AU765658B2 - Silylated and N-silylated compound synthesis - Google Patents

Description

1 SILYLATED AND N-SILYLATED COMPOUND SYNTHESIS This application is a continuation-in-part of United a States application Serial No. 09/016,641 filed 30 January 1998 and a continuation of Serial No. 09/244,779 filed 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 The discussion of the background to the invention herein is included to explain the context of the invention. This is not to be taken as an admission that any of the material referred to was published, known or part of the common general knowledge in Australia as at the priority date of any of the claims.

Typical procedures for the synthesis of silylated and N-silylated bis and mono(cyclopentadienyl) and indenyl ligands involve the addition of Cl 2 Si(CH 3 2 during synthesis 2 of monocyclopentadienyl compounds to the lithiated ligand 20 precursor. These procedures are not cost effective due to a requirement for excess C1 2 Si(CH 3 2 the production of undesirable by-products, and a consequent need for expensive purification procedures.

25 DEFINITIONS In this specification, the following expressions have the meanings set forth: 0 30

E

S1. MsO means CH 3 0 3 S or CH3-S-O 0 0 2. MsOH means CH 4 0 3 S or CH 3

-S-OH

0 W:\lary\MMHNODEL\35877-00,doc WO 00/47587 PCTnIUS00!02795 -2- 0 3. TfO means CF 3

O

3 S or CF 3

-S-O

I

0 0 4. TfOH means CHF 3

O

3 S or CF 3

-S-OH

o 0 Monocyclopentadienyl ligand means any ligand having the formulae CsHxR, wherein: X y 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 1 I 2 4 3 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 (R 3 Si)zCsHxRy, wherein CsHxRy is as defined in definition 5, Z=1-5 and R and R, are identical or different alkyl or aromatic groups.

WO 00/47587 PCTnUS0 /02795 -3- 7. N-silylated monocyclopentadienyl ligand means any ligand having the formula RNH(SiRP)CsHxRy, wherein CsHxR is as defined in definition 5, and R and R, are identical or different alkyl or aromatic groups.

8. Silylated biscyclopentadienyl ligand means any ligand having the formula (CsHxRy) 2 SiR 2 wherein CsHxRy and Ry are as defined by definitions 6 and 7.

9. Silylated monoindenyl ligand means any ligand having the formula (R 3 Si) (CgHxRy) wherein X 0-7 y 0-7 H or R can occupy any positions 1 to 7 and R 3 Si can occupy only position 3 of the formula 7 6 81 O 2 4 4 3 4 wherein R and R, are as defined by definitions 6 and 7.

N-silylated monoindenyl ligand means any ligand having the formula RNH(SiR 2 )CHxRy, wherein R and R, are as defined by definitions 6 and 7. (CgHxRy) is as defined in definition 9 and wherein X 0-7 and y 0-7.

11. Silylated bisindenyl ligand means any ligand having the formula (R2Si) CHxR, wherein R and R, are as defined in definitions 6 and 7; X 0-7 and y 0-7.

SUMMARY OF THE INVENTION According to the present invention, there is provided a process which includes reacting a compound having the formula: Me Li with a compound having the formula:

SO

2

CH

3 0 Si (Me) 2

I

HNX

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: 25 c Me Si(Me) 2 Im*x is produced.

0 W:\mayiMMHNODEL35177.doc 4a One aspect of the invention includes novel silanes having the Formula

(CX

3

SO

3 SiR 2

(I)

or the Formula (II):

(CX

3

SO

3 2 SiR (II)

I

NHR

1 in which X is H or F, each R in formula 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 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)

Y

2 Si(R) 2

(III)

or the Formula (IV) YSi (R 2

(IV)

20

NHR

1 in which Y is any organic group and in which R and R 1 are the same or different organic groups, preferably substituted or unsubstituted aliphatic or aryl groups as defined by definition The invention includes methods for reacting organic S* alkali metallides having the formula YM, in which Y is any organic group and M is any alkali metal with a silane having 30 30 the Formula or Formula (II) wherein the product is a to compound having the Formula (III) or Formula (IV).

