NL1003007C2 - Cyclopentadiene compound substituted with branched alkyl groups. - Google Patents

Description

- 1 -

BRANCHED ALKYL GROUPS SUBSTITUTED CYCLOPENTADIENE COMPOUND

The invention relates to a multi-5-substituted cyclopentadiene compound.

Cyclopentadiene compounds find general use as a ligand in metal complexes, which act as catalyst components, especially for the polymerization of olefins.

10 In the J. of Organomet. Chem, 479 (1994), 1-29 has been reviewed on the influence of the substituents on cyclopentadiene as a ligand in metal complexes. Herein, on the one hand, it is determined that the chemical and physical properties of metal complexes 15 can be varied over a wide range by adapting the substituents to the cyclopentadiene ring. On the other hand, it is noted that no predictions can be made about the expected effect of specific substituents. Depending on the metal, its valency state and the ligands used, the complexes appear to be more or less suitable for certain applications. Polyolefin polymerizations are often copolymerizations of α-olefins, for example ethylene or propylene, with one or more other olefins and / or other vinyl monomers, including vinyl aromatic monomers. The most commonly used cyclopentadiene compounds are unsubstituted or cyclopentadiene substituted with one to five methyl groups. However, these appear when used as a ligand in metal complexes, and in particular in those in which the metal is not in the highest valency state, in which the metal is, for example, Ti (III),

Hf (III), Zr (III) or V (IV) is to provide catalyst components with an unfavorable combination of molecular weight and comonomer incorporation. This means that polymerization under conditions favoring the obtainment of higher molecular weight copolymers 1003007-2 leads to polymers with relatively low comonomer incorporation. Incidentally, in the said review article in the J. of Organomet. Chem. from 1994 even found that "An important feature of 5 these catalyst systems is that tetravalent Ti centers are required for catalytic activity". It should be remembered that Ti is exemplary of the metals suitable as metal in the conventional cyclopentadienyl-substituted metal complexes.

In the following, cyclopentadiene will be abbreviated as 'Cp'. The same abbreviation will be used for a cyclopentadienyl group if it is clear from the context whether cyclopentadiene itself or its anion is meant.

The olefins are here and hereafter referred to as α-olefins, diolefins and other ethylenically unsaturated monomers. When speaking of polymerizing olefins, this includes both polymerizing a single type of olefinic monomer and copolymerizing two or more olefins.

The object of the invention is now to provide Cp compounds which, when used as a ligand in a metal complex, in which the metal is not in the highest valence state, yield catalysts with which copolymers can be manufactured with a more favorable combination of molecular weight and comonomer incorporation.

This object is achieved according to the invention in that at least one substituent has the form -RDR '', wherein R is a linking group between the Cp and the DR '' group, D a heteroatom selected from group 15 or 16 of the Periodic System of the Elements or an aryl group, R 'is a substituent and n is the number of R' groups attached to D 35, and that at least one further substituent is a branched alkyl group.

Surprisingly, when used as a ligand in the above-described metal complexes, 1003007-3-substituted Cp compounds are found to yield catalysts with a higher incorporation of comonomers in ethylene polymerization at the same molecular weight than the known compounds. Preferably, the compound contains at least two branched alkyl groups as a substituent because it involves a further improved ratio between molecular weight and comonomer incorporation.

Corresponding complexes in which the Cp compound is not substituted in the manner indicated appear to be unstable or, if otherwise stabilized, to provide less active catalysts than the complexes with substituted Cp compounds of the invention, in the especially in the polymerization of α-olefins.

Furthermore, the Cp compounds according to the invention have been found to be able to stabilize highly reactive intermediates such as organometallic hydrides, borohydrides, alkyls and -20 cations. In addition, they appear to be suitable as stable and volatile precursors for use in Metal Chemical Vapor Deposition.

From J. of Organomet. Chem. 486 (1995), 287-289, tetramethylcyclopentadiene is known with the fifth substituent being ethyldimethylamine. It is in no way to be deduced from this publication or to suspect the suitability of the Cp compounds according to the invention as ligands in metal complexes which, as catalyst component, bring about an improved comonomer incorporation in olefin copolymerizations. This is especially true for this effect with metal complexes, not in the highest valency state.

Incidentally, the Cp compounds according to the invention can also be used with good results as a ligand of metals which are in their highest valency state.

The branched alkyl groups can be the same as 1003007-4 or different. Preferably, the substituted Cp compound contains 2, 3, or 4 branched alkyl groups as a substituent. As the number of branched alkyl group substituents increases, the activity of a metal complex in which the thus substituted Cp compounds are present as a ligand appears to increase when used as a catalyst component for the polymerization of α-olefins. The branched alkyl groups do not contain a heteroatom.

Particularly suitable branched alkyl groups are, for example, 2-propyl, 2-butyl, 2-pentyl, 2-hexyl, 2-heptyl, 2-octyl, 2-nonyl, 2-decyl, 3-pentyl, 3-hexyl, 3-heptyl , 3-octyl, 3-nonyl, 3-decyl, 3-undecyl, 3-dodecyl, 2- (3-methylbutyl), 2- (3-methylpentyl), 2— (4-15 methylpentyl), 3- (2 -methylpentyl), 2- (3,3-dimethylbutyl), 2- (3-ethylpentyl), 2- (3-methylhexyl), 2- (4-methylhexyl), 2- (5-methylhexyl), 2- (3 , 3-dimethylpentyl), 2- (4,4-dimethylpentyl), 3- (4-methylhexyl), 3- (5-methylhexyl), 3- (2,4-20 dimethylpentyl), 3- (2-methylhexyl) , 3- (4,4-dimethylpentyl), 1- (2-ethylbutyl), 1- (2-methyl-3-chloropropyl), 2- (1-chloropropyl), 1- (3-methylbutyl), 4 - (2-methyl-butenyl), 1- (2-methylpropyl), 1- (2-ethylbutyl), 1- (3-chloro-2-methylpropyl), 2- (1-chloropropyl), 1- (2- Methylbutenyl) and 1- (2-methylpropyl). Cp compounds substituted two or triply alkyl-branched alkyl groups are preferred.

In addition to these branched alkyl groups, the presence of which is required in the context of the invention, other substituents may also be present, for example alkyl groups, both linear and branched and cyclic, alkenyl and aralkyl groups. It may also contain, in addition to carbon and hydrogen, one or more heteroatoms from groups 14-17 of the periodic table, for example 0, N, Si or F, in which a heteroatom is not directly bound to the Cp. Examples of suitable groups are 100 300 "- 5 * methyl, ethyl, (iso) propyl, secondary butyl, pentyl, hexyl and octyl, (tertiary) butyl and higher homologues, cyclohexyl, benzyl, phenyl, paratolyl.

The Cp compound can also be a heterocyclo-5 pentadiene compound. Here and hereafter, a heterocyclopentadiene compound is understood to mean a compound derived from cyclopentadiene, but in which at least one of the C atoms in its 5-ring is replaced by a heteroatom, wherein the heteroatom can be selected from group 14 , 15 or 16 of the Periodic Table of the Elements. If there is more than one heteroatom in the 5-ring, these heteroatoms can be the same or different. More preferably the heteroatom is selected from the group 15, even more preferably the heteroatom is phosphorus.

Substituted Cp compounds can be prepared by reacting a halide of the substituting compound in a mixture of the Cp-20 compound and an aqueous solution of a base in the presence of a phase transfer catalyst.

Cp compounds are understood to mean Cp itself and Cp already substituted at 1 to 3 positions, whereby two substituents can form a closed ring. With the method according to the invention, unsubstituted compounds can thus be converted into mono- or polysubstituted, but also one or several times substituted Cp-derived compounds can be further substituted, after which ring closure is also possible. Almost equivalent amounts of the halogenated substituents can be used. An equivalent amount is understood to mean an amount in moles corresponding to the desired substitution rate, for example 2 moles per mole of Cp compound if two-fold substitution with the respective substituent is intended.

1003007 - 6 -

Depending on the size and the associated steric hindrance of the compounds to be substituted, a maximum of three to five times substituted Cp compounds can be obtained. When reacting with tertiary halides, as a rule, only triply substituted Cp compounds can be obtained, with primary and secondary halides generally being substituted four and often even five-fold.

Particularly suitable branched alkyl have already been indicated above. The number of substituents thus applied is 2, 3 or 4 for the Cp compounds according to the invention, in addition to any other groups to be substituted in 15 free places, as defined above.

The substituents are preferably used in the process in the form of their halides, preferably in the form of their bromides. When using bromides, a smaller amount of phase transfer catalyst is found to suffice and a higher yield of the target compound is found to be obtained.

It is also possible with this method to obtain Cp compounds which are substituted with specific combinations of substituents without intermediate separation or purification. For example, a two-fold substitution can first be carried out using a certain halide and, in the same reaction mixture, a third substitution with another substituent by adding a second, different halide to the mixture after some time. This can be repeated so that it is also possible to manufacture Cp derivatives with three or more different substituents.

