Title of Invention

A PROCESS FOR PREPARING A CARBON-BRIDGED BISCYCLOPENTADIENE COMPOUND

Abstract (57) Abstract: The present invention relates to a process for preparing a carbon-bridged biscyclopentadiene compound by reacting one or two cyclopentadiene compounds LH with a carbonyl compound in the presence of at least one base and at least one phase transter catalyst This invention also includes a process for preparing carbon-bridged biscyciopentadienyi metallocene by reacting the biscyclopentadiene compound prepared by the above process with a metal compound. PRICE: THIRTY RUPEES
Full Text




The present invention relates to a process for preparing a carbon-bridged biscyclopentadiens compound and the use of tbis process as a substep in the preparation of a carbon-bridged biscyclopentadienyl metallocene whiob can be used as a catalyst component, e.g. for the preparation of polyolefins.
It is known from the literature that polyolefins can be prepared in the presence of metallocenes in combination with aliuninoxanes or other cocatalysts which, owing to their Lewis acidity, can convert the neutral metallocene into a cation and stabilize it.
Metallocenes and semisandwich complexes are of great interest not only in respect of the polymerization or oligomerization of olefins, but they can also be used as hydrogenation, epoxidation, isomerization and C-C coupling catalysts (Chem. Rev. 1992, 92, 965-994).
Carbon-bridged metallocenes are described in the literature (US 4,892,851; EP 416 566). The synthesis of these metallocenes proceeds via the preparation of the carbon-bridged biscyclopentadiene ligand system which has to be carried out in a number of stages and proceeds only in very small yields.
EP 456 455 discloses the use of quaternary ammonium compounds in the alkylation of cyclopentadienes.
Organometallics, 10, 1991, pages 3739-3745 discloses the use of triethylbenzylammonium chloride in the synthesis of biscyclopentadienyl dimetbylmethane.

It is known from tb« literature that cyclopentadiene can be reacted directly vith cyclic ketones, with addition of a base, to give a bridged biscyclopentadiane ligand (J. Cbem. Research (S), 1992, 162). This synthesis proceeds in low yield and subsequently requires a complicated chromatographic purification.
It is therefore an object of the invention to provide a preparative process for carlson-bridged biscyclopentadiene compounds which avoids the disadvantages of the prior
art.
The present invention accordingly provides a process for
preparing a carbon-bridged biscyclopentadiene compound by
where L is a cycloDentadiene group reacting one or two cyclopentadiane eompounas iSB./ of
which at least one eye1opentadiene compound is a
substituted cyclopentadiene compound, with a carbonyl
compound in the presence of at least one base and at
least one phase transfer catalyst.
The carbon-bridged biscyclopentadiene compound preferably has the formula I

where L are, independently of one another, identical or different cyclopentadiene groups, where at least one group L is a substituted cyclopeutadianyl group, and R and R^ are identical or different and are each a hydrogen atom or a C^-CSQ-hydrocarbon radical.
The cyclopentadiene groups L in formula I can be unsubstituted or substituted. They are identical or different, preferably identical.
Examples of substituted cyclopentadiene groups L are:


tetramethylcyclopantadiene, a-methylcyclopantadlene,
3-tert-butylcyclopaiitadlane, matbyl-tart-
butylcyclopentadiene, Isopropylcyclopentadian*/
dimetbylcyclopentadiane, trimathylcyclopantadiana,
trimetbyletbylcyclopentadiane, 3-plienylcyclopantadiaaa/
diphanylcyclopentadiene, indana, 2-matbylindana,
2-ettaylindene, 3-methylindane, 3-tart-butylindene,
3-trlmathylailyllndana, 2-mathyl-4-phanyllndana,
2-athy1-4-phanylindane, 2-mathy1-4-naphthylindane,
2-mathyl-4-isopropylindene, banaoindana,
2-methyl-4,S-benzoindena, 2-mettayl-a-acanaphthindena,
2-methyl-4,6-dlisopropylindana, fluorana,
2-methylfluorene or 2,7-di-tart-butylfluorana.
One or both of the cyclopentadiene groups L is a
substituted cyclopentadiene group, in particular an
indene derivative such as indana, 2-methylindene,
2-ethylindene, 3-methylindene, 3-tert-butylindena,
3-trimathylsilylindena, 2-methyl-4-pbenylindene,
2-ethyl-4-phenylindene, 2-mathyl-4-naphthylindane,
2-methyl-4-isopropylindene, benaoindena,
2-mathyl-4,5-banzoindane, 2-mathyl-a-acenanaphthindene, 2-methyl-4,6-dii3opropylindena or a fluorenyl derivative such as fluorene, 2-methylfluorene or 2,7-di-tert-butylfluorana.
The radicals R^ and R^ are identical or different, preferably identical, and are C1^-CsQ-hydrocarbon radicals such as C1-C1o-alkyl or Cs-C14-aryl. The radicals R^ and R can also, together with the atoms connecting tham, form a ring system which preferably contains from 4 to 40, particularly preferably from 5 to 15, carbon atoms.
Examples of carbon-bridged biscyclopentadiene compounds of the formula I are:
2,2-blsindenylpropane, 2,2-bi8indanylbutana,
2,2-bisindenylmethane, 2,2-bisindenylcyclopantane,
2,2-bisindenylcyclohexane, l,l-bisindenyl- 1-phenyl-ethane, 1,1-bisindenylethane, 1, i-bisindanylpropane.

