Fluorination processes

Patent metadata

Field	Value
Publication number	US-12466776-B2
Application number	US-202418582332-A
Country	US
Kind code	B2
Filing date	Feb 20, 2024
Priority date	Dec 22, 2021
Publication date	Nov 11, 2025
Grant date	Nov 11, 2025

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 fluorinating an organic compound, the method comprising:
combining an activated fluorination reagent, a powder x-ray diffraction spectrum of the activated fluorination reagent comprising characteristic 20 reflections at about 21.9°, 30.3°, or 43.4°, with the organic compound; and fluorinating the organic compound to produce an organo-fluorine compound.

2 . The method of claim 1 , wherein the organic compound is aromatic or aliphatic and comprises at least one leaving group located at a site to be fluorinated.

3 . The method of claim 2 , wherein the organic compound is a sulphonyl halide, an acyl halide, an aryl halide or an alkyl halide.

4 . The method of claim 2 , wherein the organic compound is an aromatic sulphonyl halide, a benzoyl halide, or a halobenzene.

5 . The method of claim 1 , wherein the activated fluorination reagent is obtained by applying mechanical force to a first salt and a second salt to yield the activated fluorination reagent, either in the presence of the organic compound, or prior to addition of the organic compound, wherein the first salt comprises calcium and fluorine.

6 . The method of claim 5 , wherein the organic compound is added together with one or more solvents in which the organic compound is soluble in at least one of the one or more solvents.

7 . The method of claim 6 , wherein the one or more solvents comprise a solvent selected from the group consisting of acetonitrile, propionitrile, toluene, 1,2-dichlorobenzene, chlorobenzene, fluorobenzene, 1,2-difluorobenzene, dichloroethane, trifluorotoluene, chloroform, tert-butanol, tert-amyl alcohol and water, wherein any one or more of the aforementioned organic solvents may be in admixture with water.

8 . The method of claim 1 , wherein the fluorinating is performed at a temperature of about 20-100° C.

9 . The method of claim 8 , wherein the fluorinating yield of the organofluorine compound is at least about 10% (measured based on a starting amount the organic compound).

10 . The method of claim 1 , wherein the fluorinating comprises a di-fluorination reaction.

11 . The method of claim 1 , wherein the activated fluorination reagent comprises a first salt selected from the group of CaF 2 and Ca 5 (PO 4 ) 3 F, and a second salt selected from the group of: Na 2 HPO 4 , K 2 HPO 4 , NaH 2 PO 4 , KH 2 PO 4 , Na 3 PO 4 , K 3 PO 4 , K 4 P 2 O 7 , KPO 3 , K 5 P 3 O 10 , Na 5 P 3 O 10 , and Na 4 P 2 O 7 .

12 . A fluorination reagent comprising:
calcium and fluorine, the fluorination reagent having a powder x-ray diffraction spectrum which comprises characteristic 20 reflections at about 18.0°, 18.7°, 21.9°, 22.6°, 24.5°, 25.4°, 26.5°, 27.0°, 28.0°, 29.2°, 30.3°, 31.6°, 33.0°, 34.8°, 36.4°, 37.7°, 39.5°, 40.4°, 41.7°, 42.4°, 43.4°, 46.1°, 48.4°, 49.4°, 52.8°, or 53.9°.

13 . The fluorination reagent of claim 12 , wherein the fluorination reagent comprises a salt mixture comprising a first salt and a second salt, wherein the first salt comprises the calcium and the fluorine.

14 . The fluorination reagent of claim 13 , wherein the first salt comprises CaF 2 or Ca 5 (PO 4 ) 3 F.

15 . The fluorination reagent of claim 13 , wherein the second salt comprises a metal hydroxide, a metal sulphite, a metal sulphate, a carbonate, or an inorganic phosphate.

16 . The fluorination reagent of claim 15 , wherein the inorganic phosphate is a pyrophosphate.

17 . The fluorination reagent of claim 16 , wherein the inorganic phosphate comprises K 2 HPO 4 , KH 2 PO 4 , K 3 PO 4 , K 4 P 2 O 7 , KPO 3 , K 5 P 3 O 10 , Na 5 P 3 O 10 , or Na 4 P 2 O 7 .

18 . The fluorination reagent of claim 13 , wherein a ratio of the first salt to the second salt is about 1:0.5 to 1:100.

19 . The fluorination reagent of claim 13 , wherein a ratio of the first salt to the second salt is about 1:1 to 1:5.

20 . The fluorination reagent of claim 13 , wherein the fluorination reagent comprises <1 ppm of HF.

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

• C01B9/08

  Fluorides · 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