The substitution takes place in a mixture of the Cp compound and an aqueous solution of a 1003007 - 7 - F N Br ··· base. The concentration of the base in the solution is between 20 and 80%. Hydroxides of an alkali metal, for example K or Na, are very suitable. The base is present in an amount of 5-60 moles, preferably 6-30 moles, per mole of Cp compound. It has been found that a significant reduction in the reaction time can be achieved when the caustic solution is used in parts, for example by initially mixing only a part of the solution with the other components of the reaction mixture and after some time removing the aqueous phase. and replace with a fresh amount of the lye solution.

The substitution takes place at atmospheric or elevated pressure, for example up to 100 Mpa, the latter especially when volatile components are present. The temperature at which the reaction takes place can vary between wide limits, for example from -20 to 120 ° C, preferably between 10 and 50 ° C. Starting the reaction at room temperature is usually a suitable step, after which the temperature of the reaction mixture can rise due to the heat released in the reactions.

The substitution takes place in the presence of a phase transfer catalyst capable of transferring 25 OH ions from the aqueous phase to the Cp and halide-containing organic phase, which react there with an H atom which can be separated from the Cp compound. As the phase transfer catalyst, quaternary ammonium, phosphonium, arsonium, antimony, bismuthonium, and tertiary sulfonium salts can be used. More preferably, ammonium and phosphonium salts are used, for example tricaprylmethyl ammonium chloride, commercially available under the name Aliquat 336 35 (Fluka AG, Switzerland; General Mills Co., USA) and

Adogen 464 (Aldrich Chemical Co., USA). Compounds such as benzyltriethylammonium chloride (TEBA) or bromide 1003007-8 "(TEBA-Br), benzyltrimethylammonium chloride, bromide, or hydroxide (Triton B), tetra-n-butyl ammonium chloride, bromide, iodide, hydrogen sulfate or hydroxide and cetyl trimethyl ammonium bromide or -5 chloride, benzyl tributyl, tetra-n-pentyl, tetra-n-hexyl and trioctyl propyl ammonium chlorides and bromides are also suitable Examples of useful phosphonium salts, tributylhexadecyl phosphonium bromide, ethyl phosphonium phosphonium bromide, ethyl - iodide and tetrabutylphosphonium chloride Crown ethers and crypt teeth can also be used as phase transfer catalyst, for example 15-crown-5, 18-crown-6, dibenzo-18-crown-6, dicyclohexano-18-crown-6, 15, 4, 13 , 16,21-pentaoxa-1, 10-diazabicyclo [8.8.5] tricosane (Kryptofix 221), 4,7,13,18-tetraoxa-1, 10-diazabicyclo [8.5.5] eicosane (Kryptofix 211) and 4 , 7,13,16,21,24-hexaoxa-1,1-diazabicyclo [8.8.8] hexacos to (“[2.2.2]”) and its benzo derivative Kryptofix 20 222 B. Polyethers such as ethylene glycol ethers can also be used as a phase transfer catalyst. Quaternary ammonium salts, phosphonium salts, phosphoric acid triamides, crown ethers, polyethers and crypt teeth can also be used on a support, such as, for example, on a cross-linked polystyrene or other polymer. The phase transfer catalysts are used in an amount of 0.01-2, preferably 0.05-1, equivalent to the amount of Cp.

When performing the process, the components can be added to the reactor in different sequences.

After the reaction has ended, the aqueous phase and the Cp compound-containing organic phase are separated. The Cp compound is then recovered from the organic phase by fractional distillation.

1003007 - 9 -

Subsequently, a group of the form -RDR'n is substituted on the Cp compound thus substituted.

The R group is the link between the Cp 5 and the DR group. The length of the shortest connection between the Cp and D is critical in that it uses the Cp compound as a ligand in a metal complex to determine the accessibility of the metal through the DR group to thereby achieve the desired intramolecular coordination. Too short a length of the R group (or bridge) may prevent the DR '' group from coordinating properly due to ring tension.

R is therefore at least one atom long.

The R 'groups can each individually be a hydrocarbon radical of 1-20 carbon atoms (such as alkyl, aryl, aralkyl, etc.). Examples of such hydrocarbon radicals are methyl, ethyl, propyl, butyl, hexyl, decyl, phenyl, benzyl and p-tolyl. R 'may also be a substituent which, in addition to or instead of carbon and / or hydrogen, contains one or more heteroatoms from group 14-16 of the Periodic Table of the Elements. For example, a substituent can be an N, O and / or Si-containing group. R 'must not be a cyclopentadienyl or derivative group.

The R group can be a hydrocarbon group of 1-20 carbon atoms (such as alkylidene, arylidene, arylalkylidene, etc.). Examples of such groups are methylene, ethylene, propylene, butylene, phenylene, with or without a substituted side chain. Preferably, the R group has the following structure: (-ER22-) p 35 with p = 1-4 and E an atom from group 14 of the Periodic System. The R2 groups can each be H or a group as defined for R '.

1003007 - 10 - -.-

The main chain of the R group can therefore contain, in addition to carbon, silicon or germanium.

Examples of such R groups are: dialkylsilylene, dialkylgermylene, tetraalkyl-5 disilylene or tetraalkylsilaethylene (-SiR22CR22-). The alkyl groups in such a group preferably have 1-4 C atoms and are more preferably a methyl or ethyl group.

The DR'n group consists of a heteroatom D, 10 selected from group 15 or 16 of the Periodic Table of the Elements and one or more substituent (s) R 'attached to D. The number of R 'groups (n) is linked to the nature of the heteroatom D, and sheet in that n = 2 if D is from group 15 and 15 that n = 1 if D is from group 16. Preferably, the heteroatom D is selected from the group of nitrogen (N), oxygen (0), phosphorus (P) or sulfur (S); more preferably, the heteroatom is nitrogen (N). Also preferably the R 'group is an alkyl, more preferably an n-alkyl group with 1-20 C atoms. More preferably, the R 'group is an n-alkyl of 1-10 C atoms. Another possibility is that two R 'groups in the DR' 'group are linked together to form an annular structure (so that the DR' group can be a pyrrolidinyl group). The DR group can coordinate bonding with a metal.

For the manufacture of such Cp compounds, a group of the form -RDR '' can be substituted on the substituted Cp compound as described above, for example, according to the following synthetic route.

In a first step of this route, a substituted Cp compound is deprotonated by reaction with a base, sodium or potassium.

Organolithium compounds (R3Li) or organomagnesium compounds (R3MgX) in which R3 is 100 300 / - 11 - p .. can be used as base.

alkyl, aryl, or aralkyl group and X is a halide, for example n-butyl lithium or i-propyl magnesium chloride. Potassium hydride, sodium hydride, inorganic bases, for example NaOH and KOH, and alcoholates of Li, K and Na can also be used as base. Mixtures of the above compounds are also applicable.

This reaction can be performed in a polar dispersant such as an ether.

Examples of suitable ethers are tetrahydrofuran (THF) or dibutyl ether. Non-polar solvents, such as, for example, toluene, can also be used.

Then, during a second step of the synthesis route, the cyclopentadienyl-15 anion formed reacts with a compound of the formula (DR'n-R-Y) or (X-R-Sul), wherein D, R, R's and n are as defined above. Y is a halogen atom (X) or a sulfonyl group (Sul). Chlorine, bromine and iodine can be mentioned as halogen atom X. Preferably, the halogen atom X is a chlorine or bromine atom. The sulfonyl group has the form -SO2R6 »where R6 is a hydrocarbon radical of 1-20 carbon atoms, for example alkyl, aryl, aralkyl. Examples of such hydrocarbon radicals are butane, pentane, hexane, benzene, naphthalene. R6 may also contain, in addition to or instead of carbon and / or hydrogen, one or more heteroatoms from group 14-17 of the Periodic Table of Elements, such as N, 0, Si or F. Examples of sulfonyl groups are: phenylmethanesulfonyl, benzenesulfonyl, 1 - butanesulfonyl, 2,5-dichlorobenzenesulfonyl, 5-dimethylamino-1-naphthalenesulfonyl, pentafluorobenzenesulfonyl, p-toluenesulfonyl, trichloromethanesulfonyl, trifluoromethanesulfonyl, 2,4,6-triisopropylbenzenesulfonyl, 2,4,6-trimethylene , 4-methoxybenzenesulfonyl, 1 0 0 3 C 0? - 12 - Λ; 1-naphthalene sulfonyl, 2-naphthalene sulfonyl, ethanesulfonyl, 4-fluorobenzenesulfonyl and 1-hexadecan sulfonyl. Preferably the sulfonyl group is p-toluenesulfonyl or trifluoromethanesulfonyl.

When D is a nitrogen atom and Y is a sulfonyl group, the compound of the formula (DR'n-RY) is formed in situ by reaction of an amino alcohol compound (R'2NR-OH) with a base (as defined above), potassium or sodium, followed by a reaction with a sulfonyl halide (Sul-X).

The second reaction step can also be performed in a polar dispersant, as described for the first step.

The temperature at which the reactions are carried out is between -60 and 80 ° C. Reactions with X-R-Sul and with DR'n-R-Y, in which Y is Br or I are generally carried out at a temperature between -20 and 20 ° C.

Reactions with DR'n-R-Y, where Y is Cl, are usually carried out at a higher temperature (10 to 80 ° C). The upper limit for the temperature at which the reactions are carried out is partly determined by the boiling point of the compound DR 'n -R-Y and that of the solvent used.

