# US 2024/0150271 A1 · Catalytic method for the preparation of perfluoroalkoxy-substituted arenes and heteroarenes

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- Number: US 2024/0150271 A1
- Document ID: US20240150271A1
- Status: Published application
- Kind: A1
- Application number: 18/547,486
- Filed: 2022-02-21
- Published: 2024-05-09
- Earliest claimed: 2021-02-22
- Assignees: Solvay SA
- Applicants: Solvay SA
- Inventors: Sebastian Hasenstab-Riedel; Matthew Hopkinson; Stefan Dix; Paul Golz; Jonas Rachid Schmid; Holger Pernice; Sebastian Gutmann
- Web page: https://patentgrep.com/patent/US20240150271A1

## CPC

- C07B 39/00: Halogenation
- C07C 41/06: by addition of organic compounds only
- B01J 31/0235: {Nitrogen containing compounds}
- B01J 31/0248: {Nitriles}
- C07B 41/04: of ether, acetal or ketal groups
- C07C 41/05: by addition of compounds to unsaturated compounds
- C07C 45/64: by introduction of functional groups containing oxygen only in singly bound form
- C07C 51/367: by introduction of functional groups containing oxygen only in singly bound form
- C07C 67/31: by introduction of functional groups containing oxygen only in singly bound form
- C07D 213/73: Unsubstituted amino or imino radicals
- B01J 2531/16: Copper
- B01J 2531/821: Ruthenium
- B01J 2531/827: Iridium
- B01J 2540/50: Non-coordinating groups comprising phosphorus
- C07B: GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR (preparation of carboxylic acid esters by telomerisation C07C67/47; telomerisation C08F)
- C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS
- B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- C07D: HETEROCYCLIC COMPOUNDS (macromolecular compounds C08)

## Abstract

The present invention is directed to methods for the preparation of (CnF2n+1)O-substituted arenes and heteroarenes and the direct perfluoralkoxy lation of arenes and heteroarenes with a (CnF2n+1)O-group, respectively. characterized in that a peroxide reagent according to the general formula (I): (CnF2n+1)2 (I) is fragmented in the presence of an electron transferring catalyst under (CnF2n+1)O-radical formation, and said (CnF2n+1)O-radical then substitutes a C—H bond of an arene or heteroarene C—H bond with a (CnF2n+1)O-group, wherein in the above formulae, n is an integer in the range from 1 to 4.

## Claims

### Claim 1

A method for the preparation of (CnF2n+1)O-substituted arenes and heteroarenes characterized in that
a peroxide reagent according to the following general formula (I)
CnF2n+1 (I)
is fragmented in the presence of an electron transferring catalyst under (CnF2n+1)O-radical formation, and said (CnF2n+1)O-radical then substitutes a C-H bond of an arene or heteroarene with a (CnF2n+1)O-group,
wherein in the above formulae n is an integer in the range from 1 to 4.

### Claim 2

A method for the direct perfluoroalkoxylation of arenes and heteroarenes with a (CnF2n+1)O-group, characterized in that
a peroxide reagent according to the following general formula (I)
CnF2n+1 (I)
is fragmented in the presence of an electron transferring catalyst under (CnF2n+1)O-radical formation, and said (CnF2n+1)O-radical then substitutes a C-H bond of an arene or heteroarene with a (CnF2n+1)O-group,
wherein in the above formulae n is an integer in the range from 1 to 4.

### Claim 3 (depends on 1)

The method according to claim 1, wherein n is 1 or 4.

### Claim 4 (depends on 1)

The method according to claim 1, wherein the heteroarene is a pyridine.

### Claim 5 (depends on 1)

The method according to claim 1, wherein the electron transferring catalyst is a metal salt.

### Claim 6 (depends on 1)

The method according to claim 1, wherein the electron transferring catalyst is a stable aminoxyl radical compound.

### Claim 7 (depends on 1)

The method according to claim 1, wherein the method does not depend on light irradiation.

### Claim 8 (depends on 1)

The method according to claim 1, wherein the electron transferring catalyst is a transition metal coordination complex.

### Claim 9 (depends on 8)

The method according to claim 8, wherein the electron transferring catalyst is a photocatalyst and the method is carried out under light irradiation, wherein the light is visible light having a wavelength λ in the range from 380 nm to 700 nm.

### Claim 10 (depends on 1)

The method according to claim 1, wherein the electron transferring catalyst is selected from the group consisting of Ru(bpy)3(PF6)2, [Ir(dF(CF3)ppy)2(dtbbpy)]PF6 and Ir(ppy)3, and is preferably Ru(bpy)4(P-F6)2.

### Claim 11 (depends on 1)

The [[M]]method according to claim 1, wherein the electron transferring catalyst is present in substoichiometric amounts.

### Claim 12 (depends on 1)

The method according to claim 1, wherein the arene or heteroarene is present in excess molar amounts in relation to the peroxide reagent according to the general formula (I).

### Claim 13 (depends on 1)

The method according to claim 1, wherein the method is carried out in the presence of an organic solvent, wherein the solvent is a polar aprotic solvent selected from the group consisting of acetonitrile (MeCN), acetone, N,N-dimethylformamide (DMF), dimethylsulfoxide (DMSO), tetrahydrofuran (THF), diethylether, iso-propylether (IPE), methyl-tert-butylether (MTBE), 1,4-dioxane, ethylacetate (EtOAc), dichloromethane (DCM), 1,2-dichloroethane (1,2-DCE), chloroform and mixtures thereof; or in the absence of a solvent.

### Claim 14 (depends on 1)

The method according to claim 1, wherein the method is carried out in the presence of an additive, wherein the additive is a salt additive selected from the group consisting of alkali and earth alkali metal sulfates, alkali and earth alkali metal carbonates and hydrogen carbonates, alkali and earth alkali metal phosphates, hydrogen phosphates, and dihydrogen phosphates, and alkali and earth alkali metal halides.

### Claim 15 (depends on 1)

A method for the preparation of pharmaceutical or agrochemical compounds or building blocks for the synthesis of pharmaceutical and agrochemical compounds, comprising the method according to claim 1.

### Claim 16 (depends on 5)

The method according to claim 5, wherein the electron transferring catalyst is a transition metal salt of Cu, Fe, or Ti.

### Claim 17 (depends on 17)

The method according to claim 17, wherein the electron transferring catalyst is a transition metal salt selected from the group consisting of Cu2O, CuCl, CuCl2, CuBr, CuI, CuSCN, CuSO4, CuCO3, FeSO4, and TiCl3.

### Claim 18 (depends on 6)

The method according to claim 6, wherein the electron transferring catalyst is a stable aminoxyl radical compound selected from the group consisting of 2,2,6,6-tetramethylpiperidinyloxyl (“TEMPO”) and derivatives thereof.

### Claim 19 (depends on 8)

The method according to claim 8, wherein the electron transferring catalyst is a transition metal coordination complex of Cu, Ru or Ir.

### Claim 20 (depends on 19)

The method according to claim 19, wherein the electron transferring catalyst is a transition metal coordination complex selected from the group consisting of Cu(MeCN)4PF6, Ru(bpy)3(PF6)2, [Ir(dF(CF3)ppy)2(dtbbpy)]PF6 and Ir(ppy)3.