On Water: Metal-Free Synthesis of Highly Functionalized Benzothiazolylidene from ortho-Haloanilines.

An environmentally benign, transition-metal-free organic base promoted one-pot cascade synthesis of highly functionalized benzo[ d]thiazol-2(3 H)-ylidene benzamide in the presence of water was accomplished by three-component reaction of ortho-iodoanilines, acrylates, and aroyl isothiocyanates. The protocol involves the in situ generation of thiourea intermediate followed by triethylamine induced intramolecular SN displacement reaction and subsequent Michael addition onto acrylate leads to the formation of benzo[ d]thiazol-2(3 H)-ylidene benzamide. Benzo[ b]thiazole is also generated in good yields using amidation and intramolecular aromatic nucleophilic substitution chemistry. The control experiments support the proposed mechanistic pathway. Further X-ray crystallographic studies confirmed the assigned structures of the fused benzamide.