Method for aromatic fluorination

Patent metadata

Field	Value
Publication number	US-11059782-B2
Application number	US-201716317336-A
Country	US
Kind code	B2
Filing date	Jul 13, 2017
Priority date	Jul 15, 2016
Publication date	Jul 13, 2021
Grant date	Jul 13, 2021

Abstract

Disclosed is a fluorination method comprising providing a fluorinating reagent and a solvent to a reaction mixture; providing a compound having the formula Ar—X to the reaction mixture; wherein Ar is aryl, substituted aryl, heteroaryl or substituted heteroaryl, and X is Cl, Br, I or NO2, providing tetramethylammonium 2,6-dimethylphenolate to the reaction mixture; and reacting under conditions sufficient to provide a species having the formula Ar—F.

First claim

What is claimed is:

1. A fluorination method comprising:
providing a solvent to a reaction mixture;
providing a fluorinating reagent to the reaction mixture;
providing a compound having the formula Ar—X to the reaction mixture;
wherein:
Ar is aryl, substituted aryl, heteroaryl or substituted heteroaryl, and
X is Cl, Br, I or NO 2 ;

providing a tetraalkyl ammonium phenolate salt to the reaction mixture; and
reacting under conditions sufficient to provide a species having the formula Ar—F.

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

3. The fluorination method of claim 1 , wherein Ar is iso-propyl 5-chloro-6-phenylpicolinate, 2-chloroquinoline, or (4-nitrophenyl)(phenyl)methanone.

4. The fluorination method of claim 1 , wherein the reaction temperature is from 0 to 130 degrees C.

5. The fluorination method of claim 1 , wherein the reaction mixture includes 1 equivalent of the Ar—X, 2 to 3 equivalents of tetramethylammonium 2,6-dimethylphenolate, and 3 to 10 equivalents of the fluorinating reagent.

6. The fluorination method of claim 2 , wherein the polar aprotic solvent comprises DMF, NMP, DMSO, DMPU, or DMA.

7. The fluorination method of claim 4 , wherein the reaction temperature is from 25 to 130 degrees C.

8. The fluorination method of claim 1 , wherein the tetraalkyl ammonium phenolate salt is tetramethylammonium 2,6-dimethylphenolate.

9. The fluorination method of claim 1 , wherein the reaction mixture does not contain a catalyst.

10. The fluorination method of claim 1 , wherein the fluorinating reagent is sulfuryl fluoride, an aryl fluorosulfonate or a heteroaryl fluorosulfonate.

11. The fluorination method of claim 2 , wherein Ar is iso-propyl 5-chloro-6-phenylpicolinate, 2-chloroquinoline, or (4-nitrophenyl)(phenyl)-methanone.

12. The fluorination method of claim 11 , wherein the reaction temperature is from 0 to 130 degrees C.

13. The fluorination method of claim 12 , wherein the reaction mixture includes 1 equivalent of the Ar—X, 2 to 3 equivalents of tetramethylammonium 2,6-dimethylphenolate, and 3 to 10 equivalents of the fluorinating reagent.

14. The fluorination method of claim 13 , wherein the polar aprotic solvent comprises DMF, NMP, DMSO, DMPU, or DMA.

15. The fluorination method of claim 2 , wherein the reaction temperature is from 0 to 130 degrees C.

16. The fluorination method of claim 15 , wherein the reaction mixture includes 1 equivalent of the Ar—X, 2 to 3 equivalents of tetramethylammonium 2,6-dimethylphenolate, and 3 to 10 equivalents of the fluorinating reagent.

17. The fluorination method of claim 16 , wherein the polar aprotic solvent comprises DMF, NMP, DMSO, DMPU, or CDMA.

Assignees

• Dow Global Technologies Llc
• Univ Michigan Regents

Inventors

• Sanford Melanie S
• Cismesia Megan A
• Hanley Patrick S
• Bland Douglas

Classifications

• C07C45/61

  by reactions not involving the formation of >C = O groups · CPC title

• C07D215/18

  Halogen atoms or nitro radicals · CPC title

• C07D213/79 Primary

  Acids; Esters · CPC title

• C07C45/63

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

• C07C49/215

  polycyclic · CPC title