After the reaction with a compound of the formula (X-R-Sul), a further reaction with LiDR'n or HDR'n is carried out to replace X with a DR functionality. For this purpose, optionally in the same dispersing agent as mentioned above, a reaction is carried out at 20 to 80 ° C.

During the synthesis process according to the invention partly geminal products can be formed. A geminal substitution is a substitution in which the number of substituents increases by 1, but the number of substituted carbon atoms does not increase. The amount of geminal products formed is low when the synthesis is carried out starting from a substituted Cp compound with 1 substituent and 1003007-13 - increases as the substituted Cp compound contains more substituents. In the presence of sterically large substituents on the substituted Cp compound, little or no geminal products are formed.

Examples of sterically large substituents are secondary or tertiary alkyl substituents.

The amount of the mineral product that is formed is also low when the second step of the reaction is carried out under the influence of a Lewis base, the conjugated acid of which has a dissociation constant, pKa less than or equal to -2.5. The pK values are based on D.D. Perrin: Dissociation Constants of Organic Bases in Aqueous Solution, International Union of Pure and Applied Chemistry, 15 Butterworths, London 1965. Values were determined in aqueous H 2 SO 4 solution. Ethers can be mentioned as an example of suitable weak Lewis bases.

When geminal products have been formed during the process according to the invention, these products can be easily separated from the non-geminal products by converting the mixture of geminally and non-geminally substituted products into a salt, by reaction with potassium, sodium or a base, after which the salt is washed with a dispersant, in which the salt of the non-geminal products does not dissolve, or only poorly. The compounds as mentioned above can be used as base. Suitable dispersing agents are non-polar dispersing agents, such as alkanes. Examples of suitable alkanes are heptane and hexane.

Metal complexes that are catalytically active when one of their ligands is a compound of the invention are complexes of metals from groups 4-10 of the Periodic Table and rare earths. Group 4 and 5 metal complexes are preferably used as a catalyst component for polymerizing olefins, complexes of 1003007-14 - metals of groups 6 and 7, in addition also for metathesis and ring-opening metathesis polymerisations and complexes of group metals 8-10 for olefin copolymerizations with polar comonomers, hydrogenations and carbonylations.

Particularly suitable for the polymerization of olefins are such metal complexes in which the metal is selected from the group consisting of Ti, Zr, Hf, V, and Cr.

Particularly when the metals, in particular the five individually mentioned above are not in their highest valence state, the Cp compounds appear to provide excellent stability of the formed complex without blocking the active sites, thereby increasing the catalytic activity. is then when using other Cp compounds. The invention therefore also relates to metal complexes in which at least one of the ligands is a substituted Cp compound according to the invention and in which the metal is preferably in a lower than the highest valency state and to the use of such metal complexes as a catalyst component for the copolymerizing α-olefins with other α-olefins and generally vinyl monomers and especially vinyl aromatic monomers.

Vinyl aromatic monomers which are well incorporated with these catalysts include styrene, chlorostyrene, n-butyl styrene, p-vinyl toluene and in particular styrene.

The synthesis of metal complexes with the above-described specific Cp compounds as a ligand can take place according to the methods known per se. The use of these Cp compounds does not require modifications of these known methods.

The polymerization of α-olefins, for example ethylene, propylene, butene, hexene, octene and mixtures 1 0 0 3 0 0; Thereof and combinations with dienes can be carried out in the presence of the metal complexes with the cyclopentadienyl compounds of the invention as a ligand. Particularly suitable for this are the complexes of transition metals, not in their highest valency state, in which just one of the cyclopentadienyl compounds according to the invention is present as a ligand and in which the metal is cationic during the polymerization. These polymerizations can be carried out in the known manner and the use of the metal complexes as a catalyst component does not necessitate any substantial adaptation of these processes. The known polymerizations are carried out in suspension, solution, emulsion, gas phase or as bulk polymerization. As the co-catalyst, an organometallic compound is usually used, the metal being selected from Group 1, 2, 12 or 13 of the Periodic Table of the Elements. For example, mention may be made of trialkylaluminum, alkylaluminum halides, alkylaluminoxanes (such as methylaluminoxanes), tris (pentafluorophenyl) borate, dimethylanilinium tetra (pentafluorophenyl) borate or mixtures thereof. The polymerizations are carried out at temperatures between -50 ° C and + 350 ° C, more in particular between 25 and 250 ° C. Pressures used are between generally between atmospheric pressure and 250 MPa for bulk polymerizations, more particularly between 50 and 250 Mpa, for the other polymerization processes between 0.5 and 25 MPa. As dispersants and solvents, for example, hydrocarbons can be used as pentane, heptane and mixtures thereof. Aromatic, optionally perfluorinated hydrocarbons are also eligible. The monomer to be used in the polymerization can also be used as a dispersion or solvent.

The invention will be elucidated by the following examples without, however, being limited thereto.

The following analysis methods are used in the characterization of the products obtained.

Gas chromatography (GC) was performed on a

Hewlett-Packard 5890 Series II with an HP Crosslinked Methyl Silicon Gum (25mx0.32mmxl, 05μπι) column. Combined Gas Chromatography / Mass Spectrometry (GC-MS) was performed with a Fisons MD800 equipped with a quadrupole mass detector, autoinjector Fisons AS800 and CPSil8 column (30mx0.25mmxl / m, low bleed).

NMR was performed on a Bruker ACP200 (1H = 200MHz; 13C = 50MHz) or Bruker ARX400 (1H = 400MHz; 13C = 100MHz). For the characterization of metal complexes, use was made of either a Kratos MS80 or a Finnigan Mat 4610 mass spectrometer.

Example I

Preparation of di (2-propyl) cyclopentadiene 20 In a 200 ml double-walled reactor equipped with baffles, cooler, overhead stirrer, thermometer and dropping funnel, 180 g of clear 50% NaOH (2.25 mol), 9.5 g Aliquat 336 (23 mmol) and 15 g (0.227 mol) of freshly cracked cyclopentadiene were combined. The reaction mixture became turbulent for several minutes

stirred at a speed of 1385 rpm. Then 56 g of 2-propyl bromide (0.46 mol) was added. It was cooled with water. A few minutes after adding the 2-propyl bromide, the temperature rose about 10-30 30C. It was then stirred at 50 ° C for 6 hours. With GC

it was shown that 92% di (2-propyl) cyclopentadiene was present in the mixture of di- and tri (2-propyl) cyclopentadiene at that time. The product was distilled at 10 mbar and 70 C. C. After distillation, 25.35 g of di (2-propylcyclopentadiene) were obtained.

The characterization was done by GC, GC-MS, 13C and XH-NMR.

1003007 - 17 -

Example II

Preparation of tri (2-propyl) cyclopentadiene

180 g of clear 50% NaOH (2.25 mol), 9.5 g of Aliquat 336 (23 mmol) and 15 g (0.227) were placed in a 200 ml double-walled reactor equipped with baffles, cooler, overhead stirrer, thermometer and dropping funnel. mol) freshly cracked cyclopentadiene combined. The reaction mixture was stirred turbulently for a few minutes at a speed of 1385 rpm. Then 84 g of 2-propyl bromide (0.68 mol) was added. It was cooled with water. A few minutes after adding the 2-propyl bromide, the temperature rose about 10 ° C. GC showed that 15-propyl cyclopentadiene had been formed about 30 minutes after the addition of all 2-propyl bromide (monosubstituted). Then the reaction mixture was heated to 50 C. C. After 2 hours, stirring was stopped and phase separation was awaited.

The water layer was drained and 180 g (2.25 mol) of fresh 50% NaOH were added. Then stirring was continued at 50 ° C for an additional hour. GC was used to show that between 90 and 95% tri (2-propyl) cyclopentadiene was present in the mixture of di- tri- and tetracyclopentadiene at that time. The product was distilled at 1.3 mbar and 77-78 "C. After distillation, 31.9 g of tri (2-propyl) cyclopentadiene were obtained.

The characterization was done by GC, GC-MS, 13C and -NMR.

Example III

Preparation of tetra (2-propyl-cyclopentadiene)

Analogous to Example II, but now 114 g of 2-propyl bromide (0.93 mol) was added and the water layer was replaced a second time after 7 hours. Also 5 g (12 mmol) Aliquat 336 35 was added at that time. It was then heated at 55 ° C for 16 hours. GC showed that at that time in the mixture of tri- and tetracyclopentadiene 85% tetra (2- 1003007 - 18 - Γ.

propyl) cyclopentadiene was present. The product was distilled at 1.0 mbar and 88-90 ° C. After distillation, 34.9 g of tetra (2-propyl) cyclopentadiene were obtained.

The characterization was done by GC, GC-5 MS, 13C- and -NMR.

Example IV

Preparation of di (cvclohexvl) cyclopentadiene

A 10 1 L double-walled reactor equipped with baffles, cooler, overhead stirrer, thermometer and dropping funnel was charged with 600 g of clear 50% NaOH (7.5 mol) and cooled to 8 ° C. Then 20 g of Aliguat 336 (49 mmol) and 33 g (0.5 mol) of freshly cracked cyclopentadiene were added.

