JP2001158753A - Method for synthesizing cyclopentadiene derivative - Google Patents

Abstract

(57) [Summary] [PROBLEMS] To easily form a cyclopentadiene ring. A method for synthesizing a cyclopentadiene derivative represented by the following reaction formula. Embedded image (Wherein, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ are a hydrogen atom, a hydrocarbon group, or the like, and Y is a hydrogen atom or an elimination group. A group, M is a metal of Group 3 to Group 5 of the periodic table, L ¹ and L ² are anionic ligands, and X ¹ and X ² are leaving groups An organometallic compound having a cyclopentadienyl group derived from the cyclopentadiene derivative (I) as a ligand.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a method for synthesizing a cyclopentadiene derivative.

[0002]

BACKGROUND OF THE INVENTION Cyclopentadiene derivatives, particularly cyclopentadienyl group derivatives, which are anions thereof, are used as ligands in various organometallic compounds, and are used together with carbonyl groups, phosphines and the like. , Is one of the most basic ligands. (C
^{_{5 H 5) -, (C}} 5 (CH 3) 5) -, (C 5 H (CH 3) 4) -
Is often abbreviated as Cp, and an organometallic compound containing a cyclopentadienyl group derivative as a ligand is, for example, Fe (C
p) ₂ , Co (Cp) (CO) ₂ , M (Cp) ₂ (X)
_l (wherein, M represents a metal of Groups 3 to 5 of the periodic table or a lanthanide series metal; X represents a halogen atom or the like; l
Is an integer of 1 to 3. ) Etc. are known.

[0003] Organometallic compounds containing cyclopentadienyl group derivatives as ligands are used in various reactions as catalysts. For example, M (Cp) ₂ (X) _l (where M is
X denotes a halogen atom or the like; and l denotes an integer of 1 to 3. The compound represented by the formula (1) is used as a Ziegler-Natta catalyst as a catalyst in the production of synthetic polymers such as polyolefins. Further, the stereochemistry of the catalyst, particularly the structure of the cyclopentadienyl group, may greatly affect the stereochemistry of the product, and it is desired to easily obtain various cyclopentadienyl groups.

Therefore, an object of the present invention is to provide a method for synthesizing a cyclopentadiene derivative by a novel addition reaction.

[0005]

According to a first aspect of the present invention, there is provided a method for synthesizing a cyclopentadiene derivative represented by the following formula (I):

[0006]

Embedded image

(Where R¹, R^Two, R^Three, R^Four, R^Five, R⁶,
R⁷, R⁸And R⁹Are independent of each other and
Or differently, may have a hydrogen atom, a substituent,
C₁~ C₂₀A hydrocarbon group, which may have a substituent,₁
~ C₂₀An alkoxy group, optionally having substituent (s), C₆
~ C₂₀An aryloxy group or a compound of the formula —Si (R^Ten)
(R^{1 1}) (R¹²A group represented by the formula:^Ten, R¹¹as well as
R¹²Are, independently of one another, identical or different,
C₁~ C₂₀Alkyl group, C₆~ C₂₀Arylalkyl group,
C₁~ C₂₀Alkoxy group, C₆~ C₂₀Arylalkylo
It is a xy group. ) Where R¹And R^Two, R^TwoPassing
And R^Three, R^ThreeAnd R^Four, R^FiveAnd R⁶, R⁶And R⁷, R ⁷as well as
R⁸Or R⁸And R⁹Are the same or different
And each may have a substituent,_Four~ C₂₀Bored
May form a sum or unsaturated ring, provided that the above C_Four~
C₂₀A saturated or unsaturated ring is an oxygen atom, a compound of the formula -N (R¹³)-
A group represented by the formula (wherein R¹³Is a hydrogen atom or C₁~ C₆A
Is a alkyl group. ), The formula -E (R¹⁴) (R^Fifteen)-
(Where E is a silicon atom, a germanium atom
Or a tin atom, and R¹⁴And R^FifteenAre each other
Independently, identically or differently, C₁~ C₆With an alkyl group
is there. ), Formula -E¹(R¹⁶) (R¹⁷) -E^Two(R¹⁸) (R
¹⁹A group represented by the formula:¹And E^TwoAre
Independent of each other, identical or different,
A rumanium atom or a tin atom;¹⁶, R¹⁷, R¹⁸
And R¹⁹Are independent of each other and are the same or different
C₁~ C₆It is an alkyl group. )
Y is a hydrogen atom or a leaving group. In the presence of a metal compound, a metalla represented by the following formula (II)
To cyclopentadiene,

[0008]

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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 Groups 3 to 5 of the periodic table or a lanthanide series; L ¹ and L ² are independent of each other and are the same or different and each represent an anionic ligand, provided that L ¹ and L ² may be cross-linked.) Reaction of a benzene derivative represented by the following formula (III) Step to make

[0010]

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(Wherein, R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ , and Y have the above-mentioned meanings. X ¹ and X ² are each independently of one another and are the same or different. , A leaving group) is provided.

In the present invention, the metal compound is preferably a metal compound belonging to Groups 4 to 15 of the periodic table. Preferably, the metal compound is a salt.

Further, it is preferable that M is a metal belonging to Group 4 of the periodic table or a lanthanide series, and the anionic ligand is a delocalized cyclic η ⁵ -coordination ligand. Furthermore, it is preferable that the delocalized cyclic η ⁵ -coordination system ligand is an optionally substituted cyclopentadienyl group, indenyl group, fluorenyl group or azulenyl group.

According to another aspect of the present invention, there is provided a method for synthesizing an organometallic compound represented by the following formula (IV):

[0015]

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(Where M¹Represents a transition metal; L^ThreeIs
Represents a ligand, n is an integer of 1 to 8, and m is -6
An integer of up to 6;¹, R^Two, R^Three, R^Four, R^Five, R⁶, R
⁷, R⁸And R⁹Are independent of each other,
Are different from each other, and may have a hydrogen atom or a substituent.
₁~ C₂₀A hydrocarbon group, which may have a substituent,₁~
C₂₀An alkoxy group, optionally having substituent (s), C₆~
C₂₀An aryloxy group or a compound of the formula —Si (R^Ten) (R¹¹)
(R¹²A group represented by the formula:^Ten, R¹¹And R¹²Is
Each independently of one another, identical or different,₁~ C
₂₀Alkyl group, C₆~ C₂₀Arylalkyl group, C₁~ C
₂₀Alkoxy group, C₆~ C₂₀Arylalkyloxy group
It is. ) Where R¹And R^Two, R^TwoAnd R^Three,
R^ThreeAnd R^Four, R^FiveAnd R⁶, R⁶And R⁷, R ⁷And R⁸,or
Is R⁸And R⁹Are the same or different,
May have a substituent,_Four~ C₂₀Saturated or not
A saturated ring may be formed, provided that the above C_Four~ C₂₀Saturation
Or an unsaturated ring is an oxygen atom, a compound of the formula -N (R¹³)-
Group (wherein R¹³Is a hydrogen atom or C₁~ C₆Alkyl group
It is. ), The formula -E (R¹⁴) (R^Fifteen)-
(Wherein E is a silicon atom, germanium atom or
Atom, and R¹⁴And R^FifteenAre independent of each other
And the same or different, C₁~ C₆An alkyl group
You. ), Formula -E¹(R¹⁶) (R¹⁷) -E^Two(R¹⁸)
(R ¹⁹A group represented by the formula:¹And E^TwoEach
Independent of each other, identical or different,
, A germanium atom or a tin atom;¹⁶,
R¹⁷, R¹⁸And R¹⁹Are mutually independent and identical
Or differently, C₁~ C₆It is an alkyl group. ) Interrupted
It may be. ) The cyclopentadiene derivative obtained by the above method,
Reacting with a transition metal-containing precursor in the presence of a reducing agent
A method for synthesizing an organometallic compound is provided.
It is.

In another aspect of the present invention, the following formula (IVa):
A method for synthesizing an organometallic compound represented by

[0018]

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(Where M¹Are groups 3 to 5 of the periodic table
Or a metal of the lanthanide series;¹Is a delocalized ring
Condition η^FiveA coordination ligand, L^ThreeAnd L^FourEach
Independently of each other, the same or different, represents a ligand,
R¹, R^Two, R^Three, R^Four, R^Five, R⁶, R⁷, R⁸And R⁹Is
Each independently of one another, identical or different,
C, which may have a substituent,₁~ C₂₀hydrocarbon
C, which may have a group or a substituent₁~ C₂₀Alkoxy
C, which may have a group or a substituent₆~ C₂₀Arlio
A xy group or a formula -Si (R^Ten) (R¹¹) (R¹²)
Group (wherein R^Ten, R¹¹And R¹²Are each other
Independently, the same or different,₁~ C₂₀Alkyl group,
C₆~ C₂₀Arylalkyl group, C₁~ C₂₀Alkoxy
Group, C₆~ C₂₀An arylalkyloxy group. )so
Yes, but R¹And R^Two, R^TwoAnd R^Three, R^ThreeAnd R^Four,
R^FiveAnd R⁶, R⁶And R⁷, R ⁷And R⁸Or R⁸as well as
R⁹Are the same or different and are each other
May have a C_Four~ C₂₀Form a saturated or unsaturated ring
May be formed, provided that the above C_Four~ C₂₀Saturated or unsaturated
The ring is an oxygen atom, a compound of the formula -N (R¹³)-Group represented by the formula (formula
Medium, R¹³Is a hydrogen atom or C₁~ C₆An alkyl group
You. ), The formula -E (R¹⁴) (R^Fifteen)-Group represented by the formula (formula
Where E is a silicon atom, germanium atom or tin source
Child and R¹⁴And R^FifteenAre independent of each other,
Same or different, C₁~ C₆It is an alkyl group. ),
Formula -E¹(R¹⁶) (R¹⁷) -E^Two(R¹⁸) (R ¹⁹)-
A group represented by the formula (wherein E¹And E^TwoAre independent of each other
And the same or different, silicon atom, germanium
Atom or tin atom, and R¹⁶, R¹⁷, R¹⁸And R
¹⁹Are, independently of one another, identical or different,
C₁~ C₆It is an alkyl group. May be interrupted by
No. ) The cyclopentadiene derivative obtained by the above method,
Reacting with a precursor containing the transition metal in the presence of a reducing agent
Providing a method for synthesizing an organometallic compound, characterized in that:
Is done.

In the present invention, the delocalized cyclic η ⁵ −
The coordination ligand is preferably represented by the following formula (V).

