JP2003171386A - Transition metal complex, ligand, olefin polymerization catalyst and method for producing olefin polymer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a transition metal catalyst. <P>SOLUTION: The transition metal catalyst is represented by formula (1) (wherein M represents a transition element in the 4th group; A<SP>1</SP>and A<SP>2</SP>represent each an atom in the 15th group; R<SP>1</SP>and R<SP>2</SP>represents each H, an alkyl, an aryl, an aralkyl or a hydrocarbon-substituted silyl; R<SP>3</SP>, R<SP>4</SP>, R<SP>5</SP>and R<SP>6</SP>represent each H, an alkyl, an alkoxy, an aryl, an aryloxy, an aralkyl, an aralkyloxy, a hydrocarbon-substituted silyl or a hydrocarbon substituted amino; X<SP>1</SP>, X<SP>2</SP>, R<SP>7</SP>, R<SP>8</SP>, R<SP>9</SP>and R<SP>10</SP>represent each H, a halogen, an alkyl, an alkoxy, an aryl, an aryloxy, an aralkyl, an aralkyloxy, a hydrocarbon-substituted silyl or a hydrocarbon-substituted amino; X<SP>1</SP>and X<SP>2</SP>, R<SP>1</SP>and R<SP>2</SP>, adjacent R<SP>3</SP>, R<SP>4</SP>, R<SP>5</SP>and R<SP>6</SP>, and adjacent R<SP>7</SP>, R<SP>8</SP>, R<SP>9</SP>and R<SP>10</SP>may form a ring by mutually bonding to each other. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a transition metal complex, a ligand as a component thereof, a polymerization catalyst and a method for producing a polymer.

[0002]

2. Description of the Related Art Many reports have already been made on a method for producing an olefin polymer using a metallocene complex. For example, in JP-A-58-19309,
A method for producing an olefin polymer using a metallocene complex and an aluminoxane has been reported. When olefin polymerization is carried out with a catalyst using this bis (cyclopentadienyl) zirconium dichloride and methylaluminoxane, there is a problem that the molecular weight of the olefin polymer obtained is low. To improve this problem, half metallocene type transition metal complexes have been developed. For example, in JP-A-3-163088, dimethylsilyl (tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride is disclosed in JP-A-9-87313. Silyl (tetramethylcyclopentadienyl) (tert-amido) titanium dichloride is disclosed, and its industrial utility value as an olefin polymerization catalyst component is high. However, these transition metal complexes require the use of a silicon compound that is unstable to water and difficult to handle in the production process, and has improved to a ligand system that can be handled more easily, and made the catalyst highly functional. Is desired.

[0003]

In view of the above situation, the present invention is directed to a complex which is highly active at an efficient reaction temperature in the industrial process of olefin polymerization, which is important from an industrial viewpoint, and a coordination which is a constituent of the complex. It is an object of the present invention to provide a highly active catalyst for olefin polymerization using the complex as a catalyst component, and a method for producing an olefin polymer using the same.

[0004]

Means for Solving the Problems The inventors of the present invention have made diligent studies to solve the above-mentioned problems, and as a result, for example, a functional group in which a coordinating functional group such as hydrazone and a cyclopentadiene ring are adjacent to each other on a benzene ring. The present invention has been completed by finding a stable substituted cyclopentadiene having a group and a transition metal complex having the substance as a ligand. That is, the present invention provides a compound represented by the general formula (1) (In the formula, M represents a transition metal atom of Group 4 of the periodic table of elements, A ¹ and A ² represent atoms of Group 15 of the periodic table of elements, and R ¹ and R ² are hydrogen atoms. An optionally substituted alkyl group having 1 to 10 carbon atoms, an optionally substituted carbon atom 6
To 20 aryl groups, optionally substituted carbon atoms of 7 to
20 represents an aralkyl group or a hydrocarbon-substituted silyl group having 1 to 20 carbon atoms, wherein R ³ , R ⁴ , R ⁵ and R ⁶ are each independently a hydrogen atom or an optionally substituted C 1 to 10 carbon atom. Alkyl group, optionally substituted C1-10 alkoxy group, optionally substituted C6-20 aryl group, optionally substituted C6-20 aryloxy group, substituted An optionally substituted aralkyl group having 7 to 20 carbon atoms, an optionally substituted aralkyloxy group having 7 to 20 carbon atoms, a hydrocarbon-substituted silyl group having 1 to 20 carbon atoms or a hydrocarbon having 1 to 20 carbon atoms. A substituted amino group, wherein X ¹ , X ² , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are each independently a hydrogen atom, a halogen atom, an optionally substituted alkyl group having 1 to 10 carbon atoms, or a substituted Optionally having 1 to 10 carbon atoms Alkoxy group, an optionally substituted aryl group having 6 to 20 carbon atoms, carbon atoms and optionally substituted 6
To C20 aryloxy group, optionally substituted C7 to C20 aralkyl group, optionally substituted C7 to C20 aralkyloxy group, C1 to C20 hydrocarbon substituted silyl group, or A hydrocarbon-substituted amino group having 1 to 20 carbon atoms is shown, and X ¹ and X ² , R ¹ and R ² , adjacent R ³ , R ⁴ , R ⁵ and R ⁶ and adjacent R ⁷ , R ⁸ and R ⁹ , R ¹⁰
May combine with each other to form a ring. ), And a polymerization catalyst containing the transition metal complex.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below. In the transition metal complex represented by the general formula (1),
The transition metal atom represented by M is the periodic table (IU
It is a transition metal atom of Group 4 of PAC Inorganic Chemistry Revised Edition 1989), and examples thereof include a titanium atom, a zirconium atom, and a hafnium atom.

Examples of the atoms of Group 15 of the periodic table of elements represented by A ¹ and A ² include nitrogen atom, phosphorus atom,
Examples thereof include an arsenic atom, and a nitrogen atom is preferable.

Examples of the halogen atom in X ¹ , X ² , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

X ¹ , X ² , R ¹ , R ² , R ³ , R ⁴ , R ⁵ ,
Examples of the substituent of the optionally substituted alkyl group having 1 to 10 carbon atoms in R ⁶ , R ⁷ , R ⁸ , R ⁹ , and R ¹⁰ include a halogen atom and the like, and specific examples include a methyl group, Ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, neopentyl group, amyl group, n-hexyl group, n-octyl group, n-decyl group Group, fluoromethyl group, difluoromethyl group, trifluoromethyl group, fluoroethyl group, difluoroethyl group, trifluoroethyl group, tetrafluoroethyl group, pentafluoroethyl group, perfluoropropyl group, perfluorobutyl group,
Examples include perfluoropentyl group, perfluorohexyl group, perfluorooctyl group, perfluorodecyl group, trichloromethyl group, and the like, preferably methyl group,
Examples thereof include an ethyl group, an isopropyl group, a tert-butyl group and an amyl group.

X ¹ , X ² , R ¹ , R ² , R ³ , R ⁴ , R ⁵ ,
As the optionally substituted aryl group having 6 to 20 carbon atoms in R ⁶ , R ⁷ , R ⁸ , R ⁹ , and R ¹⁰ , a phenyl group,
Examples thereof include a naphthyl group and an anthracenyl group, examples of the substituent include an alkyl group, and specific examples include, for example, a phenyl group, a 2-tolyl group, a 3-tolyl group, a 4-tolyl group, and a 2,3-group. Xylyl group, 2,4-xylyl group,
2,5-xylyl group, 2,6-xylyl group, 3,4-xylyl group, 3,5-xylyl group, 2,3,4-trimethylphenyl group, 2,3,5-trimethylphenyl group,
2,3,6-trimethylphenyl group, 2,4,6-trimethylphenyl group, 3,4,5-trimethylphenyl group, 2,3,4,5-tetramethylphenyl group, 2,
3,4,6-tetramethylphenyl group, 2,3,5,6
-Tetramethylphenyl group, pentamethylphenyl group,
Ethylphenyl group, n-propylphenyl group, isopropylphenyl group, n-butylphenyl group, sec-butylphenyl group, tert-butylphenyl group, n-pentylphenyl group, neopentylphenyl group, n-hexylphenyl group, n Examples thereof include an -octylphenyl group, an n-decylphenyl group, an n-dodecylphenyl group, an n-tetradecylphenyl group, a naphthyl group, an anthracenyl group and a fluorine atom-substituted aryl group thereof, and a phenyl group is preferable.

X ¹ , X ² , R ¹ , R ² , R ³ , R ⁴ , R ⁵ ,
Examples of the optionally substituted aralkyl group having 7 to 20 carbon atoms in R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ include a benzyl group, a naphthylmethyl group, an anthracenylmethyl group and a diphenylmethyl group. Examples of the substituent include an alkyl group, and specific examples thereof include a benzyl group, a (2-methylphenyl) methyl group, a (3-methylphenyl) methyl group, and a (4-methylphenyl) methyl group. Group, (2,3-dimethylphenyl) methyl group, (2,4
-Dimethylphenyl) methyl group, (2,5-dimethylphenyl) methyl group, (2,6-dimethylphenyl) methyl group, (3,4-dimethylphenyl) methyl group, (2,
3,4-trimethylphenyl) methyl group, (2,3,5
-Trimethylphenyl) methyl group, (2,3,6-trimethylphenyl) methyl group, (3,4,5-trimethylphenyl) methyl group, (2,4,6-trimethylphenyl) methyl group, (2,3 , 4,5-Tetramethylphenyl) methyl group, (2,3,4,6-tetramethylphenyl) methyl group, (2,3,5,6-tetramethylphenyl) methyl group, (pentamethylphenyl) methyl group Base,
(Ethylphenyl) methyl group, (n-propylphenyl) methyl group, (isopropylphenyl) methyl group,
(N-Butylphenyl) methyl group, (sec-butylphenyl) methyl group, (tert-butylphenyl) methyl group, (n-pentylphenyl) methyl group, (neopentylphenyl) methyl group, (n-hexylphenyl) Methyl group, (n-octylphenyl) methyl group, (n-decylphenyl) methyl group, (n-dodecylphenyl) methyl group, (n-tetradecylphenyl) methyl group, naphthylmethyl group, anthracenylmethyl group, Examples thereof include a diphenylmethyl group and these fluorine atom-substituted aralkyl groups, and a benzyl group is preferable.

Substituents X ¹ , X ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R
Examples of the substituent of the optionally substituted alkoxy group having 1 to 10 carbon atoms in ⁷ , R ⁸ , R ⁹ , and R ¹⁰ include a halogen atom, and specific examples include a methoxy group, an ethoxy group, and n. -Propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group, tert-butoxy group, n-pentoxy group, neopentoxy group, n-hexoxy group, n-octoxy group, n-dexoxy group, and fluorine thereof. Examples of the atom-substituted alkoxy group include a methoxy group, an ethoxy group, and a tert-butoxy group.

Substituents X ¹ , X ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R
^7, R ^8, R ^9, naphthoxy groups The aryloxy group having 6 to 20 carbon atoms which may be substituted in R ¹⁰ phenoxy group, and anthracenoxy group, examples of the substituent, include an alkyl group and the like As specific examples, phenoxy group, 2-methylphenoxy group, 3-methylphenoxy group, 4-methylphenoxy group, 2,3-dimethylphenoxy group, 2,4-dimethylphenoxy group, 2,5
-Dimethylphenoxy group, 2,6-dimethylphenoxy group, 3,4-dimethylphenoxy group, 3,5-dimethylphenoxy group, 2,3,4-trimethylphenoxy group,
2,3,5-trimethylphenoxy group, 2,3,6-trimethylphenoxy group, 2,4,5-trimethylphenoxy group, 2,4,6-trimethylphenoxy group, 3,
4,5-trimethylphenoxy group, 2,3,4,5-tetramethylphenoxy group, 2,3,4,6-tetramethylphenoxy group, 2,3,5,6-tetramethylphenoxy group, pentamethylphenoxy group Group, ethylphenoxy group, n-propylphenoxy group, isopropylphenoxy group, n-butylphenoxy group, sec-butylphenoxy group, tert-butylphenoxy group, n-hexylphenoxy group, n-octylphenoxy group, n-decylphenoxy group Group, n-tetradecylphenoxy group, naphthoxy group, anthracenoxy group, and fluorine-substituted aryloxy groups thereof.

Substituents X ¹ , X ² , R ¹ , R ² , R ³ , R ⁴ , R
⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , and R ^{10 have} 1 to 20 carbon atoms
The hydrocarbon-substituted silyl group is a silyl group substituted with a hydrocarbon group having 1 to 20 carbon atoms, and examples of the hydrocarbon group here include a methyl group, an ethyl group, an n-propyl group, Carbon atom such as isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, neopentyl group, amyl group, n-hexyl group, cyclohexyl group, n-octyl group, n-decyl group Number 1
1-10 carbon atoms such as alkyl group, phenyl group, tolyl group, xylyl group, naphthyl group and anthracenyl group
To 20 aryl groups and the like. Such carbon number 1 to
Examples of the hydrocarbon-substituted silyl group of 20 include 1 such as methylsilyl group, ethylsilyl group and phenylsilyl group.
Substituted silyl group, dimethylsilyl group, diethylsilyl group,
Disubstituted silyl group such as diphenylsilyl group, trimethylsilyl group, triethylsilyl group, tri-n-propylsilyl group, tri-isopropylsilyl group, tri-n-butylsilyl group, tri-sec-butylsilyl group, tri-t
ert-butylsilyl group, tri-isobutylsilyl group,
Examples thereof include tri-substituted silyl groups such as tert-butyldimethylsilyl group, tri-n-pentylsilyl group, tri-n-hexylsilyl group, tricyclohexylsilyl group and triphenylsilyl group, preferably trimethylsilyl group, tert- Examples thereof include a butyldimethylsilyl group and a triphenylsilyl group. The hydrocarbon group of each of these substituted silyl groups may be substituted with a fluorine atom.

