Patent Grant
7652159
The invention relates to a process for producing a metallocene compound.
Metallocene complexes are useful as one component of polymerization catalysts to be used for olefin polymerization and a large number of metallocene complexes have been reported. Particularly, a bridged half metallocene complexes having a ligand consisting of cyclopentadiene and phenol bridged by a Group 14 atom of the Periodic Table is highly expected as a metal complexes to have unique activity owing to the unique structure among the metallocene complexes (e.g., reference to Patent Document 1). The process of producing the bridged half metallocene complexes generally involves generation of an anion from a ligand by reacting the ligand with a base and reacting the resulting anion with a metal complex precursor, however it has been desired to develop an industrially advantageous method.
Patent Document 1: Japanese Patent Application Laid-Open (JP-A) No. 9-87313
Non-Patent Document 1: J. Organomet. Chem. 2000, 608, 71-75
The invention relates to an improved and more advantageous process for producing a metallocene compound.
The invention provides a process for producing a metallocene compound of formula (3)
wherein R1, R2, R3 and R4 independently denote
a hydrogen atom, a halogen atom, a substituted or unsubstituted C1-20 alkyl, a substituted or unsubstituted C6-20 aryl, or a substituted or unsubstituted C7-20 aralkyl;
R5, R6, R7, R8, and R9 independently denote
a hydrogen atom, a halogen atom, a substituted or unsubstituted C1-20 alkyl, a substituted or unsubstituted C1-20 alkoxy, a substituted or unsubstituted C6-20 aryl,
a substituted or unsubstituted C6-20 aryloxy,
a substituted or unsubstituted C7-20 aralkyl, a substituted or unsubstituted C7-20 aralkyloxy,
a silyl having a substituent of a substituted or unsubstituted C1-20 hydrocarbon group,
a silyloxy having a substituent of a substituted or unsubstituted C1-20 hydrocarbon group, or
an amino having a substituent of a substituted or unsubstituted C1-20 hydrocarbon group;
R10 denotes a halogen atom, a substituted or unsubstituted C1-20 alkyl, a substituted or unsubstituted C1-20 alkoxy, a substituted or unsubstituted C6-20 aryl,
a substituted or unsubstituted C6-20 aryloxy, a substituted or unsubstituted C7-20 aralkyl, a substituted or unsubstituted C7-20 aralkyloxy,
a silyl having a substituent of a substituted or unsubstituted C1-20 hydrocarbon group,
a silyloxy having a substituent of a substituted or unsubstituted C1-20 hydrocarbon group, or
an amino having a substituent of a substituted or unsubstituted C1-20 hydrocarbon group;
M denotes a transition metal atom of Group 4 of the Periodic Table;
X5 and X6 may be same or different and independently denote a hydrogen atom, a halogen atom, a substituted or unsubstituted C1-20 alkyl, a substituted or unsubstituted C1-20 alkoxy, a substituted or unsubstituted C6-20 aryl,
a substituted or unsubstituted C6-20 aryloxy,
a substituted or unsubstituted C7-20 aralkyl, a substituted or unsubstituted C7-20 aralkyloxy, or
an amino having a substituent of a substituted or unsubstituted C1-20 hydrocarbon group; each neighboring groups of R1, R2, R3 and R4 may be optionally bonded each other to form a ring; R5 and R6 may be bonded to each other to form a ring; and neighboring groups of R7, R8, R9 and R10 may be optionally bonded each other to form a ring,
which process comprises
reacting a silicon-substituted cyclopentadiene compound of formula (1)
wherein R1 to R10 independently are the same as described above; R11 denotes a substituted or unsubstituted hydrocarbon group or a tri-substituted silyl;
R12, R13, and R14 independently denote a halogen atom or a substituted or unsubstituted hydrocarbon group; two or three of R12, R13, and R14 may be bonded one another to form a ring; silicon may be bonded with any one of carbon atoms of the cyclopentadiene ring; and the position of the double bonds of the cyclopentadiene ring may be optional,
with a transition metal compound of formula (2)
wherein M denotes the same as described above;
X1, X2, X3, and X4 may be same or different and independently denote a hydrogen atom, a halogen atom,
a substituted or unsubstituted C1-20 alkyl,
a substituted or unsubstituted C1-20 alkoxy,
a substituted or unsubstituted C6-20 aryl,
a substituted or unsubstituted C6-20 aryloxy,
a substituted or unsubstituted C7-20 aralkyl,
a substituted or unsubstituted C7-20 aralkyloxy, or
an amino group substituted with a substituted or unsubstituted C1-20 hydrocarbon group; and n denotes 0 or 1, in a solvent containing an aromatic hydrocarbon; and a process for producing a metallocene compound of formula (3)
wherein R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, M, X5, and X6 independently denote the same as described above,
which process comprise
reacting a substituted cyclopentadiene compound of formula (4)
wherein R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, and R11 independently denote the same as described above, and the double bonds of the cyclopentadiene ring may be at optional positions,
with a base in a solvent containing an aromatic hydrocarbon, and
reacting the resulting with a silyl halide compound of formula (5)
wherein R12, R13, and R14 independently denote the same as described above; and Y denotes a halogen atom, and
reacting the resulting compound, without refining the compound, with a transition metal compound of formula (2)
wherein M, X1, X2, X3, X4, and n independently denote the same as described above.
Hereinafter, the invention will be described more in detail.
In compounds of the invention, a halogen atom represented by R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R12, R13, R14, X1, X2, X3, X4, X5, or X6 include
a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and preferred is a chlorine atom.
The substituent group of the substituted C1-20 alkyl group represented by R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, X1, X2, X3, X4, X5, or X6 include, for example, a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom. Specific examples of the substituted or unsubstituted alkyl are methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, neopentyl, amyl, n-hexyl, heptyl, n-octyl, n-nonyl, n-decyl, n-dodecyl, n-tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, n-eicosyl, fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, bromomethyl, dibromomethyl, tribromomethyl, iodomethyl, diiodomethyl, triiodomethyl, fluoroethyl, difluoroethyl, trifluoroethyl, tetrafluoroethyl, pentafluoroethyl, chloroethyl, dichloroethyl, trichloroethyl, tetrachloroethyl, pentachloroethyl, bromoethyl, dibromoethyl, tribromoethyl, tetrabromoethyl, pentabromoethyl, perfluoropropyl, perfluorobutyl, perfluoropentyl, perfluorohexyl, perfluorooctyl, perfluorododecyl, perfluoropentadecyl, perfluoroeicosyl, perchloropropyl, perchlorobutyl, perchloropentyl, perchlorohexyl, perchlorooctyl, perchlorododecyl, perchloropentadecyl, perchloroeicosyl, perbromopropyl, perbromobutyl, perbromopentyl, perbromohexyl, perbromooctyl, perbromododecyl, perbromopentadecyl, and perbromoeicosyl and preferred examples are methyl, ethyl, isopropyl, tert-butyl, and amyl.
Specific examples of the unsubstituted C7-20 aralkyl represented by R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, X1, X2, X3, X4, X5, or X6 include, benzyl, (2-methylphenyl)methyl, (3-methylphenyl)methyl, (4-methylphenyl)methyl, (2,3-dimethylphenyl)methyl, (2,4-dimethylphenyl)methyl, (2,5-dimethylphenyl)methyl, (2,6-dimethylphenyl)methyl, (3,4-dimethylphenyl)methyl, (4,6-dimethylphenyl)methyl, (2,3,4-trimethylphenyl)methyl, (2,3,5-trimethylphenyl)methyl, (2,3,6-trimethylphenyl)methyl, (3,4,5-trimethylphenyl)methyl, (2,3,6-trimethylphenyl)methyl, (2,3,4,5-tetramethylphenyl)methyl, (2,3,4,6-tetramethylphenyl)methyl, (2,3,5,6-tetramethylphenyl)methyl, (pentamethylphenyl)methyl, (ethylphenyl)methyl, (n-propylphenyl)methyl, (isopropylphenyl)methyl, (n-butylphenyl)methyl, (sec-butylphenyl)methyl, (tert-butylphenyl)methyl, (n-pentylphenyl)methyl, (neopentylphenyl)methyl, (n-hexylphenyl)methyl, (n-octylphenyl)methyl, (n-decylphenyl)methyl, (n-decylphenyl)methyl, naphthylmethyl, and anthracenylmethyl, and preferred is benzyl.
Examples of the substituted C7-20 aralkyl include those exemplified as unsubstituted C7-20 aralkyl groups substituted with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom as a substituent.
