Compound, metal complex, catalyst composition for olefin polymerization, catalyst for olefin polymerization, and method for producing olefin-based polymer

Abstract

The present invention provides a novel ligand and metal complex capable of copolymerizing an olefin and a polar group-containing monomer, a catalyst composition for olefin polymerization containing the same, an olefin polymerization catalyst, and a method for producing an olefin-based polymer using the catalyst.　The catalyst composition for olefin polymerization contains a compound represented by general formula (A), and a transition metal compound represented by general formula (E) or (F). (The definitions in the general formulae are as described in the description).

Description

Compounds, metal complexes, catalyst compositions for olefin polymerization, catalysts for olefin polymerization, and methods for producing olefin polymers.

[0001] This invention relates to polymerization catalysts for the production of olefin polymers. In particular, this invention relates to novel compounds that can be used as ligands, metal complexes using said novel compounds, catalyst compositions for olefin polymerization, and catalysts for olefin polymerization. This invention also relates to a method for producing olefin polymers using said catalyst.

[0002] Copolymers of nonpolar monomers such as ethylene and propylene (olefins) with polar group-containing monomers possess functions and properties not found in nonpolar polyethylene and polypropylene. From this perspective, research is actively being conducted to impart functionality to polyethylene and polypropylene through copolymerization of ethylene or propylene with polar group-containing monomers.

[0003] However, copolymerization with polar group-containing monomers is often inactive or has little activity even when using common olefin polymerization catalysts such as Ziegler catalysts or metallocene catalysts, because the polar groups act as catalytic poisons to olefin polymerization catalysts. Therefore, copolymerization with polar group-containing monomers such as methyl 10-undecenoate (MU), where the polar groups are located at a distance from the alkenyl structure, has been studied extensively (Patent Documents 1, 2, and 1-3). Furthermore, copolymerization of ethylene and polar group-containing monomers using a compound having a phosphine phenolate skeleton as a catalyst component has also been disclosed (Patent Document 3).

[0004] Japanese Patent Publication No. 2018-024646, Japanese Patent Publication No. 2011-088831, Japanese Patent Publication No. 2019-156764

[0005] Fang et al. , Polymer Chemistry, 2018, 9, 30, 4143-4149. Liu et al. , Organometallics, 2002, 21, 2836-2838. Wang et al. , J. Am. Chem. Soc. , 2024, 146, 10, 6837-6845.

[0006] Polar group-containing monomers such as MU mentioned above are expensive for general use and their availability is limited. Therefore, there is a desire to actively adopt polar group-containing monomers that are readily and stably available in large quantities, such as acrylic acid esters. However, acrylic acid esters, in which the distance between the alkenyl structure and the polar group is short, act as stronger catalyst poisons than MU, resulting in particularly low polymerization activity. In copolymerization using acrylic acid esters with a smaller ester group bulk than t-butyl acrylate as polar group-containing monomers and compounds with a phosphine phenolate skeleton as the catalyst component, the low activity due to poisoning by the polar group-containing monomer is significant, and the polymerization activity is insufficient. In this context, the problem that the present invention aims to solve is to provide a novel compound that can be used as a ligand for a catalyst capable of copolymerizing polar group-containing monomers and olefins with improved polymerization activity, in particular a novel compound that can be used as a ligand for a catalyst capable of copolymerizing acrylic acid esters with a relatively small number of carbon atoms and olefins with improved polymerization activity, a catalyst composition for olefin polymerization using the novel compound, a metal complex, and a catalyst for olefin polymerization, as well as a method for producing olefin polymers using the catalyst.

[0007] The present inventors have discovered a catalyst capable of copolymerizing relatively low-carbon acrylic acid esters and olefins with improved polymerization activity by combining a monovalent anionic bidentate ligand having a specific substituent with a specific nickel compound and / or palladium compound, which has an allerene having a specific structure as a ligand skeleton, with a nitrogen atom or phosphorus atom and an oxygen atom or sulfur atom as coordinating atoms. This led to the present invention.

[0008] In other words, the present invention relates to the following [1] to

[14] . [1] A compound represented by the following general formula (A).

[0009] [In formula (A), １ E represents an oxygen atom or a sulfur atom. １represents a nitrogen atom or a phosphorus atom, Z represents a hydrogen atom, a leaving group or a cation having a valence of 1 to 4, m is an integer of 1 or more and not more than the valence of Z, R １ represents a hydrocarbon group represented by the following general formula (B) or (C), R ２ represents a C1-C20 hydrocarbon group which is different from the hydrocarbon group represented by the following general formula (B) or (C) and may optionally contain at least one hetero atom, l is 1 or 2, and when l is 2, R ２ does not exist. R ３ , R ４ , R ５ , and R ６ each independently represent an atom or a group selected from the group consisting of the following (i) to (iv): (i) a hydrogen atom (ii) a halogen atom (iii) a C1-C30 hydrocarbon group which may optionally contain at least one hetero atom (iv) OR ｂ , C(O)OR ｂ , C(O)OM', C(O)N(R ａ ) ２ , C(O)R ｂ , OC(O)R ｂ , SR ｂ , S(O) ２ R ｂ , S(O)R ｂ , OS(O) ２ R ｂ , SF ５ , P(O)(OR ｂ ) ２－ｙ (R ａ ) ｙ , CN, N(H)R ａ , N(R ｂ ) ２ , Si(OR ａ ) ３－ｘ (R ａ ) ｘ , OSi(OR ａ ) ３－ｘ (R ａ ) ｘ , NO ２ , S(O) ２ OM', P(O)(OM') ２ or P(O)(OR ｂ ) ２ M' (wherein Rａ Each of these independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, R ｂ Each of these independently represents a hydrocarbon group having 1 to 20 carbon atoms, and N(R) ｂ ) ２ At that time, R ｂ They may be linked together to form a ring. (M' represents an alkali metal, alkaline earth metal, ammonium, quaternary ammonium, or phosphonium, x represents 0, 1, 2, or 3, and y represents 0, 1, or 2). ３ , R ４ , R ５ , and R ６ The adjacent substituents may be linked to each other to form an alicyclic ring, an aromatic ring, or a heterocycle containing at least one heteroatom selected from oxygen, nitrogen, or sulfur atoms.

[0010] [In equations (B) and (C), * represents E １ This represents a bonding with R ７ , R ８ , R ９ , R １０ , R １１ , R １２ and R １３ Each of these independently represents an atom or group selected from the group consisting of (i) to (iv) as defined in formula (A), and R ７ , R ８ , R ９ and R １０ R may have adjacent substituents linked to each other, forming an alicyclic ring, an aromatic ring, or a heterocycle containing at least one heteroatom selected from an oxygen atom, a nitrogen atom, or a sulfur atom, １２ and R １３ These may be linked to each other to form an aromatic ring or an unsaturated alicyclic ring which may contain at least one heteroatom selected from oxygen, nitrogen, or sulfur atoms. １ A ２ A ３ and A ４ These are, independently, an oxygen atom, a sulfur atom, and -C(R) ２ -, -C(O)-, -S(O)-, -S(O) ２-, -N(R)-, -P(R)-, or -P(O)(R)- (wherein each R independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms which may contain at least one heteroatom). Provided that in formula (B), A １ and A ３ , at least one is an oxygen atom or a sulfur atom; in formula (C), A ３ is an oxygen atom or a sulfur atom, and at least one of R １２ and R １３ represents an atom or group selected from the group consisting of the above (ii), (iii) and (iv), and R １２ and R １３ may be linked to each other to form an aromatic ring, or an unsaturated alicyclic ring which may contain at least one heteroatom selected from an oxygen atom, a nitrogen atom or a sulfur atom. W １ and W ２ each independently represent a carbon atom, a silicon atom, a nitrogen atom, a phosphorus atom, a boron atom, an oxygen atom, -C(O)-, -P(O)- or -S(O) ２ -, and when W is a nitrogen atom, a phosphorus atom, a boron atom or -P(O)-, R ８ and R １０ do not exist; when W is an oxygen atom, -C(O)- or -S(O) ２ -, R ７ and R ８ as well as R ９ and R １０ do not exist. h and i are each independently an integer of 1 to 6, and when there are plural instances of W １ , W ２ , R ７ , R ８ , R ９ and R １０ , the plural W １ , W ２ , R ７ , R ８ , R ９ and R １０ may each be the same or different.]]

[0011] [2] The compound according to [1], wherein in formulas (B) and (C), h and i are each independently 1 or 2. [3] In formulas (B) and (C), W １ and W ２ The compound according to [1] or [2] above, wherein each is independently a carbon atom or a silicon atom. [4] In formulas (B) and (C), when h and i are independently 1, R ７ , R ８ , R ９ and R １０ Each of these is an independent group selected from the group consisting of (iii) and (iv) as defined by formula (A), and when h and i are each independently 2 to 6, R ７ , R ８ , R ９ and R １０ Each of these is an atom or group independently selected from the group consisting of (i) to (iii) as defined by formula (A), and R ７ , R ８ , R ９ and R １０ The compound according to any one of the above [1] to [3], wherein adjacent substituents are linked to each other to form an alicyclic ring, an aromatic ring, or a heterocycle containing at least one heteroatom selected from an oxygen atom, a nitrogen atom, or a sulfur atom. [5] In formula (C), R １２ is an atom or group selected from the group consisting of (ii) and (iv) as defined in formula (A), or R １２ and R １３ A compound according to any one of the above [1] to [4], wherein the elements are linked to each other to form an aromatic ring.

[0012] [6] In formula (A) above, R ３ A compound according to any one of the above [1] to [5], wherein the substituent is represented by the following general formula (G).

[0013] [In formula (G), * represents a bond with an aromatic ring, and R ２１ , R ２２ , R ２３ , R ２４ and R ２５Each of these independently comprises a hydrogen atom, a substituent represented by the following general formula (H), a carbon-6 to carbon-12 aryl group which may have at least one substituent, an adamantyl group, OR ｂ , SR ｂ , or N(R ｂ ) ２ (where R ｂ (This is equivalent to [1] above), R ２１ , R ２２ , R ２３ , R ２４ and R ２５ At least one of these is a substituent represented by the following general formula (H), an aryl group having 6 to 12 carbon atoms which may have at least one substituent, an adamantyl group, OR ｂ , SR ｂ , or N(R ｂ ) ２ That is. R ２１ , R ２２ , R ２３ , R ２４ and R ２５ They do not bond to each other to form a ring.

[0014] (In formula (H), * represents a bond with an aromatic ring, R ２６ and R ２７ Each of these is a hydrocarbon group having 1 to 6 carbon atoms, which may each independently have at least one hydrogen atom or heteroatom, and may be bonded to each other to form a ring.

[0015] [7] A catalyst composition for olefin polymerization comprising a compound described in any one of the above items [1] to [6] and a transition metal compound represented by the following general formula (E) or (F).

[0016] [In formulas (E) and (F), M １ M ２ and M ３ Each of these independently represents either a nickel atom or a palladium atom, L １ , L ２ , L ３ , and L ４ Each of them is independent, M １ Represents the ligand coordinated to, where q is 0, 1, or 2, and L１ and L ２ They combine with each other to form M １ A ring containing L may be formed, ３ and L ４ They combine with each other to form M １ A ring containing L may be formed. ５ , L ６ , L ９ and L １０ Each of them is independent, M ２ or M ３ Represents a ligand coordinated to L ７ and L ８ Each of them is independent, M ２ and M ３ Represents the ligand coordinated to L ５ and L ６ They combine with each other to form M ２ A ring containing L may be formed, ９ and L １０ They combine with each other to form M ３ A ring containing [the element] may be formed.

[0017] [8] A catalyst for olefin polymerization comprising the catalyst composition for olefin polymerization described in [7] above.

[0018] [9] A metal complex represented by the following general formula (D).

[0019] [In formula (D), １ E represents an oxygen atom or a sulfur atom. １ R represents a nitrogen atom or a phosphorus atom. １ R represents a hydrocarbon group represented by the following general formula (B) or (C), and ２ This represents a hydrocarbon group having 1 to 20 carbon atoms, which may contain at least one heteroatom, and is different from the hydrocarbon group represented by the following general formula (B) or (C), where l is 1 or 2, and when l is 2, R ２ It does not exist. R ３ , R ４ , R ５ , and R ６Each of these independently represents an atom or group selected from the group consisting of (i) to (iv) below: (i) hydrogen atom (ii) halogen atom (iii) hydrocarbon group having 1 to 30 carbon atoms, which may contain at least one heteroatom (iv) OR ｂ , C(O)OR ｂ , C(O)OM', C(O)N(R ａ ) ２ , C(O)R ｂ OC(O)R ｂ , SR ｂ , S(O) ２ R ｂ S(O)R ｂ OS(O) ２ R ｂ SF ５ , P(O)(OR ｂ ) ２－ｙ (R ａ ) ｙ , CN, N(H)R ａ , N(R ｂ ) ２ , Si(OR ａ ) ３－ｘ (R ａ ) ｘ , OSi(OR ａ ) ３－ｘ (R ａ ) ｘ NO ２ , S(O) ２ OM', P(O)(OM') ２ or P(O)(OR ｂ ) ２ M' (Here, R ａ Each of these independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, R ｂ Each of these independently represents a hydrocarbon group having 1 to 20 carbon atoms, and N(R) ｂ ) ２ At that time, R ｂ They may be linked together to form a ring. (M' represents an alkali metal, alkaline earth metal, ammonium, quaternary ammonium, or phosphonium, x represents 0, 1, 2, or 3, and y represents 0, 1, or 2). ３ , R ４ , R ５ , and R ６The adjacent substituents may be linked to each other to form an alicyclic ring, an aromatic ring, or a heterocycle containing at least one heteroatom selected from an oxygen atom, a nitrogen atom, or a sulfur atom. １ L represents a nickel atom or a palladium atom. １ and L ２ Each of them is independent, M １ Represents the ligand coordinated to L １ and L ２ They combine with each other to form M １ A ring containing [the element] may be formed.

[0020] [In equations (B) and (C), * represents E １ This represents a bonding with R ７ , R ８ , R ９ , R １０ , R １１ , R １２ and R １３ Each of these independently represents an atom or group selected from the group consisting of (i) to (iv) as defined in formula (A), and R ７ , R ８ , R ９ and R １０ R may have adjacent substituents linked to each other, forming an alicyclic ring, an aromatic ring, or a heterocycle containing at least one heteroatom selected from an oxygen atom, a nitrogen atom, or a sulfur atom, １２ and R １３ These may be linked to each other to form an aromatic ring or an unsaturated alicyclic ring which may contain at least one heteroatom selected from oxygen, nitrogen, or sulfur atoms. １ A ２ A ３ and A ４ These are, independently, an oxygen atom, a sulfur atom, and -C(R) ２ -, -C(O)-, -S(O)-, -S(O) ２ -, -N(R)-, -P(R)-, or -P(O)(R)- (where R independently represents a C1-C20 hydrocarbon group which may contain at least one hydrogen atom or heteroatom). However, in formula (B), A１ and A ３ Of these, at least one is an oxygen atom or a sulfur atom, and in formula (C), A ３ is an oxygen atom or a sulfur atom, and R １２ and R １３ At least one of these represents an atom or group selected from the group consisting of (ii), (iii), and (iv), R １２ and R １３ These may be linked to each other to form an aromatic ring, or an unsaturated alicyclic ring which may contain at least one heteroatom selected from oxygen, nitrogen, or sulfur atoms. １ and W ２ These are, independently, carbon, silicon, nitrogen, phosphorus, boron, oxygen, -C(O)-, -P(O)-, or -S(O) ２ It represents -, and when it is a nitrogen atom, phosphorus atom, boron atom or -P(O)-, R ８ and R １０ It does not exist, and oxygen atoms, -C(O)-, or -S(O) ２ - When R ７ and R ８ And R ９ and R １０ It does not exist. h and i are each independent integers from 1 to 6, and W １ , W ２ , R ７ , R ８ , R ９ and R １０ If there are multiple W １ , W ２ , R ７ , R ８ , R ９ and R １０ These may be the same or different.

[0021]

[10] A catalyst for olefin polymerization comprising the metal complex described in [9] above.

[11] A method for producing an olefin polymer, comprising copolymerizing at least one C2-C20 olefin with at least one polar group-containing monomer in the presence of the catalyst for olefin polymerization described in [8] or

[10] above.

[12] The method for producing an olefin polymer according to

[11] above, wherein the olefin comprises at least ethylene.

[13] The method for producing an olefin polymer according to

[11] or

[12] above, wherein the polar group-containing monomer is an acrylic acid ester.

[14] The method for producing an olefin polymer according to

[13] above, wherein the acrylic acid ester has 6 or fewer carbon atoms.

[0022] According to the present invention, it is possible to provide novel compounds that can be used as ligands for catalysts capable of copolymerizing polar group-containing monomers and olefins with improved polymerization activity, in particular novel compounds that can be used as ligands for catalysts capable of copolymerizing acrylic acid esters with a relatively small number of carbon atoms and olefins with improved polymerization activity, a catalyst composition for olefin polymerization using the novel compound, a metal complex, and a catalyst for olefin polymerization, as well as a method for producing olefin polymers using the catalyst.

[0023] The following describes in detail, item by item, novel compounds that can be used as ligands in the present invention, catalyst compositions for olefin polymerization using the novel compounds, metal complexes, catalysts for olefin polymerization, and methods for producing olefin polymers using the catalyst. In this specification, "polymerization" refers collectively to the homopolymerization of one type of monomer and the copolymerization of multiple types of monomers, and when there is no need to distinguish between the two, it is simply referred to as "polymerization." Similarly, "polymer" refers collectively to the homopolymerization of one type of monomer and the copolymerization of multiple types of monomers, and when there is no need to distinguish between the two, it is simply referred to as "polymer." In this specification, "(meth)acrylic acid ester" includes both acrylic acid esters and methacrylic acid esters. In this specification, "~" indicating a numerical range is used to mean that the values ​​written before and after it are included as the lower and upper limits. In this specification, "a group which may contain at least one heteroatom..." includes both the case where the group written immediately after it is unsubstituted and the case where it contains at least one heteroatom. For example, a C1-C30 hydrocarbon group which may contain at least one heteroatom includes both unsubstituted C1-C30 hydrocarbon groups and C1-C30 hydrocarbon groups containing at least one heteroatom. In this specification, "Ph" represents phenyl, "Me" represents methyl, "Et" represents ethyl, "Pr" represents propyl, "Bu" represents butyl, "Py" represents pyridyl or pyridine, "acac" represents acetylacetonate, "DMP" represents 2,6-dimethoxyphenyl, and "TMS" represents trimethylsilyl. Furthermore, in the structural isomer prefixes of alkyl groups, "i" represents iso, "s" represents secondary, and "t" represents tertiary. If a structural isomer prefix is ​​not listed for an alkyl group, it indicates the normal structure.

[0024] 1. Compound The compound of the present invention is a compound represented by the following general formula (A).

[0025] [In formula (A), the symbols are as described above.] Hereafter, R in formula (A) １ ~R ６ , E１ , X １ We will now explain Z, l, n, and m.

[0026] In the above general formula (A), X １ represents an oxygen atom or a sulfur atom. That is, the compound represented by the general formula (A) can be used as a ligand having one group 16 element as a monovalent anionic coordinating atom. Because there is a wide variety of compounds that can be used as ligands, X １ Preferably, it is an oxygen atom.

[0027] In the above general formula (A), E １ represents a nitrogen atom or a phosphorus atom. That is, the compound represented by the general formula (A) can be used as a ligand having one Group 15 element as a neutral coordinating atom. There is a wide variety of compounds that can be used as ligands, and it has good coordinating properties with later transition metal elements such as nickel or palladium, E １ It is preferable that it be a phosphorus atom.

[0028] In the above general formula (A), R ３ , R ４ , R ５ , and R ６ Each of these independently represents an atom or group selected from the group consisting of (i) to (iv) below: (i) hydrogen atom (ii) halogen atom (iii) hydrocarbon group having 1 to 30 carbon atoms, which may contain at least one heteroatom (iv) OR ｂ , C(O)OR ｂ , C(O)OM', C(O)N(R ａ ) ２ , C(O)R ｂ OC(O)R ｂ , SR ｂ , S(O) ２ R ｂ S(O)R ｂ OS(O) ２ R ｂ SF ５ , P(O)(OR ｂ ) ２－ｙ (R ａ ) ｙ , CN, N(H)R ａ , N(Rｂ ) ２ , Si(OR ａ ) ３－ｘ (R ａ ) ｘ , OSi(OR ａ ) ３－ｘ (R ａ ) ｘ NO ２ , S(O) ２ OM', P(O)(OM') ２ or P(O)(OR ｂ ) ２ M' (Here, R ａ Each of these independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, R ｂ Each of these independently represents a hydrocarbon group having 1 to 20 carbon atoms, and N(R) ｂ ) ２ At that time, R ｂ They may be linked together to form a ring. (M' represents an alkali metal, alkaline earth metal, ammonium, quaternary ammonium, or phosphonium, x represents 0, 1, 2, or 3, and y represents 0, 1, or 2). ３ , R ４ , R ５ , and R ６ The adjacent substituents may be linked to each other to form an alicyclic ring, an aromatic ring, or a heterocycle containing at least one heteroatom selected from an oxygen atom, a nitrogen atom, or a sulfur atom.

[0029] (ii) Examples of halogen atoms include fluorine, chlorine, bromine, and iodine. Among these, fluorine is preferred.

[0030] (iii) A hydrocarbon group having 1 to 30 carbon atoms that may contain at least one heteroatom is a hydrocarbon group and a hydrogen atom, CH ２Examples include hydrocarbon groups in which at least one of the -CH= groups is substituted with at least one monovalent, divalent, or trivalent heteroatom and / or heteroatom-containing substituent. Examples of heteroatoms in (iii) include oxygen, nitrogen, phosphorus, sulfur, silicon, and halogen atoms. The heteroatom of the monovalent substituent may be a halogen atom, and the halogen atom may be the same as that in (ii) above. Examples of divalent heteroatoms include -O- and -S-. Examples of trivalent heteroatoms include -N=. The heteroatom-containing substituent in (iii) may be the same group as the heteroatom-containing substituent listed in (iv) below. Examples of heteroatom-containing substituents used in (iii) may be alkoxy groups, aryloxy groups, alkoxycarbonyl groups, acyl groups, or acyloxy groups, and the number of carbon atoms in these groups may be 1 to 20. Note that the carbon atoms of carbonyl and acyl groups are not included in the number of carbon atoms. Examples of divalent heteroatom-containing substituents include -C(O)-, -O-C(O)-, and -C(O)-O-.

[0031] Examples of C1-C30 hydrocarbon groups in (iii) include linear, branched, and cyclic saturated or unsaturated aliphatic hydrocarbon groups, aromatic hydrocarbon groups, and combinations thereof. More specifically, examples of C1-C30 hydrocarbon groups include linear alkyl groups having C1-C30, branched acyclic alkyl groups having C3-C30, alkenyl groups having C2-C30, cycloalkyl groups which may have C3-C30 side chains, aryl groups having C6-C30, arylalkyl groups having C7-C30, and alkylaryl groups having C7-C30.

[0032] The linear alkyl group having 1 to 30 carbon atoms may be a linear alkyl group having 1 to 10 carbon atoms, such as a methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, or decyl group, or a linear alkyl group having 1 to 4 carbon atoms. The branched acyclic alkyl group having 3 to 30 carbon atoms may be a branched acyclic alkyl group having 3 to 10 carbon atoms, such as an i-propyl group, i-butyl group, t-butyl group, s-butyl group, i-pentyl group (3-methylbutyl group), t-pentyl group (1,1-dimethylpropyl group), s-pentyl group (1-methylbutyl group), 2-methylbutyl group, neopentyl group (2,2-dimethylpropyl group), 1,2-dimethylpropyl group, or i-hexyl group (4-methylpentyl group), or a branched acyclic alkyl group having 3 to 8 carbon atoms.

[0033] Examples of alkenyl groups having 2 to 30 carbon atoms include vinyl, allyl, butenyl, pentenyl, hexenyl, styryl, and cinnamyl groups. The alkenyl group may be an alkenyl group having 3 to 8 carbon atoms, such as allyl, butenyl, pentenyl, hexenyl, or styryl, or an alkenyl group having 4 to 8 carbon atoms, such as butenyl, pentenyl, hexenyl, or styryl. The cycloalkyl groups that may have side chains of 3 to 30 carbon atoms include cyclopropyl group, cyclobutyl group, cyclopentyl group, 2-methylcyclopentyl group, 3-methylcyclopentyl group, cyclohexyl group, 4-methylcyclohexyl group, 4-ethylcyclohexyl group, 2-isopropyl-5-methylcyclohexyl group, cycloheptyl group, norbornyl group (bicyclo[2.2.1]heptyl group), cyclooctyl group, decahydronaphthyl group (bicyclo[4,4,0]decyl group), etc., which may have side chains of 1 to 6 carbon atoms, which may be cycloalkyl groups of 4 to 7 carbon atoms that may have side chains of 1 to 6 carbon atoms, and which may be cycloalkyl groups of 4 to 6 carbon atoms that may have side chains of 1 to 4 carbon atoms.

[0034] The aryl group having 6 to 30 carbon atoms may be aryl groups having 6 to 18 carbon atoms, such as phenyl group, naphthyl group, azlenyl group, biphenyl group, anthracenyl group, terphenyl group, phenantrenyl group, triphenylenyl group, chrysenyl group, pyrenyl group, and tetracerenyl group, or it may be an aryl group having 6 to 12 carbon atoms. Alternatively, it may be an aryl group having 24 or fewer carbon atoms, such as 2,6-diphenylphenyl group and 2,4,6-triphenylphenyl group, in which an aryl group is substituted with another aryl group. The arylalkyl group having 7 to 30 carbon atoms may be arylalkyl groups having 7 to 15 carbon atoms, such as benzyl group, phenethyl group (2-phenylethyl group), 2-phenylisopropyl group, 9-fluorenyl group, naphthylmethyl group, and 1-tetralinyl group, or it may be an arylalkyl group having 7 to 10 carbon atoms. The alkylaryl group having 7 to 30 carbon atoms may be an alkylaryl group having 7 to 20 carbon atoms, such as a tolyl group, xylyl group, ethylphenyl group, propylphenyl group, butylphenyl group, pentylphenyl group, hexylphenyl group, heptylphenyl group, octylphenyl group, nonylphenyl group, decylphenyl group, undecylphenyl group, dodecylphenyl group, 2,6-diisopropylphenyl group, 2,4,6-triisopropylphenyl group, or 1,2,3,5,6,7-hexahydro-s-indacenyl group, or an alkylaryl group having 7 to 15 carbon atoms, such as a tolyl group, xylyl group, ethylphenyl group, propylphenyl group, butylphenyl group, or pentylphenyl group.

[0035] In (iii), R ３ ~R ６The total number of carbon atoms of the substituent corresponding to is preferably 1 to 30, more preferably 2 to 25, and even more preferably 4 to 20. Examples of (iii) include (iii-A) a linear alkyl group having 1 to 30 carbon atoms, a branched acyclic alkyl group having 3 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, a cycloalkyl group which may have a side chain of 3 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, and an alkylaryl group having 7 to 30 carbon atoms, (iii-B) a group in which one or more of the above heteroatoms are substituted on each of the above (iii-A) groups, (iii-C) a group in which one or more of the above heteroatoms are substituted on each of the above (iii-A) groups, and one or more of the above heteroatoms are substituted on each of the above (iii-A) groups, and one or more of the above heteroatoms are substituted on each of the above (iii-A) groups. Examples of (iii-C) include alkyl groups substituted with alkoxy or acyl groups, alkoxycarbonyl groups, and aryl groups substituted with acyloxy groups.

[0036] (iii) Examples of C1 to C30 hydrocarbon groups that may contain at least one heteroatom include methyl group, trifluoromethyl group, trichloromethyl group, tribromomethyl group, triiodomethyl group, ethyl group, 2-acetylethyl group, 2,6-diphenylphenyl group, 2,4,6-triphenylphenyl group, 2,6-diisopropylphenyl group, 2,4,6-triisopropylphenyl group, 2,4,6-trimethylphenyl group, 2,6-dimethoxy-4-methylphenyl group, 2,6-dimethylamino-4-methylphenyl group, 3,5-dimethoxy-4-pyridyl group, 9-anthracenyl group, pentafluoroethyl group, pentafluorophenyl group, phenyl group, benzyl group, etc.

[0037] (iv) is a heteroatom-containing substituent, OR ｂ , C(O)OR ｂ , C(O)OM', C(O)N(R ａ ) ２ , C(O)R ｂ OC(O)R ｂ , SR ｂ , S(O)２ R ｂ S(O)R ｂ OS(O) ２ R ｂ SF ５ , P(O)(OR ｂ ) ２－ｙ (R ａ ) ｙ , CN, N(H)R ａ , N(R ｂ ) ２ , Si(OR ａ ) ３－ｘ (R ａ ) ｘ , OSi(OR ａ ) ３－ｘ (R ａ ) ｘ NO ２ , S(O) ２ OM', P(O)(OM') ２ or P(O)(OR ｂ ) ２ M' (Here, R ａ Each of these independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, R ｂ Each of these independently represents a hydrocarbon group having 1 to 20 carbon atoms, and N(R) ｂ ) ２ At that time, R ｂ They may be linked to each other to form a ring. M' is an atom or group selected from the group consisting of alkali metals, alkaline earth metals, ammonium, quaternary ammonium, or phosphonium, where x is 0, 1, 2, or 3, and y is 0, 1, or 2. R ａ and R ｂ Examples of hydrocarbon groups having 1 to 20 carbon atoms in (iii) above include those with 1 to 30 carbon atoms, similar to the hydrocarbon groups having 1 to 20 carbon atoms. Also, N(R ｂ ) ２ At that time, R ｂ These elements may link together to form a heterocycle containing a nitrogen atom.

[0038] Examples of the above (iv) include, for example, hydroxyl group, methoxy group, ethoxy group, propoxy group, i-propoxy group, butoxy group, t-butoxy group, cyclohexyloxy group, phenoxy group, p-methylphenoxy group, p-methoxyphenoxy group, methoxycarbonyl group, ethoxycarbonyl group, t-butoxycarbonyl group, phenoxycarbonyl group, dimethylamide group, acetyl group, benzoyl group, acetoxy group, methylthio group, ethylthio group, propylthio group, i-propylthio group, butylthio group, t-butylthio group, phenylthio group, methylsulfonyl group, phenylsulfonyl group, methylsulfonyloxy group, phenylsulfonyloxy group, pentafluorosulfanyl group (SF ５ ), dimethyl phosphate group, nitro group, cyano group, amino group (NH ２ Examples include methylamino group, dimethylamino group, diethylamino group, dipropylamino group, cyclohexylamino group, methylethylamino group, methylpropylamino group, methylcyclohexylamino group, carbazolyl group, piperidyl group, pyrrolidinyl group, trimethylsilyl group, triethylsilyl group, dimethylphenylsilyl group, trimethoxysilyl group, triethoxysilyl group, trimethylsilyloxy group, trimethoxysiloxy group, sodium carboxylate, sodium sulfonate, potassium sulfonate, sodium phosphate, potassium phosphate, etc.

[0039] Also, R ３ , R ４ , R ５ , and R ６ The adjacent substituents may be linked to each other to form an alicyclic ring, an aromatic ring, or a heterocycle containing at least one heteroatom selected from an oxygen atom, a nitrogen atom, or a sulfur atom. ３ , R ４ , R ５ , and R ６It may form a 5-8 membered alicyclic ring, aromatic ring, or heterocycle containing at least one heteroatom selected from oxygen, nitrogen, or sulfur atoms. The formed ring may include not only monocyclic rings but also fused polycyclic rings. Each monocyclic ring may have 5-8 members or 5-6 members. In the formed ring structure, an aromatic ring may be included within the fused ring. ３ , R ４ , R ５ , and R ６ The benzene ring to which the ions are bonded may form a naphthalene ring. Other examples of ring formation include 1,2-cyclopentylene, 1,2-cyclohexylene, 1-oxo-2,3-cyclopentylene, 1-oxo-2,3-cyclohexylene, 1,2-dihydroacenaphthylene, 9,10-dihydroanthracenylene, and the like. The formed ring may be unsubstituted, or it may have atoms or groups selected from the group consisting of (ii) to (iv) as substituents, or it may have groups selected from the group consisting of (iii) to (iv) as substituents, and the substituent may be a C1 to C12 hydrocarbon group or a C1 to C6 alkoxy group which may contain at least one halogen atom.

[0040] In particular, R is a catalyst that has a longer catalyst life and higher productivity because it increases the chemical stability when the polymerization catalyst is constructed. ３ It is more preferable that the substituent is represented by the following general formula (G). X １ Adjacent to R ３ If the substituent is represented by the general formula (G) below, it will exist as a significant steric hindrance near the polymerization reaction active site, which will suppress the deactivation reaction via dimerization or disproportionation of the polymerization reaction active site. As a result, the catalyst lifetime is expected to be extended, and the overall polymer productivity will improve.

[0041] [In formula (G), * represents a bond with an aromatic ring, and R ２１ , R ２２ , R ２３ , R ２４ and R ２５Each of these independently comprises a hydrogen atom, a substituent represented by the following general formula (H), a carbon-6 to carbon-12 aryl group which may have at least one substituent, an adamantyl group, OR ｂ , SR ｂ , or N(R ｂ ) ２ (where R ｂ R in (iv) above ｂ (Synonymous with R) ２１ , R ２２ , R ２３ , R ２４ and R ２５ At least one of these is a substituent represented by the following general formula (H), an aryl group having 6 to 12 carbon atoms which may have at least one substituent, an adamantyl group, OR ｂ , SR ｂ , or N(R ｂ ) ２ That is. R ２１ , R ２２ , R ２３ , R ２４ and R ２５ They do not bond to each other to form a ring.

[0042] (In formula (H), * represents a bond with an aromatic ring, R ２６ and R ２７ Each of these is a hydrocarbon group having 1 to 6 carbon atoms, which may each independently have at least one hydrogen atom or heteroatom, and may be bonded to each other to form a ring.

[0043] R ２６ and R ２７ Each of these is independently a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, and they may be bonded together to form a 5 to 8-membered alicyclic ring. Specifically, R ２６ and R ２７ Each of these may independently consist of a hydrogen atom, a methyl group, an ethyl group, a propyl group, a pentyl group, a phenyl group, or be bonded to each other to form a six-membered alicyclic ring. ２１ , R ２２ , R ２３ , R ２４ and R ２５Preferred substituents represented by the general formula (H), which can be at least one of the following, include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, hexyl, cyclohexyl, and phenethyl (2-phenylethyl) groups. ２１ , R ２２ , R ２３ , R ２４ and R ２５ Preferred C6-C12 aryl groups that may have at least one substituent and can be at least one of the following include phenyl group, 2,6-dimethylphenyl group, 3,5-dimethylphenyl group, 2,4,6-trimethylphenyl group, 2,6-dimethoxyphenyl group, and 2,4,6-trimethoxyphenyl group. ２１ , R ２２ , R ２３ , R ２４ and R ２５ OR which can be at least one of the following ｂ Preferred groups include methoxy, ethoxy, propoxy, isopropoxy, and butoxy groups. ２１ , R ２２ , R ２３ , R ２４ and R ２５ SR can be at least one of the following ｂ A preferred example is SCH ３ SC ２ H ５ These are some examples. ２１ , R ２２ , R ２３ , R ２４ and R ２５ N(R) can be at least one of the following. ｂ ) ２ Preferred examples include dimethylamino group, diethylamino group, and methylethylamino group.