Substituents X ¹ , X ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R
The hydrocarbon-substituted amino group having 1 to 20 carbon atoms in ⁷ , R ⁸ , R ⁹ , and R ¹⁰ is an amino group substituted with two hydrocarbon groups, and the hydrocarbon group here is, for example, Methyl group, ethyl group, n-propyl group, isopropyl group,
n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, neopentyl group, amyl group, n
-Hexyl group, cyclohexyl group, n-octyl group, n
Examples include an alkyl group having 1 to 10 carbon atoms such as a decyl group, an aryl group having 1 to 20 carbon atoms such as a phenyl group, a tolyl group, a xylyl group, a naphthyl group and an anthracenyl group. Examples of the hydrocarbon-substituted amino group having 1 to 20 carbon atoms include dimethylamino group, diethylamino group, di-n-propylamino group, diisopropylamino group, di-n-butylamino group, di-sec-butylamino group. Group, di-tert-butylamino group, di-isobutylamino group, tert-butylisopropylamino group, di-n-hexylamino group, di-n-octylamino group, di-n-decylamino group, diphenylamino group, etc. And preferably a dimethylamino group or a diethylamino group.

The halogen atom in the substituents R ⁷ , R ⁸ , R ⁹ and R ¹⁰ is a fluorine atom, a chlorine atom, a bromine atom,
Examples thereof include iodine atom, preferably fluorine atom and chlorine atom.

X ¹ and X ² , adjacent R ³ , R ⁴ , R ⁵ and R ⁶ and adjacent R ⁷ , R ⁸ , R ⁹ and R ¹⁰ may combine with each other to form a ring.

The transition metal complex represented by the general formula (1) is
For example, general formula (2) (In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R
⁹ and R ¹⁰ are the same as above, and the position of the double bond of the cyclopentadiene ring may be arbitrary or may be a mixture)
And a cyclopentadiene represented by the formula (3) MX ¹ X ² X ³ X ⁴ (3) (wherein, X ¹ and X ² are the same as defined above, and X ³ and X ⁴ are each optionally Hydrogen atom, halogen atom, optionally substituted alkyl group having 1 to 10 carbon atoms, optionally substituted alkoxy group having 1 to 10 carbon atoms, optionally substituted aryl group having 6 to 20 carbon atoms An optionally substituted aryloxy group having 6 to 20 carbon atoms, an optionally substituted aralkyl group having 7 to 20 carbon atoms, an optionally substituted aralkyloxy group having 7 to 20 carbon atoms, and a carbon number 1
To a hydrocarbon-substituted silyl group having 1 to 20 carbon atoms or a hydrocarbon-substituted amino group having 1 to 20 carbon atoms, X ¹ and X ² , and X ³
And X ⁴ may combine with each other to form a ring. ) Is produced by reacting a transition metal compound represented by

The cyclopentadiene represented by the general formula (2) includes 2- (cyclopentadienyl) benzaldehyde phenylhydrazone, 2- (2-methylcyclopentadienyl) benzaldehyde phenylhydrazone and 2- (3-methylcyclo). Pentadienyl) benzaldehyde phenylhydrazone, 2- (2,3-dimethylcyclopentadienyl) benzaldehyde phenylhydrazone, 2- (2,4-dimethylcyclopentadienyl) benzaldehyde phenylhydrazone, 2-
(3,4-Dimethylcyclopentadienyl) benzaldehyde phenylhydrazone, 2- (2,3,4-trimethylcyclopentadienyl) benzaldehyde Phenylhydrazone, 2- (2,4,5-trimethylcyclopentadienyl) benzaldehyde Phenylhydrazone, 2- (2,3,4,5-tetramethylcyclopentadienyl) benzaldehyde Phenylhydrazone, 2
-(2-tert-butylcyclopentadienyl) benzaldehyde phenylhydrazone, 2- (3-ter
t-Butylcyclopentadienyl) benzaldehyde phenylhydrazone, 2- (2-dimethylaminocyclopentadienyl) benzaldehyde phenylhydrazone, 2- (3-dimethylaminocyclopentadienyl)
Benzaldehyde phenylhydrazone, 2- (inden-1-yl) benzaldehyde phenylhydrazone, 2- (2-methylinden-1-yl) benzaldehyde phenylhydrazone, 2- (2-phenylinden-1-yl) benzaldehyde phenylhydrazone, 2 -(Fluoren-1-yl) benzaldehyde
Phenylhydrazone

2- (Cyclopentadienyl) benzaldehyde 2-methylphenylhydrazone, 2- (2-methylcyclopentadienyl) benzaldehyde 2-methylphenylhydrazone, 2- (3-methylcyclopentadienyl) benzaldehyde 2- Methylphenylhydrazone, 2- (2,3-dimethylcyclopentadienyl) benzaldehyde 2-methylphenylhydrazone, 2- (2,4-dimethylcyclopentadienyl) benzaldehyde 2-methylphenylhydrazone, 2-
(3,4-Dimethylcyclopentadienyl) benzaldehyde 2-methylphenylhydrazone, 2- (2,2
3,4-Trimethylcyclopentadienyl) benzaldehyde 2-methylphenylhydrazone, 2- (2,2
4,5-Trimethylcyclopentadienyl) benzaldehyde 2-methylphenylhydrazone, 2- (2,2
3,4,5-Tetramethylcyclopentadienyl) benzaldehyde 2-methylphenylhydrazone, 2- (2
-Tert-butylcyclopentadienyl) benzaldehyde 2-methylphenylhydrazone, 2- (3-t
ert-Butylcyclopentadienyl) benzaldehyde 2-methylphenylhydrazone, 2- (2-dimethylaminocyclopentadienyl) benzaldehyde 2-
Methylphenylhydrazone, 2- (3-dimethylaminocyclopentadienyl) benzaldehyde 2-methylphenylhydrazone, 2- (inden-1-yl) benzaldehyde 2-methylphenylhydrazone, 2-
(2-Methylinden-1-yl) benzaldehyde
2-methylphenylhydrazone, 2- (2-phenylinden-1-yl) benzaldehyde 2-methylphenylhydrazone, 2- (fluoren-1-yl) benzaldehyde 2-methylphenylhydrazone

2- (cyclopentadienyl) benzaldehyde 2,4,6-trimethylphenylhydrazone,
2- (2-methylcyclopentadienyl) benzaldehyde 2,4,6-trimethylphenylhydrazone, 2-
(3-Methylcyclopentadienyl) benzaldehyde 2,4,6-trimethylphenylhydrazone, 2-
(2,3-dimethylcyclopentadienyl) benzaldehyde 2,4,6-trimethylphenylhydrazone,
2- (2,4-dimethylcyclopentadienyl) benzaldehyde 2,4,6-trimethylphenylhydrazone, 2- (3,4-dimethylcyclopentadienyl) benzaldehyde 2,4,6-trimethylphenylhydrazone, 2- (2,3,4-trimethylcyclopentadienyl) benzaldehyde 2,4,6-trimethylphenylhydrazone, 2- (2,4,5-trimethylcyclopentadienyl) benzaldehyde 2,4,6-trimethylphenylhydrazone, 2- (2,3,4,5-
Tetramethylcyclopentadienyl) benzaldehyde 2,4,6-trimethylphenylhydrazone, 2-
(2-tert-Butylcyclopentadienyl) benzaldehyde 2,4,6-trimethylphenylhydrazone, 2- (3-tert-butylcyclopentadienyl) benzaldehyde 2,4,6-trimethylphenylhydrazone, 2- (2 -Dimethylaminocyclopentadienyl) benzaldehyde 2,4,6-trimethylphenylhydrazone, 2- (3-dimethylaminocyclopentadienyl) benzaldehyde 2,4,6-trimethylphenylhydrazone, 2- (inden-1-yl) ) Benzaldehyde 2,4,6-trimethylphenylhydrazone, 2- (2-methylinden-1-yl)
Benzaldehyde 2,4,6-trimethylphenylhydrazone, 2- (2-phenylinden-1-yl) benzaldehyde 2,4,6-trimethylphenylhydrazone, 2- (fluoren-1-yl) benzaldehyde 2,4,6- Trimethylphenylhydrazone

2- (cyclopentadienyl) benzaldehyde 2,6-diisopropylphenylhydrazone,
2- (2-methylcyclopentadienyl) benzaldehyde 2,6-diisopropylphenylhydrazone, 2-
(3-Methylcyclopentadienyl) benzaldehyde 2,6-diisopropylphenylhydrazone, 2-
(2,3-dimethylcyclopentadienyl) benzaldehyde 2,6-diisopropylphenylhydrazone,
2- (2,4-dimethylcyclopentadienyl) benzaldehyde 2,6-diisopropylphenylhydrazone, 2- (3,4-dimethylcyclopentadienyl) benzaldehyde 2,6-diisopropylphenylhydrazone, 2- (2,3 , 4-Trimethylcyclopentadienyl) benzaldehyde 2,6-diisopropylphenylhydrazone, 2- (2,4,5-trimethylcyclopentadienyl) benzaldehyde 2,6-diisopropylphenylhydrazone, 2- (2,3,4) , 5-
Tetramethylcyclopentadienyl) benzaldehyde 2,6-diisopropylphenylhydrazone, 2-
(2-tert-Butylcyclopentadienyl) benzaldehyde 2,6-diisopropylphenylhydrazone, 2- (3-tert-butylcyclopentadienyl) benzaldehyde 2,6-diisopropylphenylhydrazone, 2- (2-dimethylaminocyclo) Pentadienyl) benzaldehyde 2,6-diisopropylphenylhydrazone, 2- (3-dimethylaminocyclopentadienyl) benzaldehyde 2,6-diisopropylphenylhydrazone, 2- (inden-1-yl) benzaldehyde 2,6-diisopropylphenyl Hydrazone, 2- (2-methylinden-1-yl)
Benzaldehyde 2,6-diisopropylphenylhydrazone, 2- (2-phenylinden-1-yl) benzaldehyde 2,6-diisopropylphenylhydrazone, 2- (fluoren-1-yl) benzaldehyde 2,6-diisopropylphenylhydrazone

2- (Cyclopentadienyl) benzaldehyde 2-naphthylhydrazone, 2- (2-methylcyclopentadienyl) benzaldehyde 2-naphthylhydrazone, 2- (3-methylcyclopentadienyl)
Benzaldehyde 2-naphthylhydrazone, 2-
(2,3-Dimethylcyclopentadienyl) benzaldehyde 2-naphthylhydrazone, 2- (2,4-dimethylcyclopentadienyl) benzaldehyde 2-naphthylhydrazone, 2- (3,4-dimethylcyclopentadienyl) benzaldehyde 2-naphthylhydrazone, 2- (2,3,4-trimethylcyclopentadienyl) benzaldehyde 2-naphthylhydrazone, 2-
(2,4,5-Trimethylcyclopentadienyl) benzaldehyde 2-naphthylhydrazone, 2- (2,3,
4,5-Tetramethylcyclopentadienyl) benzaldehyde 2-naphthylhydrazone, 2- (2-ter
t-butylcyclopentadienyl) benzaldehyde
2-naphthylhydrazone, 2- (3-tert-butylcyclopentadienyl) benzaldehyde 2-naphthylhydrazone, 2- (2-dimethylaminocyclopentadienyl) benzaldehyde 2-naphthylhydrazone, 2- (3-dimethylaminocyclo) Pentadienyl)
Benzaldehyde 2-naphthylhydrazone, 2- (inden-1-yl) benzaldehyde 2-naphthylhydrazone, 2- (2-methylinden-1-yl) benzaldehyde 2-naphthylhydrazone, 2- (2-phenylinden-1-yl) ) Benzaldehyde 2-naphthylhydrazone, 2- (fluoren-1-yl) benzaldehyde 2-naphthylhydrazone

