NL1003015C2 - Cyclopentadiene compound substituted with chiral groups. - Google Patents

Description

- 1 -

CYCLOPENTADIENE COMPOUND SUBSTITUTED WITH CHIRAL GROUPS

The invention relates to a multi-substituted cyclopentadiene compound

Cyclopentadiene compounds, both substituted and unsubstituted, are widely used as a starting material for the production of ligands in metal complexes with catalytic activity.

In the J. of Organomet. Chem, 479 (1994), 1-29, has reviewed the influence of the substituents on cyclopentadiene as a ligand in metal complexes. On the one hand, it is determined that the chemical and physical properties of metal complexes 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. In the vast majority of cases, either unsubstituted or one to five methyl groups substituted cyclopentadiene is used.

In the following, cyclopentadiene 25 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.

Substituted Cp-30 compounds containing a chiral carbon atom are known from WO-A-92/12112. These Cp compounds used as a ligand in a metal complex having catalytic activity in olefin polymerization indicate that complex has the property of stereoselectively polymerizing. In WO-A-92/12112 Λ.

.35 is based on fulvene to obtain chiral compounds. A drawback of this method is that fulven must always be used and that the chiral C-1003015-2 atom is always an atom directly bound to the Cp. Nor can it be learned from said publication how, optionally, multiple chiral atoms or chiral C atoms other than those directly bound to the Cp can be applied. Since stereoselective olefin polymerization is an attractive option for producing polyolefins with interesting properties, there is a need for other Cp compounds with a chiral atom as well as the known ones.

The invention now provides substituted

Cp compounds in which a chiral atom can also be of a different nature than can be obtained by the known method. Preferably, the substituted Cp compound has at least two chiral atoms.

The presence of at least two such chiral atoms offers a considerably broader possibility than known to influence the stereoselectivity of metal complexes in the polymerization of olefins.

The chiral atoms can be either directly bonded to the Cp or separated from it by one or more C atoms or hetero atoms selected from groups 14-15 of the Periodic Table. The chiral atom itself can also be such a heteroatom.

If one chiral atom is present, it is not directly bound to the Cp in the compound of the invention.

In addition to the chiral atom-containing substituent, the presence of which is required within the scope of the invention, the Cp compound may also contain other substituents. Examples thereof are alkyl groups, both linear and (branched and) cyclic, alkenyl and aralkyl groups. In addition to carbon and hydrogen, one or more hetero atoms from groups 14-17 of the periodic table may also be included therein

Prevent system, for example, O, N, Si or F, where a heteroatom is not bonded directly to the Cp 1003015-3. Examples of suitable groups are methyl, ethyl, (iso) propyl, secondary butyl, pentyl, hexyl and octyl, (tertiary) butyl and higher homologues, cyclohexyl, benzyl.

The Cp compound can also be a heterocyclopentadiene 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-10 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.

As already noted, no more broadly applicable method of manufacturing a chiral atom containing substituted Cp compounds is known. The invention therefore also provides a method for the production of substituted Cp compounds in which at least one chiral atom is present. This method comprises reacting a halide of a substituting compound in a mixture of the Cp compound and an aqueous solution of a base in the presence of a phase transfer catalyst.

Cp compounds are here understood to mean Cp 30 itself and Cp already substituted in 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 poly-substituted, but it is also possible to further substitute one or several times substituted Cp-derived compounds, after which ring closure is also possible.

1003015 - 4 -: Ί · ·. ; λ

It is preferred to work with almost equivalent amounts of the halogenated substituents. 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.

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.

According to this method, Cp compounds can be obtained in two or more ways with the desired chiral substituent and, optionally, in free positions still substituted with other groups of Cp compounds. The substituents are preferably used in the process in the form of their halides and more 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.

