Improved process for the manufacture of rac handle-metallocenes

Abstract

The invention relates to an improved process for separating bridged, stereorigid racemic mixtures of Group 4 element-containing metallocenes from a specific solvent mixture.

Description

Technical Field

[0001] The present invention relates to an improved method for separating racemic mixtures of bridging, stereorigid metallocenes of Group 4 elements from a particular solvent mixture. Background Technology

[0002] Metallocenes based on optionally substituted cyclopentadiene, indene, and fluorene, particularly cationic Group 4 metallocene derivatives, are known to catalyze olefin polymerization efficiently when combined with cocatalysts such as aluminoxanes and modified aluminoxanes.

[0003] When chiral, stereorigid metallocene racemates are used in such polymerizations (see EP 320,762 A), stereoregular poly-α-olefins can be obtained in high yields, while the corresponding meso form of metallocenes shows no suitability for this task.

[0004] Therefore, considerable efforts have been made to synthesize the racemic form in both pure form and in high yield.

[0005] US 5,017,714 discloses the preparation of oily silicon-bridged metallocenes from which racemic and meso forms can be separated by various solvent extraction and / or crystallization steps.

[0006] EP 426,643 A discloses the preparation of metallocenes via a solid-solid reaction of transition metal salts and ligands with alkyllithium in a nonpolar hydrocarbon liquid. These metallocenes are claimed to possess sufficient purity for subsequent use as catalysts for olefin polymerization without further purification. The solid mixture of lithium salts and metallocenes is recovered.

[0007] US 5,556,997 discloses the reaction of dilithiated bisindenyl-dimethylsilane with a complex of zirconium tetrachloride and a chelated diamine, thereby obtaining high yields of racemic metallocene and only small amounts of meso form.

[0008] A similar method is reported in WO 99 / 12943, in which adducts of, for example, group 4 element halides with oligoethers or polyethers or corresponding thioethers are reacted with deprotonated metallocene ligands.

[0009] US 6,365,769 discloses a method for preparing dimethylsilyl-bis(indenyl)zirconia with a racemic / meta-rhynchocyanine ratio of 32:1 by dilithiation of bisindenyl-dimethylsilane with 20 wt.-% butyllithium in toluene, followed by reaction with zirconium tetrachloride, and then by enhanced post-treatment and washing. For similar hafnium compounds, a racemic / meta-rhynchocyanine ratio of 36:1 has been reported.

[0010] In the alternative method disclosed in DE 4406109, the preparation of pure racemic dimethylsilyl-bis(indenyl)zirconium chloride and similar hafnium compounds is carried out by reacting bis-2-indenyl-dimethylsilane with tetrabutyltin chloride, completely removing the solvent, and subsequently reacting it with zirconium tetrachloride and hafnium tetrachloride, respectively. The mechanistic aspects and explanations of the highly stereooriented synthesis are discussed in detail in M. Hüttenhofer et al., Angew. Chem., 1998, Vol. 100, No. 16, pp. 2378-2380.

[0011] However, a drawback of the methods listed above and all known to date is that multiple post-processing steps are required to obtain only the desired racemic compound. Larger quantities of the corresponding meso compounds are generally not commercially viable and must be disposed of.

[0012] Therefore, there is still a need to develop a method that allows for the high-yield preparation of racemic forms of chiral-bridged stereorigal metallocenes while avoiding the aforementioned drawbacks. Summary of the Invention

[0013] A method has now been discovered for preparing compounds of formula (I) in their racemic form. (I) in L represents the choice of free-Si(R) 3 )2-、-C(R 3 )2-、-C(R 3 )2C(R 3 )2- and BR 3 - Connecting base of the group in R 3 In -C(R) 3 )2- and -C(R 3 )2C(R 3 In the case of )2-, it represents hydrogen, alkyl, or phenyl, and In -Si(R 3 )2- and BR 3 In the case of alkyl or phenyl, or Two residues R 3 When present, they collectively represent alkane-di-yl. Wherein R is preferred 3 In -C(R) 3 In the case of )2-, it represents hydrogen, methyl, or phenyl, and In -C(R) 3 )2C(R3 In the case of )2-, it represents hydrogen. In -Si(R 3 )2- and BR 3 In the case of methyl or ethyl R 1 and R 2 Each of the residues independently represents hydrogen, alkyl, phenyl, or naphthyl, which may optionally be further substituted by alkyl or phenyl once, twice, or more than twice, or two adjacent residues R. 1 Or two adjacent residues R 2 Residues together with and independent of another cyclopentadienyl moiety represent a benzene or thiophene ring fused to the cyclopentadienyl moiety, wherein the fused benzene or thiophene ring is further substituted by one, two, three, or four phenyl or alkyl substituents or is not further substituted. The premise is that R is selected. 1 and R 2 This allows them to form racemic and meso forms of compounds having formula (I), which, for illustrative purposes only, excludes, for example, all R... 1 and R 2 The same situation M represents a lanthanide element, chromium, molybdenum, tungsten, titanium, zirconium, or hafnium, preferably lanthanum, cerium, neodymium, chromium, molybdenum, tungsten, zirconium, or hafnium, more preferably zirconium, or chromium, or molybdenum, or tungsten, even more preferably zirconium or hafnium. X represents a halide such as a fluoride, chloride, bromide, or iodide, preferably a fluoride, chloride, or bromide, and more preferably a fluoride or chloride, or represents an alkoxide having the formula OR, wherein R represents a C1-C8-alkyl group that may be substituted once or twice with a phenyl group, which may optionally be further substituted once, twice, or more than twice with a C1-C4-alkyl group or a phenyl group, preferably R represents a methyl or ethyl group. The method includes the following steps A) Contacting a mixture of a compound of formula (I) in its racemic and meso forms and an organic solvent containing at least one ether with at least one auxiliary compound selected from the group consisting of acyl chlorides, esters and nitriles.