[0044] In particular, R is more influential because it is closer to the polymerization reaction active site. ２１ and R ２５At least one of is a substituent represented by the general formula (H), an aryl group having 6 to 12 carbon atoms which may have at least one substituent, an adamantyl group, OR ｂ , SR ｂ , or N(R ｂ ) ２ It is fine if R ２１ and R ２５ A substituent represented by the general formula (H), an aryl group having 6 to 12 carbon atoms which may have at least one substituent, an adamantyl group, OR ｂ , SR ｂ , or N(R ｂ ) ２ That's fine. R ２１ and R ２５ A substituent represented by the general formula (H), an aryl group having 6 to 12 carbon atoms which may have at least one substituent, an adamantyl group, OR ｂ , SR ｂ , or N(R ｂ ) ２ And R ２２ and R ２４ is a hydrogen atom, R ２３ is a hydrogen atom, or a substituent represented by the general formula (H), an aryl group having 6 to 12 carbon atoms which may have at least one substituent, an adamantyl group, OR ｂ , SR ｂ , or N(R ｂ ) ２ That's fine.

[0045] R ３Examples of substituents represented by general formula (G) in this formula include 2,6-diethylphenyl group, 2,6-dipropylphenyl group, 2,6-dibutylphenyl group, 2,6-dipentylphenyl group, 2,6-dihexylphenyl group, 2,6-diisopropylphenyl group, 2,6-diisobutylphenyl group, 2,6-di-t-butylphenyl group, 2,6-di-s-butylphenyl group, 2,6-diisopentylphenyl group, 2,6-di-t-pentylphenyl group, 2,6-di-s-pentylphenyl group, 2,4,6-triethylphenyl group, 2,4,6-tripropylphenyl group, 2,4,6-triisopropylphenyl group, 2,4,6-tributylphenyl group, 2,6-diphenylphenyl group, 2,4,6-triphenylphenyl group, and 2,6-bis(3,5-dimethylphenyl)phenyl group. ３ More preferably, the group is a 2,6-diisopropylphenyl group, a 2,6-di-t-butylphenyl group, or a 2,6-diphenylphenyl group, and even more preferably a 2,6-diisopropylphenyl group or a 2,6-diphenylphenyl group.

[0046] R ４ , R ５ and R ６ Each of these independently comprises: (i) a hydrogen atom; (ii) a halogen atom; (iii) a C1-C10 alkyl group which may contain at least one heteroatom, or a C6-C12 aryl group which may contain at least one heteroatom; (iv) OR ｂ , SR ｂ , CN, Si (OR ａ ) ３－ｘ (R ａ ) ｘ , OSi(OR ａ ) ３－ｘ (R ａ ) ｘ , CN, N(H)R ａ , or N(R ｂ ) ２ It's okay. R ４ , R ５ and R ６Each of these groups is independently preferred, and examples include (i) hydrogen atoms; (ii) fluorine atoms, chlorine atoms, bromine atoms; (iii) methyl groups, ethyl groups, isopropyl groups, butyl groups, isobutyl groups, t-butyl groups, s-butyl groups, phenyl groups, trifluoromethyl groups, pentafluorophenyl groups, naphthyl groups, anthracenyl groups; (iv) methoxy groups, ethoxy groups, phenoxy groups, trimethylsilyl groups, triethylsilyl groups, dimethylphenylsilyl groups, trimethoxysilyl groups, triethoxysilyl groups, trimethylsilyloxy groups, trimethoxysiloxy groups, cyclohexylamino groups, cyano groups, etc. ４ , R ５ and R ６ Each of these may independently be (i) a hydrogen atom; (ii) a fluorine atom; (iii) a methyl group, isobutyl group, t-butyl group, s-butyl group, trifluoromethyl group, pentafluorophenyl group; (iv) a methoxy group, trimethylsilyl group, trimethylsilyloxy group, cyclohexylamino group, or cyano group. ５ R may be a hydrogen atom, a methyl group, a t-butyl group, or a trifluoromethyl group. ４ and R ６ It can be a hydrogen atom.

[0047] In the above general formula (A), R １ This represents a hydrocarbon group represented by the following general formula (B) or (C).

[0048] [In formulas (B) and (C), the symbols are as described above.]

[0049] In equations (B) and (C), h is A １ and A ２ {-W} exists between these two points. １ (R ７ ) (Caution ８ ) -} is the number of repetitions, where i is A ３ and A ４ {-W} exists between these two points. ２ (R ９ ) (Caution １０ ) -} is the number of repetitions. h and i are each independent integers from 1 to 6, and W １ , W ２, R ７ , R ８ , R ９ and R １０ If there are multiple W １ , W ２ , R ７ , R ８ , R ９ and R １０ These may be the same or different. h and i may be integers from 1 to 3, 1 or 2, or 1, independently of the difficulty of composition and economic rationality. In equations (B) and (C), * is E １ This represents a combination of two things.

[0050] In equations (B) and (C), A １ A ２ A ３ and A ４ These are, independently, an oxygen atom, a sulfur atom, and -C(R) ２ -, -C(O)-, -S(O)-, -S(O) ２ -, -N(R)-, -P(R)-, or -P(O)(R)- (wherein R independently represents a hydrocarbon group having 1 to 20 carbon atoms which may contain at least one hydrogen atom or a heteroatom). The hydrocarbon group having 1 to 20 carbon atoms which may contain at least one heteroatom in R may be the same as the hydrocarbon group having 1 to 20 carbon atoms which may contain at least one heteroatom in (iii) above. R may be a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, or a hydrocarbon group having 1 to 3 carbon atoms, from the viewpoint of ease of synthesis and economic rationality. １ and A ３ Of these, at least one is an oxygen atom or a sulfur atom. In formula (B), A １ and A ３ This may be an oxygen atom or a sulfur atom, and may be an oxygen atom. A ２ and A ４ is an oxygen atom, a sulfur atom, or -C(R) ２- may be an oxygen atom, or -C(R) ２ - may be. Also, in formula (C), A ３ is an oxygen atom or a sulfur atom, and may be an oxygen atom. A ４ is an oxygen atom, a sulfur atom, or -C(R) ２ - may be an oxygen atom, or -C(R) ２ - That's fine.

[0051] In equations (B) and (C), W １ and W ２ These are, independently, carbon, silicon, nitrogen, phosphorus, boron, oxygen, -C(O)-, -P(O)-, or -S(O) ２ It represents -, and when it is a nitrogen atom, phosphorus atom, boron atom or -P(O)-, R ８ and R １０ It does not exist, and oxygen atoms, -C(O)-, or -S(O) ２ - When R ７ and R ８ And R ９ and R １０ It does not exist. In equations (B) and (C), W １ and W ２ Each of these may independently be a carbon atom or a silicon atom, or may be a carbon atom, from the standpoint of ligand stability. However, in formulas (B) and (C), A １ {-W １ -} ｈ A ２ and A ３ {-W １ -} ｉ A ４ In the joining of -O-O-, -O-N(R)-, S(O) ２ -S(O)-, -S(O) ２ -S(O) ２ The structures are selected such that unstable structures like -, -N(R)-N-, and -O-N- are not included.

[0052] In equations (B) and (C), R ７ , R ８ , R ９ , R １０ , R １１ , R １２and R １３ Each of these independently represents an atom or group selected from the group consisting of (i) to (iv) as defined in formula (A) above. ７ , R ８ , R ９ , R １０ , R １１ , R １２ and R １３ The atoms or groups selected from the group consisting of (ii), (iiii), and (iv) as defined in formula (A) above include the same atoms or groups as those described in (ii), (iiii), and (iv) above in formula (A).

[0053] Also, R ７ , R ８ , R ９ and R １０ The adjacent substituents may be linked to each other to form an alicyclic ring, an aromatic ring, or a heterocycle containing at least one heteroatom selected from oxygen, nitrogen, or sulfur atoms. The formed ring may include not only monocyclic rings but also fused polycyclic rings. Each monocyclic ring may have 4 to 8 members or 5 to 6 members. ７ , R ８ , R ９ and R １０ Each of these molecules is independently linked to its neighboring substituents, and their bonded W １ or W ２ Together with it, it may form a 4- to 8-membered alicyclic ring, an aromatic ring, or a heterocycle containing at least one heteroatom selected from an oxygen atom, a nitrogen atom, or a sulfur atom. For example, h or i is 2, and W １ or W ２ If there are two of them, R ７ , R ８ , R ９ and R １０ Each of these atoms has adjacent substituents linked to each other, and the two W atoms that are bonded to them １ or two W ２ They may form a 4- to 8-membered alicyclic ring, aromatic ring, or heterocycle together.

[0054] R ７ , R ８ , R９ and R １０ The W that combines them １ or W ２ Together with the alicyclic ring, it may be an alkylene group having 3 to 7 carbon atoms in which adjacent substituents are linked to each other. For example, adjacent R ７ and R ８ The W that combines them １ It may also be a C5 alkylene group that forms a 6-membered ring. ７ , R ８ , R ９ and R １０ In each case, the aryl groups of adjacent substituents are linked to each other, and the W bond between them １ or W ２ It may be that they form a ring. For example, adjacent R ７ and R ８ The W that combines them １ It may also be a biphenylene group that forms a five-membered ring. In this case, W １ If it is a carbon atom, then W １ and R ７ and R ８ Fluorenylidene is formed by this process. Also, R ７ , R ８ , R ９ and R １０ The two Ws that join them together １ or two W ２ Together with the other, it may form an alicyclic ring, and may be a C3-C6 alkylene group in which adjacent substituents are linked to each other, or it may be a C3 or C4 alkylene group that forms a 5 or 6-membered ring. Also, R ７ , R ８ , R ９ and R １０ The two Ws that join them together １ or two W ２ It may also form an aromatic ring with 6 to 12 carbon atoms.

[0055] Furthermore, the alicyclic ring or aromatic ring may be a heterocycle in which at least one carbon atom is replaced with a heteroatom selected from oxygen, nitrogen, or sulfur atoms. ７ , R ８ , R ９ and R １０ The alicyclic ring, aromatic ring, or heterocycle formed in the above may further have atoms or groups selected from the group consisting of (ii) to (iv) as defined in formula (A) as substituents, and such substituents may be halogen atoms.

[0056] In particular, in terms of rigidity and bulkiness as substituents that easily improve polymerization activity, when h and i are independently 1 in formulas (B) and (C), R ７ , R ８ , R ９ and R １０ Each of these is an independent group selected from the group consisting of (iii) and (iv) as defined by formula (A), and when h and i are each independently 2 to 6, R ７ , R ８ , R ９ and R １０ Each of these is an atom or group independently selected from the group consisting of (i) to (iii) as defined by formula (A), and R ７ , R ８ , R ９ and R １０ The adjacent substituents may be linked to each other to form an alicyclic ring, an aromatic ring, or a heterocycle containing at least one heteroatom selected from an oxygen atom, a nitrogen atom, or a sulfur atom.

[0057] When h and i are each independently 1, the R ７ , R ８ , R ９ and R １０ The group selected from the group consisting of (iii) and (iv) as defined in formula (A) above may be a group selected from the group consisting of (iii) as defined in formula (A), and may be a hydrocarbon group having 1 to 30 carbon atoms that may contain at least one halogen atom. When h and i are each independently 2 to 6, R ７ , R８ , R ９ and R １０ The atom or group selected from the group consisting of (i) to (iii) as defined in formula (A) above may be an atom or group selected from the group consisting of (i) and (iii) as defined in formula (A), and may be an atom or group selected from the group consisting of hydrocarbon groups having 1 to 30 carbon atoms, which may contain at least one hydrogen atom and one halogen atom. ７ , R ８ , R ９ and R １０ The halogen atoms (ii) and (iii) defined in formula (A) above may be fluorine atoms or chlorine atoms, considering the difficulty of synthesis and economic rationality. ７ , R ８ , R ９ and R １０ The group selected from the group consisting of (iii) as defined in formula (A) above may be, in particular, a linear alkyl group having 1 to 10 carbon atoms which may contain at least one halogen atom, a branched acyclic alkyl group having 3 to 10 carbon atoms which may contain at least one halogen atom, a cycloalkyl group having 4 to 7 carbon atoms which may have a side chain of 1 to 6 carbon atoms which may contain at least one halogen atom, an aryl group having 6 to 10 carbon atoms which may contain at least one halogen atom, or an alkylaryl group having 7 to 17 carbon atoms which may contain at least one halogen atom, and among these, a linear alkyl group having 1 to 10 carbon atoms which may contain at least one halogen atom, a branched acyclic alkyl group having 3 to 10 carbon atoms which may contain at least one halogen atom, an aryl group having 6 to 10 carbon atoms which may contain at least one halogen atom, or a cycloalkyl group having 5 to 7 carbon atoms which may have a side chain of 1 to 5 carbon atoms. ７ , R ８ , R ９ and R １０The group selected from the group consisting of (iii) as defined in formula (A) above may be, for example, a methyl group, a trifluoromethyl group, an ethyl group, a pentafluoroethyl group, a cyclobutyl group, a cyclopentyl group, a 2-methylcyclopentyl group, a 2-fluorocyclopentyl group, a 3-methylcyclopentyl group, a 3-fluorocyclopentyl group, a cyclohexyl group, a 4-methylcyclohexyl group, a 4-fluorocyclohexyl group, a 4-ethylcyclohexyl group, a 2-isopropyl-5-methylcyclohexyl group, a cycloheptyl group, a 2-norbornyl group, a phenyl group, a 3,5-difluorophenyl group, a pentafluorophenyl group, a naphthyl group, etc. Note that when h and i are each independently 2 to 6, A １ W that is not adjacent １ Therefore R ７ and R ８ , and, A ３ W that is not adjacent ２ Therefore R ９ and R １０ Each of these may be a hydrogen atom.

[0058] R １１ In particular, from the standpoint of ease of synthesis and economic rationality, C1-C10 alkyl groups, C6-C10 aryl groups, and C(O)OR groups may contain at least one hydrogen atom, halogen atom, or heteroatom. ｂ , CN, N(R ｂ ) ２ , or Si (OR ａ ) ３－ｘ (R ａ ) ｘ It may be a hydrogen atom, a bromine atom, a methyl group, a phenyl group, a 2-acetylethyl group, or a diisopropylamino group.

[0059] Also, R １２ and R １３ In the above (ii), from the standpoint of ease of synthesis and economic rationality, it may be a fluorine atom or a chlorine atom. １２ and R １３ In the above (iii), from the standpoint of ease of synthesis and economic rationality, it may be an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms, etc.１２ and R １３ In the above (iv), from the standpoint of difficulty of synthesis and economic rationality, OR ｂ , C(O)OR ｂ , C(O)N(R ａ ) ２ , C(O)R ｂ OC(O)R ｂ , SR ｂ , S(O) ２ R ｂ S(O)R ｂ OS(O) ２ R ｂ SF ５ , P(O)(OR ｂ ) ２－ｙ (R ａ ) ｙ , CN, N(H)R ａ , N(R ｂ ) ２ , Si(OR ａ ) ３－ｘ (R ａ ) ｘ , OSi(OR ａ ) ３－ｘ (R ａ ) ｘ , or NO ２ It may be, or ｂ , C(O)OR ｂ , SR ｂ , S(O) ２ R ｂ SF ５ , or NO ２ It may be OR ｂ , SR ｂ SF ５ , or NO ２ It may be OR ｂ That's fine.

[0060] Also, R １２ and R １３These may be linked to each other to form an aromatic ring or an unsaturated alicyclic ring which may contain at least one heteroatom selected from oxygen, nitrogen, or sulfur atoms. The unsaturated alicyclic ring contains at least one unsaturated bond. If the unsaturated alicyclic ring contains at least one heteroatom selected from oxygen, nitrogen, or sulfur atoms, it may be a non-aromatic unsaturated heterocyclic ring. The formed ring may include not only monocyclic rings but also fused polycyclic rings. Each monocyclic ring may have 5 to 8 members or 5 to 6 members. For example, R １２ and R １３ These are linked to one another and may include aromatic rings to which they are joined, forming a naphthalene ring, anthracene ring, dihydronaphthalene ring, benzofuran ring, benzothiophene ring, or indole ring. Among these, R １２ and R １３ These may be linked to each other to form an aromatic ring. These rings may be unsubstituted or substituted with a group selected from the group consisting of (iii) and (iv) as defined in formula (A). The substituent may be a hydrocarbon group having 1 to 6 carbon atoms, OR ｂ , SR ｂ SF ５ , or NO ２ It may be a hydrocarbon group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, or an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms.

[0061] However, R １２ and R １３ At least one of these represents an atom or group selected from the group consisting of (ii), (iii), and (iv), R １２ and R １３ These may be linked to each other to form an aromatic ring, or an unsaturated alicyclic ring which may contain at least one heteroatom selected from oxygen, nitrogen, or sulfur atoms. Furthermore, in terms of strengthening the influence on polymerization reaction active sites and stabilizing polymerization reaction active sites, R １２ is an atom or group selected from the group consisting of (ii) and (iv), or R １２ and R １３They may be linked to each other, forming an aromatic ring. １ R is a hydrocarbon group represented by the general formula (B) or (C) above, but in particular, R is chosen because it has the effect of strengthening the influence on the polymerization reaction active site and stabilizing the polymerization reaction active site. １ It may contain at least one hydrocarbon group represented by the general formula (B).

[0062] In the above general formula (A), R ２ l represents a hydrocarbon group having 1 to 20 carbon atoms, which may contain at least one heteroatom, and is different from the hydrocarbon group represented by the general formula (B) or (C) above, and l is 1 or 2, when l is 2, R ２ It does not exist. R ２ The hydrocarbon group having 1 to 20 carbon atoms that may contain at least one heteroatom in (iii) above may be the same as the hydrocarbon group having 1 to 20 carbon atoms that may contain at least one heteroatom in (iii). ２ The group may be a hydrocarbon group having 3 to 20 carbon atoms, which may contain at least one heteroatom, for example, a propyl group, isopropyl group, isobutyl group, t-butyl group, 3-pentyl group, 2,6-dimethyl-4-heptyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, norbornyl group, adamantyl group, (1R,2S,5R)-2-isopropyl-5-methylcyclohexane-1-yl group (menthyl group), ketocyclopentyl group, ketocyclohexyl group, ketocycloheptyl group, 2-phenylisopropyl Ropyl group, phenyl group, 2-methoxyphenyl group, 2,6-diethylphenyl group (DEP), 2,6-dimethoxyphenyl group (DMP), 2',6'-dimethoxy[1,1'-biphenyl]-2-yl group, 1-naphthyl group, 2-naphthyl group, 2-methoxy-1-naphthyl group, 1-methoxy-2-naphthyl group, 1,3-dimethoxy-2-naphthyl group, 9-anthracenyl group, 9-fluorenyl group, 1,2,3,5,6,7-hexahydro-s-indacenyl group, 3,5-dimethoxy-4-pyridyl group, etc. are preferably used. ２ This may be an aryl group having 6 to 20 carbon atoms, which may contain at least one heteroatom, and said aryl group is E １The carbon atom adjacent to the carbon atom bonded to the aryl group may have a heteroatom-containing substituent. The aryl group may have a heteroatom-containing substituent. １ At least one or both of the two carbon atoms adjacent to the carbon atom bonded with, or E １ If at least one of the two carbon atoms adjacent to the carbon atom bonded to is an unsubstitutable carbon atom, then E is the nearest substituted carbon atom to that carbon atom instead. １ It may also be present on carbon atoms having a nearest-neighbor interatomic distance. Note that this aryl group also includes heteroaryl groups in which CH is replaced by a nitrogen atom. ２ As for the heteroatom-containing substituent in the above, in terms of the effect of strengthening the influence on the polymerization reaction active site and stabilizing the polymerization reaction active site, OR ｂ , OSi(OR ａ ) ３－ｘ (R ａ ), N(R ｂ ) ２ It is fine to be that, and among them OR ｂ It may be . l is either 1 or 2. From the standpoint of ease of synthesis and economic rationality, l may be 2.

[0063] In the general formula (A) above, Z is a hydrogen atom, a leaving group, or a cation having a valency of 1 to 4, and m is an integer between 1 and the valency of Z. When m is 1, examples of Z include a hydrogen atom, lithium ion, sodium ion, potassium ion, etc. When m is 2, examples of Z include a magnesium ion, calcium ion, zinc ion, etc. The leaving group is a hydrogen atom, R ｂ S(O) ２ Base (R here) ｂ This is as defined above. ), CF ３ S(O) ２ group, R ｂ S(O) ２ Group, TiOR ｂ Examples of groups include ammonium, quaternary ammonium, or phosphonium, and metal ions from groups 1 to 14 of the periodic table. Of these, hydrogen atoms and NH are preferred.４＋ , (R ｂ ) ４ N ＋ (R here) ｂ As defined earlier, the four R's ｂ They may be the same or different. The same applies below. (R ｂ ) ４ P ＋ Li ＋ Na ＋ _K ＋ ,Cd ＋ Ag ＋ Au ＋ , Mg ２＋ Ca ２＋ Al ３＋ And more preferably, a hydrogen atom, (R ｂ ) ４ N ＋ Li ＋ Na ＋ _K ＋ Ag ＋ That is the case.

[0064] Specific examples of compounds represented by general formula (A) include, but are not limited to, the following compounds.

[0065]

[0066]

[0067]

[0068]

[0069]

[0070]

[0071]

[0072]

[0073]

[0074] The compound represented by the general formula (A) can be synthesized based on known synthesis methods. For example, E １ H(R) １ )ｌ (R ２ ) ２－ｌ Using the above, E in the presence of a base or acid １ H(R) １ ) ｌ (R ２ ) ２－ｌ The compound represented by the general formula (A) can be synthesized by reacting with epoxy. Also, in the presence of a base, E １ CH ３ (R １ ) ｌ (R ２ ) ２－ｌ The general formula (A) can also be synthesized by reacting it with a ketone. Representative references include Patent Document 5, Non-Patent Document 7, and Journal of Fluorine Chemistry 2002, 117, pp. 121-129. E １ H(R) １ ) ｌ (R ２ ) ２－ｌ The compound represented by may be a commercially available product selected as appropriate. If a commercially available product is unavailable, a phosphine halogenate may be reacted with a nucleophile such as organolithium or organomagnesium to produce E. １ X (R １ ) ｌ (R ２ ) ２－ｌ It can be synthesized by first synthesizing (where X is a halogen atom) and then treating it with a hydride reducing agent such as lithium aluminum hydride. A representative reference that can be used is Japanese Patent Application Publication No. 2021-113174.

[0075] R １The compound used to introduce the substituent represented by the general formula (B) or (C) may be a commercially available product selected as appropriate. If a commercially available product is not available, it can be synthesized by intermolecular or intramolecular cyclization reactions. Examples of such cyclization reactions include nucleophilic substitution reactions of dihalogen molecules, Friedel-Crafts reactions, and cyclization reactions using transition metals. Representative references include RSC Advances 2014, 4, pp. 16312-16319, Bioorg. Med. Chem. Lett. 2014, 24, pp. 2379-2382, Chem. Eur. J. 2013, 19, pp. 17349-17357, and Org. Biomol. Chem. 2018, 16, pp. 8976-8983.

[0076] The compound represented by the general formula (A) functions as a ligand that can form a complex with the transition metal compound represented by the general formula (E) or (F) described later.

[0077] 2. Catalyst composition for olefin polymerization The catalyst composition for olefin polymerization of the present invention comprises a compound represented by the general formula (A) and a transition metal compound represented by the following general formula (E) or (F).

[0078] [In formulas (E) and (F), M １ M ２ and M ３ Each of these independently represents either a nickel atom or a palladium atom, L １ , L ２ , L ３ , and L ４ Each of them is independent, M １ Represents the ligand coordinated to, where q is 0, 1, or 2, and L １ and L ２ They combine with each other to form M １ A ring containing L may be formed, ３ and L ４ They combine with each other to form M １ A ring containing L may be formed. ５ , L ６ , L ９ and L １０ Each of them is independent, M２ or M ３ Represents a ligand coordinated to L ７ and L ８ Each of them is independent, M ２ and M ３ Represents the ligand coordinated to L ５ and L ６ They combine with each other to form M ２ A ring containing L may be formed, ９ and L １０ They combine with each other to form M ３ A ring containing [the element] may be formed.

[0079] In the catalyst composition for olefin polymerization of the present invention, the compound represented by the general formula (A) may be the same as described above, so its explanation is omitted here. A catalyst using the compound represented by the general formula (A) as a ligand can copolymerize polar group-containing monomers and olefins with improved polymerization activity, and in particular can copolymerize acrylic acid esters with a relatively small number of carbon atoms and olefins with improved polymerization activity. The compound represented by the general formula (A) is an E atom such as a phosphorus atom. １ ni R １ At least one hydrocarbon group represented by the general formula (B) or (C) is bonded to it. In the hydrocarbon group represented by the general formula (B) or (C), an E such as a phosphorus atom is bonded. １ A substituent at the ortho position relative to the bonded carbon atom (A １ and A ３ At least one of ) forms a cyclic structure, thereby suppressing the free rotation of the substituent at the ortho position. And A １ and A ３ At least one of them is an oxygen atom or a sulfur atom. １ and A ３ The structure is such that it is in a position (first coordination sphere) in which it can coordinate to a nickel atom or a palladium atom, and at least one of them is actually capable of coordinating to a nickel atom or a palladium atom. Furthermore, the hydrocarbon group represented by the general formula (B) or (C) is substituent A in the phenyl group. ３ -W ２ -A ４Because it has at least a rigid ring structure, the steric influence on the first coordination sphere is minimized, and because it has a more rigid bulk than an unsubstituted phenyl group, it is possible to restrict the stereostructure around the polymerization reaction active site (second coordination sphere). For this reason, it is thought that when a catalyst using the compound represented by the general formula (A) as a ligand is used, copolymerization of polar group-containing monomers, especially acrylic acid esters and olefins, proceeds with high activity. Due to the stereostructure of the first and second coordination spheres, poisoning of the polymerization reaction active site by the ester group of the acrylic acid ester is minimized, and even with comonomers such as methyl acrylate, where the ester group is sterically smaller than t-butyl acrylate, only the vinyl group can approach the nickel atom or palladium atom, and copolymerization of methyl acrylate and olefins, which had not been achieved conventionally, proceeds with high activity. Furthermore, the compound represented by the general formula (A) is E １ and X １ Because it has a skeleton to which is bonded to a phenylene group, １ When is an oxygen atom and Z is a hydrogen atom (OH), the pKa of the hydrogen ion becomes low, so it can easily react with transition metal compounds and coordinate to the metal. Also, E １ and X １ Because it has a skeleton bonded to a phenylene group, electrons on the transition metal easily move to the electron-deficient phenylene group, resulting in the transition metal becoming electron-deficient. Therefore, in electron-deficient transition metals, the activation barrier for concerted metal-carbon addition reactions to olefins is lowered, and copolymerization of methyl acrylate and other olefins proceeds more actively.

[0080] In the above general formula (E) or (F), M １ M ２ and M ３ These are, independently, nickel atoms or palladium atoms. Here, the valency of M refers to the formal oxidation number used in organometallic chemistry. That is, it refers to the number of charges remaining on the atom of an element when an electron pair in a bond involving that element is assigned to an element with higher electronegativity. Nickel atoms are preferred because they are inexpensive and readily available.

[0081] In the above general formula (E) or (F), L １ , L ２ , L ３ , L ４ , L ５ , L ６ , L ９ and L １０ each independently represent a ligand coordinated to M １ , M ２ or M ３ , and represent a monovalent anionic electron-donating ligand or a neutral electron-donating ligand. The monovalent anionic electron-donating ligand is electrically negative and is a ligand that forms a σ bond with the transition metal (M １ , M ２ or M ３ ), or donates non-polarized π electrons to three or more carbon atoms. One example of the neutral electron-donating ligand is an electrically neutral ligand that can form a coordinate bond by coordinating unpaired electrons to the transition metal. Said ligand is a molecule having an atom with unpaired electrons, and examples of the atom having unpaired electrons include a nitrogen atom, a phosphorus atom, an arsenic atom, an oxygen atom, a sulfur atom, and selenium. Further, another example of the neutral electron-donating ligand includes molecules such as ethylene and cyclooctadiene (cod), which form a π donor bond by donating π electrons, and molecules such as dibenzylideneacetone (dba) having both an olefin that coordinates to a metal and a hetero atom. As L １ to L ６ , L ９ , L １０ , those known as neutral ligands for metal complexes such as acetonitrile, isonitrile, carbon monoxide, ethylene, tetrahydrofuran, ketones, aldehydes, esters, amides, urea, urethane, and carbonates, and ligands that donate π electrons such as allyl and cyclopentadienyl can be used. Further, E ２ R'R''R''' or a molecule represented by X ２ R'R'' can also be used as a ligand. Here, E ２ represents N, P or As, and X ２R' represents O, S, or Se, and R', R'', and R''' each independently represent a hydrogen atom; an alkyl group, alicyclic group, alkoxy group, aryl group, or aryloxy group having 1 to 30 carbon atoms, which may be substituted; or an amino group or silyl group having 1 to 30 carbon atoms, which may be substituted with at least one hydrogen atom, and R' and R'' may be linked to form a heterocyclic structure, and R', R'', and R''' are E ２ It may also contain and bond to form an aromatic heterocyclic structure. Furthermore, L １ and L ２ , L ３ and L ４ , L ５ and L ６ , L ９ and L １０ They combine with each other to form M １ M ２ or M ３ These groups may form a ring, and when these groups form a ring, the minimum number of ring members in the ring is M. １ M ２ or M ３ The ring is a 5-membered to 10-membered ring, including the element. The ring may be a saturated or unsaturated alicyclic ring or a heterocycle containing at least one oxygen or nitrogen atom. １ ~L ６ , L ９ , L １０ Although it may have a -1 valent electron-donating ligand, it is preferable to select such that the valency of the metal complex is 1 or 2 in order to facilitate the reaction that forms the metal complex. Therefore, L １ ~L ６ , L ９ , L １０ The number of -1 valent electron-donating ligands is preferably 0 to 2.

[0082] -1 valent electron-donating ligand L １ ~L ６ , L ９ , L １０Examples include hydrocarbon groups having 1 to 20 carbon atoms, which may contain a hydrogen atom, a halogen atom, or at least one heteroatom. The structure of the hydrocarbon portion may be linear, branched, or cyclic, and may form a ring containing a heteroatom. A preferred number of carbon atoms is 1 to 16, and more preferably 1 to 10. -1 valent electron-donating ligand L １ ~L ６ , L ９ , L １０ Specific examples include, independently, hydride group, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, neopentyl group, hexyl group, octyl group, decyl group, dodecyl group, cyclopentyl group, cyclohexyl group, benzyl group, trimethylsilylmethyl group, phenyl group, p-methylphenyl group, p-fluorophenyl group, fluoride group, chloride group, bromide group, and iodide group. Preferred examples include hydride group, methyl group, neopentyl group, benzyl group, trimethylsilylmethyl group, phenyl group, p-fluorophenyl group, chloride group, bromide group, and iodide group.

[0083] Neutral electron-donating ligand L １ ~L ６ , L ９ , L １０ Examples include phosphines, pyridines, piperidines, alkyl ethers, aryl ethers, alkylaryl ethers, cyclic ethers, alkylnitrile derivatives, arylnitrile derivatives, alcohols, amides, aliphatic esters, aromatic esters, amines, cyclic unsaturated hydrocarbons, etc. Among these, phosphines, pyridines, cyclic ethers, aliphatic esters, aromatic esters, and cyclic olefins are particularly preferred, and trialkylphosphines, triarylphosphines, pyridines, lutidine (dimethylpyridine), picoline (methylpyridine), R ｂ C(O)O － (R here) ｂ (This may be as defined above.) １ and L ２ , L ３and L ４ , L ５ and L ６ , L ９ and L １０ may be bonded to each other to form a ring containing M １ , M ２ or M ３ ; examples of such cases include cyclooct-1-enyl group, acetylacetonate group, tetramethylethylenediamine group and 1,2-dimethoxyethane group, which is also a preferred embodiment.

[0084] L ７ and L ８ represents a ligand coordinated to M ２ and M ３ , and each is bonded to M ２ and M ３ in a mode called a three-center four-electron bond. Examples of the ligand for L ７ or L ８ include a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 4 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a thioalkoxy group having 1 to 6 carbon atoms, an amino group substituted by a hydrocarbon group having 1 to 6 carbon atoms, and an acetyl group. Preferred examples of L ７ and L ８ include a fluoride group, a chloride group, a bromide group, an iodide group, a methyl group, an ethyl group, a propyl group, a methoxy group, a phenoxy group, a dimethylamido group, a hydrido group, a thiomethoxy group, a thiophenoxy group, and an acetyl group; more preferred examples include a fluoride group, a chloride group, a bromide group, an iodide group, a methyl group, a methoxy group, a phenoxy group, a hydrido group, a thiomethoxy group, a thiophenoxy group, and an acetyl group; and even more preferred examples include a chloride group, a bromide group, an iodide group, a methoxy group, a phenoxy group, and an acetyl group.

[0085] In the general formula (E), q represents the number of L ４ and has a value of 0, 1 or 2. When q is 0, L ４ does not exist.

[0086] Specific examples of transition metal compounds represented by the general formula (E) or formula (F) include, but are not limited to, the following compounds. Also, Ni(CH ２ C(H)CH ２ ) ２ Ni(CH ２ C(Me)CH ２ ) ２ Ni(CH ２ Si(Me) ３ ) ２ (Py) ２ (Hereafter, Py represents pyridine.), Ni(CH ２ Si(Me) ３ ) ２ (Lut) ２ (Hereafter, Lut represents 2,6-lutidine.) NiPh ２ (Py) ２ NiPh ２ (Lut) ２ , Pd(OC(O)CH ３ ) ２ Examples include the above. These compounds are thought to form complexes with the compound represented by general formula (A). The transition metal compound represented by general formula (E) or formula (F) can be any transition metal compound that has polymerization ability. Examples of commonly used examples include Chem. Rev. 2009, 109, 11, 5215-5244 and Chem. Rev. 2000, 100, 1169-1203.

[0087]

[0088] The compound represented by general formula (A) can be used as a catalyst for the polymerization reaction of olefins in the form of a composition with a transition metal compound represented by general formula (E) or (F), or in the form of a metal complex which is a reaction product with the transition metal compound. In the polymerization reaction of olefins, the product used as a catalyst may be used after the compound represented by general formula (A) and the transition metal compound represented by general formula (E) or (F) have been reacted and the product isolated, or it may be used directly in the polymerization reaction without isolation or washing from the reaction system. Methods known in the synthesis of metal complexes can be used to react these compounds. It is preferable that all operations be carried out under an inert gas. The reaction is carried out in a homogeneous solvent, and a general hydrocarbon reaction solvent can be used as the solvent, preferably toluene. The concentration of the transition metal compound in the reaction solvent can be freely set up to the saturation concentration, but is preferably in the range of 1 mM to 50 mM. There is no restriction on the mixing order of the compound represented by general formula (A) (ligand) and the transition metal compound represented by general formula (E) or (F). A solvent can be added to a mixture of a solid ligand and a solid transition metal compound, or a transition metal compound dissolved in a solid ligand can be added. The mixing ratio of ligand to transition metal compound is preferably in the range of ligand:metal = 1:1 to 1:10. The mixing temperature can be appropriately set to 20°C or higher, with the boiling point of the solvent as the upper limit. The mixing temperature is preferably in the range of 35°C to 45°C. The time required for mixing can preferably be in the range of 1 minute to 24 hours, but more preferably 10 minutes to 30 minutes. One aspect of the present invention is a method for producing a catalyst for olefin polymerization, comprising the step of reacting a compound represented by the general formula (A) with a transition metal compound represented by the general formula (E) or (F).

[0089] 3. In one embodiment of the metal complex, the present invention provides a metal complex represented by the following general formula (D).

[0090] [In formula (D), １ , E １ , R １ , R ２ , l, R ３, R ４ , R ５ , and R ６ M is defined as the compound represented by the general formula (A) above, １ , L １ and L ２ This is defined as a transition metal compound represented by the general formula (E) or (F) above.

[0091] Specific examples of metal complexes represented by the general formula (D) above include the following complexes. However, these are illustrative examples and the complexes used in the method of the present invention are not limited to these specific examples.

