• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    Novel silanes having the formula (RSO3)2-Si-Q2•0.5HX are described. Synthesis of silylated bis-cyclopentadienyl and N-silylated mono(cyclopentadienyl) ligands and similar indenyl ligands utilizing the novel silanes is described.
    公开号:CA2324358A1
    申请号:C2324358
    申请日:2000-02-03
    公开日:2000-08-17
    发明作者:Daniel Anthony Gately
    申请人:Daniel Anthony Gately；Boulder Scientific Company；
    IPC主号:C07F7-02
    专利说明:
    SILYLATED AND N-SILYLATED COMPOUND SYNTHESIS This application is a continuation-in-part of United States application Serial No. 09/016,641 filed 30 January 1998 and a continuation of Serial No. 09/244,779 filed 05 February 1999. FIELD OF INVENTION This invention relates to certain novel silanes and to the synthesis of silylated and N-silylated organic compounds therewith. BACKGROUND OF THE INVENTION Typical procedures for the synthesis of silylated and N-silylated bis and mono(cyclopentadienyl) and indenyl ligands involve the addition of Cl2Si(CH3)2 during synthesis of monocyclopentadienyl compounds to the lithiated ligand precursor. These procedures are not cost effective due to a requirement for excess Cl2Si (CH3) 2, the production of undesirable by-products, and a consequent need for expensive purification procedures. DEFINITIONS In this specification, the following expressions have the meanings set forth: O A1. Ms0 means CH303S or CH3-S-O-O O O
    2. MsOH means CH4O3S or CH3-S-OHd O O
    3. Tf0 means CF303S or CF3-S-Op 9. TfOH means CHF303S or CF3-S-OH O5. Monocyclopentadienyl ligand means any ligand having the formulae CSHxRY, wherein: X = 0-5 y = 0-5 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 For example, 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.6. Silylated monocyclopentadienyl ligand means any ligand having the formula (R3Si)zCsHXRy, wherein CsHXRY is as defined in definition 5, Z=1-5 and R and Ry are identical or different alkyl or aromatic groups. WO OU/47587 PCTlUS00102795 7. N-silylated monocyclopentadienyl iigand means any ligand having the formula RNH (SiR2) CSHXRY, wherein CSHXRY is as defined in definition 5, and R and Ry are identical or different alkyl or aromatic groups.8. Silylated biscyclopentadienyl ligand means any ligand having the formula (CSHxRy) 2SiR2, wherein CSHXRy and Ry are as defined by definitions 6 and 7.9. Silylated monoindenyl ligand means any ligand having the formula (R3Si) (C9HxRy) wherein X = 0-7 y = 0-7 H or R can occupy any positions 1 to 7 and R3Si can occupy only position 3 of the formula ~ 2 9" wherein R and Ry are as defined by definitions 6 and 7.10. N-silylated monoindenyl ligand means any ligand having the formula RNH (SiR2) C9HXRY, wherein R and Ry are as defined by definitions 6 and 7. (C9HXRY) is as defined in definition 9 and wherein X = 0-7 and y = 0-7. I1. Silylated bisindenyl ligand means any ligand having the formula (R2Si) C9HxRy wherein R and Ry are as defined in definitions 6 and 7; X = 0-7 and y = 0-7. SLIt~ff~lP.RY OF THE INVENTION One aspect of the invention includes novel silanes having the Formula (I):(CX3S0~,) 2SiR2 ( I ) or the Formula (II):(CX3S03) 2SiR ( II) I NHRi in which X is H or F, 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 R1 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) Y2Si(R)2 (III) or the Formula (IV) YSi (R2) (IV) I NHRl in which Y is any organic group and in which R and Rl are the same or different organic groups, preferably substituted or unsubstituted aliphatic or aryl groups as defined by definition 5. 