In the method of the invention, the desired chiral group can first be synthesized separately and then substituted in suitable halogenated form on the Cp. Also, a simpler group can first be substituted on the Cp which can then be converted into the desired chiral group. Since successive substituents are built into certain preferred configurations due to, for example, steric effects, the position of the chiral atom can also be influenced by the order in which the different substituents are placed with the 1003015-5 method according to the invention. For example, if desired, the higher rank positions in the preferred order in which one does not want the chiral atom can be blocked by first substituting other groups at those locations. These should then be groups which do not significantly influence the properties of the Cp-compound as a ligand in a metal complex intended by the presence of a chiral atom. Short linear substituents are generally most suitable for this.

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 be carried out first with the aid of a certain halide, and in the same reaction mixture a third substitution with another substituent can be carried out 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 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 per mole of Cp compound.

The substitution takes place in the presence of a phase transfer catalyst capable of transferring 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. Quaternary ammonium, phosphonium, arsonium, antimony, bismuthonium, and tertiary sulfonium salts can be used as phase transfer catalyst 1003015-6. More preferred are ammonium and polyonium salts, for example tricaprylmethyl ammonium chloride, commercially available under the name Aliquat 336 (Fluka AG, Switzerland; General Mills Co., USA) and Adogen 464 (Aldrich Chemical Co., USA). Compounds such as benzyl triethylammonium chloride (TEBA) or bromide (TEBA-Br), benzyl trimethyl ammonium chloride, bromide, or hydroxide (Triton B), tetra-n-butylammonium chloride, bromide, iodide, hydrogen sulfate or hydroxonium hydroxide and cetyl trimide or -chloride, benzyltributyl, tetra-n-pentyl, tetra-n-15 hexyl and trioctylpropyl ammonium chlorides and bromides are also suitable. Examples of useful phosphonium salts are tributyl hexadecyl phosphonium bromide, ethyl triphenyl phosphonium bromide, tetraphenyl phosphonium chloride, benzyl triphenyl phosphonium iodide and tetrabutyl phosphonium 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, 4,7,13,16,21-pentaoxa -1,10-diazabicyclo [8.8.5] tr icosane 25 (Kryptofix 221), 4,7,13,18-tetraoxa-1,10-diazabicyclo [8.5.5 Jeicosane (Kryptofix 211) and 4,7,13,16 , 21,24-hexaoxa-1, 10-diazabicyclo [8.8.8} hexacosane (* [2.2.2] ") and its benzo derivative Kryptofix 222 B. Polyethers such as ethers of ethylene glycols can also be used as 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 geeross-inked polystyrene or other polymer. The phase transfer catalysts are used in an amount of 0.01 - 2, preferably 0.05 - 1 , equivalents to the amount of 1003015 - 7 - -.- .- .- ..

Cp.

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

Substituted Cp compounds having a chiral atom that can be prepared on the Cp by this method are, for example, 1,3-di - ("branched alkyl") Cp, wherein "branched alkyl" is, for example, 2-butyl, 2 pentyl, 2 hexyl and higher homologs, 3-hexyl, 3-heptyl and higher homologs, 4-octyl, 4-nonyl and higher homologs, 2- (3-methylpentyl), 2- (3-ethylpentyl). Examples of cyclic-substituted chiral Cp compounds are 1,3-dicyclopent-2-enyl-Cp and similar compounds with higher homologs. Examples of Cp compounds substituted with tertiary alkyl groups in which a chiral C atom is present are 1,3-di (1-methyl-1-ethyl'alkyl ') Cp, where' alkyl 'is butyl, pentyl, hexyl, heptyl and higher homologs.

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.

Cp-compounds substituted two, three, four and five-fold with the desired branched alkyl.

The substituted Cp compounds according to the invention are particularly suitable for being incorporated as a ligand in a metal complex and the invention therefore also relates to a metal complex in which a substituted cyclopentadiene compound is present as a ligand in which at least one and preferably two chiral atoms are present. As metal catalysts used in the polymerization of olefins, these metal complexes have been found to yield stereoselective catalysts.

1 0 0 3 0 8 - *

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, group 6 and 7 metal complexes, in addition also for metathesis and ring-opening metathesis polymerisations and group 8-10 metal complexes. 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.

