molecule in solution. Comparison of substituents with different molecular volumes makes it possible to consider substituents with smaller molecular volumes as "not bulky" compared to substituents with larger molecular volumes. Conversely, substituents with larger molecular volumes can be considered "bulky" than substituents with smaller molecular volumes.

The molecular volume is reported in "A Simple" Back of the Envelope "Method for Estimating the Densities and Molecular Volumes of Liquids and Solids," Journal of Chemical Education, v.71 (11), November 1994, pp. 962-964. It can be calculated as follows. The molecular volume (MV) (in cubic Å units) is calculated using the formula: MV = 8.3 V _s (where V _s is the scaled volume). V _s is the sum of the relative volumes of the constituent atoms and is calculated from the molecular formula of the substituent using Table A of the relative volumes below. In the case of fused rings, _Vs is reduced by 7.5% per fused ring. The calculated total MV for anions is the sum of the MVs per substituent, for example, the MV for perfluorophenyl is 183 Å ³ , and the calculated total MV for tetrakis (perfluorophenyl) borate is 4 times 183 Å ³ . That is, 732 Å ³ .

Exemplary anions useful herein and their respective scaled and molecular volumes are shown in Table B below. Dashed line bonds indicate bonds to boron.

The activator is in the form of an ion pair, for example, a di (borohydride) methylamine (“M2HTH”) cation reacting with a basic leaving group on a transition metal complex to form a transition metal complex cation and [NCA]. It may be added to the polymerization using [M2HTH] + [NCA]-to produce-. Alternatively, the transition metal complex may be reacted with a neutral NCA precursor such as B (C ₆ F ₅ ) ₃ which removes anionic groups from the complex to produce activated species. Useful activators include di (hydrogenated tallow) methylammonium [tetrakis (pentafluorophenyl) borate] (ie, [M2HTH] B (C ₆ F ₅ ) ₄ ) and di (octadecyl) trillammonium [tetrakis (ie, tetrakis). Pentafluorophenyl) borate] (ie, [DOdTH] B (C ₆ F ₅ ) ₄ ).

Activator compounds that are particularly useful in the present invention include one or more of the following:
N, N-di (hydrogenated tallow) methylammonium [tetrakis (perfluorophenyl) borate],
N-Methyl-4-nonadecil-N-octadecylanilinium [Tetrakis (perfluorophenyl) borate],
N-Methyl-4-hexadecyl-N-octadecylanilinium [Tetrakis (perfluorophenyl) borate],
N-Methyl-4-tetradecyl-N-octadecylanilinium [Tetrakis (perfluorophenyl) borate],
N-Methyl-4-dodecyl-N-octadecylanilinium [Tetrakis (perfluorophenyl) borate],
N-Methyl-4-decyl-N-octadecylanilinium [Tetrakis (perfluorophenyl) borate],
N-Methyl-4-octyl-N-octadecylanilinium [Tetrakis (perfluorophenyl) borate],
N-Methyl-4-hexyl-N-octadecylanilinium [Tetrakis (perfluorophenyl) borate],
N-Methyl-4-butyl-N-octadecylanilinium [Tetrakis (perfluorophenyl) borate],
N-Methyl-4-octadecyl-N-decylanilinium [Tetrakis (perfluorophenyl) borate],
N-Methyl-4-nonadecil-N-dodecylanilinium [Tetrakis (perfluorophenyl) borate],
N-Methyl-4-nonadecil-N-tetradecylanilinium [Tetrakis (perfluorophenyl) borate],
N-Methyl-4-nonadecil-N-hexadecylanilinium [Tetrakis (perfluorophenyl) borate],
N-Ethyl-4-nonadecil-N-octadecylanilinium [Tetrakis (perfluorophenyl) borate],
N-Methyl-N, N-dioctadecylammonium [Tetrakis (perfluorophenyl) borate],
N-Methyl-N, N-Dihexadecylammonium [Tetrakis (perfluorophenyl) borate],
N-Methyl-N, N-ditetradecylammonium [Tetrakis (perfluorophenyl) borate],
N-Methyl-N, N-didodecylammonium [Tetrakis (perfluorophenyl) borate],
N-Methyl-N, N-didecylammonium [Tetrakis (perfluorophenyl) borate],
N-Methyl-N, N-Dioctylammonium [Tetrakis (Perfluorophenyl) Borate],
N-Ethyl-N, N-Dioctadecylammonium [Tetrakis (perfluorophenyl) borate],
N, N-di (octadecyl) trillammonium [tetrakis (perfluorophenyl) borate],
N, N-di (hexadecyl) trillammonium [tetrakis (perfluorophenyl) borate],
N, N-di (tetradecyl) trillammonium [tetrakis (perfluorophenyl) borate],
N, N-di (dodecyl) trillammonium [tetrakis (perfluorophenyl) borate],
N-octadecyl-N-hexadecyl-tolylammonium [tetrakis (perfluorophenyl) borate],
N-octadecyl-N-hexadecyl-tolylammonium [tetrakis (perfluorophenyl) borate],
N-octadecyl-N-tetradecyl-tolylammonium [Tetrakis (perfluorophenyl) borate],
N-octadecyl-N-dodecyl-tolylammonium [tetrakis (perfluorophenyl) borate],
N-octadecyl-N-decyl-tolylammonium [tetrakis (perfluorophenyl) borate],
N-hexadecyl-N-tetradecyl-tolylammonium [Tetrakis (perfluorophenyl) borate],
N-hexadecyl-N-dodecyl-tolylammonium [tetrakis (perfluorophenyl) borate],
N-Hexadecyl-N-decyl-tolylammonium [Tetrakis (perfluorophenyl) borate],
N-tetradecyl-N-dodecyl-tolylammonium [Tetrakis (perfluorophenyl) borate],
N-tetradecyl-N-decyl-tolylammonium [Tetrakis (perfluorophenyl) borate],
N-dodecyl-N-decyl-tolylammonium [tetrakis (perfluorophenyl) borate],
N-Methyl-N-Octadecylanilinium [Tetrakis (Perfluorophenyl) Borate],
N-Methyl-N-Hexadecylanilinium [Tetrakis (Perfluorophenyl) Borate],
N-Methyl-N-Tetradecylanilinium [Tetrakis (Perfluorophenyl) Borate],
N-Methyl-N-Dodecylanilinium [Tetrakis (Perfluorophenyl) Borate],
N-Methyl-N-decylanilinium [tetrakis (perfluorophenyl) borate] and N-methyl-N-octylanilinium [tetrakis (perfluorophenyl) borate].

Additional useful activators and synthetic non-aromatic hydrocarbon soluble activators are incorporated herein by reference to USSN 16 / 394,166, April 2019, filed April 25, 2019. It is described in USSN 16 / 394,186 filed on 25th and USSN 16 / 394,197 filed April 25, 2019.

Similarly, particularly useful activators include dimethylanilinium tetrakis (pentafluorophenyl) borate and dimethylanilinium tetrakis (heptafluoro-2-naphthalenyl) borate. For a more detailed description of useful activators, see International Publication No. 2004/026921, pp. 72, paragraphs [00119] -81, paragraph [00151]. A list of additional particularly useful activators that can be used in the practice of the present invention can be found in WO 2004/0462114, pages 72, paragraphs [00177] to 74, paragraph [00178]. can.

See U.S. Pat. Nos. 8,658,556 and U.S. Pat. No. 6,211,105 for a description of useful activators.

Preferred activators for use herein include N-methyl-4-nonadecil-N-octadecylbenzeneaminium tetrakis (pentafluorophenyl) borate, N-methyl-4-nonadecil-N-octadecylbenzeneami. Nium tetrakis (perfluoronaphthalenyl) borate, N, N-dimethylanilinium tetrakis (perfluoronaphthalenyl) borate, N, N-dimethylanilinium tetrakis (perfluorobiphenyl) borate, N, N-dimethylanilinium tetrakis (perfluoro) Phenyl) borate, N, N-dimethylanilinium tetrakis (3,5-bis (trifluoromethyl) phenyl) borate, triphenylcarbenium tetrakis (perfluoronaphthalenyl) borate, triphenylcarbenium tetrakis (perfluorobiphenyl) borate , Triphenylcarbenium tetrakis (3,5-bis (trifluoromethyl) phenyl) borate, triphenylcarbenium tetrakis (perfluorophenyl) borate, [Me ₃ NH ⁺ ] [B (C ₆ F ₅ ) _4- ^] ; 1- (4- (Tris (pentafluorophenyl) borate) -2,3,5,6-tetrafluorophenyl) pyrrolidinium; and tetrakis (pentafluorophenyl) borate, 4- (tris (pentafluorophenyl) borate)- 2,3,5,6-tetrafluoropyridine is also included.

In a preferred embodiment, the activator is triarylcarbenium (triphenylcarbenium tetraphenylborate, triphenylcarbenium tetrakis (pentafluorophenyl) borate, triphenylcarbenium tetrakis (2,3,4,6-tetra). Fluorophenyl) borate, triphenylcarbenium tetrakis (perfluoronaphthalenyl) borate, triphenylcarbenium tetrakis (perfluorobiphenyl) borate, triphenylcarbenium tetrakis (3,5-bis (trifluoromethyl) phenyl) borate, etc.) including.

In another embodiment, the activator is trialkylammonium tetrakis (pentafluorophenyl) borate, N, N-dialkylanilinium tetrakis (pentafluorophenyl) borate, dioctadecylmethylammonium tetrakis (pentafluorophenyl) borate, di. Octadecylmethylammonium tetrakis (perfluoronaphthalenyl) borate, N, N-dimethyl- (2,4,6-trimethylanilinium) tetrakis (pentafluorophenyl) borate, trialkylammonium tetrakis (2,3,4,6- Tetrafluorophenyl) borate, N, N-dialkylanilinium tetrakis (2,3,4,6-tetrafluorophenyl) borate, trialkylammonium tetrakis (perfluoronaphthalenyl) borate, N, N-dialkylanilinium tetrakis ( Perfluoronaphthalenyl) borate, trialkylammonium tetrakis (perfluorobiphenyl) borate, N, N-dialkylanilinium tetrakis (perfluorobiphenyl) borate, trialkylammonium tetrakis (3,5-bis (trifluoromethyl) phenyl) borate, N, N-dialkylanilinium tetrakis (3,5-bis (trifluoromethyl) phenyl) borate, N, N-dialkyl- (2,4,6-trimethylanilinium) tetrakis (3,5-bis (trifluoromethyl)) Methyl) phenyl) borate, di- (i-propyl) ammonium tetrakis (pentafluorophenyl) borate (alkyls include methyl, ethyl, propyl, n-butyl, sec-butyl and t-butyl). ..

Typical activator-to-catalytic ratios, such as all NCA activator-to-catalytic ratios, have a molar ratio of approximately 1: 1. Preferred ranges of alternatives include 0.1: 1 to 100: 1, instead 0.5: 1 to 200: 1, alternatives 1: 1 to 500: 1, and alternatives 1: 1 to 1000: 1. Is done. A particularly useful range is 0.5: 1 to 10: 1, preferably 1: 1 to 5: 1.
It is also within the scope of the present disclosure that the catalytic compound can be combined with a combination of alumoxane and NCA (eg, U.S. Pat. No. 5,153,157, U.S. Pat. No. 5,discussing the use of alumoxane in combination with an ionization activator. See No. 5,453,410, European Patent No. 0573120, International Publication No. 1994/007928 and International Publication No. 1995/014044 (these disclosures are incorporated herein by reference in their entirety).

In addition to optional scavengers, co-activators, chain transfer activator compounds, scavengers or co-activators may be used. A scavenger is a compound typically added to promote polymerization by trapping impurities. Some scavengers may also act as activators and are sometimes referred to as co-activators. A co-activator that is not a scavenger may be used with the activator to produce an active catalyst. In some embodiments, the coactivator can be premixed with the transition metal compound to produce an alkylated transition metal compound.
The coactivator includes alumoxane such as methylalmoxane, modified alumoxane such as modified methylalmoxane, and trimethylaluminum, tri-isobutylaluminum, triethylaluminum and tri-isopropylaluminum, tri-n-hexylaluminum, and tri-n. -Aluminum alkyls such as octylaluminum, tri-n-decylaluminum or trin-dodecylaluminum may be included. When the precatalyst is not a dihydrocarbyl or dihydride complex, the coactivator is typically used in combination with a Lewis acid activator and an ionic activator. Occasionally, the co-activator is also used as a scavenger to inactivate impurities in the feed or in the reactor.
Aluminum alkyl or organic aluminum compounds that may be utilized as traps or coactivators include, for example, trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, and diethylzinc. Dialkyl zinc such as is included.

Chain transfer agents may be used in the compositions and / or processes described herein. Useful chain transfer agents are typically hydrogen, alkylalmoxane, diethylzinc, trimethylaluminum, triisobutylaluminum, trioctylaluminum or combinations thereof, such as formulas AlR ₃ , ZnR ₂ (wherein each R is). , Independently, a compound represented by a C1 _- C8 aliphatic group, preferably methyl, ethyl, propyl, butyl, _penyl , hexyl, octyl or an isomer thereof) or It is a combination of them.

Polymerization Process With respect to the polymerization process described herein, the term "continuous" means a system that operates uninterrupted or uninterrupted. For example, a continuous process of producing a polymer would be a process in which the reactants are continuously introduced into one or more reactors and the polymer products are continuously removed.
Solution polymerization means a polymerization process in which a polymer is dissolved in a liquid polymerization medium such as an inert solvent or monomer or a blend thereof. Solution polymerization is typically uniform. Uniform polymerization is a polymerization in which a polymer product is dissolved in a polymerization medium. Such a system is preferably not turbid as described in J. Vladimir Oliveira et al. (2000) Ind. Eng. Chem. Res., V.29, page 4627.
Bulk polymerization means a polymerization process in which the monomer and / or comonomer to be polymerized is used as the solvent or diluent with little or no inert solvent as the solvent or diluent. Very few inert solvents can be used as carriers for catalysts and scavengers. The bulk polymerization system comprises less than 25% by weight, preferably less than 10% by weight, preferably less than 1% by weight, preferably 0% by weight of an inert solvent or diluent.

In embodiments herein, the present invention relates to a polymerization process in which a monomer (such as propylene) and optionally a comonomer are contacted with a catalytic system comprising an activator and at least one catalytic compound, as described above. The catalytic compound and activator may be combined in any order and are typically combined prior to contact with the monomer.

As the monomers useful herein, substituted or unsubstituted C ₂ -C ₄₀ alpha olefins, preferably C ₂ -C ₂₀ alpha olefins, preferably C ₂ -C ₁₂ alpha olefins, preferably ethylene, propylene, butene, etc. Includes pentene, hexene, heptene, octene, nonen, decene, undecene, dodecene and their isomers. In a preferred embodiment of the invention, the monomer is optionally comprising propylene and one or more ethylenes or _C4 -C ₄₀ olefins, preferably _C4 -C ₂₀ olefins or preferably C ₆ -C ₁₂ olefins. Contains with comonomer. The C ₄ -C ₄₀ olefin monomer may be linear, branched or cyclic. The C ₄ -C ₄₀ cyclic olefin may be distorted or undistorted monocyclic or polycyclic and may contain a heteroatom and / or one or more functional groups. In another preferred embodiment, the monomer is an ethylene and an optional comonomer comprising one or more C ₃ -C ₄₀ olefins, preferably C ₄ -C ₂₀ olefins or preferably C ₆ -C ₁₂ olefins. including. The C ₃ -C ₄₀ olefin monomer may be linear, branched or cyclic. The C ₃ -C ₄₀ cyclic olefin may be distorted or undistorted monocyclic or polycyclic and may contain a heteroatom and / or one or more functional groups.

Exemplary C ₂ -C ₄₀ olefin monomers and optionally commonomers include ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, norbornene, cyclopentene, cycloheptene, cyclooctene, cyclododecene. , Their substituted derivatives and their isomers, preferably hexene, heptene, octene, nonene, decene, dodecene, cyclooctene, 5-methylcyclopentene, cyclopentene, norbornene, 5-ethylidene-2-norbornene and their respective homologues. Includes body and derivatives.

In a preferred embodiment, the diene of one or more species is up to 10% by weight, preferably 0.00001 to 1.0% by weight, preferably 0.002 to 0.5% by weight based on the total weight of the composition. %, More preferably 0.003 to 0.2% by weight, present in the polymers produced herein. In some embodiments, a diene of 500 ppm or less, preferably 400 ppm or less, or preferably 300 ppm or less is added to the polymerization. In other embodiments, at least 50 ppm, or 100 ppm or more, or 150 ppm or more of the diene is added to the polymerization.

Preferred diolefin monomers useful in the present invention contain any hydrocarbon structure with at least two unsaturated bonds, preferably C5 _- C ₃₀ , in which at least two of the unsaturated bonds are sterically specific catalysts. Alternatively, it is easily incorporated into the polymer by either a non-stereospecific catalyst. It is more preferred that the diolefin monomer is selected from non-conjugated diene monomers. More preferably, the diolefin monomer is a linear di-vinyl monomer, and most preferably a linear di-vinyl monomer containing 5 to 30 carbon atoms. Examples of preferred dienes are pentadiene, hexadiene, heptadiene, octadiene, nonadien, decadien, undecadien, dodecadien, tridecadien, tetradecadien, pentadecadien, hexadecadien, heptadecadien, octadecadien, nonadecadiene, icosadien, icosadien. Dienes, docosadiens, trichosadiens, tetrachosadiens, pentacosadiens, hexacosadiens, heptacosadiene, octacosadiene, nonacosadiene, triacotadiene are included, with particularly preferred diene being 1,6-heptadiene, 1,7-octadien, 1,8-nonadien, 1, , 9-Decadiene, 1,10-Undecadiene, 1,11-Dodecadiene, 1,12-Tridecadiene, 1,13-Tetradecadiene, divinylbenzene and low molecular weight polybutadiene (Mw less than 1000 g / mol). Preferred cyclic dienes include cyclopentadiene, vinylnorbornene, norbornadiene and dicyclopentadiene.

The polymerization process of the present invention can be carried out by any method known in the art. Any suspension, uniform, bulk, solution, slurry or gas phase polymerization process known in the art can be used. Such processes can be carried out in batch, semi-batch or continuous mode. Uniform polymerization processes and slurry processes are preferred. (The homopolymerization process is preferably a process in which at least 90% by weight of the product is soluble in the reaction medium.) Bulk homogenization is particularly preferred. (The bulk process is preferably a process in which the monomer concentration in all feeds to the reactor is 70% by volume or greater.) Instead, no solvent or diluent is present or added to the reaction medium (. Small amounts used as carriers for catalytic systems or other additives, or amounts typically found in monomers (eg, excluding propane in propylene). In another embodiment, the process is a slurry process. As used herein, the term "slurry polymerization process" means a polymerization process in which a carrier catalyst is used and the monomer is polymerized on the carrier catalyst particles. At least 95% by weight of the polymer product derived from the carrier catalyst is granular, such as solid particles (insoluble in diluent).

Diluents / solvents suitable for polymerization include non-coordinating inert liquids. Examples include linear and branched hydrocarbons such as isobutane, butane, pentane, isopentane, hexane, isohexane, heptane, octane, dodecane and mixtures thereof; as commercially available (Isopar ™ fluids). ), Cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane and mixtures thereof, and other cyclic and alicyclic hydrocarbons; perfluorinated C _4-10 alkanes, perhalogenated hydrocarbons such as chlorobenzene, and benzene, toluene. Includes aromatic and alkyl-substituted aromatic compounds such as, methithylene and xylene. Suitable solvents include ethylene, propylene, 1-butene, 1-hexene, 1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-octene, 1-decene and mixtures thereof. Also included are liquid olefins that can act as monomers or comonomer. In a preferred embodiment, isobutane, butane, pentane, isopentane, hexane, isohexane, heptane, octane, dodecane and mixtures thereof; cyclic and alicyclic such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane and mixtures thereof. An aliphatic hydrocarbon solvent such as a hydrocarbon is used as the solvent. In another embodiment, the solvent is not aromatic, preferably aromatic is present in the solvent in an amount of less than 1% by weight, preferably less than 0.5% by weight, preferably less than 0% by weight based on the mass of the solvent. do.

In a preferred embodiment, the feed concentration of the monomers and comonomer for polymerization is 60% by volume or less, preferably 40% by volume or less, or preferably 20% by volume or less, based on the total volume of the feed stream. Preferably the polymerization is carried out in a bulk process.
Preferred polymerization can be carried out at any temperature and / or pressure suitable for obtaining the desired ethylene polymer. Typical temperatures and / or pressures are preferably from about 0 ° C to about 300 ° C, preferably from about 20 ° C to about 200 ° C, preferably from about 35 ° C to about 150 ° C, preferably from about 40 ° C to about 120 ° C. Includes a temperature in the range of about 45 ° C to about 80 ° C and a pressure in the range of about 0.35 MPa to about 10 MPa, preferably about 0.45 MPa to about 6 MPa or preferably about 0.5 MPa to about 4 MPa. ..
In a typical polymerization, the reaction time is up to 300 minutes, preferably in the range of about 5 to 250 minutes or preferably in the range of about 10 to 120 minutes.
In some embodiments, hydrogen is 0.001 to 50 psig (0.007 to 345 kPa), preferably 0.01 to 25 psig (0.07 to 172 kPa), more preferably 0.1 to 10 psig (0.7 to 0.7). It exists in the polymerization reactor at a partial pressure of 70 kPa).

In an alternative embodiment, the catalytic activity is at least 10,000 g / mmol / hour, preferably 100,000 g / mmol / hour or higher, preferably 500,000 g / mmol / hour or higher, preferably 1,000,000 g / mmol. / Hour or more, preferably 2,000,000 g / mmol / hour or more, preferably 5,000,000 g / mmol / hour or more. In an alternative embodiment, the conversion of the olefin monomer is at least 10%, preferably 20% or more, preferably 30% or more, preferably 50% or more, preferably 50% or more, based on the polymer yield and the mass of the monomer entering the reaction zone. It is 80% or more.

In a preferred embodiment, alumoxane is used little or no in the process of producing the polymer. Preferably, the alumoxane is present in zero mol%, instead the alumoxane is a molar of aluminum pair transition metal less than 500: 1, preferably less than 300: 1, preferably less than 100: 1, preferably less than 1: 1. Exists in proportion.
In a preferred embodiment, the scavenger is used little or no in the process of producing the ethylene polymer. Preferably, the scavenger (such as trialkylaluminum) is present in zero mol%, instead the scavenger is less than 100: 1, preferably less than 50: 1, preferably less than 15: 1, preferably 10: 1. It is present in less than a molar ratio of scavenger metal to transition metal.

In a preferred embodiment, the polymerization: 1) is carried out at a temperature of 0-300 ° C (preferably 25-150 ° C, preferably 40-120 ° C, preferably 45-80 ° C, preferably 60-160 ° C). 2) is carried out at a pressure of atmospheric pressure to 10 MPa (preferably 0.35 to 10 MPa, preferably 0.45 to 6 MPa, preferably 0.5 to 4 MPa), and 3) is an aliphatic hydrocarbon solvent (isobutane). , Butane, pentane, isopentan, hexane, isohexane, heptane, octane, dodecane and mixtures thereof; cyclic and alicyclic hydrocarbons such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane and mixtures thereof; preferably The aromatic is carried out in less than 1% by weight, preferably less than 0.5% by weight, preferably 0% by weight, preferably present in the solvent) based on the mass of the solvent) and used in 4) polymerization. The catalytic system comprises less than 0.5 mol%, preferably less than 0 mol% alumoxane, instead the alumoxane is less than 500: 1, preferably less than 300: 1, preferably less than 100: 1, preferably less than 1: 1. 5) Polymerization preferably occurs within one reaction zone and 6) catalytic activity is at least 10,000 g / mmol / hour (preferably at least 100,000 g). / Mmol / hour, preferably at least 200,000 g / mmol / hour, preferably at least 500,000 g / mmol / hour, preferably at least 1,000,000 g / mmol / hour, preferably at least 2,000,000 g / mmol. / Hour, preferably at least 5,000,000 g / mmol / hour), 7) optionally absent of trapping agent (such as trialkylaluminum compound) (eg, present at zero mol%, instead trapping agent Is present in a molar ratio of trapping agent metal to transition metal less than 100: 1, preferably less than 50: 1, preferably less than 15: 1, preferably less than 10: 1), 8) optionally hydrogen is 0. Polymerization reactor with a partial pressure of 001 to 50 psig (0.007 to 345 kPa) (preferably 0.01 to 25 psig (0.07 to 172 kPa), more preferably 0.1 to 10 psig (0.7 to 70 kPa)). Exists in. In a preferred embodiment, the catalytic system used in the polymerization comprises one or less catalytic compounds. A "reaction zone", also referred to as a "polymerization zone", is a vessel in which polymerization occurs, such as a batch reactor. When multiple reactors are used in either series or parallel arrangement, each reactor is considered as a separate polymerization zone. For both multi-stage polymerization in batch reactors and continuous reactors, each polymerization step is considered as a separate polymerization zone. In a preferred embodiment, the polymerization takes place within one reaction zone. Room temperature is 23 ° C. unless otherwise specified.

Formula AlR ₃ such as one or more trapping agents, hydrogen, aluminum alkyl, silane or chain transfer agents (alkylalmoxane, diethylzinc, methylalumina, trimethylaluminum, triisobutylaluminum, trioctylaluminum or combinations thereof, etc. Or ZnR ₂ (in the formula, each R is independently represented by _a C1-C- ₈ aliphatic group, preferably methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl or an isomer thereof). Other additives such as (such as compounds or combinations thereof) may be used in the polymerization as desired.

Polyolefin Products The present invention also relates to compositions of substances produced by the methods described herein. The processes described herein may be used to produce polymers of olefins or mixtures of olefins. Polymers that may be prepared include polyethylene, polypropylene, homopolymers of _{C4-C 20 olefins, copolymers of C 4 - C 20} olefins, copolymers of ethylene with C ₃ -C ₂₀ olefins, and C ₄ -C ₂₀ olefins. Includes propylene copolymers, _C4 -C ₂₀ olefin tarpolymers, ethylene and propylene tarpolymers with _C4 -C ₂₀ olefins, and ethylene and propylene tarpolymers with 5-ethylidene-2-norbornene.

In a preferred embodiment, the processes described herein are propylene-ethylene and / with a Mw / Mn of between 1-10 (preferably 2-5, preferably 2-4, preferably 2-3). Alternatively, it produces a propylene homopolymer or propylene copolymer, such as a propylene-alpha olefin (preferably _C4 -C ₂₀ ) copolymer (such as a propylene-hexene copolymer or a propylene-octene copolymer).
In a preferred embodiment, the polymer produced herein is one or more of 0-25 mol% (instead 0.5-20 mol%, instead 1-15 mol%, preferably 3-10 mol%). Ethylene copolymer preferably having a C ₃ -C ₂₀ olefin comonomer (preferably C ₃ -C ₁₂ alpha-olefin, preferably propylene, butene, hexene, octene, decene, dodecene, preferably propylene, butene, hexene, octene). Or 0-25 mol% (instead 0.5-20 mol%, instead 1-15 mol%, preferably 3-10 mol%) C ₂ or C ₄ -C ₂₀ olefin comonomer (preferably ethylene or C ₄ ). -C _12alpha -olefin, preferably a copolymer of propylene having one or more of ethylene, butene, hexene, octene, decene, dodecene, preferably ethylene, butene, hexene, octene).
In a preferred embodiment, the monomer is ethylene and the comonomer is hexene, preferably 1-15 mol%, instead 1-10 mol% hexene.

Typically, the polymers produced herein are 5,000 to 1,000,000 g / mol (preferably 25,000 to 750,000 g / mol, preferably 50,000 to 500,000 g / mol). ) Mw and / or more than 1-40 (1.2-20 instead, 1.3-10 instead, 1.4-5, 1.5-4 instead, 1.5-3 instead) It has Mw / Mn.
In a preferred embodiment, the polymers produced herein have a monomodal or multimodal molecular weight distribution as measured by gel permeation chromatography (GPC). By "unimodality", it means that the GPC trace has one peak or inflection. By "multimodal", it means that the GPC trace has at least two peaks or inflections. An inflection point is a point where the sign of the quadratic derivative of a curve changes (eg, from negative to positive or vice versa).

Blend In another embodiment, the polymer produced herein (preferably polyethylene or polypropylene) is combined with one or more additional polymers prior to being molded into a film, molded part or other article. .. Other useful polymers include polyethylene, isotactic polypropylene, high isotactic polypropylene, syndiotactic polypropylene, propylene and ethylene, and / or butene, and / or hexene random copolymers, polybutene, ethylene vinyl acetate, LDPE. , LLDPE, HDPE, Ethylene Vinyl Acetate, Methyl Ethylene Acrylic Acid, Copolymers of Acrylic Acid, Polymethylmethacrylate, or Any Other Polymers Polymerizable by High Pressure Free Radical Processes, Polyvinyl Chloride, Polybutene-1, Isotactic Polybutene , ABS resin, ethylene-propylene rubber (EPR), vultured EPR, EPDM, block copolymer, styrene block copolymer, polyamide, polycarbonate, PET resin, crosslinked polyethylene, ethylene and vinyl alcohol copolymer (EVOH), polystyrene and other fragrances. Group monomer polymers include poly-1 esters, polyacetals, polyvinylidine fluorolides, polyethylene glycols and / or polyisobutylenes.

In a preferred embodiment, the polymer (preferably polyethylene or polypropylene) is 10-99% by weight, preferably 20-95% by weight, even more preferably at least 30-90% by weight, based on the weight of the polymer in the blend. More preferably at least 40-90% by weight, even more preferably at least 50-90% by weight, even more preferably at least 60-90% by weight, even more preferably at least 70-90% by weight in the above blend. ..
The above blends are made by mixing one or more polymers (above) with the polymers of the invention, connecting the reactors in series with each other to prepare a reactor blend, or in the same reactor. It may be produced by producing multiple polymers using more than one catalyst in. The polymers can be mixed with each other before being loaded into the extruder or may be mixed in the extruder.

Blending involves dry-blending the individual ingredients and then melting and mixing them in a mixer, or mixing the ingredients directly into each other in a mixer (blending resin powders or pellets in the hopper of a film extruder. A single-screw or twin-screw extruder that may include, for example, a Banbury mixer, a Hake mixer, a Bravender closed mixer, or a compound extruder and sidearm extruder used directly downstream of the polymerization process. It may be generated using conventional equipment and methods such as. In addition, the additive may be included in the product produced from the blend, such as the blend, one or more components of the blend, and / or the film, as desired. Such additives are well known in the art and include, for example, fillers; antioxidants (eg, IRGANOX ™ 1010 or IRGANOX ™ available from Ciba-Geigy). ) 1076 and other hindered phenols); phosphite (eg, IRGAFOS ™ 168 available from Ciba-Geigy); anti-adhesive additives; polybutene, terpene resins, aliphatic and aromatic hydrocarbon resins, alkali metals and Adhesives such as glycerol stearate and rosin hydride; UV stabilizers; heat stabilizers; blocking inhibitors; mold release agents; antistatic agents; pigments; colorants; dyes; waxes; silica; fillers; talc and The same kind can be included.

Any of the aforementioned polymers and compositions in combination with optional additives (see, eg, US Patent Application Publication No. 2016/0060430, paragraphs [008]-[093]) may be used in a variety of end-use applications. can. Such end applications may be produced by methods known in the art. End applications include polymer products and products with specific end uses. Exemplary end applications include films, film-based products, diaper backsheets, house wraps, wire and cable coating compositions, molding techniques such as injection or blow molding, extrusion coating, foaming, casting and combinations thereof. It is a molded article. End-uses also include products made from films, such as bags, packaging, and medical products such as personal care films, pouches, such as medical films and intravenous (IV) bags.

Films Specifically, any of the aforementioned polymers, such as the aforementioned polypropylenes or blends thereof, can be used in a variety of end-use applications. Such applications include, for example, single-layer or multi-layer inflation films, extruded films and / or shrink films. These films may be molded by any number of well-known extrusion or coextrusion techniques, such as inflation bubble film processing techniques, in which the composition is extruded in a molten state through an annular die and then After expansion to produce a uniaxial or biaxially stretched melt, it can be cooled to form a tubular inflation film, which can then be axially slit and opened to form a flat film. can. The film may not be subsequently stretched, but may be uniaxially stretched or biaxially stretched to the same or different extent. One or more layers of the film may be stretched laterally and / or longitudinally to the same or different extent. Uniaxial stretching can be achieved using a typical cold stretching method or hot stretching method. Biaxial stretching can be achieved using a tenter frame device or a double bubble process and can occur before or after combining the individual layers. For example, the polyethylene layer can be extruded or laminated onto a stretched polypropylene layer, or polyethylene and polypropylene can be co-extruded together into a film and then stretched. Similarly, stretched polypropylene can be laminated on stretched polyethylene, or stretched polyethylene can be coated on top of polypropylene, and optionally this combination can be further stretched. Typically, the film is stretched in the longitudinal direction (MD) at a ratio of up to 15, preferably between 5 and 7, and in the transverse direction (TD) at a ratio of up to 15, preferably 7-9. However, in another embodiment, the film is stretched to the same extent in both the MD and TD directions.

The film may vary in thickness depending on the intended use, but a film having a thickness of 1 to 50 μm is usually suitable. The film for packaging is usually 10 to 50 μm thick. The thickness of the seal layer is typically 0.2-50 μm. A sealing layer may be present on both the inner and outer surfaces of the film, or the sealing layer may be present only on the inner surface or only on the outer surface.

In another embodiment, one or more layers may be modified by corona treatment, electron beam irradiation, gamma ray irradiation, flame treatment or microwave treatment. In a preferred embodiment, one or both of the surface layers are modified by corona treatment.

(I)
（式中、
Ｍは、３、４、５もしくは６族遷移金属またはランタニドであり、
ＥおよびＥ’は、それぞれ独立してＯ、ＳまたはＮＲ⁹（式中、Ｒ⁹は、独立して水素、Ｃ₁－Ｃ₄₀ヒドロカルビル、Ｃ₁－Ｃ₄₀置換ヒドロカルビルまたはヘテロ原子含有基である）であり、
Ｑは、金属Ｍに対して供与結合を形成する１４、１５または１６族原子であり、
Ａ¹ＱＡ^1’は、３原子架橋を介してＡ²をＡ^2’に連結する、４～４０個の非水素原子を含む複素環式ルイス塩基の一部であり、３原子架橋の中心原子はＱであり、Ａ¹およびＡ^1’は、独立してＣ、ＮまたはＣ（Ｒ²²）（式中、Ｒ²²は、水素、Ｃ₁－Ｃ₂₀ヒドロカルビル、Ｃ₁－Ｃ₂₀置換ヒドロカルビルから選択される）であり、

は、２原子架橋を介してＡ¹をＥ結合アリール基に連結する、２～４０個の非水素原子を含む二価基であり、

は、２原子架橋を介してＡ^1’をＥ’結合アリール基に連結する、２～４０個の非水素原子を含む二価基であり、
Ｌはルイス塩基であり、
Ｘはアニオン性配位子であり、
ｎは、１、２または３であり、
ｍは、０、１または２であり、
ｎ＋ｍは４以下であり、
Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｒ^1’、Ｒ^2’、Ｒ^3’およびＲ^4’のそれぞれは、独立して水素、Ｃ₁－Ｃ₄₀ヒドロカルビル、Ｃ₁－Ｃ₄₀置換ヒドロカルビル、ヘテロ原子またはヘテロ原子含有基であり、
Ｒ¹およびＲ²、Ｒ²およびＲ³、Ｒ³およびＲ⁴、Ｒ^1’およびＲ^2’、Ｒ^2’およびＲ^3’、Ｒ^3’およびＲ^4’のうちの１つまたは複数が結合されて、５個、６個、７個または８個の環原子をそれぞれ有し、かつ環上の置換基が結合して追加の環を形成することができる１個もしくは複数の置換ヒドロカルビル環、非置換ヒドロカルビル環、置換複素環式環または非置換複素環式環を形成してよく、
任意の２個のＬ基が互いに結合されて二座ルイス塩基を形成してよく、
Ｘ基がＬ基に結合されてモノアニオン性二座基を形成してよく、
任意の２個のＸ基が互いに結合されてジアニオン性配位子基を形成してよい）
２．式（ＩＩ）により表される、式Ｉの触媒化合物。

(II)
（式中、
Ｍは、３、４、５もしくは６族遷移金属またはランタニドであり、
ＥおよびＥ’は、それぞれ独立してＯ、ＳまたはＮＲ⁹（式中、Ｒ⁹は、独立して水素、Ｃ₁－Ｃ₄₀ヒドロカルビル、Ｃ₁－Ｃ₄₀置換ヒドロカルビルまたはヘテロ原子含有基である）であり、
各Ｌは、独立してルイス塩基であり、
各Ｘは、独立してアニオン性配位子であり、
ｎは、１、２または３であり、
ｍは、０、１または２であり、
ｎ＋ｍは４以下であり、
Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｒ^1’、Ｒ^2’、Ｒ^3’およびＲ^4’のそれぞれは、独立して水素、Ｃ₁－Ｃ₄₀ヒドロカルビル、Ｃ₁－Ｃ₄₀置換ヒドロカルビル、ヘテロ原子もしくはヘテロ原子含有基であり、またはＲ¹およびＲ²、Ｒ²およびＲ³、Ｒ³およびＲ⁴、Ｒ^1’およびＲ^2’、Ｒ^2’およびＲ^3’、Ｒ^3’およびＲ^4’のうちの１つまたは複数が結合されて、５個、６個、７個または８個の環原子をそれぞれ有し、かつ環上の置換基が結合して追加の環を形成することができる１個もしくは複数の置換ヒドロカルビル環、非置換ヒドロカルビル環、置換複素環式環または非置換複素環式環を形成してよく、任意の２個のＬ基が互いに結合されて二座ルイス塩基を形成してよく、
Ｘ基がＬ基に結合されてモノアニオン性二座基を形成してよく、
任意の２個のＸ基が互いに結合されてジアニオン性配位子基を形成してよく、
Ｒ⁵、Ｒ⁶、Ｒ⁷、Ｒ⁸、Ｒ^5’、Ｒ^6’、Ｒ^7’、Ｒ^8’、Ｒ¹⁰、Ｒ¹¹およびＲ¹²のそれぞれは、独立して水素、Ｃ₁－Ｃ₄₀ヒドロカルビル、Ｃ₁－Ｃ₄₀置換ヒドロカルビル、ヘテロ原子もしくはヘテロ原子含有基であり、またはＲ⁵およびＲ⁶、Ｒ⁶およびＲ⁷、Ｒ⁷およびＲ⁸、Ｒ^5’およびＲ^6’、Ｒ^6’およびＲ^7’、Ｒ^7’およびＲ^8’、Ｒ¹⁰およびＲ¹¹もしくはＲ¹¹およびＲ¹²のうちの１つまたは複数が結合されて、５個、６個、７個または８個の環原子をそれぞれ有し、かつ環上の置換基が結合して追加の環を形成することができる１個もしくは複数の置換ヒドロカルビル環、非置換ヒドロカルビル環、置換複素環式環または非置換複素環式環を形成してよい）
３．Ｍが、Ｈｆ、ＺｒまたはＴｉである、段落１または２に記載の触媒化合物。
４．ＥおよびＥ’が、それぞれＯである、段落１、２または３に記載の触媒化合物。
５．Ｒ¹およびＲ^1’が、独立してＣ₄－Ｃ₄₀三級ヒドロカルビル基である、段落１、２、３または４に記載の触媒化合物。
６．Ｒ¹およびＲ^1’が、独立してＣ₄－Ｃ₄₀環式三級ヒドロカルビル基である、段落１、２、３、４または５に記載の触媒化合物。
７．Ｒ¹およびＲ^1’が、独立してＣ₄－Ｃ₄₀多環式三級ヒドロカルビル基である、段落１、２、３、４、５または６に記載の触媒化合物。
８．各Ｘが、独立して、１～２０個の炭素原子を有する置換または非置換ヒドロカルビル基、ヒドリド、アミド、アルコキシド、スルフィド、ホスフィド、ハライドおよびそれらの組合せからなる群から選択される、（２個のＸが縮合環または環系の一部を形成してよい）、段落１～７のいずれか１つに記載の触媒化合物。
９．各Ｌが、独立して、エーテル、チオエーテル、アミン、ホスフィン、エチルエーテル、テトラヒドロフラン、ジメチルスルフィド、トリエチルアミン、ピリジン、アルケン、アルキン、アレンおよびカルベンならびにそれらの組合せからなる群から選択され、任意に、２個以上のＬが縮合環または環系の一部を形成してよい、段落１～８のいずれか１つに記載の触媒化合物。
１０．Ｍが、ＺｒまたはＨｆであり、Ｑが窒素であり、Ａ¹およびＡ^1’の両方が炭素であり、ＥおよびＥ^’の両方が酸素であり、Ｒ¹およびＲ^1’の両方がＣ₄－Ｃ₂₀環式三級アルキルである、段落１に記載の触媒化合物。
１１．Ｍが、ＺｒまたはＨｆであり、Ｑが窒素であり、Ａ¹およびＡ^1’の両方が炭素であり、ＥおよびＥ^’の両方が酸素であり、Ｒ¹およびＲ^1’の両方がアダマンタン－１－イルまたは置換アダマンタン－１－イルである、段落１に記載の触媒化合物。
１２．Ｍが、ＺｒまたはＨｆであり、Ｑが窒素であり、Ａ¹およびＡ^1’の両方が炭素であり、ＥおよびＥ^’の両方が酸素であり、Ｒ¹およびＲ^1’の両方がＣ₆－Ｃ₂₀アリールである、段落１に記載の触媒化合物。
１３．Ｑが窒素であり、Ａ¹およびＡ^1’がいずれも炭素であり、Ｒ¹およびＲ^1’の両方が水素であり、ＥおよびＥ^’の両方がＮＲ⁹（式中、Ｒ⁹は、Ｃ₁－Ｃ₄₀ヒドロカルビル、Ｃ₁－Ｃ₄₀置換ヒドロカルビルまたはヘテロ原子含有基から選択される）である、段落１に記載の触媒化合物。
１４．Ｑが炭素であり、Ａ¹およびＡ^1’がいずれも窒素であり、ＥおよびＥ^’の両方が酸素である、段落１に記載の触媒化合物。
１５．Ｑが炭素であり、Ａ¹が窒素であり、Ａ^1’がＣ（Ｒ²²）であり、ＥおよびＥ^’の両方が酸素であり、式中、Ｒ²²が、水素、Ｃ₁－Ｃ₂₀ヒドロカルビル、Ｃ₁－Ｃ₂₀置換ヒドロカルビルから選択される、段落１に記載の触媒化合物。
１６．複素環式ルイス塩基が、以下の式により表される基から選択される、段落１に記載の触媒化合物。

（式中、各Ｒ²³は、水素、Ｃ₁－Ｃ₂₀アルキルおよびＣ₁－Ｃ₂₀置換アルキルから独立して選択される）
１７．Ｍが、ＺｒまたはＨｆであり、ＥおよびＥ^’の両方が酸素であり、Ｒ¹およびＲ^1’の両方がＣ₄－Ｃ₂₀環式三級アルキルである、段落２に記載の触媒化合物。
１８．Ｍが、ＺｒまたはＨｆであり、ＥおよびＥ^’の両方が酸素であり、Ｒ¹およびＲ^1’の両方がアダマンタン－１－イルまたは置換アダマンタン－１－イルである、段落２に記載の触媒化合物。
１９．Ｍが、ＺｒまたはＨｆであり、ＥおよびＥ^’の両方が酸素であり、Ｒ¹、Ｒ^1’、Ｒ³およびＲ^3’のそれぞれがアダマンタン－１－イルまたは置換アダマンタン－１－イルである、段落２に記載の触媒化合物。
２０．Ｍが、ＺｒまたはＨｆであり、ＥおよびＥ^’の両方が酸素であり、Ｒ¹およびＲ^1’の両方がＣ₄－Ｃ₂₀環式三級アルキルであり、Ｒ⁷およびＲ^7’の両方がＣ₁－Ｃ₂₀アルキルである、段落２に記載の触媒化合物。
２１．Ｍが、ＺｒまたはＨｆであり、ＥおよびＥ^’の両方がＯであり、Ｒ¹およびＲ^1’の両方がＣ₄－Ｃ₂₀環式三級アルキルであり、Ｒ⁷およびＲ^7’の両方がＣ₁－Ｃ₂₀アルキルである、段落２に記載の触媒化合物。
２２．Ｍが、ＺｒまたはＨｆであり、ＥおよびＥ^’の両方がＯであり、Ｒ¹およびＲ^1’の両方がＣ₄－Ｃ₂₀環式三級アルキルであり、Ｒ⁷およびＲ^7’の両方がＣ₁－Ｃ₃アルキルである、段落２に記載の触媒化合物。
２３．以下の式のうちの１つまたは複数により表される段落１に記載の触媒化合物。

２４．活性化剤と、段落１～２３のいずれか１つに記載の触媒化合物とを含む触媒系。
２５．活性化剤が、アルモキサンまたは非配位性アニオンを含む、段落２４に記載の触媒系。
２６．活性化剤が非芳香族炭化水素溶媒に可溶である、段落２４に記載の触媒系。
２７．芳香族溶媒を含まない段落２４に記載の触媒系。
２８．活性化剤が、以下の式により表される、段落２４に記載の触媒系。
（Ｚ）_d ⁺（Ａ^d-）
（式中、Ｚは、（Ｌ－Ｈ）、すなわち還元可能なルイス酸であり、Ｌは中性ルイス塩基であり、Ｈは水素であり、（Ｌ－Ｈ）⁺はブレンステッド酸であり、Ａ^d-は、電荷ｄ－を有する非配位性アニオンであり、ｄは、１～３の整数である）
２９．活性化剤が、以下の式により表される、段落２４に記載の触媒系。
［Ｒ^1’Ｒ^2’Ｒ^3’ＥＨ］_d+［Ｍｔ^k+Ｑ_n］^d-（Ｖ）
（式中、Ｅは、窒素またはリンであり、ｄは、１、２または３であり、ｋは、１、２または３であり、ｎは、１、２、３、４、５または６であり、ｎ－ｋ＝ｄであり、Ｒ^1’、Ｒ^2’およびＲ^3’は、独立して、１個もしくは複数のアルコキシ基、シリル基、ハロゲン原子またはハロゲン含有基で置換されてもよいＣ₁－Ｃ₅₀ヒドロカルビル基であり、Ｒ^1’、Ｒ^2’およびＲ^3’は合わせて１５個以上の炭素原子を含み、Ｍｔは、元素周期表の１３族から選択される元素であり、各Ｑは、独立してヒドリド、架橋もしくは非架橋ジアルキルアミド、ハライド、アルコキシド、アリールオキシド、ヒドロカルビル、置換ヒドロカルビル、ハロカルビル、置換ハロカルビルまたはハロ置換ヒドロカルビル基である）
３０．活性化剤が、以下の式により表される、段落２４に記載の触媒系。
（Ｚ）_d ⁺（Ａ^d-）
（式中、Ａ^d-は、電荷ｄ－を有する非配位性アニオンであり、ｄは、１～３の整数であり、（Ｚ）_d ⁺は、以下のうちの１つまたは複数により表される。

３１．活性化剤が、以下のうちの１種または複数種である、段落２４に記載の触媒系、
Ｎ－メチル－４－ノナデシル－Ｎ－オクタデシルベンゼンアミニウムテトラキス（ペンタフルオロフェニル）ボレート、
Ｎ－メチル－４－ノナデシル－Ｎ－オクタデシルベンゼンアミニウムテトラキス（ペルフルオロナフタレニル）ボレート、
ジオクタデシルメチルアンモニウムテトラキス（ペンタフルオロフェニル）ボレート、
ジオクタデシルメチルアンモニウムテトラキス（ペルフルオロナフタレニル）ボレート、
Ｎ，Ｎ－ジメチルアニリニウムテトラキス（ペンタフルオロフェニル）ボレート、
トリフェニルカルベニウムテトラキス（ペンタフルオロフェニル）ボレート、
トリメチルアンモニウムテトラキス（ペルフルオロナフタレニル）ボレート、
トリエチルアンモニウムテトラキス（ペルフルオロナフタレニル）ボレート、
トリプロピルアンモニウムテトラキス（ペルフルオロナフタレニル）ボレート、
トリ（ｎ－ブチル）アンモニウムテトラキス（ペルフルオロナフタレニル）ボレート、
トリ（ｔ－ブチル）アンモニウムテトラキス（ペルフルオロナフタレニル）ボレート、
Ｎ，Ｎ－ジメチルアニリニウムテトラキス（ペルフルオロナフタレニル）ボレート、
Ｎ，Ｎ－ジエチルアニリニウムテトラキス（ペルフルオロナフタレニル）ボレート、
Ｎ，Ｎ－ジメチル－（２，４，６－トリメチルアニリニウム）テトラキス（ペルフルオロナフタレニル）ボレート、
トロピリウム（ｔｒｏｐｉｌｌｉｕｍ）テトラキス（ペルフルオロナフタレニル）ボレート、
トリフェニルカルベニウムテトラキス（ペルフルオロナフタレニル）ボレート、
トリフェニルホスホニウムテトラキス（ペルフルオロナフタレニル）ボレート、
トリエチルシリリウムテトラキス（ペルフルオロナフタレニル）ボレート、
ベンゼン（ジアゾニウム）テトラキス（ペルフルオロナフタレニル）ボレート、
トリメチルアンモニウムテトラキス（ペルフルオロビフェニル）ボレート、
トリエチルアンモニウムテトラキス（ペルフルオロビフェニル）ボレート、
トリプロピルアンモニウムテトラキス（ペルフルオロビフェニル）ボレート、
トリ（ｎ－ブチル）アンモニウムテトラキス（ペルフルオロビフェニル）ボレート、
トリ（ｔ－ブチル）アンモニウムテトラキス（ペルフルオロビフェニル）ボレート、
Ｎ，Ｎ－ジメチルアニリニウムテトラキス（ペルフルオロビフェニル）ボレート、
Ｎ，Ｎ－ジエチルアニリニウムテトラキス（ペルフルオロビフェニル）ボレート、
Ｎ，Ｎ－ジメチル－（２，４，６－トリメチルアニリニウム）テトラキス（ペルフルオロビフェニル）ボレート、
トロピリウムテトラキス（ペルフルオロビフェニル）ボレート、
トリフェニルカルベニウムテトラキス（ペルフルオロビフェニル）ボレート、
トリフェニルホスホニウムテトラキス（ペルフルオロビフェニル）ボレート、
トリエチルシリリウムテトラキス（ペルフルオロビフェニル）ボレート、
ベンゼン（ジアゾニウム）テトラキス（ペルフルオロビフェニル）ボレート、
［４－ｔ－ブチル－ＰｈＮＭｅ₂Ｈ］［（Ｃ₆Ｆ₃（Ｃ₆Ｆ₅）₂）₄Ｂ］、
トリメチルアンモニウムテトラフェニルボレート、
トリエチルアンモニウムテトラフェニルボレート、
トリプロピルアンモニウムテトラフェニルボレート、
トリ（ｎ－ブチル）アンモニウムテトラフェニルボレート、
トリ（ｔ－ブチル）アンモニウムテトラフェニルボレート、
Ｎ，Ｎ－ジメチルアニリニウムテトラフェニルボレート、
Ｎ，Ｎ－ジエチルアニリニウムテトラフェニルボレート、
Ｎ，Ｎ－ジメチル－（２，４，６－トリメチルアニリニウム）テトラフェニルボレート、
トロピリウムテトラフェニルボレート、
トリフェニルカルベニウムテトラフェニルボレート、
トリフェニルホスホニウムテトラフェニルボレート、
トリエチルシリリウムテトラフェニルボレート、
ベンゼン（ジアゾニウム）テトラフェニルボレート、
トリメチルアンモニウムテトラキス（ペンタフルオロフェニル）ボレート、
トリエチルアンモニウムテトラキス（ペンタフルオロフェニル）ボレート、
トリプロピルアンモニウムテトラキス（ペンタフルオロフェニル）ボレート、
トリ（ｎ－ブチル）アンモニウムテトラキス（ペンタフルオロフェニル）ボレート、
トリ（ｓｅｃ－ブチル）アンモニウムテトラキス（ペンタフルオロフェニル）ボレート、
Ｎ，Ｎ－ジメチルアニリニウムテトラキス（ペンタフルオロフェニル）ボレート、
Ｎ，Ｎ－ジエチルアニリニウムテトラキス（ペンタフルオロフェニル）ボレート、
Ｎ，Ｎ－ジメチル－（２，４，６－トリメチルアニリニウム）テトラキス（ペンタフルオロフェニル）ボレート、
トロピリウムテトラキス（ペンタフルオロフェニル）ボレート、
トリフェニルカルベニウムテトラキス（ペンタフルオロフェニル）ボレート、
トリフェニルホスホニウムテトラキス（ペンタフルオロフェニル）ボレート、
トリエチルシリリウムテトラキス（ペンタフルオロフェニル）ボレート、
ベンゼン（ジアゾニウム）テトラキス（ペンタフルオロフェニル）ボレート、
トリメチルアンモニウムテトラキス（２，３，４，６－テトラフルオロフェニル）ボレート、
トリエチルアンモニウムテトラキス（２，３，４，６－テトラフルオロフェニル）ボレート、
トリプロピルアンモニウムテトラキス（２，３，４，６－テトラフルオロフェニル）ボレート、
トリ（ｎ－ブチル）アンモニウムテトラキス（２，３，４，６－テトラフルオロフェニル）ボレート、
ジメチル（ｔ－ブチル）アンモニウムテトラキス（２，３，４，６－テトラフルオロフェニル）ボレート、
Ｎ，Ｎ－ジメチルアニリニウムテトラキス（２，３，４，６－テトラフルオロフェニル）ボレート、
Ｎ，Ｎ－ジエチルアニリニウムテトラキス（２，３，４，６－テトラフルオロフェニル）ボレート、
Ｎ，Ｎ－ジメチル－（２，４，６－トリメチルアニリニウム）テトラキス（２，３，４，６－テトラフルオロフェニル）ボレート、
トロピリウムテトラキス（２，３，４，６－テトラフルオロフェニル）ボレート、
トリフェニルカルベニウムテトラキス（２，３，４，６－テトラフルオロフェニル）ボレート、
トリフェニルホスホニウムテトラキス（２，３，４，６－テトラフルオロフェニル）ボレート、
トリエチルシリリウムテトラキス（２，３，４，６－テトラフルオロフェニル）ボレート、
ベンゼン（ジアゾニウム）テトラキス（２，３，４，６－テトラフルオロフェニル）ボレート、
トリメチルアンモニウムテトラキス（３，５－ビス（トリフルオロメチル）フェニル）ボレート、
トリエチルアンモニウムテトラキス（３，５－ビス（トリフルオロメチル）フェニル）ボレート、
トリプロピルアンモニウムテトラキス（３，５－ビス（トリフルオロメチル）フェニル）ボレート、
トリ（ｎ－ブチル）アンモニウムテトラキス（３，５－ビス（トリフルオロメチル）フェニル）ボレート、
トリ（ｔ－ブチル）アンモニウムテトラキス（３，５－ビス（トリフルオロメチル）フェニル）ボレート、
Ｎ，Ｎ－ジメチルアニリニウムテトラキス（３，５－ビス（トリフルオロメチル）フェニル）ボレート、
Ｎ，Ｎ－ジエチルアニリニウムテトラキス（３，５－ビス（トリフルオロメチル）フェニル）ボレート、
Ｎ，Ｎ－ジメチル－（２，４，６－トリメチルアニリニウム）テトラキス（３，５－ビス（トリフルオロメチル）フェニル）ボレート、
トロピリウムテトラキス（３，５－ビス（トリフルオロメチル）フェニル）ボレート、
トリフェニルカルベニウムテトラキス（３，５－ビス（トリフルオロメチル）フェニル）ボレート、
トリフェニルホスホニウムテトラキス（３，５－ビス（トリフルオロメチル）フェニル）ボレート、
トリエチルシリリウムテトラキス（３，５－ビス（トリフルオロメチル）フェニル）ボレート、
ベンゼン（ジアゾニウム）テトラキス（３，５－ビス（トリフルオロメチル）フェニル）ボレート、
ジ－（ｉ－プロピル）アンモニウムテトラキス（ペンタフルオロフェニル）ボレート、
ジシクロヘキシルアンモニウムテトラキス（ペンタフルオロフェニル）ボレート、
トリ（ｏ－トリル）ホスホニウムテトラキス（ペンタフルオロフェニル）ボレート、
トリ（２，６－ジメチルフェニル）ホスホニウムテトラキス（ペンタフルオロフェニル）ボレート、
トリフェニルカルベニウムテトラキス（ペルフルオロフェニル）ボレート、
１－（４－（トリス（ペンタフルオロフェニル）ボレート）－２，３，５，６－テトラフルオロフェニル）ピロリジニウム、
テトラキス（ペンタフルオロフェニル）ボレート、
４－（トリス（ペンタフルオロフェニル）ボレート）－２，３，５，６－テトラフルオロピリジン、および
トリフェニルカルベニウムテトラキス（３，５－ビス（トリフルオロメチル）フェニル）ボレート）。
３２．１種または複数種のオレフィンを段落２３～３１のいずれか１つに記載の触媒系と接触させることを含む、オレフィンを重合するプロセス。
３３．約０℃～約３００℃の温度、約０．３５ＭＰａ～約１０ＭＰａの範囲内の圧力および最長３００分の時間で起こる段落３２に記載のプロセス。
３４．ポリマーを得ることをさらに含む段落３２に記載のプロセス。
３５．オレフィンが、１種もしくは複数種の置換または非置換Ｃ₂－Ｃ₄₀アルファオレフィンを含む、段落３２に記載のプロセス。 In another embodiment, the invention relates to:
1. 1. A catalytic compound represented by the formula (I).

(I)
(During the ceremony,
M is a Group 3, 4, 5 or 6 transition metal or lanthanide,
E and E'are independently O, S or NR ⁹ (in the formula, R ⁹ is independently hydrogen, C1 _- C ₄₀ hydrocarbyl, C1 _- C ₄₀ substituted hydrocarbyl or heteroatom-containing group, respectively. ) And
Q is a group 14, 15 or 16 atom forming a donor bond to the metal M.
A ¹ QA 1'is part of a heterocyclic Lewis base containing 4-40 non ^- hydrogen atoms that connects A ² to A ^2'via a triatomic bridge, and is the central atom of the triatomic bridge. Is Q, where A ¹ and A ^1'are independently C, N or C (R ²² ) (in the formula, R ²² is from hydrogen, C ₁ -C ₂₀ hydrocarbyl, C ₁ -C ₂₀ substituted hydrocarbyl. Is selected)

Is a divalent group containing 2 to 40 non-hydrogen atoms that links A ¹ to an E-bonded aryl group via biatomic cross-linking.

Is a divalent group containing 2 to 40 non-hydrogen atoms linking A ^1'to an E'bonded aryl group via biatomic cross-linking.
L is a Lewis base,
X is an anionic ligand
n is 1, 2 or 3
m is 0, 1 or 2,
n + m is 4 or less,
R ¹ , R ² , R ³ , R ⁴ , R ^1' , R ^{2' ,} R ^3'and R 4'are independently hydrogen, C ₁ -C ₄₀ hydrocarbyl, C ₁ -C ₄₀ substituted hydrocarbyl. , Heteroatom or heteroatom-containing group,
One or more of R ¹ and R ² , R ² and R ³ , R ³ and R ⁴ , R ^1'and R ^{2 '} , R 2'and R ^{3 '} , R ^3'and R 4'are combined. One or more substituted hydrocarbyl rings having 5, 6, 7 or 8 ring atoms, respectively, and the substituents on the ring can be bonded to form additional rings. An unsubstituted hydrocarbyl ring, a substituted heterocyclic ring or an unsubstituted heterocyclic ring may be formed.
Any two L groups may be attached to each other to form a bidentate Lewis base.
The X group may be attached to the L group to form a monoanionic bidentate.
Any two X groups may be bonded to each other to form a dianionic ligand group)
2. 2. A catalytic compound of formula I, represented by formula (II).

(II)
(During the ceremony,
M is a Group 3, 4, 5 or 6 transition metal or lanthanide,
E and E'are independently O, S or NR ⁹ (in the formula, R ⁹ is independently hydrogen, C1 _- C ₄₀ hydrocarbyl, C1 _- C ₄₀ substituted hydrocarbyl or heteroatom-containing group, respectively. ) And
Each L is an independent Lewis base,
Each X is an independent anionic ligand,
n is 1, 2 or 3
m is 0, 1 or 2,
n + m is 4 or less,
R ¹ , R ² , R ³ , R ⁴ , R ^1' , R ^{2' ,} R ^3'and R 4'are independently hydrogen, C ₁ -C ₄₀ hydrocarbyl, C ₁ -C ₄₀ substituted hydrocarbyl. , Heteroatom or heteroatom-containing group, or R ¹ and R ² , R ² and R ³ , R ³ and R ⁴ , R ^1'and R ^{2 '} , R 2'and R ^3' , R ^3'and One or more of R ^4'are bonded to each other to have 5, 6, 7 or 8 ring atoms, and the substituents on the ring combine to form an additional ring. One or more substituted hydrocarbyl rings, unsubstituted hydrocarbyl rings, substituted heterocyclic rings or unsubstituted heterocyclic rings which can be formed may be formed, and any two L groups are bonded to each other to form a bidentate Lewis. May form a base,
The X group may be attached to the L group to form a monoanionic bidentate.
Any two X groups may be bonded to each other to form a dianionic ligand group.
R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ^5' , R ^6' , R ^7' , R ^8' , R ¹⁰ , R ¹¹ and R ¹² are each independently hydrogen, C ₁ -C ₄₀ . Hydrocarbyl, C1 _{- C40} substituted hydrocarbyl, heteroatom or heteroatom-containing group, or R ⁵ and R ⁶ , R ⁶ and R ⁷ , R ⁷ and R ⁸ , R ^5'and R ^6' , R ^6' And one or more of R ^{7 '} , R 7'and R ^8' , R ¹⁰ and R ¹¹ or R ¹¹ and R ¹² combined to form 5, 6, 7 or 8 ring atoms. One or more substituted hydrocarbyl rings, unsubstituted hydrocarbyl rings, substituted heterocyclic rings or unsubstituted heterocyclic rings, respectively, and the substituents on the ring can be bonded to form an additional ring. May form)
3. 3. The catalytic compound according to paragraph 1 or 2, wherein M is Hf, Zr or Ti.
4. The catalytic compound according to paragraph 1, 2 or 3, wherein E and E'are O, respectively.
5. The catalytic compound according to paragraph 1, 2, 3 or 4, wherein R ¹ and R ^1'are independently _C4 -C ₄₀ tertiary hydrocarbyl groups.
6. The catalytic compound according to paragraph 1, 2, 3, 4 or 5, wherein R ¹ and R ^1'are independently _C4 -C ₄₀ cyclic tertiary hydrocarbyl groups.
7. The catalytic compound according to paragraph 1, 2, 3, 4, 5 or 6, wherein R ¹ and R ^1'are independently _C4 -C ₄₀ polycyclic tertiary hydrocarbyl groups.
8. Each X is independently selected from the group consisting of substituted or unsubstituted hydrocarbyl groups having 1 to 20 carbon atoms, hydrides, amides, alkoxides, sulfides, phosphides, halides and combinations thereof (2). X may form a fused ring or part of the ring system), the catalytic compound according to any one of paragraphs 1-7.
9. Each L is independently selected from the group consisting of ethers, thioethers, amines, phosphines, ethyl ethers, tetrahydrofurans, dimethylsulfides, triethylamines, pyridines, alkenes, alkynes, allenes and carbenes and combinations thereof, optionally 2 The catalyst compound according to any one of paragraphs 1 to 8, wherein more than one L may form a fused ring or a part of the ring system.
10. M is Zr or Hf, Q is nitrogen, both A ¹ and A ^1'are carbon, both E and ^E'are oxygen, and both R ¹ and R ^1'are C ₄ -The catalytic compound according to paragraph 1, which is a _C20 cyclic tertiary alkyl.
11. M is Zr or Hf, Q is nitrogen, both A ¹ and A ^1'are carbon, both E and ^E'are oxygen, and both R ¹ and R ^1'are adamantane-. The catalytic compound according to paragraph 1, which is 1-yl or substituted adamantane-1-yl.
12. M is Zr or Hf, Q is nitrogen, both A ¹ and A ^1'are carbon, both E and ^E'are oxygen, and both R ¹ and R ^1'are C ₆ -C ₂₀ aryl, the catalytic compound according to paragraph 1.
13. Q is nitrogen, A ¹ and A ^1'are both carbons, both R ¹ and R ^1'are hydrogen, and both E and ^E'are NR ⁹ (in the formula, R ⁹ is C). ₁ -C ₄₀ Hydrocarbyl, C1 _- C ₄₀ substituted hydrocarbyl or heteroatom-containing group), according to paragraph 1.
14. The catalytic compound according to paragraph 1, wherein Q is carbon, A ¹ and A ^1'are both nitrogen, and both E and ^E'are oxygen.
15. Q is carbon, A ¹ is nitrogen, A ^1'is C (R ²² ), both E and ^E'are oxygen, and in the formula, R ²² is hydrogen, C ₁ -C ₂₀ . The catalytic compound according to paragraph 1, selected from hydrocarbyl, C1 _- C ₂₀ substituted hydrocarbyl.
16. The catalytic compound according to paragraph 1, wherein the heterocyclic Lewis base is selected from the groups represented by the following formula.

(In the equation, each R ²³ is independently selected from hydrogen, C1-C ₂₀ alkyl and C _{1 -} C ₂₀ substituted alkyl).
17. The catalytic compound according to paragraph 2, wherein M is Zr or Hf, both E and ^E'are oxygen, and both R ¹ and R ^1'are _C4 -C ₂₀ cyclic tertiary alkyls.
18. The catalyst according to paragraph 2, wherein M is Zr or Hf, both E and ^E'are oxygen, and both R ¹ and R ^1'are adamantane-1-yl or substituted adamantane-1-yl. Compound.
19. M is Zr or Hf, both E and ^E'are oxygen, and R ¹ , R ^1' , R ³ and R ^3'are each adamantane-1-yl or substituted adamantane-1-yl. , The catalyst compound according to paragraph 2.
20. M is Zr or Hf, both E and ^E'are oxygen, both R ¹ and R 1'are _C4 -C ₂₀ cyclic tertiary alkyls, and both R ⁷ and R ^{7' .} The catalytic compound according to paragraph 2, wherein is C ₁ -C ₂₀ alkyl.
21. M is Zr or Hf, both E and ^E'are O, both R ¹ and R 1'are _C4 -C ₂₀ cyclic tertiary alkyls, and both R ⁷ and R ^{7' .} The catalytic compound according to paragraph 2, wherein is C ₁ -C ₂₀ alkyl.
22. M is Zr or Hf, both E and ^E'are O, both R ¹ and R 1'are _C4 -C ₂₀ cyclic tertiary alkyls, and both R ⁷ and R ^{7' .} The catalytic compound according to paragraph 2, wherein is C ₁ -C ₃ alkyl.
23. The catalytic compound according to paragraph 1 represented by one or more of the following formulas.