[0014] The scope of this invention covers all combinations of substituent definitions, parameters, and illustrations that are general or within the scope of preferred or preferred embodiments as set forth above and below, that is, it also covers any combination between the specific scope and the preferred scope.

[0015] Whenever the terms “including,” “for example,” “like,” and “as” are used in this document, they mean “including, but not limited to,” or “for example, but not limited to.”

[0016] As used herein, and unless otherwise expressly indicated, alkyl groups may be straight-chain, partially or entirely cyclic, branched or unbranched.

[0017] Preferably, the alkyl group is C1-C8-alkyl. The term C1-C8-alkyl indicates a straight-chain, partially or entirely cyclic, branched or unbranched alkyl substituent containing 1 to 8 carbon atoms (excluding the carbon atoms of the substituents optionally present on the C1-C8-alkyl substituent). Specific examples of C1-C8-alkyl include methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-pentyl, cyclopentyl, cyclohexyl, n-hexyl, n-heptyl, n-octyl, and isooctyl, wherein methyl, ethyl, isopropyl, n-butyl, tert-butyl, and cyclopentyl are preferred.

[0018] The term may optionally be further substituted with alkyl or phenyl. Phenyl preferably means phenyl, o-tolyl, m-tolyl, p-tolyl, 2,6-dimethylphenyl, 2,4-dimethylphenyl, 2,4,6-trimethylphenyl and p-phenyl-phenyl.

[0019] According to the invention, a mixture comprising a compound of formula (I) in its racemic and meso forms and an organic solvent containing at least one ether is contacted with at least one compound selected from the group consisting of acyl chlorides, esters and nitriles.

[0020] In one embodiment, the term mixture typically refers to a solution or suspension, preferably a suspension.

[0021] In another embodiment, an organic solvent containing at least one ether is represented.

[0022] - An ether or a mixture of ethers, wherein the ethers are preferably selected from the group consisting of diethyl ether, tert-butyl methyl ether, tetrahydrofuran, methyl-tetrahydrofuran, dioxane, dimethoxyethane, diethoxymethane and tert-amyl methyl ether, and even more preferably from the group consisting of diethyl ether, tert-butyl methyl ether, tetrahydrofuran, dioxane, dimethoxyethane and diethoxymethane, and even more preferably tetrahydrofuran.

[0023] - A mixture of at least one ether and at least one aliphatic or aromatic hydrocarbon, wherein the one or more ethers are preferably selected from those listed above (including their preferred forms), and the at least one aliphatic or aromatic hydrocarbon is preferably selected from the group consisting of benzene, toluene, o-xylene, p-xylene, m-xylene, and pentane, hexane, and heptane, including but not limited to their straight-chain, branched, and cyclic isomers, alone or in combination. In a preferred embodiment, the molar ratio of the one or more ethers used to the amount of aliphatic or aromatic solvent forming part of the organic solvent is at least 100, preferably 100 to 500, more preferably 100 to 400, and even more preferably 150 to 400.

[0024] The auxiliary compounds are selected from the group consisting of acyl chlorides, esters, and nitriles.

[0025] In one embodiment, the acyl chloride represents the following acyl chloride: (C1-C8-alkyl)-(C=O)Cl, preferably acetyl chloride.

[0026] In one embodiment, the ester represents the following esters: (C1-C8-alkyl)-(C=O)-O(C1-C8-alkyl), preferably ethyl acetate.

[0027] In one embodiment, the nitrile refers to the following nitriles: (C1-C8-alkyl)-CN, benzonitrile, and benzylnitrile, preferably acetonitrile.