The reaction mixture was stirred turbulently for several minutes. Then 172 g of cyclohexyl bromide (1.05 mol) was added. It was cooled with water. After stirring at room temperature for 2 hours, the reaction mixture was heated to 70 ° C and stirred for another 6 hours. GC showed that at that time 79% di (cyclohexyl) cyclopentadiene was present. The product was distilled at 0.04 mbar and 110-120 ° C. After distillation, 73.6 g of di (cyclohexyl) cyclopentadiene were obtained. The characterization was done by GC, GC-MS, 13C and 1 H NMR.

Example V

Preparation of di- and tri (3-pentyl) cyclopentadiene

A 30 1 L double-walled reactor equipped with baffles, cooler, overhead stirrer, thermometer and dropping funnel was charged with 430 g (5.4 mol) of clear 50% NaOH. Then 23 g of Aliguat 336 (57 mmol) and 27 g (0.41 mol) of freshly cracked cyclopentadiene were added. The reaction mixture was stirred turbulently for a few minutes, then 150 g of 3-pentyl bromide (1.0 mol) was added over an hour. It was cooled with water. After stirring for 1 hour at 1003007-19 room temperature, the reaction mixture was heated to 70 ° C, followed by stirring for another 3 hours. Stirring was stopped and phase separation was awaited. The water layer was drawn off and 540 g (6.70 mol) of fresh 50% NaOH were added. Stirring was then continued at 70 ° C for 4 hours. GC showed that at that time the mixture consisted of di- and tri (3-pentyl) cyclopentadiene (about 3: 2). The products were distilled at 0.2-10 mbar, 51 ° C and 0.2 mbar, 77-80 ° C, respectively. After distillation, 32 g of di- and 18 g of tri (3-pentyl) cyclopentadiene were obtained.

The characterization was done by GC, GC-MS, 13C and -NMR.

15

Example VI

Preparation of tri (cvclohexyl) cyclopentadiene

A 1 L double-walled reactor equipped with baffles, cooler, overhead stirrer, thermometer and dropping funnel was charged with 600 g of clear 50% NaOH (7.5 mol) and cooled to 8 ° C. Then 20 g of Aliquat 336 (49 mmol) and 33 g (0.5 mol) of freshly cracked cyclopentadiene were added. The reaction mixture was stirred turbulently for several minutes. Then 256 g cyclohexyl bromide (1.57 mol) was added. It was cooled with water. After stirring at room temperature for 1 hour, the reaction mixture was heated to 70 ° C and stirred for another 2 hours. After 2 hours, stirring was stopped and phase separation was awaited. The water layer was drained and 600 g (7.5 mol) of fresh 50% NaOH were added. Stirring was then continued at 70 ° C for 4 hours. The GC was shown to contain 10% di- and 90% tri- (cyclohexyl) cyclopentadiene at that time. The product was distilled at 0.04 mbar and 130 ° C. After distillation, 87.4 g of tri (cyclohexyl) cyclopentadiene were obtained. The characterization was done using 1003007-20 of GC, GC-MS, 13C and -NMR.

Example VII

Preparation of di (2-butylcyclopentadiene) A double-walled reactor carbon black 1 L, equipped with baffles, cooler, overhead stirrer, thermometer and dropping funnel, was filled with 600 g of clear 50% NaOH (7.5 mol) and cooled to 10 ° C Then 30 g of Aliquat 336 (74 mmol) and 48.2 g (0.73 mol) of freshly cracked cyclopentadiene were added The reaction mixture was stirred turbulently for a few minutes Then 200 g of 2-butyl bromide (1.46 mol) was added over half an hour. was cooled with water After stirring at room temperature for 2 hours, the reaction mixture was heated to 60 ° C, followed by stirring for another 4 hours Net GC was shown at that time to contain more than 90% di (2-butyl) cyclopentadiene in the mixture The product was distilled at 20 mbar and 80-90 ° C. After distillation, 90.8 g of di (2-butyl) cyclopentadiene were obtained.

The characterization was done by GC, GC-MS, 13C and -NMR.

Example VIII

Preparation of tri (2-butyl) cyclopentadiene

A 1 L double-walled reactor equipped with baffles, cooler, overhead stirrer, thermometer and dropping funnel was charged with 400 g (5.0 mol) of clear 50% NaOH (5 mol). Then 9.6 g of Aliquat 336 (24 mmol) and 15.2 g (0.23 mol) of freshly cracked cyclopentadiene were added. The reaction mixture was stirred turbulently for a few minutes, then 99.8 g of 2-butyl bromide (0.73 mol) was added over half an hour. It was cooled with water. After stirring for half an hour at room temperature, the reaction mixture was heated to 70 ° C and stirred for another three hours. Stirring was stopped and phase separation was awaited. The watec layer was drained and 400 g (5.0 mol) of fresh 50% NaOH was added. Stirring was then continued for 2 hours at 70 ° C. GC showed that at that time more than 90% tri (2-butyl) cyclopentadiene was present in the mixture of di-5 tri- and tetra (2-butyl) cyclopentadiene. The product was distilled at 1 mbar and 91 C. C. After distillation, 40.9 g of tri (2-butyl) cyclopentadiene were obtained.

Characterization was done by GC, GC-10 MS, 13C and 1 H NMR.

Example IX

Preparation of Di- and Tri (2-Pentyl) CVloDentadiene

A 15 1 L double-walled reactor equipped with baffles, cooler, overhead stirrer, thermometer and dropping funnel was charged with 900 g (11.25 mol) of clear 50% NaOH. Then 31 g of Aliquat 336 (77 mmol) and 26.8 g (0.41 mol) of freshly cracked cyclopentadiene were added. The reaction mixture was stirred turbulently for several minutes. Then 155 g of 2-pentyl bromide (1.03 mol) was added over an hour. It was cooled with water. After stirring at room temperature for 3 hours, the reaction mixture was heated to 70 ° C and stirred for another 2 hours. Stirring was stopped and phase separation was awaited. The water layer was drained and 900 g (11.25 mol) of fresh 50% NaOH were added. Stirring was then continued for 2 hours at 70 ° C. GC showed that at that time the mixture consisted of di- and tri (2-30 pentyl) cyclopentadiene (about 1: 1). The products were distilled at 2 mbar, 79-81 C C and 0.5 mbar, 102 C. C. After distillation, 28 g of di- and 40 g of tri (2-pentyl) cyclopentadiene were obtained.

The characterization was done by GC, GC-MS, 13C and -NMR.

1003007 - 22 -,. ; ~

Example X.

Preparation of di (2-propyl) cyclohexyl cyclopentadiene

150 g of clear 50% NaOH (1.9 mol), 7 g of Aliquat 336 (17.3 mmol) and 8.5 g (0.13 mol) were placed in a 200 mL double-walled reactor equipped with baffles, cooler, overhead stirrer, thermometer and dropping funnel. freshly cracked cyclopentadiene combined. The reaction mixture was stirred turbulently for a few minutes at a speed of 1385 rpm. Then 31.5 g of 2-propyl bromide (0.26 mol) was added. It was cooled with water. The total dosing time was 1 hour. After adding the bromide, the reaction mixture was heated to 50 C. C. After 2 hours, stirring was stopped and phase separation was awaited. The water layer was drained and 150 g (1.9 mol) of fresh 50% NaOH were added. Then 20.9 g (0.13 mol) of cyclohexyl bromide was added, followed by stirring for another 3 hours at 70 ° C. GC showed that 80% di (2-propyl) cyclohexyl-20 cyclopentadiene was present in the mixture at that time. The product was distilled at 0.3 mbar and 80 ° C. After distillation, 17.8 g of di (2-propyl) cyclohexyl cyclopentadiene were obtained. The characterization was done by GC, GC-MS, 13C and XH-NMR.

25

Experiment XI

Preparation of 2- (N, N-dimethylaminoethyl ethosyl leaf) in situ

In a three-necked round bottom flask equipped with a magnetic stirrer and dropping funnel, a solution of n-butyl lithium in hexane (1 equivalent) was added to a solution of 2-dimethylaminoethanol (1 equivalent) in dry THF at -10 ° C under dry nitrogen (dosing time: 60 minutes). After adding all butyl lithium, the mixture was brought to room temperature and stirred for 2 hours. The mixture was then cooled (-10 ° C) and paratoluenesulfonyl chloride (1 1003007 - 23 equivalent) was added. It was then stirred at this temperature for 15 minutes before the solution was added to a cyclopentadienyl anion.

Similar tosylates can be prepared in an analogous manner. In some of the following examples, a tosylate is always coupled to alkylated Cp compounds. In addition to the desired substitution reaction, this coupling also involves geminal coupling. In almost all cases, the geminal isomers could be separated from the non-geminal isomers by converting the non-geminal isomers into their sparingly soluble potassium salt, followed by washing this salt with a solvent in which this salt does not or poorly dissolve.