24. A catalytic system comprising an activator and the catalytic compound according to any one of paragraphs 1-23.
25. 24. The catalytic system according to paragraph 24, wherein the activator comprises an alumoxane or a non-coordinating anion.
26. The catalytic system according to paragraph 24, wherein the activator is soluble in a non-aromatic hydrocarbon solvent.
27. The catalyst system according to paragraph 24, which does not contain an aromatic solvent.
28. The catalytic system according to paragraph 24, wherein the activator is represented by the following formula.
(Z) _d ⁺ (A ^d- )
(In the formula, Z is (L—H), that is, a reducible Lewis acid, L is a neutral Lewis base, H is hydrogen, and (L—H) ⁺ is a Bronsted acid. A ^d- is a non-coordinating anion having a charge d-, and d is an integer of 1 to 3).
29. The catalytic system according to paragraph 24, wherein the activator is represented by the following formula.
[R ^{1'R 2'R 3'EH} ] _{d +} [Mt ^{k +} Q _n ] ^d- (V)
(In the formula, E is nitrogen or phosphorus, d is 1, 2 or 3, k is 1, 2 or 3, and n is 1, 2, 3, 4, 5 or 6. Yes, nk = d, and R ^{1' ,} R 2'and R ^3'may be independently substituted with one or more alkoxy groups, silyl groups, halogen atoms or halogen-containing groups. It is a C ₁ -C ₅₀ alkoxylubi group, R ^{1' ,} R 2'and R ^3'contain a total of 15 or more carbon atoms, and Mt is an element selected from Group 13 of the Periodic Table of the Elements. Each Q is independently a hydride, a crosslinked or non-bridged dialkylamide, a halide, an alkoxy, an aryloxide, a hydrocarbyl, a substituted hydrocarbyl, a halocarbyl, a substituted halocarbyl or a halo-substituted hydrocarbyl group).
30. The catalytic system according to paragraph 24, wherein the activator is represented by the following formula.
(Z) _d ⁺ (A ^d- )
(In the equation, A ^d- is a non-coordinating anion with a charge d-, d is an integer of 1 to 3, and (Z) _d ⁺ is represented by one or more of the following: Will be done.

31. The catalytic system according to paragraph 24, wherein the activator is one or more of the following:
N-Methyl-4-nonadecil-N-octadecylbenzene Aminium tetrakis (pentafluorophenyl) borate,
N-Methyl-4-nonadecil-N-octadecylbenzeneaminium tetrakis (perfluoronaphthalenyl) borate,
Dioctadecylmethylammonium tetrakis (pentafluorophenyl) borate,
Dioctadecylmethylammonium tetrakis (perfluoronaphthalenyl) borate,
N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate,
Triphenylcarbenium tetrakis (pentafluorophenyl) borate,
Trimethylammonium tetrakis (perfluoronaphthalenyl) borate,
Triethylammonium tetrakis (perfluoronaphthalenyl) borate,
Tripropylammonium tetrakis (perfluoronaphthalenyl) borate,
Tri (n-butyl) ammonium tetrakis (perfluoronaphthalenyl) borate,
Tri (t-butyl) ammonium tetrakis (perfluoronaphthalenyl) borate,
N, N-dimethylanilinium tetrakis (perfluoronaphthalenyl) borate,
N, N-diethylanilinium tetrakis (perfluoronaphthalenyl) borate,
N, N-dimethyl- (2,4,6-trimethylanilinium) tetrakis (perfluoronaphthalenyl) borate,
Tropylium tetrakis (perfluoronaphthalenyl) borate,
Triphenylcarbenium tetrakis (perfluoronaphthalenyl) borate,
Triphenylphosphonium tetrakis (perfluoronaphthalenyl) borate,
Triethylsilylium tetrakis (perfluoronaphthalenyl) borate,
Benzene (diazonium) tetrakis (perfluoronaphthalenyl) borate,
Trimethylammonium tetrakis (perfluorobiphenyl) borate,
Triethylammonium tetrakis (perfluorobiphenyl) borate,
Tripropylammonium tetrakis (perfluorobiphenyl) borate,
Tri (n-butyl) ammonium tetrakis (perfluorobiphenyl) borate,
Tri (t-butyl) ammonium tetrakis (perfluorobiphenyl) borate,
N, N-dimethylanilinium tetrakis (perfluorobiphenyl) borate,
N, N-diethylanilinium tetrakis (perfluorobiphenyl) borate,
N, N-dimethyl- (2,4,6-trimethylanilinium) tetrakis (perfluorobiphenyl) borate,
Tropyrium tetrakis (perfluorobiphenyl) borate,
Triphenylcarbenium tetrakis (perfluorobiphenyl) borate,
Triphenylphosphonium tetrakis (perfluorobiphenyl) borate,
Triethylsilylium tetrakis (perfluorobiphenyl) borate,
Benzene (diazonium) tetrakis (perfluorobiphenyl) borate,
[4-t-Butyl-PhNMe ₂ H] [(C ₆ F ₃ (C ₆ F ₅ ) ₂ ) ₄ B],
Trimethylammonium tetraphenylborate,
Triethylammonium tetraphenylborate,
Tripropylammonium tetraphenylborate,
Tri (n-butyl) ammonium tetraphenylborate,
Tri (t-butyl) ammonium tetraphenylborate,
N, N-dimethylanilinium tetraphenylborate,
N, N-diethylanilinium tetraphenylborate,
N, N-dimethyl- (2,4,6-trimethylanilinium) tetraphenylborate,
Tropyrium tetraphenylborate,
Triphenylcarbenium tetraphenylborate,
Triphenylphosphonium tetraphenylborate,
Triethylsilylium tetraphenylborate,
Benzene (diazonium) tetraphenylborate,
Trimethylammonium tetrakis (pentafluorophenyl) borate,
Triethylammonium tetrakis (pentafluorophenyl) borate,
Tripropylammonium tetrakis (pentafluorophenyl) borate,
Tri (n-butyl) ammonium tetrakis (pentafluorophenyl) borate,
Tri (sec-butyl) ammonium tetrakis (pentafluorophenyl) borate,
N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate,
N, N-diethylanilinium tetrakis (pentafluorophenyl) borate,
N, N-dimethyl- (2,4,6-trimethylanilinium) tetrakis (pentafluorophenyl) borate,
Tropyrium tetrakis (pentafluorophenyl) borate,
Triphenylcarbenium tetrakis (pentafluorophenyl) borate,
Triphenylphosphonium tetrakis (pentafluorophenyl) borate,
Triethylsilylium tetrakis (pentafluorophenyl) borate,
Benzene (diazonium) tetrakis (pentafluorophenyl) borate,
Trimethylammonium tetrakis (2,3,4,6-tetrafluorophenyl) borate,
Triethylammonium tetrakis (2,3,4,6-tetrafluorophenyl) borate,
Tripropylammonium tetrakis (2,3,4,6-tetrafluorophenyl) borate,
Tri (n-butyl) ammonium tetrakis (2,3,4,6-tetrafluorophenyl) borate,
Dimethyl (t-butyl) ammonium tetrakis (2,3,4,6-tetrafluorophenyl) borate,
N, N-dimethylanilinium tetrakis (2,3,4,6-tetrafluorophenyl) borate,
N, N-diethylanilinium tetrakis (2,3,4,6-tetrafluorophenyl) borate,
N, N-dimethyl- (2,4,6-trimethylanilinium) tetrakis (2,3,4,6-tetrafluorophenyl) borate,
Tropyrium tetrakis (2,3,4,6-tetrafluorophenyl) borate,
Triphenylcarbenium tetrakis (2,3,4,6-tetrafluorophenyl) borate,
Triphenylphosphonium tetrakis (2,3,4,6-tetrafluorophenyl) borate,
Triethylsilylium tetrakis (2,3,4,6-tetrafluorophenyl) borate,
Benzene (diazonium) tetrakis (2,3,4,6-tetrafluorophenyl) borate,
Trimethylammonium tetrakis (3,5-bis (trifluoromethyl) phenyl) borate,
Triethylammonium tetrakis (3,5-bis (trifluoromethyl) phenyl) borate,
Tripropylammonium tetrakis (3,5-bis (trifluoromethyl) phenyl) borate,
Tri (n-butyl) ammonium tetrakis (3,5-bis (trifluoromethyl) phenyl) borate,
Tri (t-butyl) ammonium tetrakis (3,5-bis (trifluoromethyl) phenyl) borate,
N, N-dimethylanilinium tetrakis (3,5-bis (trifluoromethyl) phenyl) borate,
N, N-diethylanilinium tetrakis (3,5-bis (trifluoromethyl) phenyl) borate,
N, N-dimethyl- (2,4,6-trimethylanilinium) tetrakis (3,5-bis (trifluoromethyl) phenyl) borate,
Tropyrium tetrakis (3,5-bis (trifluoromethyl) phenyl) borate,
Triphenylcarbenium tetrakis (3,5-bis (trifluoromethyl) phenyl) borate,
Triphenylphosphonium tetrakis (3,5-bis (trifluoromethyl) phenyl) borate,
Triethylsilylium tetrakis (3,5-bis (trifluoromethyl) phenyl) borate,
Benzene (diazonium) tetrakis (3,5-bis (trifluoromethyl) phenyl) borate,
Di- (i-propyl) ammonium tetrakis (pentafluorophenyl) borate,
Dicyclohexylammonium tetrakis (pentafluorophenyl) borate,
Tri (o-tolyl) phosphonium tetrakis (pentafluorophenyl) borate,
Tri (2,6-dimethylphenyl) phosphonium tetrakis (pentafluorophenyl) borate,
Triphenylcarbenium tetrakis (perfluorophenyl) borate,
1- (4- (Tris (pentafluorophenyl) borate) -2,3,5,6-tetrafluorophenyl) pyrrolidinium,
Tetrakis (pentafluorophenyl) borate,
4- (Tris (pentafluorophenyl) borate) -2,3,5,6-tetrafluoropyridine, and triphenylcarbenium tetrakis (3,5-bis (trifluoromethyl) phenyl) borate).
32.1 A process of polymerizing an olefin comprising contacting the olefin or a plurality of olefins with the catalyst system according to any one of paragraphs 23-31.
33. The process according to paragraph 32, which occurs at a temperature of about 0 ° C. to about 300 ° C., a pressure in the range of about 0.35 MPa to about 10 MPa, and a time of up to 300 minutes.
34. The process of paragraph 32, further comprising obtaining a polymer.
35. 32. The process of paragraph 32, wherein the olefin comprises one or more substituted or unsubstituted C2 _- C ₄₀ alpha olefins.

Shown in Experimental Scheme 3 are diagrams of catalyst complexes 1-32. Complexes 26 and 27 are co-filed US Patent Application No. _ entitled "Lewis Base Catalysis and Methods Thereof" claiming the priority and interests of 62 / 804,372 filed February 12, 2019. Prepared as described in (agent reference number 2019EM043). Complex 28 (comparison) was prepared as described by Golisz et al. (2009) Macromolecules, v.42, pp. 8751-8762. This is a comparative complex. Complexes 31 and 32 were prepared using procedures similar to those described for complex 29. 2- (adamantan-1-yl) -4- (tert-butyl) phenols are 4-tert-butylphenol (Merck) and adamantanol as described in Organic Letters 2015, v.17, pp. 2242-2245. Prepared from -1 (Aldrich).
Scheme 3

スキーム３（続き）

Scheme 3 (continued)

スキーム３（続き）

Scheme 3 (continued)

スキーム３（続き）

Scheme 3 (continued)

４００ｍｌのクロロホルム中の５７．６ｇ（２０３ｍｍｏｌ）の２－（アダマンタン－１－イル）－４－（ｔｅｒｔ－ブチル）フェノールの溶液に、２００ｍｌのクロロホルム中の１０．４ｍｌ（２０３ｍｍｏｌ）の臭素の溶液を室温で３０分間滴加した。生じた混合物を４００ｍｌの水で希釈した。得られた混合物をジクロロメタン（３×１００ｍｌ）で抽出し、合わせた有機抽出物を５％ ＮａＨＣＯ₃で洗浄し、Ｎａ₂ＳＯ₄で乾燥し、次いで、蒸発乾固した。収量７１．６ｇ（９７％）の白色固体。¹H NMR (CDCl₃, 400 MHz): δ 7.32 (d, J = 2.3 Hz, 1 H), 7.19 (d, J = 2.3 Hz, 1 H), 5.65 (s, 1 H), 2.18 - 2.03 (m, 9 H), 1.78 (m, 6 H), 1.29 (s, 9 H). ¹³C NMR (CDCl₃, 100 MHz): δ 148.07, 143.75, 137.00, 126.04, 123.62, 112.11, 40.24, 37.67, 37.01, 34.46, 31.47, 29.03. 2- (adamantane-1-yl) -6-bromo-4- (tert-butyl) phenol

To a solution of 57.6 g (203 mmol) of 2- (adamantane-1-yl) -4- (tert-butyl) phenol in 400 ml of chloroform is a solution of 10.4 ml (203 mmol) of bromine in 200 ml of chloroform. It was added dropwise at room temperature for 30 minutes. The resulting mixture was diluted with 400 ml of water. The resulting mixture was extracted with dichloromethane (3 x 100 ml) and the combined organic extracts were washed with 5% NaHCO ₃ and dried over Na ₂ SO ₄ and then evaporated to dryness. A white solid with a yield of 71.6 g (97%). ¹ H NMR (CDCl ₃ , 400 MHz): δ 7.32 (d, J = 2.3 Hz, 1 H), 7.19 (d, J = 2.3 Hz, 1 H), 5.65 (s, 1 H), 2.18 --2.03 ( m, 9 H), 1.78 (m, 6 H), 1.29 (s, 9 H). ¹³ C NMR (CDCl ₃ , 100 MHz): δ 148.07, 143.75, 137.00, 126.04, 123.62, 112.11, 40.24, 37.67, 37.01, 34.46, 31.47, 29.03.

１，０００ｍｌのＴＨＦ中の７１．６ｇ（１９７ｍｍｏｌ）の２－（アダマンタン－１－イル）－６－ブロモ－４－（ｔｅｒｔ－ブチル）フェノールの溶液に、８．２８ｇ（２０７ｍｍｏｌ、鉱油中６０質量％）の水素化ナトリウムを室温で分割して加えた。得られた懸濁液に、１６．５ｍｌ（２１７ｍｍｏｌ）のメトキシメチルクロリドを室温で１０分間滴加した。得られた混合物を一晩撹拌し、次いで、１，０００ｍｌの水に注いだ。得られた混合物をジクロロメタン（３×３００ｍｌ）で抽出し、合わせた有機抽出物を５％ ＮａＨＣＯ₃で洗浄し、Ｎａ₂ＳＯ₄で乾燥し、次いで、蒸発乾固した。収量８０．３ｇ（ほぼ定量的）の白色固体。¹H NMR (CDCl₃, 400 MHz): δ 7.39 (d, J = 2.4 Hz, 1 H), 7.27 (d, J = 2.4 Hz, 1 H), 5.23 (s, 2 H), 3.71 (s, 3 H), 2.20 - 2.04 (m, 9 H), 1.82 - 1.74 (m, 6 H), 1.29 (s, 9 H). ¹³C NMR (CDCl₃, 100 MHz): δ 150.88, 147.47, 144.42, 128.46, 123.72, 117.46, 99.53, 57.74, 41.31, 38.05, 36.85, 34.58, 31.30, 29.08. (1- (3-bromo-5- (tert-butyl) -2- (methoxymethoxy) phenyl) adamantin

8.28 g (207 mmol, 60 mass in mineral oil) in a solution of 71.6 g (197 mmol) of 2- (adamantane-1-yl) -6-bromo-4- (tert-butyl) phenol in 1,000 ml of THF. %) Sodium hydride was added in portions at room temperature. To the obtained suspension, 16.5 ml (217 mmol) of methoxymethyl chloride was added dropwise at room temperature for 10 minutes. The resulting mixture was stirred overnight and then poured into 1,000 ml of water. The resulting mixture was extracted with dichloromethane (3 x 300 ml) and the combined organic extracts were washed with 5% NaHCO ₃ and dried over Na ₂ SO ₄ and then evaporated to dryness. A white solid with a yield of 80.3 g (almost quantitative). ¹ H NMR (CDCl ₃ , 400 MHz): δ 7.39 (d, J = 2.4 Hz, 1 H), 7.27 (d, J = 2.4 Hz, 1 H), 5.23 (s, 2 H), 3.71 (s, 3 H), 2.20 --2.04 (m, 9 H), 1.82 --1.74 (m, 6 H), 1.29 (s, 9 H). ¹³ C NMR (CDCl ₃ , 100 MHz): δ 150.88, 147.47, 144.42, 128.46, 123.72, 117.46, 99.53, 57.74, 41.31, 38.05, 36.85, 34.58, 31.30, 29.08.

３００ｍｌの乾燥ＴＨＦ中の２２．５ｇ（５５．０ｍｍｏｌ）の（１－（３－ブロモ－５－（ｔｅｒｔ－ブチル）－２－（メトキシメトキシ）フェニル）アダマンチンの溶液に、ヘキサン中の２３．２ｍｌ（５７．９ｍｍｏｌ、２．５Ｍ）のⁿＢｕＬｉを－８０℃で２０分間滴加した。反応混合物をこの温度で１時間撹拌し、続いて、１４．５ｍｌ（７１．７ｍｍｏｌ）の２－イソプロポキシ－４，４，５，５－テトラメチル－１，３，２－ジオキサボロランを加えた。得られた懸濁液を室温で１時間撹拌し、次いで、３００ｍｌの水に注いだ。得られた混合物をジクロロメタン（３×３００ｍｌ）で抽出し、合わせた有機抽出物をＮａ₂ＳＯ₄で乾燥し、次いで、蒸発乾固した。収量２５．０ｇ（ほぼ定量的）の無色粘性油。¹H NMR (CDCl₃, 400 MHz): δ 7.54 (d, J = 2.5 Hz, 1 H), 7.43 (d, J = 2.6 Hz, 1 H), 5.18 (s, 2 H), 3.60 (s, 3 H), 2.24 - 2.13 (m, 6 H), 2.09 (br. s., 3 H), 1.85 - 1.75 (m, 6 H), 1.37 (s, 12 H), 1.33 (s, 9 H). ¹³C NMR (CDCl₃, 100 MHz): δ 159.64, 144.48, 140.55, 130.58, 127.47, 100.81, 83.48, 57.63, 41.24, 37.29, 37.05, 34.40, 31.50, 29.16, 24.79. 2- (3-adamantane-1-yl) -5- (tert-butyl) -2- (methoxymethoxy) phenyl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane

22.5 g (55.0 mmol) of (1- (3-bromo-5- (tert-butyl) -2- (methoxymethoxy) phenyl) adamantin solution in 300 ml of dry THF, 23.2 ml in hexanes (57.9 mmol, 2.5 M) ⁿ -BuLi was added dropwise at −80 ° C. for 20 minutes. The reaction mixture was stirred at this temperature for 1 hour, followed by 14.5 ml (71.7 mmol) of 2-isopropoxy. -4,4,5,5-tetramethyl-1,3,2-dioxaborolane was added. The resulting suspension was stirred at room temperature for 1 hour and then poured into 300 ml of water. The resulting mixture. Was extracted with dichloromethane (3 x 300 ml), the combined organic extracts were dried with Na ₂ SO ₄ , and then evaporated to dryness. A colorless viscous oil with a yield of 25.0 g (almost quantitative). ¹ H NMR ( CDCl ₃ , 400 MHz): δ 7.54 (d, J = 2.5 Hz, 1 H), 7.43 (d, J = 2.6 Hz, 1 H), 5.18 (s, 2 H), 3.60 (s, 3 H), 2.24 --2.13 (m, 6 H), 2.09 (br. S., 3 H), 1.85 --1.75 (m, 6 H), 1.37 (s, 12 H), 1.33 (s, 9 H). ¹³ C NMR (CDCl ₃ , 100 MHz): δ 159.64, 144.48, 140.55, 130.58, 127.47, 100.81, 83.48, 57.63, 41.24, 37.29, 37.05, 34.40, 31.50, 29.16, 24.79.

２００ｍｌのジオキサン中の２５．０ｇ（５５．０ｍｍｏｌ）の２－（３－アダマンタン－１－イル）－５－（ｔｅｒｔ－ブチル）－２－（メトキシメトキシ）フェニル）－４，４，５，５－テトラメチル－１，３，２－ジオキサボロランの溶液に、１５．６ｇ（５５．０ｍｍｏｌ）の２－ブロモヨードベンゼン、１９．０ｇ（１３７ｍｍｏｌ）の炭酸カリウムおよび１００ｍｌの水を続いて加えた。得られた混合物をアルゴンで１０分間パージし、続いて、３．２０ｇ（２．７５ｍｍｏｌ）のＰｄ（ＰＰｈ₃）₄を加えた。こうして得られた混合物を１００℃で１２時間撹拌し、次いで、室温まで冷却し、１００ｍｌの水で希釈した。得られた混合物をジクロロメタン（３×１００ｍｌ）で抽出し、合わせた有機抽出物をＮａ₂ＳＯ₄で乾燥し、次いで、蒸発乾固した。残留物をシリカゲル６０によるフラッシュクロマトグラフィー（４０～６３ｕｍ、溶離液：ヘキサン－ジクロロメタン＝１０：１、体積）により精製した。収量２３．５ｇ（８８％）の白色固体。¹H NMR (CDCl₃, 400 MHz): δ 7.68 (dd, J = 1.0, 8.0 Hz, 1 H), 7.42 (dd, J = 1.7, 7.6 Hz, 1 H), 7.37 - 7.32 (m, 2 H), 7.20 (dt, J = 1.8, 7.7 Hz, 1 H), 7.08 (d, J = 2.5 Hz, 1 H), 4.53 (d, J = 4.6 Hz, 1 H), 4.40 (d, J = 4.6 Hz, 1 H), 3.20 (s, 3 H), 2.23 - 2.14 (m, 6 H), 2.10 (br. s., 3 H), 1.86 - 1.70 (m, 6 H), 1.33 (s, 9 H). ¹³C NMR (CDCl₃, 100 MHz): δ 151.28, 145.09, 142.09, 141.47, 133.90, 132.93, 132.41, 128.55, 127.06, 126.81, 124.18, 123.87, 98.83, 57.07, 41.31, 37.55, 37.01, 34.60, 31.49, 29.17. 1- (2'-bromo-5- (tert-butyl) -2- (methoxymethoxy)-[1,1'-biphenyl] -3-yl) adamantin

25.0 g (55.0 mmol) 2- (3-adamantan-1-yl) -5- (tert-butyl) -2- (methoxymethoxy) phenyl) -4,4,5,5 in 200 ml of dioxane To a solution of -tetramethyl-1,3,2-dioxaborolane was subsequently added 15.6 g (55.0 mmol) of 2-bromoiodobenzene, 19.0 g (137 mmol) of potassium carbonate and 100 ml of water. The resulting mixture was purged with argon for 10 minutes, followed by the addition of 3.20 g (2.75 mmol) of Pd (PPh ₃ ) ₄ . The mixture thus obtained was stirred at 100 ° C. for 12 hours, then cooled to room temperature and diluted with 100 ml of water. The resulting mixture was extracted with dichloromethane (3 x 100 ml) and the combined organic extracts were dried over Na ₂ SO ₄ and then evaporated to dryness. The residue was purified by flash chromatography on silica gel 60 (40-63 um, eluent: hexane-dichloromethane = 10: 1, volume). A white solid with a yield of 23.5 g (88%). ¹ H NMR (CDCl ₃ , 400 MHz): δ 7.68 (dd, J = 1.0, 8.0 Hz, 1 H), 7.42 (dd, J = 1.7, 7.6 Hz, 1 H), 7.37 --7.32 (m, 2 H) ), 7.20 (dt, J = 1.8, 7.7 Hz, 1 H), 7.08 (d, J = 2.5 Hz, 1 H), 4.53 (d, J = 4.6 Hz, 1 H), 4.40 (d, J = 4.6 Hz, 1 H), 3.20 (s, 3 H), 2.23 --2.14 (m, 6 H), 2.10 (br. S., 3 H), 1.86 --1.70 (m, 6 H), 1.33 (s, 9) H). ¹³ C NMR (CDCl ₃ , 100 MHz): δ 151.28, 145.09, 142.09, 141.47, 133.90, 132.93, 132.41, 128.55, 127.06, 126.81, 124.18, 123.87, 98.83, 57.07, 41.31, 37.55, 37.01, 34.60 , 31.49, 29.17.

５００ｍｌの乾燥ＴＨＦ中の３０．０ｇ（６２．１ｍｍｏｌ）の１－（２’－ブロモ－５－（ｔｅｒｔ－ブチル）－２－（メトキシメトキシ）－［１，１’－ビフェニル］－３－イル）アダマンチンの溶液に、ヘキサン中の２５．６ｍｌ（６３．９ｍｍｏｌ、２．５Ｍ）のⁿＢｕＬｉを－８０℃で２０分間滴加した。反応混合物をこの温度で１時間撹拌し、続いて、１６．５ｍｌ（８０．７ｍｍｏｌ）の２－イソプロポキシ－４，４，５，５－テトラメチル－１，３，２－ジオキサボロランを加えた。得られた懸濁液を室温で１時間撹拌し、次いで、３００ｍｌの水に注いだ。得られた混合物をジクロロメタン（３×３００ｍｌ）で抽出し、合わせた有機抽出物をＮａ₂ＳＯ₄で乾燥し、次いで、蒸発乾固した。収量３２．９ｇ（ほぼ定量的）の無色ガラス状固体。¹H NMR (CDCl₃, 400 MHz): δ 7.75 (d, J = 7.3 Hz, 1 H), 7.44 - 7.36 (m, 1 H), 7.36 - 7.30 (m, 2 H), 7.30 - 7.26 (m, 1 H), 6.96 (d, J = 2.4 Hz, 1 H), 4.53 (d, J = 4.7 Hz, 1 H), 4.37 (d, J = 4.7 Hz, 1 H), 3.22 (s, 3 H), 2.26 - 2.14 (m, 6 H), 2.09 (br. s., 3 H), 1.85 - 1.71 (m, 6 H), 1.30 (s, 9 H), 1.15 (s, 6 H), 1.10 (s, 6 H). ¹³C NMR (CDCl₃, 100 MHz): δ 151.35, 146.48, 144.32, 141.26, 136.15, 134.38, 130.44, 129.78, 126.75, 126.04, 123.13, 98.60, 83.32, 57.08, 41.50, 37.51, 37.09, 34.49, 31.57, 29.26, 24.92, 24.21. 2- (3'-(adamantane-1-yl) -5'-(tert-butyl) -2'-(methoxymethoxy)-[1,1'-biphenyl] -2-yl) -4,4,5 , 5-Tetramethyl-1,3,2-dioxaborolane

30.0 g (62.1 mmol) 1- (2'-bromo-5- (tert-butyl) -2- (methoxymethoxy)-[1,1'-biphenyl] -3-yl in 500 ml of dry THF ) 25.6 ml (63.9 mmol, 2.5 M) of ⁿ -BuLi in hexane was added dropwise to the solution of adamantin at −80 ° C. for 20 minutes. The reaction mixture was stirred at this temperature for 1 hour, followed by the addition of 16.5 ml (80.7 mmol) of 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane. The resulting suspension was stirred at room temperature for 1 hour and then poured into 300 ml of water. The resulting mixture was extracted with dichloromethane (3 x 300 ml) and the combined organic extracts were dried over Na ₂ SO ₄ and then evaporated to dryness. A colorless glassy solid with a yield of 32.9 g (almost quantitative). ¹ H NMR (CDCl ₃ , 400 MHz): δ 7.75 (d, J = 7.3 Hz, 1 H), 7.44 --7.36 (m, 1 H), 7.36 --7.30 (m, 2 H), 7.30 --7.26 (m) , 1 H), 6.96 (d, J = 2.4 Hz, 1 H), 4.53 (d, J = 4.7 Hz, 1 H), 4.37 (d, J = 4.7 Hz, 1 H), 3.22 (s, 3 H) ), 2.26 --2.14 (m, 6 H), 2.09 (br. S., 3 H), 1.85 --1.71 (m, 6 H), 1.30 (s, 9 H), 1.15 (s, 6 H), 1.10 (s, 6 H). ¹³ C NMR (CDCl ₃ , 100 MHz): δ 151.35, 146.48, 144.32, 141.26, 136.15, 134.38, 130.44, 129.78, 126.75, 126.04, 123.13, 98.60, 83.32, 57.08, 41.50, 37.51 , 37.09, 34.49, 31.57, 29.26, 24.92, 24.21.

１４０ｍｌのジオキサン中の３２．９ｇ（６２．０ｍｍｏｌ）の２－（３’－（アダマンタン－１－イル）－５’－（ｔｅｒｔ－ブチル）－２’－（メトキシメトキシ）－［１，１’－ビフェニル］－２－イル）－４，４，５，５－テトラメチル－１，３，２－ジオキサボロランの溶液に、７．３５ｇ（３１．０ｍｍｏｌ）の２，６－ジブロモピリジン、５０．５ｇ（１５５ｍｍｏｌ）の炭酸セシウムおよび７０ｍｌの水を続いて加えた。得られた混合物をアルゴンで１０分間パージし、続いて、３．５０ｇ（３．１０ｍｍｏｌ）のＰｄ（ＰＰｈ₃）₄を加えた。この混合物を１００℃で１２時間撹拌し、次いで、室温まで冷却し、５０ｍｌの水で希釈した。得られた混合物をジクロロメタン（３×５０ｍｌ）で抽出し、合わせた有機抽出物をＮａ₂ＳＯ₄で乾燥し、次いで、蒸発乾固した。得られた油に、３００ｍｌのＴＨＦ、３００ｍｌのメタノールおよび２１ｍｌの１２Ｎ ＨＣｌを続いて加えた。反応混合物を６０℃で一晩撹拌し、次いで、５００ｍｌの水に注いだ。得られた混合物をジクロロメタン（３×３５０ｍｌ）で抽出し、合わせた有機抽出物を５％ ＮａＨＣＯ₃で洗浄し、Ｎａ₂ＳＯ₄で乾燥し、次いで、蒸発乾固した。残留物をシリカゲル６０によるフラッシュクロマトグラフィー（４０～６３ｕｍ、溶離液：ヘキサン－酢酸エチル＝１０：１、体積）により精製した。得られたガラス状固体を７０ｍｌのｎ－ペンタンと研和し、得られた沈殿物を濾別し、２×２０ｍｌのｎ－ペンタンで洗浄し、真空中で乾燥した。収量２１．５ｇ（８７％）の白色粉末としての２種の異性体の混合物。¹H NMR (CDCl₃, 400 MHz): δ 8.10 + 6.59 (2s, 2H), 7.53 - 7.38 (m, 10H), 7.09 + 7.08 (2d, J = 2.4 Hz, 2H), 7.04 + 6.97 (2d, J = 7.8 Hz, 2H), 6.95 + 6.54 (2d, J = 2.4 Hz), 2.03 - 1.79 (m, 18H), 1.74 - 1.59 (m, 12H), 1.16 + 1.01 (2s, 18H). ¹³C NMR (CDCl₃, 100 MHz, 副異性体のシフトを*で標識する): δ 157.86, 157.72*, 150.01, 149.23*, 141.82*, 141.77, 139.65*, 139.42, 137.92, 137.43, 137.32*, 136.80, 136.67*, 136.29*, 131.98*, 131.72, 130.81, 130.37*, 129.80, 129.09*, 128.91, 128.81*, 127.82*, 127.67, 126.40, 125.65*, 122.99*, 122.78, 122.47, 122.07*, 40.48, 40.37*, 37.04, 36.89*, 34.19*, 34.01, 31.47, 29.12, 29.07*. 2', 2'''-(pyridin-2,6-diyl) bis (3-adamantan-1-yl) -5- (tert-butyl)-[1,1'-biphenyl] -2-ol)

32.9 g (62.0 mmol) of 2- (3'-(adamantan-1-yl) -5'-(tert-butyl) -2'-(methoxymethoxy)-[1,1'" in 140 ml of dioxane -Biphenyl] -2-yl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane in a solution of 7.35 g (31.0 mmol) of 2,6-dibromopyridine, 50.5 g. (155 mmol) cesium carbonate and 70 ml of water were subsequently added. The resulting mixture was purged with argon for 10 minutes, followed by the addition of 3.50 g (3.10 mmol) of Pd (PPh ₃ ) ₄ . The mixture was stirred at 100 ° C. for 12 hours, then cooled to room temperature and diluted with 50 ml of water. The resulting mixture was extracted with dichloromethane (3 x 50 ml) and the combined organic extracts were dried over Na ₂ SO ₄ and then evaporated to dryness. To the resulting oil was subsequently added 300 ml THF, 300 ml methanol and 21 ml 12N HCl. The reaction mixture was stirred at 60 ° C. overnight and then poured into 500 ml of water. The resulting mixture was extracted with dichloromethane (3 x 350 ml) and the combined organic extracts were washed with 5% NaHCO ₃ and dried over Na ₂ SO ₄ and then evaporated to dryness. The residue was purified by flash chromatography on silica gel 60 (40-63 um, eluent: hexane-ethyl acetate = 10: 1, volume). The resulting glassy solid was triturated with 70 ml n-pentane, the resulting precipitate was filtered off, washed with 2 x 20 ml n-pentane and dried in vacuo. A mixture of the two isomers as a white powder with a yield of 21.5 g (87%). ¹ H NMR (CDCl ₃ , 400 MHz): δ 8.10 + 6.59 (2s, 2H), 7.53 --7.38 (m, 10H), 7.09 + 7.08 (2d, J = 2.4 Hz, 2H), 7.04 + 6.97 (2d, J = 7.8 Hz, 2H), 6.95 + 6.54 (2d, J = 2.4 Hz), 2.03 --1.79 (m, 18H), 1.74 --1.59 (m, 12H), 1.16 + 1.01 (2s, 18H). ¹³ C NMR (CDCl ₃ , 100 MHz, labeled by-isomer shift with *): δ 157.86, 157.72 *, 150.01, 149.23 *, 141.82 *, 141.77, 139.65 *, 139.42, 137.92, 137.43, 137.32 *, 136.80, 136.67 *, 136.29 *, 131.98 *, 131.72, 130.81, 130.37 *, 129.80, 129.09 *, 128.91, 128.81 *, 127.82 *, 127.67, 126.40, 125.65 *, 122.99 *, 122.78, 122.47, 122.07 *, 40.48, 40.37 *, 37.04, 36.89 *, 34.19 *, 34.01, 31.47, 29.12, 29.07 *.

２５０ｍｌの乾燥トルエン中の３．２２ｇ（１０．０５ｍｍｏｌ）の四塩化ハフニウム（＜０．０５％ Ｚｒ）の懸濁液に、ジエチルエーテル中の１４．６ｍｌ（４２．２ｍｍｏｌ、２．９Ｍ）のＭｅＭｇＢｒを０℃でシリンジを介して１回で加えた。得られた懸濁液を１分間撹拌し、８．００ｇ（１０．０５ｍｍｏｌ）の２’，２’’’－（ピリジン－２，６－ジイル）ビス（３－アダマンタン－１－イル）－５－（ｔｅｒｔ－ブチル）－［１，１’－ビフェニル］－２－オール）を分割して１分間加えた。反応混合物を室温で３６時間撹拌し、次いで、ほぼ乾固するまで蒸発させた。得られた固体を２×１００ｍｌの熱トルエンで抽出し、合わせた有機抽出物をＣｅｌｉｔｅ ５０３の薄いパッドに通して濾過した。次に、濾液を蒸発乾固した。残留物を５０ｍｌのｎ－ヘキサンと研和し、得られた沈殿物を濾別（Ｇ３）し、２０ｍｌのｎ－ヘキサン（２×２０ｍｌ）で洗浄し、次いで、真空中で乾燥した。収量６．６６ｇ（６１％、ｎ－ヘキサンとの約１：１溶媒和物）の淡ベージュ色固体。Ｃ₅₉Ｈ₆₉ＨｆＮＯ₂×１．０（Ｃ₆Ｈ₁₄）の解析計算値：Ｃ、７１．７０；Ｈ、７．６８；Ｎ、１．２９。測定値：Ｃ ７１．９５；Ｈ、７．８３；Ｎ １．１８。¹H NMR (C₆D₆, 400 MHz): δ 7.58 (d, J = 2.6 Hz, 2 H), 7.22 - 7.17 (m, 2 H), 7.14 - 7.08 (m, 4 H), 7.07 (d, J = 2.5 Hz, 2 H), 7.00 - 6.96 (m, 2 H), 6.48 - 6.33 (m, 3 H), 2.62 - 2.51 (m, 6H), 2.47 - 2.35 (m, 6H), 2.19 (br.s, 6H), 2.06 - 1.95 (m, 6H), 1.92 - 1.78 (m, 6H), 1.34 (s, 18 H), -0.12 (s, 6 H). ¹³C NMR (C₆D₆, 100 MHz): δ 159.74, 157.86, 143.93, 140.49, 139.57, 138.58, 133.87, 133.00, 132.61, 131.60, 131.44, 127.98, 125.71, 124.99, 124.73, 51.09, 41.95, 38.49, 37.86, 34.79, 32.35, 30.03. Dimethylhafnium [2', 2'''-(pyridin-2,6-diyl) bis (3-adamantan-1-yl) -5- (tert-butyl)-[1,1'-biphenyl] -2- Olate)] (complex 5)

14.6 ml (42.2 mmol, 2.9 M) of MeMgBr in diethyl ether in a suspension of 3.22 g (10.05 mmol) hafnium tetrachloride (<0.05% Zr) in 250 ml of dry toluene. Was added once at 0 ° C. via a syringe. The resulting suspension was stirred for 1 minute and 8.00 g (10.05 mmol) of 2', 2'''-(pyridin-2,6-diyl) bis (3-adamantan-1-yl) -5. -(Tert-Butyl)-[1,1'-biphenyl] -2-ol) was divided and added for 1 minute. The reaction mixture was stirred at room temperature for 36 hours and then evaporated to near dryness. The resulting solid was extracted with 2 x 100 ml hot toluene and the combined organic extracts were filtered through a thin pad of Celite 503. Next, the filtrate was evaporated to dryness. The residue was triturated with 50 ml of n-hexane, the resulting precipitate was filtered off (G3), washed with 20 ml of n-hexane (2 x 20 ml) and then dried in vacuo. A light beige solid with a yield of 6.66 g (61%, about 1: 1 solvate with n-hexane). Analysis of C ₅₉ H ₆₉ HfNO ₂ × 1.0 (C ₆ H ₁₄ ) Calculated value: C, 71.70; H, 7.68; N, 1.29. Measured values: C 71.95; H, 7.83; N 1.18. ¹ H NMR (C ₆ D ₆ , 400 MHz): δ 7.58 (d, J = 2.6 Hz, 2 H), 7.22 --7.71 (m, 2 H), 7.14 --7.08 (m, 4 H), 7.07 (d) , J = 2.5 Hz, 2 H), 7.00 --6.96 (m, 2 H), 6.48 --6.33 (m, 3 H), 2.62 --2.51 (m, 6H), 2.47 --2.35 (m, 6H), 2.19 ( br.s, 6H), 2.06 --1.95 (m, 6H), 1.92 --1.78 (m, 6H), 1.34 (s, 18 H), -0.12 (s, 6 H). ¹³ C NMR (C ₆ D ₆ ) , 100 MHz): δ 159.74, 157.86, 143.93, 140.49, 139.57, 138.58, 133.87, 133.00, 132.61, 131.60, 131.44, 127.98, 125.71, 124.99, 124.73, 51.09, 41.95, 38.49, 37.86, 34.79, 32.35, 30.03

３００ｍｌの乾燥トルエン中の２．９２ｇ（１２．５６ｍｍｏｌ）の四塩化ジルコニウムの懸濁液に、ジエチルエーテル中の１８．２ｍｌ（５２．７ｍｍｏｌ、２．９Ｍ）のＭｅＭｇＢｒを０℃でシリンジを介して１回で加えた。得られた懸濁液に、１０．００ｇ（１２．５６ｍｍｏｌ）の２’，２’’’－（ピリジン－２，６－ジイル）ビス（３－アダマンタン－１－イル）－５－（ｔｅｒｔ－ブチル）－［１，１’－ビフェニル］－２－オール）を直ちに１回で加えた。反応混合物を室温で２時間撹拌し、次いで、ほぼ乾固するまで蒸発させた。得られた固体を２×１００ｍｌの熱トルエンで抽出し、合わせた有機抽出物をＣｅｌｉｔｅ ５０３の薄いパッドに通して濾過した。次に、濾液を蒸発乾固した。残留物を５０ｍｌのｎ－ヘキサンと研和し、得られた沈殿物を濾別（Ｇ３）し、ｎ－ヘキサン（２×２０ｍｌ）で洗浄し、次いで、真空中で乾燥した。収量８．９５ｇ（７４％、ｎ－ヘキサンとの約１：０．５溶媒和物）のベージュ色固体。Ｃ₅₉Ｈ₆₉ＺｒＮＯ₂×０．５（Ｃ₆Ｈ₁₄）の解析計算値：Ｃ、７７．６９；Ｈ、７．９９；Ｎ、１．４６。測定値：Ｃ ７７．９０；Ｈ、８．１５；Ｎ １．３６。¹H NMR (C₆D₆, 400 MHz): δ 7.56 (d, J = 2.6 Hz, 2 H), 7.20 - 7.17 (m, 2 H), 7.14 - 7.07 (m, 4 H), 7.07 (d, J = 2.5 Hz, 2 H), 6.98 - 6.94 (m, 2 H), 6.52 - 6.34 (m, 3 H), 2.65 - 2.51 (m, 6H), 2.49 - 2.36 (m, 6H), 2.19 (br.s., 6H), 2.07 - 1.93 (m, 6H), 1.92 - 1.78 (m, 6H), 1.34 (s, 18 H), 0.09 (s, 6 H). ¹³C NMR (C₆D₆, 100 MHz): δ 159.20, 158.22, 143.79, 140.60, 139.55, 138.05, 133.77, 133.38, 133.04, 131.49, 131.32, 127.94, 125.78, 124.65, 124.52, 42.87, 41.99, 38.58, 37.86, 34.82, 32.34, 30.04. Dimethyl zirconium [2', 2'''-(pyridin-2,6-diyl) bis (3-adamantan-1-yl) -5- (tert-butyl)-[1,1'-biphenyl] -2- Olate)] (complex 6)

18.2 ml (52.7 mmol, 2.9 M) of MeMgBr in diethyl ether to a suspension of 2.92 g (12.56 mmol) of zirconium tetrachloride in 300 ml of dry toluene via a syringe at 0 ° C. Added once. In the resulting suspension, 10.00 g (12.56 mmol) of 2', 2'''- (pyridin-2,6-diyl) bis (3-adamantan-1-yl) -5- (tert-). Butyl)-[1,1'-biphenyl] -2-ol) was immediately added in one dose. The reaction mixture was stirred at room temperature for 2 hours and then evaporated to near dryness. The resulting solid was extracted with 2 x 100 ml hot toluene and the combined organic extracts were filtered through a thin pad of Celite 503. Next, the filtrate was evaporated to dryness. The residue was triturated with 50 ml of n-hexane, the resulting precipitate was filtered off (G3), washed with n-hexane (2 x 20 ml) and then dried in vacuo. A beige solid with a yield of 8.95 g (74%, about 1: 0.5 solvate with n-hexane). Analysis calculation value of C ₅₉ H ₆₉ ZrNO ₂ × 0.5 (C ₆ H ₁₄ ): C, 77.69; H, 7.99; N, 1.46. Measured values: C 77.90; H, 8.15; N 1.36. ¹ H NMR (C ₆ D ₆ , 400 MHz): δ 7.56 (d, J = 2.6 Hz, 2 H), 7.20 --7.71 (m, 2 H), 7.14 --7.07 (m, 4 H), 7.07 (d) , J = 2.5 Hz, 2 H), 6.98 --6.94 (m, 2 H), 6.52 --6.34 (m, 3 H), 2.65 --2.51 (m, 6H), 2.49 --2.36 (m, 6H), 2.19 ( br.s., 6H), 2.07 --1.93 (m, 6H), 1.92 --1.78 (m, 6H), 1.34 (s, 18 H), 0.09 (s, 6 H). ¹³ C NMR (C ₆ D ₆ ) , 100 MHz): δ 159.20, 158.22, 143.79, 140.60, 139.55, 138.05, 133.77, 133.38, 133.04, 131.49, 131.32, 127.94, 125.78, 124.65, 124.52, 42.87, 41.99, 38.58, 37.86, 34.82, 32.34, 30.

ジメチルホルムアミド（２５ｍＬ）中の１－ブロモアダマンタン（５．００ｇ、２３．２４２ｍｍｏｌ）の撹拌溶液に、塩酸（８．７ｍＬの０．６７Ｍ ＨＣｌ）、続いて、水（１５ｍＬ）を加えた。混合物を１０５℃にし、１時間撹拌した。室温まで冷却した後、水（１５０ｍＬ）を加え、生じた沈殿物を真空濾過により回収した。固体をジクロロメタン（２００ｍＬ）に取り、水（３×１００ｍＬ）で洗浄した。有機層を乾燥（ＭｇＳＯ４）し、濾過し、真空下で濃縮して、３．５１２ｇ（２３．０６９ｍｍｏｌ、収率９９％）を得た。 1-Adamantanol

Hydrochloric acid (8.7 mL 0.67M HCl) followed by water (15 mL) was added to a stirred solution of 1-bromoadamantane (5.00 g, 23.242 mmol) in dimethylformamide (25 mL). The mixture was brought to 105 ° C. and stirred for 1 hour. After cooling to room temperature, water (150 mL) was added and the resulting precipitate was recovered by vacuum filtration. The solid was taken in dichloromethane (200 mL) and washed with water (3 x 100 mL). The organic layer was dried (00544), filtered and concentrated under vacuum to give 3.512 g (23.069 mmol, 99% yield).

ジクロロメタン（ｄｉｃｈｌｒｏｒｏｍｅｔｈａｎｅ）（２０ｍＬ）中のフェノール（２．００ｇ、２１．２５２ｍｍｏｌ）および１－アダマンタノール（６．７９４ｇ、４４．６２９ｍｍｏｌ、２．１０ｅｑ）の混合物に、濃硫酸（２．５ｍＬ）を室温で（１０分にわたって）滴加した。これを室温で一晩撹拌した。水（１５ｍＬ）を反応混合物に加え、ｐＨを９～１０にした（２Ｍ水性ＮａＯＨ）。有機物をジクロロメタン（３×２０ｍＬ）で抽出し、ブラインで洗浄し、乾燥（ＭｇＳＯ₄）し、濾過し、真空下で濃縮した。残留物をカラムクロマトグラフィー（５～１０％酢酸エチル／ヘキサン）により精製して、１．２９ｇ（収率１７％）の白色固体を得た。 2,4-di (adamant-1-yl) phenol

A mixture of phenol (2.00 g, 21.252 mmol) and 1-adamantanol (6.794 g, 44.629 mmol, 2.10 eq) in dichloromethane (dichloromethane) (20 mL) with concentrated sulfuric acid (2.5 mL) at room temperature. Dropped in (over 10 minutes). This was stirred overnight at room temperature. Water (15 mL) was added to the reaction mixture to bring the pH to 9-10 (2M aqueous NaOH). Organic matter was extracted with dichloromethane (3 x 20 mL), washed with brine, dried (0054 ₄ ), filtered and concentrated under vacuum. The residue was purified by column chromatography (5-10% ethyl acetate / hexane) to give 1.29 g (17% yield) of a white solid.

テトラヒドロフラン（３ｍＬ）中の２，４－ジ（アダマンチル）フェノール（１．２９ｇ、３．５５８ｍｍｏｌ）の混合物に、水素化ナトリウム（鉱油中６０％、０．１８５ｇ、４．６２５ｍｍｏｌ、１．３０ｅｑ）をゆっくり加えた。これを室温で３０分間撹拌し、この時点でクロロメチルメチルエーテル（０．４５９ｍＬ、６．０４９ｍｍｏｌ、１．７０ｅｑ）を漸増的に加えた。反応物を室温で一晩撹拌させた。反応混合物を水（２０ｍＬ）でクエンチし、水酸化カリウムを使用してｐＨを８～１０に調整した。生成物をジエチルエーテル（３×３０ｍＬ）で抽出し、乾燥（ＭｇＳＯ４）し、濾過し、真空中で濃縮して、１．３３０ｇ（３．２７５ｍｍｏｌ、収率９２％）を得た。 1,1'-(4- (Methoxymethoxy) -1,3-phenylene) bis (adamantane)

Sodium hydride (60% in mineral oil, 0.185 g, 4.625 mmol, 1.30 eq) is added to a mixture of 2,4-di (adamantyl) phenol (1.29 g, 3.558 mmol) in tetrahydrofuran (3 mL). Added slowly. This was stirred at room temperature for 30 minutes, at which point chloromethyl methyl ether (0.459 mL, 6.049 mmol, 1.70 eq) was added incrementally. The reaction was stirred at room temperature overnight. The reaction mixture was quenched with water (20 mL) and the pH was adjusted to 8-10 using potassium hydroxide. The product was extracted with diethyl ether (3 × 30 mL), dried (00544), filtered and concentrated in vacuo to give 1.330 g (3.275 mmol, 92% yield).

ペンタン（２０ｍＬ）を１，１’－（４－（メトキシメトキシ）－１，３－フェニレン）ビス（アダマンタン）（１．３８ｇ、３．４０ｍｍｏｌ）に加えて、溶液を生成した。ＢｕＬｉの１．６Ｍヘキサン溶液（２．１３ｍＬ、３．４０ｍｍｏｌ）を滴加した。次いで、１，２－ジメトキシエタン（ＤＭＥ）を滴加した。数分以内に黄色溶液が濁り、次いで、沈殿物が生成し始めた。混合物を１．５時間撹拌させ、次いで、沈殿物をフリットディスク上で単離し、ペンタン（３×１５ｍＬ）で洗浄し、減圧下で乾燥した。生成物をオフホワイト色固体として単離した。収量：１．１５ｇ、６７．２％。 (3,5-diadamantane-1-yl) -2- (methoxymethoxy) phenyl) Lithium (1,2-dimethoxyethane)

Pentane (20 mL) was added to 1,1'-(4- (methoxymethoxy) -1,3-phenylene) bis (adamantane) (1.38 g, 3.40 mmol) to generate a solution. A 1.6 M hexane solution of BuLi (2.13 mL, 3.40 mmol) was added dropwise. Then 1,2-dimethoxyethane (DME) was added dropwise. Within minutes the yellow solution became cloudy and then a precipitate began to form. The mixture was stirred for 1.5 hours, then the precipitate was isolated on a frit disk, washed with pentane (3 x 15 mL) and dried under reduced pressure. The product was isolated as an off-white solid. Yield: 1.15 g, 67.2%.

トルエン（２０ｍＬ）を（３，５－ジアダマンタン－１－イル）－２－（メトキシメトキシ）フェニル）リチウム・（１，２－ジメトキシエタン）（１．１５ｇ、２．２９ｍｍｏｌ）に加えて、懸濁液を生成した。１－ブロモ－２－クロロベンゼン（０．４８２ｇ、２．５２ｍｍｏｌ）のトルエン溶液（１０ｍＬ）を１時間にわたって滴加して、濁った溶液を生成した。混合物をさらに１時間撹拌し、次いで、揮発物を減圧下で除去した。残留物をＣＨ₂Ｃｌ₂（８ｍＬ）で抽出し、Ｔｅｆｌｏｎフィルター上のＣｅｌｉｔｅ ５０３に通して濾過した。揮発物を蒸発させ、ペンタン（３ｍＬ）を残留物に加えた。混合物を－２０℃まで一晩冷却した。何も結晶化されなかったので、揮発物を蒸発させ、残留物を減圧下６０℃で乾燥した。収量：１．３２ｇ、９８．９％。 1,1'-(2'-bromo-2- (methoxymethoxy)-[1,1'-biphenyl] -3,5-diyl) bis (adamantane)

Toluene (20 mL) is added to (3,5-diadamantane-1-yl) -2- (methoxymethoxy) phenyl) lithium (1,2-dimethoxyethane) (1.15 g, 2.29 mmol) and suspended. A turbid liquid was produced. A toluene solution (10 mL) of 1-bromo-2-chlorobenzene (0.482 g, 2.52 mmol) was added dropwise over 1 hour to produce a turbid solution. The mixture was stirred for an additional hour and then the volatiles were removed under reduced pressure. The residue was extracted with CH ₂ Cl ₂ (8 mL) and filtered through Celite 503 on a Teflon filter. The volatiles were evaporated and pentane (3 mL) was added to the residue. The mixture was cooled to −20 ° C. overnight. Since nothing was crystallized, the volatiles were evaporated and the residue was dried under reduced pressure at 60 ° C. Yield: 1.32 g, 98.9%.

テトラヒドロフラン（１５ｍＬ）を１，１’－（２’－ブロモ－２－（メトキシメトキシ）－［１，１’－ビフェニル］－３，５－ジイル）ビス（アダマンタン）（１．３２ｇ、２．２６ｍｍｏｌ）に加えて、溶液を生成した。混合物を－４５℃まで冷却し、ヘキサン中のＢｕＬｉの１．６Ｍ溶液（１．４６ｍＬ、２．３３ｍｍｏｌ）を１分にわたって滴加した。混合物を４５分にわたって－２５℃までゆっくり昇温させた。固体ＺｎＣｌ₂（０．２１６ｇ、１．５８ｍｍｏｌ）を透明な溶液に加えた。混合物を３０分にわたって周囲温度までゆっくり昇温させた。周囲温度で３０分後、２，６－ジブロモピリジン（０．２６０ｇ、１．１０ｍｍｏｌ）およびＰｄ（Ｐ（ｔＢｕ）₃）₂（０．０２３ｇ、０．０４５ｍｍｏｌ）を無色透明の溶液に加えた。６５℃に保たれた金属ブロック上で混合物を一晩加熱した。一晩撹拌後、揮発物をロータリーエバポレーターで蒸発させた。残留物に、メタノール（２０ｍＬ）、ｔｈｆ（２０ｍＬ）および濃ＨＣｌ（１ｍＬ）を加えた。混合物を６０℃まで５時間加熱した。次いで、揮発物をロータリーエバポレーターで蒸発させ、残留物をＣＨ₂Ｃｌ₂（６０ｍＬ）で抽出した。有機物を水（３×５０ｍＬ）で洗浄し、希ＮａＨＣＯ₃で洗浄して、ｐＨを７に調整（１×５０ｍＬ）し、次いで、ブライン（４０ｍＬ）およびＭｇＳＯ₄で乾燥した。揮発物の濾過および除去により、１．２ｇの粗生成物を得た。イソヘキサン中の２～８％ ＥｔＯＡｃを使用してカラムクロマトグラフィーによりシリカゲルで精製した。イソヘキサン－ＥｔＯＡｃの蒸発により、ＣＨ₂Ｃｌ₂に不溶性である何らかの材料を含む白色残留物を得た。固体をベンゼン（１０ｍＬ）で抽出し、濾過し、蒸発させた。残留物を減圧下６０℃で乾燥して、泡状固体を得た。収量：０．３２２ｇ、３０．８％。 2', 2'''-(pyridin-2,6-diyl) bis ((3,5-diadamantane-1-yl)-[1,1'-biphenyl] -2-ol)

Tetrahydrofuran (15 mL) in 1,1'-(2'-bromo-2- (methoxymethoxy)-[1,1'-biphenyl] -3,5-diyl) bis (adamantane) (1.32 g, 2.26 mmol) ), A solution was produced. The mixture was cooled to −45 ° C. and a 1.6 M solution of BuLi in hexanes (1.46 mL, 2.33 mmol) was added dropwise over 1 minute. The mixture was slowly warmed to -25 ° C over 45 minutes. Solid ZnCl ₂ (0.216 g, 1.58 mmol) was added to the clear solution. The mixture was slowly warmed to ambient temperature over 30 minutes. After 30 minutes at ambient temperature, 2,6-dibromopyridine (0.260 g, 1.10 mmol) and Pd (P (tBu) ₃ ) ₂ (0.023 g, 0.045 mmol) were added to the clear, colorless solution. The mixture was heated overnight on a metal block kept at 65 ° C. After stirring overnight, the volatiles were evaporated on a rotary evaporator. To the residue was added methanol (20 mL), THF (20 mL) and concentrated HCl (1 mL). The mixture was heated to 60 ° C. for 5 hours. The volatiles were then evaporated on a rotary evaporator and the residue was extracted with CH ₂ Cl ₂ (60 mL). The organics were washed with water (3 x 50 mL), washed with dilute NaHCO ₃ to adjust the pH to 7 (1 x 50 mL) and then dried with brine (40 mL) and sulfonyl ₄ . Filtration and removal of volatiles gave 1.2 g of crude product. Purified on silica gel by column chromatography using 2-8% EtOAc in isohexane. Evaporation of isohexane- EtOAc gave a white residue containing some material insoluble in CH ₂ Cl ₂ . The solid was extracted with benzene (10 mL), filtered and evaporated. The residue was dried under reduced pressure at 60 ° C. to give a foamy solid. Yield: 0.322g, 30.8%.

Dibenzylzirconium [2', 2'''-(pyridin-2,6-diyl) bis (3,5-diadamantane-1-yl)-[1,1'-biphenyl] -2-olate)] ( Complex 22)
Benzene (15 mL) 2', 2'''-(pyridin-2,6-diyl) bis ((3,5-diadamantane-1-yl)-[1,1'-biphenyl] -2-ol) In addition to (0.315 g, 0.331 mmol), a solution was produced. ZrBn ₄ (0.151 g, 0.331 mmol) and benzene (2 mL) were added. The mixture was shaken to produce a yellow-orange solution. After 30 minutes, the mixture was filtered and evaporated to 1 mL. Hexane (3 mL) was added to produce a turbid mixture. The volatiles were evaporated to dryness. The yellow-orange solid was thoroughly washed with pentane (5 mL). The pentane extract was filtered and cooled to −20 ° C. for several hours. Some yellow solids were isolated from the pentane solution. The pentane-washed sample was combined with methylcyclohexane (10 mL) and the mixture was heated to near boiling for several minutes. Some crystalline solids separated from the orange solution. The mixture was allowed to stand at ambient temperature for 2 hours, then the colorless solid was isolated and dried under reduced pressure. HNMR spectroscopy showed that the product co-crystallized with 1 equivalent of methylcyclohexane. Yield: 0.092 g, 21%.

３００ｍｌの乾燥ＴＨＦ中の２１．３ｇ（６６．４ｍｍｏｌ）の２－ブロモ－６－アダマンチル－４－メチルフェノールの溶液に、２．７９ｇ（６９．７ｍｍｏｌ、鉱油中６０質量％）の水素化ナトリウムを室温で分割して加えた。その後、５．５５ｍｌ（７３．０ｍｍｏｌ）のＭＯＭＣｌを１時間滴加した。反応混合物を６０℃で２４時間加熱し、次いで、３００ｍｌの冷水に注いだ。粗生成物を３×２００ｍｌのジクロロメタンで抽出した。合わせた有機抽出物をＮａ₂ＳＯ₄で乾燥し、次いで、蒸発乾固した。収量２４．３ｇ（定量的）の無色油。¹H NMR (CDCl₃, 400 MHz): δ 7.24 (d, J = 1.5 Hz, 1H), 7.05 (d, J = 1.8 Hz, 1H), 5.22 (s, 2H), 3.71 (s, 3H), 2.27 (s, 3H), 2.07 - 2.15 (m, 9H), 1.78 (m, 6H). ¹³C NMR (CDCl₃, 100 MHz): δ 151.01, 144.92, 134.34, 131.80, 127.44, 117.57, 99.56, 57.75, 41.27, 37.71, 36.82, 29.03, 20.68. 1- (3-bromo-2- (methoxymethoxy) -5-methylphenyl) adamantin

2.79 g (69.7 mmol, 60% by weight in mineral oil) sodium hydride in a solution of 21.3 g (66.4 mmol) of 2-bromo-6-adamantyl-4-methylphenol in 300 ml of dry THF. It was added in portions at room temperature. Then, 5.55 ml (73.0 mmol) of MOMCl was added dropwise for 1 hour. The reaction mixture was heated at 60 ° C. for 24 hours and then poured into 300 ml of cold water. The crude product was extracted with 3 x 200 ml dichloromethane. The combined organic extracts were dried over Na ₂ SO ₄ and then evaporated to dryness. Colorless oil with a yield of 24.3 g (quantitative). ¹ H NMR (CDCl ₃ , 400 MHz): δ 7.24 (d, J = 1.5 Hz, 1H), 7.05 (d, J = 1.8 Hz, 1H), 5.22 (s, 2H), 3.71 (s, 3H), 2.27 (s, 3H), 2.07 --2.15 (m, 9H), 1.78 (m, 6H). ¹³ C NMR (CDCl ₃ , 100 MHz): δ 151.01, 144.92, 134.34, 131.80, 127.44, 117.57, 99.56, 57.75 , 41.27, 37.71, 36.82, 29.03, 20.68.

２５０ｍｌの乾燥ＴＨＦ中の１０．０ｇ（７４．５ｍｍｏｌ）のベンゾ［ｂ］チオフェンの溶液に、ヘキサン中の２９．８ｍｌ（７４．５ｍｍｏｌ、２．５Ｍ）のⁿＢｕＬｉを－１０℃で滴加した。反応混合物を０℃で１時間撹拌し、続いて、１１．２ｇ（８２．０ｍｍｏｌ）のＺｎＣｌ₂を加えた。次に、得られた溶液を室温まで加温し、１３．６ｇ（３７．３ｍｍｏｌ）の１－（３－ブロモ－２－（メトキシメトキシ）－５－メチルフェニル）アダマンチンおよび１．５２ｇ（２．９８ｍｍｏｌ）のＰｄ［Ｐ^tＢｕ₃］₂を続いて加えた。生じた混合物を６０℃で一晩撹拌し、次いで、２５０ｍｌの水に注いだ。粗生成物を３×１５０ｍｌのジクロロメタンで抽出した。合わせた有機抽出物をＮａ₂ＳＯ₄で乾燥し、次いで、蒸発乾固した。残留物をシリカゲル６０によるフラッシュクロマトグラフィー（４０～６３ｕｍ；溶離液：ヘキサン－酢酸エチル＝１０：１、体積）により精製した。収量５．３１ｇ（３４％）の淡黄色固体。¹H NMR (CDCl₃, 400 MHz): δ 7.88 (d, J = 7.7 Hz, 1H), 7.81 (d, J = 7.4 Hz, 1H), 7.54 (s, 1H), 7.32 - 7.42 (m, 2H), 7.18 - 7.23 (m, 2H), 4.79 (s, 2H), 3.49 (s, 3H), 2.38 (s, 3H), 2.24 (m, 6H), 2.16 (m, 3H), 1.85 (m, 6H). 2- (3-adamantane-1-yl) -2- (methoxymethoxy) -5-methylphenyl) benzo [b] thiophene

To a solution of 10.0 g (74.5 mmol) of benzo [b] thiophene in 250 ml of dry THF was added 29.8 ml (74.5 mmol, 2.5 M) of ^nBuLi in hexanes at −10 ° C. .. The reaction mixture was stirred at 0 ° C. for 1 hour, followed by the addition of 11.2 g (82.0 mmol) of ZnCl ₂ . The resulting solution was then warmed to room temperature and 13.6 g (37.3 mmol) 1- (3-bromo-2- (methoxymethoxy) -5-methylphenyl) adamantin and 1.52 g (2. 98 mmol) of Pd [P ^t Bu ₃ ] ₂ was subsequently added. The resulting mixture was stirred at 60 ° C. overnight and then poured into 250 ml of water. The crude product was extracted with 3 x 150 ml dichloromethane. The combined organic extracts were dried over Na ₂ SO ₄ and then evaporated to dryness. The residue was purified by flash chromatography on silica gel 60 (40-63 um; eluent: hexane-ethyl acetate = 10: 1, volume). A pale yellow solid with a yield of 5.31 g (34%). ¹ H NMR (CDCl ₃ , 400 MHz): δ 7.88 (d, J = 7.7 Hz, 1H), 7.81 (d, J = 7.4 Hz, 1H), 7.54 (s, 1H), 7.32 --7.42 (m, 2H) ), 7.18 --7.23 (m, 2H), 4.79 (s, 2H), 3.49 (s, 3H), 2.38 (s, 3H), 2.24 (m, 6H), 2.16 (m, 3H), 1.85 (m, 6H).

