2-Mercaptobenzimidazole (1) reacts with aromatic ketones 2a-d in acidified acetic acid giving 2-benzimidazolylthioacetophenones 3a-d. Which on cyclization yield thiazolo [3, 2-a]- benzimidazoles 4a-d. Acetylation of 3a, d gave the N-acetyl derivatives 5a, d. Cyclization of 3a-d or 5d in acetic anhydride or acetic anhydride/pyridine mixture afforded 6a-d. While reaction of 1 with aliphatic or alicyclic ketones gave directly 2, 3-disubstituted thiazolo [3, 2 ...