IP Library Granted Patent US 10,913,696
Granted Patent B2
US 10,913,696 · App. 16/847,193 · Granted Feb 9, 2021

Method for aromatic fluorination

Inventors: Melanie S. Sanford (Ann Arbor, MI); Douglas Bland (Midland, MI); Patrick S. Hanley (Midland, MI); Megan A. Cismesia (Midland, MI); Sydonie D. Schimler (Ann Arbor, MI)
Assignees: Dow Global Technologies LLC; The Regents of the University of Michigan
C07C17/02C07C17/093C07C25/13C07C41/22C07C45/63C07C67/307C07C201/12C07C231/12C07C253/30C07C317/14C07D209/08C07D209/88C07D213/57C07D213/61C07D213/75C07D213/79C07D215/18C07D279/16C07D311/16C07D453/02C07J21/008
View Patent ↗
Loading inventors, assignments & file history…
Monitor This Case
Get email alerts when status or documents change.
Order Certified Copies
Most orders are placed with the USPTO same day — all within 24 business hours.
Order via The Patent Place →
Pre-filled with this patent's details
Quick Facts
Patent No.
US 10,913,696
App. No.
16/847,193
Granted
Feb 9, 2021
Kind
B2
Abstract

Disclosed is a fluorination method comprising providing an aryl fluorosulfonate and a fluorinating reagent to a reaction mixture; and reacting the aryl fluorosulfonate and the fluorinating reagent to provide a fluorinated aryl species. Also disclosed is a fluorination method comprising providing, a salt comprising a cation and an aryloxylate, and SO 2 F 2 to a reaction mixture; reacting the SO 2 F 2 and the ammonium salt to provide a fluorinated aryl species. 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 SO 2 F 2 to the reaction mixture; providing a fluorinating reagent to the reaction mixture; reacting the SO 2 F 2 , the fluorinating reagent and the compound having the structure Ar—OH to provide a fluorinated aryl species having the structure Ar—F.

Claims (27)

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.

Assignments (4)
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Nov 18, 2024
From: DOW GLOBAL TECHNOLOGIES LLC
To: DOW AGROSCIENCES LLC
Reel/Frame 069296/0120 →
CHANGE OF NAME Recorded Nov 18, 2024
From: DOW AGROSCIENCES LLC
To: CORTEVA AGRISCIENCE LLC
Reel/Frame 069383/0319 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Apr 20, 2020
From: BLAND, DOUGLAS; HANLEY, PATRICK S.
To: DOW GLOBAL TECHNOLOGIES LLC
Reel/Frame 052442/0633 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Apr 20, 2020
From: SANFORD, MELANIE S.; CISMESIA, MEGAN A.; SCHIMLER, SYDONIE D.
To: THE REGENTS OF THE UNIVERSITY OF MICHIGAN
Reel/Frame 052442/0674 →
Continuity (6)
Division 16098296
Provisional Application 62408270 · Oct 14, 2016
Provisional Application 62376967 · Aug 19, 2016
Provisional Application 62362721 · Jul 15, 2016
Provisional Application 62330311 · May 2, 2016
Related Publication 20200239390A1 · Jul 30, 2020