Method for producing asymmetrical biphenols using selenium dioxide

Patent metadata

Field	Value
Publication number	US-9950979-B2
Application number	US-201515313606-A
Country	US
Kind code	B2
Filing date	May 20, 2015
Priority date	May 26, 2014
Publication date	Apr 24, 2018
Grant date	Apr 24, 2018

Abstract

A process for preparing unsymmetric biphenols, comprising: a) adding a first substituted phenol to the reaction mixture; b) adding a second substituted phenol having different substitution than the first phenol to the reaction mixture; c) adding selenium dioxide to the reaction mixture; d) adding a solvent; and e) heating the reaction mixture such that the first substituted phenol and the second phenol having different substitution are converted to an unsymmetric biphenol.

First claim

What is claimed is:

1. A process for preparing unsymmetric biphenols, comprising the process steps of:
a) adding a first substituted phenol to the reaction mixture,
b) adding a second substituted phenol having different substitution than the first phenol to the reaction mixture,
c) adding selenium dioxide to the reaction mixture,
d) adding a solvent,
e) heating the reaction mixture such that the first substituted phenol and the second phenol having different substitution are converted to an unsymmetric biphenol;
wherein a 2,3′-biphenol is formed.

2. The process as claimed in claim 1 , wherein the first 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,
two adjacent radicals may additionally be joined to one another to form a condensed system,
and at least one of the R 1 , R 5 , R 2 , R 4 radicals is —H,
where the alkyl and aryl groups mentioned may be substituted,
and the second phenol is a compound of the general formula (II):

where 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
two adjacent radicals may additionally be joined to one another to form a condensed system,
and at least one of the R 6 , R 10 , R 7 , R 9 radicals is —H,
where the alkyl and aryl groups mentioned may be substituted,
and formula (I) is not the same as formula (II).

3. The process as claimed in claim 2 , wherein the R 1 , R 2 , R 3 , R 4 , R 5 R 6 , R 7 , R 8 , R 9 , R 10 radicals 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, —I,
and at least one of the R 1 , R 5 , R 2 and R 3 radicals is —H,
and at least one of the R 6 , R 10 , R 7 and R 9 radicals is —H,
where the alkyl and aryl groups mentioned may be substituted,
and formula (I) is not the same as formula (II).

4. The process as claimed in claim 2 , wherein the R 1 , R 2 , R 3 , R 4 , R 5 R 6 , R 7 , R 8 , R 9 , R 10 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 and R 3 radicals is —H,
and at least one of the R 6 , R 10 , R 7 and R 9 radicals is —H,
where the alkyl and aryl groups mentioned may be substituted,
and formula (I) is not the same as formula (II).

5. The process as claimed in claim 1 ,
wherein a halogenated solvent is added in process step d).

6. The process as claimed in claim 1 ,
wherein the solvent added is a fluorinated or chlorinated solvent.

7. The process as claimed in claim 1 , wherein the solvent added is a fluorinated solvent.

8. The process as claimed in claim 1 , wherein the fluorinated solvent added is 1,1,1,3,3,3-hexafluoro-2-propanol or trifluoroacetic acid.

9. The process as claimed in claim 1 , wherein the selenium dioxide is added in a molar ratio based on the sum total of the first and second phenols within a range from 0.1 to 2.0.

10. The process as claimed in claim 1 , wherein the reaction mixture is heated to a temperature in the range from 25° C. to 120° C.

11. The process as claimed in claim 1 , wherein the heating is effected over a period in the range from 5 minutes to 24 hours.

12. The process as claimed in claim 1 ,
wherein the process is conducted in the presence of moist air.

Assignees

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

Inventors

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

Classifications

• C07C41/30 Primary

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

• C07C43/23

  containing hydroxy or O-metal groups · CPC title