W:Airy\MMHNODEL\3577-00.doc WO 00/47587 PCT!USQ/02795 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 R 3 M, 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-butyl lithium or tertbutyl 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 or the Formula Methods for such isolating such compounds are known.

In one aspect of the invention, the compound having -CH group 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, bisindenes, 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 WO 00/47587 PCT/USO0/02795 -6cyclopentadienephenanthrene 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 2 Li 2 and a compound having the formula R'aSiO 3

R

2 in a non-interfering solvent wherein said compound having the formula Q1-(Z)-Q 2 Li reacts with the compound having the formula R 1 3 SiOsR 2 to produce a compound having the formula

R

1 3 SiQ I

.Q

2 SiRs or

R'

3 SiQ 1 where Q 1 =indene or Ra 3 SiQ 2 where Q 2 =cyclopentadiene wherein 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.

Specifically, Q 1 and Q 2 may be the same or different; (ii) are preferably unsubstituted; (iii) may be substituted at any position not occupied by linkage to or to lithium and (iv) 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.

Useful 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.

WO 00/47587 PCTIUSO0!02795 -7- Compounds having the formula Q 1

Q

2 Li are prepared in known manner by reacting a compound of formula Q1(Z), 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 The reaction mixture which contains lithiated Q- Q 2 may be combined directly with R' 3 SiO 3

SR

2 to yield R' 3 SiQ (X)

Q

2 SiR 3 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'SiO 3

SR

2 DETAILED DESCRIPTION OF THE INVENTION The Formula silanes may be prepared by reacting a compound of the formula R'SO 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.

The synthesis of one Formula silane is illustrated by Equation 1: 2RSO 3 H X 2 SiQ 2 RT. (RSO 3 2 -Si-Q 2 -O.5HX Heat (1) RT Room Temperature.

The novel Formula (II) silanes are synthesized by reacting RSO a 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: WO 00/47587 PCT!USO0!02795 -8-

(RSO

3 )-Si-Q 2 -0.5HX+(YNH) 2 SiQ 2 1.5(YNH)SiQ 2

I

0 3 S (X 3 (2) EXAMPLE 1 Preparation of Formula I Silane (MSO),SiMe,-0.5 HC1 [(CHOS) Si ,~0.5HC1 To a 500 mL flask containing neat Cl 2 SiMe 2 (64 0.50 mol) was added MsOH (97 1.01 mol); the immiscible solution rapidly evolved HC1 that was scrubbed with NaOH (250 50 wt% solution) or with iced water. After the solution was stirred overnight, the homogeneous oil was sparged with N 2 gas an additional day.

This synthesis is illustrated by Equation 3: neat Cl 2 SiMe 2 2MsOH neat (MsO) 2 SiMe 2 0. 5 HC1 (3)

N

2 sparge 'H NMR analysis of the product showed that one equivalent of HC1 was present with two equivalents (MsO) 2 SiMe 2 yield is quantitative.

EXAMPLE 2 Preparation of a Formula (II) Silane MsOSiMe 2 NH(t-butyl) Preparation of (t-BuNH),SiMe, (equation 4).

A 12 L flask equipped with an additional funnel and reflux condenser was charged with t-BuNH 2 (11 mol, 805 g) and THF (7 The solution was slowly treated with Cl 2 SiMe 2 mol, 645 g) that resulted in an exothermic reaction.

After the temperature had dropped to 40*C, the white slurry was filtered, the t-BuNH 3 Cl was washed with THF (1 and the filtrate was reduced to an oil that contained 97% pure WO 00/47587 WO 0047587PCT/T TOl02795 -9- (t-BuNH) 2 SiMe2 ('IH NMR). Yield was quantitative (1 Kg).

See equation 4.

