JP2002088092A - New organometallic complex and method for synthesizing highly pure organometallic complex using the same as intermediate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for synthesizing a metallocene compound on an industrial scale in high purity and high yield by solving problems that when a metallocene compound, which is scarcely soluble in an organic solvent, is synthesized, a large amount of organic solvent is used for extracting the complex, and the yield is lowered due to decomposition caused by washing with an alcohol. SOLUTION: A compound expressed by general formula [I] is synthesized in high purity by reacting a compound of general formula [II] with a compound of general formula [III] followed by halogenating the reaction product. In these formulae, M is a transition metal of the group 4; X is a halogen; R1 to R10 are each H, an alkyl group or an aryl group; and at least one pair of groups out of pairs of neighboring groups form an aromatic ring by bonding to each other.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a method for synthesizing a high-purity metallocene compound useful as a catalyst for organic synthesis and an intermediate thereof.

[0002]

2. Description of the Related Art A general method for synthesizing a metallocene is as follows.
A widely used method is to deprotonate a ligand using a base (eg, NaH, n-BuLi, etc.) and then react with a metal halide such as zirconium tetrachloride. At this time, an inorganic salt such as lithium chloride is generated as a by-product,
As a method of removing this, a method of dissolving a metallocene compound in a solvent and separating it from an insoluble inorganic salt, which is a known method, is generally used. Also, a method of adding a polar solvent such as THF or alcohol to a metallocene compound which is slightly insoluble in an organic solvent and dissolving and removing an inorganic salt without dissolving the target metallocene compound (Japanese Patent Application Laid-Open No. 09-176178). It has been reported. However, the compound represented by the general formula [I] described in the claims of the present application is very poorly soluble in organic solvents, and requires a large amount of solvent to dissolve metallocene and remove inorganic salts. Is very bad. Also, in the method of dissolving and removing the inorganic salt, a large amount of solvent is required to dissolve the inorganic salt using an organic solvent such as THF or methylene chloride, and the metallocene itself is slightly soluble in these solvents. For,
Use of a large amount of solvent results in a decrease in yield. When an alcoholic solvent having a relatively high solubility of an inorganic salt is used, the metallocene compound is decomposed to lower the yield.

[0003] As a synthesis method that does not generate an inorganic salt, a method using a tetrakis (dialkylamide) metal compound (for example, Zr (NMe ₂ ) ₄ ) (WO95 / 32979; US Patent 549)
5035; Organometallics, 15, 4030 (1996); Organometalli
cs, 15, 4038 (1996); Organometallics, 15, 4045 (1996); O
rganometallics, 17,281, (1998); J. Am. Chem. Soc., 118,
8024, (1996)). According to this method, the tetrakis (dialkylamide) metal compound is unstable, the synthesis and handling are difficult, and the dialkylamide complex obtained by reacting the ligand with the tetrakis (dialkylamide) metal compound is also unstable. Difficult to handle from
In particular, there are numerous problems as a synthesis method for producing a metallocene compound in a large amount (industrial). As described above, a method for obtaining a compound represented by the following general formula [I], which is hardly soluble in an organic solvent, at a high purity without containing an inorganic salt, is a method that can be used industrially at present. Instead, its development was desired.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a metallocene compound which is hardly soluble in an organic solvent, by using a large amount of an organic solvent for complex extraction or by recovering the compound by alcohol washing. It is an object of the present invention to solve the problems of the prior art, that is, a reduction in the yield, and to establish an industrial synthesis method capable of obtaining a metallocene compound with high purity and high yield.

[0005]

Means for Solving the Problems In view of the above circumstances, the present inventors have conducted intensive studies on a method for synthesizing a metallocene compound which is very insoluble in a solvent. By passing a transition metal compound as an intermediate, it is possible to easily remove the inorganic salt at this stage, and then to perform a halogenation to efficiently produce a high-purity metallocene compound containing no inorganic salt. They have found that they can be synthesized, and have completed the present invention.

That is, the present invention provides a compound represented by the following general formula [I]:

Embedded image (Wherein M represents a Group 4 transition metal, and ethers or amines may be coordinated to M with a coordination number of 1 to 2, and Xs may be each independently the same or different. Represents a good halogen atom, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ and
R ₁₀ independently represents a hydrogen atom or an alkyl group or an aryl group having 1 to 30 carbon atoms which may be the same or different from each other, provided that R ₁ and R ₂ , R ₂ and R ₃ , R ₃ R ₄ ,
At least one of combinations of R ₅ and R _6, R ₆ and R _7, R ₇ and R ₈ and R ₉ and R ₁₀ bond together to form an aromatic ring together)
In the synthesis of the compound represented by the following general formula [II]

Embedded image (Wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ and R ₁₀ are the same as those described in the general formula [I], and B is A cation of an alkali metal or an alkaline earth metal) and the following general formula [III]

Embedded image (Wherein M represents a Group 4 transition metal, A independently represents an atom selected from Group 15 atoms and Group 16 atoms which may be the same or different from each other, and when A is a Group 15 atom, = 1, R ₁₁ and R ₁₂ may combine to form A or a ring containing A and M.When A is a group 16 atom, n = 0, R ₁₁ is a halogen atom, A nitrogen atom, a phosphorus atom, an oxygen atom and / or a hydrocarbon group having 1 to 10 carbon atoms which can contain a sulfur atom or an aryl group which may have a halogen atom as a substituent, and R ₁₂ is a halogen atom X represents an alkyl group or an aryl group which may have a hydrocarbon group having 1 to 10 carbon atoms which may contain a nitrogen atom, a phosphorus atom, an oxygen atom and / or a sulfur atom; Represents a halogen atom which may be the same or different,
Further, M may be a compound represented by ethers or amines may be coordinated with a coordination number of 1 to 2),
The following general formula [IV]

Embedded image (Wherein M represents a Group 4 transition metal, and ethers or amines may be coordinated to M with a coordination number of 1 to 2,
R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ and R ₁₀ are the same as those described in the general formula [I], and A and R ₁₁ R ₁₂ and n are the same as those described in formula [III])
And obtaining a compound represented by the general formula [I] with high purity.

Further, the present invention relates to a compound represented by R₁, R_Two,
R_Three, R_Four, R_Five, R₆, R₇, R₈, R₉And R_TenBut each independently
Hydrogen or carbon, which may be the same or different
An alkyl group or an aryl group having 1 to 6 atoms,
₁And R_Two, R_TwoAnd R_Three, R_ThreeAnd R_Four, R _FiveAnd R₆, R₆And R₇, R₇And R₈And R
₉And R_TenAt least one of the combinations of
Forming an aromatic ring by the method described above.
Related.

Further, the present invention relates to the above-mentioned method, wherein A in each of the general formulas is a nitrogen atom or an oxygen atom.

[0009] The present invention, R ₁₁ is a halogen atom in each formula, a nitrogen atom, phosphorus atom, oxygen atom and / or a hydrocarbon group or a halogen atom having 1 to 10 carbon atoms, which may atoms include sulfur atom A phenyl group which may have a substituent, wherein R ₁₂ has a halogen atom, a nitrogen atom, a phosphorus atom, an oxygen atom and / or a hydrocarbon group having 1 to 10 carbon atoms which may contain a sulfur atom; Or a phenyl group.

[0010] The present invention further relates to the following general formula [IV]

Embedded image (Wherein M represents a Group 4 transition metal, and ethers or amines may be coordinated to M with a coordination number of 1 to 2, R ₁ ,
R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ and R ₁₀ are each independently a hydrogen atom or a carbon atom having 1 to 30 which may be the same or different from each other. Represents an alkyl group or an aryl group, R ₁ and R ₂ , R ₂ and R ₃ , R ₃ and R ₄ , R ₅ and R ₆ , R ₆ and R ₇ , R ₇ and R ₈
And at least one of the combinations of R ₉ and R ₁₀ is bonded to each other to form an aromatic ring, and A independently represents a Group 15 atom and a Group 16 atom which may be the same or different from each other; When n is a group atom, n = 1, and R ₁₁ and R ₁₂ may combine to form A or a ring containing A and M. When A is a group 16 atom, n = 0. R ₁₁ represents a halogen atom, a nitrogen atom, a phosphorus atom, a hydrocarbon group having 1 to 10 carbon atoms which may contain an oxygen atom and / or a sulfur atom or an aryl group which may have a halogen atom as a substituent, R ₁₂ represents an alkyl group or an aryl group which may have a halogen atom, a nitrogen atom, a phosphorus atom, an oxygen atom and / or a hydrocarbon group having 1 to 10 carbon atoms which may contain a sulfur atom. Transition metal compound to be used.

