2-alkyl-4-(2,6-dialkylphenyl) indenes

Details 2-alkyl-4-(2,6-dialkylphenyl) indenes 2-alkyl-4-(2,6-dialkylphenyl) indenes

1999-08-24

2001-09-18

Nazario-Gonzalez, Porfirio (Department: 1621)

Organic compounds -- part of the class 532-570 series

Organic compounds

Silicon containing

C556S011000, C556S012000, C556S028000, C556S053000, C556S465000, C502S103000, C502S117000, C502S155000, C526S127000, C526S160000, C526S351000, C526S943000, C585S025000, C585S026000, C585S027000

Reexamination Certificate

active

06291699

ABSTRACT:

FIELD OF THE INVENTION
This invention relates to 2-alkyl-4-(2,6-dialkylphenyl) indenes, to the synthesis of said indenes, and to metallocene compounds including olefin polymerization catalysts derived therefrom.
BACKGROUND OF THE INVENTION
Unbridged and bridged substituted cyclopentadienyl and indenyl metallocene olefin polymerization catalysts are known. Particular substituted indenes useful as metallocene ligands have been synthesized by cross-coupling reactions. See
J.Org.Chem
. (1984) 99:4226-7 and U.S. Pat. No. 5,789,634.
SUMMARY OF THE INVENTION
One aspect of this invention provides 2-alkyl-4-(2,6-dialkylphenyl) indenes. Another aspect of the invention may comprise methods, including cross-coupling reactions, for the synthesis of such indenes.
A specific embodiment of the invention may comprise cross-coupling conversion of a 2-alkyl-4X indene (X=halogen or triflate) to a 2-alkyl-4-(2,6-dialkylphenyl)indene.
The invention may also comprise treating 2-alkyl-4-(2,6-dialkylphenyl) indene with a bridging reagent to provide a bridged compound useful as a metallocene ligand.
A specific aspect of the invention comprises conversion of the compounds to the corresponding bridged metallocenes. The invention also includes use of such bridged metallocenes per se or in conjunction with a cocatalyst, such as aluminoxane, as olefin polymerization catalysts and the olefin polymers so produced.
DEFINITIONS
Cross-Coupling Reaction: Any reaction of an organometallic compound
R
—
M
with an organic compound R
1
—
X
, wherein
R
and
R
1
are the same or different organic groups and
X
is a leaving group to give a product
R
—
R
1
. In the context of the invention,
R
1
—
X
is a 2-alkyl-4—
X
indene in which
X
is a halogen or triflate.
DETAILED DESCRIPTION OF THE INVENTION
1. The 2-Alkyl-4-(2,6-Dialkylphenyl) Indenes
The 2-alkyl-4-(2,6-dialkylphenyl) indenes of this invention have the Formula I:
in which R
1
, R
2
, R
3
, R
4
, and R
5
are identical or different hydrocarbyl groups, preferably a C
1
to C
6
alkyl group or a C
6
to C
10
aryl (Ar), preferably phenyl, group which aryl group may be substituted at any available ring position preferably by a C
1
to C
6
alkyl group, and in which the symbol z,
900
indicates a shift in the position of the double bond. Preferably, due to potential synthesis difficulties, only 1 of R
1
to R
4
is aryl. No like constraint applies to R
5
.
2-alkyl-4-phenyl indenes may be synthesized in known manner, e.g., U.S. Pat. No. 5,789,634 (reaction of 2-alkyl-4-chloro indenes with aryl magnesium halides) and
J.Org.Chem
. (1984) 99:4226-7 (nickel catalyzed coupling of 4-bromo indene with phenyl Grignard) or by a cross-coupling reaction, illustrated by Equation 1, in which the R
1
X
reactant is 2-alkyl-4
X
indene, wherein
X
=halogen or triflate and the
R
—M reactant is
In Equation 1, R
1
to R
5
and z,
900
are as described,
X
is any halogen or triflate, and QY is an organometallic substituent in which Q is magnesium, boron, tin, silicon or zinc, and Y may be any X or a C
1
to C
6
trialkyl tin, a C
1
to C
6
trialkyl silicon or a phenyl boronic group or —ZnX.
The cross-coupling catalysts useful in the invention may comprise metal, preferably nickel or palladium, compounds having phosphine ligands. Typical cross-coupling catalysts include Ni(dppp)Cl
2
(nickel diphenylphosphino propane dichloride), Ni(PPh
3
)
2
Cl
2
, Pd(PPh
3
)
4
, X
2
Pd(PPh
3
)
2
(X=halogen), Cl
2
Pd(dppf) (dichloro palladium diphenylphosphino ferrocene) or combination of Pd(OAc)
2
(palladium acetate) or Pd
2
dba
3
(in which dba is dibenzylidene acetone) with phosphine PR
3
, PAr
3
, or PR
2
Ar where R is a C
1
to C
6
alkyl group and Ar is a C
6
to C
10
aryl group.