2- (Cyclopentadienyl) benzaldehyde cyclohexylhydrazone, 2- (2-methylcyclopentadienyl) benzaldehyde cyclohexylhydrazone, 2- (3-methylcyclopentadienyl) benzaldehyde cyclohexylhydrazone, 2
-(2,3-Dimethylcyclopentadienyl) benzaldehyde cyclohexylhydrazone, 2- (2,4-
Dimethylcyclopentadienyl) benzaldehyde cyclohexylhydrazone, 2- (3,4-dimethylcyclopentadienyl) benzaldehyde cyclohexylhydrazone, 2- (2,3,4-trimethylcyclopentadienyl) benzaldehyde cyclohexylhydrazone, 2- (2 , 4,5-Trimethylcyclopentadienyl) benzaldehyde cyclohexylhydrazone,
2- (2,3,4,5-tetramethylcyclopentadienyl) benzaldehyde cyclohexylhydrazone,
2- (2-tert-butylcyclopentadienyl) benzaldehyde cyclohexylhydrazone, 2- (3
-Tert-Butylcyclopentadienyl) benzaldehyde cyclohexylhydrazone, 2- (2-dimethylaminocyclopentadienyl) benzaldehyde cyclohexylhydrazone, 2- (3-dimethylaminocyclopentadienyl) benzaldehyde cyclohexylhydrazone, 2- (indene- 1-yl) benzaldehyde cyclohexylhydrazone, 2- (2-methylinden-1-yl) benzaldehyde cyclohexylhydrazone, 2- (2-phenylinden-1-yl) benzaldehyde cyclohexylhydrazone, 2
-(Fluoren-1-yl) benzaldehyde cyclohexylhydrazone

2- (cyclopentadienyl) benzaldehyde tert-butylhydrazone, 2- (2-methylcyclopentadienyl) benzaldehyde tert
-Butylhydrazone, 2- (3-methylcyclopentadienyl) benzaldehyde tert-butylhydrazone, 2- (2,3-dimethylcyclopentadienyl) benzaldehyde tert-butylhydrazone, 2-
(2,4-Dimethylcyclopentadienyl) benzaldehyde tert-butylhydrazone, 2- (3,4-
Dimethylcyclopentadienyl) benzaldehyde t
ert-Butylhydrazone, 2- (2,3,4-trimethylcyclopentadienyl) benzaldehyde ter
t-Butylhydrazone, 2- (2,4,5-trimethylcyclopentadienyl) benzaldehyde tert-
Butylhydrazone, 2- (2,3,4,5-tetramethylcyclopentadienyl) benzaldehyde tert
-Butylhydrazone, 2- (2-tert-butylcyclopentadienyl) benzaldehyde tert-butylhydrazone, 2- (3-tert-butylcyclopentadienyl) benzaldehyde tert-butylhydrazone, 2- (2-dimethylaminocyclo) Pentadienyl) benzaldehyde tert-butylhydrazone,
2- (3-Dimethylaminocyclopentadienyl) benzaldehyde tert-butylhydrazone, 2- (inden-1-yl) benzaldehyde tert-butylhydrazone, 2- (2-methylinden-1-yl)
Benzaldehyde tert-butylhydrazone, 2-
(2-Phenylinden-1-yl) benzaldehyde tert-butylhydrazone, 2- (fluorene-1)
-Yl) benzaldehyde tert-butylhydrazone

2- (Cyclopentadienyl) -1-naphthaldehyde phenylhydrazone, 2- (2-methylcyclopentadienyl) -1-naphthaldehyde phenylhydrazone, 2- (3-methylcyclopentadienyl)- 1-naphthaldehyde phenylhydrazone, 2-
(2,3-Dimethylcyclopentadienyl) -1-naphthaldehyde phenylhydrazone, 2- (2,4-dimethylcyclopentadienyl) -1-naphthaldehyde phenylhydrazone, 2- (3,4-dimethylcyclopenta) Dienyl) -1-naphthaldehyde phenylhydrazone, 2- (2,3,4-trimethylcyclopentadienyl) -1-naphthaldehyde phenylhydrazone, 2- (2,4,5-trimethylcyclopentadienyl)- 1-naphthaldehyde phenylhydrazone, 2
-(2,3,4,5-tetramethylcyclopentadienyl) -1-naphthaldehyde phenylhydrazone, 2
-(2-tert-butylcyclopentadienyl) -1
-Naphthaldehyde phenylhydrazone, 2- (3-
tert-Butylcyclopentadienyl) -1-naphthaldehyde phenylhydrazone, 2- (2-dimethylaminocyclopentadienyl) -1-naphthaldehyde phenylhydrazone, 2- (3-dimethylaminocyclopentadienyl) -1 -Naphthaldehyde phenylhydrazone, 2- (inden-1-yl) -1-naphthaldehyde phenylhydrazone, 2- (2-methylinden-1-yl) -1-naphthaldehyde phenylhydrazone, 2- (2-phenylindene -1-yl)
-1-Naphthaldehyde phenylhydrazone, 2-
(Fluoren-1-yl) -1-naphthaldehyde Phenylhydrazone

2- (cyclopentadienyl) acetophenone phenylhydrazone, 2- (2-methylcyclopentadienyl) acetophenone phenylhydrazone,
2- (3-methylcyclopentadienyl) acetophenone phenylhydrazone, 2- (2,3-dimethylcyclopentadienyl) acetophenone phenylhydrazone, 2- (2,4-dimethylcyclopentadienyl) acetophenone phenylhydrazone, 2 -(3,4-Dimethylcyclopentadienyl) acetophenone phenylhydrazone, 2- (2,3,4-trimethylcyclopentadienyl) acetophenone phenylhydrazone, 2
-(2,4,5-Trimethylcyclopentadienyl) acetophenone phenylhydrazone, 2- (2,3,
4,5-Tetramethylcyclopentadienyl) acetophenone phenylhydrazone, 2- (2-tert-butylcyclopentadienyl) acetophenone phenylhydrazone, 2- (3-tert-butylcyclopentadienyl) acetophenonephenylhydrazone, 2 −
(2-Dimethylaminocyclopentadienyl) acetophenone phenylhydrazone, 2- (3-dimethylaminocyclopentadienyl) acetophenone phenylhydrazone, 2- (inden-1-yl) acetophenone phenylhydrazone, 2- (2-methylindene -1
-Yl) acetophenone phenylhydrazone, 2-
(2-Phenylinden-1-yl) acetophenone
Phenylhydrazone, 2- (fluoren-1-yl) acetophenone Phenylhydrazone

2- (Cyclopentadienyl) acetophenone 2-methylphenylhydrazone, 2- (2-methylcyclopentadienyl) acetophenone 2-methylphenylhydrazone, 2- (3-methylcyclopentadienyl) acetophenone 2- Methylphenylhydrazone, 2- (2,3-dimethylcyclopentadienyl) acetophenone 2-methylphenylhydrazone, 2-
(2,4-Dimethylcyclopentadienyl) acetophenone 2-methylphenylhydrazone, 2- (3,4-
Dimethylcyclopentadienyl) acetophenone 2-
Methylphenylhydrazone, 2- (2,3,4-trimethylcyclopentadienyl) acetophenone 2-methylphenylhydrazone, 2- (2,4,5-trimethylcyclopentadienyl) acetophenone 2-methylphenylhydrazone, 2- (2,3,4,5-Tetramethylcyclopentadienyl) acetophenone 2-methylphenylhydrazone, 2- (2-tert-butylcyclopentadienyl) acetophenone 2-methylphenylhydrazone, 2- (3-tert- Butylcyclopentadienyl) acetophenone 2-methylphenylhydrazone, 2- (2-dimethylaminocyclopentadienyl) acetophenone 2-methylphenylhydrazone,
2- (3-Dimethylaminocyclopentadienyl) acetophenone 2-methylphenylhydrazone, 2- (inden-1-yl) acetophenone 2-methylphenylhydrazone, 2- (2-methylinden-1-yl)
Acetophenone 2-methylphenylhydrazone, 2-
(2-Phenylinden-1-yl) acetophenone
2-methylphenylhydrazone, 2- (fluorene-1
-Yl) acetophenone 2-methylphenylhydrazone

2- (cyclopentadienyl) acetophenone 2,4,6-trimethylphenylhydrazone, 2
-(2-Methylcyclopentadienyl) acetophenone 2,4,6-trimethylphenylhydrazone, 2-
(3-methylcyclopentadienyl) acetophenone
2,4,6-trimethylphenylhydrazone, 2-
(2,3-Dimethylcyclopentadienyl) acetophenone 2,4,6-trimethylphenylhydrazone, 2
-(2,4-dimethylcyclopentadienyl) acetophenone 2,4,6-trimethylphenylhydrazone,
2- (3,4-dimethylcyclopentadienyl) acetophenone 2,4,6-trimethylphenylhydrazone, 2- (2,3,4-trimethylcyclopentadienyl) acetophenone 2,4,6-trimethylphenylhydrazone, 2- (2,4,5-Trimethylcyclopentadienyl) acetophenone 2,4,6-trimethylphenylhydrazone, 2- (2,3,4,5-tetramethylcyclopentadienyl) acetophenone 2,4,6
-Trimethylphenylhydrazone, 2- (2-tert
-Butylcyclopentadienyl) acetophenone 2,
4,6-Trimethylphenylhydrazone, 2- (3-t
ert-Butylcyclopentadienyl) acetophenone 2,4,6-trimethylphenylhydrazone, 2-
(2-dimethylaminocyclopentadienyl) acetophenone 2,4,6-trimethylphenylhydrazone,
2- (3-Dimethylaminocyclopentadienyl) acetophenone 2,4,6-trimethylphenylhydrazone, 2- (inden-1-yl) acetophenone 2,
4,6-Trimethylphenylhydrazone, 2- (2-methylinden-1-yl) acetophenone 2,4,6
-Trimethylphenylhydrazone, 2- (2-phenylinden-1-yl) acetophenone 2,4,6-trimethylphenylhydrazone, 2- (fluorene-1-
Ile) acetophenone 2,4,6-trimethylphenylhydrazone

2- (cyclopentadienyl) acetophenone 2,6-diisopropylphenylhydrazone, 2
-(2-Methylcyclopentadienyl) acetophenone 2,6-diisopropylphenylhydrazone, 2-
(3-methylcyclopentadienyl) acetophenone
2,6-diisopropylphenylhydrazone, 2-
(2,3-Dimethylcyclopentadienyl) acetophenone 2,6-diisopropylphenylhydrazone, 2
-(2,4-dimethylcyclopentadienyl) acetophenone 2,6-diisopropylphenylhydrazone,
2- (3,4-Dimethylcyclopentadienyl) acetophenone 2,6-diisopropylphenylhydrazone, 2- (2,3,4-trimethylcyclopentadienyl) acetophenone 2,6-diisopropylphenylhydrazone, 2- (2 , 4,5-Trimethylcyclopentadienyl) acetophenone 2,6-diisopropylphenylhydrazone, 2- (2,3,4,5-tetramethylcyclopentadienyl) acetophenone 2,6-diisopropylphenylhydrazone, 2- ( 2-tert
-Butylcyclopentadienyl) acetophenone 2,
6-diisopropylphenylhydrazone, 2- (3-t
ert-butylcyclopentadienyl) acetophenone 2,6-diisopropylphenylhydrazone, 2-
(2-dimethylaminocyclopentadienyl) acetophenone 2,6-diisopropylphenylhydrazone,
2- (3-dimethylaminocyclopentadienyl) acetophenone 2,6-diisopropylphenylhydrazone, 2- (inden-1-yl) acetophenone 2,
6-diisopropylphenylhydrazone, 2- (2-methylinden-1-yl) acetophenone 2,6-diisopropylphenylhydrazone, 2- (2-phenylinden-1-yl) acetophenone 2,6-diisopropylphenylhydrazone, 2- (Fluorene-1-
Il) acetophenone 2,6-diisopropylphenylhydrazone

2- (Cyclopentadienyl) acetophenone 2-naphthylhydrazone, 2- (2-methylcyclopentadienyl) acetophenone 2-naphthylhydrazone, 2- (3-methylcyclopentadienyl) acetophenone 2-naphthylhydrazone , 2- (2,3-
Dimethylcyclopentadienyl) acetophenone 2-
Naphthylhydrazone, 2- (2,4-dimethylcyclopentadienyl) acetophenone 2-naphthylhydrazone, 2- (3,4-Dimethylcyclopentadienyl) acetophenone 2-naphthylhydrazone, 2- (2,2
3,4-Trimethylcyclopentadienyl) acetophenone 2-naphthylhydrazone, 2- (2,4,5-trimethylcyclopentadienyl) acetophenone 2-
Naphthylhydrazone, 2- (2,3,4,5-tetramethylcyclopentadienyl) acetophenone 2-naphthylhydrazone, 2- (2-tert-butylcyclopentadienyl) acetophenone 2-naphthylhydrazone, 2- (3 -Tert-butylcyclopentadienyl) acetophenone 2-naphthylhydrazone, 2-
(2-Dimethylaminocyclopentadienyl) acetophenone 2-naphthylhydrazone, 2- (3-dimethylaminocyclopentadienyl) acetophenone 2-naphthylhydrazone, 2- (inden-1-yl) acetophenone 2-naphthylhydrazone, 2 -(2-Methylinden-1-yl) acetophenone 2-naphthylhydrazone, 2- (2-phenylinden-1-yl) acetophenone 2-naphthylhydrazone, 2- (fluoren-1-yl) acetophenone 2-naphthylhydrazone

