Method for producing alkyl-bridged ligand systems and...

Details Method for producing alkyl-bridged ligand systems and... Method for producing alkyl-bridged ligand systems and...

2003-02-25

2004-08-31

Nazario-Gonzalez, Porfirio (Department: 1621)

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

Organic compounds

Heavy metal containing

C502S103000, C502S117000, C526S160000, C526S943000

Reexamination Certificate

active

06784305

ABSTRACT:

The present invention relates to a process for preparing alkyl-bridged ligand systems and transition metal compounds.
The preparation of metallocenes is known per se (U.S. Pat. No. 4,752,597; U.S. Pat. No. 5,017,714; EP-A-320762; EP-A-416815; EP-A-537686; EP-A-669340; H. H. Brintzinger et al.; Angew. Chem., 107 (1995), 1255; H. H. Brintzinger et al., J. Organomet. Chem. 232 (1982), 233). For this purpose, it is possible, for example, to react indenyl-metal compounds with halides of transition metals such as titanium, zirconium and hafnium.
Metallocenes can, possibly in combination with one or more cocatalysts, be used as catalyst components for the polymerization and copolymerization of olefins. In particular, halogen-containing metallocenes are used as catalyst precursors which can be converted into a polymerization-active cationic metallocene complex by means of, for example, an aluminoxane (EP-A-129368).
The polymerization properties of a metallocene compound can be controlled by means of the ligand system. Derivatives of zirconocene dichloride in which the two substituted indenyl groups are joined to one another via a bridge can, owing to their conformational rigidity, be used as catalysts for the stereospecific polymerization of olefins. Variation of this bridge enables the properties of the catalyst and the resulting polymer to be controlled in a targeted manner (Chemical Reviews 2000, Volume 100, Issue 4). Apart from dialkylsilanediyl-bridged metallocenes, ethylidene-bridged metallocenes are also known (DE 19713549).
Although a number of synthetic routes have been described for preparing simple carbon-bridged ligand systems bearing a few substituents, these cannot be applied to the preparation of highly substituted bisindenyl ligands.
A further difficulty in the synthesis of carbon-bridged, highly substituted metallocenes is the metallation of the ligand. The synthesis of these complexes is thus complicated and gives poor yields, which leads directly to increased costs and to limited commercial utility.
Chem. Ber. 1994, 127, 2417-2419, describes the synthesis of 1,2-bis(fluorenyl)-1-phenylethanezirconium dichloride. This unsubstituted alkyl-bridged metal complex is obtained in a yield of 13%.
Organometallics 1992, 11, 1869-1876, describes the synthesis of 2,3-butylene-1,1′-bis(indenyl)zirconium dichloride. This metal complex unsubstituted on the indenyl ligand is obtained in a yield of 18%.
It is an object of the present invention to find a new synthetic route to this class of compounds which avoids the disadvantages of the prior art described and gives the desired compounds in better yields.
We have found that this object is achieved by preparing the ligand systems from highly substituted indene derivatives and alternative bridging reagents, which gives good yields. The use of an alternative metal source leads to the target compounds in high yields and purities. The synthetic route described here gives a high total yield and high purities.
The present invention accordingly provides a process for preparing compounds of the formula I:
where
M
1
is Ti, Zr or Hf, particularly preferably zirconium,
R
1
are identical or different and are each hydrogen or a C
1
-C
20
group, preferably C
1
-C
18
-alkyl, such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, cyclopentyl or cyclohexyl, isopropyl, isobutyl, isopentyl, isohexyl, tert-butyl, C
2
-C
10
-alkenyl, C
3
-C
15
-alkylalkenyl, C
6
-C
18
-aryl, C
4
-C
18
-heteroaryl, C
7
-C
20
-arylalkyl, C
7
-C
20
-alkylaryl, fluorinated C
1
-C
12
-alkyl, fluorinated C
6
-C
18
-aryl, fluorinated C
7
-C
20
-arylalkyl or fluorinated C
7
-C
20
-alkylaryl, and
R
2
are identical or different and are each hydrogen or a C
1
-C
20
group, preferably C
1
-C
18
