JP2002020329A - Aryl derivative and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To simply obtain an asymmetric dihaloaryl derivative. SOLUTION: This method for producing an aryl derivative represented by the following formula (I) (wherein, R1 to R6 are each independently the same or different and hydrogen atom, a hydrocarbon group or the like; A1 and A2 are each a halogen atom; and n is an integer of >=0) is characterized by reacting a metallacyclopentadiene represented by the following formula (II) (wherein, L1 and L2 are each a ligand; and M is a transition metal) with a polycyclic compound represented by the following formula (III) (wherein, X1 and X2 are each a halogen atom) in an amount of >=2 mol based on 1 mol of the metallacyclopentadiene.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

FIELD OF THE INVENTION The present invention relates to aryl derivatives, and more particularly, to asymmetric dihaloaryl derivatives.

[0002]

2. Description of the Related Art Aryl derivatives into which an arbitrary substituent is introduced are useful as a material for a conductive polymer.

Heretofore, there has been known a method of reacting zirconacyclopentadiene with tetraiodobenzene to synthesize anthracene into which a substituent is introduced. However, according to this method, the final product was a symmetric compound because zirconacyclopentadiene was added symmetrically on both sides of the benzene ring.

[0004] On the other hand, if zirconacyclopentadiene can be added to only one side of tetraiodobenzene, an asymmetric diiodoaryl derivative can be obtained. Since an arbitrary substituent can be added, it is useful as an intermediate. Therefore, it has been demanded to easily obtain an asymmetric dihaloaryl derivative.

[0005]

According to one aspect of the present invention, there is provided an aryl derivative represented by the following formula (I).

[0006]

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Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶
Are each independently the same or different and each is a hydrogen atom; a C ₁ -C ₄₀ hydrocarbon group which may have a substituent; a C ₁ -C ₄₀ alkoxy group which may have a substituent An optionally substituted C ₆ -C ₄₀ aryloxy group; an amino group, a hydroxyl group or a silyl group,
R ¹ and R ² , R ² and R ³ , or R ³ and R ⁴ may be cross-linked to each other to form a C _{4 to} C ₁₀ saturated or unsaturated ring, wherein the saturated or unsaturated ring is oxygen atom, a sulfur atom, or the formula -N (R ⁷⁾ - group represented by (wherein, R ⁷ is hydrogen atom, C ₁ -C ₄₀ hydrocarbon group or a halogen atom.)
And A ¹ and A ² may be each independently of each other, identical or different, a halogen atom, and n is an integer of 0 or more. It is. ) In the present invention, R ² and R ^3, C ₄ ~ crosslinked to each other
Forming a C ₁₀ saturated or unsaturated ring, wherein the saturated or unsaturated ring is an oxygen atom, a sulfur atom, or a compound of the formula —N (R ⁷ ) —
(Wherein R ⁷ is a hydrogen atom, a C ₁ -C ₄₀ hydrocarbon group or a halogen atom), and may have a substituent.

In another aspect of the present invention, there is provided a method for producing an aryl derivative represented by the following formula (I):

[0009]

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Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶
Are each independently the same or different and each is a hydrogen atom; a C ₁ -C ₄₀ hydrocarbon group which may have a substituent; a C ₁ -C ₄₀ alkoxy group which may have a substituent An optionally substituted C ₆ -C ₄₀ aryloxy group; an amino group, a hydroxyl group or a silyl group,
R ¹ and R ² , R ² and R ³ , or R ³ and R ⁴ may be cross-linked to each other to form a C _{4 to} C ₁₀ saturated or unsaturated ring, wherein the saturated or unsaturated ring is oxygen atom, a sulfur atom, or the formula -N (R ⁷⁾ - group represented by (wherein, R ⁷ is hydrogen atom, C ₁ -C ₄₀ hydrocarbon group or a halogen atom.)
And A ¹ and A ² may be each independently of each other, identical or different, a halogen atom, and n is an integer of 0 or more. It is. A metallacyclopentadiene represented by the following formula (II):

[0011]

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Wherein R ¹ , R ² , R ³ and R ⁴ have the above-mentioned meanings.

M represents a metal of Groups 3 to 5 of the Periodic Table or a lanthanide series; L ¹ and L ² independently of one another and, identically or differently, denote anionic ligands. However, L ¹ and L ² may be cross-linked. 2) at least 2 moles of the polycyclic compound represented by the following formula (III) per mole of the metallacyclopentadiene:

[0014]

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(Wherein R ⁵ , R ⁶ , n, A ¹ and A ² have the above-mentioned meanings.

X ¹ and X ² are each independent of each other;
The same or different and is a halogen atom. ) Is provided.

In the present invention, R ² and R ³ are cross-linked to each other to form a C ₄ -C ₁₀ saturated or unsaturated ring, wherein the saturated or unsaturated ring is an oxygen atom, a sulfur atom, −
A group represented by N (R ⁷ ) — (where R ⁵ is a hydrogen atom, C ₁
-C ₄₀ hydrocarbon group or a halogen atom. ), And may have a substituent.

Further, in the present invention, M is the fourth value in the periodic table.
A Group 5 or Group 5 or lanthanide series metal;
The anionic ligand is non-localized cyclic eta ⁵ - is preferably a coordination type ligand, wherein the delocalized cyclic eta ⁵ - coordination type ligand is substituted More preferably, it is a good cyclopentadienyl group, indenyl group, fluorenyl group or azulenyl group.

[0019]

BEST MODE FOR CARRYING OUT THE INVENTION According to one aspect of the present invention, there is provided an aryl derivative represented by the following formula (I).

[0020]

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R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are each independently of one another and are the same or different and each represents a hydrogen atom;
A C ₁ -C ₄₀ hydrocarbon group which may have a substituent; a C ₁ -C ₄₀ alkoxy group which may have a substituent; a C ₆ -C ₄₀ aryl which may have a substituent An oxy group; an amino group; a hydroxyl group or a silyl group.

In this specification, C₁-C₄₀Hydrocarbon groups are saturated
It may be a sum or unsaturated acyclic or saturated or
Or an unsaturated cyclic group. C₁-C₄₀Hydrocarbon group
When is acyclic, it may be linear or branched.
No. C₁-C₄₀Hydrocarbon groups include C₁-C₄₀Alkyl group, C
_Two-C₄₀Alkenyl group, C_Two-C₄₀Alkynyl group, C_Three-C ₄₀
Allyl group, C_Four-C₄₀Alkyldienyl group, C_Four-C₄₀Poly
Enyl group, C₆-C₄₀Aryl group, C₆-C₄₀Alkyl ants
Group, C₆-C₄₀Arylalkyl group, C_Four-C ₄₀Cyclo
Alkyl group, C_Four-C₄₀A cycloalkenyl group, (C_Three-C₂₀
Cycloalkyl) C₁-C₂₀And an alkyl group.

