# US 5,710,299 A · Production of bridged metallocene complexes and intermediates therefor

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- Number: US 5,710,299 A
- Document ID: US5710299A
- Status: Granted
- Kind: A
- Application number: 08/672,128
- Filed: 1996-06-27
- Granted: 1998-01-20
- Earliest claimed: 1996-06-27
- Assignees: Albemarle Corporation
- Inventors: Meng-Sheng Ao; Hassan Y. Elnagar; Arcelio J. Malcolm; Jamie R. Strickler
- Web page: https://patentgrep.com/patent/US5710299A

## CPC

- C07F 7/0827: {Syntheses with formation of a Si-C bond}
- C07F 7/2208: {Compounds having tin linked only to carbon, hydrogen and/or halogen}
- C07F 7/30: Germanium compounds
- C07F 17/00: Metallocenes
- Y10S 526/943: Polymerization with metallocene catalysts
- C07F: ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM (metal-containing porphyrins C07D487/22)
- Y10S: TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS

## Abstract

Bridged metallocene compounds are produced by a process of promising commercial utility for plant-sized operations. The overall process involves the direct conversion of benzoindanones to benzoindanols which, without isolation, are converted to benzoindenes. Thereupon the benzoindenes are bridged by deprotonating the benzoindenes with a strong base such as butyllithium and reacting the resultant deprotonated product with a suitable silicon-, germanium- or tin-containing bridging reactant such as dichlorodimethylsilane. The resultant bridged product is deprotonated with a strong base such as butyllithium and reacted with a suitable Group IV, V, or VI metal-containing reactant such as ZrCl.sub.4 to provide a silicon-, germanium- or tin-bridged Group IV, V, or VI metal complex, such as a dihydrocarbylsilyl-bridged zirconocene complex. The initial benzoindenones used in such sequence can be formed readily and in high yield by reaction of a 2-haloacyl halide with naphthalenes unsubstituted in at least the 1- and 2-positions.

## Claims

### Claim 1

A process which comprises:
1) mixing together at least one of each of the following: (a) a 4,5-benzoindanone, (b) an alkali or alkaline earth metal borohydride or alkali or alkaline earth metal aluminum hydride, (c) a hydroxyl-containing compound capable of interacting with (b) to serve as a hydrogen source, and (d) at least one ether;
2) maintaining the resultant mixture under reaction conditions causing a 4,5-benzoindanol to be formed;
3) terminating the reaction by quenching the reaction mixture with water or an aqueous mixture; and
4) separating 4,5-bertzoindanol from ether and water by extracting the quenched reaction mixture with a liquid aromatic hydrocarbon having a higher boiling point or a higher initial boiling point than the ether, and distilling the resultant extract to leave a liquid hydrocarbon solution of the 4,5-benzoindanol.

### Claim 2 (depends on 1)

A process according to claim 1 wherein the ether comprises at least one cyclic ether.

### Claim 3 (depends on 1)

A process according to claim 1 wherein the ether is tetrahydrofuran.

### Claim 4 (depends on 1)

A process according to claim 1 wherein the 4,5-benzoindanone is a 2-hydrocarbyl-4,5-benzoindanone.

### Claim 5 (depends on 4)

A process according to claim 4 wherein the 2-hydrocarbyl-4,5-benzoindanone is a major mount of 2-methyl-4,5-benzoindan-l-one and a minor amount of 2-methyl-4,5-benzoindan-3-one.

### Claim 6 (depends on 1)

A process according to claim 1 wherein (b) is at least one compound of the formula AMH.sub.x (OR).sub.y wherein A is an alkali metal, M is boron or aluminum, R is hydrocarbyl, x is an integer in the range of 2 to 4, and y is an integer in the range of 0 to 2, the sum of x and y being 4.

### Claim 7 (depends on 1)

A process according to claim 1 wherein (b) is sodium borohydride and (c) is water or an alcohol.

### Claim 8 (depends on 1)

A process according to claim 1 wherein (b) is an alkali metal aluminum tetrahydride and (c) is water or an alcohol.

### Claim 9 (depends on 1)

A process according to claim 1 wherein the 4,5-benzoindanone is a 2-alkyl-4,5-benzoindanone, wherein (b) is an alkali metal borohydride and wherein (c) is water or an alcohol.

### Claim 10 (depends on 9)

A process according to claim 9 wherein the ether is at least predominately tetrahydrofuran, wherein the 2-alkyl-4,5-benzoindanone is a major amount of 2-methyl-4,5-benzoindan-1-one and a minor amount of 2-methyl-4,5-benzoindan-3-one, and wherein (b) is sodium borohydride.

