Process for the preparation of 2,2′-bis-indenyl biphenyl ligands and their metallocene complexes

Abstract

The invention relates to a novel process for the preparation of 2,2′-bis indenyl biphenyl ligands of following formula (3): The invention also relates to metallocene complexes prepared using the novel process for the preparation of 2,2-bis indenyl biphenyl ligands. The invention also relates to novel intermediates used in the process for the preparation of 2,2′-bis indenyl biphenyl ligands. ##STR00001##

Claims

1. A process comprising reacting a compound of formula (1) ##STR00047## wherein R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5 and R.sup.6 each independently stand for H or a hydrocarbon radical having 1-20 C-atoms, and wherein R.sup.7 and R.sup.8 each independently stand for H, or an alkyl or aryl or wherein R.sup.7 and R.sup.8 optionally form a ring together with the oxygen atoms to which they are bound, with a compound of formula (2) ##STR00048## wherein R.sup.1a, R.sup.2a, R.sup.3a, R.sup.4a, R.sup.5a, and R.sup.6a each independently stand for H or a hydrocarbon radical having 1-20 C-atoms, and wherein X.sup.5 stands for a halogen in a solvent in the presence of a Pd catalyst and a base, to form the corresponding compound of formula (3) ##STR00049## wherein, in formula (3), R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.1a, R.sup.2a, R.sup.3a, R.sup.4a, R.sup.5a, and R.sup.6a are as defined in formula (1) and formula (2), respectively, wherein the solvent is an aromatic solvent, an ether solvent, an alcohol solvent, water, or a combination comprising at least one of the foregoing, wherein the Pd catalyst is a Pd(0) catalyst, and wherein the base is a quaternary ammonium salt, a tertiary amine, or an alkali or alkaline earth metal salt of acetate, alkoxide, carbonate, halide, hydroxide, or phosphate.

2. The process according to claim 1, wherein R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.1a, R.sup.2a, R.sup.3a, R.sup.4a, R.sup.5a, R.sup.6a are hydrogen.

3. The process according to claim 1, wherein R.sup.7 and R.sup.8 are hydrogen.

4. The process according to claim 1, wherein R.sup.7 and R.sup.8 form a pinacolyl ring together with the oxygen atoms to which they are bound.

5. The process according to claim 1, wherein X.sup.5 is Cl or Br.

6. The process according to claim 1, wherein the Pd catalyst is tetrakis(triphenylphosphine) palladium (0), tris(dibenzylideneacetone) dipalladium(0), bis(tricyclohexylphosphine) palladium(0), bis(tri-t-butylphosphine) palladium(0), bis[1.2-bis(diphenylphosphino)ethane] palladium(0), or palladium on carbon.

7. The process according to claim 1, wherein the Pd catalyst is Pd(PPh.sub.3).sub.4.

8. The process according to claim 1, wherein the solvent is methanol, ethanol, benzene, toluene, xylene, tetrahydrofuran, dioxane, dimethoxyethane, water, or a combination comprising at least one of the foregoing.

9. The process according to claim 1, wherein the solvent is toluene.

10. The process according to claim 1, wherein the base is tetrabutylammonium hydroxide, tetra n-butylammonium acetate, triethylamine, sodium carbonate, sodium acetate, sodium tert-butoxide, potassium carbonate, potassium iodide, sodium iodide, potassium acetate, cesium carbonate, cesium fluoride, lithium hydroxide, sodium hydroxide, sodium ethoxide, potassium fluoride, or potassium phosphate.

Description

EXAMPLES ACCORDING TO THE PRESENT INVENTION

Example 1. Preparation of the Compound of Formula (1), Wherein R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11 and R12 all Stand for H; Method 1

(1) Synthesis of the Compound of Formula (6):

(2) The compound of formula (7) (10 g, 49.79 mmol), 1,8-diamino naphthalene (8.66 g, 57.77 mmol) and Toluene (200 ml) were charged into a 500 ml four neck round bottom flask. The resulting solution was refluxed overnight and then checked with thin layer chromatography (TLC). The TLC showed that the reaction was complete. After this, the reaction was cooled to room temperature, water (50 ml) was added and the layers were separated. The organic layer was washed with dilute H.sub.2SO.sub.4 (10%, 50 ml) and the resulting layers were separated. Again the organic layer was washed with saturated sodium chloride solution (100 ml), the layers were separated after which the organic layer was dried over sodium sulphate and the solvent was removed by using Rota evaporator, residue crystallized in Hexane.

