Method for preparing partially fluorinated alcohol

Patent metadata

Field	Value
Publication number	US-11897832-B2
Application number	US-202017439523-A
Country	US
Kind code	B2
Filing date	Mar 18, 2020
Priority date	Mar 21, 2019
Publication date	Feb 13, 2024
Grant date	Feb 13, 2024

Abstract

A method for preparing a partially fluorinated alcohol, comprises reacting an epoxide: wherein R1, R2, R3 and R4 are independently selected from the group comprising H, F, Cl, Br, I, CF3, alkyl, fluoroalkyl, haloalkyl with a fluorinating agent.

First claim

The invention claimed is:

1. A method for preparing a partially fluorinated alcohol, comprising:
reacting an epoxide:

with a fluorinating agent;
wherein R 1 , R 2 , R 3 and R 4 are independently selected from the group consisting of H, F, Cl, Br, I, CF 3 , alkyl, fluoroalkyl, and haloalkyl; where at least one of R 1 , R 2 , R 3 and R 4 is —CF 3 , and at least one of R 1 , R 2 , R 3 and R 4 is —H.

2. The method according to claim 1 , where the fluorinating agent comprises a nucleophilic fluorinating agent.

3. The method according to claim 1 , where the fluorinating agent is selected from HF and complexes of HF with nitrogen containing species.

4. The method according to claim 3 , where the complexes of HF with nitrogen containing species are selected from the group comprise Olah's reagent (HF:Pyridine complex), HF with urea, HF with a tertiary amine, or combinations thereof.

5. The method according to claim 1 , where one of R 1 to R 4 is —CF 3 , one of R 1 to R 4 is —F and two of R 1 to R 4 are —H.

6. The method according to claim 1 , where two of R 1 to R 4 are —CF 3 and two of R 1 to R 4 are —H.

7. The method according to claim 1 , where one of R 1 to R 4 is —CF 3 and three of R 1 to R 4 are —H.

8. The method according to claim 1 , where one of R 1 to R 4 is —CF 3 , one of R 1 to R 4 is —Cl and two of R 1 to R 4 are —H.

9. The method according to claim 4 , where the complexes of HF with nitrogen containing species comprises Olah's reagent and the ratio of HF to pyridine is 7:3 by weight.

10. The method according to claim 5 , where R 1 is —F and R 3 is —CF 3 , R 2 and R 4 are —H; or R 1 is —F and R 2 is —CF 3 , and R 3 and R 4 are —H.

11. The method according to claim 5 , where or R 1 is —F and R 2 is —CF 3 , and R 3 and R 4 are —H.

12. The method according to claim 6 , where R 1 is —CF 3 and R 3 is —CF 3 ; R 2 is —H and R 4 is —H.

13. The method according to claim 7 , where R 1 is —CF 3 , R 2 , and R 3 and R 4 are —H.

14. The method according to claim 8 , where R 1 is —Cl, R 3 is —CF 3 , and R 2 and R 4 are —H.

15. The method according to claim 8 , where R 1 is —Cl, R 2 is —CF 3 , and R 3 and R 4 are —H.

16. The method according to claim 1 , with the provision that the partially fluorinated alcohol is not 1,1,1,3-tetrafluoropropan-2-ol.

17. The method according to claim 7 , with the provision that the partially fluorinated alcohol is not 1,1,1,3-tetrafluoropropan-2-ol.

18. The method according to claim 1 , further comprising preparing the epoxide by reacting a partially fluorinated alkene:

wherein R 1 , R 2 , R 3 and R 4 are independently selected from the group consisting of H, F, Cl, Br, I, CF 3 , alkyl, fluoroalkyl, and haloalkyl, where at least one of R 1 , R 2 , R 3 and R 4 is —CF 3 and at least of one of R 1 , R 2 , R 3 and R 4 is —H;
with an oxidising agent to form a partially fluorinated epoxide.

19. The method according to claim 18 , wherein the oxidising agent is selected from the group consisting of air, oxygen and oxygen containing compounds, where the oxygen containing compounds optionally comprise peroxides, per-salts or compounds of oxygen with other elements.

20. The method according to claim 18 , wherein the oxidising agent comprises a hypohalite.

21. The method according to claim 18 , wherein the alkene comprises a tetrafluoropropene or a pentafluoropropene.

22. The method according to claim 21 , wherein the alkene comprises 1,3,3,3-tetrafluoropropene (1234ze) or 2,3,3,3-tetrafluoropropene (1234yf).

23. The method according to claim 21 , wherein the alkene comprises 1,1,3,3,3-pentafluoropropene (1225zc).

24. The method according to claim 1 , wherein the epoxide is a partially fluorinated epoxide, and the method further comprises reacting the partially fluorinated epoxide with a first fluorinating agent to form a compound having at least either of the following structures:

wherein at least two of R 1 to R 4 independently are H, Cl, Br, or I; and
reacting the compound having the at least either of the above structures with a second fluorinating agent.

25. The method according to claim 20 , wherein the oxidising agent comprises chlorite.

Assignees

• Mexichem Fluor Sa De Cv

Inventors

• Sharratt Andrew
• Grundy David
• Saxena Ira

Classifications

• C07C43/12

  containing halogen · CPC title

• C07D301/26 Primary

  Y being hydrogen · CPC title

• C07D303/08

  with hydrocarbon radicals, substituted by halogen atoms, nitro radicals or nitroso radicals · CPC title

• H01M2300/0028

  characterised by the solvent · CPC title

• C07D303/48

  with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms, e.g. ester or nitrile radicals · CPC title