2,2-bis(2'-nathyl-4'-pli«nyIind«nyl)propan«,
2,2-bls(2'-athyl-4'-pban7l-ind«nyl)propmii«,
2,3-bis(2' -m-* thy 1-4 '-naphthyliiid«nyl)propan«,
2,2-bls{2'-metbyX-4',5'-b*asoind«nyl)propane,
1,1-bis(2'-methyl- 4'-phenylindenyl)-l-phenylathana,
Ifl-bis{2'-ethyl-4'-pheayl-lndenyl)-l-ph«nyl«than«,
1,l-bls(2'-ni«thyl-4'-naphtbylindenyl)-l-pbenyl«tban«,
2,2-biscyclopentadienylbutana, 2,2-bis(aatbyl-
cyelopentadlanyl)propane, 2-cyclopentadianyl-
2-fluorenylpropane, 2-(3'-metbylcyclopentadianyl) -
2-fluorenylpropane, 2-lndenyl- 2-fluorenylpropana,
2-cyclopentadienyl-2-indenylpropane, l-cyclo-pentadlanyl-
1-fluorenyl-l-phenylethana, i-lndanyl-1-fluorenyl-
1-pbanylathane, 2-(3'-tert-butylcyclopantadienyl)-
2-fluoreBylpropatta, l-cyclopentadienyl-i'lndenyl-l-pbenylethana.

vbicb the two cyclopentadiena groups L are different, two different cyclopentadiena conpounds LH are used.
The cyclopentadiene compounds LH used in tba process of the invention can be substituted or unsubstituted, with at least one cyclopentadiene compound being a substituted cyclopentadiene compound.
Examples of substituted cyclopentadiene compounds LH are
tetramethylcyclopantadiene, metfaylcyclopentadiene, tert-
butylcyclopenta-diene, mathyl-tert-butylcyelopentadiene,
isopropylcyclopentadiene, dimethylcyclopentadiene,
trimethylcyclopentadiene, trimetbylethylcyelo-pentadiene,
phenylcyclopentadiene, diphenylcyclopentadiene, indene,
2-methylindene, 2-ethylindena, 3-methylindane, 3-tert-
butylindane, 3-trimethylsilylindane, 2-mathyl-
-4-phenylindena, 2-ethyl-4-phanylindane, 2-mathyl-
-4-naphthylindene, 2-mathyl-4-iaopropylindane,


benzolndene, 2-nethyl-4,5-benzolndene/ z-methyl-
-a-acenapbthlndene/ 2-methyl- 4,6-dlisopropyllndene, fluorane, 2-metbylfluorenc or 2,7-di-tart-butyIfluorsn*.
One or both of the cyclopentadiane compounds LH used in
the process of the invention is a substituted
cyclopentadiene compound, in particular an indene
derivative such as indans/ 2-mathylindane, 3-ethylindene,
3-methylindene, 3-tert-butylindene,
3-trimethylsilylindena, 2-methyl- 4-phenylindene,
2-ethyl-4-phenylindane, 2-methy1-4-naphthylindane,
2-methyl-4-isopropyllndena, benaoindene,
2-methyl-4,5-benzoindene, 2-methyl-a-acenanaphthindane, 2-mathyl-4,6-diisopropylindene or a fluorenyl derivative such as fluorene, 2-methylfluorene or 2,7-di-tert-butylfluorena.
The carbonyl compounds uaad in the process of the
invention are preferably ketones such as acetone,
acetophenone, benzophenone, cyclo-hexanone,
eyelopantanone, 2-baxanone, 2-butanone, 2-metby1-3-pentanone or 2,2-dimethyl-3-butanone or aldehydes such as acataldehyde or benzaldehyds.
Bases which can be used are hydroxides of group la, lla or izia of the Periodic Table of the Elements, for example LiOH, MaOH, KOH, RbOH, Mg(OH)2^ Ca(OH)j and sr(0H)2> Preference is given to using one base, e.g. LlOH, MaOH or KOH.
Phase transfer catalysts which can be used are quaternary
ammonium salts and phosphonium salts of the formula
[R^4Z]'*'X~, Hbare R^ are identical or different and are
each a hydrogen atom, a halogen atom or a C1-C4o-group
such as a C1-C2o-alkyl group, a C1-C1g-alkoxy group, a
C6-C2o-aryl group, a C -C2 -f^keuyl group, a
C7-C4o-arylallcyl group, a C7-C4o-alkylaryl group, or a Cg-CjQ-arylalkenyl group, which can each bear radicals such as -NR^3, -SR^^. -siR*-> or -OSiR^-i. where R* are

