Coupling of two arenes with selenium dioxide to give a selenobiaryl ether

Patent metadata

Field	Value
Publication number	US-10106497-B2
Application number	US-201615157934-A
Country	US
Kind code	B2
Filing date	May 18, 2016
Priority date	May 20, 2015
Publication date	Oct 23, 2018
Grant date	Oct 23, 2018

Abstract

The present invention relates to a method for coupling two arenes with selenium dioxide to give a selenobiaryl ether. The method of the present invention includes: adding a first arene to the reaction mixture, adding a second arene to the reaction mixture, adding selenium dioxide to the reaction mixture, adding an acid having a pKa in the range from 0 to 5 to the reaction mixture, and adjusting the reaction temperature of the reaction mixture such that the first arene and the second arene are converted to a selenobiaryl ether. The present invention also relates to novel selenobiaryl ethers.

First claim

The invention claimed is:

1. A method for preparing selenobiaryl ethers comprising:
I) forming a reaction mixture by:
a) adding a first arene to the reaction mixture,
b) adding a second arene to the reaction mixture,
c) adding selenium dioxide to the reaction mixture,
d) adding an acid having a pKa in the range from 0 to 5 to the reaction mixture,

II) adjusting the reaction temperature of the reaction mixture to a temperature in the range from 20° C. to 100° C. such that the first arene and the second arene are converted to the selenobiaryl ether,
wherein the second arene does not include phenols, and
wherein the wherein the first arene in method step a) is a compound of the general formula I:

wherein R 1 , R 2 , R 3 , R 4 , R 5 are each independently selected from:
—H, —(C 1 -C 12 )-alkyl, —O—(C 1 -C 12 )-alkyl, —(C 6 -C 20 )-aryl, —O—(C 6 -C 20 )-aryl, -halogen, —OC═O—(C 1 -C 12 )-alkyl,
two adjacent radicals may additionally be joined to one another to form a condensed system,
where the alkyl and aryl groups mentioned may be substituted,
and at least one of the R 1 , R 2 , R 3 , R 4 , R 5 radicals is —H.

2. The method according to claim 1 , wherein R 1 , R 2 , R 3 , R 4 , R 5 are each independently selected from:
—H, —(C 1 -C 12 )-alkyl, —O—(C 1 -C 12 )-alkyl, —(C 6 -C 20 )-aryl, —O—(C 6 -C 20 )-aryl,
where the alkyl and aryl groups mentioned may be substituted,
and at least one of the R 1 , R 2 , R 3 , R 4 , R 5 radicals is —H.

3. The method according to claim 1 , wherein R 1 , R 2 , R 3 , R 4 , R 5 , are each independently selected from:
—H, —(C 1 -C 12 )-alkyl, —O—(C 1 -C 12 )-alkyl,
where the alkyl groups mentioned may be substituted,
and at least one of the R 1 , R 2 , R 3 , R 4 , R 5 radicals is —H.

4. The method according to claim 1 , wherein the second arene in method step b) is a compound of the general formula II:

wherein R 6 , R 7 , R 8 , R 9 , R 10 are each independently selected from:
—H, —(C 1 -C 12 )-alkyl, —O—(C 1 -C 12 )-alkyl, —(C 6 -C 20 )-aryl, —O—(C 6 -C 20 )-aryl, -halogen, —OC═O—(C 1 -C 12 )-alkyl,
two adjacent radicals may additionally be joined to one another to form a condensed system,
where the alkyl and aryl groups mentioned may be substituted,
and at least one of the R 6 , R 7 , R 8 , R 9 , R 10 radicals is —H.

5. The method according to claim 4 , wherein R 6 , R 7 , R 8 , R 9 , R 10 are each independently selected from:
—H, —(C 1 -C 12 )-alkyl, —O—(C 1 -C 12 )-alkyl, —(C 6 -C 20 )-aryl, —O—(C 6 -C 20 )-aryl,
where the alkyl and aryl groups mentioned may be substituted,
and at least one of the R 6 , R 7 , R 8 , R 9 , R 10 radicals is —H.

6. The method according to claim 4 , wherein R 6 , R 7 , R 8 , R 9 , R 10 are each independently selected from:
—H, —(C 1 -C 12 )-alkyl, —O—(C 1 -C 12 )-alkyl,
where the alkyl and aryl groups mentioned may be substituted,
and at least one of the R 6 , R 7 , R 8 , R 9 , R 10 radicals is —H.

7. The method according to claim 4 , wherein the first arene corresponds to the second arene.

8. The method according to claim 1 , wherein the selenium dioxide is added in method step c) in a molar ratio based on the sum total of the first and second arenes within a range from 0.25 to 1.5.

9. The method according to claim 1 , wherein the acid is acetic acid.

10. A compound of the formula 1 or 2:

11. The method according to claim 1 , wherein the added acid in step d) is present in amounts that forms a solution of dissolved first and second arenes and selenium dioxide.

Assignees

• Evonik Degussa Gmbh

Inventors

• Dyballa Katrin Marie
• Franke Robert
• Waldvogel Siegfried R
• Quell Thomas
• Mirion Michael

Classifications

• C07C391/02 Primary

  having selenium atoms bound to carbon atoms of six-membered aromatic rings · CPC title

• C07C53/08

  Acetic acid (pyroligneous acid C10C; preparation of vinegar C12J) · CPC title

• C07C43/205

  the aromatic ring being a non-condensed ring · CPC title