[0011] The present invention, in the general formula [IV], R _1,
R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ and R ₁₀ are each independently a hydrogen atom or a carbon atom having 1 to 6 which may be the same or different from each other. An alkyl group or an aryl group, R ₁ and R ₂ , R ₂ and R ₃ , R ₃ and R ₄ , R ₅ and R ₆ , R ₆ and R ₇ , R ₇ and R ₈
And at least one of the combinations of R ₉ and R ₁₀ is bonded to each other to form an aromatic ring.

[0012] The present invention further relates to a compound represented by the general formula [IV]:
Is a nitrogen atom or an oxygen atom.

[0013] Furthermore, the present invention is, in the general formula [IV], R ₁₁ is a halogen atom and / or nitrogen atom, phosphorus atom, oxygen atom, carbon atoms, which may atoms include sulfur atom 1 to 1
0 is a hydrocarbon group or a phenyl group which may have a halogen atom as a substituent, and R ₁₂ has 1 to 1 carbon atoms which may contain a halogen atom, a nitrogen atom, a phosphorus atom, an oxygen atom and / or a sulfur atom. 10 is an alkyl group or a phenyl group which may have a hydrocarbon group, and when A is a group 15 atom, R ₁₁ and R ₁₂ may combine to form a ring containing A or A and M A compound according to the preceding claims which is characterized by good properties.

[0014]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The embodiments of the present invention will be described below in detail. Usually, synthesis of a metallocene compound is carried out by reacting a metal halide such as zirconium tetrachloride with a deprotonated ligand represented by the general formula [II]. In this reaction system, an inorganic salt (for example, lithium chloride) is generated as a by-product, and in order to remove the inorganic salt, metallocene is dissolved in an organic solvent, and an inorganic salt insoluble in the organic solvent is removed. However, the compound represented by the general formula [I] has low solubility in an organic solvent, and in the conventional method, it was necessary to use a large amount of the organic solvent for separation from the inorganic salt. The compound represented by the general formula [II] and the general formula [I
The compound represented by the general formula [IV] derived from the reaction of the compound represented by the formula [II] has a high solubility even in a low-polarity solvent such as toluene which does not dissolve the inorganic salt. By extracting the compound represented by the general formula [IV] using the compound, separation from the inorganic salt becomes possible. By halogenating the compound represented by the general formula [IV] after removing the inorganic salt, a compound having a high purity represented by the general formula [I] can be efficiently obtained.

[0015] In the present invention, a hetero atom bonded to M in the compound represented by the general formula [III] (the general formula [III]
A) may be any atom as long as it is a hetero atom belonging to Group 15 or 16, and is preferably a nitrogen atom, an oxygen atom, a phosphorus atom, or a sulfur atom, and more preferably a nitrogen atom or an oxygen atom. Used. The organic moiety R ₁₁ is a halogen atom bonded to the hetero atom, a nitrogen atom perforated, as phosphorus atom, an oxygen atom and / or a substituent a hydrocarbon group or a halogen atom having 1 to 10 carbon atoms, which may atoms include sulfur atom Represents an aryl group which may be substituted, and R ₁₂ is an alkyl which may have a hydrocarbon group having 1 to 10 carbon atoms which may contain a halogen atom, a nitrogen atom, a phosphorus atom, an oxygen atom and / or a sulfur atom. Represents a group or an aryl group. Further, X in the compound represented by the general formula [III]
Is a halogen atom, preferably a chlorine atom or a bromine atom.

As the compound represented by the general formula [III], bis (N-methylanilide) titanium dichloride, bis (N-ethylanilide) titanium dichloride, bis (N-propylanilide) titanium dichloride,
Bis (N-butylanilide) titanium dichloride,
Bis ((N-methyl) tolulamido) titanium dichloride, bis ((N-ethyl) tolulamido) titanium dichloride, bis ((N-propyl) tolulamido) titanium dichloride, bis ((N-butyl) tolulamido) titanium Dichloride, bis ((N-methyl) dimethylphenylamide) titanium dichloride, bis ((N-ethyl) dimethylphenylamide) titanium dichloride, bis ((N-propyl) dimethylphenylamide) titanium dichloride, bis ((N-butyl ) Dimethylphenylamide) titanium dichloride, bis (diphenylamide) titanium dichloride, bis ((N-phenyl) tolulamido) titanium dichloride, bis (tolulamido) titanium dichlora De, N, N'-diphenyl-methylene diamide titanium dichloride, N, N'-diphenyl ethylene diamide titanium dichloride,
N, N'-diphenylpropylenediamiditanium dichloride, bis (pyrroleyl) titanium dichloride,

Bis (N-methylanilide) titanium dibromide, bis (N-ethylanilide) titanium dibromide, bis (N-propylanilide) titanium dibromide, bis (N-butylanilide) titanium dibromide, bis (( N-methyl) tolulamido) titanium dibromide, bis ((N-ethyl) tolulamido) titanium dibromide, bis ((N-propyl) tolulamido) titanium dibromide, bis ((N-butyl) tolulamido) titanium Dibromide, bis ((N-methyl) dimethylphenylamide)
Titanium dibromide, bis ((N-ethyl) dimethylphenylamide) titanium dibromide, bis ((N-propyl) dimethylphenylamide) titanium dibromide, bis ((N-butyl) dimethylphenylamide) titanium dibromide, bis (Diphenylamide) titanium dibromide, bis ((N-phenyl) tolulamido) titanium dibromide, bis (tolulamido) titanium dibromide, N, N '
Diphenylmethylenediamiditanium dibromide, N, N′-diphenylethylenediamiditanium dibromide, N, N′-diphenylpropylenediamiditanium dibromide, bis (pyrroleyl) titanium dibromide,

Bis (N-methylanilide) zirconium dichloride, bis (N-ethylanilide) zirconium dichloride, bis (N-propylanilide) zirconium dichloride, bis (N-butylanilide) zirconium dichloride, bis ((N-methyl) Toluylamide) zirconium dichloride, bis ((N-ethyl)
Toluylamide) zirconium dichloride, bis ((N-propyl) tolulamido) zirconium dichloride, bis ((N-butyl) tolulamido) zirconium dichloride, bis ((N-methyl) dimethylphenylamide) zirconium dichloride, bis ((N -Ethyl) dimethylphenylamide) zirconium dichloride, bis ((N-propyl) dimethylphenylamide) zirconium dichloride, bis ((N-
Butyl) dimethylphenylamide) zirconium dichloride, bis (diphenylamide) zirconium dichloride, bis ((N-phenyl) tolulamido) zirconium dichloride, bis (tolulamido) zirconium dichloride, N, N′-diphenylmethylenediamide zirconium dichloride, N , N'-diphenylethylenediamide zirconium dichloride, N,
N'-diphenylpropylenediamide zirconium dichloride, bis (pyrroleyl) zirconium dichloride,

