Biradicals from Thermolysis of <i>N</i>-[2-(1-Alkynyl)phenyl]-<i>N</i>‘-phenylcarbodiimides and Their Subsequent Transformations to 6<i>H</i>-Indolo[2,3-<i>b</i>]quinolines

Abstract

Thermolysis of the carbodiimide 9a in gamma-terpinene at 138 degrees C produced 2-(phenylamino)quinoline (11a, 49%) and the parent 6H-indolo[2,3-b]quinoline (14a, 16%). Apparently, 11a was produced via the biradical 10a followed by hydrogen-atom abstraction from gamma-terpinene. A two-step biradical pathway through 12a or a one-step intramolecular Diels-Alder reaction could furnish 13a, which then underwent tautomerization to give 14a. With the carbodiimide 9b having a trimethylsilyl substituent at the acetylenic terminus, thermolysis in refluxing p-xylene at 138 degrees C produced the 6H-indolo[2,3-b]quinoline 14b (86%) exclusively. Treatment of 14b with 6 N NaOH in refluxing ethanol then furnished 14a in 92% yield. Similarly, the 6H-indolo[2,3-b]quinolines 14c-f were obtained from thermolysis of the carbodiimides 9c-f. The use of the aza-Wittig reaction between 4-methoxyphenyl isocyanate and the iminophosphoranes 2d and 2f to produce the corresponding carbodiimides followed by thermolysis furnished the 6H-indolo[2,3-b]quinolines 16d and 16f having a methoxy substituent at the C-2 position. Thermolysis of the carbodiimides 25a and 25b produced 26a and 26b having two indoloquinoline units connected at the 11 and 11' positions with either a three-carbon or a five-carbon tether. Using 1,4-phenylene diisocyanate for the aza-Wittig reaction with 2 equiv of the iminophosphorane 2g followed by thermolysis furnished 31 (66%) having two indoloquinoline units incorporated in the seven fused rings.