Backfunctionalized imidazolinium salts and NHC carbene-metal complexes

Patent metadata

Field	Value
Publication number	US-10538494-B2
Application number	US-201816103267-A
Country	US
Kind code	B2
Filing date	Aug 14, 2018
Priority date	Oct 9, 2014
Publication date	Jan 21, 2020
Grant date	Jan 21, 2020

Abstract

Backfunctionalized imidazolinium salts and methods of synthesizing the same and NHC carbene-metal complexes therefrom. For backfunctionalized imidazolinium salts of the formula:

Wherein R 1 is selected from the group consisting of an ester group, an amide group, and an aromatic group; R 2 is selected from the group consisting of hydrogen, an ester group, an amide group, and an aromatic group; R 3 and R 4 are each selected from the group consisting of a C 1 -C 20 alkyl group, C 1 -C 20 partially fluorinated alkyl group, an aryl group, an aryl group with para CF 3 functionality, an aryl group having C 1 -C 20 partially fluorinated alkyl groups or partially fluorinated alkoxy groups, and a C 1 -C 20 partially fluorinated aliphatic group, and a C 1 -C 20 aryl group; and X is an anion. The method comprises cyclization of a halogenated acrylate with a formamidine with Hünig's base in a solvent.

First claim

What is claimed is:

1. A method of synthesizing the backfunctionalized imidazolinium salt comprising the formula:

R 1 being selected from the group consisting of an ester group, an amide group, and an aromatic group;
R 2 being selected from the group consisting of hydrogen, an ester group, an amide group, and an aromatic group;
each of R 3 and R 4 being separately selected from the group consisting of a C 1 -C 20 alkyl group, C 1 -C 20 partially fluorinated alkyl group, an aryl group, an aryl group with para CF 3 functionality, an aryl group having C 1 -C 20 partially fluorinated alkyl groups or partially fluorinated alkoxy groups, and a C 1 -C 20 partially fluorinated aliphatic group, and a C 1 -C 20 aryl group; and
X is an anion,

the method comprising:
formamidine cyclization of a halogenated acrylate with a primary base in a solvent, the primary base being Hünig's base.

2. The method of claim 1 , wherein the solvent is acetone and toluene.

3. The method of claim 1 , further comprising:
introducing a secondary base during the formamidine cyclization.

4. The method of claim 3 , wherein the secondary base is selected from the group consisting of triethylamine, formamidine, and Hünig's base.

5. The method of claim 1 , further comprising:
preparing halogenated, acrylate ester from an acrylate ester.

6. The method of claim 1 , wherein X is a halogen anion.

7. The method of claim 1 , wherein R 1 is in a trans-configuration with respect to R 2 .

Assignees

• Us Gov Air Force

Inventors

• Blanski Rusty L
• Grubbs Robert H

Classifications

• C07F15/0046

  Ruthenium compounds · CPC title

• C07D233/28 Primary

  with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms · CPC title

• C07F15/0033

  Iridium compounds · CPC title