Abstract Three different 1-acyl-3-(3-thienyl)-2-thioureas were cyclized to 2-acylaminothieno [3, 2-d] thiazoles with bromine in acetic acid whereas the corresponding 2-thienylthiourea derivatives were brominated under the same reaction conditions. The parent thieno [3, 2-d] thiazole was prepared by acid hydrolysis and deamination of 2-benzoylaminothieno [3, 2-d] thiazole. This new heterocyclic compound was nitrated and brominated in the 5-position.