(3) Wt.: 10.05 g (HPLC: 99.10%), Yield: 63%

(4) Synthesis of the Compound of Formula (4):

(5) The above synthesized compound-3 (10.05 g, 31.11 mmol), 2-indenyl boronic acid (5.97 g, 37.33 mmol), Tetra butyl ammonium hydroxide (1M in methanol, 94.5 ml, 37.33 mmol) [Pd(PPh.sub.3).sub.4](approx 300 mg) and Toluene (100 ml) were charged into a 500 ml four neck flask. The resulting solution was heated to reflux (77-78° C.) for 4 hrs. and then checked with TLC. TLC showed a completion of the reaction, so the reaction was cooled to 5° C. and dilute HCL (10%, 75 ml) and Dichloromethane (100 ml) were added. The obtained layers were separated and the organic layer was washed with saturated sodium chloride. Subsequently, the organic layer was dried over sodium sulphate and the remaining solvent was removed by Rota evaporator and the residue crystallized in Hexane.

(6) Wt.: 6.432 g (HPLC: 86.55%), Yield: 60.6%

(7) Synthesis of the Compound of Formula (1):

(8) The above synthesized compound of formula (4) (6.432 g, 17.95 mmol) and THF (65 ml) were charged into a 250 ml four neck flask, stirring started. Into the resulting solution, dilute H.sub.2SO.sub.4 (1 M, 20 ml) was slowly added. During addition, the temperature was raised from 15° C. to 25° C. After the addition, the reaction was stirred for 1 hr and then checked with TLC. TLC showed a completion of the reaction, so into the resulting solution Dichloromethane (50 ml) was added. The obtained layers were separated, after which the organic layer was washed with saturated sodium chloride solution, the solvent was distilled out by Rota evaporator and the residue was crystallized in Hexane.

(9) Wt.: 3.216 g (HPLC: 90%), Yield: 76%

(10) The process of this example 1 is also illustrated by the below Scheme 1.

(11) In Scheme 1, a compound of formula (7), wherein X.sup.3 stands for Br, wherein R.sup.9, R.sup.10, R.sup.11, R.sup.12, R.sup.15 and R.sup.16 all stand for H is protected with PG-L (1,8,-diamino naphthalene) to form the corresponding compound of formula (6). The compound of formula (6) is then reacted with the compound of formula (5), wherein R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.13 and R.sup.14 all stand for H, in a solvent (toluene) in the presence of the Pd catalyst (Pd(PPh.sub.3).sub.4) and the base tetrabutylammonium hydroxide to form the corresponding compound of formula (4) after which the compound of formula (4) is deprotected by reaction of the compound of formula (4) with the mild sulphuric acid to form the corresponding compound of formula (1)

(12) ##STR00042##

Example 2. Preparation of the Compound of Formula (1), wherein R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11 and R12 all Stand for H; Method 2

(13) In a 50 ml four neck flask the following components were charged Mg turning (0.224 g, 9.22 mmol), tetrahydrofuran (THF) (15 ml), Tri methyl borate (3.04 g, 11.07 mmol), Ortho-Bromo-(2-indenyl)Benzene (OBPI) (1 g, 3.69 mmol) and 1, 2-Dibromo ethane (2-3 drops). The resulting solution was heated up to 35° C. and maintained at this temperature for 1 hr. Then it was checked with TLC. TLC showed complete consumption of starting material. Therefore, the heating was stopped, the reaction was cooled down to room temperature, the solution poured into dilute HCL (5%, 25 ml), Dichloromethane (25 ml) was added. The resulting mixture was stirred for 10 minutes and the formed layers were separated. The organic layer was dried over sodium sulphate and the solvent recovered by Rota evaporator. The residue was washed with Hexane (25 ml) to remove Phenyl indene.