### Claim 11

A process which comprises:
1) mixing together at least one of each of the following: (a) a 4,5-benzoindanone, (b) an alkali or alkaline earth metal borohydride or alkali or alkaline earth metal aluminum hydride, (c) a hydroxyl-containing compound capable of interacting with (b) to serve as a hydrogen source, and (d) at least one ether;
2) maintaining the resultant mixture under reaction conditions causing a 4,5-benzoindanol to be formed;
3) terminating the reaction by quenching the reaction mixture with water or an aqueous mixture;
4) extracting the quenched reaction mixture with a liquid hydrocarbon having a higher boiling point or a higher initial boiling point than the ether;
5) distilling the resultant extract to leave a liquid hydrocarbon solution of the 4,5-benzoindanol; and
6) catalytically dehydrating said 4,5-benzoindanol using an arylsulfonic acid catalyst to thereby form a 4,5-benzoindene.

### Claim 12 (depends on 11)

A process according to claim 11 wherein the 4,5-benzoindanone is a 2-alkyl-4,5-benzoindanoine, wherein (b) is an alkali metal borohydride and wherein (c) is water or an alcohol.

### Claim 13 (depends on 12)

A process according to claim 12 wherein the ether is at least predominately tetrahydrofuran, wherein the 2-alkyl-4,5-benzoindanone is a major mount of 2-methyl-4,5-benzoindan-1-one and a minor mount of 2-methyl-4,5-benzoindan-3-one, and wherein (b) is sodium borohydride.

### Claim 14 (depends on 11)

A process according to claim 11 wherein the 4,5-benzoindanone is a 2-alkyl-4,5-benzoindanone, wherein (b) is an alkali metal borohydride, wherein (c) is water or an alcohol, wherein the liquid hydrocarbon has a higher boiling point or a higher initial boiling point not only than the ether, but, if present, the alcohol as well, wherein not only said ether but, if present, said alcohol are distilled off to leave a liquid hydrocarbon solution of the 4,5-benzoindanol, and wherein the catalytic dehydration is conducted without isolating the 4,5-benzoindanol from the liquid hydrocarbon solution.

### Claim 15 (depends on 14)

A process according to claim 14 wherein the ether is at least predominately tetrahydrofuran, wherein the 2-alkyl-4,5-benzoindanone is a major amount of 2-methyl-4,5-benzoindan-1-one and a minor amount of 2-methyl-4,5-benzoindan-3-one, and wherein (b) is sodium borohydride.

### Claim 16 (depends on 15)

A process according to claim 15 wherein (c) is an alcohol and wherein the liquid hydrocarbon is at least one aromatic hydrocarbon capable of forming an azeotrope with water.

### Claim 17 (depends on 16)

A process according to claim 16 wherein the alcohol is methanol and wherein the liquid hydrocarbon consists essentially of toluene.

### Claim 18

A process which comprises:
1) mixing together at least one of each of the following: (a) a 4,5-benzoindanone, (b) an alkali or alkaline earth metal borohydride or alkali or alkaline earth metal aluminum hydride, (c) a hydroxyl-containing compound capable of interacting with (b) to serve as a hydrogen source, and (d) at least one ether;
2) maintaining the resultant mixture under reaction conditions causing a 4,5-benzoindanol to be formed;
3) terminating the reaction by quenching the reaction mixture with water or an aqueous mixture;
4) extracting the quenched reaction mixture with a liquid hydrocarbon having a higher boiling point or a higher initial boiling point than the ether;
5) distilling the resultant extract to leave a liquid hydrocarbon solution of the 4,5-benzoindanol;
6) catalytically dehydrating said 4,5-benzoindanol using an arylsulfonic acid catalyst to thereby form a 4,5-benzoindene; and
7) deprotonating said 4,5-benzoindene with a strong base and reacting the resultant deprotonated intermediate with a reactant which in its original condition can be depicted by the formula R .sup.11 R.sup.12 M.sup.1 X.sub.2 where R.sup.11 and R.sup.12 are the same or different and each is (i) a hydrocarbyl group containing up to about 18 carbon atoms or (ii) a hydrocarbyl(oxyalkylene) or hydrocarbylpoly(oxyalkylene) group containing up to about 100 carbon atoms; M.sup.1 is a silicon, germanium or tin atom; and X is a halogen atom; such that a silicon-, germanium- or tin-bridged complex of the 4,5-benzoindene is formed.

### Claim 19 (depends on 18)

A process according to claim 18 wherein R.sup.11 and R.sup.12 are the same and are C.sub.1 to C.sub.4 alkyl groups, wherein M.sup.1 is a silicon atom, and wherein X is a bromine or chlorine atom.