15

Example XII

a. Preparation of (dimethvlaminoethyl) di-cyclohexyl-cyclopentadiene

In a 250 ml three-necked round bottom flask, equipped with magnetic stirrer and dropping funnel, was added under nitrogen atmosphere to a cooled (0 ° C) solution of dicyclohexyl cyclopentadiene (Example IV) (6.90 g; 30.0 mmol) in dry tetrahydrofuran (125 ml). a solution of n-butyl lithium in hexane (18.7 ml; 1.6 25 mol / L; 30 mmol) was added dropwise. After stirring at room temperature for 24 hours, 30.0 mmol of in situ prepared 2- (dimethylaminoethyl) tosylate was added. After stirring for 18 hours, the conversion was found to be 88¾ and water (100ml) was carefully added dropwise to the reaction mixture, after which the tetrahydrofuran was distilled off. The crude product was extracted with ether and the combined organic phase was dried (sodium sulfate) and evaporated. The residue was purified on a column with silica gel, resulting in 7.4 g of (dimethylaminoethyl) -dicyclohexylcyclopentadiene.

1003007 - 24 - b. Synthesis of 1- (dimethylaminoethyl) -2,4-dicyclohexylclopentadienyl titanium (III) dichloride and Γ1- (dimethylaminoethyl) -2,4-dicvclohexvlcvclo-pentadienyl-dimethylethyl (III) 5 J £ & III (III), III, III Cl, 1 and fCcH? (C- £ 6HX ', (CH,), NMe, Ti (III) MeT1

1.37 g (4.54 mmol) (dimethylaminoethyl) dicyclohexylcyclopentadiene were dissolved in 30 ml diethyl ether in a Schlenk vessel and the solution was cooled to -60 ° C. 2.84 mL of n-butyl lithium (1.6M in hexane; 4.54 mmol) was then added dropwise. The reaction mixture was slowly brought to room temperature and stirred for an additional 2 hours. After evaporation of the solvent, a yellow powder remained, to which 30 ml of petroleum ether were added.

In a second Schlenk vessel, 40 mL of tetrahydrofuran was added to 1.68 g of Ti (III) C13.3THF (4.53 mmol). Both Schlenk vessels were cooled to -60 ° C, after which the organolithium compound was added to the Ti (III) Cl3 suspension. The reaction mixture was then stirred at room temperature for 18 hours after which the solvent was evaporated. 50 mL of petroleum ether was added to the residue, which was then evaporated again. A green solid containing 1- (dimethylaminoethyl) -2,4-dicyclohexylcyclopentadienyl-titanium (III) dichloride remained.

0.31 g (0.671 mmol) of the 1-30 (dimethylaminoethyl) -2,4-dicyclohexylcyclopentadienyl-titanium (III) dichloride dichloride described above was dissolved in 30 ml diethyl ether in a Schlenk vessel. The solution was cooled to -60 ° C and 0.73 mL (1.84M in diethyl ether? 1.34mmol) of methyl lithium was added dropwise. The solution was slowly brought to room temperature and stirred for an additional 1 hour. The solvent was then evaporated and the residue extracted with 40 mL of petroleum ether. The 1003007-25 filtrate was evaporated and dried under vacuum for 18 hours. 0.14 g of a black / brown oil containing [1- (dimethylaminoethyl) -2,4-dicyclohexylcyclopentadienyl] dimethyl titanium (III) remained.

5

Example XIII

a. Preparation of (dimethlaminoethyl] di (2-pentyl> cyclopentadiene

In a 250 ml three-necked round bottom flask, equipped with magnetic stirrer and dropping funnel, was added to a cooled (0 ° C) solution of di-2-pentylcyclopentadiene (7.82 g; 38.0 mmol) in dry tetrahydrofuran (125 ml) under nitrogen atmosphere. a solution of n-butyl lithium in hexane (24.0 ml; 1.6 mol / L; 38 mmol) was added dropwise. After stirring at room temperature for 24 hours, 2- (dimethylaminoethyl) tosylate (38.0 mmol) prepared in situ was added. After stirring for 18 hours, the conversion was found to be 92% and water (100 ml) was carefully added dropwise to the reaction mixture, after which the tetrahydrofuran was distilled off. The crude product was extracted with ether and the combined organic phase was dried (sodium sulfate) and evaporated. The residue was purified on a column with silica gel, resulting in 8.2 g of (dimethylaminoethyl) di (2-pentyl) cyclopentadiene.

b. Synthesis of 1- (dimethvlaminoethyl) -2,4-di (2-pentyl) cyclopentadienyl titanium (Il-dichloride and Γ1-30 (dimethvlaminoethyl) -2,4-di (2-pentyl) cyclopentadienyl dimethyl-titanium (III) 1H, (2-C «H ,,), (CH,) »NMe, Ti (IinCl, 1 and fC? H7f2-C« H ,,), (CH, KNMe, Ti (III me, 1

In a Schlenk vessel, 1.60 g (5.77 mmol) of 35 (dimethylaminoethyl) di (2-pentyl) cyclopentadiene was dissolved in 40 mL of diethyl ether and the solution was cooled to -60 ° C. Then 3.6 mL of n-1003007-26 butyl lithium (1.6M in hexane; 5.77 mmol) was added dropwise. The reaction mixture was slowly brought to room temperature and stirred for an additional 2 hours.

In a second Schlenk vessel, 40 mL of tetrahydrofuran was added to 2.14 g of 5 Ti (III) C13.3THF (5.77 mmol). Both Schlenk vessels were cooled to -60 ° C, after which the organolithium compound was added to the Ti (III) Cl3 suspension. The reaction mixture was then stirred at room temperature for 18 hours after which the solvent was evaporated. 50 mL of petroleum ether was added to the residue, which was then evaporated again. 1.60 g of a green solid containing 1- (dimethylaminoethyl) -2,4-di (2-pentyl) 15 cyclopentadienyl-titanium (III) dichloride remained.

0.33 g (0.835 mmol) of 1- (dimethylaminoethyl) di (2-pentyl) cyclopentadienyl-titanium (III) dichloride were dissolved in 40 ml diethyl ether in a Schlenk vessel.

The solution was cooled to -60 ° C and 0.90 mL of methyl lithium (1.84m in diethyl ether; 1.66mmol) was added dropwise. The reaction mixture was slowly brought to room temperature and stirred for an additional 1 hour. The solvent was then evaporated. The residue was extracted with 50 mL of petroleum ether, then the filtrate was evaporated. 0.24 g of a black / brown oil containing [1- (dimethylaminoethyl) -2,4-di (2-pentyl) cyclopentadienyl] dimethyl titanium (III) remained. 1 2 3 4 5 6 100 3007

Example XIV

2 a. Preparation of (dimethvlaminoethyl) tri (2-3 propyl) cyclopentadiene 4

In a dry 500 mL three neck 5 magnetic stirrer under a dry nitrogen atmosphere 6

a solution of 62.5 mL of n-butyl lithium (1.6 M in n-hexane; 100 mmol) added to a solution of 19.2 g (100 mmol) of triisopropyl cyclopentadiene in 250 mL of THF

- 27 - i.

at -60 ° C. After warming up to room temperature (in about 1 hour), stirring was continued for 2 hours. After cooling to -60 ° C, a solution of in-situ prepared (dimethylaminoethyl) tosylate (105 mmol) was added over 5 minutes. The reaction mixture was warmed to room temperature and stirred overnight. After addition of water, the product was extracted with petroleum ether (40-60 ° C). The combined organic layer was dried (Na2 SO4) and evaporated under reduced pressure. The conversion was higher than 95%.

The yield of product after distillation (starting from triisopropyl cyclopentadiene) was about 55%.

b. Synthesis of Γ1- (dimethvlaminoethvl) -2.3.5-tri (2-15 propyl) cvclopentadienvltitanium (Illidichloride and Γ1- (dimethvlaminoethvl) -2.3.5-tr if 2-propyl) cvclopentadienvlldimethvltitaniumIIH fCcHf iPn, TirCH , 1 and re.Hf iPr), (CH., KNMe., TiaiI> Me.1 20) In a 500 mL 3-neck flask, 8.5 g (28.18 mmol) of the potassium were 1 (dimethylaminoethyl) - 2,3,5-tri (2-propyl) cyclopentadienyl 200 mL of petroleum ether.

In a second (1 L) 3-necked flask, 300 ml of tetrahydrofuran was added to 10.5 g (28.3 25 mmol) of Ti (III) C13.3THF. Both flasks were cooled to -60 ° C after which the organopotassium compound was added to the Ti (III) Cl3 suspension. The reaction mixture containing 1- (dimethylaminoethyl) -2,3,5-tri (2-30 propyl) cyclopentadienyl titanium (III) dichloride was slowly brought to room temperature and stirred for an additional 18 hours. Then it was cooled to -60 ° C after which 30.6 mL of methyl lithium (1.827 M in diethyl ether; 55.9 mmol) was added. After stirring at room temperature for 2 hours, the solvent was removed and the residue dried under vacuum for 18 hours. Then 700 ml of petroleum ether was added to the product and 1003007-28 was filtered. The filtrate was evaporated and dried under vacuum for 2 days. 9.2 g of a brown / black oil containing [1- (dimethylaminoethyl) -2,3,5-tri (2-propyl) cyclopentadienyl] dimethyl titanium 5 (III) remained.