C₁-C₄₀Alkyl group, C_Two-C₄₀Alkenyl
Group, C_Two-C₄₀Alkynyl group, C_Three-C ₄₀Allyl group, C_Four-C
₄₀An alkyldienyl group and C_Four-C₄₀Polyenyl group
Is C₁-C₂₀Alkyl group, C_Two-C₂₀Alkene
Group, C_Two-C₂₀Alkynyl group, C_Three-C₂₀Allyl group, C_Four-
C₂₀An alkyldienyl group and C_Four-C₂₀Polyenyl group
And each is preferably C₁-C_TenAlkyl
Group, C_Two-C_TenAlkenyl group, C_Two-C_TenAlkynyl group, C
_Three-C_TenAllyl group, C_Four-C_TenAn alkyldienyl group, and
C_Four-C_TenMore preferably, it is a polyenyl group.

C₆-C₄₀Aryl group, C₆-C₄₀Alkyria
Reel base, C₆-C₄₀Arylalkyl group, C_Four-C₄₀Shiku
Loalkyl group, C_Four-C₄₀A cycloalkenyl group, and
(C_Three-C₂₀Cycloalkyl) C₁-C₂₀Alkyl groups are
Each C₆-C₂₀Aryl group, C₆-C₂₀Alkyl ally
Group, C₆-C₂₀Arylalkyl group, C_Four-C₂₀Cycloa
Alkyl group, C_Four-C₂₀A cycloalkenyl group and (C_Three-
C_TenCycloalkyl) C ₁-C_TenAlkyl groups are preferred,
Each C₆-C_TenAryl group, C₆-C₁₂Alkyl ants
Group, C₆-C₁₂Arylalkyl group, C_Four-C_TenCyclo
An alkyl group and C_Four-C_TenFurther cycloalkenyl groups
preferable.

Examples of alkyl groups useful in the practice of the present invention include, but are not limited to, methyl, ethyl, propyl, n-butyl, t-butyl, dodecanyl, trifluoromethyl, perfluoro-n-butyl, 2,2,2
-Trifluoroethyl, benzyl, 2-phenoxyethyl and the like.

Examples of aryl groups useful in the practice of this invention include, but are not limited to, phenyl, 2-tolyl, 3-tolyl, 4-tolyl, naphthyl, biphenyl,
4-phenoxyphenyl, 4-fluorophenyl, 3-
Carbomethoxyphenyl, 4-carbomethoxyphenyl and the like.

Examples of alkoxy groups useful in the practice of the present invention include, but are not limited to, methoxy, ethoxy, 2-methoxyethoxy, t-butoxy, and the like.

Examples of aryloxy groups useful in the practice of this invention include, but are not limited to, phenoxy,
Naphthoxy, phenylphenoxy, 4-methylphenoxy, 2-tolyloxy, 3-tolyloxy, 4-tolyloxy, naphthyloxy, biphenyloxy, 4-phenoxyphenyloxy, 4-fluorophenyloxy,
3-carbomethoxyphenyloxy, 4-carbomethoxyphenyloxy and the like.

Examples of amino groups useful in the practice of the present invention include, but are not limited to, amino, dimethylamino, methylamino, methylphenylamino, phenylamino, and the like.

Examples of silyl groups useful in the practice of the present invention include, but are not limited to, trimethylsilyl, dimethylphenylsilyl, methyldiphenylsilyl, triphenylsilyl, dimethylethylsilyl, methylmethoxyphenylsilyl, methylethylphenoxy. Silyl and the like.

A substituent may be introduced into the C ₁ -C ₄₀ hydrocarbon group, C ₁ -C ₄₀ alkoxy group and C ₆ -C ₄₀ aryloxy group. Examples of the substituent include halogen. Examples include an atom, an amino group, a hydroxyl group, a silyl group, an alkoxy group, and an aryloxy group.

Provided that R ¹ and R ² , R ² and R ³ , or
R ³ and R ⁴ may be bridged to each other to form a C ₄ -C ₁₀ saturated or unsaturated ring. That is, the aryl derivatives include polycyclic compounds such as naphthalene derivatives, anthracene derivatives, naphthacene derivatives, and phenanthrene derivatives.

The ring formed by these substituents is a four-membered ring
It is preferably a 10-membered ring, more preferably a 4-membered to 6-membered ring. This ring may be an aromatic ring such as a benzene ring or an aliphatic ring.

[0034] The saturated or unsaturated ring, oxygen atom, sulfur atom or the formula -N (R ⁷⁾ - group represented by (wherein, R ⁷
Is a hydrogen atom, a C ₁ -C ₄₀ hydrocarbon group or a halogen atom. ) May be interrupted. That is, the saturated or unsaturated ring may be a hetero ring.

R ⁷ is preferably a hydrogen atom or a C ₁ -C ₂₀ hydrocarbon group, more preferably a hydrogen atom or a C ₁ -C ₁₄ hydrocarbon group, and R ⁷ is a hydrogen atom,
Even more preferred are C ₁ -C ₆ alkyl, phenyl, naphthyl, benzyl and naphthylmethyl.

The saturated or unsaturated ring may have a substituent, and may be a C ₁ -C ₄₀ hydrocarbon group, a C ₁ -C ₄₀ alkoxy group, a C ₆ -C ₄₀ aryloxy group, an amine group, A substituent such as a hydroxyl group or a silyl group may be introduced.

A ¹ and A ² are each independently of the other
The same or different, a halogen atom, F, Cl,
It is preferably Br or I, and particularly preferably Cl or Br.

N is an integer of 0 or more. Preferably 0
And an integer of 0 to 5, and more preferably an integer of 0 to 3.

In another aspect of the present invention, a metallacyclopentadiene represented by the following formula (II) and 2 mol or more of the following formula (I) are added to 1 mol of the metallacyclopentadiene.
A method for producing an aryl derivative represented by the following formula (I) is provided, which comprises reacting a polycyclic compound represented by the formula (II).

[0040]

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Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ ,
n, A ¹ and A ² have the meaning described above. In the present invention, the metallacyclopentadiene represented by the above formula (II) and the polycyclic compound represented by the above formula (III) are mixed under predetermined conditions, that is, with respect to 1 mol of the metallacyclopentadiene (II). By reacting 2 moles or more of the polycyclic compound (III), metallacyclopentadiene (II) and the polycyclic compound (III) are in a one-to-one correspondence.
Wherein the aryl derivative represented by the above formula (I), which is a dihalo compound, can be obtained.

In the present invention, a metallacyclopentadiene represented by the following formula (II) is used.

[0043]

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(Wherein R ¹ , R ² , R ³ and R ⁴ have the above-mentioned meanings.) M represents a metal belonging to Group 3 to Group 5 of the periodic table or a lanthanide series metal. M is preferably a metal belonging to Group 4 of the periodic table or a lanthanide series, more preferably a metal belonging to Group 4 of the periodic table, namely, titanium, zirconium and hafnium, and still more preferably zirconium.

