Photochemical preparation of fluorine-containing compounds

Patent metadata

Field	Value
Publication number	US-2024300878-A1
Application number	US-202418444075-A
Country	US
Kind code	A1
Filing date	Feb 16, 2024
Priority date	Feb 16, 2023
Publication date	Sep 12, 2024
Grant date	—

Abstract

Various embodiments disclosed relate to a method of preparing aryl fluorinated ether compounds. The method involves contacting an aryl halide with a fluorinated alcohol in the presence of a photocatalyst, a base, and irradiation with electromagnetic radiation comprising a wavelength between about 200 nm and about 800 nm. The present invention also provides a method of late-stage photochemical modification of a biologically active compound, such as drugs or agrochemicals. Fluorinated derivatives of griseofulvin, clofibrate, and 2,4-D methyl ester are described herein.

First claim

What is claimed is:

1 . A method for preparing a fluorinated compound, comprising contacting an aryl halide with a fluorinated alcohol in the presence of a photocatalyst, a base, and irradiation with electromagnetic radiation comprising a wavelength between about 200 nm and about 800 nm.

2 . The method of claim 1 , wherein the fluorinated alcohol is a fluorinated C1-C8 alcohol.

3 . The method of claim 1 , wherein the fluorinated alcohol comprises 1-15 fluorines.

4 . The method of claim 1 , wherein the fluorinated alcohol is a secondary alcohol.

5 . The method of claim 1 , wherein the fluorinated alcohol comprises one CH bond.

6 . The method of claim 1 , wherein the fluorinated alcohol has the structure:

wherein n is 1 to 3.

7 . The method of claim 1 , wherein the fluorinated alcohol is hexafluoroisopropanol.

8 . The method of claim 1 , wherein the aryl halide is an aryl chloride, aryl fluoride, or an aryl bromide.

9 . The method of claim 1 , wherein the aryl halide comprises at least one of hydroxy or alkoxy.

10 . The method of claim 1 , wherein the aryl halide comprises at least one electron-donating substituent selected from the group consisting of amino, —NHalkyl, N(alkyl) 2 , hydroxyl, alkoxy, acylamido, acyloxy, alkylthio, thiol, alkyl, and aryl.

11 . The method of claim 1 , wherein the aryl halide is an agrochemical.

12 . The method of claim 1 , wherein the photocatalyst is metal-free and comprises an aromatic cation in conjugation with one or more aromatic rings.

13 . The method of claim 1 , wherein the photocatalyst is a pyrylium salt.

14 . The method of claim 1 , wherein the photocatalyst has the structure:

wherein Ar is an aryl group and X is an anionic counterion.

15 . The method of claim 1 , wherein the photocatalyst has the structure:

wherein
R 1 is each independently H, alkyl, aryl, halide, amino, —NHalkyl, N(alkyl) 2 , hydroxyl, alkoxy, acylamido, acyloxy, alkylthio, thiol, nitro, arylsulfonyl, alkylsulfonyl, or aminosulfonyl;
R 2 is each independently H, alkyl, aryl, halide, amino, —NHalkyl, N(alkyl) 2 , hydroxyl, alkoxy, acylamido, acyloxy, alkylthio, thiol, nitro, arylsulfonyl, alkylsulfonyl, or aminosulfonyl; and
X is an anionic counterion.

16 . The method of claim 1 , wherein the photocatalyst has the structure:

wherein R 1 is each independently H, alkyl, aryl, halide, amino, —NHalkyl, N(alkyl) 2 , hydroxyl, alkoxy, acylamido, acyloxy, alkylthio, thiol, nitro, arylsulfonyl, alkylsulfonyl, or aminosulfonyl, and X is an anionic counterion.

17 . The method of claim 1 , wherein the photocatalyst is an acridinium salt.

18 . The method of claim 1 , wherein the photocatalyst has the structure:

wherein Ar is an aryl group, R is alkyl or aryl, and X is an anionic counterion.

19 . The method of claim 1 , wherein the photocatalyst has the structure:

wherein
R 1 is each independently H, alkyl, aryl, halide, amino, —NHalkyl, N(alkyl) 2 , hydroxyl, alkoxy, acylamido, acyloxy, alkylthio, thiol, nitro, arylsulfonyl, alkylsulfonyl, or aminosulfonyl,
R 2 is each independently H, alkyl, aryl, halide, amino, —NHalkyl, N(alkyl) 2 , hydroxyl, alkoxy, acylamido, acyloxy, alkylthio, thiol, nitro, arylsulfonyl, alkylsulfonyl, or aminosulfonyl; and
R is alkyl or aryl, and X is an anionic counterion.

20 . The method of claim 1 , wherein the photocatalyst has the structure:

wherein X is an anionic counterion.

Assignees

• Wisys Tech Foundation Inc

Inventors

• Mackenzie Ian Andrew
• Levenstein Mark Elliot

Classifications

• B01J31/0244

  with nitrogen contained as ring member in aromatic compounds or moieties, e.g. pyridine · CPC title

• B01J31/0204

  Ethers · CPC title

• B01J31/006

  comprising organic radicals, e.g. TEMPO · CPC title

• C07C319/24

  by reactions involving the formation of sulfur-to-sulfur bonds · CPC title

• C07B41/04

  of ether, acetal or ketal groups · CPC title