Selective enzymatic oxidation of aromatic methyl groups to aldehydes by oxygen in the presence of a laccase-mediator catalyst

• US 5,888,787 A
• Filed: 07/02/1996
• Issued: 03/30/1999
• Est. Priority Date: 07/02/1996
• Status: Expired due to Fees

• Current Assignee: North Carolina State University (University of North Carolina System)
• Original Assignee: North Carolina State University (University of North Carolina System)
• Inventors: Kirkman, Adrianna G., Potthast, Antje, Rosenau, Thomas, Gratzl, Josef S., Chen, Chen-Loung
• Primary Examiner(s): Weber, Jon P.
• Assistant Examiner(s): HANLEY, SUSAN MARIE
• Application Number:
  US08/677,338
• Time in Patent Office: 1,001 Days
• Field of Search: 435/147, 435/189, 435/254.1, 568/425, 568/426, 568/431
• US Class Current: 435/147
• CPC Class Codes: C12N 9/0061 Laccase (1.10.3.2)
• CPC Class Codes: C12P 7/24 containing a carbonyl group
• CPC Class Codes: C12Y 110/03002 Laccase (1.10.3.2)

Abstract

A method for oxidation of a pendant methyl moiety on an aromatic ring to the pendant aldehyde moiety is presented. The reaction employs laccase and the diammonium salt of 2,2'"'"'-azinobis(3-ethylbenzothiazoline-6-sulfonic acid), and is carried out in the presence of oxygen.

Claims

1. A method for manufacturing a corresponding aromatic aldehyde compound from an aromatic compound, the method comprising:

(A) providing (i) an aromatic compound, having a pendent methyl moiety substituted on at least one carbon of the aromatic compound with at least one unsubstituted position ortho to the carbon substituted with the pendent methyl moiety, for catalytic conversion into the corresponding aromatic aldehyde compound, (ii) a mediator, and (iii) a laccase, wherein the aromatic compound and the mediator are present in a mmol ratio of the aromatic compound to the mediator of about 1000;

5 to about 1000;

11, and a sufficient amount of the laccase is present to provide about 25 to about 210 Units of enzymatic activity;

(B) reacting the aromatic compound, the mediator, and the laccase of step (A) in the presence of oxygen at a temperature from about 20°

C. to about 40°

C. and a pressure from about 740 mm to about 780 mm and a pH from about 4.0 to about 6.0; and

(C) obtaining the corresponding aromatic aldehyde.

2. The method of claim 1, wherein the aromatic compound includes at least one aromatic ring substituted with at least one pendent methyl moiety, wherein said one aromatic ring is selected from the group consisting of 5-member, 6-member, and 7-member aromatic rings.

3. The method of claim 2, wherein the 5-member, 6-member, and 7-member aromatic rings are selected from the group consisting of homocyclic rings and heterocyclic rings.

4. The method of claim 1, wherein the aromatic compound is selected from the group consisting of toluene, p-nitrotoluene, m-chlorotoluene, and 3,4-dimethoxytoluene.

5. The method of claim 1, wherein the laccase is obtained from Coriolus versicolor.

6. The method of claim 1, wherein the aromatic aldehyde is selected from the group consisting of benzaldehyde, p-nitrobenzaldehyde, m-chlorobenzaldehyde, and 3,4-dimethoxybenzaldehyde.

7. The method of claim 1, wherein step (B) further includes intermittent flushing with pure oxygen.

8. The method of claim 1, wherein the aromatic aldehyde in step (C) is obtained in a yield from about 89% to about 98%.

9. The method of claim 1, wherein the mediator is selected from the group consisting of 2,2'"'"'-azinobis(3-ethylbenzothiazoline-6-sulfonic acid) diammonium salt;

1-hydroxybenzotriazole; and

combinations thereof.