Identical or different and are each a halogen atom, a C^-Cj^o-alkyl group or a C^-C2^Q-a.xyX group, or two or more radicals R^ together with the atoms connecting then can form a ring system which preferably contains from 4 to 40, particularly preferably from 5 to IS, carbon atoms, z is nitrogen or phosphorus and Z~ is a halide, hydroxide, tetrahaloborats, (e.g. tetrafluoroborate), hydrogensulfate, sulfate or hexahalophospbate, (e.g. hexafluorophosphate).
Examples of compounds suitable as phase transfer
catalysts are:
benzyltrimethylammonium chloride,
banzyltrimethylammonium hydroxide (in particular as an
aqueous 40% strength solution),
hexadecyltrimethylzunmonium bromide,
hexadecyltrimethylammonium chloride (in particular as an
aqueous 50% strength solution),
ethyIhexadecyIdimethy1ammonium bromide,
tetraethylammonium tetrafluoroborate,
tetraethylammonium bromide,
tetraethylammonium hydroxide (in particular as an aqeuous
20% strength solution),
benzyltriethylammonium chloride,
benzyltriethylammonium hydroxide,
tetrapropylammonium bromide,
tetrabutylammonium chloride,
tetrabutylammonium fluoridetrihydrate,
tetrabutylammonium tetrafluoroborate,
tetrabutylammonium hydrogensulfate,
tetrabutylammonium hydroxide (in particular as a 12.5%
strength solution in methanol)
benzeltributylammonium bromide,
tetraoctylammonium bromide,
methyltrioctylammonium chloride,
tetrabutyIphosphonium bromide,
tetrabutylphosphonium chloride,
tributylhexadecyIphosphonium bromide,
ethyltrioctylphosphonium bromide.

butyltriphenylphosphonium chloride and tetraphenylphosphonium bromide.
Further phase transfer catalysts vhicb can be used are crown compounds, in particular those of the formulae II, III and IV,

where D is S, O, NR^, PR^ and R^ are identical or different and are each a hydrogen atom, a halogen atom, a C]^-C4o-group such as a c -c^ -aljiyl group, a C1-C1Q-alkoxy group, a C6-C2o-aryl group, a C2-C12~»lJc*nyl group, a C7-C4o-arylalkyl group, a C7-C4o-alkylaryl group or a C8-C4o-arylalkenyl group, which can each bear radicals -KR^g, -SR*2» -siR*3 or -osiR^g where R* are identical or different and are each a halogen atom, a C1-C1o'^l^yl group or a C^-C1o-aryl group, w are identical or different moieties [R^2C]n' where R^ are identical or different and are each a hydrogen atom/ a halogen atom, a Cx-C4Q-group such as a C1-C2o~&llcyi group, a C1-C10-ALKOXY group, a Cg-C2o-aryl group, a C2-C12~^^^^^yl group, a C7-C4o-arylalkyl group, a C7-C4o-alkylaryl group, or a Cg-C4o-arylalkenyl group, which can each bear radicals -NR^3, -SR^2r -SiR^3 or -0SiR^3, where R^ is a halogen atom, a C1-C1Q-alkyl group or a Cg-C1Q-aryl group, or two or more radicals R^ together with the atoms connecting them can form a ring system which preferably contains from 4 to 40, particularly preferably from S to 15, atoms, in particular carbon atoms.

n, 1 and m are identical or different and are each an integer from l to 40, preferably from l to 5, and are preferably identical/
and B are identical or different and are KR* or PR ^ where R* is a hydrogen atom, a halogen atom or a C1-CfQ-group such as a C1-C2o'*&llcyi groups a C1-C1Q-allcoxy group, a c^-Cao-aryl group, a C1-C1j-alkenyl group, a C7-C4(,-arylallcyl group, a C7-C4o-alfcylaryl group, or a Cg-CfQ-arylalkenyl group, which can bear radicals -NR^°3, -SR^°2» -SiR^^a, -osiR^a, where R" is a halogen atom, a C1-C1Q-alJcyl group or a Cg-C1Q-aryl group.
Examples of crown compounds are:
12-crown-4, 15-crown-S, benzo-l5-crown-5, 18-crown-6, decyl-l8-crown-6, dibenzo-18-crown-6, dicyclohexyl-l8-crown-8, dibenzo-2 4-crown-8, ( + ) -l8-crown~fi-tetraoarboxylic acid, N-phenylaza-15-crown-5, ®Kryptofix 21, %ryptofix 22, ^Cryptofix 22 DD, ®Kryptofix 23, tris[2-(-methoxyethoxy)-ethyl]amine, ®Kryptofix 5, ®Kryptofix 111, ®Kryptofix 211, ®Kryptofix 221, ®Kryptofix 221 D, ®Kryptofix 222,
Kryptofix 222 B (50% strength solution in toluene), ®Kryptofix 222 BB, ®Kryptofix 222 cc (50% strength solution in toluene), ®Kryptofix 222 D (50% strength solution in toluene), Kryptofix 221 B (polymer), and
Kryptofix 222 B (polymer).
In the process of the invention, preference is given to using a phase transfer catalyst. The concentration of the phase transfer catalyst can be from 0.1 to 100 mol% based on the amount of cyclopentadiene compound(s) LH used, particularly preferably from i to 20 mol%.
The process of the invention is carried out in a single-phase or multiphase system in the presence of at least one base and at least one phase transfer catalyst. The process of the invention is preferably carried out in a multiphase system, in particular In a two-phase system

