EP0986567A1 - Complexes metallocenes exempts d'enantiomeres, leur preparation et leur utilisation - Google Patents

Complexes metallocenes exempts d'enantiomeres, leur preparation et leur utilisation

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Publication number
EP0986567A1
EP0986567A1 EP98925604A EP98925604A EP0986567A1 EP 0986567 A1 EP0986567 A1 EP 0986567A1 EP 98925604 A EP98925604 A EP 98925604A EP 98925604 A EP98925604 A EP 98925604A EP 0986567 A1 EP0986567 A1 EP 0986567A1
Authority
EP
European Patent Office
Prior art keywords
cio
alkyl
cyclopentadienyl
zirconium dimethyl
butyl
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP98925604A
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German (de)
English (en)
Inventor
Markus Ringwald
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
MCAT GMBH
Original Assignee
Individual
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from DE1997120592 external-priority patent/DE19720592A1/de
Application filed by Individual filed Critical Individual
Publication of EP0986567A1 publication Critical patent/EP0986567A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F17/00—Metallocenes

Definitions

  • the invention relates to enantiomerically pure metallocene complexes, a process for their preparation and their use.
  • the disadvantage is the sometimes difficult separation of the desired product, which is usually done chromatographically or by crystallization.
  • the invention is therefore based on the object of providing a way to enantiomerically pure metallocene complexes by means of which the abovementioned disadvantages of the prior art can be overcome.
  • the aim is to provide a process which is as simple as possible but also universally applicable and which also enables the production of relatively large amounts of enantiomerically pure metallocene complexes in good yield.
  • the racemic complex has a C 2 axis as the symmetry element and is therefore chiral, ie the racemate consists of enantiomers that behave like images and mirror images, whereas the meso compound is achiral due to a mirror plane in the molecule.
  • Particularly suitable metallocene complexes which can be used in the process according to the invention are those of the general formula I.
  • Ci to Cio in particular Ci, C 2 -, C 3 - or C 4 -alkyl, C 6 - to C ⁇ 5 -aryl, alkylaryl having from 1 to 10, in particular 1, 2, 3 or 4 C Atoms in the alkyl radical and 6 to 20 carbon atoms in the aryl radical, -OR 11 or NR n R 12 ,
  • R X1, R 12 Ci to Cio in particular Ci, C 2 -, C 3 - or C 4 - alkyl, C 6 - to C ⁇ 5 -aryl, alkylaryl, arylalkyl, fluoroalkyl or fluoroaryl each having from 1 to 10, in particular with 1, 2, 3 or 4 carbon atoms in the alkyl radical and 6 to 20 carbon atoms in the aryl radical,
  • n is an integer between 1 and 4, where n is the valence of M minus the number 2
  • R - ⁇ - R 10 are identical or different hydrogen, C x - to C 20 , in particular Ci-, C 2 -, C 3 - or C-alkyl, 3- to 8-membered cycloalkyl, - which in turn is a Ci to Cio , especially CT .
  • C 2 -, C 3 - or C 4 -alkyl can carry as a substituent -, C 6 - to C 5 -aryl, arylalkyl having 1 to 10, in particular 1 to 4, carbon atoms in the alkyl radical and 6 to 20 C- Atoms in the aryl radical or arylalkyl with 1 to 10 carbon atoms in the alkyl radical and 6 to 20 carbon atoms in the aryl radical, where adjacent radicals together can represent cyclic groups having 4 to 15 carbon atoms, or Si (R 13 ) 3 with R 3 the same or different Ci to Cio, in particular Ci, C 2 , C 3 or C 4 alkyl, C 6 to C 5 aryl or C 3 to Cio cycloalkyl,
  • R 2 , R 6 together can form a grouping [[T (R 14 ) (R 15 )] q - in which
  • T can be the same or different and stands for silicon, germanium, tin or carbon,
  • R 14 , R 15 may be the same or different and
  • Ci to Cio in particular C 1 ⁇ , C 2 -, C 3 - or C 4 -alkyl, C 6 - to C 5 -aryl or C 3 - to Cio-cycloalkyl, alkylaryl or Si (R 16 ) 3 mean ,
  • q represents the numbers 1, 2, 3, or 4
  • R 16 , R 17 , R 18 are the same or different and a hydrogen atom, a halogen atom, a Ci- to C ⁇ 0 - alkyl, in particular Ci-, C 2 -, C 3 - or C-alkyl, d- to Cio , in particular Ci-, C 2 -, C 3 - or C-fluoroalkyl, a C x - to Cio, in particular C ⁇ ⁇ , C 2 -, C 3 or C 4 alkoxy group, a C 6 - to C ⁇ 0 - aryl group , C_- to C ⁇ 0 aryloxy group, a C 6 - to Cio-fluoroaryl group, a C 2 -