2- (Cyclopentadienyl) acetophenone cyclohexylhydrazone, 2- (2-methylcyclopentadienyl) acetophenone cyclohexylhydrazone, 2- (3-methylcyclopentadienyl)
Acetophenone cyclohexylhydrazone, 2-
(2,3-Dimethylcyclopentadienyl) acetophenone cyclohexylhydrazone, 2- (2,4-dimethylcyclopentadienyl) acetophenone cyclohexylhydrazone, 2- (3,4-dimethylcyclopentadienyl) acetophenone cyclohexylhydrazone, 2 -(2,3,4-Trimethylcyclopentadienyl) acetophenone cyclohexylhydrazone, 2-
(2,4,5-Trimethylcyclopentadienyl) acetophenone cyclohexylhydrazone, 2- (2
3,4,5-Tetramethylcyclopentadienyl) acetophenone cyclohexylhydrazone, 2- (2-t
ert-Butylcyclopentadienyl) acetophenone cyclohexylhydrazone, 2- (3-tert-butylcyclopentadienyl) acetophenone cyclohexylhydrazone, 2- (2-dimethylaminocyclopentadienyl) acetophenone cyclohexylhydrazone, 2- (3- Dimethylaminocyclopentadienyl) acetophenone cyclohexylhydrazone, 2-
(Inden-1-yl) acetophenone cyclohexylhydrazone, 2- (2-methylinden-1-yl)
Acetophenone cyclohexylhydrazone, 2- (2
-Phenylinden-1-yl) acetophenone cyclohexylhydrazone, 2- (fluoren-1-yl)
Acetophenone cyclohexylhydrazone

2- (cyclopentadienyl) acetophenone tert-butylhydrazone, 2- (2-methylcyclopentadienyl) acetophenone tert-butylhydrazone, 2- (3-methylcyclopentadienyl) acetophenone tert-butylhydrazone Two
-(2,3-Dimethylcyclopentadienyl) acetophenone tert-butylhydrazone, 2- (2,4-
Dimethylcyclopentadienyl) acetophenone te
rt-Butylhydrazone, 2- (3,4-dimethylcyclopentadienyl) acetophenone tert-butylhydrazone, 2- (2,3,4-trimethylcyclopentadienyl) acetophenone tert-butylhydrazone, 2- (2,2 4,5-trimethylcyclopentadienyl) acetophenone tert-butylhydrazone,
2- (2,3,4,5-tetramethylcyclopentadienyl) acetophenone tert-butylhydrazone,
2- (2-tert-butylcyclopentadienyl) acetophenone tert-butylhydrazone, 2- (3
-Tert-butylcyclopentadienyl) acetophenone tert-butylhydrazone, 2- (2-dimethylaminocyclopentadienyl) acetophenone te
rt-Butylhydrazone, 2- (3-dimethylaminocyclopentadienyl) acetophenone tert-butylhydrazone, 2- (inden-1-yl) acetophenone tert-butylhydrazone, 2- (2-methylinden-1-yl) Acetophenone tert-butylhydrazone, 2- (2-phenylinden-1-yl) acetophenone tert-butylhydrazone, 2
-(Fluoren-1-yl) acetophenone tert
-Butylhydrazone and the like are exemplified. There are isomers of the cyclopentadiene ring, but they may be single or mixed.

The transition metal compound represented by the general formula (3) includes tetrakis (dimethylamino) titanium, tetrakis (diethylamino) titanium, tetrakis (dimethylamino) zirconium, tetrakis (diethylamino) zirconium, tetrakis (dimethylamino) hafnium, Tetrakis (diethylamino) hafnium, tris (dimethylamino) titanium chloride,
Tris (diethylamino) titanium chloride, tris (dimethylamino) zirconium chloride, tris (diethylamino) zirconium chloride, tris (dimethylamino) hafnium chloride, tris (diethylamino) hafnium chloride, bis (dimethylamino) titanium dichloride, bis (diethylamino) titanium Examples include dichloride, bis (dimethylamino) zirconium dichloride, bis (diethylamino) zirconium dichloride, bis (dimethylamino) hafnium dichloride, bis (diethylamino) hafnium dichloride, and the like.

The reaction is usually carried out in a solvent inert to the reaction. Examples of such a solvent include aromatic hydrocarbon solvents such as benzene and toluene, aliphatic hydrocarbon solvents such as hexane and heptane, ether solvents such as diethyl ether, tetrahydrofuran, and 1,4-dioxane, and hexamethylphosphoric. Amide solvents such as amide and dimethylformamide, polar solvents such as acetonitrile, propionitrile, acetone, diethyl ketone, methyl isobutyl ketone and cyclohexanone, aprotic solvents such as halogen solvents such as dichloromethane, dichloroethane, chlorobenzene and dichlorobenzene. And preferred are aromatic hydrocarbon solvents such as benzene and toluene, and aliphatic hydrocarbon solvents such as hexane and heptane. Such solvents may be used alone or in admixture of two or more, and the amount thereof is usually 1 to 200 times by weight, preferably 3 to 50 times by weight with respect to the substituted cyclopentadiene represented by the general formula (2). Is.

In this reaction, the substituted cyclopentadiene represented by the general formula (2) is usually added to the solvent, and then the general formula (3) is used.
The transition metal compound represented by the general formula (1) can be obtained by adding the transition metal compound represented by Specific examples of the transition metal complex (1) include transition metal complexes corresponding to the compounds exemplified by the cyclopentadiene represented by the general formula (2).

The reaction temperature is usually from -100 ° C to the boiling point of the solvent, preferably from -80 to 120 ° C.

The transition metal complex in which X ¹ and X ² are substituted amino groups is converted into a halide by reacting a halogen compound such as a chlorosilane compound or hydrogen chloride.

The cyclopentadiene represented by the general formula (2), which is a constituent component of the transition metal complex represented by the general formula (1), is, for example, the general formula (4). (In the formula, R ¹ , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R
¹⁰ represents the same as above, and the position of the double bond of the cyclopentadiene ring may be any or may be a mixture), and the carbonyl compound represented by the general formula (5) (In the formula, R ² has the same meaning as described above.) It is produced in one step by reacting with a hydrazine.

Examples of the carbonyl compound represented by the general formula (4) include 2- (cyclopentadienyl) benzaldehyde and 2- (2-methylcyclopentadienyl).
Benzaldehyde, 2- (3-methylcyclopentadienyl) benzaldehyde, 2- (2,3-dimethylcyclopentadienyl) benzaldehyde, 2- (2,4-
Dimethylcyclopentadienyl) benzaldehyde, 2
-(3,4-Dimethylcyclopentadienyl) benzaldehyde, 2- (2,3,4-trimethylcyclopentadienyl) benzaldehyde, 2- (2,4,5-trimethylcyclopentadienyl) benzaldehyde, 2-
(2,3,4,5-Tetramethylcyclopentadienyl) benzaldehyde, 2- (2-tert-butylcyclopentadienyl) benzaldehyde, 2- (3-t
ert-Butylcyclopentadienyl) benzaldehyde, 2- (2-dimethylaminocyclopentadienyl)
Benzaldehyde, 2- (3-dimethylaminocyclopentadienyl) benzaldehyde, 2- (indene-1
-Yl) benzaldehyde, 2- (2-methylinden-1-yl) benzaldehyde, 2- (2-phenylinden-1-yl) benzaldehyde

2- (cyclopentadienyl) acetophenone, 2- (2-methylcyclopentadienyl) acetophenone, 2- (3-methylcyclopentadienyl) acetophenone, 2- (2,3-dimethylcyclopentadiene (Enyl) acetophenone, 2- (2,4-dimethylcyclopentadienyl) acetophenone, 2- (3,4-dimethylcyclopentadienyl) acetophenone, 2-
(2,3,4-Trimethylcyclopentadienyl) acetophenone, 2- (2,4,5-trimethylcyclopentadienyl) acetophenone, 2- (2,3,4,5-
Tetramethylcyclopentadienyl) acetophenone,
2- (2-tert-butylcyclopentadienyl) acetophenone, 2- (3-tert-butylcyclopentadienyl) acetophenone, 2- (2-dimethylaminocyclopentadienyl) acetophenone, 2- (3-
Dimethylaminocyclopentadienyl) acetophenone, 2- (inden-1-yl) acetophenone, 2-
(2-Methylinden-1-yl) acetophenone, 2
-(2-Phenylinden-1-yl) acetophenone

2- (cyclopentadienyl) propiophenone, 2- (2-methylcyclopentadienyl) propiophenone, 2- (3-methylcyclopentadienyl) propiophenone, 2- (2,2 3-dimethylcyclopentadienyl) propiophenone, 2- (2,4-dimethylcyclopentadienyl) propiophenone, 2-
(3,4-Dimethylcyclopentadienyl) propiophenone, 2- (2,3,4-trimethylcyclopentadienyl) propiophenone, 2- (2,4,5-trimethylcyclopentadienyl) pro Piophenone, 2-
(2,3,4,5-Tetramethylcyclopentadienyl) propiophenone, 2- (2-tert-butylcyclopentadienyl) propiophenone, 2- (3-t
ert-Butylcyclopentadienyl) propiophenone, 2- (2-dimethylaminocyclopentadienyl)
Propiophenone, 2- (3-dimethylaminocyclopentadienyl) propiophenone, 2- (indene-1
-Yl) propiophenone, 2- (2-methylinden-1-yl) propiophenone, 2- (2-phenylinden-1-yl) propiophenone

2- (cyclopentadienyl) benzophenone, 2- (2-methylcyclopentadienyl) benzophenone, 2- (3-methylcyclopentadienyl) benzophenone, 2- (2,3-dimethylcyclopentadiene (Enyl) benzophenone, 2- (2,4-dimethylcyclopentadienyl) benzophenone, 2- (3,4-dimethylcyclopentadienyl) benzophenone, 2-
(2,3,4-trimethylcyclopentadienyl) benzophenone, 2- (2,4,5-trimethylcyclopentadienyl) benzophenone, 2- (2,3,4,5-
Tetramethylcyclopentadienyl) benzophenone,
2- (2-tert-butylcyclopentadienyl) benzophenone, 2- (3-tert-butylcyclopentadienyl) benzophenone, 2- (2-dimethylaminocyclopentadienyl) benzophenone, 2- (3-
Dimethylaminocyclopentadienyl) benzophenone, 2- (inden-1-yl) benzophenone, 2-
(2-methylinden-1-yl) benzophenone, 2
-(2-Phenylinden-1-yl) benzophenone, 3- (cyclopentadienyl) -2-naphthaldehyde, 3- (2-methylcyclopentadienyl) -2-
Naphthaldehyde, 3- (3-methylcyclopentadienyl) -2-naphthaldehyde, 3- (2,3-dimethylcyclopentadienyl) -2-naphthaldehyde, 3
-(2,4-Dimethylcyclopentadienyl) -2-naphthaldehyde, 3- (3,4-dimethylcyclopentadienyl) -2-naphthaldehyde, 3- (2,3,4
-Trimethylcyclopentadienyl) -2-naphthaldehyde, 3- (2,4,5-trimethylcyclopentadienyl) -2-naphthaldehyde, 3- (2,3,4,
5-tetramethylcyclopentadienyl) -2-naphthaldehyde, 3- (2-tert-butylcyclopentadienyl) -2-naphthaldehyde, 3- (3-ter
t-butylcyclopentadienyl) -2-naphthaldehyde, 3- (2-dimethylaminocyclopentadienyl) -2-naphthaldehyde, 3- (3-dimethylaminocyclopentadienyl) -2-naphthaldehyde, Three
-(Inden-1-yl) -2-naphthaldehyde, 3
-(2-Methylinden-1-yl) -2-naphthaldehyde, 3- (2-phenylinden-1-yl) -2
-Naphthaldehyde

3- (cyclopentadienyl) -2-acetylnaphthalene, 3- (2-methylcyclopentadienyl) -2-acetylnaphthalene, 3- (3-methylcyclopentadienyl) -2-acetylnaphthalene , 3-
(2,3-Dimethylcyclopentadienyl) -2-acetylnaphthalene, 3- (2,4-dimethylcyclopentadienyl) -2-acetylnaphthalene, 3- (3,4-
Dimethylcyclopentadienyl) -2-acetylnaphthalene, 3- (2,3,4-trimethylcyclopentadienyl) -2-acetylnaphthalene, 3- (2,4,5-
Trimethylcyclopentadienyl) -2-acetylnaphthalene, 3- (2,3,4,5-tetramethylcyclopentadienyl) -2-acetylnaphthalene, 3- (2-
tert-Butylcyclopentadienyl) -2-acetylnaphthalene, 3- (3-tert-butylcyclopentadienyl) -2-acetylnaphthalene, 3- (2-dimethylaminocyclopentadienyl) -2-acetylnaphthalene , 3- (3-dimethylaminocyclopentadienyl) -2-acetylnaphthalene, 3- (indene-1
-Yl) -2-acetylnaphthalene, 3- (2-methylinden-1-yl) -2-acetylnaphthalene, 3-
(2-Phenylinden-1-yl) -2-acetylnaphthalene

