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

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.

Claims41

Dependent claims

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.

3 more elements

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.

5 more elements

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.

9 more elements

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.

10 more elements

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.

10 more elements

Dependencies are inferred from the claim text.

Production of bridged metallocene complexes and intermediates therefor

Life of this patent

Production of bridged metallocene complexes and intermediates therefor

Life of this patent

Abstract

Claims41