Example XV

a. Preparation of di (n-butylaminoethyl) di (2-pentyl) cyclopentadiene 10 The reaction was carried out identically as for (dimethylaminoethyl) -di- (2-pentyl) cyclopentadiene, the tosylate of N, N- di-n-butylaminoethanol was prepared in situ. The conversion was 88%. The di- (n-butylaminoethyl) -di- (2-15 pentyl) -cyclopentadiene was obtained after preparative column purification on silica gel with petroleum ether (40-60 ° C) and THF successively, followed by distillation under reduced pressure with a yield of 51 %.

20 b. Preparation of 1- (di-n-butyl-aminoethyl) -2,4-di (2-pentyl-cyclopentadienyl titanium dichloride rC ^ H7f2-C ^ Hi, VCH-KNtn-C ^ ^ TifimCl.

In a Schlenk vessel, 0.919 g (2.54 mmol) of 25 (di-n-butylaminoethyl) di (2-pentyl) cyclopentadiene was dissolved in 40 mL of diethyl ether and the solution was cooled to -60 ° C. Then 1.6 mL of n-butyl lithium (1.6M in hexane; 2.56 mmol) was added dropwise. The reaction mixture was slowly brought to room temperature and stirred for an additional 2 hours. It was then added to 960 mg (2.59 mmol) at -60 ° C

Ti (III) C13.3THF in 20 mL of tetrahydrofuran.

The reaction mixture was then stirred at room temperature for 18 hours after which the solvent was evaporated. The residue was washed with 10 mL. 0.95 g of a green solid containing 1- (di-n-butylaminoethyl) -2,4-di (2- 100 300 - 29 - pentyl) cyclopentadienyl-titanium (III) dichloride remained.

Example XVI

A. Preparation of (dimethylaminoethyl) di (2-propyl) cyclopentadiene

The reaction was carried out in an identical manner as for (dimethylaminoethyl) tri (2-propylcyclopentadiene). The conversion was 97%. The dimethylaminoethyl diisopropylcyclopentadiene was obtained by distillation with a yield of 54%.

b. Synthesis of fl-β-dimethylaminoethyl) -2,4-di (2-propyl) cyclopentadienyl titanium (III) dichloride and -151-15 (dimethlaminoethyl) -2,4-di (2-propyl) cvelopentadienyl dimethyl titanium (III)? H? (IPr)? (CH?), NMe, Ti (III) Cl, 1 and f C, H, (iPr), (CH,), NMe, Ti (III) Me, 1

In a 250 mL 3-necked flask, 8.9 g (40.3 20 mmol) of (dimethylaminoethyl) -di- (2-propyl) cyclopentadiene in 100 mL of tetrahydrofuran were added 25.2 mL of n-butyl lithium (1.6 M, 40.3 mmol).

In a second (500 mL) 3-necked flask, 100 mL of tetrahydrofuran was added to 14.93 g (40.3 mmol) of Ti (III) C13.3THF. Both flasks were cooled to -60 ° C

after which the organolithium compound was added to the Ti (III) Cl3 suspension. The reaction mixture containing 1- (dimethylaminoethyl) -2,4-di- (2-propyl) cyclopentadienyl titanium (III) dichloride was slowly brought to room temperature and stirred for an additional 18 hours. Then it was cooled to -60 ° C after which 50.4 mL of methyl lithium (1.6 M in diethyl ether; 80.6 mmol) was added. After stirring at room temperature for 2 hours, the solvent was removed and the residue was dried under vacuum for 18 hours. 350 ml of petroleum ether were then added to the product and filtered. The filtrate was evaporated and dried under vacuum for a day 1003007-30. 11.6 g of a brown / black oil containing [1- (dimethylaminoethyl) -2,4-di (2-propyl) cyclopentadienyl] dimethyl titanium (III) remained.

Example XVII

a. Preparation of (dimethvlaminoethyl) di (2-butyl) cyclopentadiene

In a 250 ml three-necked round bottom flask equipped with magnetic stirrer and dropping funnel, 10 was added under nitrogen atmosphere to a cooled (0 ° C) solution of di- (2-butyl) cyclopentadiene (8.90 g; 50.0 mmol) in dry tetrahydrofuran ( 150 ml) a solution of n-butyl lithium in hexane (31.2 ml; 1.6 mol / L; 50 mmol) was added dropwise. After stirring at room temperature for 24 hours, the 2- (dimethylaminoethyl) tosylate (50.0 mmol) was added. After stirring for 18 hours, the conversion was found to be 96% and water (100 ml) was carefully added dropwise to the reaction mixture, after which the tetrahydrofuran was distilled off. The crude product was extracted with ether and the combined organic phase was dried (sodium sulfate) and evaporated. The residue was purified on a column with silica gel, resulting in 8.5 g of (dimethylaminoethyl) di (2-butylcyclopentadiene).

25 b. Synthesis of 1-fdimethvlaminoethyl) -2.4-di (2-butyl) cyclopentadienyl titanium (III) dichloride and fl- (dimethvlaminoethyl) -2.4-di (2-butyl) cvclopentadienyl) dimethyltitane fill) 30 fCTH7f2-CHM), fCH?) TN , TifIIHC1.1 and fC.H.f2-C1H?)? FCH,)., NMe, Tif III) Me, 1

2.36 g (9.48 mmol) (dimethylaminoethyl) di (2-butyl) cyclopentadiene was dissolved in 50 ml diethyl ether in a Schlenk vessel and the solution was cooled to -60 ° C. Then 5.9 mL of n-butyl lithium (1.6M in hexane; 9.44 mmol) was added dropwise. The reaction mixture was slowly brought to room temperature, after which 1003007 - 31 -. Stirred for another 2 hours. In a second Schlenk vessel, 50 mL of tetrahydrofuran was added to 3.51 g of Ti (III) C13.3THF (9.44 mmol). Both Schlenk vessels were cooled to -60 ° C, after which the organolithium 5 compound was added to the Ti (III) Cl3 suspension. The reaction mixture was then stirred at room temperature for 18 hours after which the solvent was evaporated. 50 mL of petroleum ether was added to the residue, which was then evaporated again. 2.15 g of a green solid containing 1- (dimethylaminoethyl) -2,4-di (2-butyl) cyclopentadienyl-titanium (III) dichloride remained.

In a Schlenk vessel, 0.45 g (1.22 mmol) of 1- (dimethylaminoethyl) di (2-butyl) cyclopentadienyl titanium 15 (III) dichloride was dissolved in 40 mL of diethyl ether. The solution was cooled to -60 ° C, after which 1.33 mL of methyl lithium (1.84M in diethyl ether; 2.44 mmol) was added dropwise. The reaction mixture was slowly brought to room temperature and stirred for an additional 1 hour. The solvent was then evaporated. The residue was extracted with 50 mL of petroleum ether and the filtrate was evaporated. 0.36 g of a black / brown oil containing [1- (dimethylaminoethyl) -2,4-di (2-butyl) cyclopenta-25 dienyl] dimethyl titanium (III) remained.

Example XVIII

Preparation of (dimethylaminoethyltri (2-butyl) cvelopentadiene) The reaction was carried out in an identical manner as for (dimethylaminoethyl) tri (2-propyl) cyclopentadiene. The conversion was 92%. The product was obtained by distillation with a yield of 64%. .

35 b. Synthesis of fl- (dimethylaminoethyl) -2.3.5-tri (2-butyl) cyclopentadienyl titanium (III) dichloride and Γ1- (dimethylaminoethyl) -2.3.5-tri (2-butyl) 10Sor7 - 32 - cvclopentadienyl1 dimethyl titanium (III) rC, H (2-C, H? l, fCHTKNMeTTifimci, l and rC.H (2- £, Hal, 1CH, J, NWe, Ti (III) Me71

In a 500 mL 3-necked flask, 200 mL of petroleum ether was added to 6.28 g of 5 (20.6 mmol) of the potassium 1- (dimethylaminoethyl) -2,3,5-tr (2-butyl) cyclopentadienyl. In a second (1 L) 3-necked flask, 300 ml of tetrahydrofuran was added to 7.65 g (20.6 mmol) of Ti (III) C13.3THF. Both flasks were cooled to -60 ° C after which the organopotassium compound was added to the Ti (III) Cl3 suspension. The reaction mixture containing 1- (dimethylaminoethyl) -2,3,5-tri (2-butyl) cyclopentadienyl titanium (III) dichloride was slowly brought to room temperature and stirred for an additional 18 hours. Then it was cooled to -60 ° C after which 22.3 mL of methyl lithium (1.827 M in diethyl ether; 40.7 mmol) was added. After stirring at room temperature for 2 hours, the solvent was removed and the residue was dried under vacuum for 18 hours. 700 ml of petroleum ether were then added to the product 20 and filtered. The filtrate was evaporated and dried under vacuum for 2 days. 7.93 g of a brown / black oil containing [1- (dimethyl aminoethyl) -2,3,5-tri (2-butyl) cyclopentadienyl] 25 dimethyl titanium (III) remained.

Example XIX

Preparation of (dimethylaminoethylIdi (3-pentyl) cyclopentadiene) The reaction was carried out in an identical manner as for (dimethylaminoethyl) di (2-propylcyclopentadiene). The conversion was 99%.