where one phase is an organic solvent, e.g. an aromatic solvent such as toluene, xylene or an aliphatic solvent such as tetrahydrofuran, hexane or dichloromethane, and the second phase is vater. Particular preference is given t o the two-phase systems toluene/water, dichloromethane/vater and tetrahydrofuran/water. The concentration of base in the aqueous phase can be between 5 and 70% by weight, preferably from 25 to 60% by weight.
To synthesize carbon-bridged biscyclopentadiene compounds containing two identical cyclopentadiene groups L, the cyclopentadiene compound LH can be used in excess (based on the carbonyl compound), preference is given to using from 2 to 3 equivalents of the cyclopentadiene compound LH, based on the carbonyl compound used (e.g. acetone or acetophenone). In the synthesis of carbon-bridged biscyclopentadiene compounds containing two different cyclopentadiene groups L, two different cyclopentadiene compounds LH are used. In this case, one of the two cyclopentadiene compounds is first reacted with the carbonyl compound, with the ratio of the two components being approximately l : l. After a reaction time, which can be between 30 minutes and 100 hours, preferably between 3 0 minutes and 2 0 hours, the second cyclopentadiene compound is added.
The reaction temperature can be between 0°c and loo'c, preferably from 0°C to 30"C. The reaction times are generally between 30 minutes and 100 hours, preferably between 30 minutes and 20 hours.
The volume ratio of organic phase/water (e.g. toluene/water, dichloromethane/water or tetrahydrofuran/water) can be between 10000:1 and 1:50, preferably between 100:1 and 1:10, particularly preferably between 10:1 and 1:1.
Preferably, a mixture of the cyclopentadiene compound LH and the carbonyl compound is initially charged in the

organic solvent and the aqueous phase containing both the base and the phase transfer catalyst is added. It is also possible to carry out the reaction the other way around. Furthermore, the carbonyl compound can be added dropvise over a period of from 1 minute to 100 hours, preferably from 15 minutes to 4 hours, to the two-phase system (e.g. toluene/water, dichloromethane/water or tetrahydrofuran/water) containing the cyclopentadiene compound LH, the base and the phase transfer catalyst.
The carboH'bridged biscyclopentadiene compounds obtainable using the process of the invention can be formed as double-bond isomers.
The process of the invention is notable, in particular, for the fact that carbon-bridged biscyclopentadiene compounds can be obtained in a simple, single-stage synthesis in high yield. The substitution pattern of the bridge (R^R^C) and of the cyclopentadiene groups L can be varied within a wide range.
The present invention also provides for the use of the process of the invention as a substep of a process for preparing a carbon-bridged biscyclopentadienyl metallocene, in particular a carbon-bridged biscyclopentadienyl metallocene of the formula V

where H^ is an element of group Illb, iVb, Vb or VIb of the Periodic Table of the Elements, in particular of group IVb,
where L' are, independently of one another, identical or different cyclopentadienyl groups, where at least one cyclopentadiene group L' is a substituted cyclopentadiene group, R^ and R^ are identical or different and are each

hydrogen or a Cj^-Cso-bydrocarbon radical sucb as
C1-C1Q-alkyl or C6-C14-aryl, the radicals R^ and R^
together with the atoms connecting them form a ring
system which preferably contains from 4 to 40,
particularly preferably from S to 15, carbon atoms, and
R^^ and R^^ are identical or different and are each
hydrogen, a halogen atom or a c^-c 4(j-radical sucb as
C1-C1o-alJcyl' C1-C1o-allco3ty, C«-C14-aryl, Cj-C14-aryloxy,
C2-C1o-alkenyl, 0,-040-arylalkyl, C7-C4o-alJcylaryl,
Cg-C4o-arylalkenyl, hydroxy, MR^ , 2*^^^'* ^^ ^^ C1-C1o-alkyl, Cj-Oio-allcoxy, c«-C14-aryl, Cfi-014-aryloxy, C2-C1o-alkenyl* C -^ -^^ylalkyl, o -c ralj^laryl or Cg-C4o-arylalkanyl.
The cyclopentadienyl groups L' in formula V can be unsubstituted or substituted. They are identical or different, preferably identical.
Examples of substituted cyclopentadienyl groups L' are:
tetramethylcyclopentadienyl, 3-methylcyclopentadienyl,
3-tert-butylcyclopentadlenyl, methyl-tert-
butylcyclopentadienyl, isopropylcyclopentadie&yl,
dimethylcyclopentadienyl, trimethylcyclopentadienyl,
trimethylethylcyclopentadlenyl, 3-phenylcyclopentadienyl,
diphenylcyclopentadienyl, indenyl, 2-methylindenyl,
2-ethylindenyl, 3-methylindenyl, 3-tert-butylindenyl,
3-trimethylsllyllndenyl, 2-methyl-4-phenylIndenyl,
2-ethyl-4-phenylindenyl, 2-methyl-4-naphthylindenyl,
2-methyl-4-isopropylindenyl, benzoindenyl,
2-methyl-4,5-benzoindenyl, 2-metbyl-a-acenanaphtblndenyl,
2-methyl-4,6-dlisopropylindenyl, fluorenyl,
2-raethylfluorenyl or 2,7-di-tert-butylfluorenyl.
One or both cyclopentadienyl groups L' is a substituted
cyclopentadienyl group, in particular an indenyl
derivative such as indenyl, 2-methylIndenyl,
2-ethyllndenyl, 3-methylindenyl, 3-tert-butylindenyl,
3-trimethylsilylindenyl, 2-methyl-4-phenylindenyl,
2-athyl-4-phenylindonyl, 2-metbyl-4-naphthylindenyl,