Specific examples of the unsubstituted C6-20 aryl represented by R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, X1, X2, X3, X4, X5, or X6 include phenyl, 2-tolyl, 3-tolyl, 4-tolyl, 2,3-xylyl, 2,4-xylyl, 2,5-xylyl, 2,6-xylyl, 3,4-xylyl, 3,5-xylyl, 2,3,4-trimethylphenyl, 2,3,5-trimethylphenyl, 2,3,6-trimethylphenyl, 2,4,6-trimethylphenyl, 3,4,5-trimethylphenyl, 2,3,4,5-tetramethylphenyl, 2,3,4,6-tetramethylphenyl, 2,3,5,6-tetramethylphenyl, pentamethylphenyl, ethylphenyl, n-propylphenyl, isopropylphenyl, n-butylphenyl, sec-butylphenyl, tert-butylphenyl, n-pentylphenyl, neopentylphenyl, n-hexylphenyl, n-octylphenyl, n-decylphenyl, n-dodecylphenyl, n-tetradecylphenyl, naphthyl, and anthracenyl, and preferably phenyl.
Examples of the substituted C6-20 aryl include these exemplified as the unsubstituted C6-20 aryl groups substituted with a halogen atom such as a fluorine atom, chlorine atom, a bromine atom, or an iodine atom as a substituent.
Specific examples of the unsubstituted C1-20 hydrocarbon in the silyl having a substituted or unsubstituted C1-20 hydrocarbon represented by R5, R6, R7, R8, R9, or R10 are a C1-10 alkyl such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, isobutyl, n-pentyl, n-hexyl, cyclohexyl, n-heptyl, n-octyl, n-nonyl, or n-decyl; and an aryl such as phenyl and these substituent groups may be bonded one another to form rings.
Specific examples of the substituted silyl having the unsubstituted C1-20 hydrocarbon as a substituent group are mono-C1-20 hydrocarbon substituted a silyl group such as methylsilyl, ethylsilyl, and phenylsilyl; a di-C1-20 hydrocarbon substituted silyl group such as dimethylsilyl, diethylsilyl, and diphenylsilyl; a tri-C1-20 hydrocarbon substituted silyl such as trimethylsilyl, triethylsilyl, tri-n-propylsilyl, triisopropylsilyl, tri-n-butylsilyl, tri-sec-butylsilyl, tri-tert-butylsilyl, triisobutylsilyl, tert-butyldimethylsilyl, tri-n-pentylsilyl, tri-n-hexylsilyl, tricyclohexylsilyl, and triphenylsilyl; and a cyclic silyl having substituent groups forming a ring such as cyclotrimethylenemethylsilyl, cyclotetramethylenemethylsilyl, cyclopentamethylenemethylsilyl, cyclotrimethylenephenylsilyl, cyclotetramethylenephenylsilyl, and cyclopentamethylenephenylsilyl and preferably trimethylsilyl, tert-butyldimethylsilyl, and triphenylsilyl. Examples of the hydrocarbon group composing these substituted silyl groups may also include substituted C1-20 hydrocarbon having, as a substituent, a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, and a iodine atom, besides the above exemplified unsubstituted hydrocarbon groups.
Specific examples of the unsubstituted C1-20 alkoxy represented by R5, R6, R7, R8, R9, R10, X1, X2, X3, X4, X5, or X6 are methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, tert-butoxy, n-pentyloxy, neopentyloxy, n-hexyloxy, n-octyloxy, n-nonyloxy, n-decyloxy, n-dodecyloxy, n-undecyloxy, n-dodecyloxy, tridecyloxy, tetradecyloxy, n-pentadecyloxy, hexadecyloxy, heptadecyloxy, octadecyloxy, nonadecyloxy, or n-eicosyloxy, and preferred are methoxy, ethoxy, and tert-butoxy.
Examples of the substituted C1-20 alkoxy include those exemplified as unsubstituted C1-20 alkoxy groups substituted with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom as a substituent.
Specific examples of the unsubstituted C7-20 aralkyloxy represented by R5, R6, R7, R8, R9, R10, X1, X2, X3, X4, X5, or X6 are benzyloxy, (2-methylphenyl)methoxy, (3-methylphenyl)methoxy, (4-methylphenyl)methoxy, (2,3-dimethylphenyl)methoxy, (2,4-dimethylphenyl)methoxy, (2,5-dimethylphenyl)methoxy, (2,6-dimethylphenyl)methoxy, (3,4-dimethylphenyl)methoxy, (3,5-dimethylphenyl)methoxy, (2,3,4-trimethylphenyl)methoxy, (2,3,5-trimethylphenyl)methoxy, (2,3,6-trimethylphenyl)methoxy, (2,4,5-trimethylphenyl)methoxy, (2,4,6-trimethylphenyl)methoxy, (3,4,5-trimethylphenyl)methoxy, (2,3,4,5-tetramethylphenyl)methoxy, (2,3,4,6-tetramethylphenyl)methoxy, (2,3,5,6-tetramethylphenyl)methoxy, (pentamethylphenyl)methoxy, (ethylphenyl)methoxy, (n-propylphenyl)methoxy, (isopropylphenyl)methoxy, (n-butylphenyl)methoxy, (sec-butylphenyl)methoxy, (tert-butylphenyl)methoxy, (n-hexylphenyl)methoxy, (n-octylphenyl)methoxy, (n-decylphenyl)methoxy, naphthylmethoxy, and anthracenylmethoxy, and preferably benzyloxy.
Examples of the substituted C7-20 aralkyloxy include these exemplified as the unsubstituted C7-20 aralkyloxy groups substituted with a halogen atom such as a fluorine atom, chlorine atom, a bromine atom, or an iodine atom as a substituent.
Specific examples of the unsubstituted C6-20 aryloxy represented by R5, R6, R7, R8, R9, R10, X1, X2, X3, X4, X5, and X6 include phenoxy, 2-methylphenoxy, 3-methylphenoxy, 4-methylphenoxy, 2,3-dimethylphenoxy, 2,4-dimethylphenoxy, 2,5-dimethylphenoxy, 2,6-dimethylphenoxy, 3,4-dimethylphenoxy, 3,5-dimethylphenoxy, 2,3,4-trimethylphenoxy, 2,3,5-trimethylphenoxy, 2,3,6-trimethylphenoxy, 2,4,5-trimethylphenoxy, 2,4,6-trimethylphenoxy, 3,4,5-trimethylphenoxy, 2,3,4,5-tetramethylphenoxy, 2,3,4,6-tetramethylphenoxy, 2,3,5,6-tetramethylphenoxy, pentamethylphenoxy, ethylphenoxy, n-propylphenoxy, isopropylphenoxy, n-butylphenoxy, sec-butylphenoxy, tert-butylphenoxy, n-hexylphenoxy, n-octylphenoxy, n-decylphenoxy, n-tetradecylphenoxy, naphthoxy, and anthracenoxy, and preferred is phenoxy.
Examples of the substituted C6-20 aryloxy include those exemplified as unsubstituted C6-20 aryloxy groups substituted with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom as a substituent.
The amino substituted with a substituted or unsubstituted C1-20 hydrocarbon group represented by R5, R6, R7, R8, R9, R10, X1, X2, X3, X4, X5 or X6 is an amino group di-substituted with substituted or unsubstituted C1-20 hydrocarbon groups, and examples of the unsubstituted C1-20 hydrocarbon group include a C1-20 alkyl such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, isobutyl, n-pentyl, n-hexyl, or cyclohexyl; and an aryl such as phenyl and these substituent groups may be bonded one another to form rings.
Examples of the amino group substituted with the unsubstituted C1-20 hydrocarbon groups include dimethylamino, diethylamino, di-n-propylamino, diisopropylamine, di-n-butylamino, di-sec-butylamino, di-tert-butylamino, di-isobutylamino, tert-butylisopropylamino, di-n-hexylamino, di-n-octylamino, di-n-decylamino, diphenylamino, bistrimethylsilylamino, bis(tert-butyldimethylsilyl)amino, pyrrolyl, pyrrolidinyl, piperidinyl, carbazolyl, dihydroindolyl, and dihydroisoindolyl and preferably dimethylamino, diethylamino, pyrrolidinyl, and piperidinyl.
Examples of the substituted C1-20 hydrocarbon group include those exemplified as C1-20 hydrocarbon groups substituted with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom as a substituent.
The silyloxy substituted with a substituted or unsubstituted C1-20 hydrocarbon group represented by R5, R6, R7, R8, R9, or R10 is a silyloxy group substituted with substituted or unsubstituted C1-20 hydrocarbon groups, and examples of the unsubstituted C1-20 hydrocarbon group include the above-exemplified C1-20 alkyl such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, isobutyl, n-pentyl, n-hexyl, or cyclohexyl; and an aryl such as phenyl, and these substituent groups may be bonded one another to form rings.
Examples of the silyloxy group substituted with the unsubstituted C1-20 hydrocarbon groups include trimethylsilyloxy, triethylsilyloxy, tri-n-butylsilyloxy, triphenylsilyloxy, triisopropylsilyloxy,
tert-butyldimethylsilyloxy, dimethylphenylsilyloxy, and methyldiphenylsilyloxy, and preferred are trimethylsilyloxy, triphenylsilyloxy, and triisopropylsilyloxy.