L ¹ and L ² are independent of each other and are the same or different and represent an anionic ligand. However, L ¹ and L ² may be cross-linked. The anionic ligand is preferably a delocalized cyclic η ⁵ -coordination ligand, a C ₁ -C ₂₀ alkoxy group, a C ₆ -C ₂₀ aryloxy group or a dialkylamide group.

L ¹ and L ² are preferably delocalized cyclic η ⁵ -coordination ligands. Delocalized cyclic eta ⁵ - Example of the coordination type ligand is an unsubstituted cyclopentadienyl group and substituted cyclopentadienyl groups. The substituted cyclopentadienyl group is, for example, methylcyclopentadienyl, ethylcyclopentadienyl, isopropylcyclopentadienyl, n-butylcyclopentadienyl, t
-Butylcyclopentadienyl, dimethylcyclopentadienyl, diethylcyclopentadienyl, diisopropylcyclopentadienyl, di-t-butylcyclopentadienyl, tetramethylcyclopentadienyl, indenyl group, 2-methylindenyl Group, 2-methyl-4-
A phenylindenyl group, a tetrahydroindenyl group, a benzoindenyl group, a fluorenyl group, a benzofluorenyl group, a tetrahydrofluorenyl group, and an octahydrofluorenyl group.

In the delocalized cyclic η ⁵ -coordination system ligand, one or more atoms of the delocalized cyclic π system may be substituted with a hetero atom. In addition to hydrogen, one such as an element of group 14 of the periodic table and / or an element of groups 15, 16 and 17 of the periodic table
It can contain more than one heteroatom.

Delocalized ring η^Five-Coordination ligands, for example
For example, a cyclopentadienyl group is
May be cross-linked by one or more cross-linking ligands.
It may be. Examples of the bridging ligand include C
H_Two, CH_TwoCH_Two, CH (CH_Three) CH_Two, CH (C
_FourH₉) C (CH_Three)_Two, C (CH_Three)_Two, (CH_Three)_TwoSi,
(CH_Three) _TwoGe, (CH_Three)_TwoSn, (C₆H_Five)_TwoSi,
(C₆H_Five) (CH_Three) Si, (C₆H _Five)_TwoGe, (C
₆H_Five)_TwoSn, (CH_Two)_FourSi, CH_TwoSi (CH_Three)_Two,
o-C₆H_FourOr 2, 2 '-(C₆H_Four)_TwoIs mentioned.

Two or more delocalized cyclic η^Five-Coordination coordination
, For example, cyclopentadienyl groups,
May be cross-linked by one or more cross-linking groups.
It may be. Examples of the crosslinking group include, for example, CH_Two, C
H_TwoCH_Two, CH (CH_Three) CH_Two, CH (C_FourH₉) C (C
H_Three)_Two, C (CH_Three)_Two, (CH_Three)_TwoSi, (CH_Three)_TwoG
e, (CH_Three)_TwoSn, (C₆H_Five)_TwoSi, (C₆H_Five)
(CH_Three) Si, (C₆H_Five) _TwoGe, (C₆H_Five)_TwoSn,
(CH_Two)_FourSi, CH_TwoSi (CH_Three)_Two, O-C₆H_Fouror
Is 2,2 '-(C₆H_Four)_TwoIs mentioned.

The metallacyclopentadiene represented by the formula (II) also includes a compound having two or more metallacyclopentadiene moieties. Such compounds are known as polynuclear metallocenes. The polynuclear metallocene may have any substitution mode and any bridged form. The independent metallocene moieties of the polynuclear metallocene may each be the same or different. Examples of the polynuclear metallocene include, for example, EP-A-632063, JP-A-4-80214, JP-A-4-85310,
A-654476.

In the present invention, a polycyclic compound represented by the following formula (III) is used.

[0052]

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(In the formula, R ⁵ , R ⁶ , n, A ¹ and A ² have the above-mentioned meanings.) X ¹ and X ² are each independently of one another and are the same or different and each represents a halogen atom. Yes, it is preferably F, Cl, Br, I, and Cl or Br is particularly preferred.

In the present invention, the metallacyclopentadiene represented by the above formula (II) and 2 mol or more of the polycyclic compound represented by the above formula (III) per 1 mol of the metallacyclopentadiene represented by the above formula (II) React with the compound. Typically, a polycyclic compound represented by the above formula (III) is added to a solution of the metallacyclopentadiene represented by the above formula (II).

The above reaction is preferably performed in the presence of a metal compound. The metal compound is represented by Periodic Table Nos. 4-1.
It is preferably a Group 5 metal compound, and in particular, a Group 8-15 metal compound is used.

The metal compound may be a metal salt,
The metal compound is V, Cr, Mn, Fe, Co, Ni, C
u or Zn, more preferably, for example, V, C
Even more preferably, it contains r, Mn, Cu or Zn, and particularly preferably it contains Cu. For example, V, C
Salts of inorganic acids such as hydrochloric acid and sulfuric acid for r, Mn, Fe, Co, Ni, Cu or Zn can be used. For example, titanium (IV) halide, iron halide (II)
I), copper (I) halide, zinc (II) halide,
Metal salts such as bismuth (III) halide are preferred, and copper (I) halides such as CuCl are particularly preferred and used.

Alternatively, as the metal compound, for example,
Bis (triphenylphosphine) dichloronickel, dichloro (2,2′-bipyridine) nickel, PdCl ₂ (2,2 ′
-Bipyridine) and the like. As the ligand of the nickel complex, phosphine; aromatic amines such as pyridine and bipyridine, and halogen atoms are preferably used. The central metal is preferably in a so-called 4 to 6 coordination, and more preferably a metal of Group 10 of the periodic table. As the phosphine, triphenylphosphine,
There are no restrictions such as methyldiphenylphosphine and bis (diphenylphosphino) alkylene. Forming a carbon-carbon bond by a coupling reaction in the presence of a nickel phosphine complex is described, for example, in T. K .; Takahash
i et. al. Am. Chem. Soc. , V
ol. 121. , No. 48, 1999, 11095.

The amount of the metal compound is preferably from 0.0001 mol to 20 mol, more preferably from 0.1 mol to 20 mol, per 1 mol of metallacyclopentadiene (II).
The amount is 10 mol, more preferably 0.9 mol to 3 mol.

In the present invention, one mole of the metallacyclopentadiene represented by the above formula (II) is
2 mol or more of the polycyclic compound represented by I) is allowed to act. Preferably, it is 2 mol to 3 mol, most preferably 2 mol.

The reaction is preferably carried out at -80 ° C to 300 ° C.
The temperature is preferably in the range of 0 ° C. to 150 ° C.
The temperature range is as follows. The pressure is, for example, in the range from 0.1 bar to 2500 bar, preferably in the range from 0.5 bar to 10 bar.

The solvent is preferably a solvent capable of dissolving the metallacyclopentadiene represented by the above formula (II). As the solvent, an aliphatic or aromatic solvent is used.
Ether solvents such as tetrahydrofuran or diethyl ether; halogenated hydrocarbons such as methylene chloride and dichloroethane; halogenated aromatic hydrocarbons such as o-dichlorobenzene; and aromatic hydrocarbons such as benzene and toluene are used.