[0092]

[0093]

[0094]

[0095]

[0096]

[0097]

[0098]

[0099]

[0100]

[0101]

[0102]

[0103]

[0104] The metal complex represented by the general formula (D) can be prepared by a method including a step of reacting a compound represented by the general formula (A) with a transition metal compound represented by the general formula (E) or (F), or by known methods. A person skilled in the art can prepare the metal complex represented by the general formula (D) by making appropriate modifications, such as changing the raw materials, based on known complex preparation methods.

[0105] For example, when producing the metal complex represented by the general formula (D), when the reaction between the compound represented by the general formula (A) and the transition metal compound represented by the general formula (E) or (F) is carried out, further, L in general formula (D) １ Ya L ２ Coordinating compounds or covalent compounds for substitution may be present. １ M ２ or M ３ For example, when using nickel or palladium, the stability of the resulting metal complex may be increased by coexisting a Lewis basic coordinating compound in the system. In such cases, the coordinating compound may be coexisted as long as it does not inhibit the polymerization or copolymerization reaction by the olefin polymerization catalyst of the present invention. The coordinating compound can be a hydrocarbon compound having 1 to 20 carbon atoms having at least one atom selected from the group consisting of oxygen, nitrogen, phosphorus, arsenic, sulfur, and selenium atoms as a coordinating atom, or a hydrocarbon compound that may contain a heteroatom having a carbon-carbon unsaturated bond that can coordinate to a transition metal, and the L １ It can be considered synonymous with a neutral electron-donating ligand among these.

[0106] Furthermore, the covalent compound is defined as a ligand derived from a transition metal compound, in the metal complex represented by general formula (D) L １ It is a compound that can be substituted with a -1 valent electron-donating ligand from among the following. The covalent compound may be an organometallic compound. A C1-C20 hydrocarbon group, which may contain at least one heteroatom, can be incorporated into the polymer as the starting end of the polymerization reaction and can greatly contribute to the initial rate of the polymerization reaction. Therefore, when producing the metal complex represented by the general formula (D), it is preferable to also use a covalent compound for introducing a C1-C20 hydrocarbon group, which may contain at least one heteroatom, depending on the situation. Examples of the covalent compound include organolithium compounds, and R ３０ Li (here, R ３０The hydrocarbon group may contain a heteroatom (a hydrocarbon group having 1 to 20 carbon atoms), and may also be an organolithium compound having a hydrocarbon group having 1 to 10 carbon atoms (which may contain a heteroatom). Examples of organolithium compounds having a hydrocarbon group having 1 to 10 carbon atoms include methyllithium, butyllithium, phenyllithium, neopentyllithium, benzyllithium, trimethylsilylmethyllithium, and p-fluorophenyllithium. Among these, methyllithium and phenyllithium are preferred, and methyllithium is even more preferred.

[0107] 4. Catalyst for Olefin Polymerization The olefin polymerization catalyst of the present invention includes the olefin-based polymerization catalyst composition of the present invention. The olefin polymerization catalyst of the present invention also includes a metal complex represented by the general formula (D) of the present invention. During the polymerization reaction of olefins, the olefin polymerization catalyst of the present invention includes a metal complex which is the product of a compound represented by the general formula (A) and a transition metal compound represented by the general formula (E) or (F), or a metal complex represented by the general formula (D) (hereinafter, these may be collectively referred to simply as "metal complex catalyst"). In the olefin polymerization catalyst of the present invention, the olefin-based polymerization catalyst composition and the metal complex represented by the general formula (D) may be the same as described above, so their explanation is omitted here. In the olefin polymerization catalyst of the present invention, as shown in the examples described later, the olefin-based polymerization catalyst composition and the metal complex represented by the general formula (D) may be used as an olefin polymerization catalyst without any particular purification.

[0108] In the olefin polymerization catalyst of the present invention, the compound represented by the general formula (A) and the transition metal compound represented by the general formula (E) or (F) below in the olefin polymerization catalyst composition may be used as single components, or multiple components may be used in combination. The olefin polymerization catalyst composition may also contain a metal complex represented by the general formula (D). The metal complex represented by the general formula (D) contained in the olefin polymerization catalyst of the present invention may be a single type or a mixture of two or more types.

[0109] In the olefin polymerization catalyst of the present invention, a co-catalyst may be added in addition to the metal complex catalyst. Examples of co-catalysts include organometallic compounds containing elements of group 1, 2, or 13 of the periodic table. In particular, examples include compounds represented by the following general formula (1), compounds represented by general formula (2), or organoaluminum oxy compounds. Multiple types of these compounds may be included in the catalyst composition.

[0110] General formula (1): Q(R ４０ ) (Caution ４１ ) R ４２ The compound represented by the general formula (1) is Q(R ４０ ) (Caution ４１ ) R ４２ It is a boron or aluminum compound represented by the formula: (wherein Q represents boron (B) or aluminum (Al), and R ４０ , R ４１ and R ４２ Each of these independently represents a hydrogen atom; an alkyl group, alicyclic group, alkoxy group, aryl group, or aryloxy group having 1 to 30 carbon atoms, which may be substituted; or an amino group or silyl group having 1 to 30 carbon atoms, which is a hydrocarbon having 1 to 30 carbon atoms substituted with one or more hydrogen atoms. ４０ ~R ４２ As for R ３ While the examples described in the explanations above are applicable, due to the ease of preparation and availability of the compounds, hydrocarbon groups such as alkyl groups and aryl groups, or alkyl or aryl groups substituted with halogens (especially fluorine) such as trifluoromethyl groups and perfluorophenyl groups are preferred.

[0111] Examples of compounds represented by the general formula (1) include, but are not limited to, trimethylborane, trimethoxyborane, perfluoromethylborane, triphenylborane, tris(perfluorophenyl)borane, triphenoxyborane, tris(dimethylamino)borane, tris(diphenylamino)borane, trimethylaluminum, triethylaluminum, tri(propyl)aluminum, tri(butyl)aluminum, triisobutylaluminum, tri(hexyl)aluminum, tri(octyl)aluminum, tri(decyl)aluminum, diethylaluminum hydride, diethylaluminum ethoxide, diethylaluminum dimethylamide, and diisobutylaluminum hydride.

[0112] General formula (2): [C(R ４３ ) (Caution ４４ ) R ４５ ] ＋ [Q(R) ４６ ) (Caution ４７ ) (Caution ４８ ) R ４９ ] － The compound represented by the general formula (2) above is [C(R ４３ ) (Caution ４４ ) R ４５ ] ＋ [Q(R) ４６ ) (Caution ４７ ) (Caution ４８ ) R ４９ ] － It is a salt of boron or aluminum carbocation represented by the formula (wherein Q is as defined in the general formula (1) above, and R ４３ ~R ４９ Each of them is independent of R ４０ (This is synonymous with R) ４３ ~R ４９ As for R ３ The examples described in the explanations above apply, but due to the ease of preparation and acquisition of the compounds, hydrocarbon groups such as alkyl groups and aryl groups are preferred, and bulky hydrocarbon groups such as t-butyl groups and aryl groups are more preferred because they make it easier to obtain carbocations.

[0113] Examples of compounds represented by the general formula (2) above include, but are not limited to, trityltetramethylborate, trityltetrakis(perfluoromethyl)borate, trityltetraphenylborate, trityltetrakis(perfluorophenyl)borate, and trityltetrakis(di(trifluoromethyl)phenyl)borate.

[0114] The compounds represented by the general formula (1) or (2) can be commercially available, or they can be obtained by appropriately modifying known methods depending on the substituents the compound has.

[0115] In addition to the compound represented by the general formula (1) or (2) above, an organoaluminum oxy compound may also be added to the olefin polymerization catalyst of the present invention. Examples of organoaluminum oxy compounds include methylaluminoxane (MAO) and modified methylaluminoxane (MMAO). These can be commercially available and there are no restrictions on grade, etc. MMAO is preferred from the viewpoint of ease of availability and handling.

[0116] In addition to the compounds represented by the general formulas (1) or (2) above, conventionally known organometallic compounds, such as alkyllithium compounds including methyllithium and butyllithium, and group 1 metal-containing compounds including Grignard reagents, can also be used as co-catalysts. These compounds can also be commercially available and there are no restrictions on grade or other aspects.

[0117] These co-catalysts can be used under the same conditions as the metal complex catalysts, but it is preferable to use them in an inert gas atmosphere, avoiding oxygen and moisture. The amount to be added can also be appropriately determined by those skilled in the art.

[0118] Furthermore, contact between the metal complex catalyst and the co-catalyst may be carried out not only during catalyst preparation, but also during prepolymerization with olefins or during polymerization of olefins. It is preferable to carry out the contact between the metal complex catalyst and the co-catalyst in an inert gas such as nitrogen, and in an inert hydrocarbon solvent such as pentane, hexane, heptane, toluene, or xylene. The contact can be carried out at temperatures between -20°C and the boiling point of the solvent, and is particularly preferable at temperatures between room temperature and the boiling point of the solvent.

[0119] 5. Method for producing olefin polymers One embodiment of the method for producing olefin polymers according to the present invention is characterized by copolymerizing at least one olefin having 2 to 20 carbon atoms with at least one polar group-containing monomer in the presence of the olefin polymerization catalyst of the present invention.

[0120] The olefin in this invention may be an acyclic olefin or a cyclic olefin, and at least one selected from the group consisting of acyclic olefins having 2 to 22 carbon atoms and cyclic olefins having 4 to 20 carbon atoms is mentioned. The acyclic olefin in this invention has the general formula: CH ２ =CHR ５０ An example of an α-olefin is represented by R. ５０ R is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and may have branching, ring, and / or unsaturated bonds. ５０ If the number of carbon atoms is greater than 20, sufficient polymerization activity tends not to be exhibited. For this reason, among them, preferred olefins are R ５０Examples of olefins include those in which the carbon atom is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms. Examples of acyclic olefins other than α-olefins include 2-butene, 2-pentene, and 2-hexene. Examples of cyclic olefins having 4 to 20 carbon atoms include cyclobutene, cyclopentene, cyclohexene, cycloheptene, norbornene, norbornadiene, etc. Preferred olefins include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 3-methyl-1-butene, 4-methyl-1-pentene, vinylcyclohexene, styrene, 4-methylstyrene, and norbornene. From the viewpoint of polymer production efficiency, it is preferable to use one or more selected from the group consisting of ethylene, propylene, 1-butene, and norbornene, and more preferably ethylene. Note that only one type of olefin may be used, or two or more types of olefins may be used simultaneously.

[0121] Examples of monomers containing polar groups include acyclic olefins and monomers in which polar functional groups (polar groups) are introduced into cyclic olefins. Among acyclic olefins, an example of a monomer in which a polar group is introduced into an α-olefin is the general formula: CH ２ = C(R ５１ ) (Caution ５２ Examples of polar group-containing monomers are those represented by ). A preferred example of a polar group-containing monomer is (meth)acrylic acid ester. Here, R ５１ R represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms. ５２ is, -(CH ２ ) ｋ -C(O)OR ５３ (Here, k represents an integer from 0 to 10, R ５３ (-) represents a hydrocarbon group with 1 to 20 carbon atoms), -C(O)N(-R ５３’ ) ２ (R here) ５３’ Each of these independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms), a cyano group, or an optionally substituted aryl group. Because this allows for greater polymerization activity, R ５１R may be a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms, or a hydrogen atom or a methyl group. ５２ As for the substituent, there are no particular restrictions, but since there are many uses for the copolymer, -(CH ２ ) ｋ -C(O)OR ５３ Alternatively, it may be an aryl group that may be substituted. In this case, R ５３ If the number of carbon atoms is 20 or less, polymerization tends to proceed sufficiently. ５３ is a hydrocarbon group having 1 to 12 carbon atoms, or a hydrocarbon group having 1 to 8 carbon atoms. k is 0 or an integer from 1 to 8, R ５３ R may be a hydrocarbon group having 1 to 8 carbon atoms. ５３ Preferably, it is composed of carbon atoms and hydrogen atoms, but R ５３ The compound may contain heteroatoms such as oxygen, sulfur, selenium, phosphorus, nitrogen, silicon, fluorine, and boron atoms. Of these heteroatoms, oxygen, silicon, and fluorine atoms are preferred, and oxygen atoms are even more preferred. ５３’ The preferred range and examples of R ５３ It is similar to that.

[0122] Examples of monomers obtained by introducing polar functional groups into acyclic olefins other than α-olefins or cyclic olefins include the R ５２ Examples include compounds in which substituents represented by are introduced at any location. Alternatively, vinylene carbonate (1,3-dioxol-2-one) may be used as the polar group-containing monomer.

[0123] Preferred examples of polar group-containing monomers include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, cyclohexyl (meth)acrylate, octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, and dodecyl (meth)acrylate. Phenyl methacrylate, toluyl methacrylate, benzyl methacrylate, hydroxyethyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, 2-aminoethyl methacrylate, 2-methoxyethyl methacrylate, 3-methoxypropyl methacrylate, glycidyl methacrylate, trifluoromethyl methacrylate, 3,3,3-trifluoropropyl methacrylate, perfluoromethyl methacrylate Ethyl, (meth)acrylamide, (meth)acryldimethylamide, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, acrylonitrile, methacrylonitrile, 5-hexen-1-ol, 2-methyl-3-buten-1-ol, 10-undecenoic acid methyl, 10-undecenoic acid ethyl, 10-undecenoic acid, 12-tridecen-2-ol, 10-undecenoic acid, methyl-9-decenate, t-butyl-10-undecenate, 1,1-dimethyl-2-propene-1-ol Examples include 9-decen-1-ol, 3-butenoic acid, 3-buten-1-ol, N-(3-buten-1-yl)phthalimide, 5-hexenoic acid, 5-methyl hexenoate, 5-hexen-2-one, vinyl acetate, 4-acetoxystyrene, vinylanisole, 5-norbornene-2-carboxylate methyl, 5-norbornene-2-carboxylate t-butyl, 5-norbornene-2-methanol, 5-norbornene-2-methylamine, 5-norbornene-2-methylpivalamide, 5-norbornene-2-yl acetate, vinylene carbonate, etc.More preferably, at least one selected from the group consisting of methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, isobutyl acrylate, t-butyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, t-butyl methacrylate, acrylonitrile, methyl 10-undecenoate, 4-acetoxystyrene, 4-nitrostyrene, vinylanisole, methyl 5-norbornene-2-carboxylate, t-butyl 5-norbornene-2-carboxylate, 5-norbornene-2-methyl pivalamide, 5-norbornene-2-yl acetate, and vinylene carbonate.

[0124] Further preferred examples of polar group-containing monomers include at least one selected from the group consisting of t-butyl acrylate, methyl acrylate, methyl methacrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, methyl 10-undecenoate, 4-acetoxystyrene, t-butyl 5-norbornene-2-carboxylate, 9-decenyl acetate, 1,2-epoxy-9-decene, and vinylene carbonate. These monomers may be used individually or in combination of multiple types.

[0125] The types of monomers described above can be appropriately selected according to the required properties of the resulting polymer. Furthermore, it is possible to copolymerize compositions of two or more monomers, and also to copolymerize compositions consisting of two or more polar group-containing monomers. The amounts of monomers blended and the ratios between each monomer can be appropriately set according to the required properties of the resulting copolymer.

[0126] In the method for producing olefin polymers of the present invention, a preferred embodiment from the viewpoint of polymerization activity is that the olefin contains at least ethylene. Furthermore, in the method for producing olefin polymers of the present invention, copolymerization of an olefin with a (meth)acrylic acid ester, and further copolymerization of an olefin with an acrylic acid ester, are preferred embodiments from the viewpoint of polymerization activity. Since the process is carried out in the presence of the olefin polymerization catalyst of the present invention, copolymerization of an acrylic acid ester with a relatively small number of carbon atoms and an olefin can be performed with improved polymerization activity, so the acrylic acid ester may have 6 or fewer carbon atoms. The acrylic acid ester with 6 or fewer carbon atoms may be at least one selected from the group consisting of methyl acrylate, ethyl acrylate, propyl acrylate, and isopropyl acrylate.

[0127] In the method for producing olefin polymers of the present invention, an olefin polymerization catalyst containing the metal complex catalyst is used as a catalyst for copolymerization of polar group-containing monomers and olefins. Each metal complex catalyst may be used in an isolated form or supported on a carrier. Such supporting may be carried out in the reactor used for copolymerization of polar group-containing monomers and olefins, in the presence or absence of these monomers, or in a container separate from the reactor.

[0128] Any support can be used as the support, as long as it does not impair the spirit of the present invention. Generally, inorganic oxides and polymer support materials are preferred. Specifically as inorganic oxides, SiO ２ Al ２ O ３ MgO, ZrO ２ , TiO ２ , B ２ O ３ , CaO, ZnO, BaO, ThO ２ Examples include SiO ２ - Al ２ O ３ SiO ２ -V ２ O ５ SiO ２ -TiO ２SiO ２ -MgO,SiO ２ -Cr ２ O ３ Mixed oxides such as those mentioned above can also be used. In addition, inorganic silicates, polyethylene carriers, polypropylene carriers, polystyrene carriers, polyacrylic acid carriers, polymethacrylic acid carriers, polyacrylic acid ester carriers, polyester carriers, polyamide carriers, and polyimide carriers can be used as carriers. There are no particular restrictions on particle size, particle size distribution, pore volume, specific surface area, etc., for these carriers, and any carrier can be used.

[0129] As inorganic silicates, clay, clay minerals, zeolites, diatomaceous earth, etc., can be used. These may be synthetic or naturally occurring minerals. Specific examples of clay and clay minerals include allophane group minerals such as allophane, kaolin group minerals such as dickite, nacrite, kaolinite, and anochite, halloysite group minerals such as metahaloysite and halloysite, serpentine group minerals such as chrysotile, lizardite, and antigorite, smectite minerals such as montmorillonite, souconite, beidelite, nontronite, saponite, and hectorite, vermiculite minerals such as vermiculite, mica minerals such as illite, sericite, and erythrolite, attapulgite, sepiolite, pygorskite, bentonite, kibushi clay, gailome clay, hisingerite, pyrophyllite, and lyokdeite group minerals. These may form mixed layers. Examples of synthetic materials include synthetic mica, synthetic hectorite, synthetic saponite, and synthetic teniolite.

[0130] Among these specific examples, preferred are kaolin group minerals such as dickite, nacrite, kaolinite, and anochite; halloysite group minerals such as metahaloysite and halloysite; serpentine group minerals such as chrysotile, lizardite, and antigorite; smectite minerals such as montmorillonite, souconite, beidelite, nontronite, saponite, and hectorite; vermiculite minerals such as vermiculite; mica minerals such as illite, sericite, and erythrolith; synthetic mica; synthetic hectorite; synthetic saponite; and synthetic teniolite. Particularly preferred are smectite minerals such as montmorillonite, souconite, beidelite, nontronite, saponite, and hectorite; vermiculite minerals such as vermiculite; synthetic mica; synthetic hectorite; synthetic saponite; and synthetic teniolite.

[0131] These carriers may be used as is, but acid treatment with hydrochloric acid, nitric acid, sulfuric acid, etc. and / or LiCl, NaCl, KCl, CaCl ２ MgCl ２ Li ２ SO ４ MgSO ４ ZnSO ４ , Ti(SO ４ ) ２ , Zr(SO ４ ) ２ Al ２ (SO ４ ) ３ Salt treatments such as those described above may be performed. In this treatment, the corresponding acid and base may be mixed to produce a salt in the reaction system. Shape control such as crushing or granulation, or drying treatments may also be performed.

[0132] In the method for producing olefin polymers of the present invention, polymerization reactions can be carried out in or without known additives in addition to the co-catalyst. Preferred additives are those that stabilize the resulting polymer. For example, quinone derivatives and hindered phenol derivatives are examples of preferred additives. Specifically, monomethyl ether hydroquinone, 2,6-di-t-butyl-4-methylphenol (BHT), reaction products of trimethylaluminum and BHT, and reaction products of tetravalent titanium alkoxide and BHT can be used. Furthermore, inorganic and / or organic fillers may be used as additives, and polymerization may be carried out in the presence of these fillers. Lewis base compounds and ionic liquids may also be used as additives.

[0133] By selecting an appropriate Lewis base compound as an additive, the activity, molecular weight, and copolymerizability of the acrylic acid ester can be improved. The amount of Lewis base compound is 0.0001 to 1000 equivalents, preferably 0.1 to 100 equivalents, and more preferably 0.3 to 30 equivalents, relative to the transition metal in the catalyst component present in the polymerization system. There are no particular restrictions on the method of adding the Lewis base compound to the polymerization system, and any method can be used. For example, the Lewis base compound may be added to the olefin polymerization catalyst of the present invention, mixed with a monomer and added, or added to the polymerization system independently of the catalyst component and monomer. Furthermore, multiple Lewis bases may be used in combination.

[0134] Examples of Lewis base compounds include aromatic amines, aliphatic amines, alkyl ethers, aryl ethers, alkylaryl ethers, cyclic ethers, alkyl nitriles, aryl nitriles, alcohols, amides, aliphatic esters, aromatic esters, phosphates, phosphites, thiophenes, thianthrenes, thiazoles, oxazoles, morpholins, and cyclic unsaturated hydrocarbons. Of these, particularly preferred Lewis base compounds are aromatic amines, aliphatic amines, cyclic ethers, aliphatic esters, and aromatic esters, with preferred Lewis bases being pyridine derivatives, pyrimidine derivatives, piperidine derivatives, imidazole derivatives, aniline derivatives, piperidine derivatives, triazine derivatives, pyrrole derivatives, and furan derivatives.

[0135] Specific Lewis base compounds include N,N,N',N'-tetramethylethylenediamine, pyridine, pentafluoropyridine, 2,6-lutidine, 2,4-lutidine, 3,5-lutidine, pyrimidine, N,N-dimethylaminopyridine, N-methylimidazole, 2,2'-bipyridine, aniline, piperidine, 1,3,5-triazine, 2,4,6-tris(trifluoromethyl)-1,3,5-triazine, 2,4,6-tris(2-pyridyl)-s-triazine, quinoline, 8-methylquinoline, phenazine, 1,10-phenanthroline, N-methylpyrrole, and 1,8-diazabicyclo Examples include -[5.4.0]-undeca-7-ene, 1,4-diazabicyclo-[2,2,2]-octane, triethylamine, benzonitrile, picoline, triphenylamine, N-methyl-2-pyrrolidone, 4-methylmorpholine, benzoxazole, benzothiazole, furan, 2,5-dimethylfuran, dibenzofuran, xanthene, 1,4-dioxane, 1,3,5-trioxane, dibenzothiophene, thianthrene, triphenylphosphonium cyclopentadienide, triphenylphosphite, triphenylphosphate, tripyrrolidinophosphine, and others.

[0136] In the method for producing olefin polymers of the present invention, there are no particular restrictions on the polymerization method. Preferred polymerization methods include solution polymerization, in which all of the resulting polymer is dissolved in the medium; slurry polymerization, in which at least a portion of the resulting polymer becomes a slurry in the medium; bulk polymerization, in which the liquefied monomer itself is used as the medium; gas-phase polymerization, which is carried out in vaporized monomer; or high-pressure ionic polymerization, in which at least a portion of the resulting polymer is dissolved in monomer liquefied at high temperature and pressure. Batch polymerization, semi-batch polymerization, or continuous polymerization may also be used. The polymerization reaction is preferably carried out under an inert gas atmosphere, such as a nitrogen atmosphere. There are no particular restrictions on the usage conditions of the metal complex catalyst as long as it is under general polymerization conditions. The amount of metal complex catalyst used is not particularly limited as long as it is within an appropriate range for use as a catalyst, and can be set appropriately by those skilled in the art.

[0137] In the method for producing olefin polymers of the present invention, suitable media include hydrocarbon solvents such as butane, isobutane, hexane, heptane, toluene, xylene, cyclohexane, and methylcyclohexane, as well as liquids such as liquefied olefins, halogenated hydrocarbon solvents such as chlorobenzene and 1,2-dichlorobenzene, and polar solvents such as diethyl ether, ethylene glycol dimethyl ether, tetrahydrofuran, dioxane, ethyl acetate, methyl benzoate, acetone, methyl ethyl ketone, formamide, acetonitrile, methanol, isopropyl alcohol, and ethylene glycol. A mixture of the liquid compounds described herein may also be used as a medium. Liquefied olefins can also be used as monomers for bulk polymerization. Furthermore, ionic liquids can also be used as a medium. For obtaining high polymerization activity and high molecular weight, the medium may be one of the hydrocarbon solvents or ionic liquids mentioned above.

[0138] Unreacted monomers and media may be separated from the resulting copolymer and recycled for reuse. During recycling, these monomers and media may be purified before reuse or reused without purification. Conventional methods can be used to separate the resulting copolymer from the unreacted monomers and media. For example, methods such as filtration, centrifugation, solvent extraction, and reprecipitation using a poor solvent can be used.

[0139] While there are no particular restrictions on polymerization temperature, polymerization pressure, and polymerization time, the optimal settings can usually be selected from the following ranges, taking into account productivity and process capabilities. Specifically, the polymerization temperature is typically -20°C to 290°C, preferably 0°C to 250°C, more preferably 0°C to 200°C, even more preferably 10°C to 150°C, and particularly preferably 20°C to 100°C. The copolymerization pressure is 0.1 MPa to 300 MPa, preferably 0.3 MPa to 200 MPa, more preferably 0.5 MPa to 150 MPa, even more preferably 1.0 MPa to 100 MPa, and particularly preferably 1.3 MPa to 50 MPa. The polymerization time can be selected from the range of 0.1 minutes to 100 hours, preferably 0.5 minutes to 70 hours, and even more preferably 1 minute to 60 hours.

[0140] In the method for producing olefin polymers of the present invention, polymerization is generally carried out under an inert gas atmosphere. For example, a nitrogen or argon atmosphere can be used, with a nitrogen atmosphere being preferred. A small amount of oxygen or air may be present. However, when using a monomer that is a gas at room temperature, such as ethylene, polymerization can be carried out after filling the reaction system with ethylene. There are no particular restrictions on the supply of catalyst and monomer to the polymerization reactor, and various supply methods can be used depending on the purpose. For example, in the case of batch polymerization, it is possible to supply a predetermined amount of monomer to the polymerization reactor in advance and then supply the catalyst to it. In this case, additional monomer or additional catalyst may be supplied to the polymerization reactor.

[0141] Regarding the control of copolymer composition, a method that can be generally used involves supplying multiple monomers to a reactor and changing their supply ratio. Other methods include controlling the copolymer composition by utilizing the difference in monomer reactivity ratio due to differences in catalyst structure, and controlling the copolymer composition by utilizing the polymerization temperature dependence of the monomer reactivity ratio. In the present invention, the total content of olefin monomers in the total monomers in the copolymerization of polar group-containing monomers and olefins can be appropriately selected according to the desired physical properties, and may be 60.0 mol% to 99.9 mol%, 70.0 mol% to 99.8 mol%, 80.0 mol% to 99.7 mol%, 85.0 mol% to 99.6 mol%, or 90.0 mol% to 99.5 mol% per 100 mol% of total monomers. It may be mol%, 90.2 mol% to 99.0 mol%, 90.5 mol% to 98.5 mol%, 90.7 mol% to 98.0 mol%, 91.0 mol% to 97.5 mol%, 91.2 mol% to 97.0 mol%, 91.5 mol% to 96.5 mol%, 91.7 mol% to 96.0 mol%, and 92.0 mol% to 95.5 mol%. In copolymerization of polar group-containing monomers with olefins, the total content of polar group-containing monomers in the total monomer can be appropriately selected according to the desired physical properties, and may be 0.1 mol% to 40.0 mol%, 0.2 mol% to 30.0 mol%, 0.3 mol% to 20.0 mol%, 0.4 mol% to 15.0 mol%, or 0.5 mol% to 10 mol% relative to 100 mol% of the total monomer. It may be 0 mol%, 1.0 mol% to 9.8 mol%, 1.5 mol% to 9.5 mol%, 2.0 mol% to 9.3 mol%, 2.5 mol% to 9.0 mol%, 3.0 mol% to 8.8 mol%, 3.5 mol% to 8.5 mol%, 4.0 mol% to 8.3 mol%, or 4.5 mol% to 8.0 mol%.By defining this range, it is possible to impart properties such as affinity and adhesion to paints without significantly impairing the inherent properties of polyolefins, such as heat resistance, and to control the physical properties.

[0142] Conventional methods can be used to control the molecular weight of polymers, including the following: 1) Controlling the polymerization temperature; 2) Controlling the monomer concentration; 3) Controlling the ligand structure in the transition metal complex; 4) Using known chain transfer agents such as hydrogen and metalalkyls.

[0143] The weight-average molecular weight (Mw) of the olefin polymer obtained by the method for producing olefin polymers of the present invention is not particularly limited. The lower limit of the Mw of the olefin polymer may be 5,000 or more, or 10,000 or more. The upper limit of the Mw of the olefin polymer may be 1,000,000 or less, or 500,000 or less. The ratio (Mw / Mn) of the Mw to the number-average molecular weight (Mn) of the olefin polymer obtained by the method for producing olefin polymers of the present invention is not particularly limited. The Mw / Mn of the olefin polymer may be 1.0 to 6.0, 1.5 to 5.0, 2.0 to 4.0, 1.5 to 3.5, or 1.5 to 3.0. The Mw and Mn of the olefin polymer are determined by gel permeation chromatography (GPC). The GPC measurement in the present invention can be performed by the method described in the examples below.

[0144] Furthermore, if the olefin polymer obtained by the method for producing olefin polymers of the present invention is an ethylene polymer, then the ethylene polymer １３ The degree of methyl branching calculated by C-NMR is not particularly limited, but may be 10 or less per 1,000 carbon atoms, or 5 or less. The number of methyl branches in this invention can be measured by the method described in the examples below.

[0145] The present invention provides a method for producing olefin polymers with improved activity, enabling the production of copolymers of polar group-containing monomers and olefins, particularly copolymers of acrylic acid esters with relatively few carbon atoms and olefins. Therefore, it can be used as a method for providing olefin polymers with functions and properties associated with polar groups. According to the present invention's method for producing olefin polymers, the consumption of expensive metal complex catalysts containing nickel or palladium is reduced due to the improved activity, and inexpensive acrylic acid esters such as methyl acrylate can be used, thus enabling a reduction in the production cost of polar group-containing polyolefins.

[0146] The present invention will be described in more detail in the following examples and comparative examples, but the present invention is not limited thereto. In the following synthesis examples, unless otherwise specified, the operations were carried out under a purified nitrogen atmosphere and dehydrated and deoxygenated solvents were used. In addition, if the amount of compound obtained in the previous step was insufficient in the synthesis examples, the steps up to the previous step were repeated the required number of times to secure the amount of compound.

[0147] [Method for analyzing the structure in the synthesis examples] The structures of the compounds disclosed in the synthesis examples were analyzed using a JEOL JNM-ECS400 NMR spectrometer, a Bruker Avance400 NMR spectrometer, or a Bruker Avance500 NMR spectrometer. １ H-NMR, １９ F-NMR and ３１ P { １ The analysis was performed by ¹H-NMR. The specific measurement method is as follows: [Sample preparation] 5 to 20 mg of the sample was mixed with deuterated chloroform (CDCl) that does not contain tetramethylsilane. ３ ) 0.6 mL, containing 0.03% (v / v) tetramethylsilane in CDCl ３ 0.6 mL of deuterated toluene (C) containing 0.03% (v / v) tetramethylsilane. ６ D ５ CD ３ ) 0.6 mL, or dimethyl sulfoxide (DMSO)-d without tetramethylsilane ６ The solution was dissolved in 0.6 mL and placed in an NMR sample tube with an inner diameter of 5 mm.

[0148] [ １ [H-NMR Measurement Conditions] Probe: 5 mmφ probe Sample temperature: Room temperature Pulse angle: 45° Pulse interval: 2.8 seconds Number of integrations: 8 Chemical shift: CDCl ３ When used as a solvent, the chemical shift was set to either 0 ppm for the tetramethylsilane proton signal or 7.26 ppm for the chloroform proton signal, and the chemical shifts of signals from other protons were based on this. ６ D ５ CD ３ When used as the solvent, the chemical shift was set to 0 ppm for the tetramethylsilane proton signal, and the chemical shifts of signals from other protons were based on this. DMSO-d ６ When using DMSO-d as a solvent, ６ The proton signal was set to 2.50 ppm, and the chemical shift of signals from other protons was referenced to this value.

[0149] [ １９ F-NMR] Probe: 5 mmφ probe Sample temperature: Room temperature Pulse angle: 45° Pulse interval: 1.8 seconds Number of integrations: 8 Chemical shift: Chemical shift is CFCl ３ This was set to 0 ppm as an external standard, and the chemical shifts of other fluorine-induced signals were based on this.

[0150] [ ３１ P { １ H-NMR: Probe: 5 mmφ probe Sample temperature: Room temperature Pulse angle: 30° Pulse interval: 0.5 seconds Number of integrations: 64-256 Chemical shift: The chemical shift was set to 0 ppm using an 85% phosphoric acid aqueous solution as an external standard, and the chemical shift of signals from other phosphorus sources was based on this.

[0151] [Method for analyzing the polymer structure] The polymer structures obtained in the examples were analyzed using a Bruker BioSpin AV400 NMR spectrometer. １ H-NMR and １３ The results were determined by 13C-NMR analysis. The specific measurement method is as follows: [Sample preparation] 100-500 mg of the sample was mixed with o-dichlorobenzene (ODCB) and deuterated bromide (13C). ６ D５ Mixed solution of Br (volume ratio: ODCB / C) ６ D ５ 2.4 ml of Br=3 / 1 was placed in a 10 mm diameter NMR sample tube along with hexamethyldisiloxane, the reference substance for chemical shifts, and uniformly dissolved using a block heater at 150°C.

[0152] [ １ [H-NMR Measurement Conditions] Probe: 10 mmφ cryoprebe Sample temperature: 120°C Pulse angle: 4.5° Pulse interval: 2 seconds Number of integrations: 256-1024 Chemical shift: The chemical shift was set to 0.09 ppm for the proton signal of hexamethyldisiloxane, and the chemical shifts of signals from other protons were based on this.

[0153] [ １３ [C-NMR Measurement Conditions] <Ethylene / MA> Probe: 10 mmφ cryoprebe Sample temperature: 120°C Pulse angle: 90° Pulse interval: 51.5 seconds Number of integrations: 256-768 Decoupling conditions: Reverse gate decoupling method Chemical shift: Chemical shift is hexamethyldisiloxane １３ Set the C signal to 1.98 ppm, and the other １３ The chemical shift of the signal due to C was based on this.

[0154] [Comonomer Calculation Method] In the following, I represents the integrated intensity, and the numerical subscript to I indicates the range of the chemical shift. For example, I ８０．０～２．０ This shows the integrated intensity of the signal detected between 80.0 ppm and 2.0 ppm.

