Process for preparing 2,2′-biphenols using selenium dioxide

Patent metadata

Field	Value
Publication number	US-9517986-B2
Application number	US-201514719900-A
Country	US
Kind code	B2
Filing date	May 22, 2015
Priority date	May 26, 2014
Publication date	Dec 13, 2016
Grant date	Dec 13, 2016

Abstract

A process for preparing a 2,2′-biphenol, proceeds by a) adding a first phenol to a reaction mixture, b) adding a second phenol to the reaction mixture, c) adding selenium dioxide to the reaction mixture, d) adding an acid having a pKa in the range from 0.0 to 5.0 to the reaction mixture, and e) heating the reaction mixture such that the first phenol and the second phenol are converted to said 2,2′-biphenol.

First claim

The invention claimed is:

1. A process for preparing a 2,2′-biphenol, comprising:
a) adding a first phenol to a reaction mixture,
b) adding a second phenol to the reaction mixture,
c) adding selenium dioxide to the reaction mixture,
d) adding an acid having a pKa in the range from 0.0 to 5.0 to the reaction mixture, and
e) heating the reaction mixture such that the first phenol and the second phenol are converted to said 2,2′-biphenol.

2. The process according to claim 1 , wherein the first phenol in process 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 the group consisting of:
—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 —OC═O—(C 1 -C 12 )-alkyl,
wherein two adjacent radicals are optionally joined to one another to form a condensed system,
wherein the alkyl and aryl groups mentioned are optionally substituted, and
wherein at least R 1 or R 5 is —H.

3. The process according to claim 2 , wherein R 1 , R 2 , R 3 , R 4 , R 5 are each independently selected from the group consisting of:
—H—, —(C 1 -C 12 )-alkyl, —O—(C 1 -C 12 )-alkyl, —(C 6 -C 20 )-aryl, and —O—(C 6 -C 20 )-aryl,
wherein the alkyl and aryl groups mentioned are optionally substituted, and
wherein at least R′ or R 5 is —H.

4. The process according to claim 2 , wherein R 1 , R 3 , R 5 are each independently selected from the group consisting of:
—H, and —(C 1 -C 12 )-alkyl,
wherein the alkyl groups mentioned are optionally substituted, and
wherein at least R 1 or R 5 is —H.

5. The process according to claim 1 , wherein the second phenol in process 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 the group consisting of:
—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 —OC═O—(C 1 -C 12 )-alkyl,
wherein two adjacent radicals are optionally joined to one another to form a condensed system,
wherein the alkyl and aryl groups mentioned are optionally substituted, and
wherein at least R 6 or R 10 is —H.

6. The process according to claim 5 , wherein R 6 , R 7 , R 8 , R 9 , R 10 are each independently selected from the group consisting of:
—H—, —(C 1 -C 12 )-alkyl, —O—(C 1 -C 12 )-alkyl-, —(C 6 -C 20 )-aryl, and —O—(C 6 -C 20 )-aryl,
wherein the alkyl and aryl groups mentioned are optionally substituted, and
wherein at least R 6 or R 10 is —H.

7. The process according to claim 5 , wherein R 6 , R 8 , R 10 are each independently selected from the group consisting of:
—H, and —(C 1 -C 12 )-alkyl,
wherein the alkyl groups mentioned are optionally substituted, and
wherein at least R 6 or R 10 is —H.

8. The process according to claim 1 , wherein the first phenol is the same as the second phenol.

9. The process according to claim 1 , wherein the selenium dioxide is added in process step c) in a molar ratio of from 0.25 to 1.2 based on a total sum of the first and second phenols.

10. The process according to claim 1 , wherein the acid in process step d) is selected from the group consisting of: acetic acid, formic acid, trifluoroacetic acid, propionic acid, and phosphoric acid.

11. The process according to claim 1 , wherein the acid is used as solvent in process step d).

12. The process according to claim 1 , wherein the reaction mixture is heated in process step e) to a temperature in the range from 50° C. to 110° C.

13. The process according to claim 1 , wherein the heating in process step e) is effected over a period in the range from 5 minutes to 24 hours.

14. The process according to claim 1 , wherein said bisphenol is selected from the group consisting of
3,3′,5,5′-tetramethylbiphenyl-2,2′-diol

3,3′-di-tert-butyl,5,5′-dimethylbiphenyl-2,2′-diol

3,3′,5,5′-tetra-tert-butylbiphenyl-2,2′-diol

3,3′-diisopropyl-5,5′,6,6′-tetramethyl-2,2′-biphenol

3,3′-di-tert-butyl-5,5′,6,6′-tetramethyl-2,2′-biphenol

and
3,3′,5,5′,6,6′-hexamethyl-2,2′-biphenol

Assignees

• Evonik Degussa Gmbh

Inventors

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

Classifications

• C07C37/11 Primary

  by reactions increasing the number of carbon atoms · CPC title

• C07C39/15

  with all hydroxy groups on non-condensed rings {, e.g. phenylphenol} · CPC title