The (dimethylaminoethyl) di (3-pentyl) cyclopentadiene was obtained after preparative column purification on silica gel with petroleum ether (40-60 ° C) and THF successively with a yield of 85%.

1003007 - 33 -? Ir: ΐ5

Example XX

Preparation of (di-n-butvlaminoethyl) -di- (3-pentyl) cyclopentadiene

The reaction was carried out identically as for (di-n-butylaminoethyl) di (2-propyl) cyclopentadiene. The conversion was 95%. The product was obtained after preparative column purification on silica gel with successively petroleum ether (40-60 ° C) and THF with a yield of 75%.

10

Example XXI

Preparation of (2-dimethlaminoethyl) tri-(3-pentyl) cyclopentadiene 15 The reaction was carried out in an identical manner as for (dimethylaminoethyl) tri (2-propyl) cyclopentadiene. The conversion was 94%. The (2-dimethylaminoethyl) -tr- (3-pentyl) cyclopentadiene was obtained after preparative column purification on silica gel with 20 successively petroleum ether (40-60 ° C) and THF with a yield of 61%.

Example XXII

a. Preparation of cclohexyl (dimethvlaminoethyl) -di- (2-25 propyl Dclopentadiene)

In a pouring vessel, a solution of n-butyl lithium in hexane (25.0 mL; 1.6, 30 mol / L) was added to a solution of cyclohexyldiisopropylcyclopentadiene (9.28 g; 40.0 mmol) in dry THF (150 mL) at room temperature. ; 40.0 mmol) was added dropwise. Then a solution of n-butyl lithium in hexane (25.0 mL; 1.6 mol / L; 40.0 mmol) in a cold (-78 ° C) solution of dimethylaminoethanol (3.56 g; 40.0 mmol) in THF (100 mL). After stirring at room temperature for an hour and a half, the mixture was again cooled to -78 ° C and the solid tosyl chloride (8.10 g; 40.0 mmol) was added slowly. The mixture 1003007 - 34 - was brought to 0 ° C with stirring for 5 minutes, again cooled to -78 ° C, after which the mixture from the first pour was added all at once. After stirring at room temperature for 16 hours, the conversion was 100%. After 5 column chromatography, 11.1 g of cyclohexyl (dimethylaminoethyl) -di- (2-propyl) cyclopentadiene were obtained.

b. Synthesis of 1-fdimethvlaminoethyl-4-cvclohexyl-10 2,5-di (2-propyl) cyclopentadienyl titan (III) dichloride and Γ1-f dimethvlaminoethyl) -4-cyclohexyl-2.5-di (2-rpylvylopentadienyl) III (dimethyl). (c-HexH2-C? H7) 7 (CH, UNMe, TiiIII1Cl · 1 and rCMifc-Hex1 (2-CH-.) i (CH.) oME.Ti (IIIIMe. 1 15) To lithium (dimethylaminoethyl) cyclohexyldi (2 -propyl) cyclopradiene (2.18 g, 7.20 mmol), dissolved in 20 mL of tetrahydrofuran, at -70 ° C a cooled slurry (-70 ° C) of Ti (III) Cl3.3THF (2.67 g, 7, 20 mmol) in 20 mL of THF The resulting dark green solution was stirred at room temperature for 72 hours After evaporation, 30 mL of petroleum ether (40-60) was added After complete evaporation, a green powder (2.37 g) was obtained, containing 1- (dimethylaminoethyl) -4-cyclohexyl-2,5-di (2-propylcyclopentadienyl 25 titanium (III) dichloride [lithium chloride].

Slurry of 0.63 g (1.36 mmol) of the above obtained 1- (dimethylaminoethyl) -4-cyclohexyl-2,5-di (2-propyl) cyclopentadienyltitanium (III) -30 dichloride, cooled to -70 ° C slurry [lithium chloride] in 30 mL diethyl ether was added 1.70 mL methyl lithium (1.6 M in diethyl ether, 2.72 mmol). The green-brown slurry immediately turned dark. The mixture was then stirred at room temperature for 1 hour, evaporated completely and dissolved in 40 mL of petroleum ether. After filtration and complete evaporation of the solvent, a black powder (0.47 g, 1.22 mmol) was obtained containing 1 - 1003007 - 35 - 'M' (dimethylaminoethyl) -4-cyclohexyl-2,5-di (2 -propyl) cyclopentadienylTi (III) dimethyl.

Example XXIII

5 Preparation of (di-n-butyl-aminoethyl) di (2-propyl-chlorofluadadiene)

The reaction was carried out in an identical manner as for (dimethylaminoethyl) di (2-propyl) cyclopentadiene to prepare the tosylate of N, N-di-n-10 butylaminoethanol in situ. The conversion was 94%. The non-geminal di-n-butylaminoethyldi (2-propyl) cyclopentadiene was obtained by distillation with a yield of 53%.

Example XXIV

Preparation of (dimethylaminoethyl) -tri- (2-pentyl-cyclopentadiene)

The reaction was carried out in an identical manner as for (dimethylaminoethyl) tri (2-20 propyl) cyclopentadiene. The conversion was 90%. The non-geminal dimethylaminoethyl diisopropyl cyclopentadiene was obtained by distillation in a yield of 54%. The (dimethylaminoethyl) -tri- (2-pentyl) cyclopentadiene was obtained after preparative column purification on silica gel with successively petroleum ether (40-60 ° C) and THF with a yield of 57%.

Example XXV

Preparation of bis (dimethylaminoethyltriisopropyl-30 cyclopentadiene)

In a dry 500 mL three-necked magnetic stirrer, a solution of 62.5 mL of n-butyl lithium (1.6 M in n-hexane; 100 mmol) was added to a solution of 19.2 35 g (100 mmol) of triisopropylcyclopentadiene in 250 mL of THF under a dry nitrogen atmosphere. at -60 ° C. After warming up to room temperature (in about 1 hour), stirring was continued for 2 hours. After cooling to -60 ° C, 1003007-36 - a solution of (dimethylaminoethyl) tosylate (105 mmol) prepared in situ was added over 5 minutes. The reaction mixture was warmed to room temperature and stirred overnight. After adding water 5, the product was extracted with petroleum ether (40 -60 ° C). The combined organic layer was dried (Na2 SO4) and evaporated under reduced pressure. The conversion was higher than 95%. Part of the product thus obtained (10.1 g; 38.2 mmole) was again alkylated with (dimethylaminoethyl) tosylate (39.0 mmole) under the same conditions.

The bis (2-dimethylaminoethyl) triisopropylcyclopentadiene was obtained in a 35% yield by column chromatography.

15

Example XXVI

a. Preparation of (dimethylaminoethyl-tricyclohexyl-cyclopentadiene)

The reaction was carried out in an identical manner as for (dimethylaminoethyl] dicyclohexyl cyclopentadiene. The conversion was 91%. The product was obtained by eluent successive column purification on silica gel with petroleum ether (40-60 ° C) and THF as a yield of 80%. .

25 b. Synthesis of 1- (dimethylaminoethylΊ-2,3,5-tricvelohexylvelopentadienvltitanium (IIDdichloride and Γl- (dimethvlaminoethvl) -2,3.5-tricvclohexvl-cvclopentadienvlIdimethvltitaniumfIII) 30 rC? Hfc-HexK (CH,) Ti and fCcHfc-Hex) T (CH ..), NMe, Ti (IinMe71

To lithium (dimethylaminoethyl) tricyclohexyl cyclopentadiene (2.11 g, 5.70 mmol) dissolved in 20 mL of tetrahydrofuran, a cooled slurry (-70 * C) of Ti (III) C13.3THF (2.11 g) was added at -70 ° C. , 5.70 mmol) in 20 mL of THF. The resulting dark green solution was stirred at room temperature for 72 hours. After evaporating 1003007 - 37, 30 mL of petroleum ether (40-60) was added. After complete evaporation again, a mint green powder (2.80 g) was obtained containing 1- (dimethylaminoethyl) -2,3,5-tricyclohexylcyclopentadienyl titanium 5 (III) dichloride. Slurry of 0.50 g (0.922 mmol) of the above obtained [1- (dimethylaminoethyl) -2,3,5-tricyclohexylcyclo-pentadienyltitanium (III) dichloride] cooled to -70 ° C. [Lithium chloride] in 30 mL diethyl ether 1.15 mL of methyl lithium (1.6 M in diethyl ether, 1.84 mmol) was added dropwise. The green-brown slurry immediately turned dark. The mixture was then stirred at room temperature for 1 hour, completely evaporated and dissolved in 40 mL of petroleum ether. After filtration and complete evaporation of the solvent, a black powder (0.40 g, 0.87 mmol) was obtained containing tricycloxexylcyclopentadienyl-dimethylaminoethylTi (III) dimethyl.

Example XXVII

A. Preparation of fdi-n-butyl-aminoethyl-tri-(2-pentyl-cyclopentadiene)

The reaction was carried out in an identical manner as for (di-n-butylaminoethyl) -di- (3-pentyl-cyclopentadiene). The conversion was 88%. The (2-25 di-n-butylaminoethyl) -di (2-pentyl) cyclopentadiene was after preparative column purification on silica gel with successively petroleum ether (40-60 ° C) and THF, followed by distillation under reduced pressure obtained with a yield of 51%.