[0155] <Ethylene (E) / MA copolymer> MA content (mol%) = I （ＭＡ） × 100 / (I （Ｅ） +I （ＭＡ） ) Here, I （ＭＡ） , I （Ｅ） These are quantities represented by the following formulas: I （ＭＡ） = I ５１．５～５０．５ I （Ｅ） = (I １８０．０～１３６．０ +I １２０．０～１００．０ +I ５５．０～２．０ -I （ＭＡ） ×4) / 2

[0156] The branching structure is, １３ This can be determined by the tertiary carbon atom spectrum of ¹³C-NMR. For example, methyl branching is １３ I is the value obtained by dividing the sum of the integrated intensities of the signals from the methyl carbon (corresponding to v in the structural formula below) and the methylene carbon (corresponding to x in the structural formula below) at 20.0–19.8 ppm in the 13C-NMR spectrum by 3. Ｂ１ Using this method, the number of methyl branches per 1,000 carbon atoms was calculated using the following formula: Number of methyl branches (number / 1,000 carbon atoms) = I Ｂ１ ×1000 / I ｔｏｔａｌ Here, I Ｂ１ , I ｔｏｔａｌ These are quantities represented by the following formulas: I Ｂ１ = (I ２０．０～１９．８ +I ３７．６～３７．３ ) / 3 I ｔｏｔａｌ = I １８０．０～１３６．０ +I １２０．０～１００．０ +I ８０．０～２．０

[0157]

[0158] [Number-average molecular weight Mn and weight-average molecular weight Mw] Mn and Mw were determined by GPC measurement using polystyrene as the molecular weight standard, and Mw / Mn was calculated. [Sample preparation] 18 mg to 22 mg of the sample (polymer) was placed in a vial for the PL-SP 260VS high-temperature GPC pretreatment device manufactured by Polymer Laboratory Co., Ltd. ODCB containing BHT as a stabilizer (BHT concentration = 0.5 g / L) was added to the vial, and the polymer concentration was adjusted to 0.1% by weight. This solution was heated to 135°C using the PL-SP 260VS to dissolve the polymer, and then filtered through a glass filter. The filtrate was used as the measurement sample. In all experimental examples, no polymer was captured on the glass filter. [Apparatus and Measurement Conditions] Apparatus: HLC-8321GPC / HT manufactured by Tosoh Corporation Detector: IR detector Column: TSKgel GMH-HT manufactured by Tosoh Corporation (30 cm x 4 columns) Mobile phase solvent: ODCB Column temperature: 135°C Flow rate: 1.0 mL / min Injection volume: 270-330 μL Molecular weight was calculated as follows. First, commercially available monodisperse polystyrene was used as a standard sample, and a calibration curve relating retention time and molecular weight was created from the viscosity formula of the polystyrene standard sample and the ethylene polymer. Next, the molecular weight was calculated based on the calibration curve. The viscosity formula used for conversion to molecular weight is [η] = K × M α The following values ​​were used: Polystyrene: K = 1.38E －４ α = 0.70 Ethylene polymer: K = 4.77E －４ α = 0.70

[0159] The catalytic activity was calculated using the following formula: Catalytic activity (kg / mol / h) = Yield of polymer obtained (kg) / {Amount of ligand used (mol) × Reaction time (h)}

[0160] The following abbreviations used in the examples are explained below: DPEPhos: bis[2-(diphenylphosphino)phenyl] ether Pd ２ (dba) ３Tris(dibenzylideneacetone)dipalladium SPhos: 2-dicyclohexylphosphin-2',6'-dimethoxybiphenyl OMOM: Methoxymethoxy OTIPS: Triisopropylsilyloxy MA: Methyl acrylate TNOA: Trioctylaluminum

[0161] (Synthesis Example 1: Synthesis of B-575) (1) Synthesis method of compound A (2,2,6,6-tetramethylbenzo[1,2-d:5,4-d']bis([1,3]dioxol)) 15 g (107 mmol) of 2,5-dihydroxy-1,4-benzoquinone was weighed into a Schlenk tube and 200 mL of water was added. 37 g (214 mmol) of sodium dithionite and 49 mL (12 M) of hydrochloric acid were added to this solution, and the mixture was stirred at room temperature for 30 minutes. Then, 200 mL of ethyl acetate was added to the mixture to extract the soluble matter. This extraction procedure was repeated twice. The collected organic layer was washed twice with 200 mL of water. After that, the collected organic layer was dried with sodium sulfate, and the sodium sulfate was removed by filtration. The filtrate was evaporated to dryness, and the compound (A-1) obtained as 6.0 g of brown solid was used as is in the next step. １ H NMR (400MHz, DMSO-d ６ ) δ: 7.94 (br, 4H), 6.20 (s, 2H)

[0162]

[0163] 6.0 g (42 mmol) of compound (A-1), 1.1 g (4.2 mmol) of pyridinium p-toluenesulfonate, and 21 g (296 mmol) of 2-methoxypropene were weighed into a Schlenk tube, 150 mL of toluene was added, and the mixture was stirred at 110°C for 12 hours. 50 mL of ethyl acetate was added to the mixture to extract the soluble substances. This extraction procedure was repeated twice. The collected organic layer was then washed twice with 50 mL of water. The collected organic layer was dried over sodium sulfate, and the sodium sulfate was removed by filtration. The filtrate was evaporated to dryness, and the resulting crude product was purified by silica gel column chromatography (eluent: petroleum ether / ethyl acetate = 20 / 1) to obtain compound A as a yellow solid of 2.7 g. １H NMR (400 MHz, CDCl ３ ) δ: 6.33 (s, 2H), 1.64 (s, 12H)

[0164]

[0165] (2) Synthesis of 575-1: In a Schlenk tube containing a stirring bar, weigh out 8.0 g (28 mmol) of 2,6-diisopropyl-1-iodobenzene, 5.7 g (31 mmol) of 2-(methoxymethoxy)phenylboronic acid, 1.6 g (1.4 mmol) of palladium tetrakis(triphenylphosphine), and 2.2 g (56 mmol) of sodium hydroxide in a glove box. Add 150 mL of tetrahydrofuran and 70 mL of distilled water by syringe at room temperature to obtain a mixture. Next, attach a condenser to the Schlenk tube and heat the mixture to 80°C in an oil bath, stirring continuously with a magnetic stirrer for 16 hours. After the resulting reaction mixture was cooled to room temperature under open air, the solid component was removed by filtration through a Celite-lined column. The filtrate was dried under reduced pressure using a rotary evaporator. After drying, 14 g of 575-1 was obtained as a yellow liquid. １ H NMR (400 MHz, CDCl ３ ) δ: 7.42-7.30 (m, 2H), 7.29-7.19 (m, 3H), 7.06 (d, J=4.4Hz, 2H), 5.08 (s, 2H), 3.36 (s, 3H), 2 .57 (sept, J=6.8Hz, 2H), 1.12 (d, J=6.8Hz, 6H), 1.07 (d, J=6.8Hz, 6H)

[0166]

[0167] (3) Synthesis of 575-2 Weighed out 1.0 g (3.4 mmol) of the above 575-1, added 10 mL of tetrahydrofuran, and cooled the mixture to 0°C. Slowly added 1.5 mL of butyllithium (BuLi) (2.5 M solution of tetrahydrofuran) dropwise to the mixture while stirring. After the addition was complete, the mixture was heated to room temperature and stirred for 2 hours. Next, the resulting reaction solution was cooled to -78°C, and then 0.88 mL (10.1 mmol) of phosphorus trichloride was added to the reaction solution while stirring. After the addition, the reaction solution was heated to room temperature and stirred for 1 hour. After that, all volatile components were removed from the reaction solution under reduced pressure. Subsequently, 1.34 g of yellow oil 575-2 was obtained. ３１ P { １ H} NMR (162MHz, CDCl ３ )δ: 158.8ppm(s)

[0168]

[0169] (4) Synthesis of 575-3 Weigh out 2.4 g (10.8 mmol) of compound A, add 20 mL of tetrahydrofuran, and cool the mixture to 0°C. Add 4.8 mL of BuLi (2.5 M tetrahydrofuran solution) to the mixture slowly dropwise while stirring. After the addition is complete, raise the temperature of the mixture to room temperature and stir for 3 hours. Next, cool the resulting reaction solution to -78°C, and then add 10 mL of tetrahydrofuran solution of 575-2 (1.4 g, 3.4 mmol) to the reaction solution slowly dropwise while stirring. After the addition is complete, raise the temperature of the reaction solution to room temperature and stir for 16 hours. Then, under open air, add 100 mL of water to the resulting mixture to stop the reaction. Next, add 100 mL of ethyl acetate to the mixture to extract and separate the soluble substances. The remaining aqueous layer was extracted twice with ethyl acetate. The collected organic layer was dried over sodium sulfate, and then the sodium sulfate was removed by filtration. The resulting filtrate was evaporated to dryness to obtain a solid. The obtained solid was purified under atmospheric conditions by silica gel column chromatography (eluent: petroleum ether / ethyl acetate = 10 / 1) to obtain 0.65 g of 575-3 as a white solid. ３１ P { １ H} NMR (162MHz, CDCl ３ ) δ: -56.5ppm(s)

[0170]

[0171] (5) Synthesis of B-575 2.4 g (3.1 mmol) of the above 575-3 was weighed out, and 50 mL of 3.5 M dioxane hydrochloride solution was added while stirring, and the mixture was stirred at room temperature for 4 hours. 100 mL of methylene chloride was added to the resulting mixture, and it was washed with 200 mL of 10% sodium hydroxide aqueous solution. After liquid-liquid extraction, the organic layer was further washed with 300 mL of saturated sodium bicarbonate aqueous solution. After liquid-liquid extraction, the organic layer was dried over sodium sulfate, and the sodium sulfate was removed by filtration. The resulting filtrate was evaporated to dryness to obtain a solid. The obtained solid was purified by silica gel column chromatography under air (developing solvent: petroleum ether / ethyl acetate = 20 / 1) to obtain 0.34 g of crude B-575 as a solid. This was recrystallized under a nitrogen atmosphere with a mixed solution of methylene chloride and ethanol to obtain 0.51 g of B-575 as a white solid (yield 54%). ３１ The purity of B-575, as determined by P NMR, was over 99%. １ H NMR (500 MHz, CDCl ３ ) δ: 7.62 (t, J = 7.0Hz, 1H), 7.38 (t, J = 7.0Hz, 1H), 7.24 (d, J = 7.0Hz, 2H), 7.01 (d, J = 7.5Hz, 1H), 6.83 (t, J = 7.5Hz, 1H) ), 6.33 (s, 2H), 5.66 (br, 1H), 2.61 (sept, J = 7.0Hz, 2H), 1.50 (s, 24H), 1.09 (d, J = 7.0Hz, 6H), 1.05 (d, J = 7.0Hz, 6H) ３１ P { １ H} NMR (162MHz, CDCl ３ ) δ: -65.3ppm(s)

[0172]

[0173] (Synthesis Example 2: Synthesis of B-601) (1) Synthesis of 601-1 2.4 g (6.8 mmol) of 2'-(methoxymethoxy)-5'-methyl-2,4,6-triisopropyl-1,1'biphenyl was weighed out, 20 mL of tetrahydrofuran was added, and the mixture was cooled to 0°C. 3.0 mL of BuLi (2.5 M tetrahydrofuran solution) was slowly added dropwise to the mixture while stirring. After the addition was complete, the mixture was heated to room temperature and stirred for 1 hour. Next, the resulting reaction solution was cooled to -78°C, and 2.8 g (1.8 mL, 20.3 mmol) of phosphorus trichloride was added to the reaction solution while stirring. After the addition, the reaction solution was heated to room temperature and stirred for 1 hour. Then, all volatile components were removed from the reaction solution under reduced pressure to obtain 3.1 g of 601-1.

[0174]

[0175] (2) Synthesis of 601-2 3.8 g (16.9 mmol) of compound A obtained in the same manner as in Synthesis Example 1 was weighed out, 40 mL of tetrahydrofuran was added, and the mixture was cooled to 0°C. 6.8 mL of BuLi (2.5 M tetrahydrofuran solution) was slowly added dropwise to the mixture while stirring. After the addition was complete, the mixture was heated to room temperature and stirred for 2 hours. Next, the resulting reaction solution was cooled to -78°C, and 20 mL of the above 601-1 (3.1 g, 6.8 mmol) tetrahydrofuran solution was added to the reaction solution while stirring. After the addition, the reaction solution was heated to room temperature and stirred for 12 hours. Then, under open air, 100 mL of distilled water was added to the reaction solution to stop the reaction. 40 mL of ethyl acetate was added to the resulting reaction solution to extract and separate the soluble substances. This extraction and separation operation was repeated four times. The collected organic layer was dried over sodium sulfate, and the sodium sulfate was removed by filtration. The obtained filtrate was evaporated to dryness to obtain a solid. The obtained solid was purified under air by silica gel column chromatography (eluent: petroleum ether / ethyl acetate = 10 / 1) to obtain 3 g of 601-2 as a white solid (yield 54%). ３１ P { １ H} NMR (162MHz, CDCl ３ ) δ: -56.5ppm(s)

[0176]

[0177] (3) Synthesis of B-601 2.9 g (3.5 mmol) of the above 601-2 was weighed out and 30 mL of methylene chloride was added. 10 mL of trifluoroacetic acid was added to the solution while stirring, and the mixture was stirred at room temperature for 4 hours. After that, it was opened to the atmosphere, and 100 mL of methylene chloride was added to the resulting mixture at room temperature, followed by 50 mL of distilled water for washing, and then liquid-liquid separation. Next, 50 mL of distilled water was added to the recovered organic layer and liquid-liquid separation was performed. This operation was repeated two more times to wash the organic layer. The collected organic layer was dried over sodium sulfate, and then the sodium sulfate was removed by filtration. The obtained filtrate was evaporated to dryness to obtain a solid. The obtained solid was purified by silica gel column chromatography under air (developing solvent: petroleum ether / ethyl acetate = 20 / 1) to obtain 1.0 g of white solid as B-601 (yield 36%). １ H NMR (400 MHz, CDCl ３ ) δ: 7.48 (dd, J=5.2, 2.0Hz, 1H), 7.08 (s, 2H), 6.83 (s, 2H), 6.32 (s, 2H), 5.57 (s, 1H), 2.94 (sept, J=6.8Hz, 1H), 2.62 (sept, J=6.8Hz, 2H), 2.21 (s, 3H), 1.51 (s, 24H), 1.31 (d, J=6.8Hz, 6H), 1.08 (d, J=6.8Hz, 6H), 1.06 (d, J=6.8Hz, 6H) ３１ P { １ H} NMR (162MHz, CDCl ３ ) δ: -65.2ppm(s)

[0178]

[0179] (Synthesis Example 3: Synthesis of B-602) (1) Synthesis of 602-1 5.0 g (22.5 mmol) of compound A, obtained in the same manner as in Synthesis Example 1, was weighed into a Schlenk tube under nitrogen, and 50 mL of tetrahydrofuran was added. After cooling the solution to 0°C, 9.9 mL (24.8 mmol) of BuLi was slowly added dropwise while stirring. After the addition was complete, the mixture was heated to room temperature and stirred for 2.5 hours to obtain a yellow solution. Next, the mixture was cooled to -78°C, 0.89 mL (10.2 mmol) of phosphorus trichloride was added, and the mixture was heated to room temperature and stirred for 1.5 hours to obtain a yellow suspension. After that, all volatile components were removed from the reaction solution under reduced pressure. 5.7 g of 602-1 was obtained as a yellow gum-like solid. ３１ P { １ H} NMR (162MHz, CDCl ３ ) δ: 46.3 ppm (s)

[0180]

[0181] (2) Synthesis of 602-2 Weighed out 2.8 g (8.2 mmol) of 2-methoxymethoxy-2',4',6'-triisopropyl-1,1'-biphenyl and added 20 mL of tetrahydrofuran. After cooling the solution to 0°C, 3.6 mL (9.0 mmol) of BuLi was slowly added dropwise while stirring. After the addition was complete, the mixture was heated to room temperature and stirred for 2 hours. Next, after cooling the mixture to -78°C, compound 602-1 (5.4 g, 10.7 mmol) dissolved in 10 mL of tetrahydrofuran was slowly added dropwise while stirring. After the addition was complete, the mixture was heated to room temperature and stirred for 12 hours. Then, the mixture was cooled to 0°C, and then 5 mL of water was added to the mixture under air to stop the reaction. The resulting reaction solution was concentrated under reduced pressure to obtain a solid. The obtained solid was purified under air by silica gel column chromatography (eluent: petroleum ether / ethyl acetate = 25 / 1) to obtain 602-2 as 3.5 g (4.3 mmol) of a white solid (yield 52%). ３１ P { １ H} NMR (162MHz, CDCl ３ ) δ: -56.6ppm(s)

[0182]

[0183] (3) Synthesis of B-602 0.6 g (0.74 mmol) of the above 602-2 was weighed out and 10 mL of dioxane was added. 5 mL of 2 M dioxane hydrochloride solution was added to the solution while stirring, and the mixture was stirred at room temperature for 2 hours. 100 mL of aqueous sodium bicarbonate solution was added to the resulting mixture and washed. Then, 50 mL of methylene chloride was added to the mixture to extract the soluble substances, and the organic layer was separated. The collected organic layer was dried over sodium sulfate, and the sodium sulfate was removed by filtration. The resulting filtrate was evaporated to dryness to obtain a solid. The obtained solid was purified under air by silica gel column chromatography (developing solvent: petroleum ether / ethyl acetate = 20 / 1) to obtain 70 mg (0.091 mmol) of white solid B-602 (yield 12%). １ H NMR (400 MHz, CDCl ３ ) δ: 7.62-7.54 (m, 1H), 7.09 (s, 2H), 7.02 (dd, J = 7.2, 1.2Hz, 1H), 6.81 (t, J = 7.6Hz, 1H), 6.32 (s, 2H), 5.56 (s, 1H), 2.95 (sep t, J=6.8Hz, 1H), 2.60 (sept, J=6.8Hz, 2H), 1.49 (s, 24H), 1.31 (d, J=6.8Hz, 6H), 1.08 (d, J=6.8Hz, 6H), 1.05 (d, J=6.8Hz, 6H) ３１ P { １ H} NMR (162MHz, CDCl ３ ) δ: -64.2ppm(s)

[0184]

[0185] (Synthesis Example 4: Synthesis of B-605) (1) Synthesis of 605-1 To 200 mL of a methylene chloride solution containing 10 g (70 mmol) of 1,2,4,5-tetrahydroxybenzene, a mixture of 30 g (422 mmol) of 2-butanone and 9.1 g (70 mmol) of dichlorodimethylsilane was added at room temperature while stirring. The mixture was then stirred at room temperature for 72 hours. After drying the resulting reaction solution under reduced pressure, the obtained solid was purified under air by silica gel column chromatography (developing solvent: petroleum ether / ethyl acetate = changed from 10 / 1 to 5 / 1) to obtain 605-1 as 5 g (20 mmol) of pale yellow oil (yield 28%). １ H NMR (400 MHz, CDCl ３ ) δ: 6.32 (s, 2H), 1.92 (q, J = 7.2Hz, 4H), 1.57 (s, 6H), 1.01 (t, J = 7.2Hz, 6H)

[0186]

[0187] (2) Synthesis of 605-2 Weighed out 1.0 g (4.0 mmol) of the above 605-1, added 2 mL of tetrahydrofuran, and cooled the mixture to 0°C. Slowly added 1.8 mL of BuLi (2.5 M tetrahydrofuran solution) to the mixture while stirring. After the addition was complete, the mixture was heated to room temperature and stirred for 2 hours. Next, the resulting reaction solution was cooled to -78°C, and 252 mg (1.8 mmol) of phosphorus trichloride was added to the reaction solution while stirring. After the addition, the reaction solution was heated to room temperature and stirred for 1 hour. Then, all volatile components were removed from the reaction solution under reduced pressure. 1.1 g of 605-2 was obtained as a yellow gum-like solid.

[0188]

[0189] (3) Synthesis of 605-3 1.1 g (2.0 mmol) of the above 605-2 was weighed out, 5 mL of tetrahydrofuran was added, and the mixture was cooled to 0°C. 1.2 mL of lithium aluminum hydride solution (2.5 M tetrahydrofuran solution) was slowly added dropwise to the mixture while stirring. After the addition was complete, the mixture was heated to room temperature and stirred for 16 hours. Next, the resulting reaction solution was cooled to 0°C, 2.5 mL of 10% sodium hydroxide aqueous solution was added under open air, and the reaction was stopped by stirring for 30 minutes. The mixture was filtered through Celite to remove solids, and the filtrate was dried under reduced pressure to obtain a white solid. 30 mL of distilled water was added to the obtained solid, and then 30 mL of methylene chloride was added to the mixture to extract and separate the soluble substances. This extraction and separation operation was repeated three times. The collected organic layer was dried over sodium sulfate, and then the sodium sulfate was removed by filtration. The filtrate was dried under reduced pressure to obtain 605-3 as a white solid. ３１ P { １ H} NMR (162MHz, CDCl ３ )δ:-125.6ppm(s)

[0190]

[0191] (4) Synthesis of 605-4 Weigh out 8.0 g (27 mmol) of 2'-(methoxymethoxy)-4,6-diisopropyl-1,1'-biphenyl and add 60 mL of tetrahydrofuran. The mixture is cooled to 0°C. 12 mL of BuLi (2.5 M tetrahydrofuran solution) is slowly added dropwise while stirring. After the addition is complete, the resulting reaction mixture is heated to room temperature and stirred for 2 hours. Next, the reaction mixture is cooled to 0°C and 10 g, 8.1 mL (40 mmol) of iodine is added. After adding the iodine, the reaction mixture is heated to room temperature and stirred for 16 hours. Then, under open air, 250 mL of saturated sodium sulfite aqueous solution is added to the reaction mixture at room temperature to stop the reaction. 200 mL of ethyl acetate is added to the resulting mixture to extract and separate the soluble substances. This extraction and separation procedure is repeated three times. The collected organic layer is dried over sodium sulfate, and then sodium sulfate is removed from the organic layer by filtration. The filtrate was dried under reduced pressure to obtain 605-4 as 11 g of brown oil. １ H NMR (500 MHz, CDCl ３) δ: 7.85 (dd, J=7.5, 1.5Hz, 1H), 7.36 (t, J=8.0Hz, 1H), 7.22 (d, J=8.0Hz, 2H), 7.12 (dd, J=7.5, 1.5Hz, 1H), 6.91 ( t, J = 7.5Hz, 1H), 4.71 (s, 2H), 3.02 (s, 3H), 2.58 (sept, J = 7.0Hz, 2H), 1.21 (d, J = 7.0Hz, 6H), 1.05 (d, J = 7.0Hz, 6H)

[0192]

[0193] (5) Synthesis of 605-5 191 mg (0.45 mmol) of the above 605-4 was weighed out and 3 mL of dioxane was added thereto. 250 mg (0.47 mmol) of the above 605-3, 585 mg (1.8 mmol) of cesium carbonate, 48 mg (0.090 mmol) of DPEPhos, and Pd (PPh ３ ) ４ 17 mg (0.045 mmol) of was added sequentially while stirring. The mixture was then heated to 100°C and stirred for 16 hours. The resulting reaction solution was cooled to room temperature under open air, and the solid was removed by filtration through silica gel. Then, 30 mL of distilled water for washing was added to the filtrate, followed by 30 mL of ethyl acetate to extract and separate the soluble substances. This extraction and separation procedure was repeated three times. The collected organic layer was washed with 50 mL of saturated brine, and the separated organic layer was dried over sodium sulfate. Then, the sodium sulfate was removed by filtration. The obtained filtrate was evaporated to dryness to obtain a solid. The obtained solid was purified by silica gel column chromatography under air (eluent: petroleum ether / ethyl acetate = 10 / 1) to obtain 180 mg of 605-5 as a white solid (yield 49%). ３１ P { １ H} NMR (162MHz, CDCl ３ ) δ: -57.9ppm(s)

[0194]

[0195] (6) Synthesis of B-605 1.7 g (2.1 mmol) of the above 605-5 was weighed out and methylene chloride was added. 15 mL of trifluoroacetic acid was added to the solution while stirring, and the mixture was stirred at room temperature for 2 hours. Under open air, 30 mL of distilled water for washing was added to the resulting mixture, and then 10 mL of methylene chloride was added to extract and separate the soluble substances. This extraction and separation procedure was repeated three times. The collected organic layer was washed with 50 mL of saturated brine, and the separated organic layer was dried with sodium sulfate. Then, sodium sulfate was removed from the organic layer by filtration. The obtained filtrate was evaporated to dryness to obtain a solid. The obtained solid was purified under air by silica gel column chromatography (developing solvent: petroleum ether / ethyl acetate = 20 / 1) to obtain 230 mg of solid (yield 14%). ３１ The purity of B-605, as determined by P NMR, was over 99%. １ H NMR (400 MHz, CDCl ３ ) δ: 7.78-7.64 (m, 1H), 7.39 (t, J = 8.0Hz, 1H), 7.26 (d, J = 8.0Hz, 2H), 7.00 (d, J = 7.6Hz, 1H), 6.83 (t, J = 7.6Hz, 1H), 6.31 (s, 2 H), 5.75 (br, 1H), 2.62 (sept, J=7.2Hz, 2H), 1.88-1.69 (m, 8H), 1.49-1.40 (m, 12H), 1.14-1.02 (m, 12H), 0.92-0.54 (m, 12H) ３１ P { １ H} NMR (162MHz, CDCl ３ ) δ: -66.9ppm(s)

[0196]

[0197] (Synthesis Example 5: Synthesis of B-604) (1) Synthesis of 604-1 To 10 mL of a methylene chloride solution containing 1,2,4,5-tetrahydroxybenzene (1 g, 7.0 mmol), a mixture of 3.6 g (42.2 mmol) of 3-pentanone and 2.7 g (21 mmol) of dichlorodimethylsilane was added at room temperature while stirring. The mixture was stirred at room temperature for 16 hours. The resulting reaction solution was then dried under reduced pressure, and the resulting solid was washed with a small amount of heptane. The resulting solid was then purified under air by silica gel column chromatography (eluent: petroleum ether / methylene chloride = changed from 10 / 1 to 5 / 1). 510 mg (1.8 mmol) of pale yellow oil was obtained as 604-1 (yield 26%). １ H NMR (400 MHz, CDCl ３ ) δ: 6.31 (s, 2H), 1.88 (q, J = 7.6Hz, 8H), 0.98 (t, J = 7.6Hz, 12H)

[0198]

[0199] (2) Synthesis of 604-2 Weighed out 3.0 g (10.8 mmol) of the above 604-1, added 15 mL of tetrahydrofuran, cooled the mixture to 0°C, and slowly added 4.7 mL of BuLi (2.5 M tetrahydrofuran solution) dropwise while stirring. After the addition was complete, the mixture was heated to room temperature and stirred for 2 hours. Next, the resulting reaction solution was cooled to -78°C, and 666 mg (4.9 mmol) of phosphorus trichloride was added to the reaction solution while stirring. After the addition, the reaction solution was heated to room temperature and stirred for 1 hour. Then, all volatile components were removed from the reaction solution under reduced pressure to obtain 3.4 g of 604-2.

[0200]

[0201] (3) Synthesis of 604-3 3.4 g (5.4 mmol) of the above 604-2 was weighed out, 10 mL of tetrahydrofuran was added, and the mixture was cooled to 0°C. 3.2 mL of lithium aluminum hydride solution (2.5 M tetrahydrofuran solution) was slowly added dropwise to the mixture while stirring. After the addition was complete, the mixture was heated to room temperature and stirred for 12 hours. Next, the resulting reaction solution was cooled to 0°C, and 1.2 mL of 10% sodium hydroxide aqueous solution was added under open air, and the reaction was stopped by stirring for 30 minutes. The mixture was filtered through Celite to remove solids, and the filtrate was dried under reduced pressure to obtain a white solid. 20 mL of distilled water was added to the obtained solid, and then 30 mL of methylene chloride was added to extract and separate the soluble substances. This extraction and separation operation was repeated three times. The collected organic layer was dried over sodium sulfate, and then the sodium sulfate was removed by filtration. The obtained filtrate was dried under reduced pressure to obtain a solid. The obtained solid was purified under air by silica gel column chromatography (eluent: petroleum ether / ethyl acetate = 20 / 1) to obtain 604-3 as 1.7 g of white solid (yield 54%). １ H NMR (400 MHz, CDCl ３ ) δ: 6.24 (s, 2H), 5.63-4.83 (br, 1H), 1.80 (q, J = 6.0Hz, 16H), 0.87 (t, J = 6.0Hz, 24H) ３１ P { １ H} NMR (162MHz, CDCl ３ ) δ: -125.7ppm(s)

[0202]

[0203] (4) Synthesis of 604-4: 1.3 g (3.1 mmol) of 605-4 obtained in the same manner as in Synthesis Example 4 was weighed out, and 20 mL of dioxane was added. To this solution, 1.5 g (2.6 mmol) of the above 604-3, 3.3 g (10.2 mmol) of cesium carbonate, 275 mg (0.51 mmol) of DPEPhos, and Pd (PPh ３ ) ４234 mg (0.26 mmol) of was added sequentially while stirring. The mixture was then heated to 100°C and stirred for 18 hours. After the mixture was cooled to room temperature under open air, the mixture was filtered through silica gel to remove the solid. The resulting filtrate was dried under reduced pressure to obtain a yellow oil. 30 mL of methylene chloride was added to this yellow oil to extract and separate the soluble substances. This extraction and separation procedure was repeated three times. The collected organic layer was dried over sodium sulfate, and the sodium sulfate was removed by filtration. The resulting filtrate was evaporated to dryness to obtain a solid. The obtained solid was purified under air by silica gel column chromatography (eluent: petroleum ether / ethyl acetate = 25 / 1) to obtain 1.5 g (1.7 mmol) of 604-4 as a white solid (yield 66%). ３１ P { １ H} NMR (162MHz, CDCl ３ )δ:-59.2ppm(s)

[0204]

[0205] (5) Synthesis of B-604 0.30 g (0.34 mmol) of the above 604-4 was weighed out, 5 mL of 2 M dioxane hydrochloride solution was added, and the mixture was stirred at room temperature for 2 hours. Then, 100 mL of saturated sodium bicarbonate for washing was added to the resulting mixture, and then 50 mL of methylene chloride was added to extract and separate the soluble substances. The collected organic layer was dried over sodium sulfate, and the sodium sulfate was removed by filtration. The resulting filtrate was evaporated to dryness to obtain a solid. The obtained solid was purified by silica gel column chromatography under a nitrogen atmosphere (developing solvent: petroleum ether / ethyl acetate = 20 / 1) to obtain 12 mg of a white solid (yield 4.2%). １ H NMR (400 MHz, CDCl ３) δ: 7.85 (t, J=6.0Hz, 1H), 7.39 (t, J=7.6Hz, 1H), 7.26 (d, J=7.6Hz , 2H), 7.01 (d, J = 6.0Hz, 1H), 6.83 (t, J = 7.6Hz, 1H), 6.30 (s, 2H), 5 96 (d, J=4.8Hz, 1H), 2.63 (sept, J=6.8Hz, 2H), 1.87-1.65 (m, 16H) ), 1.10 (d, J=6.8Hz, 6H), 1.05 (d, J=6.8Hz, 6H), 0.90-0.50 (m, 24H) ３１ P { １ H} NMR (162MHz, CDCl ３ ) δ: -68.9ppm(s)

[0206]

[0207] (Synthesis Example 6: Synthesis of B-576) (1) Synthesis of 576-1 0.5 g (1.7 mmol) of dispiro[cyclohexane-1,2'-benzo[1,2-d:4,5-d']bis[1,3]dioxol-6',1''-cyclohexane] was weighed out and 5 mL of tetrahydrofuran was added thereto. After the mixture was cooled to 0°C, 0.73 mL of BuLi (2.5 M tetrahydrofuran solution) was slowly added dropwise to the mixture while stirring. After the addition was complete, the mixture was heated to room temperature and stirred for 3 hours. Next, the resulting reaction solution was cooled to -78°C and 110 mg (0.79 mmol) of phosphorus trichloride was added to the reaction solution while stirring. After the addition, the reaction solution was heated to room temperature and stirred for 2 hours. All volatile components were removed from the reaction solution under reduced pressure to obtain 576-1.