(14) Wt.: 250 mg (HPLC: 91%), Yield: 28.7%

(15) The process of example 2 is also illustrated by the process in scheme 2.

(16) ##STR00043##

(17) In Scheme 2, a compound of formula (9), wherein R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.9, R.sup.10, R.sup.11, R.sup.12 all stand for H and wherein X.sup.4 stands for Br is reacted with the compound of formula (10), wherein R.sup.17 stands for H in the presence of magnesium and an acid to form the corresponding compound of formula (1).

Example 3. Preparation of 2,2′-bis(2-indenyl) biphenyl

(18) The compound of formula (1), wherein R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.8, R.sup.9, R.sup.10, R.sup.11 and R.sup.12 all stand for H (1 g, 4.2 mmol), Tetra butyl ammonium hydroxide (1M solution in methanol, 5.5 ml, 5.5 mmol), the compound of formula (2), wherein R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.10, R.sup.11 and R.sup.12 all stand for H and wherein X.sup.5 stands for Br (1.37 g, 5.1 mmol), Pd(PPh.sub.3).sub.4 (catalyst, 90 mg) and 15 ml of toluene were charged in 50 ml four neck round bottom flask. Resulted solution was refluxed (77-78° C.) for 1 hrs. and the product immediately started to precipitate out. Reflux continued further 1 hrs. and then checked TLC, it was showing completion of reaction. So the reaction was cooled to 0-5° C., HCl (10%, 10 ml) was added, stirred for 5 minutes, the solution was filtered, residue was washed with water and dried in an oven, to obtain 1.31 g (97% purity by HPLC, 82% yield). However, instead of Pd(PPh.sub.3).sub.4, Pd/C may also be employed.

(19) The process of example 3 is also illustrated by Scheme 3 below:

(20) ##STR00044##

(21) In Scheme 3, a compound of formula (1) (2-boronic acid phenyl indene), wherein R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.8, R.sup.9, R.sup.10, R.sup.11 and R.sup.12 all stand for H and a compound of formula (2) (2-bromo phenyl indene), wherein R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.10, R.sup.11 and R.sup.12 all stand for H and wherein X.sup.5 stands for Br are reacted in the presence of a Pd catalyst and a base to form the corresponding compound of formula (3).

Example 4. Preparation of the Compound of Formula (1), Wherein R1, R2, R3, R4, R5, R6, R9, R10, R11 and R12 all Stand for H and Wherein R7 and R8 Form a Pinacolyl Ring Together with the Oxygen Atoms to which they are Bound (=Building Block X)

(22) Step 1: 2-indenyl boronic acid (10 g, 56.7 mmol), and 1-bromo-2-chlorobenzene (13.03 g, 68.01 mmol), Tetra butyl ammonium hydroxide (1M in Methanol, 68 ml, 68.04 mmol), Tetrakis palladium triphenyl phosphine (400 mg) and Toluene (100 ml) charged in to 500 ml four neck flask. Resulted solution was heated to reflux (78° C.-80° C.) and reflux continued for further 5 hrs. Then sample submitted for HPLC, it was showing completion of reaction. So heating stopped, reaction cooled down 5° C. temperature. Then added dilute HCL (10%, 75 ml), stirred for 10 minutes, separated layers, organic layer washed with dilute sodium chloride solution and dried over Sodium sulphate. Solvent removed by Rota evaporator to afford the crude product, 2-chloro phenylindene (14.2 g, purity by HPLC 85%). Thereafter, crude 2-chloro phenyl indene was purified by high vacuum distillation. (Vapor temperature: 165-175° C., Vacuum: 0.7-0.8 mbar). After high vacuum distillation: Weight=10 g (HPLC=96.6%), Yield: 73.7%

(23) Above synthesized compound, 2-chloro phenylindene (5 g, 22.05 mmol), bis-pinacolato diboron (6.44 g, 25.36 mmol), triethyl amine (5.56 g, 55 mmol), Ni(COD).sub.2 (217 mg), triphenyl phosphine (415 mg) and Methanol (50 ml) was charged in to 100 ml RB flask. Resulted solution was heated to reflux (55° C.-57° C.) for an overnight. Then reaction was cooled to 10° C. and added dilute HCl (40 ml). Then added Dichloromethane (50 ml, Ethyl acetate also can be used), separated layers, organic layer washed with saturated sodium chloride solution. Solvents removed by Rota evaporator. Wt. of crude building block X (8.0 g).

