EP1070072A1 - Synthese de composes silyles et n-silyles - Google Patents

Synthese de composes silyles et n-silyles

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Publication number
EP1070072A1
EP1070072A1 EP00914493A EP00914493A EP1070072A1 EP 1070072 A1 EP1070072 A1 EP 1070072A1 EP 00914493 A EP00914493 A EP 00914493A EP 00914493 A EP00914493 A EP 00914493A EP 1070072 A1 EP1070072 A1 EP 1070072A1
Authority
EP
European Patent Office
Prior art keywords
formula
silylated
solution
compound
bis
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.)
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Application number
EP00914493A
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German (de)
English (en)
Other versions
EP1070072A4 (fr
Inventor
Daniel Anthony Gately
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.)
Boulder Scientific Co
Original Assignee
Boulder Scientific Co
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 US09/244,779 external-priority patent/US6087518A/en
Application filed by Boulder Scientific Co filed Critical Boulder Scientific Co
Publication of EP1070072A1 publication Critical patent/EP1070072A1/fr
Publication of EP1070072A4 publication Critical patent/EP1070072A4/fr
Withdrawn legal-status Critical Current

Links

Definitions

  • This invention relates to certain novel silanes and to the synthesis of silylated and N-silylated organic compounds therewith.
  • MsO means CH 3 0 3 S or CH 3 -S-0-
  • MsOH means CH 4 0 3 S or CH 3 -S-OH O
  • TfO means CF 3 0 3 S or CF 3 -S-0
  • TfOH means CHF 3 0 3 S or CF 3 -S-OH
  • Monocyclopentadienyl ligand means any ligand having the formulae C 5 H x R y , wherein:
  • R any alkyl or aromatic group or combination thereof, and H or R can occupy any one or more of the positions 1 to 5 of the formula
  • R may be an alkyl group having one to eight carbon atoms including but not limited to methyl, ethyl, propyl, isopropyl, butyl, tertbutyl, hexyl or octyl .
  • Methyl is the preferred alkyl group.
  • R, when an aromatic group, may be phenyl , xylyl , mesityl, naphthyl or fluorenyl .
  • N-silylated monocyclopentadienyl ligand means any ligand having the formula RNH (SiRa) C 5 H x R y , wherein C 5 H x R y is as defined in definition 5, and R and R y are identical or different alkyl or aromatic groups.
  • Silylated biscyclopentadienyl ligand means any ligand having the formula (CsHxR y JsSiRj,, wherein C 5 H x R y and R y are as de ined by definitions 6 and 7.
  • Silylated monoindenyl ligand means any ligand having the formula (R 3 Si) (CH x R y ) wherein
  • R can occupy any positions 1 to 7 and R 3 Si can occupy only position 3 of the formula
  • R and R y are as defined by definitions 6 and 7.
  • SUMMARY OF THE INVENTION One aspect of the invention includes novel silanes having the Formula (I) :
  • each R in formula (I) may be the same or a different alkyl or aromatic group as defined by definition 5 with the proviso that when X is F in formula (I) , R is not methyl, and R 1 is an alkyl or aromatic group which may be the same or different from R.
  • Another aspect of the invention is a method for the synthesis of silylated and N-silylated compounds having the Formula (III)
  • the invention includes methods for reacting organic alkali metallides having the formula YM, in which Y is any organic group and M is any alkali metal with a silane having the Formula (I) or Formula (II) wherein the product is a compound having the Formula (III) or Formula (IV) .
  • a first step of such methods includes preparation of an organic alkali metallide. Methods for the preparation of such compounds are known. For example, any compound having a -CH group, preferably acidic, is reacted with an alkali metal alkyl having the formula RM, in which R 3 may be any hydrocarbyl group and M may be lithium, potassium or sodium. M may also be a magnesium halide.
  • N-but ⁇ l lithium or tert- butyl lithium are preferred RM compounds.
  • the reaction is conducted in a non-interfering solvent, preferably diethyl ether or tetrahydrof ran, which may also include or be combined or mixed with a hydrocarbon such as toluene.
  • the reaction mixture contains a desired alkali metallide.
  • the alkali metallide product of the first step is optionally but not necessarily isolated from the first step reaction mixture and reacted with a silane having the Formula (I) or the Formula (II) .
  • a silane having the Formula (I) or the Formula (II) are known.
  • the compound having -CH group is a C 5 -ring containing compound useful as an olefin polymerization catalyst ligand or as a precursor of such a ligand.
  • ligands include but are not limited to substituted, unsubstit ted, mono-, or bis- cyclopentadienyl , indenyl , naphthenyl and antracenyl ligands . These ligands may be hydrogenated.
  • such ligands include cyclopentadienes, bis-cyclopentadienes, indenes, bis- indenes , mono- and poly- alkyl , preferably methyl , substituted cyclopentadienes and indenes, such as tetraethyl cyclopentadiene and 2-methyl indene, 2-methyl-benzo (indene) , bis-2-methyl-benzo (indene) , dimethyl silane, substituted, unsubstituted and bis-phenanthrene, and cyclopentadienephenanthrene which may be but need not be hydrogenated.
  • Another aspect of the invention may include a method which comprises combining a compound having the formula Q 1 -(Z)-Q 2 Li 2 and a compound having the formula R 1 3 Si0 3 R 2 in a non-interfering solvent wherein said compound having the formula Q 1 -(Z)-Q 2 Li reacts with the compound having the formula R ⁇ SiO a R 2 to produce a compound having the formula