Useful solvents include ethers, typically diethyl ether, tetrahydrofuran, dioxane and dimethoxyethane or aromatic hydrocarbons, typically benzene, toluene or xylenes.
Preferred conditions, which may be determined in known manner for a specific cross-coupling reaction, are a function of steric hindrance, the specific solvents used, the presence of other reactants including other ligands, and the presence of bases or reducing agents.
The Formula I indene compound may be isolated from the cross-coupling reaction mixture in known manner or further processed in situ.
2. Conversion of Formula I Indenes to Bridged Ligands
As shown by Equation 2, a bridged ligand of Formula II is produced by deprotonation of a Formula I indene with an alkali metal alkyl, followed by reaction of the metallide with an appropriate bridging reagent:
In Formula I, R
1
to R
5
are as described and Z is a bridge or linking group. Bridging agents which may be used in the invention are described in U.S. Pat. No. 5,831,105, col. 3, 11. 30-62, which is incorporated herein and made a part of this specification by reference.
Specifically, for silyl bridging, the metal salt of the deprotonated Formula I indene may be treated with a dialkyldihalosilane, preferably dimethyldichlorosilane.
For hydrocarbon bridging, the Formula I indene may be treated with a dihaloalkane or with a dimethylfulvene derivative of a Formula I indene to yield the dimethyl-carbon bridged analog.
3. Conversion of Bridged Formula II Ligands to Metallocenes
Formula II ligands may be converted to bridged metallocenes by any of the various methods known to the prior art, e.g., U.S. Pat. Nos. 5,017,714; 5,576,260 (Col. 9, 1. 14 et seq.); 5,616,747 and 5,831,105 and references cited therein. Equation 3 illustrates one such conversion:
In Equation 3, R
1
to R
5
, X and Z are as described; M typically is a Group IVA metal, preferably Zr, Ti or Hf. Preferably the alkali metal alkyl is a butyl lithium.
Cocatalyst
The cocatalyst used with a Formula III metallocene is preferably an aluminoxane which may be of the Formula V for the linear type:
or Formula VI for the cyclic type:
In the Formulae V and VI, the radicals R
14
may be identical or different and are a C
1
-C
6
alkyl group, a C
6
-C
18
aryl group, benzyl or hydrogen, and p is an integer from 2 to 50, preferably from 10 to 35.
The radicals R
14
are preferably identical and are preferably methyl, isobutyl, phenyl or benzyl, particularly preferably methyl. If the radicals R
14
are different, they are preferably methyl and hydrogen or, alternatively, methyl and isobutyl, where hydrogen and isobutyl are preferably present to the extent of 0.1-40% (number of radicals R
14
).
The aluminoxane can be prepared in various ways by known processes. One of the methods is, for example, to react an aluminum hydrocarbon compound and/or a hydridoaluminum hydrocarbon compound with water (in gas, solid, liquid or bonded form; for example, as water or crystallization) in an inert solvent (such as, for example, toluene). In order to prepare an aluminoxane containing different alkyl groups R
14
two different trialkylaluminum compounds (AIR
3
+AIR′
3
) corresponding to the desired composition are reacted with water (cf., S. Pasynakiewicz,
Polyhedron
9:429 (1990) and EPA 302 424).
Regardless of the preparation method, all the aluminoxane solutions have in common a varying content of unreacted aluminum starting compound. The metallocene may be pre-activated by means of an aluminoxane of Formula V or VI before use in the polymerization reaction to significantly increase the polymerization activity and improves the grain morphology. The pre-activation of the metallocene compound is carried out in solution. The metallocene is preferably dissolved in a solution of the aluminoxane in an inert hydrocarbon. Suitable inert hydrocarbons are aliphatic and aromatic hydrocarbons. Toluene is preferred.
The concentration of the aluminoxane in the solution is in the range from about 1% by weight to the saturation limit, preferably from 5 to 30% by weight, in each case based on the solution as a whole. The metallocene can be employed in the same concentration, but is preferably employed in an amount of from 10
−
4 to 1 mol per mol of aluminoxane. The pre-activation time may be 5 minutes to 60 minutes. The react

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