The reaction is preferably carried out in the presence of a stabilizer for stabilizing the metal compound in a solvent.
In particular, when the metal compound is a metal salt and the solvent is an organic solvent, the stabilizer stabilizes the metal salt in the organic solvent. Examples of the stabilizer include dimethylpropylene urea, hexamethylphosphamide and the like.

The metallacyclopentadiene (II) used in the present invention can be synthesized, for example, using the following metallocene.

Bis (cyclopentadienyl) dichlorozirconium; bis (methylcyclopentadienyl) dichlorozirconium; bis (butylcyclopentadienyl) dichlorozirconium; bis (indenyl)
Dichlorozirconium; bis (fluorenyl) dichlorozirconium; (indenyl) (fluorenyl) dichlorozirconium; bis (cyclopentadienyl) dichlorotitanium; (dimethylsilanediyl) bis (indenyl) dichlorozirconium; (dimethylsilanediyl)
Bis (tetrahydroindenyl) dichlorozirconium; (dimethylsilanediyl) (indenyl) dichlorozirconium; (dimethylsilanediyl) bis (2-methylindenyl) dichlorozirconium; (dimethylsilanediyl) bis (2-ethylindenyl) dichloro Zirconium; (dimethylsilanediyl) bis (2-methyl-4,5-benzoindenyl) dichlorozirconium; (dimethylsilanediyl) bis (2-ethyl-4,
(5-benzoindenyl) dichlorozirconium; (dimethylsilanediyl) bis (2-methyl-4-phenylindenyl) dichlorozirconium; (dimethylsilanediyl) bis (2-ethyl-4-phenylindenyl) dichlorozirconium; Dichloro compounds such as dimethylsilanediyl) bis (2-methyl-4,6-diisopropylindenyl) dichlorozirconium may be reduced with a strong base such as an alkali metal such as sodium or an alkaline earth metal such as magnesium, Alternatively, metallacyclopentadiene is produced after conversion to a dialkyl form. Bis (cyclopentadienyl) dibutylzirconium; bis (butylcyclopentadienyl) dibutylzirconium; bis (methylcyclopentadienyl) dibutylzirconium; bis (indenyl) dibutylzirconium; bis (fluorenyl) dibutylzirconium;
(Indenyl) (fluorenyl) dibutylzirconium; (3-methyl-5-naphthylindenyl) (2,7
-Di-tert-butylfluorenyl) dibutylzirconium; (3-methyl-5-naphthylindenyl)
(3,4,7-trimethoxyfluorenyl) dibutylzirconium; (pentamethylcyclopentadienyl)
(Tetrahydroindenyl) dibutylzirconium;
(Cyclopentadienyl) (1-octen-8-ylcyclopentadienyl) dibutylzirconium; (indenyl) (1-buten-4-ylcyclopentadienyl)
[1,3-bis (trimethylsilyl) cyclopentadienyl] (3,4-benzofluorenyl) dibutylzirconium;

Bis (cyclopentadienyl) dibutyltitanium; dimethylsilanediylbis (indenyl) dibutylzirconium; dimethylsilanediylbis (tetrahydroindenyl) dibutylzirconium; dimethylsilanediyl (cyclopentadienyl) (indenyl) dibutylzirconium; Dimethylsilanediylbis (2-methylindenyl) dibutylzirconium; dimethylsilanediylbis (2-ethylindenyl) dibutylzirconium; dimethylsilanediylbis (2-methyl-4,
5-benzoindenyl) dibutylzirconium; dimethylsilanediylbis (2-ethyl-4,5-benzoindenyl) dibutylzirconium; dimethylsilanediylbis (4,5-dihydro-8-methyl-7H-cyclopent [e] Acenaphthylene-7-ylidene) dibutylzirconium; dimethylsilanediyl (2-methyl-4,
5-benzoindenyl) (2-methyl-4-phenylindenyl) dibutylzirconium; dimethylsilanediyl (2-ethyl-4,5-benzoindenyl) (2-methyl-4-phenylindenyl) dibutylzirconium; Dimethylsilanediyl (2-methyl-4,5-benzoindenyl) (2-ethyl-4-phenylindenyl) dibutylzirconium; dimethylsilanediyl (2
-Ethylindenyl) (2-ethyl-4-phenylnaphthyl) dibutylzirconium; dimethylsilanediyl (2-methylindenyl) (4-phenylindenyl)
Dibutyl zirconium; dimethylsilanediylbis (2
-Methyl-4-phenylindenyl) dibutylzirconium; dimethylsilanediylbis (2-ethyl-4-phenylindenyl) dibutylzirconium; dimethylsilanediylbis (2-methyl-4,6-diisopropylindenyl) dibutylzirconium; Dimethylsilanediylbis (2-ethyl-4,6-diisopropylindenyl) dibutylzirconium; dimethylsilanediylbis (2-methyl-4-naphthylindenyl) dibutylzirconium; dimethylsilanediylbis (2-ethyl-
4-naphthylindenyl) dibutylzirconium;

Methylphenylsilanediylbis (indenyl) dibutylzirconium; methylphenylsilanediyl (cyclopentadienyl) (indenyl) dibutylzirconium; methylphenylsilanediylbis (tetrahydroindenyl) dibutylzirconium; methylphenylsilanediylbis (2 -Methylindenyl) dibutylzirconium; methylphenylsilanediylbis (2-ethylindenyl) dibutylzirconium; methylphenylsilanediylbis (2-methyl-4,5-benzoindenyl) dibutylzirconium; methylphenylsilanediylbis ( 2-ethyl-4,5-benzoindenyl) dibutylzirconium; methylphenylsilanediylbis (4,5-dihydro-8-methyl-7H-cyclopent [e] a Naphthylene-7-ylidene) dibutyl zirconium; methylphenyl silane diyl (2-
Methyl-4,5-benzoindenyl) (2-methyl-4
-Phenylindenyl) dibutylzirconium; methylphenylsilanediyl (2-ethylindenyl) (2-
Methyl-4-phenylindenyl) dibutylzirconium; methylphenylsilanediyl (2-methyl-4,5
-Benzoindenyl) (2-ethyl-4-phenylindenyl) dibutylzirconium; methylphenylsilanediyl (2-ethyl-4,5-benzoindenyl) (2
-Ethyl-indenyl) dibutylzirconium; methylphenylsilanediyl (2-methylindenyl) (4phenylindenyl) dibutylzirconium;