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

It was further found that the presence of at least one substituent on the Cp compound of the form -RDR 'n, wherein R is a linking group between the Cp and the DR' 'group, D is a heteroatom, selected from group 15 or 16 of the Periodic Table of the Elements R 'a substituent and n the number of D-linked R' groups, in a substituted Cp compound 30 in which at least one of the other substituents contains a chiral atom, using that Cp compound as a ligand in a metal complex, which gives a complex which, as a catalyst component used in the polymerization of α-olefins, exhibits higher activity in addition to increased stereoselectivity than when the group of the form RDR'n is not present. Corresponding complexes in which the Cp compound 1003015-9 is not substituted in the manner indicated appear to be unstable or, if otherwise stabilized, to provide less active catalysts than the complexes of substituted Cp compounds of the invention , especially in the polymerization of α-olefins.

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

The invention therefore also relates to Cp compounds thus substituted. An additional advantage of the presence of such a group is that chiral atoms can also occur therein. In particular, the R group herein may have a chiral character, making available an entirely new class of chiral substituted Cp-20 compounds.

In the RDR group, the R group forms the link between the Cp and the DR group. The length of the shortest connection between the Cp and D is critical in that it uses the Cp-25 compound as a ligand in a metal complex to determine the accessibility of the metal by 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 at least one atom long.

The R 'groups can each individually be a hydrocarbon radical of 1-20 carbon atoms (such as alkyl, aryl, arylalkyl, etc.). Examples of such hydrocarbon radicals are methyl, ethyl, propyl, butyl, hexyl, decyl, phenyl, benzyl and p-tolyl. R 'may also be a substituent containing, in addition to or instead of carbon 1003015-10 and / or hydrogen, one or more hetero atoms 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 'should not be a cyclopentadienyl or derivative group thereof.

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 15 with p = 1-4 and E an atom from group 14 of the periodic table. The R2 groups can each be H or a group as defined for R '.

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, tetraalkyldisilylene or tetraalkylsilethylene (-SiR22CR22-). The alkyl groups in such a group preferably have 1-4 C atoms and are more preferably a methyl or ethyl group.

Examples of R groups in which a chiral atom is present are those in which R is a 1 or 2-alkylethyl.

The DR '' group consists of a heteroatom D selected from group 15 or 16 of the Periodic Table 30 of the Elements and one or more substituent (s) R 'bound to D'. The number of R 'groups (n) is linked to the nature of the heteroatom D, in that n = 2 if D is from group 15 and n = 1 if D is from group 16. With preferably the heteroatom D is selected from the group nitrogen (N), oxygen (O), phosphorus (P) or sulfur (S), more preferably the heteroatom is nitrogen (N). Also preferably 1003015-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 may be a pyrrolidinyl group).

The DR group can coordinate bonding with a metal. If the thus substituted Cp compound as a ligand is part of a metal complex, the 10D atom can also have a chiral character. This is the case, for example, when several and mutually different R 'groups are present.

A group of the form -RDR '' can be substituted on the group already optionally substituted with at least one chiral atom 15 and any other groups of substituted Cp compound, for example, by 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.

As base can be used, for example, organolithium compounds (R3Li) or organomagnesium compounds (R3MgX) in which R3 is an alkyl, aryl or aralkyl group and X is a halide, for example n-butyl tyllium 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 carried out in a polar dispersant, eg 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 anion formed is reacted with a compound of the formula (DR '- - RY) or 1003015 - 12 - (XR-Sul), in which Dr R, Rs are n 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, wherein 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 the Elements, such as N, 0, Si or F.