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 R3Ni, in which R3 may be any hydrocarbyl group and M may be lithium, potassium or sodium. M may also be a magnesium halide. N-butyl lithium or tert-butyl lithium are preferred RM compounds. The reaction is conducted in a non-interfering solvent, preferably diethyl ether or tetrahydrofuran, which may also include or be combined or mixed with a hydrocarbon such as toluene. The reaction mixture contains a desired alkali metallide. In a second step, 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). Methods for such isolating such compounds are known. In one aspect of the invention, the compound having -CHgroup is a CS-ring containing compound useful as an olefin polymerization catalyst ligand or as a precursor of such a ligand. Such ligands include but are not limited.to substituted, unsubstituted, mono-, or bis- cyclopentadienyl, indenyl, naphthenyl and antracenyl ligands. These ligands may be hydrogenated. For example, 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 Q1- (Z) -Q2Li2 and a compound having the formula Rl,SiO3R2 in a non-interfering solvent wherein said compound having the formula Q1-(Z)-Q2Li reacts with the compound having the formula RljSi03R2 to produce a compound having the formula RlsSiQ1 (Z ) =Q2SiRls or RisSiQl where Q1=indene or RlsSiQ2 where Q2=cyclopentadiene wherein R1 and Q1 and Q2 each have 1 to 10 carbon atoms are the same or different aryl, preferably phenyl, and R2 are identical or different alkyl groups. Specifically, Q1 and Q2 (i) may be the same or different;(ii) are preferably unsubstituted;(iii) may be substituted at any position not occupied by linkage to (Z)= or to lithium and (iv) Z is a linking group, preferably (CH2)y in which y is 1 to 6 or Si (RZ) wherein R2 is a 1 to 6 carbon atom alkyl group. Useful Q1 and QZ substituents include one to six carbon atom alkyl, preferably methyl, groups; halogens, preferably chorine, fluorine or bromine, and substituents which form rings with two Q1 or Q2 carbon atoms.
    Compounds having the formula Ql(Z) Q2Li are prepared in known manner by reacting a compound of formula Q1(Z)x Q2 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 Ql-(X)= Q2 may be combined directly with Rl3SiO3SR2 to yield Rl3SiQl (X) X Q2SiR3. The reaction proceeds to substantial completion in about thirty minutes at room temperature. See Example 8. Alternatively, the lithium salt may be isolated prior to reaction with R'jSi03SR2. DETAILED DESCRIPTION OF THE INVENTION The Formula (I) silanes may be prepared by reacting a compound of the formula R1S03H, in which Rl is any straight or branched chain alkyl group preferably having one to eight carbon atoms, with a compound of the formula X2SiQ2, in which X and Q are as defined. The synthesis of one Formula (I) silane is illustrated by Equation 1:2RSO3H + X2SiQ2 RT ~ (R1S03) 2_Si_Q2~0 . 5HX + 1.5HX Heat (1) RT = Room Temperature. The novel Formula (II) silanes are synthesized by reacting RS03H With a compound having the formula (YNH)ZSiQ2, 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: V1'O 00/47587 PCT/USOU/02795 _g_ (RS03) -Si-Q2~0.5HX+ (YNH) 2SiQ2 > 1.5 (YNH) SiQ2 I~3S (X3) Preparation of Formula I Silane - (MSO)sSiMe2-0.5 HC1 (CHjO~S~Si (CHzy0.5HCll . To a 500 mL flask containing neat ,Cl2SiMe2 ( 64 g . , 0 . 50 mol ) was added MsOH ( 97 g . , 1 . O 1 mol ) ;the immiscible solution rapidly evolved HCl that was scrubbed with NaOH (250 g., 50 wt$ solution) or with iced water. After the solution was stirred overnight, the homogeneous oil was sparged with N2 gas an additional day. This synthesis is illustrated by Equation 3: Cl2SiMe2 + 2MsOH neat > (MsU) 2SiMe2~0. 