  • the metallocene complexes according to the invention can be bridged, but need not be.
  • a high rotation barrier, in particular in the temperature range from 20 to 80 ° C., (which can be determined using the method of NMR spectroscopy) of the cyclopentadienyl-type ligands in metallocenes is sufficient so that the metallocene complexes can be isolated directly in their enantiomerically pure form without them being isolated can convert to the racemic and / or meso form.
  • the rotation barrier that ensures this is usually above 20 kJ / mol, preference is given to values of 25 kJ / mol, better still values of 30 kJ / mol or more.
  • metallocenes with bridged ring ligands have proven particularly useful.
  • Particularly suitable ansa-metallocene complexes of the general formula I are those in which
  • M stands for titanium, zirconium or hafnium
  • X is Ci to C 6 alkyl
  • R 7 -R 10 for hydrogen, d- to C 6 -alkyl, 5- to 7-membered cycloalkyl, which in turn can carry a Ci- to Cio-alkyl as a substituent, C 3 - to C ⁇ 5 - aryl or arylalkyl, wherein optionally two adjacent residues together for 4 to 15, in particular there are cyclic groups containing 8 to 12 carbon atoms,
  • R 2 , R 6 together form a grouping - [T (R 14 ) (R 15 )] q - in which
  • T silicon or carbon
  • R, R 15 represent hydrogen or methyl
  • q represents the numbers 1 or 2.
  • Dimethylsilanediylbis (2-methyl-4- t- butyl-l-cyclopentadienyl) zirconium dimethyl
  • Dimethylsilanediylbis (2-methyl-4-trimethylsilyl-l-cyclopentadienyl) zirconiumdimethyl
  • Dimethylsilanediylbis (2-methyl-4-phenyl-1-cyclopentadienyl) zirconium dimethyl
  • Dimethylsilanediylbis (2- 1 butyl-4-naphthyl-l-indenyl) zirconium dimethyl
  • Dimethylsilanediylbis (2- t- butyl-4-naphthyl-l-indenyl) zirconium dimethyl
  • Dimethylsilanediylbis (2-trimethylsilyl-4-naphthyl-l-indenyl) zirconium dimethyl.
  • Dimethylsilanediylbis (1-cyclopentadienyl-9, 10-phenanthrene) zirconium dimethyl
  • the synthesis of the metallocene compounds can be carried out according to methods known per se, the reaction of the appropriately substituted cyclic hydrocarbon anions, for. B. with the halides or A iden of titanium, zirconium, hafnium, vanadium, niobium or tantalum is preferred. Examples are in H. Wiesenfeldt, A. Reinmuth, E. Barsties, K. Evertz, H.-H. Brintzinger, Journal Organometallic Chem., 369 (1989) pp. 359-370 or in GM Diamond, RF Jordan, Organometallics 15 (1996) pp. 4045-4053.
  • the metallocene starting material is reacted with an enantiomeric auxiliary reagent, which does not necessarily mean a stoichiometric conversion. Rather, the molar ratio of enantiomerically pure auxiliary reagent to metallocene complex can be varied as required. It is preferably 0.1: 1 to 10: 1 and in particular 0.5: 1 to 1.5: 1. Stoichiometric reactions have given particularly good results.
  • Bifunctional auxiliary reagents have proven particularly useful. These include in particular dialcohols, dialcoholates, dimercaptans or diamines. Mixed systems, i.e. those with different functionality can be used as well as mixtures of different auxiliary reagents.
  • Dialcohols which derive from the general formula (II) should be mentioned in particular R22 R19 R21 s
  • R 19 to R 22 are identical or different hydrogen
  • Ci to Cio alkyl or C 6 to Cis aryl, R 23 and R 24 are identical or different hydrogen,
  • R 25 to hydrogen, fluorine, chlorine, bromine, iodine, Ci to C ⁇ 0 - R 34 alkyl or C 6 - to C ⁇ 5 aryl, Ci to C ⁇ 0 , in particular Ci, C 2 or C 3 fluoroalkyl or C 6 to C ⁇ 5 -Fluoraryl, -OR 35 or Si (R 35 ) 3 with
  • R 36_ R 55 hydrogen, fluorine, chlorine, bromine, iodine, Ci to C ⁇ 0 - alkyl or C 6 - to C ⁇ 5 aryl, Ci to Cio, in particular Ci, C 2 or C 3 fluoroalkyl or C 6 to C ⁇ 5- fluoroaryl,
  • R 56 Ci- to Cio-alkyl, C 6 - to C ⁇ 5 aryl or C 3 - to C ⁇ 0 - cycloalkyl
  • R, R are identical or different fluorine, chlorine, bromine, iodine, Ci- to C 20 -alkyl, 3- to 8-membered cycloalkyl, which in turn is a Ci- to Cio-alkyl
  • Ci- to Cio-alkyl Can carry substituent -, C 6 - to cis-aryl, alkylaryl with 1 to 10 C atoms in the alkyl radical and 6 to 20 C atoms in the aryl radical, arylalkyl with 1 to 10 C atoms in the alkyl radical and 6 to 20 C atoms in the aryl radical, Si (R 65 ) 3 with R 65 identical or different Ci to C 20 alkyl C 3 - to Cio-cycloalkyl, C 6 - to C ⁇ 5 - aryl, the said radicals being partially or completely substituted with heteroatoms can
