JPH0987313A - Transition metal complex, production thereof, olefin polymerization catalyst containing the transition metal complex, and production of olefin polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a complex which is useful for producing an olefin polymerization catalyst highly active at industrially effective temperatures and is soluble in saturated hydrocarbon solvents by using a specific transition metal complex. SOLUTION: The complex is represented by the formula [wherein M<1> is a transition metal element belonging to the Group 4 of the Periodic Table; A is an element belonging to the Group 16 of the Periodic Table; B is an element belonging to the Group 14 of the Periodic Table; Cp <1> is a group having a cyclopentadiene type anionic skeleton; X<1> , X<2> , and R<1> to R<6> each is H, a halogen, a (halogenated) 1-20C alkyl, a (halogenated) 7-20C aralkyl, a (halogenated) 6-20C aryl, a (halogenated) 1-20C substituted silyl, a (halogenated) 1-20C alkoxy, a (halogenated) 7-20C aralkyloxy, a (halogenated) 6-20C aryloxy, or a 2-20C disubstituted amino; and R<1> to R<6> may be bonded in any manner to form a ring].

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a transition metal complex, a method for producing the same, a polymerization catalyst containing the same, and a method for producing a polymer using the same.

[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. In order to improve this problem, WO87 /
In 02370, it is reported that a reaction product of an organic compound having at least two hydroxyl groups and a transition metal compound is used. However, in the report 2,
Even in a system using 2'-thiobis (6-tert-butyl-4-methylphenoxy) titanium dichloride and methylaluminoxane, 2,2'-thiobis (6-tert-butyl) described in JP-A-5-230133. Even in a system using 4-methylphenoxy) titanium dichloride, triisobutylaluminum and triphenylmethanetetrakis (pentafluorophenyl) boron, although the molecular weight is improved, its activity is low from an industrial viewpoint. there were. Further, known metallocene complexes such as ethylenebis (indenyl) zirconium dichloride, isopropylidene (cyclopentadienyl) (fluorenyl) zirconium dichloride, dimethylsilyl (tert-butylamide) (tetramethylcyclopentadienyl) titanium dichloride, etc. Since it is soluble in an aromatic hydrocarbon solvent but insoluble in a saturated hydrocarbon solvent, a polymerization catalyst containing such a complex should be produced using a saturated hydrocarbon solvent to produce a polymer. I couldn't.

[0003]

In view of such a situation, the present invention is a complex which is highly active at a reaction temperature and soluble in a saturated hydrocarbon solvent in an industrial process of olefin polymerization which is important from an industrial viewpoint. The present invention provides a highly active catalyst for olefin polymerization containing the complex, and a method for producing an olefin polymer using the catalyst.

In order to achieve the above-mentioned objects, the present inventors have conducted extensive research on transition metal complexes and olefin polymerization catalysts. As a result, they discovered a transition metal complex soluble in a saturated hydrocarbon solvent, which has a ligand in which an aromatic ring having a hetero atom as a substituent and a cyclopentadienyl ring are linked by a covalent bond group, and completed the present invention. Came to let.

[0005]

That is, the present invention provides a compound represented by the following general formula (1): (Wherein, M ¹ represents a transition metal atom of Group 4 of the periodic table of the element, A represents an atom of Group 16 of the periodic table of the element,
B represents an atom of Group 14 of the periodic table of the elements. Cp ¹ is a group having a cyclopentadiene type anion skeleton.
X ¹ , X ² , R ¹ , R ² , R ³ , R ⁴ , R ⁵ , and R ⁶ are each independently a hydrogen atom, a halogen atom, or an alkyl group having 1 to 20 carbon atoms which may be substituted with a halogen atom. Group, 7 carbon atoms optionally substituted with halogen atom
To aralkyl group having 20 to 20 carbon atoms, aryl group having 6 to 20 carbon atoms optionally substituted with halogen atom, substituted silyl group having 1 to 20 carbon atoms optionally substituted with halogen atom, substituted with halogen atom Optionally substituted alkoxy group having 1 to 20 carbon atoms, aralkyloxy group having 7 to 20 carbon atoms optionally substituted by halogen atom, and 6 to 20 carbon atoms optionally substituted by halogen atom.
Represents an aryloxy group or a disubstituted amino group having 2 to 20 carbon atoms. R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶
May be arbitrarily bonded to form a ring. ), A transition metal complex (hereinafter referred to as compound [1]) and a polymerization catalyst containing the same.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION

[Transition Metal Complex] In the compound [1], the transition metal atom represented by M ¹ is a transition metal atom of Group 4 in the periodic table of elements (IUPAC Inorganic Chemistry Nomenclature Revised Edition 1989), for example, titanium. Atom, zirconium atom, hafnium atom and the like.

No. 16 of the Periodic Table of the elements designated as A
Examples of the atom of the group include an oxygen atom, a sulfur atom, a selenium atom and the like, and an oxygen atom is preferable.

No. 14 of the Periodic Table of the Elements, designated as B
Examples of the group atom include a carbon atom, a silicon atom, and a germanium atom.

Examples of the group having a cyclopentadiene type anion skeleton represented by the substituent Cp ¹ include, for example, η ⁵
- cycloalkyl Bae Ntajieniru group, eta ⁵ - methylcyclopentadienyl group, eta ⁵ - dimethyl cyclopentadienyl group,
[eta] ⁵ -Trimethylcyclopentadienyl group, [eta] ⁵ -tetramethylcyclopentadienyl group, [eta] ^5- ethylcyclopentadienyl group, [eta] ^5- n-propylcyclopentadienyl group, [eta] ⁵ -isopropylcyclopentadienyl group. , Η ⁵ -n-butylcyclopentadienyl group, η ⁵ −
sec-butylcyclopentadienyl group, η ⁵ -ter
t- Buchirushikuro Bae Ntajieniru group, eta ^{5-n-Penchirushikuro} Bae Ntajieniru group, eta ⁵ - neopentyl cycloalkyl Bae Ntajieniru group, eta ^{5-n-hexylcyclopentadienyl} Bae Ntajieniru group, eta ^5-n-octyl cyclopentane Bae Ntajieniru group, η ⁵ -phenylcyclopentadienyl group, η ⁵ -naphthylcyclopentadienyl group, η ⁵ -trimethylsilylcyclopentadienyl group, η ⁵ -triethylsilylcyclopentadienyl group, η ⁵ -tert-butyldimethylsilylcyclopentadienyl group, η ⁵ -indenyl group, η ⁵ -methylindenyl group, η ⁵ -dimethylindenyl group, η ⁵ -ethylindenyl group, η ⁵ -n-propylindenyl group, η ⁵ -isopropylindenyl group, η
^5-n-butyl indenyl group, eta ^5-sec-butyl indenyl group, eta ^5-tert-butyl indenyl group, eta
^5-n-pentyl indenyl group, eta ⁵ - neopentyl indenyl group, eta ^5-n-hexyl indenyl group, eta ⁵ -
n- octyl indenyl group, eta ^{5-n-Deshiruindeniru} group, eta ⁵ - phenyl indenyl group, eta ⁵ - methylphenyl indenyl group, eta ⁵ - naphthyl indenyl group, eta ⁵
- trimethylsilyl indenyl group, eta ⁵ - triethylsilyl indenyl group, eta ^{5-tert-butyldimethylsilyl} indenyl group, eta ⁵ - tetrahydroindenyl group,
η ⁵ -fluorenyl group, η ⁵ -methylfluorenyl group,
eta ⁵ - dimethyl fluorenyl group, eta ⁵ - ethyl fluorenyl group, eta ⁵ - diethyl fluorenyl group, eta ^{5-n-propyl-fluorenyl} group, eta ⁵ - di-n-propyl fluorenyl group , Η ⁵ -isopropylfluorenyl group, η ⁵ −
Diisopropyl fluorenyl group, eta ^{5-n-butyl-fluorenyl} group, eta ^{5-sec-butylfluorenyl} group, eta
^{5-tert-butyl-fluorenyl} group, eta ⁵ - di -n-
Butylfluorenyl group, eta ⁵ - di -sec- butyl-fluorenyl group, eta ⁵ - di -tert- butyl-fluorenyl group, eta ^{5-n-pentyl-fluorenyl} group, eta ⁵ - Neopentyl fluorescens Nyl group, η ⁵ -n-hexylfluorenyl group, η ⁵ -n-octylfluorenyl group, η ⁵ -n-
Decyl fluorenyl group, eta ^{5-n-dodecyl-fluorenyl} group, eta ⁵ - phenyl fluorenyl group, eta ⁵ - di - phenyl fluorenyl group, eta ⁵ - methylphenyl fluorenyl group, eta ⁵ - Naphthylfluorenyl group, η ⁵ -trimethylsilylfluorenyl group, η ⁵ -bis-trimethylsilylfluorenyl group, η ⁵ -triethylsilylfluorenyl group, η ⁵ -tert-butyldimethylsilylfluorenyl group, etc. And preferably η ⁵ -cyclopentadienyl group, η ⁵ -methylcyclopentadienyl group, η
⁵ -tert-butylcyclopentadienyl group, η ⁵ −
Examples thereof include a tetramethylcyclopentadienyl group, η ⁵ -indenyl group, η ⁵ -fluorenyl group and the like.

Substituents X ¹ , X ² , R ¹ , R ² , R ³ , R
Examples of the halogen atom in ⁴ , R ⁵ and R ⁶ include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

Substituents X ¹ , X ² , R ¹ , R ² , R ³ , R
Examples of the alkyl group having 1 to 20 carbon atoms in ⁴ , R ⁵ and R ⁶ include 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, n-dodecyl group, n-pentadecyl group, n
-Eicosyl group and the like, preferably a methyl group,
An ethyl group, an isopropyl group, a tert-butyl group, and an amyl group.

Any of these alkyl groups may be substituted with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. Examples of the alkyl group having 1 to 20 carbon atoms substituted with a halogen atom include a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a chloromethyl group, a dichloromethyl group, a trichloromethyl group, a bromomethyl group, and a dibromomethyl group. , Tribromomethyl group, iodomethyl group, diiodomethyl group, triiodomethyl group, fluoroethyl group, difluoroethyl group, trifluoroethyl group, tetrafluoroethyl group, pentafluoroethyl group, chloroethyl group, dichloroethyl group, trichloroethyl group , Tetrachloroethyl group, pentachloroethyl group, bromoethyl group, dibromoethyl group, tribromoethyl group, tetrabromoethyl group, pentabromoethyl group, perfluoropropyl group,
Perfluorobutyl group, perfluoropentyl group, perfluorohexyl group, perfluorooctyl group, perfluorododecyl group, perfluoropentadecyl group, perfluoroeicosyl group, perchloropropyl group, perchlorobutyl group, perchloropentyl group Group, perchlorohexyl group, perchlorooctyl group, perchlorododecyl group,
Perchloropentadecyl group, perchloroeicosyl group,
Examples thereof include perbromopropyl group, perbromobutyl group, perbromopentyl group, perbromohexyl group, perbromooctyl group, perbromododecyl group, perbromopentadecyl group and perbromoeicosyl group.

Substituents X ¹ , X ² , R ¹ , R ² , R ³ , R
Examples of the aralkyl group having 7 to 20 carbon atoms in ⁴ , R ⁵ and R ⁶ include benzyl group, (2-methylphenyl) methyl group, (3-methylphenyl) methyl group, (4
-Methylphenyl) methyl 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, (4,6-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 Group, (2,3,5,6-tetramethylphenyl) methyl group, (pentamethylphenyl)
Methyl group, (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-decylphenyl) methyl group, (n-tetradecylphenyl) ) A methyl group, a naphthylmethyl group, an anthracenylmethyl group and the like can be mentioned, and a benzyl group is preferable. All of these aralkyl groups are fluorine atom, chlorine atom, bromine atom,
It may be substituted with a halogen atom such as an iodine atom.

Substituents X ¹ , X ² , R ¹ , R ² , R ³ , R
Examples of the aryl group having 6 to 20 carbon atoms in ⁴ , R ⁵ , and R ⁶ include phenyl group, 2-tolyl group, 3-tolyl group, 4-tolyl group, 2,3-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-octylphenyl group, n-decylphenyl group, n-dodecylphenyl group,
Examples thereof include an n-tetradecylphenyl group, a naphthyl group and an anthracenyl group, and a phenyl group is preferable. Any of these aryl groups may be substituted with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

Substituents X ¹ , X ² , R ¹ , R ² , R ³ , R
The substituted silyl group in ⁴ , R ⁵ and R ⁶ is a silyl group substituted with a hydrocarbon group, and examples of the hydrocarbon group include methyl group, ethyl group, n-propyl group, isopropyl group, n -Butyl group, sec-butyl group, ter
1 to 10 carbon atoms such as t-butyl group, isobutyl group, n-pentyl group, n-hexyl group and cyclohexyl group
And an aryl group such as a phenyl group. Examples of the substituted silyl group having 1 to 20 carbon atoms include a monosubstituted silyl group having 1 to 20 carbon atoms such as a methylsilyl group, an ethylsilyl group and a phenylsilyl group, a dimethylsilyl group, a diethylsilyl group and a diphenylsilyl group. A 2-substituted silyl group having 2 to 20 carbon atoms,
Trimethylsilyl group, triethylsilyl group, tri-n-
Propylsilyl group, triisopropylsilyl group, tri-
n-butylsilyl group, tri-sec-butylsilyl group,
Tri-tert-butylsilyl group, tri-isobutylsilyl group, tert-butyl-dimethylsilyl group, tri-
n-pentylsilyl group, tri-n-hexylsilyl group,
Examples thereof include tri-substituted silyl groups having 3 to 20 carbon atoms such as tricyclohexylsilyl group and triphenylsilyl group, and preferred are trimethylsilyl group, tert-butyldimethylsilyl group and triphenylsilyl group. The hydrocarbon group of any of these substituted silyl groups may be substituted with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

Substituents X ¹ , X ² , R ¹ , R ² , R ³ , R
Examples of the alkoxy group having 1 to 20 carbon atoms in ⁴ , R ⁵ , and R ⁶ include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, se
c-butoxy group, tert-butoxy group, n-pentoxy group, neopentoxy group, n-hexoxy group, n-octoxy group, n-dodesoxy group, n-pentadesoxy group,
Examples thereof include an n-icosoxy group, and a methoxy group, an ethoxy group, and a tert-butoxy group are preferable. Any of these alkoxy groups may be substituted with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

Substituents X ¹ , X ² , R ¹ , R ² , R ³ , R
Examples of the aralkyloxy group having 7 to 20 carbon atoms in ⁴ , R ⁵ and R ⁶ include a benzyloxy group and (2-
Methylphenyl) methoxy group, (3-methylphenyl)
Methoxy group, (4-methylphenyl) methoxy group,
(2,3-Dimethylphenyl) methoxy group, (2,4-
Dimethylphenyl) methoxy group, (2,5-dimethylphenyl) methoxy group, (2,6-dimethylphenyl) methoxy group, (3,4-dimethylphenyl) methoxy group,
(3,5-dimethylphenyl) methoxy group, (2,3,
4-trimethylphenyl) methoxy group, (2,3,5-
Trimethylphenyl) methoxy group, (2,3,6-trimethylphenyl) methoxy group, (2,4,5-trimethylphenyl) methoxy group, (2,4,6-trimethylphenyl) methoxy group, (3,4, 5-trimethylphenyl) methoxy group, (2,3,4,5-tetramethylphenyl) methoxy group, (2,3,4,6-tetramethylphenyl) methoxy group, (2,3,5,6-tetra Methylphenyl) methoxy group, (pentamethylphenyl) methoxy group, (ethylphenyl) methoxy group, (n-propylphenyl) methoxy group, (isopropylphenyl) methoxy group, (n-butylphenyl) methoxy group, (se
c-butylphenyl) methoxy group, (tert-butylphenyl) methoxy group, (n-hexylphenyl) methoxy group, (n-octylphenyl) methoxy group, (n-
Examples thereof include a decylphenyl) methoxy group, a (n-tetradecylphenyl) methoxy group, a naphthylmethoxy group and an anthracenylmethoxy group, and a benzyloxy group is preferable. Any of these aralkyloxy groups may be substituted with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

Substituents X ¹ , X ² , R ¹ , R ² , R ³ , R
Examples of the aryloxy group in ⁴ , R ⁵ and R ⁶ include a phenoxy group, a 2-methylphenoxy group, a 3-methylphenoxy group, a 4-methylphenoxy group, a 2,3-dimethylphenoxy group and a 2,4-dimethylphenoxy group. Base,
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 Base, 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, 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, n-tetradecylphenoxy group, naphthoxy group, anthracenoxy group, etc. 6 to 20 carbon atoms
And the aryloxy group. Any of these aryloxy groups may be substituted with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

Substituents X ¹ , X ² , R ¹ , R ² , R ³ , R
^The di-substituted amino group having 2 to 20 carbon atoms in ⁴ , R ⁵ and R ⁶ is an amino group substituted with two hydrocarbon groups, and the hydrocarbon group is, for example, a methyl group or an ethyl group. , N-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, isobutyl group, n-pentyl group, n-hexyl group, cyclohexyl group and the like, having 2 to 20 carbon atoms. And aryl groups such as phenyl group. Examples of the disubstituted amino group having 1 to 10 carbon atoms include dimethylamino group, diethylamino group, di-n-propylamino group, diisopropylamino group, di-n-butylamino group, di-sec-butylamino 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, bistrimethylsilylamino group,
Examples thereof include a bis-tert-butyldimethylsilylamino group, and a dimethylamino group and a diethylamino group are preferable.

Substituents R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R
⁶ may optionally combine to form a ring.

The substituents X ¹ and X ² are preferably a halogen atom, an alkyl group or an aralkyl group, and more preferably a halogen atom. R ¹ is preferably an alkyl group having 1 to 20 carbon atoms which may be substituted with a halogen atom, an aralkyl group having 7 to 20 carbon atoms which may be substituted with a halogen atom, and a halogen atom. And an aryl group having 6 to 20 carbon atoms and a substituted silyl group having 1 to 20 carbon atoms which may be substituted with a halogen atom.

Examples of the compound [1] include methylene (cyclopentadienyl) (3,5-dimethyl-2)
-Phenoxy) titanium dichloride, methylene (cyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, methylene (cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium Dichloride, methylene (cyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, methylene (cyclopentadienyl) (3-tert-butyldimethylsilyl-
5-Methyl-2-phenoxy) titanium dichloride, methylene (cyclopentadienyl) (3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, methylene (cyclopentadienyl) (3-
tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, methylene (cyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride,

Methylene (methylcyclopentadienyl)
(3,5-dimethyl-2-phenoxy) titanium dichloride, methylene (methylcyclopentadienyl)
(3-tert-butyl-2-phenoxy) titanium dichloride, methylene (methylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, methylene (methylcyclopentadienyl) (3 -Phenyl-2-phenoxy)
Titanium dichloride, methylene (methylcyclopentadienyl) (3-tert-butyldimethylsilyl-
5-methyl-2-phenoxy) titanium dichloride, methylene (methylcyclopentadienyl) (3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, methylene (methylcyclopentadienyl) (3-tert-butyl- 5-methoxy-2-phenoxy) titanium dichloride, methylene (methylcyclopentadienyl) (3-tert-butyl-5-
Chloro-2-phenoxy) titanium dichloride,

Methylene (tert-butylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, methylene (tert-butylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride , Methylene (tert
-Butylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, methylene (tert-butylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, methylene (tert) -Butylcyclopentadienyl) (3-tert-butyldimethylsilyl-5-
Methyl-2-phenoxy) titanium dichloride, methylene (tert-butylcyclopentadienyl) (3
-Trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, methylene (tert-butylcyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, methylene (tert-butylcyclopentadiene) (Enyl) (3
-Tert-butyl-5-chloro-2-phenoxy) titanium dichloride,

Methylene (tetramethylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, methylene (tetramethylcyclopentadienyl) (3-tert-butyl-2-phenoxy)
Titanium dichloride, methylene (tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, methylene (tetramethylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride , Methylene (tetramethylcyclopentadienyl) (3-ter
t-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, methylene (tetramethylcyclopentadienyl) (3-trimethylsilyl-5-
Methyl-2-phenoxy) titanium dichloride, methylene (tetramethylcyclopentadienyl) (3-t
tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, methylene (tetramethylcyclopentadienyl) (3-tert-butyl-5-chloro-
2-phenoxy) titanium dichloride,

Methylene (trimethylsilylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, methylene (trimethylsilylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, methylene (trimethylsilyl Cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, methylene (trimethylsilylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, methylene (trimethylsilylcyclopentadienyl) ) (3-tert-Butyldimethylsilyl-5-
Methyl-2-phenoxy) titanium dichloride, methylene (trimethylsilylcyclopentadienyl) (3
-Trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, methylene (trimethylsilylcyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, methylene (trimethylsilylcyclopentadienyl) (3
-Tert-butyl-5-chloro-2-phenoxy) titanium dichloride,

Methylene (fluorenyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, methylene (fluorenyl) (3-tert-butyl-2-phenoxy) titanium dichloride, methylene (fluorenyl) (3-tert-butyl- 5-methyl-2-phenoxy) titanium dichloride, methylene (fluorenyl) (3-phenyl-2-phenoxy) titanium dichloride, methylene (fluorenyl) (3-ter
t-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, methylene (fluorenyl) (3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, methylene (fluorenyl) (3-tert-butyl-5- Methoxy-2-phenoxy) titanium dichloride, methylene (fluorenyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride,

Isopropylidene (cyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, isopropylidene (cyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, isopropylidene ( Cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (cyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, isopropylidene (cyclopentadienyl) ) (3-Tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (cyclopentadienyl)
(3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (cyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, isopropylidene (cyclopentadienyl) (3-tert
-Butyl-5-chloro-2-phenoxy) titanium dichloride,

Isopropylidene (methylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, isopropylidene (methylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, isopropylidene Ridene (methylcyclopentadienyl) (3-tert-butyl-5
-Methyl-2-phenoxy) titanium dichloride,
Isopropylidene (methylcyclopentadienyl) (3
-Phenyl-2-phenoxy) titanium dichloride, isopropylidene (methylcyclopentadienyl)
(3-tert-butyldimethylsilyl-5-methyl-
2-phenoxy) titanium dichloride, isopropylidene (methylcyclopentadienyl) (3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (methylcyclopentadienyl) (3-tert-butyl-5- Methoxy-2-
Phenoxy) titanium dichloride, isopropylidene (methylcyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride,

Isopropylidene (tert-butylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, isopropylidene (te
rt-butylcyclopentadienyl) (3-tert-
Butyl-2-phenoxy) titanium dichloride, isopropylidene (tert-butylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (t
tert-butylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, isopropylidene (tert-butylcyclopentadienyl)
(3-tert-butyldimethylsilyl-5-methyl-
2-phenoxy) titanium dichloride, isopropylidene (tert-butylcyclopentadienyl) (3
-Trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (tert-
Butylcyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, isopropylidene (tert-butylcyclopentadienyl) (3-tert-butyl-5-chloro-2)
-Phenoxy) titanium dichloride,

Isopropylidene (tetramethylcyclopentadienyl) (3,5-dimethyl-2-phenoxy)
Titanium dichloride, isopropylidene (tetramethylcyclopentadienyl) (3-tert-butyl-
2-phenoxy) titanium dichloride, isopropylidene (tetramethylcyclopentadienyl) (3-t
tert-butyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (tetramethylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, isopropylidene (tetramethylcyclopentadienyl) (3- tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (tetramethylcyclopentadienyl) (3-trimethylsilyl-5-
Methyl-2-phenoxy) titanium dichloride, isopropylidene (tetramethylcyclopentadienyl)
(3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, isopropylidene (tetramethylcyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride,

Isopropylidene (trimethylsilylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, isopropylidene (trimethylsilylcyclopentadienyl) (3-tert-
Butyl-2-phenoxy) titanium dichloride, isopropylidene (trimethylsilylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (trimethylsilylcyclopentadienyl) (3-phenyl- 2-phenoxy) titanium dichloride, isopropylidene (trimethylsilylcyclopentadienyl)
(3-tert-butyldimethylsilyl-5-methyl-
2-phenoxy) titanium dichloride, isopropylidene (trimethylsilylcyclopentadienyl) (3
-Trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (trimethylsilylcyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, isopropylidene (trimethylsilylcyclopentadienyl) (3-tert-butyl-5-chloro-2
-Phenoxy) titanium dichloride,

Isopropylidene (fluorenyl) (3,
5-dimethyl-2-phenoxy) titanium dichloride, isopropylidene (fluorenyl) (3-tert
-Butyl-2-phenoxy) titanium dichloride,
Isopropylidene (fluorenyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (fluorenyl) (3-phenyl-2-phenoxy) titanium dichloride, isopropylidene (fluorenyl) (3-tert- Butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (fluorenyl)
(3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (fluorenyl) (3-tert-butyl-5-methoxy-2
-Phenoxy) titanium dichloride, isopropylidene (fluorenyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride,

Diphenylmethylene (cyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, diphenylmethylene (cyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, diphenylmethylene ( Cyclopentadienyl) (3-tert-butyl-5-methyl-2
-Phenoxy) titanium dichloride, diphenylmethylene (cyclopentadienyl) (3-phenyl-2-
Phenoxy) titanium dichloride, diphenylmethylene (cyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (cyclopentadienyl) (3-trimethylsilyl-5-methyl- 2-
Phenoxy) titanium dichloride, diphenylmethylene (cyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, diphenylmethylene (cyclopentadienyl)
(3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride,

Diphenylmethylene (methylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, diphenylmethylene (methylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, diphenyl Methylene (methylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (methylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, diphenylmethylene ( Methylcyclopentadienyl) (3-tert-butyldimethylsilyl-5-
Methyl-2-phenoxy) titanium dichloride, diphenylmethylene (methylcyclopentadienyl) (3
-Trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (methylcyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, diphenylmethylene (methylcyclopentadienyl) (3
-Tert-butyl-5-chloro-2-phenoxy) titanium dichloride,

Diphenylmethylene (tert-butylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, diphenylmethylene (tert-butylcyclopentadienyl) (3-te
rt-Butyl-2-phenoxy) titanium dichloride, diphenylmethylene (tert-butylcyclopentadienyl) (3-tert-butyl-5-methyl-2
-Phenoxy) titanium dichloride, diphenylmethylene (tert-butylcyclopentadienyl) (3
-Phenyl-2-phenoxy) titanium dichloride, diphenylmethylene (tert-butylcyclopentadienyl) (3-tert-butyldimethylsilyl-
5-Methyl-2-phenoxy) titanium dichloride, diphenylmethylene (tert-butylcyclopentadienyl) (3-trimethylsilyl-5-methyl-2
-Phenoxy) titanium dichloride, diphenylmethylene (tert-butylcyclopentadienyl) (3
-Tert-butyl-5-methoxy-2-phenoxy)
Titanium dichloride, diphenylmethylene (ter
t-butylcyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride,

Diphenylmethylene (tetramethylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, diphenylmethylene (tetramethylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride , Diphenylmethylene (tetramethylcyclopentadienyl)
(3-tert-Butyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (tetramethylcyclopentadienyl) (3-phenyl-2
-Phenoxy) titanium dichloride, diphenylmethylene (tetramethylcyclopentadienyl) (3-t
ert-Butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (tetramethylcyclopentadienyl) (3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (tetramethylcyclopenta) Dienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, diphenylmethylene (tetramethylcyclopentadienyl)
(3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride,

Diphenylmethylene (trimethylsilylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, diphenylmethylene (trimethylsilylcyclopentadienyl) (3-te
rt-butyl-2-phenoxy) titanium dichloride, diphenylmethylene (trimethylsilylcyclopentadienyl) (3-tert-butyl-5-methyl-2)
-Phenoxy) titanium dichloride, diphenylmethylene (trimethylsilylcyclopentadienyl) (3
-Phenyl-2-phenoxy) titanium dichloride, diphenylmethylene (trimethylsilylcyclopentadienyl) (3-tert-butyldimethylsilyl-
5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (trimethylsilylcyclopentadienyl) (3-trimethylsilyl-5-methyl-2
-Phenoxy) titanium dichloride, diphenylmethylene (trimethylsilylcyclopentadienyl) (3
-Tert-butyl-5-methoxy-2-phenoxy)
Titanium dichloride, diphenylmethylene (trimethylsilylcyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride,

Diphenylmethylene (fluorenyl)
(3,5-Dimethyl-2-phenoxy) titanium dichloride, diphenylmethylene (fluorenyl) (3-
tert-butyl-2-phenoxy) titanium dichloride, diphenylmethylene (fluorenyl) (3-t
tert-butyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (fluorenyl) (3-phenyl-2-phenoxy) titanium dichloride, diphenylmethylene (fluorenyl) (3-
tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (fluorenyl) (3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (fluorenyl) (3-tert-butyl- 5-methoxy-2-phenoxy) titanium dichloride, diphenylmethylene (fluorenyl) (3-te
rt-butyl-5-chloro-2-phenoxy) titanium dichloride and the like, compounds in which titanium of these compounds is changed to zirconium and hafnium, chloride to bromide, iodide, dimethylamide, diethylamide, n-butoxide and isopropoxide. Changed compound, (cyclopentadienyl), (dimethylcyclopentadienyl), (trimethylcyclopentadienyl), (n-butylcyclopentadienyl), (ter
t-butyldimethylsilylcyclopentadienyl),
Compound changed to (indenyl), 3,5-dimethyl-
2-phenoxy was replaced with 2-phenoxy, 3-methyl-2-phenoxy, 3,5-di-tert-butyl-2-phenoxy, 3-phenyl-5-methyl-2-phenoxy, 3
-Tert-butyldimethylsilyl-2-phenoxy,
A transition metal complex in which B is a carbon atom in the general formula (1), such as a compound in which 3-trimethylsilyl-2-phenoxy is changed, a compound in which methylene is changed to diethylmethylene, and the like.

Dimethylsilyl (cyclopentadienyl)
(2-phenoxy) titanium dichloride, dimethylsilyl (cyclopentadienyl) (3-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (cyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, Dimethylsilyl (cyclopentadienyl) (3-tert-butyl-2
-Phenoxy) titanium dichloride, dimethylsilyl (cyclopentadienyl) (3-tert-butyl-
5-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (cyclopentadienyl) (3,5
-Di-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilyl (cyclopentadienyl) (5-methyl-3-phenyl-2-phenoxy) titanium dichloride, dimethylsilyl (cyclopentadienyl) (3-tert -Butyldimethylsilyl-5
-Methyl-2-phenoxy) titanium dichloride,
Dimethylsilyl (cyclopentadienyl) (5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilyl (cyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, Dimethylsilyl (cyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, dimethylsilyl (cyclopentadienyl) (3,5-diamyl-2-phenoxy) titanium dichloride,

Dimethylsilyl (methylcyclopentadienyl) (2-phenoxy) titanium dichloride, dimethylsilyl (methylcyclopentadienyl) (3-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (methylcyclopentadienyl) (3,5-
Dimethyl-2-phenoxy) titanium dichloride,
Dimethylsilyl (methylcyclopentadienyl) (3-
tert-butyl-2-phenoxy) titanium dichloride, dimethylsilyl (methylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (methylcyclopentadienyl) (3 5-di-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilyl (methylcyclopentadienyl) (5-methyl-3-phenyl-2-phenoxy) titanium dichloride, dimethylsilyl (methylcyclopentadienyl) ( 3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (methylcyclopentadienyl) (5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, dimethyi Silyl (cyclopentadienyl) (3-tert-butyl-5-methoxy-2-
Phenoxy) titanium dichloride, dimethylsilyl (methylcyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, dimethylsilyl (methylcyclopentadienyl)
(3,5-diamyl-2-phenoxy) titanium dichloride,

Dimethylsilyl (n-butylcyclopentadienyl) (2-phenoxy) titanium dichloride, dimethylsilyl (n-butylcyclopentadienyl) (3-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (n- Butylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, dimethylsilyl (n-butylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilyl (n- Butylcyclopentadienyl) (3-tert-butyl-
5-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (n-butylcyclopentadienyl) (3,5-di-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilyl (n-butylcyclopentadienyl) ) (5-Methyl-3-phenyl-2-phenoxy) titanium dichloride, dimethylsilyl (n-butylcyclopentadienyl) (3-t
tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (n
-Butylcyclopentadienyl) (5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilyl (n-butylcyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium Dichloride, dimethylsilyl (n
-Butylcyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, dimethylsilyl (n-butylcyclopentadienyl) (3,5-diamyl-2-phenoxy) titanium dichloride,

Dimethylsilyl (tert-butylcyclopentadienyl) (2-phenoxy) titanium dichloride, dimethylsilyl (tert-butylcyclopentadienyl) (3-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (tert-) Butylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, dimethylsilyl (te
rt-butylcyclopentadienyl) (3-tert-
Butyl-2-phenoxy) titanium dichloride, dimethylsilyl (tert-butylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (te
rt-butylcyclopentadienyl) (3,5-di-t
tert-butyl-2-phenoxy) titanium dichloride, dimethylsilyl (tert-butylcyclopentadienyl) (5-methyl-3-phenyl-2-phenoxy) titanium dichloride, dimethylsilyl (ter
t-butylcyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (tert-butylcyclopentadienyl) (5-methyl-3-trimethylsilyl-2- Phenoxy) titanium dichloride, dimethylsilyl (tert-butylcyclopentadienyl) (3-tert-butyl-5-methoxy-2-
Phenoxy) titanium dichloride, dimethylsilyl (tert-butylcyclopentadienyl) (3-te
rt-butyl-5-chloro-2-phenoxy) titanium dichloride, dimethylsilyl (tert-butylcyclopentadienyl) (3,5-diamyl-2-phenoxy) titanium dichloride,

Dimethylsilyl (tetramethylcyclopentadienyl) (2-phenoxy) titanium dichloride, dimethylsilyl (tetramethylcyclopentadienyl) (3-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (tetramethylcyclopenta) Dienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, dimethylsilyl (tetramethylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilyl (tetramethylcyclopentadienyl) ) (3-tert-Butyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (tetramethylcyclopentadienyl) (3,5-di-tert-butyl-2-phenoxy) titanium Chloride, dimethylsilyl (tetramethylcyclopentadienyl) (5-methyl-3-phenyl-2-phenoxy) titanium dichloride, dimethylsilyl (tetramethylcyclopentadienyl)
(3-tert-butyldimethylsilyl-5-methyl-
2-phenoxy) titanium dichloride, dimethylsilyl (tetramethylcyclopentadienyl) (5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilyl (tetramethylcyclopentadienyl) (3-tert-butyl- 5-methoxy-2-phenoxy) titanium dichloride, dimethylsilyl (tetramethylcyclopentadienyl) (3-
tert-butyl-5-chloro-2-phenoxy) titanium dichloride, dimethylsilyl (tetramethylcyclopentadienyl) (3,5-diamyl-2-phenoxy) titanium dichloride,

Dimethylsilyl (trimethylsilylcyclopentadienyl) (2-phenoxy) titanium dichloride, dimethylsilyl (trimethylsilylcyclopentadienyl) (3-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (trimethylsilylcyclopentadienyl) (3,5-Dimethyl-2-phenoxy) titanium dichloride, dimethylsilyl (trimethylsilylcyclopentadienyl) (3-tert-
Butyl-2-phenoxy) titanium dichloride, dimethylsilyl (trimethylsilylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (trimethylsilylcyclopentadienyl) (3,5- Di-t
tert-butyl-2-phenoxy) titanium dichloride, dimethylsilyl (trimethylsilylcyclopentadienyl) (5-methyl-3-phenyl-2-phenoxy) titanium dichloride, dimethylsilyl (trimethylsilylcyclopentadienyl) (3-tert- Butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (trimethylsilylcyclopentadienyl) (5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilyl (trimethylsilylcyclopentadienyl) ( 3-tert-butyl-5-methoxy-2-
Phenoxy) titanium dichloride, dimethylsilyl (trimethylsilylcyclopentadienyl) (3-te
rt-butyl-5-chloro-2-phenoxy) titanium dichloride, dimethylsilyl (trimethylsilylcyclopentadienyl) (3,5-diamyl-2-phenoxy) titanium dichloride,

Dimethylsilyl (indenyl) (2-phenoxy) titanium dichloride, dimethylsilyl (indenyl) (3-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (indenyl) (3,5
-Dimethyl-2-phenoxy) titanium dichloride, dimethylsilyl (indenyl) (3-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilyl (indenyl) (3-tert-butyl-5
-Methyl-2-phenoxy) titanium dichloride,
Dimethylsilyl (indenyl) (3,5-di-tert
-Butyl-2-phenoxy) titanium dichloride,
Dimethylsilyl (indenyl) (5-methyl-3-phenyl-2-phenoxy) titanium dichloride, dimethylsilyl (indenyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (indenyl) ) (5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilyl (indenyl) (3
-Tert-butyl-5-methoxy-2-phenoxy)
Titanium dichloride, dimethylsilyl (indenyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, dimethylsilyl (indenyl) (3,5-diamyl-2-phenoxy) titanium dichloride,

Dimethylsilyl (fluorenyl) (2-phenoxy) titanium dichloride, dimethylsilyl (fluorenyl) (3-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (fluorenyl)
(3,5-Dimethyl-2-phenoxy) titanium dichloride, dimethylsilyl (fluorenyl) (3-te
rt-butyl-2-phenoxy) titanium dichloride, dimethylsilyl (fluorenyl) (3-tert-
Butyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (fluorenyl) (3,5-
Di-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilyl (fluorenyl) (5-methyl-3-phenyl-2-phenoxy) titanium dichloride, dimethylsilyl (fluorenyl) (3-te
rt-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (fluorenyl) (5-methyl-3-trimethylsilyl-2-
Phenoxy) titanium dichloride, dimethylsilyl (fluorenyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, dimethylsilyl (fluorenyl) (3-tert-butyl-5
-Chloro-2-phenoxy) titanium dichloride,
Dimethylsilyl (fluorenyl) (3,5-diamyl-
2-phenoxy) titanium dichloride, dimethylsilyl (tetramethylcyclopentadienyl) (1-naphthoxy-2-yl) titanium dichloride and the like, and (cyclopentadienyl) of these compounds to (dimethylcyclopentadienyl), (Trimethylcyclopentadienyl), (ethylcyclopentadienyl), (n-propylcyclopentadienyl), (isopropylcyclopentadienyl), (sec-butylcyclopentadienyl), (isobutylcyclopentadienyl) ), (Ter
t-butyldimethylsilylcyclopentadienyl),
(Phenylcyclopentadienyl), (methylindenyl), compounds modified to (phenylindenyl), 2-
Compounds in which phenoxy is changed to 3-phenyl2-phenoxy, 3-trimethylsilyl-2-phenoxy, 3-tert-butyldimethylsilyl-2-phenoxy, compounds in which dimethylsilyl is changed to diethylsilyl, diphenylsilyl, dimethoxysilyl, titanium In which zirconium and hafnium have been changed to chloride, bromide in bromide, iodide, dimethylamide, diethylamide,
Examples include transition metal complexes in which B in the general formula (1) is an atom of Group 14 of the periodic table of elements other than carbon atoms, such as a compound modified to n-butoxide or isopropoxide.