[0028] Preferred compounds having formula (I) include

[0029] Racemic-1,2-ethylenebis(indenyl)-zirconium dichloride (IV), Racemic-1,2-ethylenebis(indenyl)-hafnium dichloride (IV), Racemic-1,2-ethylenebis(tetrahydroindenyl)-zirconium dichloride (IV) (CAS 100 163 29-9). Racemic-1,2-ethylenebis(tetrahydroindenyl)-hafnium dichloride (IV), racemic-dimethylsilyl-bis-(1-indenyl)-zirconium dichloride (IV), Racemic-diracemic-dimethylsilyl-bis-(1-tetrahydroindenyl)-zirconium dichloride (IV) (CAS126642-97-5). Racemic-diracemic-dimethylsilyl-bis-(1-tetrahydroindenyl)-hafnium(IV) dichloride Racemic-dimethylsilyl-bis(2-methylindenyl)zirconium dibromide, Racemic-dimethylsilyl-bis(2-methyl-4-phenylindenyl)zirconium dichloride, Racemic-dimethylsilyl-bis[2-methyl-4-(1-naphthyl)indenyl]zirconium difluoride, Racemic-dimethylsilyl-bis[2-methyl-4-(1-naphthyl)indenyl]hafnium dichloride, Racemic-dimethylsilyl-bis(2-methyl-4,5-benzoindenyl)zirconium dichloride Racemic-dimethylsilyl-bis(4,5-benzoindenyl)zirconium dichloride Racemic-dimethylsilyl-bis(2-methyl-4,6-diisopropylindenyl)zirconium difluoride Racemic-dimethylsilyl-bis(2-ethylindenyl)zirconium dichloride Racemic-dimethylsilyl-bis(2-ethyl-4-phenylindenyl)zirconium dichloride, Racemic-dimethylsilyl-bis(2-ethyl-4-phenylindenyl)hafnium dichloride, Racemic-dimethylsilyl-bis[2-ethyl-4-(1-naphthyl)indenyl]zirconium dichloride, Racemic-dimethylsilyl-bis(2-ethyl-4,5-benzoindenyl)zirconium dichloride Racemic-dimethylsilyl-bis(4,5-benzoindenyl)zirconium dichloride Racemic-dimethylsilyl-bis(2-ethyl-4,6-diisopropylindenyl)zirconium dichloride, Racemic-dimethylsilyl-bis(2-ethyl-4,6-dimethylindenyl)zirconium dichloride, Racemic-dimethylsilyl-bis(2,4,6-trimethylindenyl)zirconium dichloride, Racemic-dimethylsilyl-bis(2,4,6-trimethylindenyl)hafnium dichloride, (1H-inden-2-yl)dimethyl-silyl-(2,3,4,5-tetramethylcyclopentan-2,4-dienyl)zirconium dichloride, dimethyl-silyl-(2-phenyl-1H-inden-1-yl)(2,3,4,5-tetramethylcyclopentan-2,4-dienyl)zirconium dichloride, dimethyl-silyl-(2-methyl-4-phenyl-1-H-inden-1-yl)(2,3,4,5-tetramethylcyclopentan-2,4-dienyl)zirconium dichloride, dimethyl-silyl-(3-phenyl-1-H-inden-1-yl)(2,3,4,5-tetramethylcyclopentan-2,4-dienyl)zirconium dichloride (Methylcyclopentan-2,4-dienyl)zirconia dichloride, (2-isopropyl-1H-inden-1-yl)dimethyl-silyl-(2,3,4,5-tetramethylcyclopentan-2,4-dienyl)zirconia dichloride, (1H-inden-2-yl)dimethyl(2,3,4,5-tetramethyl-cyclopentan-2,4-dienyl)zirconia dichloride, dimethyl-silyl-(1-methyl-2-phenyl-1-H-inden-3-yl)(2,3,4,5-tetramethyl-cyclopentan-2,4-dienyl)zirconia dichloride, dimethyl-silyl-(1-methyl-2-phenyl-1-H-inden-3-yl)zirconia dichloride, dimethyl-silyl-(1-methyl-2-phenyl-1-yl)-(2,3,4,5-tetramethyl-cyclopentan-2,4-dien ...2,3,4,5-tetramethyl-1-phenyl-1-yl)-(2,3,4,5-tetramethyl-cyclopentan-2,4-dienyl)zirconia dichloride, dimethyl-silyl-(2,3,4,5-tetramethyl-1-phenyl-1-yl)-(2,3, Hafnium dichloride (H-inden-3-yl)(2,3,4,5-tetramethyl-cyclopentan-2,4-dienyl), (1H-inden-2-yl)dimethyl-silyl-(2,3,4,5-tetramethyl-cyclopentan-2,4-dienyl)hafnium dichloride, dimethyl-silyl-(2-phenyl-1H-inden-1-yl)(2,3,4,5-tetramethylcyclopentan-2,4-dienyl)hafnium dichloride, dimethyl-silyl-(2-methyl-4-phenyl-1-H-inden-1-yl)(2,3,4,5-tetramethylcyclopentan-2,4-dienyl)hafnium dichloride, dimethyl-silyl-(3-phenyl-1-H-inden-1-yl)(2,3,4,5- Hafnium dichloride is composed of tetramethylcyclopentan-2,4-dienyl)(2-isopropyl-1H-inden-1-yl)dimethyl-silyl-(2,3,4,5-tetramethyl-cyclopentan-2,4-dienyl)hafnium dichloride and dimethylsilyl-(2,5-dimethyl-7H-cyclopentan[1,2-b;4,3-b']dithiophene-7-yl)-(2,4,7-trimethyl-1H-inden-1-yl)-zirconium dichloride, among which dimethylsilyl-bis-(1-indenyl)-zirconium dichloride (IV), racemic-1,2-ethylenebis(indenyl)-zirconium dichloride (IV), and racemic-1,2-ethylenebis(tetrahydroindenyl)-zirconium dichloride (IV) (CAS) 100 163 29-9), racemic-dimethylsilyl-bis-(1-indenyl)-zirconium dichloride (IV), and racemic-di-racemic-dimethylsilyl-bis-(1-tetrahydroindenyl)-zirconium dichloride (IV) (CAS 126642-97-5) are even more preferred.

[0030] Within the meaning of this invention, contact can occur with or without active mixing, wherein active mixing is preferred and includes, for example, stirring or sonic-assisted mixing or any other technique known to those skilled in the art.

[0031] Contact can last from 1 minute to 168 hours, preferably 30 minutes to 48 hours. Longer durations generally do not provide any additional benefit.

