Photooxidation of N,N′-Diacylindigo Dyes

Authors

Bradley D. Smith, University of Notre Dame
David E. Alonso, Andrews University
Jeffrey T. Bien, University of Notre Dame
Elise C. Metzler, University of Notre Dame
Maoyu Shang, University of Notre Dame
John M. Roosenberg II, Andrews UniversityFollow

Document Type

Article

Publication Date

12-1-1994

Abstract

Irradiation of N,N′-diacylindigo dyes in the presence of oxygen resulted in an unusual oxygen insertion/acyl transfer reaction. While this process occurred over many weeks at room temperature, at 100° C it was complete in a few hours. In some cases the yield of photooxidized product was virtually quantitative. The product structures were proved by spectroscopic methods and in one example by X-ray analysis. A series of mechanistic experiments led to the conclusion that at least the oxygen insertion part of the photooxidation process proceeded via a radical mechanism. The evidence included the following observations: (1) When the photooxidation was conducted in toluene, large amounts of benzyl hydroperoxide were produced; (2) the photooxidation could be achieved in the dark with a radical initiator; (3) attempts to generate the photooxidized product using singlet oxygen chemistry failed. The postulated radical mechanism is described. © 1994, American Chemical Society. All rights reserved.

Journal Title

Journal of Organic Chemistry

Volume

59

Issue

26

First Page

8011

Last Page

8014

DOI

10.1021/jo00105a015

First Department

Chemistry and Biochemistry

Recommended Citation

Smith, Bradley D.; Alonso, David E.; Bien, Jeffrey T.; Metzler, Elise C.; Shang, Maoyu; and Roosenberg, John M. II, "Photooxidation of N,N′-Diacylindigo Dyes" (1994). Faculty Publications. 2562.
https://digitalcommons.andrews.edu/pubs/2562