The compound [1] has the general formula (10): (In the formula, Y ⁴ represents a halogen atom. R ¹ , R ² ,
R ³ and R ⁴ have the same meanings as described above. And an aryl halide compound (hereinafter, compound [10]
Called. ) Is used as a starting material in the following 3 steps or 4
It can be manufactured by a method consisting of steps.

[0049]

Examples of the halogen atom represented by the substituent Y ⁴ in the compound [10] include a chlorine atom, a bromine atom and an iodine atom.

Examples of the compound [10] include 2
-Bromophenol, 2-bromo-6-methylphenol, 2-bromo-4,6-dimethylphenol, 2-bromo-6-tert-butylphenol, 2-bromo-
6-tert-butyl-4-methylphenol, 2-bromo-4,6-di-tert-butylphenol, 2-
Bromo-6-trimethylsilylphenol, 2-bromo-4-methyl-6-trimethylsilylphenol, 2-
Bromo-6-tert-butyldimethylsilylphenol, 2-bromo-6-tert-butyldimethylsilyl-4-methylphenol, 2-bromo-6-phenylphenol, 2-bromo-4-methyl-6-phenylphenol 4 , 6-diamyl-2-bromophenol, 2-
Examples thereof include bromo-6-tert-butyl-4-methoxyphenol, 2-bromo-6-tert-butyl-4-chlorophenol, and compounds in which bromo of each of the above compounds is changed to chloro or iodo.

Each step will be described in detail below. [Step 3] General formula (2)(In the formula, Cp²Is a group having a cyclopentadiene skeleton
Show, R⁷Is a carbon atom which may be substituted with a halogen atom
A hydrogen group or a tri-substituted silyl group is shown. A, B, R ¹, R
², R^Three, R^Four, R^Five, R⁶Each has the same meaning as above
Is shown. ) Substituted cyclopentadienyl compound
(Hereinafter referred to as compound [2]) and a base.
After setting, general formula (3)(Where X^Three, X^FourEach independently water
Substituted with elementary atoms, halogen atoms, halogen atoms
Aralkyl having 1 to 20 carbon atoms, aralkyl
Group, aryl group, substituted silyl group, alkoxy group, aral
Killoxy group or aryloxy group, or carbon source
A 2-substituted amino group having 2 to 20 children is shown. M¹, X¹, X
²Each have the same meaning as described above. ) Transition
A metal compound (hereinafter referred to as compound [3]) is reacted.
To produce compound [1].

Examples of the group having a cyclopentadiene skeleton represented by the substituent Cp ² in the compound [2] include a cyclopentadienyl group, a methylcyclopentadienyl group, a dimethylcyclopentadienyl group and a trimethylcyclopentadienyl group. , Tetramethylcyclopentadienyl group, ethylcyclopentadienyl group, n-propylcyclopentadienyl group, isopropylcyclopentadienyl group, n-butylcyclopentadienyl group, sec
-Butylcyclopentadienyl group, tert-butylcyclopentadienyl group, n-pentylcyclopentadienyl group, neopentylcyclopentadienyl group, n-hexylcyclopentadienyl group, n-octylcyclopentadienyl group, phenylcyclopentadienyl group Group, naphthylcyclopentadienyl group, trimethylsilylcyclopentadienyl group, triethylsilylcyclopentadienyl group, tert-butyldimethylsilylcyclopentadienyl group, indenyl group, methylindenyl group, dimethylindenyl group, ethylindenyl group, n -Propylindenyl group, isopropylindenyl group, n-butylindenyl group, sec-butylindenyl group, ter
t-butylindenyl group, n-pentylindenyl group,
Neopentylindenyl group, n-hexylindenyl group, n-octylindenyl group, n-decylindenyl group, phenylindenyl group, methylphenylindenyl group, naphthylindenyl group, trimethylsilylindenyl group, triethylsilylindenyl group Group, tert-butyldimethylsilylindenyl group, tetrahydroindenyl group, fluorenyl group, methylfluorenyl group, dimethylfluorenyl group, ethylfluorenyl group, diethylfluorenyl group, n-propylfluorenyl group , Di-n-
Propylfluorenyl group, isopropylfluorenyl group, diisopropylfluorenyl group, n-butylfluorenyl group, sec-butylfluorenyl group, tert-
Butyl fluorenyl group, di-n-butyl fluorenyl group, di-sec-butyl fluorenyl group, di-tert
-Butylfluorenyl group, n-pentylfluorenyl group, neopentylfluorenyl group, n-hexylfluorenyl group, n-octylfluorenyl group, n-decylfluorenyl group, n-dodecylfluor group Olenyl group, phenylfluorenyl group, di-phenylfluorenyl group, methylphenylfluorenyl group, naphthylfluorenyl group, trimethylsilylfluorenyl group, bis-trimethylsilylfluorenyl group, triethylsilylfluorenyl group Base,
and a tert-butyldimethylsilylfluorenyl group, and preferably a cyclopentadienyl group, a methylcyclopentadienyl group, a tert-butylcyclopentadienyl group, a tetramethylcyclopentadienyl group,
Examples thereof include fluorenyl group and indenyl group.

The hydrocarbon group represented by the substituent R ⁷ is an alkyl group having 1 to 10 carbon atoms such as methyl group, ethyl group, propyl group, hexyl group, decyl group, vinyl group, allyl group, propenyl group, 2-Methyl-2-propenyl group, homoallyl group, hexenyl group, decenyl group and other alkenyl groups having 2 to 10 carbon atoms, methoxymethyl group, methoxyethoxymethyl group and other alkoxyalkyl groups, benzyl group, (4-methyl Phenyl) methyl group,
An aralkyl group having 7 to 12 carbon atoms such as a (2,4,6-trimethylphenyl) methyl group is exemplified. Any of these hydrocarbon groups may be substituted with a halogen atom, and examples of the hydrocarbon group substituted with a halogen atom include a 2-chloro-2-propenyl group. A trimethylsilyl group as the 3-substituted silyl group,
Triethylsilyl group, tri-n-propylsilyl group, triisopropylsilyl group, tri-n-butylsilyl group,
Tri-sec-butylsilyl group, tri-tert-butylsilyl group, tri-isobutylsilyl group, tert-butyl-dimethylsilyl group, tri-n-pentylsilyl group, tri-n-hexylsilyl group, tricyclohexylsilyl group, tri Examples thereof include a phenylsilyl group. Among such substituents R ⁷ , an alkenyl group, particularly an allyl group is preferable in that the compound [1] can be produced in good yield.

Examples of the compound [2] include 2-
[(Cyclopenta-1,4-dienyl) methyl] -1-
Methoxybenzene, 2-[(cyclopenta-1,4-dienyl) methyl] -1-methoxy-4,6-dimethylbenzene, 2-tert-butyl-6-[(cyclopenta-1,4-dienyl) methyl]- 1-methoxy-4-methylbenzene, 6-[(cyclopenta-1,4-dienyl) methyl] -1-methoxy-2-phenylbenzene,
1-tert-butyldimethylsilyl-3-[(cyclopenta-1,4-dienyl) methyl] -2-methoxy-
5-methylbenzene, 3-[(cyclopenta-1,4-
Dienyl) methyl] -2-methoxy-5-methyl-1-
Trimethylsilylbenzene, 2-tert-butyl-6
-[(Cyclopenta-1,4-dienyl) methyl]-
1,4-dimethoxybenzene, 3-tert-butyl-
1-chloro-5-[(cyclopenta-1,4-dienyl) methyl] -4-methoxybenzene, 2-tert-
Butyl-6-[(cyclopenta-1,4-dienyl) methyl] -1-methoxybenzene,

2- [1- (cyclopenta-1,4-dienyl) -1-methyl-ethyl] -1-methoxybenzene, 2- [1- (cyclopenta-1,4-dienyl)-
1-methyl-ethyl] -1-methoxy-4,6-dimethylbenzene, 6-tert-butyl-2- [1- (cyclopenta-1,4-dienyl) -1-methyl-ethyl]
-1-methoxy-4-methylbenzene, 6- [1- (cyclopenta-1,4-dienyl) -1-methyl-ethyl] -1-methoxy-2-phenylbenzene, 1-te
rt-butyldimethylsilyl-3- [1- (cyclopenta-1,4-dienyl) -1-methyl-ethyl] -2-
Methoxy-5-methylbenzene, 3- [1- (cyclopenta-1,4-dienyl) -1-methyl-ethyl] -2
-Methoxy-5-methyl-1-trimethylsilylbenzene, 6-tert-butyl-2- [1- (cyclopenta-1,4-dienyl) -1-methyl-ethyl] -1,4
-Dimethoxybenzene, 5-tert-butyl-1-chloro-3- [1- (cyclopenta-1,4-dienyl)
-1-methyl-ethyl] -4-methoxybenzene, 6-
tert-butyl-2- [1- (cyclopenta-1,4
-Dienyl) -1-methyl-ethyl] -1-methoxybenzene,

1-methoxy-2- [1- (4-methyl-
Cyclopenta-1,4-dienyl) -1-methyl-ethyl] benzene, 1-methoxy-4,6-dimethyl-2-
[1- (4-methyl-cyclopenta-1,4-dienyl) -1-methyl-ethyl] benzene, 6-tert-
Butyl-1-methoxy-4-methyl-2- [1- (4-
Methyl-cyclopenta-1,4-dienyl) -1-methyl-ethyl] benzene, 1-methoxy-6- [1- (4
-Methyl-cyclopenta-1,4-dienyl) -1-methyl-ethyl] -2-phenylbenzene, 1-tert
-Butyldimethylsilyl-2-methoxy-5-methyl-
3- [1- (4-methyl-cyclopenta-1,4-dienyl) -1-methyl-ethyl] benzene, 2-methoxy-5-methyl-3- [1- (4-methyl-cyclopenta-1,4) -Dienyl) -1-methyl-ethyl] -1-trimethylsilylbenzene, 6-tert-butyl-1,
4-dimethoxy-2- [1- (4-methyl-cyclopenta-1,4-dienyl) -1-methyl-ethyl] benzene, 5-tert-butyl-1-chloro-4-methoxy-3- [1- (4-methyl-cyclopenta-1,4-dienyl) -1-methyl-ethyl] benzene, 6-ter
t-butyl-1-methoxy-2- [1- (4-methyl-
Cyclopenta-1,4-dienyl) -1-methyl-ethyl] benzene,

2- [1- (4-tert-butyl-cyclopenta-1,4-dienyl) -1-methyl-ethyl]
-1-methoxybenzene, 2- [1- (4-tert-
Butyl-cyclopenta-1,4-dienyl) -1-methyl-ethyl] -1-methoxy-4,6-dimethylbenzene, 6-tert-butyl-2- [1- (4-tert)
-Butyl-cyclopenta-1,4-dienyl) -1-methyl-ethyl] -1-methoxy-4-methylbenzene,
6- [1- (4-tert-butyl-cyclopenta-
1,4-dienyl) -1-methyl-ethyl] -1-methoxy-2-phenylbenzene, 1-tert-butyldimethylsilyl-3- [1- (4-tert-butyl-cyclopenta-1,4-dienyl) ) -1-Methyl-ethyl] -2-methoxy-5-methylbenzene, 3- [1-
(4-tert-butylcyclopenta-1,4-dienyl) -1-methyl-ethyl] -2-methoxy-5-methyl-1-trimethylsilylbenzene, 6-tert-butyl-2- [1- (4- tert-butyl-cyclopenta-1,4-dienyl) -1-methyl-ethyl] -1,
4-dimethoxybenzene, 5-tert-butyl-1-
Chloro-3- [1- (4-tert-butyl-cyclopenta-1,4-dienyl) -1-methyl-ethyl] -4
-Methoxybenzene, 6-tert-butyl-2- [1
-(4-tert-butyl-cyclopenta-1,4-dienyl) -1-methyl-ethyl] -1-methoxybenzene,

1-methoxy-2- [1- (2,3,4,
5-tetramethyl-cyclopenta-1,4-dienyl)
-1-methyl-ethyl] benzene, 1-methoxy-4,
6-dimethyl-2- [1- (2,3,4,5-tetramethyl-cyclopenta-1,4-dienyl) -1-methyl-ethyl] benzene, 6-tert-butyl-1-methoxy-4- Methyl-2- [1- (2,3,4,5-tetramethyl-cyclopenta-1,4-dienyl) -1-methyl-ethyl] benzene, 1-methoxy-2-phenyl-6- [1- ( 2,3,4,5-tetramethyl-cyclopenta-1,4-dienyl) -1-methyl-ethyl] benzene, 1-tert-butyldimethylsilyl-2-methoxy-5-methyl-3- [1- ( 2,3,4,5-tetramethyl-cyclopenta-1,4-dienyl) -1-
Methyl-ethyl] benzene, 2-methoxy-5-methyl-3- [1- (2,3,4,5-tetramethyl-cyclopenta-1,4-dienyl) -1-methyl-ethyl]-
1-trimethylsilylbenzene, 6-tert-butyl-1,4-dimethoxy-2- [1- (2,3,4,5-
Tetramethyl-cyclopenta-1,4-dienyl) -1
-Methyl-ethyl] benzene, 5-tert-butyl-
1-chloro-4-methoxy-3- [1- (2,3,4,
5-tetramethyl-cyclopenta-1,4-dienyl)
-1-methyl-ethyl] benzene, 6-tert-butyl-1-methoxy-2- [1- (2,3,4,5-tetramethyl-cyclopenta-1,4-dienyl) -1-methyl-ethyl ]benzene,

1-methoxy-2- [1- (3-trimethylsilyl-cyclopenta-1,4-dienyl) -1-methyl-ethyl] benzene, 1-methoxy-4,6-dimethyl-2- [1- ( 3-trimethylsilyl-cyclopenta-1,4-dienyl) -1-methyl-ethyl] benzene, 6-tert-butyl-1-methoxy-4-methyl-2- [1- (3-trimethylsilyl-cyclopenta-
1,4-dienyl) -1-methyl-ethyl] benzene,
1-methoxy-2-phenyl-6- [1- (3-trimethylsilyl-cyclopenta-1,4-dienyl) -1-
Methyl-ethyl] benzene, 1-tert-butyldimethylsilyl-2-methoxy-5-methyl-3- [1-
(3-trimethylsilyl-cyclopenta-1,4-dienyl) -1-methyl-ethyl] benzene, 2-methoxy-5-methyl-1-trimethylsilyl-3- [1- (3
-Trimethylsilyl-cyclopenta-1,4-dienyl) -1-methyl-ethyl] benzene, 6-tert-
Butyl-1,4-dimethoxy-2- [1- (3-trimethylsilyl-cyclopenta-1,4-dienyl) -1-
Methyl-ethyl] benzene, 5-tert-butyl-1
-Chloro-4-methoxy-3- [1- (3-trimethylsilyl-cyclopenta-1,4-dienyl) -1-methyl-ethyl] benzene, 6-tert-butyl-1-methoxy-2- [1- ( 3-trimethylsilyl-cyclopenta-1,4-dienyl) -1-methyl-ethyl] benzene,

2- [1- (cyclopenta-1,4-dienyl) -1-ethyl-propyl] -1-methoxybenzene, 2- [1- (cyclopenta-1,4-dienyl)-
1-ethyl-propyl] -1-methoxy-4,6-dimethylbenzene, 6-tert-butyl-2- [1- (cyclopenta-1,4-dienyl) -1-ethyl-propyl] -1-methoxy- 4-methylbenzene, 6- [1-
(Cyclopenta-1,4-dienyl) -1-ethyl-propyl] -1-methoxy-2-phenylbenzene, 1-
tert-Butyldimethylsilyl-3- [1- (cyclopenta-1,4-dienyl) -1-ethyl-propyl]
-2-methoxy-5-methylbenzene, 3- [1- (cyclopenta-1,4-dienyl) -1-ethyl-propyl] -2-methoxy-5-methyl-1-trimethylsilylbenzene, 6-tert-butyl -2- [1- (cyclopenta-1,4-dienyl) -1-ethyl-propyl] -1,4-dimethoxybenzene, 5-tert-butyl-1-chloro-3- [1- (cyclopenta-1, 4
-Dienyl) -1-ethyl-propyl] -4-methoxybenzene, 6-tert-butyl-2- [1- (cyclopenta-1,4-dienyl) -1-ethyl-propyl]
-1-methoxybenzene,

2- [1- (cyclopenta-1,4-dienyl) -1,1-diphenylmethyl] -1-methoxybenzene, 2- [1- (cyclopenta-1,4-dienyl) -1,1- Diphenylmethyl] -1-methoxy-
4,6-dimethylbenzene, 6-tert-butyl-2
-[1- (cyclopenta-1,4-dienyl) -1,1
-Diphenylmethyl] -1-methoxy-4-methylbenzene, 2- [1- (cyclopenta-1,4-dienyl)
-1,1-diphenylmethyl] -1-methoxy-6-phenylbenzene, 1-tert-butyldimethylsilyl-3- [1- (cyclopenta-1,4-dienyl)-
1,1-diphenylmethyl] -2-methoxy-5-methylbenzene, 3-[(cyclopenta-1,4-dienyl) -1,1-diphenylmethyl] -2-methoxy-5
-Methyl-1-trimethylsilylbenzene, 6-ter
t-butyl-2-[(cyclopenta-1,4-dienyl) -1,1-diphenylmethyl] -1,4-dimethoxybenzene, 5-tert-butyl-1-chloro-3-
[(Cyclopenta-1,4-dienyl) -1,1-diphenylmethyl] -4-methoxybenzene, 6-tert
-Butyl-2-[(cyclopenta-1,4-dienyl)
-1,1-diphenylmethyl] -1-methoxybenzene,

1-allyloxy-2-[(cyclopenta-
1,4-dienyl) methyl] benzene, 1-allyloxy-2-[(cyclopenta-1,4-dienyl) methyl]
-4,6-dimethylbenzene, 1-allyloxy-2-t
tert-butyl-6-[(cyclopenta-1,4-dienyl) methyl] -4-methylbenzene, 1-allyloxy-6-[(cyclopenta-1,4-dienyl) methyl]
-2-phenylbenzene, 2-allyloxy-1-ter
t-Butyldimethylsilyl-3-[(cyclopenta-
1,4-dienyl) methyl] -5-methylbenzene, 2
-Allyloxy-3-[(cyclopenta-1,4-dienyl) methyl] -5-methyl-1-trimethylsilylbenzene, 1-allyloxy-2-tert-butyl-6-
[(Cyclopenta-1,4-dienyl) methyl] -4-
Methoxybenzene, 4-allyloxy-3-tert-butyl-1-chloro-5-[(cyclopenta-1,4-dienyl) methyl] benzene, 1-allyloxy-2-te
rt-butyl-6-[(cyclopenta-1,4-dienyl) methyl] benzene,

1-allyloxy-2- [1- (cyclopenta-1,4-dienyl) -1-methyl-ethyl] benzene, 1-allyloxy-2- [1- (cyclopenta-1,
4-dienyl) -1-methyl-ethyl] -4,6-dimethylbenzene, 1-allyloxy-6-tert-butyl-2- [1- (cyclopenta-1,4-dienyl) -1
-Methyl-ethyl] -4-methylbenzene, 1-allyloxy-6- [1- (cyclopenta-1,4-dienyl)
-1-methyl-ethyl] -2-phenylbenzene, 2-
Aryloxy-1-tert-butyldimethylsilyl-3
-[1- (cyclopenta-1,4-dienyl) -1-methyl-ethyl] -5-methylbenzene, 2-allyloxy-3- [1- (cyclopenta-1,4-dienyl) -1
-Methyl-ethyl] -5-methyl-1-trimethylsilylbenzene, 1-allyloxy-6-tert-butyl-
2- [1- (cyclopenta-1,4-dienyl) -1-
Methyl-ethyl] -4-methoxybenzene, 4-allyloxy-5-tert-butyl-1-chloro-3- [1-
(Cyclopenta-1,4-dienyl) -1-methyl-ethyl] benzene, 1-allyloxy-6-tert-butyl-2- [1- (cyclopenta-1,4-dienyl)-
1-methyl-ethyl] benzene,

1-allyloxy-2- [1- (4-methyl-cyclopenta-1,4-dienyl) -1-methyl-ethyl] benzene, 1-allyloxy-4,6-dimethyl-
2- [1- (4-methyl-cyclopenta-1,4-dienyl) -1-methyl-ethyl] benzene, 1-allyloxy-6-tert-butyl-4-methyl-2- [1-
(4-methyl-cyclopenta-1,4-dienyl) -1
-Methyl-ethyl] benzene, 1-allyloxy-6-
[1- (4-methyl-cyclopenta-1,4-dienyl) -1-methyl-ethyl] -2-phenylbenzene,
2-allyloxy-1-tert-butyldimethylsilyl-5-methyl-3- [1- (4-methyl-cyclopenta-1,4-dienyl) -1-methyl-ethyl] benzene, 2-allyloxy-5-methyl -3- [1- (4-Methyl-cyclopenta-1,4-dienyl) -1-methyl-ethyl] -1-trimethylsilylbenzene, 1-allyloxy-6-tert-butyl-4-methoxy-2-
[1- (4-Methyl-cyclopenta-1,4-dienyl) -1-methyl-ethyl] benzene, 4-allyloxy-5-tert-butyl-1-chloro-3- [1- (4
-Methyl-cyclopenta-1,4-dienyl) -1-methyl-ethyl] benzene, 1-allyloxy-6-ter
t-butyl-2- [1- (4-methyl-cyclopenta-
1,4-dienyl) -1-methyl-ethyl] benzene,

1-allyloxy-2- [1- (4-ter
t-butyl-cyclopenta-1,4-dienyl) -1-
Methyl-ethyl] benzene, 1-allyloxy-2- [1
-(4-Tert-butyl-cyclopenta-1,4-dienyl) -1-methyl-ethyl] -4,6-dimethylbenzene, 1-allyloxy-6-tert-butyl-2-
[1- (4-tert-butyl-cyclopenta-1,4
-Dienyl) -1-methyl-ethyl] -4-methylbenzene, 1-allyloxy-6- [1- (4-tert-butyl-cyclopenta-1,4-dienyl) -1-methyl-ethyl] -2- Phenylbenzene, 2-allyloxy-
1-tert-butyldimethylsilyl-3- [1- (4
-Tert-butyl-cyclopenta-1,4-dienyl) -1-methyl-ethyl] -5-methylbenzene, 2
-Allyloxy-3- [1- (4-tert-butylcyclopenta-1,4-dienyl) -1-methyl-ethyl]
-5-methyl-1-trimethylsilylbenzene, 1-allyloxy-6-tert-butyl-2- [1- (4-t
tert-butyl-cyclopenta-1,4-dienyl)-
1-methyl-ethyl] -4-methoxybenzene, 4-allyloxy-5-tert-butyl-1-chloro-3-
[1- (4-tert-butyl-cyclopenta-1,4
-Dienyl) -1-methyl-ethyl] benzene, 1-allyloxy-6-tert-butyl-2- [1- (4-t
tert-butyl-cyclopenta-1,4-dienyl)-
1-methyl-ethyl] benzene,

1-allyloxy-2- [1- (2,3,
4,5-tetramethyl-cyclopenta-1,4-dienyl) -1-methyl-ethyl] benzene, 1-allyloxy-4,6-dimethyl-2- [1- (2,3,4,5-tetramethyl) -Cyclopenta-1,4-dienyl) -1-
Methyl-ethyl] benzene, 1-allyloxy-6-te
rt-butyl-4-methyl-2- [1- (2,3,4,
5-tetramethyl-cyclopenta-1,4-dienyl)
-1-methyl-ethyl] benzene, 1-allyloxy-2
-Phenyl-6- [1- (2,3,4,5-tetramethyl-cyclopenta-1,4-dienyl) -1-methyl-
Ethyl] benzene, 2-allyloxy-1-tert-butyldimethylsilyl-5-methyl-3- [1- (2,
3,4,5-tetramethyl-cyclopenta-1,4-dienyl) -1-methyl-ethyl] benzene, 2-allyloxy-5-methyl-3- [1- (2,3,4,5-tetramethyl) -Cyclopenta-1,4-dienyl) -1-methyl-ethyl] -1-trimethylsilylbenzene, 1-
Allyloxy-6-tert-butyl-4-methoxy-2
-[1- (2,3,4,5-tetramethyl-cyclopenta-1,4-dienyl) -1-methyl-ethyl] benzene, 4-allyloxy-5-tert-butyl-1-chloro-3- [ 1- (2,3,4,5-tetramethyl-cyclopenta-1,4-dienyl) -1-methyl-ethyl]
Benzene, 1-allyloxy-6-tert-butyl-2
-[1- (2,3,4,5-tetramethyl-cyclopenta-1,4-dienyl) -1-methyl-ethyl] benzene,

1-allyloxy-2- [1- (3-trimethylsilyl-cyclopenta-1,4-dienyl) -1-
Methyl-ethyl] benzene, 1-allyloxy-4,6-
Dimethyl-2- [1- (3-trimethylsilyl-cyclopenta-1,4-dienyl) -1-methyl-ethyl] benzene, 1-allyloxy-6-tert-butyl-4-
Methyl-2- [1- (3-trimethylsilyl-cyclopenta-1,4-dienyl) -1-methyl-ethyl] benzene, 1-allyloxy-2-phenyl-6- [1- (3
-Trimethylsilyl-cyclopenta-1,4-dienyl) -1-methyl-ethyl] benzene, 2-allyloxy-1-tert-butyldimethylsilyl-5-methyl-
3- [1- (3-trimethylsilyl-cyclopenta-
1,4-dienyl) -1-methyl-ethyl] benzene,
2-allyloxy-5-methyl-1-trimethylsilyl-
3- [1- (3-trimethylsilyl-cyclopenta-
1,4-dienyl) -1-methyl-ethyl] benzene,
1-allyloxy-6-tert-butyl-4-methoxy-2- [1- (3-trimethylsilyl-cyclopenta-
1,4-dienyl) -1-methyl-ethyl] benzene,
4-allyloxy-5-tert-butyl-1-chloro-
3- [1- (3-trimethylsilyl-cyclopenta-
1,4-dienyl) -1-methyl-ethyl] benzene,
1-allyloxy-6-tert-butyl-2- [1-
(3-trimethylsilyl-cyclopenta-1,4-dienyl) -1-methyl-ethyl] benzene,

1-allyloxy-2- [1- (cyclopenta-1,4-dienyl) -1-ethyl-propyl] benzene, 1-allyloxy-2- [1- (cyclopenta-
1,4-dienyl) -1-ethyl-propyl] -4,6
-Dimethylbenzene, 1-allyloxy-6-tert-
Butyl-2- [1- (cyclopenta-1,4-dienyl) -1-ethyl-propyl] -4-methylbenzene,
1-allyloxy-6- [1- (cyclopenta-1,4-
Dienyl) -1-ethyl-propyl] -2-phenylbenzene, 2-allyloxy-1-tert-butyldimethylsilyl-3- [1- (cyclopenta-1,4-dienyl) -1-ethyl-propyl] -5 -Methylbenzene,
2-allyloxy-3- [1- (cyclopenta-1,4-
Dienyl) -1-ethyl-propyl] -5-methyl-1
-Trimethylsilylbenzene, 1-allyloxy-6-t
ert-butyl-2- [1- (cyclopenta-1,4-
Dienyl) -1-ethyl-propyl] -4-methoxybenzene, 4-allyloxy-5-tert-butyl-1-
Chloro-3- [1- (cyclopenta-1,4-dienyl) -1-ethyl-propyl] -benzene, 1-allyloxy-6-tert-butyl-2- [1- (cyclopenta-1,4-dienyl) -1-ethyl-propyl] benzene,

1-allyloxy-2- [1- (cyclopenta-1,4-dienyl) -1,1-diphenylmethyl]
Benzene, 1-allyloxy-2- [1- (cyclopenta-1,4-dienyl) -1,1-diphenylmethyl]-
4,6-dimethylbenzene, 1-allyloxy-6-te
rt-butyl-2- [1- (cyclopenta-1,4-dienyl) -1,1-diphenylmethyl] -4-methylbenzene, 1-allyloxy-2- [1- (cyclopenta-
1,4-dienyl) -1,1-diphenylmethyl] -6
-Phenylbenzene, 2-allyloxy-1-tert-
Butyldimethylsilyl-3- [1- (cyclopenta-
1,4-dienyl) -1,1-diphenylmethyl] -5
-Methylbenzene, 2-allyloxy-3-[(cyclopenta-1,4-dienyl) -1,1-diphenylmethyl] -5-methyl-1-trimethylsilylbenzene, 1
-Allyloxy-6-tert-butyl-2-[(cyclopenta-1,4-dienyl) -1,1-diphenylmethyl] -4-methoxybenzene, 4-allyloxy-5-t
tert-butyl-1-chloro-3-[(cyclopenta-
1,4-dienyl) -1,1-diphenylmethyl] benzene, 1-allyloxy-6-tert-butyl-2-
[(Cyclopenta-1,4-dienyl) -1,1-diphenylmethyl] benzene and the methoxy or allyloxy of these compounds are changed to ethoxy, benzyloxy, trimethylsilyloxy, tert-butyldimethylsilyloxy, methoxymethoxy Compound,
Cyclopenta-1,4-dienyl is converted to dimethylcyclopenta-1,4-dienyl, trimethylcyclopenta-1,
4-dienyl, n-butylcyclopenta-1,4-dienyl, tert-butyldimethylsilylcyclopenta-
1,4-dienyl, indenyl, a compound changed to fluorenyl, 1-methoxybenzene is converted to 1-methoxy-6-
Methylbenzene, 1-methoxy-4,6-di-tert
General formula (2a) such as -butylbenzene, 1-methoxy-4-methyl-6-phenylbenzene, 1-tert-butyldimethylsilyl-2-methoxybenzene, and a compound modified to 2-methoxy-1-trimethylsilylbenzene. (In the formula, Cp ² , A, R ¹ , R ² , R ³ , R ⁴ , R ⁵ ,
R ⁶ and R ⁷ each have the same meaning as described above. ) And a substituted cyclopentadienyl compound (hereinafter referred to as compound [2a]), and

(Cyclopenta-1,3-dienyl) (2
-Methoxyphenyl) dimethylsilane, (cyclopenta-1,3-dienyl) (2-methoxy-3-methylphenyl) dimethylsilane, (cyclopenta-1,3-dienyl) (2-methoxy-3,5-dimethylphenyl) Dimethylsilane, (3-tert-butyl-2-methoxyphenyl) (cyclopenta-1,3-dienyl) dimethylsilane, (3-tert-butyl-2-methoxy-5)
-Methylphenyl) (cyclopenta-1,3-dienyl) dimethylsilane, (3,5-di-tert-butyl-2-methoxyphenyl) (cyclopenta-1,3-dienyl) dimethylsilane, (cyclopenta-1,3) -Dienyl) (2-methoxy-5-methyl-3-phenylphenyl) dimethylsilane, (cyclopenta-1,3-dienyl) (2-methoxy-5-methyl-3-trimethylsilylphenyl) dimethylsilane, (3-tert -Butyldimethylsilyl-2-methoxy-5-methylphenyl) (cyclopenta-1,3-dienyl) dimethylsilane, (3,5-diamyl-2-methoxyphenyl) (cyclopenta-1,3-dienyl) dimethylsilane, (3
-Tert-butyl-2,5-dimethoxyphenyl)
(Cyclopenta-1,3-dienyl) dimethylsilane,
(5-tert-butyl-3-chloro-6-methoxyphenyl) (cyclopenta-1,3-dienyl) dimethylsilane, (2-methoxyphenyl) (methylcyclopenta-1,3-dienyl) dimethylsilane,

(2-methoxy-3-methylphenyl)
(Methylcyclopenta-1,3-dienyl) dimethylsilane, (2-methoxy-3,5-dimethylphenyl)
(Methylcyclopenta-1,3-dienyl) dimethylsilane, (3-tert-butyl-2-methoxyphenyl) (methylcyclopenta-1,3-dienyl) dimethylsilane, (3-tert-butyl-2-methoxy) -5
-Methylphenyl) (methylcyclopenta-1,3-dienyl) dimethylsilane, (3,5-di-tert-butyl-2-methoxyphenyl) (methylcyclopenta-
(1,3-dienyl) dimethylsilane, (2-methoxy-
5-methyl-3-phenylphenyl) (methylcyclopenta-1,3-dienyl) dimethylsilane, (2-methoxy-5-methyl-3-trimethylsilylphenyl)
(Methylcyclopenta-1,3-dienyl) dimethylsilane, (3-tert-butyldimethylsilyl-2-methoxy-5-methylphenyl) (methylcyclopenta-
(1,3-dienyl) dimethylsilane, (3,5-diamyl-2-methoxyphenyl) (methylcyclopenta-
(1,3-dienyl) dimethylsilane, (3-tert-
Butyl-2,5-dimethoxyphenyl) (methylcyclopenta-1,3-dienyl) dimethylsilane, (5-t
tert-butyl-3-chloro-6-methoxyphenyl)
(Methylcyclopenta-1,3-dienyl) dimethylsilane,

(2-methoxyphenyl) (2, 3, 4,
5-tetramethylcyclopenta-1,3-dienyl) dimethylsilane, (2-methoxy-3-methylphenyl)
(2,3,4,5-tetramethylcyclopenta-1,3
-Dienyl) dimethylsilane, (2-methoxy-3,5
-Dimethylphenyl) (2,3,4,5-tetramethylcyclopenta-1,3-dienyl) dimethylsilane,
(3-tert-butyl-2-methoxyphenyl)
(2,3,4,5-tetramethylcyclopenta-1,3
-Dienyl) dimethylsilane, (3-tert-butyl-2-methoxy-5-methylphenyl) (2,3,4,
5-tetramethylcyclopenta-1,3-dienyl) dimethylsilane, (3,5-di-tert-butyl-2-)
Methoxyphenyl) (2,3,4,5-tetramethylcyclpenta-1,3-dienyl) dimethylsilane, (2-
Methoxy-5-methyl-3-phenylphenyl) (2,
3,4,5-tetramethylcyclopenta-1,3-dienyl) dimethylsilane, (2-methoxy-5-methyl-
3-trimethylsilylphenyl) (2,3,4,5-tetramethylcyclopenta-1,3-dienyl) dimethylsilane, (3-tert-butyldimethylsilyl-2-
Methoxy-5-methylphenyl) (2,3,4,5-tetramethylcyclopenta-1,3-dienyl) dimethylsilane, (3,5-diamyl-2-methoxyphenyl)
(2,3,4,5-tetramethylcyclopenta-1,3
-Dienyl) dimethylsilane, (3-tert-butyl-2,5-dimethoxyphenyl) (2,3,4,5-tetramethylcyclopenta-1,3-dienyl) dimethylsilane, (5-tert-butyl- 3-chloro-6-methoxyphenyl) (2,3,4,5-tetramethylcyclopenta-1,3-dienyl) dimethylsilane,

(Tert-butylcyclopenta-1,3
-Dienyl) (2-methoxyphenyl) dimethylsilane, (tert-butylcyclopenta-1,3-dienyl) (2-methoxy-3-methylphenyl) dimethylsilane, (tert-butylcyclopenta-1,3-dienyl) ) (2-methoxy-3,5-dimethylphenyl) dimethylsilane, (tert-butylcyclopenta-1,
3-dienyl) (3-tert-butyl-2-methoxyphenyl) dimethylsilane, (tert-butylcyclopenta-1,3-dienyl) (3-tert-butyl-
2-methoxy-5-methylphenyl) dimethylsilane,
(Tert-butylcyclopenta-1,3-dienyl)
(3,5-di-tert-butyl-2-methoxyphenyl) dimethylsilane, (tert-butylcyclopenta-1,3-dienyl) (2-methoxy-5-methyl-3
-Phenylphenyl) dimethylsilane, (tert-butylcyclopenta-1,3-dienyl) (2-methoxy-5-methyl-3-trimethylsilylphenyl) dimethylsilane, (tert-butylcyclopenta-1,3-
Dienyl) (3-tert-butyldimethylsilyl-2
-Methoxy-5-methylphenyl) dimethylsilane,
(3,5-diamyl-2-methoxyphenyl) (ter
t-butylcyclopenta-1,3-dienyl) dimethylsilane, (tert-butylcyclopenta-1,3-dienyl) (3-tert-butyl-2,5-dimethoxyphenyl) dimethylsilane, (5-tert- Butyl-
3-chloro-6-methoxyphenyl) (tert-butylcyclopenta-1,3-dienyl) dimethylsilane,

(2-Methoxyphenyl) (trimethylsilylcyclopenta-1,3-dienyl) dimethylsilane, (2-methoxy-3-methylphenyl) (trimethylsilylcyclopenta-1,3-dienyl) dimethylsilane, (2- Methoxy-3,5-dimethylphenyl)
(Trimethylsilylcyclopenta-1,3-dienyl)
Dimethylsilane, (3-tert-butyl-2-methoxyphenyl) (trimethylsilylcyclopenta-1,3
-Dienyl) dimethylsilane, (3-tert-butyl-2-methoxy-5-methylphenyl) (trimethylsilylcyclopenta-1,3-dienyl) dimethylsilane,