[0032] The temperature during the contact can be, for example, -20°C up to the boiling point of the lowest boiling point component of the reaction mixture obtained by contact at the selected contact pressure, preferably 15°C to 70°C.

[0033] The pressure during contact is, for example, 500 hPa to 5 MPa, preferably ambient pressure.

[0034] In another step B), the desired racemic compound of formula (I) is separated from the reaction mixture obtained according to the invention by contacting a mixture comprising a compound of formula (I) in both racemic and meso forms thereof and an organic solvent containing at least one ether and at least one auxiliary compound.

[0035] Such separation can be achieved through the following methods:

[0036] i) Optionally, partially remove the organic solvent and / or the at least one auxiliary compound.

[0037] ii) Separating solids present in the reaction mixture or formed during partial removal of the solvent and / or at least one auxiliary compound.

[0038] Techniques known to those skilled in the art, including sedimentation, centrifugation, filtration, or decantation.

[0039] Without being bound by theory, it is assumed that the auxiliary compound can isomerize the compound having formula (I) by forming intermediate five- or six-coordinate metal complexes and thereby shifting the equilibrium toward the racemic form of the compound having formula (I) which is usually less soluble.

[0040] In one embodiment, a mixture comprising a compound of formula (I) in both racemic and meso forms and an organic solvent containing at least one ether, and used in the present invention, is prepared by adding the organic solvent to solid compounds of formula (I) present in a mixture of their racemic and meso forms, for example comprising 10 to 95 wt.% of the racemic form relative to the total amount of compounds of formula (I), preferably 50 to 90 wt.%.

[0041] In another embodiment, a mixture comprising a compound of formula (I) in its racemic and meso forms, and an organic solvent containing at least one ether, and used in this invention, is prepared by the following...

[0042] a) To make compounds having formula (II) (II), Among them, L and R 1 and R 2 It has the meaning defined in the above formula (I). The reaction involves reacting 1.5 to 2.5 mol equivalents, preferably 1.8 to 2.2 mol equivalents, more preferably 1.9 to 2.1 mol equivalents, and even more preferably 1.95 to 2.10 mol equivalents, of at least one organolithium compound in the presence of at least one ether, wherein the organolithium compound is used in the form of a solution in an aliphatic or aromatic solvent, wherein the at least one ether is preferably selected from the group consisting of tetrahydrofuran, methyltetrahydrofuran, dioxane, dimethoxyethane, diethoxymethane, tert-amyl methyl ether, or mixtures thereof, preferably tetrahydrofuran, methyltetrahydrofuran, or mixtures thereof, and even more preferably tetrahydrofuran. The mol ratio of the one or more ethers used to the compound having formula (II) is 5 to 70, preferably 15 to 50, and more preferably 20 to 35, and the mol ratio of the one or more ethers used to the total amount of the aliphatic or aromatic solvent forming a portion of the solution of the one or more organolithium compounds is at least 100, preferably 100 to 500, more preferably 100 to 400, and even more preferably 150 to 400. b) Subsequently react with a compound having formula (III) (D)2M(X)4 in M and X have the meanings defined for compounds having formula (I). and The absence of D indicates that a monoether is preferably tetrahydrofuran, a tertiary amine is preferably trimethylamine or tetramethylethylenediamine (TMEDA), or (D)2 represents a diether as a whole, preferably dioxane, dimethoxyethane, or diethoxymethane.

[0043] In step a), a compound having formula (II) as defined above is used.

[0044] Preferred compounds having formula (II) include 1,2-bisindenylethane, bis-(1-indenyl)-dimethyl-silane, (1H-inden-2-yl)dimethyl(2,3,4,5-tetramethylcyclopentan-2,4-dienyl)-silane, dimethyl(2-phenyl-1H-inden-1-yl)(2,3,4,5-tetramethylcyclopentan-2,4-dienyl)silane, dimethyl(2-methyl-4-phenyl-1H-inden-1-yl)(2,3,4,5-tetramethylcyclopentan-2,4-dienyl)silane, dimethyl(3-phenyl-1-H-inden-1-yl)(2,3,4,5-tetramethylcyclopentan-2,4-dienyl)silane, and (2-isopropyl-1H-inden-1-yl)dimethyl(2,3,4,5-tetramethylcyclopentan-2,4-dienyl)silane. 4,5-Tetramethylcyclopentan-2,4-dienyl)silane, (1H-inden-2-yl)dimethyl(2,3,4,5-tetramethylcyclopentan-2,4-dienyl)silane, dimethyl(1-methyl-2-phenyl-1-H-inden-3-yl)(2,3,4,5-tetramethylcyclopentan-2,4-dienyl)silane, dimethyl-bis(2-methylindenyl)silane, dimethyl-bis(2-methyl-4-phenylindenyl)silane, dimethyl-bis[2-methyl-4-(1-naphthyl)indenyl])silane, dimethyl-bis(2-methyl-4,5-benzoindenyl))silane, dimethyl-bis(2-methyl-4,6-diisopropylindenyl))silane, dimethyl-bis(2-ethylindenyl))silane )silane, dimethyl-bis(2-ethyl-4-phenylindenyl)silane, dimethyl-bis[2-ethyl-4-(1-naphthyl)indenyl]silane, dimethyl-bis(2-ethyl-4,5-benzoindenyl)silane, dimethyl-bis(4,5-benzoindenyl)silane, dimethyl-bis(2-ethyl-4,6-diisopropylindenyl)silane, dimethyl-bis(2-ethyl-4,6-dimethylindenyl)silane, dimethyl-bis(2,4,6-trimethylindenyl)silane, (2,5-dimethyl-7H-cyclopenta[1,2-b;4,3-b']dithiophene-7-yl)-dimethyl-(2,4,7-trimethyl-1H-inden-1-yl)-silane, Bis-(1-indenyl)-dimethyl-silane is even more preferred.