Bis (N-methylanilide) zirconium dibromide, bis (N-ethylanilide) zirconium dibromide, bis (N-propylanilide) zirconium dibromide, bis (N-butylanilide) zirconium dibromide, bis (( N-methyl) tolulamido) zirconium dibromide, bis ((N-ethyl)
Toluylamide) zirconium dibromide, bis ((N-propyl) tolulamido) zirconium dibromide, bis ((N-butyl) tolulamido) zirconium dibromide, bis ((N-methyl) dimethylphenylamide) zirconium dibromide, Bis ((N-ethyl) dimethylphenylamide) zirconium dibromide, bis ((N-propyl) dimethylphenylamide) zirconium dibromide, bis ((N-
Butyl) dimethylphenylamide) zirconium dibromide, bis (diphenylamide) zirconium dibromide, bis ((N-phenyl) tolulamido) zirconium dibromide, bis (tolulamido) zirconium dibromide, N, N'-diphenylmethylenediamide Zirconium dibromide, N, N'-diphenylethylenediamide zirconium dibromide,
N'-diphenylpropylenediamide zirconium dibromide, bis (pyrroleyl) zirconium dibromide,

Bis (N-methylanilide) hafnium dichloride, bis (N-ethylanilide) hafnium dichloride, bis (N-propylanilide) hafnium dichloride, bis (N-butylanilide) hafnium dichloride, bis ((N-methyl) Toluylamide) hafnium dichloride, bis ((N-ethyl) tolulamido) hafnium dichloride, bis ((N-propyl) tolulamido) hafnium dichloride, bis ((N-butyl) tolulamido) hafnium dichloride, bis ((N- Methyl) dimethylphenylamide)
Hafnium dichloride, bis ((N-ethyl) dimethylphenylamide) hafnium dichloride, bis ((N-propyl) dimethylphenylamide) hafnium dichloride, bis ((N-butyl) dimethylphenylamide) hafnium dichloride, bis (diphenylamide) Hafnium dichloride, bis ((N-phenyl) tolylamido) hafnium dichloride, bis (tolulamido) hafnium dichloride, N, N '
-Diphenylmethylenediamide hafnium dichloride, N, N'-diphenylethylenediamide hafnium dichloride, N, N'-diphenylpropylenediamide hafnium dichloride, bis (pyrroleyl) hafnium dichloride,

Bis (N-methylanilide) hafnium dibromide, bis (N-ethylanilide) hafnium dibromide, bis (N-propylanilide) hafnium dibromide, bis (N-butylanilide) hafnium dibromide, bis (( N-methyl) tolulamido) hafnium dibromide, bis ((N-ethyl) tolulamido) hafnium dibromide, bis ((N-propyl) tolulamido) hafnium dibromide, bis ((N-butyl) tolulamido) hafnium Dibromide, bis ((N-methyl) dimethylphenylamide)
Hafnium dibromide, bis ((N-ethyl) dimethylphenylamide) hafnium dibromide, bis ((N-propyl) dimethylphenylamide) hafnium dibromide, bis ((N-butyl) dimethylphenylamide) hafnium dibromide, bis (Diphenylamide) hafnium dibromide, bis ((N-phenyl) tolulamido) hafnium dibromide, bis (tolulamido) hafnium dibromide, N, N '
-Diphenylmethylene diamide hafnium dibromide, N, N'-diphenylethylene diamide hafnium dibromide, N, N'-diphenylpropylene diamide hafnium dibromide, bis (pyrroleyl) hafnium dibromide,

Bis (methoxide) zirconium dichloride, bis (ethoxide) zirconium dichloride, bis (propoxide) zirconium dichloride, bis (phenoxide) zirconium dichloride, biphenoxide zirconium dichloride, binaphthoxide zirconium dichloride,

Bis (methoxide) zirconium dibromide, bis (ethoxide) zirconium dibromide, bis (propoxide) zirconium dibromide, bis (phenoxide) zirconium dibromide, biphenoxide zirconium dibromide, binaphthoxide zirconium dibromide and these But not limited thereto. The compound represented by the general formula [III] can be easily synthesized by a method already reported (JP-A-10-109995).

As the compound represented by the general formula [II], isopropylidene (1-indene) (1- (4,5-benzoindene)), isopropylidene (1-indene) (1
-(5,6-benzoindene)), isopropylidene (1-indene) (1-cyclopenta [c] phenanthrene), isopropylidene (1-indene) (1-cyclopenta [l] phenanthrene),

Isopropylidene (1- (4,5-benzoindene)) (9-fluorene), isopropylidene (1-
(5,6-benzoindene)) (9-fluorene), isopropylidene (1-cyclopenta [c] phenanthrene) (9-fluorene), isopropylidene (1-cyclopenta [l] phenanthrene) (9-fluorene),

Isopropylidenebis (1- (4,5-benzoindene)), isopropylidene (1- (4,5-benzoindene)) (1- (5,6-benzoindene)),
Isopropylidene (1- (4,5-benzoindene))
(1-cyclopenta [c] phenanthrene), isopropylidene (1- (4,5-benzoindene)) (1-cyclopenta [l] phenanthrene),

Isopropylidenebis (1- (5,6-benzoindene)), isopropylidene (1- (5,6-benzoindene)) (1-cyclopenta [c] phenanthrene), isopropylidene (1- (5 , 6-benzoindene)) (1-cyclopenta [l] phenanthrene),

Isopropylidenebis (1-cyclopenta [c] phenanthrene), isopropylidene (1-cyclopenta [c] phenanthrene) (1-cyclopenta [l] phenanthrene),

Isopropylidenebis (1-cyclopenta [l] phenanthrene) is dissolved in an organic solvent such as THF, diethyl ether, diisopropyl ether, toluene, etc.
For example, Li, Na, K, LiH, NaH, KH, MeLi, n-BuLi, sec-B
Examples include, but are not limited to, dilithium compounds, disodium compounds, and dipotassium compounds deprotonated with uLi and tert-BuLi or a solution of these in an organic solvent such as n-hexane, cyclohexane, and diethyl ether.

The compounds represented by the general formula [IV] include isopropylidene (1-indenyl) (1- (4,5-benzoindenyl)) zirconium bis (N-methylanilide) and isopropylidene (1- Indenyl) (1-
(5,6-benzoindenyl)) zirconium bis (N
-Methylanilide), isopropylidene (1-indenyl) (1-cyclopenta [c] phenanthrenyl) zirconium bis (N-methylanilide), isopropylidene (1-indenyl) (1-cyclopenta [l] phenanthrenyl) zirconium bis (N -Methylanilide),

Isopropylidene (1- (4,5-benzoindenyl)) (9-fluorenyl) zirconiumbis (N
-Methylanilide), isopropylidene (1- (5,6
-Benzoindenyl)) (9-fluorenyl) zirconium bis (N-methylanilide), isopropylidene (1-cyclopenta [c] phenanthrenyl) (9-fluorenyl) zirconium bis (N-methylanilide), isopropylidene (1- Cyclopenta [l] phenanthrenyl) (9-fluorenyl) zirconium bis (N-methylanilide)

Isopropylidenebis (1- (4,5-benzoindenyl)) zirconium bis (N-methylanilide), isopropylidene (1- (4,5-benzoindenyl)) (1- (5,6 -Benzoindenyl)) zirconium bis (N-methylanilide), isopropylidene (1- (4,5-benzoindenyl)) (1-cyclopenta [c] phenanthrenyl) zirconium bis (N-
Methylanilide), isopropylidene (1- (4,5-
Benzoindenyl)) (1-cyclopenta [l] phenanthrenyl) zirconium bis (N-methylanilide),

Isopropylidenebis (1- (5,6-benzoindenyl)) zirconium bis (N-methylanilide), isopropylidene (1- (5,6-benzoindenyl)) (1-cyclopenta [c] Phenanthrenyl)
Zirconium bis (N-methylanilide), isopropylidene (1- (5,6-benzoindenyl)) (1-cyclopenta [l] phenanthrenyl) zirconium bis (N-methylanilide)

Isopropylidenebis (1-cyclopenta [c] phenanthrenyl) zirconium bis (N-methylanilide), isopropylidene (1-cyclopenta [c] phenanthrenyl) (1-cyclopenta [l] phenanthrenyl) zirconium bis (N-methyl) Anilide),

Isopropylidenebis (1-cyclopenta [l] phenanthrenyl) zirconiumbis (N-methylanilide)

