Catalysts, methods of making, and methods of hydrofluorination

Patent metadata

Field	Value
Publication number	US-11602739-B2
Application number	US-201917259282-A
Country	US
Kind code	B2
Filing date	Jul 22, 2019
Priority date	Jul 23, 2018
Publication date	Mar 14, 2023
Grant date	Mar 14, 2023

Abstract

Some embodiments of the invention include inventive catalysts (e.g., catalysts of Formula (I)). Other embodiments include compositions comprising the inventive catalysts. Some embodiments include methods of using the inventive catalysts (e.g., in hydrofluorination of an organic compound). Further embodiments include methods for making the inventive catalysts. Additional embodiments of the invention are also discussed herein.

First claim

What is claimed is:

1. A catalyst selected from Formula (I)
resin-anion- x HF  (I)

wherein
resin is an anion exchange resin,
anion is HSO 4 − , BzO − , AcO − , H 2 PO 4 − , HPO 4 2− , PO 4 3− , MeSO 3 − , NO 3 − , ReO 4 − , CF 3 SO 3 − , ClO 4 − , or CF 3 (CF 2 ) 3 SO 3 − ,
x is 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, or 25, and
x is the number of equivalents of HF per equivalent anion in the resin-anion.

2. The catalyst of claim 1 , wherein the resin comprises a secondary ammonium group, a tertiary ammonium group, or a quaternary ammonium group.

3. The catalyst of claim 1 , wherein x is 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20.

4. The catalyst of claim 1 , wherein x is 5, 10, or 15.

5. The catalyst of claim 1 , wherein the anion is HSO 4 − , BzO − , AcO − , H 2 PO 4 − , HPO 4 2− , or PO 4 3− .

6. The catalyst of claim 1 , wherein the anion is HSO 4 − .

7. The catalyst of claim 1 , wherein (1) the catalyst is resin-HSO 4 − -5HF, resin-HSO 4 − -10HF, or resin-HSO 4 − -15HF, (2) the resin comprises a quaternary ammonium group or trimethylammonium, or (3) both.

8. A composition comprising the catalyst of claim 1 , and a solvent.

9. The composition of claim 8 , wherein the solvent is DCM (dichloromethane), DCE (1,2 dichloroethane), dioxane, Et 2 O (diethylether), CH 3 CN, EtOAc (ethyl acetate), DMSO (dimethyl sulfoxide), DMF (dimethyl formamide), or toluene.

10. The composition of claim 8 , wherein the solvent is DCM, DCE, or toluene.

11. A method for hydrofluorination of a reactant organic compound, the method comprising contacting a composition comprising the reactant organic compound with a composition comprising a catalyst of Formula (I) of claim 1 ,
wherein
the reactant organic compound is (1) an organic compound comprising one or more alkenes or (2) an organic compound comprising an aziridine,
the composition comprising the reactant organic compound optionally comprises a solvent, the composition comprising the catalyst of Formula (I) optionally comprises a solvent, or both, and
the solvent optionally in each composition can be the same or different.

12. The method of claim 11 , wherein the composition comprising the reactant organic compound comprises a solvent, the composition comprising a catalyst of Formula (I) comprises a solvent, or both; and the solvent is the same in each composition.

13. The method of claim 11 , wherein the reactant organic compound comprises one or more alkenes and the composition comprising the reactant organic compound further comprises a reactant aldehyde.

14. The method of claim 11 , wherein the method comprises
(a) providing a composition comprising the solvent and the organic compound comprising one or more alkenes; and
(b) contacting the composition of (a) with a composition comprising the catalyst of Formula (I),

wherein the product molecule comprises one F on one of the carbons where an alkene was in the organic compound comprising one or more alkenes.

15. The method of claim 11 , wherein the composition comprising the reactant organic compound further comprises a reactant aldehyde and the product molecule comprises a cyclization with the reactant aldehyde.

16. The method of claim 11 , wherein the method comprises
(a) providing a composition comprising the solvent and the organic compound comprising an aziridine; and
(b) contacting the composition of (a) with a composition comprising the catalyst of Formula (I),

wherein the product molecule comprises an opened aziridine ring and an F added to one of the two aziridine ring carbons.

17. The method of claim 11 , wherein the contacting in step (b) comprises (i) mixing the composition of (a) with the composition comprising the catalyst of Formula (I) or (ii) moving the composition of (a) through a column with the composition comprising a catalyst of Formula (I).

18. The method of claim 11 , wherein the composition comprising the catalyst further comprises a solvent which may be the same or different as the solvent in step (a).

19. The method of claim 11 , wherein the solvent in step (a), step (b) or both is DCE.

20. The method of claim 11 , wherein the catalyst is resin-anion-xHF and x is 5, 10, or 15.

21. The method of claim 11 , wherein (1) the catalyst is resin-HSO 4 − -5HF, resin-HSO 4 − -10HF, or resin —HSO 4 − -15HF, (2) the resin comprises a quaternary ammonium group or trimethylammonium, or (3) both.

22. The method of claim 11 , wherein the amount of the reactant organic molecule is at least about 0.01 mmol.

23. The method of claim 11 , wherein the contacting occurs for at least about 0.01 hours.

24. The method of claim 11 , wherein the contacting occurs for from about 5 hours to about 100 hours.

25. The method of claim 11 , wherein the temperature during the contacting is at least about 15° C.

26. The method of claim 11 , wherein the molecular weight of the reactant organic compound, the reactant aldehyde, or both is no more than about 3,000 daltons.

27. A method for preparing the catalyst of claim 1 comprising (a) optionally contacting the resin with the anion or a salt of the anion to produce resin-anion and (b) contacting HF with resin-anion.

28. The method of claim 27 , wherein the contacting in step (b) is at a temperature of no more than about 20° C.

29. The method of claim 27 , wherein the mole ratio of HF to anion (in the resin-anion) is at least about 5.

Assignees

• Univ Louisville Res Found Inc

Inventors

• Xu Bo
• Lu Zhichao
• Hammond Gerald B

Classifications

• B01J2231/32

  Addition reactions to C=C or C-C triple bonds · CPC title

• B01J47/02

  Column or bed processes · CPC title

• B01J37/30

  Ion-exchange · CPC title

• B01J31/08 Primary

  Ion-exchange resins · CPC title

• B01J37/26

  Fluorinating · CPC title