[0045] The compound having formula (II) is reacted with a solution of an organolithium compound. Suitable organolithium compounds include phenyllithium, n-butyllithium, sec-butyllithium, tert-butyllithium, and n-hexyllithium, with n-butyllithium being preferred. Solvents used for such organolithium compounds include benzene, toluene, and alkanes such as hexane.

[0046] The preferred commercially available solution is a 10 M solution of n-butyllithium in hexane.

[0047] The method according to the invention can be carried out in batches or continuously, preferably in batches.

[0048] The reaction or residence time in step a) is, for example, 5 minutes to 12 hours, preferably 10 minutes to 4 hours.

[0049] The reaction or residence time in step b) is, for example, 30 minutes to 24 hours, preferably 30 minutes to 6 hours.

[0050] In one embodiment, step a) is performed such that a compound having formula (II) is mixed with the one or more ethers to form a solution, and a solution of an organolithium compound is added to the resulting solution. This addition can occur in one step or in batches, with batch addition being preferred to maintain complete control over the reaction temperature.

[0051] In step b), a compound having formula (III) is added to the reaction mixture obtained according to step a). This addition can occur in one step or in batches, with one-time addition being preferred.

[0052] The addition in step b) can occur all at once or in batches, with batch addition being preferred to maintain complete control over the reaction temperature.

[0053] The processes according to steps a) and b) can be carried out, for example, in any reactor that allows operation under inert conditions known to those skilled in the art. Inert conditions should specifically include operation under a nitrogen and / or rare gas atmosphere and in the absence of moisture. Suitable reactor types include stirred double-walled glass reactors, stirred stainless steel reactors, carbon steel reactors, and Hastelloy reactors.

[0054] Step a) is carried out at a reaction temperature, for example -80°C to 30°C, preferably -20°C to 30°C, more preferably -10°C to 25°C.

[0055] Step b) is carried out at a reaction temperature, for example -20°C to 80°C, preferably -10°C to 50°C, and more preferably 0°C to 25°C.

[0056] The reaction pressure is not known to be important and can be, for example, 10 kPa to 10 MPa, with ambient pressure being preferred.

[0057] In step b), a compound having formula (I) is formed.

[0058] The preferred compounds having formula (I) are those mentioned above. Detailed Implementation

[0059] The following examples are intended to illustrate the present invention, but the invention is not limited thereto.

[0060] Experimental Section

[0061] Overview

[0062] Acetyl chloride was obtained from VWR Germany and used as is.

[0063] ZrCl4 and HfCl4 used in this paper were obtained commercially from VWR GmbH, Germany, and used as is. Tetrahydrofuran (THF) and toluene used in this paper were obtained commercially from Möller Chemie Germany, Germany, and used as is.

[0064] The n-butyllithium used in this paper was commercially obtained from Albemarle Germany and used as is. The bis-indenylsilane was obtained according to the procedure described in PCT International Application (1999) WO 9905152 A1 19990204. All operations were performed using Schlenk-based preparation techniques.

[0065] A) Reactor

[0066] All experiments were conducted in a double-walled 2 L glass reactor equipped with a stainless steel paddle stirrer, connected to a protective gas flow and peripheral devices for adding solid and liquid compounds. The reactor was connected to a Petite Fleur cryostat from Huber Germany.

[0067] C) Product Analysis

[0068] The product was analyzed using a Bruker Avance II+ 400 NMR spectrometer. 1 H-NMR experiments were performed using a suitable pre-dried deuterated solvent. Zr and LiCl contents were measured using a Pectro Arcos / Blue or Agilent 7700 ICP-OES after appropriate acid-base oxidation decomposition of the metallocene. Cl content was measured by potentiometric titration using a Mettler Toledo T90 with a Mettler DM141-SC.

[0069] Preparation Examples

[0070] Comparison Examples

[0071] 86.6 g of bisindenylsilane (96% purity, 288.2 mmol, 1 equivalent) was dissolved in 649.5 g of THF and cooled to -5°C. 41.7 g of n-butyllithium (90.8% by mass, 590.8 mmol, 2.05 equivalents of active material) was added, keeping the internal temperature below 5°C. After addition, the mixture was heated to 20°C and stirred at 20°C for at least 30 minutes. The solution was then cooled to 0°C.

[0072] Meanwhile, 68.8 g of ZrCl4 (295.4 mmol, 1.03 equivalents) was suspended in 172 g of toluene, and 127.8 g of THF (1772 mmol, 6.15 equivalents) was added at 0°C to 10°C. The mixture was stirred at 20°C for 1 hour and then added in a single batch to deprotonated bisindenylsilane at 0°C. After the addition was complete, the solution was heated to 20°C and stirred at 20°C to 25°C for 10 hours. An orange precipitate settled over 2 hours, and 1000 ml of the supernatant was removed. 300 g of THF was added to the orange solid, and the mixture was stirred at 20°C for 1 hour. The product was separated by filtration, washed three times with 100 g of THF each time, and dried under vacuum.