Isopropylidene (1-indenyl) (1-
(4,5-benzoindenyl)) zirconium bis (N
-Ethylanilide), isopropylidene (1-indenyl) (1- (5,6-benzoindenyl)) zirconium bis (N-ethylanilide), isopropylidene (1
-Indenyl) (1-cyclopenta [c] phenanthrenyl) zirconium bis (N-ethylanilide), isopropylidene (1-indenyl) (1-cyclopenta [l] phenanthrenyl) zirconium bis (N-ethylanilide),

Isopropylidene (1- (4,5-benzoindenyl)) (9-fluorenyl) zirconiumbis (N
-Ethylanilide), isopropylidene (1- (5,6
-Benzoindenyl)) (9-fluorenyl) zirconium bis (N-ethylanilide), isopropylidene (1-cyclopenta [c] phenanthrenyl) (9-fluorenyl) zirconium bis (N-ethylanilide), isopropylidene (1- Cyclopenta [l] phenanthrenyl) (9-fluorenyl) zirconiumbis (N-ethylanilide)

Isopropylidenebis (1- (4,5-benzoindenyl)) zirconium bis (N-ethylanilide), isopropylidene (1- (4,5-benzoindenyl)) (1- (5,6 -Benzoindenyl)) zirconium bis (N-ethylanilide), isopropylidene (1- (4,5-benzoindenyl)) (1-cyclopenta [c] phenanthrenyl) zirconium bis (N-
Ethylanilide), isopropylidene (1- (4,5-
Benzoindenyl)) (1-cyclopenta [l] phenanthrenyl) zirconium bis (N-ethylanilide),

Isopropylidenebis (1- (5,6-benzoindenyl)) zirconium bis (N-ethylanilide), isopropylidene (1- (5,6-benzoindenyl)) (1-cyclopenta [c] Phenanthrenyl)
Zirconium bis (N-ethylanilide), isopropylidene (1- (5,6-benzoindenyl)) (1-cyclopenta [l] phenanthrenyl) zirconiumbis (N-ethylanilide)

Isopropylidenebis (1-cyclopenta [c] phenanthrenyl) zirconium bis (N-ethylanilide), isopropylidene (1-cyclopenta [c] phenanthrenyl) (1-cyclopenta [l] phenanthrenyl) zirconium bis (N-ethyl) Anilide),

Isopropylidenebis (1-cyclopenta [l] phenanthrenyl) zirconiumbis (N-ethylanilide)

Isopropylidene (1-indenyl) (1-
(4,5-benzoindenyl)) zirconium bis ((N-methyl) toluylamide), isopropylidene (1-indenyl) (1- (5,6-benzoindenyl)) zirconium bis ((N-methyl) Toluylamide), isopropylidene (1-indenyl) (1-cyclopenta [c] phenanthrenyl) zirconium bis ((N-methyl) toluylamide), isopropylidene (1-indenyl) (1-cyclopenta [l] phenanthrenyl) zirconium bis ((N-methyl) toluylamide),

Isopropylidene (1- (4,5-benzoindenyl)) (9-fluorenyl) zirconiumbis ((N-methyl) toluylamide), isopropylidene (1- (5,6-benzoindenyl)) (9-fluorenyl) zirconium bis ((N-methyl) toluylamide), isopropylidene (1-cyclopenta [c] phenanthrenyl) (9-fluorenyl) zirconium bis ((N-methyl) toluylamide), isopropylidene (1- Cyclopenta [l] phenanthrenyl) (9-fluorenyl) zirconiumbis ((N-methyl) toluylamide)

Isopropylidenebis (1- (4,5-benzoindenyl)) zirconium bis ((N-methyl) toluylamide), isopropylidene (1- (4,5-benzoindenyl)) (1- ( 5,6-benzoindenyl)) zirconium bis ((N-methyl) toluylamide), isopropylidene (1- (4,5-benzoindenyl)) (1-cyclopenta [c] phenanthrenyl)
Zirconium bis ((N-methyl) toluylamide),
Isopropylidene (1- (4,5-benzoindenyl)) (1-cyclopenta [l] phenanthrenyl) zirconium bis ((N-methyl) toluylamide),

Isopropylidenebis (1- (5,6-benzoindenyl)) zirconiumbis ((N-methyl) toluylamide), isopropylidene (1- (5,6-benzoindenyl)) (1-cyclopentane) [C] phenanthrenyl) zirconium bis ((N-methyl) toluylamide), isopropylidene (1- (5,6-benzoindenyl)) (1-cyclopenta [l] phenanthrenyl) zirconium bis ((N-methyl) toluyl Amide)

Isopropylidenebis (1-cyclopenta [c] phenanthrenyl) zirconium bis ((N-methyl) toluylamide), isopropylidene (1-cyclopenta [c] phenanthrenyl) (1-cyclopenta [l] phenanthrenyl) zirconium bis ( (N-methyl) toluylamide),

Isopropylidenebis (1-cyclopenta [l] phenanthrenyl) zirconiumbis ((N-methyl) toluylamide)

Isopropylidene (1-indenyl) (1-
(4,5-benzoindenyl)) zirconium bis (diphenylamide), isopropylidene (1-indenyl) (1- (5,6-benzoindenyl)) zirconium bis (diphenylamide), isopropylidene (1-
Indenyl) (1-cyclopenta [c] phenanthrenyl) zirconium bis (diphenylamide), isopropylidene (1-indenyl) (1-cyclopenta [l]
Phenanthrenyl) zirconium bis (diphenylamide),

Isopropylidene (1- (4,5-benzoindenyl)) (9-fluorenyl) zirconium bis (diphenylamide), isopropylidene (1- (5,6-
Benzoindenyl)) (9-fluorenyl) zirconium bis (diphenylamide), isopropylidene (1-
Cyclopenta [c] phenanthrenyl) (9-fluorenyl) zirconium bis (diphenylamide), isopropylidene (1-cyclopenta [l] phenanthrenyl) (9-fluorenyl) zirconium bis (diphenylamide)

Isopropylidenebis (1- (4,5-benzoindenyl)) zirconium bis (diphenylamide), isopropylidene (1- (4,5-benzoindenyl)) (1- (5,6-benzoin) Benzyl)) zirconium bis (diphenylamide), isopropylidene (1- (4,5-benzoindenyl)) (1-cyclopenta [c] phenanthrenyl) zirconium bis (diphenylamide), isopropylidene (1- (4 5-benzoindenyl)) (1-cyclopenta [l] phenanthrenyl) zirconium bis (diphenylamide),

Isopropylidenebis (1- (5,6-benzoindenyl)) zirconium bis (diphenylamide), isopropylidene (1- (5,6-benzoindenyl)) (1-cyclopenta [c] phenanthrenyl)
Zirconium bis (diphenylamide), isopropylidene (1- (5,6-benzoindenyl)) (1-cyclopenta [l] phenanthrenyl) zirconium bis (diphenylamide)

Isopropylidenebis (1-cyclopenta [c] phenanthrenyl) zirconium bis (diphenylamide), isopropylidene (1-cyclopenta [c] phenanthrenyl) (1-cyclopenta [l] phenanthrenyl) zirconium bis (diphenylamide),

Isopropylidenebis (1-cyclopenta [l] phenanthrenyl) zirconium bis (diphenylamide)

Isopropylidene (1-indenyl) (1-
(4,5-benzoindenyl)) zirconium bis ((N-phenyl) toluylamide), isopropylidene (1-indenyl) (1- (5,6-benzoindenyl)) zirconium bis ((N-phenyl) Toluylamide), isopropylidene (1-indenyl) (1-cyclopenta [c] phenanthrenyl) zirconium bis ((N-phenyl) toluylamide), isopropylidene (1-indenyl) (1-cyclopenta [l] phenanthrenyl) zirconium bis ((N-phenyl) toluylamide),

Isopropylidene (1- (4,5-benzoindenyl)) (9-fluorenyl) zirconiumbis ((N-phenyl) toluylamide), isopropylidene (1- (5,6-benzoindenyl)) (9-fluorenyl) zirconium bis ((N-phenyl) toluylamide), isopropylidene (1-cyclopenta [c]
Phenanthrenyl) (9-fluorenyl) zirconium bis ((N-phenyl) toluylamide), isopropylidene (1-cyclopenta [l] phenanthrenyl)
(9-Fluorenyl) zirconium bis ((N-phenyl) toluylamide)