Examples of the C1-20 hydrocarbon group-substituted silyloxy are those exemplified as silyloxy groups having a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom as a substituent in the above-exemplified unsubstituted C1-20 hydrocarbon groups.
Two neighboring substituent groups among R1 to R4 and optional two neighboring substituent groups among R7 to R10 may be bonded each other to form rings, and R5 and R6 may be bonded each other to form a ring and two or three of R12, R13, and R14 may be bonded to form a ring.
Examples of the rings formed by bonding two neighboring substituent groups among R1 to R4, two neighboring substituent groups among R7 to R10, R5 and R6, and two or three of R12, R13, and R14 may be saturated or unsaturated hydrocarbon rings having a substituted or unsubstituted C1-20 hydrocarbon group. Specific examples of the rings are alicyclic C3-8 hydrocarbon rings such as cyclopropane ring, cyclobutane ring, cyclopentane ring, cycloheptane ring, or cyclooctane ring; and aromatic C6-14 hydrocarbon rings such as benzene ring, naphthalene ring, or anthracene ring.
Examples of the unsubstituted hydrocarbon group represented by R11, R12, R13, and R14 include an C1-10 alkyl such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, or decyl; an C2-10 alkenyl such as vinyl, aryl, propenyl, 2-methyl-2-propenyl, homoallyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, or decenyl; and an C7-12 aralkyl such as benzyl, (4-methylphenyl)methyl, and (2,4,6-trimethylphenyl)methyl.
Examples of the substituted hydrocarbon include an alkyl substituted with an alkoxy or alkoxyalkyl such as methoxymethyl or methoxyethoxymethyl, and also hydrocarbon groups derived from the above-exemplified hydrocarbon groups by substituting a halogen atom for hydrogen, and specific examples of halogen-substituted hydrocarbon groups include 2-chloro-2-propenyl.
Examples of the tri-substituted silyl represented by R11 include trimethylsilyl, triethylsilyl, tri-n-propylsilyl, triisopropylsilyl, tri-n-butylsilyl, tri-sec-butylsilyl, tri-tert-butylsilyl, triisobutylsilyl, tert-butyldimethylsilyl, tri-n-pentylsilyl, tri-n-hexylsilyl, tricyclohexylsilyl, and triphenylsilyl.
Among the examples of R11, the alkyl is preferable and methyl is more preferable in that the metallocene compound of formula (3) is produced in a higher yield.
Examples of the silicon-substituted cyclopentadiene compound of formula (1) of the invention include 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, and isomers of these exemplified compounds which isomers have the double bond of the cyclopentadiene ring at different positions and isomers of these exemplified compounds which isomers have the trimethylsilyl group at a different position of the cyclopentadiene ring;
1-methoxy-2-[1-(4-methyl-3-trimethylsilyl-cyclopenta-1,4-dienyl)-1-methyl-ethyl]benzene, 1-methoxy-4,6-dimethyl-2-[1-(4-methyl-3-trimethylsilyl-cyclopenta-1,4-dienyl)-1-methyl-ethyl]benzene, 6-tert-butyl-1-methoxy-4-methyl-2-[1-(4-methyl-3-trimethylsilyl-cyclopenta-1,4-dienyl)-1-methyl-ethyl]benzene, 1-methoxy-2-phenyl-6-[1-(4-methyl-3-trimethylsilyl-cyclopenta-1,4-dienyl)-1-methyl-ethyl]benzene, 1-tert-butyldimethylsilyl-2-methoxy-5-methyl-3-[1-(4-methyl-3-trimethylsilyl-cyclopenta-1,4-dienyl)-1-methyl-ethyl)]benzene, 2-methoxy-5-methyl-1-trimethylsilyl-3-[1-(4-methyl-3-trimethylsilyl-cyclopenta-1,4-dienyl)-1-methyl-ethyl]benzene, 6-tert-butyl-1,4-dimethoxy-2-[1-(4-methyl-3-trimethylsilyl-cyclopenta-1,4-dienyl)-1-methyl-ethyl]benzene, 5-tert-butyl-1-chloro-4-methoxy-3-[1-(4-methyl-3-trimethylsilyl-cyclopenta-1,4-dienyl)-1-methyl-ethyl]benzene, 6-tert-butyl-1-methoxy-2-[1-(4-methyl-3-trimethylsilyl-cyclopenta-1,4-dienyl)-1-methyl-ethyl]benzene, and isomers of these exemplified compounds which isomers have the double bond of the cyclopentadiene ring at different positions and isomers of these exemplified compounds which isomers have the trimethylsilyl group at a different position of the cyclopentadiene ring;
1-methoxy-2-[1-(3-trimethylsilyl-cyclopenta-1,4-dienyl)-1-ethyl-propyl]benzene, 1-methoxy-4,6-dimethyl-2-[1-(3-trimethylsilyl-cyclopenta-1,4-dienyl)-1-ethyl-propyl]benzene, 6-tert-butyl-1-methoxy-4-methyl-2-[1-(3-trimethylsilyl-cyclopenta-1,4-dienyl)-1-ethyl-propyl]benzene, 1-methoxy-2-phenyl-6-[1-(3-trimethylsilyl-cyclopenta-1,4-dienyl)-1-ethyl-propyl]benzene, 1-tert-butyldimethylsilyl-2-methoxy-5-methyl-3-[1-(3-trimethylsilyl-cyclopenta-1,4-dienyl)-1-ethyl-propyl]benzene, 2-methoxy-5-methyl-1-trimethylsilyl-3-[1-(3-trimethylsilyl-cyclopenta-1,4-dienyl)-1-ethyl-propyl]benzene, 6-tert-butyl-1,4-dimethoxy-2-[1-(3-trimethylsilyl-cyclopenta-1,4-dienyl)-1-ethyl-propyl]benzene, 5-tert-butyl-1-chloro-4-methoxy-3-[1-(3-trimethylsilyl-cyclopenta-1,4-dienyl)-1-ethyl-propyl]benzene, 6-tert-butyl-1-methoxy-2-[1-(3-trimethylsilyl-cyclopenta-1,4-dienyl)-1-ethyl-propyl]benzene, and isomers of these exemplified compounds which isomers have the double bond of the cyclopentadiene ring is at different positions and isomers of these exemplified compounds which isomers have the trimethylsilyl group at a different position of the cyclopentadiene ring;
1-methoxy-2-[1-(3-trimethylsilyl-cyclopenta-1,4-dienyl)-1-cyclopentyl]benzene, 1-methoxy-4,6-dimethyl-2-[1-(3-trimethylsilyl-cyclopenta-1,4-dienyl)-1-cyclopentyl]benzene, 6-tert-butyl-1-methoxy-4-methyl-2-[1-(3-trimethylsilyl-cyclopenta-1,4-dienyl)-1-cyclopentyl]benzene, 1-methoxy-2-phenyl-6-[1-(3-trimethylsilyl-cyclopenta-1,4-dienyl)-1-cyclopentyl]benzene, 1-tert-butyldimethylsilyl-2-methoxy-5-methyl-3-[1-(3-trimethylsilyl-cyclopenta-1,4-dienyl)-1-cyclopentyl]benzene, 2-methoxy-5-methyl-1-trimethylsilyl-3-[1-(3-trimethylsilyl-cyclopenta-1,4-dienyl)-1-cyclopentyl]benzene, 6-tert-butyl-1,4-dimethoxy-2-[1-(3-trimethylsilyl-cyclopenta-1,4-dienyl)-1-cyclopentyl]benzene, 5-tert-butyl-1-chloro-4-methoxy-3-[1-(3-trimethylsilyl-cyclopenta-1,4-dienyl)-1-cyclopentyl]benzene, 6-tert-butyl-1-methoxy-2-[1-(3-trimethylsilyl-cyclopenta-1,4-dienyl)-1-cyclopentyl]benzene, and isomers of these exemplified compounds, which isomers have the double bond of the cyclopentadiene ring at different positions and isomers of these exemplified compounds, which isomers have the trimethylsilyl group at a different position of the cyclopentadiene ring;
