Synthesis of benzyloxyphenoxy phenol ligands

Patent metadata

Field	Value
Publication number	US-10815255-B2
Application number	US-201816475819-A
Country	US
Kind code	B2
Filing date	Jan 5, 2018
Priority date	Jan 6, 2017
Publication date	Oct 27, 2020
Grant date	Oct 27, 2020

Abstract

Synthetic methods for the preparation of ligands and metal-ligand complexes are disclosed.

First claim

What is claimed is:

1. A process for preparing a ligand, the process comprising
contacting 3-((2-bromobenzyl)oxy)propan-1-ol with bromocresol and triphenylphosphine in a reaction medium under reaction conditions, thereby forming a 2-bromo-1-(3-((2-bromobenzyl)oxy)propoxy)-4-methylbenzene;
contacting a first reactant with a bridging reactant in a polar aprotic reaction medium under reaction conditions, thereby forming the ligand; wherein: (a) when the first reactant is 2-((tetrahydro-2H-pyran-2-yl)oxy)-[1,1′-biphenyl]-3-yl lithium, the bridging reactant is 2-bromo-1-(3-((2-bromobenzyl)oxy)propoxy)-4-methylbenzene, and the ligand is 2-(3-((2′-hydroxy-[1,1′:3′,1″-terphenyl]-2-yl)methoxy)propoxy)-5-methyl-[1,1′:3′,1″-terphenyl]-2′-ol (Ligand AP); or wherein (b) when the first reactant is 2′,5,5′-trimethyl-2-((methoxymethoxy)-[1,1′-biphenyl]-3-yl lithium, the bridging reactant is 2-bromo-1-(3-((2-bromobenzyl)oxy)propoxy)-4-methylbenzene, and the ligand is 2-(3-((2′-hydroxy-2″,5′,5″-trimethyl-[1,1′:3′,1″-terphenyl]-2-yl)methoxy)propoxy)-2″,5,5′,5″-tetramethyl-[1,1′:3′,1″-terphenyl]-2′-ol (Ligand BP); or wherein (c) when the first reactant is 2-(methoxymethoxy)-5-methyl-3-(2-methylnaphthalen-1-yl)phenyl) lithium, the bridging reactant is 2-bromo-1-(3-((2-bromobenzyl)oxy)propoxy)-4-methylbenzene, and the ligand is 2′-(3-((2′-hydroxy-5′-methyl-3′-(2-methylnaphthalen-1-yl)-[1,1′-biphenyl]-2-yl)methoxy)propoxy)-5,5′-dimethyl-3-(2-methylnaphthalen-1-yl)-[1,1′-biphenyl]-2-ol (Ligand CP).

2. The process of claim 1 further comprising a second preliminary step to prepare the 3-((2-bromobenzyl)oxy)propan-1-ol, the second preliminary step comprising contacting 1,3-propanediol with 2-bromobenzylbromide in a reaction medium under reaction conditions, thereby forming the 3-((2-bromobenzyl)oxy)propan-1-ol.

3. The process of claim 1 wherein the bridging reactant is a 2-bromo-1-(2-((2-bromobenzyl)oxy)ethoxy)-4-methylbenzene, and the ligand is Ligand AE

respectively.

4. The process of claim 3 wherein the 2-bromo-1-(2-((2-bromobenzyl)oxy)ethoxy)-4-methylbenzene is prepared by a process comprising contacting 2-((2-bromobenzyl)oxy)ethanol with bromocresol in a reaction medium under reaction conditions, thereby forming the 2-bromo-1-(2-((2-bromobenzyl)oxy)ethoxy)-4-methylbenzene.

5. The process of claim 4 wherein the 2-((2-bromobenzyl)oxy)ethanol is prepared by a process comprising contacting ethylene glycol with 2-bromobenzylbromide in a reaction medium under reaction conditions, thereby forming the 2-((2-bromobenzyl)oxy)ethanol.

6. The process of claim 1 further comprising contacting the ligand with bis-benzyl-zirconium(IV) dichloride (ZrBn 2 Cl 2 ) in a reaction medium under reaction conditions, thereby forming the zirconium complex of the ligand.

Assignees

• Univation Tech Llc

Inventors

• Faler Catherine A
• Harlan C Jeff

Classifications

• C07C41/30

  by increasing the number of carbon atoms, e.g. by oligomerisation · CPC title

• C07C43/23

  containing hydroxy or O-metal groups · CPC title

• C07C43/225

  containing halogen · CPC title

• C07F7/003 Primary

  without C-Metal linkages · CPC title

• C07C43/1786

  containing halogen · CPC title