[0021]

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(Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ ,
R ⁷ , R ⁸ and R ⁹ have the meaning described above. Further, according to another aspect of the present invention, there is provided a method for producing a synthetic polymer, which comprises producing a synthetic polymer using the organometallic compound synthesized by the above method as a catalyst.

[0023]

BEST MODE FOR CARRYING OUT THE INVENTION According to one aspect of the present invention, there is provided a method for synthesizing a cyclopentadiene derivative represented by the above formula (I). This synthesis method is represented by the following reaction formula.

[0024]

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(Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ ,
R ⁷ , R ⁸ , R ⁹ , M, L ¹ , L ² , X ¹ , X ² and Y each have the above-mentioned meaning. ) R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ are
Each independently, identical or different, a hydrogen atom, a C ₁ -C ₂₀ hydrocarbon group which may have a substituent, a C ₁ -C ₂₀ alkoxy group which may have a substituent A C ₆ -C ₂₀ aryloxy group which may have a substituent, or a group represented by the formula —Si (R ¹⁰ ) (R ¹¹ ) (R ¹² ) (wherein R ¹⁰ , R ¹¹ and R ¹² is each independently of one another, the same or different, and is a C ₁ -C ₂₀ alkyl group;
A C ₆ -C ₂₀ arylalkyl group, a C ₁ -C ₂₀ alkoxy group, and a C ₆ -C ₂₀ arylalkyloxy group. ).

R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸
And R ^9, respectively, independently of one another, identical or different, a hydrogen atom, which may have a substituent, C ₁ -C
₂₀ hydrocarbon groups, optionally having a substituent, C ₁ -C ₂₀
An alkoxy group or an optionally substituted C ₆
Preferably -C ₂₀ aryloxy group which may have a hydrogen atom or a substituent, more preferably a C ₁ -C ₂₀ hydrocarbon group.

As used herein, a C ₁ -C ₂₀ hydrocarbon group is
It may be a saturated or unsaturated acyclic or a saturated or unsaturated cyclic. When the C ₁ -C ₂₀ hydrocarbon group is acyclic, it may be linear or branched. C ₁ -C ₂₀ hydrocarbon groups include C ₁ -C ₂₀ alkyl groups, C ₂ -C ₂₀ alkenyl groups, C ₂ -C ₂₀ alkynyl groups,
C ₃ -C ₂₀ aryl groups, C ₄ -C ₂₀ alkadienyl groups, C
₄ -C ₂₀ polyenyl group, C ₆ -C ₁₈ aryl group, C ₆ -C
₂₀ alkylaryl group, C ₆ -C ₂₀ arylalkyl group, C ₄ -C ₂₀ cycloalkyl group, and the like C ₄ -C ₂₀ cycloalkenyl group.

C₁~ C₂₀Alkyl group, C_Two~ C₂₀Alkene
Group, C_Two~ C₂₀Alkynyl group, C_Three~ C₂₀Allyl group, C
_Four~ C₂₀An alkyldienyl group and C_Four~ C₂₀Polyeni
The radicals are each C₁~ C_TenAlkyl group, C_Two~ C_TenA
Lucenyl group, C_Two~ C_TenAlkynyl group, C_Three~ C_TenAllyl
Group, C_Four~ C_TenAn alkyldienyl group and C_Four~ C_{1 0}Po
It is preferably a phenyl group.

C ₆ -C ₁₈ aryl group, C ₆ -C ₂₀ alkylaryl group, C ₆ -C ₂₀ arylalkyl group, C ₄ -C ₂₀
Cycloalkyl group, and, C ₄ -C ₂₀ cycloalkenyl group, each, C ₆ -C ₁₀ aryl group, C ₆ -C ₁₂ alkylaryl group, C ₆ -C ₁₂ arylalkyl group, C ₄ ~
C ₁₀ cycloalkyl group, and, C ₄ -C ₁₀ cycloalkenyl group.

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 the present invention include, but are not limited to, phenoxy, naphthoxy, phenylphenoxy, 4-methylphenoxy, and the like.

The group represented by the formula -Si (R ¹⁰ ) (R ¹¹ ) (R ¹² ) includes, but is not limited to, trimethylsilyl, triethylsilyl, trimethoxysilyl, triethoxysilyl, diphenylmethylsilyl, Examples include triphenylsilyl, triphenoxysilyl, dimethylmethoxysilyl, dimethylphenoxysilyl, methylmethoxyphenyl and the like.

A substituent may be introduced into the C ₁ -C ₂₀ hydrocarbon group, the C ₁ -C ₂₀ alkoxy group and the C ₆ -C ₂₀ aryloxy group. Examples of the substituent include halogen. Atoms and alkoxy groups.

Where R¹And R^Two, R^TwoAnd R^Three, R^ThreePassing
And R^Four, R^FiveAnd R⁶, R⁶And R⁷, R ⁷And R⁸Or
R⁸And R⁹Are the same or different, and
_Four~ C_{Two 0}It may form a saturated or unsaturated ring. for example
If R¹And R^Two, And R^ThreeAnd R^FourBut the same or different
May be formed. For example, R^FiveAnd R⁶, Row
And R⁷And R⁸May form the same or different rings
No. Similarly, R^FiveAnd R⁶, And R⁸And R⁹Are the same
Or they may form different rings. R⁶And R⁷, Row
And R⁸And R⁹May form the same or different rings
No.

This saturated or unsaturated ring may be a carbocyclic or heterocyclic ring. That is, the C ₄ ~
The C ₂₀ saturated or unsaturated ring is an oxygen atom, a group represented by the formula —N (R ¹³ ) —
(Wherein R ¹³ is a hydrogen atom or a C ₁ -C ₆ alkyl group), a group represented by the formula —E (R ¹⁴ ) (R ¹⁵ ) — (wherein E is A silicon atom, a germanium atom or a tin atom, and R ¹⁴ and R ¹⁵ are each independently of each other, the same or different, a C ₁ -C ₆ alkyl group, and a C ₁ -C ₃ alkyl group; preferable.),
A group represented by the formula -E ¹ (R ¹⁶ ) (R ¹⁷ ) -E ² (R ¹⁸ ) (R ¹⁹ )-, wherein E ¹ and E ² are each independently of one another, identical or different, A silicon atom, a germanium atom or a tin atom, and R ¹⁶ , R ¹⁷ , R ¹⁸ and R
¹⁹ are each independently of the other, the same or different,
A C ₁ -C ₆ alkyl group, or a C ₁ -C ₃ alkyl group. E ¹ and E ² are preferably the same atom. ) May be interrupted.

The ring formed by these substituents is a four-membered ring
It is preferably a 16-membered ring, and more preferably a 4- to 12-membered ring. This ring may be an aromatic ring or an aliphatic ring.

This saturated ring or unsaturated ring may have a substituent. For example, the ring, C ₁ -C ₂₀ hydrocarbon group, C ₁ -C ₂₀ alkoxy groups, C ₆ -C ₂₀ aryloxy group, or the formula ^{-Si (R 10) (R 12} ) with (R ¹²⁾ A group represented by the formula (wherein, R ¹⁰ , R ¹¹ and R ¹² are each independently of one another and are the same or different and each is a C ₁ -C ₂₀ alkyl group, C ₆
-C ₂₀ arylalkyl group, C ₁ -C ₂₀ alkoxy group,
A C ₆ -C ₂₀ arylalkyloxy group; ) May be introduced.

In the present invention, the metallacyclopentadiene represented by the above formula (II) is used. M represents a metal belonging to Groups 3 to 5 of the periodic table or a lanthanide series. M is preferably a metal belonging to Group 4 of the periodic table or a lanthanide series, and more preferably a metal belonging to Group 4 of the periodic table, that is, titanium, zirconium and hafnium.

L ¹ and L ² are independent of each other and are the same or different and represent an anionic ligand. The anionic ligand is non-localized cyclic eta ⁵ - it is preferred coordination type ligand, 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. This substituted cyclopentadienyl group is, for example, methylcyclopentadienyl, ethylcyclopentadienyl, isopropylcyclopentadienyl, t-butylcyclopentadienyl, dimethylcyclopentadienyl, diethylcyclopentadienyl, diisopropylcyclo. Pentadienyl, di-t
-Butylcyclopentadienyl, tetramethylcyclopentadienyl, indenyl, 2-methylindenyl, 2-methyl-4-phenylindenyl, tetrahydroindenyl, benzoindenyl, fluorenyl, benzofur An oleenyl group, a tetrahydrofluorenyl group and an octahydrofluorenyl group.

Examples of the delocalized cyclic η ⁵ -coordination system ligand further include a ligand represented by the above formula (V). 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, it may contain one or more heteroatoms, such as elements of group 14 of the periodic table and / or elements of groups 15, 16 and 17 of the periodic table.

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.

Metallacyclopentadiene also includes compounds having more than one metallacyclopentadiene moiety. 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 are described in, for example, EP-A-632063, JP-A-4-80214, JP-A-4-85310, and EP-A-654476.

In the present invention, a benzene derivative represented by the above formula (III) is used. X ¹ and X ² are each independently of each other, the same or different, and are a leaving group. Examples of the leaving group include a halogen atom such as F, Cl, Br, and I, a p-toluenesulfonyl group, and trifluoromethanesulfonic acid ester (triflate). X ¹ and X ² are each independently of one another and are the same or different and are preferably Cl, Br and I, and particularly preferably Cl and Br.

Y is a hydrogen atom or a leaving group. As the leaving group, a leaving group which may be X ^{1 or} X ² is used. Is preferred. It is particularly preferable that Y is a hydrogen atom.

In the present invention, when the metallacyclopentadiene represented by the above formula (II) is reacted with the benzene derivative represented by the above formula (III), it is required that a metal compound is present. The metal compound is preferably a metal compound belonging to Groups 4 to 15 of the periodic table, and particularly a metal compound belonging to Groups 8 to 15 of the periodic table is used.

More preferably, the metal compound is a metal salt, for example, a metal such as CuX, NiX ₂ , BiX ₃ (where X represents a halogen atom such as a chlorine atom, a bromine atom, etc.). Salt is used.

A metallacyclopentadiene such as zirconacyclopentadiene and an acetylene derivative are converted to CuCl
To form a benzene ring in the presence of T.
Takahashi et al., J. Am. Chem. Soc. 1998, 120, 1672-1
680. In the present invention, surprisingly, under the same or similar conditions as described in this document,
It has been found that the reaction of the metallacyclopentadiene represented by the formula (II) with the benzene derivative represented by the formula (III) can be advanced.