3- (cyclopentadienyl) -2-propionylnaphthalene, 3- (2-methylcyclopentadienyl) -2-propionylnaphthalene, 3- (3-methylcyclopentadienyl) -2-propionylnaphthalene , 3- (2,3-dimethylcyclopentadienyl)
-2-propionylnaphthalene, 3- (2,4-dimethylcyclopentadienyl) -2-propionylnaphthalene, 3- (3,4-dimethylcyclopentadienyl)-
2-propionylnaphthalene, 3- (2,3,4-trimethylcyclopentadienyl) -2-propionylnaphthalene, 3- (2,4,5-trimethylcyclopentadienyl) -2-propionylnaphthalene, 3- ( Two
3,4,5-tetramethylcyclopentadienyl) -2
-Propionylnaphthalene, 3- (2-tert-butylcyclopentadienyl) -2-propionylnaphthalene, 3- (3-tert-butylcyclopentadienyl) -2-propionylnaphthalene, 3- (2-dimethylaminocyclo) Pentadienyl) -2-propionylnaphthalene, 3- (3-dimethylaminocyclopentadienyl) -2-propionylnaphthalene, 3- (inden-1-yl) -2-propionylnaphthalene, 3- (2
-Methylinden-1-yl) -2-propionylnaphthalene, 3- (2-phenylinden-1-yl) -2
-Propionylnaphthalene

3- (cyclopentadienyl) -2-benzoylnaphthalene, 3- (2-methylcyclopentadienyl) -2-benzoylnaphthalene, 3- (3-methylcyclopentadienyl) -2-benzoylnaphthalene ,
3- (2,3-dimethylcyclopentadienyl) -2-
Benzoylnaphthalene, 3- (2,4-dimethylcyclopentadienyl) -2-benzoylnaphthalene, 3-
(3,4-Dimethylcyclopentadienyl) -2-benzoylnaphthalene, 3- (2,3,4-trimethylcyclopentadienyl) -2-benzoylnaphthalene, 3-
(2,4,5-Trimethylcyclopentadienyl) -2
-Benzoylnaphthalene, 3- (2,3,4,5-tetramethylcyclopentadienyl) -2-benzoylnaphthalene, 3- (2-tert-butylcyclopentadienyl) -2-benzoylnaphthalene, 3- ( 3-ter
t-butylcyclopentadienyl) -2-benzoylnaphthalene, 3- (2-dimethylaminocyclopentadienyl) -2-benzoylnaphthalene, 3- (3-dimethylaminocyclopentadienyl) -2-benzoylnaphthalene, 3- (inden-1-yl) -2-benzoylnaphthalene, 3- (2-methylinden-1-yl)-
2-benzoylnaphthalene, 3- (2-phenylinden-1-yl) -2-benzoylnaphthalene

2- (cyclopentadienyl) -1-naphthaldehyde, 2- (2-methylcyclopentadienyl) -1-naphthaldehyde, 2- (3-methylcyclopentadienyl) -1-naphthaldehyde , 2- (2
3-Dimethylcyclopentadienyl) -1-naphthaldehyde, 2- (2,4-dimethylcyclopentadienyl) -1-naphthaldehyde, 2- (3,4-dimethylcyclopentadienyl) -1-naphtho Aldehyde, 2-
(2,3,4-trimethylcyclopentadienyl) -1
-Naphthoaldehyde, 2- (2,4,5-trimethylcyclopentadienyl) -1-naphthaldehyde, 2-
(2,3,4,5-tetramethylcyclopentadienyl) -1-naphthaldehyde, 2- (2-tert-butylcyclopentadienyl) -1-naphthaldehyde,
2- (3-tert-butylcyclopentadienyl)-
1-naphthaldehyde, 2- (2-dimethylaminocyclopentadienyl) -1-naphthaldehyde, 2- (3
-Dimethylaminocyclopentadienyl) -1-naphthaldehyde, 2- (inden-1-yl) -1-naphthaldehyde, 2- (2-methylinden-1-yl)-
1-naphthaldehyde, 2- (2-phenylindene-
1-yl) -1-naphthaldehyde

2- (cyclopentadienyl) -1-acetylnaphthalene, 2- (2-methylcyclopentadienyl) -1-acetylnaphthalene, 2- (3-methylcyclopentadienyl) -1-acetylnaphthalene , 2-
(2,3-Dimethylcyclopentadienyl) -1-acetylnaphthalene, 2- (2,4-dimethylcyclopentadienyl) -1-acetylnaphthalene, 2- (3,4-
Dimethylcyclopentadienyl) -1-acetylnaphthalene, 2- (2,3,4-trimethylcyclopentadienyl) -1-acetylnaphthalene, 2- (2,4,5-
Trimethylcyclopentadienyl) -1-acetylnaphthalene, 2- (2,3,4,5-tetramethylcyclopentadienyl) -1-acetylnaphthalene, 2- (2-
tert-Butylcyclopentadienyl) -1-acetylnaphthalene, 2- (3-tert-butylcyclopentadienyl) -1-acetylnaphthalene, 2- (2-dimethylaminocyclopentadienyl) -1-acetylnaphthalene , 2- (3-dimethylaminocyclopentadienyl) -1-acetylnaphthalene, 2- (indene-1
-Yl) -1-acetylnaphthalene, 2- (2-methylinden-1-yl) -1-acetylnaphthalene, 2-
(2-Phenylinden-1-yl) -1-acetylnaphthalene

2- (cyclopentadienyl) -1-propionylnaphthalene, 2- (2-methylcyclopentadienyl) -1-propionylnaphthalene, 2- (3-methylcyclopentadienyl) -1-propionylnaphthalene , 2- (2,3-dimethylcyclopentadienyl)
-1-propionylnaphthalene, 2- (2,4-dimethylcyclopentadienyl) -1-propionylnaphthalene, 2- (3,4-dimethylcyclopentadienyl)-
1-propionylnaphthalene, 2- (2,3,4-trimethylcyclopentadienyl) -1-propionylnaphthalene, 2- (2,4,5-trimethylcyclopentadienyl) -1-propionylnaphthalene, 2- ( Two
3,4,5-Tetramethylcyclopentadienyl) -1
-Propionylnaphthalene, 2- (2-tert-butylcyclopentadienyl) -1-propionylnaphthalene, 2- (3-tert-butylcyclopentadienyl) -1-propionylnaphthalene, 2- (2-dimethylaminocyclo) Pentadienyl) -1-propionylnaphthalene, 2- (3-dimethylaminocyclopentadienyl) -1-propionylnaphthalene, 2- (inden-1-yl) -1-propionylnaphthalene, 2- (2
-Methylinden-1-yl) -1-propionylnaphthalene, 2- (2-phenylinden-1-yl) -1
-Propionylnaphthalene

2- (Cyclopentadienyl) -1-benzoylnaphthalene, 2- (2-methylcyclopentadienyl) -1-benzoylnaphthalene, 2- (3-methylcyclopentadienyl) -1-benzoylnaphthalene ,
2- (2,3-dimethylcyclopentadienyl) -1-
Benzoylnaphthalene, 2- (2,4-dimethylcyclopentadienyl) -1-benzoylnaphthalene, 2-
(3,4-Dimethylcyclopentadienyl) -1-benzoylnaphthalene, 2- (2,3,4-trimethylcyclopentadienyl) -1-benzoylnaphthalene, 2-
(2,4,5-Trimethylcyclopentadienyl) -1
-Benzoylnaphthalene, 2- (2,3,4,5-tetramethylcyclopentadienyl) -1-benzoylnaphthalene, 2- (2-tert-butylcyclopentadienyl) -1-benzoylnaphthalene, 2- ( 3-ter
t-butylcyclopentadienyl) -1-benzoylnaphthalene, 2- (2-dimethylaminocyclopentadienyl) -1-benzoylnaphthalene, 2- (3-dimethylaminocyclopentadienyl) -1-benzoylnaphthalene, 2- (inden-1-yl) -1-benzoylnaphthalene, 2- (2-methylinden-1-yl)-
1-benzoylnaphthalene, 2- (2-phenylinden-1-yl) -1-benzoylnaphthalene

2- (cyclopentadienyl) -5-te
rt-Butylbenzaldehyde, 2- (2-methylcyclopentadienyl) -5-tert-butylbenzaldehyde, 2- (3-methylcyclopentadienyl) -5
-Tert-butylbenzaldehyde, 2- (2,3-
Dimethylcyclopentadienyl) -5-tert-butylbenzaldehyde, 2- (2,4-dimethylcyclopentadienyl) -5-tert-butylbenzaldehyde, 2- (3,4-dimethylcyclopentadienyl)-
5-tert-butylbenzaldehyde, 2- (2,
3,4-trimethylcyclopentadienyl) -5-te
rt-Butylbenzaldehyde, 2- (2,4,5-trimethylcyclopentadienyl) -5-tert-butylbenzaldehyde, 2- (2,3,4,5-tetramethylcyclopentadienyl) -5-tert -Butylbenzaldehyde, 2- (2-tert-butylcyclopentadienyl) -5-tert-butylbenzaldehyde, 2- (3-tert-butylcyclopentadienyl) -5-tert-butylbenzaldehyde, 2-
(2-Dimethylaminocyclopentadienyl) -5-t
ert-Butylbenzaldehyde, 2- (3-dimethylaminocyclopentadienyl) -5-tert-butylbenzaldehyde, 2- (inden-1-yl) -5-
tert-Butylbenzaldehyde, 2- (2-methylinden-1-yl) -5-tert-butylbenzaldehyde, 2- (2-phenylinden-1-yl)-
5-tert-butylbenzaldehyde

2- (cyclopentadienyl) -5-te
rt-butylacetophenone, 2- (2-methylcyclopentadienyl) -5-tert-butylacetophenone, 2- (3-methylcyclopentadienyl) -5-t
ert-butylacetophenone, 2- (2,3-dimethylcyclopentadienyl) -5-tert-butylacetophenone, 2- (2,4-dimethylcyclopentadienyl) -5-tert-butylacetophenone, 2-
(3,4-Dimethylcyclopentadienyl) -5-te
rt-Butylacetophenone, 2- (2,3,4-trimethylcyclopentadienyl) -5-tert-butylacetophenone, 2- (2,4,5-trimethylcyclopentadienyl) -5-tert-butylacetophenone , 2- (2,3,4,5-tetramethylcyclopentadienyl) -5-tert-butylacetophenone, 2
-(2-tert-butylcyclopentadienyl) -5
-Tert-butylacetophenone, 2- (3-ter
t-butylcyclopentadienyl) -5-tert-butylacetophenone, 2- (2-dimethylaminocyclopentadienyl) -5-tert-butylacetophenone, 2- (3-dimethylaminocyclopentadienyl)
-5-tert-butylacetophenone, 2- (inden-1-yl) -5-tert-butylacetophenone, 2- (2-methylinden-1-yl) -5-te
rt-Butylacetophenone, 2- (2-phenylinden-1-yl) -5-tert-butylacetophenone

2- (cyclopentadienyl) -5-te
rt-Butylpropiophenone, 2- (2-methylcyclopentadienyl) -5-tert-butylpropiophenone, 2- (3-methylcyclopentadienyl) -5
-Tert-butylpropiophenone, 2- (2,3-
Dimethylcyclopentadienyl) -5-tert-butylpropiophenone, 2- (2,4-dimethylcyclopentadienyl) -5-tert-butylpropiophenone, 2- (3,4-dimethylcyclopentadiene Enyl)-
5-tert-butylpropiophenone, 2- (2,
3,4-trimethylcyclopentadienyl) -5-te
rt-Butylpropiophenone, 2- (2,4,5-trimethylcyclopentadienyl) -5-tert-butylpropiophenone, 2- (2,3,4,5-tetramethylcyclopentadienyl) -5-tert-butylpropiophenone, 2- (2-tert-butylcyclopentadienyl) -5-tert-butylpropiophenone, 2- (3-tert-butylcyclopentadienyl) -5-tert -Butyl propiophenone, 2-
(2-Dimethylaminocyclopentadienyl) -5-t
ert-Butylpropiophenone, 2- (3-dimethylaminocyclopentadienyl) -5-tert-butylpropiophenone, 2- (inden-1-yl) -5-
tert-Butylpropiophenone, 2- (2-methylinden-1-yl) -5-tert-butylpropiophenone, 2- (2-phenylinden-1-yl)-
5-tert-butylpropiophenone

2- (cyclopentadienyl) -5-te
rt-Butylbenzophenone, 2- (2-methylcyclopentadienyl) -5-tert-butylbenzophenone, 2- (3-methylcyclopentadienyl) -5-t
ert-butylbenzophenone, 2- (2,3-dimethylcyclopentadienyl) -5-tert-butylbenzophenone, 2- (2,4-dimethylcyclopentadienyl) -5-tert-butylbenzophenone, 2-
(3,4-Dimethylcyclopentadienyl) -5-te
rt-Butylbenzophenone, 2- (2,3,4-trimethylcyclopentadienyl) -5-tert-butylbenzophenone, 2- (2,4,5-trimethylcyclopentadienyl) -5-tert-butylbenzophenone , 2- (2,3,4,5-tetramethylcyclopentadienyl) -5-tert-butylbenzophenone, 2
-(2-tert-butylcyclopentadienyl) -5
-Tert-butylbenzophenone, 2- (3-ter
t-butylcyclopentadienyl) -5-tert-butylbenzophenone, 2- (2-dimethylaminocyclopentadienyl) -5-tert-butylbenzophenone, 2- (3-dimethylaminocyclopentadienyl)
-5-tert-butylbenzophenone, 2- (inden-1-yl) -5-tert-butylbenzophenone, 2- (2-methylinden-1-yl) -5-te
rt-Butylbenzophenone, 2- (2-phenylinden-1-yl) -5-tert-butylbenzophenone