Examples of sulfonyl groups are: phenylmethanesulfon-15-phenyl, benzenesulfonyl, 1-butanesulfonyl, 2,5-dichlorobenzenesulfonyl, 5-dimethylamino-1-naphthalenesulfonyl, pentafluorobenzenesulfonyl, p-toluenesulfonyl, trichloromethanesulfonyl, 2,4-trifluoro-sulfonyl, trifluoronyl triisopropylbenzenesulfonyl, 2,4,6-trimethylbenzenesulfonyl, 2-mesitylenesulfonyl, methanesulfonyl, 4-methoxybenzenesulfonyl, 1-naphthalenesulfonyl, 2-naphthalenesulfonyl, ethanesulfonyl, 4-fluorobenzenesulfonyl and 1-hexadecaans. Preferably the sulfonyl group is p-toluenesulfonyl or trifluoromethanesulfonyl.

When D is a nitrogen atom and Y is a sulphonyl 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 usually carried out at a temperature between -20 and 20 ° C. Reactions with DR '- - R-Y, in which 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 5 of the compound DR 'n -R-Y.

After the reaction with a compound of the formula (X-R-Sul), another reaction with LiDR'n or HDR'n is performed to replace X with a DR'n functionality. For this purpose, optionally in the same dispersant 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 where the number of substituted carbon atoms does not increase. The amount of geminal products formed is low when the synthesis is carried out from a substituted Cp compound having 1 substituent and 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 pKa values are based on D.D. Perrin: Dissociation Constants of Organic Bases in Aqueous Solution, International Union of Pure and Applied Chemistry, Butter-worths, London 1965. Values are determined in 35 H 2 SO 4 aqueous solution. Ethers can be mentioned as an example of suitable weak Lewis bases.

When geminal products are formed 1003015 - 14 -.

during the process of 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 dissolves 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, as defined above, and in which at least one cyclopentadiene-15 compound as defined above are present, have been found to be stereoselective in the polymerization of olefins. The invention therefore also relates to such metal complexes and their use as a catalyst component for the polymerization of olefins. One or more Cp compounds according to the invention may be present as a ligand in these metal complexes. Two of these ligands can be linked by a bridge.

The polymerization of α-olefins, for example ethylene, propylene, butene, hexene, octene and mixtures thereof and with should be carried out in the presence of the metal complexes with the Cp 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 Cp 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.

1003015 - 15 - -

The known polymerizations are carried out in suspension, solution, emulsion, gas phase or as bulk polymerization. As cocatalysts, for example, trialkylaluminum, alkylaluminum halides, methylaluminoxanes, tr is (pentafluorophenyl) borate, dimethylanilinium tetra (pentafluorophenyl) borate or mixtures thereof are usually used. The polymerizations are carried out at temperatures between -50 ° C and +350 ° C, more in particular between 25 ° C and 250 ° C. Applied pressures are between generally between atmospheric pressure and 2500 atmospheres, for bulk polymerizations more particularly between 500 and 2500 atmospheres, for the other polymerization processes between 5 and 250 atmospheres. As dispersants and solvents, for example, hydrocarbons can be used as pentane, heptane and mixtures thereof. Aromatic, optionally perfluorinated hydrocarbons are also eligible.

The invention will be elucidated on the basis of the following examples, without however being limited thereto. The following analysis methods were used in the characterization.

Gas chromatography (GC) was performed on a Hewlett-Packard 5890 Series II with an HP Crosslinked Methyl 25 Silicon Gum (25mx0.32mmx1.05f / m) column. Combined Gas Chromatography / Mass Spectrometry (GC-MS) was performed with a Fisons MD800 equipped with a guadrupole mass detector, autoinjector Fisons AS800 and CPSil8 column (30mx0.25mmxlpm, low bleed).

30 NMR was performed on a Bruker ACP200 (1H = 200MHz; 13C = 50MHz) or Bruker ARX400 (1H = 400MHz; 13C = 100MHz). A Kratos MS80 or a Finnigan Mat 4610 mass spectrometer was used to characterize metal complexes.

35 1003015 - 16 -. .

Experiment I

Preparation of 2- (N, N-dimethlaminoethyl 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 under dry nitrogen to a solution of 2-dimethylaminoethanol (1 equivalent) in dry THF at -10 ° C (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 equivalent) was added. Then it was 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.