As the metal compound, an organometallic complex, in particular, a nickel complex may be used. As the organometallic complex, phosphine; an aromatic amine such as pyridine and bipyridine, and a ligand such as a halogen atom are coordinated with a central metal of Groups 3 to 11 of the periodic table, preferably a central metal of groups 6 to 11 of the periodic table. Those that have been used are preferably used. The central metal is the so-called 4-
It is preferably hexacoordinate, and more preferably a metal of Group 10 of the periodic table. The phosphine is not limited, such as triphenylphosphine and methyldiphenylphosphine. Examples of the organometallic complex include bis (triphenylphosphine) dichloronickel, dichloro (2,2′-bipyridine) nickel, and PdCl ₂ (2,2′-bipyridine).

The reaction is preferably carried out in a temperature range of -80 ° C to 300 ° C, particularly preferably in a temperature range of 0 ° C to 150 ° C. Pressure is from 0.1 bar to 2500
It is in the range of bar, preferably in the range of 0.5 bar to 10 bar. The reaction can be continuous or batch
It can be carried out in one or more stages, in solution, in suspension, in the gas phase or in a supercritical medium.

As the solvent, an aliphatic or aromatic solvent is used, and preferably, a polar solvent is used. Ether solvents such as tetrahydrofuran or diethyl ether;
Halogenated hydrocarbons such as methylene chloride; halogenated aromatic hydrocarbons such as o-dichlorobenzene; N, N
Amides such as dimethylformamide and sulfoxides such as dimethylsulfoxide are used. Alternatively, aromatic hydrocarbons such as benzene, toluene and xylene may be used as the aromatic solvent.

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 metallocyclopentadiene of the above formula (II) is added to the metal of the above formula (III) in the presence of a metal compound.
The reaction of reacting the benzene derivative represented by the formula (I) to obtain the cyclopentadiene derivative represented by the above formula (I) may be proceeding according to the scheme shown below.

[0056]

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(Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ ,
R ⁷ , R ⁸ , R ⁹ , M, L ¹ , L ² , X ¹ , X ² and Y each have the above-mentioned meaning. The compounds of formulas (VI) and (VII) are imaginary intermediates and are not isolated.

The metallacyclopentadiene represented by the above formula (II) can be synthesized, for example, by the following reaction.

[0059]

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[0060]

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[0061]

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[0062]

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(Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ ,
R ⁷ , R ⁸ , R ⁹ , M, L ¹ , L ² , X ¹ , X ² and Y each have the above-mentioned meaning. Z ¹ and Z ² are the same or different and each are a removable ligand. When the cyclopentadiene derivative represented by the formula (I) is obtained from the metallacyclopentadiene represented by the formula (IIa), R ¹ , R ² , R ³ and R ⁴ are the same group.

When a cyclopentadiene derivative represented by the formula (I) is obtained from a metallacyclopentadiene represented by the formula (IIb), R ¹ and R ² are the same groups,
R ³ and R ⁴ are the same group. And R ¹ and R ² ,
R ³ and R ⁴ may be the same group or different groups.

In the formulas (15) and (16), the formula (VII)
Symmetric alkynes represented by Ia) and formula (VIIIb) were used. However, in the present invention, it is not necessary to use a symmetric alkyne.

In the chemical formulas 17 and 18, B is a crosslinking group
For example, an oxygen atom, a formula -N (R ¹³)-
(Where R¹³Is a hydrogen atom or C₁~ C₆An alkyl group
You. ), The formula -E (R¹⁴) (R^Fifteen)-Group represented by the formula (formula
Where E is a silicon atom, germanium atom or tin source
Child and R¹⁴And R^FifteenAre independent of each other,
Same or different, C₁~ C₆It is an alkyl group. ),
Formula -E¹(R¹⁶) (R¹⁷) -E^Two(R¹⁸) (R¹⁹)-
A group represented by the formula (wherein E¹And E^TwoAre independent of each other
And the same or different, silicon atom, germanium
Atom or tin atom, and R¹⁶, R¹⁷, R¹⁸And R
¹⁹Are, independently of one another, identical or different,
C₁~ C₆It is an alkyl group. May be interrupted by
And an alkylene group.

The crosslinking group B may be, for example, a group represented by the formula — (CH) ₄ —, and may be represented by the formula (IIc) or the formula (II)
The metallacyclopentadiene represented by d) may be condensed with a benzene ring. Accordingly, for example, in the cyclopentadiene ring represented by the formula (I), for example,
R ² and R ³ or R ³ and R ⁴ may form a benzene ring.

The bridging group B is, for example, of the formula — (CH ₂ ) _p —O
— (CH ₂ ) _q — may be a group represented by the formula:
And q are the same or different and are integers from 0 to 10,
Preferably, it is an integer of 1 to 6. The sum of p and q is preferably an integer of 1 or more, and preferably 1 to 10
Is an integer. ) Z ¹ and Z ² are not limited as long as they can coordinate to M. For example, an olefin such as ethylene, an alkyl group such as an n-butyl group, and the like are included.

The organometallic compound represented by the formula (IX) is
It may be an ion, for example, an anion. The above reaction is carried out preferably in a temperature range of -120 ° C to 50 ° C, more preferably -120 ° C to 0 ° C. For the production of metallacyclopentadiene, see, for example, T. Takahashi et al. J. Org. Chem. 1995, 60, 44
44.

In another aspect of the present invention, the following formula (I)
An organometallic compound represented by V) or (IVa) is provided.

[0071]

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[0072]

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In these organometallic compounds, the ligand is a cyclopentadienyl group derivative represented by the following formula (V).

[0074]

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Such an organometallic compound can be synthesized from the cyclopentadiene derivative represented by the above formula (I) by a known method. For example, F. Albert Co
tton and Geoffrey Wilkinson, "Advanced Inorganic Ch
emistry "Third Edition, John Wiley & Sons, 1972, Charles
M. Lukehart, "Fundamental Transition Metal Organom
etallic Chemistry "Brooks / Cole Publishing Company,
Monterey, California, 1985 and the like describe a reaction for preparing an organometallic compound having cyclopentadienyl or a cyclopentadienyl derivative as a ligand from cyclopentadiene or a cyclopentadiene derivative. An organometallic compound represented by the above formula (IV) or (IVa) can be synthesized.

For example, a cyclopentadiene derivative represented by the formula (I) is added to a ferrous (II) chloride in a polar solvent such as THF in the presence of a strong base such as sodium metal, potassium metal, lithium alkylated, or tetrahydrolithium aluminum. , And a metal halide such as zirconium (IV) chloride to replace the leaving group such as a halide ion with the cyclopentadienyl group. Or,
A cyclopentadiene derivative represented by the formula (I) is converted to an iron chloride (I) in the presence of a proton acceptor such as diethylamine.
I), a reaction with a metal halide such as zirconium (IV) chloride or the like may replace the cyclopentadienyl group with a leaving group such as a halide ion. In these cases, a strong base or proton acceptor is acting as the reducing agent.

Alternatively, the cyclopentadiene derivative represented by the formula (I) is reacted with a thallium compound such as thallium hydroxide (TlOH) to prepare an organometallic compound of the above formula (V) and thallium. It may be reacted with a halide.

In another aspect of the present invention, there is provided the production of a synthetic polymer using the organometallic compound represented by the above formula (IV) or (IVa) as a catalyst. In particular,
The organometallic compound represented by the above formula (IVa) can be used as a Ziegler-Natta catalyst for producing a synthetic polymer such as polyolefin. The conditions at this time can be set in the same manner as the conditions when a conventional organic metal compound having a known cyclopentadienyl group derivative as a ligand is used.