Cl 2 SiMe 2 4 t-BUNH 2 t-BuNH) 2 SiMe 2 2 t-BUNH 3 Cl (quantitative) (4) Preparation of MsOSi(CH 3 2 NH (t-butyl) The (t-BuNH) 2 SiMG 2 prepared as described in Example 2 was added to one equivalent of neat (MSO) 2 SiMe 2 -O at room temperature, resulting in a 50-60 0 C exotherm. The resulting oil which contained insoluble solids was filtered through a glass frit to give >98% pure (t-BuNH) (MSO) SiMe 2 See equation (MsO) 2 SiMe 2 -O 5HC1 (t-BuNH) 2 SiM 2 na 1.-5 (MSO) Si (Me) 2 NH (t-butyl) EXAMPLE 3 Formula (II) Silane CF 3 0 3 S-Si (Me 3 2 NH (t-butyl) was prepared as described in Example 2 (Equation 5) except that (TfO) 2 Si (Me) 2 replaces (MsO) 2 SiM9 2 O0.5 HCl.

EXAMPLE 4 Preparation of 2 -Methlcvclopentadienvl (t-Butlamnido) DiLmethylsilane (Equation A 1 L flask was charged with 2methylcyclopentadiene (16 g, 200 inmol) and THF (160 The solution was cooled and treated with n-BuLi (1.6 M, WO 00/47587 PCT!US/0!02795 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) (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.

CH3

CH

3 (t-BuNH)SiMe 2 BuLi (t-BuNH)(MsO)SiMe 2 Li o B Me (6) 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(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. Alternatively, the alkali metallide, here lithium-2-methylcyclopentadiene, may be WO 00/47587 PCT/USO/02795 -11isolated from the reaction mixture in known manner and thereafter reacted with either a type I or type II silane.

EXAMPLE Preparation of 2-Methylindenyl(t-Butylamido) Dimethylsilane (Equation A 5 L flask was charged with 2-methylindene (1.67 mol, 217 g) and ether (1.5 The solution was cooled (-10 0 C) and treated with BuLi (1.67 mol, 1.04L). After the solution was stirred for one hour at room temperature, the solution was cooled and Me 2 Si(MsO)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 and the filtrate was reduced to a yellow oil that contained >98% pure 2-methylindenyl(t-butylamido) dimethylsilane NMR) in quantitative yield.

SCH

3 +BuLi+(t-BuNH) (MsO) SiMe 2 CH3 (2-methylindene) t-BuNHSiMe 2 (quantitative) (7) In this example, (t-BuNH)TfOSiMe 2 may be used instead of t-BuNH (MsO) SiMe 2 Also, in this example, 2-methylindene may be replaced with fluorene to provide a quantitative yield of 9fluorenyl-t-butylamido dimethylsilane.

WO 00/47587 PCTSUSOO/02795 -12- Also, in this example, 2-methylindene may be replaced with bromobenzene to obtain a quantitative yield of the expected phenyl-t-butylamido dimethylsilane.

EXAMPLE 6 Preparation of bis(2-methyl-4,5-benzoindenyl) dimethylsilane (equation A 2L flask charged with 2- (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 0 C, and then treated with a neat Formula I silane (MsO) 2 SiMe 2 -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

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 CI1 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.

WO 00/47587 -13- Me 2 Si I ether S CH3+BuLi0.5(MsO),SiMe' 0.5HCI 0.-5 CH3 +LiCl I 2 2-methyl-4,5-benzo(indene) (8) The above procedure was repeated, except that

(MSO)

2 SiMe 2 O0.5HC1 was replaced with (TfO) 2 Si(Me)2. The yield of bis(2-methyl-4,5-benzoindenyl) dimethylsilane was 60-65% of the bis( 2 -methylbenzoindenyl) dimethylsilane.