(3,5-di-tert-butyl-2-methoxyphenyl) (trimethylsilylcyclopenta-
(1,3-dienyl) dimethylsilane, (2-methoxy-
5-methyl-3-phenylphenyl) (trimethylsilylcyclopenta-1,3-dienyl) dimethylsilane,
(2-Methoxy-5-methyl-3-trimethylsilylphenyl) (trimethylsilylcyclopenta-1,3-dienyl) dimethylsilane, (3-tert-butyldimethylsilyl-2-methoxy-5-methylphenyl) (trimethylsilylcyclopenta) -1,3-dienyl) dimethylsilane, (3,5-diamyl-2-methoxyphenyl) (trimethylsilylcyclopenta-1,3-dienyl) dimethylsilane, (3-tert-butyl-2,5
-Dimethoxyphenyl) (trimethylsilylcyclopenta-1,3-dienyl) dimethylsilane, (5-ter
t-butyl-3-chloro-6-methoxyphenyl) (trimethylsilylcyclopenta-1,3-dienyl) dimethylsilane,

(Inden-1-yl) (2-methoxyphenyl) dimethylsilane, (inden-2-yl) (2
-Methoxyphenyl) dimethylsilane, (indene-1)
-Yl) (2-methoxy-3-methylphenyl) dimethylsilane, (inden-2-yl) (2-methoxy-3
-Methylphenyl) dimethylsilane, (indene-1-
Yl) (2-methoxy-3,5-dimethylphenyl) dimethylsilane, (inden-2-yl) (2-methoxy-3,5-dimethylphenyl) dimethylsilane, (3-
tert-butyl-2-methoxyphenyl) (inden-1-yl) dimethylsilane, (3-tert-butyl-2-methoxyphenyl) (inden-2-yl) dimethylsilane, (3-tert-butyl-2- Methoxy-
5-methylphenyl) (inden-1-yl) dimethylsilane, (3-tert-butyl-2-methoxy-5-)
Methylphenyl) (inden-2-yl) dimethylsilane, (3,5-di-tert-butyl-2-methoxyphenyl) (inden-1-yl) dimethylsilane,
(3,5-di-tert-butyl-2-methoxyphenyl) (inden-2-yl) dimethylsilane, (inden-1-yl) (2-methoxy-5-methyl-3-phenylphenyl) dimethylsilane , (Inden-2-yl) (2-methoxy-5-methyl-3-phenylphenyl) dimethylsilane, (Inden-1-yl) (2-methoxy-5-methyl-3-trimethylsilylphenyl)
Dimethylsilane, (inden-2-yl) (2-methoxy-5-methyl-3-trimethylsilylphenyl) dimethylsilane, (3-tert-butyldimethylsilyl-
2-methoxy-5-methylphenyl) (indene-1-
Yl) dimethylsilane, (3-tert-butyldimethylsilyl-2-methoxy-5-methylphenyl) (inden-2-yl) dimethylsilane, (3,5-diamyl-2-methoxyphenyl) (indene-1- Yl) dimethylsilane, (3,5-diamyl-2-methoxyphenyl) (inden-2-yl) dimethylsilane, (3-t
tert-butyl-2,5-dimethoxyphenyl) (inden-1-yl) dimethylsilane, (3-tert-butyl-2,5-dimethoxyphenyl) (indene-2-
Yl) dimethylsilane, (5-tert-butyl-3-
Chloro-6-methoxyphenyl) (inden-1-yl) dimethylsilane, (5-tert-butyl-3-chloro-6-methoxyphenyl) (inden-2-yl)
Dimethylsilane,

(9H-fluoren-9-yl) (2-methoxyphenyl) dimethylsilane, (9H-fluoren-9-yl) (2-methoxy-3-methylphenyl) dimethylsilane, (9H-fluorene-9- Ill) (2-
Methoxy-3,5-dimethylphenyl) dimethylsilane, (3-tert-butyl-2-methoxyphenyl)
(9H-fluoren-9-yl) dimethylsilane, (3
-Tert-butyl-2-methoxy-5-methylphenyl) (9H-fluoren-9-yl) dimethylsilane,
(3,5-di-tert-butyl-2-methoxyphenyl) (9H-fluoren-9-yl) dimethylsilane,
(9H-fluoren-9-yl) (2-methoxy-5-
Methyl-3-phenylphenyl) dimethylsilane, (9
H-fluoren-9-yl) (2-methoxy-5-methyl-3-trimethylsilylphenyl) dimethylsilane,
(3-tert-butyldimethylsilyl-2-methoxy-5-methylphenyl) (9H-fluoren-9-yl) dimethylsilane, (3,5-diamyl-2-methoxyphenyl) (9H-fluoren-9-yl) ) Dimethylsilane, (3-tert-butyl-2,5-dimethoxyphenyl) (9H-fluoren-9-yl) dimethylsilane, (5-tert-butyl-3-chloro-6-methoxyphenyl) (9H-fluorene) -9-yl) dimethylsilane,

(2-Aryloxyphenyl) (cyclopenta-1,3-dienyl) dimethylsilane, (2-allyloxy-3-methylphenyl) (cyclopenta-1,3-)
(Dienyl) dimethylsilane, (2-allyloxy-3,5)
-Dimethylphenyl) (cyclopenta-1,3-dienyl) dimethylsilane, (2-allyloxy-3-tert)
-Butylphenyl) (cyclopenta-1,3-dienyl) dimethylsilane, (2-allyloxy-3-tert)
-Butyl-5-methylphenyl) (cyclopenta-1,
3-dienyl) dimethylsilane, (2-allyloxy-
3,5-di-tert-butylphenyl) (cyclopenta-1,3-dienyl) dimethylsilane, (2-allyloxy-5-methyl-3-phenylphenyl) (cyclopenta-1,3-dienyl) dimethylsilane, ( 2-allyloxy-5-methyl-3-trimethylsilylphenyl)
(Cyclopenta-1,3-dienyl) dimethylsilane,
(2-allyloxy-3-tert-butyldimethylsilyl-5-methylphenyl) (cyclopenta-1,3-dienyl) dimethylsilane, (2-allyloxy-3,5-
Diamylphenyl) (cyclopenta-1,3-dienyl) dimethylsilane, (2-allyloxy-3-tert)
-Butyl-5-methoxyphenyl) (cyclopenta-
(1,3-dienyl) dimethylsilane, (6-allyloxy-5-tert-butyl-3-chlorophenyl) (cyclopenta-1,3-dienyl) dimethylsilane,

(2-allyloxyphenyl) (methylcyclopenta1,3-dienyl) dimethylsilane, (2-allyloxy-3-methylphenyl) (methylcyclopenta1,3-dienyl) dimethylsilane, (2-allyloxy) -3,5-Dimethylphenyl) (methylcyclopenta1,3-dienyl) dimethylsilane, (2-allyloxy-3-tert-butylphenyl) (methylcyclopenta1,3-dienyl) dimethylsilane, (2-allyloxy) -3-tert-butyl-5-methylphenyl) (methylcyclopenta1,3-dienyl) dimethylsilane,
(2-allyloxy-3,5-di-tert-butylphenyl) (methylcyclopenta-1,3-dienyl) dimethylsilane, (2-allyloxy-5-methyl-3-phenylphenyl) (methylcyclopenta1,3 -Dienyl)
Dimethylsilane, (2-allyloxy-5-methyl-3-
Trimethylsilylphenyl) (methylcyclopenta1,
3-dienyl) dimethylsilane, (2-allyloxy-3
-Tert-butyldimethylsilyl-5-methylphenyl) (methylcyclopenta1,3-dienyl) dimethylsilane, (2-allyloxy-3,5-diamylphenyl) (methylcyclopenta1,3-dienyl) dimethylsilane , (2-allyloxy-3-tert-butyl-5
-Methoxyphenyl) (methylcyclopenta-1,3-dienyl) dimethylsilane, (6-allyloxy-5-te
rt-butyl-3-chlorophenyl) (methylcyclopenta1,3-dienyl) dimethylsilane,

(2-allyloxyphenyl) (2,3,
4,5-tetramethylcyclopenta-1,3-dienyl) dimethylsilane, (2-allyloxy-3-methylphenyl) (2,3,4,5-tetramethylcyclopenta-1,3-dienyl) dimethylsilane , (2-allyloxy-3,5-dimethylphenyl) (2,3,4,5-tetramethylcyclopenta-1,3-dienyl) dimethylsilane, (2-allyloxy-3-tert-butylphenyl) (2 , 3,4,5-tetramethylcyclopenta-
(1,3-dienyl) dimethylsilane, (2-allyloxy-3-tert-butyl-5-methylphenyl) (2
3,4,5-tetramethylcyclopenta-1,3-dienyl) dimethylsilane, (2-allyloxy-3,5-di-tert-butylphenyl) (2,3,4,5-tetramethylcyclopenta- (1,3-dienyl) dimethylsilane, (2-allyloxy-5-methyl-3-phenylphenyl) (2,3,4,5-tetramethylcyclopenta-1,3-dienyl) dimethylsilane, (2-allyloxy -5-methyl-3-trimethylsilylphenyl)
(2,3,4,5-tetramethylcyclopenta-1,3
-Dienyl) dimethylsilane, (2-allyloxy-3-
tert-butyldimethylsilyl-5-methylphenyl) (2,3,4,5-tetramethylcyclopenta-
(1,3-dienyl) dimethylsilane, (2-allyloxy-3,5-diamylphenyl) (2,3,4,5-tetramethylcyclopenta-1,3-dienyl) dimethylsilane, (2-allyloxy- 3-tert-butyl-5-
(Methoxyphenyl) (2,3,4,5-tetramethylcyclopenta-1,3-dienyl) dimethylsilane, (6
-Allyloxy-5-tert-butyl-3-chlorophenyl) (2,3,4,5-tetramethylcyclopenta-
1,3-dienyl) dimethylsilane,

(2-allyloxyphenyl) (tert-
Butylcyclopenta-1,3-dienyl) dimethylsilane, (2-allyloxy-3-methylphenyl) (ter
t-butylcyclopenta-1,3-dienyl) dimethylsilane, (2-allyloxy-3,5-dimethylphenyl) (tert-butylcyclopenta-1,3-dienyl) dimethylsilane, (2-allyloxy-3- tert
-Butylphenyl) (tert-butylcyclopenta-
1,3-dienyl) dimethylsilane, (2-allyloxy-3-tert-butyl-5-methylphenyl) (te
rt-butylcyclopenta-1,3-dienyl) dimethylsilane, (2-allyloxy-3,5-di-tert-
Butylphenyl) (tert-butylcyclopenta-
(1,3-dienyl) dimethylsilane, (2-allyloxy-5-methyl-3-phenylphenyl) (tert-butylcyclopenta-1,3-dienyl) dimethylsilane, (2-allyloxy-5-methyl-3- Trimethylsilylphenyl) (tert-butylcyclopenta-1,
3-dienyl) dimethylsilane, (2-allyloxy-3
-Tert-butyldimethylsilyl-5-methylphenyl) (tert-butylcyclopenta-1,3-dienyl) dimethylsilane, (2-allyloxy-3,5-diamylphenyl) (tert-butylcyclopenta-1,
3-dienyl) dimethylsilane, (2-allyloxy-3
-Tert-butyl-5-methoxyphenyl) (ter
t-butylcyclopenta-1,3-dienyl) dimethylsilane, (6-allyloxy-5-tert-butyl-3)
-Chlorophenyl) (tert-butylcyclopenta-
1,3-dienyl) dimethylsilane,

(2-allyloxyphenyl) (trimethylsilylcyclopenta-1,3-dienyl) dimethylsilane, (2-allyloxy-3-methylphenyl) (trimethylsilylcyclopenta-1,3-dienyl) dimethylsilane, (2 -Allyloxy-3,5-dimethylphenyl) (trimethylsilylcyclopenta-1,3-dienyl) dimethylsilane, (2-allyloxy-3-tert)
-Butylphenyl) (trimethylsilylcyclopenta-
(1,3-dienyl) dimethylsilane, (2-allyloxy-3-tert-butyl-5-methylphenyl) (trimethylsilylcyclopenta-1,3-dienyl) dimethylsilane, (2-allyloxy-3,5-di- tert-
Butylphenyl) (trimethylsilylcyclopenta-
(1,3-dienyl) dimethylsilane, (2-allyloxy-5-methyl-3-phenylphenyl) (trimethylsilylcyclopenta-1,3-dienyl) dimethylsilane, (2-allyloxy-5-methyl-3-trimethylsilylphenyl) ) (Trimethylsilylcyclopenta-1,
3-dienyl) dimethylsilane, (2-allyloxy-3
-Tert-butyldimethylsilyl-5-methylphenyl) (trimethylsilylcyclopenta-1,3-dienyl) dimethylsilane, (2-allyloxy-3,5-diamylphenyl) (trimethylsilylcyclopenta-1,
3-dienyl) dimethylsilane, (2-allyloxy-3
-Tert-butyl-5-methoxyphenyl) (trimethylsilylcyclopenta-1,3-dienyl) dimethylsilane, (6-allyloxy-5-tert-butyl-3)
-Chlorophenyl) (trimethylsilylcyclopenta-
1,3-dienyl) dimethylsilane,

(2-allyloxyphenyl) (indene-
1-yl) dimethylsilane, (2-allyloxyphenyl) (inden-2-yl) dimethylsilane, (2-allyloxy-3-methylphenyl) (inden-1-yl) dimethylsilane, (2-allyloxy-3) -Methylphenyl) (inden-2-yl) dimethylsilane, (2
-Allyloxy-3,5-dimethylphenyl) (inden-1-yl) dimethylsilane, (2-allyloxy-3,
5-dimethylphenyl) (inden-2-yl) dimethylsilane, (2-allyloxy-3-tert-butylphenyl) (inden-1-yl) dimethylsilane, (2
-Allyloxy-3-tert-butylphenyl) (inden-2-yl) dimethylsilane, (2-allyloxy-
3-tert-butyl-5-methylphenyl) (inden-1-yl) dimethylsilane, (2-allyloxy-3)
-Tert-butyl-5-methylphenyl) (inden-2-yl) dimethylsilane, (2-allyloxy-3,
5-di-tert-butylphenyl) (indene-1-
Yl) dimethylsilane, (2-allyloxy-3,5-di-tert-butylphenyl) (inden-2-yl)
Dimethylsilane, (2-allyloxy-5-methyl-3-
Phenylphenyl) (inden-1-yl) dimethylsilane, (2-allyloxy-5-methyl-3-phenylphenyl) (inden-2-yl) dimethylsilane, (2
-Allyloxy-5-methyl-3-trimethylsilylphenyl) (inden-1-yl) dimethylsilane, (2-
Allyloxy-5-methyl-3-trimethylsilylphenyl) (inden-2-yl) dimethylsilane, (2-allyloxy-3-tert-butyldimethylsilyl-5-
Methylphenyl) (inden-1-yl) dimethylsilane, (2-allyloxy-3-tert-butyldimethylsilyl-5-methylphenyl) (inden-2-yl)
Dimethylsilane, (2-allyloxy-3,5-diamylphenyl) (inden-1-yl) dimethylsilane,
(2-allyloxy-3,5-diamylphenyl) (inden-2-yl) dimethylsilane, (2-allyloxy-
3-tert-butyl-5-methoxyphenyl) (inden-1-yl) dimethylsilane, (2-allyloxy-
3-tert-butyl-5-methoxyphenyl) (inden-2-yl) dimethylsilane, (6-allyloxy-
5-tert-butyl-3-chlorophenyl) (inden-1-yl) dimethylsilane, (6-allyloxy-5
-Tert-butyl-3-chlorophenyl) (inden-2-yl) dimethylsilane,

(2-allyloxyphenyl) (9H-fluoren-9-yl) dimethylsilane, (2-allyloxy-3-methylphenyl) (9H-fluoren-9-yl) dimethylsilane, (2-allyloxy-3) , 5-Dimethylphenyl) (9H-fluoren-9-yl) dimethylsilane, (2-allyloxy-3-tert-butylphenyl) (9H-fluoren-9-yl) dimethylsilane, (2-allyloxy-3-tert) -Butyl-5-methylphenyl) (9H-fluoren-9-yl) dimethylsilane, (2-allyloxy-3,5-di-tert-
(Butylphenyl) (9H-fluoren-9-yl) dimethylsilane, (2-allyloxy-5-methyl-3-phenylphenyl) (9H-fluoren-9-yl) dimethylsilane, (2-allyloxy-5-methyl- 3-trimethylsilylphenyl) (9H-fluoren-9-yl)
Dimethylsilane, (2-allyloxy-3-tert-butyldimethylsilyl-5-methylphenyl) (9H-fluoren-9-yl) dimethylsilane, (2-allyloxy-3,5-diamylphenyl) (9H-fluorene −
9-yl) dimethylsilane, (2-allyloxy-3-t)
tert-butyl-5-methoxyphenyl) (9H-fluoren-9-yl) dimethylsilane, (6-allyloxy-5-tert-butyl-3-chlorophenyl) (9H
-Fluoren-9-yl) dimethylsilane, (1-allyloxynaphthalen-2-yl) dimethyl (1,2,3,
4 tetramethylcyclopentadienyl) silane, etc.,
The methoxy or allyloxy of these compounds is replaced by benzyloxy, ethoxy, trimethylsilyloxy, tert.
-Butyldimethylsilyloxy, a compound changed to methoxymethoxy, dimethylsilane to diethylsilane, diphenylsilane, a compound changed to dimethoxysilane, cyclopentadienyl to dimethylcyclopentadienyl,
Trimethylcyclopentadienyl, n-propylcyclopentadienyl, isopropylcyclopentadienyl,
n-butylcyclopentadienyl, isobutylcyclopentadienyl, sec-butylcyclopentadienyl,
tert-butyldimethylsilylcyclopentadienyl, phenylcyclopentadienyl, a compound obtained by changing to methylindenyl, 2-methoxyphenyl to 3-phenyl-2-methoxyphenyl, 3-trimethylsilyl-2
General formula (2b) such as a compound modified to -methoxyphenyl or 3-tert-butyldimethylsilyl-2-methoxyphenyl (In the formula, B'is the 14th element of the periodic table of elements other than carbon atoms.
A group element is shown, and A, Cp ² , R ¹ , R ² , R ³ ,
R ⁴ , R ⁵ , R ⁶ and R ⁷ each have the same meaning as described above. And a substituted cyclopentadienyl compound (hereinafter referred to as compound [2b]).

These compounds [2] have the substituent C
There may be a plurality of isomers derived from the difference in the position of the substituent of the cyclopentadiene skeleton and the position of the double bond in p ^2, but the compound [2] in the present invention includes all these isomers. Be done.

In the compound [3], a hydrogen atom represented by the substituents X ³ and X ⁴ , a halogen atom, an alkyl group having 1 to 20 carbon atoms which may be substituted with a halogen atom, and a halogen atom are substituted. 7 good carbon atoms
To aralkyl group having 20 to 20 carbon atoms, aryl group having 6 to 20 carbon atoms optionally substituted with halogen atom, substituted silyl group having 1 to 20 carbon atoms optionally substituted with halogen atom, substituted with halogen atom Optionally substituted alkoxy group having 1 to 20 carbon atoms, aralkyloxy group having 1 to 20 carbon atoms which may be substituted with a halogen atom, and 1 to 20 carbon atoms optionally substituted with a halogen atom.
Examples of the aryloxy group and the disubstituted amino group having 2 to 20 carbon atoms include the substituents X ¹ and X ² in the compound [1].
The same as those mentioned above can be mentioned.

Examples of the compound [3] include titanium halides such as titanium tetrachloride, titanium tetrabromide and titanium tetraiodide, tetrakis (dimethylamino) titanium, dichlorobis (dimethylamino) titanium, trichloro (dimethylamino). Titanium, alkoxyamido titanium such as tetrakis (diethylamino) titanium, tetraisopropoxy titanium, tetra-n-butoxy titanium, dichlorodiisopropoxy titanium, alkoxy titanium such as trichloroisopropoxy titanium and titanium of the above compounds are changed to zirconium and hafnium. And the like, and the amount thereof is usually 0.5 to 3 with respect to the compound [2].
The molar ratio is in the range of preferably 0.7 to 1.5.

Examples of the base include methyllithium, ethyllithium, n-butyllithium, sec-butyllithium, tert-butyllithium, lithium trimethylsilylacetylide, lithium acetylide, trimethylsilylmethyllithium, vinyllithium, phenyllithium and allyllithium. An organic alkali metal compound such as an organic lithium compound can be used, and the amount thereof used is usually in the range of 0.5 to 5 mol times that of the compound [2].

It is also possible to use an amine compound together with a base. Examples of such amine compounds include primary amine compounds such as methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, tert-butylamine, n-octylamine, n-decylamine, aniline and ethylenediamine, dimethylamine. , Diethylamine, di-n-propylamine, di-n-propylamine, di-n-butylamine,
Secondary amine compounds such as di-tert-butylamine, di-n-octylamine, di-n-decylamine, pyrrolidine, hexamethyldisilazane, diphenylamine, trimethylamine, triethylamine, tri-n-
Propylamine, tri-n-butylamine, diisopropylethylamine, tri-n-octylamine, tri-
Examples include tertiary amine compounds such as n-decylamine, triphenylamine, N, N-dimethylaniline, N, N, N ′, N′-tetramethylethylenediamine, N-methylpyrrolidine, and 4-dimethylaminopyridine.
The amount of the amine compound used is usually 10 mol times or less, preferably 0.5 to 10 mol times, and more preferably 1 to 3 mol times the base.

The reaction is usually performed 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. Is mentioned. These 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
It is in the range of 50 times the weight.

This step can be usually carried out by adding the compound [2] and the base to the solvent and then adding the compound [3]. A solid may be precipitated after adding the compound [2] and the base. In this case, the solid taken out from the reaction system may be added to the same solvent as described above, and then the compound [3] may be added. .. Further, the compound [2], the base and the compound [3] may be simultaneously added to the solvent. The reaction temperature is generally -100 ° C or higher and the boiling point of the solvent or lower, preferably -80 to 100 ° C. The reaction system is preferably shielded from the light in terms of the yield of the compound [1].

The reaction mixture thus obtained is subjected to a conventional method, for example, the formed precipitate is filtered off, and the filtrate is concentrated to give compound [1].
The target compound [1] can be obtained by, for example, a method in which the compound is precipitated and then collected by filtration.

The compound [2] used in the above-mentioned [Step 1] includes the compound [2a] and the compound [2b] as described above. The compound [2a] is [Step 2] as shown below. Can be manufactured through.

[Step 2] General Formula (9) (In the formula, A, R ¹ , R ² , R ³ , R ⁴ , R ⁷ , and Y ⁴ have the same meanings as described above.) A halogenated aryl compound (hereinafter, compound)

It is referred to as [9]. ) And an organic alkali metal salt or magnesium metal, and then reacting with the general formula (4) (In the formula, Cp ³ represents a group having a cyclopentadienylidene skeleton, and R ⁵ and R ⁶ each have the same meaning as described above.) Referred to hereinbelow), and then with water to produce the compound [2a].

Compound

As [9], 1-bromo-2-methoxybenzene, 1-bromo-3-methyl-2-methoxybenzene, 1-bromo-3,5-dimethyl-2-methoxybenzene, 1-bromo-3-tert- Butyl-2
-Methoxybenzene, 1-bromo-3-tert-butyl-2-methoxy-5-methylbenzene, 1-bromo-
3,5-di-tert-butyl-2-methoxybenzene, 1-bromo-2-methoxy-3-phenylbenzene, 1-bromo-2-methoxy-5-methyl-3-phenylbenzene, 1-bromo-2 -Methoxy-3-trimethylsilylbenzene, 1-bromo-2-methoxy-5-
Methyl-3-trimethylsilylbenzene, 1-bromo-
3-tert-butyldimethylsilyl-2-methoxybenzene, 1-bromo-3-tert-butyldimethylsilyl-2-methoxy-5-methylbenzene, 1-bromo-3-tert-butyl-2,5-dimethoxybenzene , 1-bromo-3-tert-butyl-5-chloro-
2-methoxybenzene, 3,5-diamyl-1-bromo-2-methoxybenzene,

2-allyloxy-1-bromobenzene, 2
-Allyloxy-1-bromo-3-methylbenzene, 2-
Allyloxy-1-bromo-3,5-dimethylbenzene,
2-allyloxy-1-bromo-3-tert-butylbenzene, 2-allyloxy-1-bromo-3-tert-butyl-
Butyl-5-methylbenzene, 2-allyloxy-1-bromo-3,5-di-tert-butylbenzene, 2-allyloxy-1-bromo-3-phenylbenzene, 2-allyloxy-1-bromo-5-methyl -3-Phenylbenzene, 2-allyloxy-1-bromo-3-trimethylsilylbenzene, 2-allyloxy-1-bromo-5-methyl-3-trimethylsilylbenzene, 2-allyloxy-
1-Bromo-3-tert-butyldimethylsilylbenzene, 2-allyloxy-1-bromo-3-tert-butyldimethylsilyl-5-methylbenzene, 2-allyloxy-1-bromo-3-tert-butyl-5- Methoxybenzene, 2-allyloxy-1-bromo-3-ter
t-butyl-5-chlorobenzene, 2-allyloxy-
Examples include 3,5-diamyl-1-bromobenzene and 1-allyloxy-2-bromonaphthalene. Further, a compound in which methoxy or allyloxy is changed to benzyloxy, ethoxy, tert-butyldimethylsilyloxy, trimethylsilyloxy, methoxymethoxy,
A compound in which bromo is changed to chloro or iodo can be similarly exemplified.

Examples of the group having a cyclopentadienylidene skeleton represented by the substituent Cp ³ in the compound [4] include, for example, cyclopentadienylidene group, methylcyclopentadienylidene group, dimethylcyclopentadienylidene group and trimethyl. Cyclopentadienylidene group, tetramethylcyclopentadienylidene group, ethylcyclopentadienylidene group, n-propylcyclopentadienylidene group, isopropylcyclopentadienylidene group, n-butylcyclopentadienylidene group, sec −
Butylcyclopentadienylidene group, tert-butylcyclopentadienylidene group, n-pentylcyclopentadienylidene group, neopentylcyclopentadienylidene group, n-hexylcyclopentadienylidene group, n
-Octylcyclopentadienylidene group, phenylcyclopentadienylidene group, naphthylcyclopentadienylidene group, trimethylsilylcyclopentadienylidene group, triethylsilylcyclopentadienylidene group, t
ert-Butyldimethylsilylcyclopentadienylidene group, indenylidene group, methylindenylidene group, dimethylindenylidene group, ethylindenylidene group, n
-Propylindenylidene group, isopropylindenylidene group, n-butylindenylidene group, sec-butylindenylidene group, tert-butylindenylidene group, n-pentylindenylidene group, neopentylindenylidene group Group, n-hexylindenylidene group, n-octylindenylidene group, n-decylindenylidene group, phenylindenylidene group, methylphenylindenylidene group, naphthylindenylidene group, trimethylsilylindenylidene group , Triethylsilylindenylidene group, tert-butyldimethylsilylindenylidene group, tetrahydroindenylidene group, fluorenylidene group, methylfluorenylidene group, dimethylfluorenylidene group, ethylfluorenylidene group, diethylfluorenylidene group , N-Pro Le fluorenylidene group, a di -n
-Propylfluorenylidene group, isopropylfluorenylidene group, diisopropylfluorenylidene group, n-
Butylfluorenylidene group, sec-butylfluorenylidene group, tert-butylfluorenylidene group, di-
n-butylfluorenylidene group, di-sec-butylfluorenylidene group, di-tert-butylfluorenylidene group, n-pentylfluorenylidene group, neopentylfluorenylidene group, n-hexylfluorenylidene group , N-octylfluorenylidene group, n-decylfluorenylidene group, n-dodecylfluorenylidene group, phenylfluorenylidene group, di-phenylfluorenylidene group, methylphenylfluorenylidene group, naphthylfluorenylidene group Group, trimethylsilylfluorenylidene group, bis-trimethylsilylfluorenylidene group, triethylsilylfluorenylidene group, tert-butyldimethylsilylfluorenylidene group and the like, preferably cyclopentadienylidene group, methylcyclopentadiene group Anylidene , Tert- butyl cyclopentadienylidene group, tetramethyl cyclopentadienylidene group, indenylidene group, fluorenylidene group, and the like.

Examples of the compound [4] include 5-
Methylidene-cyclopenta-1,3-diene, 2-te
rt-Butyl-5-methylidene-cyclopenta-1,3
-Diene, 2-methyl-5-methylidene-cyclopenta-1,3-diene, 2-tert-butyldimerylsilyl-5-methylidene-cyclopenta-1,3-diene,
2-Trimethylsilyl-5-methylidene-cyclopenta-1,3-diene, 5-isopropylidene-cyclopenta-1,3-diene, 2-tert-butyl-5-isopropylidene-cyclopenta-1,3-diene, 2- Methyl-5-isopropylidene-cyclopenta-1,3-
Diene, 2-tert-butyldimerylsilyl-5-isopropylidene-cyclopenta-1,3-diene, 2-
Trimethylsilyl-5-isopropylidene-cyclopenta-1,3-diene, 5- (1-ethylpropylidene)
-Cyclopenta-1,3-diene, 2-tert-butyl-5- (1-ethylpropylidene) -cyclopenta-
1,3-diene, 2-methyl-5- (1-ethylpropylidene) -cyclopenta-1,3-diene, 2-ter
t-Butyldimerylsilyl-5- (1-ethylpropylidene) -cyclopenta-1,3-diene, 2-trimethylsilyl-5- (1-ethylpropylidene) -cyclopenta-1,3-diene, 5-diphenyl Methylidene-cyclopenta-1,3-diene, 2-tert-butyl-
5-diphenylmethylidene-cyclopenta-1,3-diene, 2-methyl-5-diphenylmethylidene-cyclopenta-1,3-diene, 2-tert-butyldimethylylsilyl-5-diphenylmethylidene-cyclopenta-
1,3-diene, 2-trimethylsilyl-5-diphenylmethylidene-cyclopenta-1,3-diene and the like can be mentioned. The amount of compound [4] used is the compound

It is usually 0.5 to 3 mol times, preferably 0.7 to 1.5, relative to [9].
It is in the range of molar times.

Examples of the organic alkali metal compound include methyllithium, ethyllithium, n-butyllithium, sec-butyllithium, tert-butyllithium, lithium trimethylsilylacetylide, lithium acetylide, trimethylsilylmethyllithium, vinyllithium, phenyllithium and allyl. Examples thereof include organic lithium compounds such as lithium. The amount of such organic alkali metal compound or metal magnesium used is

[9] is usually in the range of 0.5 to 5 moles, the amount of the organic alkali metal compound used is 0.9 to 2.2 moles, and the amount of the metal magnesium used is 0.9 to 1 It is preferably in the range of 0.2 mol times.

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. Is mentioned. These solvents may be used alone or in admixture of two or more, and the amount used is the compound

[9] is usually 1 to 200 times by weight, preferably 3 to
It is in the range of 50 times the weight.

In this step, the compound is usually used in the solvent.

[9] and an organic alkali metal compound or metal magnesium are added, and then compound [4] is added, followed by adding water or an acidic aqueous solution.

[9], the compound [4] and the organic alkali metal compound or metal magnesium may be added at the same time, and then water or an acidic aqueous solution may be added. The reaction temperature is usually -10
It is 0 ° C or higher and the boiling point of the solvent or lower, and in the case of using an organic alkali metal compound, it is in the range of -80 to 40 ° C.
When metallic magnesium is used, it is preferably in the range of 10 to 100 ° C. As an acidic aqueous solution,
For example, an ammonium chloride aqueous solution, hydrochloric acid, etc. may be mentioned. The amount of water or acidic aqueous solution used is the compound used

[9] is usually 1 to 200 times by weight, preferably 3 to
It is in the range of 50 times the weight.

When metal magnesium is used, the reaction can be started quickly by using an initiator in combination. Examples of such an initiator include molecular halogens such as bromine and iodine, alkyl halides such as methyl iodide, ethyl iodide and ethyl bromide, 1,2-
Examples thereof include alkyl dihalides such as dichloroethane and 1,2-dibromoethane, and the amount thereof is usually in the range of 0.00001 to 0.1 mol times the metal magnesium.

The obtained reaction mixture is separated into an organic layer and an aqueous layer to obtain a solution of compound [2a] as an organic layer. When a solvent compatible with water is used in the above 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 above reaction, toluene and acetic acid are added to the reaction mixture. Liquid separation may be performed after adding an organic solvent insoluble in water such as ethyl or chlorobenzene.

The compound [2a] may be used in the next [Step 3] as it is as a solution thus obtained, or may be used in the next [Step 3] after being taken out from the solution. In order to take out the compound [2a] from the solution of the compound [2a], for example, the solution is washed with water, dried and then the solvent is distilled off. The compound [2a] thus obtained may be further purified by a method such as recrystallization, distillation and column chromatograph treatment.

The compound was used as the solvent.

[9] and an organic alkali metal compound or metal magnesium are added, and then compound [4] is added, or the compound is added to the solvent.

When a solid is precipitated after adding [9], the compound [4] and the organic alkali metal compound or metal magnesium, the solid taken out from the reaction system is added to a solvent usable in [Step 3], and then the compound is added. Compound [1] can also be produced by adding [3].

Compound used in the above [Step 2]

[9] can be produced through [Step 1] as shown below. [Step 1] Compound (10) and a halide represented by the general formula (11) R ⁷ Y ⁵ (11) (wherein Y ⁵ represents a halogen atom and R ⁷ has the same meaning as described above) ( Hereinafter, the compound [11] will be reacted in the presence of a base to give a compound

A step of manufacturing [9].

Examples of the halogen atom represented by the substituent Y ⁵ in the compound [11] include a chlorine atom, a bromine atom and an iodine atom.

Examples of the compound [11] include methyl bromide, ethyl bromide, vinyl bromide, allyl bromide, 2-chloro-2-propenyl bromide, 2-bromo-2-propenyl bromide and 2
-Methyl-2-propenyl bromide, homoallyl bromide, hexenyl bromide, decenyl bromide, and compounds in which the bromide of each of the above compounds is changed to chloride or iodide. Compound [11]
The amount used is usually 0.5 to 5 mol times, preferably 0.9 to 3.3 mol times the compound [10].

Examples of the base include lithium hydroxide, lithium carbonate, lithium hydrogen carbonate, lithium hydride, lithium methoxide, lithium ethoxide, sodium hydroxide, sodium carbonate, sodium hydrogen carbonate, sodium hydride, sodium methoxide, Inorganic bases such as potassium hydroxide, potassium carbonate, potassium hydrogen carbonate, potassium hydride, potassium methoxide, and potassium ethoxide, methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, tert-butylamine, n- Primary amine compounds such as octylamine, n-decylamine, aniline, ethylenediamine, dimethylamine, diethylamine, di-n-propylamine, di-n-propylamine, di-n-butylamine,
Secondary amine compounds such as di-tert-butylamine, di-n-octylamine, di-n-decylamine, pyrrolidine, hexamethyldisilazane, diphenylamine, trimethylamine, triethylamine, tri-n-
Propylamine, tri-n-butylamine, diisopropylethylamine, tri-n-octylamine, tri-
amine compounds such as n-decylamine, triphenylamine, N, N-dimethylaniline, N, N, N ', N'-tetramethylethylenediamine, N-methylpyrrolidine, and tertiary amine compounds such as 4-dimethylaminopyridine, Organic alkali metal compounds such as methyllithium, ethyllithium, n-butyllithium, sec-butyllithium, tert-butyllithium, lithium trimethylsilylacetylide, lithium acetylide, trimethylsilylmethyllithium, vinyllithium, phenyllithium, allyllithium and other organic lithium compounds The amount used is usually in the range of 0.5 to 3 times by mole, preferably 0.9 to 1.5 times by mole with respect to the compound [10].

A catalyst may be used in the reaction. Examples of such catalysts include benzyltrimethylammonium chloride, benzyltriethylammonium chloride, benzyltri-n-propylammonium chloride, benzyltri-n-butylammonium chloride, tetramethylammonium chloride, tetraethylammonium chloride, tetra-n-propylammonium chloride, tetra -N-butylammonium chloride and quaternary ammonium salts such as compounds obtained by changing the chloride of each compound to bromide or iodide, and the amount thereof is usually 0.00001 to 0.5 with respect to compound [10]. The molar ratio is in the range of preferably 0.0001 to 0.1.

The reaction is usually carried out in a solvent inert to the reaction, and examples of such a solvent include aromatic hydrocarbon solvents such as benzene, toluene and xylene, and aliphatic hydrocarbon solvents such as hexane and heptane. Solvent, diethyl ether, tetrahydrofuran, ether solvent such as 1,4-dioxane, hexamethylphosphoric amide,
Amide solvents such as dimethylformamide, acetonitrile, propionitrile, acetone, diethyl ketone,
Examples include polar solvents such as methyl isobutyl ketone and cyclohexanone, aprotic solvents such as halogen solvents such as dichloromethane, dichloroethane, chlorobenzene and dichlorobenzene, and protic solvents such as alcohol solvents such as methanol, ethanol, isopropanol and n-butanol. To be These solvents are used alone or in admixture of two or more, and the use amount thereof is usually 1 to 200 times by weight, preferably 5 to 30 times by weight with respect to the compound [10].

This step can be carried out, for example, by adding a base to a solvent, then adding the compound [10], and then adding the compound [11]. When a catalyst is used, the base and the catalyst are added to the solvent. After that, the compound [10] may be added, and then the compound [11] may be added. The reaction temperature is generally -100 ° C or higher and the boiling point of the solvent or lower, preferably 0 to 1
It is in the range of 00 ° C.

Water was added to the obtained reaction mixture, and then the mixture was separated into an organic layer and an aqueous layer to obtain a compound as an organic layer.

A solution of [9] is obtained. When a solvent compatible with water is used in the above 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 above reaction, toluene and acetic acid are added to the reaction mixture. Liquid separation may be performed after adding an organic solvent insoluble in water such as ethyl or chlorobenzene.

Compound

[9] may be used in the next step as it is as the solution thus obtained, but it is usually taken out from the solution and used. Compound

Compound from solution of [9]

To remove [9], for example, the solution may be washed with water, dried, and the solvent may be distilled off. Compound thus obtained

[9] may be further purified by a method such as recrystallization, distillation, or column chromatography.