  • R 57 -R_ identical or different hydrogen, fluorine, chlorine, and bromine, iodine, Ci to C 20 alkyl, 3- to 8-membered R 62 -R 64 cycloalkyl, - which in turn can carry a Ci to Cio alkyl as a substituent - , C 6 - to Cis-aryl, alkylaryl with 1 to 10 carbon atoms in the alkyl radical and 6 to 20 carbon atoms in the aryl radical, arylalkyl with 1 to 10 carbon atoms in the alkyl radical and 6 to 20 carbon atoms in the aryl radical, Si (R 66 ) 3 with R 66, the same or different, Ci to C 20 alkyl, C 3 to Cio cycloalkyl, C 6 to Cis aryl, neighboring radicals R 57 to R 59 and R 62 to R 64 can be used for 4 are saturated, partially saturated cyclic groups containing up to 15 carbon atoms, and the radicals
  • R 6 ⁇ R 66 are identical or different and are a hydrogen atom, a halogen atom, a Ci- to C ⁇ 0 - alkyl, Ci- to C ⁇ 0 fluoroalkyl, a Ci- to C i0 - alkoxy group, C 6 - to Cio-aryl group, C 3 - to C ⁇ 0 - aryloxy group, a C 6 - to -C 0 fluoroaryl, a C 2 - to Cio-alkenyl group, a C 7 - to C 40 -arylalkyl, a C 8 - to C 4 o ⁇ arylalkenyl group or a C 7 - to C 40 -alkylaryl group or R 14 and R 15 or R 14 and R 16 each form one or more rings with
  • M 1 is silicon, germanium or tin and
  • n 0, 1, 2, 3
  • R 68 to identical or different hydrogen f, fluorine, chlorine, R 72 bromine, iodine, Ci to Cio-alkyl or C 6 - to Cis-aryl, Ci to Cio, in particular Ci, C 2 or C 3 fluoroalkyl or C 6 to C ⁇ 5 -Fluoraryl, -OR 73 or S i (R 73 ) 3 with
  • R 73 are identical or different, hydrogen, C until C ⁇ 0 - alkyl, C 6 - to C ⁇ 5 -aryl or C 3 - to Cio-cycloalkyl
  • methyl, ethyl and propyl are preferred for substituted or unsubstituted alkyl groups.
  • Preferred cycloalkyl groups are cyclopentanyl groups.
  • Trimethylsilyl groups are preferred for trialkylsilyl radicals.
  • This conversion or transfer can generally be carried out at a temperature of 100 ° Kelvin to 800 ° Kelvin, preferably 300 ° Kelvin to 500 ° Kelvin and particularly preferably at 330 ° to 400 ° C over a period of 0.01 hours to several weeks.
  • the temperature and the time required depend on the one hand on the respective starting materials, i.e. the metallocene and the auxiliary reagent and on the other hand also from each other. These parameters can easily be determined for a given system, since the progress of the conversion is easily e.g. can be observed by NMR studies.
  • Organic solvents such as tetrahydrofuran, dichloromethane, chloroform, methanol, ethanol, aliphatic hydrocarbons such as petroleum ether, pentane, hexane and octane and in particular aromatic hydrocarbons such as toluene, benzene or decalin are preferably used.
  • aliphatic hydrocarbons such as petroleum ether, pentane, hexane and octane and in particular aromatic hydrocarbons such as toluene, benzene or decalin are preferably used.
  • the possible temperature range is naturally limited, so that the time required for the conversion must be adjusted accordingly.
  • the conversion can surprisingly be accelerated significantly by adding catalysts.
  • catalysts Compounds which have proven to be suitable are those which cleave the metal ligand Favor binding or stabilize intermediates, such as radical compounds, especially oxygen or N-oxides.
  • a mixture of racemate and meso form or only the meso form or only the racemate of a metallocene complex, the enantiomerically pure auxiliary reagent in an equi-olar amount and the solvent are placed in a reaction vessel.
  • the enantiomerically pure auxiliary reagent is then allowed to react with the metallocene complex, a mixture of monosubstituted and disubstituted complexes usually being formed.
  • Subsequent thermal treatment enables the mixture to be isomerized to a diastereomeric compound which can be used as such or after the auxiliary reagent has been split off.
  • the reaction product can be derivatized into the desired precatalyst by methods known per se.
  • FRWP Wild, L. Zsolnai, G. Huttner, HH Brintzinger., Journal Organometallic Chem., 232 (1982) pp. 233-247 describes the conversion to the dimethyl compound with, for example, methyl lithium, and the subsequent reaction with gaseous HCl in the dichloride of the metallocene.
  • the reaction product eg metallocene binaphtholate
  • the reaction product eg metallocene binaphtholate