Isopropylidenebis (1- (4,5-benzoindenyl)) zirconium bis ((N-phenyl) toluylamide), isopropylidene (1- (4,5-benzoindenyl)) (1- ( 5,6-benzoindenyl)) zirconium bis ((N-phenyl) toluylamide), isopropylidene (1- (4,5-benzoindenyl)) (1-cyclopenta [c] phenanthrenyl) zirconium bis ((N -Phenyl) toluylamide), isopropylidene (1- (4,5-benzoindenyl)) (1-cyclopenta [l] phenanthrenyl)
Zirconium bis ((N-phenyl) toluylamide),

Isopropylidenebis (1- (5,6-benzoindenyl)) zirconium bis ((N-phenyl) toluylamide), isopropylidene (1- (5,6-benzoindenyl)) (1-cyclopentane) [C] phenanthrenyl) zirconium bis ((N-phenyl) toluylamide), isopropylidene (1- (5,6-benzoindenyl)) (1-cyclopenta [l] phenanthrenyl) zirconium bis ((N-phenyl) toluyl Amide)

Isopropylidenebis (1-cyclopenta [c] phenanthrenyl) zirconium bis ((N-phenyl) toluylamide), isopropylidene (1-cyclopenta [c] phenanthrenyl) (1-cyclopenta [l] phenanthrenyl) zirconium bis ( (N-
Phenyl) toluylamide),

Isopropylidenebis (1-cyclopenta [l] phenanthrenyl) zirconiumbis ((N-phenyl) toluylamide)

[0060] Isopropylidene (1-indenyl) (1-
(4,5-benzoindenyl)) zirconium (N,
N′-diphenylmethylenediamide), isopropylidene (1-indenyl) (1- (5,6-benzoindenyl)) zirconium (N, N′-diphenylmethylenediamide), isopropylidene (1-indenyl) (1-
Cyclopenta [c] phenanthrenyl) zirconium (N, N'-diphenylmethylenediamide), isopropylidene (1-indenyl) (1-cyclopenta [l]
Phenanthrenyl) zirconium (N, N'-diphenylmethylenediamide),

Isopropylidene (1- (4,5-benzoindenyl)) (9-fluorenyl) zirconium (N,
N'-diphenylmethylenediamide), isopropylidene (1- (5,6-benzoindenyl)) (9-fluorenyl) zirconium (N, N'-diphenylmethylenediamide), isopropylidene (1-cyclopenta [c] phenanthrenyl) ) (9-Fluorenyl) zirconium (N, N'-diphenylmethylenediamide), isopropylidene (1-cyclopenta [l] phenanthrenyl) (9-fluorenyl) zirconium (N, N'-
Diphenylmethylenediamide)

Isopropylidenebis (1- (4,5-benzoindenyl)) zirconium (N, N'-diphenylmethylenediamide), isopropylidene (1- (4,5-
Benzoindenyl)) (1- (5,6-benzoindenyl)) zirconium (N, N′-diphenylmethylenediamide), isopropylidene (1- (4,5-benzoindenyl)) (1-cyclopenta [ c] phenanthrenyl) zirconium (N, N'-diphenylmethylenediamide), isopropylidene (1- (4,5-benzoindenyl)) (1-cyclopenta [l] phenanthrenyl) zirconium (N, N'-diphenylmethylenediamide) ),

Isopropylidenebis (1- (5,6-benzoindenyl)) zirconium (N, N'-diphenylmethylenediamide), isopropylidene (1- (5,6-benzoindenyl))
Benzoindenyl)) (1-cyclopenta [c] phenanthrenyl) zirconium (N, N'-diphenylmethylenediamide), isopropylidene (1- (5,6-benzoindenyl)) (1-cyclopenta [l] phenanthrenyl) Zirconium (N, N'-diphenylmethylenediamide)

Isopropylidenebis (1-cyclopenta [c] phenanthrenyl) zirconium (N, N'-diphenylmethylenediamide), isopropylidene (1-
Cyclopenta [c] phenanthrenyl) (1-cyclopenta [l] phenanthrenyl) zirconium (N, N '
-Diphenylmethylenediamide),

Isopropylidenebis (1-cyclopenta [l] phenanthrenyl) zirconium (N, N'-diphenylmethylenediamide)

Isopropylidene (1-indenyl) (1-
(4,5-benzoindenyl)) zirconium bis (pyrroleyl), isopropylidene (1-indenyl)
(1- (5,6-benzoindenyl)) zirconium bis (pyrroleyl), isopropylidene (1-indenyl) (1-cyclopenta [c] phenanthrenyl) zirconium bis (pyrroleyl), isopropylidene (1
-Indenyl) (1-cyclopenta [l] phenanthrenyl) zirconium bis (pyrroleyl),

Isopropylidene (1- (4,5-benzoindenyl)) (9-fluorenyl) zirconium bis (pyrroleyl), isopropylidene (1- (5,6-benzoindenyl)) (9-fluorenyl) zirconium Bis (pyrroleyl), isopropylidene (1-cyclopenta [c] phenanthrenyl) (9-fluorenyl) zirconiumbis (pyrroleyl), isopropylidene (1-cyclopenta [l] phenanthrenyl) (9-fluorenyl) zirconium bis (pyrroleyl)

Isopropylidenebis (1- (4,5-benzoindenyl)) zirconium bis (pyrroleyl), isopropylidene (1- (4,5-benzoindenyl))
(1- (5,6-benzoindenyl)) zirconium bis (pyrroleyl), isopropylidene (1- (4,5
-Benzoindenyl)) (1-cyclopenta [c] phenanthrenyl) zirconium bis (pyrroleyl), isopropylidene (1- (4,5-benzoindenyl))
(1-cyclopenta [l] phenanthrenyl) zirconium bis (pyrroleyl),

Isopropylidenebis (1- (5,6-benzoindenyl)) zirconium bis (pyrroleyl), isopropylidene (1- (5,6-benzoindenyl))
(1-cyclopenta [c] phenanthrenyl) zirconium bis (pyrroleyl), isopropylidene (1-
(5,6-benzoindenyl)) (1-cyclopenta [l] phenanthrenyl) zirconium bis (pyrroleyl)

Isopropylidenebis (1-cyclopenta [c] phenanthrenyl) zirconium bis (pyrroleyl), isopropylidene (1-cyclopenta [c] phenanthrenyl) (1-cyclopenta [l] phenanthrenyl) zirconium bis (pyrroleyl),

Isopropylidenebis (1-cyclopenta [l] phenanthrenyl) zirconiumbis (pyrroleyl)

Isopropylidene (1-indenyl) (1-
(4,5-benzoindenyl)) zirconium (N,
N′-diphenylethylenediamide), isopropylidene (1-indenyl) (1- (5,6-benzoindenyl)) zirconium (N, N′-diphenylethylenediamide), isopropylidene (1-indenyl) (1-
Cyclopenta [c] phenanthrenyl) zirconium (N, N'-diphenylethylenediamide), isopropylidene (1-indenyl) (1-cyclopenta [l]
Phenanthrenyl) zirconium (N, N'-diphenylethylenediamide),

Isopropylidene (1- (4,5-benzoindenyl)) (9-fluorenylzirconium (N, N ')
-Diphenylethylenediamide), isopropylidene (1- (5,6-benzoindenyl)) (9-fluorenyl) zirconium (N, N'-diphenylethylenediamide), isopropylidene (1-cyclopenta [c]
Phenanthrenyl) (9-fluorenyl) zirconium (N, N'-diphenylethylenediamide), isopropylidene (1-cyclopenta [l] phenanthrenyl)
(9-Fluorenyl) zirconium (N, N'-diphenylethylenediamide)