(24) The process of example 4 is illustrated by the below Scheme 4:

(25) In Scheme 4, a compound of formula (12X), wherein R.sup.9, R.sup.10, R.sup.11 and R.sup.12 all stand for H and wherein X.sup.1 stands for Br and wherein X.sup.2 stands for Cl is reacted with a compound of formula 5, wherein R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.13 and R.sup.14 all stand for H in a solvent (toluene) in the presence of a Pd catalyst (Pd(PPh.sub.3).sub.4) and a base (TBAOH=Tetra butyl ammonium hydroxide) to form the corresponding compound of formula (13) and reacting the compound of formula (13) with the compound of formula 14X in a solvent, in the presence of Ni(COD).sub.2, triphenylphosphine and a base to form the corresponding compound of formula (1X) (also referred to herein as building block X).

(26) ##STR00045##

Example 5. Preparation of Bis(2-Indenyl) Biphenyl from Building Block X

(27) Building block X (8.0 g), building block Y, tetra butyl ammonium hydroxide (25.13 ml, 1M solution in methanol), tetrakis palladiumtriphenyl phosphine (200 mg) and toluene (120 ml) were added into a roundbottom flask and the resulting solution was heated to reflux (78° C.-80° C.) and the product immediately started to precipitate out and heating was continued for 3 hours. Then TLC was used and it showed completion of the reaction. Then the reaction was cooled down to 10° C., dilute HCl (50 ml) was added, stirred for 10 minutes and the solution was filtered off, the residue was washed with water and methanol and dried in an oven to afford 3 g of product. (2,2′-bi(2-indenyl)biphenyl).

(28) The process of example 5 is illustrated by the below Scheme 5:

(29) ##STR00046##

(30) In Scheme 5, the compound of formula (1), wherein R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.9, R.sup.10, R.sup.11 and R.sup.12 all stand for H and wherein R.sup.7 and R.sup.8 together with the oxygen atoms to which they are bound for a pinacolyl ring (building block X) is reacted with the compound of formula (2), wherein R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.9, R.sup.10, R.sup.11 and R.sup.12 all stand for H and wherein X.sup.5 stands for Br (building block Y) in a solvent in the presence of a Pd catalyst (Pd(PPh.sub.3).sub.4) and a base.

2,2′-bis(2-indenyl)biphenyl]zirconiumdichloride

(31) 2,2′-bis(2-indenyl) biphenyl]zirconiumdichloride (the compound of formula (15), wherein R.sup.1, R.sup.2 R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.9, R.sup.10, R.sup.11 and R.sup.12 all stand for H, wherein M stands for Zr and wherein Q stands for Cl and wherein k stands for 2 can be prepared from 2,2′-bis(2-indenyl)biphenyl (the compound of formula (3), wherein (R.sup.1, R.sup.2 R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.9, R.sup.10, R.sup.11 and R.sup.12 all stand for H) as described in EP1059300A1, example VIII.4, [0106] and [107]:

(32) “A 100 cc Schlenk charged with a stirring bar and 2,2′-bis(2-indenyl)biphenyl (3.84 g, 10.0 mmol) was brought under an atmosphere of dry. Dry ether (40 mL) was added. The resulting suspension was cooled to 0° C. by ice-bath, and a solution of n-butyllithium (1.6 M in hexanes, 12.5 mL, 20.0 mmol) was added. The mixture was allowed to warm to room temperature. slowly. The crystals slowly dissolved, while a fine suspension formed. Stirring at room temperature was continued for 4 hour.