１５０ｍｌのクロロホルム中の５．３１ｇ（１２．７ｍｍｏｌ）の２－（３－アダマンタン－１－イル）－２－（メトキシメトキシ）－５－メチルフェニル）ベンゾ［ｂ］チオフェンの溶液に、２．２６ｇ（１２．７ｍｍｏｌ）のＮ－ブロモスクシンイミドを室温で加えた。反応混合物をこの温度で２時間撹拌し、次いで、１００ｍｌの水に注いだ。粗生成物を３×５０ｍｌのジクロロメタンで抽出した。合わせた有機抽出物をＮａ₂ＳＯ₄で乾燥し、次いで、蒸発乾固した。残留物を－３０℃の９０ｍｌのｎ－ヘキサンから再結晶させた。収量６．２５ｇ（９８％）の淡黄色固体。¹H NMR (CDCl₃, 400 MHz): δ 7.90 (d, J = 7.8 Hz, 1H), 7.84 (d, J = 7.9 Hz, 1H), 7.49 (dt, J = 0.9, 7.1 Hz, 1H), 7.43 (dt, J = 1.2, 8.1 Hz, 1H), 7.24 (d, J = 2.0 Hz, 1H), 7.12 (d, J = 1.7 Hz, 1H), 4.66 (s, 2H), 3.33 (s, 3H), 2.38 (s, 3H), 2.22 (m, 6H), 2.14 (br.s, 3H), 1.83 (m, 6H). ¹³C NMR (CDCl₃, 100 MHz): δ 153.19, 143.13, 138.54, 138.19, 137.38, 132.48, 130.68, 129.30, 126.06, 125.38, 125.03, 123.42, 122.19, 107.76, 99.33, 57.38, 41.17, 37.30, 36.97, 29.10, 20.98. 3-Bromo-2- (3-adamantane-1-yl) -2- (methoxymethoxy) -5-methylphenyl) benzo [b] thiophene

2.26 g in a solution of 5.31 g (12.7 mmol) 2- (3-adamantane-1-yl) -2- (methoxymethoxy) -5-methylphenyl) benzo [b] thiophene in 150 ml of chloroform. (12.7 mmol) N-bromosuccinimide was added at room temperature. The reaction mixture was stirred at this temperature for 2 hours and then poured into 100 ml of water. The crude product was extracted with 3 x 50 ml dichloromethane. The combined organic extracts were dried over Na ₂ SO ₄ and then evaporated to dryness. The residue was recrystallized from 90 ml n-hexane at −30 ° C. A pale yellow solid with a yield of 6.25 g (98%). ¹ H NMR (CDCl ₃ , 400 MHz): δ 7.90 (d, J = 7.8 Hz, 1H), 7.84 (d, J = 7.9 Hz, 1H), 7.49 (dt, J = 0.9, 7.1 Hz, 1H), 7.43 (dt, J = 1.2, 8.1 Hz, 1H), 7.24 (d, J = 2.0 Hz, 1H), 7.12 (d, J = 1.7 Hz, 1H), 4.66 (s, 2H), 3.33 (s, 3H) ), 2.38 (s, 3H), 2.22 (m, 6H), 2.14 (br.s, 3H), 1.83 (m, 6H). ¹³ C NMR (CDCl ₃ , 100 MHz): δ 153.19, 143.13, 138.54, 138.19, 137.38, 132.48, 130.68, 129.30, 126.06, 125.38, 125.03, 123.42, 122.19, 107.76, 99.33, 57.38, 41.17, 37.30, 36.97, 29.10, 20.98.

１２０ｍｌの乾燥ＴＨＦ中の３．００ｇ（６．０３ｍｍｏｌ）の３－ブロモ－２－（３－アダマンタン－１－イル）－２－（メトキシメトキシ）－５－メチルフェニル）ベンゾ［ｂ］チオフェンの溶液に、ヘキサン中の２．４１ｍｌ（６．０３ｍｍｏｌ、２．５Ｍ）のⁿＢｕＬｉを－８０℃で滴加した。反応混合物をこの温度で３０分間撹拌し、次いで、２．３２ｇ（１７．１ｍｍｏｌ）のＺｎＣｌ₂を加えた。得られた混合物を室温まで加温し、次いで、０．７２ｇ（３．０２ｍｍｏｌ）の２，６－ジブロモピリジンおよび２４５ｍｇ（０．４８ｍｍｏｌ）のＰｄ［Ｐ^tＢｕ₃］₂を続いて加えた。得られた混合物を６０℃で一晩撹拌し、１００ｍｌの水に注ぎ、粗生成物をジクロロメタン（３×５０ｍｌ）で抽出した。合わせた有機抽出物をＮａ₂ＳＯ₄で乾燥し、次いで、蒸発乾固した。得られた油に、５０ｍｌのＴＨＦ、５０ｍｌのメタノールおよび１ｍｌの１２Ｎ ＨＣｌを続いて加えた。反応混合物を６０℃で一晩撹拌し、次いで、２００ｍｌの水に注いだ。得られた混合物をジクロロメタン（３×５０ｍｌ）で抽出し、合わせた有機抽出物をＮａ₂ＳＯ₄で乾燥し、次いで、蒸発乾固した。残留物をシリカゲル６０によるフラッシュクロマトグラフィー（４０～６３ｕｍ；溶離液：ヘキサン－酢酸エチル－トリエチルアミン＝１００：１０：１、体積）により精製した。収量０．７８ｇ（３１％）の白色泡。¹H NMR (CDCl₃, 400 MHz): δ 7.87 - 7.94 (m, 4H), 7.67 (t, J = 7.8 Hz, 1H), 7.38 - 7.48 (m, 4H), 7.28 (d, J = 7.8 Hz, 2H), 6.91 - 6.99 (m, 4H), 2.23 (s, 6H), 1.82 (br.s, 6H), 1.67 (br.s, 9H), 1.57 - 1.62 (m, 6H), 1.42 - 1.50 (m, 6H). ¹³C NMR (CDCl₃, 100 MHz): δ 153.56, 150.70, 140.51, 139.91, 138.86, 138.50, 137.87, 131.91, 129.49, 128.68, 128.49, 124.92, 124.77, 123.71, 122.82, 122.00, 40.02, 36.81, 36.60, 28.98, 20.73. 6,6'-(Pyridine-2,6-diylbis (benzo [b] thiophene-3,2-diyl)) Bis (2-adamantan-1-yl) -4-methylphenol)

A solution of 3.00 g (6.03 mmol) of 3-bromo-2- (3-adamantan-1-yl) -2- (methoxymethoxy) -5-methylphenyl) benzo [b] thiophene in 120 ml of dry THF. To 2.41 ml (6.03 mmol, 2.5 M) of ^nBuLi in hexane was added dropwise at −80 ° C. The reaction mixture was stirred at this temperature for 30 minutes, then 2.32 g (17.1 mmol) of ZnCl ₂ was added. The resulting mixture was warmed to room temperature, followed by the addition of 0.72 g (3.02 mmol) of 2,6-dibromopyridine and 245 mg (0.48 mmol) of Pd [P ^t Bu ₃ ] ₂ . The resulting mixture was stirred at 60 ° C. overnight, poured into 100 ml of water and the crude product was extracted with dichloromethane (3 x 50 ml). The combined organic extracts were dried over Na ₂ SO ₄ and then evaporated to dryness. To the resulting oil was subsequently added 50 ml THF, 50 ml methanol and 1 ml 12N HCl. The reaction mixture was stirred at 60 ° C. overnight and then poured into 200 ml of water. The resulting mixture was extracted with dichloromethane (3 x 50 ml) and the combined organic extracts were dried over Na ₂ SO ₄ and then evaporated to dryness. The residue was purified by flash chromatography on silica gel 60 (40-63 um; eluent: hexane-ethyl acetate-triethylamine = 100: 10: 1, volume). White foam with a yield of 0.78 g (31%). ¹ H NMR (CDCl ₃ , 400 MHz): δ 7.87 --7.94 (m, 4H), 7.67 (t, J = 7.8 Hz, 1H), 7.38 --7.74 (m, 4H), 7.28 (d, J = 7.8 Hz) , 2H), 6.91 --6.99 (m, 4H), 2.23 (s, 6H), 1.82 (br.s, 6H), 1.67 (br.s, 9H), 1.57 --1.62 (m, 6H), 1.42 --1.50 (m, 6H). ¹³ C NMR (CDCl ₃ , 100 MHz): δ 153.56, 150.70, 140.51, 139.91, 138.86, 138.50, 137.87, 131.91, 129.49, 128.68, 128.49, 124.92, 124.77, 123.71, 122.82, 122.00, 40.02, 36.81, 36.60, 28.98, 20.73.

Dimethylhafnium [6,6'-(pyridin-2,6-diylbis (benzo [b] thiophene-3,2-diyl)) bis (2-adamantan-1-yl) -4-methylphenolate)] (complex 23)
To a suspension of 155 mg (0.485 mmol) of hafnium tetrachloride in 50 ml of dry toluene was added 0.75 ml (2.20 mmol, 2.9 M) of MeMgBr in diethyl ether in a single dose at room temperature. The resulting suspension was stirred for 1 minute and 400 mg (0.485 mmol) of 6,6'-(pyridin-2,6-diylbis (benzo [b] thiophene-3,2-diyl) in 10 ml of dry toluene. )) A solution of bis (2-adamantan-1-yl) -4-methylphenol) was added dropwise for 1 minute. The reaction mixture was stirred at room temperature overnight and then evaporated to near dryness. The resulting solid was extracted with 2 x 20 ml hot toluene and the combined organic extracts were filtered through a thin pad of Celite 503. Next, the filtrate was evaporated to dryness. The resulting solid was washed with 5 ml n-hexane and dried in vacuo. A beige solid as a hexane solvate with a yield of 303 mg (60%). Analysis of C ₅₇ H ₅₇ HfNO ₂ S ₂ × 2 (C ₆ H ₁₄ ) Calculated values: C, 68.89; H, 7.12; N, 1.16. Measured values: C 69.07; H 7.33; N 1.11. ¹ H NMR (C ₆ D ₆ , 400 MHz): δ 7.35 (dd, J = 1.9, 6.9 Hz, 2H), 7.21 (d, J = 2.1 Hz, 2H), 7.12 (d, J = 2.1 Hz, 2H) ), 7.05 --7.12 (m, 4H), 6.92 (dd, J = 2.0, 6.5 Hz, 2H), 6.69 (t, J = 7.8 Hz, 1H), 6.46 (d, J = 7.8 Hz, 2H), 2.20 (s, 6H), 2.11 --2.17 (m, 6H), 1.99 --2.07 (m, 6H), 1.75 --1.87 (m, 12H), 1.63 --1.70 (m, 6H), 0.18 (s, 6H). ¹³ C NMR (C ₆ D ₆ , 100 MHz): δ 160.12, 154.44, 150.43, 149.60, 147.46, 143.70, 141.40, 140.26, 134.21, 131.01, 130.32, 129.66, 127.31, 126.59, 125.59, 125.45, 124.83, 124.64, 122.98 , 122.68, 114.02, 52.62, 41.19, 38.05, 37.67, 32.30, 29.73, 23.39, 14.69.

Dimethylzirconium [6,6'-(pyridin-2,6-diylbis (benzo [b] thiophene-3,2-diyl)) bis (2-adamantan-1-yl) -4-methylphenolate)] (complex 24)
To a suspension of 58 mg (0.247 mmol) of zirconium tetrachloride in 30 ml of dry toluene was added 0.38 ml (1.11 mmol, 2.9 M) of MeMgBr in diethyl ether once at room temperature. The resulting suspension was stirred for 10 seconds and 204 mg (0.247 mmol) of 6,6'-(pyridin-2,6-diylbis (benzo [b] thiophene-3,2-diyl) in 10 ml of dry toluene. )) A solution of bis (2-adamantan-1-yl) -4-methylphenol) was added dropwise for 30 seconds. The reaction mixture was stirred at room temperature overnight and then evaporated to near dryness. The resulting solid was extracted with 2 x 20 ml hot toluene and the combined organic extracts were filtered through a thin pad of Celite 503. Next, the filtrate was evaporated to dryness. The resulting solid was washed with 5 ml n-hexane and then dried in vacuo. A beige solid with a yield of 140 mg (60%). Analysis calculation value of C ₅₇ H ₅₇ ZrNO ₂ S ₂ : C, 72.57; H, 6.09; N, 1.48. Measured values: C 72.78; H 6.29; N 1.31. ¹ H NMR (C ₆ D ₆ , 400 MHz): δ 7.34 (dd, J = 1.9, 6.7 Hz, 2H), 7.20 (d, J = 2.2 Hz, 2H), 7.12 (d, J = 2.5 Hz, 2H) ), 7.08 (m, 4H), 7.02 (m, 2H), 6.91 (dd, J = 1.8, 6.4 Hz, 2H), 6.69 (t, J = 7.6 Hz, 1H), 6.45 (d, J = 7.8 Hz) , 2H), 2.20 (s, 6H), 2.15 --2.21 (m, 6H), 2.02 --2.09 (m, 6H), 1.75 --1.85 (m, 12H), 1.64 --1.72 (m, 6H), 0.40 (s) , 6H). ¹³ C NMR (C ₆ D ₆ , 100 MHz): δ 160.18, 155.17, 149.57, 141.60, 140.66, 140.29, 139.81, 130.94, 130.24, 129.66, 128.88, 127.40, 126.54, 126.12, 126.02, 125.72, 125.45, 125.07, 122.93, 122.73, 44.72, 41.44, 38.36, 37.83, 29.99, 21.65, 21.18.

１５０ｍｌのジクロロメタン中の８．４０ｇ（７５．０ｍｍｏｌ）の４－フルオロフェノールおよび１３．５ｇ（７５．０ｍｍｏｌ）の３，５－ジメチルアダマンタン－１－オールの溶液に、１００ｍｌのジクロロメタン中の４．９０ｍｌ（７５．０ｍｍｏｌ）のメタンスルホン酸および５ｍｌの酢酸の溶液を室温で１時間滴加した。生じた混合物を室温で４８時間撹拌し、次いで、３００ｍｌの５％ ＮａＨＣＯ₃に注意深く注いだ。得られた混合物をジクロロメタン（３×５０ｍｌ）で抽出し、合わせた有機抽出物をＮａ₂ＳＯ₄で乾燥し、次いで、蒸発乾固した。クーゲルロール装置（１ｍｂａｒ、７０℃）を使用して残留物を精製して、１４．２ｇ（６８％）の表題生成物を淡黄色油として得た。¹H NMR (CDCl₃, 400 MHz): δ 6.93 (dd, J = 3.1, 11.2 Hz, 1H), 6.73 (ddd, J = 3.1, 7.4, 8.6 Hz, 1H), 6.55 (dd, J = 4.9, 8.6 Hz), 4.62 (s, 1H), 2.16 (dt, J = 3.1, 6.3 Hz, 1H), 1.91 (m, 2H), 1.64 - 1.74 (m, 4H), 1.35 - 1.45 (m, 4H), 1.20 (br.s, 2H), 0.87 (s, 6H). ¹³C NMR (CDCl₃, 100 MHz): δ 158.49 (J_F = 236 Hz), 150.19 (J_F = 2.0 Hz), 137.69 (J_F = 5.9 Hz), 117.12 (J_F = 8.1 Hz), 114.13 (J_F = 24.0 Hz), 112.57 (J_F = 22.9 Hz), 50.92, 46.44, 43.05, 38.70, 38.48, 31.38, 30.84, 29.90. 2- (3,5-dimethyladamantane-1-yl) -4-fluorophenol

4.90 ml in 100 ml dichloromethane in a solution of 8.40 g (75.0 mmol) 4-fluorophenol in 150 ml dichloromethane and 13.5 g (75.0 mmol) 3,5-dimethyladamantane-1-ol. A solution of (75.0 mmol) methanesulfonic acid and 5 ml of acetic acid was added dropwise at room temperature for 1 hour. The resulting mixture was stirred at room temperature for 48 hours and then carefully poured into 300 ml of 5% NaHCO ₃ . The resulting mixture was extracted with dichloromethane (3 x 50 ml) and the combined organic extracts were dried over Na ₂ SO ₄ and then evaporated to dryness. The residue was purified using a Kugelrohr device (1 mbar, 70 ° C.) to give 14.2 g (68%) of the title product as a pale yellow oil. ¹ H NMR (CDCl ₃ , 400 MHz): δ 6.93 (dd, J = 3.1, 11.2 Hz, 1H), 6.73 (ddd, J = 3.1, 7.4, 8.6 Hz, 1H), 6.55 (dd, J = 4.9, 8.6 Hz), 4.62 (s, 1H), 2.16 (dt, J = 3.1, 6.3 Hz, 1H), 1.91 (m, 2H), 1.64 --1.74 (m, 4H), 1.35 --1.45 (m, 4H), 1.20 (br.s, 2H), 0.87 (s, 6H). ¹³ C NMR (CDCl ₃ , 100 MHz): δ 158.49 (J _F = 236 Hz), 150.19 (J _F = 2.0 Hz), 137.69 (J _F ) = 5.9 Hz), 117.12 (J _F = 8.1 Hz), 114.13 (J _F = 24.0 Hz), 112.57 (J _F = 22.9 Hz), 50.92, 46.44, 43.05, 38.70, 38.48, 31.38, 30.84, 29.90.

２００ｍｌのジクロロメタン中の１４．２ｇ（５１．７ｍｍｏｌ）の２－（３，５－ジメチルアダマンタン－１－イル）－４－フルオロフェノールの溶液に、１００ｍｌのジクロロメタン中の２．６７ｍｌ（５１．７ｍｍｏｌ）の臭素の溶液を室温で１時間滴加した。生じた混合物を室温で４８時間撹拌し、次いで、２００ｍｌの５％ ＮａＨＣＯ₃に注意深く注いだ。得られた混合物をジクロロメタン（３×５０ｍｌ）で抽出し、合わせた有機抽出物をＮａ₂ＳＯ₄で乾燥し、次いで、蒸発乾固した。収量１７．５ｇ（９６％）の淡黄色固体。¹H NMR (CDCl₃, 400 MHz): δ 7.06 (dd, J = 3.0, 7.0 Hz, 1H), 6.93 (dd, J = 2.9, 10.8 Hz, 1H), 5.59 (s, 1H), 2.16 (m, 1H), 1.89 (br.s, 2H), 1.63 - 1.73 (m, 4H), 1.34 - 1.44 (m, 4H), 1.19 (br.s, 2H), 0.86 (s, 6H). ¹³C NMR (CDCl₃, 100 MHz): δ 157.21 (J_F = 241 Hz), 146.61 (J_F = 2.8 Hz), 137.97 (J_F = 6.1 Hz), 115.34 (J_F = 25.8 Hz), 113.64 (J_F = 23.6 Hz), 110.83 (J_F = 10.9 Hz), 54.77, 50.48, 45.71, 42.61, 38.96, 38.03, 31.02, 30.42, 29.49. 2-Bromo-6- (3,5-dimethyladamantane-1-yl) -4-fluorophenol

To a solution of 14.2 g (51.7 mmol) of 2- (3,5-dimethyladamantane-1-yl) -4-fluorophenol in 200 ml of dichloromethane, 2.67 ml (51.7 mmol) in 100 ml of dichloromethane. A solution of bromine was added dropwise at room temperature for 1 hour. The resulting mixture was stirred at room temperature for 48 hours and then carefully poured into 200 ml of 5% NaHCO ₃ . The resulting mixture was extracted with dichloromethane (3 x 50 ml) and the combined organic extracts were dried over Na ₂ SO ₄ and then evaporated to dryness. A pale yellow solid with a yield of 17.5 g (96%). ¹ H NMR (CDCl ₃ , 400 MHz): δ 7.06 (dd, J = 3.0, 7.0 Hz, 1H), 6.93 (dd, J = 2.9, 10.8 Hz, 1H), 5.59 (s, 1H), 2.16 (m) , 1H), 1.89 (br.s, 2H), 1.63 --1.73 (m, 4H), 1.34 --1.44 (m, 4H), 1.19 (br.s, 2H), 0.86 (s, 6H). ¹³ C NMR (CDCl ₃ , 100 MHz): δ 157.21 (J _F = 241 Hz), 146.61 (J _F = 2.8 Hz), 137.97 (J _F = 6.1 Hz), 115.34 (J _F = 25.8 Hz), 113.64 (J _F =) 23.6 Hz), 110.83 (J _F = 10.9 Hz), 54.77, 50.48, 45.71, 42.61, 38.96, 38.03, 31.02, 30.42, 29.49.

２００ｍｌの乾燥ＴＨＦ中の１７．５ｇ（４９．５ｍｍｏｌ）の２－ブロモ－６－（３，５－ジメチルアダマンタン－１－イル）－４－フルオロフェノールの溶液に、２．１７ｇ（５４．４ｍｍｏｌ、鉱油中６０質量％）の水素化ナトリウムを室温で分割して加えた。その後、４．５３ｍｌ（６０．０ｍｍｏｌ）のＭＯＭＣｌを１時間滴加した。反応混合物を６０℃で２４時間加熱し、次いで、３００ｍｌの冷水に注いだ。粗生成物を３×２００ｍｌのジクロロメタンで抽出した。合わせた有機抽出物をＮａ₂ＳＯ₄で乾燥し、次いで、蒸発乾固した。収量１９．６ｇ（定量的）の白色固体。¹H NMR (CDCl₃, 400 MHz): δ 7.13 (dd, J = 3.1, 6.8 Hz, 1H), 6.98 (dd, J = 3.1, 10.9 Hz, 1H), 5.19 (s, 2H), 3.68 (s, 3H), 2.16 (m, 1H), 1.89 (br.s, 2H), 1.64 - 1.74 (m, 4H), 1.34 - 1.44 (m, 4H), 1.19 (br.s, 2H), 0.87 (s, 6H). ¹³C NMR (CDCl₃, 100 MHz): δ 159.47 (J_F = 245 Hz), 150.08 (J_F = 3.3 Hz), 146.34 (J_F = 6.4 Hz), 118.13 (J_F = 25.4 Hz), 117.65 (J_F = 10.7 Hz), 114.01 (J_F = 23.4 Hz), 99.95, 57.89, 50.69, 47.13, 42.84, 39.78, 39.55, 31.50, 30.84, 29.94. 1- (3-bromo-5-fluoro-2- (methoxymethoxy) phenyl) -3,5-dimethyladamantane

2.17 g (54.4 mmol, 54.4 mmol, in a solution of 17.5 g (49.5 mmol) of 2-bromo-6- (3,5-dimethyladamantan-1-yl) -4-fluorophenol in 200 ml of dry THF. Sodium hydride (60% by weight in mineral oil) was added in portions at room temperature. Then, 4.53 ml (60.0 mmol) of MOMCl was added dropwise for 1 hour. The reaction mixture was heated at 60 ° C. for 24 hours and then poured into 300 ml of cold water. The crude product was extracted with 3 x 200 ml dichloromethane. The combined organic extracts were dried over Na ₂ SO ₄ and then evaporated to dryness. A white solid with a yield of 19.6 g (quantitative). ¹ H NMR (CDCl ₃ , 400 MHz): δ 7.13 (dd, J = 3.1, 6.8 Hz, 1H), 6.98 (dd, J = 3.1, 10.9 Hz, 1H), 5.19 (s, 2H), 3.68 (s) , 3H), 2.16 (m, 1H), 1.89 (br.s, 2H), 1.64 --1.74 (m, 4H), 1.34 --1.44 (m, 4H), 1.19 (br.s, 2H), 0.87 (s) , 6H). ¹³ C NMR (CDCl ₃ , 100 MHz): δ 159.47 (J _F = 245 Hz), 150.08 (J _F = 3.3 Hz), 146.34 (J _F = 6.4 Hz), 118.13 (J _F = 25.4 Hz) ), 117.65 (J _F = 10.7 Hz), 114.01 (J _F = 23.4 Hz), 99.95, 57.89, 50.69, 47.13, 42.84, 39.78, 39.55, 31.50, 30.84, 29.94.

２００ｍｌの乾燥ＴＨＦ中の３．３８ｇ（２５．２ｍｍｏｌ）のベンゾ［ｂ］チオフェンの溶液に、ヘキサン中の９．５０ｍｌ（２３．９ｍｍｏｌ、２．５Ｍ）のⁿＢｕＬｉを－１０℃で滴加した。反応混合物を０℃で２時間撹拌し、続いて、３．３０ｇ（２３．９ｍｍｏｌ）のＺｎＣｌ₂を加えた。次に、得られた溶液を室温まで加温し、５．００ｇ（１２．６ｍｍｏｌ）の１－（３－ブロモ－５－フルオロ－２－（メトキシメトキシ）フェニル）－３，５－ジメチルアダマンタンおよび６４３ｍｇ（１．２６ｍｍｏｌ）のＰｄ［Ｐ^tＢｕ₃］₂を続いて加えた。生じた混合物を６０℃で一晩撹拌し、次いで、２５０ｍｌの水に注いだ。粗生成物を３×１５０ｍｌのジクロロメタンで抽出した。合わせた有機抽出物をＮａ₂ＳＯ₄で乾燥し、次いで、蒸発乾固した。残留物をシリカゲル６０によるフラッシュクロマトグラフィー（４０～６３ｕｍ；溶離液：ヘキサン－酢酸エチル＝１０：１、体積）により精製した。収量４．５２ｇ（８０％）の淡黄色油。¹H NMR (CDCl₃, 400 MHz): δ 7.85 (dd, J = 1.1, 7.3 Hz, 1H), 7.79 (dd, J = 1.5, 7.0 Hz, 1H), 7.51 (s, 1H), 7.35 (qd, J = 5.7, 7.2, 7.2, 7.2, 2H), 7.06 (s, 1H), 7.04 (m, 1H), 4.72 (s, 2H), 3.45 (s, 3H), 2.20 (m, 1H), 1.98 (br.s, 2H), 1.71 - 1.83 (m, 4H), 1.37 - 1.47 (m, 4H), 1.22 (br.s, 2H), 0.90 (s, 6H). ¹³C NMR (CDCl₃, 100 MHz): δ 159.72 (J_F = 241 Hz), 150.30, 150.28, 145.71, 140.51 (J_F = 2.0 Hz), 140.29, 139.92, 129.86, 129.78, 124.51 (J_F = 3.5 Hz), 123.64 (J_F = 3.5 Hz), 122.15, 115.46 (J_F = 23.7 Hz), 114.68 (J_F = 23.6 Hz), 99.29, 57.73, 50.84, 47.25, 42.97, 39.59, 39.47, 31.54, 30.92, 30.03. 2- (3- (3,5-dimethyladamantane-1-yl) -5-fluoro-2- (methoxymethoxy) phenyl) benzo [b] thiophene

To a solution of 3.38 g (25.2 mmol) of benzo [b] thiophene in 200 ml of dry THF was added 9.50 ml (23.9 mmol, 2.5 M) of ^nBuLi in hexanes at −10 ° C. .. The reaction mixture was stirred at 0 ° C. for 2 hours, followed by the addition of 3.30 g (23.9 mmol) of ZnCl ₂ . The resulting solution was then heated to room temperature and 5.00 g (12.6 mmol) of 1- (3-bromo-5-fluoro-2- (methoxymethoxy) phenyl) -3,5-dimethyladamantane and 643 mg (1.26 mmol) of Pd [P ^t Bu ₃ ] ₂ was subsequently added. The resulting mixture was stirred at 60 ° C. overnight and then poured into 250 ml of water. The crude product was extracted with 3 x 150 ml dichloromethane. The combined organic extracts were dried over Na ₂ SO ₄ and then evaporated to dryness. The residue was purified by flash chromatography on silica gel 60 (40-63 um; eluent: hexane-ethyl acetate = 10: 1, volume). A pale yellow oil with a yield of 4.52 g (80%). ¹ H NMR (CDCl ₃ , 400 MHz): δ 7.85 (dd, J = 1.1, 7.3 Hz, 1H), 7.79 (dd, J = 1.5, 7.0 Hz, 1H), 7.51 (s, 1H), 7.35 (qd) , J = 5.7, 7.2, 7.2, 7.2, 2H), 7.06 (s, 1H), 7.04 (m, 1H), 4.72 (s, 2H), 3.45 (s, 3H), 2.20 (m, 1H), 1.98 (br.s, 2H), 1.71 --1.83 (m, 4H), 1.37 --1.47 (m, 4H), 1.22 (br.s, 2H), 0.90 (s, 6H). ¹³ C NMR (CDCl ₃ , 100 MHz): δ 159.72 (J _F = 241 Hz), 150.30, 150.28, 145.71, 140.51 (J _F = 2.0 Hz), 140.29, 139.92, 129.86, 129.78, 124.51 (J _F = 3.5 Hz), 123.64 (J _F =) 3.5 Hz), 122.15, 115.46 (J _F = 23.7 Hz), 114.68 (J _F = 23.6 Hz), 99.29, 57.73, 50.84, 47.25, 42.97, 39.59, 39.47, 31.54, 30.92, 30.03.

１５０ｍｌのクロロホルム中の４．５０ｇ（１０．０ｍｍｏｌ）の２－（３－（３，５－ジメチルアダマンタン－１－イル）－５－フルオロ－２－（メトキシメトキシ）フェニル）ベンゾ［ｂ］チオフェンの溶液に、１．８２ｇ（１０．２ｍｍｏｌ）のＮ－ブロモスクシンイミドを室温で加えた。反応混合物をこの温度で１２時間撹拌し、次いで、１００ｍｌの水に注いだ。粗生成物を３×５０ｍｌのジクロロメタンで抽出した。合わせた有機抽出物をＮａ₂ＳＯ₄で乾燥し、次いで、蒸発乾固した。残留物を１１０ｍｌのｎ－ヘキサンから再結晶させた。収量４．８８ｇ（９２％）のベージュ色固体。¹H NMR (CDCl₃, 400 MHz): δ 7.87 (d, J = 7.4 Hz, 1H), 7.83 (d, J = 8.0 Hz, 1H), 7.49 (dt, J = 1.1, 7.1 Hz, 1H), 7.43 (dt, J = 1.3, 7.3 Hz, 1H), 7.11 (dd, J = 3.2, 10.9 Hz, 1H), 6.99 (dd, J = 3.2, 7.6 Hz, 1H), 4.59 (s, 2H), 3.31 (s, 3H), 2.19 (m, 1H), 1.98 (br.s, 2H), 1.70 - 1.83 (m, 4H), 1.36 - 1.46 (m, 4H), 1.21 (br.s, 2H), 0.89 (s, 6H). ¹³C NMR (CDCl₃, 100 MHz): δ 159.24 (J_F = 242 Hz), 151.76 (J_F = 2.9 Hz), 145.29 (J_F = 6.4 Hz), 138.60, 138.01, 135.93, 127.35 (J_F = 9.0 Hz), 125.76, 125.22, 123.64, 122.29, 116.40 (J_F = 23.4 Hz), 115.67 (J_F = 23.6 Hz), 108.29, 99.65, 57.51, 50.86, 47.09, 42.98, 39.41, 39.36, 31.51, 30.92, 29.99. 3-Bromo-2- (3- (3,5-dimethyladamantane-1-yl) -5-fluoro-2- (methoxymethoxy) phenyl) benzo [b] thiophene

4.50 g (10.0 mmol) of 2- (3- (3,5-dimethyladamantan-1-yl) -5-fluoro-2- (methoxymethoxy) phenyl) benzo [b] thiophene in 150 ml of chloroform 1.82 g (10.2 mmol) of N-bromosuccinimide was added to the solution at room temperature. The reaction mixture was stirred at this temperature for 12 hours and then poured into 100 ml of water. The crude product was extracted with 3 x 50 ml dichloromethane. The combined organic extracts were dried over Na ₂ SO ₄ and then evaporated to dryness. The residue was recrystallized from 110 ml of n-hexane. A beige solid with a yield of 4.88 g (92%). ¹ H NMR (CDCl ₃ , 400 MHz): δ 7.87 (d, J = 7.4 Hz, 1H), 7.83 (d, J = 8.0 Hz, 1H), 7.49 (dt, J = 1.1, 7.1 Hz, 1H), 7.43 (dt, J = 1.3, 7.3 Hz, 1H), 7.11 (dd, J = 3.2, 10.9 Hz, 1H), 6.99 (dd, J = 3.2, 7.6 Hz, 1H), 4.59 (s, 2H), 3.31 (s, 3H), 2.19 (m, 1H), 1.98 (br.s, 2H), 1.70 --1.83 (m, 4H), 1.36 --1.46 (m, 4H), 1.21 (br.s, 2H), 0.89 (s, 6H). ¹³ C NMR (CDCl ₃ , 100 MHz): δ 159.24 (J _F = 242 Hz), 151.76 (J _F = 2.9 Hz), 145.29 (J _F = 6.4 Hz), 138.60, 138.01, 135.93 , 127.35 (J _F = 9.0 Hz), 125.76, 125.22, 123.64, 122.29, 116.40 (J _F = 23.4 Hz), 115.67 (J _F = 23.6 Hz), 108.29, 99.65, 57.51, 50.86, 47.09, 42.98, 39.41, 39.36, 31.51, 30.92, 29.99.

５０ｍｌの乾燥ＴＨＦ中の４．００ｇ（７．５５ｍｍｏｌ）の３－ブロモ－２－（３－（３，５－ジメチルアダマンタン－１－イル）－５－フルオロ－２－（メトキシメトキシ）フェニル）ベンゾ［ｂ］チオフェンの溶液に、ヘキサン中の３．０８ｍｌ（７．７０ｍｍｏｌ、２．５Ｍ）のⁿＢｕＬｉを－８０℃で滴加した。反応混合物をこの温度で３０分間撹拌し、次いで、１．０２ｇ（７．７０ｍｍｏｌ）のＺｎＣｌ₂を加えた。得られた混合物を室温まで加温し、次いで、０．８６ｇ（３．６３ｍｍｏｌ）の２，６－ジブロモピリジンおよび１９４ｍｇ（０．３８ｍｍｏｌ）のＰｄ［Ｐ^tＢｕ₃］₂を続いて加えた。得られた混合物を６０℃で一晩撹拌し、１００ｍｌの水に注ぎ、粗生成物をジクロロメタン（３×５０ｍｌ）で抽出した。合わせた有機抽出物をＮａ₂ＳＯ₄で乾燥し、次いで、蒸発乾固した。得られた油に、５０ｍｌのＴＨＦ、５０ｍｌのメタノールおよび２ｍｌの１２Ｎ ＨＣｌを続いて加えた。反応混合物を６０℃で一晩撹拌し、次いで、２００ｍｌの水に注いだ。得られた混合物をジクロロメタン（３×５０ｍｌ）で抽出し、合わせた有機抽出物をＮａ₂ＳＯ₄で乾燥し、次いで、蒸発乾固した。残留物をシリカゲル６０によるフラッシュクロマトグラフィー（４０～６３ｕｍ；溶離液：ヘキサン－酢酸エチル－トリエチルアミン＝１００：１０：１、体積）により精製した。収量１．８０ｇ（５６％、回転異性体の混合物として）の淡黄色泡。¹H NMR (CDCl₃, 400 MHz): δ 7.85 - 7.91 (m, 4H), 7.71 (t, J = 7.8 Hz, 1H), 7.43 (m, 4H), 7.27 (m, 2H), 6.82 - 6.87 (m, 4H), 0.91 - 2.15 (m, 26H), 0.69 - 0.87 (m, 12H). ¹³C NMR (CDCl₃, 100 MHz): δ 157.34, 154.97, 153.27, 148.98, 140.47 (J_F = 5.9 Hz), 140.03, 138.96, 138.56, 138.09, 132.36, 125.19, 124.00, 122.91, 122.19, 119.08, 115.02 (J_F = 11.0 Hz), 114.79 (J_F = 10.7 Hz), 50.73, 46.35, 46.14, 43.07, 42.71, 38.59, 37.57, 31.39, 31.15, 30.87, 30.74, 30.03, 29.93. 6,6'-(Pyridine-2,6-diylbis (benzo [b] thiophene-3,2-diyl)) Bis (2- (3,5-dimethyladamantane-1-yl) -4-fluorophenol)

4.00 g (7.55 mmol) 3-bromo-2- (3- (3,5-dimethyladamantan-1-yl) -5-fluoro-2- (methoxymethoxy) phenyl) benzo in 50 ml dry THF [B] 3.08 ml (7.70 mmol, 2.5 M) of ^nBuLi in hexane was added dropwise to the solution of thiophene at −80 ° C. The reaction mixture was stirred at this temperature for 30 minutes, then 1.02 g (7.70 mmol) of ZnCl ₂ was added. The resulting mixture was warmed to room temperature, followed by the addition of 0.86 g (3.63 mmol) of 2,6-dibromopyridine and 194 mg (0.38 mmol) of Pd [P ^t Bu ₃ ] ₂ . The resulting mixture was stirred at 60 ° C. overnight, poured into 100 ml of water and the crude product was extracted with dichloromethane (3 x 50 ml). The combined organic extracts were dried over Na ₂ SO ₄ and then evaporated to dryness. To the resulting oil was subsequently added 50 ml THF, 50 ml methanol and 2 ml 12N HCl. The reaction mixture was stirred at 60 ° C. overnight and then poured into 200 ml of water. The resulting mixture was extracted with dichloromethane (3 x 50 ml) and the combined organic extracts were dried over Na ₂ SO ₄ and then evaporated to dryness. The residue was purified by flash chromatography on silica gel 60 (40-63 um; eluent: hexane-ethyl acetate-triethylamine = 100: 10: 1, volume). A pale yellow foam with a yield of 1.80 g (56%, as a mixture of rotamers). ¹ H NMR (CDCl ₃ , 400 MHz): δ 7.85 --7.91 (m, 4H), 7.71 (t, J = 7.8 Hz, 1H), 7.43 (m, 4H), 7.27 (m, 2H), 6.82 --6.87 (m, 4H), 0.91 --2.15 (m, 26H), 0.69 --0.87 (m, 12H). ¹³ C NMR (CDCl ₃ , 100 MHz): δ 157.34, 154.97, 153.27, 148.98, 140.47 (J _F = 5.9) Hz), 140.03, 138.96, 138.56, 138.09, 132.36, 125.19, 124.00, 122.91, 122.19, 119.08, 115.02 (J _F = 11.0 Hz), 114.79 (J _F = 10.7 Hz), 50.73, 46.35, 46.14, 43.07, 42.71 , 38.59, 37.57, 31.39, 31.15, 30.87, 30.74, 30.03, 29.93.

Dimethylhafnium [6,6'-(pyridin-2,6-diylbis (benzo [b] thiophene-3,2-diyl)) bis (2- (3,5-dimethyladamantan-1-yl) -4-fluoro Phenolate] (complex 25).
3.01 ml (8.73 mmol, 2.9 M) of MeMgBr in diethyl ether to a suspension of 623 mg (1.94 mmol) of hafnium tetrachloride (<0.05% Zr) in 70 ml of dry toluene at room temperature. It was added once. The resulting suspension was stirred for 1 minute and 1.73 g (1.94 mmol) of 6,6'-(pyridin-2,6-diylbis (benzo [b] thiophene-3,2) in 20 ml of dry toluene was stirred. -Diyl)) A solution of bis (2- (3,5-dimethyladamantane-1-yl) -4-fluorophenol) was added dropwise over 1 minute. The reaction mixture was stirred at room temperature overnight and then evaporated to near dryness. The resulting solid was extracted with 2 x 50 ml hot toluene and the combined organic extracts were filtered through a thin pad of Celite 503. Next, the filtrate was evaporated to dryness. The resulting solid was washed with 15 ml n-hexane and then dried in vacuo. A beige solid as a hexane solvate with a yield of 1.40 g (66%). Analysis of C ₅₉ H ₅₉ F ₂ HfNO ₂ S ₂ × 0.5 (C ₆ H ₁₄ ) Calculated values: C, 65.45; H, 5.85; N, 1.23. Measured values: C 65.68; H 6.07; N 1.14. ¹ H NMR (C ₆ D ₆ , 400 MHz): δ 7.31 (m, 2H), 7.23 (dd, J = 3.3, 11.1 Hz, 2H), 7.09 (dd, J = 3.2, 7.7 Hz, 2H), 7.04 (m, 4H), 6.83 (m, 2H), 6.74 (t, J = 7.8 Hz, 1H), 6.35 (d, J = 7.8 Hz, 2H), 2.33 (d, J = 12.1 Hz, 2H), 2.05 (d, J = 11.7 Hz, 2H), 1.66 (br.s, 2H), 1.03 --1.50 (m, 20H), 0.83 (s, 6H), 0.76 (s, 6H), -0.10 (s, 6H) . ¹³ C NMR (CD ₂ Cl ₂ , 100 MHz): δ 158.62, 156.35 (J _F = 234 Hz), 154.17, 147.34 (J _F = 1.8 Hz), 141.61, 141.52 (J _F = 6.1 Hz), 141.02, 139.98, 127.11, 126.43, 126.18, 126.01, 124.23 (J _F = 8.8 Hz), 122.81, 115.91 (J _F = 16.8 Hz), 115.68 (J _F = 16.8 Hz), 52.36, 51.64, 48.47, 45.29, 43.61, 42.34 , 39.67, 37.98, 31.91, 31.44, 31.38, 30.79, 29.98, 27.47.

２，６－ジブロモピリジン（３．７３ｇ、１５．７ｍｍｏｌ）、２－ブロモフェニルボロン酸（６．２６ｇ、３１．４ｍｍｏｌ）、炭酸ナトリウム（８．３３ｇ、７８．６ｍｍｏｌ）、ジオキサン（６６ｍＬ）および水（３３ｍＬ）を丸底フラスコ内で合わせた。混合物を窒素で１時間スパージし、次いで、Ｐｄ（ＰＰｈ₃）₄（１．８２ｇ、１．５７ｍｍｏｌ）を速やかに加えた。混合物を３０分間スパージし、次いで、１００℃まで一晩加熱した。翌日、混合物を水（２００ｍＬ）に注ぎ、ジクロロメタン（４×６０ｍＬ）で抽出した。合わせた有機物をブライン、次いで、Ｎａ₂ＳＯ₄で乾燥した。蒸発により、粗生成物を黄橙色油状固体として得た。これを熱トルエンからの結晶化により精製する。収量３．４２ｇ、５５．９％。 2,6-bis (2-bromophenyl) pyridine

2,6-Dibromopyridine (3.73 g, 15.7 mmol), 2-bromophenylboronic acid (6.26 g, 31.4 mmol), sodium carbonate (8.33 g, 78.6 mmol), dioxane (66 mL) and water. (33 mL) was combined in a round bottom flask. The mixture was spurged with nitrogen for 1 hour, then Pd (PPh ₃ ) ₄ (1.82 g, 1.57 mmol) was added rapidly. The mixture was spurged for 30 minutes and then heated to 100 ° C. overnight. The next day, the mixture was poured into water (200 mL) and extracted with dichloromethane (4 x 60 mL). The combined organics were brined and then dried over Na ₂ SO ₄ . Evaporation gave the crude product as a yellow-orange oily solid. This is purified by crystallization from hot toluene. Yield 3.42 g, 55.9%.

テトラヒドロフラン（２０ｍＬ）を１－ブロモ－３－（２，３－ジメチルブタン－２－イル）－２－（メトキシメトキシ）－５－メチルベンゼン（２．８９ｇ、９．１７ｍｍｏｌ）に加えて、薄褐色溶液を生成した。－５０℃でＢｕＬｉのヘキサン溶液（６．３０ｍＬ、１０．１ｍｍｏｌ）を５分にわたって滴加して、褐色懸濁液を生成した。混合物を４５分間撹拌し、次いで、２－イソプロポキシ－４，４，５，５－テトラメチル－１，３，２－ジオキサボロラン（２．２２ｇ、１１．９ｍｍｏｌ）を加えて、透明な褐色溶液を生成した。混合物を周囲温度までゆっくり昇温させた。一晩撹拌後、混合物を水（１００ｍＬ）に注ぎ、振盪した。混合物をジクロロメタン（５×５０ｍＬ）で抽出した。合わせた有機物を水、ブラインで洗浄し、次いで、ＭｇＳＯ₄で乾燥した。揮発物の除去により、生成物を褐色油として得た。収量：２．４５ｇ、７３．７％。 2- (3- (2,3-dimethylbutane-2-yl) -2- (methoxymethoxy) -5-methylphenyl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane

Tetrahydrofuran (20 mL) is added to 1-bromo-3- (2,3-dimethylbutane-2-yl) -2- (methoxymethoxy) -5-methylbenzene (2.89 g, 9.17 mmol) to give a light brown color. A solution was produced. A hexane solution of BuLi (6.30 mL, 10.1 mmol) was added dropwise at −50 ° C. over 5 minutes to form a brown suspension. The mixture is stirred for 45 minutes, then 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (2.22 g, 11.9 mmol) is added to make a clear brown solution. Generated. The mixture was slowly warmed to ambient temperature. After stirring overnight, the mixture was poured into water (100 mL) and shaken. The mixture was extracted with dichloromethane (5 x 50 mL). The combined organics were washed with water and brine and then dried with ו ₄ . Removal of the volatiles gave the product as a brown oil. Yield: 2.45 g, 73.7%.

１００ｍＬ丸底フラスコに１－ブロモ－３－（２，３－ジメチルブタン－２－イル）－２－（メトキシメトキシ）－５－メチルベンゼン（２．４５ｇ、６．７６ｍｍｏｌ）、２，６－ビス（２－ブロモフェニル）ピリジン（１．３２ｇ、３．３８ｍｍｏｌ）、Ｎａ₂ＣＯ₃（１．７９ｇ、１６．９ｍｍｏｌ）、ジオキサン（２０ｍＬ）および水（１０ｍＬ）を入れた。混合物を窒素で３０分間スパージし、次いで、固体Ｐｄ（ＰＰｈ₃）₄（０．３９１ｇ、０．３４０ｍｍｏｌ）を加えた。混合物をさらに１５分間スパージし、次いで、撹拌し、１００℃に維持された油浴中で加熱した。１７時間後、褐色混合物を分液漏斗内で水（１００ｍＬ）と合わせた。混合物をＣＨ₂Ｃｌ₂（６×２５ｍＬ）で抽出した。合わせた有機物をブライン、次いで、ＭｇＳＯ₄で乾燥した。揮発物の除去により、３．１ｇの褐色油を得、これをテトラヒドロフラン（２０ｍＬ）、メタノール（２０ｍＬ）および濃ＨＣｌ（１．０ｍＬ）と合わせた。混合物を撹拌し、６０℃まで４時間加熱した。次いで、揮発物を蒸発させ、残留物をＣＨ₂Ｃｌ₂（１００ｍＬ）で抽出し、水（３×５０ｍＬ）で洗浄し、ブライン（２０ｍＬ）で乾燥した。混合物をＭｇＳＯ₄で乾燥し、濾過し、次いで蒸発させて、粗生成物を得、これを、シリカゲルによるカラムクロマトグラフィーにより精製し、ヘキサン中の２～８％酢酸エチルで溶出した。収量：０．８７ｇ、４２％。 2', 2'''-(pyridin-2,6-diyl) bis (3- (2,3-dimethylbutane-2-yl) -5-methyl- [1,1'-biphenyl] -2-ol )

1-bromo-3- (2,3-dimethylbutane-2-yl) -2- (methoxymethoxy) -5-methylbenzene (2.45 g, 6.76 mmol), 2,6-bis in a 100 mL round bottom flask (2-Bromophenyl) Pyridine (1.32 g, 3.38 mmol), Na ₂ CO ₃ (1.79 g, 16.9 mmol), dioxane (20 mL) and water (10 mL) were added. The mixture was spurged with nitrogen for 30 minutes, then solid Pd (PPh ₃ ) ₄ (0.391 g, 0.340 mmol) was added. The mixture was spagged for an additional 15 minutes, then stirred and heated in an oil bath maintained at 100 ° C. After 17 hours, the brown mixture was combined with water (100 mL) in a separatory funnel. The mixture was extracted with CH ₂ Cl ₂ (6 x 25 mL). The combined organics were brined and then dried with ו ₄ . Removal of the volatiles gave 3.1 g of brown oil, which was combined with tetrahydrofuran (20 mL), methanol (20 mL) and concentrated HCl (1.0 mL). The mixture was stirred and heated to 60 ° C. for 4 hours. The volatiles were then evaporated and the residue was extracted with CH ₂ Cl ₂ (100 mL), washed with water (3 x 50 mL) and dried with brine (20 mL). The mixture was dried on regsvr ₄ , filtered and then evaporated to give the crude product, which was purified by column chromatography on silica gel and eluted with 2-8% ethyl acetate in hexanes. Yield: 0.87 g, 42%.

Dibenzylzirconium [2', 2'''-(pyridin-2,6-diyl) bis (3- (2,3-dimethylbutane-2-yl) -5-methyl- [1,1'-biphenyl] -2-Olate)] (complex 29).
Toluene (5 mL) 2', 2'''-(pyridin-2,6-diyl) bis (3- (2,3-dimethylbutane-2-yl) -5-methyl- [1,1'-biphenyl ] -2-ol) (0.260 g, 0.425 mmol) and tetrabenzylzirconinum (0.194 g, 0.425 mmol) to produce a slightly cloudy orange solution. After stirring overnight, the mixture was evaporated and the residue was extracted with methylcyclohexane (5 mL). The cloudy orange solution was filtered, evaporated to residue and pentane (4 mL) was added. The mixture was triturated to produce a separated yellow-orange solid. The mixture was cooled to −15 ° C. for 1 hour and then the solid was recovered on a frit disk. The solid was washed with cold pentane (2 x 5 mL) and dried under reduced pressure. The product co-crystallized with 1 equivalent of hexane. Yield: 0.233g, 56.5%.

Dibenzylhafnium [2', 2'''-(pyridin-2,6-diyl) bis (3- (2,3-dimethylbutane-2-yl) -5-methyl- [1,1'-biphenyl] -2-Olate)] (complex 30).
Toluene (5 mL) 2', 2'''-(pyridin-2,6-diyl) bis (3- (2,3-dimethylbutane-2-yl) -5-methyl- [1,1'-biphenyl ] -2-ol) (0.208 g, 0.340 mmol) and tetrabenzylhafnium (0.185 g, 0.340 mmol) were added to produce a clear yellow-orange solution. The mixture was stirred overnight. The mixture was filtered and evaporated to residue. Pentane (3 mL) was added and the mixture was triturated until a separated solid was formed. The mixture was cooled to −15 ° C. for 1 hour. The yellow solid was then recovered on a frit disk, washed with cold pentane (2 x 5 mL) and dried under reduced pressure. The product is co-crystallized with 1 equivalent of hexane. Yield: 0.160g, 44.5%.

２００ｍＬのジクロロメタン中の２１．２ｇ（８７．０ｍｍｏｌ）の２－（アダマンタン－１－イル）－４－メチルフェノールの溶液に、１００ｍＬのジクロロメタン中の４．５０ｍＬ（８７．０ｍｍｏｌ）の臭素の溶液を室温で１０分間滴加した。生じた混合物を４００ｍＬの水で希釈した。粗生成物をジクロロメタン（３×７０ｍＬ）で抽出し、合わせた有機抽出物を５％ ＮａＨＣＯ₃で洗浄し、Ｎａ₂ＳＯ₄で乾燥し、次いで、蒸発乾固した。収量２１．５ｇ（７７％）の白色固体。¹H NMR (CDCl₃, 400 MHz): δ 7.17 (s, 1H), 6.98 (s, 1H), 5.65 (s, 1H), 2.27 (s, 3H), 2.10 - 2.13 (m, 9H), 1.80 (m, 6H), ¹³C NMR (CDCl₃, 100 MHz): δ 148.18, 137.38, 130.24, 129.32, 127.26, 112.08, 40.18, 37.32, 36.98, 28.99, 20.55. 2- (adamantane-1-yl) -6-bromo-4-methylphenol

To a solution of 21.2 g (87.0 mmol) of 2- (adamantane-1-yl) -4-methylphenol in 200 mL of dichloromethane, a solution of 4.50 mL (87.0 mmol) of bromine in 100 mL of dichloromethane. The solution was added dropwise at room temperature for 10 minutes. The resulting mixture was diluted with 400 mL of water. The crude product was extracted with dichloromethane (3 x 70 mL) and the combined organic extracts were washed with 5% NaHCO ₃ and dried over Na ₂ SO ₄ and then evaporated to dryness. A white solid with a yield of 21.5 g (77%). ¹ H NMR (CDCl ₃ , 400 MHz): δ 7.17 (s, 1H), 6.98 (s, 1H), 5.65 (s, 1H), 2.27 (s, 3H), 2.10 --2.13 (m, 9H), 1.80 (m, 6H), ¹³ C NMR (CDCl ₃ , 100 MHz): δ 148.18, 137.38, 130.24, 129.32, 127.26, 112.08, 40.18, 37.32, 36.98, 28.99, 20.55.

４００ｍＬのＴＨＦ中の２１．３ｇ（６６．４ｍｍｏｌ）の２－（アダマンタン－１－イル）－６－ブロモ－４－メチルフェノールの溶液に、２．７９ｇ（６９．７ｍｍｏｌ、鉱油中６０質量％）の水素化ナトリウムを室温で分割して加えた。得られた懸濁液に、５．５５ｍＬ（７３．０ｍｍｏｌ）のメトキシメチルクロリドを室温で１０分間滴加した。得られた混合物を一晩撹拌し、次いで、２００ｍＬの水に注いだ。こうして得られた混合物をジクロロメタン（３×２００ｍＬ）で抽出し、合わせた有機抽出物を５％ ＮａＨＣＯ₃で洗浄し、Ｎａ₂ＳＯ₄で乾燥し、次いで、蒸発乾固した。収量２４．３ｇ（定量的）の白色固体。¹H NMR (CDCl₃, 400 MHz): δ 7.24 (d, J = 1.5 Hz, 1H), 7.05 (d, J = 1.8 Hz, 1H), 5.22 (s, 2H), 3.71 (s, 3H), 2.27 (s, 3H), 2.05 - 2.12 (m, 9H), 1.78 (m, 6H). ¹³C NMR (CDCl₃, 100 MHz): δ 151.01, 144.92, 134.34, 131.80, 127.44, 117.57, 99.56, 57.75, 41.27, 37.71, 36.82, 29.03, 20.68. (1- (3-bromo-5-methyl-2- (methoxymethoxy) phenyl) adamantin

2.79 g (69.7 mmol, 60% by weight in mineral oil) in a solution of 21.3 g (66.4 mmol) of 2- (adamantane-1-yl) -6-bromo-4-methylphenol in 400 mL of THF. Sodium hydride was added in portions at room temperature. 5.55 mL (73.0 mmol) of methoxymethyl chloride was added dropwise to the resulting suspension at room temperature for 10 minutes. The resulting mixture was stirred overnight and then poured into 200 mL of water. The mixture thus obtained was extracted with dichloromethane (3 x 200 mL), the combined organic extracts were washed with 5% NaHCO ₃ and dried over Na ₂ SO ₄ , then evaporated to dryness. A white solid with a yield of 24.3 g (quantitative). ¹ H NMR (CDCl ₃ , 400 MHz): δ 7.24 (d, J = 1.5 Hz, 1H), 7.05 (d, J = 1.8 Hz, 1H), 5.22 (s, 2H), 3.71 (s, 3H), 2.27 (s, 3H), 2.05 --2.12 (m, 9H), 1.78 (m, 6H). ¹³ C NMR (CDCl ₃ , 100 MHz): δ 151.01, 144.92, 134.34, 131.80, 127.44, 117.57, 99.56, 57.75 , 41.27, 37.71, 36.82, 29.03, 20.68.

４００ｍＬの乾燥ＴＨＦ中の２０．０ｇ（５５．０ｍｍｏｌ）の（１－（３－ブロモ－５－メチル－２－（メトキシメトキシ）フェニル）アダマンチンの溶液に、ヘキサン中の２２．５ｍＬ（５６．４ｍｍｏｌ）の２．５Ｍ ⁿＢｕＬｉを－８０℃で２０分間滴加した。反応混合物をこの温度で１時間撹拌し、続いて、１６．７ｍＬ（８２．２ｍｍｏｌ）の２－イソプロポキシ－４，４，５，５－テトラメチル－１，３，２－ジオキサボロランを加えた。得られた懸濁液を室温で１時間撹拌し、次いで、３００ｍＬの水に注いだ。粗生成物をジクロロメタン（３×３００ｍＬ）で抽出し、合わせた有機抽出物をＮａ₂ＳＯ₄で乾燥し、次いで、蒸発乾固した。収量２２．４ｇ（９９％）の無色粘性油。¹H NMR (CDCl₃, 400 MHz): δ 7.35 (d, J = 2.3 Hz, 1H), 7.18 (d, J = 2.3 Hz, 1H), 5.14 (s, 2H), 3.58 (s, 3H), 2.28 (s, 3H), 2.14 (m, 6H), 2.06 (m, 3H), 1.76 (m, 6H), 1.35 (s, 12H). ¹³C NMR (CDCl₃, 100 MHz): δ 159.68, 141.34, 134.58, 131.69, 131.14, 100.96, 83.61, 57.75, 41.25, 37.04, 29.14, 24.79, 20.83. 2- (3-adamantan-1-yl) -5-methyl-2- (methoxymethoxy) phenyl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane

A solution of 20.0 g (55.0 mmol) of (1- (3-bromo-5-methyl-2- (methoxymethoxy) phenyl) adamantin in 400 mL of dry THF to 22.5 mL (56.4 mmol) in hexanes. ) 2.5 M ⁿ BuLi was added dropwise at −80 ° C. for 20 minutes. The reaction mixture was stirred at this temperature for 1 hour, followed by 16.7 mL (82.2 mmol) of 2-isopropoxy-4,4. 5,5-Tetramethyl-1,3,2-dioxaborolane was added. The resulting suspension was stirred at room temperature for 1 hour and then poured into 300 mL of water. The crude product was dichloromethane (3 x 300 mL). ), The combined organic extracts were dried in Na ₂ SO ₄ , and then evaporated to dryness. A colorless viscous oil with a yield of 22.4 g (99%). ¹ H NMR (CDCl ₃ , 400 MHz) :. δ 7.35 (d, J = 2.3 Hz, 1H), 7.18 (d, J = 2.3 Hz, 1H), 5.14 (s, 2H), 3.58 (s, 3H), 2.28 (s, 3H), 2.14 (m, 6H), 2.06 (m, 3H), 1.76 (m, 6H), 1.35 (s, 12H). ¹³ C NMR (CDCl ₃ , 100 MHz): δ 159.68, 141.34, 134.58, 131.69, 131.14, 100.96, 83.61, 57.75, 41.25, 37.04, 29.14, 24.79, 20.83.

１００ｍＬの１，４－ジオキサン中の１０．０ｇ（２４．３ｍｍｏｌ）の２－（３－アダマンタン－１－イル）－５－メチル－２－（メトキシメトキシ）フェニル）－４，４，５，５－テトラメチル－１，３，２－ジオキサボロランの溶液に、７．２２ｇ（２５．５ｍｍｏｌ）の２－ブロモヨードベンゼン、８．３８ｇ（６０．６ｍｍｏｌ）の炭酸カリウムおよび５０ｍＬの水を続いて加えた。得られた混合物をアルゴンで１０分間パージし、続いて、１．４０ｇ（１．２１ｍｍｏｌ）のＰｄ（ＰＰｈ₃）₄を加えた。この混合物を１００℃で１２時間撹拌し、次いで、室温まで冷却し、１００ｍＬの水で希釈した。粗生成物をジクロロメタン（３×１５０ｍＬ）で抽出し、合わせた有機抽出物をＮａ₂ＳＯ₄で乾燥し、次いで、蒸発乾固した。残留物をシリカゲル６０によるフラッシュクロマトグラフィー（４０～６３ｕｍ、溶離液：ヘキサン－ジクロロメタン＝１０：１、体積）により精製した。収量１０．７ｇ（定量的）の白色固体。¹H NMR (CDCl₃, 400 MHz): δ 7.72 (d, J = 7.9 Hz, 1H), 7.35 - 7.44 (m, 3H), 7.19 - 7.26 (m, 1H), 6.94 (m, 1H), 4.53 (dd, J = 20.0, 4.6 Hz, 2H), 3.24 (s, 3H), 2.38 (s, 3H), 2.23 (m, 6H), 2.15 (m, 3H), 1.84 (m, 6H). ¹³C NMR (CDCl₃, 100 MHz): δ 151.51, 142.78, 141.11, 134.63, 132.76, 132.16, 132.13, 129.83, 128.57, 127.76, 127.03, 124.05, 98.85, 56.95, 41.21, 37.18, 36.94, 29.07, 21.00. 1- (2'-bromo-5-methyl-2- (methoxymethoxy)-[1,1'-biphenyl] -3-yl) adamantin

10.0 g (24.3 mmol) 2- (3-adamantan-1-yl) -5-methyl-2- (methoxymethoxy) phenyl) -4,4,5,5 in 100 mL of 1,4-dioxane -To a solution of tetramethyl-1,3,2-dioxaborolane was subsequently added 7.22 g (25.5 mmol) of 2-bromoiodobenzene, 8.38 g (60.6 mmol) of potassium carbonate and 50 mL of water. .. The resulting mixture was purged with argon for 10 minutes, followed by the addition of 1.40 g (1.21 mmol) of Pd (PPh ₃ ) ₄ . The mixture was stirred at 100 ° C. for 12 hours, then cooled to room temperature and diluted with 100 mL of water. The crude product was extracted with dichloromethane (3 x 150 mL) and the combined organic extracts were dried over Na ₂ SO ₄ and then evaporated to dryness. The residue was purified by flash chromatography on silica gel 60 (40-63 um, eluent: hexane-dichloromethane = 10: 1, volume). A white solid with a yield of 10.7 g (quantitative). ¹ H NMR (CDCl ₃ , 400 MHz): δ 7.72 (d, J = 7.9 Hz, 1H), 7.35 --7.44 (m, 3H), 7.19 --7.26 (m, 1H), 6.94 (m, 1H), 4.53 (dd, J = 20.0, 4.6 Hz, 2H), 3.24 (s, 3H), 2.38 (s, 3H), 2.23 (m, 6H), 2.15 (m, 3H), 1.84 (m, 6H). ¹³ C NMR (CDCl ₃ , 100 MHz): δ 151.51, 142.78, 141.11, 134.63, 132.76, 132.16, 132.13, 129.83, 128.57, 127.76, 127.03, 124.05, 98.85, 56.95, 41.21, 37.18, 36.94, 29.07, 21.00.

２５０ｍＬの乾燥ＴＨＦ中の１０．７ｇ（２４．３ｍｍｏｌ）の１－（２’－ブロモ－５－メチル－２－（メトキシメトキシ）－［１，１’－ビフェニル］－３－イル）アダマンチンの溶液に、ヘキサン中の１１．６ｍＬ（２９．１ｍｍｏｌ）の２．５Ｍ ⁿＢｕＬｉを－８０℃で２０分間滴加した。反応混合物をこの温度で１時間撹拌し、続いて、８．４３ｍＬ（４１．３ｍｍｏｌ）の２－イソプロポキシ－４，４，５，５－テトラメチル－１，３，２－ジオキサボロランを加えた。得られた懸濁液を室温で１時間撹拌し、次いで、３００ｍＬの水に注いだ。粗生成物をジクロロメタン（３×３００ｍＬ）で抽出し、合わせた有機抽出物をＮａ₂ＳＯ₄で乾燥し、次いで、蒸発乾固した。残留物をシリカゲル６０によるフラッシュクロマトグラフィー（４０～６３ｕｍ、溶離液：ヘキサン－ジエチルエーテル＝１０：１、体積）により精製した。収量８．６０ｇ（７２％）の無色ガラス状固体。¹H NMR (CDCl₃, 400 MHz): δ 7.75 (d, J = 7.4 Hz, 1H), 7.33 - 7.44 (m, 2H), 7.29 - 7.33 (m, 1H), 7.07 (br.s, 1H), 6.84 (br.s, 1H), 4.50 (d, J = 4.4 Hz, 1H), 4.40 (d, J = 4.4 Hz, 1H), 3.27 (s, 3H), 2.30 (s, 3H), 2.21 (br.s, 6H), 2.11 (m, 3H), 1.80 (m, 6H), 1.21 (s, 6H), 1.15 (s, 6H). ¹³C NMR (CDCl₃, 100 MHz): δ 151.52, 145.68, 142.04, 136.74, 134.30, 131.47, 130.51, 130.23, 129.79, 126.69, 126.06, 98.73, 83.39, 57.22, 41.47, 37.20, 37.04, 29.19, 25.00, 24.16, 20.97. 2- (3'-(adamantane-1-yl) -5'-methyl-2'-(methoxymethoxy)-[1,1'-biphenyl] -2-yl) -4,4,5,5-tetra Methyl-1,3,2-dioxaborolane

A solution of 10.7 g (24.3 mmol) of 1- (2'-bromo-5-methyl-2- (methoxymethoxy)-[1,1'-biphenyl] -3-yl) adamantin in 250 mL of dry THF. 11.6 mL (29.1 mmol) of 2.5 M ⁿ BuLi in hexane was added dropwise at −80 ° C. for 20 minutes. The reaction mixture was stirred at this temperature for 1 hour, followed by the addition of 8.43 mL (41.3 mmol) of 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane. The resulting suspension was stirred at room temperature for 1 hour and then poured into 300 mL of water. The crude product was extracted with dichloromethane (3 x 300 mL) and the combined organic extracts were dried over Na ₂ SO ₄ and then evaporated to dryness. The residue was purified by flash chromatography on silica gel 60 (40-63 um, eluent: hexane-diethyl ether = 10: 1, volume). A colorless glassy solid with a yield of 8.60 g (72%). ¹ H NMR (CDCl ₃ , 400 MHz): δ 7.75 (d, J = 7.4 Hz, 1H), 7.33 --7.44 (m, 2H), 7.29 --7.33 (m, 1H), 7.07 (br.s, 1H) , 6.84 (br.s, 1H), 4.50 (d, J = 4.4 Hz, 1H), 4.40 (d, J = 4.4 Hz, 1H), 3.27 (s, 3H), 2.30 (s, 3H), 2.21 ( br.s, 6H), 2.11 (m, 3H), 1.80 (m, 6H), 1.21 (s, 6H), 1.15 (s, 6H). ¹³ C NMR (CDCl ₃ , 100 MHz): δ 151.52, 145.68 , 142.04, 136.74, 134.30, 131.47, 130.51, 130.23, 129.79, 126.69, 126.06, 98.73, 83.39, 57.22, 41.47, 37.20, 37.04, 29.19, 25.00, 24.16, 20.97.

