Synthesis of highly soluble fluorescent π-extended 2-(2-thienyl)benzothiazole derivatives via oxidative cyclization of 2-thienylthioanilide as the key step

In this Letter, we synthesize highly soluble push-pull type fluorescent 2-(2-thienyl)benzothiazole dyes and evaluate their photophysical properties. The key step is the synthesis of 2-(5′-bromothien-2′-yl)-6-alkoxybenzothiazole (2) via oxidative cyclization of 2-thienylthioanilide using PhI(OAc)2 as the oxidant. The target dyes could be easily synthesized by the Suzuki-Miyaura cross-coupling reaction of 2 and an appropriate π-donor. The photophysical properties of the 2-thienylbenzothiazole chromophore were controlled by the π-donor moiety. It was found that 2 exhibited large Stokes shifts (5345 cm−1) and a high quantum efficiency for fluorescence (ΦF = 0.94 in CH2Cl2). Therefore, it can be expected to be a useful photofunctional material in liquid crystal laser dyes and nonlinear optical materials.

Graphical abstractWe report the synthesis of highly soluble push-pull type fluorescent 2-(2-thienyl)benzothiazole dyes and the evaluation of their photophysical properties. The key step is the synthesis of the 2-(5′-bromothien-2′-yl)-6-alkoxybenzothiazole via oxidative cyclization of 2-thienylcarbothioamide using PhI(OAc)2 as an oxidant.Download full-size image