1-methoxy-2-[1-(3-trimethylsilyl-cyclopenta-1,4-dienyl)-2,2-dimethylpropyl]benzene, 1-methoxy-4,6-dimethyl-2-[1-(3-trimethylsilyl-cyclopenta-1,4-dienyl)-2,2-dimethylpropyl]benzene, 6-tert-butyl-1-methoxy-4-methyl-2-[1-(3-trimethylsilyl-cyclopenta-1,4-dienyl)-2,2-dimethylpropyl]benzene, 1-methoxy-2-phenyl-6-[1-(3-trimethylsilyl-cyclopenta-1,4-dienyl)-2,2-dimethylpropyl]benzene, 1-tert-butyldimethylsilyl-2-methoxy-5-methyl-3-[1-(3-trimethylsilyl-cyclopenta-1,4-dienyl)-2,2-dimethylpropyl]benzene, 2-methoxy-5-methyl-1-trimethylsilyl-3-[1-(3-trimethylsilyl-cyclopenta-1,4-dienyl)-2,2-dimethylpropyl]benzene, 6-tert-butyl-1,4-dimethoxy-2-[1-(3-trimethylsilyl-cyclopenta-1,4-dienyl)-2,2-dimethylpropyl]benzene, 5-tert-butyl-1-chloro-4-methoxy-3-[1-(3-trimethylsilyl-cyclopenta-1,4-dienyl)-2,2-dimethylpropyl]benzene, 6-tert-butyl-1-methoxy-2-[1-(3-trimethylsilyl-cyclopenta-1,4-dienyl)-2,2-dimethylpropyl]benzene, and isomers of these exemplified compounds which isomers have the double bond of the cyclopentadiene ring at different positions and isomers of these exemplified compounds which isomers have the trimethylsilyl group at a different position of the cyclopentadiene ring;
1-methoxy-2-[1-(3-tert-butyldimethylsilyl-cyclopenta-1,4-dienyl)-1-methyl-ethyl]benzene, 1-methoxy-4,6-dimethyl-2-[1-(3-tert-butyldimethylsilyl-cyclopenta-1,4-dienyl)-1-methyl-ethyl]benzene, 6-tert-butyl-1-methoxy-4-methyl-2-[1-(3-tert-butyldimethylsilyl-cyclopenta-1,4-dienyl)-1-methyl-ethyl]benzene, 1-methoxy-2-phenyl-6-[1-(3-tert-butyldimethylsilyl-cyclopenta-1,4-dienyl)-1-methyl-ethyl]benzene, 1-tert-butyldimethylsilyl-2-methoxy-5-methyl-3-[1-(3-tert-butyldimethylsilyl-cyclopenta-1,4-dienyl)-1-methyl-ethyl]benzene, 2-methoxy-5-methyl-1-trimethylsilyl-3-[1-(3-tert-butyldimethylsilyl-cyclopenta-1,4-dienyl)-1-methyl-ethyl]benzene, 6-tert-butyl-1,4-dimethoxy-2-[1-(3-tert-butyldimethylsilyl-cyclopenta-1,4-dienyl)-1-methyl-ethyl]benzene, 5-tert-butyl-1-chloro-4-methoxy-3-[1-(3-tert-butyldimethylsilyl-cyclopenta-1,4-dienyl)-1-methyl-ethyl]benzene, 6-tert-butyl-1-methoxy-2-[1-(3-tert-butyldimethylsilyl-cyclopenta-1,4-dienyl)-1-methyl-ethyl]benzene, and isomers of these exemplified compounds which isomers have the double bond of the cyclopentadiene ring at different positions and isomers of these exemplified compounds which isomers have the trimethylsilyl group at a different position of the cyclopentadiene ring;
1-methoxy-2-[1-(9-trimethylsilyl-fluorenyl)-1-methyl-ethyl]benzene, 1-methoxy-4,6-dimethyl-2-[1-(9-trimethylsilyl-fluorenyl)-1-methyl-ethyl]benzene, 6-tert-butyl-1-methoxy-4-methyl-2-[1-(9-trimethylsilyl-fluorenyl)-1-methyl-ethyl]benzene, 1-methoxy-2-phenyl-6-[1-(9-trimethylsilyl-fluorenyl)-1-methyl-ethyl]benzene, 1-tert-butyldimethylsilyl-2-methoxy-5-methyl-3-[1-(9-trimethylsilyl-fluorenyl)-1-methyl-ethyl]benzene, 2-methoxy-5-methyl-1-trimethylsilyl-3-[1-(9-trimethylsilyl-fluorenyl)-1-methyl-ethyl]benzene, 6-tert-butyl-1,4-dimethoxy-2-[1-(9-trimethylsilyl-fluorenyl)-1-methyl-ethyl]benzene, 5-tert-butyl-1-chloro-4-methoxy-3-[1-(9-trimethylsilyl-fluorenyl)-1-methyl-ethyl]benzene, 6-tert-butyl-1-methoxy-2-[1-(9-trimethylsilyl-fluorenyl)-1-methyl-ethyl]benzene, and isomers of these exemplified compounds which isomers have the double bond of the fluorene ring at different positions and isomers of these exemplified compounds which isomers have the trimethylsilyl group bonded with the fluorene ring at a different position;
1-methoxy-2-[1-(1-trimethylsilyl-indenyl)-1-methyl-ethyl]benzene, 1-methoxy-4,6-dimethyl-2-[1-(1-trimethylsilyl-indenyl)-1-methyl-ethyl]benzene, 6-tert-butyl-1-methoxy-4-methyl-2-[1-(1-trimethylsilyl-indenyl)-1-methyl-ethyl]benzene, 1-methoxy-2-phenyl-6-[1-(1-trimethylsilyl-indenyl)benzene, 1-tert-butyldimethylsilyl-2-methoxy-5-methyl-3-[1-(1-trimethylsilyl-indenyl)-1-methyl-ethyl]benzene, 2-methoxy-5-methyl-1-trimethylsilyl-3-[1-(1-trimethylsilyl-indenyl)-1-methyl-ethyl]benzene, 6-tert-butyl-1,4-dimethoxy-2-[1-(1-trimethylsilyl-indenyl)-1-methyl-ethyl]benzene, 5-tert-butyl-1-chloro-4-methoxy-3-[1-(1-trimethylsilyl-indenyl)-1-methyl-ethyl]benzene, 6-tert-butyl-1-methoxy-2-[1-(1-trimethylsilyl-indenyl)-1-methyl-ethyl]benzene, and isomers of these exemplified compounds which isomers have the double bond of the indenyl ring at different positions and isomers of these exemplified compounds which isomers have the trimethylsilyl group bonded with the indenyl ring at a different position; and compounds obtained by replacing methoxy of these exemplified compounds with ethoxy, isopropoxy, benzoyloxy, trimethylsilyloxy, tert-butyldimethylsilyloxy, or methoxymethoxy.
Silicon of the silicon-substituted cyclopentadiene compound of formula (1) of the invention may be bonded to any carbon atom of the cyclopentadiene ring and double bond of the cyclopentadiene ring may be at any position. For example, the following substituting styles for cyclopentadiene and silicon can be exemplified and the silicon-substituted cyclopentadiene compound of the invention may be a mixture of any of these substituted compounds.
The silicon-substituted cyclopentadiene compound of formula (1) of the invention can be produced by, for example, a process which comprises reacting a substituted cyclopentadiene compound of formula (4)
wherein R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, and R11 independently denote the same as described above, and the double bond of the cyclopentadiene may be at any position, with a base and successively reacting the resulting product with a halogenated silyl compound of formula (5)
wherein R12, R13, and R14 independently denote same as described above and Y denote a halogen atom, reference to Non-Patent Document 1.
Example of the transition metal compound of formula (2) are a titanium halide such as titanium tetrachloride, titanium trichloride, titanium tetrabromide, and titanium tetraiodide; amido titanium such as tetrakis(dimethylamino)titanium, dichlorobis(dimethylamino)titanium, trichloro(dimethylamino)titanium, or tetrakis(diethylamino)titanium; an alkoxytitanium such as tetraisopropoxytitanium, tetra(n-butoxy)titanium, dichlorodiisopropoxytitanium, or trichloroisopropoxytitanium; and
compounds obtained by replacing titanium of the above-mentioned-respective compounds with zirconium, or hafnium, and preferred is titanium tetrachloride. The amount of the transition metal compound is generally 0.8 mole or higher, preferably 1 mole or higher, and further preferably 1.1 moles or higher per mole of the silicon-substituted cyclopentadiene compound of formula (2) or the substituted cyclopentadiene compound of formula (4) and the upper limit is not particularly limited, however it is generally about 3 moles and preferably about 2 moles.