Methylphenylsilanediylbis (2-methyl-4phenylindenyl) dibutylzirconium;
Methylphenylsilanediylbisdibutylzirconium; methylphenylsilanediylbis (2-methyl-
4,6-diisopropylindenyl) dibutylzirconium; methylphenylsilanediylbis (2-ethyl-
4,6-diisopropylindenyl) dibutylzirconium; methylphenylsilanediylbis (4-naphthylindenyl) dibutylzirconium; methylphenylsilanediylbis (2-ethyl-4-naphthylindenyl) dibutylzirconium; diphenylsilanediylbis ( Indenyl) dibutylzirconium; diphenylsilanediylbis (2-methylindenyl) dibutylzirconium; diphenylsilanediylbis (2-ethylindenyl) dibutylzirconium; diphenylsilanediyl (cyclopentadienyl) (indenyl) dibutylzirconium; diphenylsilane Diylbis (2-methyl-4,5-benzoindenyl) dibutylzirconium; diphenylsilanediylbis (2-ethyl-4,5
-Benzoindenyl) dibutylzirconium; diphenylsilanediyl (2-methyl-4,5-benzoindenyl) (2-methyl-4phenylindenyl) dibutylzirconium; diphenylsilanediyl (2-ethyl-
4,5-benzoindenyl) (2-methyl-4phenylindenyl) dibutylzirconium; diphenylsilanediyl (2-methyl-4,5-benzoindenyl) (2
-Ethyl-4phenylindenyl) dibutylzirconium; diphenylsilanediyl (2-ethyl-4,5-benzoindenyl) (2-ethyl-4naphthylindenyl) dibutylzirconium; diphenylsilanediyl (2-methylindenyl) (4phenylindenyl) dibutylzirconium; diphenylsilanediylbis (2
-Methyl-4phenylindenyl) dibutylzirconium; diphenylsilanediylbis (2-ethyl-4phenylindenyl) dibutylzirconium; diphenylsilanediylbis (2-methyl-4,6-diisopropylindenyl) dibutylzirconium;

Diphenylsilanediylbis; (2-ethyl-4,6-diisopropylindenyl) dibutylzirconiumdiphenylsilanediylbis (2-methyl-4
-Naphthylindenyl) dibutylzirconium; diphenylsilanediylbis (2-ethyl-4-naphthylindenyl) dibutylzirconium; 1-silacyclopentane-1,1-bis (indenyl) dibutylzirconium; 1-silacyclopentane-1 1-bis (2-methylindenyl) dibutylzirconium; 1-silacyclopentane-1,1-bis (2-ethylindenyl) dibutylzirconium; 1-silacyclopentane-1,1-
Bis (2-methyl-4,5-benzoindenyl) dibutylzirconium; 1-silacyclopentane-1,1-bis (2-ethyl-4,5-benzoindenyl) dibutylzirconium; 1-silacyclopentane- 1- (2-methyl-4,5-benzoindenyl) -1- (2-methyl-4-phenylindenyl) dibutylzirconium; 1
-Silacyclopentane-1- (2-ethyl-4,5-benzoindenyl) -1- (2-methyl-4-phenylindenyl) dibutylzirconium; 1-silacyclopentane-1- (2-methyl- 4,5-benzoindenyl)
-1- (2-ethyl-4-phenylindenyl) dibutylzirconium; 1-silacyclopentane-1- (2-
Ethyl-4,5-benzoindenyl) -1- (2-ethyl-4-naphthylindenyl) dibutylzirconium;
1-silacyclopentane-1- (2-methylindenyl) -1- (4-phenylindenyl) dibutylzirconium; 1-silacyclopentane-1,1-bis (2-
Methyl-1-phenylindenyl) dibutylzirconium; 1-silacyclopentane-1,1-bis (2-ethyl-4-phenylindenyl) dibutylzirconium;
1-silacyclopentane-1,1-bis (2-methyl-
4,6-diisopropylindenyl) dibutylzirconium; 1-silacyclopentane-1,1-bis (2-ethyl-4,6-diisopropylindenyl) dibutylzirconium; 1-silacyclopentane-1,1-bis ( 2-methyl-4-naphthylindenyl) dibutylzirconium; 1-silacyclopentane-1,1-bis (2
-Ethyl-4-naphthylindenyl) dibutylzirconium; bis (cyclopentadienyl) dibutyltitanium;
Ethylene-1,2-bis (indenyl) dibutylzirconium; ethylene-1,2-bis (tetrahydroindenyl) dibutylzirconium; ethylene-1- (cyclopentadienyl) -2- (1-indenyl) dibutylzirconium; ethylene -1- (cyclopentadienyl)
-2- (2-indenyl) dibutyl zirconium; ethylene-1- (cyclopentadienyl) -2- (2-methyl-1-indenyl) dibutyl zirconium; ethylene-1,2-bis (2-methylindenyl) Dibutyl zirconium; ethylene-1,2-bis (2-ethylindenyl) dibutyl zirconium; ethylene-1,2-bis (2-methyl-4,5-benzoindenyl) dibutyl zirconium; ethylene-1,2-bis (2-ethyl-
4,5-benzoindenyl) dibutylzirconium;