2-methyl-4-lsopropylindenyl, beazoiudenyl,
2-methy 1-4 , 5-benzoindeny 1, 2-methy 1-a-acenanapbthindeny 1, 2-mathyl-4,6-dilsopropylindenyl or a fluorenyl derivative such as fluorenyl, 2-metbylfluorenyl or 2,7-di-tert-butylfluorenyl.
The radicals R^ and R^ are identical or different, preferably identical, and are C1-C30-bydrocarbon radicals such as Cj^-C1^Q-alkyl or Cg-C14-aryl. Tbe radicals R^ and R^ can also, together with tbe atoms connecting them, form a ring system which preferably contains from 4 to 40, particularly preferably from 5 to IS, carbon atoms.
Preferably, H^ is an element of group ZV of the Periodic Table of the Elements, for example titanium, sirconium or hafnium, in particular zirconium, R^ and R^ are Identical or different, preferably identical, and are hydrogen, C1-C10-alkyl or C6-C14-aryl, in particular C1-C5-alkyl, and the radicals R11 and R12 are preferably identical and are C1-C4-alkyl such as methyl or a halogen atom such as chlorine.
Examples of carbon-bridged blscyclopentadianyl
metallocenes obtainable by the metallocene preparation process of tbe invention are:
isopropylidenebis (2, 3 , 4, 5-tetramethylcyclopentadlenyl)zirconium dichloride, methylnaphthylmethylenebis (2 , 3 , 4-trimethylcyclopentadienyl)zirconium dichloride, diphenylmethylenabia (2 , 3 , 4 , S-tetramethylcyclopentadienyl)dimethyl-zirconium, methylenebis(l-indenyl)zirconium dichloride, isopropylidenebis(i-indenyl)zirconium dichloride, methylphenylmethylenebis(l-indenyl)zirconium dichloride, diphenylmethylenebis(l-indenyl)zirconium dichloride, methylenebis(1-(4-phenylindenyl))zirconium dichloride, isopropylidenebis(l-(4-phenylindenyl))zirconium dichloride, isopropylidenebis(1-
dichloride,
methylpbenylinethylenebis(l-(4-phenylindenyl))airconium
dicbloride,
diphenylmethylenebis(1-(4-phenylindenyl))airconium
dicbloride,
methylenebis(l-(4-isopropylindenyl)) airconium dichloride,
isopropylidenebis(l-(4-isopropylindenyl})airconium
dichloride/
mettaylphenylmethylenebis (l- ( 4-
isopropylindenyl))dimethylzirconium,
diphenylmethylenebis(l-(4-isopropylindenyl))hafnium
dichloride,
methylenebis{l-(4,S-benzoindenyl))zirconium dichloride,
isopropylidenebis(1-(4,5-banzoindenyl)zirconium
dichloride,
methylphenylmethylenebis (1- (4,5-benzoindenyl)) zirconium
dichloride,
diphenylmethylenebis(1-(4,s-benzoindenyl))airconium
dichloride,
isopropylidena(i-indenyl)(cyclopentadienyl)airconium
dichloride,
isopropylidene{l-indenyl) (3-
methylcyclopentadienyl)airconium dichloride,
methylphenylmethylene(l-indenyl)(cyclopentadienyl)-
zirconium dichloride,
diphenylmethylene(l-indenyl) (cyclopentadienyl) airconium
dichloride,
diphenylmethylene(1-(4-isopropyl)Indenyl)
(cyclopentadienyl)zirconium dichloride,
isopropylidene(l-indenyl)(cyclopentadienyl)titanium
dichloride,
isopropylidene(1-Indenyl)(3-methylcyclopentadienyl)-
titanium dichloride,
methylphenylmethylane(l-indenyl)(cyclopentadienyl)-
titanium dichloride,
diphenylmethylene(l-indenyl)(cyclopentadienyl)titanium
dichloride,
isopropylidene(l-indenyl)(9-fluorenyl)airconium
dichloride.

isopropylideneO-fluorenyl) O-methylcyclopentadianyl)-zirconium dichloride/
i8opropylidene(9-fluoranyl)(3-tert-butyloyclo-pentadienyl) zirconimn dichloride,
nethylphenylmethyIene(9-fIuoranyl}(cyclopantadisnyl)-zirconium dichloride,
diphenylmethylene(9-fluorenyl)(cyclopentadianyl)-zirconiiua dichloride,
diphenyluethylene(9-fluorenyl)(3-pbenylcyclo¬pentadianyl) zirconium dichloride,
diphenylmethylene(l-(4-isopropyl)indenyl) (9-f luorenyl)-zirconium dichloride,
iaopropylidena(9-fluorenyl)(cyclopentadianyl)zircpnium dichloride,
methylphenylmethylene(9-fluorenyl)(cyclopentadianyl)-titanium dichloride,
diphenylmethylene(9-fluorenyl)(cyclopentadianyl)-dimethyltitanium,
diphenylmethylene(9-(2,7-di-tart-butyl)fluorenyl)(cyclo¬pentadianyl) zirconium dichloride,
iaopropylidena(9-(2,7-di-tert-butyl)fluorenyl)-(cyclopentadianyl)zirconium dichloride.
The present invention thus also provides a process for
preparing a carbon-bridged biscyclopantadienyl
metallocene, comprising the steps:
a) Reacting one or two cyclopentadiene compounds LS, of which at least one cyclopentadiene compound is a substituted cyclopentadiana compound, with a carbonyl compound in the presence of at least one base and at least one phase transfer catalyst to give a carbon-bridged biscyclopentadiene compound, and
b) Reacting the carbon-bridged blscyclopentadiana compound obtained in step a) with a metal compound H1Xp, where H1 is an element of group lllb,IVb, Vb or VIb of the Periodic Table of the Elements, X is a C1-C40-radical such as Cx-C1Q-alkyl or NR13, where R13 is a C1-C20-hydrocarbon radical such as C1-C10-