Examples of the metallocene compound of formula (3) 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-butylcyclopentadienyl)(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-tert-butyldimethylsilyl-5-methyl-2-phenoxy)titanium dichloride, methylene(tetramethylcyclopentadienyl)(3-trimethylsilyl-5-methyl-2-phenoxy)titanium dichloride, methylene(tetramethylcyclopentadienyl)(3-tert-butyl-5-methoxy-2-phenoxy)titanium dichloride, methylene(tetramethylcyclopentadienyl)(3-tert-butyl-5-chloro-2-phenoxy)titanium dichloride,
methylene(indenyl)(3,5-dimethyl-2-phenoxy)titanium dichloride, methylene(indenyl)(3-tert-butyl-2-phenoxy)titanium dichloride, methylene(indenyl)(3-tert-butyl-5-methyl-2-phenoxy)titanium dichloride, methylene(indenyl)(3-phenyl-2-phenoxy)titanium dichloride, methylene(indenyl)(3-tert-butyldimethylsilyl-5-methyl-2-phenoxy)titanium dichloride, methylene(indenyl)(3-trimethylsilyl-5-methyl-2-phenoxy)titanium dichloride, methylene(indenyl)(3-tert-butyl-5-methoxy-2-phenoxy)titanium dichloride, methylene(indenyl)(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-tert-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(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(tert-butylcyclopentadienyl)(3-tert-butyl-2-phenoxy)titanium dichloride, isopropylidene(tert-butylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titanium dichloride, isopropylidene(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-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(indenyl)(3,5-dimethyl-2-phenoxy)titanium dichloride, isopropylidene(indenyl)(3-tert-butyl-2-phenoxy)titanium dichloride, isopropylidene(indenyl)(3-tert-butyl-5-methyl-2-phenoxy)titanium dichloride, isopropylidene(indenyl)(3-phenyl-2-phenoxy)titanium dichloride, isopropylidene(indenyl)(3-tert-butyldimethylsilyl-5-methyl-2-phenoxy)titanium dichloride, isopropylidene(indenyl)(3-trimethylsilyl-5-methyl-2-phenoxy)titanium dichloride, isopropylidene(indenyl)(3-tert-butyl-5-methoxy-2-phenoxy)titanium dichloride, isopropylidene(indenyl)(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,
diethylmethylene(cyclopentadienyl)(3,5-dimethyl-2-phenoxy)titanium dichloride, diethylmethylene(cyclopentadienyl)(3-tert-butyl-2-phenoxy)titanium dichloride, diethylmethylene(cyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titanium dichloride, diethylmethylene(cyclopentadienyl)(3-phenyl-2-phenoxy)titanium dichloride, diethylmethylene(cyclopentadienyl)(3-tert-butyldimethylsilyl-5-methyl-2-phenoxy)titanium dichloride, diethylmethylene(cyclopentadienyl)(3-trimethylsilyl-5-methyl-2-phenoxy)titanium dichloride, diethylmethylene(cyclopentadienyl)(3-tert-butyl-5-methoxy-2-phenoxy)titanium dichloride, diethylmethylene(cyclopentadienyl)(3-tert-butyl-5-chloro-2-phenoxy)titanium dichloride,
diethylmethylene(methylcyclopentadienyl)(3,5-dimethyl-2-phenoxy)titanium dichloride, diethylmethylene(methylcyclopentadienyl)(3-tert-butyl-2-phenoxy)titanium dichloride, diethylmethylene(methylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titanium dichloride, diethylmethylene(methylcyclopentadienyl)(3-phenyl-2-phenoxy)titanium dichloride, diethylmethylene(methylcyclopentadienyl)(3-tert-butyldimethylsilyl-5-methyl-2-phenoxy)titanium dichloride, diethylmethylene(methylcyclopentadienyl)(3-trimethylsilyl-5-methyl-2-phenoxy)titanium dichloride, diethylmethylene(methylcyclopentadienyl)(3-tert-butyl-5-methoxy-2-phenoxy)titanium dichloride, diethylmethylene(methylcyclopentadienyl)(3-tert-butyl-5-chloro-2-phenoxy)titanium dichloride,
diethylmethylene(tert-butylcyclopentadienyl)(3,5-dimethyl-2-phenoxy)titanium dichloride, diethylmethylene(tert-butylcyclopentadienyl)(3-tert-butyl-2-phenoxy)titanium dichloride, diethylmethylene(tert-butylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titanium dichloride, diethylmethylene(tert-butylcyclopentadienyl)(3-phenyl-2-phenoxy)titanium dichloride, diethylmethylene(tert-butylcyclopentadienyl)(3-tert-butyldimethylsilyl-5-methyl-2-phenoxy)titanium dichloride, diethylmethylene(tert-butylcyclopentadienyl)(3-trimethylsilyl-5-methyl-2-phenoxy)titanium dichloride, diethylmethylene(tert-butylcyclopentadienyl)(3-tert-butyl-5-methoxy-2-phenoxy)titanium dichloride, diethylmethylene(tert-butylcyclopentadienyl)(3-tert-butyl-5-chloro-2-phenoxy)titanium dichloride,
diethylmethylene(tetramethylcyclopentadienyl)(3,5-dimethyl-2-phenoxy)titanium dichloride, diethylmethylene(tetramethylcyclopentadienyl)(3-tert-butyl-2-phenoxy)titanium dichloride, diethylmethylene(tetramethylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titanium dichloride, diethylmethylene(tetramethylcyclopentadienyl)(3-phenyl-2-phenoxy)titanium dichloride, diethylmethylene(tetramethylcyclopentadienyl)(3-tert-butyldimethylsilyl-5-methyl-2-phenoxy)titanium dichloride, diethylmethylene(tetramethylcyclopentadienyl)(3-trimethylsilyl-5-methyl-2-phenoxy)titanium dichloride, diethylmethylene(tetramethylcyclopentadienyl)(3-tert-butyl-5-methoxy-2-phenoxy)titanium dichloride, diethylmethylene(tetramethylcyclopentadienyl)(3-tert-butyl-5-chloro-2-phenoxy)titanium dichloride,
diethylmethylene(indenyl)(3,5-dimethyl-2-phenoxy)titanium dichloride, diethylmethylene(indenyl)(3-tert-butyl-2-phenoxy)titanium dichloride, diethylmethylene(indenyl)(3-tert-butyl-5-methyl-2-phenoxy)titanium dichloride, diethylmethylene(indenyl)(3-phenyl-2-phenoxy)titanium dichloride, diethylmethylene(indenyl)(3-tert-butyldimethylsilyl-5-methyl-2-phenoxy)titanium dichloride, diethylmethylene(indenyl)(3-trimethylsilyl-5-methyl-2-phenoxy)titanium dichloride, diethylmethylene(indenyl)(3-tert-butyl-5-methoxy-2-phenoxy)titanium dichloride, diethylmethylene(indenyl)(3-tert-butyl-5-chloro-2-phenoxy)titanium dichloride,
diethylmethylene(fluorenyl)(3,5-dimethyl-2-phenoxy)titanium dichloride, diethylmethylene(fluorenyl)(3-tert-butyl-2-phenoxy)titanium dichloride, diethylmethylene(fluorenyl)(3-tert-butyl-5-methyl-2-phenoxy)titanium dichloride, diethylmethylene(fluorenyl)(3-phenyl-2-phenoxy)titanium dichloride, diethylmethylene(fluorenyl)(3-tert-butyldimethylsilyl-5-methyl-2-phenoxy)titanium dichloride, diethylmethylene(fluorenyl)(3-trimethylsilyl-5-methyl-2-phenoxy)titanium dichloride, diethylmethylene(fluorenyl)(3-tert-butyl-5-methoxy-2-phenoxy)titanium dichloride, diethylmethylene(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, diphenylmethylene(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-tert-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(tert-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-tert-butyldimethylsilyl-5-methyl-2-phenoxy)titanium dichloride, diphenylmethylene(tetramethylcyclopentadienyl)(3-trimethylsilyl-5-methyl-2-phenoxy)titanium dichloride, diphenylmethylene(tetramethylcyclopentadienyl)(3-tert-butyl-5-methoxy-2-phenoxy)titanium dichloride, diphenylmethylene(tetramethylcyclopentadienyl)(3-tert-butyl-5-chloro-2-phenoxy)titanium dichloride,
diphenylmethylene(indenyl)(3,5-dimethyl-2-phenoxy)titanium dichloride, diphenylmethylene(indenyl)(3-tert-butyl-2-phenoxy)titanium dichloride, diphenylmethylene(indenyl)(3-tert-butyl-5-methyl-2-phenoxy)titanium dichloride, diphenylmethylene(indenyl)(3-phenyl-2-phenoxy) titanium dichloride, diphenylmethylene(indenyl)(3-tert-butyldimethylsilyl-5-methyl-2-phenoxy)titanium dichloride, diphenylmethylene(indenyl)(3-trimethylsilyl-5-methyl-2-phenoxy)titanium dichloride, diphenylmethylene(indenyl)(3-tert-butyl-5-methoxy-2-phenoxy)titanium dichloride, diphenylmethylene(indenyl)(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-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-tert-butyl-5-chloro-2-phenoxy)titanium dichloride, compounds obtained by replacing titanium of these exemplified compounds with zirconium and hafnium, compounds obtained by replacing these exemplified chlorides into bromides, iodides, dimethylamides, diethylamides, n-butoxides, and isopropoxides, compounds obtained by replacing (cyclopentadienyl) of the above-exemplified compounds with (dimethylcyclopentadienyl), (trimethylcyclopentadienyl), and (n-butylcyclopentadienyl), and compounds obtained by replacing 3,5-dimethyl-2-phenoxy of the above-exemplified compounds 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, and 3-trimethylsilyl-2-phenoxy.