Isopropylidenebis (1- (4,5-benzoindenyl)) zirconium (N, N'-diphenylethylenediamide), isopropylidene (1- (4,5-benzoindenyl))
Benzoindenyl)) (1- (5,6-benzoindenyl)) zirconium (N, N′-diphenylethylenediamide), isopropylidene (1- (4,5-benzoindenyl)) (1-cyclopenta [ c] phenanthrenyl) zirconium (N, N'-diphenylethylenediamide), isopropylidene (1- (4,5-benzoindenyl)) (1-cyclopenta [l] phenanthrenyl) zirconium (N, N'-diphenylethylenediamide ),

Isopropylidenebis (1- (5,6-benzoindenyl)) zirconium (N, N'-diphenylethylenediamide), isopropylidene (1- (5,6-benzoindenyl))
Benzoindenyl)) (1-cyclopenta [c] phenanthrenyl) zirconium (N, N'-diphenylethylenediamide), isopropylidene (1- (5,6-benzoindenyl)) (1-cyclopenta [l] phenanthrenyl) Zirconium (N, N'-diphenylethylenediamide)

Isopropylidenebis (1-cyclopenta [c] phenanthrenyl) zirconium (N, N'-diphenylethylenediamide), isopropylidene (1-
Cyclopenta [c] phenanthrenyl) (1-cyclopenta [l] phenanthrenyl) zirconium (N, N '
-Diphenylethylenediamide),

Examples include, but are not limited to, isopropylidenebis (1-cyclopenta [l] phenanthrenyl) zirconium (N, N'-diphenylethylenediamide) and each compound in which a zirconium atom is substituted with a titanium atom and a hafnium atom. . The compound represented by the general formula [IV] is synthesized by mixing the compound represented by the general formula [II] and the compound represented by the general formula [III] in the presence of an organic solvent. Organic solvents that can be used for the reaction include, but are not limited to, n-hexane, cyclohexane, petroleum ether, benzene and toluene, and other hydrocarbon solvents in general, and non-limiting solvents such as chloroform, dichloromethane, and chlorobenzene. Halogenated hydrocarbon solvents that can be mentioned as examples, and ether solvents that can be mentioned as non-limiting examples of THF, diethyl ether and diisopropyl ether, and mixed solvents thereof. Preferably, it is a polar organic solvent in which the reaction reagent is slightly or more soluble, and specific examples thereof include, but are not limited to, toluene, chloroform, dichloromethane, THF, diethyl ether and diisopropyl ether. it can. Naturally, the present reaction can be allowed to proceed with other solvents not exemplified here, and the choice of the solvent is not important in carrying out the present reaction. However, when an amine-based solvent is used in this reaction, care must be taken because reactivity and the like may be affected.

The molar ratio of each reaction reagent in this reaction is such that the amount of the compound represented by the general formula [II] is 0.5 to 2 with respect to the compound represented by the general formula [III]. Equivalents, preferably 0.8 to 1.3 equivalents can be used. This reaction is carried out in a temperature range of -80 ° C to 150 ° C.
The reaction is completed after stirring for 1 minute to 24 hours. However, the temperature range and reaction time in this reaction are not limited, and the reaction can be carried out in any temperature range and reaction time. Usually, the reaction is completed at room temperature for about 30 minutes to 3 hours. Thereafter, the solvent is distilled off, and n-hexane, cyclohexane, petroleum ether, benzene, toluene, and the like can be cited as non-limiting examples.General hydrocarbon solvents and THF, diethyl ether, diisopropyl ether, and the like can be used as non-limiting examples. Compounds represented by the general formula [IV] by all ether solvents that can be mentioned, preferably n-hexane, cyclohexane, petroleum ether, benzene and toluene, etc. are hydrocarbon solvents that can be mentioned as non-limiting examples. Is extracted and separated from an insoluble inorganic salt to obtain a compound represented by the general formula [IV] containing no inorganic salt. When an ether solvent is used at the time of extraction, the use amount thereof is desirably within 5 times the volume of the compound represented by the general formula [IV] in order to suppress the elution of the inorganic salt.

The compound represented by the general formula [I] is synthesized by a halogenation reaction of the compound represented by the general formula [IV] by adding a halogenating agent in the presence of an organic solvent and stirring the mixture. Solvents that can be used in the reaction include, but are not limited to, n-hexane, cyclohexane, petroleum ether, benzene, toluene, and other hydrocarbon solvents in general, and chloroform, dichloromethane, chlorobenzene, and the like, without limitation. Halogenated hydrocarbon solvents in general, and THF,
Diethyl ether, diisopropyl ether and the like are non-limiting examples of general ether solvents and mixed solvents thereof. Preferably, it is a polar organic solvent in which the reaction reagent or the compound represented by the general formula [IV] can be slightly or more dissolved.
Non-limiting examples include toluene, chloroform, dichloromethane, THF, diethyl ether or diisopropyl ether. The reaction is carried out according to the general formula [I
When the compound represented by V] is in a liquid state, a solvent is not necessarily required. This reaction can be carried out at a temperature in the range of -100 ° C to 150 ° C, preferably at -80 ° C.
４０40 ° C. Examples of the halogenating agent include halotrialkylsilanes such as Me ₃ SiCl and Me ₃ SiBr, and Me ₂ NH.
HCl, Me ₂ NH.HBr, Et ₂ NH.HCl, and hydrohalides of amines such as aniline hydrochloride, and HC
1, a hydrogen halide gas such as HBr and an aqueous solution of hydrogen halide such as hydrochloric acid can be used. Preferred are hydrogen halide salts of dialkylamines and hydrogen halide gas. This reaction is completed only by stirring for about 1 minute to 3 hours.

However, in this reaction, the temperature range and reaction time are not limited, and the reaction can be carried out in any temperature range and reaction time. The molar ratio of the reaction reagent in this reaction is based on the compound represented by the general formula [IV], and the charged amount of the halogenating agent is 1.0 equivalent or more. It is preferable to use 1.8 to 2.0 equivalents. From this reaction solution, the compound represented by the general formula [I] can be obtained in a high yield without containing an inorganic salt by ordinary purification operations such as recrystallization.

[0081]

Examples, Reference Examples and Comparative Examples Next, the present invention will be described with reference to Examples,
The present invention is not limited by these examples, which will be described more specifically with reference examples and comparative examples. In Examples, Reference Examples and Comparative Examples, the reaction was performed in an atmosphere of an inert gas such as an argon gas or a nitrogen gas, and the solvent used was dehydrated.

Reference Example 1 Synthesis of compound represented by general formula [III] Synthesis of bis (N-methylanilide) zirconium dichloride / bistetrahydrofuran 400 g of N-methylaniline, THF 4.7 in a 10 L four-necked flask under an argon atmosphere. L was charged and cooled to 0 ° C. Then at the same temperature 2.45 L of n-BuLi / n-hexane solution (1.63 mol / l)
It was added dropwise over 1.5 hours. The temperature was raised to room temperature, and the mixture was further stirred overnight. To a separately prepared 10L four-necked flask THF 1.2L, ZrC
They were charged l ₄ · 2THF 705 g, while stirring was added dropwise anion of N- methylaniline over 1 hour and stirred for 2 hours at room temperature. After completion of the reaction, the solvent was distilled off under reduced pressure, and the obtained viscous liquid was extracted with 6 L of methylene chloride to remove insoluble lithium chloride. The solvent was concentrated under reduced pressure to about 1.8 L,
It was left at 5 ° C for a while. Thereafter, the precipitated crystals were collected by filtration, washed with 200 ml of methylene chloride, and dried under reduced pressure. Further, the mother liquor and the washing solution were concentrated to obtain secondary crystals, and a total of 702 g (yield 72%) of bis (N-methylanilide) was obtained.
Zirconium dichloride bistetrahydrofuran (yellow powder) was obtained. The analysis data of this compound are as follows, and it was confirmed that the compound was the title compound. ¹ H-NMR (400 MHz, CDCl ₃ / TMS) δ (ppm) 1.7 to 1.9 (m, THF, 8
H), 3.36 (s, N -CH 3, 6H) 4.0~4.2 (m, THF, 8H), 6.6~7.3 (m, phenyl, 1
0H)