Metallacyclopentadiene is, for example,
It can be synthesized using the metallocene described above. Screw
(Cyclopentadienyl) dibutylzirconium; bis
(Indenyl) dibutylzirconium; bis (fluorene)
(Nil) dibutyl zirconium; (indenyl) (fluoro
(Renyl) dibutylzirconium; (3-methyl-5-na
Fthylindenyl) (2,7-di-tert-butylphenyl)
(Ruenyl) dibutylzirconium; (3-methyl-5
-Naphthylindenyl) (3,4,7-trimethoxyph
(Ruenyl) dibutylzirconium;
Clopentadienyl) (tetrahydroindenyl) dib
Tylzirconium; (cyclopentadienyl) (1-O
Octen-8-ylcyclopentadienyl) dibutylzyl
Conium; (indenyl) (1-buten-4-ylsic)
Lopentadienyl) dibutylzirconium; [1,3-
Bis (trimethylsilyl) cyclopentadienyl]
(3,4-benzofluorenyl) dibutyl zirconium
Bis (cyclopentadienyl) dibutyltitanium; di
Methylsilanediylbis (indenyl) dibutylzirco
And dimethylsilanediylbis (tetrahydroin
Denenyl) dibutylzirconium; dimethylsilanediyl
(Cyclopentadienyl) (indenyl) dibutylzyl
Conium; dimethylsilanediylbis (2-methylin
Denenyl) dibutylzirconium; dimethylsilanediyl
Bis (2-ethylindenyl) dibutylzirconium;
Dimethylsilanediylbis (2-methyl-4,5-ben
Zoindenyl) dibutylzirconium; dimethylsilane
Diylbis (2-ethyl-4,5-benzoindenyl)
Dibutyl zirconium; dimethylsilanediylbis
(4,5-dihydro-8-methyl-7H-cyclopent
[E] acenaphthylene-7-ylidene) dibutylzirco
And dimethylsilanediyl (2-methyl-4,5-
Benzoindenyl) (2-methyl-4-phenylinde
Nyl) dibutylzirconium; dimethylsilanediyl
(2-ethyl-4,5-benzoindenyl) (2-methyl
Ru-4-phenylindenyl) dibutylzirconium;
Dimethylsilanediyl (2-methyl-4,5-benzoy
Ndenyl) (2-ethyl-4-phenylindenyl) di
Butyl zirconium; dimethylsilanediyl (2-ethyl
Ruindenyl) (2-ethyl-4-phenylnaphthyl)
Dibutyl zirconium; dimethylsilanediyl (2-meth
Tylindenyl) (4-phenylindenyl) dibutyl
Zirconium; dimethylsilanediylbis (2-methyl
-4-phenylindenyl) dibutylzirconium;
Methylsilanediylbis (2-ethyl-4-phenyli
Ndenyl) dibutylzirconium; dimethylsilanediyl
Rubis (2-methyl-4,6-diisopropylindeni
B) Dibutyl zirconium; dimethylsilanediylbis
(2-ethyl-4,6-diisopropylindenyl) di
Butyl zirconium; dimethylsilanediylbis (2-
Methyl-4-naphthylindenyl) dibutylzirconium
Dimethylsilanediylbis (2-ethyl-4-naph
Cylindenyl) dibutylzirconium; methylphenyl
Lusilanediylbis (indenyl) dibutylzirconium
M; methylphenylsilanediyl (cyclopentadienyl)
Le) (indenyl) dibutyl zirconium; methylphen
Nylsilanediylbis (tetrahydroindenyl) dib
Tyl zirconium; methylphenylsilanediylbis
(2-methylindenyl) dibutylzirconium; methyl
Luphenylsilanediylbis (2-ethylindenyl)
Dibutyl zirconium; methylphenylsilanediylbi
(2-methyl-4,5-benzoindenyl) dibutyl
Zirconium; methylphenylsilanediylbis (2-
Ethyl-4,5-benzoindenyl) dibutylzirconi
And methylphenylsilanediylbis (4,5-dihi
Dro-8-methyl-7H-cyclopent [e] acenaf
(Tylene-7-ylidene) dibutylzirconium; methyl
Phenylsilanediyl (2-methyl-4,5-benzoi
Ndenyl) (2-methyl-4-phenylindenyl) di
Butyl zirconium; methylphenylsilanediyl (2
-Ethylindenyl) (2-methyl-4-phenylin
Denenyl) dibutylzirconium; methylphenylsilane
Diyl (2-methyl-4,5-benzoindenyl) (2
-Ethyl-4-phenylindenyl) dibutylzirconi
Um; methylphenylsilanediyl (2-ethyl-4,
5-benzoindenyl) (2-ethyl-indenyl) di
Butyl zirconium; methylphenylsilanediyl (2
-Methylindenyl) (4-phenylindenyl) dibutyl
Ruzirconium; methylphenylsilanediylbis (2
-Methyl-4phenylindenyl) dibutylzirconium
Methyl; methylphenylsilanediylbisdibutylzirconi
And methylphenylsilanediylbis (2-methyl-
4,6-diisopropylindenyl) dibutylzirconi
And methylphenylsilanediylbis (2-ethyl-
4,6-diisopropylindenyl) dibutylzirconi
And methylphenylsilanediylbis (4-naphthyl)
Indenyl) dibutylzirconium; methylphenyl
Landiyl bis (2-ethyl-4-naphthylindeni
B) dibutyl zirconium; diphenylsilanediylbi
Di (indenyl) dibutylzirconium;
Landiylbis (2-methylindenyl) dibutylzyl
Conium; diphenylsilanediylbis (2-ethyli
Ndenyl) dibutylzirconium; diphenylsilanedi
Yl (cyclopentadienyl) (indenyl) dibutyl
Zirconium; diphenylsilanediylbis (2-methyl
-4,5-benzoindenyl) dibutylzirconium
Diphenylsilanediylbis (2-ethyl-4,5
-Benzoindenyl) dibutylzirconium; diphenyl
Lusilanediyl (2-methyl-4,5-benzoindenyl)
) (2-methyl-4phenylindenyl) dibutyldi
Ruconium; diphenylsilanediyl (2-ethyl-
4,5-benzoindenyl) (2-methyl-4phenyl
Indenyl) dibutylzirconium; diphenylsilane
Diyl (2-methyl-4,5-benzoindenyl) (2
-Ethyl-4phenylindenyl) dibutylzirconium
Diphenylsilanediyl (2-ethyl-4,5-
Nzoindenyl) (2-ethyl-4naphthylindenyl
B) dibutyl zirconium; diphenylsilanediyl
(2-methylindenyl) (4-phenylindenyl) di
Butyl zirconium; diphenylsilanediylbis (2
-Methyl-4phenylindenyl) dibutylzirconium
Diphenylsilanediylbis (2-ethyl-4fe)
Nylindenyl) dibutylzirconium;
Landiylbis (2-methyl-4,6-diisopropyl
Indenyl) dibutylzirconium; diphenylsilane
Diylbi; s (2-ethyl-4,6-diisopropyli
Ndenyl) dibutylzirconiumdiphenylsilanediyl
Rubis (2-methyl-4-naphthylindenyl) dibuty
Ruzirconium; diphenylsilanediylbis (2-E
Tyl-4-naphthylindenyl) dibutylzirconium
1-silacyclopentane-1,1-bis (indeni
1) dibutyl zirconium; 1-silacyclopentane
1,1-bis (2-methylindenyl) dibutylzirco
And 1-silacyclopentane-1,1-bis (2-
Ethylindenyl) dibutylzirconium; 1-silicone
Clopentane-1,1-bis (2-methyl-4,5-beta
Nzoindenyl) dibutylzirconium; 1-silashic
Lopentane-1,1-bis (2-ethyl-4,5-ben
Zoindenyl) dibutylzirconium; 1-silacyclo
Pentane-1- (2-methyl-4,5-benzoindenyl)
L) -1- (2-Methyl-4-phenylindenyl) di
Butyl zirconium; 1-silacyclopentane-1-
(2-ethyl-4,5-benzoindenyl) -1- (2
-Methyl-4-phenylindenyl) dibutylzirconi
1-silacyclopentane-1- (2-methyl-
4,5-benzoindenyl) -1- (2-ethyl-4-
Phenylindenyl) dibutylzirconium; 1-sila
Cyclopentane-1- (2-ethyl-4,5-benzoi
Ndenyl) -1- (2-ethyl-4-naphthylindenyl
1) dibutyl zirconium; 1-silacyclopentane
1- (2-methylindenyl) -1- (4-phenyli
Ndenyl) dibutylzirconium; 1-silacyclopen
Tan-1,1-bis (2-methyl-4-phenylindene
Nyl) dibutylzirconium; 1-silacyclopentane
-1,1-bis (2-ethyl-4-phenylindenyl)
1) dibutyl zirconium; 1-silacyclopentane
1,1-bis (2-methyl-4,6-diisopropyli
Ndenyl) dibutylzirconium; 1-silacyclopen
Tan-1,1-bis (2-ethyl-4,6-diisopro
Pyrindenyl) dibutylzirconium; 1-silashic
Lopentane-1,1-bis (2-methyl-4-naphthyl
Indenyl) dibutylzirconium; 1-silacyclope
1,1-bis (2-ethyl-4-naphthylin
Denenyl) dibutyl zirconium; bis (cyclopentadi
Enyl) dibutyltitanium; ethylene-1,2-bis (a
Ndenyl) dibutylzirconium; ethylene-1,2-
Bis (tetrahydroindenyl) dibutyl zirconium
Ethylene; 1- (cyclopentadienyl) -2-
(1-indenyl) dibutylzirconium; ethylene-
1- (cyclopentadienyl) -2- (2-indenyl
B) dibutyl zirconium; ethylene-1- (cyclope
Antadienyl) -2- (2-methyl-1-indenyl)
Dibutyl zirconium; ethylene-1,2-bis (2-
Methylindenyl) dibutylzirconium; ethylene-
1,2-bis (2-ethylindenyl) dibutyl zircon
Ium; ethylene-1,2-bis (2-methyl-4,5
-Benzoindenyl) dibutylzirconium; ethylene
-1,2-bis (2-ethyl-4,5-benzoindenyl)
B) dibutyl zirconium; ethylene-1,2-bis
(4,5-dihydro-8-methyl-7H-cyclopent
[E] acenaphthylene-7-ylidene) dibutylzirco
Ium; ethylene-1- (2-methyl-4,5-benzo)
Indenyl) -2- (2-methyl-4-phenylindene
Nyl) dibutylzirconium; ethylene-1- (2-e
Tyl-4,5-benzoindenyl) -2- (2-methyl
-4-phenylindenyl) dibutylzirconium; d.
Tylene-1- (2-methyl-4,5-benzoindeni)
) -2- (2-ethyl-4-phenylindenyl) di
Butyl zirconium; ethylene-1- (2-ethyl-
4,5-benzoindenyl) -2- (2-ethyl-4-
Naphthylindenyl) dibutylzirconium; ethylene
-1- (2-methylindenyl) -2- (4-phenyl
Indenyl) dibutylzirconium; ethylene-1,2
-Bis (2-methyl-4-phenylindenyl) dibutyl
Ruzirconium; ethylene-1,2-bis (2-ethyl
-4-phenylindenyl) dibutylzirconium; d.
Tylene-1,2-bis (2-methyl-4,6-diisoprop
Ropylindenyl) dibutylzirconium; ethylene-
1,2-bis (2-ethyl-4,6-diisopropyli
Ndenyl) dibutylzirconium; ethylene-1,2-
Bis (2-methyl-4-naphthylindenyl) dibutyl
Zirconium; ethylene-1,2-bis (2-ethyl-
4-naphthylindenyl) dibutylzirconium; pro
Pyrene-2,2-bis (indenyl) dibutylzirconi
Propylene-2-cyclopentadienyl-2-
(1-indenyl) dibutyl zirconium; propylene
-2-cyclopentadienyl-2- (4-phenyl-1
-Indenyl) dibutylzirconium; propylene-2
-Cyclopentadienyl-2- (9-fluorenyl) di
Butyl zirconium; propylene-2-cyclopentadi
Enyl-2- (2,7-dimethoxy-9-fluorenyl
L) dibutyl zirconium; propylene-2-cyclope
Antadenyl-2- (2,7-di-tert-butyl-
9-fluorenyl) dibutylzirconium; propylene
-2-cyclopentadienyl-2- (2,7-dibromo
-9-fluorenyl) dibutylzirconium; propyle
2-cyclopentadienyl-2- (2,7-dife
Nil-9-fluorenyl) dibutylzirconium;
Pyrene-2-cyclopentadienyl-2- (2,7-di
Methyl-9-fluorenyl) dibutylzirconium;
Ropylene-2- (3-methylcyclopentadienyl)-
2- (2,7-dibutyl-9-fluorenyl) dibutyl
Zirconium; propylene-2- (3-tert-butyl)
Rucyclopentadienyl) -2- (2,7-dibutyl-
9-fluorenyl) dibutylzirconium; propylene
-2- (3-trimethylsilylcyclopentadienyl)
-2- (3,6-di-tert-butyl-9-fluoro)
Nyl) dibutylzirconium; propylene-2-cyclo
Pentadienyl-2- [2,7-bis (3-butene-1
-Yl) -9-fluorenyl] dibutylzirconium;
Propylene-2-cyclopentadienyl-2- (3-t
tert-butyl-9-fluorenyl) dibutylzirconi
Propylene-2,2-bis (tetrahydroindene
Nyl) dibutylzirconium; propylene-2,2-bi
(2-methylindenyl) dibutyl zirconium;
Ropylene-2,2-bis (2-ethylindenyl) dib
Tyl zirconium; propylene-2,2-bis (2-meth
Tyl-4,5-benzoindenyl) dibutylzirconium
Propylene-2,2-bis (2-ethyl-4,5-
Benzoindenyl) dibutyl zirconium; 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; propyl
Len-2- (2-ethyl-4,5-benzoindenyl)
-2- (2-methyl-4-phenylindenyl) dibuty
Ruzirconium; propylene-2- (2-methyl-4,
5-benzoindenyl) -2- (2-ethyl-4-fe
Nylindenyl) dibutylzirconium; propylene-
2- (2-ethyl-4,5-benzoindenyl) -2-
(2-ethyl-4-naphthylindenyl) dibutylzyl
Conium; propylene-2- (2-methylindenyl)
-2- (4-phenylindenyl) dibutylzirconium
Propylene-2,2-bis (2-methyl-4-fe
Nylindenyl) dibutylzirconium; propylene-
2,2-bis (2-ethyl-4-phenylindenyl)
Dibutyl zirconium; propylene-2,2-bis (2
-Methyl-4,6-diisopropylindenyl) dibuty
Ruzirconium; propylene-2,2-bis (2-ethyl
-4,6-diisopropylindenyl) dibutylzyl
Conium; propylene-2,2-bis (2-methyl-4
-Naphthylindenyl) dibutylzirconium;
Len-2,2-bis (2-ethyl-4-naphthylindene
Nyl) dibutylzirconium; 1,6-bis [methylsi
Rilbis (2-methyl-4-phenylindenyl) dib
Tyl zirconium] hexane; 1,6-bis [methylsi
