The industrial route entails the high temperature reaction of aniline and carbon disulfide in the presence of sulfur, which proceeds by this idealized equation:[3] The traditional route is the reaction of 2-aminothiophenol and carbon disulfide: This method was developed by the discoverer of the compound, A. W. Hoffmann.

Other routes developed by Hoffmann include the reactions of carbon disulfide with 2-aminophenol and of sodium hydrosulfide with chlorobenzothiazole.

[5] Further synthetic advances were reported in the 1920s that included demonstration that phenyldithiocarbamates pyrolyze to benzothiazole derivative.

[7] Treatment with Raney nickel results in monodesulfurization, giving benzothiazole:[3] The benzo ring undergoes electrophilic aromatic substitution at the position para to nitrogen.

Using 2-mercaptobenzothiazole, rubber vulcanizes with less sulfur and at milder temperatures, both factors give a stronger product.

[8] The compound has also been used in the past in the gold-mining industry for the froth flotation of gold from ore residue as part of the extraction process.

[9] Sodium salt is used as a biocide and preservative in adhesives (especially based on latex, starch, casein, and animal glues), paper, textiles.