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

Patent metadata

Field	Value
Publication number	US-9828447-B2
Application number	US-201414911562-A
Country	US
Kind code	B2
Filing date	Aug 19, 2014
Priority date	Aug 20, 2013
Publication date	Nov 28, 2017
Grant date	Nov 28, 2017

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.

First claim

The invention claimed is:

1. A process comprising
reacting a compound of formula (1)

wherein R 1 , R 2 , R 3 , R 4 , R 5 and R 6 each independently stand for H or a hydrocarbon radical having 1-20 C-atoms, and
wherein R 7 and R 8 each independently stand for H, or an alkyl or aryl or wherein R 7 and R 8 optionally form a ring together with the oxygen atoms to which they are bound,
with a compound of formula (2)

wherein R 1a , R 2a , R 3a , R 4a , R 5a , and R 6a each independently stand for H or a hydrocarbon radical having 1-20 C-atoms,
and wherein X 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)

wherein, in formula (3),
R 1 , R 2 , R 3 , R 4 , R 5 , R 1a , R 2a , R 3a , R 4a , R 5a , and R 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 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 1a , R 2a , R 3a , R 4a , R 5a , R 6a are hydrogen.

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

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

5. The process according to claim 1 , wherein X 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 3 ) 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.

Assignees

• Saudi Basic Ind Corp
• Sabic Global Technologies Bv

Inventors

• Kumar Mudubagilu Udaya
• Rasadiya Paresh Bhagvanbhai
• Paghadar Bharatkumar Ravjibhai
• Chougule Sambhaji Nanasaheb

Classifications

• C07F5/025

  Boronic and borinic acid compounds · CPC title

• C08F10/02 Primary

  Ethene · CPC title

• C07C1/321 Primary

  the hetero-atom being a non-metal atom · CPC title

• C07C2523/44

  Palladium · CPC title

• C07C2521/18

  Carbon · CPC title