Lilbis (2-methyl-4,5-benzoindenyl) di
Butylzirconium] hexane; 1,6-bis [methyl
Silylbis (2-ethyl-4-phenylindenyl) di
Butylzirconium] hexane; 1,6-bis [methyl
Silylbis (2-methyl-4-naphthylindenyl) di
Butylzirconium] hexane; 1,6-bis [methyl
Silylbis (2-methyl-4,6-diisopropylin
Denenyl) dibutylzirconium] hexane; 1,6-bi
[Methylsilyl (2-methyl-4phenylindenyl)
Le) (4,5-benzoindenyl) dibutyl zirconium
Hexane]; 1- [methylsilylbis (tetrahydro
Indenyl) dibutylzirconium] -6- [ethyls
Tanyl (cyclopentadienyl) (fluorenyl) dib
Tyl zirconium] hexane; 1,6-disila-1,
1,6,6-tetramethyl-1,6-bis [methylsilyl
Rubis (2-methyl-4phenylindenyl) dibutyl
Zirconium] hexane; 1,4-disila 1,4-bis
[Methylsilylbis (2-methyl-4phenylindenyl)
L) dibutylzirconium] cyclohexane; [1,4
-Bis (1-indenyl) -1,1,4,4-tetrame
Tyl-1,4-disilabutane] bis (pentamethylcyclyl
Lopentadienyl dibutyl zirconium); [1,4-
Bis (9-fluorenyl) -1,1,4,4-tetrame
Tyl-1,4-disilabutane] bis (cyclopentadie
Nyldibutylzirconium); [1,4-bis (1-a
Ndenyl) -1,1,4,4-tetramethyl-1,4-
Disilabutane] bis (cyclopentadienyldibutyldi
Ruconium); [1- (1-indenyl) -6- (2-
Phenyl-1-indenyl) -1,1,6,6-tetra
Ethyl-1,6-disila-4-oxahexane] bis
(Tert-butylcyclopentadienyldibutylzyl
Conium); [1,10-bis (2,3-dimethyl-1)
-Indenyl) -1,1,10,10-tetramethyl-
1,10-Digelmadecan] bis (2-methyl-4-f
(Enylindenyldibutylzirconium); (1-methyl
3-tert-butylcyclopentadienyl) (1
-Phenyl-4-methoxy-7-chlorofluorenyl)
Dibutyl zirconium; (4,7-dichloroindeni
Le) (3,6-dimesitylfluorenyl) dibutylzyl
Conium; bis (2,7-di-tert-butyl-9-
Cyclohexylfluorenyl) dibutylzirconium;
(2,7-dimesitylfluorenyl) [2,7-bis
(1-Naphthyl) fluorenyl] dibutylzirconium
Dimethylsilylbis (fluorenyl) dibutylzyl
Conium; dibutylstannylbis (2-methylfluore
Nyl) dibutylzirconium; 1,1,2,2-tetra
Ethyldisilanediyl (2-methylindenyl) (4-
Phenylfluorenyl) dibutylzirconium; propyl
Len-1- (2-indenyl) -2- (9-fluorenyl)
L) dibutyl zirconium; 1,1-dimethyl-1-si
Laethylenebis (fluorenyl) dibutylzirconium
[4- (cyclopentadienyl) 4,7,7-tri
Methyl (tetrahydroindenyl) dibutyl zirconium
[4- (cyclopentadienyl) 4,7-dimethyl
-7-phenyl (5,6-dimethyltetrahydroindene
Nyl] dibutylzirconium; [4- (cyclopentadi
Enyl) -4,7-dimethyl-7- (1-naphthyl)
(7-phenyltetrahydroindenyl)] dibutyldi
Ruconium; [4- (cyclopentadienyl) -4,7
-Dimethyl-7-butyl (6,6-diethyltetrahydride
Loindenyl)] dibutylzirconium; [4- (3-
tert-butylcyclopentadienyl) -4,7,7
-Trimethyl (tetrahydroindenyl)] dibutyldi
Ruconium; [4- (1-indenyl) -4,7,7-
Trimethyl (tetrahydroindenyl)] dibutylzyl
Conium; bis (cyclopentadienyl) dibutylhaf
Bis (indenyl) dibutyl vanadium; bis
(Fluorenyl) dibutyl scandium; (indeni
L) (fluorenyl) dibutyl niobium; (2-methyl-
7-naphthylindenyl) (2,6-di-tert-butyl
Tylfluorenyl) dibutyltitanium; bromide (pentamethyi)
Rucyclopentadienyl) (tetrahydroindenyl)
Butylhafnium; (cyclopentadienyl) (1-O
Octen-8-ylcyclopentadienyl) dibutylhaf
Ium; (indenyl) (2-buten-4-ylcyclo)
[Pentadienyl) dibutyltitanium; [1,3-bis (g
[Limethylsilyl) cyclopentadienyl] (3,4-
Bis (fluorenyl) dibutylniobium; bis (cyclopentene)
Tadienyl) dibutyltitanium; dimethylsilanediylbi
(Indenyl) dibutyltitanium; dimethylsilanediyl
Rubis (tetrahydroindenyl) dibutylhafnium
Dimethylsilanediyl (cyclopentadienyl)
(Indenyl) dibutyltitanium; dimethylsilanediyl
Bis (2-methylindenyl) dibutylhafnium; di
Methylsilanediylbis (2-ethylindenyl) methyl
Luscandium; dimethylsilanediylbis (2-buty
-4,5-benzoindenyl) dibutylniobium;
Tylsilanediylbis (2-ethyl-4,5-benzoy
Ndenyl) dibutyltitanium; dimethylsilanediylbis
(4,5-dihydro-8-methyl-7H-cyclopent
[E] acenaphthylene-7-ylidene) dibutyl tita
Dimethylsilanediyl (2-methyl-4,5-ben
Zoindenyl) (2-methyl-4-phenylindenyl
B) dibutyltitanium; dimethylsilanediyl (2-ethyl
-4,5-benzoindenyl) (2-methyl-4-f
Enylindenyl) dibutylhafnium; dimethylsila
Ndiyl (2-ethyl-4,5-benzoindenyl)
(2-ethyl-4-phenylindenyl) methyl scan
Diium; dimethylsilanediyl (2-ethyl-4,5-
Benzoindenyl) (2-ethyl-4-naphthylinde
Nil) dibutyltitanium; dimethylsilanediyl (2-
Tylindenyl) (4-phenylindenyl) dibutyl
Hafnium; dimethylsilanediylbis (2-methyl-
4-phenylindenyl) dibutylniobium;
Landiylbis (2-ethyl-4-phenylindenyl)
B) Dibutyl vanadium; dimethylsilanediylbis
(2-methyl-4,6-diisopropylindenyl) di
Butylhafnium; dimethylsilanediylbis (2-E
Cyl-4,6-diisopropylindenyl) dibutylba
Nadium; dimethylsilanediyl bis (2-methyl bromide)
-4-naphthylindenyl) butylhafnium; dimethyl
Lusilanediylbis (2-ethyl-4-naphthylindene
Nyl) dibutyltitanium; methylphenylsilanediylbi
(Indenyl) dibutyltitanium; methylphenylsila
Ndiyl (cyclopentadienyl) (indenyl) Hough
Ium; methylphenylsilanediylbis (tetrahydrid
Loindenyl) dibutyl hafnium; methyl phenyl
Landiyl bis (2-methylindenyl) dibutyl tita
Methylphenylsilanediylbis (2-ethylin
Denenyl) dibutylhafnium; methylphenylsilanedi
Ilbis (2-methyl-4,5-benzoindenyl) di
Butylhafnium; methylphenylsilanediylbis
(2-ethyl-4,5-benzoindenyl) dibutylba
Nadium; methylphenylsilanediylbis (4,5-
Dihydro-8-methyl-7H-cyclopent [e] ace
Naphthylene-7-ylidene) dibutyltitanium;
Ruphenylsilanediylbis (2-methyl-4,5-
Nzoindenyl) (2-methyl-4-phenylindenyl
Le) Butyl titanium; methylphenylsilanediylbis
(2-ethyl-4,5-benzoindenyl) (2-methyl
Ru-4-phenylindenyl) dibutyltitanium; methyl
Phenylsilanediylbis (2-methyl-4,5-ben
Zoindenyl) (2-ethyl-4-phenylindenyl
Le) dibutyl hafnium; methylphenylsilanediyl
Bis (2-ethyl-4,5-benzoindenyl) (2-
Ethyl-4-phenylindenyl) dibutylhafnium
Methyl; methylphenylsilanediyl (2-methylindeni
M) (4-phenylindenyl) dibutyltitanium;
Ruphenylsilanediylbis (2-methyl-4-phenyl
Ruindenyl) dibutylhafnium;
Landiylbis (2-ethyl-4-phenylindenyl)
B) dibutyl vanadium; methylphenylsilanediyl
Bis (2-methyl-4,6-diisopropylindeni
B) dibutyl titanium; methylphenylsilanediylbis
(2-ethyl-4,6-diisopropylindenyl) di
Butylhafnium; methylphenylsilanediylbis
(2-methyl-4-naphthylindenyl) dibutylhaf
And methylphenylsilanediylbis (2-ethyl
-4-naphthylindenyl) dibutyltitanium; diphenyl
Disilanediylbis (indenyl) dibutyltitanium; di
Phenylsilanediylbis (2-methylindenyl) di
Butylhafnium; diphenylsilanediylbis (2-
Ethylindenyl) dibutyltitanium; diphenylsilane
Diylbis (cyclopentadienyl) (indenyl) di
Butylhafnium; diphenylsilanediylbis (2-
Methyl-4,5-benzoindenyl) dibutyltitanium;
Diphenylsilanediylbis (2-ethyl-4,5-
Nzoindenyl) dibutylhafnium; diphenylsila
Ndiyl (2-methyl-4, -benzoindenyl)
(2-methyl-4,5-phenylindenyl) dibutyl
Hafnium; diphenylsilanediyl (2-ethyl-
4,5-benzoindenyl) (2-methyl-4,5-f
Enylindenyl) dibutyltitanium; diphenylsilane
Diyl (2-methyl-4,5-benzoindenyl) (2
-Ethyl-4,5-phenylindenyl) dibutylhaf
And diphenylsilanediyl (2-ethyl-4,5
-Benzoindenyl) (2-ethyl-4,5-phenyl
Indenyl) dibutyltitanium; diphenylsilanediyl
(2-methylindenyl) (4-phenylindenyl)
Dibutyltitanium; diphenylsilanediylbis (2-meth
Tyl-4-phenylindenyl) dibutyltitanium; diph
Enylsilanediylbis (2-ethyl-4-phenyli
Ndenyl) dibutylhafnium; diphenylsilanedii
Rubis (2-methyl-4,6-diisopropylindeni
B) dibutylhafnium; diphenylsilanediylbis
(2-ethyl-4,6-diisopropylindenyl) di
Butylhafnium; diphenylsilanediylbis (2-
Methyl-4-naphthylindenyl) dibutylhafnium
Diphenylsilanediylbis (2-ethyl-4-na)
Fthylindenyl) dibutyltitanium; 1-silacyclope
1,1-bis (indenyl) dibutylhafnium
1-silacyclopentane-1,1-bis (2-methyl
Ruindenyl) dibutylhafnium; 1-silacyclope
1,1-bis (2-ethylindenyl) dibutyl
Luhafnium; 1-silacyclopentane-1,1-bis
(2-methyl-4,5-benzoindenyl) dibutylthio
Tan; 1-silacyclopentane-1,1-bis (2-e
Tyl-4,5-benzoindenyl) dibutylhafnium
1-silacyclopentane-1- (2-methyl-4,
5-benzoindenyl) -1- (2-methyl-4-fe
Nylindenyl) methyl scandium; 1-silacyclo
Pentane-1- (2-ethyl-4,5-benzoindenyl)
L) -1- (2-Methyl-4-phenylindenyl) di
Butylhafnium; 1-silacyclopentane-1- (2
-Methyl-4,5-benzoindenyl) -1- (2-E
Tyl-4-phenylindenyl) dibutyltitanium; 1-
Silacyclopentane-1- (2-ethyl-4,5-ben
Zoindenyl) -1- (2-ethyl-4-phenylin
Denenyl) dibutylhafnium; 1-silacyclopentane
-1- (2-methylindenyl) -1- (4-phenyl
Indenyl) dibutylhafnium; 1-silacyclopen
Tan-1,1-bis (2-methyl-4-phenylindene
Nyl) dibutylhafnium; 1-silacyclopentabromide
1,1-bis (2-ethyl-4-phenylindenyl)
1) dibutyl titanium; 1-silacyclopentane-1,1
-Bis (2-methyl-4,6-diisopropylindenyl
1) dibutyl titanium; 1-silacyclopentane-1,1
-Bis (2-ethyl-4,6-diisopropylindeni
1) dibutyl titanium; 1-silacyclopentane-1,1
-Bis (2-methyl-4-naphthylindenyl) methyl
Scandium; 1-silacyclopentane-1,1-bis
(2-ethyl-4-naphthylindenyl) dibutylhaf
Ium; bis (cyclopentadienyl) dibutyl tita
Ethylene-1,2-bis (indenyl) methylska
Nd; ethylene-1,2-bis (tetrahydroin
Denenyl) dibutyltitanium; ethylene-1- (cyclopen
Tadienyl) -2- (1-indenyl) dibutylhafni
Um; ethylene-1- (cyclopentadienyl) -bromide
2- (2-indenyl) butyl titanium; ethylene-1-
(Cyclopentadienyl) -2- (2-methyl-1-i
Ndenyl) dibutylhafnium; ethylene-1,2-bi
2- (2-methylindenyl) dibutylhafnium;
Len-1,2-bis (2-ethylindenyl) dibutyl
Hafnium; ethylene-1,2-bis (2-methyl-
4,5-benzoindenyl) dibutylhafnium;
Len-1,2-bis (2-ethyl-4,5-benzoin
Denenyl) dibutyltitanium; ethylene-1,2-bis
(4,5-dihydro-8-methyl-7H-cyclopent
[E] acenaphthylene-7-ylidene) dibutyl tita
Ethylene-1- (2-methyl-4,5-benzoin)
Denenyl) -2- (2-methyl-4-phenylindenyl)
B) dibutyl titanium; ethylene-1- (2-ethyl-
4,5-benzoindenyl) -2- (2-methyl-4-
Phenylindenyl) dibutyltitanium; ethylene-1-
(2-methyl-4,5-benzoindenyl) -2- (2
-Ethyl-4-phenylindenyl) methylscandiu
Ethylene; 1- (2-ethyl-4,5-benzoin)
Denenyl) -2- (2-ethyl-4-naphthylindenyl
L) dibutyl hafnium; ethylene-1- (2-methyl)
Indenyl) -2- (4-phenylindenyl) dibutyi
Rutitanium; ethylene-1,2-bis (2-methyl-4-
Phenylindenyl) dibutylhafnium; ethylene-
1,2-bis (2-ethyl-4-phenylindenyl)
Dibutylhafnium; ethylene-1,2-bis (2-meth
Butyl-4,6-diisopropylindenyl) dibutyl
Funium; ethylene-1,2-bis (2-ethyl-4,
6-diisopropylindenyl) dibutyltitanium;
Len-1,2-bis (2-methyl-4-naphthylindene
Nyl) dibutyltitanium; ethylene-1,2-bis (2-
Ethyl-4-naphthylindenyl) dibutylhafnium
Propylene-2,2-bis (indenyl) dibutyl
Hafnium; propylene-2-cyclopentadienyl-
2- (1-indenyl) dibutyltitanium.