### Claim 20 (depends on 19)

A process according to claim 19 wherein the 4,5-benzoindanone is a 2-alkyl-4,5-benzoindanone, wherein (b) is an alkali metal borohydride and wherein (c) is water or an alcohol.

### Claim 21 (depends on 20)

A process according to claim 20 wherein the ether is at least predominately tetrahydrofuran, wherein the 2-alkyl-4,5-benzoindanone is a major mount of 2-methyl-4,5-benzoindan-1-one and a minor amount of 2-methyl-4,5-benzoindan-3-one, and wherein (b) is sodium borohydride.

### Claim 22 (depends on 19)

A process according to claim 19 wherein the 4,5-benzoindanone is a 2-alkyl-4,5-benzoindanone, wherein (b) is an alkali metal borohydride, wherein (c) is water or an alcohol, wherein the liquid hydrocarbon has a higher boiling point or a higher initial boiling point not only than the ether, but, if present, the alcohol as well, wherein not only said ether but, if present, said alcohol are distilled off to leave a liquid hydrocarbon solution of the 4,5-benzoindanol, and wherein the catalytic dehydration is conducted without isolating the 4,5-benzoindanol from the liquid hydrocarbon solution.

### Claim 23 (depends on 22)

A process according to claim 22 wherein the ether is at least predominately tetrahydrofuran, wherein the 2-alkyl-4,5-benzoindanone is a major amount of 2-methyl-4,5-benzoindan-1-one and a minor amount of 2-methyl-4,5-benzoindan-3-one, and wherein (b) is sodium borohydride.

### Claim 24 (depends on 23)

A process according to claim 23 wherein (c) is an alcohol and wherein the liquid hydrocarbon is predominately one or more one aromatic hydrocarbons capable of forming azeotrope with water.

### Claim 25 (depends on 18)

A process according to claim 18 wherein the strong base is a lithium alkyl.

### Claim 26

A process which comprises:
1) mixing together at least one of each of the following: (a) a 4,5-benzoindanone, (b) an alkali or alkaline earth metal borohydride or alkali or alkaline earth metal aluminum hydride, (c) a hydroxyl-containing compound capable of interacting with (b) to serve as a hydrogen source, and (d) at least one ether;
2) maintaining the resultant mixture under reaction conditions causing a 4,5-benzoindanol to be formed;
3) terminating the reaction by quenching the reaction mixture with water or an aqueous mixture;
4) extracting the quenched reaction mixture with a liquid hydrocarbon having a higher boiling point or a higher initial boiling point than the ether;
5) distilling the resultant extract to leave a liquid hydrocarbon solution of the 4,5-benzoindanol;
6) catalytically dehydrating said 4,5-benzoindanol using an arylsulfonic acid catalyst to thereby form a 4,5-benzoindene;
7) deprotonating said 4,5-benzoindene with a strong base and reacting the resultant deprotonated intermediate with a reactant which in its original condition can be depicted by the formula R.sup.11 R.sup.12 M.sup.1 X.sub.2 where R.sup.11 and R.sup.12 are the same or different and each is (i) a hydrocarbyl group containing up to about 18 carbon atoms or (ii) a hydrocarbyl(oxyalkylene) or hydrocarbylpoly(oxyalkylene) group containing up to about 100 carbon atoms; M.sup.1 is a silicon, germanium or tin atom; and X is a halogen atom; such that a silicon-, germanium- or tin-bridged complex of the 4,5-benzoindene is formed; and
8) deprotonating said bridged complex with a strong base and reacting the resultant deprotonated intermediate with a Group IV, V, or VI metal tetrahalide to thereby form a silicon-, germanium- or tin-bridged Group IV, V, or VI metal-containing metallocene complex.

### Claim 27 (depends on 26)

A process according to claim 26 wherein R.sup.11 and R.sup.12 are the same and are C.sub.1 to C.sub.4 alkyl groups, wherein M.sup.1 is a silicon atom, wherein X is a bromine or chlorine atom, and wherein the Group IV, V, or VI metal-containing reactant is a zirconium tetrahalide.

### Claim 28 (depends on 27)

A process according to claim 27 wherein the 4,5-benzoindanone is a 2-alkyl-4,5-benzoindanone, wherein (b) is an alkali metal borohydride, wherein (c) is water or an alcohol, and wherein the zirconium tetrahalide is zirconium tetrachloride or zirconium tetrabromide.

### Claim 29 (depends on 28)

A process according to claim 28 wherein the ether is at least predominately tetrahydrofuran, wherein the 2-alkyl-4,5-benzoindanone is a major mount of 2-methyl-4,5-benzoindan-1-one and a minor amount of 2-methyl-4,5-benzoindan-3-one, and wherein (b) is sodium borohydride.