alkyl or C6-C16-aryl, a halogen or a pseudobalogen and p is an integer from 0 to 4, under conditions under which the carbon-bridged biscyclopentadiena compound obtained in step a) is oomplexed to give the carbon-bridged biacyclopentadienyl metallooene.
The second step (b) of the preparative process for the carbon-bridged biscyclopentadienyl metallooene can be carried out by literature methods ( e.g. AD-A-3147S/89; J. Organomet. cfaem. 19B8, 342, 21 or EF-A 284 707, which are hereby expressly incorporated by reference). The carbon-bridged biscyclopentadiene compound is preferably first reacted with a compound of the formula R14M2 where M^ is a metal of group la, lla or llla of the Periodic Table of the Elements and R^^ is a C1-C20-tiydrocarbon radical such as C1-C1Q-alkyl or Cg-C14-aryl, and subsequently with the metal compound H^Xp. The reactions preferably take place in a suitable solvent, e.g. an aliphatic or aromatic solvent such as hexane or toluene, an ether solvent such as tetrahydrofuran or diethyl ether or in balogenated hydrocarbons such as methylene chloride or o-dichlorobenzene. In the metal compound of the formula H^Xp, M^ is preferably an element of group Illb of the Periodic Table of the Elements, X is preferably a halogen atom or HB13 where R13 is a C1-C10-hydrocarbon radical such as C1-C10-alkyl or Cg-C10-aryl, and p is preferably 4. The carbon-bridged biscyclopentadienyl compound can be used as a mixture of isomers.
Carbon-bridged biscyclopentadienyl metallooene halides of the formula V can be converted into the corresponding monoalkyl or dialkyl compounds by literature methods, e.g. by reaction with alkylating agents such as lithium alkyls, (J. Am. Chem. Soc. 1973, 95, 6263).
The carbon-bridged biscyclopentadienyl metallocenes of the formula V can be formed as a mixture of the racemie form and the meso form. The separation of the isomeric forms, in particular the removal of the meso form, is

known in principle (AD-A-31478/89; J. Organomet. Cham. 1986, 342, 21; EP-A 284 707) and can be carried out by extraction or recrystallization using various solvents.
The process of the invention allows the simple preparation of carbon-bridged biscyolopentadienyl matallocenes in high yield.
The carbon-bridged biscyclopentadienyl metallocenea obtainable using the metallocene preparation process of the invention can, together with a cocatalyst, be used as highly active catalyst components, e.g. for the preparation of olefin polymers.
It is possible to polymerize olefins, in particular those of the formula R*-CH=CH-R^, where R* and R^ are identical or different and are each a hydrogen atom or a hydrocarbon radical having from 1 to 20 carbon atoms. R* and R^ can also, together with the carbon atoms connecting them, form a ring. Examples of such olefins are ethylene, propylene, l-butene, l-hexene, i-octena, 4-methyl-l-pentana, 1,3-butadiene, isoprene, norbornene, dimethanooctahydronaphthalene or norbornadiena. In particular, propylene and ethylene can be homopolymerized, ethylene can be copolymerized with a C3-C2o~olefin and/or a C4-C2o~diene or ethylene can be copolymerized with a cycloolafin.
The polymerization can be a homopolymerization or a copolymerization and can be carried out in solution, in suspension or in the gas phase, continuously or batchwise, in one or more stages, at a temperature of from 0 to 200'C, preferably from 30 to lOO'C.
In principle, a suitable cocatalyst in the polymerization is any compound which, owing to its Lewis acidity, can convert the neutral metallocene into a cation and stabilize the latter {"labile coordination"). In addition, the cocatalyst or the anion formed therefrom

should undergo no further reactions with the cation formed (EP 427 697). As cocatalyst, preference is given to using an aluminum compound and/or boron compound.
Cocatalysts used are preferably aluminoxanes (EP-A 129-368, Polyhedron 1990, 9, 429). In place of or in addition to an aluminoxane, it is possible to use boron compounds, in particular of the formulae RxMH4_xBR4', R^VH^-^SR^', R3CBR4' or BR3', as cocatalysts. In these formulae, x is an integer from l to 4, preferably 3, the radicals R are identical or different, preferably identical, and are Cj^—Cj^Q—alfcyl, Cg—Cj^g—aryl or 2 radicals R together with the atoms connecting them form a ring, and the radicals R' are identical or different, preferably identical, and are Cg—Cj^g—alkyl or Cg~Cj_g~aryl which can be substituted by alkyl, haloalkyl or fluorine (EP-A 277 003, 277 004, 426 638, 427697).
It is possible to preactivate the metallocene with a cocatalyst, in particular an aluminoxane, prior to use in the polymerization reaction. This can significantly increase the polymerization activity. The preaetivation of the metallocene is preferably carried out in solution. Here, the metallocene is preferably dissolved in a solution of the aluminoxane in an inert hydrocarbon. Suitable inert hydrocarbons are aliphatic or aromatic hydrocarbons. Preference is given to using toluene.
To remove catalyst poisons present in the olefin, purification using an aluminum compound, preferably an aluminum alkyl such as trimsthylaluminum or triethylaliuninum, is advantageous. This purification can either be carried out in the polymerization system itself or the olefin is, prior to addition to the polymerization system, brought into contact with the aluminum compound and subsequently separated off again.
As molecular weight regulator and/or to increase the catalyst activity, hydrogen can be added in the