Example II

Preparation of di- and tri (2-pentyl) cyclopentadiene 30 A 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 a few minutes, then 155 g of 2-pentyl bromide (1.03 mol) was added over an hour.

1003015 - 17 -

It was cooled with water. After stirring at room temperature for 3 hours, the reaction mixture was heated to 70 ° C, followed by stirring for another 2 hours. Stirring was stopped and ase 5 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-pentylcyclopentadiene (about 1: 1). The 10 products were distilled at 2 mbar, 79-81 ° C and 0.5 mbar, 102 ° C, respectively. After distillation, 28 g of di- and 40 g of tri (2-pentyl) cyclopentadiene were obtained Characterization was by GC, GC-MS, 13C- and -NMR.

15 b. Preparation of (dimethvlaminoethyl) di (2-pentyl) cyclopentadiene

In a 250 ml three neck round bottom flask equipped with magnetic stirrer and dropping funnel, 20 was added under nitrogen atmosphere to a cooled (0 ° C) solution of di-2-pentylcyclopentadiene (7.82 g; 38.0 mmol) in dry tetrahydrofuran (125 ml) 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 (2-35 pentyl) cyclopentadiene.

1003015 - 18 - t: c. Synthesis of 1- (dimethvlaminoethyl] -2,4-di (2-pentyl) cyclopentadienyl titanium (III) dichloride and Γ1- (dimethlaminoethyl) -2,4-di (2-pentyl) cyclopentadienyl dimethyl titanium fIII) 5 € (2-0, Η1Έ), (CH,), NMe, Ti (III) C1,1 and iC «H, (2-

CcH2), (CH2), NMe, Ti (III) Me, l

In a Schlenk vessel, 1.60 g (5.77 mmol) (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-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 Ti (III) Cl3.3THF (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 time the solvent was evaporated in two steps. 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 (2-25 pentyl) cyclopentadienyl-titanium (III) dichloride remained.

0.33 g (0.835 mmol) of 1- (dimethylaminoethyl) -2,4-di (2-pentyl) cyclopentadienyl titanium (III) dichloride was dissolved in 40 ml diethyl ether in a Schlenk vessel. The solution was cooled to -30 60 ° C, after which 0.90 mL of methyl lithium (1.84M in diethyl ether? 1.66 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. 0.24 g of a black / brown oil containing (1- (dimethylaminoethyl) - 1003015 - 19 -) remained.

2,4-di (2-pentyl) cyclopentadienyl] dimethyl titanium (III). Example III

a. Preparation of di (n-butvlaminoethyl) di (2-5 pentyl) cyclopentadiene

The reaction was carried out in an identical manner as for (dimethylaminoethyl) -di (2-pentyl) cyclopentadiene, the tosylate of N, N-di-n-butylaminoethanol being prepared in situ. The 10 conversion was 88%. The di- (n-butylaminoethyl) -di (2-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 %.

b. Synthesis of 1- (di-n-butylaminoethyl) -2,4-di (2-pentyl) cvylopentadienyl titanium III) dichloride 20 f C, H, (2 - (:, ^,), (CH ^ Ntn-CH,), Ti ( III) C1.1

In a Schlenk vessel, 0.919 g (2.54 mmol) (di-n-butylaminoethyl) di (2-pentyl) cyclopentadiene was dissolved in 40 mL diethyl ether and the solution was cooled to -60 ° C. 1.6 mL of n-25 butyl lithium (1.6M in hexane; 2.56 mmol) was then 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 (2-35 pentyl) cyclopentadienyl-titanium (III) dichloride remained.

1003015 - 20 -

Example IV

a. Preparation of di- (n-butvlaminoethyl) -tri-f2-pentyl-cycloentadiene

The reaction was carried out in an identical manner as for (dimethylaminoethyl) -di- (2-pentyl) cyclopentadiene, whereby the tosylate of N, N-di-n-butylaminoethanol was prepared in situ. The conversion was 88%. The di-n-butylaminoethyl) -tri- (2-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%.