### Claim 30 (depends on 27)

A process according to claim 27 wherein the liquid hydrocarbon is a liquid aromatic hydrocarbon.

### Claim 31 (depends on 27)

A process according to claim 27 wherein the 4,5-benzoindanone is a 2-alkyl-4,5-benzoindanone, wherein (b) is an alkali metal borohydride, wherein (c) is water or an alcohol, wherein the liquid hydrocarbon has a higher boiling point or a higher initial boiling point not only than the ether, but also, if present, the alcohol, wherein said ether and, if present, said alcohol are distilled off, and wherein the catalytic dehydration is conducted without isolating the 4,5-benzoindanol from the liquid hydrocarbon solution.

### Claim 32 (depends on 31)

A process according to claim 31 wherein the ether is at least predominately tetrahydrofuran, wherein the 2-alkyl-4,5-benzoindanone is a mixture of a major mount of 2-methyl-4,5-benzoindan-1-one and a minor mount of 2-methyl-4,5-benzoindan-3-one, and wherein (b) is sodium borohydride.

### Claim 33 (depends on 32)

A process according to claim 32 wherein (c) is an alcohol and wherein the liquid hydrocarbon consists essentially of at least one aromatic hydrocarbon capable of forming an azeotrope with water.

### Claim 34 (depends on 26)

A process according to claim 26 wherein each of the respective strong bases used in 7) and in 8) is a lithium alkyl.

### Claim 35 (depends on 26)

A process according to claim 26 wherein the deprotonating of the 4,5-benzoindene with a strong base and the reacting of the resultant deprotonated intermediate are conducted while the 4,5-benzoindene and the resultant deprotonated intermediate, respectively, are dissolved in a liquid lower dialkyl ether.

### Claim 36 (depends on 35)

A process according to claim 35 wherein the 4,5-benzoindene is a 2-alkyl-4,5-benzoindene, wherein each of the respective strong bases used in 7) and in 8) is a lithium alkyl, and wherein said reactant is a dialkyldihalosilane.

### Claim 37 (depends on 36)

A process according to claim 36 wherein the alkyl groups of the dialkyldihalosilane contain no more than 4 carbon atoms each.

### Claim 38 (depends on 35)

A process according to claim 35 wherein the 4,5-benzoindene is 2-methyl-4,5-benzoindene, wherein each of the respective strong bases used in 7) and in 8) is butyllithium, wherein said ether is diethyl ether, wherein said reactant is dichlorodimethylsilane, and wherein said solids are separated from the liquid phase by filtration.

### Claim 39

A process which comprises:
1) mixing together at least one of each of the following: (a) a 4,5-benzoindanone, (b) an alkali or alkaline earth metal borohydride or alkali or alkaline earth metal aluminum hydride, and (c) a hydroxyl-containing compound selected from the group consisting of water, an alcohol, and a mixture thereof capable of interacting with (b) to serve as a hydrogen source, under reaction conditions causing a 4,5-benzoindanol to be formed;
2) terminating the reaction by quenching the reaction mixture with water or an aqueous mixture;
3) extracting the quenched reaction mixture with a liquid hydrocarbon;
4) distilling the resultant extract to leave a liquid hydrocarbon solution of the 4,5- benzoindanol;
5) catalytically dehydrating said 4,5-benzoindanol using a arylsulfonic acid catalyst to thereby form a 4,5-benzoindene;
6) deprotonating said 4,5-benzoindene with a strong base and reacting the resultant deprotonated intermediate with a reactant which in its original condition can be depicted by the formula R.sup.11 R.sup.12 M.sup.1 X.sub.2 where R.sup.11 and R.sup.12 are the same or different and each is (i) a hydrocarbyl group containing up to about 18 carbon atoms or (ii) a hydrocarbyl(oxyalkylene) or hydrocarbylpoly(oxyalkylene) group containing up to about 100 carbon atoms; M.sup.1 is a silicon, germanium or tin atom; and X is a halogen atom; such that a silicon-, germanium- or tin-bridged complex of the 4,5-benzoindene is formed;
7) deprotonating said bridged complex with a strong base and reacting the resultant deprotonated intermediate with a Group IV, V, or VI metal tetrahalide to thereby form solids comprising a silicon-, germanium- or tin-bridged Group IV, V, or VI metal-containing metallocene complex; and
8) forming and heating a slurry of said solids at an elevated temperature in an aprotic, polar solvent so as to extract impurities from said solids to said solvent and then separating the impurity-containing solvent and the solids from each other.

### Claim 40 (depends on 39)

A process according to claim 39 wherein said aprotic, polar solvent is an ether.

### Claim 41 (depends on 40)

A process in accordance to claim 40 wherein said ether is tetrahydrofuran.