On the other hand, the compound [2b] can be produced through the [Step 5] as shown below. [Step 5] General formula (5) (In the formula, Y ¹ represents a halogen atom, A, B ′, R ¹ ,
R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ have the same meanings as described above. ) Halide compound (hereinafter,
It is called the compound [5]. ) And a general formula (6) M ² Cp ² (6) (in the formula, M ² represents an alkali metal atom, and Cp ² has the same meaning as described above) (hereinafter, referred to as a cyclopentadienyl metal salt). A compound [6]) is reacted to produce a compound [2b].

Examples of the halogen atom represented by the substituent Y ¹ in the compound [5] include chlorine atom, bromine atom and iodine atom.

As the compound [5], chloro (2-
Methoxyphenyl) dimethylsilane, chloro (2-methoxy-3-methylphenyl) dimethylsilane, chloro (2-methoxy-3,5-dimethylphenyl) dimethylsilane, (3-tert-butyl-2-methoxyphenyl) chlorodimethyl Silane, (3-tert-butyl-
2-methoxy-5-methylphenyl) chlorodimethylsilane, (3,5-di-tert-butyl-2-methoxyphenyl) chlorodimethylsilane, chloro (2-methoxy-3-phenylphenyl) dimethylsilane, chloro (2 -Methoxy-5-methyl-3-phenylphenyl)
Dimethylsilane, (3-tert-butyldimethylsilyl-2-methoxyphenyl) chlorodimethylsilane,
(3-tert-butyldimethylsilyl-2-methoxy-5-methylphenyl) chlorodimethylsilane, chloro (2-methoxy-3-trimethylsilylphenyl) dimethylsilane, chloro (2-methoxy-5-methyl-3-)
Trimethylsilylphenyl) dimethylsilane, (3,5
-Diamyl-2-methoxyphenyl) chlorodimethylsilane, (3-tert-butyl-2,5-dimethoxypheni) chlorodimethylsilane, (3-tert-butyl-5-chloro-2-methoxyphenyl) chlorodimethylsilane,

(2-allyloxy-phenyl) chlorodimethylsilane, (2-allyloxy-3-methylphenyl)
Chlorodimethylsilane, (2-allyloxy-3,5-dimethylphenyl) chlorodimethylsilane, (2-allyloxy-3-tert-butylphenyl) chlorodimethylsilane, (2-allyloxy-3-tert-butyl-5)
-Methylphenyl) chlorodimethylsilane, (2-allyloxy-3,5-di-tert-butylphenyl) chlorodimethylsilane, (2-allyloxy-3-phenylphenyl) chlorodimethylsilane, (2-allyloxy-5)
-Methyl-3-phenylphenyl) chlorodimethylsilane, (2-allyloxy-3-tert-butyldimethylsilylphenyl) chlorodimethylsilane, (2-allyloxy-3-tert-butyldimethylsilyl-4-methylphenyl) chlorodimethyl Silane, (2-allyloxy-3-trimethylsilylphenyl) chlorodimethylsilane, (2-allyloxy-5-methyl-3-trimethylsilylphenyl) chlorodimethylsilane, (2-allyloxy-3,5-diamylphenyl) chlorodimethylsilane , (2-allyloxy-3-tert-butyl-5-methoxyphenyl) chlorodimethylsilane, (2-allyloxy-3-tert-butyl-5-chlorophenyl) chlorodimethylsilane, (1-allyloxynaphthalene-2)
-Yl) chlorodimethylsilane and the like. Also, compounds in which methoxy or allyloxy is changed to benzyloxy, ethoxy, trimethylsilyloxy, tert-butyldimethylsilyloxy, methoxymethoxy, chlorodimethylsilane is chlorodiethylsilane, chlorodiphenylsilane, chlorodimethoxysilane, bromodimethylsilane, dimethyliodide Compounds changed to silane can be similarly exemplified.

Examples of the alkali metal represented by the substituent M ² in the compound [6] include lithium, potassium and sodium.

Examples of the compound [6] include cyclopentadienyllithium, methylcyclopentadienyllithium, ditylcyclopentadienyllithium, trimethylcyclopentadienyllithium, tetramethylcyclopentadienyllithium, ethylcyclopenta. Dienyllithium, n-propylcyclopentadienyllithium, isopropylcyclopentadienyllithium,
tert-butylcyclopentadienyl lithium, n-
Butylcyclopentadienyllithium, sec-butylcyclopentadienyllithium, isobutylcyclopentadienyllithium, di-tert-butylcyclopentadienyllithium, n-hexylcyclopentadienyllithium, phenylcyclopentadienyllithium,
Trimethylsilyl cyclopentadienyl lithium, te
rt-butyldimethylsilylcyclopentadienyl lithium, indenyl lithium, methyl indenyl lithium, phenyl indenyl lithium, fluorenyl lithium,

Cyclopentadienyl sodium, methylcyclopentadienyl sodium, tetramethylcyclopentadienyl sodium, tert-butylcyclopentadienyl sodium, n-butylcyclopentadienyl sodium, trimethylsilylcyclopentadienyl sodium, tert. -Butyldimethylsilylcyclopentadienyl sodium, indenyl sodium, fluorenyl sodium,

Cyclopentadienyl potassium, methylcyclopentadienyl potassium, tetramethylcyclopentadienyl potassium, tert-butylcyclopentadienyl potassium, n-butylcyclopentadienyl potassium, trimethylsilylcyclopentadienyl potassium, tert. -Butyldimethylsilylcyclopentadienyl potassium, indenyl potassium, fluorenyl potassium and the like can be mentioned. The amount of the compound [6] used is usually 0.5 to 3 times the molar amount of the compound [5], preferably 0.
It is in the range of 9 to 1.1 mol times.

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, toluene and xylene, aliphatic hydrocarbon solvents such as hexane and heptane, ether solvents such as diethyl ether, tetrahydrofuran and 1,4-dioxane, and hexamethyl. Phosphoric amide,
Examples thereof include amide-based solvents such as dimethylformamide, aprotic solvents such as halogen-based solvents such as dichloromethane, dichloroethane, chlorobenzene and dichlorobenzene. These solvents may be used alone or in admixture of two or more, and the amount thereof used is usually 1 to 200 times by weight, preferably 5 to 5 times the amount of the compound [5].
It is in the range of 30 times the weight.

This step can be carried out, for example, by mixing the compound [5] and the compound [6] in a solvent. The reaction temperature is usually -100 ° C or higher and the boiling point of the solvent or lower, and preferably in the range of -80 to 35 ° C.

Water or an aqueous ammonium chloride solution or an acidic aqueous solution such as hydrochloric acid is added to the obtained reaction mixture, and the mixture is separated into an organic layer and an aqueous layer to obtain a solution of the compound [2b] as an organic layer. When a solvent compatible with water is used in the above 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 above reaction, toluene and acetic acid are added to the reaction mixture. Liquid separation may be performed after adding an organic solvent insoluble in water such as ethyl or chlorobenzene.

The compound [2b] may be used as it is in the solution thus obtained in the next [Step 3] or may be used after being taken out from the solution. Compound [2b]
To take out the compound [2b] from the solution (1), for example, the solution may be washed with water, dried and the solvent may be distilled off. The compound [2b] thus obtained may be further purified by a method such as recrystallization, distillation and column chromatography.

The compound [5] used in the above [Step 5] can be produced through the [Step 4] as shown below. [Step 4] Compound

[9] and general formula (7) (In the formula, Y ² represents a halogen atom, and B ′, R ⁵ ,
R ⁶ and Y ¹ have the same meanings as described above. ) Is reacted with a dihalide compound represented by the formula (hereinafter referred to as compound [7]) in the presence of an organic alkali metal compound or metal magnesium to produce compound [5].

Compound

[9] can be manufactured through [Step 1] as described above. In that case, the obtained compound

[9] may be used as it is as a solution obtained as an organic layer by liquid separation, or may be taken out from the solution and used.

Examples of the halogen atom represented by the substituent Y ² in the compound [7] include chlorine atom, bromine atom and iodine atom.

Examples of the compound [7] include dichlorodimethylsilane, dichlorodiphenylsilane, dichlorodiethylsilane, dichlorodi-n-propylsilane, dichlorodimethoxysilane, diallyldichlorosilane, dichlorodivinylsilane, dichloromethylvinylsilane, dichlorodibenzylsilane, Examples include dichlorochloromethylmethylsilane, dibromodimethylsilane, diiododimethylsilane and the like. The amount of the compound [7] used is the compound

It is usually in the range of 0.5 to 50 mol times, preferably 0.9 to 5 mol times, relative to [9].

As the organic alkali metal compound, methyllithium, ethyllithium, n-butyllithium, sec
-Butyllithium, tert-butyllithium, lithium trimethylsilyl acetylide, lithium acetylide,
Examples thereof include organic lithium compounds such as organic lithium compounds such as trimethylsilylmethyllithium, vinyllithium, phenyllithium, and allyllithium. The amount of such organic alkali metal compound or metal magnesium used is

It is usually in the range of 0.5 to 5 mol times, preferably 0.9 to 2.2 mol times the amount of [9].

The reaction is usually carried out in a solvent inert to the reaction, and examples of such a solvent include aromatic hydrocarbon solvents such as benzene, toluene and xylene, and aliphatic hydrocarbon solvents such as hexane and heptane. Solvent, diethyl ether, tetrahydrofuran, ether solvent such as 1,4-dioxane, hexamethylphosphoric amide,
Amide solvents such as dimethylformamide, acetonitrile, propionitrile, acetone, diethyl ketone,
Examples include polar solvents such as methyl isobutyl ketone and cyclohexanone, and aprotic solvents such as halogenated solvents such as dichloromethane, dichloroethane, chlorobenzene and dichlorobenzene. These solvents may be used alone or in admixture of two or more, and the amount used is the compound

The amount is usually 1 to 200 times by weight, preferably 5 to 30 times by weight with respect to [9].

In this step, for example, the compound is used in a solvent.

[9] and an organic alkali metal compound or metal magnesium may be added, and then compound [7] may be added, or the compound may be added to a solvent.

It can also be carried out by simultaneously adding [9], compound [7] and an organic alkali metal compound or metal magnesium. The reaction temperature is not lower than -100 ° C and not higher than the boiling point of the solvent, and is preferably in the range of -80 to 40 ° C when an organic alkali metal compound is used and in the range of 10 to 100 ° C when metal magnesium is used.

When metal magnesium is used, the reaction can be started quickly by using an initiator in combination. Examples of such an initiator include molecular halogens such as bromine and iodine, alkyl halides such as methyl iodide, ethyl iodide and ethyl bromide, 1,2-
Examples thereof include alkyl dihalides such as dichloroethane and 1,2-dibromoethane, and the amount thereof is usually in the range of 0.00001 to 0.1 mol times the metal magnesium.

The compound [5] thus obtained may be used in the next [Step 5] as it is as the reaction mixture thus obtained.
The reaction mixture may be used as a residue obtained by concentration, or may be taken out from the reaction mixture and used. To take out the compound [5] from the reaction mixture, for example, the residue obtained by concentrating the reaction mixture is used as a solvent such as an aromatic hydrocarbon solvent such as toluene or a hydrophobic solvent such as an aliphatic hydrocarbon solvent such as hexane or heptane. And the insoluble matter is filtered off, and then the solvent is distilled off. Compound [5] thus obtained
May be further purified by a method such as recrystallization, distillation, or column chromatography.

The compound [2b] can also be produced via the [Step 6] as shown below.

[Step 6] Compound

[9] and general formula (8) (In the formula, Y ³ represents a halogen atom, and B ′, Cp ² , R
⁵ and R ⁶ have the same meanings as described above. )) In the presence of an organic alkali metal compound or metal magnesium to produce a compound [2b].

Compound

[9] can be produced through [Step 1] as described above. In that case, the obtained compound

[9] may be used as it is as a solution obtained as an organic layer by liquid separation, or may be taken out from the solution and used.

Examples of the halogen atom represented by the substituent Y ³ in the compound [8] include a chlorine atom, a bromine atom and an iodine atom.

Examples of the compound [8] include chloro (cyclopentadienyl) dimethylsilane, chlorodimethyl (methylcyclopentadienyl) silane, chlorodimethyl (tetramethylcyclopentadienyl) silane and chlorodimethyl (tetramethylcyclotetramethylcyclopentadienyl) silane. Pentadienyl) silane, chloro (tert-butylcyclopentadienyl) dimethylsilane, chlorodimethyl (trimethylsilylcyclopentadienyl) silane, (indene-1
-Yl) chlorodimethylsilane, (inden-2-yl) chlorodimethylsilane, chloro (9H-fluoren-9-yl) dimethylsilane and the like. Also,
Cyclopentadienyl of these compounds is replaced with dimethylcyclopentadienyl, n-butylcyclopentadienyl,
sec-butylcyclopentadienyl, tert-butyldimethylsilylcyclopentadienyl, trimethylcyclopentadienyl, ethylcyclopentadienyl, n
-Propylcyclopentadienyl, isopropylcyclopentadienyl, isobutylcyclopentadienyl, phenylcyclopentadienyl, compounds in which methylinden-1-yl or methylinden-2-yl is substituted, dimethyl is diethyl, diphenyl, dimethoxy Compounds in which chloro is replaced by bromo or iodo can be similarly exemplified. The amount of the compound [8] used is the compound

It is usually in the range of 0.5 to 3 times, preferably 0.9 to 1.2 times the molar amount of [9].

As the organic alkali metal compound, methyllithium, ethyllithium, n-butyllithium, sec
-Butyllithium, tert-butyllithium, lithium trimethylsilyl acetylide, lithium acetylide,
Examples include organic lithium compounds such as trimethylsilylmethyllithium, vinyllithium, phenyllithium, and allyllithium. The amount of organic alkali metal salt or metal magnesium used is the compound

[9] is usually 0.5 to 5 mol times, the amount of the organic alkali metal compound used is in the range of 0.9 to 2.2 mol times, and the amount of metal magnesium used is 0.9 to 1.2. It is preferably in the molar range.

The reaction is usually performed in a solvent inert to the reaction. Examples of such a solvent include aromatic hydrocarbon solvents such as benzene, toluene and xylene, aliphatic hydrocarbon solvents such as hexane and heptane, ether solvents such as diethyl ether, tetrahydrofuran and 1,4-dioxane, and hexamethyl. Phosphoric amide,
Amide solvents such as dimethylformamide, acetonitrile, propionitrile, acetone, diethyl ketone,
Examples include polar solvents such as methyl isobutyl ketone and cyclohexanone, and aprotic solvents such as halogenated solvents such as dichloromethane, dichloroethane, chlorobenzene and dichlorobenzene. These solvents may be used alone or in admixture of two or more, and the amount used is the compound

The amount is usually 1 to 200 times by weight, preferably 5 to 30 times by weight with respect to [9].

In this step, for example, the compound is used in a solvent.

[9] and an organic alkali metal salt or metal magnesium, and then compound [8] can be added.

It can also be carried out by simultaneously adding [9], compound [8] and an organic alkali metal salt or metal magnesium. Reaction temperature is usually -100 ° C
The boiling point is not higher than the boiling point of the solvent, and is preferably in the range of −78 ° C. to 40 ° C. when using an organic alkali metal compound, and is preferably in the range of 10 to 100 ° C. when using metallic magnesium.

When metallic magnesium is used, the reaction can be started quickly by using an initiator in combination. Examples of such an initiator include molecular halogens such as bromine and iodine, alkyl halides such as methyl iodide, ethyl iodide and ethyl bromide, 1,2-
Examples thereof include alkyl dihalides such as dichloroethane and 1,2-dibromoethane, and the amount thereof is usually in the range of 0.00001 to 0.1 mol times the metal magnesium.

Water or an aqueous ammonium chloride solution or an acidic aqueous solution such as hydrochloric acid was added to the obtained reaction mixture, and then the mixture was separated into an organic layer and an aqueous layer, and the compound [2
b) is obtained. In the case of using a solvent compatible with water in the previous 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 previous reaction,
A water-insoluble organic solvent such as toluene, ethyl acetate, or chlorobenzene may be added to the reaction mixture, and then the organic layer may be separated.

The compound [2b] may be used as it is in the solution thus obtained in the next [Step 3], or may be used after being taken out from the solution. To take out the compound [2b] from the solution of the compound [2b], for example, the solution may be washed with water, dried, and the solvent may be distilled off. The compound [2b] thus obtained may be further purified by a method such as recrystallization, distillation and column chromatography.

[Organoaluminum Compound (A)] The Present Invention
Examples of the compound (A) used in
Minium compounds can be used. Preferably, (A1)
General E¹ _aAlZ_3-aOrganoaluminization represented by
Compound, (A2) general formula {-Al (E²) -O-｝_bso
A cyclic aluminoxane having the structure shown, and (A
3) General formula E^Three｛-Al (E^Three) -O-｝_cAlE^Three
₂A linear aluminoxane having the structure
Then E¹, E², E^ThreeIs a hydrocarbon group having 1 to 8 carbon atoms
Yes, all E¹, All E ²And all E^ThreeIs the same
May be different. Z is a hydrogen atom or halogen
And all Zs are the same or different
Is also good. a is a number 0 <a ≦ 3, b is an integer of 2 or more,
c represents an integer of 1 or more. ) Either
Can exemplify a mixture of two or three of them.

Specific examples of the organoaluminum compound (A1) represented by the general formula E ¹ _a AlZ _3-a include trialkylaluminums such as trimethylaluminum, triethylaluminum, tripropylaluminum, triisobutylaluminum and trihexylaluminum;
Dialkylaluminum chlorides such as dimethylaluminum chloride, diethylaluminum chloride, dipropylaluminum chloride, diisobutylaluminum chloride and dihexylaluminum chloride; alkylaluminums such as methylaluminum dichloride, ethylaluminum dichloride, propylaluminum dichloride, isobutylaluminum dichloride and hexylaluminum dichloride Dichloride; dialkylaluminum hydride such as dimethylaluminum hydride, diethylaluminum hydride, dipropylaluminum hydride, diisobutylaluminum hydride and dihexylaluminum hydride; Preferably, it is a trialkylaluminum, and more preferably, triethylaluminum and triisobutylaluminum.

[0150] In the general formula {-Al (E ²⁾ -O-} cyclic aluminoxane having a structure represented by _b (A2), the general formula ^{E 3 {-Al (E 3)} -O-} c AlE 3 2 Specific examples of E ² and E ^{3 in} the linear aluminoxane (A3) having the structure shown are a methyl group, an ethyl group, a normal propyl group, an isopropyl group, a normal butyl group, an isobutyl group, a normal pentyl group, and neopentyl. An alkyl group such as a group can be exemplified. b is 2
And c is an integer of 1 or more. Preferably, E ² and E ³ 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, a solution prepared by dissolving a trialkylaluminum (for example, trimethylaluminum) in a suitable organic solvent (benzene, aliphatic hydrocarbon, or the like) is brought into contact with water. In addition, a method in which a trialkylaluminum (for example, trimethylaluminum or the like) is brought into contact with a metal salt (for example, copper sulfate hydrate or the like) containing water of crystallization can be exemplified.

[Compound B] In the present invention, the compound (B)
Are (B1) a boron compound represented by the general formula BQ ¹ Q ² Q ³ , and (B 2) a general formula Z ⁺ (BQ ¹ Q ² Q
³ Q ^{4) -} boron compound represented by, (B3) the general formula ^{(L-H) + (BQ} 1 Q 2 Q 3 Q 4) - one of boron compound represented by the used.

In the boron compound (B1) represented by the general formula BQ ¹ Q ² Q ³ , B is a boron atom in a trivalent valence state, Q ^{1 to} Q ³ are halogen atoms, and 1 to 20 Hydrocarbon group containing carbon atoms, 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 A disubstituted amino group containing 20 carbon atoms, which may be the same or different. Preferred Q ^{1 to} Q ³ 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 the Lewis acid (B1) include tris (pentafluorophenyl) borane and tris (2,2).
3,5,6-tetrafluorophenyl) borane, tris (2,3,4,5-tetrafluorophenyl) borane,
Tris (3,4,5-trifluorophenyl) borane,
Tris (2,3,4-trifluorophenyl) borane,
Phenylbis (pentafluorophenyl) borane and the like can be mentioned, and most preferred is tris (pentafluorophenyl) borane.

In the boron compound (B2) represented by the general formula Z ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ^- , Z ⁺ is an inorganic or organic cation, and B is boron in a trivalent valence state. Is an atom, and Q ^{1 to} Q ⁴ are Q in (B1) above.
Is the same as that of the ¹ ~Q ^3.

As specific examples of the compound represented by the general formula Z ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ^- , inorganic cations Z ⁺ include a ferrocenium cation and an alkyl-substituted ferrocenium cation. Z ⁺ , which is an organic cation such as silver cation, includes triphenylmethyl cation. ^{(BQ 1 Q 2 Q 3 Q} 4) - , the tetrakis (pentafluorophenyl) borate, tetrakis (2,3,5,6-tetrafluorophenyl) borate, tetrakis (2,3,4,5-tetrafluoro Phenyl) borate, tetrakis (3,4,5-trifluorophenyl) borate, tetrakis (2,2,4-trifluorophenyl) borate, phenylbis (pentafluorophenyl) borate, tetrakis (3,5-bistriborate) Fluoromethylphenyl) borate and the like.

Specific combinations of these 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, but most preferred is triphenylmethyltetrakis (pentafluorophenyl) borate.

In addition, the general formula (L-H) ⁺ (BQ ¹ Q ² Q
^{In the} boron compound (B3) NI represented by ³ Q ⁴ ) ^- , L is a neutral Lewis base, (L-H) ⁺ is a Bronsted acid, and B is a trivalent valence state. a boron atom, Q ¹ ~Q Q ¹ ~Q ⁴ is in the above (B1)
^Same as ³ .

General formula (L-H) ⁺ (BQ ¹ Q ² Q
³ Q ^{4) -} Examples of compound represented by is a Bronsted acid (the L-H) ⁺ is a trialkyl-substituted ammonium, N, N-dialkyl anilinium, dialkylammonium, triarylphosphonium, etc. can be ^{mentioned, (BQ 1 Q 2 Q 3} Q 4) - to include the same as described 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. Most preferably, tri (normal butyl) ammonium tetrakis (pentane) Fluorophenyl) borate or N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate.

In the present invention, the transition metal complex represented by the general formula (1) and the compound (A), or further the compound (B) can be added in any order at the time of polymerization and used. A reaction product obtained by previously contacting a combination of any of those compounds may be used.

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. 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 should not be 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, decene-1, 5-methyl-2-pentene-1,
Examples thereof include vinylcyclohexene. Examples of diolefin compounds include conjugated dienes and non-conjugated dienes of hydrocarbon compounds. Specific examples of such compounds include 1,5-hexadiene, 1,4-hexadiene, and 1-hexadiene as specific examples of non-conjugated diene compounds. , 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-endomethylenehexahydronaphthalene and the like are exemplified, and specific examples of the conjugated diene compound include
Examples thereof include 1,3-butadiene, isoprene, 1,3-hexadiene, 1,3-octadiene, 1,3-cyclooctadiene, and 1,3-cyclohexadiene.

Specific examples of the monomer constituting the copolymer include ethylene and propylene, ethylene and butene-1,
Ethylene and hexene-1, propylene and butene-1, etc.,
And combinations thereof using 5-ethylidene-2-norbornene and the like are exemplified, but the present invention is
It should not be 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, divinylbenzene and the like.

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, or methylene dichloride. 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 may be in the range of -50 ° C to 200 ° C, but is particularly preferably in the range of -20 ° C to 100 ° C, and the polymerization pressure is preferably atmospheric pressure to 60 kg / cm 2 G. Generally, the polymerization time is appropriately determined depending on the kind of the desired polymer and the reaction apparatus, but can be in the range of 1 minute to 20 hours. In the present invention, a chain transfer agent such as hydrogen may be added to adjust the molecular weight of the copolymer.

[0168]

The present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto. The properties of the polymers in the examples were measured by the following methods.

(1) Intrinsic viscosity [η ₁ ]: 100 mg of the obtained copolymer was dissolved in 50 ml of tetralin at 135 ° C., and an Ubbelohde viscometer set in a hot water bath kept at 135 ° C. was used. It was determined from the falling rate of the tetralin solution in which the sample was dissolved.

(2) Intrinsic viscosity [η ₂ ]: 300 mg of the obtained copolymer was dissolved in 100 ml of xylene to obtain about 3 m.
g / ml concentration, then the solution is 1/2, 1 /
The sample was diluted to 3/5 with xylene to prepare samples with three levels of concentration. The measurement was performed using an Ubbelohde viscometer set in an oil bath maintained at 70 ° C., and was determined from the falling rate of the xylene solution in which the sample was dissolved.

(3) Content of α-olefin in copolymer: The content of α-olefin in the obtained polymer was determined from infrared absorption spectrum. The measurements and calculations are based on the literature (characterization of polyethylene by infrared absorption spectrum, Takayama, Usami et al., Or Die Makrom.
oleculare Chemie, 177, 461 (1976) McRae, MA, Mad
ams WF) according to the method described, characteristic absorption derived from α-olefin, for example, 1375 cm ⁻¹ (propylene), 77
It was carried out using 2 cm ^-1 . Short chain branching degree (SCB)
Is expressed as the number of short chain branches per 1000 carbons.

(4) Content of diolefin in the copolymer:
When diolefin is present in the copolymer, (3)
Similarly, the infrared absorption spectrum was used to quantify the characteristic peak derived from the diolefin used. For example,
When 5-ethylidene-2-norbornene (ENB) was used, quantification was carried out using the peak at 1688 cm ⁻¹ (peak derived from double bond of ENB).

(5) Melting point of copolymer: Seiko SSC-
5200 was used and it calculated | required on condition of the following. Temperature increase: 40 ° C to 150 ° C (10 ° C / min), hold for 5 minutes Cooling: 150 ° C to 10 ° C (5 ° C / min), hold for 10 minutes Measurement: 10 ° C to 160 ° C (5 ° C / min)

(6) Molecular weight and molecular weight distribution: gel permeation chromatograph (manufactured by Waters)
150, C) and the following conditions were used. Column: TSK gel GMH-HT Measuring temperature: 145 ° C. Setting measuring concentration: 10 mg / 10 ml-orthodichlorobenzene

(7) Structure of ligand and complex: ¹ H-NM
It was confirmed by R measurement (AM-400 manufactured by Bruker).

Example 1 (1) Synthesis of Transition Metal Complex (1-1) 1-Bromo-3-tert-butyl-5-me
Synthesis of chill-2-phenol Under a nitrogen atmosphere, 500 ml four-necked frass equipped with a stirrer
2-tert-butyl-5-methyl-2-phen
20.1 g (123 mmol) of norol was added to toluene 150.
Dissolve in ml, followed by tert-butylamine 25.9.
ml (18.0 g, 246 mmol) was added. This solution
The liquid was cooled to -70 ° C, and 10.5 ml of bromine (3
Slowly add 2.6 g, 204 mmol) with a syringe.
I got it. The solution was kept at -70 ° C and stirred for 2 hours. So
After that, the temperature is raised to room temperature, and 10% diluted hydrochloric acid 10
0 ml was added and the mixture was washed 3 times. Organic layer obtained after washing
Is dried over anhydrous sodium sulfate and evaporated.
The solvent was removed using a filter. Orange oil remains
Was. This orange oil is passed through a silica gel column (Wako gel
C-100), develop with hexane, and remove the solvent of the fraction.
Purified by removing. Purified colorless oyster
To obtain 18.4 g (75.7 mmol). That ¹H-
NMR (CD₂Cl₂Solvent) data are shown below. δ 1.32 (s, 9H), 2.19 (s, 6H),
6.98 (s, 1H), 7.11 (s, 1H)¹From the H-NMR data, the colorless oil obtained was
1-Bromo-3-tert-butyl-5-methyl-2-
It was identified as phenol. The yield was 62%.

(1-2) Synthesis of 1-bromo-3-tert-butyl-2-methoxy-5-methylbenzene In a 100 ml four-necked flask equipped with a stirrer under a nitrogen atmosphere, the above (1-1) 1-bromo-3-t synthesized in
ert-Butyl-5-methyl-2-phenol 13.9
g (57.2 mmol) was dissolved in 40 ml of acetonitrile, followed by 3.8 g of potassium hydroxide (67.9 mmo).
l) was added. Further, 17.8 ml of methyl iodide (4
0.6 g, 286 mmol) was added slowly with a syringe and stirring was continued for 12 hours. Thereafter, the solvent was removed by an evaporator, and 40 ml of hexane was added to the residue to extract hexane-soluble components. The extraction was repeated three times. The solvent was removed from the extract to give 13.8 g (53.7 g) of a pale yellow oil.
mmol). The ¹ H-NMR (CD ₂ Cl ₂ solvent) data is shown below. δ 1.31 (s, 9H), 2.20 (s, 3H),
3.81 (s, 3H), 7.02 (s, 1H), 7.1
8 (s, 1H) From the ¹ H-NMR data, the obtained pale yellow oil was converted to 1-bromo-3-tert-butyl-2-methoxy-
It was identified as 5-methylbenzene. The yield was 94%.

(1-3) 2-Cyclopentadienyl-2
Synthesis of-(3-tert-butyl-2-methoxy-5-methylphenyl) propane In a 100 ml four-necked flask equipped with a stirrer under a nitrogen atmosphere, 1-bromo-3 synthesized in (1-2) above. -T
4.61 g (17.9 mmol) of ert-butyl-2-methoxy-5-methylbenzene was dissolved in 10 ml of dry diethyl ether and cooled to -70 ° C. There, ⁿ
Slowly added BuLi 18.0mol ⁽ⁿ BuLi / hexane solution 11.1ml of 1.62 mol / liter concentration), stirring was continued for 2 hours at -70 ° C.. further,
A solution prepared by dissolving 1.91 g (18.0 mmol) of 6,6-dimethylfulvene in 10 ml of diethyl ether was added to this reaction solution, and then the temperature was slowly raised to room temperature.
Subsequently, 25 ml of 5 wt% diluted hydrochloric acid was added. 30 ml of hexane was added to this reaction solution to extract a hexane-soluble component. This extraction was repeated 3 times. The extract was dried over anhydrous sodium sulfate, and the solvent was removed by an evaporator. A yellow oil remained. The yellow oil was passed through a silica gel column (Wako Gel C-100), developed with hexane, and purified by removing the solvent of the fraction. 3.0 g of a purified pale yellow oil was obtained. Part ¹ H-NM
The data for R (CD ₂ Cl ₂ solvent) are shown below. δ 1.48 (s, 9H), 1.71 (s, 6H),
2.26 (s, 3H), 3.26 (s, 3H), 6.0
7 to 6.62 (m, 5H), 7.22 to 7.28 (m,
2H) From the ¹ H-NMR data, the obtained yellow oil was identified as 2-cyclopentadienyl-2- (3-tert-butyl-2-methoxy-5-methylphenyl) propane. The yield was 60%.

(1-4): 2- (cyclopentadienyl) (lithium) -2- (3-tert-butyl-2-
Synthesis of white solid presumed to be methoxy-5-methylphenyl) propane 2-cyclopentadienyl-2 synthesized in (1-3) above in a 50 ml four-necked flask equipped with a stirrer under a nitrogen atmosphere. -(3-tert-butyl-2-methoxy-
5-methylphenyl) propane 0.28g (0.99m
(mol) was dissolved in 20 ml of hexane and cooled to -70 ° C. There, ⁿ BuLi 1.09mol (1.62
ⁿ BuLi / hexane solution 0 mol / liter concentration.
67 ml) was added slowly. Then, the temperature was slowly raised to room temperature. White solid precipitated. Filter this, 1
Each time, it was washed 3 times with 10 ml of hexane and dried under reduced pressure to give 2- (cyclopentadienyl) (lithium) -2.
0.28 g of a white solid presumed to be-(3-tert-butyl-2-methoxy-5-methylphenyl) propane was obtained. The yield was 97%.

(1-5) Isopropylidene (cyclopentadienyl) (3-tert-butyl-5-methyl-2)
-Phenoxy) titanium dichloride synthesis 2- (cyclopentadienyl) (lithium) -2- (3-) synthesized in (1-4) above in a 50 ml four-necked flask equipped with a stirrer under a nitrogen atmosphere. 0.20 g (2.3 mmol) of a white solid assumed to be tert-butyl-2-methoxy-5-methylphenyl) propane was added to 10 ml of hexane, and the mixture was cooled to -70 ° C. There, Ti
Cl ₄ 0.077 ml (0.13 g, 0.70 mmo
1) was added slowly with a syringe. Then, the temperature was slowly raised to room temperature. The solution turned brown and a dark orange solid precipitated. This was filtered and separated into a solution and a solid, and a component soluble in hexane as a saturated hydrocarbon solvent was extracted three times from the solid with 10 ml of hexane each time.
Combine these hexane solutions and concentrate to 10 ml,
The concentrate was cooled at −20 ° C. and left standing for 12 hours. A yellow solid precipitated. This was filtered and dried under reduced pressure. The data of ¹ H-NMR (CD ₂ Cl ₂ solvent) of this yellow solid is shown below. δ 1.33 (s, 9H), 1.51 (s, 6H),
2.30 (s, 3H), 6.06 (t, 2H), 6.9
2 (t, 2H), 6.99 (s, 1H), 7.19
(S, 1H) From this ¹ H-NMR data, the obtained yellow solid was converted into isopropylidene (cyclopentadienyl) having the following structural formula.
It was identified as (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride. The yield is 34
%Met.

(2) Polymerization An autoclave equipped with a stirrer and having an internal volume of 3 liters was vacuum dried.
After drying and replacing with argon, 1 liter of toluene as solvent
20 ml of hexene-1 as α-olefin
Then, the temperature of the reactor was raised to 80 ° C. After heating, ethylene pressure
12 kg / cm ²Feeding while adjusting to
After stabilization, triisobutylaluminum 0.5mmo
l, followed by isopropylidene (cyclopentadiene
(Enyl) (3-tert-butyl-5-methyl-2-phenyl)
Enoxy) Titanium dichloride 2.0 μmol
, Followed by triphenylmethyl tetrakis (pentaf
Luorophenyl) borate (6.0 μmol) was added.
Polymerization was carried out for 30 minutes while controlling the temperature at 80 ° C.
As a result of the polymerization, SCB = 22.8, [η] = 1.13, min
Molecular weight (Mw) = 64000, molecular weight distribution (Mw / Mn)
= 2.0, ethylene-hexene having a melting point of 96.1 ° C
-1 copolymer for 1 hour per 1 mol of titanium
Or 4.0x10⁷g.

Example 2 (1) Polymerization An autoclave equipped with a stirrer and having an internal volume of 0.4 liter was vacuum-dried and replaced with argon, and toluene 19 was used as a solvent.
5 ml and 5 ml of hexene-1 as an α-olefin were charged, and the temperature of the reactor was raised to 60 ° C. After the temperature was raised, feed was performed while adjusting the ethylene pressure to 6 kg / cm ² , and after the system was stabilized, triisobutylaluminum 0.25 mm
ol, followed by 1.0 μmol of isopropylidene (cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride synthesized in Example (1), and triphenyl. 3.0 μmol of methyltetrakis (pentafluorophenyl) borate was added. Polymerization was carried out for 30 minutes while controlling the temperature at 60 ° C. As a result of polymerization, SCB = 3
2.8, [η] = 0.98, molecular weight (Mw) = 9500
0, molecular weight distribution (Mw / Mn) = 2.8, melting point 11
An ethylene-hexene-1 copolymer having a temperature of 0.5 ° C. was added in an amount of 4.0 × 10 per 1 mol of titanium per 1 hour.
⁷ g was produced.

Example 3 (1) Polymerization An autoclave equipped with a stirrer and having an internal volume of 0.4 liter was vacuum dried and replaced with argon, and then toluene 19 was used as a solvent.
5 ml and 5 ml of hexene-1 as an α-olefin were charged, and the temperature of the reactor was raised to 60 ° C. After the temperature was raised, feed was performed while adjusting the ethylene pressure to 6 kg / cm ^2. After the inside of the system was stabilized, 0.25 mmol of triethylaluminum was added.
Was added, followed by 1.0 μmol of isopropylidene (cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride synthesized in Example (1), and triphenylmethyl. Tetrakis (pentafluorophenyl) borate 3.0
μmol was added. While adjusting the temperature to 60 ℃, 6
Polymerization was performed for 0 minutes. As a result of the polymerization, SCB = 18.0,
An ethylene-hexene-1 copolymer having [η] = 1.20 and a melting point of 120.8 ° C. was produced in an amount of 9.9 × 10 ⁵ g per 1 mol of titanium per 1 hour.

Example 4 (1) Polymerization An autoclave equipped with a stirrer and having an internal volume of 0.4 liter was vacuum-dried and replaced with argon, and toluene 17 was used as a solvent.
0 ml, 30 ml of hexene-1 as α-olefin
After charging, the temperature of the reactor was raised to 60 ° C. After the temperature was raised, ethylene was fed while adjusting the ethylene pressure to 6 kg / cm ² , and after the system was stabilized, 5.0 mmol of methylaluminoxane (MMAO-3A manufactured by Tosoh Akzo Co., Ltd.) was added as the amount of aluminum atom. Then, isopropylidene (cyclopentadienyl) (3- synthesized in Example (1)
1.0 μmol of tert-butyl-5-methyl-2-phenoxy) titanium dichloride was added. 60 ° C
Polymerization was carried out for 60 minutes while controlling the temperature. As a result of the polymerization, an ethylene-hexene-1 copolymer having SCB = 28.6 and a melting point of 82.3 ° C. was produced in an amount of 7.7 × 10 ⁵ g per 1 mol of titanium per 1 hour.

Example 5 (1) Polymerization An autoclave equipped with a stirrer and having an internal volume of 0.4 liter was vacuum-dried and replaced with argon, and toluene 17 was used as a solvent.
0 ml, 30 ml of hexene-1 as α-olefin
After charging, the temperature of the reactor was raised to 60 ° C. After the temperature was raised, ethylene was fed while adjusting the pressure to 6 kg / cm ² , and after the system was stabilized, methylaluminoxane (MMAO-3A manufactured by Tosoh Akzo Co., Ltd.) was added as the amount of aluminum atom, and 0.5 mmol was added. Then, isopropylidene (cyclopentadienyl) (3- synthesized in Example (1)
0.5 mmol of tert-butyl-5-methyl-2-phenoxy) titanium dichloride (1.0 μmol) and methylaluminoxane as the amount of aluminum atoms.
Was preliminarily contacted in advance and then charged into the autoclave.
Polymerization was carried out for 60 minutes while controlling the temperature at 60 ° C.
As a result of the polymerization, an ethylene-hexene-1 copolymer having SCB = 32.4, [η] = 1.99, and a melting point of 82.0 ° C. was added for 5.5 mol per 1 hour per 1 mol of titanium.
× 10 ⁵ g was produced.