[0208]

[0209] (2) Synthesis of 576-2 3.3 g (5.0 mmol) of the above 576-1 was weighed out and 50 mL of tetrahydrofuran was added thereto. After the mixture was cooled to 0°C, 3.0 mL of lithium aluminum hydride solution (2.5 M tetrahydrofuran solution) was slowly added dropwise while stirring. After the addition was complete, the mixture was heated to room temperature and stirred for 12 hours. Next, the resulting reaction solution was cooled to 0°C and then 1.5 mL of 10% sodium hydroxide aqueous solution was added to the reaction solution while stirring to stop the reaction. The resulting mixture was then filtered through Celite to remove the solids. The obtained solids were further washed with 30 mL of methylene chloride, and the solution after washing was collected. The collected filtrate and the collected solution were mixed, and 100 mL of methylene chloride was added to the mixture to extract and separate the soluble substances. This extraction and separation operation was repeated three times. The collected organic layer was washed with 30 mL of distilled water, and the separated organic layer was further washed with 30 mL of saturated brine and separated. Subsequently, the organic layer was dried over sodium sulfate, and the sodium sulfate was removed by filtration. The resulting filtrate was evaporated to dryness to obtain a solid. The obtained solid was purified by silica gel column chromatography (eluent: petroleum ether / methylene chloride = 5 / 1) to obtain 2 g of 576-2 as a white solid (yield 64%). １ H NMR (400 MHz, CDCl ３ ) δ: 6.28 (s, 2H), 5.19 (d, J=232.4Hz, 1H), 1.91-1.72 (m, 16H), 1.72-1.53 ​​(m, 16H), 1.53-1.36 (m, 8H)

[0210]

[0211] (3) Weigh 6.0 g (20 mmol) of 2'(methoxymethoxy)-2,6-diisopropyl-1,1'-biphenyl into the 576-3 synthesis Schlenk tube, add 60 mL of tetrahydrofuran, and cool the mixture to 0°C. Slowly add 9.7 mL of BuLi (2.5 M tetrahydrofuran solution) to the mixture while stirring. After the addition was complete, raise the temperature of the mixture to room temperature and stir for 3 hours. After cooling the resulting reaction to -78°C, slowly add 9.8 g (30 mmol) of 1,2-dibromo-1,1,2,2-tetrachloroethane in 100 mL of tetrahydrofuran solution to the reaction while stirring. After the addition was complete, raise the temperature of the reaction to room temperature and stir for 12 hours. Then, add 150 mL of saturated sodium sulfite aqueous solution to the reaction obtained under open air to stop the reaction. Then, add 150 mL of ethyl acetate to the resulting mixture and extract and separate the soluble substances. This extraction and separation procedure was repeated twice. The collected organic layer was dried with sodium sulfate, and then the sodium sulfate was removed by filtration. The resulting filtrate was evaporated to dryness to obtain 576-3 as 8 g of yellow oil. １ H NMR (400 MHz, CDCl ３ ) δ: 7.53 (dd, J=8.0, 1.2Hz, 1H), 7.41 (t, J=7.6Hz, 1H), 7.28 (d, J=8.0Hz, 2H), 7.02 (d, J=7.6Hz, 1 H), 6.88 (t, J=7.6Hz, 1H), 2.57 (sept, J=6.8Hz, 2H), 1.15 (d, J=6.8Hz, 6H), 1.07 (d, J=6.8Hz, 6H)

[0212]

[0213] (4) Synthesis of 576-4 595 mg (1.6 mmol) of 576-3, 1 g (1.6 mmol) of 576-2, 2.1 g (6.3 mmol) of cesium carbonate, 170 mg (0.32 mmol) of DPEPhos, Pd ２ (dba) ３144 mg (0.16 mmol) of each was weighed out, and 7 mL of dioxane was added to this mixture. The mixture was heated to 100°C while stirring and stirred for 18 hours. The solid was then filtered from the resulting reaction product, and the resulting filtrate was dried under reduced pressure to obtain a solid. The obtained solid was purified by silica gel column chromatography (eluent: petroleum ether / ethyl acetate = changed from 10 / 1 to 5 / 1) to obtain 576-4 as 620 mg of white solid (yield 42%). ３１ P { １ H} NMR (162MHz, CDCl ３ ) δ: -57.2ppm(s)

[0214]

[0215] (5) Synthesis of B-576: 0.80 g (0.86 mmol) of 576-4 was weighed into a Schlenk tube, and 15 mL of methylene chloride and 15 mL of trifluoroacetic acid were added while stirring under an argon atmosphere at room temperature. The mixture was stirred at room temperature for 2 hours. Next, 80 mL of saturated sodium bicarbonate aqueous solution was added to the resulting reaction product to neutralize it, and then the mixture was separated. This neutralization and separation procedure was repeated twice. Then, 30 mL of methylene chloride was added to the aqueous layer to extract and separate the soluble substances. The collected organic layer was dried under reduced pressure to obtain a solid. The obtained solid was purified by silica gel column chromatography (eluent: petroleum ether / ethyl acetate = 20 / 1) to obtain 400 mg of B-576 as a white solid (yield 52%). １ H NMR (500 MHz, CDCl ３ ) δ: 7.70-7.40 (m, 1H), 7.38 (t, J = 7.5Hz, 1H), 7.23 (d, J = 7.5Hz, 2H), 6.99 (dd, J = 7.5, 1.5Hz, 1H), 6.84 (t, J = 7.5Hz, 1H), 6.33 (s, 2H), 5.78 (s, 1H), 2.62 (sept , J=7.0Hz, 2H), 1.88-1.75 (m, 8H), 1.74-1.64 (m, 8H), 1.64-1.57 (m, 8H), 1.49 -1.37 (m, 12H), 1.37-1.26 (m, 4H), 1.08 (d, J=7.0Hz, 6H), 1.04 (d, J=7.0Hz, 6H) ３１ P { １H} NMR (162MHz, CDCl ３ ) δ: -66.3ppm(s)

[0216]

[0217] (Synthesis Example 7: Synthesis of B-578) (1) Synthesis of 578-1 4.5 g (12 mmol) of the above 576-3 was weighed out and 50 mL of methylene chloride was added at room temperature to make a solution. Next, 3 mL of 4 M ethyl hydrochloride solution was added to the solution while stirring, and the mixture was stirred at room temperature for 2 hours. The resulting mixture was dried under reduced pressure to obtain a yellow oil. 50 mL of methylene chloride was added to this yellow oil at room temperature under open air to make a solution. 100 mL of saturated sodium bicarbonate aqueous solution for washing was added to this solution and the liquid-liquid was separated. 100 mL of methylene chloride was added to the aqueous layer to extract and separate the soluble substances. This extraction and separation operation was repeated three times. The collected organic layer was dried with sodium sulfate, and then the sodium sulfate was removed by filtration. The obtained filtrate was evaporated to dryness to obtain 578-1 as 3.5 g (10.5 mmol) of white solid (yield 54%). １ H NMR (400 MHz, CDCl ３ ) δ: 7.53 (dd, J=8.0, 1.2Hz, 1H), 7.41 (t, J=7.6Hz, 1H), 7.28 (d, J=8.0Hz, 2H), 7.02 (d, J=7.6Hz, 1 H), 6.88 (t, J=7.6Hz, 1H), 2.57 (sept, J=6.8Hz, 2H), 1.15 (d, J=6.8Hz, 6H), 1.07 (d, J=6.8Hz, 6H)

[0218]

[0219] (2) Synthesis of 578-2 2.3 g (6.9 mmol) of 578-1 was weighed out and 30 mL of methylene chloride was added to make a solution. 1.4 g (1.9 mL, 13.8 mmol) of triethylamine and 1.5 g (1.2 mL, 10.4 mmol) of benzoyl chloride were added to the solution while stirring, and the mixture was stirred at room temperature for 2 hours. 100 mL of distilled water was added to the resulting reaction mixture under open air and the mixture was separated. Next, 50 mL of ethyl acetate was added to the aqueous layer to extract and separate the soluble substances. This extraction and separation procedure was repeated twice. The collected organic layer was washed with 50 mL of saturated brine and then separated, and this washing was repeated twice. Sodium sulfate was added to the organic layer after separation and dried, and then the sodium sulfate was removed by filtration. The obtained filtrate was dried under reduced pressure, and the resulting yellow oil was purified by silica gel column chromatography (eluent: petroleum ether / ethyl acetate = changed from 50 / 1 to 20 / 1) to obtain 578-2 as 2.1 g of yellow solid (yield 70%). １ H NMR (400 MHz, CDCl ３ ) δ: 7.87 (d, J=7.2Hz, 2H), 7.70 (dd, J=7.2, 1.6Hz, 1H), 7.53 (t, J=7.2Hz, 1H), 7.37 (d, J=8.4Hz , 2H), 7.28-7.08 (m, 5H), 2.64 (sept, J = 6.8Hz, 2H), 1.16 (d, J = 6.8Hz, 6H), 1.04 (d, J = 6.8Hz, 6H)

[0220]

[0221] (3) Synthesis of 578-3 1.0 g (4.5 mmol) of compound A obtained in the same manner as in Synthesis Example 1 was weighed out, 25 mL of tetrahydrofuran was added, and the mixture was cooled to 0°C. 1.7 mL of BuLi (2.5 M tetrahydrofuran solution) was slowly added dropwise to the mixture while stirring. After the addition was complete, the mixture was heated to room temperature and stirred for 2 hours. Next, 830 mg (5.9 mmol) of methyl iodide was added to the resulting reaction solution while stirring. After the addition, the reaction solution was heated to room temperature and stirred for 18 hours. Then, 20 mL of aqueous sodium sulfite solution was added to the reaction solution at room temperature under open air and the mixture was separated. Next, 10 mL of ethyl acetate was added to the aqueous layer to extract and separate the soluble substances. This extraction and separation operation was repeated three times. The collected organic layer was dried with sodium sulfate, and then the sodium sulfate was removed by filtration. The resulting filtrate was evaporated to dryness to obtain 578-3. １ H NMR (400 MHz, CDCl ３ ) δ: 6.32 (s, 1H), 2.09 (s, 3H), 1.64 (s, 12H)

[0222]

[0223] (4) Synthesis of 578-4 Weigh out 0.5 g (2.1 mmol) of 578-3, add 3 mL of tetrahydrofuran under a nitrogen atmosphere, and cool the mixture to 0°C. Add 0.93 mL of BuLi (2.5 M tetrahydrofuran solution) to the mixture slowly dropwise while stirring. After the addition is complete, raise the temperature of the mixture to room temperature and stir for 3 hours. Next, cool the resulting reaction solution to -78°C and add 131 mg (0.95 mmol) of phosphorus trichloride while stirring. After the addition, raise the temperature of the reaction solution to room temperature and stir for 2 hours. Then, remove all volatile components from the reaction solution under reduced pressure to obtain 578-4.

[0224]

[0225] (5) Synthesis of 578-5 Weigh out 0.56 g (1.0 mmol) of the above 578-4, add 5 mL of tetrahydrofuran, and cool the mixture to 0°C. Add 59 mg (1.6 mmol) of lithium aluminum hydride solution to the mixture slowly dropwise while stirring. After the addition is complete, raise the temperature of the mixture to room temperature and stir for 12 hours. Next, cool the resulting reaction solution to 0°C, add 0.3 mL of 10% sodium hydroxide aqueous solution, and stir for 30 minutes to stop the reaction. Then, filter the mixture through Celite to remove the solid, and dry the filtrate under reduced pressure to obtain a white solid. Add 3 mL of distilled water to the obtained solid at room temperature under open air, then add 3 mL of methylene chloride to extract and separate the soluble substances. Repeat this extraction and separation procedure three times. Dry the collected organic layer over sodium sulfate, and then remove the sodium sulfate by filtration. Dry the obtained filtrate under reduced pressure to obtain a solid. The obtained solid was purified by silica gel column chromatography (eluent: petroleum ether / ethyl acetate = 10 / 1) to obtain 578-5 as 0.20 g (0.40 mmol) of a white solid (yield 40%). ３１ P { １ H} NMR (162MHz, CDCl ３ )δ:-127.3ppm(s)

[0226]

[0227] (6) Synthesis of 578-6 0.80 g (1.6 mmol) of 578-5, 0.77 g (1.8 mmol) of 578-2, 1.6 g (4.8 mmol) of cesium carbonate, and 171 mg (0.32 mmol) of DPEPhos were weighed out and 15 mL of dioxane was added at room temperature to make a solution. Pd ２ (dba) ３ 146 mg (0.16 mmol) of was added while stirring. After addition, the mixture was heated to 110°C and reacted for 16 hours. The resulting reaction solution was then cooled to room temperature, and the solid was removed by passing it through Celite. The resulting filtrate was dried under reduced pressure to obtain a solid. The obtained solid was purified by silica gel column chromatography (eluent: petroleum ether / methylene chloride = changed from 50 / 1 to 20 / 1) to obtain 0.80 g of yellow solid 578-6. The purity was 78%.３１ P { １ H} NMR (162MHz, CDCl ３ ) δ: -58.3ppm(s)

[0228]

[0229] (7) Synthesis of B-578 0.5 g (0.58 mmol) of the above 578-6 was weighed out and 5 mL of tetrahydrofuran was added at room temperature to make a solution. 0.78 g (14.6 mmol) of sodium methoxide in 8 mL of methanol was added dropwise to the solution while stirring. After the addition was complete, the solution was heated to 60°C and reacted for 40 hours. The resulting reaction mixture was then cooled to room temperature and filtered through Celite to remove solids. The resulting filtrate was dried under reduced pressure to obtain a solid. The obtained solid was dissolved in 5 mL of ethyl acetate. The solution was washed with 10 mL of saturated ammonium chloride aqueous solution, and the soluble matter was extracted from the aqueous layer three times with 10 mL of ethyl acetate. The collected organic layer was dried over sodium sulfate, and the sodium sulfate was removed by filtration. The resulting filtrate was dried under reduced pressure to obtain a solid. The obtained solid was purified by silica gel column chromatography (eluent: petroleum ether / methylene chloride = changed from 50 / 1 to 10 / 1) to obtain B-578 as 0.10 g (0.13 mmol) of white solid (yield 23%). １ H NMR (400 MHz, CDCl ３ ) δ: 7.62 (t, J = 7.6 Hz, 1H), 7.37 (t, J = 7.6 Hz, 1H), 7.23 (d, J = 7.6 Hz, 1H), 6.98 (dd, J = 7.2, 1.6 Hz, 1H), 6.82 (t, J = 7.6 Hz) , 1H), 5.86 (br, 1H), 2.62 (sept, J = 6.8Hz, 2H), 2.08 (s, 6H), 1.49 (s, 24H), 1.09 (d, J = 6.8Hz, 2H), 1.04 (d, J = 6.8Hz, 2H) ３１ P { １ H} NMR (162MHz, CDCl ３ ) δ: -66.5ppm(s)

[0230]

[0231] (Synthesis Example 8: Synthesis of B-577) (1) Synthesis of 577-1 0.50 g (1.9 mmol) of 2-iodo-1,3-dimethoxybenzene was weighed into a Schlenk tube, and 3.0 mL of tetrahydrofuran was added under a nitrogen atmosphere. The mixture was cooled to 0°C. 0.99 mL (2.0 M) of i-PrMgCl was added to the mixture and stirred at room temperature for 2.5 hours. The resulting reaction solution was then cooled to -78°C, and 0.50 mL (5.7 mmol) of phosphorus trichloride was quickly added to the reaction solution. After the addition, the mixture was heated to room temperature and stirred for 1 hour. All volatile components were removed from the reaction solution under reduced pressure to obtain 577-1 as 0.45 g of yellow solid. 577-1 was used as is in the next step.

[0232]

[0233] (2) Synthesis of 577-2: 0.56 g (1.9 mmol) of 2'-(methoxymethoxy)-2,6-bis(1-methylethyl)-1,1'-biphenyl was weighed into a Schlenk tube, and 3.0 mL of tetrahydrofuran was added. The mixture was cooled to 0°C. 0.83 mL of BuLi (2.5 M solution) was added to the mixture, and the mixture was stirred at 0°C for 1.5 hours. The resulting reaction solution was cooled to -78°C, and the above 577-1 (0.45 g, 1.9 mmol) in tetrahydrofuran (3.0 mL) solution was added. After addition, the mixture was heated to room temperature and stirred for 2 hours. 577-2 was obtained as 0.92 g of yellow solution (6.0 mL). 577-2 was used as is in the next step.

[0234]

[0235] (3) Synthesis of 577-3: 0.61 g (2.8 mmol) of compound A, obtained in the same manner as in Synthesis Example 1, was weighed into a Schlenk tube, and 4.0 mL of tetrahydrofuran was added under an argon atmosphere. The mixture was cooled to 0°C. 1.2 mL (2.5 M) of BuLi was added to the mixture, and the mixture was stirred at room temperature for 2 hours. The reaction solution was cooled to -78°C under an argon atmosphere, and 6.0 mL of the above 577-2 (0.92 g, 1.8 mmol) tetrahydrofuran solution was added. After addition, the temperature was raised to room temperature and the mixture was stirred for 12 hours. All volatile components were removed from the reaction solution under reduced pressure, and the resulting crude product was purified by silica gel column chromatography (acidic silica gel, developing solvent: petroleum ether / ethyl acetate = 8 / 1) to obtain 577-3 as 0.30 g of white solid. ３１ P { １ H} NMR (162MHz, CDCl ３ ) δ: -54.4ppm(s)

[0236]

[0237] (4) Synthesis of B-577: 2.0 g (2.9 mmol) of the above 577-3 was weighed into a Schlenk tube and 40 mL of 4.0 M dioxane hydrochloride solution was added. The mixture was stirred at room temperature for 2 hours. The resulting mixture was washed with 200 mL of 1.0 M aqueous sodium hydroxide solution, and then 50 mL of methylene chloride was added to extract the soluble matter. The collected organic layer was dried over sodium sulfate, and the sodium sulfate was removed by filtration. The filtrate was evaporated to dryness, and the resulting crude product was purified by silica gel column chromatography (acidic silica gel, developing solvent: petroleum ether / ethyl acetate = 10 / 1) to obtain B-577 as 1.0 g of yellow solid (yield 53%). ３１ The purity of B-577, as determined by P NMR, was over 99%. １ H NMR (400 MHz, CDCl ３) δ: 7.44 (ddd, J=10.8, 7.2, 1.6Hz, 1H), 7.34 (d, J=7.2Hz, 1H), 7.26-7.18 (m, 3H), 6.94 (dd, J=8.0, 1.6Hz, 1H), 6.83 (t, J=8.0Hz, 1H), 6.45 (dd, J=8.0, 2.8Hz, 1H2H) , 6.31 (s, 1H), 5.76 (s, 1H), 3.59 (s, 6H), 2.65 (sept, J=6.8Hz, 1H), 2.60 (sept, J= 6.8Hz, 1H), 1.52 (s, 6H), 1.45 (s, 6H), 1.07 (d, J = 6.8Hz, 6H), 1.03 (d, J = 6.8Hz, 6H) ３１ P { １ H} NMR (162MHz, CDCl ３ )δ:-63.1ppm(s)

[0238]

[0239] (Synthesis Example 9: Synthesis of B-579) (1) Synthesis of 579-1 Weigh 0.50 g (1.4 mmol) of 2'(methoxymethoxy)-2,6-diphenyl-1,1'-biphenyl into a Schlenk tube, add 3.0 mL of tetrahydrofuran, and cool the mixture to 0°C. Add 0.60 mL of BuLi (2.5 M tetrahydrofuran solution) to this mixture, then raise the temperature to room temperature and stir for 1.5 hours. Cool the resulting reaction solution to -78°C, then add 0.36 mL (4.1 mmol) of phosphorus trichloride. After addition, raise the temperature to room temperature and stir for 1 hour. Then, remove all volatile components from the reaction solution under reduced pressure to obtain 579-1 as 0.63 g of a yellow gum-like solid. 579-1 was used as is in the next step.

[0240]

[0241] (2) Synthesis of 579-2: 0.72 g (3.2 mmol) of compound A, obtained in the same manner as in Synthesis Example 1, was weighed into a Schlenk tube, and 4.0 mL of tetrahydrofuran was added. The mixture was cooled to 0°C. 1.4 mL of BuLi (2.5 M tetrahydrofuran solution) was slowly added dropwise to the mixture, and then the temperature was raised to room temperature and the mixture was stirred for 2 hours. The resulting reaction solution was cooled to -78°C. 0.63 g (1.4 mmol) of the above 579-1 was weighed into another Schlenk tube, and 4.0 mL of tetrahydrofuran was added. The mixture was slowly added dropwise to the above reaction solution at -78°C. After the addition was complete, the temperature was raised to room temperature and the mixture was stirred for 14 hours. All volatile components were removed from the resulting reaction solution under reduced pressure. The obtained solid was purified by silica gel column chromatography under air (eluent: petroleum ether / ethyl acetate = 10 / 1) to obtain 0.15 g of white solid 579-2. ３１ P { １ H} NMR (162MHz, CDCl ３ ) δ: -57.5ppm(s)

[0242]

[0243] (3) Synthesis of B-579: 0.10 g (0.12 mmol) of the above 579-2 was weighed into a Schlenk tube and 10 mL of 4.0 M dioxane hydrochloride solution was added under an argon atmosphere. The mixture was stirred at room temperature for 0.5 hours. The resulting mixture was washed with 10 mL of aqueous sodium hydroxide solution and 5.0 mL of methylene chloride was added to extract the organic layer soluble matter. The collected organic layer was dried over sodium sulfate and the sodium sulfate was removed by filtration. The filtrate was evaporated to dryness and the resulting solid was purified by preparative thin-layer chromatography to obtain B-579 as 0.050 g of white solid (yield 53%). ３１ The purity of B-579, as determined by P NMR, was 89%. １ H NMR (400 MHz, CDCl ３) δ: 7.46-7.37 (m, 1H), 7.37-7.31 (m, 2H), 7.24 (t, J=6.0Hz, 1H), 7.13-7.05 (m, 4H), 7.00-6.90 (m, 6H), 6. 57 (d, J=6.0Hz, 1H), 6.34 (t, J=6.0Hz, 1H), 6.24 (s, 2H), 5.96 (d, J=7.2Hz, 1H), 1.38 (s, 12H), 1.30 (s, 12H) ３１ P { １ H} NMR (162MHz, CDCl ３ ) δ: -67.8ppm(s)

[0244]

[0245] (Synthesis Example 10: Synthesis of B-588) (1) Synthesis of 588-1 207 mg (1.1 mmol) of copper iodide, 248 mg (2.2 mmol) of (1R,2R)-cyclohexane-1,2-diamine, and 4.6 g (22 mmol) of tripotassium phosphate were weighed into a Schlenk tube, and 15 mL of dioxane was added. The mixture was stirred at room temperature for 5 minutes. 2.0 g (12 mmol) of carbazole and 2.4 g (11 mmol) of 1-bromo-2-(methoxymethoxy)bencene were added to the resulting reaction solution, and the temperature was raised to 110°C and stirred for 16 hours. The reaction solution was returned to room temperature, diluted with methylene chloride (20 mL), and all volatile components were removed under reduced pressure. The resulting solid was diluted with acetone (20 mL), and the solid obtained by filtration was dried under reduced pressure. 1.6 g of gray solid was obtained as 588-1. 588-1 was used as is in the next step. １ H NMR (400 MHz, CDCl ３ ) δ: 8.07 (d, J=7.6Hz, 2H), 7.47-7.28 (m, 5H), 7.25-7.05 (m, 5H), 4.89 (s, 2H), 3.11 (s, 3H)

[0246]

[0247] (2) Synthesis of 588-2 Weighed out 0.50 g (1.7 mmol) of the above 588-1, added 5.0 mL of tetrahydrofuran, and cooled the mixture to 0°C. Slowly added 0.79 mL of BuLi (2.5 M tetrahydrofuran solution) dropwise to this mixture, then raised the temperature to room temperature and stirred for 2 hours. After that, the resulting reaction solution was cooled to -78°C, and 0.81 g (2.5 mmol) of 1,2-dibromo-1,1,2,2-tetrachloroethane in a tetrahydrofuran solution (8.0 mL) was added. After the addition, raised the temperature to room temperature and stirred for 12 hours. To stop the reaction, 5.0 mL of water was added to the resulting reaction solution at room temperature under open air, and the organic layer soluble matter was extracted twice with 10 mL of ethyl acetate and twice with 10 mL of methylene chloride. The collected organic layer was dried over sodium sulfate, and then the sodium sulfate was removed by filtration. The filtrate was evaporated to dryness, and the resulting solid was purified under air by silica gel chromatography (developing solvent: ethyl acetate / petroleum ether = changed from 0 / 1 to 0.06 / 0.94) to obtain 0.25 g of yellow oil, 588-2. 588-2 was used directly in the next step. １ H NMR (400 MHz, CDCl ３ ) δ: 8.13 (d, J=7.6Hz, 2H), 7.76 (dd, J=8.4, 1.6Hz, 1H), 7.50-7.38 (m, 3H), 7.36-7.15 (m, 5H), 4.53 (s, 2H), 2.70 (s, 3H)

[0248]

[0249] (3) Synthesis of 588-3 4.8 g (13 mmol) of 588-2 was weighed out, 50 mL of hydrochloric acid / ethyl acetate solution was added, and the mixture was stirred at room temperature for 12 hours. The pH of the mixture was adjusted to 6.5-7.0 with saturated sodium bicarbonate aqueous solution, and the organic layer soluble matter was extracted twice with 30 mL of methylene chloride. The collected organic layer was dried with sodium sulfate, and the sodium sulfate was removed by filtration. The filtrate was evaporated to dryness to obtain 588-3 as a 4.1 g white solid. 588-3 was used as is in the next step.

[0250]

[0251] (4) In a Schlenk tube of synthesis 588-4, the above solution of 602-1 (5.7 g, 11.2 mmol) dissolved in 50 mL of tetrahydrofuran was placed and cooled to 0°C. 0.64 g (11.2 mmol) of lithium aluminum hydride (LAH) was slowly added. After the addition was complete, the mixture was heated to 20°C and stirred for 12 hours to obtain a brown suspension. The mixture was cooled to 0°C, and 0.6 mL of water was added to stop the reaction. Then, 0.6 mL of 10% aqueous sodium hydroxide solution was added, followed by 1.8 mL of water. The mixture was stirred at room temperature for 30 minutes, then filtered, and the resulting filtrate was evaporated to dryness to obtain a white solid. 30 mL of water was added to this white solid, and the soluble substances were extracted with 30 mL of methylene chloride. This extraction procedure was performed three times. The collected organic layer was dried over sodium sulfate, and the sodium sulfate was removed by filtration. The filtrate was then evaporated to dryness to obtain a yellow solid. The obtained solid was purified under air by silica gel column chromatography (eluent: petroleum ether / ethyl acetate = 20 / 1) to obtain 588-4 as 3.5 g of white solid. １ H NMR (400 MHz, CDCl ３ ) δ: 6.27 (s, 1H), 5.16 (d, J=188.0Hz, 1H), 1.59 (s, 24H) ３１ P { １ H} NMR (162MHz, CDCl ３ )δ:-126.8ppm(s)

[0252]

[0253] (5) In a Schlenk tube for the synthesis of B-588, weigh out 2.0 g (5.9 mmol) of 588-3, 2.5 g (5.3 mmol) of 588-4, 7.7 g (24 mmol) of cesium carbonate, 0.68 g (0.59 mmol) of tetrakis(triphenylphosphine)palladium, and 0.64 g (1.2 mmol) of [2-(2-diphenylphosphanylphenoxy)phenyl]diphenylphosphine, and add 20 mL of dioxane. The mixture was heated to 100°C and stirred for 18 hours. After that, the reaction solution was cooled to 0°C, and 50 mL of water was added to stop the reaction. The organic layer soluble matter was extracted three times with 50 mL of ethyl acetate. The collected organic layer was dried over sodium sulfate, and the sodium sulfate was removed by filtration. The filtrate was evaporated to dryness, and the resulting solid was purified under air by silica gel column chromatography (eluent: petroleum ether / ethyl acetate = changed from 20 / 1 to 10 / 1) to obtain 1.4 g of B-588 as a white solid (yield 31%). ３１ The purity of B-575, as determined by P NMR, was over 99%. １ H NMR (400 MHz, CDCl ３ ) δ: 8.15 (d, J = 7.6 Hz, 2H), 7.59 (t, J = 6.0 Hz, 1H), 7.44-7.35 (m, 3H), 7.34-7.20 (m , 4H), 7.03 (t, J=6.0Hz, 1H), 6.34 (s, 2H), 5.83 (s, 1H), 1.50 (s, 12H), 1.49 (s, 12H) ３１ P { １ H} NMR (162MHz, CDCl ３ )δ:-61.0ppm(s)

[0254]

[0255] (Synthesis Example 11: Synthesis of B-591) (1) Synthesis of 591-1 10 g (0.062 mol) of 1,3-dihydroxynaphthalene was weighed into a Schlenk tube and 100 mL of acetone was added. The mixture was cooled to 0°C, and 26 g (0.19 mol) of potassium carbonate was added and stirred at 0°C for 0.5 hours. 24 mL (0.25 mol) of dimethyl sulfate was slowly added dropwise to the resulting reaction solution at 0°C. After the addition was complete, the reaction solution was heated to 50°C and stirred for 15 hours. The reaction solution was cooled to room temperature, and the solid obtained by filtration was washed three times with 50 mL of methylene chloride. The filtrate was evaporated to dryness, and the resulting crude product was purified under air by silica gel column chromatography (developing solvent: petroleum ether / ethyl acetate = changed from 20 / 1 to 10 / 1) to obtain 591-1 as 10 g of yellow oil. １ H NMR (400 MHz, CDCl ３ ) δ: 8.19 (d, J = 8.4 Hz, 1H), 7.72 (d, J = 8.4 Hz, 1H), 7.47 (t, J = 6.8 Hz, 1H), 7 .36 (t, J=6.8Hz, 1H), 6.77 (s, 1H), 6.54 (s, 1H), 4.00 (s, 3H), 3.94 (s, 3H)

[0256]

[0257] (2) Synthesis of 591-2: 1.0 g (3.4 mmol) of 2'-(methoxymethoxy)-2,6-bis(1-methylethyl)-1,1'-biphenyl was weighed into a Schlenk tube, 20 mL of tetrahydrofuran was added, and the mixture was cooled to 0°C. 1.5 mL of BuLi (2.5 M tetrahydrofuran solution) was added to the mixture, and the temperature was raised to room temperature and stirred for 2 hours. The resulting reaction solution was cooled to -78°C, and 0.88 mL (10 mmol) of phosphorus trichloride was quickly added. After adding the phosphorus trichloride, the reaction solution was raised to room temperature and stirred for 1 hour. Then, all volatile components were removed under reduced pressure to obtain 591-2 as 1.3 g of a yellow gum-like solid. 591-2 was used as is in the next step.

[0258]

[0259] (3) Synthesis of 591-3: 0.63 g (3.4 mmol) of 591-1 was weighed into a Schlenk tube, and 5 mL of tetrahydrofuran was added under an argon atmosphere. The mixture was cooled to 0°C. 1.5 mL of BuLi (2.5 M tetrahydrofuran solution) was added to this mixture, and the mixture was stirred at 0°C for 0.5 hours. The resulting mixture was then heated to room temperature and stirred for a further 2 hours to obtain the reaction solution. 1.3 g (3.4 mmol) of 591-2 was weighed into another Schlenk tube, and 10 mL of tetrahydrofuran was added. The mixture was cooled to -78°C, and the reaction solution was slowly added dropwise. After the addition was complete, the mixture was heated to room temperature and stirred for 2 hours. 591-3 was obtained as 1.9 g (15 mL) of yellow solution. 591-3 was used as is in the next step.

[0260]

[0261] (4) Synthesis of 591-4: 0.90 g (4.0 mmol) of compound A, obtained in the same manner as in Synthesis Example 1, was weighed into a Schlenk tube, 5.0 mL of tetrahydrofuran was added, and the mixture was cooled to 0°C. 1.8 mL of BuLi (2.5 M tetrahydrofuran solution) was added to the mixture, and the temperature was raised to room temperature and stirred for 2 hours. The mixture was cooled to -78°C, and 15 mL of the tetrahydrofuran solution of 591-3 (1.9 g) was added. After the addition, the mixture was raised to room temperature and stirred for 12 hours. The mixture was cooled to 0°C, 5.0 mL of water was added to stop the reaction, and all volatile components were removed under reduced pressure. The resulting yellow gum-like solid was purified under air by silica gel column chromatography (developing solvent: petroleum ether / ethyl acetate = 20 / 1) to obtain 1.2 g of white solid 591-4. ３１ P { １ H} NMR (162MHz, CDCl ３ ) δ: -51.4ppm(s)

[0262]

[0263] (5) Synthesis of B-591: 0.30 g (0.41 mmol) of the above 591-4 was weighed into a Schlenk tube, and 0.20 mL of 2.0 M dioxane hydrochloride solution was added under an argon atmosphere. The mixture was stirred at room temperature for 2 hours. The resulting mixture was washed twice with 30 mL of saturated sodium bicarbonate aqueous solution, and then methylene chloride was added to extract the organic layer soluble matter. After liquid-liquid separation, the organic layer was dried over sodium sulfate, and the sodium sulfate was removed by filtration. The filtrate was evaporated to dryness, and the resulting solid was purified under air by silica gel column chromatography (eluent: petroleum ether / ethyl acetate = 20 / 1) to obtain 0.12 g of white solid B-591 (yield 43%). ３１ The purity of B-591, as determined by P NMR, was over 99%. １ H NMR (400 MHz, CDCl ３ ) δ: 7.97 (d, J = 6.8 Hz, 1H), 7.68 (d, J = 6.8 Hz, 1H), 7.50-7.40 (m, 2H), 7.38-7.29 (m, 2H), 7.25- 7.18 (m, 2H), 6.97 (d, J = 6.4Hz, 1H), 6.86 (t, J = 5.2Hz, 1H), 6.80 (s, 1H), 6.33 (s, 1H), 5.47 (s, 1H), 3.79 (s, 3H), 3.62 (s, 3H), 2.69 (sept, J = 5.6Hz, 1H), 2.58 (sept, J = 5.6Hz, 1H), 1.50 (s, 6 H), 1.38 (s, 6H), 1.09 (d, J = 5.6Hz, 3H), 1.08 (d, J = 5.6Hz, 3H), 1.04 (d, J = 5.6Hz, 3H), 0.95 (3H) ３１ P { １ H} NMR (162MHz, CDCl ３ ) δ: -57.3ppm(s)

[0264]

[0265] (Synthesis Example 12: Synthesis of B-593) (1) Synthesis of 593-1 In a Schlenk tube, add 8.0 g (30 mmol) of 2-bromo-3-methoxymethoxynaphthalene, 9.3 g (45 mmol) of 2,6-diisopropylphenylboronic acid, and Pd ２ (dba) ３2.7g (3.0 mmol) of [ingredient], 2.5g (6.0 mmol) of SPhos, K ３ PO ４ 13 g (60 mmol) of the substance was weighed out, and 80 mL of toluene was added. The mixture was heated to 110°C and stirred for 48 hours. The reaction solution was cooled to room temperature, and the filtrate obtained by Celite filtration was evaporated to dryness. 100 mL of ethyl acetate was added to extract the soluble substances. This extraction procedure was repeated three times. The collected organic layer was dried over sodium sulfate, and the sodium sulfate was removed by filtration. The filtrate was evaporated to dryness, and the resulting crude product was purified by silica gel column chromatography (eluent: petroleum ether) under air to obtain yellow oil 593-1. １ H NMR (400 MHz, CDCl ３ ) δ: 7.83 (d, J = 8.0 Hz, 1H), 7.83-7.75 (m, 2H), 7.61 (s, 1H), 7.55 (s, 1H), 7.53-7.34 (m, 2H), 7.25 (s, 2 H), 5.22 (s, 2H), 3.41 (s, 3H), 2.60 (sept, J = 6.8Hz, 2H), 1.11 (d, J = 6.8Hz, 6H), 1.08 (d, J = 6.8Hz, 6H)

[0266]

[0267] (2) Weigh 1.0 g (2.9 mmol) of the above 593-1 into the synthetic Schlenk tube of 593-2, add 10 mL of tetrahydrofuran, and cool the mixture to 0°C. Add 1.4 mL of BuLi (2.5 M tetrahydrofuran solution) to this mixture. After the addition, raise the temperature of the mixture to room temperature and stir for 3 hours. Cool the mixture to -78°C and add 10 mL of tetrahydrofuran solution of 1.1 g (4.3 mmol) of iodine. After the addition, raise the temperature of the mixture to room temperature and stir for 16 hours. Add 30 mL of water to the mixture to stop the reaction. Then, add 50 mL of ethyl acetate to extract the soluble matter. This extraction procedure was repeated three times. After that, add 50 mL of methylene chloride to extract the soluble matter. This extraction procedure was repeated three times. The collected organic layer was dried over sodium sulfate, and then the sodium sulfate was removed by filtration. The filtrate was evaporated to dryness, and the resulting crude product was purified under air by silica gel column chromatography (eluent: petroleum ether / ethyl acetate = 100 / 1) to obtain 593-2 as yellow oil. １ H NMR (400 MHz, CDCl ３ ) δ: 8.25 (d, J=8.4Hz, 1H), 7.76 (d, J=8.0Hz, 1H), 7.68-7.27 (m, 6H), 4.81 (s, 2H), 3 .04 (s, 3H), 2.59 (sept, J=6.8Hz, 2H), 1.23 (d, J=6.8Hz, 6H), 1.06 (d, J=6.8Hz, 6H)

[0268]

[0269] (3) In a Schlenk tube of synthesis 593-3, weigh out 1.8 g (3.8 mmol) of 593-2, 1.8 g (3.8 mmol) of 588-4 obtained in the same manner as in Synthesis Example 10, 3.7 g (11 mmol) of cesium carbonate, and 0.41 g (0.76 mmol) of DPEPhos, and add 20 mL of dioxane. Add 0.44 g (0.38 mmol) of tetrakis(triphenylphosphine)palladium to this mixture, and then stir the mixture at 110°C for 20 hours. Add 100 mL of water to the resulting reaction solution at room temperature under open air, and extract the organic layer soluble matter with 100 mL of ethyl acetate. After liquid-liquid separation, wash the organic layer with 50 mL of saturated brine, dry with sodium sulfate, and then remove sodium sulfate by filtration. The filtrate was evaporated to dryness, and the resulting crude product was purified under air by silica gel column chromatography (eluent: petroleum ether / ethyl acetate = changed from 20 / 1 to 10 / 1) to obtain 593-3 as 2.2 g of yellow solid. ３１ P { １ H} NMR (162MHz, CDCl ３ ) δ: -53.8ppm(s)

[0270]

[0271] (4) Synthesis of B-593: 2.2 g (2.7 mmol) of the above 593-3 was weighed into a Schlenk tube, 9.0 mL of methylene chloride and 3.0 mL of trifluoroacetic acid were added, and the mixture was stirred at room temperature for 4 hours. 100 mL of methylene chloride was added to the resulting mixture, and the organic layer was washed four times with 30 mL of water. After liquid-liquid separation, the organic layer was dried over sodium sulfate, and the sodium sulfate was removed by filtration. The filtrate was evaporated to dryness, and the resulting solid was purified by silica gel column chromatography (eluent: petroleum ether / ethyl acetate = 30 / 1) to obtain 0.86 g of B-593 as a white solid (yield 41%). ３１ The purity of B-593, as determined by P NMR, was over 99%. １ H NMR (400 MHz, CDCl ３) δ: 8.05 (d, J = 5.2 Hz, 1H), 7.64-7.58 (m, 1H), 7.42 (t, J = 7.6Hz, 1H), 7.27 (d, J = 7.6Hz, 2H), 7.19-7.14 (m, 2H), 7.04-6.97 (m, 1H) ), 6.26 (s, 2H), 5.33 (s, 1H), 2.32 (sept, J = 7.2Hz, 2H), 1.40 (s, 12H), 1.34 (s, 12H), 0.93 (d, J = 7.2Hz, 6H), 0.82 (d, J = 7.2Hz, 6H) ３１ P { １ H} NMR (162MHz, CDCl ３ ) δ: -60.3ppm(s)

[0272]

[0273] (Synthesis Example 13: Synthesis of B-606) (1) Synthesis of 606-1 10 g (70 mmol) of 1,2,4,5-benzenetetraol was weighed into a Schlenk tube and 100 mL of dichloroethane was added. 16 mL (141 mmol) of acetophenone and 17 mL (141 mmol) of dichloro(dimethyl)silane were added to this mixture, and the mixture was heated to 80°C and stirred for 24 hours. 200 mL of water was added to the resulting reaction solution, and 100 mL of ethyl acetate was added to extract the organic layer soluble matter three times. The collected organic layer was dried over sodium sulfate, and the sodium sulfate was removed by filtration. The filtrate was evaporated to dryness, and the resulting crude product was purified under air by silica gel column chromatography (developing solvent: petroleum ether / ethyl acetate = 20 / 1). The obtained compound was further washed with petroleum ether / ethyl acetate = 10 / 1 to obtain 4.3 g of 606-1 as a white solid. １ H NMR (400 MHz, CDCl ３ ) δ: 7.58 (d, J=5.2Hz, 2H), 7.54 (d, J=5.2Hz, 2H), 7.43-7.30 (m, 6H), 6.44 (s, 2H), 1.95 (s, 3H), 1.91 (s, 3H)

[0274]

[0275] (2) Synthesis of 606-2: 1.8 g (5.1 mmol) of 606-1 was weighed into a Schlenk tube, 20 mL of tetrahydrofuran was added, and the mixture was cooled to 0°C. 2.3 mL of BuLi (2.5 M tetrahydrofuran solution) was slowly added dropwise to the mixture, and then the temperature was raised to room temperature and the mixture was stirred for 2 hours. The resulting reaction solution was cooled to -78°C, and 0.20 mL (2.3 mmol) of phosphorus trichloride was added. The reaction solution was raised to room temperature and stirred for 1 hour. All volatile components were removed from the reaction solution under reduced pressure. 606-2 was obtained as 1.7 g of yellow solid. 606-2 was used as is in the next step.

