Hodgson, Herbert H. published the artcileSome derivatives of benz-1-thia-2,3-diazole, the nature of the thiadiazole ring, and a note on the thiolation of 2-chloro-5-nitroaniline, Application of Benzo[d][1,2,3]thiadiazol-5-amine, the publication is Journal of the Chemical Society (1948), 870-4, database is CAplus.
2,5-Cl(O2N)C6H3NH2 (I) results in about 45% yield on treatment of 20.25 g. 2,4-(O2N)2C6H3Cl in 40 cc. boiling AcOH with 57 g. SnCl2 and distillation with steam; an equal quantity of 4,3-Cl(O2N)C6H3NH2 is nonvolatile with steam. I (17.5 g.) in 250 cc. boiling EtOH, treated gradually with 36 g. Na2S.9H2O and 12.6 g. NaHCO3 in 100 cc. H2O, the mixture heated 1 h. on the water bath, treated with 20 cc. 20% NaOH, added to 750 cc. ice and H2O, and 7 g. NaNO2 added to the filtrate, which was poured into a mixture of 25 cc. concentrated H2SO4 and 250 g. ice, gives 97% 5-nitrobenzothiadiazole (II), m. 143-5°, sublimes at 80-100°/atm. pressure, volatility with steam about 1 g./l.; II in Me2CO, treated with a drop aqueous NaOH, gives a violet color which is discharged by acid and restored by alkali; on standing the color slowly changes to brown. I. (1.725 g.) in 6 cc. boiling EtOH, treated with 1.8 g. Na2S.9H2O and 0.36 g. S in 2 cc. H2O, the mixture heated 1 h. on the steam bath, and treated as above, gives 1.3 g. impure II. The above alk. mixture, shaken with 20% aqueous NaOH and Me2SO4, gives 4,2-O2N(H2N)C6H3SMe, m. 105° (Ac derivative, pale lemon-yellow, m. 157°); (2-methylmercapto-5-nitro-2-phenylazo)-2-naphthol, scarlet, m. 236°. A solution of 4,2-O2N(H2N)C6H3SNa, shaken at room temperature with Ac2O, gives 4-nitro-2-(acetamidomercapto)phenyl acetate, pale cream, m. 150°. I (1.725 g.) in 96 cc. hot EtOH, treated with 0.36 g. S and 1.8 g. Na2S.9H2O in 2 cc. H2O and the mixture refluxed 5 h., gives [4,2-O2N(H2N)C6H3]2S, m. 218°. Reduction of 0.45 g. II in 20 cc. hot aqueous NaOH with 2 g. Na2S2O4 gives 0.15 g. 5-aminobenzothiadiazole (III), yellow, m. 95°; reduction of 0.02 g.-mol. II with 0.24 g.-mol. Fe powder in 1 cc. H2SO4, 30 cc. H2O, and 100 cc. EtOH (refluxed 3 h.) gives 82% III; diazotization of the filtrate and coupling with 2-naphthol gave 17% benzothiadiazol-5-ylazo-2-naphthol, bright red, m. 209°; H2SO4 gives a reddish pink color, changing to pale pink on dilution with H2O. III, through the diazo reaction, yields 5-bromobenzothiadiazole, m. 106°, and the 5-I derivative, m. 103° (solubility of the latter in H2O at room temperature 0.3 g./l.). The yields of thiol and monosulfide from I and Na2S, Na2S2, Na2S2.5, and NaSH are given; Na2S2O3 does not react with I. A cyclic structure is preferred for the thiadiazole ring in contrast to the quinonoid resonance structure of the analogous diazoöxides.
Journal of the Chemical Society published new progress about 1753-29-3. 1753-29-3 belongs to thiazole, auxiliary class Other Aromatic Heterocyclic,Amine, name is Benzo[d][1,2,3]thiadiazol-5-amine, and the molecular formula is C6H5N3S, Application of Benzo[d][1,2,3]thiadiazol-5-amine.
Referemce:
https://pubchem.ncbi.nlm.nih.gov/compound/thiazole,
Thiazole | chemical compound | Britannica