Example 6 (1) Synthesis of transition metal complex (1-1) Synthesis of 1-bromo-2-methoxybenzene 1-Bromo-2 in a 50 ml four-necked flask equipped with a stirrer under a nitrogen atmosphere. -Phenol 1.03 g (5.9
2 mmol) was dissolved in 20 ml of acetonitrile, and subsequently 0.51 g (9.07 mmol) of potassium hydroxide was added. Furthermore, 1.90 ml of methyl iodide (4.33 ml
g, 30.5 mmol) slowly with a syringe, 1
Stirring was continued for 2 hours. Then, the solvent was removed by an evaporator, and 20 ml of hexane was added to the residue to extract a hexane-soluble component. The extraction was repeated three times. The solvent was removed from the extract to obtain 0.97 g of a pale yellow oil. The yield is
It was 89%. The ¹ H-NMR (CD ₂ Cl ₂ solvent) data is shown below. δ 3.89 (s, 3H), 6.7 to 7.7 (m, 4)
H) From the ¹ H-NMR data, the obtained pale yellow oil was identified as 1-bromo-2-methoxybenzene.

(1-2) 2- (cyclopentadienyl)
Synthesis of 2- (2-methoxyphenyl) propane Under a nitrogen atmosphere, 1-bromo-2-synthesized in (1-1) above in a 100 ml four-necked flask equipped with a stirrer.
Methoxybenzene 4.50g of (24.1 mmol) was dissolved in dry diethyl ether 20 ml, cooled to -70 ° C., thereto, ⁿ BuLi 24.0mol (1.62m
ⁿ BuLi / hexane solution having a concentration of ol / liter 14.
8 ml) was added slowly and stirring was continued at -70 ° C for 2 hours. Furthermore, 10 ml of diethyl ether was added to this reaction solution.
2.64 g of 6,6-dimethylfulvene dissolved in
4.9 mmol) was added, and then the temperature was slowly raised to room temperature. A white solid precipitated and was filtered. This white solid was washed with 10 ml of hexane each time to 3
It was washed twice and dried under reduced pressure. 4.0 g of white powder was obtained. The ¹ H-NMR (C ₆ D ₆ solvent) data of the obtained organic substance obtained by hydrolyzing a small amount of this white powder with dilute hydrochloric acid was as follows. δ 1.66 (s, 3H), 1.75 (s, 3H), 3.
26 (s, 3H), 5.9 to 7.5 (m, 9H) From this ¹ H-NMR data, the organic substance obtained by hydrolysis was treated with 2-cyclopentadienyl-2- (1-methoxyphenyl). ) Identified as propane and thus the white powder
It was estimated to be (cyclopentadienyl) (lithium) -2- (2-methoxyphenyl) propane. The yield was 75%.

(1-3) Synthesis of isopropylidene (cyclopentadienyl) (2-phenoxy) titanium dichloride It was synthesized in (1-2) above in a 50 ml four-necked flask equipped with a stirrer under a nitrogen atmosphere. , 2- (cyclopentadienyl) (lithium) -2- (2-methoxyphenyl) propane, a white powder 0.20 g (0.9
2 mmol) was added to 15 ml of hexane and cooled to −70 ° C., where 0.10 ml of TiCl ₄ (0.17 g,
A solution of 0.91 mmol) dissolved in 5 ml of hexane was slowly added by a syringe. Then, the temperature was slowly raised to room temperature. The solution turned brown and a brown solid precipitated. This was filtered and separated into a solution and a solid, and a component soluble in hexane as a saturated hydrocarbon solvent was extracted three times from the solid with 10 ml of hexane each time. These hexane solutions were combined, concentrated to 10 ml, and the concentrated solution was cooled at -20 ° C and allowed to stand for 12 hours. A yellow solid precipitated. This was filtered and dried under reduced pressure to obtain 0.10 g of a yellow solid. ¹ H-NMR (CD ₂ C of this yellow solid
shows data l ₂ solvent) below. δ 1.62 (s, 6H), 6.17 (t, 2H),
6.80 (d, 1H), 7.00 (t, 2H), 7.2
0 (t, 1H), 7.21 (t, 1H), 7.58
(D, 1H) Furthermore, ¹³ C-NMR (CD ₂ Cl ₂ solvent) data is shown below. δ 29.8, 37.3, 114.9, 119.8, 1
22.4, 125.6, 126.7, 127.8, 13
6.5, 143.8, 162.7 From the ¹ H-NMR data and ¹³ C-NMR data,
The yellow solid obtained was identified as isopropylidene (cyclopentadienyl) (2-phenoxy) titanium dichloride having the following structural formula.

(2) Polymerization An autoclave equipped with a stirrer and having an internal volume of 0.4 liter was vacuum-dried and replaced with argon, and toluene 19 was used as a solvent.
5 ml and 5 ml of hexene-1 as an α-olefin were charged, and the temperature of the reactor was raised to 60 ° C. After the temperature was raised, feed was performed while adjusting the ethylene pressure to 6 kg / cm ² , and after the system was stabilized, triisobutylaluminum 0.25 mm
ol, followed by isopropylidene (cyclopentadienyl) (2-phenoxy) synthesized in (1) above.
2.0 μmol of titanium dichloride was added, and then 6.0 μmol of triphenylmethyltetrakis (pentafluorophenyl) borate was added. Polymerization was carried out for 60 minutes while controlling the temperature at 60 ° C. As a result of the polymerization, an ethylene-hexene-1 copolymer having SCB = 28.1 and [η] = 1.08 was produced at 1.8 × 10 ⁶ g per 1 mol of titanium per 1 hour.

Example 7 (1) Polymerization An autoclave with an internal volume of 0.4 liter equipped with a stirrer was vacuum dried and replaced with argon, and then toluene 19 was used as a solvent.
5 ml and 5 ml of hexene-1 as an α-olefin were charged, and the temperature of the reactor was raised to 60 ° C. After the temperature was raised, ethylene was fed while adjusting the ethylene pressure to 6 kg / cm ² to stabilize the system, and then triisobutylaluminum 0.15 mm
ol, and subsequently preliminarily contacting 2.0 μmol of isopropylidene (cyclopentadienyl) (2-phenoxy) titanium dichloride synthesized in Example 6 (1) with 0.1 mmol of triisobutylaluminum, and then autoclaving I put it in. Polymerization was carried out for 60 minutes while controlling the temperature at 60 ° C. As a result of polymerization, SCB
= 29.0, an ethylene-hexene-1 copolymer,
Per 1 mol of titanium per hour 3.3 x 1
0 ⁶ g was produced.

Example 8 (1) Polymerization An autoclave equipped with a stirrer and having an internal volume of 0.4 liter was vacuum-dried and replaced with argon, and toluene 17 was used as a solvent.
0 ml, 30 ml of hexene-1 as α-olefin
After charging, the temperature of the reactor was raised to 60 ° C. After the temperature was raised, ethylene was fed while adjusting the ethylene pressure to 30 kg / cm ^2, and after the inside of the system was stabilized, methylaluminoxane (MMAO-3A manufactured by Tosoh Akzo Co., Ltd.) was added as the amount of aluminum atom, and 2.0 mmol was added. Then, isopropylidene (cyclopentadienyl) synthesized in Example 6 (1)
(2-phenoxy) titanium dichloride 2.0 μm
ol. Polymerization was carried out for 20 minutes while controlling the temperature at 60 ° C. As a result of the polymerization, an ethylene-hexene-1 copolymer having SCB = 7.0 and a melting point of 123.7 ° C. was added for 2.3 mol per 1 mol of titanium per 1 mol of titanium.
× 10 ⁵ g was produced.

Comparative Example 1 (1) Polymerization An autoclave equipped with a stirrer and having an internal volume of 400 ml was vacuum-dried and replaced with argon, and then 170 m of toluene was used as a solvent.
l, 30 ml of hexene-1 was charged as an α-olefin, and the reactor was heated to 80 ° C. After the temperature was raised, feed was performed while adjusting the ethylene pressure to 6 kg / cm ^2. After the inside of the system was stabilized, 0.25 mmol of triethylaluminum was added.
5.0 gmol of 2,2′-thiobis (6-tert-butyl-4-methylphenoxy) titanium dichloride synthesized by the method described in WO87 / 02370 and JP-A-5-230133.
Was added, and subsequently 15.0 μmol of triphenylmethyl tetrakis (pentafluorophenyl) borate was added. Polymerization was carried out for 60 minutes while controlling the temperature at 80 ° C. As a result of the polymerization, SCB = 26.1, [η ₁ ] = 3.7.
8, ethylene-hexene-1 having a melting point of 116.8 ° C.
2.9 × 10 copolymer per mol of titanium
⁴ g was produced.

Example 9 1,5-Dimethyl-3- (1-cyclopentadienyl-
Synthesis of 1-methyl-ethyl) -2-methoxybenzene 2-Bromo-4,6-dimethylanisole (10.32)
g) in anhydrous ether (100 ml) at -78 ° C with 1.69 M hexane solution of n-butyllithium (56.
(8 ml) was added dropwise, the temperature was raised to room temperature over 2 hours, and the obtained yellow solution was cooled to -78 ° C. 5-Isopropylidene-cyclopenta-1,3-diene (5.87 ml) was added dropwise to the solution, the temperature was raised to room temperature over 12 hours, and the mixture was further stirred at room temperature for 1 hour. After adding an ammonium chloride aqueous solution to the reaction mixture, the aqueous layer and the organic layer were separated. After the toluene-soluble component was extracted from the aqueous layer with toluene, the organic solution obtained by combining the organic layer and the toluene solution was washed with saturated saline and then dried with anhydrous sodium sulfate. The solvent was distilled off from the organic solution under reduced pressure, and the residue was treated by silica gel column chromatography to give 1,5-dimethyl-3- (1-cyclopentadienyl-1-methyl-ethyl) as a yellow oil. ) -2-Methoxybenzene was obtained as a mixture of isomers (2.5
6 g, yield 22%). ¹ H NMR (CDCl ₃ ) δ1.58 (s, 6 H), 2.22 (s, 3 H),
2.28 (s, 3 H), 2.81-2.97 (2 H, 2.81: m; 2.97: m),
3.26-3.29 (3 H, 3.26: m; 3.29: m), 6.08-6.48 (m, 3
H), 6.86 (d, 1 H, J = 1 Hz), 6.87 (d, 1 H, J = 1 H
z) Mass spectrum (EI, m / e) 242, 227, 211, 19
6, 177, 162, 149, 136, 119, 105, 91, 81, 65

Example 10 Isopropylidene (cyclopentadienyl) (3,5-
Synthesis of dimethyl-2-phenoxy) titanium dichloride 1,5-dimethyl-3- (1-cyclopentadienyl-
1-methyl-ethyl) -2-methoxybenzene (0.7
27 g) in hexane solution (10 mL) at 0 ° C. with 1.69 M hexane solution of n-butyllithium (1.95 m).
L) was added dropwise, the temperature was raised to room temperature, and the mixture was stirred for 12 hours. Titanium tetrachloride (0.33 mL) was added to the obtained mixture at -50 ° C under light shielding, the temperature was raised to room temperature over 2 hours, and the mixture was further stirred at room temperature for 12 hours. The obtained slurry was filtered and the filtrate was concentrated to obtain a crude product. This was recrystallized from hexane to obtain orange crystals of isopropylidene (cyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride (0.15 g, yield 14%). ¹ H NMR (C ₆ D ₆ ) δ0.99 (s, 6 H), 2.18 (s, 3 H), 2.
29 (s, 3 H), 5.46 (t, 2H, J = 3 Hz), 6.30 (t, 2 H,
3 Hz), 6.65 (d, 1 H, J = 2 Hz), 6.95 (d, 1H, J = 2
Hz)

Example 11 1-Phenyl-3- (1-cyclopentadienyl-1-
Synthesis of methyl-ethyl) -2-methoxybenzene 2-bromo-6-phenylanisole (14.00 g)
In anhydrous ether solution (100 ml) at -78 ° C.
1.69 M hexane solution of butyl lithium (63.9 m
1) was added dropwise, and then the temperature was raised to room temperature over 2 hours, and the obtained yellow solution was cooled to -78 ° C. 5-isopropylidene-cyclopenta-1,3-diene (6.
(51 ml) was added dropwise, the temperature was raised to room temperature over 12 hours, and the mixture was further stirred at room temperature for 1 hour. Aqueous ammonium chloride solution was added to the reaction mixture, and the aqueous layer and the organic layer were separated. After extracting the toluene-soluble component from the aqueous layer with toluene,
The organic solution obtained by combining the organic layer and the toluene solution was washed with saturated saline and then dried with anhydrous sodium sulfate. The solvent was distilled off from the organic solution under reduced pressure, and the residue was treated by silica gel column chromatography to give 1-phenyl-3- (1-cyclopentadienyl-1-methyl-ethyl) -2 as a yellow oil. -Methoxybenzene was obtained as a mixture of isomers (6.60 g, yield 4
3%) ¹ H NMR (CDCl ₃ ) δ 1.66 (s, 6 H), 2.82-2.96 (m, 5
H), 6.07-6.45 (m, 3 H), 7.05-7.60 (m, 8 H) Mass spectrum (EI, m / e) 290, 275, 260, 210, 18
3, 165, 152, 115, 91, 77

Example 12 Isopropylidene (cyclopentadienyl) (3-phen
Synthesis of (nyl-2-phenoxy) titanium dichloride 1-phenyl-3- (1-cyclopentadienyl-1-)
Methyl-ethyl) -2-methoxybenzene (1.45
g) in hexane solution (20 mL) at 0 ° C. with n-butyl.
1.69 M hexane solution of lithium (3.08 mL)
The mixture was added dropwise, heated to room temperature and stirred for 12 hours. Got
The mixture was treated with titanium tetrachloride (0.55
(mL) was added, the temperature was raised to room temperature, and the mixture was stirred for 12 hours. Profit
The resulting slurry is filtered and the filtrate is concentrated to give a crude product.
Was. This was recrystallized from hexane to give isopropylidene.
(Cyclopentadienyl) (3-phenyl-2-pheno
Xy) orange crystals of titanium dichloride were obtained.
(0.46 g, 23% yield). ¹ H NMR (C₆D₆) δ 1.20 (s, 6 H), 5.39 (t, 2 H, J
= 3 Hz), 6.26 (t, 2 H, J = 3 Hz), 7.00-7.20 (m, 5
H), 7.26 (dd, 1 H, J = 2 and 8 Hz), 7.40 (t, 1 H, J
 = 8 Hz), 7.75 (dd, 1 H, 2 and 8 Hz)

Example 13 Synthesis of 1-tert-butyl-3- [1- (3-tert-butylcyclopentadienyl) -1-methyl-ethyl] -2-methoxy-5-methylbenzene 2-bromo- To a solution of 6-tert-butyl-4-methylanisole (3.86 g) in anhydrous ether (30 ml),
A 1.69 M hexane solution of n-butyllithium (17.8 ml) was added dropwise at 78 ° C, and then the temperature was raised to room temperature over 2 hours. The resulting yellow solution was cooled to -78 ° C,
An anhydrous ether solution (10 ml) of 2-tert-butyl-5-isopropylidene-cyclopenta-1,3-diene (2.43 g) was added dropwise to the solution, and the temperature was raised to room temperature over 12 hours, and further at room temperature. Stir for 1 hour. Aqueous ammonium chloride solution was added to the reaction mixture, and the aqueous layer and the organic layer were separated. After the toluene-soluble component was extracted from the aqueous layer with toluene, the organic solution obtained by combining the organic layer and the toluene solution was washed with saturated saline and then dried with anhydrous sodium sulfate. The solvent was distilled off from the organic solution under reduced pressure, and the residue was treated by silica gel column chromatography to give 1-tert-butyl-3- [1-
(3-tert-Butylcyclopentadienyl) -1-methyl-ethyl] -2-methoxy-5-methylbenzene was obtained as a mixture of isomers (1.80 g, 35 yield).
%). ¹ H NMR (CDCl ₃ ) δ 1.06-1.19 (m, 15H), 1.37-1.38
(9 H; 1.37: s; 1.38: s), 2.31 (s, 3 H), 2.76-2.90
(2 H; 2.76: m; 2.90: m), 3.24-3.26 (3 H; 3.24: s;
3.26: s), 5.72-6.26 (m, 2 H), 7.06 (d, 1 H, J = 1
Hz), 7.10 (d, 1H, J = 1 Hz)

Example 14 Synthesis of isopropylidene (3-tert-butylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride 1-tert-butyl-3- [1- ( 3-tert-Butylcyclopentadienyl) -1-methyl-ethyl] -2-methoxy-5-methylbenzene (0.202 g) in hexane (3 mL) at 0 ° C. with n-butyllithium 1.6.
A 3M hexane solution (0.55 mL) was added dropwise, the temperature was raised to room temperature, and the mixture was stirred for 12 hours. Titanium tetrachloride (0.066 ml) was added to the obtained mixture at -50 ° C under light shielding,
The temperature was raised to room temperature over 2 hours, and the mixture was further stirred at room temperature for 12 hours. The obtained slurry was filtered and the filtrate was concentrated to obtain a crude product. This was recrystallized from hexane to give isopropylidene (3-tert-butylcyclopentadienyl)
Orange crystals of (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride were obtained (0.04
0 g, yield 15%). ¹ H NMR (C ₆ D ₆ ) δ 1.27 (s, 3 H), 1.35 (s, 9 H),
1.40 (s, 3 H), 1.64 (s, 9H), 2.27 (s, 3 H), 5.01
(t, 1 H, J = 3 Hz), 6.41 (t, 1 H, J = 3 Hz), 6.52
(t, 1 H, J = 3 Hz), 7.11 (d, 1 H, J = 2 Hz), 7.14
(d, 1 H, J = 2 Hz)

Example 15 1-tert-Butyl-3- [1- (3-methylcyclopentadienyl) -1-methyl-ethyl] -2-methoxy-
Synthesis of 5-methylbenzene Under a nitrogen atmosphere, 2-bromo-6-tert-butyl-4-
To an anhydrous ether solution (300 ml) of methylanisole (20.97 g), a 1.69 M hexane solution of n-butyllithium (100 ml) was added dropwise at -78 ° C, and then the temperature was raised to room temperature over 1 hour to obtain a product. Yellow solution
Cooled to 78 ° C. 2-Methyl-5-isopropylidene-cyclopenta-1,3-diene (9.78) was added to the solution.
An anhydrous ether solution (20 ml) of g) was added dropwise, the temperature was raised to room temperature over 12 hours, and the mixture was further stirred at room temperature for 1 hour.
Aqueous ammonium chloride solution was added to the reaction mixture, and the aqueous layer and the organic layer were separated. After the toluene-soluble component was extracted from the aqueous layer with toluene, the organic solution obtained by combining the organic layer and the toluene solution was washed with saturated saline and then dried with anhydrous sodium sulfate. After distilling off the solvent from the organic solution under reduced pressure, the residue was treated by silica gel column chromatography to give 1-tert-butyl-yellow oily product.
3- [1- (3-methylcyclopentadienyl) -1-
Methyl-ethyl] -2-methoxy-5-methylbenzene was obtained as a mixture of isomers (3.27 g, yield 1).
3%) ¹ H NMR (CDCl ₃ ) δ1.37-1.39 (9 H; 1.37: s; 1.38:
s; 1.39: s), 1.59-1.61 (6 H; 1.56: s; 1.60: s; 1.6
1: s), 1.98 (m, 3 H), 2.30 (s, 3 H), 2.70-2.84 (m,
2 H), 3.30-3.35 (3 H; 3.30: s; 3.31: s; 3.35: s),
5.75-6.19 (m, 2H), 7.02-7.08 (m, 2H) mass spectrum (EI, m / e) 298, 283, 267, 241,
227, 219, 189, 179, 161, 147, 121, 105, 91, 57

Example 16 Isopropylidene (3-methylcyclopentadienyl)
Synthesis of (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride 1-tert-butyl-3- [1- (3-methylcyclopentadienyl) -1-methyl-ethyl] -2-methoxy −
To a solution of 5-methylbenzene (0.298 g) in hexane (10 mL) at 0 ° C was added 1.56 of n-butyllithium.
M hexane solution (0.96 mL) was added dropwise, the temperature was raised to room temperature, and the mixture was stirred for 12 hours. Titanium tetrachloride (0.11 mL) was added to the obtained mixture at -50 ° C under light shielding, the temperature was raised to room temperature over 3 hours, and the mixture was further stirred at room temperature for 12 hours. The resulting slurry was filtered and the filtrate was concentrated to give isopropylidene (3-methylcyclopentadienyl) (3
An orange oil of -tert-butyl-5-methyl-2-phenoxy) titanium dichloride was obtained (0.10).
g, yield 25%). ¹ H NMR (C ₆ D ₆ ) δ 1.38 (s, 3 H), 1.41 (s, 3 H),
1.68 (s, 9 H), 2.24 (s, 3 H), 2.27 (s, 3 H), 5.34
(t, 1 H, J = 3 Hz), 5.72 (t, 1 H, J = 3 Hz), 6.23
(t, 1 H, J = 3 Hz), 7.13 (d, 1 H, J = 1 Hz), 7.14
(d, 1 H, J = 1 Hz)

Example 17 1-tert-Butyldimethylsilyl-3- (1-cyclopentadienyl-1-methyl-ethyl) -2-methoxy-
Synthesis of 5-Methylbenzene Under a nitrogen atmosphere, a solution of 2-bromo-6-tert-butyldimethylsilyl-4-methylanisole (6.00 g) in anhydrous ether (80 ml) was added to n-butyllithium at -78 ° C. A 1.60 M hexane solution (24.0 ml) was added dropwise, the temperature was raised to room temperature over 2 hours, and the obtained yellow solution was cooled to -78 ° C. An anhydrous ether solution (10 ml) of 5-isopropylidene-cyclopenta-1,3-diene (2.43 g) was added dropwise to the solution, the temperature was raised to room temperature over 12 hours, and the mixture was further stirred at room temperature for 1 hour. Aqueous ammonium chloride solution was added to the reaction mixture, and the aqueous layer and the organic layer were separated. After the toluene-soluble component was extracted from the aqueous layer with toluene, the organic solution obtained by combining the organic layer and the toluene solution was washed with saturated saline and then dried with anhydrous sodium sulfate. The solvent was distilled off from the organic solution under reduced pressure, and the residue was treated by silica gel column chromatography to give 1-tert-butyldimethylsilyl-3- (1-cyclopentadienyl-1-methyl-yellow-yellow oily matter. Ethyl) -2-methoxy-5-methylbenzene was obtained as a mixture of isomers (2.80 g, 43% yield) ¹ H NMR (CDCl ₃ ) δ 0.30 (s, 6 H), 0.79 (s, 9 H),
1.61 (s, 3 H), 1.62 (s, 3 H), 2.31 (s, 3 H), 2.80
(d, 1 H, J = 2 Hz), 2.95 (d, 1 H, J = 2 Hz), 3.19
(s, 3 H), 6.10-6.40 (m, 3 H), 7.09 (d, 1 H, J = 2
Hz), 7.19 (d, 1H, J = 2 Hz)

Example 18 Isopropylidene (cyclopentadienyl) (3-tert
Synthesis of -butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride 1-tert-butyldimethylsilyl-3- (1-cyclopentadienyl-1-methyl-ethyl) -2-methoxy-
A solution of 5-methylbenzene (1.25 g) in hexane (3
To the mixture (0 mL), a 1.69 M hexane solution of n-butyllithium (3.25 mL) was added dropwise at 0 ° C., the temperature was raised to room temperature, and the mixture was stirred for 12 hours. The resulting mixture was protected from light by -5
Titanium tetrachloride (0.41 mL) was added at 0 ° C., the temperature was raised to room temperature over 3 hours, and the mixture was further stirred at room temperature for 12 hours.
The obtained slurry was filtered and the filtrate was concentrated to obtain a crude product. This was recrystallized from hexane to obtain orange crystals of isopropylidene (cyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride (0.40 g, yield). 26%). ¹ H NMR (C ₆ D ₆ ) δ 0.65 (s, 6 H), 1.10 (s, 9 H),
1.23 (s, 6 H), 2.25 (s, 3 H), 5.56 (t, 2 H, J = 3
Hz), 6.31 (t, 2 H, J = 3 Hz), 7.20 (d, 1 H, J = 2 H
z), 7.28 (d, 1 H, J = 2 Hz)

Example 20 Isopropylidene (cyclopentadienyl) (3-t-
Synthesis of butyl-5-methyl-2-phenoxy) titanium dichloride A white solid obtained in the same manner as in (1-4) of Example 1 (0.
51 g, 1.7 mmol) in hexane (25 ml)
Titanium tetrachloride (0.18 ml, 1.6 m
mol) was added. Then, the temperature was raised to room temperature over 3 hours, and the mixture was further stirred at room temperature for 12 hours. The solution was colored brown and a dark orange solid precipitated. The reaction mixture was filtered to remove a solid, and hexane-soluble matter was extracted from the solid with hexane (120 ml). The obtained hexane solutions were combined, concentrated to 30 ml, cooled to -20 ° C, and allowed to stand for 12 hours. The precipitated yellow crystals were collected by filtration,
This was dried under reduced pressure to obtain isopropylidene (cyclopentadienyl) (3-t-butyl-5-methyl-2-phenoxy) titanium dichloride as yellow needle crystals (0.40 g, yield 64%). ). ¹ H NMR (CD ₂ Cl ₂ ) δ1.33 (s, 9 H), 1.51 (s, 6 H), 2.30
(s, 3H), 6.06 (t, J = 2.7Hz, 2H), 6.92 (t, J = 2.7Hz, 2
H), 6.99 (s, 1H), 7.19 (s, 1H) mass spectrum (CI, m / e) 386

Example 21 Synthesis of (2-allyloxy-3-tert-butyl-5-methylphenyl) chlorodimethylsilane 2-allyloxy-1-bromo-3-tert-butyl-5-
Methylbenzene (3.40g) in hexane (25m
l) at -10 ° C in 1.66 of n-butyllithium.
M hexane solution (7.46 ml) was added dropwise, and the mixture was stirred at -10 ° C for 30 minutes. Dichlorodimethylsilane (1.75 g) was added dropwise to the above-obtained mixture over 1 minute, the temperature was raised to room temperature and the mixture was stirred for 2 hours, and then the solvent and excess dichlorodimethylsilane were distilled off under reduced pressure. Hexane (10 ml) was added to the residue and filtered, and the solvent was distilled off from the filtrate under reduced pressure to give a pale yellow oil (purity 80%) (2
-Allyloxy-3-tert-butyl-5-methylphenyl) chlorodimethylsilane (3.50 g, yield 78%)
I got Mass spectrum (EI, m / e) 296, 281, 2
53, 245, 220, 205, 189, 161, 14
5,128,115,93,75,41

Example 22 Synthesis of (2-allyloxy-3-tert-butyl-5-methylphenyl) dimethyl (2,3,4,5-tetramethylcyclopentadienyl) silane Tetramethylcyclopentadiene (1.55 g N) in a tetrahydrofuran solution (50 ml) at -10 ° C.
-Butyllithium 1.66M hexane solution (7.87M)
(ml) was added dropwise, the temperature was raised to room temperature, and the mixture was stirred for 3 hours.
Cooled to -10 ° C. In the mixture obtained above, (2-allyloxy-3-tert-butyl-5-methylphenyl) chlorodimethylsilane (purity 80%,
A tetrahydrofuran solution (25 ml) of 3.50 g) was added dropwise over 1 minute. After warming the resulting mixture to room temperature,
Stir for 20 hours. Water (50 ml) was added to the reaction mixture, and the aqueous layer and the organic layer were separated. The organic layer was washed with a saturated aqueous solution of ammonium chloride (50 ml), the solvent was distilled off, and (2-allyloxy-3-tert-butyl-5-methylphenyl) dimethyl (2) was obtained as a pale yellow oil (purity 58%). , 3,4,5-Tetramethylcyclopentadienyl) silane (4.52 g, yield 72%) was obtained. ¹ H NMR (CDCl3) δ0.13 (s, 6H), 1.42 (s, 9H),
1.69 (s, 6H), 1.79 (s, 6H), 2.28 (s, 3H), 3.42 (s, 1
H), 4.40 (dt, 2H, J ＝ 2, 2Hz), 5.28 (dq, 1H, J ＝ 2, 1
1Hz), 5.54 (dq, 1H, J ＝ 2, 17Hz), 5.99 (ddt, 1H, J ＝
2, 11,17Hz), 7.03 (d, 1H, J = 2Hz), 7.17 (d, 1H, J =
2Hz) Mass spectrum (EI, m / e) 382, 341, 261, 162, 1
21, 41

Example 23 Synthesis of (2-allyloxy-3-tert-butyl-5-methylphenyl) dimethyl (2,3,4,5-tetramethylcyclopentadienyl) silane 2-Allyloxy-1-bromo- 3-tert-butyl-5-
To a tetrahydrofuran solution (500 ml) of methylbenzene (33.98 g), a 1.56 M hexane solution of n-butyllithium (76.92 ml) was added dropwise at -78 ° C, and the mixture was stirred for 1 hour. Dichlorodimethylsilane (10
The mixture obtained above was added dropwise to 0.0 g) of a hexane solution (200 ml) at −78 ° C. over 30 minutes while keeping the temperature at −20 ° C. or lower. Then, the mixture was heated to room temperature over 2 hours and stirred for 1 hour, and then the solvent and excess dichlorodimethylsilane were distilled off under reduced pressure. The obtained mixture was dissolved in tetrahydrofuran (200 ml),
In this solution, tetramethylcyclopentadiene (1
4.67 g) in tetrahydrofuran (400 ml)
And n-butyllithium 1.56M hexane solution (7
A solution of tetramethylcyclopentadienyllithium prepared from 6.92 ml) was added dropwise at -78 ° C over 30 minutes, the temperature was raised to room temperature over 2 hours, and the mixture was further stirred for 12 hours. Then, an aqueous solution of ammonium chloride was added to the reaction mixture, and the aqueous layer and the organic layer were separated. After the hexane-soluble component in the aqueous layer was extracted with hexane, the organic solution obtained by combining the organic layer and the hexane solution was washed with saturated saline and then dried with anhydrous sodium sulfate. After the solvent was distilled off from the organic solution, the residue was treated with silica gel column chromatography (solvent: hexane) to give colorless oily (2-allyloxy-3-tert-butyl-5-
Methylphenyl) dimethyl (2,3,4,5-tetramethylcyclopentadienyl) silane was obtained (24.
4 g, 53% yield).

Example 24 Synthesis of (2-allyloxy-3-tert-butyl-5-methylphenyl) dimethyl (2,3,4,5-tetramethylcyclopentadienyl) silane Magnesium (0.80 g), iodine 2-Aryloxy-1-bromo-3-tert-butyl-5-methylbenzene (0.10 g) was added to a mixture of (0.05 g) and tetrahydrofuran (200 ml) at room temperature, and the mixture was heated at 50 ° C for 1 hour. It was stirred. In the mixture obtained above, 2-allyloxy-1-bromo-3-tert-butyl-5-methylbenzene (8.10 g) and dichlorodimethylsilane (10.9 g).
g) and a toluene solution (20 ml) containing
Was added dropwise over 6 hours, and the mixture was further stirred for 1 hour. The solvent and excess dichlorodimethylsilane were distilled off from the resulting mixture under reduced pressure, and tetrahydrofuran (100 m) was added to the residue.
1) was added and cooled to -78 ° C. In the resulting mixture, a suspension of tetramethylcyclopentadierlithium (3.71 g) in tetrahydrofuran at -78 ° C (100
(ml) over 5 minutes, warming to room temperature over 2 hours,
It was stirred for a further 15 hours. Water (100 ml) in the reaction mixture
Was added, and the aqueous layer and the organic layer were separated. The organic layer was evaporated to give a pale yellow oil (purity 45%) (2
-Allyloxy-3-tert-butyl-5-methylphenyl) dimethyl (tetramethylcyclopentadienyl) silane (9.70 g, yield 39%) was obtained.

Example 25 Dimethylsilyl (tetramethylcyclopentadienyl)
Synthesis of (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride (2-allyloxy-3-tert-butyl-5-methylphenyl) dimethyl (2,3,4,5-tetramethylcyclopentadiene To a chlorobenzene solution (10 ml) containing (enyl) silane (0.96 g) and triethylamine (0.70 ml) was added dropwise a 1.56 M hexane solution of n-butyllithium (1.61 ml) at -78 ° C. Then, the temperature was raised to room temperature over 2 hours, and the mixture was further stirred for 6 hours. The resulting mixture was cooled to -78 ° C and a solution of titanium tetrachloride (0.276 ml) in chlorobenzene (3 m
l) was added. The resulting mixture was allowed to reach room temperature in the dark and kept at room temperature.
After heating for 1 hour and stirring for 1 hour,
The temperature was raised to 20 ° C. and the mixture was stirred for 35 hours. The reaction mixture was filtered and the solvent was distilled off from the filtrate to obtain a reddish brown solid. This solid was recrystallized from a hexane-toluene mixed solvent to give dimethylsilyl (tetramethylcyclopentadienyl).
Red needle-like crystals of (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride (0.58 g, yield 50%) were obtained.

Example 26 Dimethylsilyl (tetramethylcyclopentadienyl)
Synthesis of (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride (2-allyloxy-3-tert-butyl-5-methylphenyl) dimethyl (2,3,4,5-tetramethylcyclopentadiene To a toluene solution (8 ml) of (enyl) silane (0.28 g) was added dropwise a 1.56 M hexane solution of n-butyllithium (0.70 ml) at -78 ° C, and then the mixture was allowed to reach room temperature over 2 hours. The temperature was raised and the mixture was further stirred for 12 hours. The resulting mixture was cooled to -78 ° C and a solution of titanium tetrachloride (0.080 ml) in chlorobenzene (2 m
l) was added. The obtained mixture was heated to room temperature over 3 hours while protected from light, stirred for 1 hour, and then stirred for 1 hour over 9 hours.
The temperature was raised to 0 ° C. and the mixture was stirred for 10 hours. The reaction mixture was filtered and the solvent was distilled off from the filtrate to obtain a reddish brown solid. This solid was recrystallized from a hexane-toluene mixed solvent to obtain dimethylsilyl (tetramethylcyclopentadienyl) (3
Red needle crystals of -tert-butyl-5-methyl-2-phenoxy) titanium dichloride (0.14 g, yield 4
2%) was obtained.

