Fluorination processes

Patent metadata

Field	Value
Publication number	US-12071390-B2
Application number	US-202318201571-A
Country	US
Kind code	B2
Filing date	May 24, 2023
Priority date	Dec 22, 2021
Publication date	Aug 27, 2024
Grant date	Aug 27, 2024

Abstract

A process for preparing a fluorinating reagent from a calcium-containing compound is disclosed. The process bypasses the requirement to form hydrofluoric acid. The fluorinating reagent can be used to prepare high-value fluorochemicals.

First claim

The invention claimed is:

1. A method of manufacturing an activated fluorination reagent, the method comprising:
combining a first salt, the first salt comprising calcium and fluorine, with a second salt, the second salt comprising an anion, which said anion when combined with Ca 2+ to form a third salt has a lattice energy greater than 2450 KJ/mol, to form a salt mixture; and
applying mechanical force to the salt mixture to yield the activated fluorination reagent.

2. The method of claim 1 , wherein the first salt is CaF 2 or Ca 5 (PO 4 ) 3 F.

3. The method of claim 1 , wherein the second salt is a metal hydroxide, a metal sulphite, a metal sulphate, a carbonate, or an inorganic phosphate.

4. The method of claim 3 , wherein the inorganic phosphate is a pyrophosphate.

5. The method of claim 1 , wherein a ratio of the first salt to the second salt is about 1:0.5 to 1:100.

6. The method of claim 5 , wherein the mechanical force is applied using a ball mill, a mortar and pestle, a twin-screw extruder, using an ultrasonic bath, a resonant acoustic mixer, and/or a mechanical press.

7. The method of claim 6 , wherein the mechanical press comprises a jaw crusher.

8. The method of claim 6 , wherein the ball mill comprises a vibratory mill, a planetary mill, a drum mill, and/or an attritor mill.

9. The method of claim 6 , wherein the method does not comprise reacting a strong acid with the first salt to form hydrofluoric acid.

10. The method of claim 9 , wherein <1 ppm of HF is produced at any point during the reaction.

11. The method of any of claim 10 , wherein the mechanical force is applied at a frequency of about 0.5 Hz-60 kHz.

12. The method of claim 11 , wherein the mechanical force is applied at a temperature of about −20-100° C.

13. The method of claim 1 , further comprising combining the activated fluorination reagent,
with a reactant; and fluorinating the reactant to produce a fluorinated compound.

14. The method of claim 13 , wherein the fluorinated compound is an organo-fluorine compound.

15. The method of claim 13 , wherein the activated fluorination reagent comprises characteristic 2θ reflections at about 21.9°, 30.3°, 31.6°, and/or 43.4°.

16. The method of claim 13 , wherein the reactant is an aromatic or aliphatic compound comprising at least one leaving group located at a site to be fluorinated.

17. The method of claim 16 , wherein the leaving group is a halogen.

18. The method of claim 17 , wherein a fluorination reaction yield of the organofluorine compound is at least about 10% measured based on a starting amount of the reactant.

19. The method of claim 18 , wherein the fluorination reaction is a mono-fluorination reaction.

20. The method of claim 18 , wherein the fluorination reaction is a di-fluorination reaction.

Assignees

• Univ Oxford Innovation Ltd

Inventors

• Gouverneur Veronique
• Pupo Gabriele
• Browne Duncan
• Leitch Jamie

Classifications

• C01P2006/80

  Compositional purity · CPC title

• C01P2002/72

  by d-values or two theta-values, e.g. as X-ray diagram · CPC title

• C07C17/208 Primary

  the other compound being MX · CPC title

• C01B25/16

  Oxyacids of phosphorus; Salts thereof (peroxyacids or salts thereof C01B15/00) · CPC title

• C01B9/08

  Fluorides · CPC title