15 b. Synthesis of 1- (di-n-butvlaminoethyl) -2,3.5-tri (2-pentyl) cycloentadienyl titanium (III) dichloride 1C «H (2rC« H ,, U (CH 3), N (n-Bu), Ti (III) Cl, 2.633 g (6.11 mmol) (di-n-butylaminoethyl) tri (2-pentyl) cyclopentadiene was dissolved in 50 mL diethyl ether and cooled to -78 ° C. Then, 3.8 mL of n-butyl lithium (1.6 M in hexane; 6.11 mmol) was added. After stirring at room temperature for 18 hours, the clear light yellow solution was evaporated and washed 1 time 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 remained. The organolithium compound was then dissolved in 50 mL of tetrahydrofuran and added at -78 ° C to 9.23 g (24.9 mmol) of 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-tr (2-pentyl) cyclopentadienyltitanium (III) dichloride.

1003015 - 21 -

Example V

a. Preparation of di (2-butylcyclopentadiene)

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 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 several minutes. Then 200 g of 2-butyl bromide (1.46 mol) was added over half an hour. It 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. GC showed that at that time, more than 90% di (2-butyl) cyclopentadiene was present 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 product was characterized by GC, GC-MS, 13C- and -NMR.

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

In a 500 ml three-necked round bottom flask, equipped with magnetic stirrer and dropping funnel, was added under a 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 30 mmol) was added dropwise. After stirring at room temperature for 24 hours, 2- (dimethylaminoethyl) tosylate (50.0 mmol) prepared in situ 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

to o 3 o 1S

- 22 - 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).

5 c. Synthesis of 1- (dimethylaminoethyl) -2,4-di (2-butyl) cyclopentadienyl titanium (III dichloride and Γ1- (dimethlaminoethyl) -2,4-di (2-butyl) cyclopentadienyl1 dimethyl titanium fIII) 10 rC, H? (2-CtH?) T ( CHT), NMe, Ti (III) Cl «1 and fC« H, (2-, (CH,) ·> ΝΜθ ·> Τΐ (III) Me? 1

2.36 g (9.48 mmol) (dimethylaminoethyl) di (2-butyl) cyclopentadiene were 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 and stirred for an additional 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 compound was added to the Ti (III) Cl3 suspension. The reaction mixture was then stirred at room temperature for 18 hours after which time the solvent was evaporated for 25 a £. 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 (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. After this, 1003015-23, the solvent was 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) -5 2,4-di (2-butyl) cyclopentadienyl] dimethyl titanium (III) remained.

Example VI

a. Preparation of tri (2-butyl) cyclopentadiene

A 10 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 at room temperature for half an hour, the reaction mixture was heated to 70 ° C, followed by stirring for another three hours. Stirring was stopped and phase separation was awaited. The water layer was drained and 400 g (5.0 mol) of fresh 50% NaOH were 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-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.

The product was characterized by GC, GC-MS, 13C- and 1 H-NMR.

b. Preparation of (dimethvlaminoethyl) tri (2-butyl) cyclopentadiene

The reaction was carried out in an analogous manner as for (dimethylaminoethyl) di (2-butyl) cyclopentadiene. The conversion was 92%. The product was obtained by distillation with a yield of 64%.

c. Synthesis of ri- (dimethvlaminoethvl) -2.3.5-tri (2-butvl) cvcloDentadienvltitanium (III) dichloride and fl-5 (dimethvlaminoethvl) -2.3.5-tr i (2-butvl) cvclopentadienvl1 dimethyltitanium (III) f CgH ( 2-CH?) ·> (CH · »KNMe-Ti (Illicit! And fCcH (2- C.Ha), (CH, KNMe, Tif IIime71

In a 500 mL 3-neck flask, 200 mL of petroleum ether was added to 6.28 g of 10 (20.6 mmol) of the potassium 1- (dimethylaminoethyl) -2,3,5-tri (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) C13 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 was then added to the product and filtered. The filtrate was evaporated and dried under vacuum for 2 days. 7.93 g of a brown / black oil containing [1-30 (dimethylaminoethyl) -2,3,5-tr (2-butyl) cyclopentadienyl] dimethyl titanium (III) remained.