Example 27 Synthesis of (cyclopentadienyl) (2-methoxy-3,5-dimethylphenyl) dimethylsilane 2-bromo-4,6-dimethylanisole (6.45)
In a tetrahydrofuran solution (100 ml) of g), -7
A 1-M hexane solution of n-butyllithium (37.5 ml) was added dropwise at 8 ° C, and then the temperature was raised to room temperature over 2 hours. The mixture obtained above was added dropwise to a hexane solution (200 ml) of dimethyldichlorosilane (19.3 6 g) at -78 ° C over 10 minutes. Then, the temperature was raised to room temperature over 2 hours, and the mixture was further stirred for 1 hour, then, the solvent and excess dimethyldichlorosilane were distilled off under reduced pressure. The resulting mixture was dissolved in tetrahydrofuran (300 ml), and a 2.0 M tetrahydrofuran solution of cyclopentadienyl sodium (15.0 ml) was added to this solution.
The mixture was added dropwise at 78 ° C., then the temperature was raised to room temperature over 2 hours, and the mixture was further stirred for 12 hours. Aqueous ammonium chloride solution was added to the reaction mixture, and the aqueous layer and the organic layer were separated. After extracting the hexane-soluble component from the aqueous layer with hexane, the organic solution obtained by combining the organic layer and the hexane solution was washed with saturated saline and dried with anhydrous sodium sulfate. The solvent was distilled off from the organic solution under reduced pressure, and the residue was treated with silica gel column chromatography (developing solution: hexane) to give colorless oily (cyclopentadienyl) (2-methoxy-3,5-dimethylphenyl). ) Dimethylsilane (4.30 g, yield 33%) was obtained. ¹ H NMR (CDCl3) δ 0.17 (s, 6H), 2.05 (s, 3H), 2.31
(s, 3H), 3.65 ~ 3.80 (m, 2H), 3.77 (s, 3H), 5.98 ~ 6.
45 (m, 3H), 7.12 (d, 1H, J = 3Hz), 7.22 (d, 1H, J = 3H
z)

Example 28 Synthesis of (3-tert-butyl-2-methoxy-5-methylphenyl) (cyclopentadienyl) diphenylsilane 1-Bromo-3-tert-butyl-2-methoxy-5-methylbenzene To a tetrahydrofuran solution (200 ml) of (7.72 g), a 1.60 M hexane solution of n-butyllithium (37.5 ml) was added dropwise at -78 ° C, and then the temperature was raised to room temperature over 2 hours. A solution of diphenyldichlorosilane (7.60 g) in -78 ° C hexane (20
(0 ml), the mixture obtained above was added dropwise over 15 minutes. Then, the temperature was raised to room temperature over 2 hours, the mixture was further stirred for 1 hour, and then the solvent was distilled off under reduced pressure. The obtained mixture was dissolved in tetrahydrofuran (300 ml), and 2.0 M of cyclopentadienyl sodium was added to this solution.
A tetrahydrofuran solution (15.0 ml) was added dropwise at -78 ° C, the temperature was raised to room temperature over 2 hours, and the mixture was further stirred for 12 hours. Ammonium chloride aqueous solution was added to the reaction mixture,
The aqueous layer and the organic layer were separated. After extracting the hexane-soluble component from the aqueous layer with hexane, the organic solution obtained by combining the organic layer and the hexane solution was washed with saturated saline and dried with anhydrous sodium sulfate. After distilling off the solvent from the organic solution under reduced pressure, the residue was treated with silica gel column chromatography (developing solution: hexane) to give colorless oily (3-tert-butyl-2-methoxy-5-methylphenyl) ( Cyclopentadienyl) diphenylsilane (3.59 g, yield 28%) was obtained. 1H NMR (CDCl3) δ 1.38 (s, 9H), 2.21 (s,
3H), 3.21 (s, 3H), 4.17 (d, 1H, J = 6Hz), 4.60 (d, 1
H, J = 14Hz), 6.35 ~ 6.78 (m, 3H), 6.98 (d, 1H, J = 2H
z), 7.01 (d, 1H, J = 2Hz), 7.20 ~ 7.68 (m, 10H) Mass spectrum (EI, m / e) 424, 359, 283, 183, 105

Example 29 Synthesis of (3-tert-butyl-2-methoxy-5-methylphenyl) dimethyl (methylcyclopentadienyl) silane 1-Bromo-3-tert-butyl-2-methoxy-5-methyl To a solution of benzene (23.16 g) in tetrahydrofuran (400 ml) was added dropwise a solution of n-butyllithium (1.6M) in hexane (112.5 ml) at -78 ° C.
Then, the temperature was raised to room temperature over 2 hours. Dimethyldichlorosilane (58.1 g) in hexane at -78 ° C (20
The mixture obtained above was added dropwise to 0 ml) over 30 minutes. Then, the temperature was raised to room temperature over 2 hours, and the mixture was further stirred for 1 hour, and then the solvent and excess dichlorodimethylsilane were distilled off under reduced pressure. The obtained mixture was dissolved in tetrahydrofuran (200 ml), and in this solution, a solution of methylcyclopentadiene (7.21 g) in tetrahydrofuran (400 ml) and a solution of n-butyllithium in 1.60 M hexane (57.69 ml) were added. The prepared solution of methylcyclopentadienyllithium was added dropwise at -78 ° C. After the resulting mixture was warmed to room temperature over 2 hours,
It was stirred for a further 12 hours. Aqueous ammonium chloride solution was added to the reaction mixture, and the aqueous layer and the organic layer were separated. After extracting the hexane-soluble component from the aqueous layer with hexane, the organic solution obtained by combining the organic layer and the hexane solution was washed with saturated saline and dried with anhydrous sodium sulfate. After the solvent was distilled off from the organic solution under reduced pressure, the residue was subjected to silica gel column chromatography (developing solution: hexane).
To obtain colorless oily (3-tert-butyl-2-methoxy-5-methylphenyl) dimethyl (methylcyclopentadienyl) silane (18.05 g) as a mixture of isomers in a yield of 64%. did. ¹ H NMR (CDCl3) δ 0.16-0.49 (6H; 0.16: s; 0.18:
s; 0.48: s; 0.49: s), 1.39-1.42 (9H; 1.39: s; 1.42:
s), 2.04-2.08 (3H; 2.04: s; 2.08: s), 2.31-2.32 (3
H; 2.31: s; 2.32: s), 2.97-3.05 (m, 1H), 3.61-3.78
(3H; 3.61: s; 3.78: s), 5.98-6.73 (m, 3H), 6.82 (d, 1
H, J = 2Hz), 7.20 (d, 1H, J = 2Hz)

Example 30 (tert-Butylcyclopentadienyl) (3-tert
Synthesis of -butyl-2-methoxy-5-methylphenyl) dimethylsilane 1-Bromo-3-t-butyl-2-methoxy-5-methylbenzene (23.16 g) in tetrahydrofuran (400 ml) at -78 ° C. Then, a 1.60 M hexane solution of n-butyllithium (112.5 ml) was added dropwise.
Then, the temperature was raised to room temperature over 2 hours. Dimethyldichlorosilane (58.1 g) in hexane at -78 ° C (20
The mixture obtained above was added dropwise to 0 ml) over 30 minutes. Then, the mixture was heated to room temperature over 2 hours and stirred for 1 hour, and then the solvent and excess dichlorodimethylsilane were distilled off under reduced pressure. The obtained mixture was dissolved in tetrahydrofuran (200 ml), and in this solution, tert
A solution of tert-butylcyclopentadienyllithium prepared from a solution of -butylcyclopentadiene (11.00g) in tetrahydrofuran (400ml) and a solution of n-butyllithium in 1.60M hexane (57.69ml) at -78 ° C. The mixture was added dropwise over 30 minutes, heated to room temperature over 2 hours, and further stirred for 12 hours. Aqueous ammonium chloride solution was added to the reaction mixture, and the aqueous layer and the organic layer were separated.
After extracting the hexane-soluble component from the aqueous layer with hexane, the organic solution obtained by combining the organic layer and the hexane solution was washed with saturated saline and dried with anhydrous sodium sulfate. After distilling off the solvent from the organic solution under reduced pressure, the residue was treated with silica gel column chromatography (developing solution: hexane) to obtain colorless oily (3-tert-butyl-2-methoxy-5-methylphenyl) dimethyl. (Methylcyclopentadienyl) silane (18.94 g) was obtained as a mixture of isomers with a yield of 59%. ¹ H NMR (CDCl3) δ 0.08-0.43 (6H; 0.08: s; 0.13:
s; 0.42: s; 0.43: s), 1.12-1.13 (9H; 1.12: s; 1.13:
s), 1.33-1.36 (9H; 1.33: s; 1.36: s), 2.22-2.25 (3
H; 2.22: s; 2.25: s), 2.97-3.61 (1H; 2.97: s; 3.61:
s) 3.71 (3H, s), 5.99-6.70 (m, 3H), 7.05 (d, 1H, J =
2Hz), 7.13 (d, 1H, J = 2Hz)

Example 31 Synthesis of (3-tert-butyl-2-methoxy-5-methylphenyl) (1H-inden-1-yl) dimethylsilane 1-Bromo-3-tert-butyl-2-methoxy-5 To a tetrahydrofuran solution (400 ml) of -methylbenzene (23.16 g) was added dropwise a solution of n-butyllithium in hexane (1.65 M, 112.5 ml) at -78 ° C.
Then, the temperature was raised to room temperature over 2 hours. Dimethyldichlorosilane (58.10 g) in hexane at -78 ° C (2
(00 ml), the mixture obtained above was added dropwise over 30 minutes. Then the mixture was warmed to room temperature over 2 hours,
After stirring for a further 1 hour, the solvent and excess dichlorodimethylsilane were distilled off under reduced pressure. The obtained mixture was dissolved in tetrahydrofuran (200 ml), and the solution of indene (10.4 5 g) in tetrahydrofuran (4
00 ml) and a solution of n-butyllithium in 1.60 M hexane (57.69 ml) were added dropwise to the solution of indenyllithium at -78 ° C over 15 hours, and the temperature was raised to room temperature over 2 hours. , And stirred for another 12 hours. Aqueous ammonium chloride solution was added to the reaction mixture, and the aqueous layer and the organic layer were separated. After extracting the hexane-soluble component in the aqueous layer with hexane, the organic solution obtained by combining the organic layer and the hexane solution was washed with saturated saline and then dried with anhydrous sodium sulfate. After distilling off the solvent from the organic solution under reduced pressure, the residue was treated with silica gel column chromatography (developing solution: hexane) to give colorless oily (3-tert-butyl-2-methoxy-5-methylphenyl). (1H-Inden-1-yl) dimethylsilane (23.63 g) was obtained with a yield of 75%. 1H NMR (CDCl3) δ 0.03 (s, 3H), 0.14 (s, 3
H), 1.44 (s, 9H), 2.29 (s, 3H), 3.45 (d, 1H, J = 1H
z), 3.81 (s, 3H), 6.57 (dd, 1H, J = 2, 5Hz), 6.89 (d
d, 1H, J = 2, 5Hz), 7.03 (d, 1H, J = 2Hz), 7.20 (d, 1
H, J = 2Hz), 7.04 to 7.50 (m, 4H)

Example 32 Synthesis of (3-tert-butyl-2-methoxy-5-methylphenyl) (9H-fluoren-9-yl) dimethylsilane 1-Bromo-3-tert-butyl-2-methoxy-5 To a tetrahydrofuran solution (100 ml) of -methylbenzene (7.72 g), was added dropwise a 1.60 M hexane solution of n-butyllithium (37.5 ml) at -78 ° C, and the temperature was raised to room temperature over 2 hours. It was stirred for another 3 hours.
The mixture obtained above was added dropwise to a solution of dichlorodimethylsilane (19.3 6 g) in a hexane solution (100 ml) at -78 ° C over 10 minutes. Warm to room temperature over 2 hours,
The mixture was further stirred for 1 hour, and the solvent and excess dichlorodimethylsilane were distilled off under reduced pressure. The obtained mixture was dissolved in tetrahydrofuran (150 ml), and a solution of fluorene (4.99 g) in tetrahydrofuran (100
ml) and a solution of n-butyllithium in 1.60 M hexane (18.25 ml) prepared dropwise at −78 ° C., the temperature was raised to room temperature over 2 hours, and the mixture was further stirred for 12 hours. did. . Then, an aqueous solution of ammonium chloride was added to the reaction mixture, and the aqueous layer and the organic layer were separated. The hexane-soluble component was extracted from the aqueous layer with hexane using hexane, and the organic solution obtained by combining the organic layer and the hexane solution was washed with saturated saline and dried over anhydrous sodium sulfate. After distilling off the solvent from the organic solution under reduced pressure, the residue was recrystallized from a mixed solvent of tetrahydrofuran-hexane to give colorless crystals of (3-tert-butyl-2-methoxy-5-methylphenyl) (9H-fluorene. -9-yl) dimethylsilane (6.82 g) was obtained with a yield of 57%. 1H NMR (CDCl3) δ 0.21 (s, 6H), 1.50 (s, 9
H), 2.33 (s, 3H), 3.82 (s, 3H), 4.40 (s, 1H), 6.99 (d,
1H, J ＝ 2Hz), 7.29 (d, 1H, J ＝ 2Hz), 7.12〜7.38
(m, 6H), 7.82 (d, 2H, J = 8Hz)

Example 33 Synthesis of (3-tert-butyl-2-methoxy-5-methylphenyl) (9H-fluoren-9-yl) diphenylsilane 1-Bromo-3-t-butyl-2-methoxy-5 To a tetrahydrofuran solution (100 ml) of -methylbenzene (5.24 g), a 1.60 M hexane solution of n-butyllithium (25.0 ml) was added dropwise at -78 ° C, and then the temperature was raised to room temperature over 2 hours. A solution of diphenyldichlorosilane (5.06 g) in hexane at -78 ° C (10
0 ml), the mixture obtained above was added dropwise over 10 minutes. Then, the temperature was raised to room temperature over 2 hours, the mixture was further stirred for 1 hour, and then the solvent was distilled off under reduced pressure. The resulting mixture was dissolved in tetrahydrofuran (150 ml) and -78
A solution of fluorenyllithium prepared from fluorene (3.32 g) tetrahydrofuran solution (100 ml) and n-butyllithium 1.60 M hexane solution (12.5 ml) was added dropwise at ℃, and the temperature was raised to room temperature over 2 hours. After warming, stirring was continued for another 12 hours. Aqueous ammonium chloride solution was added to the reaction mixture to separate it into an aqueous layer and an organic layer. After extracting the hexane-soluble component from the aqueous layer with hexane, the organic solution obtained by combining the organic layer and the hexane solution was washed with saturated saline and dried with anhydrous sodium sulfate. The solvent was distilled off from the organic solution under reduced pressure, and the residue was recrystallized from pentane to give colorless crystals of (3-tert-butyl-2-methoxy-5-methylphenyl) (9H-fluoren-9-yl). Diphenylsilane (4.31 g, 40% yield) was obtained. 1H NMR (CDCl3) δ 1.46 (s, 9H), 2.23 (s, 3
H), 3.39 (s, 3H), 4.92 (s, 1H), 7.00 (dt, 2H, J = 1, 7
Hz), 7.10 (d, 1H, J = 1Hz), 7.14 (d, 4H, J = 8Hz),
7.19 (d, 1H, J = 1Hz), 7.21 ~ 7.30 (m, 10H), 7.52 (d,
2H, J = 8Hz) Mass spectrum (EI, m / e) 524, 359, 282, 177, 1
65, 77

Example 34 (3-tert-butyl-2-methoxymethyloxy-5-
Synthesis of methylphenyl) dimethyl (2,3,4,5-tetramethylcyclopentadienyl) silane 1-Bromo-3-t-butyl-2-methoxymethyloxy-5-methylbenzene (11.48 g) in tetrahydrofuran To the solution (300 ml) at -78 ° C, a solution of n-butyllithium in 1.60 M hexane (25.0 ml).
Was added dropwise and stirred for 1 hour. Dimethyldichlorosilane (5.16 g) in hexane at -78 ° C (200 m
The mixture obtained above was added dropwise into 1) at a temperature of -20 ° C or lower over 30 minutes. Then, the temperature was raised to room temperature over 2 hours, the mixture was further stirred for 1 hour, and then the solvent was distilled off under reduced pressure. Tetrahydrofuran (200 m
l) and dissolved in this solution, a solution of tetramethylcyclopentadiene (4.88 g) in tetrahydrofuran (30
0 ml) and a solution of tetramethylcyclopentadienyllithium prepared from a 1.60 M hexane solution of n-butyllithium (25.0 ml) were added dropwise at −78 ° C., and then the temperature was raised to room temperature over 2 hours. After that, the mixture was further stirred for 12 hours. Ammonium chloride aqueous solution was added to the reaction mixture,
The aqueous layer and the organic layer were separated. After extracting the hexane-soluble component from the aqueous layer with hexane, the organic solution obtained by combining the organic layer and the hexane solution was washed with saturated saline and dried with anhydrous sodium sulfate. After distilling off the solvent from the organic solution under reduced pressure, the residue was treated with silica gel column chromatography (developing solution: hexane) to give colorless oily (3-tert-butyl-2-methoxymethyloxy-5-methyl). Phenyl) dimethyl (2,3,4,5
-Tetramethylcyclopentadienyl) silane (5.6
0 g) was obtained with a yield of 36%. ¹ H NMR (CDCl3) δ 0.13 (s, 6H), 1.39 (s, 9H), 1.6
9 (s, 6H), 1.78 (s, 6H), 2.29 (s, 3H), 3.43 (s, 1H), 4.
40 (dd, 2H, J ＝ 2, 2Hz), 5.27 (ddd, 1H, J ＝ 2, 2, 9H
z), 5.53 (ddd, 1H, J = 2, 2, 17Hz), 6.03 (ddddd, 1H,
J = 2,2,2,9,17Hz), 7.03 (d, 1H, J = 2Hz), 7.17
(d, 1H, J = 2Hz)

Example 35 Synthesis of (2-benzyloxy-3-tert-butyl-5-methylphenyl) dimethyl (2,3,4,5-tetramethylcyclopentadienyl) silane 2-benzyloxy-1-bromo- 3-t-butyl-5
To a tetrahydrofuran solution (300 ml) of methylbenzene (29.30 g), a 1.56 M hexane solution of n-butyllithium (51.28 ml) was added dropwise at -78 ° C, and the mixture was stirred for 1 hour. Dimethyldichlorosilane (10
0.0 g) was dissolved in a hexane solution (150 ml)-
The mixture obtained above was added dropwise to the solution at 78 ° C at a temperature of -20 ° C or lower over 30 minutes. Then, the temperature was raised to room temperature and the mixture was stirred for another hour, then, the solvent and excess dichlorodimethylsilane were distilled off under reduced pressure. The obtained mixture was dissolved in tetrahydrofuran (200 ml), and tetramethylcyclopentadiene (9.
78 g) in tetrahydrofuran (500 ml) and n
-Butyllithium 1.56M hexane solution (51.2
(8 ml) and a solution of tetramethylcyclopentadienyllithium prepared from the above was added dropwise, the temperature was raised to room temperature over 2 hours, and the mixture was further stirred for 12 hours. Aqueous ammonium chloride solution was added to the reaction mixture, and the aqueous layer and the organic layer were separated. The hexane-soluble matter was extracted from the aqueous layer with hexane, and the organic solution obtained by combining the organic layer and the hexane solution was washed with saturated saline and dried over anhydrous sodium sulfate. After distilling off the solvent from the organic solution under reduced pressure, the residue was treated with silica gel column chromatography (developing solution: hexane) to give colorless oily (2-benzyloxy-3-tert-butyl-5-methylphenyl). ) Dimethyl (2,3,4,5-tetramethylcyclopentadienyl) silane (17.6 g, yield 51%) was obtained. 1H NMR (CDCl3) δ 0.01 (s, 6H), 1.33 (s, 9
H), 1.52 (s, 6H), 1.67 (s, 6H), 2.24 (s, 3H), 3.32 (s,
1H), 4.94 (s, 2H), 6.99 (d, 1H, J = 2Hz), 7.13 (d, 1
H, J = 2Hz), 7.21 (dd, 2H, J = 7,7Hz), 7.29 (dt, 1H,
J = 1, 7Hz), 7.40 (dd, 2H, J = 1, 7Hz) Mass spectrum (EI, m / e) 432, 341, 311, 295,
255, 91, 57

Example 36 (2-tert-butyldimethylsilyloxy-3-tert-
Butyl-5-methylphenyl) dimethyl (2,3,4,
Synthesis of 5-tetramethylcyclopentadienyl) silane 3-tert-butyl-2-tert-butyldimethylsilyloxy-1-bromo-5-methylbenzene (0.715
g) in tetrahydrofuran solution (10 ml) at -78 ° C
And cooled to n-butyllithium in hexane (1.2
8 ml) was added and stirring was continued for 1 hour as it was. The resulting mixture was mixed with (2,3,4,5-tetramethyl-cyclopentadienyl) dimethylsilyl chloride (0.429
g) was added and stirring was continued at room temperature for 10 hours. A saturated aqueous ammonium chloride solution (10 ml) was added to the reaction mixture, and the mixture was separated into an aqueous layer and an organic layer. The ethyl acetate-soluble matter was extracted from the aqueous layer with ethyl acetate. The organic solution obtained by combining the organic layer and the ethyl acetate solution was dried over anhydrous sodium sulfate, the solvent was distilled off, and the residue was treated by silica gel column chromatography (developing solution: hexane) to give a yellow oil. (2-tert-butyldimethylsilyloxy-3-tert-butyl-5-methylphenyl) dimethyl (2,3,4,5-tetramethylcyclopentadienyl) silane (0.30 g, yield 34%) Got ¹ H NMR (CDCl ₃ ) δ 0.21 (s, 12 H), 0.67 (s, 9
H), 1.38 (s, 9 H), 1.85 (s, 6 H), 2.10 (s, 6 H),
2.28 (s, 3 H), 3.32 (s, 1 H), 6.91 (d, 1 H, J = 2 H
z), 7.05 (d, 1 H, J = 2 Hz) Mass spectrum (EI, m / e) 456, 399, 326, 223, 17
8, 147, 133, 105, 57, 41

Example 37 Synthesis of (2-allyloxy-3-tert-butyl-5-methylphenyl) dimethyl (cyclopentadienyl) silane 2-Allyloxy-1-bromo-3-tert-butyl-5-
To a tetrahydrofuran solution (200 ml) of methylbenzene (17.0 g) was added dropwise a 1.66 M hexane solution of n-butyllithium (36.2 ml) at -78 ° C.
Stir for 1 hour. Dimethyldichlorosilane (50.0
g) in a solution of -78 ° C in hexane (100 ml), the mixture obtained above was added dropwise at a temperature below -20 ° C over 15 minutes. Then, the obtained mixture was heated to room temperature over 2 hours and stirred for 1 hour, and then the solvent and excess dichlorodimethylsilane were distilled off under reduced pressure. The resulting mixture was dissolved in tetrahydrofuran (75 ml) and cyclopentadienyl sodium 2M was added at -78 ° C.
Tetrahydrofuran solution (30 ml) was added dropwise, the temperature was raised to room temperature over 2 hours, and the mixture was further stirred for 12 hours. Aqueous ammonium chloride solution was added to the reaction mixture, and the aqueous layer and the organic layer were separated. After extracting the hexane-soluble component from the aqueous layer with hexane, the organic solution obtained by combining the organic layer and the hexane solution was washed with saturated saline and dried with anhydrous sodium sulfate. After distilling off the solvent from the organic solution under reduced pressure, the residue was treated with silica gel column chromatography (developing solution: hexane) to give colorless oily (2-allyloxy-3-tert-butyl-5-methylphenyl). Dimethyl (cyclopentadienyl) silane (7.
3 g, yield 37%) was obtained. 1H NMR (CDCl3) δ 0.19 (s, 6H), 1.45 (s, 9H),
2.36 (s, 3H), 3.11 (s, 1H), 4.43 (dt, 2H, J ＝ 2, 5H
z), 5.31 (dq, 1H, J ＝ 2, 11Hz), 5.57 (dq, 1H, J ＝ 2,
17Hz), 6.07 (ddt, 1H, J = 5, 11, 17Hz), 6.40 ~ 6.70
(m, 4H), 7.16 (d, 1H, J = 2Hz), 7.22 (d, 1H, J = 2Hz) Mass spectrum (EI, m / e) 326, 311, 285, 220, 41

Example 38 Dimethylsilyl (cyclopentadienyl) (3-tert-
Synthesis of butyl-5-methyl-2-phenoxy) titanium dichloride (2-allyloxy-3-tert-butyl-5-methylphenyl) dimethyl (cyclopentadienyl) silane (1.
62g) in toluene solution (15ml) at -78 ° C
-Butyl lithium in 1.66M hexane solution (2.99
ml) was added dropwise. Then, the temperature was raised to room temperature over 2 hours, and the mixture was further stirred for 12 hours. The resulting mixture is -78 ° C.
After cooling to room temperature, a solution of titanium tetrachloride (0.545 ml) in toluene (5 ml) was added. The resulting mixture was warmed to room temperature over 2 hours while protected from light, and further stirred for 12 hours. The reaction mixture was filtered, and the solvent was distilled off from the filtrate under reduced pressure to obtain a reddish brown solid. This solid was recrystallized from a hexane-toluene mixed solvent to give red needle crystals of dimethylsilyl (cyclopentadienyl) (3-tert-butyl-5-
Methyl-2-phenoxy) titanium dichloride (0.72 g, yield 36%) was obtained. 1H NMR (C6D6) δ 0.27 (s, 6H), 1.63 (s, 9
H), 2.21 (s, 3H), 6.09 (t, 2H, J = 2Hz), 6.65 (t, 2H,
J = 2Hz), 7.08 (d, 1H, J = 2Hz), 7.21 (d, 1H, J = 2H
z)

Example 39 (2-Aryloxy-3-tert-butyl-5-methylphenyl) dimethyl (tert-butylcyclopentadienyl)
Synthesis of Silane To a tetrahydrofuran solution (200 ml) of 2-allyloxy-1-bromo-3-t-butyl-5-methylbenzene (17.00 g) was added a 1.66 M hexane solution of n-butyllithium (36 ml) at -78 ° C. .2 ml) and add 1
Stirred for hours. Dimethyldichlorosilane (50.0g)
Was dissolved in hexane (100 ml) at -78 ° C and the mixture obtained above was stirred at a temperature below -20 ° C for 1
It was added dropwise over 5 minutes. Then, the temperature was raised to room temperature over 2 hours, and the mixture was further stirred for 1 hour, then, the solvent and excess didichloromethylsilane were distilled off under reduced pressure. The resulting mixture was dissolved in tetrahydrofuran (75 ml) and in this solution-
5-isopropylidenecyclopenta-1,3 at 78 ° C
A solution of diene (6.37 g) in tetrahydrofuran (2
50 ml) and a 1.05 M methyllithium-ether solution (57.2 ml) were added dropwise to a solution of tert-butylcyclopentadienyllithium, then the temperature was raised to room temperature over 2 hours, and a further 12 Stir for hours. Aqueous ammonium chloride solution was added to the reaction mixture, and the aqueous layer and the organic layer were separated. After extracting the hexane-soluble component from the aqueous layer with hexane, the organic solution obtained by combining the organic layer and the hexane solution was washed with saturated saline and dried with anhydrous sodium sulfate. After distilling off the solvent from the organic solution under reduced pressure, the residue was subjected to silica gel column chromatography.
(Developing solution: hexane) and treated as a colorless oil (2-
Allyloxy-3-tert-butyl-5-methylphenyl)
Dimethyl (tert-butylcyclopentadienyl) silane (6.58 g, 29% yield) was obtained as a mixture of isomers. 1H NMR (CDCl3) δ 0.17-0.55 (6H; 0.17: s; 0.
22: s; 0.54: s; 0.55: s), 1.22-1.23 (9H; 1.22: s; 1.
23: s), 1.43-1.46 (9H; 1.43: s; 1.46: s), 2.34-2.36
(3H; 2.34: s; 2.36: s), 3.08-3.76 (1H; 3.08: s; 3.7
6: s), 4.27-4.60 (m, 2H), 5.30-5.62 (m, 2H), 6.08-6.1
2 (m, 1H), 6.20-6.60 (m, 3H), 7.17 (d, 1H, J = 2Hz),
7.23 (d, 1H, J = 2Hz) Mass spectrum (EI, m / e) 382, 325, 261, 203, 17
2, 41

Example 40 Synthesis of dimethylsilyl (3-tert-butylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride (2-allyloxy-3-tert-butyl-5) -Methylphenyl) dimethyl (tert-butylcyclopentadienyl)
To a toluene solution (15 ml) of silane (1.53 g),
At −78 ° C., a 1.66M hexane solution of n-butyllithium (2.41 ml) was added dropwise, and then the temperature was raised to room temperature over 2 hours, and the mixture was further stirred for 12 hours. The resulting mixture was cooled to −78 ° C. and treated with titanium tetrachloride (0.440 m
l) Toluene solution (5 ml) was added. The obtained mixture was warmed to room temperature over 2 hours while protected from light, and further stirred for 12 hours. The reaction mixture was filtered and the solvent was distilled off from the filtrate to obtain a reddish brown solid. This solid was recrystallized from a mixed solvent of hexane and toluene to give dimethylsilyl (3-tert-butylcyclopentadienyl) as orange crystals.
(3-tert-Butyl-5-methyl-2-phenoxy) titanium dichloride (0.09 g, yield 5%) was obtained. 1H NMR (C6D6) δ 0.36 (s, 3H), 0.40 (s, 3
H), 1.38 (s, 9H), 1.65 (s, 9H), 2.24 (s, 3H), 5.73 (dd,
1H, J = 2, 3Hz), 6.79 (dd, 1H, J = 2, 3Hz), 6.82 (d
d, 1H, J = 2, 3Hz), 7.15 (d, 1H, J = 2Hz), 7.25
(d, 1H, J ＝ 2Hz)

Example 41 Synthesis of (2-allyloxy-3-tert-butyl-5-methylphenyl) dimethyl (methylcyclopentadienyl) silane 2-allyloxy-1-bromo-3-tert-5-methylbenzene ( 5.6 g of tetrahydrofuran solution (50 m
1.65M hexane solution of n-butyllithium (12.5 ml) was added dropwise to l) at -78 ° C, and the mixture was stirred at -78 ° C for 1.
Stir for 5 hours. Dichlorodimethylsilane (12.1
The mixture obtained above was added dropwise to a solution of g) in -78 ° C in hexane (25 ml) over 3 minutes. Then, the temperature was raised to room temperature over 2 hours, the mixture was stirred for 24 hours, and then the solvent and dichlorodimethylsilane were distilled off under reduced pressure. Tetrahydrofuran (50 ml) was added to the obtained mixture, and lithium methylcyclopentadienide (3.
A tetrahydrofuran solution (30 ml) of 0 g) was added over 1 minute, the temperature was raised to room temperature over 2 hours, and the mixture was further stirred for 3 hours. Water (40 ml) was added to the reaction mixture, and the mixture was separated into an aqueous layer and an organic layer. The solvent was distilled off from the organic layer, and the obtained residue was treated with a silica gel column to give (2-allyloxy-3
A pale yellow oil (2.5 g, 90% pure) of an isomer mixture of -tert-butyl-5-methylphenyl) dimethyl (methylcyclopentadienyl) silane was obtained. The yield of the desired product was 33%. 1H-NMR (C6D6) δ 0.08-0.09 (3H; 0.08:
s; 0.09: s), 0.39-0.41 (3H; 0.39: s; 0.41: s), 1.32
-1.51 (9H; 1.32: s; 1.36: s; 1.39: s; 1.51: s), 1.9
6-2.03 (3H; 1.96: s; 1.99: s; 2.03: s), 2.24-2.27 (3
H; 2.24: s; 2.27: s), 2.90-3.68 (1H; 2.90: s; 2.98:
s; 3.68: s), 4.17-4.50 (2H; 4.17: m; 4.33: s; 4.50:
d, J = 5Hz), 5.22 (d, 1H, J = 10Hz), 5.48 (d, 1H, J = 17H
z), 5.79-5.98 (m, 1H), 6.14 (d, 1H, J = 10Hz), 6.38 (d,
1H), 7.07-7.16 (m, 3H) Mass spectrum (EI, m / e) 340, 325, 2
98, 283, 245, 221, 205, 189, 15
9, 145, 120, 91, 75, 61, 41

Example 42 Dimethylsilyl (methylcyclopentadienyl) (3-
Synthesis of tert-butyl-5-methyl-2-phenoxy) titanium dichloride (2-allyloxy-3-tert-butyl-5-methylphenyl) dimethyl (methylcyclopentadienyl) silane (0.75 g) in hexane ( 10 ml), -78
A 1.66M hexane solution of n-butyllithium (2.1 ml) was added dropwise at C. Then, the temperature was raised to room temperature over 2 hours, and the mixture was further stirred for 12 hours. Toluene (25 ml) was added to the obtained mixture, titanium tetrachloride (0.40 g) was added at room temperature, and the mixture was stirred at 75 ° C. for 24 hours under light shielding. The reaction mixture is filtered, the solvent is distilled off from the filtrate,
Black tar was obtained. A hexane-soluble component was extracted from this tar with hexane (5 ml), and the solvent was distilled off from the resulting hexane solution to obtain dimethylsilyl (methylcyclopentadienyl) (3-tert-butyl-5-methyl). A red-black tar (2-phenoxy) titanium dichloride (0.3 g, yield 33%) was obtained as an isomer mixture. 1H-NMR data (C6D6) δ 0.24-0.34 (6H;
0.24: s; 0.32: s; 0.33: s; 0.34: s), 1.58-1.64 (9H;
1.58: s; 1.59: s; 1.62: s; 1.69: s), 2.15-2.26 (6H;
2.15: s; 2.19: s; 2.21: s; 2.24: s; 2.26: s), 5.81
(s, 1H), 6.14 (t, 1H, J = 2Hz), 6.46 (t, 1H, J = 2Hz), 7.
12 (d, 1H, J = 1Hz), 7.24 (d, 1H, J = 1Hz)

Example 43 Synthesis of (2-allyloxy-3-tert-butyl-5-methylphenyl) (indenyl) dimethylsilane 2-allyloxy-1-bromo-3-tert-butyl-5-
To a tetrahydrofuran solution (150 ml) of methylbenzene (18.9 g) was added dropwise a 1.65 M hexane solution of n-butyllithium (40.4 ml) at -78 ° C,
The mixture was stirred at 78 ° C for 2 hours. Dichlorodimethylsilane (12.1g) in hexane at -78 ° C (80ml)
The mixture obtained above was added dropwise to the mixture over 5 minutes, the temperature was raised to room temperature over 2 hours, the mixture was stirred for 24 hours, and then the solvent and dichlorodimethylsilane were distilled off under reduced pressure. To the resulting mixture was added tetrahydrofuran (150 ml) to obtain -78.
The mixture was cooled to 0 ° C., a tetrahydrofuran solution (100 ml) of indenyllithium (8.2 g) was added over 3 minutes, the temperature was raised to room temperature over 2 hours, and the mixture was stirred for 5 hours. Water (100 ml) was added to the reaction mixture, and the aqueous layer and the organic layer were separated.
The oil obtained by distilling off the solvent from the organic layer was treated with a silica gel column to obtain a yellow oil ((2-aryloxy-3-tert-butyl-5-methylphenyl) (indenyl) dimethylsilane isomer mixture yellow oil ( 11.0 g, purity 94
%) Was obtained. The yield of the desired product was 43%. 1H-NMR (C6D6) δ 0.09 (s, 3H), 0.55 (s,
3H), 1.32-1.41 (9H; 1.32: s; 1.41: s), 2.28-2.29 (3H;
2.28: s; 2.29: s), 3.40 (s, 1H), 4.03 (s, 1H), 4.15
(t, 1H, J = 2Hz), 4.39 (dd, 2H, J = 2.2Hz), 5.05-5.24 (1
H, 5.05: s; 5.08: s; 5.18: s; 5.24: d, J = 9Hz), 5.5
1 (d, 1H, J = 17Hz), 5.69-6.08 (m, 1H), 6.54 (dd, 1H, J
= 2.6Hz), 6.80-7.50 (m, 5H) Mass spectrum (EI, m / e) 340, 325, 2
98, 283, 245, 221, 205, 189, 15
9, 145, 120, 91, 75, 61, 41

Example 44 Dimethylsilyl (indenyl) (3-tert-butyl-5
-Methyl-2-phenoxy) titanium dichloride Synthesis of (2-allyloxy-3-tert-butyl-5-methylphenyl) (indenyl) dimethylsilane (2.2 g) in toluene solution (20 ml) at room temperature with triethylamine ( 1.50 g) was added, the mixture was cooled to -30 ° C, and a 1.66 M hexane solution of n-butyllithium (4.8 ml) was added dropwise. The temperature was raised to room temperature, and the mixture was stirred for 12 hours. Titanium tetrachloride (1.35 g) was added dropwise to the obtained mixture at room temperature, and the mixture was stirred at 95 ° C. for 24 hours in the dark. The reaction mixture was filtered, the solid was washed with toluene (15 ml), and the solvent was distilled off from the filtrate to give a red-black oil (2.9
g) was obtained. Pentane (10 ml) was added to this oil, and the insoluble matter was dried under reduced pressure to obtain a reddish brown powder of dimethylsilyl (indenyl) (3-tert-butyl-5-methyl-2).
-Phenoxy) titanium dichloride (0.25 g,
Yield 11%) was obtained. 1H-NMR (C6D6) δ 0.45 (s, 3H), 0.50 (s,
3H), 1.44 (s, 9H), 2.27 (s, 3H), 6.69-6.75 (m, 2H),
6.78-6.80 (1H; 6.79: d, J = 1Hz; 6.80: d, J = 1Hz), 6.92
-6.98 (m, 1H), 7.15 (s, 1H), 7.23 (dd, 2H, J = 2.6Hz),
7.57 (dt, 1H, J = 9.1Hz)

Example 45 Synthesis of (2-allyloxy-3-tert-butyl-5-methylphenyl) dimethyl (9H-fluoren-9-yl) silane 2-Allyloxy-1-bromo-3-t-butyl-5 To a tetrahydrofuran solution (200 ml) of -methylbenzene (17.0 g), a 1.66 M hexane solution of n-butyllithium (36.2 ml) was added dropwise at -78 ° C.
Stirred for hours. Dimethyldichlorosilane (50.0g)
Was dissolved in hexane (100 ml) at −78 ° C. The mixture obtained above was added dropwise at a temperature below −20 ° C. over 15 minutes. The temperature was raised to room temperature over 2 hours, and the mixture was further stirred for 1 hour, then, the solvent and excess dichlorodimethylsilane were distilled off under reduced pressure. The obtained mixture was dissolved in tetrahydrofuran (75 ml), and this solution was added at -78 ° C to a solution of fluorene (9.97 g) in tetrahydrofuran (25
(0 ml) and 1.66 M n-butyllithium-hexane solution (36.2 ml) were added dropwise, and the temperature was raised to room temperature over 2 hours, and the mixture was further stirred for 12 hours. Aqueous ammonium chloride solution was added to the reaction mixture, and the aqueous layer and the organic layer were separated. After extracting the hexane-soluble component from the aqueous layer with hexane, the organic solution obtained by combining the organic layer and the hexane solution was washed with saturated saline and dried with anhydrous sodium sulfate. After distilling off the solvent from the organic solution under reduced pressure, the residue was treated with silica gel column chromatography (developing solution: hexane) to give colorless oily (2-allyloxy-3-tert-
Butyl-5-methylphenyl) dimethyl (9H-fluoren-9-yl) silane (12.04 g, yield 47%)
Got 1 H NMR (CDCl3) δ 0.10 (s, 6H), 1.56 (s, 9H),
2.40 (s, 3H), 4.51 (s, 1H), 4.52 (dt, 2H, J = 2, 4H
z), 5.37 (dq, 1H, J ＝ 2, 8Hz), 5.63 (dq, 1H, J ＝ 2,
17Hz), 6.14 (ddt, 1H, J = 4, 8, 17Hz), 7.08 (d, 1H,
J = 2Hz), 7.23 (d, 1H, J = 2Hz), 7.23 (dd, 2H, J = 7, 8
Hz), 7.39 (dd, 2H, J = 7, 8Hz), 7.40 (d, 2H, J = 7Hz)
, 7.92 (d, 2H, J = 8Hz)

Example 46 Synthesis of 2-allyloxy-1-bromo-3.5-dimethylbenzene 2-bromo-4,6-dimethylphenol (88.02)
g) was added to a solution of acetonitrile (500 ml) at 0 ° C. and potassium hydroxide (30.0 g) was added, and 2
Stirred for hours. Allyl bromide (100 g) was added dropwise to the obtained blue solution at 10 ° C or lower, the temperature was raised to room temperature, and the mixture was further stirred for 6 hours. Aqueous ammonium chloride solution was added to the reaction mixture to separate it into an aqueous layer and an organic layer. After extracting the hexane-soluble component from the aqueous layer with hexane, the organic solution obtained by combining the organic layer and the hexane solution was washed with saturated saline and dried with anhydrous sodium sulfate.
After distilling the solvent away from the organic solution under reduced pressure, the residue was treated with silica gel column chromatography (developing solution: hexane) to give colorless oily 2-allyloxy-1-bromo-3.5-dimethylbenzene (85 .73 g, 81% yield) was obtained. 1H NMR (CDCl3) δ 2.24 (s, 3H), 2.27 (s, 3
H), 4.40 (dt, 2H, J = 1, 6Hz), 5.27 (dq, 1H, J = 1, 1
0Hz), 5.43 (dq, 1H, J = 2, 17Hz), 6.13 (ddt, 1H, J = 6,
10, 17Hz), 6.91 (dd, 1H, J = 1, 1Hz), 7.19 (dd, 1H,
J = 1, 1Hz)