  • R 1 and Q 1 and Q 2 each have 1 to 10 carbon atoms are the same or different aryl , preferably phenyl , and R 2 are identical or different alkyl groups .
  • Q 1 and Q 2 are identical or different alkyl groups .
  • (i) may be the same or different; (ii) are preferably unsubstituted; (iii) may be substituted at any position not occupied by linkage to (Z) x or to lithium and
  • Z is a linking group, preferably (CH 2 ) y in which y is 1 to 6 or Si (R 2 ) wherein R 2 is a 1 to 6 carbon atom alkyl group.
  • Q 1 and Q 2 substituents include one to six carbon atom alkyl , preferably methyl , groups ; halogens , preferably chorine, fluorine or bromine, and substituents which form rings with two Q 1 or Q 2 carbon atoms.
  • Compounds having the formula Q 1 (Z) Q 2 Li are prepared in known manner by reacting a compound of formula Q 1 (Z) X Q 2 with an alkyl lithium compound, preferably n-butyl or t-butyl lithium in a non-interfering solvent, preferably ether or tetrahydrofuran .
  • the lithiation reaction is appropriately conducted at a temperature of from about -80°C to about 40°C.
  • the reaction mixture which contains lithiated Q X -(X) X Q 2 may be combined directly with R 1 3 Si0 3 SR 2 to yield R 1 3 SiQ 1 (X) x Q 2 SiR 3 .
  • the reaction proceeds to substantial completion in about thirty minutes at room temperature . See Example 8.
  • the lithium salt may be isolated prior to reaction with R 1 3 Si0 3 SR 2 .
  • the Formula (I) silanes may be prepared by reacting a compound of the formula R 1 S0 3 H, in which R 1 is any straight or branched chain alkyl group preferably having one to eight carbon atoms, with a compound of the formula X 2 SiQ 2 , in which X and Q are as defined.
  • Equation 1 The synthesis of one Formula (I) silane is illustrated by Equation 1 :
  • the novel Formula (II) silanes are synthesized by reacting RS0 3 H with a compound having the formula (YNH) 2 SiQ 2 , in which R and Q are as defined, and Y is an alkyl group which may be the same as or different from Q. See Equation 2 : (RSO 3 ) -Si-Q 2 -0 .5HX+ (YNH) 2 SiQ 2 > 1 .5 (YNH) SiQ 2
  • Dimethylsilane (Equation 6) .
  • a I L flask was charged with 2- methylcyclopentadiene (16 g, 200 mol) and THF (160 g) .
  • the solution was cooled (-10°C) and treated with n-BuLi (1.6 M, 125 rtiL, 200 mmol) .
  • n-BuLi 1.6 M, 125 rtiL, 200 mmol
  • the solution was treated with (t-BuNH) (MsO) SiMe 2 (47 g, 190 mmol) and the solution was stirred overnight.
  • the solution was filtered through Celite, the residual LiOMs was washed with ether (500 mL) , and the filtrate was reduced to a light-green oil. No further purification was necessary. Yield was quantitative.
  • 2-methylcyclopentadiene may be replaced by cyclopentadiene to provide a quantitative yield of cyclopentadienyl (t-butyl amido) dimethylsilane.
  • 2-methylcyclopentadiene may be replaced by 3-methyl-2-ethyl-cyclopentadiene to provide a quantitative yield of 3-methyl-2-ethyl-cyclopentadienyl (t-butyl amido) dimethylsilane.
  • t-BuNH(TfO) Si (Me) 2 may be used with similar results.
  • This example illustrates a method in which a type II silane is added directly to the reaction mixture in which an alkali metallide is formed.
  • the alkali metallide here lithium-2-methylcyclopentadiene, may be isolated from the reaction mixture in known manner and thereafter reacted with either a type I or type II silane.
  • ( -BuNH) TfOSiMe 2 may be used instead of t-BuNH (MsO) SiMe 2 .
  • 2-methylindene may be replaced with fluorene to provide a quantitative yield of 9- fluorenyl-t-butylamido dimethylsilane.
  • 2-methylindene may be replaced with bromobenzene to obtain a quantitative yield of the expected phenyl- -butylamido dimethylsilane.
  • the white slurry was treated with CH 2 C1 2 (500 mL) , and the solution was filtered through Celite into a 5L flask. The solids were washed with CH 2 C1 2 (500 mL) , and the filtrate was evacuated to dryness . The white solid residue was treated with ether (200 mL) , and the solvent was evacuated so that most of the residual CH 2 C1 2 was removed. The solid was then treated with ether (1 L) and triturated for thirty minutes before filtering and washing the white solid with ether (200 mL) . Yields vary from 20-50%. The 2-methyl-4 ,5-benzo (indene) was recovered by treatment of the filtrate with NaOH (20 wt%) in THF.
  • EXAMPLE 8 Preparation of Bis (3-Trimethylsilyl (TMS) indenyl) ethane (Equation 10) .
  • EBI ethylene bis-indene
  • THF 260g
  • the solution was cooled (-10°C) and treated with BuLi (0.200 mol. 125 mL) .
  • the solution was cooled (-10°C) and treated with Me 3 Si (OMS) (0.200 mol., 34 g) in one portion.
  • EBI EBIbis (2-methylindenyl) ethane, bis (4 , 7-dimethylindenyl) ethane, cyclopentadiene and methylcyclopentadiene.
  • Me 3 Si (OT ) may be used instead of Me 3 Si(OMs) .
  • CF 3 S0 3 Si (CH 3 ) 2 NH t-butyl may be used instead of CH 3 S0 3 SI (CH 3 ) 2 NH t-butyl.
  • R 1 , Q and Z are the same or different one to eight carbon atom alkyl groups, preferably methyl groups, with the exception that Z is preferably a t-butyl group.
  • Example I synthesis is preferably conducted at a temperature of from about -30°C to about -10°C for a time period of from about 0.5 to 1.5 hours .