EXAMPLE 7 Preparation of Metallocene Catalyst from the Example Product (Equation A 1 L flask was charged with bis(2dimethylsilane (48 g, 115 mmol), toluene (480 mL), and ether (20 g, 270 mmol). The solution was cooled 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 0 C) and treated with ZrCl 4 (27 g, 115 mmol). By the time the solution had warmed to 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 CH 2 Cl 2 and the product was extracted with CH 2 Cl 2 through a layer of Celite into a 12 L flask that contained toluene (1 the extraction was WO 00/47587 PCTUS0/02795 -14stopped when the yellow color of the filtrate had turned translucent. The CH 2 C1 2 solvent was evaporated to give a toluene-slurry of yellow crystals. The solution was filtered, the yellow crystals were washed with toluene (1 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 NMR; yield 38%).

Me 2 Si Me 2 Si

S

C H 3 toen

CH

3 2 BuLi 0.5ZrClether 3/ 0 C 2 Cl Cl EXAMPLE 8 Preparation of Bis(3-Trimethylsilyl (TMS) indenyl) ethane (Equation 10). A 1L flask was charged with ethylene bis-indene (EBI) (0.100 mol, 26g) and THF (260g). The solution was cooled and treated with BuLi (0.200 mol. 125 mL). After one hour at RT, the solution was cooled and treated with Me 3 Si(OMS) (0.200 mol., 34 g) in one portion. After thirty minutes at RT, the solution was filtered through Celite, the solids containing rac/meso bis (TMS) EBI were washed with THF (130 and the filtrate was reduced giving a solid that contained 98% rac-meso WO 00/47587 WO 0047587PCT/USOO/102795 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

THF

EBI+2BuLi+2Me 3 Si (OMS) rac/meso-bis (TMS) EBI I 2Li (OSO 2 Me) Ifilter, wash w/THF meso-bis(TMS)EBI <rac/meso bis(TMS) EBI (solid) 1. Add heptane, strip THF 2. 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 7-dimethylindenyl) ethane, cyclopentadiene and methylcyclopentadiene. In this example, Me 3 Si (OTf may be used instead Of Me 3 Si (OMs).

EXAMPLE 9 Preparation of N-Silylated Cyclopentadienephenanthrene.

This procedure is illustrated by equation 11: NH (t-butyl) SiMe 2 1-BuLi+t-butyl (NH) (MsO) SiMe 2 Et 2 O Q FW 816 1.6M 223 345 32.1g 92.9m1 33.2g Quantitative 0.1486 0.1486 0.1486 1 HNMR WO 00/47587 PCT/US00!02795 -16- Cyclopentadienephenanthrene is mostly dissolved in diethyl ether (800 mL), n-BuLi is added, and the reaction mixture was stirred overnight.

O CH 3 I I

CH

3 S OSi NH t-butyl I I O CH 3 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 page 4, may be used instead of t-butyl NHMsOSiMe 2 Compounds which have the corresponding R groups instead of t-butyl are produced.

In this example, CF 3

SO

3 Si(CH 3 2 NH t-butyl may be used instead of CH 3

SO

3 SI (CH) 2 NH t-butyl.

EXAMPLE This example illustrates the preparation of n-silylated indenes of formula Si(Q) 2

I

NH

z in which 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 (154g, 0.906 mol) and ether (1500g) was cooled and WO 00/47587 PCTIUS00/02795 -17treated with n-BuLi (1.6M, 0.906 mol, 0.566 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 and then treated with the mesylate

CH

3

I

0 s 0 O=S=O CH3 Si CH 3

I

NH

t-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

SCH

3 Si(CH3)2

NH

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 0 C for a time period of from about 0.5 to 1.5 hours.

Claims (1)

1. 2. A process of claim 1, substantially as herein described with reference to any one of the Examples. DATED: 23 May 2002 PHILLIPS ORMONDE FITZPATRICK Patent Attorneys for: BOULDER SCIENTIFIC COMPANY o o W:\muay\MMHNODEL35877-00.doc