30 b. Synthesis of 1- (di-n-butvlaminoethyl) -2,3,5-tri (2-pentyl) cvelopentadienyl titanium (III dichloride rCcH (2-C5Ht, KfCH.UNfn-BuKTifimCl, 1 2.633 g (6.11 mmol) (di-n 35 butylaminoethyl) tri (2-pentyl) cyclopentadiene was dissolved in 50 mL diethyl ether and cooled to -78 ° C. Then 3.8 mL n-butyl lithium (1.6 M in 1003007 - 38 -: hexane; 6, 11 mmol) After stirring at room temperature for 18 hours, the clear pale yellow solution was evaporated and washed once with 25 mL of petroleum ether, then the solvent was evaporated completely and 1.58 g of a yellow oil containing lithium 1- (di -n-butylaminoethyl) -2,3,5-tri (2-pentyl-cyclopentadienyl). Then the organolithium compound was dissolved in 50 mL of tetrahydrofuran and added at -78 ° C to 9.23 g of 10 (24.9 mmol) Ti (III). ) C13.3THF in 50 mL of tetrahydrofuran.

After stirring at room temperature for 18 hours, a dark green solution had formed. This solution was evaporated completely, leaving 1.52 g of a green oil containing 1- (di-n-butylaminoethyl) -2,3,5-15 tri (2-pentyl) cyclopentadienyl titanium (III) dichloride.

Polymerization Experiments XXVIII-XXXVII ft. The copolymerization of ethylene with propylene was carried out on the following phase.

A 1-liter stainless steel reactor was charged under dry N2 with 400 ml of pentamethyl heptane (PMH) and 30 µl tritlethyl aluminum (TEA) or trioctyl aluminum (TOA) as a scavenger. The reactor was pressurized to 0.9 MPa with 25 purified monomers and conditioned so that the propylene: ethylene ratio in the gas was 1: 1 over the PMH. The reactor contents were brought to the desired temperature with stirring.

After conditioning the reactor, the metal complex (5 / mol) and the cocatalyst (30 / mol BF 2 O) to be used as the catalyst component was premixed for 1 minute and fed to the reactor by means of a pump. The mixture was premixed in ± 25 ml PMH in a catalyst dosing vessel and rinsed with ± 35 ml PMH all under dry N2 flow.

During the polymerization, the concentrations of monomers were kept as constant as possible from 1003007 to 39 by adding propylene (125 normal liters / hour) and ethylene (125 normal liters / hour) to the reactor. The reaction was monitored according to the temperature course and the course of the monomer feed.

After 10 minutes of polymerization, the monomer feed was stopped and the solution was drained under pressure and collected. The polymer was dried under vacuum at about 120 ° C for 16 hours.

B. The homopolymerization of ethylene and the copolymerization of ethylene with octene were carried out in the following mode.

600 ml of an alkane mixture 15 (pentamethyl heptane or boiling point gasoline was charged as a reaction medium under dry N 2 as reaction medium in a stainless steel reactor with a capacity of 1.5 liters. Then the intended amount of dry octene was introduced into the reactor (so this amount can also be zero 20). The reactor was then heated with stirring to the desired temperature under a desired ethylene pressure.

25 ml of the alkane mixture as a solvent was dosed into a 100 ml catalyst dosing vessel. Herein, the desired amount of an Al-containing cocatalyst was premixed with the desired amount of metal complex for 1 minute such that the ratio Al / (metal in the complex) in the reaction mixture is equal to 2000.

This mixture was then metered into the reactor and polymerization started. The polymerization reaction thus started was carried out isothermally. The ethylene pressure was kept constant at the set pressure. After the desired reaction time, the ethylene feed was stopped and the reaction mixture was drained and quenched with methanol.

1003007 - 40 - ir

The reaction mixture with methanol was washed with water and HCl to remove catalyst residues. The mixture was then neutralized with NaHCO 3. An anti-oxidant (Irganox 1076, TM) was then added to the organic fraction to stabilize the polymer. The polymer was dried under vacuum at 70 ° C for 24 hours.

In both cases the following conditions were varied: 10 - metal complex - type and amount of scavenger - type and amount of cocatalyst - temperature 15

The current conditions are shown in Table I.

7 0 0 3 0 0?

XJ

Δ υ <*> • ο «Μ Ο« ^> ο 2 *, m in λ

I - I I N CH wo I <M

I _ o υ u «>« 9 6 Λ q d? ”^ _ * 1 ® g £. , * Λ e> to *> in yy «m o *« c s «9> M \. - λ o c.

J J ΐ 1A ^ o r- * o <n vo ° B- *** _ oo cp m m σ «η, m m ^ ω e <D cm ®

S H H -M \ H

G BC S * c SHeSH

• o SS · O · · 0 · · O

SS · ft «H · ft Μ φ ft« Η

• C χ> · ^> · Ο x * ** · 0 4J · O <U

J S u μ υ m u n Um u η v u u * ** e _ Q — _ o I ft u \ Q pi I ft u o p> cu u

X

0 \

Tj * ® o oo © © Ϊ ^ O oo oo • ^ ^ o oo oo

• * ° ™ ™ H CM Μ M CM _ ^ __ £ __CM

U ^ -.

0 u «in ·

/ 1 rM

O O O O O

CO η l *> r * r * ONONONOMIC

£ * hlfiK '<Bui <C54 «e« CBu 55 o -g-- „--a - a - s - a - s - s - s - 2 2« _ fti λ -η h βh in H j = φ * • Η ΟΊ O β C \

Φ Φ M

>> 0 CM M

® «6 CM CM Ο * o ο υ ε. T. ® _ £ _β w ° ο I ο I I ο__I__I__o M '——- «0> e φ> <e <<^

Ο Ο Η Ο M

I —yyy - fc - fc -! - a __! __! __ fc__1__1__H

9 - *

iH 9 M

Σ2 *> ® ^ * C Λ

Vi 0 w 1 1-. G 8 gup ° o ο ο ο ο ο o xt a '' “inomoinoN moo mow ο n · - <

jt Ό Μ <N H W fici MM CP Η N HOI B h rt (Tt · S

Ό ~ - "'- -" - U

«W on • <" Λ ft) • C r-4 «Η K O>,»

«« \ B C

® Η Η O ig> ft 0% 4 m

£ E S

mm5335m ° S5 C g o s si

ΐ 3 2 H

"£ · ji ° ri Η Λ Γ?

• 0lk <H Η H

tt Β Ο> Μ Η Η H>> S H M C C

j_ £ ï £ sEÈÈ >> “

• ft v y —g - x - X - X— X K _ X X x X

• * D M HH> HH ° - j> 5 x a s s sü s i 2 s> * s a a a 5 a h h M Ml: x m o in

τΗ «H

* Λ 0. ’Γ; TO

Claims (8)

1. Poly-substituted cyclopentadiene compound, characterized in that at least one substituent has the form -RDR'n, where R is a linking group, D a heteroatom, selected from group 15 or 16 of the Periodic Table of the Elements, R 'a substituent and n is the number of R 'groups bound to D, and that at least one further substituent is a branched alkyl group. The cyclopentadiene compound according to claim 1, wherein at least two branched alkyl groups are present as a substituent. The cyclopentadiene compound according to claim 2, wherein 2 or 3 linear branched alkyl groups are present as a substituent. Metal complex containing at least one cyclopentadiene compound according to any one of claims 1-3 as a ligand. Use of the metal complex according to claim 5 as a catalyst component in the copolymerization of olefins, in particular of ethylene with other olefins. Use according to claim 5, wherein at least another olefin is a vinyl aromatic monomer. Metal complex according to claim 4, wherein the metal is in a lower than the highest valency state. Use of the metal complex according to claim 7 as a catalyst component for copolymerizing α-olefins with vinyl aromatic monomer and. 1003007 COOPERATION TREATY (PCT) REPORT ON NEWNESS RESEARCH OF INTERNATIONAL TYPE IDENTIFICATION OF THE NATIONAL APPLICATION Kanmark of the applicant «(of the common application __8645 NL_ Dutch application no. research of ntemaionaai type By o # Insenee enter mwnaaonaai Research (ISA) to the request for research of wsmaaona * kmeB rijiKkne nr. SN 27494 EN L CLASSIFICATION OF THE SUBJECT (in case of patong of verts * len dassitcaaas. all da tsrticaoetym boats opgavan) According to, inter alia, nameeonsie damlicaoe (1PC) Int Cl.6: C 07 C 211/25, C 08 F 10/00, C 07 F 9/50, C 07 F 17/00, B 01 J 31/22 II FIELDS OF TECHNIQUE RESEARCHED ___._ Unforeseen minimum aocomantnit_ Classifications vsiaam Classification companies Int Cl.6 C 07 C, C 07 F, C 08 F, B 01 J Onearzoente documentation other than eg minmum documenaee insofar as dargaijka do cumaη · η n da prayers examined ajn included III. i x i NO EXAMINATION FOR CERTAIN CONCLUSIONS (comments on supplementary sheet) IV. 1 LACK OF UNIT OF INVENTION (comments on supplement sheet) i ll