Method for aromatic fluorination

Patent metadata

Field	Value
Publication number	US-10913696-B2
Application number	US-202016847193-A
Country	US
Kind code	B2
Filing date	Apr 13, 2020
Priority date	May 2, 2016
Publication date	Feb 9, 2021
Grant date	Feb 9, 2021

Abstract

Further disclosed a fluorination method comprising providing a compound having the structure Ar—OH to a reaction mixture; where Ar is an aryl or heteroaryl; providing SO2F2 to the reaction mixture; providing a fluorinating reagent to the reaction mixture; reacting the SO2F2, the fluorinating reagent and the compound having the structure Ar—OH to provide a fluorinated aryl species having the structure Ar—F.

First claim

What is claimed is:

1. A fluorination method comprising:
providing a salt having the following structure to a reaction mixture:

where Ar is an aryl or heteroaryl;
where M is a cation;

providing SO 2 F 2 to the reaction mixture;
reacting the SO 2 F 2 and the ammonium salt to provide a fluorinated aryl species having the following structure:
Ar—F.

2. A method according to claim 1 , further comprising providing a solvent to the reaction mixture.

3. The fluorination method of claim 2 , wherein the solvent is selected from the group consisting of polar aprotic solvents, alkoxy ether solvents, nitrile solvents, and aromatic solvents, or a mixture thereof.

4. The fluorination method of claim 1 , wherein the cation is selected from the group consisting of, sodium, potassium, cesium, tetramethylammonium, and tetrabutylammonium.

5. The fluorination method of claim 3 , wherein the cation is selected from the group consisting of, sodium, potassium, cesium, tetramethylammonium, and tetrabutylammonium.

6. A method according to claim 1 , wherein

is tetramethylammonium 4-cyanophenolate.

7. A method according to claim 2 , wherein the solvent comprises a polar aprotic solvent.

8. A method according to claim 2 , wherein the solvent comprises an alkoxy ether solvent.

9. A method according to claim 2 , wherein the solvent comprises a nitrile solvent.

10. A method according to claim 2 , wherein the solvent comprises an aromatic solvent.

11. A method according to claim 3 , wherein the cation is sodium.

12. A method according to claim 3 , wherein the cation is potassium.

13. A method according to claim 3 , wherein the cation is cesium.

14. A method according to claim 3 , wherein the cation is tetramethylammonium.

15. A method according to claim 3 , wherein the cation is tetrabutylammonium.

16. A method according to claim 2 , wherein the solvent comprises dimethyl formamide, dimethyl sulfoxide, N-methyl-2-pyrrolidone, dimethylacetamide, 1,3-dimethyl-3,4,5,6-tetrahydro-2-pyrimidinone, dichloromethane, acetonitrile, ethyl acetate, hexamethylphosphoric triamide, or 1,3-dimethyl-2-imidazolidinone.

17. A method according to claim 2 , wherein the solvent comprises DMF.

18. A method according to claim 2 , wherein the solvent comprises tetrahydrofuran, diglyme, or dimethoxyethane.

19. A method according to claim 2 , wherein the solvent comprises benzonitrile.

20. A method according to claim 2 , wherein the solvent comprises toluene.

Assignees

• Dow Global Technologies Llc
• Univ Michigan Regents

Inventors

• Sanford Melanie S
• Bland Douglas
• Hanley Patrick S
• Cismesia Megan A
• Schimler Sydonie D

Classifications

• C07C67/307 Primary

  by introduction of halogen; by substitution of halogen atoms by other halogen atoms · CPC title

• C07C231/12

  by reactions not involving the formation of carboxamide groups · CPC title

• C07C253/30 Primary

  by reactions not involving the formation of cyano groups · CPC title

• C07C17/093

  by replacement by halogens · CPC title

• C07D279/16

  condensed with one six-membered ring · CPC title