(33) Meanwhile, a suspension of zirconium tetrachloride (2.34 g, 10 mmol) in dry ether (40 mL) was prepared. The suspensions (of dianion in ether and of zirconium tetrachloride in ether) were cooled in an acetone/dry ice bath, and mixed via a bended connection tube. The temperature was allowed to rise to room temperature. After stirring for two days, the suspension was filtered (under nitrogen atmosphere), and the residue washed with dry ether three times (the last washing was colourless). The residue was dissolved partly in boiling toluene (260 mL), and the suspension filtered hot under an atmosphere of dry nitrogen The clear yellow filtrate was cooled slowly to ambient temperature, giving yellow crystals of pure product (3.30 g, 6.08 mmol, 60.6%). The filtrate was used to extract the residue once more (boiling), and cooling to −20 DEG C. afforded another crop (0.65 g, 1.2 mmol, 12%).”

(34) 2,2′-bis(2-indenyl) biphenyl zirconiumdichloride can then be placed on a support as described in EP1059300A1, paragraphs [0109] and [0110]:

“Supported 2,2′-bis(2-indenyl)biphenyl zirconiumdichloride

(35) Silica (Grace Davison 2101) was heated at 200° C. under a stream of nitrogen for 6 hours. To 7.3 g of this silica was added 70 ml of toluene. The slurry was stirred and 49.4 ml of a 10 wt-% of methylalumoxane (diluted from a 30 wt % solution in toluene obtained from Albemarle) was added slowly. The resulting slurry was stirred for 16 hours at room temperature (20° C.), after which the solvent was removed by evaporation at 30° C.

(36) To a slurry of 2.1 g of the obtained solid in 30 ml of toluene was added a solution of 24 mg of [2,2′-bis(2-indenyl)biphenyl]-zirconiumdichloride in 20 mL of toluene, and the resulting slurry was stirred overnight. The slurry was then decanted and dried by evaporation at 35° C.”

(37) An improved way of preparing the supported 2,2′-bis(2-indenyl)biphenyl zirconiumdichloride from diphenyl(2-indenyl).sub.2ZrCl.sub.2 is described in WO 2013/097936A1, example 9:

Example 9. Large Scale Preparation of the Catalyst Composition of the Invention

(38) At room temperature, 0.595 kg of diphenyl(2-indenyl).sub.2ZrCl.sub.2 was added to 36.968 kg of a 30% methylaluminoxane solution (Al content 13.58 wt %) and stirred for 30 minutes to form activated metallocene. About 172 kg of dry toluene was added to 43 kg of silica 955 to form a silica slurry. At about 30° C., the activated metallocene was added to the silica slurry under agitation. After the activated metallocene was added, the temperature was increased to 50° C. After 2 hours at 50° C., all of modifier F (wherein modifier F was prepared by, at room temperature, slowly adding 0.114 kg of neat triisobutylaluminum to a solution of 0.059 of cyclohexylamine in 9.7 kg of dry toluene) was added. After addition the mixture was kept at 50° C. for 1 hour. The reaction temperature was then reduced to 30° C. The toluene was removed by filtration and the obtained catalysts composition was dried by raising the temperature to 55° C. and using a flow of warm nitrogen. The Al/Zr ratio used in this experiment was approximately 150.”

(39) The supported 2,2′-bis(2-indenyl)biphenyl zirconiumdichloride can then be used in a polymerization, for example as described in WO2013/097936A1 or for example as described in EP1059300A1, examples X-IX:

(40) “400 ml of pentamethyl heptane (abbreviation: PMH), ethylene and, eventually, 25 ml 1-octene were supplied to a 1.3-liter reactor, with heating to polymerisation temperature (Tp); the pressure was 2 MPa. Next, 0.78 ml (1.6 M solution in toluene) of methylaluminoxane (Witco) and the catalyst solution or slurry (0.125 ml of a 0.001 m solution in toluene) were premixed at room temperature for 1 minute and then supplied to the reactor. The catalyst supply vessel was rinsed out with 100 ml of pentamethylheptane (PMH). The pressure in the reactor was kept constant by supplying ethene. By cooling the reactor the temperature deviation from the setting was limited to a maximum of 5° C. After 10 minutes the polymerisation was stopped and the polymer was worked up by draining the solution and boiling it down under vacuum at 50° C.”.