USRE38683E1 - Preparation of titanocenes - Google Patents

Preparation of titanocenes Download PDF

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Publication number
USRE38683E1
USRE38683E1 US10/053,997 US5399702A USRE38683E US RE38683 E1 USRE38683 E1 US RE38683E1 US 5399702 A US5399702 A US 5399702A US RE38683 E USRE38683 E US RE38683E
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Prior art keywords
alkyl
methyl
rac
reaction mixture
indene
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US10/053,997
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English (en)
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Jeffrey M. Sullivan
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Boulder Scientific Co
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Boulder Scientific Co
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Priority claimed from PCT/US1996/018666 external-priority patent/WO1998022476A1/fr
Priority claimed from US08/885,805 external-priority patent/US5847176A/en
Application filed by Boulder Scientific Co filed Critical Boulder Scientific Co
Priority to US10/053,997 priority Critical patent/USRE38683E1/en
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    • 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

  • This invention relates to the preparation of chiral titanocenes. More particularly, the invention relates to dialkylsilylbis(2-alkyl-4-arylindenyl) metallocenes.
  • R a may be a 1 to 20 carbon atom hydrocarbon group
  • R b may be a 6 to 16 carbon atom aryl group
  • M may be titanium, zirconium or hafnium
  • X 1 and X 2 may be a halogen atom and Y 1 may be a divalent-silicon containing group.
  • transition metal compounds obtained by substituting titanium metal of hafnium metal . . . for zirconium metal in the above-exemplified compounds. [Col. 32, 11. 5-9]
  • transition metal compounds according to the present invention can be prepared in accordance with the methods described in Journal of Organometallic Chem. 288 (1985), pages 63 to 67, European Patent Publication No. 0,320,762 specification and Examples thereof . . . .
  • This invention provides a method for preparing the titanocene compounds of Formula Ia.
  • a 2-alkyl-4-aryl indene is converted to a dialkali metal salt, preferably a dilithium salt.
  • dialkali metal salt is then reacted in a second step with a dihalodialkyl silane to produce a bis-indenyl compound of Formula II: in which R a and R b are as described with respect to Formula Ia and in which R c is a one to ten carbon atom alkyl group.
  • the Formula II compound is combined with a titanium trichloride (TiCl 3 ) containing mixture formed by reacting titanium tetrachloride (TiCl 4 ) with an alkali metal alkyl compound, wherein a metallocene ligand is produced in which titanium is present in a plus three oxidation state.
  • TiCl 3 titanium trichloride
  • TiCl 4 titanium tetrachloride
  • alkali metal alkyl compound wherein a metallocene ligand is produced in which titanium is present in a plus three oxidation state.
  • the titanium is oxidized to the plus four state, for example, by reaction with cuprous chloride or chloroform, wherein a reaction mixture which contains contain the desired titanocene of Formula III is produced.
  • FIG. 1 is a proton nuclear magnetic resonance (NMR) spectrum of rac-dimethylsilyl(2-methyl-4-phenyl indenyl) titanium dichloride acquired with a JEOL Eclipse 400 NMR spectrometer prepared by the method of the sample labelled 552-001(c).3.
  • NMR nuclear magnetic resonance
  • a typical Formula Ia titanocene synthesis includes a first step in which a 2-alkyl-4-aryl indene having the Formula IV: in which R a and R b are as previously described and which is reacted in a first reaction vessel with an alkali metal alkyl compound having the formula RM in which R is a straight or branched chain 2 to 10 carbon atom alkyl group and M is sodium, potassium or, preferably, lithium to provide a first reaction mixture which contains a dialkali metal salt of the Formula II compound.
  • the reactants are combined in substantially stoichiometric amounts in a non-interfering, preferably hydrocarbon, medium.
  • Useful hydrocarbon media include aliphatic or aromatic hydrocarbons such as hexane, heptane, cyclohexane, benzene, toluene and xylene. Toluene is preferred.
  • titanium tetrachloride in a second reaction vessel is reacted as in the first step in a non-interfering, preferably hydrocarbon medium as in the first step with an alkali metal alkyl compound RM to produce a second reaction mixture containing titanium trichloride.
  • the titanium trichloride containing mixtures are produced by the preferably stoichiometric (1:1) reaction of an organometallic compounds, such as n-butyl lithium or n-butyl magnesium chloride, with titanium tetrachloride in the non-interfering solvent medium. These mixtures are used directly without isolation of the titanium trichloride.
  • organometallic compounds such as n-butyl lithium or n-butyl magnesium chloride
  • a third step the first and second reaction mixtures are combined, for example, in the second reaction vessel for reaction to produce a titanocene catalyst ligand in which titanium is present in a plus three oxidation state.
  • An oxidizing agent e.g., cuprous chloride or chloroform, is added with agitation to produce a third reaction mixture in which the desired titanocene of Formula III is present as a mixture of rac solid and meso isomers.
  • the isomer mixture is separated from the reaction mixture and dried.
  • the dry mixture of rac and meso isomers is resolved, for example, by treatment with a selective solvent preferably for the meso isomer to provide the rac isomer in substantially pure form.
  • the isomer mixture may also be resolved by the method described in Gately application entitled “Preparation and Separation of Rac and Meso Compound Mixtures” filed Jun. 9, 1997.
  • a first flask was charged with toluene (300 mL) and tetrahydrofuran (THF) (15 g, 0.2 mol) and 2-methyl-4phenylindene (21.2 g, 0.2 mol). The mixture was cooled to ⁇ 20° C. followed by the addition of 1.6M butyllithium in hexanes (125 mL). The mixture which contained 2-methyl-4-phenylindene lithium was warmed to 25° C. and stirred for four hours. The stirred contents were cooled to ⁇ 20° C. and dichlorodimethylsilane (12.9 g) was added. The reaction mixture so formed was warmed to 25° C. and stirred for 12-16 hours and then cooled to ⁇ 20° C.
  • THF tetrahydrofuran
  • the first flask reaction mixture contained the dilithium salt of Me 2 Si bis(2-methyl-4-phenylindene).
  • Example 1 is repeated with the 2-methyl-4- ⁇ -naphthylindenyl used as a first flask reactant instead of 2-methyl-4-phenylindene.
  • Example 1 is repeated with the 2-methyl-4-anthracenyl indene used as a first flask reactant instead of 2-methyl-4-phenylindene.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
US10/053,997 1996-11-22 2002-01-19 Preparation of titanocenes Expired - Lifetime USRE38683E1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US10/053,997 USRE38683E1 (en) 1996-11-22 2002-01-19 Preparation of titanocenes