2- (Cyclopentadienyl) -5-chlorobenzaldehyde, 2- (2-methylcyclopentadienyl) -5-chlorobenzaldehyde, 2- (3-methylcyclopentadienyl) -5-chlorobenzaldehyde , 2- (2,3-dimethylcyclopentadienyl)
-5-chlorobenzaldehyde, 2- (2,4-dimethylcyclopentadienyl) -5-chlorobenzaldehyde, 2- (3,4-dimethylcyclopentadienyl)-
5-chlorobenzaldehyde, 2- (2,3,4-trimethylcyclopentadienyl) -5-chlorobenzaldehyde, 2- (2,4,5-trimethylcyclopentadienyl) -5-chlorobenzaldehyde, 2- ( Two
3,4,5-Tetramethylcyclopentadienyl) -5
-Chlorobenzaldehyde, 2- (2-tert-butylcyclopentadienyl) -5-chlorobenzaldehyde, 2- (3-tert-butylcyclopentadienyl) -5-chlorobenzaldehyde, 2- (2-dimethylaminocyclo) Pentadienyl) -5-chlorobenzaldehyde, 2- (3-dimethylaminocyclopentadienyl) -5-chlorobenzaldehyde, 2- (inden-1-yl) -5-chlorobenzaldehyde, 2- (2
-Methylinden-1-yl) -5-chlorobenzaldehyde, 2- (2-phenylinden-1-yl) -5
-Chlorobenzaldehyde

2- (cyclopentadienyl) -5-chloroacetophenone, 2- (2-methylcyclopentadienyl) -5-chloroacetophenone, 2- (3-methylcyclopentadienyl) -5-chloroacetophenone ,
2- (2,3-dimethylcyclopentadienyl) -5-
Chloroacetophenone, 2- (2,4-dimethylcyclopentadienyl) -5-chloroacetophenone, 2-
(3,4-Dimethylcyclopentadienyl) -5-chloroacetophenone, 2- (2,3,4-trimethylcyclopentadienyl-5-chloroacetophenone, 2-
(2,4,5-Trimethylcyclopentadienyl) -5
-Chloroacetophenone, 2- (2,3,4,5-tetramethylcyclopentadienyl) -5-chloroacetophenone, 2- (2-tert-butylcyclopentadienyl) -5-chloroacetophenone, 2- ( 3-ter
t-butylcyclopentadienyl) -5-chloroacetophenone, 2- (2-dimethylaminocyclopentadienyl) -5-chloroacetophenone, 2- (3-dimethylaminocyclopentadienyl) -5-chloroacetophenone, 2- (inden-1-yl) -5-chloroacetophenone, 2- (2-methylinden-1-yl)-
5-chloroacetophenone, 2- (2-phenylinden-1-yl) -5-chloroacetophenone

2- (Cyclopentadienyl) -5-chloropropiophenone, 2- (2-methylcyclopentadienyl) -5-chloropropiophenone, 2- (3-methylcyclopentadienyl)- 5-chloropropiophenone, 2- (2,3-dimethylcyclopentadienyl)
-5-chloropropiophenone, 2- (2,4-dimethylcyclopentadienyl) -5-chloropropiophenone, 2- (3,4-dimethylcyclopentadienyl)-
5-chloropropiophenone, 2- (2,3,4-trimethylcyclopentadienyl-5-chloropropiophenone, 2- (2,4,5-trimethylcyclopentadienyl) -5-chloropropio Phenon, 2- (2,3,
4,5-tetramethylcyclopentadienyl) -5-chloropropiophenone, 2- (2-tert-butylcyclopentadienyl) -5-chloropropiophenone,
2- (3-tert-butylcyclopentadienyl)-
5-chloropropiophenone, 2- (2-dimethylaminocyclopentadienyl) -5-chloropropiophenone, 2- (3-dimethylaminocyclopentadienyl)
-5-chloropropiophenone, 2- (indene-1-
Yl) -5-chloropropiophenone, 2- (2-methylinden-1-yl) -5-chloropropiophenone, 2- (2-phenylinden-1-yl) -5-chloropropiophenone

2- (cyclopentadienyl) -5-chlorobenzophenone, 2- (2-methylcyclopentadienyl) -5-chlorobenzophenone, 2- (3-methylcyclopentadienyl) -5-chlorobenzophenone ,
2- (2,3-dimethylcyclopentadienyl) -5-
Chlorobenzophenone, 2- (2,4-dimethylcyclopentadienyl) -5-chlorobenzophenone, 2-
(3,4-Dimethylcyclopentadienyl) -5-chlorobenzophenone, 2- (2,3,4-trimethylcyclopentadienyl) -5-chlorobenzophenone, 2-
(2,4,5-Trimethylcyclopentadienyl) -5
-Chlorobenzophenone, 2- (2,3,4,5-tetramethylcyclopentadienyl) -5-chlorobenzophenone, 2- (2-tert-butylcyclopentadienyl) -5-chlorobenzophenone, 2- ( 3-ter
t-butylcyclopentadienyl) -5-chlorobenzophenone, 2- (2-dimethylaminocyclopentadienyl) -5-chlorobenzophenone, 2- (3-dimethylaminocyclopentadienyl) -5-chlorobenzophenone, 2- (inden-1-yl) -5-chlorobenzophenone, 2- (2-methylinden-1-yl)-
5-chlorobenzophenone, 2- (2-phenylinden-1-yl) -5-chlorobenzophenone

2- (cyclopentadienyl) -5-methoxybenzaldehyde, 2- (2-methylcyclopentadienyl) -5-methoxybenzaldehyde, 2- (3
-Methylcyclopentadienyl) -5-methoxybenzaldehyde, 2- (2,3-dimethylcyclopentadienyl) -5-methoxybenzaldehyde, 2- (2,4
-Dimethylcyclopentadienyl) -5-methoxybenzaldehyde, 2- (3,4-dimethylcyclopentadienyl) -5-methoxybenzaldehyde, 2- (2,2
3,4-Trimethylcyclopentadienyl) -5-methoxybenzaldehyde, 2- (2,4,5-trimethylcyclopentadienyl) -5-methoxybenzaldehyde, 2- (2,3,4,5-tetramethyl Cyclopentadienyl) -5-methoxybenzaldehyde, 2- (2
-Tert-butylcyclopentadienyl) -5-methoxybenzaldehyde, 2- (3-tert-butylcyclopentadienyl) -5-methoxybenzaldehyde, 2- (2-dimethylaminocyclopentadienyl)
-5-methoxybenzaldehyde, 2- (3-dimethylaminocyclopentadienyl) -5-methoxybenzaldehyde, 2- (inden-1-yl) -5-methoxybenzaldehyde, 2- (2-methylinden-1-yl) ) -5-Methoxybenzaldehyde, 2- (2-phenylinden-1-yl) -5-methoxybenzaldehyde

2- (cyclopentadienyl) -5-methoxyacetophenone, 2- (2-methylcyclopentadienyl) -5-methoxyacetophenone, 2- (3-methylcyclopentadienyl) -5-methoxyacetophenone , 2- (2,3-dimethylcyclopentadienyl)
-5-methoxyacetophenone, 2- (2,4-dimethylcyclopentadienyl) -5-methoxyacetophenone, 2- (3,4-dimethylcyclopentadienyl)-
5-methoxyacetophenone, 2- (2,3,4-trimethylcyclopentadienyl) -5-methoxyacetophenone, 2- (2,4,5-trimethylcyclopentadienyl) -5-methoxyacetophenone, 2- ( Two
3,4,5-Tetramethylcyclopentadienyl) -5
-Methoxyacetophenone, 2- (2-tert-butylcyclopentadienyl) -5-methoxyacetophenone, 2- (3-tert-butylcyclopentadienyl) -5-methoxyacetophenone, 2- (2-dimethylaminocyclo) Pentadienyl) -5-methoxyacetophenone, 2- (3-dimethylaminocyclopentadienyl) -5-methoxyacetophenone, 2- (inden-1-yl) -5-methoxyacetophenone, 2- (2
-Methylinden-1-yl) -5-methoxyacetophenone, 2- (2-phenylinden-1-yl) -5
-Methoxyacetophenone

2- (cyclopentadienyl) -5-methoxypropiophenone, 2- (2-methylcyclopentadienyl) -5-methoxypropiophenone, 2- (3
-Methylcyclopentadienyl) -5-methoxypropiophenone, 2- (2,3-dimethylcyclopentadienyl) -5-methoxypropiophenone, 2- (2,4
-Dimethylcyclopentadienyl) -5-methoxypropiophenone, 2- (3,4-dimethylcyclopentadienyl) -5-methoxypropiophenone, 2- (2,2
3,4-Trimethylcyclopentadienyl) -5-methoxypropiophenone, 2- (2,4,5-trimethylcyclopentadienyl) -5-methoxypropiophenone, 2- (2,3,4,) 5-tetramethylcyclopentadienyl) -5-methoxypropiophenone, 2- (2
-Tert-butylcyclopentadienyl) -5-methoxypropiophenone, 2- (3-tert-butylcyclopentadienyl) -5-methoxypropiophenone, 2- (2-dimethylaminocyclopentadienyl)
-5-methoxypropiophenone, 2- (3-dimethylaminocyclopentadienyl) -5-methoxypropiophenone, 2- (inden-1-yl) -5-methoxypropiophenone, 2- (2- Methylinden-1-yl) -5-methoxypropiophenone, 2- (2-phenylinden-1-yl) -5-methoxypropiophenone

2- (cyclopentadienyl) -5-methoxybenzophenone, 2- (2-methylcyclopentadienyl) -5-methoxybenzophenone, 2- (3-methylcyclopentadienyl) -5-methoxybenzophenone , 2- (2,3-dimethylcyclopentadienyl)
-5-methoxybenzophenone, 2- (2,4-dimethylcyclopentadienyl) -5-methoxybenzophenone, 2- (3,4-dimethylcyclopentadienyl)-
5-methoxybenzophenone, 2- (2,3,4-trimethylcyclopentadienyl) -5-methoxybenzophenone, 2- (2,4,5-trimethylcyclopentadienyl) -5-methoxybenzophenone, 2- ( Two
3,4,5-Tetramethylcyclopentadienyl) -5
-Methoxybenzophenone, 2- (2-tert-butylcyclopentadienyl) -5-methoxybenzophenone, 2- (3-tert-butylcyclopentadienyl) -5-methoxybenzophenone, 2- (2-dimethylaminocyclo) Pentadienyl) -5-methoxybenzophenone, 2- (3-dimethylaminocyclopentadienyl) -5-methoxybenzophenone, 2- (inden-1-yl) -5-methoxybenzophenone, 2- (2
-Methylinden-1-yl) -5-methoxybenzophenone, 2- (2-phenylinden-1-yl) -5
-Methoxybenzophenone

2- (cyclopentadienyl) -5-methoxybenzophenone, 2- (methylcyclopentadienyl) -5-methoxybenzophenone, 2- (dimethylcyclopentadienyl) -5-methoxybenzophenone,
2- (trimethylcyclopentadienyl) -5-methoxybenzophenone, 2- (tetramethylcyclopentadienyl) -5-methoxybenzophenone, 2- (ter
t-butylcyclopentadienyl) -5-methoxybenzophenone, 2- (dimethylaminocyclopentadienyl) -5-methoxybenzophenone, 2- (indene-
1-yl) -5-methoxybenzophenone, 2- (methylinden-1-yl) -5-methoxybenzophenone, 2- (phenylinden-1-yl) -5-methoxybenzophenone and the like, of cyclopentadiene ring The double bond isomers may be single or mixed.

As hydrazine used in the reaction, phenylhydrazine, 2-methylphenylhydrazine, 3-methylphenylhydrazine, 4-methylphenylhydrazine, 2,4-dimethylphenylhydrazine, 2,6-dimethylphenylhydrazine, 3,5 -Dimethylphenylhydrazine, 2,4,6-trimethylphenylhydrazine, 2-isopropylphenylhydrazine, 3-iropropylphenylhydrazine, 4-isopropylphenylhydrazine, 2,6-diisopropylphenylhydrazine, 2-tert-butylphenylhydrazine, 4-t
ert-Butylphenylhydrazine, 2,4-di-te
rt-butylphenylhydrazine, 2,6-di-ter
t-butylphenylhydrazine, 2-phenylphenylhydrazine, 4-phenylphenylhydrazine, 2,4
-Aromatic hydrazine such as diphenylphenylhydrazine, 2,6-diphenylphenylhydrazine, pentafluorophenylhydrazine, 3,5-bis (trifluoromethyl) phenylhydrazine and naphthylhydrazine,
And methylhydrazine, ethylhydrazine, isopropylhydrazine, tert-butylhydrazine, n-
Examples of the aliphatic hydrazine include butylhydrazine, isobutylhydrazine, n-pentylhydrazine, n-hexylhydrazine, cyclohexylhydrazine, n-decylhydrazine and benzylhydrazine. The amount used is usually about 0.5-1.5 mol times the carbonyl compound.