polymerization process. This enables low molecular weight polyolefins such as waxes to be obtained.
The metallocene is preferably reacted with the cocatalyst outside the polymerization reactor in a separate step using a suitable solvent. J^plication to a support can be carried out during this step.
In the process, a prapolymerization can be carried out by means of the metallocene. The prapolymerization is preferably carried out using the (or one of the) olefin(s) used in the polymerization.
The catalyst used for the olefin polymerization can be supported. The application to a support allows, for example, the particle morphology of the polymer prepared to be controlled. The metallocene can be reacted first with the support and subsec[uently with the cocatalyst. The cocatalyst can also first be supported and subsec[uently reacted with the metallocene. It is also possible to support the reaction product of metallocene and cocatalyst. Suitable support materials are, for example, silica gels, aluminum oxides, solid aluminoxane or other inorganic support materials such as magnesium chloride. Another suitable support material is a polyolefin powder in finely divided form. The preparation of the supported cocatalyst can, for excunple, be carried out as described ih EP S67 952.
Preferably, the cocatalyst, e.g. aluminoxane, is applied to a support such as silica gels, aluminum oxides, solid aluminoxane or oth«r inorganic support materials such as magnesium chloride or else a polyolefin powder in finely divided form and is than reacted with the metallocene.
If the polymerization is carried out as a suspension or solution polymerization, an inert solvent customary for the Ziegler low-pressure process is used. For example, the polymerization is carried out in an aliphatic or

cycloaliphatic hydrocarbon; examples which may be mentioned are propane, butane, hexane, heptane, isooctane, cyclohexane, methylcyclohexane. Furthermore, a petroleiim or hydrogenated diesel oil fraction can also be used. It is also possible to use toluene. Preference is given to carrying out the polymerization in the liquid monomer.
Use of hydrogen or increasing the polymerization temperature also makes it possible to obtain polyoleflns of low molecular weight, for example waxes, whose hardness or melting point can be varied by means of the comonomer content. Selection of the polymerization process and the type (s) of comonomer (s), and also the amount(s) of comonomer(s), enables olefin copolymers having elastomeric properties, e.g. ethylene/propylene/I,4-hexadiene terpolymers, to be prepared.

Accordingly, the present invention provides a process for preparing a catbon-bridged biscyclopentadiene compound of the formula 1

where L are, independently of one another, identical or different cyclopentadiene groups, where at least one group is a substituted cyclopentadienyl group, and R' and R are identical or different and are each a hydrogen atom or a C1-Cso-hydrocarbon radical or R' and R^ together with the atoms connecting them form a ring system, by reacting one or two cyclopentadiene compounds LH, of which at least one cyclopentadiene compound is a substituted cyclopentadiene compound, with a carbonyl compound, which is a ketone or an aldehyde of formula R'-C(0)-R^, in which R' and R^ are identical or different and are each a hydrogen atom or a C1-C30-hydrocarbon radical or R' and R together with the atoms connecting them form a ring system, in the presence of at least one base, wherein the base is selected from the group consisting of LiOH, NaOH, KOH, RbOH, Mg(0H)2, Ca(0H)2 and Sr(0H)2, and at least one phase transfer catalyst such as a quaternary ammonium salt, a quaternary phosphonium salt or a crown compound, where the process is carried out in a two-phase system comprising an organic solvent, such as an aromatic solvent or an aliphatic solvent, as one phase and water as the second phase.
Accordingly, the present invention also provides a process for preparing a carbon-bridged biscyclopentadienyl metallocene, comprising the steps; (a) preparing a carbon-bridged biscyclopentadiene compound of formula I by the process as claimed in one or more of claims 1 and 2, and (b) reacting the carbon-bridged biscyclopentadiene compound obtained in step a) with a metal compound M'Xp, where M' is titanium, zirconium or hafnium, X is halogen and p is 4, under conditions under which the carbon-bridged biscyclopentadiene compound obtained in step a) is complexed to give the carbon-bridged biscyclopentadienyl metallocene.
1 9 NOV Z003

Tbe following examples illustrate the invention.
1) 2/2-Bisindenylpropane
100.0 g (0.86 mol) of indene are dissolved in 400 ml of toluene and a solution of 86.2 g (2.2 mol) of sodium hydroxide and 19.6 g (86 mmol) of triethyIbenzylammonium chloride In 86.2 ml of water (50% strength HaOH solution) is then added. The addition of 25.o g (0.43 mol) of acetone is carried out dropwise over a period of 30 minutes. After a reaction time of 5 hours, the agueoua phase is separated off, extracted twice with 100 ml each time of diethyl ether and the combined organic phases are dried over MgSO^. The solvent is removed under reduced pressure and the crude product is purified by recrystallization from toluene/hexane. This gives 99.6 g of 2,2-bisindenyIpropane in 85% yield in the form of a yellow powder.
^H-NMR (200 MHZ, CDCI3) : 7.4 - 6.9 (m, 8H, arom. H) , 6.42