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
PCT/US1996/018666 WO1998022476A1 (fr) 1996-11-22 1996-11-22 Synthese de titanocenes
US08/885,805 US5847176A (en) 1997-06-30 1997-06-30 Preparation of chiral titanocenes
US10/053,997 USRE38683E1 (en) 1996-11-22 2002-01-19 Preparation of titanocenes

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
US08/885,805 Reissue US5847176A (en) 1996-11-22 1997-06-30 Preparation of chiral titanocenes

Publications (1)

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USRE38683E1 true USRE38683E1 (en) 2005-01-04

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US10/053,997 Expired - Lifetime USRE38683E1 (en) 1996-11-22 2002-01-19 Preparation of titanocenes

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US (1) USRE38683E1 (fr)
EP (1) EP0883623B1 (fr)
CA (1) CA2246417C (fr)
DE (1) DE69719490T2 (fr)
DK (1) DK0883623T3 (fr)
WO (1) WO1998022477A1 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101153095B1 (ko) 2009-01-20 2012-06-04 주식회사 엘지화학 신규한 시클로알켄 유도체 및 이를 이용한 유기전자소자

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5329033A (en) * 1991-08-26 1994-07-12 Hoechst Aktiengesellschaft Process for the preparation of an olefin polymer
US5693836A (en) * 1992-08-15 1997-12-02 Hoechst Aktiengesellschaft Process for the preparation of polyolefins

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DK0574597T3 (da) * 1992-06-13 1998-09-14 Targor Gmbh Fremgangsmåde til fremstilling af brosluttede chirale metallocenkatalysatorer af bisindenyltypen
DE4344689A1 (de) * 1993-12-27 1995-06-29 Hoechst Ag Metallocenverbindung
TW454020B (en) * 1994-08-09 2001-09-11 Mitsui Chemicals Inc Olefin polymerization catalyst
MY112177A (en) * 1994-09-30 2001-04-30 Mitsui Chemicals Inc Olefin polymerization catalyst and process for olefin polymerization
DE19739946A1 (de) * 1997-09-11 1999-03-18 Targor Gmbh Verfahren zur Herstellung von Metallocenen

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5329033A (en) * 1991-08-26 1994-07-12 Hoechst Aktiengesellschaft Process for the preparation of an olefin polymer
US5693836A (en) * 1992-08-15 1997-12-02 Hoechst Aktiengesellschaft Process for the preparation of polyolefins

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Ewen et al., Macromol. Rapid Commun., vol. 19, No. 1, pp. 71-73, 1998. *

Also Published As

Publication number Publication date
DK0883623T3 (da) 2003-04-07
DE69719490T2 (de) 2003-09-25
DE69719490D1 (de) 2003-04-10
WO1998022477A1 (fr) 1998-05-28
CA2246417A1 (fr) 1998-05-28
CA2246417C (fr) 2009-09-08
EP0883623B1 (fr) 2003-03-05
EP0883623A1 (fr) 1998-12-16
EP0883623A4 (fr) 2000-06-28

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