Backfunctionalized imidazolinium salts and NHC carbene-metal complexes

Patent metadata

Field	Value
Publication number	US-10150738-B2
Application number	US-201715596780-A
Country	US
Kind code	B2
Filing date	May 16, 2017
Priority date	Oct 9, 2014
Publication date	Dec 11, 2018
Grant date	Dec 11, 2018

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 an aliphatic group; and

X is an anion; the method comprises cyclization of a halogenated acrylate with Hünig's base in a solvent.

First claim

What is claimed is:

1. A method of synthesizing a 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;
R 3 and R 4 are each an aliphatic group; and
X is an anion,

the method comprising:
providing a halogenated acrylate or maleate having R 1 and R 2 groups; and
cyclization of the halogenated acrylate with a primary base in a solvent and a formamidine complex having R 3 and R 4 groups, the primary base being Hünig's base.

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

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

4. The method of claim 3 , wherein the secondary base is triethylamine.

5. The method of claim 1 , wherein each of R 3 and R 4 is separately selected from the group consisting of a C1-C20 alkyl group, C1-C20 partially fluorinated alkyl group, an aryl group, an aryl group with para CF 3 functionality, an aryl group having C1-C20 partially fluorinated alkyl groups or partially fluorinated alkoxy groups, and a C1-C20 partially fluorinated aliphatic group, and a C1-C20 aryl group.

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

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

8. The method of claim 1 , wherein the solvent is a polar aprotic solvent.

9. The method of claim 8 , wherein the polar aprotic solvent is selected from the group consisting of ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, and triethylene glycol dimethyl ether.

10. A method of synthesizing a 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;
R 3 and R 4 are each an aliphatic group; and
X is an anion,

the method comprising:
providing a halogenated acrylate or maleate having R 1 and R 2 groups; and
formamidine cyclization of a halogenated, fluorinated allyl ether with Hünig's base in polar aprotic solvent, the formamidine having R 3 and R 4 groups.

11. The method of claim 10 , further comprising:
introducing a secondary base during the cyclization.

12. The method of claim 11 , wherein the secondary base is triethylamine.

13. The method of claim 10 , wherein each of R 3 and R 4 is separately selected from the group consisting of a C1-C20 alkyl group, C1-C20 partially fluorinated alkyl group, an aryl group, an aryl group with para CF 3 functionality, an aryl group having C1-C20 partially fluorinated alkyl groups or partially fluorinated alkoxy groups, and a C1-C20 partially fluorinated aliphatic group, and a C1-C20 aryl group.

14. The method of claim 10 , wherein the R 1 group is in a trans-configuration with respect to the R 2 group.

15. The method of claim 10 , wherein the polar aprotic solvent is selected from the group consisting of ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, and triethylene glycol dimethyl ether.

Assignees

• Us Air Force

Inventors

• Blanski Rusty L
• Grubbs Robert H

Classifications

• C07F15/0033

  Iridium compounds · CPC title

• 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