Example 47 Synthesis of (2-allyloxy-3,5-dimethylphenyl) dimethyl (2,3,4,5-tetramethylcyclopentadienyl) silane 2-Allyloxy-1-bromo-3,5- A solution of dimethylbenzene (24.1 g) in tetrahydrofuran (200
ml), at -78 ° C, 1.66M of n-butyllithium.
A hexane solution (60.24 ml) was added dropwise, and the mixture was stirred for 20 minutes. To a solution of dichlorodimethylsilane (100.0 g) in hexane (100 ml) at -78 ° C, the mixture obtained above was added dropwise at a temperature below -20 ° C over 30 minutes and then to room temperature. After the temperature was raised and the mixture was further stirred for 1 hour, the solvent and excess dichlorodimethylsilane were distilled off under reduced pressure. The resulting mixture was added with tetrahydrofuran (20
0 ml), and at -78 ° C., tetramethylcyclopentadiene (12.22 g) in tetrahydrofuran (400 ml) and n-butyllithium 1.
A solution of tetramethylcyclopentadienyllithium prepared from a 66M hexane solution (60.24 ml) was added dropwise, the temperature was raised to room temperature over 2 hours, and the mixture was further stirred for 12 hours. Ammonium chloride aqueous solution was added to the reaction mixture,
It was separated into an aqueous layer and an organic layer. After extracting the hexane-soluble component from the aqueous layer with hexane, the organic solution obtained by combining the organic layer and the hexane solution was washed with saturated saline and dried with anhydrous sodium sulfate. After distilling off the solvent from the organic solution under reduced pressure, the residue was treated with silica gel column chromatography (developing solution: hexane) to give colorless oily (2-allyloxy-3,5-dimethylphenyl) dimethyl (2,2). 3,4,5-Tetramethylcyclopentadienyl) silane (18.8 g, yield 56%) was obtained. 1H NMR (CDCl3) δ 0.10 (s, 6H), 1.70 (s, 6H),
1.80 (s, 6H), 2.27 (s, 3H), 2.28 (s, 3H), 3.40 (s, 1
H), 4.41 (dt, 2H, J = 2, 5Hz), 5.28 (dq, 1H, J = 2, 1
1Hz), 5.41 (dq, 1H, J ＝ 2, 17Hz), 6.12 (ddt, 1H, J ＝
5,11, 17Hz), 6.94 (d, 1H, J = 2Hz), 7.02 (d, 1H, J =
2Hz) Mass spectrum (EI, m / e) 340, 299, 219, 178, 41

Example 48 2-Allyloxy-1-bromo-3-tert-butyl-5-
Synthesis of methylbenzene To a solution of 2-bromo-4-methyl-6-tert-butylphenol (43.8 g) in acetonitrile (250 ml) at 0 ° C was added potassium hydroxide (13.2 g), Stir for 2 hours. Allyl bromide (65 g) was added dropwise to the obtained blue solution at 10 ° C or lower, and the temperature was raised to room temperature, followed by stirring for 6 hours. Aqueous ammonium chloride solution was added to the reaction mixture, and the aqueous layer and the organic layer were separated. After extracting the hexane-soluble component from the aqueous layer with hexane, the organic solution obtained by combining the organic layer and the hexane solution was washed with saturated saline and dried with anhydrous sodium sulfate. After the solvent was distilled off from the organic solution under reduced pressure, the residue was subjected to silica gel column chromatography (developing solution: hexane).
Treatment with 2-allyloxy-1-bromo-3-tert-butyl-5-methylbenzene (46.0) as a colorless oil.
7 g, yield 90%) was obtained. 1H NMR (CDCl3) δ 1.38 (s, 9H), 2.27 (s, 3H),
4.57 (dt, 2H, J = 2,5Hz), 5.29 (dq, 1H, J = 2, 11Hz),
5.49 (dq, 1H, J = 2, 17Hz), 6.13 (ddt, 1H, J = 5, 11,
17Hz), 7.07 (d, 1H, J = 2Hz), 7.25 (d, 1H, J = 2Hz)

Example 49 2-Allyloxy-1-bromo-3-tert-butyl-5-
Synthesis of Methylbenzene To a mixture of 85% potassium hydroxide (76.61 g) and methyl isobutyl ketone (1000 ml) was added 2-bromo-.
6-tert-butyl-4-methylphenol (230.9
8g) at 10 ° C over 2 hours, then at 25 ° C for 1 hour.
Stirring was continued for hours. To the resulting dark blue mixture was added allyl bromide (133.07g) at 10 ° C, and then stirring was continued at 25 ° C for 12 hours. Water (500 ml) in the reaction mixture
Was added and the mixture was separated into an aqueous layer and an organic layer. The organic layer was washed with saturated saline and dried over anhydrous sodium sulfate. The solvent was distilled off from the organic layer under reduced pressure, and the residue was distilled to give a colorless oil 2-allyloxy-1-bromo-3-tert-butyl-5-methylbenzene (245.25 g, yield 91).
%) Was obtained. Boiling point 74-75 ° C (0.08 mmHg) ¹ H NMR (CDCl ₃ ) δ1.38 (s, 9 H), 2.27 (s, 3 H),
4.57 (dt, 2 H, J = 2, 5Hz), 5.29 (dq, 1 H, J = 2, 1
1 Hz), 5.49 (dq, 1 H, J = 2, 17 Hz), 6.13 (ddt, 1
H, J = 5, 11, 17 Hz), 7.07 (d, 1 H, J = 2 Hz), 7.2
5 (d, 1 H, J = 2 Hz) Mass spectrum (EI, M / e) 282, 269, 241, 226, 203,
162, 147, 122, 91,41

Example 50 2-Allyloxy-1-bromo-3-tert-butyl-5-
Synthesis of Methylbenzene To a mixture (30 ml) of 85% potassium hydroxide (1.82 g), tetra-n-butylammonium bromide (0.040 g) and toluene under stirring at 50 ° C., 2-bromo-6- t-Butyl-4-methylphenol (6.0
8 g) and allyl bromide (3.38 g) were added dropwise. Then, stirring was continued at 50 ° C. for 3 hours. After cooling to 25 ° C, water was added to the reaction mixture, and the mixture was separated into an aqueous layer and an organic layer.
The organic layer was washed with saturated saline and dried over anhydrous sodium sulfate. By gas chromatography internal standard analysis, 2-allyloxy-1-bromo-3-tert
-Butyl-5-methylbenzene was used 2-bromo-
It was found to be produced in a yield of 93% based on 6-t-butyl-4-methylphenol.

Example 51 2-Allyloxy-1-bromo-3-tert-butyl-5-
Synthesis of methoxybenzene To a mixture of 85% potassium hydroxide (4.57 g) and methyl isobutyl ketone (30 ml) was added 2-bromo-6-te.
rt-Butyl-4-methytoxyphenol (16.02
g) was added at 10 ° C and then stirred at 25 ° C for 1 hour.
Allyl bromide (8.47 g) was added to the obtained dark blue liquor at 10 ° C.
And then stirred at 25 ° C. for 12 hours. Water was added to the reaction mixture, and the mixture was separated into an aqueous layer and an organic layer. The obtained organic layer was washed with saturated saline and then dried over anhydrous sodium sulfate. The solvent was distilled off from the organic layer under reduced pressure, and the residue was distilled to give a pale yellow oily form of 2-allyloxy-1-bromo-3-tert-butyl-5-methoxybenzene (15.8).
0 g, yield 85%) was obtained. Boiling point 115-117 ° C (0.8 mmHg) ¹ H NMR (CDCl ₃ ) δ1.38 (s, 9 H), 3.76 (s, 3 H),
4.55 (dt, 2 H, J = 2, 5Hz), 5.29 (dq, 1 H, J = 2, 1
1 Hz), 5.48 (dq, 1 H, J = 2, 17 Hz), 6.13 (ddt, 1
H, J = 5, 9, 17 Hz), 6.86 (d, 1 H, J = 3 Hz), 6.95
(d, 1 H, J = 3 Hz) Mass spectrum (EI, m / e) 300, 257, 178, 138, 91,
44

Example 52 Synthesis of (2-allyloxy-3-tert-butyl-5-methoxyphenyl) dimethyl (2,3,4,5-tetramethyl-cyclopentadienyl) silane 2-Allyloxy-1-bromo -3-tert-butyl-5-
Methoxybenzene (8.98g) in hexane (90
ml) at 1.78M of n-butyllithium at -78 ° C.
A hexane solution (18.07 ml) was added dropwise, the temperature was raised to -30 ° C, and the mixture was stirred for 1 hour. The obtained mixture was cooled to −78 ° C., dichlorodimethylsilane (4.26 g) was added, the temperature was raised to 25 ° C. over 2 hours, and the mixture was further stirred for 3 hours. Then, the solvent and excess dichlorodimethylsilane were distilled off under reduced pressure. The obtained mixture was dissolved in tetrahydrofuran (50 ml), the solution was added dropwise to a tetrahydrofuran solution (100 ml) of tetramethylcyclopentadienyl lithium (3.84 g) at −78 ° C., and the temperature was raised to room temperature over 2 hours. After warming, the mixture was stirred for another 12 hours. Aqueous ammonium chloride solution was added to the reaction mixture, and the aqueous layer and the organic layer were separated. After extracting the hexane-soluble component from the aqueous layer with hexane, the organic solution obtained by combining the organic layer and the hexane solution was washed with saturated saline and dried with anhydrous sodium sulfate. After distilling off the solvent from the organic solution under reduced pressure, the residue was treated with silica gel column chromatography (developing solution: hexane) to give a colorless oily (2
-Allyloxy-3-tert-butyl-5-methoxyphenyl) dimethyl (2,3,4,5-tetramethylcyclopentadienyl) silane (5.00 g, yield 42%) was obtained. ¹ H NMR (CDCl ₃ ) δ 0.14 (s, 6 H), 1.39 (s, 9 H),
1.70 (s, 6 H), 1.78 (s, 6H), 3.42 (s, 1 H), 3.80 (s,
3 H), 4.39 (dt, 2 H, J = 2, 2 Hz), 5.27 (dq, 1 H, J
= 2, 11 Hz), 5.53 (dq, 1 H, J = 2, 17 Hz), 6.03
(ddt, 1 H, J = 2, 11, 17 Hz), 6.75 (d, 1 H, J = 3
Hz), 6.93 (d, 1 H, J = 3 Hz) Mass spectrum (EI, m / e) 399, 261, 236, 221, 162, 1
47, 75

Example 53 Dimethylsilyl (tetramethylcyclopentadienyl)
Synthesis of (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride (3-tert-butyl-2-allyloxy-5-methylphenyl) dimethyl (2,3,4,5-tetramethylcyclopentadiene Enyl) silane (117.5 g, purity 85%)
1.66 M hexane solution of n-butyllithium (340 ml) was added dropwise to the hexane solution of (1170 ml) at room temperature, and the mixture was stirred for 12 hours. After removing the supernatant of the reaction solution, toluene (1400 ml) and titanium tetrachloride (61 g) were added at room temperature, and the mixture was stirred at 95 ° C. for 10 hours in the dark. The reaction mixture was filtered and the solid was washed with toluene (50
0 ml). After the obtained filtrate and washing liquid were combined, the solvent was distilled off to obtain reddish black tar. Toluene (250 ml) and hexane (1150 ml) were added to this tar.
Was added, and the mixture was heated to 65 ° C. to dissolve it, and allowed to stand at −20 ° C. for 24 hours. The precipitate was filtered off, washed with hexane (80 ml) and dried under reduced pressure to give a red solid. This was recrystallized from a mixed solvent of toluene (240 ml) and hexane (720 ml) to give red needle crystals of dimethylsilyl (tetramethylcyclopentadienyl) (3-tert-butyl-
5-Methyl-2-phenoxy) titanium dichloride (29.1 g, yield 22.6%) was obtained.

Example 54 Synthesis of (3,5-di-tert-butyl-2-trimethylsiloxyphenyl) chlorodimethylsilane 1-Bromo-3,5-di-tert-butyl-2-trimethylsiloxybenzene (39. 0 g) in a solution of tetrahydrofuran (100 ml) at -70 ° C, n-
1.68M hexane solution of butyllithium (71.4m
1) was added dropwise, and stirring was continued at -70 ° C for 2 hours. The mixture obtained above was added dropwise to a solution of dichlorodimethylsilane (66.1 ml) dissolved in tetrahydrofuran (70 ml) at −70 ° C., and then the temperature was raised to room temperature over 2 hours. The solvent was distilled off from the reaction mixture, and the hexane-soluble component was extracted from the residue with hexane (70 ml). The solvent was distilled off from the obtained hexane solution, and pale yellow (3,5-di-tert-butyl-2-trimethylsiloxyphenyl) chlorodimethylsilane (40.0 g, yield 9
9%) was obtained. 1 H-NMR (CDCl3) δ 0.34 (s, 9
H), 0.60 (s, 6H), 1.28 (s, 9H),
1.41 (s, 9H), 7.25 (d, J = 2.6H
z, 1H), 7.38 (d, J = 2.6 Hz, 1H) Mass spectrum (EI, m / e) 370, 355, 3
13, 247, 167

Example 55 Synthesis of (3,5-di-tert-butyl-2-trimethylsiloxyphenyl) cyclopentadienyldimethylsilane Cyclopentadienyllithium (2.20 g) -70
In a tetrahydrofuran solution (100 ml) at ℃, (3,
A tetrahydrofuran solution (50 ml) of 5-di-tert-butyl-2-trimethylsiloxyphenyl) chlorodimethylsilane (9.83 g) was added dropwise. Then, the temperature was raised to room temperature over 2 hours, and the mixture was further stirred at room temperature for 12 hours.
The solvent was distilled off from the reaction mixture, and the hexane-soluble component was extracted from the residue with hexane. The solvent was distilled off from the obtained hexane solution to obtain pale yellow (3,5-di-tert-butyl-2-trimethylsiloxyphenyl) cyclopentadienyldimethylsilane (10.43 g, yield 98%). It was 1 H-NMR (CDCl3) δ 0.28 (s, 6
H), 0.35 (s, 9H), 1.29 (s, 9H),
1.42 (s, 9H), 6.57 (s, 1H), 7.2
2 (s, 1H), 7.24 (s, 2H), 7.34
(S, 1H), 7.39 (s, 2H) mass spectrum (EI, m / e) 400, 385, 326, 311, 29
8, 247, 215

Example 56 Synthesis of (3,5-di-tert-butyl-2-trimethylsiloxyphenyl) dimethyl (trimethylsilylcyclopentadienyl) silane (trimethylsilylcyclopentadienyl) lithium (0.85 g) -70 In a tetrahydrofuran solution (20 ml) at 0 ° C, a tetrahydrofuran solution (15 ml) of (3,5-di-tert-butyl-2-trimethylsiloxyphenyl) chlorodimethylsilane (1.86 g) was added.
The solution was added dropwise. Then, the temperature was raised to room temperature over 2 hours, and the mixture was further stirred at room temperature for 12 hours. The solvent was distilled off from the reaction mixture, and the hexane-soluble component was extracted from the residue with hexane. The solvent was distilled off from the obtained hexane solution,
Pale yellow oily (3,5-di-tert-butyl-2-trimethylsiloxyphenyl) dimethyl (trimethylsilylcyclopentadienyl) silane (2.0 g, yield 84
%) Was obtained. 1H NMR (CDCl ₃ ) δ 0.11 (s, 9H), 0.30 (s, 9H), 0.37
(s, 6H), 1.31 (s, 9H), 1.33 (s, 9H), 6.45 (m, 1H), 7.
25 (s, 1H), 7.28 (m, 2H), 7.37 (s, 1H), 7.41 (s, 1H) Mass spectrum (EI, m / e) 472, 457, 417, 397, 382,
369, 327, 310, 147, 73

Example 57 Synthesis of (3-tert-butyl-5-methyl-2-trimethylsiloxyphenyl) chlorodimethylsilane 1-Bromo-3-tert-butyl-5-methyl-2-trimethylsiloxybenzene (24. 18 g) and tetrahydrofuran (180 ml) at −60 ° C. to a mixture of n-butyllithium in 1.6 M hexane (5
(4.2 ml) was added dropwise over 30 minutes, and the resulting mixture was kept at -40 ° C for 3.75 hours. Dichlorodimethylsilane (49.5 g) and tetrahydrofuran (1
80 ml) and the mixture obtained above was added dropwise to a solution at -60 ° C. The resulting solution was warmed to room temperature over 2 hours and stirred for a further 15 hours, after which the solvent and excess dichlorodimethylsilane were distilled off under reduced pressure. Hexane was used to extract a hexane-soluble component from the mixture obtained above, and the solvent was distilled off from the obtained hexane solution under reduced pressure to obtain a white powder of (3-tert-butyl-5-methyl- 2-Trimethylsiloxyphenyl) chlorodimethylsilane (24.7 g, yield 98%) was obtained. 1 H-NMR (CDCl 3) δ 0.35 (s, 9
H), 0.62 (s, 6H), 1.42 (s, 9H),
2.28 (s, 3H) 7.06 (s, 1H), 7.19
(S, 1H) Mass spectrum (EI, m / e) 328, 313, 271, 205, 167,
93, 73

Example 58 Synthesis of (3-tert-butyl-5-methyl-2-trimethylsiloxyphenyl) dimethyl (trimethylsilylcyclopentadienyl) silane (Trimethylsilylcyclopentadienyl) lithium (1.43 g) in tetrahydrofuran (20 ml)
At -70 ° C, (3-tert-butyl-5-methyl-2)
A solution containing -trimethylsiloxyphenyl) chlorodimethylsilane (2.59 g) and tetrahydrofuran (15 ml) was added dropwise, then the temperature was raised to room temperature over 2 hours, and the mixture was further stirred at room temperature for 12 hours. The solvent was distilled off from the reaction mixture under reduced pressure, and a hexane-soluble component was extracted from the residue with hexane. The solvent was distilled off from the obtained hexane solution to give a pale yellow oily (3-tert-butyl-5-
Methyl-2-trimethylsiloxyphenyl) dimethyl (trimethylsilylcyclopentadienyl) silane (2.9 g, yield 86%) was obtained. 1 H-NMR (CDCl 3) δ 0.14 (s, 9
H), 0.25 (s, 9H), 0.34 (s, 6H),
1.28 (s, 9H), 1.42 (s, 3H), 6.45
(S, 1H), 7.23 (s, 1H), 7.25 (s,
2H), 7.34 (s, 1H), 7.39 (s. 1H) mass spectrum (CI, m / e) 430

Example 59 Synthesis of (3-tert-butyl-2-methoxy-5-methylphenyl) dimethyl (cyclopentadienyl) silane (3-tert-butyl-2-methoxy-5-methylphenyl) chlorodimethyl Cyclopentadienyl lithium (1.45 g) was added at -35 ° C to a solution consisting of silane (5.0 g), tetrahydrofuran (35 ml), and hexane (35 ml). The resulting mixture was warmed to room temperature over 2 hours and stirred at room temperature for another 10 hours. The solvent was distilled off from the obtained white suspension under reduced pressure, the hexane-soluble matter was extracted from the residue with hexane, and the solvent was distilled off from the obtained hexane solution under reduced pressure to give a yellow oil. (3-tert-butyl-2-methoxy-5-methylphenyl) dimethyl (cyclopentadienyl) silane (5.07 g, yield 91%) was obtained. 1 H-NMR (CDCl3) δ 0.22 (s, 6
H), 1.35 (s, 9H), 2.26 (s. 3H),
3.56 (s, 3H), 5.25 (s, 1H), 5.8
4 (br, 1H), 5.87 (br, 1H), 6.99
(Br, 2H), 7.08 (s, 1H), 7.16
(S, 1H) Mass spectrum (EI, m / e) 300, 255, 205, 179, 161,
89

Example 60 Synthesis of (3-tert-butyl-5-methyl-2-trimethylsiloxyphenyl) dimethyl (cyclopentadienyl) silane (3-tert-butyl-5-methyl-2-trimethylsiloxyphenyl) A solution composed of chlorodimethylsilane (2.5 g) and tetrahydrofuran (10 ml) was added dropwise at −40 ° C. to a solution composed of cyclopentadienyl lithium (0.56 g) and tetrahydrofuran (20 ml). The obtained mixture was heated to room temperature over 2 hours, and further stirred at room temperature for 10 hours. The solvent was distilled off from the reaction mixture under reduced pressure, the hexane-soluble component was extracted from the residue using hexane, and the solvent was distilled off from the obtained hexane solution under reduced pressure to give a pale yellow oily ( 3-tert
-Butyl-5-methyl-2-trimethylsiloxyphenyl) dimethyl (cyclopentadienyl) silane (2.5
g, yield 92%) was obtained. Mass spectrum (EI, m / e) 358, 284, 269, 213, 205,
147, 95, 73

Example 61 Synthesis of (3-tert-butyl-5-methyl-2-trimethylsiloxyphenyl) dimethyl (2,3,4,5-tetramethylcyclopentadienyl) silane 1-Bromo-3-tert -Butyl-5-methyl-2-trimethylsiloxybenzene (1.54 g) and tetrahydrofuran (15 ml) in a solution of -55 ° C.
, A 1.6 M hexane solution of n-butyllithium (3.
15 ml) was added dropwise over 10 minutes. After the resulting mixture was kept warm at -45 ° C for 45 minutes,
Chlorodimethyl (tetramethylcyclopentadienyl)
Silane (1.0 g) and tetrahydrofuran (5 ml)
Was added dropwise and the temperature was raised to room temperature over 2 hours. After stirring at room temperature for 13 days, the solvent was distilled off from the reaction mixture under reduced pressure. Hexane-soluble matter was extracted from the obtained mixture with hexane, the obtained hexane solution was allowed to stand at -40 ° C overnight, and the produced white solid was dried to give a pale yellow oily ( 3-tert-butyl-5-methyl-2-trimethylsiloxyphenyl) dimethyl (2,
3,4,5-Tetramethylcyclopentadienyl) silane (0.97 g, yield 48%) was obtained. 1 H-NMR (CDCl3) δ 0.01 (s, 6
H), 0.42 (s, 9H), 1.50 (s, 9H),
2.01 (s, 6H), 2.10 (s, 6H), 2.3
3 (s, 3H), 3.59 (s, 1H), 7.11
(S, 1H), 7.23 (s, 1H)

Example 62 Synthesis of (3-tert-butyl-2-methoxy-5-methylphenyl) chlorodimethylsilane Tetrahydrofuran (31.5 ml), hexane (13
9 ml) and 3-tert-butyl-1-bromo-2-methoxy-5-methylbenzene (45 g),
At −40 ° C., a 1.6M hexane solution of n-butyllithium (115 ml) was added dropwise over 20 minutes. The resulting mixture was kept warm at -40 ° C for 1 hour, and then tetrahydrofuran (31.5 ml) was added dropwise. The mixture obtained above was added dropwise at −40 ° C. to a solution consisting of dichlorodimethylsilane (131 g) and hexane (306 ml). The resulting mixture was heated to room temperature over 2 hours, and further stirred at room temperature for 12 hours. The solvent and excess dichlorodimethylsilane were distilled off from the reaction mixture under reduced pressure, the hexane-soluble component was extracted from the residue with hexane, and the solvent was distilled off from the obtained hexane solution to give a pale yellow oil. (3-tert-butyl-2-methoxy-5-methylphenyl) chlorodimethylsilane (41.9 g, yield 84)
%) Was obtained. 1 H-NMR (CDCl 3) δ 0.68 (s, 6
H), 1.32 (s, 9H), 2.23 (s, 3H),
3.70 (s, 3H), 7.20 (s, 1H), 7.2
1 (s, 1H) mass spectrum (EI, m / e) 270, 255, 219, 189, 145,
128, 109, 93

Example 63 Synthesis of (3-tert-butyl-2-methoxy-5-methylphenyl) dimethyl (2,3,4,5-tetramethylcyclopentadienyl) silane (3-tert-butyl-2 -Methoxy-5-methylphenyl) chlorodimethylsilane (5.24 g) and tetrahydrofuran (50 ml) in a solution of -35 ° C.
In, tetramethylcyclopentadienyl lithium (2.73 g) was added, the temperature was raised to room temperature over 2 hours, and the mixture was further stirred at room temperature for 10 hours. The solvent was distilled off from the obtained reaction mixture under reduced pressure, the hexane-soluble component was extracted from the residue with hexane, and the solvent was distilled off from the obtained hexane solution under reduced pressure to obtain a yellow oily substance. (3-tert
-Butyl-2-methoxy-5-methylphenyl) dimethyl (2,3,4,5-tetramethylcyclopentadienyl) silane (6.69 g, yield 97%) was obtained. 1 H-NMR (C6D6) δ 0.31 (s, 6
H), 1.49 (s, 9H), 1.81 (s, 6H),
1.89 (s, 6H), 2.22 (s, 3H), 3.6
0 (s, 3H), 5.23 (s, 3H), 7.23 (b
r, 2H) Mass spectrum (EI, m / e) 356, 299, 235, 205, 179,
161, 89

Example 64 Dimethylsilyl (tetramethylcyclopentadienyl)
Synthesis of (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride (3-tert-butyl-2-methoxy-5-methyl-phenyl) dimethyl (tetramethylcyclopentadienyl)
A solution of silane (10.04 g), toluene (100 ml) and triethylamine (6.30 g) was added with -7.
A 1.63 M hexane solution of n-butyllithium (19.0 ml) was added dropwise at 0 ° C, then the temperature was raised to room temperature over 2 hours, and the temperature was further kept at room temperature for 12 hours. The mixture obtained above was added dropwise to a toluene solution (50 ml) of titanium tetrachloride (4.82 g) at 0 ° C. under a nitrogen atmosphere,
Then, the temperature was raised to room temperature over 1 hour, and the mixture was heated under reflux for 10 hours. The reaction mixture was filtered, the solvent was distilled off from the filtrate, and the residue was recrystallized from a toluene-hexane mixed solvent to give orange columnar crystals of dimethylsilyl (tetramethylcyclopentadienyl) (3-tert-butyl-5- Methyl-
2-phenoxy) titanium dichloride (3.46
g, yield 27%). 1 H-NMR (CDCl 3) δ 0.57 (s, 6
H), 1.41 (s, 9H), 2.15 (s, 6H),
2.34 (s, 6H), 2.38 (s, 3H), 7.1
5 (s, 1H), 7.18 (s, 1H) 13 C-NMR (CDCl 3) δ 1.25, 14.
48, 16.28, 22.47, 31.25, 36.2
9, 120.23, 130.62, 131.47, 13
3.86, 135.50, 137.37, 140.8
2, 142.28, 167.74 Mass spectrum (CI, m / e) 458

Example 65 An autoclave equipped with a stirrer having an internal volume of 3 liters was vacuum-dried and purged with argon. Then, 1 liter of toluene as a solvent and 20 ml of hexene-1 as an α-olefin were charged, and the reactor was heated to 80 ° C. Warmed. After the temperature was raised, ethylene was fed while adjusting the ethylene pressure to 12 kg / cm ² to stabilize the system, and then triisobutylaluminum 1.0 mmo
1, and subsequently 2.0 μmol of isopropylidene (cyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride synthesized in Example 18 was added, followed by tris. Phenylmethyl tetrakis (pentafluorophenyl)
6.0 μmol of borate was added. Polymerization was performed for 30 minutes while controlling the temperature at 80 ° C. As a result of polymerization, SC
B = 25.0, [η ₁ ] = 0.77, molecular weight (Mw) =
Ethylene-hexene-1 copolymer having a molecular weight distribution (Mw / Mn) of 2.1, and a melting point of 94.2 ° C. was 32.6 per 1 mol of titanium per 2.6 hours.
5 × 10 ⁷ g was produced.

Example 66 An autoclave equipped with a stirrer having an internal volume of 0.4 liter was vacuum dried and replaced with argon, and then toluene 19 was used as a solvent.
8 ml and 2 ml of hexene-1 as an α-olefin were charged, and the temperature of the reactor was raised to 60 ° C. After the temperature was raised, feed was performed while adjusting the ethylene pressure to 6 kg / cm ² , and after the system was stabilized, triisobutylaluminum 0.25 mm
ol, and then isopropylidene (cyclopentadienyl) (3,5-dimethyl-synthesized in Example 10).
2-phenoxy) titanium dichloride 1.0 μmo
1, and then 3.0 μmol of triphenylmethyltetrakis (pentafluorophenyl) borate was added. Polymerization was carried out for 10 minutes while controlling the temperature at 60 ° C. As a result of the polymerization, SCB = 14.7, [η ₁ ] = 1.
67, molecular weight (Mw) = 120,000, molecular weight distribution (M
2.65 × 10 ⁷ g of an ethylene-hexene-1 copolymer having w / Mn) = 11.3 and a melting point of 110.6 ° C. was produced per 1 mol of titanium per 1 hour.

Example 67 An autoclave equipped with a stirrer having an internal volume of 0.4 liter was vacuum-dried and replaced with argon, and toluene 19 was used as a solvent.
8 ml and 2 ml of hexene-1 as an α-olefin were charged, and the temperature of the reactor was raised to 60 ° C. After the temperature was raised, feed was performed while adjusting the ethylene pressure to 6 kg / cm ² , and after the system was stabilized, triisobutylaluminum 0.25 mm
ol, and then isopropylidene (cyclopentadienyl) (3-phenyl-2-) synthesized in Example 12
1.0 μmol of phenoxy) titanium dichloride was added, and then 3.0 μmol of triphenylmethyltetrakis (pentafluorophenyl) borate was added. Polymerization was carried out for 10 minutes while controlling the temperature at 60 ° C. As a result of the polymerization, SCB = 18.7, [η ₁ ] = 0.6
2, molecular weight (Mw) = 27,000, molecular weight distribution (Mw /
Mn) = 6.7, ethylene having a melting point of 106.0 ° C.
The hexene-1 copolymer was added per 1 mol of titanium,
8.82 × 10 ⁶ g was produced per hour.

Example 68 An autoclave equipped with a stirrer having an internal volume of 0.4 liter was vacuum-dried and replaced with argon, and then hexane 19 was used as a solvent.
8 ml and 2 ml of hexene-1 as an α-olefin were charged, and the temperature of the reactor was raised to 60 ° C. After the temperature was raised, feed was performed while adjusting the ethylene pressure to 6 kg / cm ² , and after the system was stabilized, triisobutylaluminum 0.25 mm
ol, and then isopropylidene (3-tert-butylcyclopentadienyl) synthesized in Example 14
(3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride 1.0 μmol was added,
Subsequently, 3.0 μmol of triphenylmethyltetrakis (pentafluorophenyl) borate was added. 60 ° C
Polymerization was carried out for 10 minutes while controlling the temperature. As a result of the polymerization, SCB = 32.0, [η ₁ ] = 1.34, molecular weight (Mw) = 69000, molecular weight distribution (Mw / Mn) =
Ethylene-hexene-having a melting point of 1.9 and a melting point of 82.7 ° C.
One copolymer was produced in an amount of 1.75 × 10 ⁸ g per 1 mol of titanium per 1 hour.

Example 69 An autoclave equipped with a stirrer having an internal volume of 0.4 liter was vacuum-dried and replaced with argon, and then 185 ml of cyclohexane as a solvent and 1 part of hexene-1 as an α-olefin.
5 ml was charged and the temperature of the reactor was raised to 180 ° C. After the temperature was raised, ethylene was fed while adjusting the ethylene pressure to 25 kg / cm ² , and after the system became stable, 0.25 mmol of triisobutylaluminum was charged, and subsequently, dimethylsilyl (tetramethylcyclopenta) synthesized in Example 64 was added. 1.0 μmol of dienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride was added, followed by addition of 3.0 μmol of N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate to N, N. -Injected as a toluene solution of dimethylanilinium tetrakis (pentafluorophenyl) borate. Polymerization was carried out for 2 minutes while controlling the temperature at 180 ° C. As a result of the polymerization, SCB = 33.6, [η ₁ ] = 1.0
3, molecular weight (Mw) = 51,000, molecular weight distribution (Mw /
Mn) = 2.0 and a melting point of 87.4 ° C., an ethylene-hexene-1 copolymer was used in an amount of 2 per 1 mol of titanium.
3.36 × 10 ⁶ g was produced per minute.

Example 70 An autoclave equipped with a stirrer and having an internal volume of 3 liters was vacuum dried.
After drying and replacing with argon, 1 liter of hexane as a solvent
10 ml of hexene-1 as α-olefin
Then, the temperature of the reactor was raised to 80 ° C. After heating, ethylene pressure
6 kg / cm ²Feed while adjusting to
After determination, triisobutylaluminum 1.0 mmol
Was added, followed by isopropylamine synthesized in Example 1 (1).
Ridene (cyclopentadienyl) (3-tert-butyl
Ru-5-methyl-2-phenoxy) titanium dichlora
0.5 μmol id was added, followed by N, N-dimethyl.
Anilinium tetrakis (pentafluorophenyl) bo
A rate of 3.0 μmol was added. Adjust temperature to 80 ℃
Meanwhile, polymerization was carried out for 30 minutes. As a result of polymerization, SCB
= 27.7, [η₁] = 0.99, molecular weight (Mw) = 4
6000, molecular weight distribution (Mw / Mn) = 1.7, melting point
The ethylene-hexene-1 copolymer having a temperature of 93.4 ° C.
1.60 × per 1 mol of titanium per 1 hour
10⁷g.

Example 71 An autoclave equipped with a stirrer having an internal volume of 3 liters was vacuum-dried and replaced with argon. Then, 1 liter of hexane as a solvent and 20 ml of hexene-1 as an α-olefin were charged, and the reactor was heated to 80 ° C. Warmed. After the temperature was raised, ethylene was fed while adjusting the pressure to 12 kg / cm ² , and after the system became stable, 0.5 mmol of triethylaluminum was added, and subsequently, isopropylidene (cyclopentadiene) synthesized in Example 1 (1) was added. 2.0 μmol of dienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride was added, followed by triphenylmethyltetrakis (pentafluorophenyl) borate 6.0.
μmol was added. While adjusting the temperature to 80 ℃, 3
Polymerization was performed for 0 minutes. As a result of the polymerization, SCB = 21.8,
[Η ₁ ] = 1.06, molecular weight (Mw) = 52000, molecular weight distribution (Mw / Mn) = 1.8, melting point 99.5 ° C. ethylene-hexene-1 copolymer
1.52 × 10 ⁷ g was produced per mol per hour.

Example 72 An autoclave equipped with a stirrer and having an internal volume of 3 liters was vacuum-dried and replaced with argon. Then, 1 liter of toluene as a solvent and 20 ml of hexene-1 as an α-olefin were charged, and the reactor was heated to 80 ° C. Warmed. After the temperature was raised, ethylene was fed while adjusting the pressure to 12 kg / cm ² , and after the system was stabilized, 12.0 μmol of triphenylmethyltetrakis (pentafluorophenyl) borate was added,
Subsequently, 0.5 mmol of triisobutylaluminum was added, and then triisobutylaluminum was added in advance.
The isopropylidene (cyclopentadienyl) (3) synthesized in Example 1 (1) was pre-contacted with 5 mmol for 2 minutes.
2.0 μmol of -tert-butyl-5-methyl-2-phenoxy) titanium dichloride was added. 80
Polymerization was carried out for 40 minutes while adjusting the temperature to ° C. As a result of the polymerization, SCB = 25.8, [η ₁ ] = 1.18, molecular weight (Mw) = 60,000, molecular weight distribution (Mw / Mn) =
Ethylene-hexene-having a melting point of 1.9 and a melting point of 94.9 ° C.
One copolymer was produced in an amount of 2.27 × 10 ⁷ g per mol of titanium per hour.

Example 73 An autoclave equipped with a stirrer and having an internal volume of 3 liters was vacuum-dried and replaced with argon. Then, 1 liter of toluene as a solvent and 20 ml of hexene-1 as an α-olefin were charged, and the reactor was heated to 80 ° C. Warmed. After the temperature was raised, ethylene was fed while adjusting the ethylene pressure to 12 kg / cm ² to stabilize the system, and then triisobutylaluminum 1.0 mmo
1 of the isopropylidene (cyclopentadienyl) (3-tert) synthesized in Example 1 (1), which was stored as a hexane solution at room temperature under nitrogen for 1 month.
2.0 μmol of -butyl-5-methyl-2-phenoxy) titanium dichloride was added, followed by 6.0 μmol of triphenylmethyltetrakis (pentafluorophenyl) borate. Polymerization was performed for 30 minutes while controlling the temperature at 80 ° C. As a result of polymerization, SCB = 2
4.8, [η ₁ ] = 1.18, molecular weight (Mw) = 610
00, molecular weight distribution (Mw / Mn) = 1.9, melting point 9
An ethylene-hexene-1 copolymer having a temperature of 6.3 ° C. was added at 3.51 × 1 per 1 mol of titanium per 1 hour.
0 ⁷ g was produced.

Example 74 An autoclave equipped with a stirrer having an internal volume of 3 liters was vacuum-dried and purged with argon. Then, 1 liter of toluene as a solvent and 20 ml of hexene-1 as an α-olefin were charged, and the reactor was heated to 80 ° C. Warmed. After the temperature was raised, ethylene was fed while adjusting the ethylene pressure to 12 kg / cm ² to stabilize the system, and then triisobutylaluminum 1.0 mmo
1, followed by 2.0 μmol of isopropylidene (cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride synthesized in Example 1 (1), followed by 1.0 μmol of triphenylmethyl tetrakis (pentafluorophenyl) borate was added. Polymerization was performed for 30 minutes while controlling the temperature at 80 ° C. As a result of polymerization, SCB = 2
3.3, [η ₁ ] = 1.24, molecular weight (Mw) = 670
00, molecular weight distribution (Mw / Mn) = 1.7, melting point 9
An ethylene-hexene-1 copolymer having a temperature of 6.7 ° C. was added in an amount of 2.00 × 1 per 1 mol of titanium per 1 hour.
0 ⁷ g was produced.