Ethylene-1,2-bis (4,5-dihydro-8-methyl-7H-cyclopent [e] acenaphthylene-7-ylidene) dibutylzirconium; ethylene-1- (2-methyl-4,5-benzoin Denenyl) -2
-(2-methyl-4-phenylindenyl) dibutylzirconium; ethylene-1- (2-ethyl-4,5-benzoindenyl) -2- (2-methyl-4-phenylindenyl) dibutylzirconium; ethylene -1- (2
-Methyl-4,5-benzoindenyl) -2- (2-ethyl-4-phenylindenyl) dibutylzirconium; ethylene-1- (2-ethyl-4,5-benzoindenyl) -2- (2 -Ethyl-4-naphthylindenyl) dibutylzirconium; ethylene-1- (2-methylindenyl) -2- (4-phenylindenyl) dibutylzirconium; ethylene-1,2-bis (2-methyl-4- Phenylindenyl) dibutylzirconium;
Ethylene-1,2-bis (2-ethyl-4-phenylindenyl) dibutylzirconium; ethylene-1,2-
Bis (2-methyl-4,6-diisopropylindenyl) dibutylzirconium; ethylene-1,2-bis (2-ethyl-4,6-diisopropylindenyl) dibutylzirconium; ethylene-1,2-bis (2- Methyl-4-naphthylindenyl) dibutylzirconium; ethylene-1,2-bis (2-ethyl-4-naphthylindenyl) dibutylzirconium; propylene-
2,2-bis (indenyl) dibutylzirconium; propylene-2-cyclopentadienyl-2- (1-indenyl) dibutylzirconium; propylene-2-cyclopentadienyl-2- (4-phenyl-1-indenyl) Dibutyl zirconium; propylene-2-cyclopentadienyl-2- (9-fluorenyl) dibutyl zirconium; propylene-2-cyclopentadienyl-2
-(2,7-dimethoxy-9-fluorenyl) dibutylzirconium; propylene-2-cyclopentadienyl-2- (2,7-di-tert-butyl-9-fluorenyl) dibutylzirconium; propylene-2-cyclopentane Dienyl-2- (2,7-dibromo-9-fluorenyl) dibutylzirconium; propylene-2-cyclopentadienyl-2- (2,7-diphenyl-9-fluorenyl) dibutylzirconium; propylene-2-
Cyclopentadienyl-2- (2,7-dimethyl-9-
Fluorenyl) dibutylzirconium; propylene-2
-(3-methylcyclopentadienyl) -2- (2,7
-Dibutyl-9-fluorenyl) dibutylzirconium; propylene-2- (3-tert-butylcyclopentadienyl) -2- (2,7-dibutyl-9-fluorenyl) dibutylzirconium; propylene-2- (3
-Trimethylsilylcyclopentadienyl) -2-
(3,6-di-tert-butyl-9-fluorenyl)
Dibutyl zirconium; propylene-2-cyclopentadienyl-2- [2,7-bis (3-buten-1-yl) -9-fluorenyl] dibutyl zirconium; propylene-2-cyclopentadienyl-2- (3 −ter
t-butyl-9-fluorenyl) dibutylzirconium; propylene-2,2-bis (tetrahydroindenyl) dibutylzirconium; propylene-2,2-bis (2-methylindenyl) dibutylzirconium; propylene-2,2-bis (2-ethylindenyl) dibutylzirconium; propylene-2,2-bis (2-methyl-4,5-benzoindenyl) dibutylzirconium; propylene-2,2-bis (2-ethyl-4,5-
Benzoindenyl) dibutylzirconium; propylene-2,2-bis (4,5-dihydro-8-methyl-7H
-Cyclopent [e] acenaphthylene-7-ylidene)
Dibutyl zirconium; propylene-2- (2-methyl-4,5-benzoindenyl) -2- (2-methyl-4
-Phenylindenyl) dibutylzirconium; propylene-2- (2-ethyl-4,5-benzoindenyl)
-2- (2-methyl-4-phenylindenyl) dibutylzirconium; propylene-2- (2-methyl-4,
5-benzoindenyl) -2- (2-ethyl-4-phenylindenyl) dibutylzirconium; propylene-
2- (2-ethyl-4,5-benzoindenyl) -2-
(2-ethyl-4-naphthylindenyl) dibutylzirconium; propylene-2- (2-methylindenyl)
-2- (4-phenylindenyl) dibutylzirconium; propylene-2,2-bis (2-methyl-4-phenylindenyl) dibutylzirconium; propylene-
2,2-bis (2-ethyl-4-phenylindenyl)
Dibutyl zirconium; propylene-2,2-bis (2
-Methyl-4,6-diisopropylindenyl) dibutylzirconium; propylene-2,2-bis (2-ethyl-4,6-diisopropylindenyl) dibutylzirconium; propylene-2,2-bis (2-methyl-4
-Naphthylindenyl) dibutylzirconium; propylene-2,2-bis (2-ethyl-4-naphthylindenyl) dibutylzirconium.

[0070]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below based on embodiments.
However, the present invention is not limited to the following examples.

All reactions were performed under a nitrogen atmosphere. THF, diethyl ether, hexane, and benzene used as solvents were distilled under a nitrogen stream with sodium metal and benzophenone to be anhydrous. The zirconocene dichloride used was purchased from Nichia Corporation. Alkynes were purchased from Tokyo Chemical Industry, and butyl lithium (1.6 M hexane solution) and phenyl lithium (
0.88 M cyclohexane diethyl ether solution) used was purchased from Kanto Chemical. Other reagents are Aldr
The one purchased from ich Chemical Company, Inc. was used.

¹ H-NMR (400 MHz) and ¹³ C-NMR (100 MHz)
The spectrum was measured at 25 ° C. using a Bruker ARX-400. At this time, deuterated chloroform (containing 1% TMS)
And TMS was used as an internal standard.

Gas chromatography was performed using SHIMADZU CBP1-
M25-025 SHIMA with fused silica capillary column
Measured by DZU GC-14A gas chromatograph, and recorded by SHIMAD
ZU CR6A-Chromatopac integrator was used. When the yield was determined by GC, mesitylene and n-dodecane were used as internal standards. As column packing material for column chromatography, Kanto Chemical Silica Gel 60N (spherical, neutral) 40-100
Micrometer was used.

Reference Example 1 bis (η ⁵ -cyclopentadienyl) 2,3,4,5-
Tetrapropyl-1-Jirukona 2,4 cyclopentadiene bis (eta ⁵ - cyclopentadienyl) zirconium dichloride (1.2 mmol) and THF (10ml) were placed in a Schlenk tube. The solution was cooled to -78 C and then n-butyllithium (2.4 mmol) was added. The solution for 1 hour at -78 ° C., stirred, bis - was obtained (eta ⁵ cyclopentadienyl) dibutyl zirconium. At -78 ° C, 4-octyne (4.0 mmol) was added to the reaction mixture, then warmed to room temperature and stirred for 1 hour to give the title compound. The title compound was used as is without isolation.

Reference Example 2 bis (η ⁵ -cyclopentadienyl) -2,3,4,5
-Tetraethyl-1-zircona-2,4-cyclopentadiene The same procedure as in Reference Example 1 was performed. However, 3-hexyne was used instead of 4-octyne.

Reference Example 3 bis (η ⁵ -cyclopentadienyl) -1,3-diethyl-4,5,6,7-tetrahydro-2-zirconaindene bis (η ⁵ -cyclopentadienyl) dichlorozirconium (1.0 mmol) and THF (10 ml) were charged into a Schlenk tube. The solution was cooled to -78 C, then n-butyllithium (2.0 mmol) was added. The solution for 1 hour at -78 ° C., stirred, bis - was obtained (eta ⁵ cyclopentadienyl) dibutyl zirconium.

At -78.degree. C., dodeca was added to the reaction mixture.
3,9-Diyne (1.0 mmol) was added, then warmed to room temperature and left for 1 hour to give the title compound. The title compound was used as is without isolation.

Reference Example 4 bis (η ⁵ -cyclopentadienyl) -1,2-dipropyl-3-zirconaindene Bis (η ⁵ -cyclopentadienyl) dichlorozirconium (1.0 mmol) and THF (10 ml) were used. It was put into a Schlenk tube. The solution was cooled to -78 C, then phenyllithium (2.0 mmol) was added. 1 hour the solution at -78 ° C., and stirred, bis - was obtained (eta ⁵ cyclopentadienyl) diphenyl zirconium.

At -78.degree. C., 4-octyne (1.0 mmol) is added to the reaction mixture, then warmed to 80.degree.
Stir for 2 hours to give the title compound. The title compound was used as is without isolation.

Reference Example 5 bis (η ⁵ -cyclopentadienyl) -2,3,4,5
-Tetraphenyl-1-zircona-2,4-cyclopentadiene The same procedure as in Reference Example 1 was performed. However, 1,2-diphenylacetylene was used instead of 4-octyne.

Reference Example 6 Bis (η ⁵ -cyclopentadienyl) -1,3-dipropyl-4,5,6,7-tetrahydro-2-zirconaindene The same procedure as in Reference Example 3 was performed. However, Dodeca-3,
Instead of 9-diyne, tetradeca-4,10-diyne was used.