[0073] Yield: 49.5 g / 38% / 100% racemic isomer

[0074] 1 H-NMR (400MHz, CDCl3): δ (ppm) = 1.13 (s, 6H, Si(C H 3)), 6.09 (d, 2H,J3 = 3.2 Hz, C H C5 ), 6.92 (d, 2H, J3 = 3.2 Hz, C H C5 ), 7.07-7.11 (m, 2H, C H -芳香 ), 7.35-7.37 (m, 2H, C H 芳香 ), 7.49 (d, 2H, J3 = 8.8 Hz, C H 芳香 ), 7.57 (d, 2H, J3 = 8.8 Hz, C H -芳香 )

[0075] Elemental analysis: Cl content 15.9% by mass, Zr content 20.4% by mass, LiCl content 0.01% by mass.

[0076] Example 1 of the present invention

[0077] 40.0 g of bis(indene)ethane (99.7% purity, 154.4 mmol, 1 equivalent) was dissolved in 300 g of THF and cooled to -5°C. 22.3 g of n-butyllithium (91.0% by mass, 316.5 mmol, 2.05 equivalents of active material) was added while maintaining an internal temperature not exceeding 25°C. After the addition was complete, the mixture was heated to 50°C and stirred at 50°C for at least 60 minutes. The solution was then cooled to 0°C.

[0078] At the same time, 49.5 g of ZrCl4 2. A THF complex (131.2 mmol, 0.85 equivalents) was suspended in 100 g THF. The mixture was stirred at 20°C for 1 hour, and a deprotonated bis(indenylethane) solution was added to the suspension in a single step at 0°C. After the addition was complete, the solution was heated to 20°C and stirred at 20°C for 1 hour, then heated to 50°C and stirred at 50°C for another 4 hours. During cooling to 20°C, 3.0 g acetyl chloride (38.6 mmol, 0.25 equivalents) was added, and the reaction was stirred at 20°C for 8 hours.

[0079] The yellow precipitate settled, and the product was separated by filtration, washed three times with 100 g of THF each time, and dried in a vacuum.

[0080] Yield: 30.3 g / 55% / 100% racemic isomer

[0081] 1 H-NMR (400MHz, CDCl3): δ (ppm) = 3.73-3.81 (m, 4H, C H 2-C H 2 ), 6.22 (d,2H, J3 = 3.2 Hz C H C5 ), 6.61 (d, 2H, J3 = 2.8 Hz, C H C5 ), 7.20-7.36 (m, 4H,C H 芳香 ), 7.49 (d, 2H, J = 8.8 Hz, CH 芳香 ), 7.67 (d, 2H, J = 8.4 Hz, C H -芳香 ), Elemental analysis: Cl content 16.2% by mass, Zr content 21.2% by mass, LiCl content 0.5% by mass.

[0082] ZrCl4 Preparation of 2THF complex

[0083] 233.3 g of ZrCl4 was suspended in 485 mL of dichloromethane, and 485 mL of THF was slowly added at 0°C to 5°C. After the addition, the mixture was stirred at 20°C to 25°C for one hour, and then the dichloromethane was removed. 375 mL of hexane was added to the nearly dried remaining suspension, and ZrCl4 was separated by filtration. The 2THF complex was obtained and then dried under vacuum. The separated product was used without further analysis.

Claims

1. A method for preparing compounds of formula (I) in their racemic form. (I) in L represents the choice of free choice -Si(R) 3 )2-、-C(R 3 )2-、-C(R 3 )2C(R 3 )2- and BR 3 - Connecting base of the group in R 3 In -C(R) 3 )2- and -C(R 3 )2C(R 3 In the case of )2-, it represents hydrogen, alkyl, or phenyl, and In -Si(R 3 )2- and BR 3 In the case of alkyl or phenyl, or Two residues R 3 When present, they collectively represent alkane-di-yl. Wherein R is preferred 3 In -C(R) 3 In the case of )2-, it represents hydrogen, methyl, or phenyl, and In -C(R) 3 )2C(R 3 In the case of )2-, it represents hydrogen. In -Si(R 3 )2- and BR 3 In the case of methyl or ethyl R 1 and R 2 Each of the residues independently represents hydrogen, alkyl, phenyl, or naphthyl, which may optionally be further substituted by alkyl or phenyl once, twice, or more than twice, or two adjacent residues R. 1 Or two adjacent residues R 2 Residues together with and independent of another cyclopentadienyl moiety represent a benzene or thiophene ring fused to the cyclopentadienyl moiety, wherein the fused benzene or thiophene ring is further substituted by one, two, three, or four phenyl or alkyl substituents or is not further substituted. The premise is that R is selected. 1 and R 2 This allows them to form racemic and meso forms of compounds having formula (I). M represents a lanthanide element, chromium, molybdenum, tungsten, titanium, zirconium, or hafnium, preferably lanthanum, cerium, neodymium, chromium, molybdenum, tungsten, zirconium, or hafnium, more preferably zirconium, or chromium, or molybdenum, or tungsten, even more preferably zirconium or hafnium. X represents a halide such as a fluoride, chloride, bromide, or iodide, preferably a fluoride, chloride, or bromide, and more preferably a fluoride or chloride, or represents an alkoxy group having the formula OR, wherein R represents a C1-C8-alkyl group that may be substituted once or twice with a phenyl group, which may optionally be further substituted once, twice, or more than twice with a C1-C4-alkyl group or a phenyl group, preferably R represents a methyl or ethyl group. The method includes the following steps A) Contacting a mixture of a compound of formula (I) in its racemic and meso forms and an organic solvent containing at least one ether with at least one auxiliary compound selected from the group consisting of acyl chlorides, esters and nitriles.