The metallocene compound of formula (3) of the invention can be produced by reaction of the silicon-substituted cyclopentadiene compound of formula (1) and the transition metal complex of formula (2) in a solvent containing an aromatic hydrocarbon.
It has been known that the metallocene compound of formula (3) can be obtained by, for example, a method similar to the method (e.g., the above-mentioned Non-Patent Document 1) of causing reaction of a brominated phenol and a base and successively reacting the resulting product with dimethylfulvene, and thereafter with titanium tetrachloride, or the method (e.g., the above-mentioned Non-Patent Document 1) of heating a compound obtained by bonding methoxyphenol and cyclopentadienyltitanium trichloride at 110° C. under reduced pressure, however the technique of the invention is more advantageous in terms of the yield.
The metallocene compound of formula (3) of the invention can be produced also by reacting a substituted cyclopentadiene compound of formula (4) and a base in a solvent containing an aromatic hydrocarbon, successively reacting the resulting reaction product with a halogenated silyl compound of formula (5), and without refining the produced substance, and reacting the resulting substance with a transition metal compound of formula (2).
The base that may be used in these production processes are bases capable of substract a proton from a cyclopentadiene ring, and of which examples are organic alkali metal compounds such as organic lithium compounds, e.g., methyllithium, ethyllithium, n-butyllithium, sec-butyllithium, tert-butyllithium, lithium trimethylsilylacetylide, lithium acetylide, trimethylsilylmethyllithium, vinyllithium, phenyllithium, and allyllithium and the use amount of the base is generally in a range from 0.5 to 5 moles and preferably in a range from 1.1 to 2 moles to 1 mole of the substituted cyclopentadiene compound of formula (4).
The substituted cyclopentadiene compound of formula (4) is obtained, for example, by a method similar to the method (e.g., the above-mentioned Patent Document 1) of causing reaction of a halogenated aryl compound with an organic alkali metal compound or metal magnesium and thereafter successively reaction of the reaction product with a cyclopentadienylidene compound.
Examples of the substituted cyclopentadiene compound of formula (4) are 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-methoxybenzene, 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-tert-butyldimethylsilyl-3-[1-(cyclopenta-1,4-dienyl)-1-methyl-ethyl]-2-methoxy-5-methoxybenzene, 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-methylcyclopenta-1,4-dienyl)-1-methyl-ethyl]benzene, 1-methoxy-4,6-dimethyl-2-[1-(4-methylcyclopenta-1,4-dienyl)-1-methyl-ethyl]benzene, 6-tert-butyl-1-methoxy-4-methyl-2-[1-(4-methylcyclopenta-1,4-dienyl)-1-methyl-ethyl]benzene, 1-methoxy-6-[1-(4-methylcyclopenta-1,4-dienyl)-1-methyl-ethyl]-2-phenylbenzene, 1-tert-butyldimethylsilyl-2-methoxy-5-methyl-3-[1-(4-methylcyclopenta-1,4-dienyl)-1-methyl-ethyl]benzene, 2-methoxy-5-methyl-3-[1-(4-methylcyclopenta-1,4-dienyl)-1-methyl-ethyl]-1-trimethylsilylbenzene, 6-tert-butyl-1,4-dimethoxy-2-[1-(4-methylcyclopenta-1,4-dienyl)-1-methyl-ethyl]benzene, 5-tert-butyl-1-chloro-4-methoxy-3-[1-(4-methylcyclopenta-1,4-dienyl)-1-methyl-ethyl]benzene, 6-tert-butyl-1-methoxy-2-[1-(4-methylcyclopenta-1,4-dienyl)-1-methyl-ethyl]benzene,
2-[1-(4-tert-butylcyclopenta-1,4-dienyl)-1-methyl-ethyl]-1-methoxybenzene, 2-[1-(4-tert-butylcyclopenta-1,4-dienyl)-1-methyl-ethyl]-1-methoxy-4,6-dimethyl-benzene, 6-tert-butyl-2-[1-(4-tert-butylcyclopenta-1,4-dienyl)-1-methyl-ethyl]-1-methoxy-4-methylbenzene, 6-[1-(4-tert-butylcyclopenta-1,4-dienyl)-1-methyl-ethyl]-1-methoxy-2-phenylbenzene, 1-tert-butyldimethylsilyl-3-[1-(4-tert-butylcyclopenta-1,4-dienyl)-1-methyl-ethyl]-2-methoxy-5-methyl-benzene, 3-[1-(4-tert-butylcyclopenta-1,4-dienyl)-1-methyl-ethyl]-2-methoxy-5-methyl-1-trimethylsilylbenzene, 6-tert-butyl-2-[1-(4-tert-butylcyclopenta-1,4-dienyl)-1-methyl-ethyl]-1,4-dimethoxybenzene, 5-tert-butyl-1-chloro-3-[1-(4-tert-butylcyclopenta-1,4-dienyl)-1-methyl-ethyl]-4-methoxybenzene, 6-tert-butyl-2-[1-(4-tert-butylcyclopenta-1,4-dienyl)-1-methyl-ethyl]-1-methoxybenzene,
1-methoxy-2-[1-(2,3,4,5-tetramethylcyclopenta-1,4-dienyl)-1-methyl-ethyl]benzene, 1-methoxy-4,6-dimethyl-2-[1-(2,3,4,5-tetramethylcyclopenta-1,4-dienyl)-1-methyl-ethyl]benzene, 6-tert-butyl-1-methoxy-4-methyl-2-[1-(2,3,4,5-tetramethylcyclopenta-1,4-dienyl)-1-methyl-ethyl]benzene, 1-methoxy-2-phenyl-6-[1-(2,3,4,5-tetramethylcyclopenta-1,4-dienyl)-1-methyl-ethyl]benzene, 1-tert-butyldimethylsilyl-2-methoxy-5-methyl-3-[1-(2,3,4,5-tetramethylcyclopenta-1,4-dienyl)-1-methyl-ethyl]benzene, 2-methoxy-5-methyl-3-[1-(2,3,4,5-tetramethylcyclopenta-1,4-dienyl)-1-methyl-ethyl]-1-trimethylsilylbenzene, 6-tert-butyl-1,4-dimethoxy-2-[1-(2,3,4,5-tetramethylcyclopenta-1,4-dienyl)-1-methyl-ethyl]benzene, 5-tert-butyl-1-chloro-4-methoxy-3-[1-(2,3,4,5-tetramethylcyclopenta-1,4-dienyl)-1-methyl-ethyl]benzene, 6-tert-butyl-1-methoxy-2-[1-(2,3,4,5-tetramethylcyclopenta-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-dimethyl-benzene, 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-methyl-benzene, 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-dimethyl-benzene, 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-methyl-benzene, 3-[(cyclopenta-1,4-dienyl)-1,1-diphenylmethyl]-2-methoxy-5-methyl-1-trimethylsilylbenzene, 6-tert-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, compounds obtained by replacing methoxy of these exemplified compounds with ethoxy, isopropoxy, benzoyloxy, trimethylsilyloxy, tert-butyldimethylsilyloxy, and methoxymethoxy, compounds obtained by replacing cyclopenta-1,4-dienyl of these exemplified compounds with dimethylcyclopenta-1,4-dienyl, trimethylcyclopenta-1,4-dienyl, n-butylcyclopenta-1,4-dienyl, indenyl, and fluorenyl, compounds obtained by replacing 1-methoxybenzene of these exemplified compounds with 1-methoxy-6-methylbenzene, 1-methoxy-4,6-di-tert-butylbenzene, 1-methoxy-4-methyl-6-phenylbenzene, 1-tert-butyldimethylsilyl-2-methoxybenzene, and 2-methoxy-1-trimethylsilylbenzene, and isomers of these exemplified compounds in which the double bond of the cyclopentadiene ring is at different positions.
Examples of the halogenated silyl compound of formula (5) are chlorotrimethylsilane, chlorotriethylsilane, chlorotriisopropylylsilane, chlorotri-n-propylsilane, chlorotri-n-butylsilane, chlorotri-sec-butylsilane, chloro-tri-tert-butylsilane, tert-butyldimethylchlorosilane, dimethylphenylchlorosilane, chloromethylsilacyclohexane, chloromethylsilacyclobutane, chloromethylsilacyclopentane, chlorotriphenylsilane, 3-chloropropyldimethylchlorosilane, dichlorodimethylsilane, methyltrichlorosilane, tetrachlorosilane, and compounds obtained by replacing chlorine of these exemplified compounds with fluorine, bromine, and iodine and preferably chlorotrimethylsilane and tert-butyldimethylchlorosilane.