４０ｍＬの１，４－ジオキサン中の４．００ｇ（８．１９ｍｍｏｌ）の２－（３’－（アダマンタン－１－イル）－５’－メチル－２’－（メトキシメトキシ）－［１，１’－ビフェニル］－２－イル）－４，４，５，５－テトラメチル－１，３，２－ジオキサボロランの溶液に、９６９ｍｇ（４．０９ｍｍｏｌ）の２，６－ジブロモピリジン、６．６８ｇ（２０．５ｍｍｏｌ）の炭酸セシウムおよび２０ｍＬの水を続いて加えた。得られた混合物をアルゴンで１０分間パージし、続いて、４７０ｍｇ（０．４１ｍｍｏｌ）のＰｄ（ＰＰｈ₃）₄を加えた。この混合物を１００℃で１２時間撹拌し、次いで、室温まで冷却し、５０ｍＬの水で希釈した。こうして得られた混合物をジクロロメタン（３×５０ｍＬ）で抽出し、合わせた有機抽出物をＮａ₂ＳＯ₄で乾燥し、次いで、蒸発乾固した。得られた油に、５０ｍＬのＴＨＦ、５０ｍＬのメタノールおよび３ｍＬの１２Ｎ ＨＣｌを続いて加えた。反応混合物を６０℃で一晩撹拌し、次いで、２００ｍＬの水に注いだ。粗生成物をジクロロメタン（３×７０ｍＬ）で抽出し、合わせた有機抽出物を５％ ＮａＨＣＯ₃で洗浄し、Ｎａ₂ＳＯ₄で乾燥し、次いで、蒸発乾固した。残留物をシリカゲル６０によるフラッシュクロマトグラフィー（４０～６３ｕｍ、溶離液：ヘキサン－酢酸エチル＝１０：１、体積）により精製した。得られたガラス状固体を３０ｍＬのｎ－ペンタンと研和し、こうして得られた沈殿物を濾別（Ｇ３）し、２×１０ｍＬのｎ－ペンタンで洗浄し、真空中で乾燥した。収量２．１０ｇ（７２％）の白色粉末としての２種の異性体の混合物。¹H NMR (CDCl₃, 400 MHz): δ 7.64 (s, 1H), 7.41 - 7.59 (m, 7H), 7.33 - 7.38 (m, 2H), 7.27 (br.s, 1H), 7.02 (d, J = 7.9 Hz, 1H), 7.00 (d, J = 7.8 Hz, 1H), 6.87 - 6.92 (m, 3H), 6.21 (d, J = 1.7 Hz, 1H), 2.26 (s, 3H), 1.55 - 1.98 (m, 33H). ¹³C NMR (CDCl₃, 100 MHz) δ 157.91, 157.89, 150.24, 149.65, 139.70, 138.49, 137.93, 137.58, 137.54, 137.44, 137.06, 136.80, 132.39, 131.36, 130.48, 130.34, 130.17, 129.97, 129.36, 129.09, 128.90, 128.82, 128.70, 128.45, 127.78, 127.71, 126.90, 126.54, 122.30, 122.02, 40.35, 40.17, 37.00, 36.78, 36.66, 36.46, 29.09, 28.96, 20.85, 20.52. 2', 2'''-(pyridin-2,6-diyl) bis (3-adamantan-1-yl) -5-methyl- [1,1'-biphenyl] -2-ol)

4.00 g (8.19 mmol) of 2- (3'-(adamantan-1-yl) -5'-methyl-2'-(methoxymethoxy)-[1,1') in 40 mL of 1,4-dioxane -Biphenyl] -2-yl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane in a solution of 969 mg (4.09 mmol) of 2,6-dibromopyridine, 6.68 g (20). .5 mmol) of cesium carbonate and 20 mL of water were subsequently added. The resulting mixture was purged with argon for 10 minutes, followed by the addition of 470 mg (0.41 mmol) of Pd (PPh ₃ ) ₄ . The mixture was stirred at 100 ° C. for 12 hours, then cooled to room temperature and diluted with 50 mL of water. The mixture thus obtained was extracted with dichloromethane (3 x 50 mL) and the combined organic extracts were dried over Na ₂ SO ₄ and then evaporated to dryness. 50 mL of THF, 50 mL of methanol and 3 mL of 12N HCl were subsequently added to the resulting oil. The reaction mixture was stirred at 60 ° C. overnight and then poured into 200 mL of water. The crude product was extracted with dichloromethane (3 x 70 mL) and the combined organic extracts were washed with 5% NaHCO ₃ and dried over Na ₂ SO ₄ and then evaporated to dryness. The residue was purified by flash chromatography on silica gel 60 (40-63 um, eluent: hexane-ethyl acetate = 10: 1, volume). The resulting glassy solid was triturated with 30 mL of n-pentane, the precipitate thus obtained was filtered off (G3), washed with 2 × 10 mL n-pentane and dried in vacuo. A mixture of the two isomers as a white powder with a yield of 2.10 g (72%). ¹ H NMR (CDCl ₃ , 400 MHz): δ 7.64 (s, 1H), 7.41 --7.51 (m, 7H), 7.33 --7.38 (m, 2H), 7.27 (br.s, 1H), 7.02 (d, J = 7.9 Hz, 1H), 7.00 (d, J = 7.8 Hz, 1H), 6.87 --6.92 (m, 3H), 6.21 (d, J = 1.7 Hz, 1H), 2.26 (s, 3H), 1.55- 1.98 (m, 33H). ¹³ C NMR (CDCl ₃ , 100 MHz) δ 157.91, 157.89, 150.24, 149.65, 139.70, 138.49, 137.93, 137.58, 137.54, 137.44, 137.06, 136.80, 132.39, 131.36, 130.48, 130.34, 130.17, 129.97, 129.36, 129.09, 128.90, 128.82, 128.70, 128.45, 127.78, 127.71, 126.90, 126.54, 122.30, 122.02, 40.35, 40.17, 37.00, 36.78, 36.66, 36.46, 29.09, 28.96, 20.85, 20.52

１００ｍＬの１，４－ジオキサン中の６．１１ｇ（１４．８ｍｍｏｌ）の２－（３－アダマンタン－１－イル）－５－メチル－２－（メトキシメトキシ）フェニル）－４，４，５，５－テトラメチル－１，３，２－ジオキサボロランの溶液に、４．６２ｇ（１５．６ｍｍｏｌ）の２－ブロモ－４－メチルヨードベンゼン、５．１２ｇ（３７．０ｍｍｏｌ）の炭酸カリウムおよび５０ｍＬの水を続いて加えた。得られた混合物をアルゴンで１０分間パージし、続いて、８５０ｍｇ（０．７４１ｍｍｏｌ）のＰｄ（ＰＰｈ₃）₄を加えた。この混合物を１００℃で１２時間撹拌し、次いで、室温まで冷却し、１００ｍＬの水で希釈した。粗生成物をジクロロメタン（３×１５０ｍＬ）で抽出し、合わせた有機抽出物をＮａ₂ＳＯ₄で乾燥し、次いで、蒸発乾固した。残留物をシリカゲル６０によるフラッシュクロマトグラフィー（４０～６３ｕｍ、溶離液：ヘキサン－ジクロロメタン＝１０：１、体積）により精製した。収量４．８８ｇ（７３％）の白色固体。¹H NMR (CDCl₃, 400 MHz): δ 7.53 (s, 1H), 7.27 (d, J = 7.8 Hz, 1H), 7.16 - 7.19 (m, 2H), 6.90 (d, J = 1.7 Hz, 1H), 4.40 (m, 2H), 3.27 (s, 3H), 2.40 (s, 3H), 2.35 (s, 3H), 2.20 (m, 6H), 2.12 (m, 3H), 1.81 (m, 6H). ¹³C NMR (CDCl₃, 100 MHz): δ 151.72, 142.67, 138.73, 138.09, 134.43, 133.20, 132.02, 131.82, 130.08, 127.94, 127.61, 123.70, 98.79, 57.06, 41.21, 37.19, 36.98, 29.11, 21.03, 20.75. (3r, 5r, 7r) -1- (2'-bromo-2- (methoxymethoxy) -4', 5-dimethyl- [1,1'-biphenyl] -3-yl) adamantin

6.11 g (14.8 mmol) 2- (3-adamantan-1-yl) -5-methyl-2- (methoxymethoxy) phenyl) -4,4,5,5 in 100 mL of 1,4-dioxane -To a solution of tetramethyl-1,3,2-dioxaborolane, add 4.62 g (15.6 mmol) of 2-bromo-4-methyliodobenzene, 5.12 g (37.0 mmol) of potassium carbonate and 50 mL of water. Then added. The resulting mixture was purged with argon for 10 minutes, followed by the addition of 850 mg (0.741 mmol) of Pd (PPh ₃ ) ₄ . The mixture was stirred at 100 ° C. for 12 hours, then cooled to room temperature and diluted with 100 mL of water. The crude product was extracted with dichloromethane (3 x 150 mL) and the combined organic extracts were dried over Na ₂ SO ₄ and then evaporated to dryness. The residue was purified by flash chromatography on silica gel 60 (40-63 um, eluent: hexane-dichloromethane = 10: 1, volume). A white solid with a yield of 4.88 g (73%). ¹ H NMR (CDCl ₃ , 400 MHz): δ 7.53 (s, 1H), 7.27 (d, J = 7.8 Hz, 1H), 7.16 --7.19 (m, 2H), 6.90 (d, J = 1.7 Hz, 1H) ), 4.40 (m, 2H), 3.27 (s, 3H), 2.40 (s, 3H), 2.35 (s, 3H), 2.20 (m, 6H), 2.12 (m, 3H), 1.81 (m, 6H) . ¹³ C NMR (CDCl ₃ , 100 MHz): δ 151.72, 142.67, 138.73, 138.09, 134.43, 133.20, 132.02, 131.82, 130.08, 127.94, 127.61, 123.70, 98.79, 57.06, 41.21, 37.19, 36.98, 29.11, 21.03 , 20.75.

１２０ｍＬの乾燥ＴＨＦ中の４．８８ｇ（１０．７ｍｍｏｌ）の（３ｒ，５ｒ，７ｒ）－１－（２’－ブロモ－２－（メトキシメトキシ）－４’，５－ジメチル－［１，１’－ビフェニル］－３－イル）アダマンチンの溶液に、ヘキサン中の５．２０ｍＬ（１２．８ｍｍｏｌ）の２．５Ｍ ⁿＢｕＬｉを－８０℃で２０分間滴加した。反応混合物をこの温度で１時間撹拌し、続いて、４．４３ｍＬ（２１．４ｍｍｏｌ）の２－イソプロポキシ－４，４，５，５－テトラメチル－１，３，２－ジオキサボロランを加えた。得られた懸濁液を室温で１時間撹拌し、次いで、３００ｍＬの水に注いだ。粗生成物をジクロロメタン（３×３００ｍＬ）で抽出し、合わせた有機抽出物をＮａ₂ＳＯ₄で乾燥し、次いで、蒸発乾固した。残留物をシリカゲル６０によるフラッシュクロマトグラフィー（４０～６３ｕｍ、溶離液：ヘキサン－ジエチルエーテル＝１０：１、体積）により精製した。収量３．０４ｇ（５７％）の無色ガラス状固体。¹H NMR (CDCl₃, 400 MHz): δ 7.53 (s, 1H), 7.19 - 7.23 (m, 2H), 7.02 (d, J = 2.1 Hz, 1H), 6.79 (d, J = 1.7 Hz, 1H), 4.43 (m, 2H), 3.27 (s, 3H), 2.37 (s, 3H), 2.26 (s, 3H), 2.17 (m, 6H), 2.08 (m, 6H), 1.77 (m, 6H), 1.18 (s, 6H), 1.13 (s, 6H). ¹³C NMR (CDCl₃, 100 MHz): δ 151.71, 142.84, 141.95, 136.61, 135.53, 134.91, 131.41, 130.65, 130.63, 130.21, 126.52, 98.73, 83.38, 57.28, 41.49, 37.20, 37.07, 29.22, 25.02, 24.20, 21.03, 20.99. 2- (3'-((3r, 5r, 7r) -adamantane-1-yl) -2'-(methoxymethoxy) -4,5'-dimethyl- [1,1'-biphenyl] -2-yl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane

4.88 g (10.7 mmol) of (3r, 5r, 7r) -1- (2'-bromo-2- (methoxymethoxy) -4', 5-dimethyl- [1,1'" in 120 mL of dry THF -Biphenyl] -3-yl) To a solution of adamantin, 5.20 mL (12.8 mmol) of 2.5 M ⁿ BuLi in hexane was added dropwise at −80 ° C. for 20 minutes. The reaction mixture was stirred at this temperature for 1 hour, followed by the addition of 4.43 mL (21.4 mmol) 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane. The resulting suspension was stirred at room temperature for 1 hour and then poured into 300 mL of water. The crude product was extracted with dichloromethane (3 x 300 mL) and the combined organic extracts were dried over Na ₂ SO ₄ and then evaporated to dryness. The residue was purified by flash chromatography on silica gel 60 (40-63 um, eluent: hexane-diethyl ether = 10: 1, volume). A colorless glassy solid with a yield of 3.04 g (57%). ¹ H NMR (CDCl ₃ , 400 MHz): δ 7.53 (s, 1H), 7.19 --7.23 (m, 2H), 7.02 (d, J = 2.1 Hz, 1H), 6.79 (d, J = 1.7 Hz, 1H) ), 4.43 (m, 2H), 3.27 (s, 3H), 2.37 (s, 3H), 2.26 (s, 3H), 2.17 (m, 6H), 2.08 (m, 6H), 1.77 (m, 6H) , 1.18 (s, 6H), 1.13 (s, 6H). ¹³ C NMR (CDCl ₃ , 100 MHz): δ 151.71, 142.84, 141.95, 136.61, 135.53, 134.91, 131.41, 130.65, 130.63, 130.21, 126.52, 98.73 , 83.38, 57.28, 41.49, 37.20, 37.07, 29.22, 25.02, 24.20, 21.03, 20.99.

４０ｍＬの１，４－ジオキサン中の３．０４ｇ（６．０５ｍｍｏｌ）の２－（３’－（（３ｒ，５ｒ，７ｒ）－アダマンタン－１－イル）－２’－（メトキシメトキシ）－４，５’－ジメチル－［１，１’－ビフェニル］－２－イル）－４，４，５，５－テトラメチル－１，３，２－ジオキサボロランの溶液に、７１６ｍｇ（３．０２ｍｍｏｌ）の２，６－ジブロモピリジン、４．９２ｇ（１５．１ｍｍｏｌ）の炭酸セシウムおよび２０ｍＬの水を続いて加えた。得られた混合物をアルゴンで１０分間パージし、続いて、３５０ｍｇ（０．３０ｍｍｏｌ）のＰｄ（ＰＰｈ₃）₄を加えた。この混合物を１００℃で１２時間撹拌し、次いで、室温まで冷却し、５０ｍＬの水で希釈した。こうして得られた混合物をジクロロメタン（３×５０ｍＬ）で抽出し、合わせた有機抽出物をＮａ₂ＳＯ₄で乾燥し、次いで、蒸発乾固した。得られた油に、５０ｍＬのＴＨＦ、５０ｍＬのメタノールおよび３ｍＬの１２Ｎ ＨＣｌを続いて加えた。反応混合物を６０℃で一晩撹拌し、次いで、２００ｍＬの水に注いだ。粗生成物をジクロロメタン（３×７０ｍＬ）で抽出し、合わせた有機抽出物を５％ ＮａＨＣＯ₃で洗浄し、Ｎａ₂ＳＯ₄で乾燥し、次いで、蒸発乾固した。残留物をシリカゲル６０によるフラッシュクロマトグラフィー（４０～６３ｕｍ、溶離液：ヘキサン－酢酸エチル＝１０：１、体積）により精製した。収量０．７４ｇ（３３％）の白色泡としての２種の異性体の混合物。¹H NMR (CDCl₃, 400 MHz): δ 7.66 (s, 1H), 7.39 - 7.42 (m, 3H), 7.22 - 7.35 (m, 5H), 6.96 - 7.01 (m, 2H), 6.85 - 6.91 (m, 3H), 6.16 (d, J = 1.5 Hz, 1H), 2.49 (s, 3H), 2.47 (s, 3H), 2.26 (s, 3H), 1.58 - 2.04 (m, 33H). ¹³C NMR (CDCl₃, 100 MHz) δ 158.05, 157.98, 150.39, 149.80, 139.62, 138.29, 137.77, 137.61, 137.55, 136.94, 136.62, 134.64, 134.44, 132.31, 131.18, 130.90, 130.77, 130.39, 130.15, 129.95, 129.55, 129.13, 128.99, 128.62, 128.34, 126.74, 126.34, 122.22, 121.95, 40.35, 40.21, 37.07, 36.88, 36.65, 36.46, 29.15, 29.04, 21.09, 21.06, 20.86, 20.51. 2', 2'''-(pyridin-2,6-diyl) bis (3-((3r, 5r, 7r) -adamantan-1-yl) -4', 5-dimethyl- [1,1'- Biphenyl] -2-ol)

3.04 g (6.05 mmol) 2- (3'-((3r, 5r, 7r) -adamantan-1-yl) -2'-(methoxymethoxy) -4, in 40 mL of 1,4-dioxane, In a solution of 5'-dimethyl- [1,1'-biphenyl] -2-yl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane, 716 mg (3.02 mmol) 2, 6-Dibromopyridine, 4.92 g (15.1 mmol) of cesium carbonate and 20 mL of water were subsequently added. The resulting mixture was purged with argon for 10 minutes, followed by the addition of 350 mg (0.30 mmol) of Pd (PPh ₃ ) ₄ . The mixture was stirred at 100 ° C. for 12 hours, then cooled to room temperature and diluted with 50 mL of water. The mixture thus obtained was extracted with dichloromethane (3 x 50 mL) and the combined organic extracts were dried over Na ₂ SO ₄ and then evaporated to dryness. 50 mL of THF, 50 mL of methanol and 3 mL of 12N HCl were subsequently added to the resulting oil. The reaction mixture was stirred at 60 ° C. overnight and then poured into 200 mL of water. The crude product was extracted with dichloromethane (3 x 70 mL) and the combined organic extracts were washed with 5% NaHCO ₃ and dried over Na ₂ SO ₄ and then evaporated to dryness. The residue was purified by flash chromatography on silica gel 60 (40-63 um, eluent: hexane-ethyl acetate = 10: 1, volume). A mixture of the two isomers as a white foam with a yield of 0.74 g (33%). ¹ H NMR (CDCl ₃ , 400 MHz): δ 7.66 (s, 1H), 7.39 --7.42 (m, 3H), 7.22 --7.35 (m, 5H), 6.96 --7.01 (m, 2H), 6.85 --6.91 ( m, 3H), 6.16 (d, J = 1.5 Hz, 1H), 2.49 (s, 3H), 2.47 (s, 3H), 2.26 (s, 3H), 1.58 --2.04 (m, 33H). ¹³ C NMR (CDCl ₃ , 100 MHz) δ 158.05, 157.98, 150.39, 149.80, 139.62, 138.29, 137.77, 137.61, 137.55, 136.94, 136.62, 134.64, 134.44, 132.31, 131.18, 130.90, 130.77, 130.39, 130.15, 129.95, 129.5 129.13, 128.99, 128.62, 128.34, 126.74, 126.34, 122.22, 121.95, 40.35, 40.21, 37.07, 36.88, 36.65, 36.46, 29.15, 29.04, 21.09, 21.06, 20.86, 20.51.

５０ｍＬの１，４－ジオキサン中の８．００ｇ（１９．４ｍｍｏｌ）の２－（３－アダマンタン－１－イル）－５－メチル－２－（メトキシメトキシ）フェニル）－４，４，５，５－テトラメチル－１，３，２－ジオキサボロランの溶液に、７．２２ｇ（２１．３ｍｍｏｌ）の２－ブロモ－４－（ｔｅｒｔ－ブチル）ヨードベンゼン、６．７０ｇ（４８．５ｍｍｏｌ）の炭酸カリウムおよび２５ｍＬの水を続いて加えた。得られた混合物をアルゴンで１０分間パージし、続いて、２．２０ｇ（１．９０ｍｍｏｌ）のＰｄ（ＰＰｈ₃）₄を加えた。この混合物を１００℃で１２時間撹拌し、次いで、室温まで冷却し、１００ｍＬの水で希釈した。粗生成物をジクロロメタン（３×１５０ｍＬ）で抽出し、合わせた有機抽出物をＮａ₂ＳＯ₄で乾燥し、次いで、蒸発乾固した。残留物をシリカゲル６０によるフラッシュクロマトグラフィー（４０～６３ｕｍ、溶離液：ヘキサン－ジクロロメタン＝１０：１、体積）により精製した。収量５．２０ｇ（５４％）の白色固体。¹H NMR (CDCl₃, 400 MHz): δ 7.68 (s, 1H), 7.30 - 7.38 (m, 2H), 7.16 (s, 1H), 6.92 (s, 1H), 4.49 (m, 2H), 3.18 (s, 3H), 2.35 (s, 3H), 2.19 (m, 6H), 2.12 (m, 3H), 1.81 (m, 6H), 1.37 (s, 9H). ¹³C NMR (CDCl₃, 100 MHz): δ 152.30, 151.61, 142.80, 138.05, 134.67, 132.11, 131.74, 130.01, 129.70, 127.66, 124.22, 123.89, 98.83, 56.93, 41.29, 37.24, 37.00, 34.60, 31.22, 29.14, 21.05. (3r, 5r, 7r) -1- (2'-bromo-4'-(tert-butyl) -2- (methoxymethoxy) -5-methyl- [1,1'-biphenyl] -3-yl) adamantin

8.00 g (19.4 mmol) 2- (3-adamantan-1-yl) -5-methyl-2- (methoxymethoxy) phenyl) -4,4,5,5 in 50 mL of 1,4-dioxane -To a solution of tetramethyl-1,3,2-dioxaborolane, 7.22 g (21.3 mmol) of 2-bromo-4- (tert-butyl) iodobenzene, 6.70 g (48.5 mmol) of potassium carbonate and 25 mL of water was subsequently added. The resulting mixture was purged with argon for 10 minutes, followed by the addition of 2.20 g (1.90 mmol) of Pd (PPh ₃ ) ₄ . The mixture was stirred at 100 ° C. for 12 hours, then cooled to room temperature and diluted with 100 mL of water. The crude product was extracted with dichloromethane (3 x 150 mL) and the combined organic extracts were dried over Na ₂ SO ₄ and then evaporated to dryness. The residue was purified by flash chromatography on silica gel 60 (40-63 um, eluent: hexane-dichloromethane = 10: 1, volume). A white solid with a yield of 5.20 g (54%). ¹ H NMR (CDCl ₃ , 400 MHz): δ 7.68 (s, 1H), 7.30 --7.38 (m, 2H), 7.16 (s, 1H), 6.92 (s, 1H), 4.49 (m, 2H), 3.18 (s, 3H), 2.35 (s, 3H), 2.19 (m, 6H), 2.12 (m, 3H), 1.81 (m, 6H), 1.37 (s, 9H). ¹³ C NMR (CDCl ₃ , 100 MHz) ): δ 152.30, 151.61, 142.80, 138.05, 134.67, 132.11, 131.74, 130.01, 129.70, 127.66, 124.22, 123.89, 98.83, 56.93, 41.29, 37.24, 37.00, 34.60, 31.22, 29.14, 21.05.

１２０ｍＬの乾燥ＴＨＦ中の５．１２ｇ（１０．３ｍｍｏｌ）の（３ｒ，５ｒ，７ｒ）－１－（２’－ブロモ－４’－（ｔｅｒｔ－ブチル）－２－（メトキシメトキシ）－５－メチル－［１，１’－ビフェニル］－３－イル）アダマンチンの溶液に、ヘキサン中の６．２０ｍＬ（１５．４ｍｍｏｌ）の２．５Ｍ ⁿＢｕＬｉを－８０℃で２０分間滴加した。反応混合物をこの温度で１時間撹拌し、続いて、５．２３ｍＬ（２５．６ｍｍｏｌ）の２－イソプロポキシ－４，４，５，５－テトラメチル－１，３，２－ジオキサボロランを加えた。得られた懸濁液を室温で１時間撹拌し、次いで、３００ｍＬの水に注いだ。粗生成物をジクロロメタン（３×３００ｍＬ）で抽出し、合わせた有機抽出物をＮａ₂ＳＯ₄で乾燥し、次いで、蒸発乾固した。残留物をシリカゲル６０によるフラッシュクロマトグラフィー（４０～６３ｕｍ、溶離液：ヘキサン－ジエチルエーテル＝１０：１、体積）により精製した。収量３．３０ｇ（５９％）の無色ガラス状固体。¹H NMR (CDCl₃, 400 MHz): δ 7.72 (d, J = 2.1 Hz, 1H), 7.44 (dd, J = 8.1, 2.2 Hz, 1H), 7.29 (d, J = 8.1 Hz, 1H), 7.05 (d, J = 2.0 Hz, 1H), 6.83 (d, J = 1.7 Hz, 1H), 4.45 (m, 2H), 3.24 (s, 3H), 2.28 (s, 3H), 2.20 (m, 6H), 2.10 (m, 3H), 1.79 (m, 6H), 1.37 (s, 9H), 1.20 (br.s, 6H), 1.14 (br.s, 6H). ¹³C NMR (CDCl₃, 100 MHz): δ 151.61, 148.72, 142.79, 141.98, 136.75, 131.35, 130.67, 130.64, 129.95, 126.89, 126.48, 98.70, 83.33, 57.20, 41.51, 37.22, 37.08, 34.45, 31.41, 29.22, 25.03, 24.22, 20.96. 2- (3'-((3r, 5r, 7r) -adamantane-1-yl) -4- (tert-butyl) -2'-(methoxymethoxy) -5'-methyl- [1,1'-biphenyl ] -2-yl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane

5.12 g (10.3 mmol) of (3r, 5r, 7r) -1- (2'-bromo-4'-(tert-butyl) -2- (methoxymethoxy) -5-methyl in 120 mL of dry THF To a solution of-[1,1'-biphenyl] -3-yl) adamantin, 6.20 mL (15.4 mmol) of 2.5 M ⁿ BuLi in hexane was added dropwise at −80 ° C. for 20 minutes. The reaction mixture was stirred at this temperature for 1 hour, followed by the addition of 5.23 mL (25.6 mmol) of 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane. The resulting suspension was stirred at room temperature for 1 hour and then poured into 300 mL of water. The crude product was extracted with dichloromethane (3 x 300 mL) and the combined organic extracts were dried over Na ₂ SO ₄ and then evaporated to dryness. The residue was purified by flash chromatography on silica gel 60 (40-63 um, eluent: hexane-diethyl ether = 10: 1, volume). A colorless glassy solid with a yield of 3.30 g (59%). ¹ H NMR (CDCl ₃ , 400 MHz): δ 7.72 (d, J = 2.1 Hz, 1H), 7.44 (dd, J = 8.1, 2.2 Hz, 1H), 7.29 (d, J = 8.1 Hz, 1H), 7.05 (d, J = 2.0 Hz, 1H), 6.83 (d, J = 1.7 Hz, 1H), 4.45 (m, 2H), 3.24 (s, 3H), 2.28 (s, 3H), 2.20 (m, 6H) ), 2.10 (m, 3H), 1.79 (m, 6H), 1.37 (s, 9H), 1.20 (br.s, 6H), 1.14 (br.s, 6H). ¹³ C NMR (CDCl ₃ , 100 MHz) ): δ 151.61, 148.72, 142.79, 141.98, 136.75, 131.35, 130.67, 130.64, 129.95, 126.89, 126.48, 98.70, 83.33, 57.20, 41.51, 37.22, 37.08, 34.45, 31.41, 29.22, 25.03, 24.22, 20.96.

４０ｍＬの１，４－ジオキサン中の１．７５ｇ（３．２１ｍｍｏｌ）の２－（３’－（（３ｒ，５ｒ，７ｒ）－アダマンタン－１－イル）－４－（ｔｅｒｔ－ブチル）－２’－（メトキシメトキシ）－５’－メチル－［１，１’－ビフェニル］－２－イル）－４，４，５，５－テトラメチル－１，３，２－ジオキサボロランの溶液に、３８１ｍｇ（１．６１ｍｍｏｌ）の２，６－ジブロモピリジン、２．６２ｇ（８．０３ｍｍｏｌ）の炭酸セシウムおよび２０ｍＬの水を続いて加えた。得られた混合物をアルゴンで１０分間パージし、続いて、１８０ｍｇ（０．１６ｍｍｏｌ）のＰｄ（ＰＰｈ₃）₄を加えた。この混合物を１００℃で１２時間撹拌し、次いで、室温まで冷却し、５０ｍＬの水で希釈した。こうして得られた混合物をジクロロメタン（３×５０ｍＬ）で抽出し、合わせた有機抽出物をＮａ₂ＳＯ₄で乾燥し、次いで、蒸発乾固した。得られた油に、５０ｍＬのＴＨＦ、５０ｍＬのメタノールおよび３ｍＬの１２Ｎ ＨＣｌを続いて加えた。反応混合物を６０℃で一晩撹拌し、次いで、２００ｍＬの水に注いだ。粗生成物をジクロロメタン（３×７０ｍＬ）で抽出し、合わせた有機抽出物を５％ ＮａＨＣＯ₃で洗浄し、Ｎａ₂ＳＯ₄で乾燥し、次いで、蒸発乾固した。残留物をシリカゲル６０によるフラッシュクロマトグラフィー（４０～６３ｕｍ、溶離液：ヘキサン－酢酸エチル＝１０：１、体積）により精製した。収量０．６０ｇ（４５％）の白色泡としての２種の異性体の混合物。¹H NMR (CDCl₃, 400 MHz): δ 7.72および7.08 (2s, 2H), 7.40 - 7.53 (m, 5H), 7.21 - 7.26 (m, 2H), 6.94 - 7.00 (m, 2H), 6.80 - 6.86および6.09 (2m, 4H), 1.53 - 1.95 (m, 30H), 1.39および1.40 (2s, 18H). ¹³C NMR (CDCl₃, 100 MHz) δ 158.53, 150.71, 150.54, 149.85, 139.47, 137.94, 137.52, 136.66, 134.45, 132.05, 130.80, 130.68, 129.49, 129.04, 128.58, 128.41, 127.40, 127.24, 126.78, 126.36, 125.72, 122.26, 122.02, 40.38, 40.28, 37.05, 36.87, 36.70, 36.52, 34.67, 31.58, 31.39, 29.11, 28.98, 20.87, 20.52. 2', 2'''-(pyridin-2,6-diyl) bis (3-((3r, 5r, 7r) -adamantan-1-yl) -4'-(tert-butyl) -5-methyl- [1,1'-biphenyl] -2-ol)

1.75 g (3.21 mmol) 2- (3'-((3r, 5r, 7r) -adamantan-1-yl) -4- (tert-butyl) -2'in 40 mL of 1,4-dioxane -(Methoxymethoxy) -5'-methyl- [1,1'-biphenyl] -2-yl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane in a solution of 381 mg (1) .61 mmol) of 2,6-dibromopyridine, 2.62 g (8.03 mmol) of cesium carbonate and 20 mL of water were subsequently added. The resulting mixture was purged with argon for 10 minutes, followed by the addition of 180 mg (0.16 mmol) of Pd (PPh ₃ ) ₄ . The mixture was stirred at 100 ° C. for 12 hours, then cooled to room temperature and diluted with 50 mL of water. The mixture thus obtained was extracted with dichloromethane (3 x 50 mL) and the combined organic extracts were dried over Na ₂ SO ₄ and then evaporated to dryness. 50 mL of THF, 50 mL of methanol and 3 mL of 12N HCl were subsequently added to the resulting oil. The reaction mixture was stirred at 60 ° C. overnight and then poured into 200 mL of water. The crude product was extracted with dichloromethane (3 x 70 mL) and the combined organic extracts were washed with 5% NaHCO ₃ and dried over Na ₂ SO ₄ and then evaporated to dryness. The residue was purified by flash chromatography on silica gel 60 (40-63 um, eluent: hexane-ethyl acetate = 10: 1, volume). A mixture of the two isomers as a white foam with a yield of 0.60 g (45%). ¹ H NMR (CDCl ₃ , 400 MHz): δ 7.72 and 7.08 (2s, 2H), 7.40 --7.53 (m, 5H), 7.21 --7.26 (m, 2H), 6.94 --7.00 (m, 2H), 6.80- 6.86 and 6.09 (2m, 4H), 1.53 --1.95 (m, 30H), 1.39 and 1.40 (2s, 18H). ¹³ C NMR (CDCl ₃ , 100 MHz) δ 158.53, 150.71, 150.54, 149.85, 139.47, 137.94, 137.52, 136.66, 134.45, 132.05, 130.80, 130.68, 129.49, 129.04, 128.58, 128.41, 127.40, 127.24, 126.78, 126.36, 125.72, 122.26, 122.02, 40.38, 40.28, 37.05, 36.87, 36.70, 36.52, 34. 31.39, 29.11, 28.98, 20.87, 20.52.

４０ｍＬの１，４－ジオキサン中の１．５０ｇ（２．７５ｍｍｏｌ）の２－（３’－（（３ｒ，５ｒ，７ｒ）－アダマンタン－１－イル）－４－（ｔｅｒｔ－ブチル）－２’－（メトキシメトキシ）－５’－メチル－［１，１’－ビフェニル］－２－イル）－４，４，５，５－テトラメチル－１，３，２－ジオキサボロランの溶液に、３６７ｍｇ（１．３８ｍｍｏｌ）の２，６－ジブロモ－４－メトキシピリジン、２．２５ｇ（６．９０ｍｍｏｌ）の炭酸セシウムおよび２０ｍＬの水を続いて加えた。得られた混合物をアルゴンで１０分間パージし、続いて、１６０ｍｇ（０．１３８ｍｍｏｌ）のＰｄ（ＰＰｈ₃）₄を加えた。この混合物を１００℃で１２時間撹拌し、次いで、室温まで冷却し、５０ｍＬの水で希釈した。こうして得られた混合物をジクロロメタン（３×５０ｍＬ）で抽出し、合わせた有機抽出物をＮａ₂ＳＯ₄で乾燥し、次いで、蒸発乾固した。得られた油に、５０ｍＬのＴＨＦ、５０ｍＬのメタノールおよび３ｍＬの１２Ｎ ＨＣｌを続いて加えた。反応混合物を６０℃で一晩撹拌し、次いで、２００ｍＬの水に注いだ。粗生成物をジクロロメタン（３×７０ｍＬ）で抽出し、合わせた有機抽出物を５％ ＮａＨＣＯ₃で洗浄し、Ｎａ₂ＳＯ₄で乾燥し、次いで、蒸発乾固した。残留物をシリカゲル６０によるフラッシュクロマトグラフィー（４０～６３ｕｍ、溶離液：ヘキサン－酢酸エチル＝１０：１、体積）により精製した。収量１．０４ｇ（８９％）の白色泡としての２種の異性体の混合物。¹H NMR (CDCl₃, 400 MHz): δ 7.88および7.31 (2s, 2H), 7.46 - 7.57 (m, 4H), 7.21 - 7.27 (m, 2H), 6.83 (m, 2H), 6.46 - 6.48 (m, 2H), 6.12および6.88 (2m, 2H), 3.50および3.41 (2s, 3H), 1.57 - 1.95 (m, 30H), 1.40および1.41 (2s, 18H). ¹³C NMR (CDCl₃, 100 MHz) δ 160.07, 150.75, 150.50, 139.59, 137.92, 134.48, 131.99, 130.84, 130.77, 129.49, 129.11, 128.53, 127.13, 126.42, 125.79, 108.64, 108.33, 55.22, 40.54, 40.29, 37.08, 36.92, 36.77, 34.69, 31.46, 31.42, 29.17, 29.06, 20.57. 2', 2'''-(4-Methoxypyridin-2,6-diyl) bis (3-((3r, 5r, 7r) -adamantan-1-yl) -4'-(tert-butyl) -5 -Methyl- [1,1'-biphenyl] -2-ol)

1.50 g (2.75 mmol) 2- (3'-((3r, 5r, 7r) -adamantan-1-yl) -4- (tert-butyl) -2'in 40 mL of 1,4-dioxane -(Methoxymethoxy) -5'-methyl- [1,1'-biphenyl] -2-yl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane in a solution of 367 mg (1) .38 mmol) of 2,6-dibromo-4-methoxypyridine, 2.25 g (6.90 mmol) of cesium carbonate and 20 mL of water were subsequently added. The resulting mixture was purged with argon for 10 minutes, followed by the addition of 160 mg (0.138 mmol) of Pd (PPh ₃ ) ₄ . The mixture was stirred at 100 ° C. for 12 hours, then cooled to room temperature and diluted with 50 mL of water. The mixture thus obtained was extracted with dichloromethane (3 x 50 mL) and the combined organic extracts were dried over Na ₂ SO ₄ and then evaporated to dryness. 50 mL of THF, 50 mL of methanol and 3 mL of 12N HCl were subsequently added to the resulting oil. The reaction mixture was stirred at 60 ° C. overnight and then poured into 200 mL of water. The crude product was extracted with dichloromethane (3 x 70 mL) and the combined organic extracts were washed with 5% NaHCO ₃ and dried over Na ₂ SO ₄ and then evaporated to dryness. The residue was purified by flash chromatography on silica gel 60 (40-63 um, eluent: hexane-ethyl acetate = 10: 1, volume). A mixture of the two isomers as a white foam with a yield of 1.04 g (89%). ¹ H NMR (CDCl ₃ , 400 MHz): δ 7.88 and 7.31 (2s, 2H), 7.46 --7.57 (m, 4H), 7.21 --7.27 (m, 2H), 6.83 (m, 2H), 6.46 --6.48 ( m, 2H), 6.12 and 6.88 (2m, 2H), 3.50 and 3.41 (2s, 3H), 1.57 --1.95 (m, 30H), 1.40 and 1.41 (2s, 18H). ¹³ C NMR (CDCl ₃ , 100 MHz). ) δ 160.07, 150.75, 150.50, 139.59, 137.92, 134.48, 131.99, 130.84, 130.77, 129.49, 129.11, 128.53, 127.13, 126.42, 125.79, 108.64, 108.33, 55.22, 40.54, 40.29, 37.08, 36.92, 36.77 31.46, 31.42, 29.17, 29.06, 20.57.

２０００ｍＬのジクロロメタン中の２３６ｇ（８３０ｍｍｏｌ）の２－（アダマンタン－１－イル）－４－（ｔｅｒｔ－ブチル）フェノールの溶液に、４００ｍＬのジクロロメタン中の１３２ｇ（８３０ｍｍｏｌ）の臭素の溶液を室温で１時間滴加した。生じた混合物を２，０００ｍＬの水で希釈した。得られた混合物をジクロロメタン（３×５００ｍＬ）で抽出し、合わせた有機抽出物を５％ ＮａＨＣＯ₃で洗浄し、Ｎａ₂ＳＯ₄で乾燥し、次いで、蒸発乾固した。収量２９９ｇ（９９％）の白色固体。¹H NMR (CDCl₃, 400 MHz): δ 7.32 (d, J = 2.3 Hz, 1 H), 7.19 (d, J = 2.3 Hz, 1 H), 5.65 (s, 1 H), 2.18 - 2.03 (m, 9 H), 1.78 (m, 6 H), 1.29 (s, 9 H). ¹³C NMR (CDCl₃, 100 MHz): δ 148.07, 143.75, 137.00, 126.04, 123.62, 112.11, 40.24, 37.67, 37.01, 34.46, 31.47, 29.03. 2- (adamantane-1-yl) -6-bromo-4- (tert-butyl) phenol

A solution of 236 g (830 mmol) of 2- (adamantane-1-yl) -4- (tert-butyl) phenol in 2000 mL of dichloromethane to a solution of 132 g (830 mmol) of bromine in 400 mL of dichloromethane at room temperature for 1 hour. Dropped. The resulting mixture was diluted with 2,000 mL of water. The resulting mixture was extracted with dichloromethane (3 x 500 mL) and the combined organic extracts were washed with 5% NaHCO ₃ and dried over Na ₂ SO ₄ and then evaporated to dryness. A white solid with a yield of 299 g (99%). ¹ H NMR (CDCl ₃ , 400 MHz): δ 7.32 (d, J = 2.3 Hz, 1 H), 7.19 (d, J = 2.3 Hz, 1 H), 5.65 (s, 1 H), 2.18 --2.03 ( m, 9 H), 1.78 (m, 6 H), 1.29 (s, 9 H). ¹³ C NMR (CDCl ₃ , 100 MHz): δ 148.07, 143.75, 137.00, 126.04, 123.62, 112.11, 40.24, 37.67, 37.01, 34.46, 31.47, 29.03.

３，０００ｍＬのＴＨＦ中の３３０ｇ（９１０ｍｍｏｌ）の２－（アダマンタン－１－イル）－６－ブロモ－４－（ｔｅｒｔ－ブチル）フェノールの溶液に、４０．０ｇ（１．００ｍｏｌ、鉱油中６０質量％）の水素化ナトリウムを室温で分割して加えた。得られた懸濁液に、７６．０ｍＬ（１．００ｍｏｌ）のメトキシメチルクロリドを室温で４０分間滴加した。得られた混合物を一晩撹拌し、次いで、２，０００ｍＬの水に注いだ。所望の生成物をジクロロメタン（３×９００ｍＬ）で抽出し、合わせた有機抽出物を５％ ＮａＨＣＯ₃で洗浄し、Ｎａ₂ＳＯ₄で乾燥し、次いで、蒸発乾固した。収量３６７ｇ（９９％）の白色固体。¹H NMR (CDCl₃, 400 MHz): δ 7.39 (d, J = 2.4 Hz, 1 H), 7.27 (d, J = 2.4 Hz, 1 H), 5.23 (s, 2 H), 3.71 (s, 3 H), 2.20 - 2.04 (m, 9 H), 1.82 - 1.74 (m, 6 H), 1.29 (s, 9 H). ¹³C NMR (CDCl₃, 100 MHz): δ 150.88, 147.47, 144.42, 128.46, 123.72, 117.46, 99.53, 57.74, 41.31, 38.05, 36.85, 34.58, 31.30, 29.08. (1- (3-bromo-5- (tert-butyl) -2- (methoxymethoxy) phenyl) adamantin

In a solution of 330 g (910 mmol) of 2- (adamantane-1-yl) -6-bromo-4- (tert-butyl) phenol in 3,000 mL of THF, 40.0 g (1.00 mol, 60 mass in mineral oil). %) Sodium hydride was added in portions at room temperature. To the obtained suspension, 76.0 mL (1.00 mol) of methoxymethyl chloride was added dropwise at room temperature for 40 minutes. The resulting mixture was stirred overnight and then poured into 2,000 mL of water. The desired product was extracted with dichloromethane (3 x 900 mL) and the combined organic extracts were washed with 5% NaHCO ₃ and dried over Na ₂ SO ₄ and then evaporated to dryness. A white solid with a yield of 367 g (99%). ¹ H NMR (CDCl ₃ , 400 MHz): δ 7.39 (d, J = 2.4 Hz, 1 H), 7.27 (d, J = 2.4 Hz, 1 H), 5.23 (s, 2 H), 3.71 (s, 3 H), 2.20 --2.04 (m, 9 H), 1.82 --1.74 (m, 6 H), 1.29 (s, 9 H). ¹³ C NMR (CDCl ₃ , 100 MHz): δ 150.88, 147.47, 144.42, 128.46, 123.72, 117.46, 99.53, 57.74, 41.31, 38.05, 36.85, 34.58, 31.30, 29.08.

２，５００ｍＬの乾燥ＴＨＦ中の１８３．５ｇ（４５０ｍｍｏｌ）の（１－（３－ブロモ－５－（ｔｅｒｔ－ブチル）－２－（メトキシメトキシ）フェニル）アダマンチンの溶液に、ヘキサン中の１９０ｍＬ（４７３ｍｍｏｌ）の２．５Ｍ ⁿＢｕＬｉを－８０℃で２０分間滴加した。反応混合物をこの温度で１時間撹拌し、続いて、１２０ｍＬ（５８５ｍｍｏｌ）の２－イソプロポキシ－４，４，５，５－テトラメチル－１，３，２－ジオキサボロランを加えた。得られた懸濁液を室温で１時間撹拌し、次いで、３００ｍＬの水に注いだ。得られた混合物を約１リットルまで蒸発させ、粗生成物をジクロロメタン（３×８００ｍＬ）で抽出し、合わせた有機抽出物をＮａ₂ＳＯ₄で乾燥し、次いで、蒸発乾固した。収量２０４．７ｇ（定量的）の無色固体。¹H NMR (CDCl₃, 400 MHz): δ 7.54 (d, J = 2.5 Hz, 1 H), 7.43 (d, J = 2.6 Hz, 1 H), 5.18 (s, 2 H), 3.60 (s, 3 H), 2.24 - 2.13 (m, 6 H), 2.09 (br. s., 3 H), 1.85 - 1.75 (m, 6 H), 1.37 (s, 12 H), 1.33 (s, 9 H). ¹³C NMR (CDCl₃, 100 MHz): δ 159.64, 144.48, 140.55, 130.58, 127.47, 100.81, 83.48, 57.63, 41.24, 37.29, 37.05, 34.40, 31.50, 29.16, 24.79. 2- (3-adamantane-1-yl) -5- (tert-butyl) -2- (methoxymethoxy) phenyl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane

190 mL (473 mmol) in hexane to a solution of 183.5 g (450 mmol) of (1- (3-bromo-5- (tert-butyl) -2- (methoxymethoxy) phenyl) adamantin in 2,500 mL of dry THF. ) 2.5 M ⁿ BuLi was added dropwise at −80 ° C. for 20 minutes. The reaction mixture was stirred at this temperature for 1 hour, followed by 120 mL (585 mmol) of 2-isopropoxy-4,4,5,5-. Tetramethyl-1,3,2-dioxaborolane was added. The resulting suspension was stirred at room temperature for 1 hour and then poured into 300 mL of water. The resulting mixture was evaporated to about 1 liter and crude. The product was extracted with dichloromethane (3 x 800 mL) and the combined organic extracts were dried with Na ₂ SO ₄ and then evaporated to dryness. A colorless solid with a yield of 204.7 g (quantitative). ¹ H NMR ( CDCl ₃ , 400 MHz): δ 7.54 (d, J = 2.5 Hz, 1 H), 7.43 (d, J = 2.6 Hz, 1 H), 5.18 (s, 2 H), 3.60 (s, 3 H), 2.24 --2.13 (m, 6 H), 2.09 (br. S., 3 H), 1.85 --1.75 (m, 6 H), 1.37 (s, 12 H), 1.33 (s, 9 H). ¹³ C NMR (CDCl ₃ , 100 MHz): δ 159.64, 144.48, 140.55, 130.58, 127.47, 100.81, 83.48, 57.63, 41.24, 37.29, 37.05, 34.40, 31.50, 29.16, 24.79.

２ｌ圧力容器内で、１５０ｇ（３３０ｍｍｏｌ）の２－（３－アダマンタン－１－イル）－５－（ｔｅｒｔ－ブチル）－２－（メトキシメトキシ）フェニル）－４，４，５，５－テトラメチル－１，３，２－ジオキサボロラン、１０００ｍＬのジオキサン、９３．４ｇ（３３０ｍｍｏｌ）の２－ブロモヨードベンゼン、１１４ｇ（８２５ｍｍｏｌ）の炭酸カリウムおよび５００ｍＬの水を続いて加えた。得られた混合物をアルゴンで１０分間パージし、続いて、１９．１ｇ（１７．０ｍｍｏｌ）のＰｄ（ＰＰｈ₃）₄を加えた。この混合物を１１５℃で１２時間撹拌し、次いで、室温まで冷却し、５００ｍＬの水で希釈した。粗生成物をジクロロメタン（３×７００ｍＬ）で抽出し、合わせた有機抽出物をＮａ₂ＳＯ₄で乾燥し、次いで、蒸発乾固した。残留物をシリカゲル６０によるフラッシュクロマトグラフィー（４０～６３ｕｍ、溶離液：ヘキサン－ジクロロメタン＝１０：１、体積）により精製した。収量１１２ｇ（７０％）の白色固体。¹H NMR (CDCl₃, 400 MHz): δ 7.68 (dd, J = 1.0, 8.0 Hz, 1 H), 7.42 (dd, J = 1.7, 7.6 Hz, 1 H), 7.37 - 7.32 (m, 2 H), 7.20 (dt, J = 1.8, 7.7 Hz, 1 H), 7.08 (d, J = 2.5 Hz, 1 H), 4.53 (d, J = 4.6 Hz, 1 H), 4.40 (d, J = 4.6 Hz, 1 H), 3.20 (s, 3 H), 2.23 - 2.14 (m, 6 H), 2.10 (br. s., 3 H), 1.86 - 1.70 (m, 6 H), 1.33 (s, 9 H). ¹³C NMR (CDCl₃, 100 MHz): δ 151.28, 145.09, 142.09, 141.47, 133.90, 132.93, 132.41, 128.55, 127.06, 126.81, 124.18, 123.87, 98.83, 57.07, 41.31, 37.55, 37.01, 34.60, 31.49, 29.17. 1- (2'-bromo-5- (tert-butyl) -2- (methoxymethoxy)-[1,1'-biphenyl] -3-yl) adamantin

In a 2 liter pressure vessel, 150 g (330 mmol) 2- (3-adamantan-1-yl) -5- (tert-butyl) -2- (methoxymethoxy) phenyl) -4,4,5,5-tetramethyl -1,3,2-dioxaborolane, 1000 mL dioxane, 93.4 g (330 mmol) 2-bromoiodobenzene, 114 g (825 mmol) potassium carbonate and 500 mL water were subsequently added. The resulting mixture was purged with argon for 10 minutes, followed by the addition of 19.1 g (17.0 mmol) of Pd (PPh ₃ ) ₄ . The mixture was stirred at 115 ° C. for 12 hours, then cooled to room temperature and diluted with 500 mL of water. The crude product was extracted with dichloromethane (3 x 700 mL) and the combined organic extracts were dried over Na ₂ SO ₄ and then evaporated to dryness. The residue was purified by flash chromatography on silica gel 60 (40-63 um, eluent: hexane-dichloromethane = 10: 1, volume). A white solid with a yield of 112 g (70%). ¹ H NMR (CDCl ₃ , 400 MHz): δ 7.68 (dd, J = 1.0, 8.0 Hz, 1 H), 7.42 (dd, J = 1.7, 7.6 Hz, 1 H), 7.37 --7.32 (m, 2 H) ), 7.20 (dt, J = 1.8, 7.7 Hz, 1 H), 7.08 (d, J = 2.5 Hz, 1 H), 4.53 (d, J = 4.6 Hz, 1 H), 4.40 (d, J = 4.6 Hz, 1 H), 3.20 (s, 3 H), 2.23 --2.14 (m, 6 H), 2.10 (br. S., 3 H), 1.86 --1.70 (m, 6 H), 1.33 (s, 9) H). ¹³ C NMR (CDCl ₃ , 100 MHz): δ 151.28, 145.09, 142.09, 141.47, 133.90, 132.93, 132.41, 128.55, 127.06, 126.81, 124.18, 123.87, 98.83, 57.07, 41.31, 37.55, 37.01, 34.60 , 31.49, 29.17.

３，０００ｍＬの乾燥ＴＨＦ中の２２３ｇ（４６２ｍｍｏｌ）の１－（２’－ブロモ－５－（ｔｅｒｔ－ブチル）－２－（メトキシメトキシ）－［１，１’－ビフェニル］－３－イル）アダマンチンの溶液に、ヘキサン中の１９４ｍＬ（４８５ｍｍｏｌ）の２．５Ｍ ⁿＢｕＬｉを－８０℃で２０分間滴加した。反応混合物をこの温度で１時間撹拌し、続いて、１２２ｍＬ（６００ｍｍｏｌ）の２－イソプロポキシ－４，４，５，５－テトラメチル－１，３，２－ジオキサボロランを加えた。得られた懸濁液を室温で１時間撹拌し、次いで、３００ｍＬの水に注いだ。得られた混合物を約１リットルまで蒸発させ、粗生成物をジクロロメタン（３×３００ｍＬ）で抽出し、合わせた有機抽出物をＮａ₂ＳＯ₄で乾燥し、次いで、蒸発乾固した。収量２４０．９ｇ（定量的）の白色固体。¹H NMR (CDCl₃, 400 MHz): δ 7.75 (d, J = 7.3 Hz, 1 H), 7.44 - 7.36 (m, 1 H), 7.36 - 7.30 (m, 2 H), 7.30 - 7.26 (m, 1 H), 6.96 (d, J = 2.4 Hz, 1 H), 4.53 (d, J = 4.7 Hz, 1 H), 4.37 (d, J = 4.7 Hz, 1 H), 3.22 (s, 3 H), 2.26 - 2.14 (m, 6 H), 2.09 (br. s., 3 H), 1.85 - 1.71 (m, 6 H), 1.30 (s, 9 H), 1.15 (s, 6 H), 1.10 (s, 6 H). ¹³C NMR (CDCl₃, 100 MHz): δ 151.35, 146.48, 144.32, 141.26, 136.15, 134.38, 130.44, 129.78, 126.75, 126.04, 123.13, 98.60, 83.32, 57.08, 41.50, 37.51, 37.09, 34.49, 31.57, 29.26, 24.92, 24.21. 2- (3'-(adamantane-1-yl) -5'-(tert-butyl) -2'-(methoxymethoxy)-[1,1'-biphenyl] -2-yl) -4,4,5 , 5-Tetramethyl-1,3,2-dioxaborolane

223 g (462 mmol) 1- (2'-bromo-5- (tert-butyl) -2- (methoxymethoxy)-[1,1'-biphenyl] -3-yl) adamantin in 3,000 mL dry THF To the solution of, 194 mL (485 mmol) of 2.5 M ⁿ BuLi in hexane was added dropwise at −80 ° C. for 20 minutes. The reaction mixture was stirred at this temperature for 1 hour, followed by the addition of 122 mL (600 mmol) 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane. The resulting suspension was stirred at room temperature for 1 hour and then poured into 300 mL of water. The resulting mixture was evaporated to about 1 liter, the crude product was extracted with dichloromethane (3 x 300 mL), the combined organic extracts were dried over Na ₂ SO ₄ , and then evaporated to dryness. A white solid with a yield of 240.9 g (quantitative). ¹ H NMR (CDCl ₃ , 400 MHz): δ 7.75 (d, J = 7.3 Hz, 1 H), 7.44 --7.36 (m, 1 H), 7.36 --7.30 (m, 2 H), 7.30 --7.26 (m) , 1 H), 6.96 (d, J = 2.4 Hz, 1 H), 4.53 (d, J = 4.7 Hz, 1 H), 4.37 (d, J = 4.7 Hz, 1 H), 3.22 (s, 3 H) ), 2.26 --2.14 (m, 6 H), 2.09 (br. S., 3 H), 1.85 --1.71 (m, 6 H), 1.30 (s, 9 H), 1.15 (s, 6 H), 1.10 (s, 6 H). ¹³ C NMR (CDCl ₃ , 100 MHz): δ 151.35, 146.48, 144.32, 141.26, 136.15, 134.38, 130.44, 129.78, 126.75, 126.04, 123.13, 98.60, 83.32, 57.08, 41.50, 37.51 , 37.09, 34.49, 31.57, 29.26, 24.92, 24.21.

４０ｍＬのジオキサン中の２．００ｇ（３．７７ｍｍｏｌ）の２－（３’－（アダマンタン－１－イル）－５’－（ｔｅｒｔ－ブチル）－２’－（メトキシメトキシ）－［１，１’－ビフェニル］－２－イル）－４，４，５，５－テトラメチル－１，３，２－ジオキサボロランの溶液に、５０３ｍｇ（１．８８ｍｍｏｌ）の２，６－ジブロモ－４－メトキシピリジン、３．０７ｇ（９．４２ｍｍｏｌ）の炭酸セシウムおよび２０ｍＬの水を続いて加えた。得られた混合物をアルゴンで１０分間パージし、続いて、４４０ｍｇ（０．３８０ｍｍｏｌ）のＰｄ（ＰＰｈ₃）₄を加えた。この混合物を１００℃で１２時間撹拌し、次いで、室温まで冷却し、５０ｍＬの水で希釈した。こうして得られた混合物をジクロロメタン（３×５０ｍＬ）で抽出し、合わせた有機抽出物をＮａ₂ＳＯ₄で乾燥し、次いで、蒸発乾固した。得られた油に、５０ｍＬのＴＨＦ、５０ｍＬのメタノールおよび３ｍＬの１２Ｎ ＨＣｌを続いて加えた。反応混合物を６０℃で一晩撹拌し、次いで、２００ｍＬの水に注いだ。粗生成物をジクロロメタン（３×７０ｍＬ）で抽出し、合わせた有機抽出物を５％ ＮａＨＣＯ₃で洗浄し、Ｎａ₂ＳＯ₄で乾燥し、次いで、蒸発乾固した。残留物をシリカゲル６０によるフラッシュクロマトグラフィー（４０～６３ｕｍ、溶離液：ヘキサン－酢酸エチル＝１０：１、体積）により精製した。収量１．３３ｇ（８６％）の白色泡としての２種の異性体の混合物。¹H NMR (CDCl₃, 400 MHz): δ 8.31および7.13 (2s, 2H), 7.37 - 7.60 (m, 8H), 7.09 - 7.11 (m, 2H), 6.55および6.98 (2m, 2H), 6.50および6.42 (2s, 2H), 3.37および+ 3.36 (2s, 3H), 1.87 - 2.00 (m, 18H), 1.60 - 1.69 (m, 12H), 1.21および1.00 (2s, 18H). ¹³C NMR (CDCl₃, 100 MHz) δ 165.87, 159.18, 149.98, 141.89, 139.42, 137.80, 137.42, 131.50, 130.81, 129.86, 129.05, 127.75, 126.53, 122.80, 108.97, 55.12, 40.57, 40.32, 37.07, 37.01, 34.02, 31.58, 31.46, 29.11, 29.02. 2', 2'''-(4-Methoxypyridin-2,6-diyl) bis (3-((3r, 5r, 7r) -adamantan-1-yl) -5- (tert-butyl)-[1 , 1'-biphenyl] -2-ol)

2.00 g (3.77 mmol) 2- (3'-(adamantan-1-yl) -5'-(tert-butyl) -2'-(methoxymethoxy)-[1,1'" in 40 mL of dioxane -Biphenyl] -2-yl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane in a solution of 503 mg (1.88 mmol) of 2,6-dibromo-4-methoxypyridine, 3 .07 g (9.42 mmol) of cesium carbonate and 20 mL of water were subsequently added. The resulting mixture was purged with argon for 10 minutes, followed by the addition of 440 mg (0.380 mmol) of Pd (PPh ₃ ) ₄ . The mixture was stirred at 100 ° C. for 12 hours, then cooled to room temperature and diluted with 50 mL of water. The mixture thus obtained was extracted with dichloromethane (3 x 50 mL) and the combined organic extracts were dried over Na ₂ SO ₄ and then evaporated to dryness. 50 mL of THF, 50 mL of methanol and 3 mL of 12N HCl were subsequently added to the resulting oil. The reaction mixture was stirred at 60 ° C. overnight and then poured into 200 mL of water. The crude product was extracted with dichloromethane (3 x 70 mL) and the combined organic extracts were washed with 5% NaHCO ₃ and dried over Na ₂ SO ₄ and then evaporated to dryness. The residue was purified by flash chromatography on silica gel 60 (40-63 um, eluent: hexane-ethyl acetate = 10: 1, volume). A mixture of the two isomers as a white foam with a yield of 1.33 g (86%). ¹ H NMR (CDCl ₃ , 400 MHz): δ 8.31 and 7.13 (2s, 2H), 7.37 --7.60 (m, 8H), 7.09 --7.11 (m, 2H), 6.55 and 6.98 (2m, 2H), 6.50 and 6.42 (2s, 2H), 3.37 and + 3.36 (2s, 3H), 1.87 --2.00 (m, 18H), 1.60 --1.69 (m, 12H), 1.21 and 1.00 (2s, 18H). ¹³ C NMR (CDCl ₃ ) , 100 MHz) δ 165.87, 159.18, 149.98, 141.89, 139.42, 137.80, 137.42, 131.50, 130.81, 129.86, 129.05, 127.75, 126.53, 122.80, 108.97, 55.12, 40.57, 40.32, 37.07, 37.01, 34.02, 31. , 29.11, 29.02.

４０ｍＬのジオキサン中の２．００ｇ（３．７７ｍｍｏｌ）の２－（３’－（アダマンタン－１－イル）－５’－（ｔｅｒｔ－ブチル）－２’－（メトキシメトキシ）－［１，１’－ビフェニル］－２－イル）－４，４，５，５－テトラメチル－１，３，２－ジオキサボロランの溶液に、４０６ｍｇ（１．８８ｍｍｏｌ）の２，６－ジクロロ－４－トリフルオロメチルピリジン、３．０７ｇ（９．４２ｍｍｏｌ）の炭酸セシウムおよび２０ｍＬの水を続いて加えた。得られた混合物をアルゴンで１０分間パージし、続いて、４４０ｍｇ（０．３８０ｍｍｏｌ）のＰｄ（ＰＰｈ₃）₄を加えた。この混合物を１００℃で１２時間撹拌し、次いで、室温まで冷却し、５０ｍＬの水で希釈した。こうして得られた混合物をジクロロメタン（３×５０ｍＬ）で抽出し、合わせた有機抽出物をＮａ₂ＳＯ₄で乾燥し、次いで、蒸発乾固した。得られた油に、５０ｍＬのＴＨＦ、５０ｍＬのメタノールおよび３ｍＬの１２Ｎ ＨＣｌを続いて加えた。反応混合物を６０℃で一晩撹拌し、次いで、２００ｍＬの水に注いだ。粗生成物をジクロロメタン（３×７０ｍＬ）で抽出し、合わせた有機抽出物を５％ ＮａＨＣＯ₃で洗浄し、Ｎａ₂ＳＯ₄で乾燥し、次いで、蒸発乾固した。残留物をシリカゲル６０によるフラッシュクロマトグラフィー（４０～６３ｕｍ、溶離液：ヘキサン－酢酸エチル＝１０：１、体積）により精製した。収量１．３１ｇ（８３％）の白色泡としての２種の異性体の混合物。¹H NMR (CDCl₃, 400 MHz): δ 7.40 - 7.55 (m, 8H), 7.04 - 7.14 + 5.62 (2m, 6H), 6.86 + 6.56 (2d, J = 2.4 Hz, 2H), 1.90 - 2.02 (m, 18H), 1.60 - 1.74 (m, 12H), 1.16 + 1.01 (2s, 18H). ¹³C NMR (CDCl₃, 100 MHz) δ 159.29, 159.09, 149.57, 148.84, 142.43, 142.33, 139.45, 138.78, 138.45, 137.60, 137.22, 136.72, 136.24, 131.62, 131.51, 130.76, 130.52, 129.76, 129.71, 128.53, 128.39, 128.16, 127.42, 126.03, 125.28, 123.46, 123.34, 118.20 (q, Jc,_F = 3.5 Hz), 40.45, 40.34, 37.07, 37.03, 34.21, 34.06, 31.45, 31.42, 29.11, 29.06. 2', 2'''-(4- (trifluoromethyl) pyridine-2,6-diyl) bis (3-((3r, 5r, 7r) -adamantane-1-yl) -5- (tert-butyl) )-[1,1'-biphenyl] -2-ol)

2.00 g (3.77 mmol) 2- (3'-(adamantan-1-yl) -5'-(tert-butyl) -2'-(methoxymethoxy)-[1,1'" in 40 mL of dioxane -Biphenyl] -2-yl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane in a solution of 406 mg (1.88 mmol) of 2,6-dichloro-4-trifluoromethylpyridine , 3.07 g (9.42 mmol) of cesium carbonate and 20 mL of water were subsequently added. The resulting mixture was purged with argon for 10 minutes, followed by the addition of 440 mg (0.380 mmol) of Pd (PPh ₃ ) ₄ . The mixture was stirred at 100 ° C. for 12 hours, then cooled to room temperature and diluted with 50 mL of water. The mixture thus obtained was extracted with dichloromethane (3 x 50 mL) and the combined organic extracts were dried over Na ₂ SO ₄ and then evaporated to dryness. 50 mL of THF, 50 mL of methanol and 3 mL of 12N HCl were subsequently added to the resulting oil. The reaction mixture was stirred at 60 ° C. overnight and then poured into 200 mL of water. The crude product was extracted with dichloromethane (3 x 70 mL) and the combined organic extracts were washed with 5% NaHCO ₃ and dried over Na ₂ SO ₄ and then evaporated to dryness. The residue was purified by flash chromatography on silica gel 60 (40-63 um, eluent: hexane-ethyl acetate = 10: 1, volume). A mixture of the two isomers as a white foam with a yield of 1.31 g (83%). ¹ H NMR (CDCl ₃ , 400 MHz): δ 7.40 --7.55 (m, 8H), 7.04 --7.14 + 5.62 (2m, 6H), 6.86 + 6.56 (2d, J = 2.4 Hz, 2H), 1.90 --2.02 ( m, 18H), 1.60 --1.74 (m, 12H), 1.16 + 1.01 (2s, 18H). ¹³ C NMR (CDCl ₃ , 100 MHz) δ 159.29, 159.09, 149.57, 148.84, 142.43, 142.33, 139.45, 138.78, 138.45, 137.60, 137.22, 136.72, 136.24, 131.62, 131.51, 130.76, 130.52, 129.76, 129.71, 128.53, 128.39, 128.16, 127.42, 126.03, 125.28, 123.46, 123.34, 118.20 (q, Jc, _F = 3.5 Hz), 40.45, 40.34, 37.07, 37.03, 34.21, 34.06, 31.45, 31.42, 29.11, 29.06.

１００ｍＬの１，４－ジオキサン中の１０．０ｇ（２２．０ｍｍｏｌ）の２－（３－アダマンタン－１－イル）－５－（ｔｅｒｔ－ブチル）－２－（メトキシメトキシ）フェニル）－４，４，５，５－テトラメチル－１，３，２－ジオキサボロランの溶液に、６．８３ｇ（２３．０ｍｍｏｌ）の２－ブロモ－４－メチルヨードベンゼン、７．６０ｇ（５５．０ｍｍｏｌ）の炭酸カリウムおよび５０ｍＬの水を続いて加えた。得られた混合物をアルゴンで１０分間パージし、続いて、１．２７ｇ（１．１０ｍｍｏｌ）のＰｄ（ＰＰｈ₃）₄を加えた。この混合物を１００℃で１２時間撹拌し、次いで、室温まで冷却し、１００ｍＬの水で希釈した。粗生成物をジクロロメタン（３×１５０ｍＬ）で抽出し、合わせた有機抽出物をＮａ₂ＳＯ₄で乾燥し、次いで、蒸発乾固した。残留物をシリカゲル６０によるフラッシュクロマトグラフィー（４０～６３ｕｍ、溶離液：ヘキサン－ジクロロメタン＝１０：１、体積）により精製した。収量８．７７ｇ（８０％）の白色固体。¹H NMR (CDCl₃, 400 MHz): δ 7.56 (m, 1H), 7.32 - 7.39 (m, 2H), 7.19 (d, J = 7.8 Hz, 1H), 7.11 (d, J = 2.5 Hz, 1H), 4.59 (m, 1H), 4.47 (m, 1H), 3.29 (s, 3H), 2.41 (s, 3H), 2.25 (m, 6H), 2.15 (m, 3H), 1.84 (m, 6H), 1.37 (s, 9H). ¹³C NMR (CDCl₃, 100 MHz): δ 151.48, 144.93, 141.94, 138.66, 138.46, 133.66, 133.32, 132.02, 127.90, 127.02, 123.82, 123.66, 98.75, 57.09, 41.30, 37.53, 37.04, 34.56, 31.48, 29.19, 20.76. (3r, 5r, 7r) -1- (2'-bromo-5- (tert-butyl) -2- (methoxymethoxy) -4'-methyl- [1,1'-biphenyl] -3-yl) adamantane

10.0 g (22.0 mmol) 2- (3-adamantan-1-yl) -5- (tert-butyl) -2- (methoxymethoxy) phenyl) -4,4 in 100 mL of 1,4-dioxane , 5,5-Tetramethyl-1,3,2-dioxaborolane in a solution of 6.83 g (23.0 mmol) 2-bromo-4-methyliodobenzene, 7.60 g (55.0 mmol) potassium carbonate and 50 mL of water was subsequently added. The resulting mixture was purged with argon for 10 minutes, followed by the addition of 1.27 g (1.10 mmol) of Pd (PPh ₃ ) ₄ . The mixture was stirred at 100 ° C. for 12 hours, then cooled to room temperature and diluted with 100 mL of water. The crude product was extracted with dichloromethane (3 x 150 mL) and the combined organic extracts were dried over Na ₂ SO ₄ and then evaporated to dryness. The residue was purified by flash chromatography on silica gel 60 (40-63 um, eluent: hexane-dichloromethane = 10: 1, volume). A white solid with a yield of 8.77 g (80%). ¹ H NMR (CDCl ₃ , 400 MHz): δ 7.56 (m, 1H), 7.32 --7.39 (m, 2H), 7.19 (d, J = 7.8 Hz, 1H), 7.11 (d, J = 2.5 Hz, 1H) ), 4.59 (m, 1H), 4.47 (m, 1H), 3.29 (s, 3H), 2.41 (s, 3H), 2.25 (m, 6H), 2.15 (m, 3H), 1.84 (m, 6H) , 1.37 (s, 9H). ¹³ C NMR (CDCl ₃ , 100 MHz): δ 151.48, 144.93, 141.94, 138.66, 138.46, 133.66, 133.32, 132.02, 127.90, 127.02, 123.82, 123.66, 98.75, 57.09, 41.30, 37.53, 37.04, 34.56, 31.48, 29.19, 20.76.