2. The method according to claim 1, wherein, These auxiliary compounds are selected from the group consisting of the following acyl chlorides: (C1-C8-alkyl)-(C=O)Cl, preferably acetyl chloride; Or the following esters: (C1-C8-alkyl)-(C=O)-O(C1-C8-alkyl), preferably ethyl acetate; or the following nitriles: (C1-C8-alkyl)-CN, benzonitrile and benzylnitrile, wherein acetonitrile is preferred.

3. The method according to claim 1 or 2, wherein, The auxiliary compound is acetyl chloride.

4. The method according to any one of claims 1 to 3, wherein, These compounds having formula (I) are selected from the group consisting of: Racemic-1,2-ethylenebis(indenyl)-hafnium dichloride (IV), Racemic-1,2-ethylenebis(tetrahydroindenyl)-zirconium dichloride (IV) (CAS 100 163 29-9). Racemic-1,2-ethylenebis(tetrahydroindenyl)-hafnium dichloride (IV), racemic-dimethylsilyl-bis-(1-indenyl)-zirconium dichloride (IV), Racemic-diracemic-dimethylsilyl-bis-(1-tetrahydroindenyl)-zirconium dichloride (IV) (CAS 126642-97-5). Racemic-diracemic-dimethylsilyl-bis-(1-tetrahydroindenyl)-hafnium(IV) dichloride Racemic-dimethylsilyl-bis(2-methylindenyl)zirconium dibromide, Racemic-dimethylsilyl-bis(2-methyl-4-phenylindenyl)zirconium dichloride, Racemic-dimethylsilyl-bis[2-methyl-4-(1-naphthyl)indenyl]zirconium difluoride, Racemic-dimethylsilyl-bis[2-methyl-4-(1-naphthyl)indenyl]hafnium dichloride, Racemic-dimethylsilyl-bis(2-methyl-4,5-benzoindenyl)zirconium dichloride Racemic-dimethylsilyl-bis(4,5-benzoindenyl)zirconium dichloride Racemic-dimethylsilyl-bis(2-methyl-4,6-diisopropylindenyl)zirconium difluoride Racemic-dimethylsilyl-bis(2-ethylindenyl)zirconium dichloride Racemic-dimethylsilyl-bis(2-ethyl-4-phenylindenyl)zirconium dichloride, Racemic-dimethylsilyl-bis(2-ethyl-4-phenylindenyl)hafnium dichloride, Racemic-dimethylsilyl-bis[2-ethyl-4-(1-naphthyl)indenyl]zirconium dichloride, Racemic-dimethylsilyl-bis(2-ethyl-4,5-benzoindenyl)zirconium dichloride Racemic-dimethylsilyl-bis(4,5-benzoindenyl)zirconium dichloride Racemic-dimethylsilyl-bis(2-ethyl-4,6-diisopropylindenyl)zirconium dichloride, Racemic-dimethylsilyl-bis(2-ethyl-4,6-dimethylindenyl)zirconium dichloride, Racemic-dimethylsilyl-bis(2,4,6-trimethylindenyl)zirconium dichloride, Racemic-dimethylsilyl-bis(2,4,6-trimethylindenyl)hafnium dichloride, (1H-inden-2-yl)dimethyl-silyl-(2,3,4,5-tetramethylcyclopentan-2,4-dienyl)zirconium dichloride, dimethyl-silyl-(2-phenyl-1H-inden-1-yl)(2,3,4,5-tetramethylcyclopentan-2,4-dienyl)zirconium dichloride, dimethyl-silyl-(2-methyl-4-phenyl-1-H-inden-1-yl)(2,3,4,5-tetramethylcyclopentan-2,4-dienyl)zirconium dichloride, dimethyl-silyl-(3-phenyl-1-H-inden-1-yl)(2,3,4,5-tetramethylcyclopentan-2,4-dienyl)zirconium dichloride (Methylcyclopentan-2,4-dienyl)zirconia dichloride, (2-isopropyl-1H-inden-1-yl)dimethyl-silyl-(2,3,4,5-tetramethylcyclopentan-2,4-dienyl)zirconia dichloride, (1H-inden-2-yl)dimethyl(2,3,4,5-tetramethyl-cyclopentan-2,4-dienyl)zirconia dichloride, dimethyl-silyl-(1-methyl-2-phenyl-1-H-inden-3-yl)(2,3,4,5-tetramethyl-cyclopentan-2,4-dienyl)zirconia dichloride, dimethyl-silyl-(1-methyl-2-phenyl-1-H-inden-3-yl)zirconia dichloride, dimethyl-silyl-(1-methyl-2-phenyl-1-yl)-(2,3,4,5-tetramethyl-cyclopentan-2,4-dien ...2,3,4,5-tetramethyl-1-phenyl-1-yl)-(2,3,4,5-tetramethyl-cyclopentan-2,4-dienyl)zirconia dichloride, dimethyl-silyl-(2,3,4,5-tetramethyl-1-phenyl-1-yl)-(2,3, Hafnium dichloride (H-inden-3-yl)(2,3,4,5-tetramethyl-cyclopentan-2,4-dienyl), (1H-inden-2-yl)dimethyl-silyl-(2,3,4,5-tetramethyl-cyclopentan-2,4-dienyl)hafnium dichloride, dimethyl-silyl-(2-phenyl-1H-inden-1-yl)(2,3,4,5-tetramethylcyclopentan-2,4-dienyl)hafnium dichloride, dimethyl-silyl-(2-methyl-4-phenyl-1-H-inden-1-yl)(2,3,4,5-tetramethylcyclopentan-2,4-dienyl)hafnium dichloride, dimethyl-silyl-(3-phenyl-1-H-inden-1-yl)(2,3,4,5- Hafnium dichloride is composed of tetramethylcyclopentan-2,4-dienyl)(2-isopropyl-1H-inden-1-yl)dimethyl-silyl-(2,3,4,5-tetramethyl-cyclopentan-2,4-dienyl)hafnium dichloride and dimethylsilyl-(2,5-dimethyl-7H-cyclopentan[1,2-b;4,3-b']dithiophene-7-yl)-(2,4,7-trimethyl-1H-inden-1-yl)-zirconium dichloride, among which dimethylsilyl-bis-(1-indenyl)-zirconium dichloride (IV), racemic-1,2-ethylenebis(indenyl)-zirconium dichloride (IV), and racemic-1,2-ethylenebis(tetrahydroindenyl)-zirconium dichloride (IV) (CAS) 100 163 29-9), racemic-dimethylsilyl-bis-(1-indenyl)-zirconium dichloride (IV), and racemic-di-racemic-dimethylsilyl-bis-(1-tetrahydroindenyl)-zirconium dichloride (IV) (CAS 126642-97-5) are even more preferred.