The metallocene compound of formula (3) can be produced in a particularly high yield in a solvent containing an aromatic, hydrocarbon. As the aromatic hydrocarbon is exemplified benzene which may have a substituent such as a halogen atom, a C1-5 alkyl, or a C1-5 alkoxy and practical examples are benzene, toluene, o-xylene, m-xylene, p-xylene, ethylbenzene, n-propylbenzene, cumene, n-butylbenzene, sec-butylbenzene, isobutylbenzene, tert-butylbenzene, amylbenzene, isoamylbenzene, 2-ethyltoluene, 3-ethyltoluene, 4-ethyltoluene, mesitylene, anisole, 2-methylanisole, 3-methylanisole, 4-methylanisole, phenetole, propyl phenyl ether, butyl phenyl ether, pentyl phenyl ether, chlorobenzene, dichlorobenzene, and trichlorobenzene, preferably benzene, toluene and xylene and particularly preferably toluene. These aromatic hydrocarbon solvents may be used alone while mixtures of the organic solvent containing further one or more organic solvents that are inert to the reaction such as aliphatic hydrocarbon solvents, e.g., pentane, hexane, heptane, octane and the like; ether solvents such as diethyl ether, tetrahydrofuran, 1,4-dioxane or the like; and halogenated solvents such as dichloromethane, dichloroethane or the like may be used. The amount of the aromatic hydrocarbon solvent that may be used is generally in a range of about 1 to 200 parts by weight and preferably in a range of about 3 to 50 parts by weight per 1 part by weight of the silicon-substituted cyclopentadiene compound of formula (1), and the aromatic hydrocarbon solvent may be used as a mixture of organic solvents containing an organic solvent that is inert to the reaction and the aromatic hydrocarbon solvent, preferably in the amount of 50% by weight of the mixture.
The reaction temperature is generally −100° C. to a boiling point of the solvent, preferably −80 to 100° C., more preferably −10 to 100° C., and even more preferably −10 to 60° C.
After completion of the reaction, the metallocene compound of formula (3) can be obtained, for example, by removal of insoluble solid matter and followed by evaporation of the solvent, or it can be obtained from a filtrate after removal of the insoluble matter, which filtrate is obtained by concentration of the reaction mixture. If necessary, the obtained metallocene compound can be purified by conventional method such as recrystallization, sublimation or the like.
The metallocene compound of formula (3) produced by the above-mentioned method can be used for polymerization reaction while being reacted with an activation cocatalyst.
Examples of the activation cocatalyst include compounds such as a zinc compound, an aluminum compound, or a boron compound which may be used commonly in polymerization reaction.
The activation cocatalyst is preferably an aluminum compound and a non-aluminum compound which is coupled with a transition metal to form an ion complex and the compounds may be used alone or in combination for polymerization reaction while being reacted with a metal complex.
The metallocene compound produced by the invention is effective in, for example, polymerization reaction of olefins and has industrial advantage.
Hereinafter, the invention will be described more in detail along with Examples, however it is not intended that the invention be limited to the illustrated Examples.
[NMR Measurement Conditions]
Apparatus: JEOL EX 270 model NMR spectrometer or Bruker DPX-300 model NMR spectrometer
Sample: 5 mmF tube; sample concentration: 10 mg/0.5 mL (CDCl3 or toluene-d8)
Measurement parameters: 5 mmF probe; MENUF: NON, OBNUC: 1H; times: 256 times
Internal standard: CDCl3 (7.26 ppm), toluene-d8 (2.09 ppm)
Pulse angle: 450
Temperature: room temperature (about 25° C.)
Repeating time (ACQTM+PD): about 7 seconds
[MS Measurement Conditions (EI)]
Apparatus: JMS-AX 505W, manufactured by JEOL Ltd.
Ionization voltage: 70 eV
Ion source temperature: 230° C.
Data processing apparatus: MS-MP 8020D
MASS RANGE: m/z 35-1000
Under nitrogen atmosphere, a toluene solution (27 mL) containing titanium tetrachloride (0.67 g, 3.52 mmol) was stirred at −50° C. A solution of 6-tert-butyl-2-[1-(3-trimethylsilylcyclopenta-1,4-dienyl)-1-methyl-ethyl]-1-methoxy-4-methylbenzene (1.26 g, 3.52 mmol) in toluene (10 mL) was added dropwise to the toluene solution. After the mixture was warmed to a room temperature, the solution was heated at 90° C. for 2 hours. After being cooled to a room temperature, the solution was filtered through Celite and the obtained filtrate was concentrated. Hexane was added to the mixture to obtain isopropylidene(cyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titanium dichloride as a brown solid (0.68 g, yield 49.7%).
1H-NMR (CDCl3, d(ppm)): 1.42 (s, 9H, Ar-tBu), 1.60 (s, 6H, Me2C), 2.39 (s, 3H, Ar-Me), 6.12 (t, J=2.7 Hz, 2H, Cp), 6.97 (t, J=2.7 Hz, 2H, Cp), 7.22 (s, 1H, Ar), 7.26 (s, 1H, Ar)
Mass spectrum (EI, m/z): 386 (M+), 371, 335
In nitrogen atmosphere, 6-tert-butyl-2-[1-(cyclopenta-1,4-dienyl)-1-methyl-ethyl]-1-methoxy-4-methylbenzene (1.00 g, 3.52 mmol) was dissolved in toluene (30 mL) and cooled to 10° C. After that, a solution of n-butyllithium in hexane (2.73 mL, 1.58 M, 4.31 mmol) was added dropwise to the obtained toluene solution and stirred at 50° C. for 1 hour. After the reaction mixture was cooled to 0° C., a solution of chlorotrimethylsilane (0.47 g, 4.31 mmol) in toluene (5.78 mL) was added dropwide and stirred at 50° C. for 1 hour. After the reaction mixture was cooled to −50° C., a solution obtained by dissolving titanium tetrachloride (0.82 g, 4.31 mmol) in toluene (5.78 mL) was added dropwise and the mixture was heated to a room temperature. After that, the mixture was heated at 90° C. for 2 hours and successively cooled to a room temperature and the reaction mixture was filtered through Celite and the obtained filtrate was concentrated. Hexane was added to the mixture to obtain isopropylidene(cyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titanium dichloride as a brown solid (0.80 g, yield 58.8%).
The reaction was carried out in the same manner as Example 2, except that 0.52 g (4.74 mmol) of chlorotrimethylsilane was used to obtain isopropylidene(cyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titanium dichloride as a brown solid (0.73 g, yield 53.6%).
The reaction was carried out in the same manner as Example 3, except that the addition temperature of titanium tetrachloride was changed to 0° C. and the heating temperature after addition of titanium tetrachloride was changed to 70° C. to obtain isopropylidene(cyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titanium dichloride as a brown solid (0.65 g, yield 48.1%).
The reaction was carried out in the same manner as Example 3, except that the addition temperature of titanium tetrachloride was changed to 0° C. and the heating temperature after addition of titanium tetrachloride was changed to 50° C. to obtain isopropylidene(cyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titanium dichloride as a brown solid (0.77 g, yield 56.5%).
In nitrogen atmosphere, 6-tert-butyl-2-[1-(cyclopenta-1,4-dienyl)-1-methyl-ethyl]-1-methoxy-4-methylbenzene (1.00 g, 3.52 mmol) was dissolved in toluene (30 mL) and cooled to 0° C. After that, a solution of n-butyllithium in hexane (2.80 mL, 1.58 M, 4.42 mmol) was added dropwise to the obtained toluene solution and stirred at 50° C. for 1 hour. After the reaction mixture was cooled to 0° C., a solution containing chlorotrimethylsilane (0.48 g, 4.42 mmol) in toluene (5.78 mL) was added dropwise and stirred at 50° C. for 1 hour. After the reaction mixture was cooled to 0° C., a solution obtained by dissolving titanium tetrachloride (0.84 g, 4.42 mmol) in toluene (5.78 mL) was added dropwise and the mixed solution was warmed to a room temperature. After that, the solution was heated at 50° C. for 2 hours and successively cooled to a room temperature and the reaction mixture was filtered through Celite and the obtained filtrate was concentrated. The obtained filtrate was subjected to 1H-NMR analysis (toluene-d8) using dibromoethane as an internal standard to measure the content of isopropylidene(cyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titanium dichloride (0.89 g, yield 65.8%).
1H-NMR (toluene-d8, d(ppm)): 1.23 (s, 6H, Me2C), 1.52 (s, 9H, Ar-tBu), 2.09 (s, 3H, Ar-Me), 5.47 (t, J=2.7 Hz, 2H, Cp), 6.29 (t, J=2.7 Hz, 2H, Cp), 6.97-7.09 (2H, Ar)
The reaction was carried out in the same manner as Example 6, except that 1.01 g (5.30 mmol) of titanium tetrachloride was used. The content of isopropylidene(cyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titanium dichloride was confirmed by 1H-NMR analysis (0.94 g, yield 69.2%).
The reaction was carried out in the same manner as Example 6, except that the method was changed by addition of the reaction mixture to the titanium tetrachloride solution. The content of isopropylidene(cyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titanium dichloride was confirmed by 1H-NMR analysis (0.84 g, yield 61.8%).