[0276]

[0277] (3) Synthesis of 606-3: 1.7 g (2.3 mmol) of 606-2 was weighed into a Schlenk tube and 20 mL of tetrahydrofuran was added. After the mixture was cooled to 0°C, 1.4 mL of lithium aluminum hydride (2.5 M solution) was slowly added dropwise to the mixture. After the addition was complete, the mixture was heated to room temperature and stirred for 12 hours. The resulting reaction solution was cooled to 0°C and 0.13 mL of water was added to the reaction solution to stop the reaction. Then, 0.13 mL of 10% sodium hydroxide aqueous solution and 0.39 mL of water were added to the reaction solution and the mixture was heated to room temperature and stirred for 30 minutes. The mixture was filtered and all volatile components were removed from the filtrate under reduced pressure. The obtained crude product was purified under air by silica gel column chromatography (acidic silica gel, developing solvent: petroleum ether / ethyl acetate = changed from 20 / 1 to 10 / 1) to obtain 606-3 as 1.1 g of white solid.

[0278]

[0279] (4) Synthesis of 606-4 Weigh 2.8 g, 6.7 mmol of 605-4 obtained in the same manner as in Synthesis Example 4 into a Schlenk tube and dissolve it in 10 mL of methylene chloride. The solution was cooled to 0°C. 50 mL of 4 M ethyl hydrogen chloride solution was added to the solution, and after raising the temperature to 25°C, the mixture was stirred for 5 hours to obtain a yellow solution. All volatile components were removed from the reaction mixture under reduced pressure. 50 mL of saturated sodium bicarbonate aqueous solution was added to the obtained solid, and the soluble substances were extracted with 50 mL of methylene chloride. This extraction procedure was repeated three times. The collected organic layer was evaporated to dryness under reduced pressure to obtain 2.6 g of 606-4. 606-4 was used directly in the next step.

[0280]

[0281] (5) Synthesize 606-5. 3 g (7.9 mmol) of the above 606-4 was weighed into a Schlenk tube, then 40 mL of methylene chloride, 2.1 mL (14.2 mmol) of diazabicycloundecene, and 0.1 g (0.79 mmol) of DMAP were added, and the mixture was stirred at room temperature for 1 hour. Then 2.5 mL (11.8 mmol) of triisopropylsilyl chloride was added to the mixture, and the mixture was stirred for 11 hours to obtain a yellow suspension. 250 mL of 1 M hydrochloric acid was added to the obtained mixture, and the mixture was stirred at room temperature for 1 hour, after which the soluble substances were extracted with 250 mL of methylene chloride. This extraction procedure was repeated three times. The collected organic layer was dried over sodium sulfate, and the sodium sulfate was removed by filtration. The filtrate was evaporated to dryness, and the obtained crude product was purified by silica gel column chromatography (eluent: petroleum ether) under air to obtain 3.3 g of yellow solid 606-5.

[0282]

[0283] (6) Synthesis of 606-6: 1.0 g (1.9 mmol) of 606-5, 1.0 g (1.4 mmol) of 606-3, 0.15 g (0.28 mmol) of DPEPhos, 1.8 g (5.5 mmol) of cesium carbonate, and 31 mg (0.14 mmol) of palladium acetate were weighed into a Schlenk tube, and 20 mL of dioxane was added. The mixture was heated to 110°C and stirred for 48 hours. 100 mL of water was added to the resulting reaction solution and cooled, and then 100 mL of ethyl acetate was added to extract the organic layer soluble matter. After liquid-liquid separation, the organic layer was washed twice with 20 mL of saturated brine, dried over sodium sulfate, and then the sodium sulfate was removed by filtration. The filtrate was evaporated to dryness, and the resulting crude product was purified under air by silica gel column chromatography (developing solvent: petroleum ether / ethyl acetate = 10 / 1) to obtain 606-6 as a yellow solid.

[0284]

[0285] (7) Synthesis of B-606: 1.5 g (1.3 mmol) of the above 606-6 was weighed into a Schlenk tube, 10 mL of tetrahydrofuran and 2.0 mL of tetrabutylammonium fluoride (1 M) were added, and the mixture was stirred at room temperature for 2 hours. 50 mL of water was added to the resulting reaction solution, and then 50 mL of ethyl acetate was added to extract the organic layer soluble matter. After liquid-liquid separation, the organic layer was washed twice with 20 mL of saturated brine, dried over sodium sulfate, and then the sodium sulfate was removed by filtration. The filtrate was evaporated to dryness, and the resulting crude product was purified under air by silica gel column chromatography (eluent: petroleum ether / ethyl acetate = 10 / 1) to obtain 0.84 g of a yellow solid, which is a mixture of diastereoisomers of B-606 (yield 65%). ３１ P { １ H} NMR (162MHz, CDCl ３ δ: -64.5 ppm(s), -65.3 ppm(s), -65.5 ppm(s), -65.9 ppm(s), -66.5 ppm(s) (Composition ratio of each component: 12 / 37 / 20 / 25 / 6)

[0286]

[0287] (Synthesis Example 14: Synthesis of B-609) (1) Synthesis of 609-1 0.70 g (1.9 mmol) of 2'(methoxymethoxy)-2,6-diphenyl-1,1'-biphenyl was weighed into a Schlenk tube and 10 mL of tetrahydrofuran was added. The mixture was cooled to 0°C, and 0.84 mL of BuLi (2.5 M tetrahydrofuran solution) was added to the mixture. The mixture was then heated to room temperature and stirred for 2 hours. The resulting reaction solution was cooled to -78°C, and 0.50 mL (5.7 mmol) of phosphorus trichloride was quickly added to the reaction solution. After the addition, the reaction solution was heated to room temperature and stirred for 1 hour. All volatile components were removed from the reaction solution under reduced pressure. 0.89 g of a white gum-like solid was obtained as 609-1. 609-1 was used as is in the next step.

[0288]

[0289] (2) Synthesis of 609-2 609-2 was obtained as 10 g of yellow oil in the same manner as in 591-1 of Synthesis Example 11.

[0290]

[0291] (3) Synthesis of 609-3: 0.36 g (1.9 mmol) of 609-2 was weighed into a Schlenk tube, and 10 mL of tetrahydrofuran was added under an argon atmosphere. The mixture was cooled to 0°C. 0.84 mL of BuLi (2.5 M tetrahydrofuran solution) was added to this mixture, and the mixture was stirred at 0°C for 0.5 hours, and then stirred at room temperature for 2 hours to obtain the reaction solution. 0.89 g (1.9 mmol) of 609-1 was weighed into another Schlenk tube, and 5.0 mL of tetrahydrofuran was added. The mixture was cooled to -78°C, and the reaction solution was slowly added dropwise to the mixture. After the addition was complete, the mixture was heated to room temperature and stirred for 2 hours. 609-3 was obtained as 1.2 g (15 mL) of yellow solution. 609-3 was used as is in the next step.

[0292]

[0293] (4) Synthesis of 609-4 0.64 g (2.9 mmol) of compound A obtained in the same manner as in Synthesis Example 1 was weighed out, 20 mL of tetrahydrofuran was added, and the mixture was cooled to 0°C. 1.2 mL of BuLi (2.5 M tetrahydrofuran solution) was slowly added dropwise to the mixture, and the mixture was then heated to room temperature and stirred for 2 hours. The mixture was cooled to -78°C under a nitrogen atmosphere, and 15 mL of the above 609-3 (1.2 g) tetrahydrofuran solution was added to the mixture, and the mixture was then heated to room temperature and stirred for 12 hours. The mixture was cooled to 0°C, 5.0 mL of water was added to stop the reaction, and all volatile components were removed from the reaction solution under reduced pressure. The resulting yellow gum-like solid was purified by silica gel column chromatography under air (developing solvent: petroleum ether / ethyl acetate = 20 / 1) to obtain 0.40 g of white solid 609-4. ３１ P { １ H} NMR (162MHz, CDCl ３ ) δ: -53.7ppm(s)

[0294]

[0295] (5) Synthesis of B-609: 2.2 g (2.7 mmol) of the above 609-4 was weighed into a Schlenk tube, and 20 mL of 2.0 M dioxane hydrochloride solution was added under an argon atmosphere. The mixture was stirred at room temperature for 1 hour. The resulting mixture was washed with 100 mL of aqueous sodium bicarbonate solution, and 50 mL of methylene chloride was added to extract the organic layer soluble matter. After liquid-liquid separation, the organic layer was dried over sodium sulfate, and the sodium sulfate was removed by filtration. The filtrate was evaporated to dryness, and the resulting solid was purified by silica gel column chromatography (eluent: petroleum ether / ethyl acetate = 20 / 1) to obtain 0.75 g of B-609 as a white solid (yield 36%). ３１ The purity of B-609, as determined by P NMR, was over 99%. １ H NMR (400 MHz, CDCl ３) δ: 7.91 (d, J=8.4Hz, 1H), 7.63 (d, J=8.0Hz, 1H), 7.45-7.22 (m, 5H), 7. 17-7.07 (m, 3H), 7.05-6.98 (m, 3H), 6.94 (d, J=7.2Hz, 2H), 6.69 (t, J=7. 2Hz, 3H), 6.62 (t, J=7.2Hz, 1H), 6.38 (t, J=7.2Hz, 1H), 6.23 (s, 1H), 6. 00 (d, J=4.8Hz, 1H), 3.52 (s, 3H), 3.44 (s, 3H), 1.37 (s, 6H), 1.29 (s, 6H) ３１ P { １ H} NMR (162MHz, CDCl ３ )δ:-61.0ppm(s)

[0296]

[0297] (Synthesis Example 15: Synthesis of B-610) (1) Synthesis of 610-1 1.3 g (4.7 mmol) of 2-iodo-1,3-dimethoxybenzene was weighed into a Schlenk tube, and 15 mL of tetrahydrofuran was added under a nitrogen atmosphere. The mixture was cooled to 0°C. 2.5 mL (5.0 mmol) of i-PrMgCl (2.0 M solution) was added to the mixture, and the mixture was heated to room temperature and stirred for 2 hours. The resulting reaction solution was cooled to -78°C, and 1.2 mL (14 mmol) of phosphorus trichloride was quickly added. The reaction solution was then heated to room temperature and stirred for 1 hour. All volatile components were removed from the reaction solution under reduced pressure. 610-1 was obtained as 1.1 g of yellow solid. 610-1 was used as is in the next step.

[0298]

[0299] (2) Synthesis of 610-2: 1.7 g (4.7 mmol) of 2'-(methoxymethoxy)-2,6-diphenyl-1,1'-biphenyl was weighed into a Schlenk tube, 20 mL of tetrahydrofuran was added, and the mixture was cooled to 0°C. 2.1 mL of BuLi (2.5 M tetrahydrofuran solution) was slowly added dropwise to the mixture, and the mixture was then heated to room temperature and stirred for 2 hours. The resulting reaction solution was cooled to -78°C, and the above 610-1 (1.1 g, 4.7 mmol) in tetrahydrofuran (10 mL) solution was added dropwise, and the mixture was then heated to room temperature and stirred for 2 hours. The yellow liquid reaction solution containing 2.7 g of 610-2 was used as is in the next step.

[0300]

[0301] (3) 610-3 Synthesis: 1.3 g (5.9 mmol) of compound A obtained in the same manner as in Synthesis Example 1 was weighed into a Schlenk tube, 20 mL of tetrahydrofuran was added, and the mixture was cooled to 0°C. 2.6 mL of BuLi (2.5 M tetrahydrofuran solution) was slowly added dropwise to the mixture, and the mixture was then heated to room temperature and stirred for 2 hours. The reaction solution was cooled to -78°C, and the reaction solution of 610-2 (3.3 g, 5.9 mmol) (30 mL of tetrahydrofuran) was added, and the reaction solution was then heated to room temperature and stirred for 12 hours. The resulting reaction solution was cooled to 0°C, 100 mL of water was slowly added to the reaction solution, and the reaction solution was then heated to room temperature and stirred for 10 minutes. 50 mL of ethyl acetate was added to the reaction solution and the organic layer soluble matter was extracted three times. The collected organic layer was dried over sodium sulfate, and the sodium sulfate was removed by filtration. The filtrate was evaporated to dryness, and the resulting crude product was purified by silica gel column chromatography under air (eluent: petroleum ether / ethyl acetate = 10 / 1). Washing with 10 mL of hexane yielded 610-3 as a white solid. ３１ P { １ H} NMR (162MHz, CDCl ３ ) δ: -55.6ppm(s)

[0302]

[0303] (4) Synthesis of B-610: 1.2 g (1.5 mmol) of the above 610-3 was weighed into a Schlenk tube, 20 mL (2.0 M solution) of dioxane hydrochloride was added, and the mixture was stirred at room temperature for 2 hours. 200 mL of saturated sodium bicarbonate aqueous solution was added to the mixture to adjust the pH to 6.5-7.0, and 80 mL of methylene chloride was added to extract the organic layer soluble matter. After liquid-liquid separation, the organic layer was dried over sodium sulfate, and the sodium sulfate was removed by filtration. The filtrate was evaporated to dryness, and the resulting crude product was purified by silica gel column chromatography (developing solvent: petroleum ether / ethyl acetate = changed from 20 / 1 to 10 / 1) to obtain 0.59 g of B-610 as a white solid. ３１ The purity of B-610, as determined by P NMR, was over 97%. １ H NMR (400 MHz, CDCl ３ ) δ: 7.52-7.26 (m, 4H), 7.22-7.10 (m, 5H), 7.07-7.01 (m, 3H), 7.00-6.92 (m, 3H), 6.6 3 (dd, J=7.6, 2,0Hz, 1H), 6.48-6.37 (m, 4H), 6.30 (s, 1H), 3.49 (s, 6H), 1.43 (s, 12H) ３１ P { １ H} NMR (162MHz, CDCl ３ ) δ: -67.6ppm(s)

[0304]

[0305] (Synthesis Example 16: Synthesis of B-613) (1) Synthesis of 613-1 1.05 g (6.99 mmol) of 3,5-dimethylphenylboronic acid was weighed into a Schlenk tube and 10 mL of toluene was added. To the resulting mixture, 1.0 g (2.69 mmol) of 2,6-dibromo-2'-(methoxymethoxy)-1,1'-biphenyl, 2.28 g (10.75 mmol) of potassium phosphate, and Pd ２ (dba) ３0.050 g (0.054 mmol) of and 0.11 g (0.27 mmol) of SPhos were added, and the mixture was then heated to 105°C and stirred for 12 hours. The mixture was cooled to 25°C, 10 mL of water was added to the mixture, and the organic layer soluble matter was extracted with 10 mL of ethyl acetate. This extraction procedure was performed three times. The collected organic layer was dried over sodium sulfate, and the sodium sulfate was removed by filtration. The filtrate was dried under reduced pressure, and the resulting solid was purified by silica gel column chromatography under air (eluent: petroleum ether / ethyl acetate = 1 / 0) to obtain 613-1 as 230 mg of white solid. １ H NMR (400 MHz, CDCl ３ ) δ: 7.48-7.38 (m, 3H), 7.05-6.90 (m, 2H), 6.83-6.67 (m, 8H), 4.56 (s, 2H), 3.26 (s, 3H), 2.15 (s, 12H)

[0306]

[0307] (2) Synthesis of 613-2: 1.0 g (2.4 mmol) of 613-1 was weighed into a Schlenk tube, 15 mL of diethyl ether was added, and the mixture was then cooled to 0°C. 0.50 mL (3.3 mmol) of trimethylethylenediamine and 2.6 mL (1.3 M solution) of t-butyllithium were slowly added dropwise to the mixture, and the mixture was stirred at 0°C for 1 hour. The reaction solution was cooled to -78°C, 0.72 mL (3.6 mmol) of iodine was added, and the mixture was then heated to room temperature and stirred for 10 hours. 10 mL of saturated sodium sulfite aqueous solution was added to the mixture at room temperature under open air to stop the reaction, and the organic layer soluble matter was extracted with 10 mL of ethyl acetate. This extraction procedure was performed three times. The collected organic layer was dried over sodium sulfate, and the sodium sulfate was removed by filtration. The filtrate was dried under reduced pressure to obtain 613-2 as 1.2 g of brown solid. １ H NMR (400 MHz, CDCl ３ ) δ: 7.54 (d, J = 6.4Hz, 1H), 7.48-7.37 (m, 3H), 6.89 (d, J = 6.4Hz, 1H), 6.87- 6.75 (m, 6H), 6.55 (t, J=6.8Hz, 1H), 4.74 (s, 2H), 3.06 (s, 3H), 2.19 (s, 12H)

[0308]

[0309] (3) In a Schlenk tube of synthesis 613-3, 0.30 g (0.63 mmol) of 588-4 obtained in the same manner as in synthesis example 10 was weighed out, and 5.0 mL of dioxane was added. To this mixture, 0.38 g (0.70 mmol) of 613-2, 34 mg (0.063 mmol) of DPEPhos, 0.41 g (1.3 mmol) of cesium carbonate, and Pd ２ (dba) ３ 12 mg (0.013 mmol) of was added, and the mixture was then heated to 100°C and stirred for 18 hours. 10 mL of water was added to the mixture at room temperature under open air to stop the reaction, and the organic layer soluble matter was extracted with 30 mL of methylene chloride. This extraction procedure was performed three times. The collected organic layer was washed three times with 30 mL of saturated brine, dried over sodium sulfate, and then the sodium sulfate was removed by filtration. The filtrate was evaporated to dryness, and the resulting solid was purified by silica gel column chromatography under air (developing solvent: petroleum ether) to obtain 613-3 as 300 mg of yellow solid (yield 53%). ３１ P { １ H} NMR (162MHz, CDCl ３ ) δ: -56.9ppm(s)

[0310]

[0311] (4) Synthesis of B-613: 2.5 g (2.8 mmol) of the above 613-2 was weighed into a Schlenk tube, 30 mL of methylene chloride and 10 mL of trifluoroacetic acid were added, and the mixture was stirred at room temperature for 4 hours. 30 mL of water for washing was added to the resulting mixture, and then 30 mL of methylene chloride was added to extract the organic layer soluble matter. After liquid-liquid separation, the organic layer was dried over sodium sulfate, and the sodium sulfate was removed by filtration. The filtrate was evaporated to dryness, and the resulting solid was purified under air by silica gel column chromatography (developing solvent: petroleum ether / ethyl acetate = changed from 1 / 0 to 20 / 1) to obtain 1.13 g of white solid as B-613. ３１ The purity of B-613, as determined by P NMR, was 92%. １ H NMR (400 MHz, CDCl ３) δ: 7.47-7.32 (m, 4H), 6.82 (s, 4H), 6.77-6.66 (m, 3H), 6.45 (t, J=7.6Hz, 1H), 6.27 (s, 2H), 6.08 (br, 1H), 2.09 (s, 12H), 1.46 (s, 12H), 1.34 (s, 12H) ３１ P { １ H} NMR (162MHz, CDCl ３ )δ:-67.1ppm(s)

[0312]

[0313] (Synthesis Example 17: Synthesis of B-615) (1) Synthesis of 615-1 1.0 g (4.5 mmol) of compound A, obtained in the same manner as in Synthesis Example 1, was weighed into a Schlenk tube, 10 mL of tetrahydrofuran was added, and the mixture was cooled to 0°C. 2.0 mL of BuLi (2.5 M tetrahydrofuran solution) was slowly added dropwise to the mixture, and the mixture was then heated to room temperature and stirred for 1.5 hours. The resulting reaction solution was cooled to -78°C, 0.19 mL (2.2 mmol) of phosphorus trichloride was added, and the reaction solution was then heated to room temperature and stirred for 1 hour. All volatile components were removed from the reaction solution under reduced pressure. 615-1 was obtained as 1.1 g of a yellow gum-like solid. 615-1 was used as is in the next step.

[0314]

[0315] (2) Put 2.0 g (5.2 mmol) of 2-bromo-1,3,5-triphenylbenzene, 1.4 g (7.8 mmol) of 2-(methoxymethoxy)phenylboronic acid, and Pd into a 615-2 synthetic screw-cap tube. ２ (dba) ３ 0.24 g (0.26 mmol), K ３ PO ４3.3 g (16 mmol) of and 0.21 g (0.52 mmol) of SPhos were weighed out, 20 mL of toluene was added under an argon atmosphere, and the mixture was stirred at 110°C for 48 hours. The mixture was cooled to room temperature and filtered. The solid obtained by filtration was extracted twice with 20 mL of methylene chloride to remove the organic layer soluble components, and the resulting organic layer was washed twice with 50 mL of saturated sodium bicarbonate aqueous solution. After liquid-liquid separation, the organic layer was evaporated to dryness, and the resulting oily liquid was purified under air by silica gel column chromatography (developing solvent: petroleum ether / ethyl acetate = 20 / 1) to obtain 615-2 as 1.9 g of white solid. １ H NMR (400 MHz, CDCl ３ ) δ: 7.73 (d, J=7.2Hz, 2H), 7.70 (s, 2H), 7.45 (t, J=7.6Hz, 2H), 7.38 (t, J=7.6Hz, 2H), 7.25-7.12 (m, 10H), 7.0 6 (t, J=8.0Hz, 1H), 6.94 (t, J=8.0Hz, 1H), 6.88-6.82 (m, 1H), 6.72 (t, J=8.0Hz, 1H), 4.55 (s, 2H), 3.25 (s, 2H)

[0316]

[0317] (3) Synthesis of 615-3: 0.79 g (1.8 mmol) of 615-2 was weighed into a Schlenk tube, 10 mL of tetrahydrofuran was added, and the mixture was cooled to 0°C. 0.79 mL of BuLi (2.5 M tetrahydrofuran solution) was slowly added dropwise to this mixture, and the temperature was raised to room temperature and stirred for 2 hours. The resulting reaction solution was cooled to -78°C, and 10 mL of tetrahydrofuran solution of 615-1 (1.1 g, 2.2 mmol) was slowly added dropwise, and the temperature was raised to room temperature and stirred for 14 hours. 5 mL of water was added to the reaction solution at 0°C under open air to stop the reaction, and all volatile components were removed under reduced pressure. The resulting gum-like solid was purified by silica gel column chromatography under air (developing solvent: petroleum ether / ethyl acetate = 25 / 1) to obtain 0.40 g of white solid 615-3. ３１ P { １ H} NMR (162MHz, CDCl ３ ) δ: -57.5ppm(s)

[0318]

[0319] (4) Synthesis of B-615: 0.50 g (0.55 mmol) of 615-3 was weighed into a Schlenk tube, 10 mL of hydrochloric acid / dioxane solution (2.0 mL of hydrochloric acid) was added, and the mixture was stirred at room temperature for 2 hours. The resulting mixture was washed with 100 mL of aqueous sodium bicarbonate solution, and 50 mL of methylene chloride was added to extract the organic layer soluble matter. After liquid-liquid separation, the organic layer was dried over sodium sulfate, and the sodium sulfate was removed by filtration. The filtrate was evaporated to dryness, and the resulting solid was purified under air by silica gel column chromatography (eluent: petroleum ether / ethyl acetate = 20 / 1) to obtain 0.10 g of B-615 as a white solid (yield 21%). ３１ The purity of B-615, as determined by P NMR, was over 99%. １ H NMR (400 MHz, CDCl ３ ) δ: 7.72 (d, J = 8.4Hz, 2H), 7.66 (s, 2H), 7.45 (t, J = 7.6Hz, 2H), 7.40-7.32 (m, 2H), 7.25-7.17 (m, 4H), 7.10-7.00 (m, 6H) ), 6.71 (dd, J = 6.8, 2.0Hz, 1H), 6.43 (t, J = 6.8Hz, 1H), 6.31 (s, 2H), 6.11 (d, J = 7.2Hz, 1H), 1.49 (s, 12H), 1.41 (s, 12H) ３１ P { １ H} NMR (162MHz, CDCl ３ ) δ: -68.3ppm(s)

[0320]

[0321] (Synthesis Example 18: Synthesis of B-616) (1) Synthesis of 616-1: 2.0 g (9.0 mmol) of compound A, obtained in the same manner as in Synthesis Example 1, was weighed into a Schlenk tube, 20 mL of tetrahydrofuran was added, and the mixture was cooled to 0°C. 4.0 mL of BuLi (2.5 M tetrahydrofuran solution) was added to this mixture, and the mixture was heated to room temperature and stirred for 2 hours. The mixture was cooled to -78°C under a nitrogen atmosphere, and 10 mL of tetrahydrofuran solution of 2.7 g (10.8 mmol) of iodine was added. After the addition, the mixture was heated to room temperature and stirred for 12 hours. The mixture was added to 80 mL of aqueous sodium thiosulfate solution. Then, 30 mL of ethyl acetate was added to extract the soluble matter. This extraction procedure was repeated three times. The collected organic layer was dried over sodium sulfate, and the sodium sulfate was removed by filtration. The filtrate was evaporated to dryness, and the resulting crude product was purified under air by silica gel column chromatography (acidic silica gel, developing solvent: petroleum ether / ethyl acetate = changed from 1 / 0 to 20 / 1) to obtain 616-1 as a white solid. １ H NMR (400 MHz, CDCl ３ ) δ: 6.27 (s, 1H), 1.68 (s, 12H)

[0322]

[0323] (2) In a synthetic Schlenk tube of 616-2, add 0.20 g (0.57 mmol) of the above 616-1, 0.10 mL (1.2 mmol) of 3-buten-2-ol, and Pd(OAc) ２13 mg (0.057 mmol) of tetrabutylammonium chloride, 0.16 mL (0.57 mmol) of tetrabutylammonium chloride, and 0.12 g (1.4 mmol) of sodium bicarbonate were weighed out, and 5.0 mL of dimethylformamide was added. The mixture was heated to 100°C and stirred for 16 hours. Then, 20 mL of water was added to the mixture while cooling, and then 10 mL of ethyl acetate was added to extract the soluble substances. This extraction procedure was repeated three times. The collected organic layer was washed with 10 mL of saturated saline solution. This washing procedure was repeated three times. The organic layer was dried over sodium sulfate, and the sodium sulfate was removed by filtration. The filtrate was evaporated to dryness, and the resulting crude product was purified by silica gel column chromatography under air (eluent: petroleum ether / ethyl acetate = 10 / 1) to obtain 616-2 as 50 mg of yellow solid. １ H NMR (400 MHz, CDCl ３ ) δ: 6.18 (s, 1H), 2.82-2.72 (m, 4H), 2.16 (s, 3H), 1.61 (s, 12H)

[0324]

[0325] (3) 0.10 g (0.34 mmol) of the above 616-2 was weighed into the synthetic Schlenk tube of 616-3, and 2.0 mL of toluene, 0.19 mL (3.4 mmol) of ethylene glycol, and 6.5 mg (0.034 mmol) of p-toluenesulfonic acid monohydrate were added. The mixture was heated to 50°C and stirred for 14 hours. 10 mL of water was added to the mixture while cooling, and then 10 mL of ethyl acetate was added to extract the soluble substances. This extraction procedure was repeated twice. 10 mL of saturated saline solution was added to the collected organic layer and washed. After liquid-liquid separation, the organic layer was dried with sodium sulfate, and then the sodium sulfate was removed by filtration. The filtrate was evaporated to dryness, and 616-3 was obtained as 0.12 g of yellow solid. １ H NMR (400 MHz, CDCl ３ ) δ: 6.18 (s, 1H), 3.98 (s, 4H), 2.68-2.57 (m, 2H), 2.03-1.94 (m, 2H), 1.64 (s, 12H), 1.39 (s, 3H)

[0326]

[0327] (4) 0.40 g (1.2 mmol) of the above 616-3 was weighed into the Schlenk tube of synthesis 616-4, 6.0 mL of tetrahydrofuran was added, and the mixture was cooled to 0°C. 0.48 mL of BuLi (2.5 M solution) was slowly added dropwise to this mixture. After the addition, the mixture was heated to room temperature and stirred for 2 hours. The resulting reaction solution was cooled to -78°C, and a solution of 591-2 (0.20 g, 0.50 mmol) in tetrahydrofuran (5.0 mL), obtained in the same manner as in Synthesis Example 11, was slowly added dropwise. After the addition, the mixture was heated to room temperature and stirred for 12 hours. The reaction solution was cooled to 0°C, and 20 mL of water was slowly added. Then, the mixture was heated to room temperature and stirred for 10 minutes. 10 mL of ethyl acetate was added to the mixture to extract the soluble matter. This extraction procedure was repeated three times. The collected organic layer was dried with sodium sulfate, and the sodium sulfate was removed by filtration. The filtrate was evaporated to dryness to obtain 616-4.

[0328]

[0329] (5) Synthesis of B-616: 1.9 g (1.9 mmol) of the above 616-4 was weighed into a Schlenk tube, 30 mL of methylene chloride and 10 mL of trifluoroacetic acid were added, and the mixture was stirred at room temperature for 16 hours. 200 mL of saturated sodium bicarbonate aqueous solution was added to the mixture to adjust the pH to 6.5-7.0, and then 80 mL of methylene chloride was added to extract the soluble substances. The collected organic layer was dried over sodium sulfate, and the sodium sulfate was removed by filtration. The filtrate was evaporated to dryness, and the obtained crude product was purified by silica gel column chromatography (developing solvent: petroleum ether / ethyl acetate = 3 / 1). The obtained yellow solid was dissolved in acetonitrile / water = 2 mL / 10 mL and freeze-dried to obtain 1.2 g of yellow solid, which was B-616. ３１ The purity of B-616, as determined by P NMR, was over 99%. １ H NMR (400 MHz, CDCl ３) δ: 7.58-7.48 (m, 1H), 7.29 (t, J = 7.6Hz, 1H), 7.16 (t, J = 7.6Hz, 2H), 6.91 (d, J = 7.6Hz, 1H), 6.74 (t, J = 7.6Hz, 1H), 5.63 (s, 1H), 2.78-2.62 (m, 8H), 2.54 (sept, J = 6.8Hz, 2H), 2.09 (s, 6H), 1.40 (s, 24H), 1.01 (d, J = 6.8Hz, 6H), 0.97 (d, J = 6.8Hz, 6H) ３１ P { １ H} NMR (162MHz, CDCl ３ ) δ: -66.3ppm(s)

[0330]

[0331] (Synthesis Example 19: Synthesis of B-617) (1) Synthesis of 617-1 5.0 g (33 mmol) of 1-(methoxymethoxy)-4-methylbenzene was weighed into a Schlenk tube, 50 mL of tetrahydrofuran was added, and the mixture was cooled to 0°C. 15 mL of BuLi (2.5 M solution of tetrahydrofuran) was added to the mixture. The mixture was then heated to room temperature and stirred for 2 hours. The resulting reaction solution was cooled to -78°C, and 23 mL (99 mmol) of triisopropyl borate was added. After the addition, the reaction solution was heated to room temperature and stirred for 3 hours. The reaction solution was cooled to 0°C, and 100 mL of water was added. Then, it was neutralized with hydrochloric acid (1.0 M) and separated. The resulting organic layer was concentrated. It was washed with 100 mL of petroleum ether to obtain 617-1 as 2.4 g of white solid. １ H NMR (400 MHz, CDCl ３ ) δ: 7.66 (s, 1H), 7.23 (dd, J = 8.4, 2.0Hz, 2H), 7.03 (d, J = 8.4Hz, 2H), 5.86 (s, 2H), 5.28 (s, 2H), 3.51 (s, 3H), 2.32 (s, 3H)

[0332]

[0333] (2) 4.4 g (11 mmol) of 2-bromo-1,3,5-triphenylbenzene was weighed into a Schlenk tube of 617-2 and 100 mL of toluene was added. Furthermore, 2.7 g (14 mmol) of 617-1 was added to the mixture, K３ PO ４ 6.1 g (29 mmol), Pd ２ (dba) ３ 0.11 g (0.11 mmol) of and 0.23 g (0.57 mmol) of SPhos were added. The mixture was then heated to 110°C and stirred for 12 hours. Next, the mixture was cooled to room temperature, and 50 mL of water was added under open air to stop the reaction. Furthermore, 50 mL of methylene chloride was added to extract the soluble substances. This extraction procedure was repeated twice. The collected organic layer was washed with 50 mL of saturated saline solution. This washing procedure was repeated twice. After liquid-liquid separation, the organic layer was dried with sodium sulfate, and the sodium sulfate was removed by filtration. The filtrate was evaporated to dryness, and the resulting crude product was purified by silica gel column chromatography (developing solvent: petroleum ether) under air to obtain 617-2 as 1.8 g of white solid. １ H NMR (400 MHz, CDCl ３ ) δ: 7.74 (d, J = 7.6 Hz, 2H), 7.71 (s, 2H), 7.45 (t, J = 7.6 Hz, 2H), 7.37 (t, J = 7.6 Hz, 1H), 7.22-7.11 (m, 10H), 6.82 (s, 2H), 6.63 (s, 1H), 4.48 (s, 2H), 3.22 (s, 3H), 2.04 (s, 3H)

[0334]

[0335] (3) Synthesis of 617-3: 0.60 g (2.7 mmol) of compound A, obtained in the same manner as in Synthesis Example 1, was weighed into a Schlenk tube, 10 mL of tetrahydrofuran was added, and the mixture was cooled to 0°C. 1.2 mL of BuLi (2.5 M tetrahydrofuran solution) was slowly added dropwise to the mixture. After addition, the mixture was heated to room temperature and stirred for 2.5 hours. The resulting reaction solution was cooled to -78°C, and 0.11 mL (1.2 mmol) of phosphorus trichloride was quickly added. After addition, the reaction solution was heated to room temperature and stirred for 1.5 hours. All volatile components were removed from the reaction solution under reduced pressure. 617-3 was obtained as 0.69 g of a yellow gum-like solid. 617-3 was used as is in the next step.