5. The method according to any one of claims 1 to 4, wherein, The contact lasts from 1 minute to 168 hours, preferably from 30 minutes to 48 hours.

6. The method according to any one of claims 1 to 5, wherein, The contact occurs at a temperature from -20°C up to the boiling point of the lowest boiling point component of the reaction mixture obtained by the contact at the selected contact pressure, preferably from 15°C to 70°C.

7. The method according to any one of claims 1 to 6, wherein, This contact occurs under pressures of 500 hPa to 5 MPa, preferably under ambient pressure.

8. The method according to any one of claims 1 to 7, wherein, In a further step B), the desired racemic compound of formula (I) is separated from the reaction mixture obtained from the contact of the mixture comprising a compound of formula (I) in both racemic and meso forms, an organic solvent containing at least one ether, and at least one auxiliary compound.

9. The method according to claim 8, wherein, This separation is achieved through the following i) Optionally, partially remove the organic solvent and / or the at least one auxiliary compound. ii) Separate the solids present in the reaction mixture or formed during partial removal of the solvent and / or the at least one auxiliary compound. Through sedimentation, centrifugation, filtration, or decantation.

10. The method according to any one of claims 1 to 9, wherein, These mixtures, comprising compounds of formula (I) in both racemic and meso forms and an organic solvent containing at least one ether, and used in the method according to any one of claims 1 to 9, are prepared by adding the organic solvent to solid compounds of formula (I) present in a mixture of their racemic and meso forms, for example comprising 10 to 95 wt.% of the racemic form relative to the total amount of compounds of formula (I), preferably 50 to 90 wt.%.

11. The method according to any one of claims 1 to 10, wherein, These mixtures, comprising compounds of formula (I) in their racemic and meso forms, and an organic solvent containing at least one ether, and used in this invention, are prepared by the following... a) Make compounds having formula (II) (II), Among them, L and R 1 and R 2 It has the meaning defined in claim 1 for formula (I) above. The reaction involves reacting 1.5 to 2.5 mol equivalents, preferably 1.8 to 2.2 mol equivalents, more preferably 1.9 to 2.1 mol equivalents, and even more preferably 1.95 to 2.10 mol equivalents, of at least one organolithium compound in the presence of at least one ether, wherein the organolithium compound is used in the form of a solution in an aliphatic or aromatic solvent, wherein the at least one ether is preferably selected from the group consisting of tetrahydrofuran, methyltetrahydrofuran, dioxane, dimethoxyethane, diethoxymethane, tert-amyl methyl ether, or mixtures thereof, preferably tetrahydrofuran, methyltetrahydrofuran, or mixtures thereof, and even more preferably tetrahydrofuran. The mol ratio of the one or more ethers used to the compound having formula (II) is 5 to 70, preferably 15 to 50, and more preferably 20 to 35, and the mol ratio of the one or more ethers used to the total amount of the aliphatic or aromatic solvent forming a portion of the solution of the one or more organolithium compounds is at least 100, preferably 100 to 500, more preferably 100 to 400, and even more preferably 150 to 400. b) Subsequently react with a compound having formula (III) (D)2M(X)4 in M and X have the meanings defined for compounds having formula (I). and The absence of D indicates that the monoether is preferably tetrahydrofuran, the tertiary amine is preferably trimethylamine or tetramethylethylenediamine (TMEDA), or (D)2 represents a diether as a whole, preferably dioxane, dimethoxyethane, or diethoxymethane.

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