5 HCl (3) N2 sparge 'H NMR analysis of the product showed that one equivalent of HC1 was present with two equivalents (Ms0)ZSiMez; yield is quantitative. Preparation of a Formula (II) Silane - MsOSiMe2 I NH(t-butyl) (a) Preparation of ( t-BuNH)~SiMe~ (equation 4 ) .A 12 L flask equipped with an additional funnel and reflux condenser was charged with t-BuNH2 (11 mol, 805 g) and THF (7 L) . The solution was slowly treated with Cl2SiMe2 (5 mol, 645 g) that resulted in an exothermic reaction. After the temperature had dropped to 40°C, the white slurry was filtered, the t-BuNH3C1 was washed with THF (1 L), and the filtrate was reduced to an oil that contained 97$ pure -g_ ( t-BuNH) 2SiMe2 (1H NMR) . Yield was quantitative (1 Kg) . See equation 4. ClzSiMe2 + 4 t-g~2 THF ~ ( t-Buff) ZSiMe2 + 2 t-BuNH9Cl (quantitative) (4) (b) Preparation of MsOSi (CH9) 2 ' I NH(t-butyl) The (t-BuNH)ZSiMe2 prepared as described in Example 2 (a) was added to one equivalent of neat (Ms0) 2SiMe2-0 . 5HC1 at room temperature, resulting in a 50-60°C exotherm. The resulting oil which contained insoluble solids was filtered through a glass frit to give >98~ pure (t-BuNH)(Ms0)SiMe2 (1NMR) . See equation 5.(Ms0) 2SiMe2-0 . 5HC1 + ( t-BuNH) 2SiMe2 neat ~ 1, 5 (Ms0) Si (Me) Z Irix ( t-butyl ) (5) Formula (II) Silane - CF903S-Si (Me3)2 i NH(t-butyl) was prepared as described in Example 2 (Equation 5) except that (Tf0) 2Si (Me) 2 replaces (Ms0) 2SiMe2-0 . 5 HCl . Preparation of 2-Methylcyclonentadien~ICt-ButylamidoZ Dimethvlsilane iEauation 6). A 1 L flask was charged with 2-methylcyclopentadiene (16 g, 200 mmol) and THF (160 g). The solution was cooled (-10°C) and treated with n-BuLi (1.6 M, V'O 00147587 I'CT/USOO/OZ795 125 mL, 200 mmol). After the resulting white heterogeneous solution was stirred at room temperature for thirty minutes, the solution was treated with (t-BuNH)(Ms0)SiMe2 (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. (t-BuNH)SiMez + BuLi + (t-BuNH)(Ms0)SiMe 2 _L M Me In this example, 2-methylcyclopentadiene may be replaced by cyclopentadiene to provide a quantitative yield of cyclopentadienyl (t-butyl amido) dimethylsilane. Also in this example, 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. Also in this example, t-BuNH (Tf0) Si (Me) 2 may be used with similar results. This example illustrates a method in which a type IIsilane is added directly to the reaction mixture in which an alkali metallide is formed. Alternatively, the alkali metallide, here lithium-2-methylcyclopentadiene, may be VVO 00/47587 FCTIt7S00102795 isolated from the reaction mixture in known manner and thereafter reacted with either a type I or type II silane. Pret~aration of 2-Methylindenyl(t-Butylamido) Dimethvlsilane (Equation 7). A 5 L flask was charged with 2-methylindene (1.67 mol, 217 g) and ether (1.5 L). The solution was cooled (-10°C) and treated with BuLi (1.67 mol, 1.09L). After the solution was stirred for one hour at room temperature, the solution was cooled (-10°C) and Me2Si(Ms0)NH(t-Bu) (a type II silane) was added in one portion, resulting in a 20°C exotherm. After one hour at room temperature, the solution was filtered through Celite, the residual solid LiOMs was washed With ether (1.5 L), and the filtrate was reduced to a yellow oil that contained >98~pure 2-methylindenyl(t-butylamido) dimethylsilane (1H NMR) in quantitative yield. CH3+BuLi+ ( t-BuNH) (Ms0) SiMe, E10°C~ / ~ ~ Hs (2-methylindene) t-BuNHSiMez (quantitative) (7) In this example, (t-BuNH)TfOSiMe2 may be used