The reaction is usually carried out in a solvent. Examples of the solvent include alcohol solvents such as methanol, ethanol and isopropanol, aromatic hydrocarbon solvents such as benzene and toluene, aliphatic hydrocarbon solvents such as hexane and heptane, diethyl ether, tetrahydrofuran, 1,4- Ether solvents such as dioxane, amide solvents such as hexamethylphosphoric amide, dimethylformamide, etc., polar solvents such as acetonitrile, propionitrile, acetone, diethyl ketone, methyl isobutyl ketone, cyclohexanone, dichloromethane, dichloroethane, chlorobenzene, dichlorobenzene And an aprotic solvent such as a halogen-based solvent. These solvents are used alone or in admixture of two or more, and the amount thereof is usually 1 to 2 with respect to the carbonyl compound represented by the general formula (4).
The amount is 00 times by weight, preferably 3 to 50 times by weight.

The reaction temperature is usually from -100 ° C to the boiling point of the solvent, preferably from -80 to 120 ° C.

After the reaction, water is added to the obtained reaction mixture if necessary, and then the organic layer and the aqueous layer are separated to obtain a solution of the target compound as the organic layer. When a solvent compatible with water is used in the reaction or when the organic layer and the aqueous layer cannot be easily separated due to the small amount of the solvent used in the reaction, toluene, ethyl acetate, chlorobenzene, etc. are added to the reaction mixture. The organic solvent insoluble in water may be added, and the organic layer may be separated. The cyclopentadiene represented by the general formula (2) is
For example, the solution can be washed with water, dried, evaporated to remove the solvent, and further purified by a method such as recrystallization, distillation, or column chromatography.

The thus-produced transition metal complex represented by the general formula (1) can be used by adding the compound (A) or the compound (B) in any order at the time of polymerization. It is also possible to use the reaction product obtained by previously contacting any combination of the compounds of.

[Compound (A)] As the compound (A) used in the present invention, a known organoaluminum compound can be used. Preferably, as the compound (A),
Known organoaluminum compounds can be used, and preferably, any one of the following compounds (A1) to (A3) or a mixture of 2 to 3 types thereof is used. (A1): Organoaluminum compound represented by the general formula E1aAl (Z) 3-a (A2): Cyclic aluminoxane (A3) having a structure represented by the general formula {-Al (E2) -O-} b : General formula E3 {-Al (E3) -O-} c
A linear aluminoxane having a structure represented by Al (E3) 2 (wherein E 1 to E 3 are the same or different, a hydrocarbon group having 1 to 8 carbon atoms, Z is the same or different,
Represents a hydrogen atom or a halogen atom, a represents 1, 2, or 3, b represents an integer of 2 or more, and c represents an integer of 1 or more. )

Specific examples of the organoaluminum compound (A1) represented by the general formula E1 a AlZ3-a include trialkyl aluminum such as trimethyl aluminum, triethyl aluminum, tripropyl aluminum, triisobutyl aluminum and trihexyl aluminum;
Dialkyl aluminum chlorides such as dimethyl aluminum chloride, diethyl aluminum chloride, dipropyl aluminum chloride, diisobutyl aluminum chloride and dihexyl aluminum chloride; alkyl aluminum dichlorides such as methyl aluminum dichloride, ethyl aluminum dichloride, propyl aluminum dichloride, isobutyl aluminum dichloride and hexyl aluminum dichloride. Examples thereof include dimethyl aluminum hydride, diethyl aluminum hydride, dipropyl aluminum hydride, diisobutyl aluminum hydride, dihexyl aluminum hydride, and other dialkyl aluminum hydrides. Trialkylaluminum is preferable, and triethylaluminum and triisobutylaluminum are more preferable.

A cyclic aluminoxane (A2) having a structure represented by the general formula {-Al (E2) -O-} b, and a structure represented by the general formula E3 {-Al (E3) -O-} c AlE3 2 Specific examples of E2 and E3 in the linear aluminoxane (A3) having are alkyl groups such as methyl group, ethyl group, normal propyl group, isopropyl group, normal butyl group, isobutyl group, normal pentyl group and neopentyl group. It can be illustrated. b is 2
The above is an integer, and c is an integer of 1 or more. Preferably, E2 and E3 are a methyl group, an isobutyl group, and b
Is 2 to 40 and c is 1 to 40.

The above aluminoxanes can be made by various methods. The method is not particularly limited, and it may be produced according to a known method. For example, it is prepared by bringing a solution of trialkylaluminum (eg, trimethylaluminum) dissolved in a suitable organic solvent (benzene, aliphatic hydrocarbon, etc.) into contact with water. In addition, a method in which a trialkylaluminum (eg, trimethylaluminum) is brought into contact with a metal salt containing crystal water (eg, copper sulfate hydrate) can be exemplified.

[Compound B] In the present invention, the compound (B)
Are (B1) a boron compound represented by the general formula BQ1 Q2 Q3, and (B2) a general formula Z + (BQ1 Q2 Q3 Q4
)-, A boron compound represented by the formula (B3), a general formula (L-
H) + (BQ1 Q2 Q3 Q4)-, or any one of the boron compounds, or a mixture of two or three of them.

In the boron compound (B1) represented by the general formula BQ1 Q2 Q3, B is a boron atom in a trivalent valence state, Q1 to Q3 are halogen atoms, and carbonization containing 1 to 20 carbon atoms. Hydrogen group, halogenated hydrocarbon group containing 1 to 20 carbon atoms, substituted silyl group containing 1 to 20 carbon atoms, alkoxy group containing 1 to 20 carbon atoms or 2 to 20 carbon atoms And a disubstituted amino group, which may be the same or different. Preferred Q1 to Q3 are a halogen atom, a hydrocarbon group containing 1 to 20 carbon atoms, and a halogenated hydrocarbon group containing 1 to 20 carbon atoms.

Specific examples of (B1) include tris (pentafluorophenyl) borane and tris (2,3,5,6).
-Tetrafluorophenyl) borane, Tris (2,3,3
Examples include 4,5-tetrafluorophenyl) borane, tris (3,4,5-trifluorophenyl) borane, tris (2,3,4-trifluorophenyl) borane, and phenylbis (pentafluorophenyl) borane. However, preferably tris (pentafluorophenyl)
Boran.

In the boron compound (B2) represented by the general formula Z + (BQ1 Q2 Q3 Q4)-, Z + is an inorganic or organic cation, B is a boron atom in a trivalent valence state, Q1 to Q4 are Q in (B1) above
The same as 1 to Q3.

Specific examples of the compound represented by the general formula Z + (BQ1 Q2 Q3 Q4)-include inorganic cations Z + such as ferrocenium cations, alkyl-substituted ferrocenium cations, and silver cations. Examples of Z + which is an organic cation include a triphenylmethyl cation. (BQ1 Q2 Q3 Q4)-includes tetrakis (pentafluorophenyl) borate, tetrakis (2,3,5,6-tetrafluorophenyl) borate, tetrakis (2,3,4,5-tetrafluorophenyl) borate, Tetrakis (3,4,5-trifluorophenyl) borate, tetrakis (2,2,4-trifluorophenyl) borate, phenylbis (pentafluorophenyl) borate, tetrakis (3,5-bistrifluoromethylphenyl) Examples include borate.

Specific examples of these combinations include ferrocenium tetrakis (pentafluorophenyl) borate, 1,1'-dimethylferrocenium tetrakis (pentafluorophenyl) borate, silver tetrakis (pentafluorophenyl) borate, tri Phenylmethyltetrakis (pentafluorophenyl) borate,
Examples thereof include triphenylmethyltetrakis (3,5-bistrifluoromethylphenyl) borate, and preferably triphenylmethyltetrakis (pentafluorophenyl) borate.

In addition, the general formula (L-H) + (BQ1 Q2 Q
In the boron compound (B3) represented by 3 Q4)-, L is a neutral Lewis base, (L-H) + is a Bronsted acid, and B is a boron atom in a trivalent valence state. Yes, Q1 to Q4 are Q1 to Q in (B1) above.
Same as 3.

General formula (L-H) + (BQ1 Q2 Q3 Q4
Specific examples of the compound represented by)-include (L-H) + which is a Bronsted acid, such as trialkyl-substituted ammonium, N, N-dialkylanilinium, dialkylammonium and triarylphosphonium. , (BQ1 Q2 Q3 Q4)-are the same as those mentioned above.

Specific combinations of these include triethylammonium tetrakis (pentafluorophenyl) borate, tripropylammonium tetrakis (pentafluorophenyl) borate, tri (normal butyl) ammonium tetrakis (pentafluorophenyl) borate, tri (normal). Butyl) ammonium tetrakis (3,5-bistrifluoromethylphenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, N, N-diethylanilinium tetrakis (pentafluorophenyl) borate, N, N- 2,4,6-Pentamethylanilinium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (3,5
-Bistrifluoromethylphenyl) borate, diisopropylammonium tetrakis (pentafluorophenyl) borate, dicyclohexylammonium tetrakis (pentafluorophenyl) borate, triphenylphosphonium tetrakis (pentafluorophenyl)
Examples thereof include borate, tri (methylphenyl) phosphonium tetrakis (pentafluorophenyl) borate, and tri (dimethylphenyl) phosphonium tetrakis (pentafluorophenyl) borate, but preferably tri (normal butyl) ammonium tetrakis (pentafluoro). Examples thereof include phenyl) borate and N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate.

The amount of each catalyst component used is such that the compound (A) / transition metal complex molar ratio is 0.1 to 10000, preferably 5 to 2000, and the compound (B) / transition metal complex molar ratio is 0.1. It is desirable to use each component so that it is in the range of 01 to 100, preferably 0.5 to 10. Regarding the concentration when each catalyst component is used in a solution state, the transition metal complex represented by the general formula (1) is 0.0001 to 5 mmol / liter, preferably 0.001 to 1 mmol / liter. Compound (A) is converted into Al atom,
0.01-500 mmol / l, preferably
0.1 to 100 mmol / liter, compound (B) is
0.0001 to 5 mmol / liter, preferably
It is desirable to use each component so that it is in the range of 0.001 to 1 mmol / liter.

In the present invention, the monomer used for polymerization may be any of olefins and diolefins having 2 to 20 carbon atoms, and it is also possible to use two or more kinds of monomers at the same time. Examples of such monomers are shown below, but the present invention is not limited to the following compounds. Specific examples of such olefins include ethylene, propylene, butene-1, pentene-1, hexene-1, heptene-1, octene-1, nonene-1,
Examples include decene-1,5-methyl-2-pentene-1, vinylcyclohexene and the like. Examples of the diolefin compound include a conjugated diene and a non-conjugated diene of a hydrocarbon compound, and specific examples of the compound include 1,5-hexadiene and 1,4 as specific examples of the non-conjugated diene compound.
-Hexadiene, 1,4-pentadiene, 1,7-octadiene, 1,8-nonadiene, 1,9-decadiene,
4-methyl-1,4-hexadiene, 5-methyl-1,
4-hexadiene, 7-methyl-1,6-octadiene, 5-ethylidene-2-norbornene, dicyclopentadiene, 5-vinyl-2-norbornene, 5-methyl-2-norbornene, norbornadiene, 5-methylene-2- Norbornene, 1,5-cyclooctadiene,
5,8-endomethylene hexahydronaphthalene and the like are exemplified, and specific examples of the conjugated diene compound include 1,3-
Butadiene, isoprene, 1,3-hexadiene, 1,
3-octadiene, 1,3-cyclooctadiene, 1,
3-cyclohexadiene etc. can be illustrated. Specific examples of the monomer constituting the copolymer include ethylene and propylene, ethylene and butene-1, ethylene and hexene-1, propylene and butene-1, and the like, and further 5-ethylidene-2-norbornene. Combinations and the like are exemplified, but the present invention is not limited to the above compounds.

In the present invention, an aromatic vinyl compound can also be used as a monomer. Specific examples of the aromatic vinyl compound include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, o, p-dimethylstyrene, o-ethylstyrene, m-ethylstyrene,
Examples thereof include p-ethylstyrene, o-chlorostyrene, p-chlorostyrene, α-methylstyrene and divinylbenzene.

The polymerization method is also not particularly limited, but for example, aliphatic hydrocarbons such as butane, pentane, hexane, heptane and octane, aromatic hydrocarbons such as benzene and toluene, methylene dichloride and the like. Solvent polymerization using a halogenated hydrocarbon as a solvent, slurry polymerization, gas phase polymerization in a gaseous monomer or the like is possible, and either continuous polymerization or batchwise polymerization is possible.

The polymerization temperature can be in the range of -50 ° C to 200 ° C, but is preferably in the range of -20 ° C to 100 ° C, and the polymerization pressure is from normal pressure to 6 MPa (60 kg / cm).
2 G) is preferred. The polymerization time is generally determined appropriately depending on the type of the target polymer and the reaction device,
It can range from 1 minute to 20 hours. Further, in the present invention, a chain transfer agent such as hydrogen may be added to control the molecular weight of the copolymer.

[0086]

According to the present invention, no silicon atom is contained,
A water stable monocyclopentadiene ligand can be synthesized and the complex obtained from the ligand is highly active and gives a high molecular weight polymer.

[0087]

EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited thereto.