Further, 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) dichlorozirconium;
(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; (dimethylsilanediyl) bis (2-methyl-
The dichloro form such as (4,6-diisopropylindenyl) dichlorozirconium is reduced with a strong base such as an alkali metal such as sodium, an alkaline earth metal such as magnesium, lithium alkylated, or tetrahydrolithium aluminum, or After converting the dichloro form into the dialkyl form, metallacyclopentadiene can be produced.

[0081]

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

The following reactions were performed using standard Schlenk techniques under an argon or nitrogen atmosphere. The solvent was refluxed in the presence of a suitable desiccant and then made anhydrous by distillation under a stream of argon or nitrogen before use.

¹ H NMR and ¹³ C NMR were measured at 25 ° C. on a Bruker ARX-400 NMR spectrometer. 1
CDCl ₃ containing% trimethylsilane as an internal standard was used as a solvent. GC is a fused silica capillary column, Shimadzu DBP1-M25-O25 and Shimadzu C-R6A.
The analysis was performed using Shimadzu GC-14A equipped with a chromatopack integration analyzer. n-Dodecane was used as an internal standard for gas chromatography. Reference Example 1 bis (η ⁵ -cyclopentadienyl) 2,3,4,5-
Tetraethyl-1-zirconacyclopenta cyclopentadiene-2,4-diene-bis - was charged (eta ⁵ cyclopentadienyl) dichloro zirconium (1.0 mmol) and THF (5 ml) in a Schlenk tube. The solution was cooled to -78 C and then n-butyllithium (2.0 mmol) was added. This solution was stirred at -78 ° C for 1 hour. -78
At 0 ° C., 3-hexyne (1.0 mmol) was added to the reaction mixture.
And then warmed to room temperature and left for 1 hour,
The title compound was obtained. Example 1 1,2,3,4-tetraethyl-5-phenylcyclopentadiene bis (η ⁵ -cyclopentadienyl) 2,3,4,5-tetraethyl-1-zirconacyclo obtained in Reference Example 1 Penta-2,4-diene was used as a solution without separation. That is, (η ⁵ -cyclopentadienyl)
2,3,4,5-tetraethyl-1-zirconacyclopenta-2,4-diene (1.0 mmol) in THF (5
ml) solution, CuCl (2.0 mmol, 198 m
g) was added and then stirred. A yellow precipitate was obtained. Then, dimethyl propylene urea (DMPU)
(2.5 mmol, 0.3 ml) was added, resulting in a homogeneous solution. Furthermore, dichloromethylbenzene (1.0
eq) at 0 ° C. and then the reaction mixture is brought to 50 ° C.
And stirred at that temperature for 12 hours. The reaction was monitored by gas chromatography. After cooling to room temperature, 3N hydrochloric acid was added to terminate the reaction. Then it was extracted with ether and washed with aqueous sodium hydrogen carbonate solution,
And it dried with anhydrous magnesium sulfate. After concentration under reduced pressure, the residue was subjected to column chromatography using hexane using silica gel as a filler.