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne un procédé de préparation de complexes métallocènes exempts d'énantiomères, résultant de la mésoforme achirale ou du racémate du complexe métallocène correspondant ou de leurs mélanges en présence d'un réactif auxiliaire exempt d'énantiomères, par voie thermique. L'invention concerne en outre des complexes énantiomères et leur utilisation dans la synthèse stéréosélective.
EP98925604A 1997-05-16 1998-05-14 Complexes metallocenes exempts d'enantiomeres, leur preparation et leur utilisation Withdrawn EP0986567A1 (fr)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
DE1997120592 DE19720592A1 (de) 1997-05-16 1997-05-16 Verfahren zur Umwandlung der achiralen meso-Form oder des Racemates gines ansa-Metallocenkomplexes oder deren Mischungen in einer seiner Enantiomeren, wobei die Umwandlung thermisch in Anwesenheit eines enantiomeren Hilfsreagens erfolgt
DE19720592 1997-05-16
DE1998100394 DE19800394A1 (de) 1997-05-16 1998-01-08 Verfahren zur Umwandlung der achiralen meso-Form oder des Racemates eines Metallocenkomplexes oder deren Mischungen in eines seiner Enantiomeren, wobei die Umwandlung thermisch und/oder katalytisch in Anwesenheit eines enantiomeren Hilfsreagens erfolgt
DE19800394 1998-01-08
PCT/EP1998/002858 WO1998052956A1 (fr) 1997-05-16 1998-05-14 Complexes metallocenes exempts d'enantiomeres, leur preparation et leur utilisation

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EP0986567A1 true EP0986567A1 (fr) 2000-03-22

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JP2007106734A (ja) * 2005-10-13 2007-04-26 Tokyo Institute Of Technology 新規な光学活性遷移金属錯体，及びその製造方法

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DE19525184A1 (de) * 1995-07-11 1997-01-16 Basf Ag Verfahren zur Umwandlung der achiralen meso-Form oder des Racemats eines ansa-Metallocenkomplexes oder deren Mischungen in eines seiner Enantiomeren

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
SCHMIDT, K. ET AL.: "photochemical isomerization of me2si-bridged zirconocene complexes. application to stereoselective synthesis of ansa-zirconocene binaphtholate stereoisomers", ORGANOMETALLICS, AMERICAN CHEMICAL SOCIETY, US, vol. 16., no. 08., 15 April 1997 (1997-04-15), US, pages 1724 - 1728., XP002089634, ISSN: 0276-7333, DOI: 10.1021/om961089d *

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