Polymerization Experiment VII

A. 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 1003015 - 25 - 30 μl triethyl aluminum (TEA) or trioctyl aluminum (TOA) as a scavenger. The reactor was pressured to 0.9 MPa with 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 μπιοί) to be used as the catalyst component and the cocatalyst (30 μπιοί BF20) were 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 ± 75 ml PMH all under dry Na-flow.

During the polymerization, the concentrations of monomers were kept as constant as possible by adding propylene (125 normal liters / hour) and ethylene (125 normal liters / hour) to the reactor. The reaction was monitored by 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 copolmerization of ethylene with octene were carried out in the following manner.

600 ml of an alkane mixture 30 (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 target amount of dry octene was introduced into the reactor (this amount can therefore also be zero 35). The reactor was then heated with stirring to the desired temperature under a desired ethylene pressure.

1003015 - 26 -

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 5 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 was 2000.

This mixture was then dosed to the reactor after which the 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 guenched with methanol.

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 25 conditions were varied: - metal complex - type and amount of scavenger - type and amount of cocatalyst - temperature 30

The current conditions are always stated in Table I.

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Claims (6)

1. Substituted cyclopentadiene compound in which at least one chiral atom is present, characterized in that the chiral atom is not directly bound to the cyclopentadiene. 2. Substituted cyclopentadiene compound in which at least two chiral atoms are present. A compound according to claim 1 or 2, wherein at least one chiral atom is a heteroatom selected from groups 14-15 of the Periodic Table. 4. Substituted cyclopentadiene compound in which, in addition to at least one chiral atom-containing substituent, there is also a group of the form RDR'n as substituent, wherein R is a linking group between the cyclopentadiene and the DR 'group, D a heteroatom, selected from the group 15 or 16 of the Periodic Table, of the Elements, 20 R 'a substituent and n the number of D' bound R 'groups. Metal complex in which at least one compound according to any one of claims 1-4 is present as a ligand. Use of a metal complex according to claim 5 as a catalyst component in the polymerization of α-olefins. 1003015 - - —- · ·· - ww τ mi * mm · · η «ρ ι» w - ι REPORT ON THE NEW 1ND SECURITY OF INTERNATIONAL TYPE IOENT1FICATION OF THE NATIONAL APPLICATION Character of m applicant ol of 0 · macnogoe __8673 NL no Neoenanase Mienngsoaijm 1003015 May 3, 1996 In9 · invoke voonengsoeum Applicant (Name) DSM NV Oaaan of wet sweeten * for an examination of vuemaaowaiai type By oe Insane * for Iniemaionaai Onoerzoak (ISA) to wet request for an ean onoerzoe * of namaDoneai type eegekeno no. SN 27502 EN L CLASSIFICATION OF THE SUBJECT MATTER (for eepesamg of varacnillanoe dassitcaeas. Aito dassifieaoeymboien tasen) II · I · ™ ·. - ----- · * According oe mamaoonae aassihcao * (IPC) Int.Cl.6: C 07 C 13/15, C 07 C 211/25, C 07 F 17/00, C 08 F 10/00 II . FIELDS OF TECHNIQUE RESEARCHED __Onoereocme minimum documentation _ Classification system Classificationymooltn _ Int.Cl.6: C 07 C, C 08 F Undozocme an oer · ooajmtnao * o an o · minimum eooiminaM for 20 before «atrgtkfk * ooeumontn oe oe oe obees · oeb o P9 on om on '^ III.! X: NO EXAMINATION FOR CERTAIN CONCLUSIONS (comments on supplemental pay) j IV .'_ 1 LACK OF UNIT OF INVENTION (ODmerxingen including supplemental charge) I = orm PCT.1SA.rDt ia ι CS 195: iC