According to GC, the yield was 63%, and after column chromatography, the yield was 84 mg, 33%. ¹ H NMR (CDCl ₃ , Me ₄ Si) δ 0.91 (t, J = 7.56, 6H), 1.0
8 (t, J = 7.58, 6H), 1.82-1.87 (m, 2H), 2.25-2.40
(m, 6H), 3.88 ( s, 1H), 6.91-7.24 (m, 5H) ppm. 13 CN
MR (CDCl ₃ , Me ₄ Si) δ 15.25 (2C), 15.40 (2C), 18.72
(2C), 19.64 (2C), 58.87, 125.91 (2C), 128.21, 12
8.33 (2C), 140.27, 141.15 (2C), 145.19 (2C). High resolution MS calculated: C ₁₉ H ₂₆ 254.2033,
Experimental value 254.2030 Reference Example 2 bis (η ⁵ -cyclopentadienyl) 2,3,4,5-
Tetrapropyl-1-zirconacyclopenta-2,4-
Diene The title compound was obtained in the same manner as in Reference Example 1. However, 3
-Instead of hexine, 4-octyne was used. Reference Example 3 bis (η ⁵ -cyclopentadienyl) 2,3,4,5-
Tetrabutyl-1-zirconacyclopenta-2,4-diene The title compound was obtained in the same manner as in Reference Example 1. However, 3
-5-decyne was used instead of hexine. Reference Example 4 bis (η ⁵ -cyclopentadienyl) 2,3-dibutyl-4,5-dipropyl-1-zirconacyclopenta-
2,4-diene-bis (eta ⁵ - cyclopentadienyl) dichloro zirconium (1.0 mmol) and THF (5 ml) were charged to a Schlenk tube. The solution was cooled to -78 C and then n-butyllithium (1.0 mmol) was added. This solution was stirred at -78 ° C for 1 hour. -78
At C, 5-decyne (0.5 mmol) was added to the reaction mixture, then warmed to room temperature and left for 1 hour.
The solution was cooled to -78 C and then n-butyllithium (1.0 mmol) was added. This solution was -78
Stirred at C for 1 hour. Then, it was cooled again to -78 ° C and at -78 ° C, 4-octyne (0.
5 mmol) was added, then warmed to room temperature and left for 1 hour to give the title compound. Reference Example 5 bis (η ⁵ -cyclopentadienyl) 2H-1,3-diethyl-4,5,6,7-tetrahydro-2-zirconaindene In the same manner as in Reference Example 1, the title compound was obtained. However, 3
3,9-dodecadine was used instead of hexine. Reference Example 6 bis (eta ⁵ - cyclopentadienyl) 2H-1,3-diphenyl-4,5,6,7-tetrahydro-2-zirconate in the same manner as Nine den Reference Example 1 to give the title compound. However, 3
-Instead of hexine, 1,8-diphenyl-1,7-
Octadiyne was used. Reference Example 7 bis (η ⁵ -cyclopentadienyl) 1,3-dibutyl-2,4,5,6,7,8-hexahydro-2-zirconaazulene The title compound was obtained in the same manner as in Reference Example 1. Was. However, 3
5,12-heptadecadine was used instead of -hexyne. Examples 2 to 8 As in Example 1, as dihalogenomethylbenzene,
When dichloromethylbenzene was used, dichloromethylbenzene was added at 0 ° C, then heated to 50 ° C, and the reaction was allowed to proceed at 50 ° C. On the other hand, when dibromomethylbenzene or a derivative thereof, for example, 3-chloro-1-dibromomethylbenzene, is used as dihalogenomethylbenzene, dibromomethylbenzene or a derivative thereof is added at 0 ° C., and then warmed to room temperature. The reaction was allowed to proceed at room temperature. In each case, the reaction conditions and products are as shown in Table 1.

[0085]

[Table 1]

[0086]^*The isolated yield is shown in parentheses. Example 2 1,2,3,4-tetraethyl-5- (3-chlorophene
Nyl) cyclopentadiene The solution obtained in Reference Example 1 was used as it was. Dihalogeno
As methylbenzene, 3-chloro-1-dibromomethyl
The reaction was carried out at room temperature for 1 hour using benzene. GC income
The rate was 61%, and 1
18 mg (41%) of a colorless liquid was obtained.¹ H NMR (CDCl_Three, Me_FourSi) δ 0.91 (t, J = 7.50, 6H), 1.
07 (t, J = 7.50, 6H), 1.78-1.87 (m, 2H), 2.25-2.34
(m, 6H), 3.84 (s, 1H), 6.81-7.28 (m, 4H).¹³ C NMR (CDCl_Three, Me_FourSi) δ 15.20 (2C), 15.42 (2C),
18.71 (2C), 19.59 (2C), 58.33, 126.18 (2C), 129.60
 (2C), 134.02, 141.73 (2C), 142.56, 144.72 (2C).₁₉H_{twenty five}Cl 288.164
5, experimental value 288.1649 Example 3 1,2,3,4-tetrapropyl-5-phenylcyclo
Pentadiene The solution obtained in Reference Example 2 was used as it was. Dihalogeno
1-dichloromethylbenzene as methylbenzene
The reaction was performed at 50 ° C. for 12 hours. GC yield is 62
% And 146 mg by column chromatography.
(47%) of a colorless liquid was obtained.¹ H NMR (CDCl_Three, Me_FourSi) δ 0.80 (t, J = 7.36, 6H), 0.
95 (t, J = 7.30, 6H), 1.22-1.51 (m, 8H), 1.76-1.83
(m, 2H), 2.16-2.24 (m, 6H), 3.81 (s, 1H), 6.89-7.4
0 (m, 5H).¹³ C NMR (CDCl_Three, Me_FourSi) δ 14.24 (2C), 14.37 (2C),
23.76 (2C), 23.88 (2C), 27.97 (2C), 28.95 (2C), 5
9.55, 125.87 (2C), 128.21, 128.33 (2C), 140.23 (2
C), 140.57, 144.26 (2C). High resolution MS calculated C_{twenty three}H₃₄ 310.2659,
Experimental value 310.2657 Example 4 1,2,3,4-tetrabutyl-5- (3-chlorophene
Nyl) cyclopentadiene The solution obtained in Reference Example 3 was used as it was. Dihalogeno
As methylbenzene, 3-chloro-1-dibromomethyl
The reaction was carried out at room temperature for 1 hour using benzene. GC income
The ratio was 76%, and 1
85 mg (46%) of a yellow liquid was obtained.¹ H NMR (CDCl_Three, Me_FourSi) δ 0.83 (t, J = 6.7, 6H), 0.9
4 (t, J = 7.0, 6H), 1.19-1.53 (m, 16H), 1.73-1.80
(m, 2H), 2.21-2.27 (m, 6H), 3.77 (s, 1H), 6.79-6.8
5 (m, 1H), 7.10-7.24 (m, 3H).¹³ C NMR (CDCl_Three, Me_FourSi) δ 13.98 (2C), 14.04 (2C),
22.76 (2C), 23.03 (2C), 25.57 (2C), 26.37 (2C), 3
2.78 (2C), 33.01 (2C), 58.97, 126.47 (2C), 129.56
(2C), 134.00, 140.80 (2C), 142.82, 143.64 (2C). High resolution MS calculated C₂₇H₄₁Cl 400.289
5, experimental value 400.899 Example 5 1,2-dibutyl-3,4-dipropyl-5-phenyl
Cyclopentadiene The solution obtained in Reference Example 4 was used as it was. Screw (η^Five
-Cyclopentadienyl) 1,2-dibutyl-3,4-
Dipropyl-1-zirconacyclopenta-2,4-die
And 1-dichloromethylbenzene at 50 ° C. for 12 hours.
Allowed to react for hours. The GC yield was 50% and the column chromatography
119 mg (35%) of yellow liquid by chromatography
was gotten.¹ H NMR (CDCl_Three, Me_FourSi) δ 0.79-0.93 (m, 12H), 1.20
-1.50 (m, 12H), 1.76-1.82 (m, 2H), 2.16-2.27 (m, 6
H), 3.81 (s, 1H), 6.90-7.32 (m, 5H).¹³ C NMR (CDCl_Three, Me_FourSi) δ 14.00, 14.06, 14.26, 14.
38, 22.80, 23.06, 23.78, 23.89, 25.62, 26.46, 27.9
7, 28.96, 32.87, 33.04, 59.55, 125.85 (2C), 128.2
3, 128.32 (2C), 140.22, 140.24, 140.57, 144.20, 14
4.26. High resolution MS calculated value C_{twenty five}H₃₈ 338.2972,
Experimental value 338.2974 Example 6 1H-1,3-diethyl-2- (3-chlorophenyl)
-4,5,6,7-Tetrahydroindene The solution obtained in Reference Example 5 was used as it was. Screw (η^Five
-Cyclopentadienyl) 2H-1,3-diethyl-
4,5,6,7-tetrahydro-2-zirconaindene
With 1-dibromomethyl-3-chlorobenzene at room temperature
For 12 hours. The GC yield was 64%.
89 mg (31%) of no
A colored liquid was obtained.¹ H NMR (CDCl_Three, Me_FourSi) δ 0.37 (t, J = 7.40, 3H), 1.
12 (t, J = 7.60, 3H), 1.55-1.85 (m, 6H), 2.20-2.50
(m, 6H), 3.28 (s, br, 1H), 7.08-7.26 (m, 4H). ¹³ C NMR (CDCl_Three, Me_FourSi) δ 7.39, 14.52, 19.38, 20.8
5, 23.03, 23.09, 23.20, 24.18, 54.36, 125.45, 126.
44, 128.18, 129.31, 134.00, 138.83, 139.25,139.3
9, 142.67, 145.11. High resolution MS calculated value C₁₉H_{twenty three}Cl 286.148
7, experimental value 286.1489 Example 7 1H-1,2,3-triphenyl-4,5,6,7-te
Trahydroindene The solution obtained in Reference Example 6 was used as it was. Screw (η^Five
-Cyclopentadienyl) 2H-1,3-diphenyl-
4,5,6,7-tetrahydro-2-zirconaindene
With dibromomethylbenzene at room temperature for 72 hours
I let it. The GC yield was 67%, and column chromatography was performed.
The fee gives 94 mg (27%) of a colorless liquid
Was.¹ H NMR (CDCl_Three, Me_FourSi) δ 1.60-1.72 (m, 2H), 1.75-
1.85 (m, 2H), 2.61-2.73 (m, 2H), 2.81-2.92 (m, 2
H), 4.89 (t, J = 2.2, 1H), 6.90-7.49 (m, 15H).¹³ C NMR (CDCl_Three, Me_FourSi) δ 23.57 (2C), 26.44 (2C),
60.66, 125.77 (2C), 125.97 (2C), 127.46, 127.93 (3
C), 128.17 (3C), 128.19 (3C), 129.97, 136.31 (2C),
139.28, 140.29 (2C), 143.49 (2C). High resolution MS calculated value C₂₇H_{twenty four} 348.1877,
Experimental value 348.1886 Example 8 1,3-dibutyl-2-phenyl-2,4,5,6
7,8-Hexahydroazulene The solution obtained in Reference Example 7 was used as it was. Screw (η^Five
-Cyclopentadienyl) 1,3-dibutyl-2,4,
5,6,7,8-hexahydro-2-zirconaazulene
With dibromomethylbenzene at room temperature for 18 hours
I let it. The GC yield was 35%, and the column chromatography was
Fee gives 68 mg (21%) of a colorless liquid
Was.¹ H NMR (CDCl_Three, Me_FourSi) δ 0.80 (t, J = 5.43, 6H), 1.1
0-1.40 (m, 9H), 1.50-1.83 (m, 7H), 2.19-2.43 (m, 6
H), 3.82 (s, 1H), 6.91-6.92 (m, 2H), 7.12-7.31 (m,
 3H).¹³ C NMR (CDCl_Three, Me_FourSi) δ 13.92 (2C), 22.52 (2C),
26.00 (2C), 27.45 (2C), 30.29 (2C), 32.74, 33.10
(2C), 60.40, 125.92 (2C), 128.28 (3C), 140.51, 14
1.84 (2C), 142.85 (2C), high resolution MS calculated value C_{twenty four}H₃₄ 322.2659,
Experimental value 322.2657