Example 1 isopropylidene (1-indenyl) (1- (4,5-
Benzoindenyl)) Synthesis of Zirconium Bis (N-methylanilide) and Chlorination Reaction Under argon atmosphere, 100ml Schlenk 0.50g of isopropylidene (1-indene) (1- (4,5-benzoindene)), 10ml of THF Was cooled to 0 ° C. 2.01 ml of an n-BuLi / hexane solution (1.59 mol / l) was added thereto, and 4
Stirred for hours. Then, add bis (N-methylanilide) zirconium dichloride to 20 ml Schlenk prepared separately.
0.82 g of bistetrahydrofuran was charged, and the isopropylidene (1-indene) (1- (4,5-
The dilithium salt of benzoindene)) was added and stirred for 3 hours. Methylene chloride is added to the viscous solid obtained by evaporating the solvent.
40 ml was added for extraction, and insoluble lithium chloride was removed by filtration. The solvent of the mother liquor was concentrated, and isopropylidene (1-indenyl) (1- (4,5-benzoindenyl)) zirconium bis (N-methylanilide) as a red powder was added to 0.78.
g (80.0% yield). The analysis data of this compound are as follows, and it was confirmed that the compound was the title compound. ¹ H-NMR (400 MHz, CDCl ₃ / TMS) 2.41 (s, C-CH ₃ , 3H), 2.43
_{(s, C-CH 3,} 3H), 2.68 (s, N-CH 3, 6H), 5.93 (d, C 5 ring, 2H), 6.49~8.03 (m, C 5 rin
g and C ₆ ring and N-Phenyl, 22H) isopropylidene (1-indenyl) (1- (4,5-
To 0.78 g of benzoindenyl)) zirconium bis (N-methylanilide) were added 10 ml of methylene chloride and 0.254 g of dimethylamine hydrochloride, and the mixture was stirred for 1 hour. Thereafter, the solvent was distilled off, and the obtained crystals were washed with 20 ml of methylene chloride to remove organic substances such as ligands, dried under reduced pressure, and dried in red and orange isopropylidene (1-indenyl) (1- (4,5). -Benzoindenyl)) 0.36 g of zirconium dichloride (60% yield)
Obtained. ¹ H-NMR (400 MHz, CDCl ₃ / TMS) 2.38 (s, C-CH ₃ , 3H), 2.41 (s, C
-CH ₃ , 3H), 6.19 (d, C ₅ ring, 1H), 6.25 (d, C ₅ ring, 1H), 6.74 (d, C ₅ ring, 1H),
_{7.17 (d, C 5 ring,} 1H), 7.05~8.04 (m, C 6 ring, 10H)

Example 2 Synthesis of rac-isopropylidenebis (1- (4,5-benzoindenyl)) zirconiumbis (N-methylanilide) and Chlorination Reaction Under argon atmosphere, 100 ml of isopropylidenebis (1 -(4,5-benzoindene)) 4.69 g, THF
50 ml was charged and cooled to 0 ° C. Thereto, 14.4 ml of an n-BuLi / hexane solution (1.59 mol / l) was added, and the mixture was stirred for 2.5 hours. Then, 6.54 g of bis (N-methylanilide) zirconium dichloride bistetrahydrofuran was charged into a separately prepared 100 ml Schlenk, and the dilithium salt of isopropylidenebis (1- (4,5-benzoindene)) was added thereto. Stirred for half an hour. 100 ml of methylene chloride was added to the viscous solid obtained by concentrating the solvent and extracted, and the insoluble lithium chloride was removed by filtration. The solvent of the mother liquor was concentrated, and isopropylidenebis (1- (4,5-
9.64 g of benzoindenyl)) zirconium bis (N-methylanilide) was obtained. 20 ml of toluene is added to this, and -4
Leave at 0 ° C. overnight. The precipitated crystals were collected, dried under reduced pressure, and dried as rac-isopropylidenebis (1-
(4,5-benzoindenyl)) zirconium bis (N
-Methylanilide) was obtained 6.76 g (yield 79.6%). The analysis data of this compound are as follows, and it was confirmed that the compound was the title compound. ¹ H-NMR (400 MHz, CDCl _{3 /} TMS) 2.07 (s, N-CH ₃ , 6H), 2.41 (s, C-
CH ₃ , 6H), 6.35 (d, C ₅ ring, 2H), 6.45 (d, C ₅ ring, 2H), 6.65
(d, N-phenyl, 4H), 6.83 (t, N-phenyl, 2H), 7.25 (m, N-pheny
l, 4H), 7.35-8.04 (m, C ₆ ring, 12H) rac-isopropylidenebis (1- (4,5-benzoindenyl)) zirconium bis (N-methylanilide) 6.76g and methylene chloride 50ml In addition, 1.64 g of dimethylamine hydrochloride was added thereto, followed by stirring for 30 minutes. Thereafter, the solvent was distilled off, and the obtained crystals were washed with methylene chloride to remove organic substances such as ligands, and then dried under reduced pressure.
3.45 g of c-isopropylidenebis (1- (4,5-benzoindenyl)) zirconium dichloride (yield 64.
4%). The analysis data of this compound are as follows, and it was confirmed that the compound was the title compound. 1H-NMR (400 MHz, CDCl _{3 /} TMS) 2.45 (s, C-CH ₃ , 6H), 6.27 (d, C ₅
ring, 2H), 7.20 (d, C ₅ ring, 2H), 7.37-8.03 (m, C ₆ ring, 12
H)

Comparative Example 1 Synthesis of rac-isopropylidenebis (1- (4,5-benzoindenyl)) zirconium dichloride (conventional method) Under an argon atmosphere, isopropylidenebis (1- (4,5- Benzoindene)) (5.0 g) and diethyl ether (150 ml) were charged and cooled to 0 ° C. There n
18.8 ml of a -BuLi / hexane solution (1.50 mol / l) was added, and the mixture was heated to room temperature and stirred for 4 hours. Concentrate the solvent, toluene 150m
l, 3.13 g of ZrCl ₄ were added and stirred overnight. Concentrate the solvent,
The obtained yellow-orange solid was washed with 80 ml of THF and 170 ml of methylene chloride to remove ligands and other organic substances, and then dried under reduced pressure. Rac-isopropylidenebis (1- (4,5-
Benzoindenyl)) 4.2 g of zirconium dichloride
(Yield 54.6% (converted from C in elemental analysis)).

Example 3 Synthesis of rac-isopropylidenebis (1-cyclopenta [c] phenanthrenyl) zirconium bis (N-methylanilide) and chlorination reaction Under argon atmosphere, isopropylidenebis (1-cyclopenta [c ] Phenanthrene) 0.50
g and 10 ml of THF were charged and cooled to 0 ° C., and 1.36 ml of an n-BuLi / hexane solution (1.59 mol / l) was added thereto. Warm to room temperature,
Stir for 4 hours. 0.55 g of bis (N-methylanilide) zirconium dichloride bistetrahydrofuran was charged into a separately prepared 20 ml Schlenk, and the prepared dilithium salt of isopropylidenebis (1-cyclopenta [c] phenanthrene) was added thereto. After stirring overnight, the solvent was concentrated, and 40 ml of methylene chloride was added to the obtained red-orange solid for extraction to remove insoluble lithium chloride. The solvent of the mother liquor was concentrated, and 0.767 g of rac-isopropylidenebis (1-cyclopenta [c] phenanthrenyl) zirconiumbis (N-methylanilide) as an orange solid was obtained (yield 93.5).
%)Obtained. The analysis data of this compound are as follows, and it was confirmed that the compound was the title compound. ¹ H-NMR (400 MHz, CDCl ₃ / TMS) 1.79 (s, N-CH ₃ , 6H), 2.53 (s, C
-CH ₃ , 6H), 6.56 (d, phenyl, 4H), 6.68 (d, C ₅ ring, 2H), 6.86
(t, phenyl, 2H), 6.95 (d, C ₅ ring, 2H), 7.17 (m, phenyl, 4H),
_{7.45~7.79 (m, C 6 ring,} 12H) 8.34 (d, C 6 ring, 2H), 8.53 (dd, C 6 ring, 2H) rac- isopropylidene-bis (1-cyclopenta [c] phenanthryl) zirconium bis ( To 0.767 g of N-methylanilide) were added 10 ml of methylene chloride and 0.17 g of dimethylamine hydrochloride, and the mixture was stirred at room temperature for 30 minutes. Thereafter, the solvent was concentrated, and the obtained orange solid was treated with methylene chloride 30.
After washing with ml to remove organic substances such as ligands, the mixture was dried under reduced pressure.
0.41 g (yield 61.2%) of rac-isopropylidenebis (1-cyclopenta [c] phenanthrenyl) zirconium dichloride as orange crystals was obtained. ¹ H-NMR (400 MHz, CDCl _{3 /} TMS) 2.55 (s, C-CH ₃ , 6H), 6.49 (d, C ₅
ring, 2H), 7.79 (d, C ₅ ring, 2H), 7.50-8.02 (m, C ₆ ring, 14
H), 8.82 (d, C ₆ ring, 2H)