１２０ｍＬの乾燥ＴＨＦ中の８．７５ｇ（１７．６ｍｍｏｌ）の（３ｒ，５ｒ，７ｒ）－１－（２’－ブロモ－５－（ｔｅｒｔ－ブチル）－２－（メトキシメトキシ）－４’－メチル－［１，１’－ビフェニル］－３－イル）アダマンタンの溶液に、ヘキサン中の８．４４ｍＬ（２１．１ｍｍｏｌ）の２．５Ｍ ⁿＢｕＬｉを－８０℃で２０分間滴加した。反応混合物をこの温度で１時間撹拌し、続いて、６．１２ｍＬ（３０．０ｍｍｏｌ）の２－イソプロポキシ－４，４，５，５－テトラメチル－１，３，２－ジオキサボロランを加えた。得られた懸濁液を室温で１時間撹拌し、次いで、３００ｍＬの水に注いだ。粗生成物をジクロロメタン（３×３００ｍＬ）で抽出し、合わせた有機抽出物をＮａ₂ＳＯ₄で乾燥し、次いで、蒸発乾固した。残留物を２０ｍＬの熱イソプロパノールから再結晶させ、得られた結晶性材料を濾別（Ｇ３）し、５ｍＬの冷イソプロパノールで洗浄し、真空中で乾燥した。収量４．９０ｇ（５１％）の白色結晶。¹H NMR (CDCl₃, 400 MHz): δ 8.07 (d, J = 8.3 Hz, 1H), 8.03 (d, J = 2.0 Hz, 1H), 7.87 (m, 1H), 7.46 (d, J = 8.2 Hz, 1H), 7.40 (d, J = 2.0 Hz, 1H), 5.25 (七重線, J = 6.1 Hz, 1H), 2.46 (s, 3H), 2.30 (m, 6H), 2.16 (m, 3H), 1.85 (m, 6H), 1.42 (s, 9H), 1.42 (d, J = 6.0 Hz, 6H). ¹³C NMR (CDCl₃, 100 MHz): δ 147.99, 143.84, 138.75, 138.38, 136.14, 133.08, 132.97, 123.55, 122.32, 121.59, 117.90, 65.66, 40.77, 37.45, 37.19, 34.75, 31.67, 29.17, 24.74, 21.21. 4-((3r, 5r, 7r) -adamantane-1-yl) -2- (tert-butyl) -6-isopropoxy-8-methyl-6H-dibenzo [c, e] [1,2] oxabolinine

8.75 g (17.6 mmol) of (3r, 5r, 7r) -1- (2'-bromo-5- (tert-butyl) -2- (methoxymethoxy) -4'-methyl in 120 mL of dry THF To a solution of-[1,1'-biphenyl] -3-yl) adamantane was added 8.44 mL (21.1 mmol) of 2.5 M ⁿ BuLi in hexanes at −80 ° C. for 20 minutes. The reaction mixture was stirred at this temperature for 1 hour, followed by the addition of 6.12 mL (30.0 mmol) 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane. The resulting suspension was stirred at room temperature for 1 hour and then poured into 300 mL of water. The crude product was extracted with dichloromethane (3 x 300 mL) and the combined organic extracts were dried over Na ₂ SO ₄ and then evaporated to dryness. The residue was recrystallized from 20 mL of hot isopropanol, the resulting crystalline material was filtered off (G3), washed with 5 mL of cold isopropanol and dried in vacuo. White crystals with a yield of 4.90 g (51%). ¹ H NMR (CDCl ₃ , 400 MHz): δ 8.07 (d, J = 8.3 Hz, 1H), 8.03 (d, J = 2.0 Hz, 1H), 7.87 (m, 1H), 7.46 (d, J = 8.2) Hz, 1H), 7.40 (d, J = 2.0 Hz, 1H), 5.25 (seven-fold line, J = 6.1 Hz, 1H), 2.46 (s, 3H), 2.30 (m, 6H), 2.16 (m, 3H) , 1.85 (m, 6H), 1.42 (s, 9H), 1.42 (d, J = 6.0 Hz, 6H). ¹³ C NMR (CDCl ₃ , 100 MHz): δ 147.99, 143.84, 138.75, 138.38, 136.14, 133.08 , 132.97, 123.55, 122.32, 121.59, 117.90, 65.66, 40.77, 37.45, 37.19, 34.75, 31.67, 29.17, 24.74, 21.21.

４０ｍＬの１，４－ジオキサン中の１．６０ｇ（３．６２ｍｍｏｌ）の４－（（３ｒ，５ｒ，７ｒ）－アダマンタン－１－イル）－２－（ｔｅｒｔ－ブチル）－６－イソプロポキシ－８－メチル－６Ｈ－ジベンゾ［ｃ，ｅ］［１，２］オキサボリニンの溶液に、４２９ｍｇ（１．８１ｍｍｏｌ）の２，６－ジブロモピリジン、２．９５ｇ（９．１０ｍｍｏｌ）の炭酸セシウムおよび２０ｍＬの水を続いて加えた。得られた混合物をアルゴンで１０分間パージし、続いて、２１０ｍｇ（０．１８０ｍｍｏｌ）のＰｄ（ＰＰｈ₃）₄を加えた。この混合物を１００℃で１２時間撹拌し、次いで、室温まで冷却し、５０ｍＬの水で希釈した。粗生成物をジクロロメタン（３×５０ｍＬ）で抽出し、合わせた有機抽出物をＮａ₂ＳＯ₄で乾燥し、次いで、蒸発乾固した。残留物をシリカゲル６０によるフラッシュクロマトグラフィー（４０～６３ｕｍ、溶離液：ヘキサン－酢酸エチル＝１０：１、体積）により精製した。収量１．１１ｇ（７４％）の白色泡としての２種の異性体の混合物。¹H NMR (CDCl₃, 400 MHz): δ 8.15 + 6.81 (2s, 2H), 7.31 - 7.40 (m, 3H), 7.21 - 7.24 (m, 2H), 6.90 - 7.03 + 6.49 (2m, 6H), 2.42 + 2.41 (2s, 6H), 1.73 - 2.06 (m, 18H), 1.60 - 1.67 (m, 12H), 1.13 + 0.97 (2s, 18H). ¹³C NMR (CDCl₃, 100 MHz) δ 157.96, 157.77, 150.22, 149.45, 141.67, 139.30, 137.45, 137.40, 136.71, 135.04, 131.60, 131.43, 130.82, 129.84, 129.64, 126.50, 125.77, 122.58, 122.42, 40.52, 40.39, 37.11, 37.03, 36.85, 33.99, 31.48, 29.19, 29.11, 21.14. 2', 2'''-(pyridin-2,6-diyl) bis (3-((3r, 5r, 7r) -adamantan-1-yl) -5- (tert-butyl) -4'-methyl- [1,1'-biphenyl] -2-ol)

1.60 g (3.62 mmol) 4-((3r, 5r, 7r) -adamantan-1-yl) -2- (tert-butyl) -6-isopropoxy-8 in 40 mL of 1,4-dioxane -Methyl-6H-dibenzo [c, e] [1,2] oxabolinine solution with 429 mg (1.81 mmol) of 2,6-dibromopyridine, 2.95 g (9.10 mmol) of cesium carbonate and 20 mL of water. Was subsequently added. The resulting mixture was purged with argon for 10 minutes, followed by the addition of 210 mg (0.180 mmol) of Pd (PPh ₃ ) ₄ . The mixture was stirred at 100 ° C. for 12 hours, then cooled to room temperature and diluted with 50 mL of water. The crude product was extracted with dichloromethane (3 x 50 mL) and the combined organic extracts were dried over Na ₂ SO ₄ and then evaporated to dryness. The residue was purified by flash chromatography on silica gel 60 (40-63 um, eluent: hexane-ethyl acetate = 10: 1, volume). A mixture of the two isomers as a white foam with a yield of 1.11 g (74%). ¹ H NMR (CDCl ₃ , 400 MHz): δ 8.15 + 6.81 (2s, 2H), 7.31 --7.74 (m, 3H), 7.21 --7.24 (m, 2H), 6.90 --7.03 + 6.49 (2m, 6H), 2.42 + 2.41 (2s, 6H), 1.73 --2.06 (m, 18H), 1.60 --1.67 (m, 12H), 1.13 + 0.97 (2s, 18H). ¹³ C NMR (CDCl ₃ , 100 MHz) δ 157.96, 157.77 , 150.22, 149.45, 141.67, 139.30, 137.45, 137.40, 136.71, 135.04, 131.60, 131.43, 130.82, 129.84, 129.64, 126.50, 125.77, 122.58, 122.42, 40.52, 40.39, 37.11, 37.03, 36.85, 33.99 , 29.11, 21.14.

４０ｍＬの１，４－ジオキサン中の１．６０ｇ（３．６２ｍｍｏｌ）の４－（（３ｒ，５ｒ，７ｒ）－アダマンタン－１－イル）－２－（ｔｅｒｔ－ブチル）－６－イソプロポキシ－８－メチル－６Ｈ－ジベンゾ［ｃ，ｅ］［１，２］オキサボリニンの溶液に、３９１ｍｇ（１．８１ｍｍｏｌ）の２，６－ジクロロ－４－トリフルオロメチルピリジン、２．９５ｇ（９．１０ｍｍｏｌ）の炭酸セシウムおよび２０ｍＬの水を続いて加えた。得られた混合物をアルゴンで１０分間パージし、続いて、２１０ｍｇ（０．１８０ｍｍｏｌ）のＰｄ（ＰＰｈ₃）₄を加えた。この混合物を１００℃で１２時間撹拌し、次いで、室温まで冷却し、５０ｍＬの水で希釈した。粗生成物をジクロロメタン（３×５０ｍＬ）で抽出し、合わせた有機抽出物をＮａ₂ＳＯ₄で乾燥し、次いで、蒸発乾固した。残留物をシリカゲル６０によるフラッシュクロマトグラフィー（４０～６３ｕｍ、溶離液：ヘキサン－酢酸エチル＝１０：１、体積）により精製した。収量１．０１ｇ（６２％）の白色泡としての２種の異性体の混合物。¹H NMR (CDCl₃, 400 MHz): δ 7.44および5.97 (2s, 2H), 7.34 - 7.38 (m, 6H), 7.12 (d, J = 2.4 Hz, 2H), 7.07 (s, 2H), 6.92および6.56 (2m, 2H), 2.49および2.48 (2s, 6H), 1.85 - 2.04 (m, 18H), 1.65 - 1.75 (m, 12H), 1.18および1.03 (s, 18H). ¹³C NMR (CDCl₃, 100 MHz) δ 159.41, 159.19, 149.81, 149.80, 149.05, 142.20, 142.16, 139.08, 138.70, 138.57, 138.37, 138.10, 138.01, 137.26, 136.25, 134.77, 134.03, 131.51, 131.27, 130.91, 130.49, 130.41, 128.66, 127.64, 126.17, 125.43, 123.69, 123.31, 123.12, 118.23 (q, Jc,_F = 3.8 Hz), 117.88 (q, Jc,_F = 3.8 Hz), 40.47, 40.34, 37.08, 37.06, 34.02, 31.42, 29.17, 29.08, 26.91, 21.14. 2', 2'''-(4- (trifluoromethyl) pyridine-2,6-diyl) bis (3-((3r, 5r, 7r) -adamantane-1-yl) -5- (tert-butyl) ) -4'-Methyl- [1,1'-biphenyl] -2-ol)

1.60 g (3.62 mmol) 4-((3r, 5r, 7r) -adamantan-1-yl) -2- (tert-butyl) -6-isopropoxy-8 in 40 mL of 1,4-dioxane In a solution of -methyl-6H-dibenzo [c, e] [1,2] oxabolinine, 391 mg (1.81 mmol) of 2,6-dichloro-4-trifluoromethylpyridine, 2.95 g (9.10 mmol). Cesium carbonate and 20 mL of water were subsequently added. The resulting mixture was purged with argon for 10 minutes, followed by the addition of 210 mg (0.180 mmol) of Pd (PPh ₃ ) ₄ . The mixture was stirred at 100 ° C. for 12 hours, then cooled to room temperature and diluted with 50 mL of water. The crude product was extracted with dichloromethane (3 x 50 mL) and the combined organic extracts were dried over Na ₂ SO ₄ and then evaporated to dryness. The residue was purified by flash chromatography on silica gel 60 (40-63 um, eluent: hexane-ethyl acetate = 10: 1, volume). A mixture of the two isomers as white foam with a yield of 1.01 g (62%). ¹ H NMR (CDCl ₃ , 400 MHz): δ 7.44 and 5.97 (2s, 2H), 7.34 --7.38 (m, 6H), 7.12 (d, J = 2.4 Hz, 2H), 7.07 (s, 2H), 6.92 And 6.56 (2m, 2H), 2.49 and 2.48 (2s, 6H), 1.85 --2.04 (m, 18H), 1.65 --1.75 (m, 12H), 1.18 and 1.03 (s, 18H). ¹³ C NMR (CDCl ₃ ) , 100 MHz) δ 159.41, 159.19, 149.81, 149.80, 149.05, 142.20, 142.16, 139.08, 138.70, 138.57, 138.37, 138.10, 138.01, 137.26, 136.25, 134.77, 134.03, 131.51, 131.27, 130.91, 130.49, 130. , 127.64, 126.17, 125.43, 123.69, 123.31, 123.12, 118.23 (q, Jc, _F = 3.8 Hz), 117.88 (q, Jc, _F = 3.8 Hz), 40.47, 40.34, 37.08, 37.06, 34.02, 31.42, 29.17 , 29.08, 26.91, 21.14.

４０ｍＬの１，４－ジオキサン中の１．６０ｇ（３．６２ｍｍｏｌ）の４－（（３ｒ，５ｒ，７ｒ）－アダマンタン－１－イル）－２－（ｔｅｒｔ－ブチル）－６－イソプロポキシ－８－メチル－６Ｈ－ジベンゾ［ｃ，ｅ］［１，２］オキサボリニンの溶液に、４８３ｍｇ（１．８１ｍｍｏｌ）の２，６－ジブロモ－４－メトキシピリジン、２．９５ｇ（９．１０ｍｍｏｌ）の炭酸セシウムおよび２０ｍＬの水を続いて加えた。得られた混合物をアルゴンで１０分間パージし、続いて、２１０ｍｇ（０．１８０ｍｍｏｌ）のＰｄ（ＰＰｈ₃）₄を加えた。この混合物を１００℃で１２時間撹拌し、次いで、室温まで冷却し、５０ｍＬの水で希釈した。粗生成物をジクロロメタン（３×５０ｍＬ）で抽出し、合わせた有機抽出物をＮａ₂ＳＯ₄で乾燥し、次いで、蒸発乾固した。残留物をシリカゲル６０によるフラッシュクロマトグラフィー（４０～６３ｕｍ、溶離液：ヘキサン－酢酸エチル＝１０：１、体積）により精製した。収量９１０ｍｇ（５８％）の白色泡としての２種の異性体の混合物。¹H NMR (CDCl₃, 400 MHz): δ 8.39 + 6.52 (2s, 2H), 7.25 - 7.45 (m, 7H), 7.00 - 7.12 (m, 2H), 6.42 - 6.56 (m, 3H), 3.41 + 3.38 (2s, 3H), 2.47 (s, 6H), 1.87 - 2.02 (m, 18H), 1.62 - 1.75 (m, 12H), 1.24 + 1.02 (2s, 18H). ¹³C NMR (CDCl₃, 100 MHz) δ 165.79, 159.28, 159.22, 150.13, 149.66, 141.90, 141.78, 139.28, 138.72, 137.54, 137.36, 136.77, 134.89, 134.80, 132.26, 131.39, 131.37, 130.94, 130.08, 129.87, 129.75, 129.34, 126.60, 125.60, 123.01, 122.58, 108.92, 108.34, 55.09, 54.73, 40.61, 40.35, 37.08, 37.07, 36.87, 34.22, 33.99, 31.56, 31.46, 29.19, 29.07, 26.90, 22.65, 21.15. 2', 2'''-(4-Methoxypyridin-2,6-diyl) bis (3-((3r, 5r, 7r) -adamantan-1-yl) -5- (tert-butyl) -4' -Methyl- [1,1'-biphenyl] -2-ol)

1.60 g (3.62 mmol) 4-((3r, 5r, 7r) -adamantan-1-yl) -2- (tert-butyl) -6-isopropoxy-8 in 40 mL of 1,4-dioxane In a solution of -methyl-6H-dibenzo [c, e] [1,2] oxabolinine, 483 mg (1.81 mmol) of 2,6-dibromo-4-methoxypyridine and 2.95 g (9.10 mmol) of cesium carbonate. And 20 mL of water was subsequently added. The resulting mixture was purged with argon for 10 minutes, followed by the addition of 210 mg (0.180 mmol) of Pd (PPh ₃ ) ₄ . The mixture was stirred at 100 ° C. for 12 hours, then cooled to room temperature and diluted with 50 mL of water. The crude product was extracted with dichloromethane (3 x 50 mL) and the combined organic extracts were dried over Na ₂ SO ₄ and then evaporated to dryness. The residue was purified by flash chromatography on silica gel 60 (40-63 um, eluent: hexane-ethyl acetate = 10: 1, volume). A mixture of the two isomers as a white foam with a yield of 910 mg (58%). ¹ H NMR (CDCl ₃ , 400 MHz): δ 8.39 + 6.52 (2s, 2H), 7.25 --7.75 (m, 7H), 7.00 --7.12 (m, 2H), 6.42 --6.56 (m, 3H), 3.41 + 3.38 (2s, 3H), 2.47 (s, 6H), 1.87 --2.02 (m, 18H), 1.62 --1.75 (m, 12H), 1.24 + 1.02 (2s, 18H). ¹³ C NMR (CDCl ₃ , 100 MHz) ) δ 165.79, 159.28, 159.22, 150.13, 149.66, 141.90, 141.78, 139.28, 138.72, 137.54, 137.36, 136.77, 134.89, 134.80, 132.26, 131.39, 131.37, 130.94, 130.08, 129.87, 129.75, 129.34 123.01, 122.58, 108.92, 108.34, 55.09, 54.73, 40.61, 40.35, 37.08, 37.07, 36.87, 34.22, 33.99, 31.56, 31.46, 29.19, 29.07, 26.90, 22.65, 21.15.

１００ｍＬの１，４－ジオキサン中の１０．０ｇ（２２．０ｍｍｏｌ）の２－（３－アダマンタン－１－イル）－５－（ｔｅｒｔ－ブチル）－２－（メトキシメトキシ）フェニル）－４，４，５，５－テトラメチル－１，３，２－ジオキサボロランの溶液に、６．８３ｇ（２３．０ｍｍｏｌ）の２－ブロモ－４－イソプロピルヨードベンゼン、７．６０ｇ（５５．０ｍｍｏｌ）の炭酸カリウムおよび５０ｍＬの水を続いて加えた。得られた混合物をアルゴンで１０分間パージし、続いて、１．２７ｇ（１．１０ｍｍｏｌ）のＰｄ（ＰＰｈ₃）₄を加えた。この混合物を１００℃で１２時間撹拌し、次いで、室温まで冷却し、１００ｍＬの水で希釈した。粗生成物をジクロロメタン（３×１５０ｍＬ）で抽出し、合わせた有機抽出物をＮａ₂ＳＯ₄で乾燥し、次いで、蒸発乾固した。残留物をシリカゲル６０によるフラッシュクロマトグラフィー（４０～６３ｕｍ、溶離液：ヘキサン－ジクロロメタン＝１０：１、体積）により精製した。収量１１．５ｇ（９５％）の白色固体。¹H NMR (CDCl₃, 400 MHz): δ 7.53 (d, J = 1.7 Hz, 1H), 7.30 - 7.33 (m, 2H), 7.19 (dd, J = 8.0, 1.7 Hz, 1H), 7.08 (d, J = 2.5 Hz, 1H), 4.52 (m, 1H), 4.39 (m, 1H), 3.18 (s, 3H), 2.92 (七重線, J = 6.9 Hz, 1H), 2.14 - 2.20 (m, 6H), 2.10 (br.s, 3H), 1.74 - 1.84 (m, 6H), 1.32 (s, 9H), 1.28 (d, J = 6.9 Hz, 6H). ¹³C NMR (CDCl₃, 100 MHz): δ 151.35, 149.85, 145.03, 142.04, 138.73, 133.91, 132.21, 130.79, 126.96, 125.33, 124.02, 123.71, 98.76, 57.03, 41.35, 37.57, 37.04, 33.63, 31.50, 29.20, 24.83, 23.90. (3r, 5r, 7r) -1- (2'-bromo-5- (tert-butyl) -4'-isopropyl-2- (methoxymethoxy)-[1,1'-biphenyl] -3-yl) adamantin

10.0 g (22.0 mmol) 2- (3-adamantan-1-yl) -5- (tert-butyl) -2- (methoxymethoxy) phenyl) -4,4 in 100 mL of 1,4-dioxane , 5,5-Tetramethyl-1,3,2-dioxaborolane in a solution of 6.83 g (23.0 mmol) 2-bromo-4-isopropyliodobenzene, 7.60 g (55.0 mmol) potassium carbonate and 50 mL of water was subsequently added. The resulting mixture was purged with argon for 10 minutes, followed by the addition of 1.27 g (1.10 mmol) of Pd (PPh ₃ ) ₄ . The mixture was stirred at 100 ° C. for 12 hours, then cooled to room temperature and diluted with 100 mL of water. The crude product was extracted with dichloromethane (3 x 150 mL) and the combined organic extracts were dried over Na ₂ SO ₄ and then evaporated to dryness. The residue was purified by flash chromatography on silica gel 60 (40-63 um, eluent: hexane-dichloromethane = 10: 1, volume). A white solid with a yield of 11.5 g (95%). ¹ H NMR (CDCl ₃ , 400 MHz): δ 7.53 (d, J = 1.7 Hz, 1H), 7.30 --7.33 (m, 2H), 7.19 (dd, J = 8.0, 1.7 Hz, 1H), 7.08 (d) , J = 2.5 Hz, 1H), 4.52 (m, 1H), 4.39 (m, 1H), 3.18 (s, 3H), 2.92 (7-fold line, J = 6.9 Hz, 1H), 2.14 --2.20 (m, 6H) ), 2.10 (br.s, 3H), 1.74 --1.84 (m, 6H), 1.32 (s, 9H), 1.28 (d, J = 6.9 Hz, 6H). ¹³ C NMR (CDCl ₃ , 100 MHz): δ 151.35, 149.85, 145.03, 142.04, 138.73, 133.91, 132.21, 130.79, 126.96, 125.33, 124.02, 123.71, 98.76, 57.03, 41.35, 37.57, 37.04, 33.63, 31.50, 29.20, 24.83, 23.90.

２００ｍＬの乾燥ＴＨＦ中の１１．３ｇ（２１．５ｍｍｏｌ）の（３ｒ，５ｒ，７ｒ）－１－（２’－ブロモ－５－（ｔｅｒｔ－ブチル）－４’－イソプロピル－２－（メトキシメトキシ）－［１，１’－ビフェニル］－３－イル）アダマンチンの溶液に、ヘキサン中の９．００ｍＬ（２２．６ｍｍｏｌ）の２．５Ｍ ⁿＢｕＬｉを－８０℃で２０分間滴加した。反応混合物をこの温度で１時間撹拌し、続いて、６．９８ｍＬ（３２．２ｍｍｏｌ）の２－イソプロポキシ－４，４，５，５－テトラメチル－１，３，２－ジオキサボロランを加えた。得られた懸濁液を室温で１時間撹拌し、次いで、１００ｍＬの水に注いだ。得られた混合物を約１５０ｍＬまで蒸発させ、次いで、粗生成物をジクロロメタン（３×１００ｍＬ）で抽出した。合わせた有機抽出物をＮａ₂ＳＯ₄で乾燥し、次いで、蒸発乾固した。残留物をシリカゲル６０によるフラッシュクロマトグラフィー（４０～６３ｕｍ、溶離液：ヘキサン－ジエチルエーテル＝１０：１、体積）により精製した。収量６．８０ｇ（５６％）の白色固体。¹H NMR (CDCl₃, 400 MHz): δ 7.57 (s, 1H), 7.24 - 7.28 (m, 3H), 6.97 (d, J = 2.4 Hz, 1H), 4.52 (m, 1H), 4.37 (m, 1H), 3.20 (s, 3H), 2.95 (七重線, J = 6.9 Hz, 1H), 2.17 - 2.21 (m, 6H), 2.09 (br.s, 3H), 1.73 - 1.84 (m, 6H), 1.29 (s, 9H), 1.28 (d, J = 6.9 Hz, 6H), 1.15 (s, 6H), 1.10 (s, 6H). ¹³C NMR (CDCl₃, 100 MHz): δ 151.43, 146.50, 144.22, 143.92, 141.17, 136.17, 132.40, 130.45, 127.73, 126.84, 122.94, 98.52, 83.26, 57.06, 41.50, 37.49, 37.10, 34.48, 33.86, 31.58, 29.26, 24.94, 24.41, 24.13, 24.07. 2- (3'-((3r, 5r, 7r) -adamantane-1-yl) -5'-(tert-butyl) -4-isopropyl-2'-(methoxymethoxy)-[1,1'-biphenyl ] -2-yl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane

11.3 g (21.5 mmol) of (3r, 5r, 7r) -1- (2'-bromo-5- (tert-butyl) -4'-isopropyl-2- (methoxymethoxy) in 200 mL of dry THF -[1,1'-Biphenyl] -3-yl) To a solution of adamantin was added 9.00 mL (22.6 mmol) of 2.5 M ⁿ BuLi in hexanes at −80 ° C. for 20 minutes. The reaction mixture was stirred at this temperature for 1 hour, followed by the addition of 6.98 mL (32.2 mmol) of 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane. The resulting suspension was stirred at room temperature for 1 hour and then poured into 100 mL of water. The resulting mixture was evaporated to about 150 mL and the crude product was then extracted with dichloromethane (3 x 100 mL). The combined organic extracts were dried over Na ₂ SO ₄ and then evaporated to dryness. The residue was purified by flash chromatography on silica gel 60 (40-63 um, eluent: hexane-diethyl ether = 10: 1, volume). A white solid with a yield of 6.80 g (56%). ¹ H NMR (CDCl ₃ , 400 MHz): δ 7.57 (s, 1H), 7.24 --7.28 (m, 3H), 6.97 (d, J = 2.4 Hz, 1H), 4.52 (m, 1H), 4.37 (m) , 1H), 3.20 (s, 3H), 2.95 (7-fold line, J = 6.9 Hz, 1H), 2.17 --2.21 (m, 6H), 2.09 (br.s, 3H), 1.73 --1.84 (m, 6H) , 1.29 (s, 9H), 1.28 (d, J = 6.9 Hz, 6H), 1.15 (s, 6H), 1.10 (s, 6H). ¹³ C NMR (CDCl ₃ , 100 MHz): δ 151.43, 146.50, 144.22, 143.92, 141.17, 136.17, 132.40, 130.45, 127.73, 126.84, 122.94, 98.52, 83.26, 57.06, 41.50, 37.49, 37.10, 34.48, 33.86, 31.58, 29.26, 24.94, 24.41, 24.13, 24.07.

４０ｍＬの１，４－ジオキサン中の３．２０ｇ（５．６６ｍｍｏｌ）の２－（３’－（アダマンタン－１－イル）－５’－（ｔｅｒｔ－ブチル）－２’－（メトキシメトキシ）－［１，１’－ビフェニル］－２－イル）－４，４，５，５－テトラメチル－１，３，２－ジオキサボロランの溶液に、６０９ｍｇ（２．８３ｍｍｏｌ）の２，６－ジブロモピリジン、５．００ｇ（１４．２ｍｍｏｌ）の炭酸セシウムおよび２０ｍＬの水を続いて加えた。得られた混合物をアルゴンで１０分間パージし、続いて、３００ｍｇ（０．２６０ｍｍｏｌ）のＰｄ（ＰＰｈ₃）₄を加えた。この混合物を１００℃で１２時間撹拌し、次いで、室温まで冷却し、５０ｍＬの水で希釈した。こうして得られた混合物をジクロロメタン（３×５０ｍＬ）で抽出し、合わせた有機抽出物をＮａ₂ＳＯ₄で乾燥し、次いで、蒸発乾固した。得られた油に、５０ｍＬのＴＨＦ、５０ｍＬのメタノールおよび３ｍＬの１２Ｎ ＨＣｌを続いて加えた。反応混合物を６０℃で一晩撹拌し、次いで、２００ｍＬの水に注いだ。粗生成物をジクロロメタン（３×７０ｍＬ）で抽出し、合わせた有機抽出物を５％ ＮａＨＣＯ₃で洗浄し、Ｎａ₂ＳＯ₄で乾燥し、次いで、蒸発乾固した。残留物をシリカゲル６０によるフラッシュクロマトグラフィー（４０～６３ｕｍ、溶離液：ヘキサン－酢酸エチル＝１０：１、体積）により精製した。収量１．３４ｇ（５４％）の白色泡としての２種の異性体の混合物。¹H NMR (CDCl₃, 400 MHz): δ 8.26 + 6.83 (2s, 2H), 6.95 - 7.58 + 6.52 (2m, 13H), 3.01 (七重線, J = 6.9 Hz, 2H), 1.85 - 2.02 (m, 18H), 1.62 - 1.68 (m, 12H), 1.33 (d, J = 6.9 Hz, 6H), 1.32 (d, J = 6.9 Hz, 6H), 1.13 + 1.00 (2s, 18H). ¹³C NMR (CDCl₃, 100 MHz) δ 158.28, 157.98, 150.28, 149.48, 148.14, 148.02, 141.61, 141.46, 139.28, 137.50, 136.74, 136.20, 135.43, 135.13, 132.10, 131.67, 130.07, 129.29, 128.97, 128.07, 127.18, 126.90, 126.58, 125.77, 122.74, 122.50, 122.44, 122.20, 40.51, 40.30, 37.08, 37.05, 36.81, 34.17, 34.00, 33.84, 33.78, 31.50, 31.40, 29.15, 29.10, 24.14, 23.81. 2', 2'''-(pyridin-2,6-diyl) bis (3-((3r, 5r, 7r) -adamantan-1-yl) -5- (tert-butyl) -4'-isopropyl- [1,1'-biphenyl] -2-ol)

3.20 g (5.66 mmol) of 2- (3'-(adamantan-1-yl) -5'-(tert-butyl) -2'-(methoxymethoxy)-[in 40 mL of 1,4-dioxane 1,1'-biphenyl] -2-yl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane in a solution of 609 mg (2.83 mmol) of 2,6-dibromopyridine, 5 .00 g (14.2 mmol) of cesium carbonate and 20 mL of water were subsequently added. The resulting mixture was purged with argon for 10 minutes, followed by the addition of 300 mg (0.260 mmol) of Pd (PPh ₃ ) ₄ . The mixture was stirred at 100 ° C. for 12 hours, then cooled to room temperature and diluted with 50 mL of water. The mixture thus obtained was extracted with dichloromethane (3 x 50 mL) and the combined organic extracts were dried over Na ₂ SO ₄ and then evaporated to dryness. 50 mL of THF, 50 mL of methanol and 3 mL of 12N HCl were subsequently added to the resulting oil. The reaction mixture was stirred at 60 ° C. overnight and then poured into 200 mL of water. The crude product was extracted with dichloromethane (3 x 70 mL) and the combined organic extracts were washed with 5% NaHCO ₃ and dried over Na ₂ SO ₄ and then evaporated to dryness. The residue was purified by flash chromatography on silica gel 60 (40-63 um, eluent: hexane-ethyl acetate = 10: 1, volume). A mixture of the two isomers as a white foam with a yield of 1.34 g (54%). ¹ H NMR (CDCl ₃ , 400 MHz): δ 8.26 + 6.83 (2s, 2H), 6.95 --7.58 + 6.52 (2m, 13H), 3.01 (seven-fold line, J = 6.9 Hz, 2H), 1.85 --2.02 (m) , 18H), 1.62 --1.62 (m, 12H), 1.33 (d, J = 6.9 Hz, 6H), 1.32 (d, J = 6.9 Hz, 6H), 1.13 + 1.00 (2s, 18H). ¹³ C NMR ( CDCl ₃ , 100 MHz) δ 158.28, 157.98, 150.28, 149.48, 148.14, 148.02, 141.61, 141.46, 139.28, 137.50, 136.74, 136.20, 135.43, 135.13, 132.10, 131.67, 130.07, 129.29, 128.97, 128.07, 127. , 126.58, 125.77, 122.74, 122.50, 122.44, 122.20, 40.51, 40.30, 37.08, 37.05, 36.81, 34.17, 34.00, 33.84, 33.78, 31.50, 31.40, 29.15, 29.10, 24.14, 23.81.

４０ｍＬのジオキサン中の１．７７ｇ（３．０９ｍｍｏｌ）の２－（３’－（アダマンタン－１－イル）－５’－（ｔｅｒｔ－ブチル）－２’－（メトキシメトキシ）－［１，１’－ビフェニル］－２－イル）－４，４，５，５－テトラメチル－１，３，２－ジオキサボロランの溶液に、３２５ｍｇ（１．５１ｍｍｏｌ）の２，６－ジクロロ－４－トリフルオロメチルピリジン、３．００ｇ（９．０４ｍｍｏｌ）の炭酸セシウムおよび２０ｍＬの水を続いて加えた。得られた混合物をアルゴンで１０分間パージし、続いて、２００ｍｇ（０．１９０ｍｍｏｌ）のＰｄ（ＰＰｈ₃）₄を加えた。この混合物を１００℃で１２時間撹拌し、次いで、室温まで冷却し、５０ｍＬの水で希釈した。こうして得られた混合物をジクロロメタン（３×５０ｍＬ）で抽出し、合わせた有機抽出物をＮａ₂ＳＯ₄で乾燥し、次いで、蒸発乾固した。得られた油に、５０ｍＬのＴＨＦ、５０ｍＬのメタノールおよび３ｍＬの１２Ｎ ＨＣｌを続いて加えた。反応混合物を６０℃で一晩撹拌し、次いで、２００ｍＬの水に注いだ。粗生成物をジクロロメタン（３×７０ｍＬ）で抽出し、合わせた有機抽出物を５％ ＮａＨＣＯ₃で洗浄し、Ｎａ₂ＳＯ₄で乾燥し、次いで、蒸発乾固した。残留物をシリカゲル６０によるフラッシュクロマトグラフィー（４０～６３ｕｍ、溶離液：ヘキサン－酢酸エチル＝１０：１、体積）により精製した。収量１．１７ｇ（８２％）の白色泡としての２種の異性体の混合物。¹H NMR (CDCl₃, 400 MHz): δ 7.35 - 7.46および5.99 (2m, 8H), 7.06 - 7.13 (m, 4H), 6.95および6.56 (2m, 2H), 3.05 (七重線, J = 6.9 Hz, 2H), 1.86 - 2.04 (m, 18H), 1.63 - 1.71 (m, 12H), 1.36 (d, J = 6.9 Hz, 6H), 1.34 (d, J = 6.9 Hz, 6H), 1.15および1.01 (2s, 18H). ¹³C NMR (CDCl₃, 100 MHz) δ 159.68, 149.86, 149.11, 148.81, 142.12, 138.59, 137.29, 136.18, 135.10, 131.67, 131.57, 128.98, 128.81, 127.66, 126.29, 125.43, 123.10, 118.27 (q, J_C,F = 3.5 Hz), 40.48, 40.28, 37.06, 36.87, 34.02, 33.84, 31.43, 31.39, 29.12, 29.07, 24.07, 23.86. 2', 2'''-(4- (trifluoromethyl) pyridine-2,6-diyl) bis (3-((3r, 5r, 7r) -adamantane-1-yl) -5- (tert-butyl) ) -4'-Isopropyl- [1,1'-biphenyl] -2-ol)

1.77 g (3.09 mmol) of 2- (3'-(adamantan-1-yl) -5'-(tert-butyl) -2'-(methoxymethoxy)-[1,1'" in 40 mL of dioxane -Biphenyl] -2-yl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane in a solution of 325 mg (1.51 mmol) of 2,6-dichloro-4-trifluoromethylpyridine , 3.00 g (9.04 mmol) of cesium carbonate and 20 mL of water were subsequently added. The resulting mixture was purged with argon for 10 minutes, followed by the addition of 200 mg (0.190 mmol) of Pd (PPh ₃ ) ₄ . The mixture was stirred at 100 ° C. for 12 hours, then cooled to room temperature and diluted with 50 mL of water. The mixture thus obtained was extracted with dichloromethane (3 x 50 mL) and the combined organic extracts were dried over Na ₂ SO ₄ and then evaporated to dryness. 50 mL of THF, 50 mL of methanol and 3 mL of 12N HCl were subsequently added to the resulting oil. The reaction mixture was stirred at 60 ° C. overnight and then poured into 200 mL of water. The crude product was extracted with dichloromethane (3 x 70 mL) and the combined organic extracts were washed with 5% NaHCO ₃ and dried over Na ₂ SO ₄ and then evaporated to dryness. The residue was purified by flash chromatography on silica gel 60 (40-63 um, eluent: hexane-ethyl acetate = 10: 1, volume). A mixture of the two isomers as a white foam with a yield of 1.17 g (82%). ¹ H NMR (CDCl ₃ , 400 MHz): δ 7.35 --7.46 and 5.99 (2m, 8H), 7.06 --7.13 (m, 4H), 6.95 and 6.56 (2m, 2H), 3.05 (7-fold line, J = 6.9 Hz) , 2H), 1.86 --2.04 (m, 18H), 1.63 --1.71 (m, 12H), 1.36 (d, J = 6.9 Hz, 6H), 1.34 (d, J = 6.9 Hz, 6H), 1.15 and 1.01 ( 2s, 18H). ¹³ C NMR (CDCl ₃ , 100 MHz) δ 159.68, 149.86, 149.11, 148.81, 142.12, 138.59, 137.29, 136.18, 135.10, 131.67, 131.57, 128.98, 128.81, 127.66, 126.29, 125.43, 123.10, 118.27 (q, J _{C, F} = 3.5 Hz), 40.48, 40.28, 37.06, 36.87, 34.02, 33.84, 31.43, 31.39, 29.12, 29.07, 24.07, 23.86.

４０ｍＬのジオキサン中の１．７７ｇ（３．０９ｍｍｏｌ）の２－（３’－（アダマンタン－１－イル）－５’－（ｔｅｒｔ－ブチル）－２’－（メトキシメトキシ）－［１，１’－ビフェニル］－２－イル）－４，４，５，５－テトラメチル－１，３，２－ジオキサボロランの溶液に、４００ｍｇ（１．５１ｍｍｏｌ）の２，６－ジブロモ－４－メトキシピリジン、３．００ｇ（９．０４ｍｍｏｌ）の炭酸セシウムおよび２０ｍＬの水を続いて加えた。得られた混合物をアルゴンで１０分間パージし、続いて、２００ｍｇ（０．１９０ｍｍｏｌ）のＰｄ（ＰＰｈ₃）₄を加えた。この混合物を１００℃で１２時間撹拌し、次いで、室温まで冷却し、５０ｍＬの水で希釈した。こうして得られた混合物をジクロロメタン（３×５０ｍＬ）で抽出し、合わせた有機抽出物をＮａ₂ＳＯ₄で乾燥し、次いで、蒸発乾固した。得られた油に、５０ｍＬのＴＨＦ、５０ｍＬのメタノールおよび３ｍＬの１２Ｎ ＨＣｌを続いて加えた。反応混合物を６０℃で一晩撹拌し、次いで、２００ｍＬの水に注いだ。粗生成物をジクロロメタン（３×７０ｍＬ）で抽出し、合わせた有機抽出物を５％ ＮａＨＣＯ₃で洗浄し、Ｎａ₂ＳＯ₄で乾燥し、次いで、蒸発乾固した。残留物をシリカゲル６０によるフラッシュクロマトグラフィー（４０～６３ｕｍ、溶離液：ヘキサン－酢酸エチル＝１０：１、体積）により精製した。収量１．０１ｇ（７４％）の白色泡としての２種の異性体の混合物。¹H NMR (CDCl₃, 400 MHz): δ 8.40および7.02 (2s, 2H), 7.23 - 7.44 (m, 6H), 7.07 (m, 2H), 6.56 - 6.58 (m, 2H), 6.41 (m, 2H), 3.50および3.37 (2s, 3H), 3.02 (七重線, J = 6.9 Hz, 2H), 1.85 - 2.02 (m, 18H), 1.62 - 1.70 (m, 12H), 1.34 (d, J = 6.9 Hz, 12H), 1.19 + 1.00 (2s, 18H). ¹³C NMR (CDCl₃, 100 MHz) δ 165.74, 159.62, 150.20, 148.30, 141.73, 139.35, 137.37, 135.18, 131.38, 129.99, 129.03, 127.34, 127.03, 126.71, 125.71, 122.56, 108.94, 55.12, 40.61, 37.08, 37.06, 34.01, 33.76, 31.48, 29.13, 24.12, 23.83. 2', 2'''-(4-Methoxypyridin-2,6-diyl) bis (3-((3r, 5r, 7r) -adamantan-1-yl) -5- (tert-butyl) -4' -Isopropyl- [1,1'-biphenyl] -2-ol)

1.77 g (3.09 mmol) of 2- (3'-(adamantan-1-yl) -5'-(tert-butyl) -2'-(methoxymethoxy)-[1,1'" in 40 mL of dioxane -Biphenyl] -2-yl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane in a solution of 400 mg (1.51 mmol) of 2,6-dibromo-4-methoxypyridine, 3 .00 g (9.04 mmol) of cesium carbonate and 20 mL of water were subsequently added. The resulting mixture was purged with argon for 10 minutes, followed by the addition of 200 mg (0.190 mmol) of Pd (PPh ₃ ) ₄ . The mixture was stirred at 100 ° C. for 12 hours, then cooled to room temperature and diluted with 50 mL of water. The mixture thus obtained was extracted with dichloromethane (3 x 50 mL) and the combined organic extracts were dried over Na ₂ SO ₄ and then evaporated to dryness. 50 mL of THF, 50 mL of methanol and 3 mL of 12N HCl were subsequently added to the resulting oil. The reaction mixture was stirred at 60 ° C. overnight and then poured into 200 mL of water. The crude product was extracted with dichloromethane (3 x 70 mL) and the combined organic extracts were washed with 5% NaHCO ₃ and dried over Na ₂ SO ₄ and then evaporated to dryness. The residue was purified by flash chromatography on silica gel 60 (40-63 um, eluent: hexane-ethyl acetate = 10: 1, volume). A mixture of the two isomers as white foam with a yield of 1.01 g (74%). ¹ H NMR (CDCl ₃ , 400 MHz): δ 8.40 and 7.02 (2s, 2H), 7.23 --7.44 (m, 6H), 7.07 (m, 2H), 6.56 --6.58 (m, 2H), 6.41 (m, 2H), 3.50 and 3.37 (2s, 3H), 3.02 (seven-fold wire, J = 6.9 Hz, 2H), 1.85 --2.02 (m, 18H), 1.62 --1.70 (m, 12H), 1.34 (d, J = 6.9) Hz, 12H), 1.19 + 1.00 (2s, 18H). ¹³ C NMR (CDCl ₃ , 100 MHz) δ 165.74, 159.62, 150.20, 148.30, 141.73, 139.35, 137.37, 135.18, 131.38, 129.99, 129.03, 127.34, 127.03 , 126.71, 125.71, 122.56, 108.94, 55.12, 40.61, 37.08, 37.06, 34.01, 33.76, 31.48, 29.13, 24.12, 23.83.

３００ｍＬのジクロロメタン中の３０．０ｇ（２６８ｍｍｏｌ）の４－フルオロフェノールおよび４０．８ｇ（２６８ｍｍｏｌ）のアダマンタン－１－オールの溶液に、１００ｍＬのジクロロメタン中の１７．４ｍＬ（２６８ｍｍｏｌ）のメタンスルホン酸および２０ｍＬの酢酸の溶液を室温で１時間滴加した。生じた混合物を室温で４８時間撹拌し、次いで、３００ｍＬの５％ ＮａＨＣＯ₃に注意深く注いだ。粗生成物をジクロロメタン（３×５０ｍＬ）で抽出し、合わせた有機抽出物をＮａ₂ＳＯ₄で乾燥し、次いで、蒸発乾固した。クーゲルロール装置（０．３ｍｂａｒ、９５℃）を使用して残留物を精製して、４９．３ｇ（７５％）の表題生成物を淡黄色油として得た。¹H NMR (CDCl₃, 400 MHz): δ 6.92 (dd, J = 11.2, 3.1 Hz, 1H), 6.73 (ddd, J = 8.7, 7.4, 3.1 Hz, 1H), 6.60 (dd, J = 8.7, 5.0 Hz, 1H), 4.34 (br.s, 1H), 2.08 - 2.11 (m, 9H), 1.75 - 1.80 (m, 9H), 1.58 - 1.67 (m, 3H), ¹³C NMR (CDCl₃, 100 MHz): δ 158.28 (d, J_C,F = 236 Hz), 150.60 (d, J_C,F = 2.0 Hz), 138.27 (d, J_C,F = 5.9 Hz), 117.07 (d, J_C,F = 8.1 Hz), 113.88 (d, J_C,F = 23.9 Hz), 112.36 (d, J_C,F = 23.0 Hz), 45.05, 40.13, 36.88, 35.90, 30.65, 28.88. 2- (adamantane-1-yl) -4-fluorophenol

To a solution of 30.0 g (268 mmol) 4-fluorophenol and 40.8 g (268 mmol) adamantane-1-ol in 300 mL dichloromethane, 17.4 mL (268 mmol) methanesulfonic acid and 20 mL in 100 mL dichloromethane. A solution of acetic acid was added dropwise at room temperature for 1 hour. The resulting mixture was stirred at room temperature for 48 hours and then carefully poured into 300 mL of 5% NaHCO ₃ . The crude product was extracted with dichloromethane (3 x 50 mL) and the combined organic extracts were dried over Na ₂ SO ₄ and then evaporated to dryness. The residue was purified using a Kugelrohr device (0.3 mbar, 95 ° C.) to give 49.3 g (75%) of the title product as a pale yellow oil. ¹ H NMR (CDCl ₃ , 400 MHz): δ 6.92 (dd, J = 11.2, 3.1 Hz, 1H), 6.73 (ddd, J = 8.7, 7.4, 3.1 Hz, 1H), 6.60 (dd, J = 8.7, 5.0 Hz, 1H), 4.34 (br.s, 1H), 2.08 --2.11 (m, 9H), 1.75 --1.80 (m, 9H), 1.58 --1.17 (m, 3H), ¹³ C NMR (CDCl ₃ , 100 MHz): δ 158.28 (d, J _{C, F} = 236 Hz), 150.60 (d, J _{C, F} = 2.0 Hz), 138.27 (d, J _{C, F} = 5.9 Hz), 117.07 (d, J _{C, F} = 8.1 Hz), 113.88 (d, J _{C, F} = 23.9 Hz), 112.36 (d, J _{C, F} = 23.0 Hz), 45.05, 40.13, 36.88, 35.90, 30.65, 28.88.

５００ｍＬのジクロロメタン中の４９．３ｇ（２００ｍｍｏｌ）の２－（アダマンタン－１－イル）－４－フルオロフェノールの溶液に、１００ｍＬのジクロロメタン中の１０．３ｍＬ（２００ｍｍｏｌ）の臭素の溶液を室温で１時間滴加した。生じた混合物を室温で４８時間撹拌し、次いで、２００ｍＬの５％ ＮａＨＣＯ₃に注意深く注いだ。粗生成物をジクロロメタン（３×１５０ｍＬ）で抽出し、合わせた有機抽出物をＮａ₂ＳＯ₄で乾燥し、次いで、蒸発乾固した。収量６５．０ｇ（定量的）の淡黄色固体。¹H NMR (CDCl₃, 400 MHz): δ 7.07 (dd, J = 7.0, 3.0 Hz, 1H), 6.92 (dd, J = 10.8, 3.0 Hz, 1H), 5.60 (s, 1H), 2.07 (br.s, 9H), 1.77 (br.s, 6H). ¹³C NMR (CDCl₃, 100 MHz): δ 157.21 (d, J_C,F = 241 Hz), 147.03 (d, J_C,F = 3.0 Hz), 138.91 (d, J_C,F = 5.9 Hz), 115.66 (d, J_C,F = 25.8 Hz), 113.97 (d, J_C,F = 23.6 Hz), 111.21 (d, J_C,F = 10.9 Hz), 39.88, 37.60, 36.82, 28.86. 2-Bromo-6- (adamantane-1-yl) -4-fluorophenol

A solution of 49.3 g (200 mmol) of 2- (adamantane-1-yl) -4-fluorophenol in 500 mL of dichloromethane to a solution of 10.3 mL (200 mmol) of bromine in 100 mL of dichloromethane for 1 hour at room temperature. Dropped. The resulting mixture was stirred at room temperature for 48 hours and then carefully poured into 200 mL of 5% NaHCO ₃ . The crude product was extracted with dichloromethane (3 x 150 mL) and the combined organic extracts were dried over Na ₂ SO ₄ and then evaporated to dryness. A pale yellow solid with a yield of 65.0 g (quantitative). ¹ H NMR (CDCl ₃ , 400 MHz): δ 7.07 (dd, J = 7.0, 3.0 Hz, 1H), 6.92 (dd, J = 10.8, 3.0 Hz, 1H), 5.60 (s, 1H), 2.07 (br .s, 9H), 1.77 (br.s, 6H). ¹³ C NMR (CDCl ₃ , 100 MHz): δ 157.21 (d, J _{C, F} = 241 Hz), 147.03 (d, J _{C, F} = 3.0) Hz), 138.91 (d, J _{C, F} = 5.9 Hz), 115.66 (d, J _{C, F} = 25.8 Hz), 113.97 (d, J _{C, F} = 23.6 Hz), 111.21 (d, J _{C, F} ) = 10.9 Hz), 39.88, 37.60, 36.82, 28.86.

５００ｍＬの乾燥ＴＨＦ中の４８．４ｇ（１５０ｍｍｏｌ）の２－ブロモ－６－（アダマンタン－１－イル）－４－フルオロフェノールの溶液に、６．３０ｇ（１５５ｍｍｏｌ、鉱油中６０質量％）の水素化ナトリウムを室温で分割して加えた。その後、１３．７ｍＬ（１８０ｍｍｏｌ）のＭＯＭＣｌを１時間滴加した。反応混合物を６０℃で２４時間加熱し、次いで、３００ｍＬの冷水に注いだ。粗生成物を３×２００ｍＬのジクロロメタンで抽出した。合わせた有機抽出物をＮａ₂ＳＯ₄で乾燥し、次いで、蒸発乾固した。収量５６．０ｇ（定量的）の白色固体。¹H NMR (CDCl₃, 400 MHz): δ 7.12 (dd, J = 6.9, 3.1 Hz, 1H), 6.98 (dd, J = 10.9, 3.1 Hz, 1H), 5.20 (s, 2H), 3.69 (s, 3H), 2.07 (br.s, 9H), 1.76 (br.s, 6H). ¹³C NMR (CDCl₃, 100 MHz): δ 159.51 (d, J_C,F = 245 Hz), 149.86 (d, J_C,F = 3.3 Hz), 146.93 (d, J_C,F = 6.5 Hz), 118.09 (d, J_C,F = 25.4 Hz), 117.67 (d, J_C,F = 10.5 Hz), 113.99 (d, J_C,F = 23.6 Hz), 99.72, 57.83, 40.99, 38.06, 36.67, 28.92. (3r, 5r, 7r) -1- (3-bromo-5-fluoro-2- (methoxymethoxy) phenyl) adamantin

Hydrogenation of 6.30 g (155 mmol, 60% by weight in mineral oil) in 48.4 g (150 mmol) of 2-bromo-6- (adamantan-1-yl) -4-fluorophenol solution in 500 mL of dry THF. Sodium was added in portions at room temperature. Then, 13.7 mL (180 mmol) of MOMCl was added dropwise for 1 hour. The reaction mixture was heated at 60 ° C. for 24 hours and then poured into 300 mL of cold water. The crude product was extracted with 3 x 200 mL dichloromethane. The combined organic extracts were dried over Na ₂ SO ₄ and then evaporated to dryness. A white solid with a yield of 56.0 g (quantitative). ¹ H NMR (CDCl ₃ , 400 MHz): δ 7.12 (dd, J = 6.9, 3.1 Hz, 1H), 6.98 (dd, J = 10.9, 3.1 Hz, 1H), 5.20 (s, 2H), 3.69 (s) , 3H), 2.07 (br.s, 9H), 1.76 (br.s, 6H). ¹³ C NMR (CDCl ₃ , 100 MHz): δ 159.51 (d, J _{C, F} = 245 Hz), 149.86 (d) , J _{C, F} = 3.3 Hz), 146.93 (d, J _{C, F} = 6.5 Hz), 118.09 (d, J _{C, F} = 25.4 Hz), 117.67 (d, J _{C, F} = 10.5 Hz), 113.99 (d, J _{C, F} = 23.6 Hz), 99.72, 57.83, 40.99, 38.06, 36.67, 28.92.

４００ｍＬの乾燥ＴＨＦ中の２８．０ｇ（７５．８ｍｍｏｌ）の（１－（３－ブロモ－５－フルオロ－２－（メトキシメトキシ）フェニル）アダマンチンの溶液に、ヘキサン中の３０．３ｍＬ（７５．８ｍｍｏｌ）の２．５Ｍ ⁿＢｕＬｉを－８０℃で２０分間滴加した。反応混合物をこの温度で１時間撹拌し、続いて、２０．１ｍＬ（９８．５ｍｍｏｌ）の２－イソプロポキシ－４，４，５，５－テトラメチル－１，３，２－ジオキサボロランを加えた。得られた懸濁液を室温で１時間撹拌し、次いで、３００ｍＬの水に注いだ。粗生成物をジクロロメタン（３×３００ｍＬ）で抽出し、合わせた有機抽出物をＮａ₂ＳＯ₄で乾燥し、次いで、蒸発乾固した。残留物をイソプロパノールから再結晶させた。収量２７．８ｇ（８８％）の白色固体。¹H NMR (CDCl₃, 400 MHz): δ 7.19 (dd, J = 7.7, 3.3 Hz, 1H), 7.06 (dd, J = 10.9, 3.3 Hz, 1H), 5.12 (s, 2H), 3.57 (s, 3H), 2.10 (br.s, 6H), 2.06 (br.s, 3H), 1.75 (br.,s 6H), 1.34 (s, 12H). ¹³C NMR (CDCl₃, 100 MHz): δ 159.46 (d, J_C,F = 241 Hz), 157.48 (d, J_C,F = 2.0 Hz), 144.23 (d, J_C,F = 5.7 Hz), 119.42 (d, J_C,F = 21.0 Hz), 117.35 (d, J_C,F = 24.0 Hz), 100.98, 83.96, 57.73, 40.97, 37.29, 36.87, 28.99, 24.79. 2-((3r, 5r, 7r) -3-adamantan-1-yl) -5-fluoro-2- (methoxymethoxy) phenyl) -4,4,5,5-tetramethyl-1,3,2- Dioxaborolan

30.3 mL (75.8 mmol) in hexane to a solution of 28.0 g (75.8 mmol) of (1- (3-bromo-5-fluoro-2- (methoxymethoxy) phenyl) adamantin in 400 mL of dry THF. ) 2.5 M ⁿ BuLi was added dropwise at −80 ° C. for 20 minutes. The reaction mixture was stirred at this temperature for 1 hour, followed by 20.1 mL (98.5 mmol) of 2-isopropoxy-4,4. 5,5-Tetramethyl-1,3,2-dioxaborolane was added. The resulting suspension was stirred at room temperature for 1 hour and then poured into 300 mL of water. The crude product was dichloromethane (3 x 300 mL). ), The combined organic extracts were dried on Na ₂ SO ₄ , then evaporated to dryness. The residue was recrystallized from isopropanol. A white solid with a yield of 27.8 g (88%). ¹ H. NMR (CDCl ₃ , 400 MHz): δ 7.19 (dd, J = 7.7, 3.3 Hz, 1H), 7.06 (dd, J = 10.9, 3.3 Hz, 1H), 5.12 (s, 2H), 3.57 (s, 3H) ), 2.10 (br.s, 6H), 2.06 (br.s, 3H), 1.75 (br., S 6H), 1.34 (s, 12H). ¹³ C NMR (CDCl ₃ , 100 MHz): δ 159.46 ( d, J _{C, F} = 241 Hz), 157.48 (d, J _{C, F} = 2.0 Hz), 144.23 (d, J _{C, F} = 5.7 Hz), 119.42 (d, J _{C, F} = 21.0 Hz), 117.35 (d, J _{C, F} = 24.0 Hz), 100.98, 83.96, 57.73, 40.97, 37.29, 36.87, 28.99, 24.79.

６０ｍＬの１，４－ジオキサン中の８．００ｇ（１９．２１ｍｍｏｌ）の２－（（３ｒ，５ｒ，７ｒ）－３－アダマンタン－１－イル）－５－フルオロ－２－（メトキシメトキシ）フェニル）－４，４，５，５－テトラメチル－１，３，２－ジオキサボロランの溶液に、６．２４ｇ（１９．２ｍｍｏｌ）の２－ブロモ－４－イソプロピルヨードベンゼン、６．６３ｇ（４８．０ｍｍｏｌ）の炭酸カリウムおよび５０ｍＬの水を続いて加えた。得られた混合物をアルゴンで１０分間パージし、続いて、１．１０ｇ（０．９６ｍｍｏｌ）のＰｄ（ＰＰｈ₃）₄を加えた。この混合物を１００℃で１２時間撹拌し、次いで、室温まで冷却し、１００ｍＬの水で希釈した。粗生成物をジクロロメタン（３×１５０ｍＬ）で抽出し、合わせた有機抽出物をＮａ₂ＳＯ₄で乾燥し、次いで、蒸発乾固した。残留物をシリカゲル６０によるフラッシュクロマトグラフィー（４０～６３ｕｍ、溶離液：ヘキサン－ジクロロメタン＝１０：１、体積）により精製した。収量４．７０ｇ（５０％）の白色固体。¹H NMR (CDCl₃, 400 MHz): δ 7.53 (d, J = 1.6 Hz, 1H), 7.27 (d, J = 7.9 Hz, 1H), 7.20 (dd, J = 7.9, 1.6 Hz, 1H), 7.03 (dd, J = 11.0, 3.2 Hz, 1H), 6.79 (dd, J = 7.9, 3.2 Hz, 1H), 4.48 (m, 1H), 4.40 (m, 1H), 3.16 (s, 3H), 2.93 (七重線, J = 6.9 Hz, 1H), 2.13 (br.s, 6H), 2.10 (br.s, 3H), 1.78 (br.s, 6H), 1.28 (d, J = 6.9 Hz, 6H). ¹³C NMR (CDCl₃, 100 MHz): δ 159.33 (d, J_C,F = 240 Hz), 150.47, 145.50 (d, J_C,F = 5.9 Hz), 137.28, 136.00 (d, J_C,F = 8.8 Hz), 131.87, 130.86, 125.47, 123.65, 115.67 (d, J_C,F = 23.6 Hz), 113.95 (d, J_C,F = 23.6 Hz), 98.98, 57.03, 41.03, 37.57, 36.85, 33.66, 29.03, 23.84. (3r, 5r, 7r) -1- (2'-bromo-5-fluoro-4'-isopropyl-2- (methoxymethoxy)-[1,1'-biphenyl] -3-yl) adamantin

8.00 g (19.21 mmol) 2-((3r, 5r, 7r) -3-adamantan-1-yl) -5-fluoro-2- (methoxymethoxy) phenyl in 60 mL of 1,4-dioxane) 6.24 g (19.2 mmol) of 2-bromo-4-isopropyliodobenzene in a solution of -4,4,5,5-tetramethyl-1,3,2-dioxaborolane, 6.63 g (48.0 mmol). Potassium carbonate and 50 mL of water were subsequently added. The resulting mixture was purged with argon for 10 minutes, followed by the addition of 1.10 g (0.96 mmol) of Pd (PPh ₃ ) ₄ . The mixture was stirred at 100 ° C. for 12 hours, then cooled to room temperature and diluted with 100 mL of water. The crude product was extracted with dichloromethane (3 x 150 mL) and the combined organic extracts were dried over Na ₂ SO ₄ and then evaporated to dryness. The residue was purified by flash chromatography on silica gel 60 (40-63 um, eluent: hexane-dichloromethane = 10: 1, volume). A white solid with a yield of 4.70 g (50%). ¹ H NMR (CDCl ₃ , 400 MHz): δ 7.53 (d, J = 1.6 Hz, 1H), 7.27 (d, J = 7.9 Hz, 1H), 7.20 (dd, J = 7.9, 1.6 Hz, 1H), 7.03 (dd, J = 11.0, 3.2 Hz, 1H), 6.79 (dd, J = 7.9, 3.2 Hz, 1H), 4.48 (m, 1H), 4.40 (m, 1H), 3.16 (s, 3H), 2.93 (Seven-fold line, J = 6.9 Hz, 1H), 2.13 (br.s, 6H), 2.10 (br.s, 3H), 1.78 (br.s, 6H), 1.28 (d, J = 6.9 Hz, 6H) . ¹³ C NMR (CDCl ₃ , 100 MHz): δ 159.33 (d, J _{C, F} = 240 Hz), 150.47, 145.50 (d, J _{C, F} = 5.9 Hz), 137.28, 136.00 (d, J _{C, F} = 8.8 Hz), 131.87, 130.86, 125.47, 123.65, 115.67 (d, J _{C, F} = 23.6 Hz), 113.95 (d, J _{C, F} = 23.6 Hz), 98.98, 57.03, 41.03, 37.57, 36.85, 33.66, 29.03, 23.84.

１００ｍＬの乾燥ＴＨＦ中の４．７０ｇ（９．６４ｍｍｏｌ）の（３ｒ，５ｒ，７ｒ）－１－（２’－ブロモ－５－フルオロ－４’－イソプロピル－２－（メトキシメトキシ）－［１，１’－ビフェニル］－３－イル）アダマンチンの溶液に、ヘキサン中の３．８６ｍＬ（９．６４ｍｍｏｌ）の２．５Ｍ ⁿＢｕＬｉを－８０℃で２０分間滴加した。反応混合物をこの温度で１時間撹拌し、続いて、２．３３ｍＬ（１２．５ｍｍｏｌ）の２－イソプロポキシ－４，４，５，５－テトラメチル－１，３，２－ジオキサボロランを加えた。得られた懸濁液を室温で１時間撹拌し、次いで、３００ｍＬの水に注いだ。粗生成物をジクロロメタン（３×３００ｍＬ）で抽出し、合わせた有機抽出物をＮａ₂ＳＯ₄で乾燥し、次いで、蒸発乾固した。残留物をシリカゲル６０によるフラッシュクロマトグラフィー（４０～６３ｕｍ、溶離液：ヘキサン－ジエチルエーテル＝１０：１、体積）により精製した。収量５．１０ｇ（９９％）の無色ガラス状固体。¹H NMR (CDCl₃, 400 MHz): δ 7.59 (d, J = 1.9 Hz), 7.29 (dd, J = 7.9, 1.9 Hz, 1H), 7.24 (d, J = 7.9 Hz), 6.95 (dd, J = 11.2, 3.2 Hz, 1H), 6.71 (dd, J = 8.0, 3.2 Hz, 1H), 4.30 - 4.42 (m, 2H), 3.20 (s, 3H), 2.95 (七重線, J = 6.9 Hz, 1H), 2.14 (br.s, 6H), 2.08 (br.s, 6H), 1.74 - 1.80 (m, 6H), 1.28 (d, J = 6.9 Hz, 6H), 1.17 (br.s, 12H). ¹³C NMR (CDCl₃, 100 MHz): δ 159.31 (d, J_C,F = 240 Hz), 149.77 (d, J_C,F = 2.4 Hz), 147.17, 144.55 (d, J_C,F = 6.6 Hz), 142.17, 138.49 (d, J_C,F = 8.1 Hz), 132.80, 130.14, 128.01, 115.90 (d, J_C,F = 22.5 Hz), 112.61 (d, J_C,F = 23.6 Hz), 98.69, 83.48, 57.23, 41.26, 37.52, 36.91, 33.86, 29.09, 25.07 (広幅), 24.26 (広幅), 24.04. 2- (3'-((3r, 5r, 7r) -adamantane-1-yl) -5'-fluoro-4-isopropyl-2'-(methoxymethoxy)-[1,1'-biphenyl] -2- Il) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane

4.70 g (9.64 mmol) of (3r, 5r, 7r) -1- (2'-bromo-5-fluoro-4'-isopropyl-2- (methoxymethoxy)-[1, in 100 mL of dry THF To a solution of 1'-biphenyl] -3-yl) adamantin was added 3.86 mL (9.64 mmol) of 2.5 M ⁿ BuLi in hexanes at −80 ° C. for 20 minutes. The reaction mixture was stirred at this temperature for 1 hour, followed by the addition of 2.33 mL (12.5 mmol) 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane. The resulting suspension was stirred at room temperature for 1 hour and then poured into 300 mL of water. The crude product was extracted with dichloromethane (3 x 300 mL) and the combined organic extracts were dried over Na ₂ SO ₄ and then evaporated to dryness. The residue was purified by flash chromatography on silica gel 60 (40-63 um, eluent: hexane-diethyl ether = 10: 1, volume). A colorless glassy solid with a yield of 5.10 g (99%). ¹ H NMR (CDCl ₃ , 400 MHz): δ 7.59 (d, J = 1.9 Hz), 7.29 (dd, J = 7.9, 1.9 Hz, 1H), 7.24 (d, J = 7.9 Hz), 6.95 (dd, dd, J = 11.2, 3.2 Hz, 1H), 6.71 (dd, J = 8.0, 3.2 Hz, 1H), 4.30 --4.42 (m, 2H), 3.20 (s, 3H), 2.95 (7-fold line, J = 6.9 Hz, 1H), 2.14 (br.s, 6H), 2.08 (br.s, 6H), 1.74 --1.80 (m, 6H), 1.28 (d, J = 6.9 Hz, 6H), 1.17 (br.s, 12H) . ¹³ C NMR (CDCl ₃ , 100 MHz): δ 159.31 (d, J _{C, F} = 240 Hz), 149.77 (d, J _{C, F} = 2.4 Hz), 147.17, 144.55 (d, J _{C, F} = 6.6 Hz), 142.17, 138.49 (d, J _{C, F} = 8.1 Hz), 132.80, 130.14, 128.01, 115.90 (d, J _{C, F} = 22.5 Hz), 112.61 (d, J _{C, F} = 23.6 Hz) , 98.69, 83.48, 57.23, 41.26, 37.52, 36.91, 33.86, 29.09, 25.07 (wide), 24.26 (wide), 24.04.