-alkyl such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, cyclopentyl or cyclohexyl, isopropyl, isobutyl, isopentyl, isohexyl, tert-butyl, C
2
-C
10
-alkenyl, C
3
-C
15
-alkylalkenyl, C
6
-C
18
-aryl, C
4
-C
18
-heteroaryl, C
7
-C
20
-arylalkyl, C
7
-C
20
-alkylaryl, fluorinated C
1
-C
12
-alkyl, fluorinated C
6
-C
18
-aryl, fluorinated C
7
-C
20
-arylalkyl or fluorinated C
7
-C
20
-alkylaryl, where R
1
together with R
2
may also form a monocyclic or polycyclic ring system, and
R
3
are identical or different and are each a hydrogen atom or a C
6
-C
18
-aryl group which may be substituted, in particular phenyl, 4-methylphenyl, 4-ethylphenyl, 4-propylphenyl, 4-isopropylphenyl, 4-tert-butylphenyl, 4-methoxyphenyl, 1-naphthyl, 9-anthracenyl, 3,5-di-tert-butylphenyl, 4-trifluoromethylphenyl, C
5
-C
18
-heteroaryl, C
7
-C
20
-arylalkyl, C
7
-C
20
-alkylaryl, fluorinated C
6
-C
18
-aryl, fluorinated C
7
-C
20
-arylalkyl or fluorinated C
7
-C
20
-alkylaryl and two radicals R
3
and R
4
may form a monocyclic or polycyclic ring system, particularly preferably 4,5-benzindenyl,
R
4
are identical or different and are each either a hydrogen atom or together with R
3
form a monocyclic or polycyclic ring system,
R
5
, R
6
are identical or different and are each a hydrogen atom or a C
1
-C
20
group, preferably C
2
-C
10
-alkenyl, C
3
-C
15
-alkylalkenyl, C
6
-C
18
-aryl, C
4
-C
18
-heteroaryl, C
7
-C
20
-arylalkyl, C
7
-C
20
-alkylaryl, fluorinated C
1
-C
12
-alkyl, fluorinated C
6
-C
18
-aryl, fluorinated C
7
-C
20
-arylalkyl or fluorinated C
7
-C
20
-alkylaryl,
R
7
, R
8
, R
9
, R
10
are identical or different and are each a hydrogen atom or a C
1
-C
20
group, e.g. methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, cyclopentyl or cyclohexyl, isopropyl, isobutyl, isopentyl, isohexyl, tert-butyl, C
2
-C
10
-alkenyl, C
3
-C
15
-alkylalkenyl, C
6
-C
18
-aryl, C
4
-C
18
-heteroaryl, C
7
-C
20
-arylalkyl, C
7
-C
20
-alkylaryl, fluorinated C
1
-C
12
-alkyl, fluorinated C
6
-C
18
-aryl, fluorinated C
7
-C
20
-arylalkyl or fluorinated C
7
-C
20
-alkylaryl, and may among one another form a monocyclic or bicyclic ring system, e.g. cis- or trans-cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl,
i is from 1 to 10, preferably from 1 to 8, very particularly preferably from 1 to 3, and
j is from 1 to 10, preferably from 1 to 8, very particularly preferably from 1 to 3, and
X
1
, X
2
may be identical or different and are each a halogen atom, in particular chlorine, an alkyl group, in particular methyl, or a substituted or unsubstituted phenoxide. X
1
together with one or more radicals X
1
or X
2
may also form a monocyclic or polycyclic ring system.
Despite being indexed the same, the two indenyl radicals can be substituted differently, e.g. R
3
may be phenyl in the first indenyl radical and may be naphthyl in the second indenyl radical.
For this purpose, a compound of the formula II
where
R
1
, R
2
, R
3
, R
4
, R
5
and R
6
are as defined above and
R
11
is a hydrogen atom and
R
12
is a hydrogen atom or a group which can be replaced by a metal, preferably chlorine, bromine or iodine,
is firstly reacted with a compound of the formula III
M
2
R
13
n
X
3
m
  (III)
where
M
2
is an element of main group I or II of the Periodic Table of the Elements, preferably lithium, sodium, potassium or magnesium, particularly preferably lithium, and
R
13
is a hydrogen atom or a C
1
-C
20
group, preferably C
1
-C
18
-alkyl such as methyl, ethyl, n-butyl, n-hexyl, sec-butyl, tert-butyl, cyclohexyl or cyclooctyl, C
2
-C
10
-alkenyl, C
3
-C
15
-alkylalkenyl, C
6
-C
18
-aryl, such as phenyl, tolyl, xylyl, C
5
-C
18
-heteroaryl, C
7
-C
20
-arylalkyl, C
7
-C
20
-alkylaryl, fluorinated C
1
-C
12
-alkyl, fluorinated C
6
-C
18
-aryl, fluorinated C
7
-C
20
-arylalkyl or fluorinated C
7
-C
20
-alkylaryl, preferably C
1
-C
18
-alkyl such as methyl, ethyl, n-butyl, n-hexyl, tert-butyl, C
6
-C
18
-aryl such as phenyl, tolyl, xylyl, particularly preferably methyl, ethyl, n-butyl, n-hexyl, tert-butyl, phenyl or tolyl, and
X
3
is a halogen atom, preferably chlorine, bromine or iodine, and
n is 1 or 2 and
m is 0 or 1,
in a solvent. The compounds of the formula III c

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