[0336]

[0337] (4) 0.68 g (1.5 mmol) of 617-2 was weighed into the Schlenk tube of 617-4, 10 mL of tetrahydrofuran was added, and the mixture was cooled to 0°C. 0.59 mL of BuLi (2.5 M tetrahydrofuran solution) was slowly added dropwise to the mixture and stirred at 0°C for 0.5 hours. Then the resulting reaction solution was raised to room temperature and stirred for a further 2 hours. 0.69 g (1.4 mmol) of 617-3 was weighed into another Schlenk tube and 10 mL of tetrahydrofuran was added. The mixture was cooled to -78°C, and the reaction solution was slowly added dropwise. After addition, the mixture was raised to room temperature and stirred for 12 hours. The mixture was cooled to 0°C, and 10 mL of water was added to stop the reaction. Then 5 mL of ethyl acetate was added to extract the soluble matter. This extraction procedure was repeated twice. The collected organic layer was washed with 5 mL of saturated saline solution. This washing procedure was repeated twice. After liquid-liquid separation, the organic layer was dried over sodium sulfate, and the sodium sulfate was removed by filtration. The filtrate was evaporated to dryness, and the resulting crude product was purified under air by silica gel column chromatography (eluent: petroleum ether / ethyl acetate = changed from 1 / 0 to 20 / 1) to obtain 617-4 as 0.19 g of white solid. ３１ P { １ H} NMR (162MHz, CDCl ３ ) δ: -57.3ppm(s)

[0338]

[0339] (5) Synthesis of B-617: 3.8 g (4.1 mmol) of the above 617-4 was weighed into a Schlenk tube, 60 mL of dioxane and 30 mL of hydrochloric acid were added, and the mixture was stirred at room temperature for 2 hours. The resulting mixture was washed with 100 mL of aqueous sodium bicarbonate solution. Then, 100 mL of methylene chloride was added to extract the soluble matter. The collected organic layer was dried over sodium sulfate, and the sodium sulfate was removed by filtration. The filtrate was evaporated to dryness, and the resulting solid was purified under air by silica gel column chromatography (developing solvent: petroleum ether / ethyl acetate = changed from 20 / 1 to 10 / 1) to obtain 1.2 g of B-617 as a white solid (yield 33%). ３１The purity of B-617, as determined by P NMR, was 96%. １ H NMR (400 MHz, CDCl ３ ) δ: 7.62 (d, J = 7.2Hz, 2H), 7.58 (s, 2H), 7.39 (t, J = 8.0Hz, 2H), 7.3 6 (t, J=8.0Hz, 1H), 7.19 (s, 2H), 7.17-7.10 (m, 4H), 7.12 (dd, J=5. 2, 2.0Hz, 1H), 7.03-6.92 (m, 6H), 6.42 (d, J=2.0Hz, 1H), 6.24 (s, 2 H), 5.86 (d, J=7.6Hz, 1H), 1.83 (s, 3H), 1.41 (s, 12H), 1.33 (s, 12H) ３１ P { １ H} NMR (162MHz, CDCl ３ ) δ: -68.0ppm(s)

[0340]

[0341] (Synthesis Example 20: Synthesis of B-621) (1) Synthesis of 621-1 In a Schlenk tube, add 1.0 g (2.9 mmol) of 616-1 obtained in the same manner as in Synthesis Example 18, 0.42 g (3.5 mmol) of phenylboronic acid, and Pd ２ (dba) ３ 26 mg (0.029 mmol) of , 59 mg (0.14 mmol) of SPhos, K ３ PO ４ 1.3 g (6.0 mmol) was weighed out and 10 mL of toluene was added. The mixture was heated to 115°C and stirred for 12 hours. The resulting reaction solution was cooled to room temperature and filtered through Celite. The filtrate was diluted with 20 mL of water and 20 mL of ethyl acetate was added to extract the soluble substances. This extraction procedure was repeated three times. The collected organic layer was washed with 30 mL of saturated brine and separated. The organic layer was dried over sodium sulfate, and the sodium sulfate was removed by filtration. The filtrate was evaporated to dryness, and the resulting crude product was purified under air by silica gel column chromatography (acidic silica gel, developing solvent: petroleum ether / ethyl acetate = changed from 1 / 0 to 20 / 1) to obtain 621-1 as a white solid. １ H NMR (400 MHz, CDCl ３) δ: 7.82 (d, J = 8.0 Hz, 2H), 7.43 (t, J = 8.0 Hz, 2H), 7.35-7.27 (m, 1H), 6.32 (s, 1H), 1.69 (s, 12H)

[0342]

[0343] (2) Synthesis of 621-2: 0.80 g (2.7 mmol) of 621-1 was weighed into a Schlenk tube, 8.0 mL of tetrahydrofuran was added, and the mixture was cooled to 0°C. 1.2 mL of BuLi (2.5 M tetrahydrofuran solution) was added to this mixture. The mixture was then heated to room temperature and stirred for 1.5 hours. The reaction solution was cooled to -78°C and slowly added to 0.18 g (1.3 mmol) of phosphorus trichloride in a tetrahydrofuran solution (4.0 mL). After addition, the mixture was stirred at room temperature for 1 hour. All volatile components were removed from the reaction solution under reduced pressure to obtain 621-2. The obtained 621-2 was used as is in the next step.

[0344]

[0345] (3) Synthesis of 621-3: 0.32 g (1.1 mmol) of 2'-(methoxymethoxy)-2,6-bis(1-methylethyl)-1,1'-biphenyl was weighed into a Schlenk tube, 3.0 mL of tetrahydrofuran was added, and the mixture was cooled to 0°C. 0.47 mL of BuLi (2.5 M tetrahydrofuran solution) was added dropwise to the mixture. The mixture was then heated to room temperature and stirred for 2 hours. The mixture was cooled to -78°C, and the solution of 621-2 (0.85 g, 1.3 mmol) was added dropwise. After the addition, the mixture was heated to room temperature and stirred for 12 hours. The mixture was then cooled to 0°C, 1.0 mL of water was added to stop the reaction, and all volatile components were removed under reduced pressure. The obtained crude product was purified by silica gel column chromatography under air (eluent: petroleum ether / ethyl acetate = changed from 1 / 0 to 20 / 1) to obtain 621-3 as a white solid. ３１ P { １ H} NMR (162MHz, CDCl ３ )δ:-56.0ppm(s)

[0346]

[0347] (4) Synthesis of B-621: 1.5 g (1.6 mmol) of the above 621-3 was weighed into a Schlenk tube, 24 mL of dioxane and 6.0 mL of 12 M hydrochloric acid were added, and the mixture was stirred at room temperature for 36 hours. 100 mL of saturated sodium bicarbonate aqueous solution was added to the resulting reaction solution to adjust the pH to 6.5-7.0. Then, 80 mL of methylene chloride was added to the reaction solution to extract the soluble substances. This extraction procedure was repeated twice. 100 mL of saturated saline solution was added to the collected organic layer to wash it, and the mixture was separated. The organic layer was dried over sodium sulfate, and the sodium sulfate was removed by filtration. The filtrate was evaporated to dryness, and the resulting crude product was purified under air by silica gel column chromatography (developing solvent: petroleum ether / ethyl acetate = changed from 1 / 0 to 20 / 1) to obtain B-621 as a white solid. ３１ The purity of B-621, as determined by P NMR, was over 99%. １ H NMR (400 MHz, CDCl ３ ) δ: 7.83 (d, J = 8.0 Hz, 4H), 7.72 (t, J = 5.2 Hz, 1H), 7.47-7.36 (m, 5H), 7.35-7.20 (m, 4H), 7.03 (, J = 7.2Hz, 1H), 6.87 ( t, J = 8.0Hz, 1H), 5.72 (s, 1H), 2.65 (sept, J = 6.8Hz, 2H), 1.55 (s, 24H), 1.11 (d, J = 6.8Hz, 6H), 1.07 (d, J = 6.8Hz, 6H) ３１ P { １ H} NMR (162MHz, CDCl ３ ) δ: -64.8ppm(s)

[0348]

[0349] (Synthesis Example 21: Synthesis of B-622) (1) Synthesis of 622-1 2.3 g (5.1 mmol) of 2-hydroxy-3-iodo-2',6'-diphenyl-1,1'-biphenyl and 1.6 g (10 mmol) of diazabicycloundecene were weighed into a Schlenk tube, and 10 mL of methylene chloride was added. The mixture was cooled to 0°C. 1.5 g (7.7 mmol) of triisopropylsilyl chloride was added dropwise to this mixture. After addition, the mixture was stirred at room temperature for 12 hours. The resulting reaction solution was added to 10 mL of water, and then 20 mL of ethyl acetate was added to extract the soluble substances. This extraction procedure was repeated twice. The collected organic layer was dried over sodium sulfate, and the sodium sulfate was removed by filtration. The filtrate was evaporated to dryness, and the resulting crude product was purified under air by silica gel column chromatography (acidic silica gel, developing solvent: petroleum ether) to obtain 622-1 as a white solid. １ H NMR (400 MHz, CDCl ３ ) δ: 7.48-7.32 (m, 4H), 7.17-7.05 (m, 10H), 6.87 (dd, J=8.0, 2.0Hz, 1H), 6.35 (t, J=8.0Hz, 1H), 1,13 (sept, J=7.6Hz, 3H), 0.77 (d, J=7.6Hz, 18H)

[0350]

[0351] (2) Synthesis of 622-2: 5 g (35.18 mmol) of 1,2,4,5-tetrahydroxybenzene was weighed into a Schlenk tube and dissolved in 100 mL of methylene chloride. 12.5 mL (140.8 mmol) of cyclopentanone and 11.4 g (88.0 mmol) of dichloro(dimethyl)silane were added to the resulting solution. The mixture was then heated to 20°C and stirred for 12 hours to obtain a brown solution. 10 mL of heptane was added to this solution, stirred for 3 minutes, and then filtered. The resulting solid was recrystallized with acetone to obtain 622-2 as a white solid. １ H NMR (400 MHz, CDCl ３ ) δ: 6.34 (s, 2H), 2.10-2.04 (m, 8H), 1.83-1.79 (m, 8H)

[0352]

[0353] (3) Synthesis of 622-3: 7 g (25.5 mmol) of 622-2 was weighed into a Schlenk tube and dissolved in 70 mL of tetrahydrofuran, then cooled to 0°C. 11.2 mL of BuLi (2.5 M tetrahydrofuran solution) was slowly added to this mixture, and the temperature was raised to 20°C and stirred for 2.5 hours to obtain a yellow solution. This solution was cooled to -78°C, 1.7 g (12.3 mmol) of phosphorus trichloride was added, and the mixture was raised to 20°C and stirred for 1.5 hours to obtain a yellow suspension. The solvent of this suspension was removed under reduced pressure to obtain 622-3, a yellow, gum-like solid. This 622-3 was used directly in the next step.

[0354]

[0355] (4) 7.8 g (12.8 mmol) of the above 622-3 was weighed into a Schlenk tube of the 622-4 synthesis and dissolved in 70 mL of tetrahydrofuran, and cooled to 0°C. 6.1 mL (2.5 M) of LAH was added to this mixture, and the temperature was raised to 20°C and stirred for 12 hours. The resulting brown solution was cooled to 0°C and the reaction was stopped with 0.6 mL of water. Then, 0.6 mL of 10% sodium hydroxide solution and 1.8 mL of water were added to the resulting reaction solution and stirred at room temperature for 30 minutes. The resulting suspension was filtered and the filtrate was concentrated to obtain a white solid. 30 mL of this white solid was added and the soluble matter was extracted with methylene chloride (30 mL). This extraction procedure was repeated three times. The collected organic layer was dried over sodium sulfate and then the sodium sulfate was removed by filtration. The filtrate was evaporated to dryness, and the resulting crude product was purified under air by silica gel column chromatography (acidic silica gel, developing solvent: petroleum ether = 20:1) to obtain 622-4 as a white solid. １ H NMR (400 MHz, CDCl ３ ) δ: 6.28 (s, 2H), 5.19 (d, J = 186.8, 1H), 2.03-1.96 (m, 16H), 1.78-1.72 (m, 16H) ３１ P { １ H} NMR (162MHz, CDCl ３ )δ:-125.2ppm(s)

[0356]

[0357] (5) Put 0.20 g (0.33 mmol) of 622-1, 0.19 g (0.33 mmol) of 622-4, 0.43 g (1.3 mmol) of cesium carbonate, and Pd into a synthetic Schlenk tube of 622-5. ２ (dba) ３ 30 mg (0.033 mmol) of and 36 mg (0.066 mmol) of DPEPhos were weighed out, and 5.0 mL of dioxane was added. The mixture was heated to 100°C and stirred for 18 hours. The resulting reaction solution was then filtered, and the filtrate was evaporated to dryness. Next, 30 mL of methylene chloride was added to the solid to extract the soluble substances. This extraction procedure was repeated three times. The collected organic layer was dried over sodium sulfate, and the sodium sulfate was removed by filtration. The filtrate was evaporated to dryness, and the resulting crude product was purified under air by silica gel column chromatography (acidic silica gel, developing solvent: petroleum ether / ethyl acetate = 20 / 1) to obtain 622-5 as a yellow solid. ３１ P { １ H} NMR (162MHz, CDCl ３ )δ:-53.0ppm(s)

[0358]

[0359] (6) Synthesis of B-622: 1.6 g (1.5 mmol) of the above 622-5 was weighed into a Schlenk tube, and 10 mL of tetrahydrofuran and 25 mL of tetrabutylammonium fluoride were added under an argon atmosphere. The mixture was stirred at room temperature for 0.5 hours. 20 mL of ethyl acetate was added to the resulting reaction solution to extract the soluble substances. This extraction procedure was repeated twice. 50 mL of saturated saline solution was added to the collected organic layer for washing. This washing procedure was repeated three times. After liquid-liquid separation, the organic layer was dried over sodium sulfate, and the sodium sulfate was removed by filtration. The filtrate was evaporated to dryness, and the resulting crude product was purified under air by silica gel column chromatography (acidic silica gel, developing solvent: petroleum ether / ethyl acetate = 20 / 1) to obtain B-622 as a white solid. ３１ The purity of B-622, as determined by P NMR, was over 99%. １ H NMR (400 MHz, CDCl３ ) δ: 7.47 (t, J = 6.8 Hz, 1H), 7.42 (d, J = 7.6 Hz, 2H), 7.33-7.27 (m, 1H), 7.18-7.08 (m, 4H), 7.05-6.93 ( m, 6H), 6.67 (d, J = 6.8Hz, 1H), 6.41 (t, J = 7.6Hz, 1H), 6.33 (s, 2H), 6.00 (br, 1H), 2.00-1.50 (m, 32H) ３１ P { １ H} NMR (162MHz, CDCl ３ ) δ: -67.6ppm(s)

[0360]

[0361] (Synthesis Example 22: Synthesis of B-624) (1) Synthesis of 624-1 8.0 g (49 mmol) of 4-(trifluoromethyl)phenol and 19 g (148 mmol) of N,N-diisopropylethylamine were weighed into a Schlenk tube, and 80 mL of methylene chloride was added. The mixture was cooled to 0°C. 12 g (99 mmol) of bromo(methoxy)methane was added to this mixture, and the mixture was heated to room temperature and stirred for 12 hours. 50 mL of saturated sodium bicarbonate aqueous solution was added to the mixture to stop the reaction. Then 100 mL of ethyl acetate was added to the mixture to extract the soluble product. This extraction procedure was repeated twice. The obtained crude product was purified by silica gel column chromatography (acidic silica gel, developing solvent: petroleum ether) under air to obtain 624-1 as a colorless liquid. １ H NMR (400 MHz, CDCl ３ ) δ: 7.56 (d, J=8.4Hz, 2H), 7.12 (d, J=8.4Hz, 2H), 5.23 (s, 2H), 3.49 (s, 3H)

[0362]

[0363] (2) Synthesis of 624-2: 2.0 g (9.7 mmol) of 624-1 was weighed into a Schlenk tube and 20 mL of tetrahydrofuran was added. The mixture was cooled to 0°C. 4.3 mL of BuLi (2.5 M tetrahydrofuran solution) was slowly added dropwise to the mixture. After addition, the mixture was heated to room temperature and stirred for 2 hours. The reaction solution was cooled to -78°C and 10 mL of tetrahydrofuran solution containing 3.0 g (12 mmol) of iodine was slowly added dropwise. After addition, the mixture was stirred at room temperature for 12 hours. The resulting reaction solution was added to 80 mL of sodium thiosulfate solution, and then 80 mL of ethyl acetate was added to extract the soluble substances. This extraction procedure was repeated three times. The collected organic layer was dried over sodium sulfate, and the sodium sulfate was removed by filtration. The filtrate was evaporated to dryness, and the resulting crude product was purified under air by silica gel column chromatography (acidic silica gel, developing solvent: petroleum ether) to obtain 624-2 as a yellow liquid. １ H NMR (400 MHz, CDCl ３ ) δ: 8.03 (s, 1H), 7.56 (d, J = 8.4Hz, 1H), 7.14 (d, J = 8.4Hz, 1H), 5.30 (s, 2H), 3.5 2 (s, 3H), 2.41 (sept, J = 6.8Hz, 2H), 1.05 (d, J = 6.8Hz, 6H), 1.00 (d, J = 6.8Hz, 6H)

[0364]

[0365] (3) Put 8.0 g (24 mmol) of 624-2, 6.5 g (31 mmol) of 2,6-diisopropylphenylboronic acid, and Pd into a synthetic Schlenk tube of 624-3. ２ (dba) ３1.1 g (1.2 mmol) of t-BuONa, 5.8 g (60 mmol) of t-BuONa, and 0.99 g (2.4 mmol) of SPhos were weighed out, and 160 mL of dioxane was added. The mixture was heated to 110°C and stirred for 14 hours. 200 mL of water was added to the resulting reaction solution, followed by 200 mL of ethyl acetate to extract the soluble substances. This extraction procedure was repeated three times. The collected organic layer was washed with 200 mL of saturated brine. After liquid-liquid separation, the organic layer was dried over sodium sulfate, and the sodium sulfate was removed by filtration. The filtrate was evaporated to dryness, and the resulting crude product was purified under air by silica gel column chromatography (acidic silica gel, developing solvent: petroleum ether / ethyl acetate = changed from 1 / 0 to 20 / 1). Washing with 6.0 mL of hexane yielded 624-3 as a white solid. １ H NMR (400 MHz, CDCl ３ ) δ: 7.54 (d, J = 6.8Hz, 1H), 7.37-7.13 (m, 5H), 5.06 (s, 2H), 3.30 (s, 3H) , 2.41 (sept, J=6.8Hz, 2H), 1.05 (d, J=6.8Hz, 6H), 1.00 (d, J=6.8Hz, 6H) １９ F NMR (376 MHz, CDCl ３ ) δ: -61.7ppm(s)

[0366]

[0367] (4) Synthesis of 624-4: 1.1 g (3.0 mmol) of 624-3 was weighed into a Schlenk tube, 12 mL of tetrahydrofuran was added, and the mixture was cooled to 0°C. 1.3 mL of BuLi (2.5 M hexane solution) was slowly added dropwise to the mixture, and the temperature was raised to room temperature and the mixture was stirred for 3 hours. The reaction solution was cooled to -78°C, and 10 mL of tetrahydrofuran solution of 1.1 g (4.5 mmol) of iodine was slowly added dropwise. After the addition, the mixture was stirred at room temperature for 10 hours. The resulting reaction solution was cooled to 0°C, 10 mL of water was added to stop the reaction, and then 100 mL of saturated sodium thiosulfate aqueous solution and 100 mL of ethyl acetate were added to extract the soluble product. This extraction procedure was repeated three times. The collected organic layer was dried over sodium sulfate, and the sodium sulfate was removed by filtration. The filtrate was evaporated to dryness to obtain 624-4 as a yellow gum-like solid. 624-4 was used directly in the next step. １ H NMR (400 MHz, CDCl ３ ) δ: 8.10 (s, 1H), 7.45-7.34 (m, 2H), 7.29-7.18 (m, 2H), 4.73 (s, 2H), 3.07 (s , 3H), 2.51 (sept, J = 7.2Hz, 2H), 1.23 (d, J = 7.2Hz, 6H), 1.05 (d, J = 7.2Hz, 6H)

[0368]

[0369] (5) In a Schlenk tube of the synthesis of 624-5, add 0.20 g (0.41 mmol) of the above 624-4, 0.20 g (0.41 mmol) of 588-4 obtained in the same manner as in Synthesis Example 10, 0.53 g (1.6 mmol) of cesium carbonate, 44 mg (0.081 mmol) of DPEPhos, and Pd ２ (dba) ３37 mg (0.041 mmol) of the compound was weighed out, and 5.0 mL of dioxane was added. The mixture was heated to 100°C and stirred for 18 hours. After cooling, the resulting reaction solution was filtered, and the filtrate was evaporated to dryness. 30 mL of methylene chloride was added to the solid to extract the soluble substances. This extraction procedure was repeated three times. The collected organic layer was dried over sodium sulfate, and the sodium sulfate was removed by filtration. The filtrate was evaporated to dryness, and the resulting crude product was purified under air by silica gel column chromatography (acidic silica gel, developing solvent: petroleum ether / ethyl acetate = 20 / 1) to obtain 624-5 as a yellow solid. ３１ P { １ H} NMR (162MHz, CDCl ３ )δ:-56.0ppm(s)

[0370]

[0371] (6) Synthesis of B-624: 4.0 g (4.8 mmol) of the above 624-5 was weighed into a Schlenk tube, 30 mL of dioxane hydrochloride solution (3.0 mL of hydrochloric acid) was added, and the mixture was stirred at room temperature for 2 hours. 100 mL of aqueous sodium bicarbonate solution was added to the resulting mixture for washing, and then 50 mL of methylene chloride was added to extract the soluble matter. The collected organic layer was dried over sodium sulfate, and the sodium sulfate was removed by filtration. The filtrate was evaporated to dryness, and the resulting crude product was purified by silica gel column chromatography (acidic silica gel, developing solvent: petroleum ether / ethyl acetate = 18 / 1) to obtain B-624 as 1.9 g of yellow solid (yield 50%). ３１ The purity of B-624, as determined by P NMR, was over 99%. １ H NMR (400 MHz, CDCl ３ ) δ: 8.06 (s, 1H), 7.41 (t, J = 8.0Hz, 1H), 7.33-7.23 (m, 3H), 6.34 (s, 2H), 6.12 (d, J = 3.6Hz, 1H), 2.52 (sept, J = 6.8Hz, 2H), 1.51 (s, 12H), 1.49 (s, 12H), 1.08 (dd, J = 12.4, 6.8Hz, 12H) １９ F NMR (376 MHz, CDCl ３ )δ:-61.2ppm(s) ３１ P {１ H} NMR (162MHz, CDCl ３ ) δ: -66.3ppm(s)

[0372]

[0373] (Synthesis Example 23: Synthesis of B-626) (1) Synthesis of 626-1: 1.0 g (4.5 mmol) of compound A, obtained in the same manner as in Synthesis Example 1, was weighed into a Schlenk tube, 5.0 mL of tetrahydrofuran was added, and the mixture was cooled to 0°C. 5.4 mL of BuLi (2.5 M solution of tetrahydrofuran) and 2.0 mL (14 mmol) of tetramethylethylenediamine were slowly added dropwise to this mixture. After the addition, the mixture was heated to room temperature and stirred for 1.5 hours. The reaction solution was cooled to -78°C, and 4.7 g (18 mmol) of 1,2-dibromo-1,1,2,2-tetrafluoroethane was added. After the addition, the mixture was heated to room temperature and stirred for 12 hours. 20 mL of sodium sulfite solution was added to the resulting reaction solution, and then 10 mL of ethyl acetate was added to extract the soluble substances. This extraction procedure was repeated three times. The collected organic layer was dried over sodium sulfate, and the sodium sulfate was removed by filtration. The filtrate was evaporated to dryness, and the resulting crude product was purified under air by silica gel column chromatography (acidic silica gel, developing solvent: petroleum ether / ethyl acetate = 20 / 1). Washing with 10 mL of hexane yielded 626-1 as a yellow solid. １ H NMR (400 MHz, CDCl ３ ) δ: 1.74 (s, 12H)

[0374]

[0375] (2) Synthesis of 626-2: Weigh 1.5 g (5.0 mmol) of 2'-(methoxymethoxy)-2,6-bis(1-methylethyl)-1,1'-biphenyl into a Schlenk tube, add 10 mL of tetrahydrofuran, and cool the mixture to 0°C. Slowly add 2.2 mL of BuLi (2.5 M tetrahydrofuran solution) dropwise to the mixture. After addition, raise the temperature of the mixture to room temperature and stir for 1.5 hours. Cool the resulting reaction solution to -78°C and quickly add 1.5 mL (18 mmol) of phosphorus trichloride. After addition, raise the temperature of the mixture to room temperature and stir for 1 hour. Remove all volatile components from the reaction solution under reduced pressure. 626-2 was obtained as 2.0 g of a yellow gum-like solid. 626-2 was used as is in the next step. ３１ P { １ H} NMR (162MHz, CDCl ３ )δ: 158.8ppm(s)

[0376]

[0377] (3) Synthesis of 626-3: 4.4 g (12 mmol) of 626-1 was weighed into a Schlenk tube, 10 mL of tetrahydrofuran was added, and the mixture was cooled to -78°C. 4.8 mL of BuLi (2.5 M tetrahydrofuran solution) was slowly added dropwise to the mixture and stirred at -78°C for 1 hour. 20 mL of tetrahydrofuran solution of 626-2 (2.0 g, 5.0 mmol) was slowly added dropwise to the resulting reaction solution at -78°C. After the addition, the mixture was heated to room temperature and stirred for 14 hours. The crude product obtained was purified under air by silica gel column chromatography (acidic silica gel, developing solvent: petroleum ether / ethyl acetate = 20 / 1) to obtain 626-3 as 2.2 g of white solid. ３１ P { １ H} NMR (162MHz, CDCl ３ )δ:-56.0ppm(s)

[0378]

[0379] (4) Synthesis of B-626: 2.0 g (2.2 mmol) of the above 626-3 was weighed into a Schlenk tube, 5 mL of trifluoroacetic acid and 15 mL of methylene chloride were added, and the mixture was stirred at room temperature for 4 hours. 100 mL of aqueous sodium bicarbonate solution was added to the resulting mixture for washing, and then 25 mL of methylene chloride was added to extract the soluble matter. The collected organic layer was dried over sodium sulfate, and the sodium sulfate was removed by filtration. The filtrate was evaporated to dryness, and the resulting crude product was purified by silica gel column chromatography (acidic silica gel, developing solvent: petroleum ether / ethyl acetate = 18 / 1) to obtain B-626 as 1.1 g of white solid (yield 58%). ３１ The purity of B-626, as determined by P NMR, was over 97%. １ H NMR (400 MHz, CDCl ３ ) δ: 7.51 (t, J = 6.0Hz, 1H), 7.39 (t, J = 7.6Hz, 1H), 7.27-7.24 (m, 2H), 7.01 (d, J = 6.0Hz, 1H), 6.86 (t, J=7.6Hz, 1H), 5.40 (br, 1H), 2.57 (sept, J=6.8Hz, 2H), 1.55 (s, 24H), 1.06 (dd, J=12.4, 6.8Hz, 12H) ３１ P { １ H} NMR (162MHz, CDCl ３ ) δ: -63.5ppm(s)

[0380]

[0381] (Synthesis Example 24: Synthesis of B-629) (1) Synthesis of 629-1 In a Schlenk tube, add 4.0 g (10 mmol) of 2,4,6-triphenylbromobenzene, 2.5 g (14 mmol) of 2-(methoxymethoxy)phenylboronic acid, and Pd ２ (dba) ３ 0.48 g (0.52 mmol), K ３ PO ４6.6 g (31 mmol) of and 0.43 g (1.0 mmol) of SPhos were weighed out, and 30 mL of toluene was added under an argon atmosphere. The mixture was heated to 105°C and stirred for 18 hours. The mixture was cooled to room temperature and filtered. 20 mL of methylene chloride was added to the obtained solid to extract the soluble substances. This extraction procedure was repeated twice. 50 mL of saturated sodium bicarbonate aqueous solution was added to the collected organic layer and washed. This washing procedure was repeated twice. The collected organic layer was evaporated to dryness to obtain an oily liquid. The obtained oily liquid was purified under air by silica gel column chromatography (acidic silica gel, developing solvent: petroleum ether / ethyl acetate = 25 / 1) to obtain 629-1 as 3.0 g of white solid. １ H NMR (400 MHz, CDCl ３ ) δ: 7.74 (d, J=6.8Hz, 2H), 7.70 (s, 2H), 7.46 (t, J=6.4Hz, 2H), 7.38 (t, J=6.4Hz, 1H), 7.24-7.13 (m, 10H), 7.05 (t, J=6.4Hz, 1H), 6.93 (d, J=6.8Hz, 1H), 6.84 (d, J=6.8Hz, 1H), 6.72 (t, J=6.8Hz, 1H), 4.55 (s, 2H), 3.74 (s, 3H)

[0382]

[0383] (2) Synthesis of 629-2: 1.0 g (2.3 mmol) of 629-1 was weighed into a Schlenk tube, 10 mL of tetrahydrofuran was added, and the mixture was cooled to 0°C. 0.99 mL of BuLi (2.5 M solution) was slowly added dropwise to the mixture. After addition, the mixture was heated to room temperature and stirred for 2 hours. The resulting reaction solution was cooled to -78°C, and 0.59 mL (6.8 mmol) of phosphorus trichloride was quickly added. After addition, the mixture was heated to room temperature and stirred for 1 hour. All volatile components were removed from the reaction solution under reduced pressure. 1.2 g of yellow gum-like solid was obtained as 629-2. 629-2 was used as is in the next step.

[0384]

[0385] (3) Synthesizing 629-3: 0.43 g (2.3 mmol) of 1,3-dimethoxynaphthalene was weighed into a Schlenk tube, and 10 mL of tetrahydrofuran was added under an argon atmosphere. The mixture was cooled to 0°C. 1.0 mL of BuLi (2.5 M solution) was slowly added dropwise to the mixture and stirred at 0°C for 0.5 hours. The mixture was then heated to room temperature and stirred for 2 hours. The resulting reaction solution was cooled to -78°C and slowly added dropwise to a tetrahydrofuran (10 mL) solution of 629-2 (1.2 g, 2.3 mmol). After the addition, the mixture was heated to room temperature and stirred for 2 hours. A 1.6 g yellow liquid reaction solution containing 629-3 was obtained. This reaction solution was used directly in the next step.

[0386]

[0387] (4) Synthesis of 629-4: 0.60 g (2.7 mmol) of compound A, obtained in the same manner as in Synthesis Example 1, was weighed into a Schlenk tube, 10 mL of tetrahydrofuran was added, and the mixture was cooled to 0°C. 1.2 mL of BuLi (2.5 M solution) was slowly added dropwise to this mixture. After addition, the mixture was heated to room temperature and stirred for 2 hours. The resulting reaction solution was cooled to -78°C, and the reaction solution of 629-3 (1.6 g, 2.3 mmol) (diluted with 15 mL of tetrahydrofuran) was added. After addition, the mixture was heated to room temperature and stirred for 12 hours. The resulting crude product was purified under air by silica gel column chromatography (acidic silica gel, developing solvent: petroleum ether / ethyl acetate = 20 / 1). Washing with 10 mL of hexane yielded 629-4 as 0.40 g of white solid. ３１ P { １ H} NMR (162MHz, CDCl ３ )δ:-53.6ppm(s)

[0388]

[0389] (5) Synthesis of B-629: 2.5 g (2.8 mmol) of the above 629-4 was weighed into a Schlenk tube, 20 mL of methylene chloride and 20 mL of trifluoroacetic acid were added, and the mixture was stirred at room temperature for 4 hours. The resulting mixture was washed with 200 mL of aqueous sodium bicarbonate solution, and then 60 mL of methylene chloride was added to extract the soluble matter. The collected organic layer was dried over sodium sulfate, and the sodium sulfate was removed by filtration. The filtrate was evaporated to dryness, and the resulting crude product was purified by silica gel column chromatography (acidic silica gel, developing solvent: petroleum ether / ethyl acetate = 18 / 1) to obtain B-629 as 1.5 g of white solid (yield 64%). ３１ The purity of B-629, as determined by P NMR, was over 99%. １ H NMR (400 MHz, CDCl ３ ) δ: 8.00 (d, J = 8.4Hz, 1H), 7.77-7.64 (m, 4H), 7.59 (s, 1H), 7.53-7.40 (m, 3H), 7.40-7.32 (m, 2H), 7.26-7.21 (m, 3H), 7.17-7.05 (m, 5 H), 6.86-6.68 (m, 5H), 6.49 (t, J = 7.6Hz, 1H), 6.32 (s, 1H), 6.12 (d, J = 5.2Hz, 1H), 3.61 (s, 3H), 3.54 (s, 3H), 1.46 (s, 6H), 1.39 (s, 6H) ３１ P { １ H} NMR (162MHz, CDCl ３ ) δ: -61.4ppm(s)

[0390]

[0391] (Synthesis Example 25: Synthesis of B-630) (1) Synthesis of 630-1 Weigh 0.83 g (1.8 mmol) of 2'-(methoxymethoxy)-5'-methyl-2,4,6-triphenyl-1,1'-biphenyl into a Schlenk tube, add 10 mL of tetrahydrofuran, and cool the mixture to 0°C. Slowly add 0.80 mL of BuLi (2.5 M solution) dropwise to this mixture. After addition, raise the temperature of the mixture to room temperature and stir for 2 hours. Cool the resulting reaction solution to -78°C and quickly add 0.95 mL (11 mmol) of phosphorus trichloride. After addition, raise the temperature of the mixture to room temperature and stir for 1 hour. Remove all volatile components from the reaction solution under reduced pressure. 630-1 was obtained as a white solid. 630-1 was used as is in the next step.

[0392]

[0393] (2) Synthesizing 630-2: 0.34 g (1.8 mmol) of 1,3-dimethoxynaphthalene was weighed into a Schlenk tube, and 10 mL of tetrahydrofuran was added under an argon atmosphere. The mixture was cooled to 0°C. 0.79 mL of BuLi (2.5 M solution) was slowly added dropwise to the mixture and stirred at 0°C for 0.5 hours. The mixture was then heated to room temperature and stirred for 2 hours. The resulting reaction solution was slowly added dropwise to a solution of 630-1 (1.0 g, 1.8 mmol) in tetrahydrofuran (5.0 mL) that had been cooled to -78°C. After the addition, the mixture was heated to room temperature and stirred for 2 hours. The reaction solution containing 630-2 obtained in this way was used as is in the next step.

[0394]

[0395] (3) Synthesis of 630-3: 0.60 g (2.7 mmol) of compound A, obtained in the same manner as in Synthesis Example 1, was weighed into a Schlenk tube, 10 mL of tetrahydrofuran was added, and the mixture was cooled to 0°C. 0.79 mL of BuLi (2.5 M solution) was slowly added dropwise to the mixture. After addition, the mixture was heated to room temperature and stirred for 2 hours. The resulting reaction solution was cooled to -78°C, and the reaction solution of 630-2 (1.3 g, 1.8 mmol) (diluted with 15 mL of tetrahydrofuran) was added. After addition, the mixture was heated to room temperature and stirred for 12 hours. The reaction solution was cooled to 0°C, 5.0 mL of water was added to stop the reaction, and all volatile components were removed from the mixture under reduced pressure. The resulting crude product was purified by silica gel column chromatography under air (eluent: petroleum ether / ethyl acetate 0-5%) to obtain 630-3 as 0.70 g of yellow solid. ３１ P { １ H} NMR (162MHz, CDCl ３ )δ:-53.3ppm(s)

[0396]

[0397] (4) Synthesis of B-630 3.0 g (3.4 mmol) of the above 630-3 was weighed into a Schlenk tube, and under an argon atmosphere, 100 mL of methylene chloride and hydrochloric acid were added, and the mixture was stirred at room temperature for 16 hours. The resulting mixture was washed with 100 mL of water. This washing operation was repeated five times to adjust the pH of the washing solution to 6.5-7.0. The collected organic layer was dried over sodium sulfate, and the sodium sulfate was removed by filtration. The filtrate was evaporated to dryness, and the resulting crude product was purified by silica gel column chromatography (developing solvent: petroleum ether / ethyl acetate = changed from 0 / 1 to 20 / 1). The product was dissolved in acetonitrile / water = 2 mL / 10 mL, and then freeze-dried to obtain B-630 as 1.1 g of white solid (yield 40%). ３１ The purity of B-630, as determined by P NMR, was over 99%. １ H NMR (400 MHz, CDCl ３) δ: 8.01 (d, J = 8.4Hz, 1H), 7.77-7.62 (m, 4H), 7.58 (s, 1H), 7.52-7.30 (m, 5H), 7.26-7.22 (m, 2H), 7.15-6.99 (m, 6H), 6.83-6.75 (m, 3H), 6.65 (t, J = 8.0Hz, 1H), 6.52 (s, 1H), 6.32 (s, 1H), 5.95 (d, J = 5.2Hz, 1 H), 3.64 (s, 3H), 3.53 (s, 3H), 1.94 (s, 3H), 1.46 (s, 6H), 1.38 (s, 6H) ３１ P { １ H} NMR (162MHz, CDCl ３ )δ:-61.2ppm(s)

[0398]

[0399] (Synthesis Example 26: Synthesis of B-659) (1) Synthesis of 659-1 1.3 g (6.0 mmol) of compound A obtained in the same manner as in Synthesis Example 1 was weighed into a Schlenk tube, 10 mL of tetrahydrofuran was added, and the mixture was cooled to 0°C. 2.6 mL of BuLi (2.5 M solution) was slowly added dropwise to this mixture. After addition, the mixture was stirred at room temperature for 2 hours. The resulting reaction solution was cooled to -78°C and added to a solution of 630-1 (3.7 g, 6.6 mmol) in tetrahydrofuran (20 mL) obtained in the same manner as in Synthesis Example 25. The mixture was stirred at room temperature for 1 hour. The reaction solution containing 659-1 was used as is in the next step.