The reaction was carried out in the same manner as Example 6, except that the amount of toluene to dissolve 6-tert-butyl-2-[1-(cyclopenta-1,4-dienyl)-1-methyl-ethyl]-1-methoxy-4-methylbenzene was changed to 15 mL. The content of isopropylidene(cyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titanium dichloride was confirmed by 1H-NMR analysis (0.85 g, yield 62.7%).
The reaction was carried out in the same manner as Example 9, except that neat chlorotrimethylsilane was added dropwise as it was without being dissolved in toluene. The content of isopropylidene(cyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titanium dichloride was confirmed by 1H-NMR analysis (0.93 g, yield 69.0%).
The reaction was carried out in the same manner as Example 10, except that addition temperature of chlorotrimethylsilane was changed to 50° C. The content of isopropylidene(cyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titanium dichloride was confirmed by 1H-NMR analysis (0.87 g, yield 63.8%).
The reaction was carried out in the same manner as Example 11, except that 1.01 g (5.30 mmol) of titanium tetrachloride was used. The content of isopropylidene(cyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titanium dichloride was confirmed by 1H-NMR analysis (1.02 g, yield 75.2%).
The reaction was carried out in the same manner as Example 7, except that 0.67 g (3.55 mmol) of titanium tetrachloride was used. The content of isopropylidene(cyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titanium dichloride was confirmed by 1H-NMR analysis (0.65 g, yield 47.7%).
The reaction was carried out in the same manner as Example 7, except that 0.75 g (3.97 mmol) of titanium tetrachloride was used. The content of isopropylidene(cyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titanium dichloride was confirmed by 1H-NMR analysis (0.67 g, yield 49.6%).
The reaction was carried out in the same manner as Example 7, except that 0.84 g (4.42 mmol) of titanium tetrachloride was used. The content of isopropylidene(cyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titanium dichloride was confirmed by 1H-NMR analysis (0.89 g, yield 65.8%).
The reaction was carried out in the same manner as Example 7, except that 0.92 g (4.88 mmol) of titanium tetrachloride was used. The content of isopropylidene(cyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titanium dichloride was confirmed by 1H-NMR analysis (0.88 g, yield 64.5%).
The reaction was carried out in the same manner as Example 7, except that 1.10 g (5.76 mmol) of titanium tetrachloride was used. The content of isopropylidene(cyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titanium dichloride was confirmed by 1H-NMR analysis (0.94 g, yield 69.4%).
The reaction was carried out in the same manner as Example 7, except that 1.18 g (6.18 mmol) of titanium tetrachloride was used. The content of isopropylidene(cyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titanium dichloride was confirmed by 1H-NMR analysis (0.92 g, yield 68.1%).
In nitrogen atmosphere, 6-tert-butyl-2-[1-(cyclopenta-1,4-dienyl)-1-methyl-ethyl]-1-methoxy-4-methylbenzene (3.00 g, 10.55 mmol) was dissolved in toluene (43 mL) and cooled to 0° C. After that, a solution of n-butyllithium in hexane (9.48 mL, 1.58 M, 14.98 mmol) was added dropwise to the obtained toluene solution and stirred at 50° C. for 1 hour. chlorotrimethylsilane (1.63 g, 14.98 mmol) was added dropwise and stirred at 50° C. for 1 hour. After the reaction mixture was cooled to 0° C., the reaction mixture was added dropwise to a suspension of zirconium tetrachloride (4.18 g, 17.93 mmol) in toluene (9 mL) and the mixture was heated to a room temperature. After that, the mixture was heated at 60° C. for 2 hours and successively cooled to a room temperature and the reaction mixture was filtered through Celite and the obtained filtrate was concentrated to obtain isopropylidene(cyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)zirconium dichloride as a brown solid.
The obtained mixture was subjected to 1H-NMR analysis using dibromoethane as an internal standard to measure the content of isopropylidene(cyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)zirconium dichloride (0.28 g, yield 6.2%).
1H-NMR (CDCl3, d(ppm)): 1.41 (s, 9H, Ar-tBu), 1.59 (s, 6H, Me2C), 2.40 (s, 3H, Ar-Me), 6.10 (t, J=2.7 Hz, 2H, Cp), 6.80 (t, J=2.7 Hz, 2H, Cp), 7.20 (s, 1H, Ar), 7.28 (s, 1H, Ar)
Mass spectrum (EI, m/z): 430 (M+), 415, 377
In nitrogen atmosphere, 6-tert-butyl-2-[1-(cyclopenta-1,4-dienyl)-1-methyl-ethyl]-1-methoxy-4-methylbenzene (3.00 g, 10.55 mmol) was dissolved in toluene (43 mL) and cooled to 0° C. After that, a solution of n-butyllithium solution in hexane (9.48 mL, 1.58 M, 14.98 mmol) was added dropwise to the obtained toluene solution and stirred at 50° C. for 1 hour chlorotrimethylsilane (1.63 g, 14.98 mmol) was added dropwise and stirred at 50° C. for 1 hour. After the reaction mixture was cooled to 0° C., the reaction mixture was added dropwise to a suspension of hafnium tetrachloride (5.74 g, 17.93 mmol) in toluene (9 mL) and the mixture was warmed to a room temperature. After that, the solution was heated at 60° C. for 2 hours and successively cooled to a room temperature and the reaction mixture was filtered through Celite and the obtained filtrate was concentrated to obtain isopropylidene(cyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)hafnium dichloride as a brown solid. The obtained mixture was subjected to 1H-NMR analysis using dibromoethane as an internal standard to measure the content of isopropylidene(cyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)hafnium dichloride (3.61 g, yield 66.1%).
1H-NMR (CDCl3, d(ppm)): 1.38 (s, 9H, Ar-tBu), 1.60 (s, 6H, Me2C), 2.38 (s, 3H, Ar-Me), 6.10 (t, J=2.7 Hz, 2H, Cp), 6.70 (t, J=2.7 Hz, 2H, Cp), 7.10 (s, 1H, Ar), 7.21 (s, 1H, Ar)
Mass spectrum (EI, m/z): 518 (M+), 503, 467
In nitrogen atmosphere, 6-tert-butyl-2-[1-(cyclopenta-1,4-dienyl)-1-methyl-ethyl]-1-methoxy-4-methylbenzene (1.00 g, 3.52 mmol) was dissolved in toluene (35 mL) and cooled to 0° C. After that, a solution of n-butyllithium in hexane (2.89 mL, 1.58 M, 4.57 mmol) was added dropwise to the obtained toluene solution and stirred at 50° C. for 4 hours. After the reaction mixture was cooled to −50° C., a solution of titanium tetrachloride (0.67 g, 3.52 mmol) in toluene (8.09 mL) was added dropwise to the reaction mixture and the mixture was heated to a room temperature. After that, the mixture was heated at 90° C. for 2 hours and successively cooled to a room temperature and the reaction mixture was filtered through Celite and the obtained filtrate was concentrated. Hexane was added to the obtained filtrate to obtain isopropylidene(cyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titanium dichloride as a brown solid (0.46 g, yield 33.6%)
In nitrogen atmosphere, 6-tert-butyl-2-[1-(cyclopenta-1,4-dienyl)-1-methyl-ethyl]-1-methoxy-4-methylbenzene (1.00 g, 3.52 mmol) was dissolved in toluene (25 mL) and cooled to 0° C. After that, a solution of n-butyllithium in hexane (2.80 mL, 1.58 M, 4.42 mmol) was added dropwise to the obtained toluene solution and stirred at 50° C. for 1 hour. After the reaction mixture was cooled to 0° C., a solution of titanium tetrachloride (0.84 g, 3.52 mmol) in toluene (11.56 mL) was added dropwise to the reaction mixture and the mixture was heated to a room temperature. After that, the mixture was heated at 50° C. for 2 hours, and successively cooled to a room temperature and the reaction mixture was filtered through Celite and the obtained filtrate was concentrated. The concentrated filtrate was analyzed by 1H-NMR to find it was complicated mixture and production of isopropylidene(cyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titanium dichloride was slight (0.06 g, yield 4.2%)
| Number | Date | Country | Kind |
|---|---|---|---|
| 2004-249649 | Aug 2004 | JP | national |
| Filing Document | Filing Date | Country | Kind | 371c Date |
|---|---|---|---|---|
| PCT/JP2005/013197 | 7/11/2005 | WO | 00 | 2/23/2007 |
| Publishing Document | Publishing Date | Country | Kind |
|---|---|---|---|
| WO2006/025159 | 3/9/2006 | WO | A |
| Number | Name | Date | Kind |
|---|---|---|---|
| 6329478 | Katayama et al. | Dec 2001 | B1 |
| Number | Date | Country |
|---|---|---|
| 09-087313 | Mar 1997 | JP |
| Number | Date | Country | |
|---|---|---|---|
| 20080319213 A1 | Dec 2008 | US |
