Coupling a phenol and an arene using selenium dioxide

Patent metadata

Field	Value
Publication number	US-9771311-B2
Application number	US-201615160367-A
Country	US
Kind code	B2
Filing date	May 20, 2016
Priority date	May 20, 2015
Publication date	Sep 26, 2017
Grant date	Sep 26, 2017

Abstract

Method for coupling a phenol and an arene using selenium dioxide, and also novel phenol-arene derivatives.

First claim

The invention claimed is:

1. Method for preparing phenol-arene derivatives, comprising the method steps of:
a) adding a phenol to the reaction mixture,
b) adding an arene from the group of mono- and bicyclic arenes,
c) adding selenium dioxide to the reaction mixture,
d) adding a solvent,
e) heating the reaction mixture so that the substituted phenol and the arene, from
f) the group of mono- or bicyclic arenes, are converted to a phenol-arene derivative.

2. Method according to claim 1 ,
wherein the phenol is a compound of the general formula (I):

where 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,
where the alkyl and aryl groups mentioned may be substituted,
and at least R 1 or R 5 or R 2 or R 4 is —H,
and the monocyclic arene is a compound of the general formula (II):

where R 6 , R 7 , R 8 , R 9 , R 10 , R 11 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,
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 19 or R 11 radicals is —H.

3. Method according to claim 2 ,
wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 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 , R 11 radicals is —H.

4. Method according to claim 2 ,
wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 are each independently selected from:
—H, —(C 1 -C 12 )-alkyl, —O—(C 1 -C 12 )-alkyl, —(C 6 -C 20 )-aryl,
where the alkyl and aryl groups mentioned may be substituted,
and at least one R 6 , R 7 , R 8 , R 9 , R 10 , R 11 radical is —H.

5. Method according to claim 2 ,
wherein the R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 radicals are each independently selected from:
—H, —(C 1 -C 12 )-alkyl, —O—(C 1 -C 12 )-alkyl,
and at least one of the R 1 , R 5 , R 2 , R 3 radicals is —H,
and at least one of the R 6 , R 7 , R 8 , R 9 , R 10 , R 11 radicals is —H,
where the alkyl groups mentioned may be substituted.

6. Method according to claim 2 ,
wherein the R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 radicals are each independently selected from:
—H, —(C 1 -C 12 )-alkyl, —O—(C 1 -C 12 )-alkyl,
and at least one of the R 1 , R 5 , R 2 , R 3 radicals is —H,
and at least one of the R 6 , R 7 , R 8 , R 9 , R 10 , R 11 radicals is —H,
where the alkyl groups mentioned may be substituted.

7. Method according to claim 1 ,
wherein the phenol is a compound of the general formula (I):

where 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,
where the alkyl and aryl groups mentioned may be substituted,
and at least one of the R 1 or R 5 or R 2 or R 4 radicals is —H,
and the bicyclic arene is a compound of the general formula (III):

where R 12 , R 13 , R 14 , R 1 s, R 16 , R 17 , R 18 , R 19 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,
and at least one of the R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 or R 19 radicals is —H,
where the alkyl groups mentioned may be substituted.

8. Method according to claim 7 ,
where 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, —Cl,
where the alkyl and aryl groups mentioned may be substituted,
and at least one of the R 1 or R 5 or R 2 or R 4 radicals is —H,
and the bicyclic arene is preferably a compound of the general formula (III), where R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 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, —Cl,
where the alkyl and aryl groups mentioned may be substituted,
and at least one R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 or R 19 radical is —H.

9. Method according to claim 7 ,
wherein the R 1 , R 2 , R 3 , R 4 , R 5 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 radicals are each independently selected from:
—H, —(C 1 -C 12 )-alkyl, —O—(C 1 -C 12 )-alkyl, —Cl,
where the alkyl groups mentioned may be substituted,
and at least one of the R 1 or R 5 or R 2 or R 3 radicals is —H,
and at least one of the R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 or R 19 radicals is —H.

10. Method according to claim 7 ,
wherein the R 1 , R 2 , R 3 , R 4 , R 5 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , radicals 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 or R 5 or R 2 or R 3 radicals is —H,
and at least one of the R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 or R 19 radicals is —H.

11. Method according to claim 1 or 2 ,
wherein the monocyclic arene is a phenyl derivative and the bicyclic arene is a naphthyl derivative.

12. Method according to claim 1 or 2 ,
wherein one of the group of fluorinated alcohols, fluorinated carboxylic acids or organic carboxylic acids is added as solvent to the reaction mixture in method step d).

13. Method according to claim 1 or 2 ,
wherein 1,1,1,3,3,3-hexafluoro-2-propanol or trifluoroacetic acid is added as solvent.

14. Method according to claim 1 or 2 ,
wherein the selenium dioxide is added in a molar ratio based on the sum total of the phenol and the arene within a range from 0.1 to 2.0.

Assignees

• Evonik Degussa Gmbh

Inventors

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

Classifications

• C07C43/23

  containing hydroxy or O-metal groups · CPC title

• C07C41/30 Primary

  by increasing the number of carbon atoms, e.g. by oligomerisation · CPC title

• C07C43/225

  containing halogen · CPC title

• C07C43/2055

  containing more than one ether bond · CPC title

• C07C43/205

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