Example 1 Synthesis of 2- (2,3,4,5-tetramethylcyclopentadienyl) benzaldehyde phenylhydrazone 2- (2,3,4,5-tetramethylcyclopentadienyl) under a nitrogen atmosphere. ) Benzaldehyde (20.0mmo
Phenylhydrazine (22.0 mmol) was added dropwise to a solution of 1) in ethanol (60.0 mL), and the mixture was stirred at room temperature for 2 hours. By distilling off the solvent under reduced pressure and recrystallizing from hexane, 4.8 g (yield 76.3%) of 2- (2,3,4,5-tetramethylcyclopentadienyl) benzaldehyde phenylhydrazone was obtained. . ¹ H-NMR (C ₆ D ₆ ) d 8
1.3-8.08 (m, 1H), 7.62-7.53 (m, 2H), 7.30-7.23 (m,
4H), 7.10-7.06 (m, 3H), 6.86-6.82 (m, 1H), 3.13-2.
73 (m, 1H), 1.93-1.88 (m, 5H), 1.71-1.58 (m, 4H), 1.2
0-0.91 (m, 3H).

Example 2 Synthesis of Complex 1 2- (2,3,4,5-tetramethylcyclopentadienyl) benzaldehyde phenylhydrazone (1.00 m
Toluene (5.30 mL) solution of tetrakis (dimethylamino) titanium (1.00 mmol) in toluene (1.90 mL) was added dropwise at -78 ° C, and then at room temperature for 1 hour at 100 ° C. After stirring for 5 hours, a red solution was obtained. The solvent was distilled off under reduced pressure to obtain a red solid complex 1 (2.23 g, yield 100).
%). ¹ H-NMR (C ₆ D ₆ ) d 8.55 (s, 1H), 7.31-6.88 (m, 9
H), 3.18 (s, 12H), 2.09 (s, 6H), 1.50 (s, 6H).

Example 3 Synthesis of Complex 2 Toluene (32.0 m) of complex 1 (5.00 mmol)
L) solution to trimethylsilyl chloride (55.0mmo
l) solution of toluene (24.0 mL) at 0 ° C.,
Then, it stirred at room temperature for 16 hours. The solvent was distilled off under reduced pressure, hexane (25 mL) was added, and the precipitated solid was filtered off,
An orange solid complex 2 was obtained (2.20 g, 99.5).
%). ¹ H-NMR (C ₆ D ₆ ) d 8.05 (s, 1H), 7.63-7.61 (m, 2
H), 7.13-6.84 (m, 7H), 2.11 (s, 6H), 1.59 (s, 6H).

Example 4 Synthesis of Complex 3 2- (2,3,4,5-tetramethylcyclopentadienyl) benzaldehyde phenylhydrazone (3.00m
tetrakis (dimethylamino) zirconium (3.00 mmol) in a toluene (15.0 mL) solution of
Of toluene (10.0 mL) was added dropwise at -78 ° C.
Then, a yellow solution was obtained by stirring at room temperature for 1 hour and at 100 ° C. for 5 hours. The solvent was distilled off under reduced pressure to obtain brown solid complex 3 (1.47 g, 100).
%). ¹ H-NMR (C ₆ D ₆ ) d 8.15 (s, 1H), 7.28-6.90 (m, 9H),
3.00 (s, 12H), 2.09 (s, 6H), 1.79 (s, 6H).

Example 5 Synthesis of complex 4 Hexane (24.0 m) of complex 3 (3.00 mmol)
L) solution to trimethylsilyl chloride (33.0mmo
A solution of 1) in hexane (6.00 ml) was added dropwise at 0 ° C.
Then, it stirred at room temperature for 20 hours. The precipitated solid was filtered off to obtain yellowish green powder of complex 4 (0.83 g, 58.1).
%). ¹ H-NMR (C ₆ D ₆ ) d 7.94 (s, 1H), 7.44-7.42 (m, 2
H), 7.16-6.86 (m, 7H), 2.10 (s, 6H), 1.64 (s, 6H).

Polymerization Example 6 Toluene (5.00 mL) was charged into an autoclave under nitrogen, and after stabilizing at 70 ° C., ethylene was added at 0.60 MP.
The pressure was increased to a and stabilized. Here, MMAO (250μ
mol, 5.8 wt% Al, Tosoh Akzo Co., Ltd.) and complex 2 (0.25 μmol) were added and polymerized for 30 minutes. As a result of the polymerization, the molecular weight (Mw) = 4.53 × 10 ⁵ ,
A polymer having a molecular weight distribution (Mw / Mn) of 2.1 was added per mol of titanium to 1.07 × 10 ⁶ per 1 hour.
g produced.

Example 7 An autoclave was charged with 5 ml of toluene under nitrogen,
After stabilizing at 70 ° C., ethylene was pressurized to 0.60 MPa to stabilize. A hexane solution of triisobutylaluminum (100 μL, 1.0 M, Kanto Kagaku), complex 2 (0.25 μmol), and triphenylcarbenium tetrakispentafluorophenylborate (0.75 μmol) were added thereto, and the mixture was polymerized for 30 minutes. .
As a result of the polymerization, a polymer having a molecular weight (Mw) = 6.58 × 10 ⁵ and a molecular weight distribution (Mw / Mn) = 2.2 was produced in an amount of 1.11 × 10 ⁶ g per 1 mol of titanium per 1 hour.

Example 8 Except that dimethylanilinium tetrakispentafluorophenylborate was used instead of triphenylcarbenium tetrakispentafluorophenylborate.
Polymerization was carried out in the same manner as in Example 7. As a result of the polymerization, the molecular weight (M
w) = 6.11 × 10 ⁵ , molecular weight distribution (Mw / Mn) = 2.2
The polymer was 1.07 × 10 ⁶ g per 1 mol of titanium per 1 hour.

Example 9 Polymerization was performed in the same manner as in Example 6 except that Complex 1 was used instead of Complex 2. As a result of polymerization, molecular weight (Mw) = 4.16
x10 ⁵ and a polymer having a molecular weight distribution (Mw / Mn) = 2.1 per mol of titanium per hour of 2.42
x10 ⁵ g was produced.

Example 10 Polymerization was carried out in the same manner as in Example 7 except that the complex 4 was used instead of the complex 2. As a result of the polymerization, the molecular weight (Mw) = 5.87
x10 ⁴ , a polymer having a molecular weight distribution (Mw / Mn) of 13.0 was added per 1 mol of titanium to 5.2 per hour.
6 × 10 ⁵ g was produced.

Example 11 Polymerization was conducted in the same manner as in Example 8 except that Complex 4 was used instead of Complex 2. As a result of the polymerization, the molecular weight (Mw) = 9.40
x10 ⁴ , a polymer having a molecular weight distribution (Mw / Mn) = 17.3 per mol of titanium, and 4.9 per hour.
1 × 10 ⁵ g was produced.

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 4H049 VN05 VN06 VN07 VP01 VQ07                       VQ35 VQ39 VQ43 VQ93 VR21                       VR54 VU33 VW01                 4J028 AA01A AB01A AC01A AC02A                       AC09A AC19A AC22A AC32A                       AC38A BA00A BA01B BA02B                       BA03B BB00A BB01B BB02B                       BC12B BC13B BC14B BC15B                       BC16B BC17B BC18B BC25B                       EB01

Claims (9)

[Claims] 1. A general formula (1) (In the formula, M represents a transition metal atom of Group 4 of the periodic table of elements, A ¹ and A ² represent atoms of Group 15 of the periodic table of elements, and R ¹ and R ² are hydrogen atoms. An optionally substituted alkyl group having 1 to 10 carbon atoms, an optionally substituted carbon atom 6
To 20 aryl groups, optionally substituted carbon atoms of 7 to
20 represents an aralkyl group or a hydrocarbon-substituted silyl group having 1 to 20 carbon atoms, wherein R ³ , R ⁴ , R ⁵ and R ⁶ are each independently a hydrogen atom or an optionally substituted C 1 to 10 carbon atom. Alkyl group, optionally substituted C1-10 alkoxy group, optionally substituted C6-20 aryl group, optionally substituted C6-20 aryloxy group, substituted An optionally substituted aralkyl group having 7 to 20 carbon atoms, an optionally substituted aralkyloxy group having 7 to 20 carbon atoms, a hydrocarbon-substituted silyl group having 1 to 20 carbon atoms or a hydrocarbon having 1 to 20 carbon atoms. A substituted amino group, wherein X ¹ , X ² , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are each independently a hydrogen atom, a halogen atom, an optionally substituted alkyl group having 1 to 10 carbon atoms, or a substituted Optionally having 1 to 10 carbon atoms Alkoxy group, an optionally substituted aryl group having 6 to 20 carbon atoms, carbon atoms and optionally substituted 6
To C20 aryloxy group, optionally substituted C7 to C20 aralkyl group, optionally substituted C7 to C20 aralkyloxy group, C1 to C20 hydrocarbon substituted silyl group, or A hydrocarbon-substituted amino group having 1 to 20 carbon atoms is shown, and X ¹ and X ² , R ¹ and R ² , adjacent R ³ , R ⁴ , R ⁵ and R ⁶ and adjacent R ⁷ , R ⁸ and R ⁹ , R ¹⁰
May combine with each other to form a ring. ) A transition metal complex represented by. 2. The transition metal complex according to claim ¹ , wherein A ¹ and A ² in the general formula (1) are both nitrogen atoms. 3. The transition metal complex according to claim 1, wherein R ³ , R ⁴ , R ⁵ and R ⁶ are the same or different and each is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. 4. X ¹ and X ² in the general formula (1) are each independently a halogen atom, an alkyl group having 1 to 20 carbon atoms which may be substituted with a halogen atom, or a halogen atom. A transition metal complex according to any one of claims 1 to 3, which is a good aralkyl group having 7 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms which may be substituted with a halogen atom. . 5. A general formula (2) (In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R
⁹ and R ¹⁰ are the same as above, and the position of the double bond of the cyclopentadiene ring may be arbitrary or may be a mixture)
The cyclopentadiene represented by. 6. In the general formula (2), R ⁴ , R ⁵ , R ⁶ ,
R ⁷ is the same or different, and is a hydrogen atom or has 1 carbon atom
The cyclopentadiene according to claim 5, which is an alkyl group of -5. 7. An olefin polymerization catalyst comprising a combination of the transition metal complex according to any one of claims 1 to 4 and the following compound (A). (A): any of the following compounds (A1) to (A3),
Alternatively, a mixture of two or three kinds thereof (A1): an organoaluminum compound represented by the general formula E1aAl (Z) 3-a (A2): represented by the general formula {-Al (E2) -O-} b Cyclic aluminoxane (A3) having a structure: General formula E3 {-Al (E3) -O-} c
A linear aluminoxane having a structure represented by Al (E3) 2 (wherein E 1 to E 3 are the same or different, a hydrocarbon group having 1 to 8 carbon atoms, Z is the same or different,
Represents a hydrogen atom or a halogen atom, a represents 1, 2, or 3, b represents an integer of 2 or more, and c represents an integer of 1 or more. ) 8. An olefin polymerization catalyst comprising a combination of the transition metal complex according to any one of claims 1 to 4 and the following compounds (A) and (B). (A): any of the following compounds (A1) to (A3),
Alternatively, a mixture of two or three kinds thereof (A1): an organoaluminum compound represented by the general formula E1aAl (Z) 3-a (A2): represented by the general formula {-Al (E2) -O-} b A cyclic aluminoxane having a structure, (A3): general formula E3 {-Al (E3) -O-} c
A linear aluminoxane having a structure represented by Al (E3) 2 (wherein E 1 to E 3 are the same or different, a hydrocarbon group having 1 to 8 carbon atoms, Z is the same or different,
A hydrogen atom or a halogen atom, a is 1, 2 or 3, b is an integer of 2 or more, and c is an integer of 1 or more. ) (B): Any of the following compounds (B1) to (B3),
Alternatively, a mixture of two or three of them (B1): a boron compound represented by the general formula BQ1 Q2 Q3, (B2): a boron compound represented by the general formula Z + (BQ1 Q2 Q3 Q4)-, (B3) : General formula (L-H) + (BQ1 Q2 Q3 Q4
)-Is a boron compound represented by the formula (wherein B is a boron atom in a trivalent valence state, and Q is
1 to Q4 are the same or different, and are a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, a substituted silyl group having 1 to 20 carbon atoms, and the number of carbon atoms. 1-20 alkoxy group or a C2-C20 disubstituted amino group is shown. ) A catalyst for olefin polymerization, comprising the transition metal complex according to any one of claims 1 to 4 and the following compound (A). (A) Any of the following compounds (A1) to (A3) or a mixture of two or three kinds thereof (A1) General formula E1 a
Organoaluminum compound represented by AlZ3-a (A2)
Cyclic aluminoxane (A3) having a structure represented by the general formula {-Al (E2) -O-} b General formula E3 {-
A linear aluminoxane having a structure represented by Al (E3) -O-} c AlE3 2 (provided that E1 to E3 are hydrocarbon groups having 1 to 8 carbon atoms, all E1 and all E
2 and all E3 may be the same or different. Z represents a hydrogen atom or a halogen atom, and all Z may be the same or different. a represents 1, 2 or 3, b represents an integer of 2 or more, and c represents an integer of 1 or more. ) 9. A method for producing an olefin polymer, which comprises using the catalyst for olefin polymerization according to claim 7 or 8.