instead of t-BuNH (Ms0) SiMe2.Also, in this example, 2-methylindene may be replaced with fluorene to provide a quantitative yield of 9-fluorenyl-t-butylamido dimethylsilane. Also, in this example, 2-methylindene may be replaced with bromobenzene to obtain a quantitative yield of the expected phenyl-t-butylamido dimethylsilane. Pret~aration of bis(2-methyl-4 5-benzoindenyl) dimethylsilane (ectuation 8) A 2L flask charged with 2-methyl-4,5-benzo(indene) (73 g, 405 mmol) and ether (500 mL) was cooled to -10°C and treated with n-BuLi (1.6 M, 255 mL, 405 mmol). The solution was allowed to warm to room temperature for 30 minutes, cooled to about -10°C, and then treated With a neat Formula I silane (Ms0)2SiMe2-0.5 HC1 (54g, 203 mmol) resulting in a 10-15°C exotherm. After one hour at room temperature, the white slurry was treated with CH2C12 (500 mL), and the solution was filtered through Celite into a 5L flask. The solids were washed with CHZC12 (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 CH2C12 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$. The 2-methyl-4,5-benzo(indene) was recovered by treatment of the filtrate with NaOH (20 wt~) in THF. Me2S i / ether / Cl~~+BuLi+G.5(MsOi2SiPfe~~ G.5NC1_1Go G'S ~ CI13 +LiCl / 2-methyl-4,5-benzo(indene) (s> The above procedure was repeated, except that (MSO) 2SiMe2-0. 5HC1 was replaced. with (Tf0) 2Si (Me) 2 . The yield of bis(2-methyl-4,5-benzoindenyl) dimethylsilane was 60-65~of the bis(2-methylbenzoindenyl) dimethylsilane. Prebaration of Metallocene Catalvst from the Example 5 Product (Eguation 9). A 1 L flask was charged with bis(2-methyl-4,5-benzoindenyl) dimethylsilane (48 g, 115 mmol), toluene (480 mL) , and ether (20 g, 270 m~nol) . The solution was cooled (-10°C) and then treated with BuLi (1.6 M, 145 mL, 230 mmol). After the tanned-colored heterogeneous solution was stirred at room temperature for two hours, the solution was cooled (-20°C) and treated with ZrCl, (27 g, 115 mmol). By the time the solution had warmed to -10°C, a bright yellow solution had resulted. After the yellow solution was stirred at room temperature for 2 hours, the solution was filtered, and the yellow solid was washed with toluene until the filtrate was pale yellow. The yellow filter cake was treated with an equal mass of Celite, the solids were slurried in dry CH2C12, and the product was extracted with CH2C12 through a layer of Celite into a 12 Lflask that contained toluene (1 L); the extraction was WO 00/47587 PCTIUSOOl02795 stopped when the yellow color of the filtrate had turned translucent. The CHZCI2 solvent was evaporated to give a toluene-slurry of yellow crystals. The solution was filtered, the yellow crystals were washed with toluene (1 L), and the yellow solid was slurried in toluene (5 L) for four hours. The solution was filtered to give 28 grams of diastereomerically pure metallocene (iH Nt~; yield -38$) .MezSi toulene/ ~ CH ~' + 2 BuLi + O. SZrCl4ether ~.-20"C O 2 r z C1 Cl Preparation of Bis(3-Trimethylsilvl (TMS) indenvl ethane (EcZUation 10). A 1L flask was charged with ethylene bis-indene (EBI) (0.100 mol, 26g) and THF (260g). The solution was cooled (-10°C) and treated With BuLi (0.200 mol. 125 mL). After one hour at RT, the solution was cooled (-10°C) and treated with Me3Si (OMS) (0.200 mol . , 34 g) in one portion. After thirty minutes at RT, the solution was filtered through Celi te, the solids containing rac/meso bis(TMS) EBI were washed with THF (130 g), and the filtrate was reduced giving a solid that contained 98~ rac-meso product in >98$ yield. The product was extracted