Example 1 6,7-diiodo-1,2,3,4-tetrapropylnaphthalene

[0083]

Embedded image

The bis (η ⁵ -cyclopentadienyl) 2,3,4,5-tetrapropyl-1- obtained in Reference Example 1
In a THF solution of zircona-2,4-cyclopentadiene,
At room temperature, 2.1 equivalents of copper (I) chloride, 3 equivalents of dimethylpropylene urea, and 2 equivalents of tetraiodobenzene were added. After stirring at 50 ° C. for 1 hour, the reaction was terminated by adding 3N HCl and extracted with ethyl acetate. The extract was washed with an aqueous solution of sodium hydrogen carbonate and brine.
After concentration, the residue was subjected to column chromatography using silica gel as a filler and hexane. The title compound (0.542 g) was obtained as a pale yellow solid in an isolated yield of 49%. As a by-product, 1,2,3,4,5,6,7,8-octapropylanthracene was obtained in an isolated yield of 13%. _{^{. 1 H NMR (CDCl 3,}} Me 4 Si) δ1.09 (t, J = 7.3 Hz, 6H),
1.09 (t, J = 7.3 Hz, 6H), 1.51-1.65 (m, 8H), 2.68
(t, J = 8.4 Hz, 4H), 2.88 (t, J = 8.3 Hz, 4H), 8.47
(s, 2H); ¹³ C NMR (CDCl ₃ , Me ₄ Si) δ 14.80 (2C), 1
5.02 (2C), 24.53 (2C), 24.72 (2C), 30.78 (2C), 32.
57 (2C), 102.56 (2C), 132.10 (2C), 133.16 (2C), 13
5.51 (2C), 138.60 (2C). HRMS Calculated C ₂₂ H ₃₀ I ₂ 548.
0438, experimental: 548.0449.

Example 2 6,7-diiodo-1,2,3,4-tetraethylnaphthalene

[0086]

Embedded image

The procedure was performed in the same manner as in Example 1. However,
Bis (η ⁵ -cyclopentadienyl) 2,3,4,5-
Instead of tetrapropyl-1-zircona-2,4-cyclopentadiene, bis (η ⁵ −) obtained in Reference Example 2 was used.
(Cyclopentadienyl) 2,3,4,5-tetraethyl-1-zircona-2,4-cyclopentadiene was used. The residue was subjected to column chromatography using silica gel as a filler and hexane. 0.202 g of the title compound was obtained as a white solid in 34% isolated yield.

¹ H NMR (CDCl ₃ , Me ₄ Si) δ 1.22 (t, J =
7.4 Hz, 6H), 1.27 (t, J = 7.5 Hz, 6H), 2.80 (q, J
= 7.5 Hz, 4H), 2.99 (t, J = 7.5 Hz, 4H), 8.52 (s,
2H); ¹³ C NMR (CDCl ₃ , Me ₄ Si) δ 15.57 (2C), 15.64 (2
C), 21.44 (2C), 22.85 (2C), 102.64 (2C), 131.95 (2
C), 134.45 (2C), 135.46 (2C).

Example 3 9,10-Diethyl-6,7-diiodo-1,2,3,3
4-tetrahydroanthracene

[0090]

Embedded image

The procedure was performed in the same manner as in Example 1. However,
Bis (η ⁵ -cyclopentadienyl) 2,3,4,5-
Instead of tetrapropyl-1-zircona-2,4-cyclopentadiene, bis (η ⁵ −) obtained in Reference Example 3 was used.
Cyclopentadienyl) -1,3-diethyl-4,5
6,7-Tetrahydro-2-zirconaindene was used. The residue was subjected to column chromatography using silica gel as a filler and hexane. 0.328 g of the title compound was obtained as a white solid in 33% isolated yield.
1,2,3,4,8,9,10,11-octahydro-5,
7,12,14-Tetraethylpentacene was produced in an isolated yield of 25%.

¹ H NMR (CDCl ₃ , Me ₄ Si) δ 1.17 (t, J =
7.5 Hz, 6H), 1.79 (bs, 4H), 2.83 (bs, 4H), 2.88 (q,
J = 7.5 Hz, 4H), 8.47 (s, 2H); ¹³ C NMR (CDCl ₃ , Me
₄ Si) δ 14.23 (2C), 20.66 (2C), 22.81 (2C), 27.59
(2C), 102.51 (2C), 131.11 (2C), 134.02 (2C), 134.56
(2C), 134.97 (2C).

Example 4 2,3-diiodo-9,10-dipropylphenanthrene

[0094]

Embedded image

The procedure was the same as in Example 1. However,
Bis (η ⁵ -cyclopentadienyl) 2,3,4,5-
Instead of tetrapropyl-1-zircona-2,4-cyclopentadiene, bis (η ⁵ −) obtained in Reference Example 4 was used.
(Cyclopentadienyl) -1,2-dipropyl-3-zirconaindene was used. The residue was subjected to column chromatography using hexane using silica gel as a filler and recrystallized from ethanol to give 0.093 g of the title compound as white needles in an isolated yield of 18%.

¹ H NMR (CDCl ₃ , Me ₄ Si) δ 1.13 (t, J =
7.4 Hz, 3H), 1.13 (t, J = 7.4 Hz, 3H), 1.61-1.76
(m, 4H), 2.99 (t, J = 8.1 Hz, 2H), 2.88 (t, J = 8.
3 Hz, 2H), 7.53-7.63 (m, 2H), 8.01-8.04 (m, 1H), 8.
49-8.52 (m, 2H), 9.10 (s, 1H); ¹³ C NMR (CDCl ₃ , Me ₄ S
i) δ 14.70, 14.76, 23.85, 23.92, 31.05, 31.53,10
3.73, 105.28, 122.67, 124.85, 126.00, 127.49, 128.
10, 130.88, 131.55, 132.32, 133.92, 135.60, 135.79,
147.67.

Example 5 6,7-diiodo-1,2,3,4-tetraphenylnaphthalene

[0098]

Embedded image

The procedure was performed in the same manner as in Example 1. However,
Bis (η ⁵ -cyclopentadienyl) 2,3,4,5-
Instead of tetrapropyl-1-zircona-2,4-cyclopentadiene, bis (η ⁵ −) obtained in Reference Example 5 was used.
(Cyclopentadienyl) -2,3,4,5-tetraphenyl-1-zircona-2,4-cyclopentadiene was used. The residue was subjected to column chromatography using silica gel as a filler and hexane. 0.411 g of the title compound was obtained as a pale yellow solid in 60% isolated yield.

¹ H NMR (CDCl ₃ , Me ₄ Si) δ 6.77-6.82 (m,
10H), 7.13-7.24 (m, 10H), 8.14 (s, 2H); ¹³ C NMR (C
DCl ₃ , Me ₄ Si) δ 104.87 (2C), 125.59 (2C), 126.65
(4C), 126.90 (2C), 127.77 (4C), 130.98 (4C), 131.0
8 (4C), 132.72 (2C), 137.44 (2C), 137.65 (2C), 13
8.19 (2C), 139.87 (2C), 140.36 (2C).