Comparative Example 2 Purification of rac-isopropylidenebis (1- (4,5-benzoindenyl)) zirconium dichloride with ethanol Under a argon atmosphere, rac-isopropylidenebis (1- (4,5- Benzoindenyl))
0.649 g of zirconium dichloride (89% purity) was charged, and 30 ml of ethanol was added thereto, followed by stirring for 15 minutes. The crystals were collected by filtration and dried under reduced pressure to obtain 0.467 g of an orange solid. ^{When 1} H-NMR was measured, a signal of isopropylidenebis (1- (4,5-benzoindene)) which was not confirmed at the time of charging was observed, and decomposition of the complex was confirmed.

Claims (8)

[Claims] 1. A compound represented by the following general formula [I] (Wherein M represents a Group 4 transition metal, and ethers or amines may be coordinated to M with a coordination number of 1 to 2, and Xs may be each independently the same or different. Represents a good halogen atom, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ and
R ₁₀ independently represents a hydrogen atom or an alkyl group or an aryl group having 1 to 30 carbon atoms which may be the same or different from each other, provided that R ₁ and R ₂ , R ₂ and R ₃ , R ₃ R ₄ ,
At least one of combinations of R ₅ and R _6, R ₆ and R _7, R ₇ and R ₈ and R ₉ and R ₁₀ bond together to form an aromatic ring together)
In the synthesis of the compound represented by the following general formula [II]: (Wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ and R ₁₀ are the same as those described in the general formula [I], and B is A cation of an alkali metal or an alkaline earth metal) and a compound represented by the following general formula [III]: (Wherein M represents a Group 4 transition metal, A independently represents an atom selected from Group 15 atoms and Group 16 atoms which may be the same or different from each other, and when A is a Group 15 atom, = 1, R ₁₁ and R ₁₂ may combine to form A or a ring containing A and M.When A is a group 16 atom, n = 0, R ₁₁ is a halogen atom, A nitrogen atom, a phosphorus atom, a hydrocarbon group having 1 to 10 carbon atoms which can contain an oxygen atom and / or a sulfur atom or an aryl group which may have a halogen atom as a substituent, R ₁₂ is a halogen atom, A nitrogen atom, a phosphorus atom, represents an alkyl group or an aryl group which may have a hydrocarbon group having 1 to 10 carbon atoms which may contain an oxygen atom and / or a sulfur atom, and X is independently the same as each other Represents a halogen atom which may be different, and M is an ether or an amine having 1 to 2 By reacting a compound represented by In coordination number may be coordinated), the following general formula [IV] embedded image (Wherein M represents a Group 4 transition metal, and ethers or amines may be coordinated to M with a coordination number of 1 to 2,
R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ and R ₁₀ are the same as those described in the general formula [I], and A and R ₁₁ R ₁₂ and n are the same as those described in formula [III])
A method for obtaining a compound represented by the general formula [I] with high purity, comprising obtaining a compound represented by the formula: and halogenating the compound. [2] R in each general formula₁, R_Two, R_Three, R_Four, R_Five,
R₆, R₇, R₈, R₉And R_TenBut each independently is the same as each other
May also be different from a hydrogen atom or 1 to 6 carbon atoms
Alkyl or aryl group of R₁And R_Two, R_TwoWhen
R_Three, R_ThreeAnd R_Four, R_FiveAnd R ₆, R₆And R₇, R₇And R₈And R₉And R_TenPair of
At least one of the combinations is bonded to an aromatic ring
2. The method of claim 1, wherein 3. The method according to claim 1, wherein A in each general formula is a nitrogen atom or an oxygen atom. 4. R ₁₁ in each of the general formulas has, as a substituent, a hydrocarbon group having 1 to 10 carbon atoms or a halogen atom which may contain a halogen atom, a nitrogen atom, a phosphorus atom, an oxygen atom and / or a sulfur atom. A phenyl group which may be
R ₁₂ is a halogen atom, a nitrogen atom, a phosphorus atom, an alkyl group or a phenyl group which may have a hydrocarbon group having 1 to 10 carbon atoms which may contain an oxygen atom and / or a sulfur atom, A method according to any of claims 1 to 3. 5. The following general formula [IV]: (Wherein M represents a Group 4 transition metal, and ethers or amines may be coordinated to M with a coordination number of 1 to 2, R ₁ ,
R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ and R ₁₀ are each independently a hydrogen atom or a carbon atom having 1 to 30 which may be the same or different from each other. Represents an alkyl group or an aryl group, R ₁ and R ₂ , R ₂ and R ₃ , R ₃ and R ₄ , R ₅ and R ₆ , R ₆ and R ₇ , R ₇ and R ₈
And at least one of the combinations of R ₉ and R ₁₀ is bonded to each other to form an aromatic ring, and A independently represents a Group 15 atom and a Group 16 atom which may be the same or different from each other; When n is a group atom, n = 1, and R ₁₁ and R ₁₂ may combine to form A or a ring containing A and M. When A is a group 16 atom, n = 0. R ₁₁ represents a halogen atom, a nitrogen atom, a phosphorus atom, a hydrocarbon group having 1 to 10 carbon atoms which may contain an oxygen atom and / or a sulfur atom or an aryl group which may have a halogen atom as a substituent, R ₁₂ represents an alkyl group or an aryl group which may have a halogen atom, a nitrogen atom, a phosphorus atom, an oxygen atom and / or a hydrocarbon group having 1 to 10 carbon atoms which may contain a sulfur atom. Transition metal compound. 6. In the general formula [IV], R₁, R_Two, R_Three,
R_Four, R_Five, R₆, R₇, R₈, R ₉And R_TenBut each independently
A hydrogen atom or a carbon atom which may be the same or different
An alkyl group or an aryl group of Formulas 1 to 6,₁And R
_Two, R_TwoAnd R_Three, R_ThreeAnd R _Four, R_FiveAnd R₆, R₆And R₇, R₇And R₈And R₉And R
_TenAt least one of the combinations of
It is characterized by forming an aromatic ring, according to claim 5
Compound. 7. The compound according to claim 5, wherein in the general formula [IV], A is a nitrogen atom or an oxygen atom. 8. In the general formula [IV], R ₁₁ is a halogen atom and / or a hydrocarbon group having 1 to 10 carbon atoms or a halogen atom which may contain a nitrogen atom, a phosphorus atom, an oxygen atom, and a sulfur atom. A phenyl group which may have a group, wherein R ₁₂ is a carbon atom which may contain a halogen atom, a nitrogen atom, a phosphorus atom, an oxygen atom and / or a sulfur atom.
An alkyl group or a phenyl group which may have 1 to 10 hydrocarbon groups, and when A is a group 15 atom, R ₁₁ and R ₁₂ combine to form a ring containing A or A and M The compound according to any one of claims 5 to 7, which may be used.