with heptane to separate the rac and meso isomers.this procedure is illustrated by the following equation 10: THF EBI+2BuLi+2MejSi (OMS) > rac/meso-bis (TMS) EBI1 2Li (OSOzMe) 1 filter, wash w/THFmeso-bis(TMS)EBI < rac/meso bis(TMS) EBI(solid) 1. Add heptane, strip THF2. Cool solution to -20°C, filter rac-bis(TMS)EBI(heptane solution of) The above procedure was repeated with several analogs of EBI with similar results. Specific analogs of EBI were bis(2-methylindenyl) ethane, bis(4,7-dimethylindenyl) ethane, cyclopentadiene and methylcyclopentadiene. In this example, Me3Si (OTf) may be used instead of Me3Si (OMs) . Preparation of N-Silylated Cvclot~entadienephenanthrene This procedure is illustrated by equation 11: NH(t-butyl) SiMey EtiO+BuLi+t-butyl (NH) (Ms0) SiMez ---~~ FW 816 1.6M 223 395 32.1g 92.9m1 33.2g Quantitative 0.1986 0.1986 0.1486 I HNMR Cyclopentadienephenanthrene is mostly dissolved in diethyl ether (B00 mL), n-BuLi is added, and the reaction mixture was stirred overnight. I CH3 S - OSi - NH t-butyl O CH3 was added neat, followed by stirring for one-half hour. The reaction mixture was filtered. Ether was removed. Yield - quantitative. In this reaction, any compound of Formula (II), page 4, may be used instead of t-butyl NHMsOSiMe2. Compounds which have the corresponding R groups instead of t-butyl are produced. In this example, CF3SO,Si (CH3) 2NH t-butyl may be used instead of CH3SO3SI (CH3) 2NH t-butyl . This example illustrates the preparation of n-silylated indenes of formula si (Q) 2 z in which Rl, 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. A 5 L flask charged with the an indene of formula II(1548, 0.906 mol) and ether (1500g) was cooled (-20°C) and treated with n-BuLi (1.6M, 0.906 mol, 0.566 L). After the solution which contained the lithium salt of the indene was allowed to warm to room temperature for one hour, the solution was cooled (-20°C) and then treated with the mesylate O = S = O I CH3 - Sl - CH3 I NH It-butyl. After one hour at room temperature, the slurry was filtered through Celite, and the filter cake was washed with either (750g). The ether was removed affording the expected compound cH3 i si ( CH3 ) 2 Nx t-butyl as an oil in quantitative yield (0.906 mol, 272g). The 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.
    权利要求:
    Claims I CLAIM:
    1. A process which comprises reacting a compound having the formula: with a compound having the formula: Wherein X is a one to ten carbon atom alkyl group, preferably a t-butyl group, and wherein a reaction mixture containing a compound having the formula: is produced.
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    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    AT276263T|1996-08-08|2004-10-15|Dow Global Technologies Inc|METAL COMPLEXES CONTAINING A CYCLOPENTADIENYL GROUP SUBSTITUTED IN POSITION 3 AND AN OLEFIN POLYMERIZATION METHOD|
    US5965756A|1996-12-19|1999-10-12|The Dow Chemical Company|Fused ring substituted indenyl metal complexes and polymerization process|
    WO1998049212A1|1997-04-30|1998-11-05|The Dow Chemical Company|Ethylene/alpha-olefin/diene interpolymers and their preparation|
    法律状态:
    2003-03-18| FZDC| Correction of dead application (reinstatement)|
    2006-02-03| FZDE| Dead|
    优先权:
    申请号 | 申请日 | 专利标题
    US09/244,779||1999-02-05||
    US09/244,779|US6087518A|1998-01-30|1999-02-05|Silylated and N-silylated compound synthesis|
    PCT/US2000/002795|WO2000047587A1|1998-01-30|2000-02-03|Silylated and n-silylated compound synthesis|
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