Example 6 9,10-Dipropyl-6,7-diiodo-1,2,2
3,4-tetrahydroanthracene

[0102]

Embedded image

The procedure was the same as in Example 1. However,
Bis (η ⁵ -cyclopentadienyl) 2,3,4,5-
Instead of tetrapropyl-1-zircona-2,4-cyclopentadiene, the bis (η ⁵ −
Cyclopentadienyl) -1,3-dipropyl-4,
5,6,7-tetrahydro-2-zirconaindene was used. The residue was subjected to column chromatography using silica gel as a filler and hexane. 0.148 g of the title compound was obtained as a white solid in 57% isolated yield.

¹ H NMR (CDCl ₃ , Me ₄ Si) δ 1.07 (t, J =
7.4 Hz, 6H), 1.51-1.63 (m, 4H), 1.79-1.83 (m, 4H),
2.83-2.89 (m, 8H), 8.47 (s, 2H); ¹³ C NMR (CDCl ₃ , M
e ₄ Si) δ 14.68 (2C), 22.80 (2C), 23.36 (2C), 27.81
(2C), 29.86 (2C), 102.38 (2C), 131.58 (2C), 132.88
(2C), 135.16 (2C), 135.29 (2C).

Reference Example 7 5,12-dihydro-8,9-diiodo-1,2,3
4,6,11-hexapropylnaphthacene

[0106]

Embedded image

The same procedure as in Example 1 was performed. However,
Instead of tetraiodobenzene, 9,10-dipropyl-1,2,3,4-tetrahydro-2,3,6,7-
Tetraiodoanthracene was used. The residue was subjected to column chromatography using silica gel as a filler and hexane (ethyl acetate / hexane, 1/99). 0.47
7 g of the title compound were obtained as a pink solid in 33% isolated yield.

¹ H NMR (CDCl ₃ , Me ₄ Si) δ 1.06 (t, J =
7.2 Hz, 6H), 1.15 (t, J = 7.2 Hz, 12H), 1.49-1.72
(m, 12H), 2.56 (t, J = 8.4 Hz, 4H), 2.74 (t, J =
8.4Hz, 4H), 3.07 (t, J = 8.1 Hz, 4H), 3.98 (s, 4
H), 8.52 (s, 2H); ¹³ C NMR (CDCl ₃ , Me ₄ Si) δ 14.78
(2C), 15.07 (2C), 15.13 (2C), 24.25 (2C), 24.68 (2
C), 25.04 (2C), 30.47 (2C), 30.59 (2C), 32.21 (2
C), 32.34 (2C), 102.71 (2C), 131.01 (2C), 131.97 (2
C), 133.47 (2C), 135.09 (2C), 135.50 (2C), 136.08
(2C), 136.84 (2C).

[0109]

According to the present invention, an asymmetric aryl derivative which is a dihalo compound can be easily obtained.

Claims (6)

[Claims] 1. An aryl derivative represented by the following formula (I). Embedded image (Wherein, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are each independently of one another and are the same or different and are a hydrogen atom; C ₁ -C 5 which may have a substituent; _A C ₁ -C ₄₀ alkoxy group which may have a substituent; a C ₆ -C ₄₀ aryloxy group which may have a substituent; an amino group; a hydroxyl group or a silyl group; Provided that R ¹ and R ² , R ² and R ³ , or R ³ and R
⁴ may be bridged to each other to form a C ₄ -C ₁₀ saturated or unsaturated ring, wherein the saturated or unsaturated ring is represented by an oxygen atom, a sulfur atom, or a formula —N (R ⁷ ) — A ¹ and A ¹ and A 2 may be interrupted by a group (wherein R ⁷ is a hydrogen atom, a C ₁ -C ₄₀ hydrocarbon group or a halogen atom), and may have a substituent; ² is each independently, identical or different, and is a halogen atom, and n is an integer of 0 or more. ) 2. R ² and R ³ are bridged to each other to form C ₄ -C
₁₀ forms a saturated or unsaturated ring, wherein the saturated or unsaturated ring is an oxygen atom, a sulfur atom, or a group represented by the formula —N (R ⁷ ) — (where R ⁷ is a hydrogen atom, ₁ -C ₄₀ hydrocarbon group or a halogen atom.) may be interrupted by, and may have a substituent, an aryl derivative of claim 1. 3. A method for producing an aryl derivative represented by the following formula (I): (Wherein, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are each independently of one another and are the same or different and are a hydrogen atom; C ₁ -C 5 which may have a substituent; _A C ₁ -C ₄₀ alkoxy group which may have a substituent; a C ₆ -C ₄₀ aryloxy group which may have a substituent; an amino group; a hydroxyl group or a silyl group; Provided that R ¹ and R ² , R ² and R ³ , or R ³ and R
⁴ may be bridged to each other to form a C ₄ -C ₁₀ saturated or unsaturated ring, wherein the saturated or unsaturated ring is represented by an oxygen atom, a sulfur atom, or a formula —N (R ⁷ ) — A ¹ and A ¹ and A 2 may be interrupted by a group (wherein R ⁷ is a hydrogen atom, a C ₁ -C ₄₀ hydrocarbon group or a halogen atom), and may have a substituent; ² is each independently, identical or different, and is a halogen atom, and n is an integer of 0 or more. A metallacyclopentadiene represented by the following formula (II): (Wherein R ¹ , R ² , R ³ and R ⁴ have the above meanings. M represents a metal belonging to Groups 3 to 5 of the periodic table or a lanthanide series; L ¹ and L ² represent , Independently of each other, the same or different, and represents an anionic ligand, provided that L ¹
And L ² may be cross-linked. 2) At least 2 moles of the polycyclic compound represented by the following formula (III) with respect to 1 mole of the metallacyclopentadiene: (In the formula, R ⁵ , R ⁶ , n, A ¹ and A ² have the above-mentioned meanings. X ¹ and X ² are each independently of one another and are the same or different and are halogen atoms.) A method for producing an aryl derivative, which comprises reacting. 4. R ² and R ³ are cross-linked to form C ₄ -C
₁₀ forms a saturated or unsaturated ring, wherein the saturated or unsaturated ring is an oxygen atom, a sulfur atom, or a group represented by the formula —N (R ⁷ ) — (wherein R ⁵ is a hydrogen atom, ₁ -C ₄₀ hydrocarbon group or a halogen atom.) may be interrupted by, and may have a substituent group, the manufacturing method of the aryl derivative of claim 3. 5. M is a metal of Group 4 or 5 of the periodic table or a lanthanide series metal, and the anionic ligand is a delocalized cyclic η ⁵ -coordination ligand. A method for producing the aryl derivative according to claim 3. 6. The method according to claim ⁵ , wherein the delocalized cyclic η ⁵ -coordination ligand is an optionally substituted cyclopentadienyl group, indenyl group, fluorenyl group or azulenyl group. A method for producing an aryl derivative.