To our delight, S-arylation with a mercaptothiazole 37 delivered the novel, heterocyclic azobenzene product 8 in excellent yield (93%). The arylation of thioamide to thioimidates 9 was more difficult. Even the C-arylation of a substituted nitroester 39 could be performed to provide the sterically congested product 10. Methods for N-arylation were next explored, and the arylation of a primary amine proved to be challenging. The novel, amino-substituted product 11 was obtained in 22% yield due to partial decomposition of 3a under the reaction conditions. On the other hand, the arylation of acetanilide proceeded smoothly to give the tertiary amide 12 in 79% yield. Furthermore, arylation of sodium nitrite 42 delivered ortho-nitro azobenzene ( ) in 63% yield.