Abstract

L'invention concerne de nouveaux silanes de formule (RSO3)2-Si-Q2•0.5HX. Cette invention concerne également la synthèse de ligands de bis-cyclopentadiényle sylilés et de mono(cyclopentadiényle) N-sylilés, et de ligands d'indényle identiques utilisant les nouveaux silanes susmentionnés.
EP00914493A 1999-02-05 2000-02-03 Synthese de composes silyles et n-silyles Withdrawn EP1070072A4 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US244779 1999-02-05
US09/244,779 US6087518A (en) 1998-01-30 1999-02-05 Silylated and N-silylated compound synthesis
PCT/US2000/002795 WO2000047587A1 (fr) 1998-01-30 2000-02-03 Synthese de composes silyles et n-silyles

Publications (2)

Publication Number Publication Date
EP1070072A1 true EP1070072A1 (fr) 2001-01-24
EP1070072A4 EP1070072A4 (fr) 2002-09-25

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP00914493A Withdrawn EP1070072A4 (fr) 1999-02-05 2000-02-03 Synthese de composes silyles et n-silyles

Country Status (5)

Country Link
EP (1) EP1070072A4 (fr)
JP (1) JP2002536451A (fr)
AU (1) AU765658B2 (fr)
CA (1) CA2324358A1 (fr)
NZ (1) NZ507044A (fr)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998006727A1 (fr) * 1996-08-08 1998-02-19 The Dow Chemical Company Complexes metalliques contenant du cyclopentadienyle a substitution d'heteroatome en position 3 et procede de polymerisation d'olefine
WO1998027103A1 (fr) * 1996-12-19 1998-06-25 The Dow Chemical Company Complexes metalo-indenyliques substitues par des anneaux condenses et procede de polymerisation
WO1998049212A1 (fr) * 1997-04-30 1998-11-05 The Dow Chemical Company Interpolymeres d'etylene/alpha-olefine/diene et leur preparation

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998006727A1 (fr) * 1996-08-08 1998-02-19 The Dow Chemical Company Complexes metalliques contenant du cyclopentadienyle a substitution d'heteroatome en position 3 et procede de polymerisation d'olefine
WO1998027103A1 (fr) * 1996-12-19 1998-06-25 The Dow Chemical Company Complexes metalo-indenyliques substitues par des anneaux condenses et procede de polymerisation
WO1998049212A1 (fr) * 1997-04-30 1998-11-05 The Dow Chemical Company Interpolymeres d'etylene/alpha-olefine/diene et leur preparation

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of WO0047587A1 *

Also Published As

Publication number Publication date
JP2002536451A (ja) 2002-10-29
CA2324358A1 (fr) 2000-08-17
NZ507044A (en) 2002-08-28
AU765658B2 (en) 2003-09-25
EP1070072A4 (fr) 2002-09-25
AU3587700A (en) 2000-08-29

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