４０ｍＬの１，４－ジオキサン中の２．００ｇ（３．７４ｍｍｏｌ）の２－（３’－（（３ｒ，５ｒ，７ｒ）－アダマンタン－１－イル）－５’－フルオロ－４－イソプロピル－２’－（メトキシメトキシ）－［１，１’－ビフェニル］－２－イル）－４，４，５，５－テトラメチル－１，３，２－ジオキサボロランの溶液に、５００ｍｇ（１．８７ｍｍｏｌ）の２，６－ジブロモ－４－メトキシピリジン、３．０４ｇ（９．３５ｍｍｏｌ）の炭酸セシウムおよび２０ｍＬの水を続いて加えた。得られた混合物をアルゴンで１０分間パージし、続いて、２１６ｍｇ（０．１８７ｍｍｏｌ）のＰｄ（ＰＰｈ₃）₄を加えた。この混合物を１００℃で１２時間撹拌し、次いで、室温まで冷却し、５０ｍＬの水で希釈した。こうして得られた混合物をジクロロメタン（３×５０ｍＬ）で抽出し、合わせた有機抽出物をＮａ₂ＳＯ₄で乾燥し、次いで、蒸発乾固した。得られた油に、５０ｍＬのＴＨＦ、５０ｍＬのメタノールおよび３ｍＬの１２Ｎ ＨＣｌを続いて加えた。反応混合物を６０℃で一晩撹拌し、次いで、２００ｍＬの水に注いだ。粗生成物をジクロロメタン（３×７０ｍＬ）で抽出し、合わせた有機抽出物を５％ ＮａＨＣＯ₃で洗浄し、Ｎａ₂ＳＯ₄で乾燥し、次いで、蒸発乾固した。残留物をシリカゲル６０によるフラッシュクロマトグラフィー（４０～６３ｕｍ、溶離液：ヘキサン－酢酸エチル＝１０：１、体積）により精製した。収量１．３１ｇ（８３％）の白色泡としての２種の異性体の混合物。¹H NMR (CDCl₃, 400 MHz): δ 7.95 (s, 1H), 7.20 - 7.46 (m, 8H), 6.73 - 6.84および6.06 - 6.09 (2m, 3H), 6.59および6.51 (2s, 2H), 3.63および3.46 (2s, 3H), 2.95 - 3.10 (2本の七重線, 2H), 1.57 - 2.15 (m, 30H), 1.28 - 1.37 (m, 12H). ¹³C NMR (CDCl₃, 100 MHz) δ 166.41, 166.10, 159.62, 159.46, 157.73 (d, J_C,F = 237 Hz), 157.62 (d, J_C,F = 237 Hz), 148.99, 148.74, 148.66, 148.29, 139.95, 139.89, 139.39, 138.30, 133.96, 131.90, 131.14, 129.34, 128.13, 128.03, 127.84, 127.59, 127.03, 114.54 (d, J_C,F = 22.7 Hz), 114.19 (d, J_C,F = 22.9 Hz), 113.01 (d, J_C,F = 23.2 Hz), 112.70 (d, J_C,F = 24.1 Hz), 108.57, 108.45, 55.25, 54.97, 40.16, 39.96, 37.00, 36.93, 36.89, 36.83, 36.68, 33.83, 33.65, 28.99, 28.90, 23.99, 23.93, 23.76. 2', 2'''-(4-Methoxypyridin-2,6-diyl) bis (3-((3r, 5r, 7r) -adamantan-1-yl) -5-fluoro-4'-isopropyl- [ 1,1'-biphenyl] -2-ol)

2.00 g (3.74 mmol) 2- (3'-((3r, 5r, 7r) -adamantan-1-yl) -5'-fluoro-4-isopropyl-2 in 40 mL of 1,4-dioxane In a solution of'-(methoxymethoxy)-[1,1'-biphenyl] -2-yl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane, 500 mg (1.87 mmol). 2,6-Dibromo-4-methoxypyridine, 3.04 g (9.35 mmol) of cesium carbonate and 20 mL of water were subsequently added. The resulting mixture was purged with argon for 10 minutes, followed by the addition of 216 mg (0.187 mmol) of Pd (PPh ₃ ) ₄ . The mixture was stirred at 100 ° C. for 12 hours, then cooled to room temperature and diluted with 50 mL of water. The mixture thus obtained was extracted with dichloromethane (3 x 50 mL) and the combined organic extracts were dried over Na ₂ SO ₄ and then evaporated to dryness. 50 mL of THF, 50 mL of methanol and 3 mL of 12N HCl were subsequently added to the resulting oil. The reaction mixture was stirred at 60 ° C. overnight and then poured into 200 mL of water. The crude product was extracted with dichloromethane (3 x 70 mL) and the combined organic extracts were washed with 5% NaHCO ₃ and dried over Na ₂ SO ₄ and then evaporated to dryness. The residue was purified by flash chromatography on silica gel 60 (40-63 um, eluent: hexane-ethyl acetate = 10: 1, volume). A mixture of the two isomers as a white foam with a yield of 1.31 g (83%). ¹ H NMR (CDCl ₃ , 400 MHz): δ 7.95 (s, 1H), 7.20 --7.46 (m, 8H), 6.73 --6.84 and 6.06 --6.09 (2m, 3H), 6.59 and 6.51 (2s, 2H), 3.63 and 3.46 (2s, 3H), 2.95 ―― 3.10 (two seven wires, 2H), 1.57 ―― 2.15 (m, 30H), 1.28 ―― 1.37 (m, 12H). ¹³ C NMR (CDCl ₃ , 100 MHz) δ 166.41, 166.10, 159.62, 159.46, 157.73 (d, J _{C, F} = 237 Hz), 157.62 (d, J _{C, F} = 237 Hz), 148.99, 148.74, 148.66, 148.29, 139.95, 139.89, 139.39, 138.30 , 133.96, 131.90, 131.14, 129.34, 128.13, 128.03, 127.84, 127.59, 127.03, 114.54 (d, J _{C, F} = 22.7 Hz), 114.19 (d, J _{C, F} = 22.9 Hz), 113.01 (d, J) _{C, F} = 23.2 Hz), 112.70 (d, J _{C, F} = 24.1 Hz), 108.57, 108.45, 55.25, 54.97, 40.16, 39.96, 37.00, 36.93, 36.89, 36.83, 36.68, 33.83, 33.65, 28.99, 28.90 , 23.99, 23.93, 23.76.

１５０ｍＬのジクロロメタン中の８．４０ｇ（７５．０ｍｍｏｌ）の４－フルオロフェノールおよび１３．５ｇ（７５．０ｍｍｏｌ）の３，５－ジメチルアダマンタン－１－オールの溶液に、１００ｍＬのジクロロメタン中の４．９０ｍＬ（７５．０ｍｍｏｌ）のメタンスルホン酸および５ｍＬの酢酸の溶液を室温で１時間滴加した。生じた混合物を室温で４８時間撹拌し、次いで、３００ｍＬの５％ ＮａＨＣＯ₃に注意深く注いだ。粗生成物をジクロロメタン（３×５０ｍＬ）で抽出し、合わせた有機抽出物をＮａ₂ＳＯ₄で乾燥し、次いで、蒸発乾固した。クーゲルロール装置（１ｍｂａｒ、７０℃）を使用して残留物を精製して、１４．２ｇ（６８％）の表題生成物を淡黄色油として得た。¹H NMR (CDCl₃, 400 MHz): δ 6.93 (dd, J = 3.1, 11.2 Hz, 1H), 6.73 (ddd, J = 3.1, 7.4, 8.6 Hz, 1H), 6.55 (dd, J = 4.9, 8.6 Hz), 4.62 (s, 1H), 2.16 (dt, J = 3.1, 6.3 Hz, 1H), 1.91 (m, 2H), 1.64 - 1.74 (m, 4H), 1.35 - 1.45 (m, 4H), 1.20 (br.s, 2H), 0.87 (s, 6H). ¹³C NMR (CDCl₃, 100 MHz): δ 158.49 (J_F = 236 Hz), 150.19 (J_F = 2.0 Hz), 137.69 (J_F = 5.9 Hz), 117.12 (J_F = 8.1 Hz), 114.13 (J_F = 24.0 Hz), 112.57 (J_F = 22.9 Hz), 50.92, 46.44, 43.05, 38.70, 38.48, 31.38, 30.84, 29.90. 2- (3,5-dimethyladamantane-1-yl) -4-fluorophenol

4.90 mL in 100 mL dichloromethane to a solution of 8.40 g (75.0 mmol) 4-fluorophenol in 150 mL dichloromethane and 13.5 g (75.0 mmol) 3,5-dimethyladamantane-1-ol. A solution of (75.0 mmol) methanesulfonic acid and 5 mL of acetic acid was added dropwise at room temperature for 1 hour. The resulting mixture was stirred at room temperature for 48 hours and then carefully poured into 300 mL of 5% NaHCO ₃ . The crude product was extracted with dichloromethane (3 x 50 mL) and the combined organic extracts were dried over Na ₂ SO ₄ and then evaporated to dryness. The residue was purified using a Kugelrohr device (1 mbar, 70 ° C.) to give 14.2 g (68%) of the title product as a pale yellow oil. ¹ H NMR (CDCl ₃ , 400 MHz): δ 6.93 (dd, J = 3.1, 11.2 Hz, 1H), 6.73 (ddd, J = 3.1, 7.4, 8.6 Hz, 1H), 6.55 (dd, J = 4.9, 8.6 Hz), 4.62 (s, 1H), 2.16 (dt, J = 3.1, 6.3 Hz, 1H), 1.91 (m, 2H), 1.64 --1.74 (m, 4H), 1.35 --1.45 (m, 4H), 1.20 (br.s, 2H), 0.87 (s, 6H). ¹³ C NMR (CDCl ₃ , 100 MHz): δ 158.49 (J _F = 236 Hz), 150.19 (J _F = 2.0 Hz), 137.69 (J _F ) = 5.9 Hz), 117.12 (J _F = 8.1 Hz), 114.13 (J _F = 24.0 Hz), 112.57 (J _F = 22.9 Hz), 50.92, 46.44, 43.05, 38.70, 38.48, 31.38, 30.84, 29.90.

２００ｍＬのジクロロメタン中の１４．２ｇ（５１．７ｍｍｏｌ）の２－（３，５－ジメチルアダマンタン－１－イル）－４－フルオロフェノールの溶液に、１００ｍＬのジクロロメタン中の２．６７ｍＬ（５１．７ｍｍｏｌ）の臭素の溶液を室温で１時間滴加した。生じた混合物を室温で４８時間撹拌し、次いで、２００ｍＬの５％ ＮａＨＣＯ₃に注意深く注いだ。粗生成物をジクロロメタン（３×５０ｍＬ）で抽出し、合わせた有機抽出物をＮａ₂ＳＯ₄で乾燥し、次いで、蒸発乾固した。収量１７．５ｇ（９６％）の淡黄色固体。¹H NMR (CDCl₃, 400 MHz): δ 7.06 (dd, J = 3.0, 7.0 Hz, 1H), 6.93 (dd, J = 2.9, 10.8 Hz, 1H), 5.59 (s, 1H), 2.16 (m, 1H), 1.89 (br.s, 2H), 1.63 - 1.73 (m, 4H), 1.34 - 1.44 (m, 4H), 1.19 (br.s, 2H), 0.86 (s, 6H). ¹³C NMR (CDCl₃, 100 MHz): δ 157.21 (J_F = 241 Hz), 146.61 (J_F = 2.8 Hz), 137.97 (J_F = 6.1 Hz), 115.34 (J_F = 25.8 Hz), 113.64 (J_F = 23.6 Hz), 110.83 (J_F = 10.9 Hz), 54.77, 50.48, 45.71, 42.61, 38.96, 38.03, 31.02, 30.42, 29.49. 2-Bromo-6- (3,5-dimethyladamantane-1-yl) -4-fluorophenol

To a solution of 14.2 g (51.7 mmol) of 2- (3,5-dimethyladamantane-1-yl) -4-fluorophenol in 200 mL of dichloromethane, 2.67 mL (51.7 mmol) in 100 mL of dichloromethane. A solution of bromine was added dropwise at room temperature for 1 hour. The resulting mixture was stirred at room temperature for 48 hours and then carefully poured into 200 mL of 5% NaHCO ₃ . The crude product was extracted with dichloromethane (3 x 50 mL) and the combined organic extracts were dried over Na ₂ SO ₄ and then evaporated to dryness. A pale yellow solid with a yield of 17.5 g (96%). ¹ H NMR (CDCl ₃ , 400 MHz): δ 7.06 (dd, J = 3.0, 7.0 Hz, 1H), 6.93 (dd, J = 2.9, 10.8 Hz, 1H), 5.59 (s, 1H), 2.16 (m) , 1H), 1.89 (br.s, 2H), 1.63 --1.73 (m, 4H), 1.34 --1.44 (m, 4H), 1.19 (br.s, 2H), 0.86 (s, 6H). ¹³ C NMR (CDCl ₃ , 100 MHz): δ 157.21 (J _F = 241 Hz), 146.61 (J _F = 2.8 Hz), 137.97 (J _F = 6.1 Hz), 115.34 (J _F = 25.8 Hz), 113.64 (J _F =) 23.6 Hz), 110.83 (J _F = 10.9 Hz), 54.77, 50.48, 45.71, 42.61, 38.96, 38.03, 31.02, 30.42, 29.49.

２００ｍＬの乾燥ＴＨＦ中の１７．５ｇ（４９．５ｍｍｏｌ）の２－ブロモ－６－（３，５－ジメチルアダマンタン－１－イル）－４－フルオロフェノールの溶液に、２．１７ｇ（５４．４ｍｍｏｌ、鉱油中６０質量％）の水素化ナトリウムを室温で分割して加えた。その後、４．５３ｍＬ（６０．０ｍｍｏｌ）のＭＯＭＣｌを１時間滴加した。反応混合物を６０℃で２４時間加熱し、次いで、３００ｍＬの冷水に注いだ。粗生成物を３×２００ｍＬのジクロロメタンで抽出した。合わせた有機抽出物をＮａ₂ＳＯ₄で乾燥し、次いで、蒸発乾固した。収量１９．６ｇ（定量的）の白色固体。¹H NMR (CDCl₃, 400 MHz): δ 7.13 (dd, J = 3.1, 6.8 Hz, 1H), 6.98 (dd, J = 3.1, 10.9 Hz, 1H), 5.19 (s, 2H), 3.68 (s, 3H), 2.16 (m, 1H), 1.89 (br.s, 2H), 1.64 - 1.74 (m, 4H), 1.34 - 1.44 (m, 4H), 1.19 (br.s, 2H), 0.87 (s, 6H). ¹³C NMR (CDCl₃, 100 MHz): δ 159.47 (J_F = 245 Hz), 150.08 (J_F = 3.3 Hz), 146.34 (J_F = 6.4 Hz), 118.13 (J_F = 25.4 Hz), 117.65 (J_F = 10.7 Hz), 114.01 (J_F = 23.4 Hz), 99.95, 57.89, 50.69, 47.13, 42.84, 39.78, 39.55, 31.50, 30.84, 29.94. 1- (3-bromo-5-fluoro-2- (methoxymethoxy) phenyl) -3,5-dimethyladamantane

2.17 g (54.4 mmol, 54.4 mmol, in a solution of 17.5 g (49.5 mmol) of 2-bromo-6- (3,5-dimethyladamantan-1-yl) -4-fluorophenol in 200 mL of dry THF. Sodium hydride (60% by weight in mineral oil) was added in portions at room temperature. Then, 4.53 mL (60.0 mmol) of MOMCl was added dropwise for 1 hour. The reaction mixture was heated at 60 ° C. for 24 hours and then poured into 300 mL of cold water. The crude product was extracted with 3 x 200 mL dichloromethane. The combined organic extracts were dried over Na ₂ SO ₄ and then evaporated to dryness. A white solid with a yield of 19.6 g (quantitative). ¹ H NMR (CDCl ₃ , 400 MHz): δ 7.13 (dd, J = 3.1, 6.8 Hz, 1H), 6.98 (dd, J = 3.1, 10.9 Hz, 1H), 5.19 (s, 2H), 3.68 (s) , 3H), 2.16 (m, 1H), 1.89 (br.s, 2H), 1.64 --1.74 (m, 4H), 1.34 --1.44 (m, 4H), 1.19 (br.s, 2H), 0.87 (s) , 6H). ¹³ C NMR (CDCl ₃ , 100 MHz): δ 159.47 (J _F = 245 Hz), 150.08 (J _F = 3.3 Hz), 146.34 (J _F = 6.4 Hz), 118.13 (J _F = 25.4 Hz) ), 117.65 (J _F = 10.7 Hz), 114.01 (J _F = 23.4 Hz), 99.95, 57.89, 50.69, 47.13, 42.84, 39.78, 39.55, 31.50, 30.84, 29.94.

２５０ｍＬの乾燥ＴＨＦ中の１４．０ｇ（３５．３ｍｍｏｌ）の１－（３－ブロモ－５－フルオロ－２－（メトキシメトキシ）フェニル）－３，５－ジメチルアダマンタンの溶液に、ヘキサン中の１６．９ｍＬ（４２．３ｍｍｏｌ）の２．５Ｍ ⁿＢｕＬｉを－８０℃で２０分間滴加した。反応混合物をこの温度で１時間撹拌し、続いて、１１．０ｍＬ（５２．９ｍｍｏｌ）の２－イソプロポキシ－４，４，５，５－テトラメチル－１，３，２－ジオキサボロランを加えた。得られた懸濁液を室温で１時間撹拌し、次いで、３００ｍＬの水に注いだ。粗生成物をジクロロメタン（３×１００ｍＬ）で抽出し、合わせた有機抽出物をＮａ₂ＳＯ₄で乾燥し、次いで、蒸発乾固した。残留物をイソプロパノールから再結晶させた。収量９．６５ｇ（６２％）の白色固体。¹H NMR (CDCl₃, 400 MHz): δ 7.19 (dd, J = 7.7, 3.3 Hz, 1H), 7.08 (dd, J = 11.0, 3.3 Hz, 1H), 5.11 (s, 2H), 3.57 (s, 3H), 2.13 - 2.16 (m, 1H), 1.92 (br.s, 2H), 1.66 - 1.77 (m, 4H), 1.34 (s, 12H), 1.33 - 1.44 (m, 4H), 1.18 (br.s, 2H), 0.85 (s, 6H). ¹³C NMR (CDCl₃, 100 MHz): δ 159.41 (d, J_C,F = 240 Hz), 157.64, 143.65 (d, J_C,F = 5.5 Hz), 119.53 (d, J_C,F = 21.0 Hz), 117.42 (d, J_C,F = 24.0 Hz), 101.19, 84.00, 57.86, 50.91, 47.15, 43.03, 39.51, 39.03, 31.48, 30.90, 30.00, 24.78. 2- (3-((1r, 3R, 5S, 7r) -3,5-dimethyladamantane-1-yl) -5-fluoro-2- (methoxymethoxy) phenyl) -4,4,5,5-tetra Methyl-1,3,2-dioxaborolane

16. In hexane to a solution of 14.0 g (35.3 mmol) of 1- (3-bromo-5-fluoro-2- (methoxymethoxy) phenyl) -3,5-dimethyladamantane in 250 mL of dry THF. 9 mL (42.3 mmol) of 2.5 M ⁿ BuLi was added dropwise at −80 ° C. for 20 minutes. The reaction mixture was stirred at this temperature for 1 hour, followed by the addition of 11.0 mL (52.9 mmol) 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane. The resulting suspension was stirred at room temperature for 1 hour and then poured into 300 mL of water. The crude product was extracted with dichloromethane (3 x 100 mL) and the combined organic extracts were dried over Na ₂ SO ₄ and then evaporated to dryness. The residue was recrystallized from isopropanol. A white solid with a yield of 9.65 g (62%). ¹ H NMR (CDCl ₃ , 400 MHz): δ 7.19 (dd, J = 7.7, 3.3 Hz, 1H), 7.08 (dd, J = 11.0, 3.3 Hz, 1H), 5.11 (s, 2H), 3.57 (s) , 3H), 2.13 --2.16 (m, 1H), 1.92 (br.s, 2H), 1.66 ―― 1.77 (m, 4H), 1.34 (s, 12H), 1.33 --1.44 (m, 4H), 1.18 (br .s, 2H), 0.85 (s, 6H). ¹³ C NMR (CDCl ₃ , 100 MHz): δ 159.41 (d, J _{C, F} = 240 Hz), 157.64, 143.65 (d, J _{C, F} = 5.5) Hz), 119.53 (d, J _{C, F} = 21.0 Hz), 117.42 (d, J _{C, F} = 24.0 Hz), 101.19, 84.00, 57.86, 50.91, 47.15, 43.03, 39.51, 39.03, 31.48, 30.90, 30.00 , 24.78.

２０ｍＬの１，４－ジオキサン中の４．０２ｇ（９．０９ｍｍｏｌ）の２－（（３ｒ，５ｒ，７ｒ）－３－アダマンタン－１－イル）－５－フルオロ－２－（メトキシメトキシ）フェニル）－４，４，５，５－テトラメチル－１，３，２－ジオキサボロランの溶液に、３．５５ｇ（１０．９ｍｍｏｌ）の２－ブロモ－４－イソプロピルヨードベンゼン、７．４０ｇ（２２．７ｍｍｏｌ）の炭酸セシウムおよび１０ｍＬの水を続いて加えた。得られた混合物をアルゴンで１０分間パージし、続いて、５２５ｍｇ（０．４８ｍｍｏｌ）のＰｄ（ＰＰｈ₃）₄を加えた。この混合物を１００℃で１２時間撹拌し、次いで、室温まで冷却し、１００ｍＬの水で希釈した。粗生成物をジクロロメタン（３×５０ｍＬ）で抽出し、合わせた有機抽出物をＮａ₂ＳＯ₄で乾燥し、次いで、蒸発乾固した。残留物をシリカゲル６０によるフラッシュクロマトグラフィー（４０～６３ｕｍ、溶離液：ヘキサン－ジクロロメタン＝１０：１、体積）により精製した。収量４．００ｇ（８６％）の白色固体。¹H NMR (CDCl₃, 400 MHz): δ 7.52 (d, J = 1.5 Hz, 1H), 7.26 (d, J = 7.7 Hz, 1H), 7.20 (dd, J = 7.8, 1.6 Hz, 1H), 7.03 (dd, J = 11.1, 3.2 Hz, 1H), 6.78 (dd, J = 7.9, 3.2 Hz, 1H), 4.47 (m, 1H), 4.36 (m, 1H), 3.18 (s, 3H), 2.92 (七重線, J = 6.9 Hz, 1H), 2.15 - 2.20 (m, 1H), 1.92 - 1.99 (m, 2H), 1.77 - 1.83 (m, 2H), 1.65 - 1.71 (m, 2H), 1.34 - 1.47 (m, 4H), 1.27 (d, J = 6.9 Hz, 6H), 1.20 (br.s, 2H), 0.88 (s, 6H). ¹³C NMR (CDCl₃, 100 MHz): δ 159.24 (d, J_C,F = 240 Hz), 150.45, 150.18 (d, J_C,F = 2.6 Hz), 144.82 (d, J_C,F = 6.5 Hz), 137.25, 135.86 (d, J_C,F = 8.7 Hz), 131.90, 130.88, 125.50, 123.59, 115.76 (d, J_C,F = 22.9 Hz), 113.96 (d, J_C,F = 23.8 Hz), 99.13, 57.10, 50.89, 47.25, 47.20, 43.01, 39.47, 39.28, 33.65, 31.50, 30.95, 30.02, 23.86, 23.84. (1r, 3R, 5S, 7r) -1- (2'-bromo-5-fluoro-4'-isopropyl-2- (methoxymethoxy)-[1,1'-biphenyl] -3-yl) -3, 5-Dimethyl Adamantane

4.02 g (9.09 mmol) 2-((3r, 5r, 7r) -3-adamantan-1-yl) -5-fluoro-2- (methoxymethoxy) phenyl in 20 mL of 1,4-dioxane) 3.55 g (10.9 mmol) of 2-bromo-4-isopropyliodobenzene in a solution of -4,4,5,5-tetramethyl-1,3,2-dioxaborolane, 7.40 g (22.7 mmol). Cesium carbonate and 10 mL of water were subsequently added. The resulting mixture was purged with argon for 10 minutes, followed by the addition of 525 mg (0.48 mmol) of Pd (PPh ₃ ) ₄ . The mixture was stirred at 100 ° C. for 12 hours, then cooled to room temperature and diluted with 100 mL of water. The crude product was extracted with dichloromethane (3 x 50 mL) and the combined organic extracts were dried over Na ₂ SO ₄ and then evaporated to dryness. The residue was purified by flash chromatography on silica gel 60 (40-63 um, eluent: hexane-dichloromethane = 10: 1, volume). A white solid with a yield of 4.00 g (86%). ¹ H NMR (CDCl ₃ , 400 MHz): δ 7.52 (d, J = 1.5 Hz, 1H), 7.26 (d, J = 7.7 Hz, 1H), 7.20 (dd, J = 7.8, 1.6 Hz, 1H), 7.03 (dd, J = 11.1, 3.2 Hz, 1H), 6.78 (dd, J = 7.9, 3.2 Hz, 1H), 4.47 (m, 1H), 4.36 (m, 1H), 3.18 (s, 3H), 2.92 (Seven-fold line, J = 6.9 Hz, 1H), 2.15 --2.20 (m, 1H), 1.92 --1.99 (m, 2H), 1.77 --1.83 (m, 2H), 1.65 --1.71 (m, 2H), 1.34 - 1.47 (m, 4H), 1.27 (d, J = 6.9 Hz, 6H), 1.20 (br.s, 2H), 0.88 (s, 6H). ¹³ C NMR (CDCl ₃ , 100 MHz): δ 159.24 (d) , J _{C, F} = 240 Hz), 150.45, 150.18 (d, J _{C, F} = 2.6 Hz), 144.82 (d, J _{C, F} = 6.5 Hz), 137.25, 135.86 (d, J _{C, F} = 8.7) Hz), 131.90, 130.88, 125.50, 123.59, 115.76 (d, J _{C, F} = 22.9 Hz), 113.96 (d, J _{C, F} = 23.8 Hz), 99.13, 57.10, 50.89, 47.25, 47.20, 43.01, 39.47 , 39.28, 33.65, 31.50, 30.95, 30.02, 23.86, 23.84.

５０ｍＬの乾燥ＴＨＦ中の４．００ｇ（７．７６ｍｍｏｌ）の（１ｒ，３Ｒ，５Ｓ，７ｒ）－１－（２’－ブロモ－５－フルオロ－４’－イソプロピル－２－（メトキシメトキシ）－［１，１’－ビフェニル］－３－イル）－３，５－ジメチルアダマンタンの溶液に、ヘキサン中の３．１７ｍＬ（７．９１ｍｍｏｌ）の２．５Ｍ ⁿＢｕＬｉを－８０℃で２０分間滴加した。反応混合物をこの温度で１時間撹拌し、続いて、２．３５ｍＬ（１１．６ｍｍｏｌ）の２－イソプロポキシ－４，４，５，５－テトラメチル－１，３，２－ジオキサボロランを加えた。得られた懸濁液を室温で１時間撹拌し、次いで、３００ｍＬの水に注いだ。粗生成物をジクロロメタン（３×１００ｍＬ）で抽出し、合わせた有機抽出物をＮａ₂ＳＯ₄で乾燥し、次いで、蒸発乾固した。残留物をシリカゲル６０によるフラッシュクロマトグラフィー（４０～６３ｕｍ、溶離液：ヘキサン－ジエチルエーテル＝１０：１、体積）により精製した。収量３．９７ｇ（９１％）の無色ガラス状固体。¹H NMR (CDCl₃, 400 MHz): δ 7.59 (d, J = 1.8 Hz, 1H), 7.29 (dd, J = 7.9, 1.9 Hz, 1H), 7.24 (d, J = 7.9 Hz, 1H), 6.95 (dd, J = 11.2, 3.2 Hz, 1H), 6.72 (dd, J = 8.1, 3.2 Hz, 1H), 4.34 (s, 2H), 3.22 (s, 3H), 2.95 (七重線, J = 6.9 Hz, 1H), 2.14- 2.19 (m, 1H), 1.72 - 1.98 (m, 6H), 1.31 - 1.45 (m, 4H), 1.28 (d, J = 6.9 Hz, 6H), 1.13 - 1.22 (m, 14H). ¹³C NMR (CDCl₃, 100 MHz): δ 159.29 (d, J_C,F = 240 Hz), 150.01 (d, J_C,F = 2.6 Hz), 147.15, 143.88 (d, J_C,F = 6.5 Hz), 142.10 (d, J_C,F = 1.7 Hz), 132.85, 130.16, 128.06, 115.85 (d, J_C,F = 22.7 Hz), 112.63 (d, J_C,F = 23.6 Hz), 98.83, 83.46, 57.24, 50.90, 47.44 (広幅), 43.04, 39.69, 39.20, 33.85, 31.52, 30.94, 30.08, 25.20 (広幅), 24.17 (広幅), 24.04. 2- (3'-((1r, 3R, 5S, 7r) -3,5-dimethyladamantane-1-yl) -5'-fluoro-4-isopropyl-2'-(methoxymethoxy)-[1,1 '-Biphenyl] -2-yl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane

4.00 g (7.76 mmol) of (1r, 3R, 5S, 7r) -1- (2'-bromo-5-fluoro-4'-isopropyl-2- (methoxymethoxy)-[in 50 mL of dry THF. To a solution of 1,1'-biphenyl] -3-yl) -3,5-dimethyladamantane, 3.17 mL (7.91 mmol) of 2.5 M ⁿ BuLi in hexane was added dropwise at -80 ° C for 20 minutes. .. The reaction mixture was stirred at this temperature for 1 hour, followed by the addition of 2.35 mL (11.6 mmol) 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane. The resulting suspension was stirred at room temperature for 1 hour and then poured into 300 mL of water. The crude product was extracted with dichloromethane (3 x 100 mL) and the combined organic extracts were dried over Na ₂ SO ₄ and then evaporated to dryness. The residue was purified by flash chromatography on silica gel 60 (40-63 um, eluent: hexane-diethyl ether = 10: 1, volume). A colorless glassy solid with a yield of 3.97 g (91%). ¹ H NMR (CDCl ₃ , 400 MHz): δ 7.59 (d, J = 1.8 Hz, 1H), 7.29 (dd, J = 7.9, 1.9 Hz, 1H), 7.24 (d, J = 7.9 Hz, 1H), 6.95 (dd, J = 11.2, 3.2 Hz, 1H), 6.72 (dd, J = 8.1, 3.2 Hz, 1H), 4.34 (s, 2H), 3.22 (s, 3H), 2.95 (seven-fold line, J = 6.9) Hz, 1H), 2.14- 2.19 (m, 1H), 1.72 --1.98 (m, 6H), 1.31 --1.45 (m, 4H), 1.28 (d, J = 6.9 Hz, 6H), 1.13 --1.22 (m, 14H). ¹³ C NMR (CDCl ₃ , 100 MHz): δ 159.29 (d, J _{C, F} = 240 Hz), 150.01 (d, J _{C, F} = 2.6 Hz), 147.15, 143.88 (d, J _{C, F} = 6.5 Hz), 142.10 (d, J _{C, F} = 1.7 Hz), 132.85, 130.16, 128.06, 115.85 (d, J _{C, F} = 22.7 Hz), 112.63 (d, J _{C, F} = 23.6 Hz) , 98.83, 83.46, 57.24, 50.90, 47.44 (wide), 43.04, 39.69, 39.20, 33.85, 31.52, 30.94, 30.08, 25.20 (wide), 24.17 (wide), 24.04.

４０ｍＬの１，４－ジオキサン中の３．９７ｇ（７．７６ｍｍｏｌ）の２－（３’－（（１ｒ，３Ｒ，５Ｓ，７ｒ）－３，５－ジメチルアダマンタン－１－イル）－５’－フルオロ－４－イソプロピル－２’－（メトキシメトキシ）－［１，１’－ビフェニル］－２－イル）－４，４，５，５－テトラメチル－１，３，２－ジオキサボロランの溶液に、８８０ｍｇ（３．７２ｍｍｏｌ）の２，６－ジブロモピリジン、６．４０ｇ（１９．４ｍｍｏｌ）の炭酸セシウムおよび２０ｍＬの水を続いて加えた。得られた混合物をアルゴンで１０分間パージし、続いて、４００ｍｇ（０．３８０ｍｍｏｌ）のＰｄ（ＰＰｈ₃）₄を加えた。この混合物を１００℃で１２時間撹拌し、次いで、室温まで冷却し、５０ｍＬの水で希釈した。こうして得られた混合物をジクロロメタン（３×５０ｍＬ）で抽出し、合わせた有機抽出物をＮａ₂ＳＯ₄で乾燥し、次いで、蒸発乾固した。得られた油に、５０ｍＬのＴＨＦ、５０ｍＬのメタノールおよび３ｍＬの１２Ｎ ＨＣｌを続いて加えた。反応混合物を６０℃で一晩撹拌し、次いで、２００ｍＬの水に注いだ。粗生成物をジクロロメタン（３×７０ｍＬ）で抽出し、合わせた有機抽出物を５％ ＮａＨＣＯ₃で洗浄し、Ｎａ₂ＳＯ₄で乾燥し、次いで、蒸発乾固した。残留物をシリカゲル６０によるフラッシュクロマトグラフィー（４０～６３ｕｍ、溶離液：ヘキサン－酢酸エチル＝１０：１、体積）により精製した。収量２．１１ｇ（６６％）の白色泡としての２種の異性体の混合物。¹H NMR (CDCl₃, 400 MHz): δ 7.87および7.04 (2s, 2H), 7.63および7.42 (2t, 1H), 7.21 - 7.38 (m, 7H), 7.15および6.98 (2d, J = 7.8 Hz, 2H), 6.80 (dd, J = 11.0, 3.0 Hz, 1H), 6.74 (dd, J = 8.0, 3.0 Hz, 1H), 6.69 (dd, J = 11.1, 3.0 Hz, 1H), 6.11 (dd, J = 8.1, 3.1 Hz, 1H), 2.94 - 3.06 (2本の七重線, 2H), 1.41 - 1.85 (m, 12H), 0.96 - 1.35 (m, 24H), 0.78 (s, 3H), 0.77 (s, 3H), 0.72 (s, 3H), 0.69 (s, 3H). ¹³C NMR (CDCl₃, 100 MHz) δ 157.65 (d, J_C,F = 238 Hz), 149.11, 148.67, 148.01, 140.28, 139.20, 138.29, 137.09, 134.11, 133.64, 132.05, 131.61, 128.58, 127.93, 122.28, 114.60 (d, J_C,F = 22.3 Hz), 114.13 (d, J_C,F = 23.0 Hz), 113.22 (d, J_C,F = 23.4 Hz), 51.07, 50.72, 47.18, 46.97, 46.09, 46.03, 43.18, 42.89, 42.68, 42.63, 38.59, 38.47, 37.89, 33.85, 33.73, 31.45, 31.27, 31.20, 31.09, 31.01, 30.89, 30.82, 30.70, 30.01, 29.96. 2', 2'''-(pyridin-2,6-diyl) bis (3-((1r, 3R, 5S, 7r) -3,5-dimethyladamantane-1-yl) -5-fluoro-4' -Isopropyl- [1,1'-biphenyl] -2-ol)

3.97 g (7.76 mmol) 2- (3'-((1r, 3R, 5S, 7r) -3,5-dimethyladamantane-1-yl) -5'- in 40 mL of 1,4-dioxane In a solution of fluoro-4-isopropyl-2'-(methoxymethoxy)-[1,1'-biphenyl] -2-yl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane, 880 mg (3.72 mmol) of 2,6-dibromopyridine, 6.40 g (19.4 mmol) of cesium carbonate and 20 mL of water were subsequently added. The resulting mixture was purged with argon for 10 minutes, followed by the addition of 400 mg (0.380 mmol) of Pd (PPh ₃ ) ₄ . The mixture was stirred at 100 ° C. for 12 hours, then cooled to room temperature and diluted with 50 mL of water. The mixture thus obtained was extracted with dichloromethane (3 x 50 mL) and the combined organic extracts were dried over Na ₂ SO ₄ and then evaporated to dryness. 50 mL of THF, 50 mL of methanol and 3 mL of 12N HCl were subsequently added to the resulting oil. The reaction mixture was stirred at 60 ° C. overnight and then poured into 200 mL of water. The crude product was extracted with dichloromethane (3 x 70 mL) and the combined organic extracts were washed with 5% NaHCO ₃ and dried over Na ₂ SO ₄ and then evaporated to dryness. The residue was purified by flash chromatography on silica gel 60 (40-63 um, eluent: hexane-ethyl acetate = 10: 1, volume). A mixture of the two isomers as a white foam with a yield of 2.11 g (66%). ¹ H NMR (CDCl ₃ , 400 MHz): δ 7.87 and 7.04 (2s, 2H), 7.63 and 7.42 (2t, 1H), 7.21--7.38 (m, 7H), 7.15 and 6.98 (2d, J = 7.8 Hz, 2H), 6.80 (dd, J = 11.0, 3.0 Hz, 1H), 6.74 (dd, J = 8.0, 3.0 Hz, 1H), 6.69 (dd, J = 11.1, 3.0 Hz, 1H), 6.11 (dd, J = 8.1, 3.1 Hz, 1H), 2.94 --3.06 (two seven-fold wires, 2H), 1.41 --1.85 (m, 12H), 0.96 --1.35 (m, 24H), 0.78 (s, 3H), 0.77 (s) , 3H), 0.72 (s, 3H), 0.69 (s, 3H). ¹³ C NMR (CDCl ₃ , 100 MHz) δ 157.65 (d, J _{C, F} = 238 Hz), 149.11, 148.67, 148.01, 140.28, 139.20, 138.29, 137.09, 134.11, 133.64, 132.05, 131.61, 128.58, 127.93, 122.28, 114.60 (d, J _{C, F} = 22.3 Hz), 114.13 (d, J _{C, F} = 23.0 Hz), 113.22 (d, J _{C, F} = 23.4 Hz), 51.07, 50.72, 47.18, 46.97, 46.09, 46.03, 43.18, 42.89, 42.68, 42.63, 38.59, 38.47, 37.89, 33.85, 33.73, 31.45, 31.27, 31.20, 31.09, 31.01, 30.89 , 30.82, 30.70, 30.01, 29.96.

３０ｍＬのジクロロメタン中の２．８０ｇ（２５．０ｍｍｏｌ）の４－フルオロフェノールおよび４．４０ｇ（２２．７ｍｍｏｌ）の３，５，７－トリメチルアダマンタン－１－オールの溶液に、３０ｍＬのジクロロメタン中の１．６０ｍＬ（２５．０ｍｍｏｌ）のメタンスルホン酸および２ｍＬの酢酸の溶液を室温で１時間滴加した。生じた混合物を室温で４８時間撹拌し、次いで、３００ｍＬの５％ ＮａＨＣＯ₃に注意深く注いだ。粗生成物をジクロロメタン（３×５０ｍＬ）で抽出し、合わせた有機抽出物をＮａ₂ＳＯ₄で乾燥し、次いで、蒸発乾固した。クーゲルロール装置（１ｍｂａｒ、８０℃）を使用して残留物を精製して、３．９ｇ（６０％）の表題生成物を淡黄色油として得た。¹H NMR (CDCl₃, 400 MHz): δ 6.93 (dd, J = 11.3, 3.1 Hz, 1H), 6.70 - 6.74 (m, 1H), 6.55 (dd, J = 8.6, 5.0 Hz, 1H), 4.87 (br.s, 1H), 1.62 (br.s, 6H), 1.00 - 1.18 (m, 6H), 0.87 (s, 9H). ¹³C NMR (CDCl₃, 100 MHz): δ 158.44 (d, J_C,F = 237 Hz), 150.28 (d, J_C,F = 2.0 Hz), 137.44 (d, J_C,F = 5.9 Hz), 117.10 (d, J_C,F = 8.3 Hz), 114.13 (d, J_C,F = 24.0 Hz), 112.56 (d, J_C,F = 23.0 Hz), 50.28, 45.77, 39.34, 32.12, 30.46. 4-Fluoro-2-((3r, 5r, 7r) -3,5,7-trimethyladamantane-1-yl) phenol

1.80 g (25.0 mmol) of 4-fluorophenol in 30 mL of dichloromethane and 4.40 g (22.7 mmol) of 3,5,7-trimethyladamantane-1-ol in a solution of 1 in 30 mL of dichloromethane. A solution of .60 mL (25.0 mmol) methanesulfonic acid and 2 mL acetic acid was added dropwise at room temperature for 1 hour. The resulting mixture was stirred at room temperature for 48 hours and then carefully poured into 300 mL of 5% NaHCO ₃ . The crude product was extracted with dichloromethane (3 x 50 mL) and the combined organic extracts were dried over Na ₂ SO ₄ and then evaporated to dryness. The residue was purified using a Kugelrohr device (1 mbar, 80 ° C.) to give 3.9 g (60%) of the title product as a pale yellow oil. ¹ H NMR (CDCl ₃ , 400 MHz): δ 6.93 (dd, J = 11.3, 3.1 Hz, 1H), 6.70 --6.74 (m, 1H), 6.55 (dd, J = 8.6, 5.0 Hz, 1H), 4.87 (br.s, 1H), 1.62 (br.s, 6H), 1.00 --1.18 (m, 6H), 0.87 (s, 9H). ¹³ C NMR (CDCl ₃ , 100 MHz): δ 158.44 (d, J) _{C, F} = 237 Hz), 150.28 (d, J _{C, F} = 2.0 Hz), 137.44 (d, J _{C, F} = 5.9 Hz), 117.10 (d, J _{C, F} = 8.3 Hz), 114.13 (d) , J _{C, F} = 24.0 Hz), 112.56 (d, J _{C, F} = 23.0 Hz), 50.28, 45.77, 39.34, 32.12, 30.46.

２０ｍＬのＤＭＦ中の３．６０ｇ（１２．５ｍｍｏｌ）の４－フルオロ－２－（（３ｒ，５ｒ，７ｒ）－３，５，７－トリメチルアダマンタン－１－イル）フェノールの溶液に、２．２２ｇ（１２．５ｍｍｏｌ）のＮＢＳを室温で１回で加えた。生じた混合物を室温で４８時間撹拌し、次いで、２００ｍＬの５％ ＮａＨＣＯ₃に注意深く注いだ。粗生成物をジクロロメタン（３×５０ｍＬ）で抽出し、合わせた有機抽出物をＮａ₂ＳＯ₄で乾燥し、次いで、蒸発乾固した。残留物をシリカゲル６０によるフラッシュクロマトグラフィー（４０～６３ｕｍ、溶離液：ヘキサン－ジクロロメタン＝１０：１、体積）により精製した。収量３．００ｇ（６５％）の白色固体。¹H NMR (CDCl₃, 400 MHz): δ 7.06 (dd, J = 6.9, 3.0 Hz, 1H), 6.94 (dd, J = 10.8, 3.0 Hz, 1H), 5.60 (s, 1H), 1.61 (br.s, 6H), 1.06 - 1.18 (m, 6H), 0.87 (s, 9H). ¹³C NMR (CDCl₃, 100 MHz): δ 157.20 (d, J_C,F = 241 Hz), 146.99 (d, J_C,F = 3.0 Hz), 138.10 (d, J_C,F = 6.0 Hz), 115.76 (d, J_C,F = 26.0 Hz), 114.06 (d, J_C,F = 23.6 Hz), 111.22 (d, J_C,F = 10.9 Hz), 50.20, 45.45, 40.19, 32.14, 30.42. 2-Bromo-4-fluoro-6-((3r, 5r, 7r) -3,5,7-trimethyladamantane-1-yl) phenol

2.22 g in a solution of 3.60 g (12.5 mmol) 4-fluoro-2-((3r, 5r, 7r) -3,5,7-trimethyladamantan-1-yl) phenol in 20 mL DMF. (12.5 mmol) NBS was added in one dose at room temperature. The resulting mixture was stirred at room temperature for 48 hours and then carefully poured into 200 mL of 5% NaHCO ₃ . The crude product was extracted with dichloromethane (3 x 50 mL) and the combined organic extracts were dried over Na ₂ SO ₄ and then evaporated to dryness. The residue was purified by flash chromatography on silica gel 60 (40-63 um, eluent: hexane-dichloromethane = 10: 1, volume). A white solid with a yield of 3.00 g (65%). ¹ H NMR (CDCl ₃ , 400 MHz): δ 7.06 (dd, J = 6.9, 3.0 Hz, 1H), 6.94 (dd, J = 10.8, 3.0 Hz, 1H), 5.60 (s, 1H), 1.61 (br .s, 6H), 1.06 --1.18 (m, 6H), 0.87 (s, 9H). ¹³ C NMR (CDCl ₃ , 100 MHz): δ 157.20 (d, J _{C, F} = 241 Hz), 146.99 (d) , J _{C, F} = 3.0 Hz), 138.10 (d, J _{C, F} = 6.0 Hz), 115.76 (d, J _{C, F} = 26.0 Hz), 114.06 (d, J _{C, F} = 23.6 Hz), 111.22 (d, J _{C, F} = 10.9 Hz), 50.20, 45.45, 40.19, 32.14, 30.42.

２０ｍＬの乾燥ＴＨＦ中の２．２０ｇ（６．００ｍｍｏｌ）の２－ブロモ－４－フルオロ－６－（（３ｒ，５ｒ，７ｒ）－３，５，７－トリメチルアダマンタン－１－イル）フェノールの溶液に、２７０ｍｇ（６．６０ｍｍｏｌ、鉱油中６０質量％）の水素化ナトリウムを室温で加えた。その後、６３０ｕｌ（７．８０ｍｍｏｌ）のＭＯＭＣｌを１回で加えた。反応混合物を６０℃で２４時間加熱し、次いで、３０ｍＬの冷水に注いだ。粗生成物を３×２０ｍＬのジクロロメタンで抽出した。合わせた有機抽出物をＮａ₂ＳＯ₄で乾燥し、次いで、蒸発乾固した。収量２．５０ｇ（９７％）の白色固体。¹H NMR (CDCl₃, 400 MHz): δ 7.14 (dd, J = 6.9, 3.1 Hz, 1H), 6.99 (dd, J = 10.9, 3.1 Hz, 1H), 5.19 (s, 2H), 3.67 (s, 3H), 1.62 (br.s, 6H), 1.06 - 1.17 (m, 6H), 0.88 (s, 9H). ¹³C NMR (CDCl₃, 100 MHz): δ 159.50 (d, J_C,F = 245 Hz), 150.15, 146.11 (d, J_C,F = 6.4 Hz), 118.17 (d, J_C,F = 25.4 Hz), 117.67 (d, J_C,F = 10.5 Hz), 114.05 (d, J_C,F = 23.6 Hz), 100.08, 57.93, 50.07, 46.53, 40.65, 32.25, 30.46. (3r, 5r, 7r) -1- (3-bromo-5-fluoro-2- (methoxymethoxy) phenyl) -3,5,7-trimethyladamantane

A solution of 2.20 g (6.00 mmol) of 2-bromo-4-fluoro-6-((3r, 5r, 7r) -3,5,7-trimethyladamantane-1-yl) phenol in 20 mL of dry THF. To 270 mg (6.60 mmol, 60% by weight in mineral oil) sodium hydride was added at room temperature. Then 630 ul (7.80 mmol) MOMCl was added in one dose. The reaction mixture was heated at 60 ° C. for 24 hours and then poured into 30 mL of cold water. The crude product was extracted with 3 x 20 mL dichloromethane. The combined organic extracts were dried over Na ₂ SO ₄ and then evaporated to dryness. A white solid with a yield of 2.50 g (97%). ¹ H NMR (CDCl ₃ , 400 MHz): δ 7.14 (dd, J = 6.9, 3.1 Hz, 1H), 6.99 (dd, J = 10.9, 3.1 Hz, 1H), 5.19 (s, 2H), 3.67 (s) , 3H), 1.62 (br.s, 6H), 1.06 --1.17 (m, 6H), 0.88 (s, 9H). ¹³ C NMR (CDCl ₃ , 100 MHz): δ 159.50 (d, J _{C, F} = 245 Hz), 150.15, 146.11 (d, J _{C, F} = 6.4 Hz), 118.17 (d, J _{C, F} = 25.4 Hz), 117.67 (d, J _{C, F} = 10.5 Hz), 114.05 (d, J) _{C, F} = 23.6 Hz), 100.08, 57.93, 50.07, 46.53, 40.65, 32.25, 30.46.

３０ｍＬの乾燥ＴＨＦ中の２．５０ｇ（５．８９ｍｍｏｌ）の（３ｒ，５ｒ，７ｒ）－１－（３－ブロモ－５－フルオロ－２－（メトキシメトキシ）フェニル）－３，５，７－トリメチルアダマンタンの溶液に、ヘキサン中の２．６８ｍＬ（６．７０ｍｍｏｌ）の２．５Ｍ ⁿＢｕＬｉを－８０℃で２０分間滴加した。反応混合物をこの温度で１時間撹拌し、続いて、１．８４ｍＬ（７．１２ｍｍｏｌ）の２－イソプロポキシ－４，４，５，５－テトラメチル－１，３，２－ジオキサボロランを加えた。得られた懸濁液を室温で１時間撹拌し、次いで、３０ｍＬの水に注いだ。粗生成物をジクロロメタン（３×４０ｍＬ）で抽出し、合わせた有機抽出物をＮａ₂ＳＯ₄で乾燥し、次いで、蒸発乾固した。収量２．７０ｇ（９６％）の白色固体。¹H NMR (CDCl₃, 400 MHz): δ 7.20 (dd, J = 7.6, 3.2 Hz, 1H), 7.08 (dd, J = 10.9, 3.3 Hz, 1H), 5.11 (s, 2H), 3.57 (s, 3H), 1.65 (br.s, 6H), 1.34 (s, 12H), 1.06 - 1.17 (m, 6H), 0.86 (s, 9H). ¹³C NMR (CDCl₃, 100 MHz): δ 159.39 (d, J_C,F = 240 Hz), 157.71 (d, J_C,F = 2.0 Hz), 143.38 (d, J_C,F = 5.7 Hz), 119.59 (d, J_C,F = 21.0 Hz), 117.46 (d, J_C,F = 24.0 Hz), 101.29, 84.01, 57.92, 50.24, 46.51, 39.88, 32.20, 30.52, 24.77. 2- (5-Fluoro-2- (Methoxymethoxy) -3-((3r, 5r, 7r) -3,5,7-trimethyladamantane-1-yl) phenyl) -4,4,5,5-tetra Methyl-1,3,2-dioxaborolane

2.50 g (5.89 mmol) of (3r, 5r, 7r) -1- (3-bromo-5-fluoro-2- (methoxymethoxy) phenyl) -3,5,7-trimethyl in 30 mL of dry THF 2.68 mL (6.70 mmol) of 2.5 M ⁿ BuLi in hexane was added dropwise to the solution of adamantane at −80 ° C. for 20 minutes. The reaction mixture was stirred at this temperature for 1 hour, followed by the addition of 1.84 mL (7.12 mmol) of 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane. The resulting suspension was stirred at room temperature for 1 hour and then poured into 30 mL of water. The crude product was extracted with dichloromethane (3 x 40 mL) and the combined organic extracts were dried over Na ₂ SO ₄ and then evaporated to dryness. A white solid with a yield of 2.70 g (96%). ¹ H NMR (CDCl ₃ , 400 MHz): δ 7.20 (dd, J = 7.6, 3.2 Hz, 1H), 7.08 (dd, J = 10.9, 3.3 Hz, 1H), 5.11 (s, 2H), 3.57 (s) , 3H), 1.65 (br.s, 6H), 1.34 (s, 12H), 1.06 --1.17 (m, 6H), 0.86 (s, 9H). ¹³ C NMR (CDCl ₃ , 100 MHz): δ 159.39 ( d, J _{C, F} = 240 Hz), 157.71 (d, J _{C, F} = 2.0 Hz), 143.38 (d, J _{C, F} = 5.7 Hz), 119.59 (d, J _{C, F} = 21.0 Hz), 117.46 (d, J _{C, F} = 24.0 Hz), 101.29, 84.01, 57.92, 50.24, 46.51, 39.88, 32.20, 30.52, 24.77.

２０ｍＬの１，４－ジオキサン中の２．７０ｇ（５．８９ｍｍｏｌ）の２－（５－フルオロ－２－（メトキシメトキシ）－３－（（３ｒ，５ｒ，７ｒ）－３，５，７－トリメチルアダマンタン－１－イル）フェニル）－４，４，５，５－テトラメチル－１，３，２－ジオキサボロランの溶液に、２．２４ｇ（７．９０ｍｍｏｌ）の２－ブロモヨードベンゼン、５．００ｇ（１５．２ｍｍｏｌ）の炭酸セシウムおよび１０ｍＬの水を続いて加えた。得られた混合物をアルゴンで１０分間パージし、続いて、３５０ｍｇ（０．３０ｍｍｏｌ）のＰｄ（ＰＰｈ₃）₄を加えた。この混合物を１００℃で１２時間撹拌し、次いで、室温まで冷却し、１００ｍＬの水で希釈した。粗生成物をジクロロメタン（３×５０ｍＬ）で抽出し、合わせた有機抽出物をＮａ₂ＳＯ₄で乾燥し、次いで、蒸発乾固した。残留物をシリカゲル６０によるフラッシュクロマトグラフィー（４０～６３ｕｍ、溶離液：ヘキサン－ジクロロメタン＝１０：１、体積）により精製した。収量２．５０ｇ（８５％）の白色固体。¹H NMR (CDCl₃, 400 MHz): δ 7.73 (d, J = 7.9 Hz, 1H), 7.40 - 7.42 (m, 2H), 7.26 - 7.30 (m, 1H), 7.10 (dd, J = 11.1, 3.2 Hz, 1H), 6.83 (dd, J = 7.8, 3.2 Hz, 1H), 4.53 (m, 1H), 4.42 (m, 1H), 3.27 (s, 3H), 1.73 (s, 6H), 1.14 - 1.25 (m, 6H), 0.95 (s, 9H). ¹³C NMR (CDCl₃, 100 MHz): δ 159.22 (d, J_C,F = 241 Hz), 150.23 (d, J_C,F = 2.7 Hz), 140.01 (d, J_C,F = 1.84 Hz), 135.75 (d, J_C,F = 8.5 Hz), 133.03, 132.12, 129.11, 127.24, 123.75, 115.69 (d, J_C,F = 23.2 Hz), 114.14 (d, J_C,F = 23.8 Hz), 99.24, 57.16, 50.21, 46.52, 40.13, 32.21, 30.55. (3r, 5r, 7r) -1- (2'-bromo-5-fluoro-2- (methoxymethoxy)-[1,1'-biphenyl] -3-yl) -3,5,7-trimethyladamantane

2.70 g (5.89 mmol) 2- (5-fluoro-2- (methoxymethoxy) -3-((3r, 5r, 7r) -3,5,7-trimethyl) in 20 mL of 1,4-dioxane 2.24 g (7.90 mmol) of 2-bromoiodobenzene in a solution of adamantane-1-yl) phenyl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane, 5.00 g ( 15.2 mmol) of cesium carbonate and 10 mL of water were subsequently added. The resulting mixture was purged with argon for 10 minutes, followed by the addition of 350 mg (0.30 mmol) of Pd (PPh ₃ ) ₄ . The mixture was stirred at 100 ° C. for 12 hours, then cooled to room temperature and diluted with 100 mL of water. The crude product was extracted with dichloromethane (3 x 50 mL) and the combined organic extracts were dried over Na ₂ SO ₄ and then evaporated to dryness. The residue was purified by flash chromatography on silica gel 60 (40-63 um, eluent: hexane-dichloromethane = 10: 1, volume). A white solid with a yield of 2.50 g (85%). ¹ H NMR (CDCl ₃ , 400 MHz): δ 7.73 (d, J = 7.9 Hz, 1H), 7.40 --7.42 (m, 2H), 7.26 --7.30 (m, 1H), 7.10 (dd, J = 11.1, 3.2 Hz, 1H), 6.83 (dd, J = 7.8, 3.2 Hz, 1H), 4.53 (m, 1H), 4.42 (m, 1H), 3.27 (s, 3H), 1.73 (s, 6H), 1.14- 1.25 (m, 6H), 0.95 (s, 9H). ¹³ C NMR (CDCl ₃ , 100 MHz): δ 159.22 (d, J _{C, F} = 241 Hz), 150.23 (d, J _{C, F} = 2.7 Hz) ), 140.01 (d, J _{C, F} = 1.84 Hz), 135.75 (d, J _{C, F} = 8.5 Hz), 133.03, 132.12, 129.11, 127.24, 123.75, 115.69 (d, J _{C, F} = 23.2 Hz) , 114.14 (d, J _{C, F} = 23.8 Hz), 99.24, 57.16, 50.21, 46.52, 40.13, 32.21, 30.55.

２０ｍＬの乾燥ＴＨＦ中の２．３４ｇ（４．８０ｍｍｏｌ）の（３ｒ，５ｒ，７ｒ）－１－（２’－ブロモ－５－フルオロ－２－（メトキシメトキシ）－［１，１’－ビフェニル］－３－イル）－３，５，７－トリメチルアダマンタンの溶液に、ヘキサン中の２．００ｍＬ（５．０４ｍｍｏｌ）の２．５Ｍ ⁿＢｕＬｉを－８０℃で２０分間滴加した。反応混合物をこの温度で１時間撹拌し、続いて、１．３４ｍＬ（７．２１ｍｍｏｌ）の２－イソプロポキシ－４，４，５，５－テトラメチル－１，３，２－ジオキサボロランを加えた。得られた懸濁液を室温で１時間撹拌し、次いで、１００ｍＬの水に注いだ。粗生成物をジクロロメタン（３×１００ｍＬ）で抽出し、合わせた有機抽出物をＮａ₂ＳＯ₄で乾燥し、次いで、蒸発乾固した。残留物をシリカゲル６０によるフラッシュクロマトグラフィー（４０～６３ｕｍ、溶離液：ヘキサン－ジエチルエーテル＝１０：１、体積）により精製した。収量２．５０ｇ（９７％）の無色ガラス状固体。¹H NMR (CDCl₃, 400 MHz): δ 7.76 (d, J = 7.6 Hz, 1H), 7.43 (td, J = 7.5, 1.5 Hz, 1H), 7.31 - 7.35 (m, 2H), 6.98 (dd, J = 11.2, 3.2 Hz, 1H), 6.73 (dd, J = 8.0, 3.2 Hz, 1H), 4.33 (s, 2H), 3.25 (s, 3H), 1.70 (br.s, 6H), 1.08 - 1.21 (m, 18H), 0.88 (s, 9H). ¹³C NMR (CDCl₃, 100 MHz): δ 159.30 (d, J_C,F = 240 Hz), 150.06 (d, J_C,F = 2.4 Hz), 144.58, 143.70 (d, J_C,F = 6.6 Hz), 138.28 (d, J_C,F = 8.3 Hz), 134.75, 130.20, 130.11, 126.61, 115.78 (d, J_C,F = 22.7 Hz), 112.86 (d, J_C,F = 23.6 Hz), 98.97, 83.53, 57.26, 50.22, 46.71, 40.02, 32.24, 30.55, 25.20 (広幅), 24.12 (広幅). 2- (5'-Fluoro-2'-(methoxymethoxy) -3'-((3r, 5r, 7r) -3,5,7-trimethyladamantane-1-yl)-[1,1'-biphenyl] -2-yl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane

2.34 g (4.80 mmol) of (3r, 5r, 7r) -1- (2'-bromo-5-fluoro-2- (methoxymethoxy)-[1,1'-biphenyl] in 20 mL of dry THF] To a solution of -3-yl) -3,5,7-trimethyladamantane, 2.00 mL (5.04 mmol) of 2.5 M ⁿ BuLi in hexane was added dropwise at −80 ° C. for 20 minutes. The reaction mixture was stirred at this temperature for 1 hour, followed by the addition of 1.34 mL (7.21 mmol) of 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane. The resulting suspension was stirred at room temperature for 1 hour and then poured into 100 mL of water. The crude product was extracted with dichloromethane (3 x 100 mL) and the combined organic extracts were dried over Na ₂ SO ₄ and then evaporated to dryness. The residue was purified by flash chromatography on silica gel 60 (40-63 um, eluent: hexane-diethyl ether = 10: 1, volume). A colorless glassy solid with a yield of 2.50 g (97%). ¹ H NMR (CDCl ₃ , 400 MHz): δ 7.76 (d, J = 7.6 Hz, 1H), 7.43 (td, J = 7.5, 1.5 Hz, 1H), 7.31 --7.35 (m, 2H), 6.98 (dd) , J = 11.2, 3.2 Hz, 1H), 6.73 (dd, J = 8.0, 3.2 Hz, 1H), 4.33 (s, 2H), 3.25 (s, 3H), 1.70 (br.s, 6H), 1.08- 1.21 (m, 18H), 0.88 (s, 9H). ¹³ C NMR (CDCl ₃ , 100 MHz): δ 159.30 (d, J _{C, F} = 240 Hz), 150.06 (d, J _{C, F} = 2.4 Hz) ), 144.58, 143.70 (d, J _{C, F} = 6.6 Hz), 138.28 (d, J _{C, F} = 8.3 Hz), 134.75, 130.20, 130.11, 126.61, 115.78 (d, J _{C, F} = 22.7 Hz) , 112.86 (d, J _{C, F} = 23.6 Hz), 98.97, 83.53, 57.26, 50.22, 46.71, 40.02, 32.24, 30.55, 25.20 (wide), 24.12 (wide).

２０ｍＬの１，４－ジオキサン中の２．５０ｇ（４．８０ｍｍｏｌ）の２－（５’－フルオロ－２’－（メトキシメトキシ）－３’－（（３ｒ，５ｒ，７ｒ）－３，５，７－トリメチルアダマンタン－１－イル）－［１，１’－ビフェニル］－２－イル）－４，４，５，５－テトラメチル－１，３，２－ジオキサボロランの溶液に、５４６ｍｇ（２．３０ｍｍｏｌ）の２，６－ジブロモピリジン、４．０２ｇ（１２．０ｍｍｏｌ）の炭酸セシウムおよび１０ｍＬの水を続いて加えた。得られた混合物をアルゴンで１０分間パージし、続いて、３０４ｍｇ（０．２４０ｍｍｏｌ）のＰｄ（ＰＰｈ₃）₄を加えた。この混合物を１００℃で１２時間撹拌し、次いで、室温まで冷却し、５０ｍＬの水で希釈した。得られた混合物をジクロロメタン（３×５０ｍＬ）で抽出し、合わせた有機抽出物をＮａ₂ＳＯ₄で乾燥し、次いで、蒸発乾固した。得られた油に、５０ｍＬのＴＨＦ、５０ｍＬのメタノールおよび３ｍＬの１２Ｎ ＨＣｌを続いて加えた。反応混合物を６０℃で一晩撹拌し、次いで、２００ｍＬの水に注いだ。粗生成物をジクロロメタン（３×７０ｍＬ）で抽出し、合わせた有機抽出物を５％ ＮａＨＣＯ₃で洗浄し、Ｎａ₂ＳＯ₄で乾燥し、次いで、蒸発乾固した。残留物をシリカゲル６０によるフラッシュクロマトグラフィー（４０～６３ｕｍ、溶離液：ヘキサン－酢酸エチル＝１０：１、体積）により精製した。収量６９０ｍｇ（３７％）の白色泡としての２種の異性体の混合物。¹H NMR (CDCl₃, 400 MHz): δ 7.37 - 7.54 (m, 8H), 6.65 - 7.04および6.29 - 6.32 (m, 9H), 1.43 (s, 6H), 1.22 - 1.40 (m, 6H), 0.95 - 1.15 (m, 12H), 0.78 (s, 9H), 0.72 (s, 9H). ¹³C NMR (CDCl₃, 100 MHz) δ 157.71 (d, J_C,F = 240 Hz), 157.68 (d, J_C,F = 240 Hz), 148.03, 147.62 (d, J_C,F = 2.0 Hz), 139.79, 138.99, 138.91, 138.70, 138.64, 136.92, 136.82, 135.82, 135.67, 132.05, 131.43, 130.60, 130.00, 129.82, 129.20, 128.57, 128.44, 122.41, 122.18, 114.26 (d, J_C,F = 22.7 Hz), 113.84 (d, J_C,F = 23.0 Hz), 113.51 (d, J_C,F = 23.4 Hz), 113.12 (d, J_C,F = 23.7 Hz), 50.30, 50.05, 45.71, 39.55, 39.49, 32.17, 32.00, 31.89, 30.60, 30.44. 2', 2'''-(pyridin-2,6-diyl) bis (5-fluoro-3-((3r, 5r, 7r) -3,5,7-trimethyladamantane-1-yl)-[1 , 1'-biphenyl] -2-ol)

2.50 g (4.80 mmol) 2- (5'-fluoro-2'-(methoxymethoxy) -3'-((3r, 5r, 7r) -3,5) in 20 mL of 1,4-dioxane 7-trimethyladamantan-1-yl)-[1,1'-biphenyl] -2-yl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane in a solution of 546 mg (2. 30 mmol) of 2,6-dibromopyridine, 4.02 g (12.0 mmol) of cesium carbonate and 10 mL of water were subsequently added. The resulting mixture was purged with argon for 10 minutes, followed by the addition of 304 mg (0.240 mmol) of Pd (PPh ₃ ) ₄ . The mixture was stirred at 100 ° C. for 12 hours, then cooled to room temperature and diluted with 50 mL of water. The resulting mixture was extracted with dichloromethane (3 x 50 mL) and the combined organic extracts were dried over Na ₂ SO ₄ and then evaporated to dryness. 50 mL of THF, 50 mL of methanol and 3 mL of 12N HCl were subsequently added to the resulting oil. The reaction mixture was stirred at 60 ° C. overnight and then poured into 200 mL of water. The crude product was extracted with dichloromethane (3 x 70 mL) and the combined organic extracts were washed with 5% NaHCO ₃ and dried over Na ₂ SO ₄ and then evaporated to dryness. The residue was purified by flash chromatography on silica gel 60 (40-63 um, eluent: hexane-ethyl acetate = 10: 1, volume). A mixture of the two isomers as a white foam with a yield of 690 mg (37%). ¹ H NMR (CDCl ₃ , 400 MHz): δ 7.37 --7.54 (m, 8H), 6.65 --7.04 and 6.29 --6.32 (m, 9H), 1.43 (s, 6H), 1.22 --1.40 (m, 6H), 0.95 --1.15 (m, 12H), 0.78 (s, 9H), 0.72 (s, 9H). ¹³ C NMR (CDCl ₃ , 100 MHz) δ 157.71 (d, J _{C, F} = 240 Hz), 157.68 (d) , J _{C, F} = 240 Hz), 148.03, 147.62 (d, J _{C, F} = 2.0 Hz), 139.79, 138.99, 138.91, 138.70, 138.64, 136.92, 136.82, 135.82, 135.67, 132.05, 131.43, 130.60, 130.00 , 129.82, 129.20, 128.57, 128.44, 122.41, 122.18, 114.26 (d, J _{C, F} = 22.7 Hz), 113.84 (d, J _{C, F} = 23.0 Hz), 113.51 (d, J _{C, F} = 23.4 Hz) ), 113.12 (d, J _{C, F} = 23.7 Hz), 50.30, 50.05, 45.71, 39.55, 39.49, 32.17, 32.00, 31.89, 30.60, 30.44.