[0400]

[0401] (2) Synthesize 659-2. Weigh 1.3 g (9.0 mmol) of 3,5-dimethoxypyridine into a Schlenk tube, add 10 mL of tetrahydrofuran, and cool the mixture to -78°C. Slowly add 3.4 mL of BuLi (2.5 M solution) dropwise to the mixture and stir at -78°C for 20 minutes. Add the reaction solution of 659-1 (4.4 g, 6.0 mmol) to the resulting reaction solution at -78°C and stir the mixture at room temperature for 16 hours. Add 50 mL of water to the reaction solution to stop the reaction. Then, add 50 mL of ethyl acetate to extract the soluble product. This extraction procedure was repeated three times. The collected organic layer was dried over sodium sulfate, and the sodium sulfate was removed by filtration. The filtrate was evaporated to dryness, and the resulting crude product was purified by silica gel column chromatography (acidic silica gel, developing solvent: petroleum ether / ethyl acetate = 1 / 1) to obtain 659-2 as 1.7 g of yellow solid. ３１ P { １ H} NMR (162MHz, CDCl ３ )δ:-57.0ppm(s)

[0402]

[0403] (3) Synthesis of B-659: 0.90 g (1.1 mmol) of the above 659-2 was weighed into a Schlenk tube, 10 mL (2.0 M) of hydrochloric acid / dioxane solution and 2.0 mL (12 M) of hydrochloric acid were added, and the mixture was stirred at room temperature for 1 hour. 200 mL of aqueous sodium bicarbonate solution was added to the mixture to neutralize it, and 50 mL of methylene chloride was added to extract the soluble substances. The collected organic layer was evaporated to dryness, and the resulting red solid was washed with 10 mL of hexane. The green solid collected by centrifugation was washed with 5.0 mL of methylene chloride, and then 8.0 mL of ethanol was added to extract the soluble substances. After filtration, the resulting yellow solid was washed with 5.0 mL of hexane, and the excess solvent was evaporated to dryness to obtain 0.41 g of yellow solid, which was B-659. ３１ The purity of B-659, as determined by P NMR, was over 99%. １ H NMR (400 MHz, CDCl ３) δ: 7.89 (d, J = 2.8 Hz, 2H), 7.70 (d, J = 7.6 Hz, 2H), 7.65 (dd, J = 8.8, 2.8 Hz , 2H), 7.45 (t, J = 8.4Hz, 2H), 7.37 (t, J = 8.4Hz, 2H1H), 7.24-7.14 (m, 4H), 7.09-6.98 (m, 6H), 6.92 (dd, J=8.4, 2.8Hz 1H), 6.52 (s, 1H), 6.33 (s, 1H) , 5.79 (d, J=6.0Hz, 1H), 3.55 (s, 6H), 1.92 (s, 3H), 1.45 (d, J=6.0Hz, 12H) ３１ P { １ H} NMR (162MHz, CDCl ３ ) δ: -66.7ppm(s)

[0404]

[0405] (Synthesis Example 27: Synthesis of B-665) (1) Synthesis of 665-1 1.0 g (4.5 mmol) of compound A, obtained in the same manner as in Synthesis Example 1, was weighed into a Schlenk tube, 10 mL of tetrahydrofuran was added, and the mixture was cooled to 0°C. 2.2 mL of BuLi (2.5 M solution) was slowly added dropwise to this mixture. After addition, the mixture was stirred at room temperature for 2 hours. The resulting reaction solution was cooled to -78°C, and 1.1 mL (5.4 mmol) of iodine was added. After addition, the mixture was stirred at room temperature for 16 hours. The reaction solution was added to 50 mL of aqueous sodium sulfite solution. Then, 50 mL of ethyl acetate was added to extract the soluble substances. This extraction procedure was repeated three times. The collected organic layer was dried over sodium sulfate, and the sodium sulfate was removed by filtration. The filtrate was evaporated to dryness, and 1.3 g of yellow solid (purity 87%) was obtained as 665-1. 665-1 was used as is in the next step. １ H NMR (400 MHz, CDCl ３ ) δ: 6.27 (s, 1H), 1.68 (s, 12H)

[0406]

[0407] (2) In a Schlenk tube of the 665-2 synthesis, add 1.0 g (2.9 mmol) of the above 665-1, 0.32 mL (3.7 mmol) of propan-2-amine, and Pd (dba) ２33 mg (0.057 mmol) of was weighed out and 15 mL of toluene was added. To this mixture, 72 mg (0.11 mmol) of 2,2'-bis(diphenylphosphin)-1,1'-binaphthyl and 0.41 g (4.3 mmol) of sodium t-butoxide were added, and the mixture was heated to 110°C and stirred for 16 hours. The mixture was filtered to remove the solid components, and the solid components were further washed with 50 mL of ethyl acetate. The solvent was then evaporated from the collected organic layer to dryness. The resulting crude product was purified by silica gel column chromatography (acidic silica gel, developing solvent: hexane / ethyl acetate = 20 / 1) to obtain 665-2 as 0.22 g of yellow solid. １ H NMR (400 MHz, CDCl ３ ) δ: 6.32 (s, 1H), 5.90 (s, 1H), 3.89 (sept, J = 6.4Hz, 1H), 1.64 (s, 12H), 1.18 (d, J = 6.4Hz, 6H)

[0408]

[0409] (3) Weigh 4.8 g (17 mmol) of the above 665-2 into the synthetic Schlenk tube of 665-3, add 100 mL of tetrahydrofuran, and cool the mixture to 0°C. Add 6.9 g (172 mmol, purity 60%) of sodium hydride to this mixture. After addition, raise the temperature of the mixture to room temperature and stir for 1 hour. Cool the reaction solution to 0°C and add 34 mL (344 mmol) of 2-iodopropane. After addition, raise the temperature of the mixture to 80°C and stir for 48 hours. Cool the resulting reaction solution to 0°C and add 200 mL of water to stop the reaction. Then, add 100 mL of ethyl acetate to extract the soluble substances. This extraction procedure was repeated three times. Wash the collected organic layer with 100 mL of saturated saline solution. After liquid-liquid separation, the organic layer was dried with sodium sulfate and then the sodium sulfate was removed by filtration. The filtrate was evaporated to dryness, and the resulting crude product was purified by silica gel column chromatography (acidic silica gel, developing solvent: hexane / ethyl acetate = 50 / 1 to 20 / 1). The resulting yellow gum-like solid was washed with methanol / methylene chloride = 50 / 1 (10 mL). The solid was then dried to obtain 665-3 as 3.1 g of white solid. １H NMR (400 MHz, CDCl ３ ) δ: 6.22 (s, 1H), 3.63 (sept, J = 6.4Hz, 2H), 1.62 (s, 12H), 1.04 (d, J = 6.4Hz, 12H)

[0410]

[0411] (4) Weigh 0.91 g (2.8 mmol) of the above 665-3 into the synthetic Schlenk tube of 665-4, add 10 mL of tetrahydrofuran, and cool the mixture to 0°C. Slowly add 1.1 mL of BuLi (2.5 M solution) dropwise to this mixture. After addition, raise the temperature of the mixture to room temperature and stir for 3 hours. Cool the resulting reaction solution to -78°C and add the above 629-2 (0.61 g, 1.1 mmol) in a tetrahydrofuran (10 mL) solution. After addition, raise the temperature to room temperature and stir for 12 hours. Cool the reaction solution to 0°C, slowly add 30 mL of water, then raise the temperature to room temperature and stir for 5 minutes. Add 10 mL of ethyl acetate to the resulting reaction solution to extract the soluble matter. This extraction procedure was repeated three times. The collected organic layer was dried over sodium sulfate, and then the sodium sulfate was removed by filtration. The filtrate was evaporated to dryness, and the resulting crude product was purified by silica gel column chromatography (eluent: hexane / ethyl acetate = 10 / 1) to obtain 665-4 as 0.12 g of white solid.

[0412]

[0413] (5) Synthesis of B-665: 0.70 g (0.63 mmol) of the above 665-5 was weighed into a Schlenk tube, 10 mL (2.0 M) of hydrochloric acid / dioxane solution and 5.0 mL (12 M) of hydrochloric acid were added, and the mixture was stirred at room temperature for 1 hour. 300 mL of saturated sodium bicarbonate aqueous solution was added to the mixture to neutralize it, and then 100 mL of methylene chloride was added to extract the soluble product. The collected organic layer was evaporated to dryness, and the resulting crude product was purified by silica gel column chromatography (developing solvent: hexane / ethyl acetate = 10 / 1). The resulting pale yellow solid was cooled to -78°C and washed with methanol / hexane = 2 / 1 (20 mL). Subsequently, 70 mg of B-665 was obtained as a white solid by freeze-drying. Yield 10%.３１ The purity of B-665, as determined by P NMR, was over 99%. １ H NMR (400 MHz, CDCl ３ ) δ: 7.71 (d, J = 7.2Hz, 2H), 7.66 (s, 2H), 7.45 (t, J = 7.2Hz, 3H), 7.36 (t, J = 7.2Hz, 1H), 7.27-7.25 (m, 3H), 7.13-6.98 (m, 6) H), 6.72 (d, J = 7.2Hz, 1H), 6.54-6.42 (m, 2H), 3.63 (sept, J = 6.4Hz, 4H), 1.47 (s, 12H), 1.39 (s, 12H), 1.10-0.96 (m, 24H) ３１ P { １ H} NMR (162MHz, CDCl ３ ) δ: -71.7ppm(s)

[0414]

[0415] (Synthesis Example 28: Synthesis of B-679) (1) Synthesis of 679-1 Weigh 10 g (62 mmol) of 2,3-dihydroxynaphthalene into a Schlenk tube, add 100 mL of toluene, then add 12 mL (125 mmol) of 2-methoxypropene and 1.1 g (6.2 mmol) of p-toluenesulfonic acid. Heat the mixture to 110°C and stir for 48 hours. After cooling, add 300 mL of water to the reaction solution. Then add 100 mL of ethyl acetate to extract the soluble substances. This extraction procedure was repeated three times. Dry the collected organic layer over sodium sulfate and remove the sodium sulfate by filtration. Evaporate the filtrate to dryness, and purify the resulting crude product by silica gel column chromatography (eluent: petroleum ether / ethyl acetate = 20 / 1) to obtain 679-1 as a yellow oil. １ H NMR (400 MHz, CDCl ３ ) δ: 7.68-7.62 (m, 2H), 7.35-7.28 (m, 2H), 7.04 (s, 1H), 1.75 (s, 6H)

[0416]

[0417] (2) Synthesize 679-2. 3.2 g (16 mmol) of 679-1 was weighed into a Schlenk tube, 30 mL of acetic acid and 30 mL of methylene chloride were added, and the mixture was cooled to 0°C. 2.8 g (16 mmol) of N-bromosuccinimide was added to this mixture. After the addition, the mixture was heated to room temperature and stirred for 3 hours. 200 mL of saturated sodium bicarbonate aqueous solution was added to the resulting reaction solution to neutralize it, and 100 mL of methylene chloride was added to extract the soluble product. The collected organic layer was evaporated to dryness, and the resulting crude product was purified by silica gel column chromatography (eluent: petroleum ether / ethyl acetate = 20 / 1) to obtain 679-2 as yellow oil. １ H NMR (500 MHz, CDCl ３ ) δ: 8.03 (d, J=8.0Hz, 1H), 7.65 (d, J=8.0Hz, 1H), 7.47-7.42 (m, 1H), 7.39-7.34 (m, 1H), 7.02 (s, 1H), 1.80 (s, 6H)

[0418]

[0419] (3) Synthesis of 679-3: Weigh 2.0 g (4.5 mmol) of 615-2, obtained in the same manner as in Synthesis Example 17, into a Schlenk tube, add 20 mL of tetrahydrofuran, and cool the mixture to 0°C. Slowly add 2.2 mL of BuLi (2.5 M solution) dropwise to this mixture. After addition, raise the temperature of the mixture to room temperature and stir for 2 hours. Cool the resulting reaction solution to -78°C and quickly add 1.2 mL (14 mmol) of phosphorus trichloride. After addition, raise the temperature of the mixture to room temperature and stir for 1 hour. Remove all volatile components from the reaction solution under reduced pressure to obtain 679-3 as a white solid. 679-3 was used as is in the next step. ３１ P { １ H} NMR (162MHz, CDCl ３ )δ: 158.6ppm(s)

[0420]

[0421] (4) Weigh 3.1 g (11 mmol) of the above 679-2 into the synthetic Schlenk tube of 679-4, add 30 mL of tetrahydrofuran, and cool the mixture to -78°C. Add 4.5 mL of BuLi (2.5 M solution) to this mixture and stir at -78°C for 0.5 hours. Add the above 679-3 (2.5 g, 4.5 mmol) in a tetrahydrofuran (20 mL) solution to the mixture at -78°C. After the addition, raise the temperature of the mixture to room temperature and stir for 12 hours. Cool the mixture to 0°C, slowly add 100 mL of water, then raise the temperature to room temperature and stir for 3 minutes. Add 30 mL of ethyl acetate to the mixture and extract the soluble matter. This extraction procedure was repeated three times. The collected organic layer was dried over sodium sulfate, and the sodium sulfate was removed by filtration. The filtrate was evaporated to dryness, and the resulting crude product was purified by silica gel column chromatography (eluent: petroleum ether / ethyl acetate = changed from 20 / 1 to 10 / 1) to obtain 679-4 as a white solid.

[0422]

[0423] (5) Synthesis of B-679: 2.9 g (3.3 mmol) of the above 679-4 was weighed into a Schlenk tube, 40 mL of 2.0 M dioxane hydrochloride solution was added, and then 8.0 mL of 12 M hydrochloric acid was added, and the mixture was stirred at room temperature for 4 hours. 300 mL of saturated sodium bicarbonate aqueous solution was added to the resulting reaction solution to neutralize it, and 100 mL of methylene chloride was added to extract the soluble product. The collected organic layer was evaporated to dryness, and the resulting crude product was washed with hexane / ethyl acetate = 10 / 1 (30 mL). After filtration, the solvent contained in the solid was evaporated to dry it, and B-679 was obtained as a white solid (yield 59%). ３１ The purity of B-679, as determined by P NMR, was over 99%. １ H NMR (400 MHz, CDCl ３) δ: 7.98 (dd, J=8.0, 3.6Hz, 2H), 7.71 (d, J=8.4Hz, 2H), 7.67 (s, 2H), 7.64 (d, J=8.0Hz, 2H), 7.47 (t, J=8.0Hz, 2H), 7.39 (t, J=8.0Hz, 1H), 7.34-7.2 5 (m, 3H), 7.24-7.14 (m, 6H), 7.10-6.93 (m, 8H), 6.79 (dd, J = 8.0, 1.2Hz, 1 H), 6.47 (t, J=8.0Hz, 1H), 6.28 (d, J=5.6Hz, 1H), 1.34 (s, 6H), 1.19 (s, 6H) ３１ P { １ H} NMR (162MHz, CDCl ３ ) δ: -62.4ppm(s)

[0424]

[0425] (Synthesis Example 101: Synthesis of B-499) (1) Synthesis of 499-1 6.9 g (50 mmol) of 1,3-dimethoxybenzene in 70 mL of tetrahydrofuran solution was added, and the mixture was cooled to 0°C. 21 mL of BuLi (2.5 M tetrahydrofuran solution) was slowly added dropwise to the mixture while stirring. After the addition was complete, the mixture was heated to room temperature and stirred for 2 hours. Next, the resulting reaction solution was cooled to -78°C, and 10 g (22.5 mmol) of 601-1 in 70 mL of tetrahydrofuran solution was added dropwise while stirring. After the addition was complete, the reaction solution was heated to room temperature and stirred for 14 hours. The mixture was then concentrated, and the resulting concentrate was column purified (eluent: petroleum ether / ethyl acetate = 5 / 1) to obtain 6.8 g (15 mmol) of 499-1 as a white solid (yield 46%).

[0426]

[0427] (2) Synthesis of B-499 A 3 mL solution of 499-1 (2.5 g, 3.8 mmol) in ethyl acetate was prepared, and the solution was cooled on ice. 150 mL of 4 M hydrochloric acid / ethyl acetate was added while stirring. The mixture was then heated to room temperature and stirred for 2 hours. After that, the resulting reaction solution was neutralized by adding saturated sodium bicarbonate aqueous solution at room temperature under open air. After neutralization, the reaction solution was washed with 150 mL of saturated saline solution. After washing and separation, the organic matter contained in the aqueous layer was extracted and separated three times with 50 mL of ethyl acetate. The collected organic layer was dehydrated with sodium sulfate, filtered, and the resulting filtrate was concentrated to obtain 2.3 g (3.7 mmol) of B-499 as a white solid (yield 98%).

[0428]

[0429] (Synthesis Example 102: Synthesis of B-423) It was synthesized according to the method described in Japanese Patent Publication No. 2019-156764.

[0430]

[0431] (Synthesis Example 103: Synthesis of B-572) (1) Synthesis of 572-1 In a Schlenk tube, add 0.50 g (1.1 mmol) of 593-2 obtained in the same manner as in Synthesis Example 12, 0.36 g (1.2 mmol) of bis(2,6-dimethoxyphenyl)phosphine, 0.69 g (2.1 mmol) of cesium carbonate, and Pd ２ (dba) ３ 97 mg (0.11 mmol) of and 0.11 g (0.21 mmol) of DPEPhos were weighed out, and 5.0 mL of dioxane was added. The mixture was heated to 110°C and stirred for 16 hours. The mixture was cooled to room temperature, and the filtrate obtained by Celite filtration was evaporated to dryness. Then 10 mL of ethyl acetate was added to extract the soluble substances. This extraction procedure was repeated three times. The collected organic layer was dried over sodium sulfate, and the sodium sulfate was removed by filtration. The filtrate was evaporated to dryness, and the resulting crude product was purified under air by silica gel column chromatography (developing solvent: petroleum ether / ethyl acetate = changed from 40 / 1 to 10 / 1) to obtain 572-1 as a white solid. ３１ P { １ H} NMR (162MHz, CDCl ３) δ: -57.9ppm(s)

[0432]

[0433] (2) Synthesis of B-572: 3.5 g (5.4 mmol) of the above 572-1 was weighed into a Schlenk tube, 30 mL of methylene chloride and 100 mL of 4.0 M ethyl hydrochloride solution were added, and the mixture was stirred at room temperature for 0.5 hours. All volatile components were removed from the reaction solution under reduced pressure, and 50 mL of methylene chloride was added. Then 50 mL of saturated sodium bicarbonate aqueous solution was added to wash the organic layer. This washing operation was repeated three times. The collected organic layer was dried with sodium sulfate, and the sodium sulfate was removed by filtration. The filtrate was evaporated to dryness, and B-572 was obtained as a yellow solid. ３１ The purity of B-572, as determined by P NMR, was over 99%. １ H NMR (400 MHz, CDCl ３ ) δ: 8.97 (t, J=6.8Hz, 1H), 7.73 (d, J=8.0Hz, 1H), 7.56-7.52 (m, 2H), 7.46 (t, J=8.0Hz, 1H), 7.39 (t, J=8.0Hz, 1H), 7.35-7.1 9 (m, 5H), 6.49 (dd, J = 8.0, 3.2Hz, 4H), 3.56 (s, 12H), 2.64 (sept, J = 6.8Hz, 2H), 1.80 (d, J = 6.8Hz, 6H), 1.70 (d, J = 6.8Hz, 6H) ３１ P { １ H} NMR (162MHz, CDCl ３ ) δ: -75.6ppm(s)

[0434]

[0435] The autoclave used in the following copolymerization experiments of ethylene and methyl acrylate was thoroughly dried and purged with nitrogen before use.

[0436] (Example 1) Dry toluene (1 L), methyl acrylate (21.6 ml, 240 mmol), and aluminum trioctyl (0.1 mmol) were supplied to a 2 L induction stirring autoclave. After raising the internal temperature of the autoclave to 110°C while stirring, ethylene was supplied to the autoclave and adjusted to a partial pressure of ethylene of 3.0 MPa. After the adjustment was complete, 1 mL of a toluene solution containing ligand B-575 (7.3 mg, 0.01 mmol) and the transition metal compound nickel bis(acetylacetonate) (2.6 mg, 0.01 mmol) as a catalyst composition was supplied to the autoclave to start copolymerization. After polymerization for 60 minutes, 1,2-butanediol was supplied to stop the reaction. After removing unreacted gas, the autoclave was opened and ethanol was added to precipitate the copolymer. The precipitated copolymer was collected and filtered. The copolymer was then washed with ethanol. After washing, the collected copolymer was dried at 90°C under a nitrogen flow. The polymerization results are shown in Table 2.

[0437] (Examples 2-29, Comparative Examples 1-4) In Example 1, a copolymer of ethylene and methyl acrylate was produced in the same manner as in Example 1, except that at least one condition selected from the group consisting of ligand in the catalyst composition, transition metal compound, amount of catalyst composition used, and amount of methyl acrylate used was changed as shown in Table 1. The amount of toluene solution containing 0.01 mmol of ligand and 0.01 mmol of transition metal compound used was 1 mL, the amount of toluene solution containing 0.02 mmol of ligand and 0.02 mmol of transition metal compound used was 2 mL, and the amount of toluene solution containing 0.04 mmol of ligand and 0.04 mmol of transition metal compound used was 4 mL.

[0438]

[0439] The results of Examples 1 to 29 and Comparative Examples 1 to 4 are summarized in Table 2.

[0440]

[0441] By comparing the examples with the comparative examples, it was found that when obtaining an ethylene copolymer containing approximately 5 mol% methyl acrylate, the examples all exhibited approximately 1.6 to 18 times the copolymerization activity compared to the comparative examples. In conclusion, it was revealed that the novel compound that can be used as a ligand in the present invention, the catalyst composition for olefin polymerization using the novel compound, the metal complex, and the catalyst for olefin polymerization, as well as the method for producing olefin polymers using the catalyst, improve copolymerization activity and can be used for the polymerization or copolymerization of olefins. In particular, it was revealed that copolymerization of acrylic acid esters with a relatively small number of carbon atoms and olefins is possible with improved polymerization activity.

Claims

1. A compound represented by the following general formula (A). [In the formula (A), X １ represents an oxygen atom or a sulfur atom, E １ represents a nitrogen atom or a phosphorus atom, Z represents a hydrogen atom, a leaving group or a cation having a valence of 1 to 4, m is an integer of 1 or more and not more than the valence of Z, R １ represents a hydrocarbon group represented by the following general formula (B) or (C), R ２ represents a C1-C20 hydrocarbon group which is different from the hydrocarbon group represented by the following general formula (B) or (C) and may optionally contain at least one hetero atom, l is 1 or 2, and when l is 2, R ２ is absent. R ３ , R ４ , R ５ , and R ６ each independently represent an atom or a group selected from the group consisting of the following (i) to (iv): (i) a hydrogen atom (ii) a halogen atom (iii) a C1-C30 hydrocarbon group which may optionally contain at least one hetero atom (iv) OR ｂ , C(O)OR ｂ , C(O)OM', C(O)N(R ａ ) ２ , C(O)R ｂ , OC(O)R ｂ , SR ｂ , S(O) ２ R ｂ , S(O)₂R ｂ , OS(O)₂ ２ R ｂ , SF₅ ５ , P(O)(OR ｂ ) ２－ｙ (R ａ ) ｙ , CN, N(H)R ａ , N(R ｂ )₂ ２ , Si(OR ａ ) ３－ｘ (R ａ ) ｘ , OSi(OR ａ ) ３－ｘ (R ａ ) ｘ , NO₂ ２ , S(O)₂ ２ OM', P(O)(OM') ２ or P(O)(OR ｂ ) ２ M' (Here, R ａ Each of these independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, R ｂ Each of these independently represents a hydrocarbon group having 1 to 20 carbon atoms, and N(R) ｂ ) ２ At that time, R ｂ They may be linked together to form a ring. (M' represents an alkali metal, alkaline earth metal, ammonium, quaternary ammonium, or phosphonium, x represents 0, 1, 2, or 3, and y represents 0, 1, or 2). ３ , R ４ , R ５ , and R ６ The adjacent substituents may be linked to each other to form an alicyclic ring, an aromatic ring, or a heterocycle containing at least one heteroatom selected from oxygen, nitrogen, or sulfur atoms. [In equations (B) and (C), * represents E １ This represents a bonding with R ７ , R ８ , R ９ , R １０ , R １１ , R １２ and R １３ Each of these independently represents an atom or group selected from the group consisting of (i) to (iv) as defined in formula (A), and R ７ , R ８ , R ９ and R １０ R may have adjacent substituents linked to each other, forming an alicyclic ring, an aromatic ring, or a heterocycle containing at least one heteroatom selected from an oxygen atom, a nitrogen atom, or a sulfur atom, １２ and R １３ These may be linked to each other to form an aromatic ring or an unsaturated alicyclic ring which may contain at least one heteroatom selected from oxygen, nitrogen, or sulfur atoms. １ A ２ A ３ and A ４ each independently represents an oxygen atom, a sulfur atom, or -C(R) ２ -, -C(O)-, -S(O)-, -S(O) ２ -, -N(R)-, -P(R)- or -P(O)(R)- (wherein each R independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms which may optionally contain at least one heteroatom). Provided that in formula (B), A １ and A ３ at least one of which is an oxygen atom or a sulfur atom; in formula (C), A ３ is an oxygen atom or a sulfur atom, and R １２ and R １３ at least one of which represents an atom or a group selected from the group consisting of the above (ii), (iii) and (iv), R １２ and R １３ may be bonded to each other to form an aromatic ring, or an unsaturated alicyclic ring which may optionally contain at least one heteroatom selected from an oxygen atom, a nitrogen atom or a sulfur atom. W １ and W ２ each independently represent a carbon atom, a silicon atom, a nitrogen atom, a phosphorus atom, a boron atom, an oxygen atom, -C(O)-, -P(O)- or -S(O) ２ -, when W1 or W2 is a nitrogen atom, a phosphorus atom, a boron atom or -P(O)-, R ８ and R １０ do not exist; when W1 or W2 is an oxygen atom, -C(O)- or -S(O) ２ -, R ７ and R ８ and R ９ and R １０ do not exist. h and i are each independently an integer of 1 to 6, when W １ , W ２ , R ７ , R ８ , R ９ and R １０ are present in plurality, a plurality of W １ , W ２ , R ７ , R ８ , R ９ and R １０ may each be the same or different.]] 2. The compound according to claim 1, wherein in formulas (B) and (C), h and i are independently 1 or 2.

3. In the above formulas (B) and (C), W １ and W ２ The compound according to claim 1, wherein each atom is independently a carbon atom or a silicon atom.

4. In equations (B) and (C) above, when h and i are each independently 1, R ７ , R ８ , R ９ and R １０ Each of these is an independent group selected from the group consisting of (iii) and (iv) as defined by formula (A), and when h and i are each independently 2 to 6, R ７ , R ８ , R ９ and R １０ Each of these is an atom or group independently selected from the group consisting of (i) to (iii) as defined by formula (A), and R ７ , R ８ , R ９ and R １０ The compound according to claim 1, wherein adjacent substituents are linked to each other to form an alicyclic ring, an aromatic ring, or a heterocycle containing at least one heteroatom selected from an oxygen atom, a nitrogen atom, or a sulfur atom.

5. In the above formula (C), R １２ is an atom or group selected from the group consisting of (ii) and (iv) as defined in formula (A), or R １２ and R １３ The compound according to claim 1, wherein the elements are linked to each other to form an aromatic ring.

6. In formula (A) above, R ３ The compound according to claim 1, wherein the substituent is represented by the following general formula (G). [In formula (G), * represents a bond with an aromatic ring, and R ２１ , R ２２ , R ２３ , R ２４ and R ２５ Each of these independently comprises a hydrogen atom, a substituent represented by the following general formula (H), a carbon-6 to carbon-12 aryl group which may have at least one substituent, an adamantyl group, OR ｂ , SR ｂ , or N(R ｂ ) ２ (where R ｂ (This is equivalent to claim 1), R ２１ , R ２２ , R ２３ , R ２４ and R ２５ At least one of these is a substituent represented by the following general formula (H), an aryl group having 6 to 12 carbon atoms which may have at least one substituent, an adamantyl group, OR ｂ , SR ｂ , or N(R ｂ ) ２ That is. R ２１ , R ２２ , R ２３ , R ２４ and R ２５ They do not bond to each other to form a ring. (In formula (H), * represents a bond with an aromatic ring, R ２６ and R ２７ Each of these is a hydrocarbon group having 1 to 6 carbon atoms, which may each independently have at least one hydrogen atom or heteroatom, and may be bonded to each other to form a ring.

7. A catalyst composition for olefin polymerization comprising the compound described in claim 1 and a transition metal compound represented by the following general formula (E) or (F). [In formulas (E) and (F), M １ M ２ and M ３ Each of these independently represents either a nickel atom or a palladium atom, L １ , L ２ , L ３ , and L ４ Each of them is independent, M １ Represents the ligand coordinated to, where q is 0, 1, or 2, and L １ and L ２ They combine with each other to form M １ A ring containing L may be formed, ３ and L ４ They combine with each other to form M １ A ring containing L may be formed. ５ , L ６ , L ９ and L １０ Each of them is independent, M ２ or M ３ Represents a ligand coordinated to L ７ and L ８ Each of them is independent, M ２ and M ３ Represents the ligand coordinated to L ５ and L ６ They combine with each other to form M ２ A ring containing L may be formed, ９ and L １０ They combine with each other to form M ３ A ring containing [the element] may be formed.

8. A catalyst for olefin polymerization comprising the catalyst composition for olefin polymerization described in claim 7.

9. A metal complex represented by the following general formula (D). [In formula (D), １ E represents an oxygen atom or a sulfur atom. １ R represents a nitrogen atom or a phosphorus atom. １ R represents a hydrocarbon group represented by the following general formula (B) or (C), and ２ This represents a hydrocarbon group having 1 to 20 carbon atoms, which may contain at least one heteroatom, and is different from the hydrocarbon group represented by the following general formula (B) or (C), where l is 1 or 2, and when l is 2, R ２ It does not exist. R ３ , R ４ , R ５ , and R ６ Each of these independently represents an atom or group selected from the group consisting of (i) to (iv) below: (i) hydrogen atom (ii) halogen atom (iii) hydrocarbon group having 1 to 30 carbon atoms, which may contain at least one heteroatom (iv) OR ｂ , C(O)OR ｂ , C(O)OM', C(O)N(R ａ ) ２ , C(O)R ｂ OC(O)R ｂ , SR ｂ , S(O) ２ R ｂ S(O)R ｂ OS(O) ２ R ｂ SF ５ , P(O)(OR ｂ ) ２－ｙ (R ａ ) ｙ , CN, N(H)R ａ , N(R ｂ ) ２ , Si(OR ａ ) ３－ｘ (R ａ ) ｘ , OSi(OR ａ ) ３－ｘ (R ａ ) ｘ NO ２ , S(O) ２ OM', P(O)(OM') ２ or P(O)(OR ｂ ) ２ M' (Here, R ａ Each of these independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, R ｂ Each of these independently represents a hydrocarbon group having 1 to 20 carbon atoms, and N(R) ｂ ) ２ At that time, R ｂ They may be linked together to form a ring. (M' represents an alkali metal, alkaline earth metal, ammonium, quaternary ammonium, or phosphonium, x represents 0, 1, 2, or 3, and y represents 0, 1, or 2). ３ , R ４ , R ５ , and R ６ The adjacent substituents may be linked to each other to form an alicyclic ring, an aromatic ring, or a heterocycle containing at least one heteroatom selected from an oxygen atom, a nitrogen atom, or a sulfur atom. １ L represents a nickel atom or a palladium atom. １ and L ２ Each of them is independent, M １ Represents the ligand coordinated to L １ and L ２ They combine with each other to form M １ A ring containing [the element] may be formed. [In equations (B) and (C), * represents E １ This represents a bonding with R ７ , R ８ , R ９ , R １０ , R １１ , R １２ and R １３ Each of these independently represents an atom or group selected from the group consisting of (i) to (iv) as defined in formula (A), and R ７ , R ８ , R ９ and R １０ R may have adjacent substituents linked to each other, forming an alicyclic ring, an aromatic ring, or a heterocycle containing at least one heteroatom selected from an oxygen atom, a nitrogen atom, or a sulfur atom, １２ and R １３ These may be linked to each other to form an aromatic ring or an unsaturated alicyclic ring which may contain at least one heteroatom selected from oxygen, nitrogen, or sulfur atoms. １ A ２ A ３ and A ４ These are, independently, an oxygen atom, a sulfur atom, and -C(R) ２ -, -C(O)-, -S(O)-, -S(O) ２ -, -N(R)-, -P(R)-, or -P(O)(R)- (where R independently represents a C1-C20 hydrocarbon group which may contain at least one hydrogen atom or heteroatom). However, in formula (B), A １ and A ３ Of these, at least one is an oxygen atom or a sulfur atom, and in formula (C), A ３ is an oxygen atom or a sulfur atom, and R １２ and R １３ At least one of these represents an atom or group selected from the group consisting of (ii), (iii), and (iv), R １２ and R １３ These may be linked to each other to form an aromatic ring, or an unsaturated alicyclic ring which may contain at least one heteroatom selected from oxygen, nitrogen, or sulfur atoms. １ and W ２ These are, independently, carbon, silicon, nitrogen, phosphorus, boron, oxygen, -C(O)-, -P(O)-, or -S(O) ２ It represents -, and when it is a nitrogen atom, phosphorus atom, boron atom or -P(O)-, R ８ and R １０ It does not exist, and oxygen atoms, -C(O)-, or -S(O) ２ - When R ７ and R ８ And R ９ and R １０ It does not exist. h and i are each independent integers from 1 to 6, and W １ , W ２ , R ７ , R ８ , R ９ and R １０ If there are multiple W １ , W ２ , R ７ , R ８ , R ９ and R １０ These may be the same or different.

10. A catalyst for olefin polymerization comprising the metal complex described in claim 9.

11. A method for producing an olefin polymer, comprising copolymerizing at least one C2-C20 olefin with at least one polar group-containing monomer in the presence of the olefin polymerization catalyst described in claim 8 or 10.

12. The method for producing an olefin polymer according to claim 11, wherein the olefin comprises at least ethylene.

13. The method for producing an olefin polymer according to claim 11, wherein the polar group-containing monomer is an acrylic acid ester.

14. The method for producing an olefin polymer according to claim 13, wherein the acrylic acid ester has 6 or fewer carbon atoms.

Images