Process for the preparation of arylsulfonylpropenenitriles by photocatalytic reactions

Patent metadata

Field	Value
Publication number	US-10919847-B2
Application number	US-201816642385-A
Country	US
Kind code	B2
Filing date	Aug 27, 2018
Priority date	Aug 29, 2017
Publication date	Feb 16, 2021
Grant date	Feb 16, 2021

Abstract

A process for a preparation of arylsulfonylpropenenitriles is disclosed. A reaction starting from arylsulfonyl iodides is catalyzed by light. The process is scalable, environmentally benign and provides the product in good yield.

First claim

The invention claimed is:

1. A process for a preparation of a compound of a general formula (I)

wherein R 1 , R 2 and R 3 independently represent a hydrogen atom, a halogen atom, a hydroxy group, an amino group, an alkylamino group, an alkyl group, a hydroxyalkyl group, a haloalkyl group or an alkoxy group having 1 to 4 carbon atoms, or an acylamido group having 1 to 10 carbon atoms, said process comprising steps of:
i) mixing a sulfonyliodide and acrylonitrile in a solvent;
ii) initiating a radical reaction after step i) by irradiation with visible light;
iii) quenching the reaction; and
iv) adding a base to eliminate an iodide to form a desired product,
wherein the solvent is propylene carbonate and comprises 3% to 10% (V/V) water and the reaction is performed at a temperature of 25° C.-50° C.

2. The process according to claim 1 , wherein, in Formula (I):
R 1 represents a methyl group, an ethyl group, a propyl group, a butyl group, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, an n-butoxy group, or a tertiary butoxy group; and
R 2 and R 3 represent independently a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, an n-butoxy group, a tertiary butoxy group.

3. The process according to claim 1 , wherein, in Formula (I):
R 1 represents a methyl group in the 4-position; and
R 2 and R 3 represent hydrogen atoms.

4. The process according to claim 1 , wherein the sulfonyliodide is formed in situ prior to step i).

5. The process according to claim 1 , wherein the water content of said organic solvent is 5% (V/V).

6. The process according to claim 1 , wherein the base used for elimination in step iii) is an organic or inorganic base.

7. The process according to claim 6 , wherein the inorganic base is sodium bicarbonate, sodium hydroxide, sodium carbonate, or a mixture thereof.

8. The process according to claim 6 , wherein the organic base is triethylamine, diethylamine, trimethylamine, sodium acetate, piperidine, pyridine, or a mixture thereof.

9. The process according to claim 1 , wherein the reaction is performed in a batch or continuous flow reactor setup.

10. The process according to claim 7 , wherein the inorganic base is sodium bicarbonate.

11. The process according to claim 8 , wherein the organic base is triethylamine.

Assignees

• Kemira Oyj

Inventors

• Aaltonen Toni
• Kallatsa Oili
• Simell Jaakko
• Sneitz Nina
• Konn Jonas
• Hiltunen Jaakko
• Koskinen Ari

Classifications

• C07C317/14

  having sulfone or sulfoxide groups bound to carbon atoms of six-membered aromatic rings · CPC title

• C07C315/04 Primary

  by reactions not involving the formation of sulfone or sulfoxide groups · CPC title

• C07C317/32 Primary

  with sulfone or sulfoxide groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton · CPC title

• C07C315/00 Primary

  Preparation of sulfones; Preparation of sulfoxides · CPC title

• A01N31/08

  Oxygen or sulfur directly attached to an aromatic ring system · CPC title