[0087]

According to the method of the present invention, a cyclopentadiene ring can be easily formed.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08F 4/64 C08F 4/64 // C07F 17/00 C07F 17/00 F-term (Reference) 4H006 AA02 AC28 BA05 BA13 BA21 BA25 BA37 BA47 BA48 EA39 4H050 AA02 AB40 BE21 BE62 WB11 WB21 4J028 AA01A AB00A AB01A AC01A AC10A AC20A AC28A AC31A AC38A AC49A BA00A BA00B BA01A BA01B BB00A BB00B BB01A BB01B

Claims (9)

[Claims] 1. A cyclopentadiene represented by the following formula (I):
A method for synthesizing an ene derivative, comprising:(Where R¹, R^Two, R^Three, R^Four, R^Five, R⁶, R⁷, R⁸as well as
R⁹Are independent of each other and are the same or different
And a hydrogen atom, which may have a substituent,₁~ C₂₀
A hydrocarbon group, which may have a substituent,₁~ C₂₀A
Alkoxy group, optionally having substituent (s), C₆~ C₂₀A
A reeloxy group or a compound of the formula -Si (R^Ten) (R^{1 1})
(R¹²A group represented by the formula:^Ten, R¹¹And R¹²Is
Each independently of one another, identical or different,₁~ C
₂₀Alkyl group, C₆~ C₂₀Arylalkyl group, C₁~ C
₂₀Alkoxy group, C₆~ C₂₀Arylalkyloxy group
It is. ) Where R¹And R^Two, R^TwoAnd R^Three, R^ThreeAnd R^Four, R^FivePassing
And R⁶, R⁶And R⁷, R ⁷And R⁸Or R⁸And R
⁹Are the same or different, and
May have, C_Four~ C₂₀Forms a saturated or unsaturated ring
But the above C_Four~ C₂₀Saturated or unsaturated ring
Is an oxygen atom, the formula -N (R¹³A group represented by the formula:
R¹³Is a hydrogen atom or C₁~ C₆It is an alkyl group. ),
Formula -E (R¹⁴) (R^FifteenA group represented by the formula: wherein E is
A silicon atom, a germanium atom or a tin atom,
R¹⁴And R^FifteenAre independent of each other and are the same or
Differently, C₁~ C₆It is an alkyl group. ), Formula -E
¹(R¹⁶) (R¹⁷) -E^Two(R¹⁸) (R ¹⁹)-
Group (wherein E¹And E^TwoAre independent of each other,
One or different, silicon atoms, germanium atoms or
Is a tin atom and R¹⁶, R¹⁷, R¹⁸And R¹⁹Is it
Each independently of one another, identical or different, C₁~ C₆A
Is a alkyl group. ) May be interrupted; Y is water
An element atom or a leaving group. In the presence of a metal compound, a metalla represented by the following formula (II)
In cyclopentadiene,(Where R¹, R^Two, R^ThreeAnd R^FourHas the above meaning
You. M is group 3 to group 5 of the periodic table or a lanthanide series
L;¹And L^TwoAre independent of each other and are the same or
Differently indicate anionic ligands, except that L¹as well as
L^TwoMay be crosslinked. ) Reacting a benzene derivative represented by the following formula (III):
[Step 3](Where R^Five, R⁶, R⁷, R⁸And R⁹, And Y is
Has the above meaning. X¹And X^TwoAre each other
Independently, identical or different, are leaving groups. )
A method for synthesizing a cyclopentadiene derivative. 2. The method according to claim 1, wherein the metal compound is a metal compound belonging to Groups 4 to 15 of the periodic table. 3. The method according to claim 2, wherein the metal compound is a salt. 4. The method according to claim 1, wherein M is a metal belonging to Group 4 of the periodic table or a lanthanide series, and the anionic ligand is a delocalized cyclic η ⁵ -coordination ligand. The method according to any of the above. 5. The cyclopentadienyl group, wherein the delocalized cyclic η ⁵ -coordination ligand may be substituted.
A method according to any of the preceding claims, which is an indenyl group, a fluorenyl group or an azulenyl group. 6. An organometallic compound represented by the following formula (IV):
A method of synthesizing a product, comprising:(Where M¹Represents a transition metal; L^ThreeIndicates a ligand
And n is an integer of 1 to 8; m is an integer of -6 to 6;¹, R^Two, R^Three, R^Four, R^Five, R⁶, R⁷, R⁸And R⁹Is
Each independently of one another, identical or different,
C, which may have a substituent,₁~ C₂₀hydrocarbon
C, which may have a group or a substituent₁~ C₂₀Alkoxy
C, which may have a group or a substituent₆~ C₂₀Arlio
A xy group or a formula -Si (R^Ten) (R¹¹) (R¹²)
Group (wherein R^Ten, R¹¹And R¹²Are each other
Independently, the same or different,₁~ C₂₀Alkyl group,
C₆~ C₂₀Arylalkyl group, C₁~ C₂₀Alkoxy
Group, C₆~ C₂₀An arylalkyloxy group. )so
Yes, but R¹And R^Two, R^TwoAnd R^Three, R^ThreeAnd R^Four, R^FivePassing
And R⁶, R⁶And R⁷, R ⁷And R⁸Or R⁸And R
⁹Are the same or different, and
May have, C_Four~ C₂₀Forms a saturated or unsaturated ring
But the above C_Four~ C₂₀Saturated or unsaturated ring
Is an oxygen atom, the formula -N (R¹³A group represented by the formula:
R¹³Is a hydrogen atom or C₁~ C₆It is an alkyl group. ),
Formula -E (R¹⁴) (R^FifteenA group represented by the formula: wherein E is
A silicon atom, a germanium atom or a tin atom,
R¹⁴And R^FifteenAre independent of each other and are the same or
Differently, C₁~ C₆It is an alkyl group. ), Formula -E
¹(R¹⁶) (R¹⁷) -E^Two(R¹⁸) (R ¹⁹)-
Group (wherein E¹And E^TwoAre independent of each other,
One or different, silicon atoms, germanium atoms or
Is a tin atom and R¹⁶, R¹⁷, R¹⁸And R¹⁹Is it
Each independently of one another, identical or different, C₁~ C₆A
Is a alkyl group. ) May be interrupted. A cyclopentadi obtained by the method according to claim 1.
An ene derivative and a precursor containing the transition metal,
Organometallic compounds characterized by reacting in the presence
Synthesis method. 7. An organometallic compound represented by the following formula (IVa):
A method of synthesizing a compound, comprising:(Where M¹Is group 3 to group 5 of the periodic table or Lantani
Denote metal of the series; L¹Is the delocalized ring η^Five-Coordination system
A ligand, L^ThreeAnd L^FourAre independent of each other and are the same or different
Represents a ligand;¹, R^Two, R^Three, R^Four, R^Five, R⁶,
R⁷, R⁸And R⁹Are independent of each other and
Or differently, may have a hydrogen atom, a substituent,
C₁~ C₂₀A hydrocarbon group, which may have a substituent,₁
~ C₂₀An alkoxy group, optionally having substituent (s), C₆
~ C₂₀An aryloxy group or a compound of the formula —Si (R^Ten)
(R¹¹) (R¹²A group represented by the formula:^Ten, R¹¹as well as
R¹²Are, independently of one another, identical or different,
C₁~ C₂₀Alkyl group, C₆~ C₂₀Arylalkyl group,
C₁~ C₂₀Alkoxy group, C₆~ C₂₀Arylalkylo
It is a xy group. ) Where R¹And R^Two, R^TwoAnd R^Three, R^ThreeAnd R^Four, R^FivePassing
And R⁶, R⁶And R⁷, R ⁷And R⁸Or R⁸And R
⁹Are the same or different, and
May have, C_Four~ C₂₀Forms a saturated or unsaturated ring
But the above C_Four~ C₂₀Saturated or unsaturated ring
Is an oxygen atom, the formula -N (R¹³A group represented by the formula:
R¹³Is a hydrogen atom or C₁~ C₆It is an alkyl group. ),
Formula -E (R¹⁴) (R^FifteenA group represented by the formula: wherein E is
A silicon atom, a germanium atom or a tin atom,
R¹⁴And R^FifteenAre independent of each other and are the same or
Differently, C₁~ C₆It is an alkyl group. ), Formula -E
¹(R¹⁶) (R¹⁷) -E^Two(R¹⁸) (R ¹⁹)-
Group (wherein E¹And E^TwoAre independent of each other,
One or different, silicon atoms, germanium atoms or
Is a tin atom and R¹⁶, R¹⁷, R¹⁸And R¹⁹Is it
Each independently of one another, identical or different, C₁~ C₆A
Is a alkyl group. ) May be interrupted. A cyclopentadi obtained by the method according to claim 1.
An ene derivative and a precursor containing the transition metal,
Organometallic compounds characterized by reacting in the presence
Synthesis method. 8. The delocalized cyclic η ⁵ -coordination system ligand represented by the following formula (V): (Wherein, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ have the above-mentioned meanings.) Synthesis of the organometallic compound according to claim 7. Method. 9. A method for producing a synthetic polymer, comprising using the organometallic compound synthesized by the method according to claim 7 as a catalyst to produce a synthetic polymer.