Example 75 An autoclave equipped with a stirrer having an internal volume of 3 liters was vacuum-dried and replaced with argon. Then, 1 liter of toluene as a solvent and 20 ml of hexene-1 as an α-olefin were charged, and the temperature of the reactor was raised to 40 ° C. Warmed. After the temperature was raised, ethylene was fed while adjusting the ethylene pressure to 12 kg / cm ² to stabilize the system, and then triisobutylaluminum 1.0 mmo
1, followed by 2.0 μmol of isopropylidene (cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride synthesized in Example 1 (1), followed by Triphenylmethyl tetrakis (pentafluorophenyl) borate 6.0 μmol was added. Polymerization was carried out for 10 minutes while controlling the temperature at 40 ° C. As a result of polymerization, SCB = 1
4.8, [η ₁ ] = 1.93, molecular weight (Mw) = 110
000, molecular weight distribution (Mw / Mn) = 2.1, melting point 1
The ethylene-hexene-1 copolymer having a temperature of 0.
1.27 × per 1 mol of titanium per 1 hour
10 ⁸ g was produced.

Example 76 An autoclave equipped with a stirrer having an internal volume of 3 liters was vacuum-dried and purged with argon. Then, 1 liter of hexane as a solvent and 10 ml of hexene-1 as an α-olefin were charged, and 100 mmHg of hydrogen was added to the reactor. Was heated to 80 ° C. After the temperature was raised, ethylene was fed while adjusting the ethylene pressure to 6 kg / cm ² , and after the system became stable, 1.0 mmol of triisobutylaluminum was added, followed by Example 6
Dimethylsilyl (tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2)
-Phenoxy) titanium dichloride 2.0 μmol
And then N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate 3.0 μmo
1 was added. Polymerization was performed for 30 minutes while controlling the temperature at 80 ° C. As a result of the polymerization, SCB = 27.2,
[Η ₁ ] = 1.69, molecular weight (Mw) = 99,000, molecular weight distribution (Mw / Mn) = 1.9, and melting point of 83.1 ° C. ethylene-hexene-1 copolymer, titanium 1
1.50 × 10 ⁷ g per mol was produced per hour.

Example 77 An autoclave equipped with a stirrer having an internal volume of 3 liters was vacuum dried and purged with argon. Then, 1 liter of hexane as a solvent and 20 ml of hexene-1 as an α-olefin were charged, and 200 mmHg of hydrogen was added to the reactor. Was heated to 80 ° C. After the temperature was raised, ethylene was fed while adjusting the pressure to 12 kg / cm ^2, and after the inside of the system was stabilized, 0.75 mmol of triisobutylaluminum was added, followed by dimethylsilyl (tetramethylcyclopenta) synthesized in Example 64. Dienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride 0.5 μm
ol, followed by N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate 1.5μ
mol was added. 30 while adjusting the temperature to 80 ℃
Polymerization was performed for minutes. As a result of the polymerization, SCB = 26.8,
[Η ₁ ] = 2.22, molecular weight (Mw) = 140,000,
Molecular weight distribution (Mw / Mn) = 1.6, melting point 85.6 ° C.
The ethylene-hexene-1 copolymer which is the above was produced in an amount of 2.00 × 10 ⁷ g per 1 mol of titanium per 1 hour.

Example 78 An autoclave equipped with a stirrer having an internal volume of 3 liters was vacuum-dried and replaced with argon. Then, 1 liter of hexane as a solvent and 20 ml of hexene-1 as an α-olefin were charged, and 100 mmHg of hydrogen was added to the reactor. Was heated to 80 ° C. After the temperature was raised, ethylene was fed while adjusting the pressure to 12 kg / cm ^2, and after the inside of the system was stabilized, 0.75 mmol of triisobutylaluminum was added, followed by dimethylsilyl (tetramethylcyclopenta) synthesized in Example 64. Dienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride 1.0 μm
ol, followed by N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate 2.0μ
mol was added. 30 while adjusting the temperature to 80 ℃
Polymerization was performed for minutes. As a result of the polymerization, SCB = 24.7,
[Η ₁ ] = 2.77, molecular weight (Mw) = 17,000,
Molecular weight distribution (Mw / Mn) = 1.8, melting point 87.4 ° C.
The ethylene-hexene-1 copolymer having the above formula was produced in an amount of 3.60 × 10 ⁷ g per 1 mol of titanium per 1 hour.

Example 79 An autoclave equipped with a stirrer having an internal volume of 3 liters was vacuum-dried and replaced with argon. Then, 1 liter of hexane as a solvent and 10 ml of hexene-1 as an α-olefin were charged, and 100 mmHg of hydrogen was added to the reactor. Was heated to 80 ° C. After the temperature was raised, ethylene was fed while adjusting the ethylene pressure to 6 kg / cm ² , and after the system became stable, 1.0 mmol of triisobutylaluminum was added, followed by Example 6
Dimethylsilyl (tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2)
-Phenoxy) titanium dichloride 0.5 μmol
Was added, and then 3.0 μmol of triphenylmethyl tetrakis (pentafluorophenyl) borate was added. Polymerization was performed for 30 minutes while controlling the temperature at 80 ° C. As a result of the polymerization, SCB = 25.2 and [η ₁ ] = 1.8.
0, molecular weight (Mw) = 110,000, molecular weight distribution (Mw
Ethylene having a melting point of 84.8 ° C./Mn)=1.8
The hexene-1 copolymer was added per 1 mol of titanium,
4.00 × 10 ⁷ g was produced per hour.

Example 80 An autoclave equipped with a stirrer having an internal volume of 3 liters was vacuum-dried and purged with argon. Then, 1 liter of hexane as a solvent and 20 ml of hexene-1 as an α-olefin were charged, and the reactor was heated to 80 ° C. Warmed. After the temperature was raised, ethylene was fed while adjusting the ethylene pressure to 12 kg / cm ² to stabilize the system, and then triisobutylaluminum 1.0 mmo
1, and subsequently dimethylsilyl (tetramethylcyclopentadienyl) (3-ter synthesized in Example 64).
2.0 μmol of t-butyl-5-methyl-2-phenoxy) titanium dichloride was added, and then 6.0 μmol of triphenylmethyltetrakis (pentafluorophenyl) borate was added. Polymerization was performed for 30 minutes while controlling the temperature at 80 ° C. As a result of polymerization, SCB =
24.5, [η ₁ ] = 4.06, melting point 84.9 ° C. ethylene-hexene-1 copolymer, titanium 1 m
3.88 × 10 ⁷ g was produced per ol per hour.

Example 81 An autoclave equipped with a stirrer and having an internal volume of 3 liters was vacuum-dried and replaced with argon. Then, 1 liter of toluene as a solvent and 20 ml of hexene-1 as an α-olefin were charged, and the reactor was heated to 80 ° C. Warmed. After the temperature was raised, ethylene was fed while adjusting the pressure to 12 kg / cm ² , and after the system became stable, 1.0 mmol of triethylaluminum was added, followed by dimethylsilyl (tetramethylcyclopentadiene) synthesized in Example 64. Enyl) (3-tert
2.0 μmol of -butyl-5-methyl-2-phenoxy) titanium dichloride was added, followed by 6.0 μmol of triphenylmethyltetrakis (pentafluorophenyl) borate. Polymerization was performed for 30 minutes while controlling the temperature at 80 ° C. As a result of polymerization, SCB = 2
5.8, [η ₁ ] = 2.97, melting point 85.9 ℃ ethylene-hexene-1 copolymer, titanium 1mo
1.87 × 10 ⁷ g was produced per liter per hour.

Example 82 An autoclave equipped with a stirrer having an internal volume of 3 liters was vacuum-dried and replaced with argon. Then, 1 liter of toluene as a solvent and 20 ml of hexene-1 as an α-olefin were charged, and the reactor was heated to 80 ° C. Warmed. After the temperature was raised, ethylene was fed while adjusting the ethylene pressure to 12 kg / cm ² to stabilize the system, and then triisobutylaluminum 1.0 mmo
1, and subsequently dimethylsilyl (tetramethylcyclopentadienyl) (3-ter synthesized in Example 64).
1.0 μmol of t-butyl-5-methyl-2-phenoxy) titanium dichloride was added, and subsequently 6.0 μmol of triphenylmethyltetrakis (pentafluorophenyl) borate was added. Polymerization was performed for 30 minutes while controlling the temperature at 80 ° C. As a result of polymerization, SCB =
27.2, [η ₁ ] = 4.27, melting point 84.1 ° C. ethylene-hexene-1 copolymer, titanium 1 m
8.70 × 10 ⁷ g was produced per ol per hour.

Example 83 An autoclave equipped with a stirrer having an internal volume of 0.4 liter was vacuum dried and replaced with argon, and then toluene 19 was used as a solvent.
8 ml and 2 ml of hexene-1 as an α-olefin were charged, and the temperature of the reactor was raised to 60 ° C. After the temperature was raised, ethylene was fed while adjusting the pressure to 6 kg / cm ² , and after the system was stabilized, 1.0 mmol of methylalumoxane (PMAO manufactured by Tosoh Akzo Co., Ltd.) was added, followed by Example 64.
Dimethylsilyl (tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-)
1.0 μmol of phenoxy) titanium dichloride was added, and then 3.0 μmol of triphenylmethyltetrakis (pentafluorophenyl) borate was added. Polymerization was carried out for 10 minutes while controlling the temperature at 60 ° C. As a result of the polymerization, SCB = 28.3, [η ₁ ] = 3.0
1, an ethylene-hexene-1 copolymer having a melting point of 80.6 ° C. per 1 mol of titanium per 1 hour,
2.76 × 10 ⁷ g was produced.

Example 84 An autoclave equipped with a stirrer having an internal volume of 0.4 liter was vacuum dried and replaced with argon, and then toluene 19 was used as a solvent.
8 ml and 2 ml of hexene-1 as an α-olefin were charged, and the temperature of the reactor was raised to 60 ° C. After the temperature was raised, feed was performed while adjusting the ethylene pressure to 6 kg / cm ² , and after the system was stabilized, triisobutylaluminum 0.25 mm
ol, and then dimethylsilyl (tetramethylcyclopentadienyl) (3-te synthesized in Example 64).
1.0 μmol of rt-butyl-5-methyl-2-phenoxy) titanium dichloride was added, and then 3.0 μmol of tris (pentafluorophenyl) borane was added. Polymerization was carried out for 10 minutes while controlling the temperature at 60 ° C. As a result of the polymerization, SCB = 25.4, [η ₁ ] =
An ethylene-hexene-1 copolymer having a melting point of 4.45 and a melting point of 85.2 ° C. was produced at 6.48 × 10 ⁶ g per 1 mol of titanium per hour.

Example 85 An autoclave equipped with a stirrer having an internal volume of 0.4 liter was vacuum dried and replaced with argon, and then hexane 19 was used as a solvent.
8 ml and 2 ml of hexene-1 as an α-olefin were charged, and the temperature of the reactor was raised to 60 ° C. After the temperature was raised, ethylene was fed while adjusting the ethylene pressure to 6 kg / cm ² , and after the system became stable, methylalumoxane (MMAOtype3A manufactured by Tosoh Akzo Co., toluene solution) 1.0 mmol
Was added, followed by dimethylsilyl (tetramethylcyclopentadienyl) (3-tert) synthesized in Example 64.
1.0 μmol of -butyl-5-methyl-2-phenoxy) titanium dichloride was added, followed by 3.0 μmol of triphenylmethyltetrakis (pentafluorophenyl) borate. Polymerization was carried out for 10 minutes while controlling the temperature at 60 ° C. As a result of polymerization, SCB = 2
4.7, [η ₁ ] = 1.74, molecular weight (Mw) = 100
000, molecular weight distribution (Mw / Mn) = 2.5, melting point 9
An ethylene-hexene-1 copolymer having a temperature of 3.8 ° C. was added at 1.29 × 1 per 1 mol of titanium per 1 hour.
0 ⁷ g was produced.

Example 86 An autoclave equipped with a stirrer having an internal volume of 0.4 liter was vacuum-dried and replaced with argon, and then hexane 19 was used as a solvent.
8 ml and 2 ml of hexene-1 as an α-olefin were charged, and the temperature of the reactor was raised to 60 ° C. After the temperature was raised, ethylene was fed while adjusting the pressure to 6 kg / cm ² , and after the system became stable, 1.0 mmol of isobutylalumoxane (PBAO manufactured by Tosoh Akzo Co., Ltd.) was added, followed by synthesis in Example 64. Dimethylsilyl (tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride 1.0 μm
was added, and then 3.0 μmol of triphenylmethyltetrakis (pentafluorophenyl) borate was added. Polymerization was carried out for 10 minutes while controlling the temperature at 60 ° C. As a result of the polymerization, SCB = 35.0, [η ₁ ] =
An ethylene-hexene-1 copolymer having a melting point of 3.51 and a melting point of 74.1 ° C. was produced at 3.67 × 10 ⁷ g per 1 mol of titanium per 1 hour.

Example 87 A toluene solution of methylalumoxane (PMAO manufactured by Tosoh Akzo Co., Ltd.) was dried under reduced pressure to remove the solvent and dried. The dried solid methylalumoxane was redissolved in toluene. An autoclave with an internal volume of 0.4 liter equipped with a stirrer was vacuum dried and purged with argon. Then, 198 ml of toluene as a solvent and 2 ml of hexene-1 as an α-olefin were charged, and the temperature of the reactor was raised to 60 ° C. After the temperature rise,
After feeding ethylene while adjusting the ethylene pressure to 6 kg / cm ² , the system was stabilized, and the toluene solution of methylalumoxane treated, dried and redissolved as described above was 1.0 mm.
ol, and then dimethylsilyl (tetramethylcyclopentadienyl) (3-te synthesized in Example 64).
1.0 μmol of rt-butyl-5-methyl-2-phenoxy) titanium dichloride was added, and then 3.0 μmol of triphenylmethyltetrakis (pentafluorophenyl) borate was added. Polymerization was carried out for 10 minutes while controlling the temperature at 60 ° C. As a result of polymerization, SCB
= 33.8, [η ₁ ] = 3.54, and a melting point of 75.6 ° C., an ethylene-hexene-1 copolymer was added to titanium 1
3.21 × 10 ⁷ g was produced per mol and per hour.

Example 88 An autoclave equipped with a stirrer having an internal volume of 0.4 liter was vacuum-dried and replaced with argon, and toluene 19 was used as a solvent.
8 ml and 2 ml of hexene-1 as an α-olefin were charged, and the temperature of the reactor was raised to 60 ° C. After the temperature was raised, feed was performed while adjusting the ethylene pressure to 6 kg / cm ² , and after the system was stabilized, triisobutylaluminum 0.25 mm
ol, and then dimethylsilyl (tetramethylcyclopentadienyl) (3-te synthesized in Example 64).
rt-Butyl-5-methyl-2-phenoxy) titanium dichloride 1.0 μmol was added, followed by N, N
-Dimethylanilinium tetrakis (pentafluorophenyl) borate 3.0 μmol was added. Polymerization was carried out for 10 minutes while controlling the temperature at 60 ° C. As a result of the polymerization, SCB = 31.4, [η ₁ ] = 4.17, melting point 8
An ethylene-hexene-1 copolymer having a temperature of 3.0 ° C. was added at 3.56 × 1 per 1 mol of titanium per 1 hour.
0 ⁷ g was produced.

Example 89 An autoclave equipped with a stirrer having an internal volume of 0.4 liter was vacuum-dried and replaced with argon, and then hexane 19 was used as a solvent.
8 ml and 2 ml of hexene-1 as an α-olefin were charged, and the temperature of the reactor was raised to 60 ° C. After the temperature was raised, ethylene was fed while adjusting the ethylene pressure to 6 kg / cm ² , and after the system was stabilized, triisobutylaluminium 0.25 m was added.
mol, followed by dimethylsilyl (tetramethylcyclopentadienyl) (3-t synthesized in Example 64).
ert-Butyl-5-methyl-2-phenoxy) titanium dichloride (1.0 μmol), followed by N,
3.0 μmol of N-dimethylanilinium tetrakis (pentafluorophenyl) borate was added. 60 ° C
Polymerization was carried out for 10 minutes while controlling the temperature. As a result of the polymerization, an ethylene-hexene-1 copolymer having SCB = 29.0, [η ₁ ] = 3.64 and a melting point of 80.9 ° C.
3.17x per 1 mol of titanium per 1 hour
10 ⁷ g was produced.

Example 90 A 2-liter glass separable flask equipped with a reflux tube, three dropping funnels, a thermometer, and a monomer blowing tube was sufficiently replaced with nitrogen, and then 1 liter of hexane was charged, and ethylene gas was added. At the rate of 8 liters / minute and propylene gas at a rate of 2 liters / minute, supply was started through the blowing tube, and while controlling the internal temperature to 30 ° C by the external water bath jacket, each gas was sufficiently saturated. After checking, from the dropping funnel, triisobutylaluminum 0.25 mmol (1 mmol / ml hexane solution),
Dimethylsilyl (tetramethylcyclopentadienyl) (3-t synthesized in Example 1 (1) dissolved in hexane
Polymerization was initiated by adding a catalyst in the order of 0.001 mmol of ert-butyl-5-methyl-2-phenoxy) titanium dichloride and 0.005 mmol of triphenylmethyltetrakis (pentafluorophenyl) borate dissolved in toluene. 10m after 30 minutes
l of ethanol was added to terminate the polymerization. After the termination of the polymerization, the hexane solution containing the polymer was concentrated under reduced pressure and then added to 1 liter of ethanol solvent to precipitate the polymer. The precipitated polymer was vacuum dried at 80 ° C. for one day. As a result, 5.6 g of a polymer was obtained. As a result of the analysis, propylene units were 57.8 wt% and ethylene units were 42.2% in the polymer.
It is contained in wt% and the intrinsic viscosity of the polymer [η
₂ ] was 5.64 dl / g.

Example 91 In the polymerization of ethylene and propylene of Example 90, 5
-Echilidene-2-norbornene (ENB) 8mmo
Polymerization was performed in the same manner as in Example 90 except that 1 was added. As a result, 1.7 g of a polymer was obtained. As a result of the analysis, propylene unit was 39.7 wt in the polymer.
%, Ethylene unit 53.5 wt%, ENB unit 6.
It was contained in an amount of 75 wt% and the intrinsic viscosity [η ₂ ] of the polymer was 5.64 dl / g.

Example 92 In the polymerization of ethylene and propylene of Example 90, butene-1 was supplied at a rate of 0.06 l / min instead of propylene to obtain dimethylsilyl (tetramethylcyclopentadienyl) (3- tert-butyl-5-methyl-2-phenoxy) titanium dichloride to 0.00
Polymerization was carried out in the same manner as in Example 90 except that 02 mmol and 0.001 mmol of triphenylmethyltetrakis (pentafluorophenyl) borate were used. As a result, 1.7 g of a polymer was obtained. As a result of analysis, the polymer contained 9.3 wt% of butene-1 units and 90.7 wt% of ethylene units, and the intrinsic viscosity [η ₂ ] of the polymer was 5.99 dl / g.

Example 93 A stainless steel autoclave with an internal volume of 2 liter equipped with an electromagnetic stirring blade, a thermometer, and a catalyst additive was sufficiently replaced with nitrogen, and then 800 ml of toluene and 32 of propylene were added.
g, ENB 16 mmol, and ethylene 50 g were charged.
Then, the internal temperature was adjusted to 60 ° C. by an external hot water jacket, and after the temperature became stable, 0.50 mmol of triisobutylaluminum and dimethylsilyl (tetramethyl) synthesized in Example 1 (1) dissolved in hexane were added from a catalyst adder. Cyclopentadienyl) (3-tert-butyl-5-
Methyl-2-phenoxy) titanium dichloride 0.
001 mmol, triphenylmethyl tetrakis (pentafluorophenyl) borate dissolved in toluene.
Polymerization was initiated by adding 015 mmol in that order. When 1 hour had passed after the initiation of the polymerization, 10 ml of ethanol was added to terminate the polymerization. After the termination of the polymerization, unreacted monomers were purged, the toluene solution in which the polymer was dissolved was recovered, heated and concentrated, and then added to about 1 liter of ethanol to precipitate the polymer. The precipitated polymer was dried overnight in a vacuum drier, and as a result, 53.2 g of a polymer was obtained. As a result of the analysis, the polymer composition was such that the propylene unit was 30.8 wt% and the ethylene unit was 66.7.
wt%, ENB unit was 2.5 wt%. The intrinsic viscosity [η ₂ ] was 5.98 dl / g.

Example 94 In the polymerization of Example 93, ENB was not used, but dimethylsilyl (tetramethylcyclopentadienyl) (3-
Polymerization was carried out in the same manner as in Example 93 except that tert-butyl-5-methyl-2-phenoxy) titanium dichloride was changed to 0.0005 mmol. As a result, 4
0.6 g of polymer was obtained. As a result of the analysis, the polymer composition was such that the propylene unit was 32.4 wt% and the ethylene unit was 67.6 wt%. The intrinsic viscosity [η ₂ ] was 5.21 dl / g.

Example 95 In the polymerization of Example 94, butene-1 was replaced with 120.0 g and ethylene was replaced with 59.0 g in place of propylene,
Ethylene and butene were prepared in the same manner as in Example 94 except that triphenylmethyltetrakis (pentafluorophenyl) borate was set to 0.002 mmol and the polymerization was stopped at the time when the pressure-holding ethylene absorption amount reached 3.0 g. 1 was polymerized. As a result, 3.45 g of polymer was obtained. As a result of analysis, the polymer composition was such that the butene-1 unit was 53.5 wt% and the ethylene unit was 46.5 wt%. The intrinsic viscosity [η ₂ ] was 1.46 dl / g.

Example 96 In the polymerization of Example 95, 15.0 g of butene-1 was added,
Ethylene 43.0g, triphenylmethyl tetrakis (pentafluorophenyl) borate 0.003mm
was used, and ethylene and butene-1 were polymerized in the same manner as in Example 95 except that the polymerization temperature was 80 ° C.
As a result, 3.47 g of polymer was obtained. As a result of the analysis, the composition of the polymer is such that the butene-1 unit is 12.0 wt.
%, The ethylene unit was 88.0 wt%. The intrinsic viscosity [η ₂ ] was 3.37 dl / g.

Example 97 In the polymerization of Example 95, ethylene was 56 g, butene-1 was 56 g, ENB was 8 mmol, and dimethylsilyl (tetramethylcyclopentadienyl) (3-tert-butyl- 0.002 mmol of 5-methyl-2-phenoxy) titanium dichloride,
Polymerization was performed in the same manner as in Example 95, except that triphenylmethyltetrakis (pentafluorophenyl) borate was 0.0025 mmol and triisobutylaluminum was 1.00 mmol. As a result, 10.65 g of a polymer was obtained. As a result of the analysis, the composition of the polymer is
Butene-1 unit is 26.7 wt%, ethylene unit is 7
It was 1.8 wt% and the ENB unit was 1.46 wt%.
The intrinsic viscosity [η ₂ ] was 2.08 dl / g.

Example 98 A 2-liter glass separable flask equipped with a reflux tube, three dropping funnels, a thermometer, and a monomer blowing tube was sufficiently replaced with nitrogen, and then 1 liter of toluene was charged, and ethylene gas was added. At the rate of 8 liters / minute and propylene gas at a rate of 2 liters / minute, supply was started through a blowing tube, and the internal temperature was kept at 30 ° C by an external water bath jacket.
After confirming that each gas is sufficiently saturated while controlling to, 0.10 mmol (1 mmol / ml hexane solution) of triisobutylaluminum was added from the dropping funnel.
0.002 mmol of isopropylidene (cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride synthesized in Example 1 (1) dissolved in hexane, triphenylmethyl dissolved in toluene Tetrakis (pentafluorophenyl)
Polymerization was initiated by adding the catalyst in the order of 0.010 mmol of borate. After 30 minutes, 10 ml of ethanol was added to terminate the polymerization. After termination of the polymerization, the hexane solution containing the polymer was concentrated under reduced pressure and then added to 1 liter of an ethanol solvent to precipitate the polymer, and the precipitated polymer was vacuum dried at 80 ° C. for one day. As a result, 15.4 g of polymer was obtained. As a result of the analysis, the polymer contained 49.0 wt% of propylene units and 51.0 wt% of ethylene units, and the intrinsic viscosity [η ₂ ] of the polymer was 0.50 dl / g.

Example 99 In the polymerization of ethylene and propylene of Example 98, the feed rate of ethylene was changed to 7 liters / minute and the feed rate of propylene was changed to 1 liter / minute to prepare 5-ethylidene-2.
-Polymerization was carried out in the same manner as in Example 98 except that 4 mmol of norbornene (ENB) was added. as a result,
6.6 g of polymer was obtained. As a result of the analysis, the polymer contained 39.0 wt% of propylene units, 59.3 wt% of ethylene units, and 1.75 wt% of ENB units, and the intrinsic viscosity [η ₂ ] of the polymer was 1.
It was 35 dl / g.

Example 100 Polymerization was carried out in the same manner as in Example 98, except that butene-1 was supplied at a rate of 0.11 l / min instead of propylene in the polymerization of ethylene and propylene of Example 98. As a result, 4.2 g of a polymer was obtained. As a result of the analysis, the butene-1 unit was 9.2 wt in the polymer.
%, Ethylene unit 90.8 wt% was contained, and the intrinsic viscosity [η ₂ ] of the polymer was 1.70 dl / g.

Example 101 In the polymerization of butene-1 with ethylene of Example 100,
The polymerization temperature was 60 ° C., and the butene-1 feed rate was 0.1.
Polymerization was performed in the same manner as in Example 100 except that the rate was 3 liters / minute. As a result, 10.6 g of polymer was obtained. As a result of the analysis, the polymer contained 9.2 wt% of butene-1 units and 90.8 wt% of ethylene units, and the intrinsic viscosity [η ₂ ] of the polymer was 1.11.
It was dl / g.

Example 102 In the polymerization of butene-1 with ethylene of Example 100,
Polymerization was performed in the same manner as in Example 100, except that trimethylaluminum was used instead of triisobutylaluminum. As a result, 4.8 g of a polymer was obtained. As a result of the analysis, the butene-1 unit was 1 in the polymer.
It contains 1.4 wt% and 88.6 wt% of ethylene unit, and the polymer has an intrinsic viscosity [η ₂ ] of 0.87.
It was dl / g.

[0286]

As described in detail above, according to the present invention,
A complex soluble in a saturated hydrocarbon solvent having a ligand in which an aromatic ring having a hetero atom as a substituent and a cyclopentadienyl ring are linked by a covalent bond group, and an industrially effective complex containing the complex An olefin polymerization catalyst that is highly active at temperature is obtained. Further, using the catalyst, an olefin polymer having a high molecular weight and a narrow composition distribution, particularly linear low density polyethylene,
The ethylene-α-olefin copolymer rubber and the ethylene-α-olefin-non-conjugated diene copolymer rubber can be efficiently produced.

[Brief description of drawings]

FIG. 1 is a flowchart for helping the understanding of the present invention. The flowchart is a representative example of the embodiment of the present invention, and the present invention is not limited to this.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Akira Miyashita 84-90 Koizumi, Ageo City, Saitama Prefecture (72) Inventor Takeshi Watanabe 5-1 Anesakikaigan, Ichihara City, Chiba Sumitomo Chemical Co., Ltd. (72) Inventor Hirofumi Johoji 1-5-5 Anezaki Kaigan, Ichihara-shi, Chiba Sumitomo Chemical Co., Ltd. (72) Inventor Yoshiaki Oda 2-10-1 Tsukahara, Takatsuki, Osaka Sumitomo Chemical Co., Ltd. (72) Inventor Hanaoka Hidenori 2-10-1 Tsukahara, Takatsuki-shi, Osaka Sumitomo Chemical Co., Ltd.

Claims (27)

[Claims] 1. A general formula (1) (Wherein, M ¹ represents a transition metal atom of Group 4 of the periodic table of the element, A represents an atom of Group 16 of the periodic table of the element,
B represents an atom of Group 14 of the periodic table of the elements. Cp ¹ is a group having a cyclopentadiene type anion skeleton.
X ¹ , X ² , R ¹ , R ² , R ³ , R ⁴ , R ⁵ , and R ⁶ are each independently a hydrogen atom, a halogen atom, or an alkyl group having 1 to 20 carbon atoms which may be substituted with a halogen atom. Group, 7 carbon atoms optionally substituted with halogen atom
To aralkyl group having 20 to 20 carbon atoms, aryl group having 6 to 20 carbon atoms optionally substituted with halogen atom, substituted silyl group having 1 to 20 carbon atoms optionally substituted with halogen atom, substituted with halogen atom Optionally substituted alkoxy group having 1 to 20 carbon atoms, aralkyloxy group having 7 to 20 carbon atoms optionally substituted by halogen atom, and 6 to 20 carbon atoms optionally substituted by halogen atom.
Represents an aryloxy group or a disubstituted amino group having 2 to 20 carbon atoms. R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶
May be arbitrarily bonded to form a ring. ) A transition metal complex represented by. 2. The transition metal complex according to claim 1, wherein A in the general formula (1) is an oxygen atom. 3. R ¹ in the general formula (1) is an alkyl group having 1 to 20 carbon atoms which may be substituted with a halogen atom, and 7 carbon atoms which may be substituted with a halogen atom.
To an aralkyl group having 20 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms which may be substituted with a halogen atom, or a substituted silyl group having 1 to 20 carbon atoms which may be substituted with a halogen atom. The transition metal complex according to claim 1 or 2. 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. The general formula (2)(In the formula, Cp²Is a group having a cyclopentadiene skeleton
Show, R⁷Is a carbon atom which may be substituted with a halogen atom
A hydrogen group or a tri-substituted silyl group is shown. A, B, R ¹, R
², R^Three, R^Four, R^Five, R⁶Each has the same meaning as above
Is shown. ) Substituted cyclopentadienyl compound
After reacting with a base, the compound of the general formula (3)(Where X^Three, X^FourAre independently hydrogen atom and halogen
Carbon atom, carbon atom which may be substituted with halogen atom
Substituted with an alkyl group of number 1 to 20, a halogen atom
Aralkyl group having 7 to 20 carbon atoms, halogen
Ali having 6 to 20 carbon atoms which may be substituted with atoms
Group, carbon atom which may be substituted with halogen atom
Substituted silyl group of number 1-20, substituted with halogen atom
Alkoxy group having 1 to 20 carbon atoms, halogen
1-20 carbon atoms, which may be substituted with a hydrogen atom.
Aralkyloxy group, may be substituted with halogen atom
Aryloxy group having 1 to 20 carbon atoms or carbon atom
A 2-substituted amino group having 2 to 20 children is shown. M¹, X¹, X
²Each have the same meaning as described above. ) Transition
The method according to claim 1, wherein a metal compound is reacted.
A method for producing the above transition metal complex. 6. A substituted cyclopentadienyl compound represented by the general formula (2) is produced by the method according to any one of the following [I] to [III].
The method for producing a transition metal complex according to 1. [I] General formula (9) (In the formula, Y ⁴ represents a halogen atom. A, R ¹ , R ² ,
R ³ , R ⁴ and R ⁷ each have the same meaning as described above. )
After reacting the aryl halide compound represented by and an organic alkali metal salt or metal magnesium, the compound represented by the general formula (4) (In the formula, Cp ³ represents a group having a cyclopentadienylidene skeleton, and R ⁵ and R ⁶ each have the same meaning as described above.), And then a cyclopentadienylidene compound represented by How to react. [II] An aryl halide compound represented by the general formula (9) and the general formula (7) (In the formula, Y ¹ and Y ² each represent a halogen atom,
B'represents an atom of Group 14 other than carbon atom. R ⁵ , R
Each ⁶ has the same meaning as described above. ) Is reacted in the presence of an organic alkali metal compound or metal magnesium to give a compound of the general formula (5) (In the formula, A, B ′, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , and R
⁶ , R ⁷ and Y ¹ each have the same meaning as described above. ), And then the halide compound and the general formula (6) M ² Cp ² (6) (in the formula, M ² represents an alkali metal atom, and Cp ² has the same meaning as described above). A method of reacting a cyclopentadienyl metal salt represented by: [III] Aryl halide compound represented by the general formula (9) and the general formula (8) (In the formula, Y ³ represents a halogen atom, and B ′, Cp ² , R
⁵ and R ⁶ have the same meanings as described above. ) The method of reacting the halide compound represented by the formula (1) in the presence of an organic alkali metal compound or metal magnesium. 7. A halogenated aryl compound represented by the general formula (9) is converted to the general formula (10). (In the formula, A, R ¹ , R ² , R ³ , R ⁴ , and Y ⁴ each have the same meaning as described above.) And a halogenated aryl compound represented by the general formula (11) R ⁷ Y ⁵ (11) (Wherein Y ⁵ represents a halogen atom and R ⁷ has the same meaning as described above), and is produced in the presence of a base. Method for producing transition metal complex. 8. A substituted cyclopentadienyl compound represented by the general formula (2). 9. A halogenated aryl compound represented by the general formula (9) is reacted with an organic alkali metal salt or magnesium metal, then a cyclopentadienylidene compound represented by the general formula (4) is reacted, and then water is added. A general formula (2a) characterized by reacting (In the formula, A, Cp ² , R ¹ , R ² , R ³ , R ⁴ , R ⁵ ,
R ⁶ and R ⁷ each have the same meaning as described above. The manufacturing method of the substituted cyclopentadienyl compound shown by these. 10. An aryl halide compound represented by the general formula (9) is reacted with an aryl halide compound represented by the general formula (10) and a halide represented by the general formula (11) in the presence of a base. The method for producing a substituted cyclopentadienyl compound according to claim 9, wherein the substituted cyclopentadienyl compound is produced. 11. A general formula (2b) characterized by reacting a halide compound represented by the general formula (5) with a cyclopentadienyl metal salt represented by the general formula (6). (In the formula, A, B ′, Cp ² , R ¹ , R ² , R ³ , R ⁴ ,
R ⁵ , R ⁶ and R ⁷ each have the same meaning as described above. )
A method for producing a substituted cyclopentadienyl compound represented by: 12. A halide compound represented by the general formula (5), an aryl halide compound represented by the general formula (9) and a dihalide compound represented by the general formula (7) in the presence of an organic alkali metal compound or metal magnesium. The method for producing a substituted cyclopentadienyl compound according to claim 11, wherein the substituted cyclopentadienyl compound is produced by reacting below. 13. An aryl halide compound represented by the general formula (9) is reacted with an aryl halide compound represented by the general formula (10) and a halide represented by the general formula (11) in the presence of a base. The method for producing a substituted cyclopentadienyl compound according to claim 12, wherein the substituted cyclopentadienyl compound is produced. 14. A halogenated compound represented by the general formula (9) and a halide compound represented by the general formula (8) are reacted in the presence of an organic alkali metal compound or metallic magnesium to produce the compound. A method for producing a substituted cyclopentadienyl compound represented by the general formula (2b). 15. An aryl halide compound represented by the general formula (9) is reacted with an aryl halide compound represented by the general formula (10) and a halide represented by the general formula (11) in the presence of a base. 15. The method for producing a substituted cyclopentadienyl compound according to claim 14, wherein the method is produced. 16. A halide compound represented by the general formula (5). 17. The aryl halide compound represented by the general formula (9) and the dihalide compound represented by the general formula (7) are reacted in the presence of an organic alkali metal compound or metal magnesium. The method for producing a halide compound according to 1. 18. An aryl halide compound represented by the general formula (9) is reacted with an aryl halide compound represented by the general formula (10) and a halide represented by the general formula (11) in the presence of a base. The manufacturing method according to claim 17, wherein the manufacturing method is: 19. A halogenated aryl compound represented by the general formula (9) (wherein R ⁷ represents an alkenyl group). 20. A halogenated aryl compound represented by the general formula (10) and a halide represented by the general formula (11) (wherein R ⁷ represents an alkenyl group) are reacted in the presence of a base. The method for producing an aryl halide compound according to claim 19, wherein 21. An olefin polymerization catalyst 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 of them (A1) General formula E ¹ _a
Organoaluminum compound represented by AlZ _3-a (A2)
Formula {-Al (E ²⁾ -O-} cyclic aluminoxane (A3) having the structure represented by _b general formula E ³ {-
A linear aluminoxane having a structure represented by Al (E ³ ) -O-} _c AlE ³ ₂ (provided that E ^{1 to} E ³ are hydrocarbon groups having 1 to 8 carbon atoms, and all E ¹ , All E
² and all E ³ 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 is a number of 0 <a ≦ 3, b is an integer of 2 or more, and c is an integer of 1 or more. ) 22. An olefin polymerization catalyst comprising 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), or a mixture of two or three of them (A1) General formula E ¹ _a
Organoaluminum compound represented by AlZ _3-a (A2)
Formula {-Al (E ²⁾ -O-} cyclic aluminoxane (A3) having the structure represented by _b general formula E ³ {-
A linear aluminoxane having a structure represented by Al (E ³ ) -O-} _c AlE ³ ₂ (provided that E ^{1 to} E ³ are hydrocarbon groups having 1 to 8 carbon atoms, and all E ¹ , All E
² and all E ³ 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 is a number of 0 <a ≦ 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) (B
1) a boron compound represented by the general formula BQ ¹ Q ² Q ³ ;
(B2) a boron compound represented by the general formula Z ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ^- , (B3) a general formula (L-H) ⁺ (BQ
^{1 Q 2 Q 3 Q 4)} - In the boron compound represented by (wherein, B
Is a boron atom in a trivalent valence state, Q ^{1 to} Q ⁴ are a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, and 1 carbon atom.
A substituted silyl group having 20 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or a disubstituted amino group having 2 to 20 carbon atoms, which may be the same or different. ) 23. The olefin polymerization catalyst according to claim 21, wherein the compound (A) is triethylaluminum, triisobutylaluminum or methylaluminoxane. 24. A method for producing an olefin polymer, which comprises using the olefin polymerization catalyst according to any one of claims 21 to 23. 25. The method for producing an olefin polymer according to claim 24, wherein the olefin polymer is an ethylene-α-olefin copolymer. 26. The olefin polymer is an ethylene-α-olefin copolymer rubber.
A method for producing the olefin polymer described. 27. The method for producing an olefin polymer according to claim 24, wherein the olefin polymer is an ethylene-α-olefin-non-conjugated diene copolymer rubber.