(S, 2H, olefin, H), 3.35 (S, 4H, CH2), 1.70 (S, 6H, CH3). Mass spectrum: 272 M'*', correct disintegration pattern.
2) 1,1-Bisindenylethane
100.0 g (0.86 mol) of indene are dissolved in 400 ml of toluene and a solution of 86.2 g (2.2 mol) of sodium hydroxide and 19.6 g (86 mmol) of triethylbensylammonium chloride in 86.2 ml of water (50% strength MaOH solution) is then added. The addition of 18.9 g (0.43 mol) of acetaldehyde is carried out dropwise over a period of 30 minutes. After a reaction time of 5 hours* the aqueous phase is separated off, extracted twice with 100 ml each time of diethyl ether and the combined organic phases are dried over HgS04. The solvent is removed under reduced pressure and the crude product is purified by recrystallization from toluene/hexane. This gives 91.5 g of 1,1-bisindenylethane in 82% yield in the form of a yellow powder.
^H-NMR (200 MHz, CDCI3) : 7.3 - 6.9 (m, 8H, arom. H) , 6.47
(S, 2H, olefin R), 3.41 (S, 4H, CHj), 3.10 (S, IH, CH),
1.65 (s, 3H, CH3). Mass spectrum: 259 H*, correct
disintegration pattern.
3) Isopropylidenebis(i-indenyl)zirconium dlchloride
A solution of 10 g (37 mmol) of 2,2-bisindenylpropane in 30 ml of diethyl ether is admixed at room temperature under argon protection with 29.6 ml (74 mmol) of a 2.5 H butyllithium solution in hexane and stirred overnight. After addition of 20 ml of hexane, the beige suspension is filtered and the residue is washed with 20 ml of pentane. The dilithlo salt is dried in an oil pump vacuum and then added at -78'C to a suspension of 8.6 g (37 mmol) of ZrC14 in dichloromethane. The mixture ia warmed to room temperature over a period of 1 hour and stirred for a further 30 minutes at this temperature. After taking off the solvent, the orange-brown residue is

extracted with 50 ml of toluene. Taking off the solvent gives 8• 8 g (55%) of an orange powder. The ratio of racemate to meso form was determined as 2 : 1. Recryst^llization from toluene enabled 4.1 g (26%) of the pure racemate to be obtained.
1H-MMR (200 MHz, CDCI3) : 7.8 - 6.9 (m, 8H, arom. H), 6.72 (m, 2H, Cp-H), 6.17 (m, 2H, Cp-H) , 2.15 (s, 6H, CH3) .
Mass spectriim: 432 M'^, correct disintegration pattern.


WE CLAIM:
1. A process for preparing a carbon-bridged biscyclopentadiene compound of the formula I

where L are, independently of one another, identical or different cyclopentadiene groups, where at least one cyclopentadiene group is a substituted cyclopentadienyl group, such as herein described, and R1 and R2 are identical or different and are each a hydrogen atom or a C1-C20-hydrocarbon radical or R and R together with the atoms connecting them form a ring system, by reacting one or two cyclopentadiene compounds LH, of which at least one cyclopentadiene compound is a substituted cyclopentadiene compound, with a carbonyl compound, which is a ketone or an aldehyde of formula R1-C(0)-R2 in which R1 and R2 are identical or different and are each a hydrogen atom or a C|-C3o-hydrocarbon radical or R1 and R2 together with the atoms connecting them form a ring system, in the presence of at least one base, wherein the base is selected from the group consisting of LiOH, NaOH, KOH, RbOH, Mg(0H)2, Ca(0H)2 and Sr(0H)2, and at least one phase transfer catalyst such as a quaternary ammonium salt, a quaternary phosphonium salt or a crown compound, where the process is carried out in a two-phase system comprising an organic solvent, such as an aromatic solvent or an aliphatic solvent, as one phase and water as the second phase.

2. The process as claimed in claim 1, wherein, in formula I, both cyclopentadienyl groups L are substituted cyclopentadienyl groups, such as herein described.
3. A process for preparing a carbon-bridged biscyclopentadienyl metallocene, comprising the steps;
(a) preparing a carbon-bridged biscyclopentadiene compound of formula I
by the process as claimed in one or more of claims 1 and 2, and
(b) reacting the carbon-bridged biscyclopentadiene compound obtained in
step a) with a metal compound M1Xp, where M1 is titanium, zirconium
or hafnium, X is halogen and p is 4, in a known manner to obtain the
carbon-bridged biscyclopentadienyl metallocene.
4. A process for preparing a carbon-bridged biscyclopentadiene compound
substantially as herein described.
5. A process for preparing a carbon-bridged biscyclopentadienyl metallocene
substantially as herein described.


Documents:

1108-mas-1996 abstract.pdf

1108-mas-1996 claims.pdf

1108-mas-1996 correspondence others.pdf

1108-mas-1996 correspondence po.pdf

1108-mas-1996 description (complete).pdf

1108-mas-1996 form-2.pdf

1108-mas-1996 form-26.pdf

1108-mas-1996 form-4.pdf

1108-mas-1996 form-6.pdf

1108-mas-1996 others.pdf

1108-mas-1996 petition.pdf


Patent Number 194097
Indian Patent Application Number 1108/MAS/1996
PG Journal Number 30/2009
Publication Date 24-Jul-2009
Grant Date 02-Jan-2006
Date of Filing 24-Jun-1996
Name of Patentee M/S. HOECHST AKTIENGESELLSCHAFT
Applicant Address D-65926 FRANKFURT AM MAIN
Inventors:
# Inventor's Name Inventor's Address
1 DR. FRANK KUBER NEBLEIBISKOPFSTRASSE 10, 61440 OBERURSEL,
2 DR. MICHAEL RIEDEL GEISENHEIMERSTRASSE 95, 60529 FRANKFURT,
PCT International Classification Number C 07 17/00
PCT International Application Number N/A
PCT International Filing date
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 19523595.9 1995-06-30 Germany