５０ｍＬの乾燥トルエン中の２２５ｍｇ（０．７０２ｍｍｏｌ）の四塩化ハフニウム（＜０．５％ Ｚｒ）の懸濁液に、ジエチルエーテル中の１．１０ｍＬ（３．１６ｍｍｏｌ）の２．９Ｍ ＭｅＭｇＢｒを０℃でシリンジを介して１回で加えた。得られた懸濁液に、５００ｍｇ（０．７０２ｍｍｏｌ）の２’，２’’’－（ピリジン－２，６－ジイル）ビス（３－（（３ｒ，５ｒ，７ｒ）－アダマンタン－１－イル）－５－メチル－［１，１’－ビフェニル］－２－オール）を直ちに１回で加えた。反応混合物を室温で４時間撹拌し、次いで、ほぼ乾固するまで蒸発させた。得られた固体を２×２０ｍＬの熱トルエンで抽出し、合わせた有機抽出物をＣｅｌｉｔｅ ５０３の薄いパッドに通して濾過した。次に、濾液を蒸発乾固した。残留物を５ｍＬのｎ－ヘキサンと研和し、得られた沈殿物を濾別（Ｇ４）し、２×５ｍＬのｎ－ヘキサンで洗浄し、次いで、真空中で乾燥した。収量４７３ｍｇ（７３％）のホワイトベージュ色固体。Ｃ₅₃Ｈ₅₇ＨｆＮＯ₂の解析計算値：Ｃ、６９．３０；Ｈ、６．２６；Ｎ、１．５２。測定値：Ｃ ６９．５８；Ｈ、６．３９；Ｎ １．４０。¹H NMR (CDCl₃, 400 MHz): δ 7.69 (t, J = 7.8 Hz, 1H), 7.54 (td, J = 7.6, 1.4 Hz, 2H), 7.35 (td, J = 7.5, 1.3 Hz, 2H), 7.30 (dd, J = 7.8, 1.2 Hz, 2H), 7.10 - 7.14 (m, 4H), 7.02 (d, J = 2.3 Hz, 2H), 6.69 (dd, J = 2.3, 0.6 Hz, 2H), 2.23 (s, 6H), 2.18 - 2.24 (m, 6H), 2.04 - 2.14 (m, 12H), 1.68 - 1.85 (m, 12H), -0.78 (s, 6H). ¹³C NMR (CDCl₃, 100 MHz) δ 158.78, 157.35, 142.53, 139.60, 138.26, 132.88, 132.34, 131.79, 130.83, 130.69, 128.66, 127.52, 127.40, 126.22, 124.77, 49.51, 40.85, 37.15, 37.00, 29.06, 20.76. Dimethylhafnium [2', 2'''-(pyridin-2,6-diyl) bis (3-((3r, 5r, 7r) -adamantan-1-yl) -5-methyl- [1,1'- Biphenyl] -2-olate)] (complex 1)

1.10 mL (3.16 mmol) of 2.9 M MeMgBr in diethyl ether to a suspension of 225 mg (0.702 mmol) hafnium tetrachloride (<0.5% Zr) in 50 mL of dry toluene at 0 ° C. It was added once via a syringe. In the resulting suspension, 500 mg (0.702 mmol) of 2', 2'''-(pyridin-2,6-diyl) bis (3-((3r, 5r, 7r) -adamantan-1-yl) ) -5-Methyl- [1,1'-biphenyl] -2-ol) was immediately added in one dose. The reaction mixture was stirred at room temperature for 4 hours and then evaporated to near dryness. The resulting solid was extracted with 2 x 20 mL hot toluene and the combined organic extracts were filtered through a thin pad of Celite 503. Next, the filtrate was evaporated to dryness. The residue was triturated with 5 mL of n-hexane, the resulting precipitate was filtered off (G4), washed with 2 x 5 mL of n-hexane and then dried in vacuo. A white beige solid with a yield of 473 mg (73%). Analysis of C ₅₃ H ₅₇ HfNO ₂ Calculated values: C, 69.30; H, 6.26; N, 1.52. Measured values: C 69.58; H, 6.39; N 1.40. ¹ H NMR (CDCl ₃ , 400 MHz): δ 7.69 (t, J = 7.8 Hz, 1H), 7.54 (td, J = 7.6, 1.4 Hz, 2H), 7.35 (td, J = 7.5, 1.3 Hz, 2H) ), 7.30 (dd, J = 7.8, 1.2 Hz, 2H), 7.10 --7.74 (m, 4H), 7.02 (d, J = 2.3 Hz, 2H), 6.69 (dd, J = 2.3, 0.6 Hz, 2H) , 2.23 (s, 6H), 2.18 --2.24 (m, 6H), 2.04 --2.14 (m, 12H), 1.68 --1.85 (m, 12H), -0.78 (s, 6H). ¹³ C NMR (CDCl ₃ ,, 100 MHz) δ 158.78, 157.35, 142.53, 139.60, 138.26, 132.88, 132.34, 131.79, 130.83, 130.69, 128.66, 127.52, 127.40, 126.22, 124.77, 49.51, 40.85, 37.15, 37.00, 29.06, 20.76.

５０ｍＬの乾燥トルエン中の１３１ｍｇ（０．５６２ｍｍｏｌ）の四塩化ジルコニウムの懸濁液に、ジエチルエーテル中の８７０ｕｌ（２．５３ｍｍｏｌ）の２．９Ｍ ＭｅＭｇＢｒを－３０℃でシリンジを介して１回で加えた。得られた懸濁液に、４００ｍｇ（０．５６２ｍｍｏｌ）の２’，２’’’－（ピリジン－２，６－ジイル）ビス（３－（（３ｒ，５ｒ，７ｒ）－アダマンタン－１－イル）－５－メチル－［１，１’－ビフェニル］－２－オール）を直ちに１回で加えた。反応混合物を室温で４時間撹拌し、次いで、ほぼ乾固するまで蒸発させた。得られた固体を２×２０ｍＬの熱トルエンで抽出し、合わせた有機抽出物をＣｅｌｉｔｅ ５０３の薄いパッドに通して濾過した。次に、濾液を蒸発乾固した。残留物を５ｍＬのｎ－ヘキサンと研和し、得られた沈殿物を濾別（Ｇ４）し、２×５ｍＬのｎ－ヘキサンで洗浄し、次いで、真空中で乾燥した。収量３１８ｍｇ（６８％）のベージュ色固体。Ｃ₅₃Ｈ₅₇ＺｒＮＯ₂の解析計算値：Ｃ、７６．５８；Ｈ、６．９１；Ｎ、１．６９。測定値：Ｃ ７６．８９；Ｈ、７．０６；Ｎ １．５２。¹H NMR (C₆D₆, 400 MHz): 7.11 - 7.20 (m, 8H), 7.02 - 7.04 (m, 2H), 6.76 (d, J = 2.2 Hz, 2H), 6.39 - 6.50 (m, 3H), 2.45 - 2.54 (m, 6H), 2.32 - 2.37 (m, 6H), 2.23 (s, 6H), 2.17 (br.s, 6H), 1.94 - 2.03 (m, 6H), 1.80 - 1.89 (m, 6H), -0.10 (s, 6H). ¹³C NMR (CDCl₃, 100 MHz) δ 159.31, 158.31, 143.44, 139.58, 138.60, 133.65, 133.59, 133.18, 131.42, 131.13, 129.36, 128.54, 128.06, 127.20, 124.43, 42.89, 41.95, 38.18, 37.85, 30.01, 21.41. Dimethylzirconium [2', 2'''-(pyridin-2,6-diyl) bis (3-((3r, 5r, 7r) -adamantan-1-yl) -5-methyl- [1,1'- Biphenyl] -2-olate)] (complex 3)

To a suspension of 131 mg (0.562 mmol) of zirconium tetrachloride in 50 mL of dry toluene, 870 ul (2.53 mmol) of 2.9 M MeMgBr in diethyl ether is added in a single dose at -30 ° C via a syringe. rice field. In the resulting suspension, 400 mg (0.562 mmol) of 2', 2'''-(pyridin-2,6-diyl) bis (3-((3r, 5r, 7r) -adamantan-1-yl) ) -5-Methyl- [1,1'-biphenyl] -2-ol) was immediately added in one dose. The reaction mixture was stirred at room temperature for 4 hours and then evaporated to near dryness. The resulting solid was extracted with 2 x 20 mL hot toluene and the combined organic extracts were filtered through a thin pad of Celite 503. Next, the filtrate was evaporated to dryness. The residue was triturated with 5 mL of n-hexane, the resulting precipitate was filtered off (G4), washed with 2 x 5 mL of n-hexane and then dried in vacuo. A beige solid with a yield of 318 mg (68%). Analysis calculation value of C ₅₃ H ₅₇ ZrNO ₂ : C, 76.58; H, 6.91; N, 1.69. Measured value: C 76.89; H, 7.06; N 1.52. ¹ H NMR (C ₆ D ₆ , 400 MHz): 7.11 --7.20 (m, 8H), 7.02 --7.04 (m, 2H), 6.76 (d, J = 2.2 Hz, 2H), 6.39 --6.50 (m, 3H) ), 2.45 --2.54 (m, 6H), 2.32 --2.37 (m, 6H), 2.23 (s, 6H), 2.17 (br.s, 6H), 1.94 --2.03 (m, 6H), 1.80 --1.89 (m) , 6H), -0.10 (s, 6H). ¹³ C NMR (CDCl ₃ , 100 MHz) δ 159.31, 158.31, 143.44, 139.58, 138.60, 133.65, 133.59, 133.18, 131.42, 131.13, 129.36, 128.54, 128.06, 127.20 , 124.43, 42.89, 41.95, 38.18, 37.85, 30.01, 21.41.

５０ｍＬの乾燥トルエン中の１１８ｍｇ（０．３６９ｍｍｏｌ）の四塩化ハフニウム（＜０．５％ Ｚｒ）の懸濁液に、ジエチルエーテル中の５７０ｕｌ（１．６６ｍｍｏｌ）の２．９Ｍ ＭｅＭｇＢｒを０℃でシリンジを介して１回で加えた。得られた懸濁液に、２７３ｍｇ（０．３６９ｍｍｏｌ）の２’，２’’’－（ピリジン－２，６－ジイル）ビス（３－（（３ｒ，５ｒ，７ｒ）－アダマンタン－１－イル）－４’，５－ジメチル－［１，１’－ビフェニル］－２－オール）を直ちに１回で加えた。反応混合物を室温で４時間撹拌し、次いで、ほぼ乾固するまで蒸発させた。得られた固体を２×２０ｍＬの熱トルエンで抽出し、合わせた有機抽出物をＣｅｌｉｔｅ ５０３の薄いパッドに通して濾過した。次に、濾液を蒸発乾固した。残留物を５ｍＬのｎ－ヘキサンと研和し、得られた沈殿物を濾別（Ｇ４）し、２×５ｍＬのｎ－ヘキサンで洗浄し、次いで、真空中で乾燥した。収量２４０ｍｇ（６９％）のホワイトベージュ色固体。Ｃ₅₅Ｈ₆₁ＨｆＮＯ₂の解析計算値：Ｃ、６９．７９；Ｈ、６．５０；Ｎ、１．４８。測定値：Ｃ ７０．０８；Ｈ、６．７３；Ｎ １．３５。¹H NMR (C₆D₆, 400 MHz): δ 7.20 (d, J = 2.4 Hz, 2H), 7.12 (d, J = 8.0 Hz, 2H), 6.97 (dd, J = 7.8, 1.8 Hz, 2H), 6.84 (m, 2H), 6.74 - 6.76 (m, 2H), 6.43 - 6.56 (m, 3H), 2.45 - 2.53 (m, 6H), 2.30 - 2.38 (m, 6H), 2.23 (s, 6H), 2.21 (s, 6H), 2.15 (br.s, 6H), 1.94 - 2.03 (m, 6H), 1.76 - 1.84 (m, 6H), -0.03 (s, 6H). ¹³C NMR (C₆D₆, 100 MHz) δ 159.99, 158.16, 140.99, 139.42, 139.03, 137.75, 133.71, 133.23, 133.14, 132.44, 131.03, 129.60, 128.29, 126.99, 125.20, 51.24, 41.67, 38.04, 37.81, 30.04, 21.41, 21.39. Dimethylhafnium [2', 2'''-(pyridin-2,6-diyl) bis (3-((3r, 5r, 7r) -adamantan-1-yl) -4', 5-dimethyl- [1, 1'-biphenyl] -2-oleate)] (complex 2)

Syringe 570 ul (1.66 mmol) of 2.9 M MeMgBr in diethyl ether into a suspension of 118 mg (0.369 mmol) hafnium tetrachloride (<0.5% Zr) in 50 mL of dry toluene at 0 ° C. Was added once via. In the resulting suspension, 273 mg (0.369 mmol) of 2', 2'''-(pyridin-2,6-diyl) bis (3-((3r, 5r, 7r) -adamantan-1-yl) ) -4', 5-dimethyl- [1,1'-biphenyl] -2-ol) was immediately added in one dose. The reaction mixture was stirred at room temperature for 4 hours and then evaporated to near dryness. The resulting solid was extracted with 2 x 20 mL hot toluene and the combined organic extracts were filtered through a thin pad of Celite 503. Next, the filtrate was evaporated to dryness. The residue was triturated with 5 mL of n-hexane, the resulting precipitate was filtered off (G4), washed with 2 x 5 mL of n-hexane and then dried in vacuo. A white beige solid with a yield of 240 mg (69%). Analysis of C ₅₅ H ₆₁ HfNO ₂ Calculated values: C, 69.79; H, 6.50; N, 1.48. Measured value: C 70.08; H, 6.73; N 1.35. ¹ H NMR (C ₆ D ₆ , 400 MHz): δ 7.20 (d, J = 2.4 Hz, 2H), 7.12 (d, J = 8.0 Hz, 2H), 6.97 (dd, J = 7.8, 1.8 Hz, 2H) ), 6.84 (m, 2H), 6.74 --6.76 (m, 2H), 6.43 --6.56 (m, 3H), 2.45 --2.53 (m, 6H), 2.30 --2.38 (m, 6H), 2.23 (s, 6H) ), 2.21 (s, 6H), 2.15 (br.s, 6H), 1.94 --2.03 (m, 6H), 1.76 --1.84 (m, 6H), -0.03 (s, 6H). ¹³ C NMR (C ₆ ) D ₆ , 100 MHz) δ 159.99, 158.16, 140.99, 139.42, 139.03, 137.75, 133.71, 133.23, 133.14, 132.44, 131.03, 129.60, 128.29, 126.99, 125.20, 51.24, 41.67, 38.04, 37.81, 30.04, 21.41, 21.39 ..

３０ｍＬの乾燥トルエン中の８３ｍｇ（０．３５４ｍｍｏｌ）の四塩化ジルコニウムの懸濁液に、ジエチルエーテル中の５４０ｕｌ（１．５９ｍｍｏｌ）の２．９Ｍ ＭｅＭｇＢｒを－３０℃でシリンジを介して１回で加えた。得られた懸濁液に、２６２ｍｇ（０．３５４ｍｍｏｌ）の２’，２’’’－（ピリジン－２，６－ジイル）ビス（３－（（３ｒ，５ｒ，７ｒ）－アダマンタン－１－イル）－４’，５－ジメチル－［１，１’－ビフェニル］－２－オール）を直ちに１回で加えた。反応混合物を室温で４時間撹拌し、次いで、ほぼ乾固するまで蒸発させた。得られた固体を２×２０ｍＬの熱トルエンで抽出し、合わせた有機抽出物をＣｅｌｉｔｅ ５０３の薄いパッドに通して濾過した。次に、濾液を蒸発乾固した。残留物を５ｍＬのｎ－ヘキサンと研和し、得られた沈殿物を濾別（Ｇ４）し、２×５ｍＬのｎ－ヘキサンで洗浄し、次いで、真空中で乾燥した。収量１９３ｍｇ（６３％）のベージュ色固体。Ｃ₅₅Ｈ₆₁ＺｒＮＯ₂の解析計算値：Ｃ、７６．８８；Ｈ、７．１６；Ｎ、１．６３。測定値：Ｃ ７７．０６；Ｈ、７．４３；Ｎ １．５１。¹H NMR (C₆D₆, 400 MHz): δ 7.19 (d, J = 1.8 Hz, 2H), 7.13 (d, J = 7.8 Hz, 2H), 6.96 (ddd, J = 7.8, 1.8, 0.6 Hz, 2H), 6.82 (dd, J = 1.2, 0.6 Hz, 2H), 6.76 (dd, J = 2.4, 0.6 Hz, 2H), 6.42 - 6.57 (m, 3H), 2.48 - 2.55 (m, 6H), 2.34 - 2.42 (m, 6H), 2.22 (s, 6H), 2.20 (s, 6H), 2.15 (br.s, 6H), 1.95 - 2.02 (m, 6H), 1.77 - 1.84 (m, 6H), -0.20 (s, 6H). ¹³C NMR (C₆D₆, 100 MHz) δ 159.46, 158.49, 140.84, 139.40, 138.49, 137.69, 133.62, 133.59, 133.51, 132.31, 130.93, 129.66, 128.89, 128.22, 127.09, 126.03, 124.74, 42.91, 41.72, 38.14, 37.80, 30.04, 21.42, 21.38. Dimethyl zirconium [2', 2'''-(pyridin-2,6-diyl) bis (3-((3r, 5r, 7r) -adamantan-1-yl) -4', 5-dimethyl- [1, 1'-biphenyl] -2-oleate)] (complex 4)

To a suspension of 83 mg (0.354 mmol) of zirconium tetrachloride in 30 mL of dry toluene, 540 ul (1.59 mmol) of 2.9 M MeMgBr in diethyl ether is added in a single dose at -30 ° C via a syringe. rice field. In the resulting suspension, 262 mg (0.354 mmol) of 2', 2'''-(pyridin-2,6-diyl) bis (3-((3r, 5r, 7r) -adamantan-1-yl) ) -4', 5-dimethyl- [1,1'-biphenyl] -2-ol) was immediately added in one dose. The reaction mixture was stirred at room temperature for 4 hours and then evaporated to near dryness. The resulting solid was extracted with 2 x 20 mL hot toluene and the combined organic extracts were filtered through a thin pad of Celite 503. Next, the filtrate was evaporated to dryness. The residue was triturated with 5 mL of n-hexane, the resulting precipitate was filtered off (G4), washed with 2 x 5 mL of n-hexane and then dried in vacuo. A beige solid with a yield of 193 mg (63%). Analysis calculation value of C ₅₅ H ₆₁ ZrNO ₂ : C, 76.88; H, 7.16; N, 1.63. Measured value: C 77.06; H, 7.43; N 1.51. ¹ H NMR (C ₆ D ₆ , 400 MHz): δ 7.19 (d, J = 1.8 Hz, 2H), 7.13 (d, J = 7.8 Hz, 2H), 6.96 (ddd, J = 7.8, 1.8, 0.6 Hz) , 2H), 6.82 (dd, J = 1.2, 0.6 Hz, 2H), 6.76 (dd, J = 2.4, 0.6 Hz, 2H), 6.42 --6.57 (m, 3H), 2.48 --2.55 (m, 6H), 2.34 --2.42 (m, 6H), 2.22 (s, 6H), 2.20 (s, 6H), 2.15 (br.s, 6H), 1.95 --2.02 (m, 6H), 1.77 --1.84 (m, 6H), -0.20 (s, 6H). ¹³ C NMR (C ₆ D ₆ , 100 MHz) δ 159.46, 158.49, 140.84, 139.40, 138.49, 137.69, 133.62, 133.59, 133.51, 132.31, 130.93, 129.66, 128.89, 128.22, 127.09 , 126.03, 124.74, 42.91, 41.72, 38.14, 37.80, 30.04, 21.42, 21.38.

５０ｍＬの乾燥トルエン中の１５５ｍｇ（０．４８４ｍｍｏｌ）の四塩化ハフニウム（＜０．５％ Ｚｒ）の懸濁液に、ジエチルエーテル中の７５０ｕｌ（２．１８ｍｍｏｌ）の２．９Ｍ ＭｅＭｇＢｒを０℃でシリンジを介して１回で加えた。得られた懸濁液に、４００ｍｇ（０．４８４ｍｍｏｌ）の２’，２’’’－（４－メトキシピリジン－２，６－ジイル）ビス（３－（（３ｒ，５ｒ，７ｒ）－アダマンタン－１－イル）－５－（ｔｅｒｔ－ブチル）－［１，１’－ビフェニル］－２－オール）を直ちに１回で加えた。反応混合物を室温で４時間撹拌し、次いで、ほぼ乾固するまで蒸発させた。得られた固体を２×２０ｍＬの熱トルエンで抽出し、合わせた有機抽出物をＣｅｌｉｔｅ ５０３の薄いパッドに通して濾過した。次に、濾液を蒸発乾固した。残留物を５ｍＬのｎ－ヘキサンと研和し、得られた沈殿物を濾別（Ｇ４）し、２×５ｍＬのｎ－ヘキサンで洗浄し、次いで、真空中で乾燥した。収量３３８ｍｇ（６８％）のホワイトベージュ色固体。Ｃ₆₀Ｈ₇₁ＨｆＮＯ₃の解析計算値：Ｃ、６９．７８；Ｈ、６．９３；Ｎ、１．３６。測定値：Ｃ ７０．０４；Ｈ、７．１６；Ｎ １．２４。¹H NMR (C₆D₆, 400 MHz): δ 7.59 (d, J = 2.6 Hz, 2H), 7.19 - 7.21 (m, 2H), 7.09 - 7.16 (m, 8H), 6.08 (s, 2H), 2.57 - 2.63 (m, 6H), 2.55 (s, 3H), 2.43 - 2.49 (m, 6H), 2.21 (br.s, 6H), 1.99 - 2.06 (m, 6H), 1.83 - 1.90 (m, 6H), 1.33 (s, 18H), -0.10 (s, 6H). ¹³C NMR (C₆D₆, 100 MHz) δ 167.56, 159.92, 159.70, 143.99, 140.37, 138.65, 133.99, 133.04, 132.78, 131.59, 131.32, 129.66, 128.90, 127.90, 125.85, 124.81, 111.17, 55.17, 50.99, 41.98, 38.57, 37.89, 34.79, 32.36, 30.08. Dimethylhafnium [2', 2'''-(4-methoxypyridin-2,6-diyl) bis (3-((3r, 5r, 7r) -adamantan-1-yl) -5- (tert-butyl) -[1,1'-biphenyl] -2-olate)] (complex 7)

Syringe 750 ul (2.18 mmol) of 2.9 M MeMgBr in diethyl ether into a suspension of 155 mg (0.484 mmol) of hafnium tetrachloride (<0.5% Zr) in 50 mL of dry toluene at 0 ° C. Was added once via. 400 mg (0.484 mmol) of 2', 2'''-(4-methoxypyridin-2,6-diyl) bis (3-((3r, 5r, 7r) -adamantane-) was added to the resulting suspension. 1-Il) -5- (tert-butyl)-[1,1'-biphenyl] -2-ol) was immediately added in one dose. The reaction mixture was stirred at room temperature for 4 hours and then evaporated to near dryness. The resulting solid was extracted with 2 x 20 mL hot toluene and the combined organic extracts were filtered through a thin pad of Celite 503. Next, the filtrate was evaporated to dryness. The residue was triturated with 5 mL of n-hexane, the resulting precipitate was filtered off (G4), washed with 2 x 5 mL of n-hexane and then dried in vacuo. A white beige solid with a yield of 338 mg (68%). Analysis of C ₆₀ H ₇₁ HfNO ₃ Calculated values: C, 69.78; H, 6.93; N, 1.36. Measured values: C 70.04; H, 7.16; N 1.24. ¹ H NMR (C ₆ D ₆ , 400 MHz): δ 7.59 (d, J = 2.6 Hz, 2H), 7.19 --7.21 (m, 2H), 7.09 --7.16 (m, 8H), 6.08 (s, 2H) , 2.57 --2.63 (m, 6H), 2.55 (s, 3H), 2.43 --2.49 (m, 6H), 2.21 (br.s, 6H), 1.99 --2.06 (m, 6H), 1.83 --1.90 (m, 6H), 1.33 (s, 18H), -0.10 (s, 6H). ¹³ C NMR (C ₆ D ₆ , 100 MHz) δ 167.56, 159.92, 159.70, 143.99, 140.37, 138.65, 133.99, 133.04, 132.78, 131.59 , 131.32, 129.66, 128.90, 127.90, 125.85, 124.81, 111.17, 55.17, 50.99, 41.98, 38.57, 37.89, 34.79, 32.36, 30.08.

５０ｍＬの乾燥トルエン中の１４８ｍｇ（０．４６３ｍｍｏｌ）の四塩化ハフニウム（＜０．５％ Ｚｒ）の懸濁液に、ジエチルエーテル中の７２０ｕｌ（２．１０ｍｍｏｌ）の２．９Ｍ ＭｅＭｇＢｒを０℃でシリンジを介して１回で加えた。得られた懸濁液に、４００ｍｇ（０．４６３ｍｍｏｌ）の２’，２’’’－（４－（トリフルオロメチル）ピリジン－２，６－ジイル）ビス（３－（（３ｒ，５ｒ，７ｒ）－アダマンタン－１－イル）－５－（ｔｅｒｔ－ブチル）－［１，１’－ビフェニル］－２－オール）を直ちに１回で加えた。反応混合物を室温で４時間撹拌し、次いで、ほぼ乾固するまで蒸発させた。得られた固体を２×２０ｍＬの熱トルエンで抽出し、合わせた有機抽出物をＣｅｌｉｔｅ ５０３の薄いパッドに通して濾過した。次に、濾液を蒸発乾固した。残留物を５ｍＬのｎ－ヘキサンと研和し、得られた沈殿物を濾別（Ｇ４）し、２×５ｍＬのｎ－ヘキサンで洗浄し、次いで、真空中で乾燥した。収量３４２ｍｇ（６９％）の黄色固体。Ｃ₆₀Ｈ₆₈Ｆ₃ＨｆＮＯ₂の解析計算値：Ｃ、６７．３１；Ｈ、６．４０；Ｎ、１．３１。測定値：Ｃ ６７．６５；Ｈ、６．６６；Ｎ １．２０。¹H NMR (C₆D₆, 400 MHz): δ 7.55 (d, J = 2.6 Hz, 2H), 7.07 - 7.18 (m, 4H), 7.03 (td, J = 7.4, 1.6 Hz, 2H), 6.99 (d, J = 2.5 Hz, 2H), 6.91 (dd, J = 7.4, 1.1 Hz, 2H), 6.82 (s, 2H), 2.47 - 2.53 (m, 6H), 2.32 - 2.39 (m, 6H), 2.17 (br.s, 6H), 1.94 - 2.01 (m, 6H), 1.80 - 1.89 (m, 6H), 1.30 (s, 18H), -0.13 (s, 6H). ¹³C NMR (C₆D₆, 100 MHz) δ 160.03, 159.46, 143.80, 141.05, 138.65, 133.82, 132.47, 132.08, 131.72, 131.25, 125.67, 124.93, 121.29 (q, Jc,_F = 3.1 Hz), 51.49, 41.94, 38.49, 37.79, 34.78, 32.23, 29.98. Dimethylhafnium [2', 2'''-(4- (trifluoromethyl) pyridin-2,6-diyl) bis (3-((3r, 5r, 7r) -adamantane-1-yl) -5-( tert-butyl)-[1,1'-biphenyl] -2-olate)] (complex 8)

Syringe 720 ul (2.10 mmol) of 2.9 M MeMgBr in diethyl ether into a suspension of 148 mg (0.463 mmol) of hafnium tetrachloride (<0.5% Zr) in 50 mL of dry toluene at 0 ° C. Was added once via. 400 mg (0.463 mmol) of 2', 2'''-(4- (trifluoromethyl) pyridine-2,6-diyl) bis (3-((3r, 5r, 7r)) was added to the resulting suspension. ) -Adamantane-1-yl) -5- (tert-butyl)-[1,1'-biphenyl] -2-ol) was immediately added in one dose. The reaction mixture was stirred at room temperature for 4 hours and then evaporated to near dryness. The resulting solid was extracted with 2 x 20 mL hot toluene and the combined organic extracts were filtered through a thin pad of Celite 503. Next, the filtrate was evaporated to dryness. The residue was triturated with 5 mL of n-hexane, the resulting precipitate was filtered off (G4), washed with 2 x 5 mL of n-hexane and then dried in vacuo. A yellow solid with a yield of 342 mg (69%). Analysis of C ₆₀ H ₆₈ F ₃ HfNO ₂ Calculated values: C, 67.31; H, 6.40; N, 1.31. Measured values: C 67.65; H, 6.66; N 1.20. ¹ H NMR (C ₆ D ₆ , 400 MHz): δ 7.55 (d, J = 2.6 Hz, 2H), 7.07 --7.71 (m, 4H), 7.03 (td, J = 7.4, 1.6 Hz, 2H), 6.99 (d, J = 2.5 Hz, 2H), 6.91 (dd, J = 7.4, 1.1 Hz, 2H), 6.82 (s, 2H), 2.47 --2.53 (m, 6H), 2.32 --2.39 (m, 6H), 2.17 (br.s, 6H), 1.94 --2.01 (m, 6H), 1.80 --1.89 (m, 6H), 1.30 (s, 18H), -0.13 (s, 6H). ¹³ C NMR (C ₆ D ₆ ) , 100 MHz) δ 160.03, 159.46, 143.80, 141.05, 138.65, 133.82, 132.47, 132.08, 131.72, 131.25, 125.67, 124.93, 121.29 (q, Jc, _F = 3.1 Hz), 51.49, 41.94, 38.49, 37.79, 34.78 , 32.23, 29.98.

５０ｍＬの乾燥トルエン中の１５５ｍｇ（０．４８５ｍｍｏｌ）の四塩化ハフニウム（＜０．５％ Ｚｒ）の懸濁液に、ジエチルエーテル中の７５０ｕｌ（２．２０ｍｍｏｌ）の２．９Ｍ ＭｅＭｇＢｒを０℃でシリンジを介して１回で加えた。得られた懸濁液に、４００ｍｇ（０．４８５ｍｍｏｌ）の２’，２’’’－（ピリジン－２，６－ジイル）ビス（３－（（３ｒ，５ｒ，７ｒ）－アダマンタン－１－イル）－５－（ｔｅｒｔ－ブチル）－４’－メチル－［１，１’－ビフェニル］－２－オール）を直ちに１回で加えた。反応混合物を室温で４時間撹拌し、次いで、ほぼ乾固するまで蒸発させた。得られた固体を２×２０ｍＬの熱トルエンで抽出し、合わせた有機抽出物をＣｅｌｉｔｅ ５０３の薄いパッドに通して濾過した。次に、濾液を蒸発乾固した。残留物を５ｍＬのｎ－ヘキサンと研和し、得られた沈殿物を濾別（Ｇ４）し、２×５ｍＬのｎ－ヘキサンで洗浄し、次いで、真空中で乾燥した。収量２８７ｍｇ（５７％）のホワイトベージュ色固体。Ｃ₆₁Ｈ₇₃ＨｆＮＯ₂の解析計算値：Ｃ、７１．０８；Ｈ、７．１４；Ｎ、１．３６。測定値：Ｃ ７１．３１；Ｈ、７．３２；Ｎ １．２４。¹H NMR (C₆D₆, 400 MHz): δ 7.58 (d, J = 2.6 Hz, 2H), 7.12 (d, J = 7.8 Hz, 2H), 7.03 (d, J = 2.6 Hz, 2H), 6.95 (dd, J = 7.9, 1.3 Hz, 2H), 6.75 (d, J = 0.7 Hz, 2H), 6.39 - 6.52 (m, 3H), 2.55 - 2.62 (m, 6H), 2.40 - 2.48 (m, 6H), 2.19 (s, 6H), 2.19 (br.s, 6H), 1.98 - 2.05 (m, 6H), 1.78 - 1.86 (m, 6H), 1.33 (s, 18H), -0.02 (s, 6H). ¹³C NMR (C₆D₆, 100 MHz) δ 159.90, 158.06, 141.34, 140.38, 139.30, 138.47, 137.64, 133.82, 133.12, 132.86, 132.49, 131.21, 129.66, 128.90, 126.00, 125.32, 124.41, 51.20, 41.77, 38.48, 37.81, 34.76, 32.35, 30.07, 21.31. Dimethylhafnium [2', 2'''-(pyridin-2,6-diyl) bis (3-((3r, 5r, 7r) -adamantan-1-yl) -5- (tert-butyl) -4' -Methyl- [1,1'-biphenyl] -2-olate)] (complex 9)

Syringe 750 ul (2.20 mmol) 2.9 M MeMgBr in diethyl ether into a suspension of 155 mg (0.485 mmol) hafnium tetrachloride (<0.5% Zr) in 50 mL dry toluene at 0 ° C. Was added once via. In the resulting suspension, 400 mg (0.485 mmol) of 2', 2'''-(pyridin-2,6-diyl) bis (3-((3r, 5r, 7r) -adamantan-1-yl) ) -5- (tert-butyl) -4'-methyl- [1,1'-biphenyl] -2-ol) was immediately added in one dose. The reaction mixture was stirred at room temperature for 4 hours and then evaporated to near dryness. The resulting solid was extracted with 2 x 20 mL hot toluene and the combined organic extracts were filtered through a thin pad of Celite 503. Next, the filtrate was evaporated to dryness. The residue was triturated with 5 mL of n-hexane, the resulting precipitate was filtered off (G4), washed with 2 x 5 mL of n-hexane and then dried in vacuo. A white beige solid with a yield of 287 mg (57%). Analysis of C ₆₁ H ₇₃ HfNO ₂ Calculated values: C, 71.08; H, 7.14; N, 1.36. Measured values: C 71.31; H, 7.32; N 1.24. ¹ H NMR (C ₆ D ₆ , 400 MHz): δ 7.58 (d, J = 2.6 Hz, 2H), 7.12 (d, J = 7.8 Hz, 2H), 7.03 (d, J = 2.6 Hz, 2H), 6.95 (dd, J = 7.9, 1.3 Hz, 2H), 6.75 (d, J = 0.7 Hz, 2H), 6.39 --6.52 (m, 3H), 2.55 --2.62 (m, 6H), 2.40 --2.48 (m, 6H), 2.19 (s, 6H), 2.19 (br.s, 6H), 1.98 --2.05 (m, 6H), 1.78 --1.86 (m, 6H), 1.33 (s, 18H), -0.02 (s, 6H) ). ¹³ C NMR (C ₆ D ₆ , 100 MHz) δ 159.90, 158.06, 141.34, 140.38, 139.30, 138.47, 137.64, 133.82, 133.12, 132.86, 132.49, 131.21, 129.66, 128.90, 126.00, 125.32, 124.41, 51.20 , 41.77, 38.48, 37.81, 34.76, 32.35, 30.07, 21.31.

５０ｍＬの乾燥トルエン中の１３５ｍｇ（０．４２１ｍｍｏｌ）の四塩化ハフニウム（＜０．５％ Ｚｒ）の懸濁液に、ジエチルエーテル中の６５０ｕｌ（１．８９ｍｍｏｌ）の２．９Ｍ ＭｅＭｇＢｒを０℃でシリンジを介して１回で加えた。得られた懸濁液に、４００ｍｇ（０．４２１ｍｍｏｌ）の２’，２’’’－（４－（トリフルオロメチル）ピリジン－２，６－ジイル）ビス（３－（（３ｒ，５ｒ，７ｒ）－アダマンタン－１－イル）－５－（ｔｅｒｔ－ブチル）－４’－イソプロピル－［１，１’－ビフェニル］－２－オール）を直ちに１回で加えた。反応混合物を室温で４時間撹拌し、次いで、ほぼ乾固するまで蒸発させた。得られた固体を２×２０ｍＬの熱トルエンで抽出し、合わせた有機抽出物をＣｅｌｉｔｅ ５０３の薄いパッドに通して濾過した。次に、濾液を蒸発乾固した。残留物を５ｍＬのｎ－ヘキサンと研和し、得られた沈殿物を濾別（Ｇ４）し、２×５ｍＬのｎ－ヘキサンで洗浄し、次いで、真空中で乾燥した。収量３５６ｍｇ（７３％）の黄色固体。Ｃ₆₆Ｈ₈₀Ｆ₃ＨｆＮＯ₂の解析計算値：Ｃ、６８．６４；Ｈ、６．９８；Ｎ、１．２１。測定値：Ｃ ６８．８８；Ｈ、７．１６；Ｎ １．１３。¹H NMR (C₆D₆, 400 MHz): δ 7.57 (d, J = 2.6 Hz, 2H), 7.19 - 7.22 (m, 4H), 7.02 (s, 2H), 6.98 (d, J = 2.5 Hz, 2H), 6.93 (d, J = 1.7 Hz, 2H), 2.91 (七重線, J = 6.9 Hz, 2H), 2.53 - 2.60 (m, 6H), 2.40 - 2.47 (m, 6H), 2.15 (br.s, 6H), 1.96 - 2.03 (m, 6H), 1.77 - 1.85 (m, 6H), 1.28 (s, 18H), 1.23 (d, J = 6.9 Hz, 6H), 1.07 (d, J = 6.9 Hz, 6H), 0.00 (s, 6H). ¹³C NMR (C₆D₆, 100 MHz) δ 160.39, 159.75, 149.13, 141.82, 140.98, 138.51, 134.19, 132.28, 129.29, 125.96, 124.61, 121.84 (q, Jc,_F = 3.0 Hz), 51.54, 41.81, 38.53, 37.78, 34.77, 33.85, 32.24, 29.95, 26.57, 22.32. Dimethylhafnium [2', 2'''-(4- (trifluoromethyl) pyridin-2,6-diyl) bis (3-((3r, 5r, 7r) -adamantane-1-yl) -5-( tert-butyl) -4'-isopropyl- [1,1'-biphenyl] -2-olate)] (complex 10)

Syringe 650 ul (1.89 mmol) of 2.9 M MeMgBr in diethyl ether into a suspension of 135 mg (0.421 mmol) hafnium tetrachloride (<0.5% Zr) in 50 mL of dry toluene at 0 ° C. Was added once via. 400 mg (0.421 mmol) of 2', 2'''-(4- (trifluoromethyl) pyridine-2,6-diyl) bis (3-((3r, 5r, 7r)) was added to the resulting suspension. ) -Adamantane-1-yl) -5- (tert-butyl) -4'-isopropyl- [1,1'-biphenyl] -2-ol) was immediately added in one dose. The reaction mixture was stirred at room temperature for 4 hours and then evaporated to near dryness. The resulting solid was extracted with 2 x 20 mL hot toluene and the combined organic extracts were filtered through a thin pad of Celite 503. Next, the filtrate was evaporated to dryness. The residue was triturated with 5 mL of n-hexane, the resulting precipitate was filtered off (G4), washed with 2 x 5 mL of n-hexane and then dried in vacuo. A yellow solid with a yield of 356 mg (73%). Analysis of C ₆₆ H ₈₀ F ₃ HfNO ₂ Calculated values: C, 68.64; H, 6.98; N, 1.21. Measured values: C 68.88; H, 7.16; N 1.13. ¹ H NMR (C ₆ D ₆ , 400 MHz): δ 7.57 (d, J = 2.6 Hz, 2H), 7.19 --7.22 (m, 4H), 7.02 (s, 2H), 6.98 (d, J = 2.5 Hz) , 2H), 6.93 (d, J = 1.7 Hz, 2H), 2.91 (7-fold line, J = 6.9 Hz, 2H), 2.53 --2.60 (m, 6H), 2.40 --2.47 (m, 6H), 2.15 (br .s, 6H), 1.96 --2.03 (m, 6H), 1.77 --1.85 (m, 6H), 1.28 (s, 18H), 1.23 (d, J = 6.9 Hz, 6H), 1.07 (d, J = 6.9) Hz, 6H), 0.00 (s, 6H). ¹³ C NMR (C ₆ D ₆ , 100 MHz) δ 160.39, 159.75, 149.13, 141.82, 140.98, 138.51, 134.19, 132.28, 129.29, 125.96, 124.61, 121.84 (q) , Jc, _F = 3.0 Hz), 51.54, 41.81, 38.53, 37.78, 34.77, 33.85, 32.24, 29.95, 26.57, 22.32.

５０ｍＬの乾燥トルエン中の１４０ｍｇ（０．４４０ｍｍｏｌ）の四塩化ハフニウム（＜０．５％ Ｚｒ）の懸濁液に、ジエチルエーテル中の６８０ｕｌ（１．９８ｍｍｏｌ）の２．９Ｍ ＭｅＭｇＢｒを０℃でシリンジを介して１回で加えた。得られた懸濁液に、４００ｍｇ（０．４４０ｍｍｏｌ）の２’，２’’’－（４－メトキシピリジン－２，６－ジイル）ビス（３－（（３ｒ，５ｒ，７ｒ）－アダマンタン－１－イル）－５－（ｔｅｒｔ－ブチル）－４’－イソプロピル－［１，１’－ビフェニル］－２－オール）を直ちに１回で加えた。反応混合物を室温で４時間撹拌し、次いで、ほぼ乾固するまで蒸発させた。得られた固体を２×２０ｍＬの熱トルエンで抽出し、合わせた有機抽出物をＣｅｌｉｔｅ ５０３の薄いパッドに通して濾過した。次に、濾液を蒸発乾固した。残留物を５ｍＬのｎ－ヘキサンと研和し、得られた沈殿物を濾別（Ｇ４）し、２×５ｍＬのｎ－ヘキサンで洗浄し、次いで、真空中で乾燥した。収量３１０ｍｇ（６３％）の白色固体。Ｃ₆₆Ｈ₈₃ＨｆＮＯ₃の解析計算値：Ｃ、７０．９８；Ｈ、７．４９；Ｎ、１．２５。測定値：Ｃ ７１．２４；Ｈ、７．５２；Ｎ １．１４。¹H NMR (C₆D₆, 400 MHz): δ 7.60 (d, J = 2.6 Hz, 2H), 7.25 (d, J = 8.1 Hz, 2H), 7.18 (m, 2H), 7.07 (d, J = 2.5 Hz, 2H), 7.02 (d, J = 1.8 Hz, 2H), 6.21 (s, 2H), 2.98 (七重線, J = 6.8 Hz, 2H), 2.60 - 2.67 (m, 6H), 2.61 (s, 3H), 2.48 - 2.56 (m, 6H), 2.18 (br.s, 6H), 2.01 - 2.08 (m, 6H), 1.80 - 1.87 (m, 6H), 1.31 (s, 18H), 1.25 (d, J = 6.8 Hz, 6H), 1.12 (d, J = 6.8 Hz, 6H), -0.02 (s, 6H). ¹³C NMR (C₆D₆, 100 MHz) δ 167.36, 160.15, 160.03, 148.56, 141.83, 140.28, 138.50, 134.24, 133.36, 132.93, 129.58, 128.24, 126.19, 124.50, 111.80, 55.16, 51.06, 41.85, 38.60, 37.87, 34.79, 33.77, 32.38, 30.03, 26.54, 22.31. Dimethylhafnium [2', 2'''-(4-methoxypyridin-2,6-diyl) bis (3-((3r, 5r, 7r) -adamantan-1-yl) -5- (tert-butyl) -4'-Isopropyl- [1,1'-biphenyl] -2-olate)] (complex 11)

Syringe 680 ul (1.98 mmol) 2.9 M MeMgBr in diethyl ether into a suspension of 140 mg (0.440 mmol) hafnium tetrachloride (<0.5% Zr) in 50 mL dry toluene at 0 ° C. Was added once via. 400 mg (0.440 mmol) of 2', 2'''-(4-methoxypyridin-2,6-diyl) bis (3-((3r, 5r, 7r) -adamantane-) was added to the resulting suspension. 1-Il) -5- (tert-butyl) -4'-isopropyl- [1,1'-biphenyl] -2-ol) was immediately added in one dose. The reaction mixture was stirred at room temperature for 4 hours and then evaporated to near dryness. The resulting solid was extracted with 2 x 20 mL hot toluene and the combined organic extracts were filtered through a thin pad of Celite 503. Next, the filtrate was evaporated to dryness. The residue was triturated with 5 mL of n-hexane, the resulting precipitate was filtered off (G4), washed with 2 x 5 mL of n-hexane and then dried in vacuo. A white solid with a yield of 310 mg (63%). Analysis of C ₆₆ H ₈₃ HfNO ₃ Calculated values: C, 70.98; H, 7.49; N, 1.25. Measured values: C 71.24; H, 7.52; N 1.14. ¹ H NMR (C ₆ D ₆ , 400 MHz): δ 7.60 (d, J = 2.6 Hz, 2H), 7.25 (d, J = 8.1 Hz, 2H), 7.18 (m, 2H), 7.07 (d, J) = 2.5 Hz, 2H), 7.02 (d, J = 1.8 Hz, 2H), 6.21 (s, 2H), 2.98 (7-fold line, J = 6.8 Hz, 2H), 2.60 --2.67 (m, 6H), 2.61 ( s, 3H), 2.48 --2.56 (m, 6H), 2.18 (br.s, 6H), 2.01 --2.08 (m, 6H), 1.80 --1.87 (m, 6H), 1.31 (s, 18H), 1.25 ( d, J = 6.8 Hz, 6H), 1.12 (d, J = 6.8 Hz, 6H), -0.02 (s, 6H). ¹³ C NMR (C ₆ D ₆ , 100 MHz) δ 167.36, 160.15, 160.03, 148.56 , 141.83, 140.28, 138.50, 134.24, 133.36, 132.93, 129.58, 128.24, 126.19, 124.50, 111.80, 55.16, 51.06, 41.85, 38.60, 37.87, 34.79, 33.77, 32.38, 30.03, 26.54, 22.31.

５０ｍＬの乾燥トルエン中の１４４ｍｇ（０．４４８ｍｍｏｌ）の四塩化ハフニウム（＜０．５％ Ｚｒ）の懸濁液に、ジエチルエーテル中の６９５ｕｌ（２．０２ｍｍｏｌ）の２．９Ｍ ＭｅＭｇＢｒを０℃でシリンジを介して１回で加えた。得られた懸濁液に、４００ｍｇ（０．４４８ｍｍｏｌ）の２’，２’’’－（４－（トリフルオロメチル）ピリジン－２，６－ジイル）ビス（３－（（３ｒ，５ｒ，７ｒ）－アダマンタン－１－イル）－５－（ｔｅｒｔ－ブチル）－４’－メチル－［１，１’－ビフェニル］－２－オール）を直ちに１回で加えた。反応混合物を室温で４時間撹拌し、次いで、ほぼ乾固するまで蒸発させた。得られた固体を２×２０ｍＬの熱トルエンで抽出し、合わせた有機抽出物をＣｅｌｉｔｅ ５０３の薄いパッドに通して濾過した。次に、濾液を蒸発乾固した。残留物を５ｍＬのｎ－ヘキサンと研和し、得られた沈殿物を濾別（Ｇ４）し、２×５ｍＬのｎ－ヘキサンで洗浄し、次いで、真空中で乾燥した。収量３９８ｍｇ（８１％）の黄色固体。Ｃ₆₂Ｈ₇₂Ｆ₃ＨｆＮＯ₂の解析計算値：Ｃ、６７．７８；Ｈ、６．６１；Ｎ、１．２７。測定値：Ｃ ６８．０３；Ｈ、６．７４；Ｎ １．１５。¹H NMR (C₆D₆, 400 MHz): δ 7.55 (d, J = 2.6 Hz, 2H), 7.07 (d, J = 7.9 Hz, 2H), 6.95 (d, J = 2.6 Hz, 2H), 6.93 (dd, J = 7.8, 1.2 Hz, 2H), 6.84 (s, 2H), 6.69 (d, J = 0.7 Hz, 2H), 2.50 - 2.57 (m, 6H), 2.37 - 2.45 (m, 6H), 2.16 (s, 6H), 2.15 (br.s, 6H), 1.96 - 2.04 (m, 6H), 1.78 - 1.86 (m, 6H), 1.30 (s, 18H), -0.03 (s, 6H). ¹³C NMR (C₆D₆, 100 MHz) δ 160.17, 159.61, 141.22, 140.90, 138.47, 137.94, 133.72, 132.95, 132.29, 132.16, 130.86, 129.66, 128.90, 126.03, 125.92, 124.58, 121.56 (q, J^F = 3.5 Hz), 51.51, 41.74, 38.48, 37.76, 34.76, 32.25, 30.04, 21.27 Dimethylhafnium [2', 2'''-(4- (trifluoromethyl) pyridine-2,6-diyl) bis (3-((3r, 5r, 7r) -adamantane-1-yl) -5-( tert-butyl) -4'-methyl- [1,1'-biphenyl] -2-olate)] (complex 12)

A suspension of 144 mg (0.448 mmol) of hafnium tetrachloride (<0.5% Zr) in 50 mL of dry toluene is syringed with 695 ul (2.02 mmol) of 2.9 M MeMgBr in diethyl ether at 0 ° C. Was added once via. 400 mg (0.448 mmol) of 2', 2'''-(4- (trifluoromethyl) pyridine-2,6-diyl) bis (3-((3r, 5r, 7r)) was added to the resulting suspension. ) -Adamantane-1-yl) -5- (tert-butyl) -4'-methyl- [1,1'-biphenyl] -2-ol) was immediately added in one dose. The reaction mixture was stirred at room temperature for 4 hours and then evaporated to near dryness. The resulting solid was extracted with 2 x 20 mL hot toluene and the combined organic extracts were filtered through a thin pad of Celite 503. Next, the filtrate was evaporated to dryness. The residue was triturated with 5 mL of n-hexane, the resulting precipitate was filtered off (G4), washed with 2 x 5 mL of n-hexane and then dried in vacuo. A yellow solid with a yield of 398 mg (81%). Analysis of C ₆₂ H ₇₂ F ₃ HfNO ₂ Calculated values: C, 67.78; H, 6.61; N, 1.27. Measured values: C 68.03; H, 6.74; N 1.15. ¹ H NMR (C ₆ D ₆ , 400 MHz): δ 7.55 (d, J = 2.6 Hz, 2H), 7.07 (d, J = 7.9 Hz, 2H), 6.95 (d, J = 2.6 Hz, 2H), 6.93 (dd, J = 7.8, 1.2 Hz, 2H), 6.84 (s, 2H), 6.69 (d, J = 0.7 Hz, 2H), 2.50 --2.57 (m, 6H), 2.37 --2.45 (m, 6H) , 2.16 (s, 6H), 2.15 (br.s, 6H), 1.96 --2.04 (m, 6H), 1.78 --1.86 (m, 6H), 1.30 (s, 18H), -0.03 (s, 6H). ¹³ C NMR (C ₆ D ₆ , 100 MHz) δ 160.17, 159.61, 141.22, 140.90, 138.47, 137.94, 133.72, 132.95, 132.29, 132.16, 130.86, 129.66, 128.90, 126.03, 125.92, 124.58, 121.56 (q, J) ^F = 3.5 Hz), 51.51, 41.74, 38.48, 37.76, 34.76, 32.25, 30.04, 21.27

５０ｍＬの乾燥トルエン中の１０５ｍｇ（０．４４８ｍｍｏｌ）の四塩化ジルコニウムの懸濁液に、ジエチルエーテル中の６９５ｕｌ（２．０２ｍｍｏｌ）の２．９Ｍ ＭｅＭｇＢｒを－３０℃でシリンジを介して１回で加えた。得られた懸濁液に、４００ｍｇ（０．４４８ｍｍｏｌ）の２’，２’’’－（４－（トリフルオロメチル）ピリジン－２，６－ジイル）ビス（３－（（３ｒ，５ｒ，７ｒ）－アダマンタン－１－イル）－５－（ｔｅｒｔ－ブチル）－４’－メチル－［１，１’－ビフェニル］－２－オール）を直ちに１回で加えた。反応混合物を室温で４時間撹拌し、次いで、ほぼ乾固するまで蒸発させた。得られた固体を２×２０ｍＬの熱トルエンで抽出し、合わせた有機抽出物をＣｅｌｉｔｅ ５０３の薄いパッドに通して濾過した。次に、濾液を蒸発乾固した。残留物を５ｍＬのｎ－ヘキサンと研和し、得られた沈殿物を濾別（Ｇ４）し、２×５ｍＬのｎ－ヘキサンで洗浄し、次いで、真空中で乾燥した。収量３３０ｍｇ（７３％）の黄色固体。Ｃ₆₂Ｈ₇₂Ｆ₃ＺｒＮＯ₂の解析計算値：Ｃ、７３．６２；Ｈ、７．１８；Ｎ、１．３８。測定値：Ｃ ７３．９０；Ｈ、７．３２；Ｎ １．２１。¹H NMR (C₆D₆, 400 MHz): δ 7.54 (d, J = 2.6 Hz, 2H), 7.07 (d, J = 7.8 Hz, 2H), 6.95 (d, J = 2.5 Hz, 2H), 6.91 (dd, J = 7.8, 1.2 Hz, 2H), 6.83 (s, 2H), 6.67 (m, 2H), 2.52 - 2.59 (m, 6H), 2.39 - 2.47 (m, 6H), 2.15 (s, 6H), 2.15 (br.s, 6H), 1.96 - 2.04 (m, 6H), 1.79 - 1.86 (m, 6H), 1.30 (s, 18H), -0.20 (s, 6H). ¹³C NMR (C₆D₆, 100 MHz) δ 160.53, 159.08, 141.06, 141.00, 137.91, 137.88, 133.60, 132.81, 132.64, 132.55, 130.76, 129.66, 128.90, 125.99, 124.49, 121.05 (q, J^F = 3.0 Hz), 43.38, 41.78, 38.58, 37.75, 34.79, 32.24, 30.04, 21.25. Dimethylzirconium [2', 2'''-(4- (trifluoromethyl) pyridin-2,6-diyl) bis (3-((3r, 5r, 7r) -adamantan-1-yl) -5-( tert-butyl) -4'-methyl- [1,1'-biphenyl] -2-olate)] (complex 13)

To a suspension of 105 mg (0.448 mmol) of zirconium tetrachloride in 50 mL of dry toluene, 695 ul (2.02 mmol) of 2.9 M MeMgBr in diethyl ether is added in a single dose at -30 ° C via a syringe. rice field. 400 mg (0.448 mmol) of 2', 2'''-(4- (trifluoromethyl) pyridine-2,6-diyl) bis (3-((3r, 5r, 7r)) was added to the resulting suspension. ) -Adamantane-1-yl) -5- (tert-butyl) -4'-methyl- [1,1'-biphenyl] -2-ol) was immediately added in one dose. The reaction mixture was stirred at room temperature for 4 hours and then evaporated to near dryness. The resulting solid was extracted with 2 x 20 mL hot toluene and the combined organic extracts were filtered through a thin pad of Celite 503. Next, the filtrate was evaporated to dryness. The residue was triturated with 5 mL of n-hexane, the resulting precipitate was filtered off (G4), washed with 2 x 5 mL of n-hexane and then dried in vacuo. A yellow solid with a yield of 330 mg (73%). Analysis of C ₆₂ H ₇₂ F ₃ ZrNO ₂ Calculated value: C, 73.62; H, 7.18; N, 1.38. Measured values: C 73.90; H, 7.32; N 1.21. ¹ H NMR (C ₆ D ₆ , 400 MHz): δ 7.54 (d, J = 2.6 Hz, 2H), 7.07 (d, J = 7.8 Hz, 2H), 6.95 (d, J = 2.5 Hz, 2H), 6.91 (dd, J = 7.8, 1.2 Hz, 2H), 6.83 (s, 2H), 6.67 (m, 2H), 2.52 --2.59 (m, 6H), 2.39 --2.47 (m, 6H), 2.15 (s, 6H), 2.15 (br.s, 6H), 1.96 --2.04 (m, 6H), 1.79 --1.86 (m, 6H), 1.30 (s, 18H), -0.20 (s, 6H). ¹³ C NMR (C) ₆ D ₆ , 100 MHz) δ 160.53, 159.08, 141.06, 141.00, 137.91, 137.88, 133.60, 132.81, 132.64, 132.55, 130.76, 129.66, 128.90, 125.99, 124.49, 121.05 (q, J ^F = 3.0 Hz), 43.38 , 41.78, 38.58, 37.75, 34.79, 32.24, 30.04, 21.25.

５０ｍＬの乾燥トルエン中の１４５ｍｇ（０．４５４ｍｍｏｌ）の四塩化ハフニウム（＜０．５％ Ｚｒ）の懸濁液に、ジエチルエーテル中の７０４ｕｌ（２．０４ｍｍｏｌ）の２．９Ｍ ＭｅＭｇＢｒを０℃でシリンジを介して１回で加えた。得られた懸濁液に、４００ｍｇ（０．４５４ｍｍｏｌ）の２’，２’’’－（ピリジン－２，６－ジイル）ビス（３－（（３ｒ，５ｒ，７ｒ）－アダマンタン－１－イル）－５－（ｔｅｒｔ－ブチル）－４’－イソプロピル－［１，１’－ビフェニル］－２－オール）を直ちに１回で加えた。反応混合物を室温で４時間撹拌し、次いで、ほぼ乾固するまで蒸発させた。得られた固体を２×２０ｍＬの熱トルエンで抽出し、合わせた有機抽出物をＣｅｌｉｔｅ ５０３の薄いパッドに通して濾過した。次に、濾液を蒸発乾固した。残留物を５ｍＬのｎ－ヘキサンと研和し、得られた沈殿物を濾別（Ｇ４）し、２×５ｍＬのｎ－ヘキサンで洗浄し、次いで、真空中で乾燥した。収量３３３ｍｇ（６７％）の白色固体。Ｃ₆₅Ｈ₈₁ＨｆＮＯ₂の解析計算値：Ｃ、７１．８３；Ｈ、７．５１；Ｎ、１．２９。測定値：Ｃ ７２．０９；Ｈ、７．６７；Ｎ １．２０。¹H NMR (C₆D₆, 400 MHz): δ 7.58 (d, J = 2.6 Hz, 2H), 7.25 (d, J = 8.1 Hz, 2H), 7.17 - 7.19 (m, 2H), 7.04 (d, J = 2.6 Hz, 2H), 6.92 (d, J = 1.8 Hz, 2H), 6.43 - 6.55 (m, 3H), 2.95 (七重線, J = 6.9 Hz, 2H), 2.56 - 2.63 (m, 6H), 2.44 - 2.50 (m, 6H), 2.17 (br.s, 6H), 1.99 - 2.06 (m, 6H), 1.78 - 1.86 (m, 6H), 1.31 (s, 18H), 1.25 (d, J = 6.9 Hz, 6H), 1.10 (d, J = 6.9 Hz, 6H), 0.00 (s, 6H). ¹³C NMR (C₆D₆, 100 MHz) δ 158.67, 157.62, 147.92, 140.68, 139.28, 138.93, 137.17, 133.04, 132.32, 131.59, 128.97, 127.37, 125.20, 125.15, 123.24, 49.62, 40.65, 37.42, 37.04, 34.15, 33.03, 31.72, 29.08, 26.02, 21.86. Dimethylhafnium [2', 2'''-(pyridin-2,6-diyl) bis (3-((3r, 5r, 7r) -adamantan-1-yl) -5- (tert-butyl) -4' -Isopropyl- [1,1'-biphenyl] -2-olate)] (complex 14)

Syringe 704 ul (2.04 mmol) 2.9 M MeMgBr in diethyl ether into a suspension of 145 mg (0.454 mmol) hafnium tetrachloride (<0.5% Zr) in 50 mL dry toluene at 0 ° C. Was added once via. In the resulting suspension, 400 mg (0.454 mmol) of 2', 2'''-(pyridin-2,6-diyl) bis (3-((3r, 5r, 7r) -adamantan-1-yl) ) -5- (tert-butyl) -4'-isopropyl- [1,1'-biphenyl] -2-ol) was immediately added in one dose. The reaction mixture was stirred at room temperature for 4 hours and then evaporated to near dryness. The resulting solid was extracted with 2 x 20 mL hot toluene and the combined organic extracts were filtered through a thin pad of Celite 503. Next, the filtrate was evaporated to dryness. The residue was triturated with 5 mL of n-hexane, the resulting precipitate was filtered off (G4), washed with 2 x 5 mL of n-hexane and then dried in vacuo. A white solid with a yield of 333 mg (67%). Analysis of C ₆₅ H ₈₁ HfNO ₂ Calculated values: C, 71.83; H, 7.51; N, 1.29. Measured values: C 72.09; H, 7.67; N 1.20. ¹ H NMR (C ₆ D ₆ , 400 MHz): δ 7.58 (d, J = 2.6 Hz, 2H), 7.25 (d, J = 8.1 Hz, 2H), 7.17 --7.19 (m, 2H), 7.04 (d) , J = 2.6 Hz, 2H), 6.92 (d, J = 1.8 Hz, 2H), 6.43 --6.55 (m, 3H), 2.95 (7-fold line, J = 6.9 Hz, 2H), 2.56 --2.63 (m, 6H) ), 2.44 --2.50 (m, 6H), 2.17 (br.s, 6H), 1.99 --2.06 (m, 6H), 1.78 --1.86 (m, 6H), 1.31 (s, 18H), 1.25 (d, J) = 6.9 Hz, 6H), 1.10 (d, J = 6.9 Hz, 6H), 0.00 (s, 6H). ¹³ C NMR (C ₆ D ₆ , 100 MHz) δ 158.67, 157.62, 147.92, 140.68, 139.28, 138.93 , 137.17, 133.04, 132.32, 131.59, 128.97, 127.37, 125.20, 125.15, 123.24, 49.62, 40.65, 37.42, 37.04, 34.15, 33.03, 31.72, 29.08, 26.02, 21.86.

５０ｍＬの乾燥トルエン中の１１２ｍｇ（０．３５１ｍｍｏｌ）の四塩化ハフニウム（＜０．５％ Ｚｒ）の懸濁液に、ジエチルエーテル中の５４４ｕｌ（１．５６ｍｍｏｌ）の２．９Ｍ ＭｅＭｇＢｒを０℃でシリンジを介して１回で加えた。得られた懸濁液に、３００ｍｇ（０．３５１ｍｍｏｌ）の２’，２’’’－（４－メトキシピリジン－２，６－ジイル）ビス（３－（（３ｒ，５ｒ，７ｒ）－アダマンタン－１－イル）－５－（ｔｅｒｔ－ブチル）－４’－メチル－［１，１’－ビフェニル］－２－オール）を直ちに１回で加えた。反応混合物を室温で４時間撹拌し、次いで、ほぼ乾固するまで蒸発させた。得られた固体を２×２０ｍＬの熱トルエンで抽出し、合わせた有機抽出物をＣｅｌｉｔｅ ５０３の薄いパッドに通して濾過した。次に、濾液を蒸発乾固した。残留物を５ｍＬのｎ－ヘキサンと研和し、得られた沈殿物を濾別（Ｇ４）し、２×５ｍＬのｎ－ヘキサンで洗浄し、次いで、真空中で乾燥した。収量２８４ｍｇ（７６％）の白色固体。Ｃ₆₂Ｈ₇₅ＨｆＮＯ₃の解析計算値：Ｃ、７０．２０；Ｈ、７．１３；Ｎ、１．３２。測定値：Ｃ ７０．４５；Ｈ、７．３３；Ｎ １．２３。¹H NMR (C₆D₆, 400 MHz): δ 7.59 (d, J = 2.6 Hz, 2H), 7.12 - 7.14 (m, 2H), 7.05 (d, J = 2.6 Hz, 2H), 6.95 (dd, J = 7.9, 1.2 Hz, 2H), 6.85 (m, 2H), 6.09 (s, 2H), 2.63 (s, 3H), 2.59 - 2.65 (m, 6H), 2.44 - 2.53 (m, 6H), 2.22 (s, 6H), 2.19 (br.s, 6H), 2.01 - 2.08 (m, 6H), 1.80 - 1.87 (m, 6H), 1.33 (s, 18H), 0.00 (s, 6H). ¹³C NMR (C₆D₆, 100 MHz) δ 166.82, 159.09, 158.73, 140.36, 139.21, 137.23, 137.08, 132.94, 132.42, 131.61, 131.51, 130.47, 123.29, 110.90, 55.69, 49.23, 40.68, 37.47, 37.02, 34.15, 31.72, 29.16, 21.01. Dimethylhafnium [2', 2'''-(4-methoxypyridin-2,6-diyl) bis (3-((3r, 5r, 7r) -adamantan-1-yl) -5- (tert-butyl) -4'-Methyl- [1,1'-biphenyl] -2-olate)] (complex 15)

Syringe 544 ul (1.56 mmol) 2.9 M MeMgBr in diethyl ether into a suspension of 112 mg (0.351 mmol) hafnium tetrachloride (<0.5% Zr) in 50 mL dry toluene at 0 ° C. Was added once via. 300 mg (0.351 mmol) of 2', 2'''-(4-methoxypyridin-2,6-diyl) bis (3-((3r, 5r, 7r) -adamantane-) was added to the resulting suspension. 1-Il) -5- (tert-butyl) -4'-methyl- [1,1'-biphenyl] -2-ol) was immediately added in one dose. The reaction mixture was stirred at room temperature for 4 hours and then evaporated to near dryness. The resulting solid was extracted with 2 x 20 mL hot toluene and the combined organic extracts were filtered through a thin pad of Celite 503. Next, the filtrate was evaporated to dryness. The residue was triturated with 5 mL of n-hexane, the resulting precipitate was filtered off (G4), washed with 2 x 5 mL of n-hexane and then dried in vacuo. A white solid with a yield of 284 mg (76%). Analysis of C ₆₂ H ₇₅ HfNO ₃ Calculated values: C, 70.20; H, 7.13; N, 1.32. Measured values: C 70.45; H, 7.33; N 1.23. ¹ H NMR (C ₆ D ₆ , 400 MHz): δ 7.59 (d, J = 2.6 Hz, 2H), 7.12 --7.14 (m, 2H), 7.05 (d, J = 2.6 Hz, 2H), 6.95 (dd) , J = 7.9, 1.2 Hz, 2H), 6.85 (m, 2H), 6.09 (s, 2H), 2.63 (s, 3H), 2.59 --2.65 (m, 6H), 2.44 --2.53 (m, 6H), 2.22 (s, 6H), 2.19 (br.s, 6H), 2.01 --2.08 (m, 6H), 1.80 --1.87 (m, 6H), 1.33 (s, 18H), 0.00 (s, 6H). ¹³ C NMR (C ₆ D ₆ , 100 MHz) δ 166.82, 159.09, 158.73, 140.36, 139.21, 137.23, 137.08, 132.94, 132.42, 131.61, 131.51, 130.47, 123.29, 110.90, 55.69, 49.23, 40.68, 37.47, 37.02, 34.15 , 31.72, 29.16, 21.01.

５０ｍＬの乾燥トルエン中の１５３ｍｇ（０．４７９ｍｍｏｌ）の四塩化ハフニウム（＜０．０５％ Ｚｒ）の懸濁液に、ジエチルエーテル中の７４３ｕｌ（２．１６ｍｍｏｌ）の２．９Ｍ ＭｅＭｇＢｒを０℃でシリンジを介して１回で加えた。得られた懸濁液に、４００ｍｇ（０．４７９ｍｍｏｌ）の２’，２’’’－（４－メトキシピリジン－２，６－ジイル）ビス（３－（（３ｒ，５ｒ，７ｒ）－アダマンタン－１－イル）－５－フルオロ－４’－イソプロピル－［１，１’－ビフェニル］－２－オール）を直ちに１回で加えた。反応混合物を室温で４時間撹拌し、次いで、ほぼ乾固するまで蒸発させた。得られた固体を２×２０ｍＬの熱トルエンで抽出し、合わせた有機抽出物をＣｅｌｉｔｅ ５０３の薄いパッドに通して濾過した。次に、濾液を蒸発乾固した。残留物を５ｍＬのｎ－ヘキサンと研和し、得られた沈殿物を濾別（Ｇ４）し、２×５ｍＬのｎ－ヘキサンで洗浄し、次いで、真空中で乾燥した。収量２８６ｍｇ（５７％）の白色固体。Ｃ₅₈Ｈ₆₅Ｆ₂ＨｆＮＯ₃の解析計算値：Ｃ、６６．９４；Ｈ、６．３０；Ｎ、１．３５。測定値：Ｃ ６７．２３；Ｈ、６．５１；Ｎ １．２５。¹H NMR (C₆D₆, 400 MHz): δ 7.11 - 7.20 (m, 6H), 7.02 (m, 2H), 6.72 (dd, J = 7.8, 3.2 Hz, 2H), 6.21 (s, 2H), 2.94 (七重線, J = 6.8 Hz, 2H), 2.52 (s, 3H), 2.33 - 2.42 (m, 6H), 2.20 - 2.30 (m, 6H), 2.07 (br.s, 6H), 1.87 - 1.95 (m, 6H), 1.72 - 1.80 (m, 6H), 1.24 (d, J = 6.8 Hz, 6H), 1.14 (d, J = 6.8 Hz, 6H), -0.05 (s, 6H). ¹³C NMR (C₆D₆, 100 MHz) δ 167.75, 159.75, 158.49, 157.28 (d, Jc,_F = 235 Hz), 149.31, 141.11 (d, Jc,_F = 5.7 Hz), 140.05 (d, Jc,_F = 1.7 Hz), 133.81, 133.47 (d, Jc,_F = 7.7 Hz), 133.28, 129.32, 128.51, 115.00 (d, Jc,_F = 22.3 Hz), 114.58 (d, Jc,_F = 23.0 Hz), 111.65, 55.26, 51.57, 41.18, 38.28, 37.59, 33.99, 29.77, 26.37, 22.34. Dimethylhafnium [2', 2'''-(4-methoxypyridin-2,6-diyl) bis (3-((3r, 5r, 7r) -adamantan-1-yl) -5-fluoro-4'- Isopropyl- [1,1'-biphenyl] -2-olate)] (complex 16)

Syringe 743 ul (2.16 mmol) of 2.9 M MeMgBr in diethyl ether into a suspension of 153 mg (0.479 mmol) of hafnium tetrachloride (<0.05% Zr) in 50 mL of dry toluene at 0 ° C. Was added once via. 400 mg (0.479 mmol) of 2', 2'''-(4-methoxypyridin-2,6-diyl) bis (3-((3r, 5r, 7r) -adamantane-) was added to the resulting suspension. 1-Il) -5-fluoro-4'-isopropyl- [1,1'-biphenyl] -2-ol) was immediately added in one dose. The reaction mixture was stirred at room temperature for 4 hours and then evaporated to near dryness. The resulting solid was extracted with 2 x 20 mL hot toluene and the combined organic extracts were filtered through a thin pad of Celite 503. Next, the filtrate was evaporated to dryness. The residue was triturated with 5 mL of n-hexane, the resulting precipitate was filtered off (G4), washed with 2 x 5 mL of n-hexane and then dried in vacuo. A white solid with a yield of 286 mg (57%). Analysis of C ₅₈ H ₆₅ F ₂ HfNO ₃ Calculated values: C, 66.94; H, 6.30; N, 1.35. Measured values: C 67.23; H, 6.51; N 1.25. ¹ H NMR (C ₆ D ₆ , 400 MHz): δ 7.11 --7.20 (m, 6H), 7.02 (m, 2H), 6.72 (dd, J = 7.8, 3.2 Hz, 2H), 6.21 (s, 2H) , 2.94 (7-fold line, J = 6.8 Hz, 2H), 2.52 (s, 3H), 2.33 --2.42 (m, 6H), 2.20 --2.30 (m, 6H), 2.07 (br.s, 6H), 1.87- 1.95 (m, 6H), 1.72- 1.80 (m, 6H), 1.24 (d, J = 6.8 Hz, 6H), 1.14 (d, J = 6.8 Hz, 6H), -0.05 (s, 6H). ¹³ C NMR (C ₆ D ₆ , 100 MHz) δ 167.75, 159.75, 158.49, 157.28 (d, Jc, _F = 235 Hz), 149.31, 141.11 (d, Jc, _F = 5.7 Hz), 140.05 (d, Jc, _F ) = 1.7 Hz), 133.81, 133.47 (d, Jc, _F = 7.7 Hz), 133.28, 129.32, 128.51, 115.00 (d, Jc, _F = 22.3 Hz), 114.58 (d, Jc, _F = 23.0 Hz), 111.65 , 55.26, 51.57, 41.18, 38.28, 37.59, 33.99, 29.77, 26.37, 22.34.

５０ｍＬの乾燥トルエン中の１６５ｍｇ（０．５１５ｍｍｏｌ）の四塩化ハフニウム（＜０．０５％ Ｚｒ）の懸濁液に、ジエチルエーテル中の８００ｕｌ（２．３２ｍｍｏｌ）の２．９Ｍ ＭｅＭｇＢｒを０℃でシリンジを介して１回で加えた。得られた懸濁液に、４４０ｍｇ（０．５１５ｍｍｏｌ）の２’，２’’’－（４－メトキシピリジン－２，６－ジイル）ビス（３－（（３ｒ，５ｒ，７ｒ）－アダマンタン－１－イル）－４’－（ｔｅｒｔ－ブチル）－５－メチル－［１，１’－ビフェニル］－２－オール）を直ちに１回で加えた。反応混合物を室温で４時間撹拌し、次いで、ほぼ乾固するまで蒸発させた。得られた固体を２×２０ｍＬの熱トルエンで抽出し、合わせた有機抽出物をＣｅｌｉｔｅ ５０３の薄いパッドに通して濾過した。次に、濾液を蒸発乾固した。残留物を５ｍＬのｎ－ヘキサンと研和し、得られた沈殿物を濾別（Ｇ４）し、２×５ｍＬのｎ－ヘキサンで洗浄し、次いで、真空中で乾燥した。収量３８０ｍｇ（７０％）の白色固体。Ｃ₆₂Ｈ₇₅ＨｆＮＯ₃の解析計算値：Ｃ、７０．２０；Ｈ、７．１３；Ｎ、１．３２。測定値：Ｃ ７０．４６；Ｈ、７．２９；Ｎ １．２５。¹H NMR (C₆D₆, 400 MHz): δ 7.36 (dd, J = 8.3, 2.0 Hz, 2H), 7.24 (m, 4H), 7.20 (d, J = 2.0 Hz, 2H), 6.70 (d, J = 2.0 Hz, 2H), 6.26 (s, 2H), 2.52 - 2.59 (m, 6H), 2.47 (s, 3H), 2.41 - 2.48 (m, 6H), 2.19 (s, 6H), 2.17 (br.s, 6H), 1.98 - 2.06 (m, 6H), 1.76 - 1.84 (m, 6H), 1.34 (s, 18H), -0.06 (s, 6H). ¹³C NMR (C₆D₆, 100 MHz) δ 167.46, 160.77, 160.29, 151.37, 141.42, 139.12, 134.02, 133.98, 133.05, 129.71, 129.56, 126.86, 125.47, 112.05, 55.00, 51.36, 41.67, 38.26, 37.81, 35.15, 31.74, 29.98, 21.34. Dimethylhafnium [2', 2'''-(4-methoxypyridin-2,6-diyl) bis (3-((3r, 5r, 7r) -adamantan-1-yl) -4'-(tert-butyl) ) -5-Methyl- [1,1'-biphenyl] -2-olate)] (complex 17)

Syringe 800 ul (2.32 mmol) of 2.9 M MeMgBr in diethyl ether into a suspension of 165 mg (0.515 mmol) hafnium tetrachloride (<0.05% Zr) in 50 mL of dry toluene at 0 ° C. Was added once via. In the resulting suspension, 440 mg (0.515 mmol) of 2', 2'''-(4-methoxypyridin-2,6-diyl) bis (3-((3r, 5r, 7r) -adamantane-) 1-Il) -4'-(tert-butyl) -5-methyl- [1,1'-biphenyl] -2-ol) was immediately added in one dose. The reaction mixture was stirred at room temperature for 4 hours and then evaporated to near dryness. The resulting solid was extracted with 2 x 20 mL hot toluene and the combined organic extracts were filtered through a thin pad of Celite 503. Next, the filtrate was evaporated to dryness. The residue was triturated with 5 mL of n-hexane, the resulting precipitate was filtered off (G4), washed with 2 x 5 mL of n-hexane and then dried in vacuo. A white solid with a yield of 380 mg (70%). Analysis of C ₆₂ H ₇₅ HfNO ₃ Calculated values: C, 70.20; H, 7.13; N, 1.32. Measured values: C 70.46; H, 7.29; N 1.25. ¹ H NMR (C ₆ D ₆ , 400 MHz): δ 7.36 (dd, J = 8.3, 2.0 Hz, 2H), 7.24 (m, 4H), 7.20 (d, J = 2.0 Hz, 2H), 6.70 (d , J = 2.0 Hz, 2H), 6.26 (s, 2H), 2.52 --2.59 (m, 6H), 2.47 (s, 3H), 2.41 --2.48 (m, 6H), 2.19 (s, 6H), 2.17 ( br.s, 6H), 1.98 --2.06 (m, 6H), 1.76 --1.84 (m, 6H), 1.34 (s, 18H), -0.06 (s, 6H). ¹³ C NMR (C ₆ D ₆ , 100 MHz) δ 167.46, 160.77, 160.29, 151.37, 141.42, 139.12, 134.02, 133.98, 133.05, 129.71, 129.56, 126.86, 125.47, 112.05, 55.00, 51.36, 41.67, 38.26, 37.81, 35.15, 31.74, 29.98, 21.34.

５０ｍＬの乾燥トルエン中の１２４ｍｇ（０．３８８ｍｍｏｌ）の四塩化ハフニウム（＜０．０５％ Ｚｒ）の懸濁液に、ジエチルエーテル中の６００ｕｌ（１．７５ｍｍｏｌ）の２．９Ｍ ＭｅＭｇＢｒを０℃でシリンジを介して１回で加えた。得られた懸濁液に、３２０ｍｇ（０．３８８ｍｍｏｌ）の２’，２’’’－（ピリジン－２，６－ジイル）ビス（３－（（３ｒ，５ｒ，７ｒ）－アダマンタン－１－イル）－４’－（ｔｅｒｔ－ブチル）－５－メチル－［１，１’－ビフェニル］－２－オール）を直ちに１回で加えた。反応混合物を室温で４時間撹拌し、次いで、ほぼ乾固するまで蒸発させた。得られた固体を２×２０ｍＬの熱トルエンで抽出し、合わせた有機抽出物をＣｅｌｉｔｅ ５０３の薄いパッドに通して濾過した。次に、濾液を蒸発乾固した。残留物を５ｍＬのｎ－ヘキサンと研和し、得られた沈殿物を濾別（Ｇ４）し、２×５ｍＬのｎ－ヘキサンで洗浄し、次いで、真空中で乾燥した。収量３０１ｍｇ（７５％）の白色固体。Ｃ₆₁Ｈ₇₃ＨｆＮＯ₂の解析計算値：Ｃ、７１．０８；Ｈ、７．１４；Ｎ、１．３２。測定値：Ｃ ７１．３９；Ｈ、７．２７；Ｎ １．２２。¹H NMR (C₆D₆, 400 MHz): δ 7.35 (dd, J = 8.3, 2.0 Hz, 2H), 7.22 (d, J = 8.3 Hz, 2H), 7.19 (d, J = 2.0 Hz, 2H), 7.14 (d, J = 2.0 Hz, 2H), 6.66 (d, J = 1.7 Hz, 2H), 6.45 - 6.53 (m, 3H), 2.48 - 2.56 (m, 6H), 2.37 - 2.45 (m, 6H), 2.19 (s, 6H), 2.16 (br.s, 6H), 1.96 - 2.05 (m, 6H), 1.75 - 1.84 (m, 6H), 1.32 (s, 18H), 0.07 (s, 6H). ¹³C NMR (C₆D₆, 100 MHz) δ 160.12, 158.83, 151.36, 141.36, 139.48, 139.01, 133.84, 132.99, 129.65, 129.57, 126.93, 125.76, 125.54, 51.54, 41.59, 38.17, 37.75, 35.12, 31.69, 29.92, 21.33. Dimethylhafnium [2', 2'''-(pyridin-2,6-diyl) bis (3-((3r, 5r, 7r) -adamantan-1-yl) -4'-(tert-butyl) -5 -Methyl- [1,1'-biphenyl] -2-olate)] (complex 18)

A suspension of 124 mg (0.388 mmol) of hafnium tetrachloride (<0.05% Zr) in 50 mL of dry toluene is syringed with 600 ul (1.75 mmol) of 2.9 M MeMgBr in diethyl ether at 0 ° C. Was added once via. 320 mg (0.388 mmol) of 2', 2'''-(pyridin-2,6-diyl) bis (3-((3r, 5r, 7r) -adamantan-1-yl)-is added to the resulting suspension. ) -4'-(tert-butyl) -5-methyl- [1,1'-biphenyl] -2-ol) was immediately added in one dose. The reaction mixture was stirred at room temperature for 4 hours and then evaporated to near dryness. The resulting solid was extracted with 2 x 20 mL hot toluene and the combined organic extracts were filtered through a thin pad of Celite 503. Next, the filtrate was evaporated to dryness. The residue was triturated with 5 mL of n-hexane, the resulting precipitate was filtered off (G4), washed with 2 x 5 mL of n-hexane and then dried in vacuo. A white solid with a yield of 301 mg (75%). Analysis of C ₆₁ H ₇₃ HfNO ₂ Calculated values: C, 71.08; H, 7.14; N, 1.32. Measured values: C 71.39; H, 7.27; N 1.22. ¹ H NMR (C ₆ D ₆ , 400 MHz): δ 7.35 (dd, J = 8.3, 2.0 Hz, 2H), 7.22 (d, J = 8.3 Hz, 2H), 7.19 (d, J = 2.0 Hz, 2H) ), 7.14 (d, J = 2.0 Hz, 2H), 6.66 (d, J = 1.7 Hz, 2H), 6.45 --6.53 (m, 3H), 2.48 --2.56 (m, 6H), 2.37 --2.45 (m, 6H), 2.19 (s, 6H), 2.16 (br.s, 6H), 1.96 --2.05 (m, 6H), 1.75 --1.84 (m, 6H), 1.32 (s, 18H), 0.07 (s, 6H) . ¹³ C NMR (C ₆ D ₆ , 100 MHz) δ 160.12, 158.83, 151.36, 141.36, 139.48, 139.01, 133.84, 132.99, 129.65, 129.57, 126.93, 125.76, 125.54, 51.54, 41.59, 38.17, 37.75, 35.12, 31.69, 29.92, 21.33.

５０ｍＬの乾燥トルエン中の２１０ｍｇ（０．６５４ｍｍｏｌ）の四塩化ハフニウム（＜０．０５％ Ｚｒ）の懸濁液に、ジエチルエーテル中の９００ｕｌ（２．６１ｍｍｏｌ）の２．９Ｍ ＭｅＭｇＢｒを０℃でシリンジを介して１回で加えた。得られた懸濁液に、５６２ｍｇ（０．６５４ｍｍｏｌ）の２’，２’’’－（ピリジン－２，６－ジイル）ビス（３－（（１ｒ，３Ｒ，５Ｓ，７ｒ）－３，５－ジメチルアダマンタン－１－イル）－５－フルオロ－４’－イソプロピル－［１，１’－ビフェニル］－２－オール）を直ちに１回で加えた。反応混合物を室温で４時間撹拌し、次いで、ほぼ乾固するまで蒸発させた。得られた固体を２×２０ｍＬの熱トルエンで抽出し、合わせた有機抽出物をＣｅｌｉｔｅ ５０３の薄いパッドに通して濾過した。次に、濾液を蒸発乾固した。残留物を５ｍＬのｎ－ヘキサンと研和し、得られた沈殿物を濾別（Ｇ４）し、２×５ｍＬのｎ－ヘキサンで洗浄し、次いで、真空中で乾燥した。収量５３０ｍｇ（７６％）の白色固体。Ｃ₆₁Ｈ₇₁Ｆ₂ＨｆＮＯ₂の解析計算値：Ｃ、６８．６８；Ｈ、６．７１；Ｎ、１．３１。測定値：Ｃ ６８．８１；Ｈ、６．９９；Ｎ １．２３。¹H NMR (CD₂Cl₂, 400 MHz): δ 7.77 (t, J = 7.7 Hz, 1H), 7.47 (dd, J = 8.1, 1.8 Hz, 2H), 7.18 (d, J = 8.1 Hz, 2H), 7.16 (d, J = 7.7 Hz, 2H), 6.90 - 6.94 (m, 4H), 6.49 (dd, J = 7.9, 3.2 Hz, 2H), 2.97 (七重線, J = 6.9 Hz, 2H), 2.60 - 2.67 (m, 2H), 2.45 - 2.52 (m, 2H), 2.00 - 2.05 (m, 2H), 1.52 - 1.63 (m, 6H), 1.33 - 1.42 (m, 4H), 1.33 (d, J = 6.9 Hz, 6H), 1.30 - 1.34 (m, 2H), 1.22 (d, J = 6.9 Hz, 6H), 1.11 - 1.24 (m, 6H), 1.02 - 1.09 (m, 2H), 0.91 (s, 6H), 0.77 (s, 6H), -0.68 (s, 6H). ¹³C NMR (CD₂Cl₂, 100 MHz) δ 157.97, 157.89, 156.47 (d, Jc,_F = 234 Hz), 149.58, 140.27, 140.15 (d, Jc,_F = 6.1 Hz), 139.42 (d d, Jc,_F = 1.7 Hz), 133.12, 133.03 (d, Jc,_F = 7.9 Hz), 132.88, 129.52, 129.43, 128.70, 128.49, 125.85, 125.78, 114.45 (d, Jc,_F = 22.3 Hz), 113.65 (d, Jc,_F = 23.2 Hz), 51.75, 50.95, 49.61, 45.53, 43.87, 42.50, 39.57, 38.24, 33.76, 32.22, 31.58, 31.56, 30.92, 30.37, 25.85, 22.39. Dimethylhafnium [2', 2'''-(pyridin-2,6-diyl) bis (3-((1r, 3R, 5S, 7r) -3,5-dimethyladamantane-1-yl) -5-fluoro -4'-Isopropyl- [1,1'-biphenyl] -2-olate)] (complex 19)

Syringe 900 ul (2.61 mmol) of 2.9 M MeMgBr in diethyl ether into a suspension of 210 mg (0.654 mmol) of hafnium tetrachloride (<0.05% Zr) in 50 mL of dry toluene at 0 ° C. Was added once via. In the resulting suspension, 562 mg (0.654 mmol) of 2', 2'''-(pyridin-2,6-diyl) bis (3-((1r, 3R, 5S, 7r) -3,5) -Dimethyladamantane-1-yl) -5-fluoro-4'-isopropyl- [1,1'-biphenyl] -2-ol) was immediately added in one dose. The reaction mixture was stirred at room temperature for 4 hours and then evaporated to near dryness. The resulting solid was extracted with 2 x 20 mL hot toluene and the combined organic extracts were filtered through a thin pad of Celite 503. Next, the filtrate was evaporated to dryness. The residue was triturated with 5 mL of n-hexane, the resulting precipitate was filtered off (G4), washed with 2 x 5 mL of n-hexane and then dried in vacuo. A white solid with a yield of 530 mg (76%). Analysis of C ₆₁ H ₇₁ F ₂ HfNO ₂ Calculated values: C, 68.68; H, 6.71; N, 1.31. Measured values: C 68.81; H, 6.99; N 1.23. ¹ H NMR (CD ₂ Cl ₂ , 400 MHz): δ 7.77 (t, J = 7.7 Hz, 1H), 7.47 (dd, J = 8.1, 1.8 Hz, 2H), 7.18 (d, J = 8.1 Hz, 2H) ), 7.16 (d, J = 7.7 Hz, 2H), 6.90 --6.94 (m, 4H), 6.49 (dd, J = 7.9, 3.2 Hz, 2H), 2.97 (7-fold line, J = 6.9 Hz, 2H), 2.60 --2.67 (m, 2H), 2.45 --2.52 (m, 2H), 2.00 --2.05 (m, 2H), 1.52 --1.63 (m, 6H), 1.33 --1.42 (m, 4H), 1.33 (d, J) = 6.9 Hz, 6H), 1.30 --1.34 (m, 2H), 1.22 (d, J = 6.9 Hz, 6H), 1.11 --1.24 (m, 6H), 1.02 --1.09 (m, 2H), 0.91 (s, 6H), 0.77 (s, 6H), -0.68 (s, 6H). ¹³ C NMR (CD ₂ Cl ₂ , 100 MHz) δ 157.97, 157.89, 156.47 (d, Jc, _F = 234 Hz), 149.58, 140.27 , 140.15 (d, Jc, _F = 6.1 Hz), 139.42 (dd, Jc, _F = 1.7 Hz), 133.12, 133.03 (d, Jc, _F = 7.9 Hz), 132.88, 129.52, 129.43, 128.70, 128.49, 125.85 , 125.78, 114.45 (d, Jc, _F = 22.3 Hz), 113.65 (d, Jc, _F = 23.2 Hz), 51.75, 50.95, 49.61, 45.53, 43.87, 42.50, 39.57, 38.24, 33.76, 32.22, 31.58, 31.56 , 30.92, 30.37, 25.85, 22.39.

５０ｍＬの乾燥トルエン中の１３５ｍｇ（０．５８１ｍｍｏｌ）の四塩化ジルコニウムの懸濁液に、ジエチルエーテル中の８００ｕｌ（２．３２ｍｍｏｌ）の２．９Ｍ ＭｅＭｇＢｒを－３０℃でシリンジを介して１回で加えた。得られた懸濁液に、５００ｍｇ（０．５８１ｍｍｏｌ）の２’，２’’’－（ピリジン－２，６－ジイル）ビス（３－（（１ｒ，３Ｒ，５Ｓ，７ｒ）－３，５－ジメチルアダマンタン－１－イル）－５－フルオロ－４’－イソプロピル－［１，１’－ビフェニル］－２－オール）を直ちに１回で加えた。反応混合物を室温で４時間撹拌し、次いで、ほぼ乾固するまで蒸発させた。得られた固体を２×２０ｍＬの熱トルエンで抽出し、合わせた有機抽出物をＣｅｌｉｔｅ ５０３の薄いパッドに通して濾過した。次に、濾液を蒸発乾固した。残留物を５ｍＬのｎ－ヘキサンと研和し、得られた沈殿物を濾別（Ｇ４）し、２×５ｍＬのｎ－ヘキサンで洗浄し、次いで、真空中で乾燥した。収量３９０ｍｇ（６８％）のホワイトベージュ色固体。Ｃ₆₁Ｈ₇₁Ｆ₂ＺｒＮＯ₂の解析計算値：Ｃ、７４．８０；Ｈ、７．３１；Ｎ、１．４３。測定値：Ｃ ７５．０６；Ｈ、７．６４；Ｎ １．１９。¹H NMR (CD₂Cl₂, 400 MHz): δ 7.76 (t, J = 7.8 Hz, 1H), 7.46 (dd, J = 8.1, 1.8 Hz, 2H), 7.19 (d, J = 8.0 Hz, 2H), 7.15 (d, J = 7.8 Hz, 2H), 6.92 (dd, J = 11.7, 3.3 Hz, 2H), 6.89 (d, J = 1.8 Hz, 2H), 6.51 (dd, J = 8.0, 3.3 Hz, 2H), 2.97 (七重線, J = 6.9 Hz, 2H), 2.65 - 2.73 (m, 2H), 2.48 - 2.56 (m, 2H), 2.00 - 2.06 (m, 2H), 1.52 - 1.65 (m, 6H), 1.33 - 1.43 (m, 6H), 1.33 (d, J = 6.9 Hz, 6H), 1.22 (d, J = 6.9 Hz, 6H), 1.15 - 1.23 (m, 6H), 1.06 - 1.14 (m, 2H), 0.92 (s, 6H), 0.79 (s, 6H), -0.42 (s, 6H). ¹³C NMR (CD₂Cl₂, 100 MHz) δ 158.29, 157.34, 156.51 (d, Jc,_F = 235 Hz), 149.53, 140.25, 139.61 (d, Jc,_F = 6.1 Hz), 139.29 (d, Jc,_F = 1.7 Hz), 133.42 (d, Jc,_F = 7.9 Hz), 133.26, 133.03, 129.53, 129.35, 128.72, 128.37, 125.79, 125.39, 114.57 (d, Jc,_F = 22.3 Hz), 113.61 (d, Jc,_F = 23.2 Hz), 51.76, 49.61, 45.66, 43.88, 42.81, 42.52, 39.67, 38.30, 33.77, 32.23, 31.59, 31.56, 30.94, 30.39. Dimethyl zirconium [2', 2'''-(pyridin-2,6-diyl) bis (3-((1r, 3R, 5S, 7r) -3,5-dimethyladamantane-1-yl) -5-fluoro -4'-Isopropyl- [1,1'-biphenyl] -2-olate)] (complex 20)

To a suspension of 135 mg (0.581 mmol) zirconium tetrachloride in 50 mL of dry toluene, 800 ul (2.32 mmol) of 2.9 M MeMgBr in diethyl ether is added at -30 ° C via a syringe in a single dose. rice field. In the resulting suspension, 500 mg (0.581 mmol) of 2', 2'''-(pyridin-2,6-diyl) bis (3-((1r, 3R, 5S, 7r) -3,5) -Dimethyladamantane-1-yl) -5-fluoro-4'-isopropyl- [1,1'-biphenyl] -2-ol) was immediately added in one dose. The reaction mixture was stirred at room temperature for 4 hours and then evaporated to near dryness. The resulting solid was extracted with 2 x 20 mL hot toluene and the combined organic extracts were filtered through a thin pad of Celite 503. Next, the filtrate was evaporated to dryness. The residue was triturated with 5 mL of n-hexane, the resulting precipitate was filtered off (G4), washed with 2 x 5 mL of n-hexane and then dried in vacuo. A white beige solid with a yield of 390 mg (68%). Analysis of C ₆₁ H ₇₁ F ₂ ZrNO ₂ Calculated values: C, 74.80; H, 7.31; N, 1.43. Measured values: C 75.06; H, 7.64; N 1.19. ¹ H NMR (CD ₂ Cl ₂ , 400 MHz): δ 7.76 (t, J = 7.8 Hz, 1H), 7.46 (dd, J = 8.1, 1.8 Hz, 2H), 7.19 (d, J = 8.0 Hz, 2H) ), 7.15 (d, J = 7.8 Hz, 2H), 6.92 (dd, J = 11.7, 3.3 Hz, 2H), 6.89 (d, J = 1.8 Hz, 2H), 6.51 (dd, J = 8.0, 3.3 Hz) , 2H), 2.97 (seven-fold line, J = 6.9 Hz, 2H), 2.65 --2.73 (m, 2H), 2.48 --2.56 (m, 2H), 2.00 --2.06 (m, 2H), 1.52 --1.65 (m, 6H), 1.33 --1.43 (m, 6H), 1.33 (d, J = 6.9 Hz, 6H), 1.22 (d, J = 6.9 Hz, 6H), 1.15 --1.23 (m, 6H), 1.06 --1.14 (m) , 2H), 0.92 (s, 6H), 0.79 (s, 6H), -0.42 (s, 6H). ¹³ C NMR (CD ₂ Cl ₂ , 100 MHz) δ 158.29, 157.34, 156.51 (d, Jc, _F ) = 235 Hz), 149.53, 140.25, 139.61 (d, Jc, _F = 6.1 Hz), 139.29 (d, Jc, _F = 1.7 Hz), 133.42 (d, Jc, _F = 7.9 Hz), 133.26, 133.03, 129.53 , 129.35, 128.72, 128.37, 125.79, 125.39, 114.57 (d, Jc, _F = 22.3 Hz), 113.61 (d, Jc, _F = 23.2 Hz), 51.76, 49.61, 45.66, 43.88, 42.81, 42.52, 39.67, 38.30 , 33.77, 32.23, 31.59, 31.56, 30.94, 30.39.

５０ｍＬの乾燥トルエン中の１１９ｍｇ（０．３７３ｍｍｏｌ）の四塩化ハフニウム（＜０．０５％ Ｚｒ）の懸濁液に、ジエチルエーテル中の５１０ｕｌ（１．４９ｍｍｏｌ）の２．９Ｍ ＭｅＭｇＢｒを０℃でシリンジを介して１回で加えた。得られた懸濁液に、３００ｍｇ（０．３７３ｍｍｏｌ）の２’，２’’’－（ピリジン－２，６－ジイル）ビス（５－フルオロ－３－（（３ｒ，５ｒ，７ｒ）－３，５，７－トリメチルアダマンタン－１－イル）－［１，１’－ビフェニル］－２－オール）を直ちに１回で加えた。反応混合物を室温で４時間撹拌し、次いで、ほぼ乾固するまで蒸発させた。得られた固体を２×２０ｍＬの熱トルエンで抽出し、合わせた有機抽出物をＣｅｌｉｔｅ ５０３の薄いパッドに通して濾過した。次に、濾液を蒸発乾固した。残留物を５ｍＬのｎ－ヘキサンと研和し、得られた沈殿物を濾別（Ｇ４）し、２×５ｍＬのｎ－ヘキサンで洗浄し、次いで、真空中で乾燥した。収量２７１ｍｇ（７２％）の白色固体。Ｃ₅₇Ｈ₆₃Ｆ₂ＨｆＮＯ₂の解析計算値：Ｃ、６７．７４；Ｈ、６．２８；Ｎ、１．３９。測定値：Ｃ ６７．９８；Ｈ、６．４２；Ｎ １．３７。¹H NMR (CD₂Cl₂, 400 MHz): δ 7.79 (t, J = 7.7 Hz, 1H), 7.55 (td, J = 7.5, 1.5 Hz, 2H), 7.49 (td, J = 7.4, 1.3 Hz, 2H), 7.22 (dd, J = 7.4, 0.9 Hz, 2H), 7.18 (d, J = 7.8 Hz, 2H), 7.11 (dd, J = 7.4, 0.9 Hz, 2H), 6.97 (dd, J = 11.7, 3.3 Hz, 2H), 6.52 (dd, J = 7.8, 3.3 Hz, 2H), 1.74 - 1.80 (m, 6H), 1.58 - 1.64 (m, 6H), 1.17 - 1.24 (m, 6H), 1.00 - 1.07 (m, 6H), 0.88 (s, 18H), -0.74 (s, 6H). ¹³C NMR (CD₂Cl₂, 100 MHz) δ 158.06, 158.04, 157.51, 156.37 (d, Jc,_F = 234 Hz), 141.79 (d, Jc,_F = 1.7 Hz), 140.46, 140.05 (d, Jc,_F = 5.9 Hz), 139.99, 132.98, 132.90, 132.79 (d, Jc,_F = 7.9 Hz), 131.28, 130.17, 130.08, 129.52, 128.71, 125.79, 125.52, 114.23 (d, Jc,_F = 23.2 Hz), 114.02 (d, Jc,_F = 22.4 Hz), 50.73, 46.62, 40.75, 32.64, 31.09. Dimethylhafnium [2', 2'''-(pyridin-2,6-diyl) bis (5-fluoro-3-((3r, 5r, 7r) -3,5,7-trimethyladamantane-1-yl)) -[1,1'-biphenyl] -2-olate)] (complex 21)

Syringe 510 ul (1.49 mmol) of 2.9 M MeMgBr in diethyl ether into a suspension of 119 mg (0.373 mmol) hafnium tetrachloride (<0.05% Zr) in 50 mL of dry toluene at 0 ° C. Was added once via. In the resulting suspension, 300 mg (0.373 mmol) of 2', 2'''-(pyridin-2,6-diyl) bis (5-fluoro-3-((3r, 5r, 7r) -3) , 5,7-trimethyladamantane-1-yl)-[1,1'-biphenyl] -2-ol) was immediately added in one dose. The reaction mixture was stirred at room temperature for 4 hours and then evaporated to near dryness. The resulting solid was extracted with 2 x 20 mL hot toluene and the combined organic extracts were filtered through a thin pad of Celite 503. Next, the filtrate was evaporated to dryness. The residue was triturated with 5 mL of n-hexane, the resulting precipitate was filtered off (G4), washed with 2 x 5 mL of n-hexane and then dried in vacuo. A white solid with a yield of 271 mg (72%). Analysis of C ₅₇ H ₆₃ F ₂ HfNO ₂ Calculated values: C, 67.74; H, 6.28; N, 1.39. Measured values: C 67.98; H, 6.42; N 1.37. ¹ H NMR (CD ₂ Cl ₂ , 400 MHz): δ 7.79 (t, J = 7.7 Hz, 1H), 7.55 (td, J = 7.5, 1.5 Hz, 2H), 7.49 (td, J = 7.4, 1.3 Hz) , 2H), 7.22 (dd, J = 7.4, 0.9 Hz, 2H), 7.18 (d, J = 7.8 Hz, 2H), 7.11 (dd, J = 7.4, 0.9 Hz, 2H), 6.97 (dd, J = 11.7, 3.3 Hz, 2H), 6.52 (dd, J = 7.8, 3.3 Hz, 2H), 1.74 ―― 1.80 (m, 6H), 1.58 ―― 1.64 (m, 6H), 1.17 ―― 1.24 (m, 6H), 1.00 --1.07 (m, 6H), 0.88 (s, 18H), -0.74 (s, 6H). ¹³ C NMR (CD ₂ Cl ₂ , 100 MHz) δ 158.06, 158.04, 157.51, 156.37 (d, Jc, _F = 234 Hz), 141.79 (d, Jc, _F = 1.7 Hz), 140.46, 140.05 (d, Jc, _F = 5.9 Hz), 139.99, 132.98, 132.90, 132.79 (d, Jc, _F = 7.9 Hz), 131.28, 130.17, 130.08, 129.52, 128.71, 125.79, 125.52, 114.23 (d, Jc, _F = 23.2 Hz), 114.02 (d, Jc, _F = 22.4 Hz), 50.73, 46.62, 40.75, 32.64, 31.09.

Polymerization Example Solvents (polymerization grade toluene and / or isohexane) are supplied from the Exxon Mobile Chemical Company, which is a series of columns: two ^Labclear (Oakland, California) cylinders in series, followed by a dried 3 Å molecular. Two 500 cm ³ columns in series filled with sheaves (8-12 mesh; Aldrich Chemical Company) and two in series filled with dry 5 Å molecular sieves (8-12 mesh; Aldrich Chemical Company). Purified by passing through a 500 cm ³ column.

1-Octene (98%) (Aldrich Chemical Company) was dried by stirring overnight on a Na-K alloy, followed by filtration through basic alumina (Aldrich Chemical Company, Blockman Basic 1). Tri- (n-octyl) aluminum (TNOA) was purchased from either Aldrich Chemical Company or Akzo Nobel and used as received.

A series of columns of polymerized grade ethylene: a 500 cm ³ Oxyclear cylinder made by Labclear (Oakland, California), followed by a 500 cm ³ column filled with a dry 3 Å molecular sieve (8 to 12 mesh; Aldrich Chemical Company), and dried. Further purified by passing through a 500 cm ³ column filled with 5 Å molecular sieves (8 to 12 mesh; Aldrich Chemical Company).

A series of columns of polymerized grade propylene: 2,250 cm ³ Oxyclear cylinders from Labclear, followed by 2,250 cm ³ columns filled with 3 Å molecular sieves (8 to 12 mesh; Aldrich Chemical Company), followed by 5 Å molecular sieves (8 Å to 12 mesh; Aldrich Chemical Company). 8 to 12 mesh; 2 series 500 cm ³ columns filled with Aldrich Chemical Company), 500 cm ³ columns filled with Propenesorb CD (BASF), and finally 500 cm ³ columns filled with Propenesorb COS (BASF) Further purified by passing through.

Methylarmoxane (MAO) was purchased from Albemarle Corporation as 10% by weight in toluene. N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate was purchased from Albemarle Corporation. All complexes and activators were added to the reactor as a dilute solution in toluene. The concentration of the activator, scavenger and complex solution added to the reactor was chosen to add a solution between 40 μL and 200 μL to the reactor to ensure accurate delivery.

Reactor description and preparation. External heater for temperature control, glass insert (reactor internal volume = 23.5 mL for C ₂ and C ₂ / C ₈ implementation; 22.5 mL for C ₃ implementation), septum inlet, nitrogen, ethylene Polymerization was carried out in an inert atmosphere (N ₂ ) dry box using an autoclave equipped with a controlled supply of propylene and a disposable polyether ether ketone mechanical stirrer (800 RPM). The autoclave was prepared by purging with dry nitrogen at 110 ° C. or 115 ° C. for 5 hours and then at 25 ° C. for 5 hours.

Ethylene Polymerization (PE) or Ethylene / 1-Octene Copolymerization (EO)
The reactor was prepared as above and then purged with ethylene. Toluene (solvent unless otherwise stated), optional 1-octene (0.1 mL if used) and optional MAO were added via syringe at room temperature and atmospheric pressure. The reactor was then brought to process temperature (typically 80 ° C.) with stirring at 800 RPM and filled with ethylene to process pressure (typically 75 psig = 618.5 kPa or 200 psig = 1480.3 kPa). An optional scavenger solution (eg, TNOA in isohexane) was then added to the reactor under process conditions via a syringe. A solution of an optional non-coordinating activator (eg, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate) solution (in toluene) is added to the reactor under process conditions via a syringe and subsequently pre. A catalytic (ie, complex or catalytic) solution (in toluene) was added to the reactor under process conditions via a syringe. During the polymerization, ethylene was placed in an autoclave (using a computer controlled solenoid valve) to maintain the gauge pressure of the reactor (+/- 2 psi). Reactor temperature was monitored and typically kept within +/- 1 ° C. Polymerization was terminated by adding an O ₂ / Ar (5 mol% O ₂ ) gas mixture of approximately 50 psi to the autoclave for approximately 30 seconds. Polymerization was quenched after the addition of a predetermined cumulative amount of ethylene or after a polymerization time of up to 30 minutes. The reactor was cooled and evacuated. After removing the solvent in vacuo, the polymer was isolated. The reported yields include the total mass of polymer and residual catalyst. Catalytic activity is reported as the number of grams (g / mmol / hour) of polymer per 1 mmol of transition metal compound per hour reaction time.

The propylene polymerization reactor was prepared as described above, then heated to 40 ° C. and purged with atmospheric pressure propylene gas. Toluene (solvent unless otherwise stated), optional MAO and liquid propylene (1.0 mL) were added via syringe. The reactor was then heated to process temperature (70 ° C or 100 ° C) with stirring at 800 RPM. An optional scavenger solution (eg, TNOA in isohexane) was then added to the reactor under process conditions via a syringe. An optional non-coordinating activator (eg, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate) solution (in toluene) is then added to the reactor under process conditions via a syringe, followed by , Pre-catalytic (ie, complex or catalytic) solution (in toluene) was added to the reactor under process conditions via a syringe. Reactor temperature was monitored and typically kept within +/- 1 ° C. Polymerization was terminated by adding an O ₂ / Ar (5 mol% O ₂ ) gas mixture of approximately 50 psi to the autoclave for approximately 30 seconds. Polymerization was quenched based on a given pressure loss of approximately 8 psi or a polymerization time of up to 30 minutes. The reactor was cooled and evacuated. After removing the solvent in vacuo, the polymer was isolated. The reported yields include the total mass of polymer and residual catalyst. Catalytic activity is typically reported as the number of grams (g / mmol / hour) of polymer per 1 mmol of transition metal compound per hour reaction time.

Polymer characterization For analytical testing, 1,2,4-trichlorobenzene (Sigma-) containing 2,6-di-tert-butyl-4-methylphenol (Aldrich BHT, 99%) in a shaker oven. A polymer sample solution was prepared by dissolving the polymer in Aldrich TCB (purity 99 +%) at 165 ° C. for approximately 3 hours. Typical concentrations of polymer in solution were between 0.1 and 0.9 mg / mL, and BHT concentration was 1.25 mg BHT per 1 mL of TCB. The sample was cooled to 135 ° C. for testing.

US Pat. Nos. 6,491,816, 6,491,823, 6,475,391, 6,461,515, 6, 6, respectively, which are incorporated herein by reference. 436,292, 6,406,632, 6,175,409, 6,454,947, 6,260,407 and 6,294,388 High temperature size exclusion chromatography was performed using the automated "fast GPC" system described. Symyx Technology equipped with an evaporative light scattering detector and calibrated using a polystyrene standard (Polymer Laboratories: Polymer Laboration Kit S-M-10: Mp (Peak Mw) between 5,000 and 3,390,000). By gel permeation chromatography using GPC, molecular weight (mass average molecular weight (Mw) and number average molecular weight (Mn)) and molecular weight distribution (MWD = Mw / Mn) (which is the polydispersity of the polymer (PDI)). (Sometimes called) was measured. Samples (in TCB) at 2.0 mL / min eluent flow rate (sample temperature 135 ° C., oven / column 165 ° C.) using three Polymer Laboratories: PLgel 10 μm Mixed-B 300 × 7.5 mm columns in series. 250 μL of polymer solution was injected into this system). No column diffusion correction was used. Numerical analysis was performed using Epoch® software available from Symyx Technologies or Automation Studio software available from Freeslate. The molecular weights obtained are relative to the linear polystyrene standard.
Differential scanning calorimetry (DSC) measurements were performed on the TA-Q100 device to measure the melting point of the polymer. The sample was pre-annealed at 220 ° C. for 15 minutes and then slowly cooled to room temperature overnight. The sample was then heated to 220 ° C. at a rate of 100 ° C./min and then cooled at a rate of 50 ° C./min. Melting points were collected during the heating period.

Table 1 shows the results of ethylene polymerization obtained using the catalytic complexes 1-21 and 23-27. General conditions: catalytic complex = 25 nmol, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate activator = 1.1 equivalent, ethylene 75 psig, Al (n-octyl) ₃ = 500 nmol, temperature = 80 ° C. , Total volume = 5 mL.

Table 2 shows the results of ethylene-octene copolymerization obtained using catalysts 1-21 and 23-27. General conditions: catalytic complex = 25 nmol, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate activator = 27.5 nmol, octene 0.1 mL, Al (n-octyl) ₃ = 500 nmol, temperature = 80 ° C, total volume = 5 mL, ethylene = 75 psi.

Table 3 shows the results of ethylene-octene copolymerization obtained using catalysts 1-21 and 23-27. General conditions: catalytic complex = 25 nmol, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate activator = 27.5 nmol, octene 0.1 mL, Al (n-octyl) ₃ = 500 nmol, temperature = 80 ° C, total volume = 5 mL, ethylene = 200 psi.

Table 4 shows the results of propylene polymerization obtained for catalysts 1-28. General conditions: for catalytic complex = 15 nmol (exception is 25 nmol of catalyst 26, 20 nmol of catalysts 22 and 28), N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate activator = catalytic complex. 1.1 mol equivalent, propylene = 1 mL, Al (n-octyl) ₃ = 500 nmol, total volume = 5 mL.

Table 5 shows the results of propylene polymerization obtained for catalysts 1-28. General conditions: catalyst complex = 15 nmol (exception is 25 nmol of catalyst 26, exception is 20 nmol of catalysts 22 and 28), N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate activator. = 1.1 mol equivalents relative to the catalyst complex, propylene = 1 mL, Al (n-octyl) ₃ = 500 nmol, total volume = 5 mL.

All documents described herein, including all priority documents and / or test procedures, are incorporated herein by reference to the extent consistent with this specification. Although embodiments of the invention have been exemplified and described as will be apparent from the general description and specific embodiments described above, various modifications can be made without departing from the spirit and scope of the invention. Therefore, the invention is not intended to be limited thereby. Similarly, the term "comprising" is considered synonymous with the term "inclusion". Similarly, whenever a composition, element or group of elements is preceded by the transition phrase "comprising", we are "essentially" preceding the description of the composition or element. It is understood that the same composition or group of elements with the transitional phrase "consists of", "selected from the group consisting of" or "is" is also contemplated and vice versa. ..

Claims (35)

A catalytic compound represented by the formula (I).

(I)
(During the ceremony,
M is a Group 3, 4, 5 or 6 transition metal or lanthanide,
E and E'are independently O, S or NR ⁹ (in the formula, R ⁹ is independently hydrogen, C1 _- C ₄₀ hydrocarbyl, C1 _- C ₄₀ substituted hydrocarbyl or heteroatom-containing group, respectively. ) And
Q is a group 14, 15 or 16 atom forming a donor bond to the metal M.
A ¹ QA 1'is part of a heterocyclic Lewis base containing 4-40 non ^- hydrogen atoms that connects A ² to A ^2'via a triatomic bridge and is the center of the triatomic bridge. The atom is Q and A ¹ and A ^1'are independently C, N or C (R ²² ) (in the formula, R ²² is hydrogen, C ₁ -C ₂₀ hydrocarbyl, C ₁ -C ₂₀ substituted hydrocarbyl. (Selected from) and

Is a divalent group containing 2 to 40 non-hydrogen atoms that links A ¹ to an E-bonded aryl group via biatomic cross-linking.

Is a divalent group containing 2 to 40 non-hydrogen atoms linking A ^1'to an E'bonded aryl group via biatomic cross-linking.
L is a Lewis base,
X is an anionic ligand
n is 1, 2 or 3
m is 0, 1 or 2,
n + m is 4 or less,
R ¹ , R ² , R ³ , R ⁴ , R ^1' , R ^{2' ,} R ^3'and R 4'are independently hydrogen, C ₁ -C ₄₀ hydrocarbyl, C ₁ -C ₄₀ substituted hydrocarbyl. , Heteroatom or heteroatom-containing group,
One or more of R ¹ and R ² , R ² and R ³ , R ³ and R ⁴ , R ^1'and R ^{2 '} , R 2'and R ^{3 '} , R ^3'and R 4'are combined. One or more substituted hydrocarbyl rings having 5, 6, 7 or 8 ring atoms, respectively, and the substituents on the ring can be bonded to form additional rings. An unsubstituted hydrocarbyl ring, a substituted heterocyclic ring or an unsubstituted heterocyclic ring may be formed.
Any two L groups may be attached to each other to form a bidentate Lewis base.
The X group may be attached to the L group to form a monoanionic bidentate.
Any two X groups may be bonded to each other to form a dianionic ligand group) A catalytic compound of formula I, represented by formula (II).

(II)
(During the ceremony,
M is a Group 3, 4, 5 or 6 transition metal or lanthanide,
E and E'are independently O, S or NR ⁹ (in the formula, R ⁹ is independently hydrogen, C1 _- C ₄₀ hydrocarbyl, C1 _- C ₄₀ substituted hydrocarbyl or heteroatom-containing group, respectively. ) And
Each L is an independent Lewis base,
Each X is an independent anionic ligand,
n is 1, 2 or 3
m is 0, 1 or 2,
n + m is 4 or less,
R ¹ , R ² , R ³ , R ⁴ , R ^1' , R ^{2' ,} R ^3'and R 4'are independently hydrogen, C ₁ -C ₄₀ hydrocarbyl, C ₁ -C ₄₀ substituted hydrocarbyl. , Heteroatom or heteroatom-containing group, or R ¹ and R ² , R ² and R ³ , R ³ and R ⁴ , R ^1'and R ^{2 '} , R 2'and R ^3' , R ^3'and One or more of R ^4'are bonded to each other to have 5, 6, 7 or 8 ring atoms, and the substituents on the ring combine to form an additional ring. One or more substituted hydrocarbyl rings, unsubstituted hydrocarbyl rings, substituted heterocyclic rings or unsubstituted heterocyclic rings which can be formed may be formed, and any two L groups are bonded to each other to form a bidentate Lewis. May form a base,
The X group may be attached to the L group to form a monoanionic bidentate.
Any two X groups may be bonded to each other to form a dianionic ligand group.
R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ^5' , R ^6' , R ^7' , R ^8' , R ¹⁰ , R ¹¹ and R ¹² are each independently hydrogen, C ₁ -C ₄₀ . Hydrocarbyl, C1 _{- C40} substituted hydrocarbyl, heteroatom or heteroatom-containing group, or R ⁵ and R ⁶ , R ⁶ and R ⁷ , R ⁷ and R ⁸ , R ^5'and R ^6' , R ^6' And one or more of R ^{7 '} , R 7'and R ^8' , R ¹⁰ and R ¹¹ or R ¹¹ and R ¹² combined to form 5, 6, 7 or 8 ring atoms. One or more substituted hydrocarbyl rings, unsubstituted hydrocarbyl rings, substituted heterocyclic rings or unsubstituted heterocyclic rings, respectively, and the substituents on the ring can be bonded to form an additional ring. May form) The catalytic compound according to claim 1 or 2, wherein M is Hf, Zr or Ti. The catalytic compound according to claim 1, 2 or 3, wherein E and E'are O, respectively. The catalytic compound according to claim 1, 2, 3 or 4, wherein R ¹ and R ^1'are independently _C4 -C ₄₀ tertiary hydrocarbyl groups. The catalytic compound according to claim 1, 2, 3 or 4, wherein R ¹ and R ^1'are independently _C4 -C ₄₀ cyclic tertiary hydrocarbyl groups. The catalytic compound according to claim 1, 2, 3 or 4, wherein R ¹ and R ^1'are independently _C4 -C ₄₀ polycyclic tertiary hydrocarbyl groups. Each X is independently selected from the group consisting of substituted or unsubstituted hydrocarbyl groups having 1 to 20 carbon atoms, hydrides, amides, alkoxides, sulfides, phosphides, halides and combinations thereof (2). The catalyst compound according to any one of claims 1 to 7 (X may form a fused ring or a part of the ring system). Each L is independently selected from the group consisting of ethers, thioethers, amines, phosphines, ethyl ethers, tetrahydrofurans, dimethylsulfides, triethylamines, pyridines, alkenes, alkynes, allenes and carbenes and combinations thereof, optionally 2 The catalytic compound according to any one of claims 1 to 8, wherein more than one L may form a fused ring or a part of the ring system. M is Zr or Hf, Q is nitrogen, both A ¹ and A ^1'are carbon, both E and ^E'are oxygen, and both R ¹ and R ^1'are C ₄ The catalytic compound according to claim 1, which is a _C20 cyclic tertiary alkyl. M is Zr or Hf, Q is nitrogen, both A ¹ and A ^1'are carbon, both E and ^E'are oxygen, and both R ¹ and R ^1'are adamantane-. The catalytic compound according to claim 1, which is 1-yl or substituted adamantane-1-yl. M is Zr or Hf, Q is nitrogen, both A ¹ and A ^1'are carbon, both E and ^E'are oxygen, and both R ¹ and R ^1'are C ₆ The catalytic compound according to claim 1, which is C ₂₀ aryl. Q is nitrogen, A ¹ and A ^1'are both carbons, both R ¹ and R ^1'are hydrogen, and both E and ^E'are NR ⁹ (in the formula, R ⁹ is C). The catalytic compound according to claim 1, which is selected from ₁ -C ₄₀ hydrocarbyl, C1 _- C ₄₀ substituted hydrocarbyl or a heteroatom-containing group). The catalytic compound according to claim 1, wherein Q is carbon, A ¹ and A ^1'are both nitrogen, and both E and ^E'are oxygen. Q is carbon, A ¹ is nitrogen, A ^1'is C (R ²² ), both E and ^E'are oxygen, and in the formula, R ²² is hydrogen, C ₁ -C ₂₀ . The catalytic compound according to claim ₁ , which is selected from hydrocarbyl and C1- _C20 substituted hydrocarbyl. The catalytic compound according to claim 1, wherein the heterocyclic Lewis base is selected from the groups represented by the following formulas.

(In the equation, each R ²³ is independently selected from hydrogen, C1-C ₂₀ alkyl and C _{1 -} C ₂₀ substituted alkyl). The catalytic compound according to claim 2, wherein M is Zr or Hf, both E and ^E'are oxygen, and both R ¹ and R ^1'are _C4 -C ₂₀ cyclic tertiary alkyls. .. The second aspect of claim 2, wherein M is Zr or Hf, both E and ^E'are oxygen, and both R ¹ and R ^1'are adamantane-1-yl or substituted adamantane-1-yl. Catalyst compound. M is Zr or Hf, both E and ^E'are oxygen, and R ¹ , R ^1' , R ³ and R ^3'are each adamantane-1-yl or substituted adamantane-1-yl. , The catalyst compound according to claim 2. M is Zr or Hf, both E and ^E'are oxygen, both R ¹ and R 1'are _C4 -C ₂₀ cyclic tertiary alkyls, and both R ⁷ and R ^{7' .} The catalytic compound according to claim 2, wherein is C ₁ -C ₂₀ alkyl. M is Zr or Hf, both E and ^E'are O, both R ¹ and R 1'are _C4 -C ₂₀ cyclic tertiary alkyls, and both R ⁷ and R ^{7' .} The catalytic compound according to claim 2, wherein is C ₁ -C ₂₀ alkyl. M is Zr or Hf, both E and ^E'are O, both R ¹ and R 1'are _C4 -C ₂₀ cyclic tertiary alkyls, and both R ⁷ and R ^{7' .} The catalytic compound according to claim 2, wherein is C ₁ -C ₃ alkyl. The catalytic compound according to claim 1, which is represented by one or more of the following formulas.

A catalytic system containing an activator and the catalytic compound according to any one of claims 1 to 23. 24. The catalytic system of claim 24, wherein the activator comprises an alumoxane or a non-coordinating anion. The catalytic system according to claim 24, wherein the activator is soluble in a non-aromatic hydrocarbon solvent. The catalyst system according to claim 24, which does not contain an aromatic solvent. The catalyst system according to claim 24, wherein the activator is represented by the following formula.
(Z) _d ⁺ (A ^d- )
(In the formula, Z is (L—H), that is, a reducible Lewis acid, L is a neutral Lewis base, H is hydrogen, and (L—H) ⁺ is a Bronsted acid. A ^d- is a non-coordinating anion having a charge d-, and d is an integer of 1 to 3). The catalyst system according to claim 24, wherein the activator is represented by the following formula.
[R ^{1'R 2'R 3'EH} ] _{d +} [Mt ^{k +} Q _n ] ^d- (V)
(During the ceremony,
E is nitrogen or phosphorus,
d is 1, 2 or 3, k is 1, 2 or 3, n is 1, 2, 3, 4, 5 or 6, and n−k = d.
R ^{1' ,} R ^2'and R 3'are independently C ₁ -C ₅₀ hydrocarbyl groups which may be substituted with one or more alkoxy groups, silyl groups, halogen atoms or halogen-containing groups.
R ^{1' ,} R ^2'and R 3'contain more than 15 carbon atoms in total.
Mt is an element selected from Group 13 of the Periodic Table of the Elements.
Each Q is an independently hydride, crosslinked or non-crosslinked dialkylamide, halide, alkoxide, aryloxide, hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl or halo-substituted hydrocarbyl group). The catalyst system according to claim 24, wherein the activator is represented by the following formula.
(Z) _d ⁺ (A ^d- )
(In the equation, A ^d- is a non-coordinating anion with a charge d-, d is an integer of 1 to 3, and (Z) _d ⁺ is represented by one or more of the following: Will be done.

The catalyst system according to claim 24, wherein the activator is one or more of the following.
N-Methyl-4-nonadecil-N-octadecylbenzene Aminium tetrakis (pentafluorophenyl) borate,
N-Methyl-4-nonadecil-N-octadecylbenzeneaminium tetrakis (perfluoronaphthalenyl) borate,
Dioctadecylmethylammonium tetrakis (pentafluorophenyl) borate,
Dioctadecylmethylammonium tetrakis (perfluoronaphthalenyl) borate,
N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate,
Triphenylcarbenium tetrakis (pentafluorophenyl) borate,
Trimethylammonium tetrakis (perfluoronaphthalenyl) borate,
Triethylammonium tetrakis (perfluoronaphthalenyl) borate,
Tripropylammonium tetrakis (perfluoronaphthalenyl) borate,
Tri (n-butyl) ammonium tetrakis (perfluoronaphthalenyl) borate,
Tri (t-butyl) ammonium tetrakis (perfluoronaphthalenyl) borate,
N, N-dimethylanilinium tetrakis (perfluoronaphthalenyl) borate,
N, N-diethylanilinium tetrakis (perfluoronaphthalenyl) borate,
N, N-dimethyl- (2,4,6-trimethylanilinium) tetrakis (perfluoronaphthalenyl) borate,
Tropyrium tetrakis (perfluoronaphthalenyl) borate,
Triphenylcarbenium tetrakis (perfluoronaphthalenyl) borate,
Triphenylphosphonium tetrakis (perfluoronaphthalenyl) borate,
Triethylsilylium tetrakis (perfluoronaphthalenyl) borate,
Benzene (diazonium) tetrakis (perfluoronaphthalenyl) borate,
Trimethylammonium tetrakis (perfluorobiphenyl) borate,
Triethylammonium tetrakis (perfluorobiphenyl) borate,
Tripropylammonium tetrakis (perfluorobiphenyl) borate,
Tri (n-butyl) ammonium tetrakis (perfluorobiphenyl) borate,
Tri (t-butyl) ammonium tetrakis (perfluorobiphenyl) borate,
N, N-dimethylanilinium tetrakis (perfluorobiphenyl) borate,
N, N-diethylanilinium tetrakis (perfluorobiphenyl) borate,
N, N-dimethyl- (2,4,6-trimethylanilinium) tetrakis (perfluorobiphenyl) borate,
Tropyrium tetrakis (perfluorobiphenyl) borate,
Triphenylcarbenium tetrakis (perfluorobiphenyl) borate,
Triphenylphosphonium tetrakis (perfluorobiphenyl) borate,
Triethylsilylium tetrakis (perfluorobiphenyl) borate,
Benzene (diazonium) tetrakis (perfluorobiphenyl) borate,
[4-t-Butyl-PhNMe ₂ H] [(C ₆ F ₃ (C ₆ F ₅ ) ₂ ) ₄ B],
Trimethylammonium tetraphenylborate,
Triethylammonium tetraphenylborate,
Tripropylammonium tetraphenylborate,
Tri (n-butyl) ammonium tetraphenylborate,
Tri (t-butyl) ammonium tetraphenylborate,
N, N-dimethylanilinium tetraphenylborate,
N, N-diethylanilinium tetraphenylborate,
N, N-dimethyl- (2,4,6-trimethylanilinium) tetraphenylborate,
Tropyrium tetraphenylborate,
Triphenylcarbenium tetraphenylborate,
Triphenylphosphonium tetraphenylborate,
Triethylsilylium tetraphenylborate,
Benzene (diazonium) tetraphenylborate,
Trimethylammonium tetrakis (pentafluorophenyl) borate,
Triethylammonium tetrakis (pentafluorophenyl) borate,
Tripropylammonium tetrakis (pentafluorophenyl) borate,
Tri (n-butyl) ammonium tetrakis (pentafluorophenyl) borate,
Tri (sec-butyl) ammonium tetrakis (pentafluorophenyl) borate,
N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate,
N, N-diethylanilinium tetrakis (pentafluorophenyl) borate,
N, N-dimethyl- (2,4,6-trimethylanilinium) tetrakis (pentafluorophenyl) borate,
Tropyrium tetrakis (pentafluorophenyl) borate,
Triphenylcarbenium tetrakis (pentafluorophenyl) borate,
Triphenylphosphonium tetrakis (pentafluorophenyl) borate,
Triethylsilylium tetrakis (pentafluorophenyl) borate,
Benzene (diazonium) tetrakis (pentafluorophenyl) borate,
Trimethylammonium tetrakis (2,3,4,6-tetrafluorophenyl) borate,
Triethylammonium tetrakis (2,3,4,6-tetrafluorophenyl) borate,
Tripropylammonium tetrakis (2,3,4,6-tetrafluorophenyl) borate,
Tri (n-butyl) ammonium tetrakis (2,3,4,6-tetrafluorophenyl) borate,
Dimethyl (t-butyl) ammonium tetrakis (2,3,4,6-tetrafluorophenyl) borate,
N, N-dimethylanilinium tetrakis (2,3,4,6-tetrafluorophenyl) borate,
N, N-diethylanilinium tetrakis (2,3,4,6-tetrafluorophenyl) borate,
N, N-dimethyl- (2,4,6-trimethylanilinium) tetrakis (2,3,4,6-tetrafluorophenyl) borate,
Tropyrium tetrakis (2,3,4,6-tetrafluorophenyl) borate,
Triphenylcarbenium tetrakis (2,3,4,6-tetrafluorophenyl) borate,
Triphenylphosphonium tetrakis (2,3,4,6-tetrafluorophenyl) borate,
Triethylsilylium tetrakis (2,3,4,6-tetrafluorophenyl) borate,
Benzene (diazonium) tetrakis (2,3,4,6-tetrafluorophenyl) borate,
Trimethylammonium tetrakis (3,5-bis (trifluoromethyl) phenyl) borate,
Triethylammonium tetrakis (3,5-bis (trifluoromethyl) phenyl) borate,
Tripropylammonium tetrakis (3,5-bis (trifluoromethyl) phenyl) borate,
Tri (n-butyl) ammonium tetrakis (3,5-bis (trifluoromethyl) phenyl) borate,
Tri (t-butyl) ammonium tetrakis (3,5-bis (trifluoromethyl) phenyl) borate,
N, N-dimethylanilinium tetrakis (3,5-bis (trifluoromethyl) phenyl) borate,
N, N-diethylanilinium tetrakis (3,5-bis (trifluoromethyl) phenyl) borate,
N, N-dimethyl- (2,4,6-trimethylanilinium) tetrakis (3,5-bis (trifluoromethyl) phenyl) borate,
Tropyrium tetrakis (3,5-bis (trifluoromethyl) phenyl) borate,
Triphenylcarbenium tetrakis (3,5-bis (trifluoromethyl) phenyl) borate,
Triphenylphosphonium tetrakis (3,5-bis (trifluoromethyl) phenyl) borate,
Triethylsilylium tetrakis (3,5-bis (trifluoromethyl) phenyl) borate,
Benzene (diazonium) tetrakis (3,5-bis (trifluoromethyl) phenyl) borate,
Di- (i-propyl) ammonium tetrakis (pentafluorophenyl) borate,
Dicyclohexylammonium tetrakis (pentafluorophenyl) borate,
Tri (o-tolyl) phosphonium tetrakis (pentafluorophenyl) borate,
Tri (2,6-dimethylphenyl) phosphonium tetrakis (pentafluorophenyl) borate,
Triphenylcarbenium tetrakis (perfluorophenyl) borate,
1- (4- (Tris (pentafluorophenyl) borate) -2,3,5,6-tetrafluorophenyl) pyrrolidinium,
Tetrakis (pentafluorophenyl) borate,
4- (Tris (pentafluorophenyl) borate) -2,3,5,6-tetrafluoropyridine, and triphenylcarbenium tetrakis (3,5-bis (trifluoromethyl) phenyl) borate). A process of polymerizing an olefin comprising contacting one or more olefins with the catalyst system according to any one of claims 23-31. 32. The process of claim 32, which occurs at a temperature of about 0 ° C. to about 300 ° C., a pressure in the range of about 0.35 MPa to about 10 MPa, and a time of up to 300 minutes. 32. The process of claim 32, further comprising obtaining a polymer. 32. The process of claim 32, wherein the olefin comprises one or more substituted or unsubstituted C2 _- C ₄₀ alpha olefins.