Summary
Pyridine catalyzed acylation of 5-amino-1,2,3,4-thiatriazole with chloroformates and chlorothioformates afforded 3,5-bis(ethoxycarbonylamino)-1,2,4-thiadiazoles in the former and 2,5-bis(phenoxy)-1,6,6a,Δ4-trithia-3,4-diazapentalenes in the latter case. An unstable, but isolable intermediate 2-phenoxy-1-aza-3,4-dithiolium-5-imide has been found if the chlorothioformate acylation was performed in acetonitrile in the absence of pyridine. The bis(phenoxy)trithiapentalenes are prone to nucleophilic displacement reactions at positions 2 and 5, exchanging in a stepwise manner one or both phenoxy groups. The structures of the compounds described could be inferred from their1H-NMR13C-NMR, and mass spectra and were corroborated by the comparison with the data of authentic and similar derivatives as well as by chemical means.
Zusammenfassung
Die durch Pyridine katalysierte Acylierung von 5-Amino-1,2,3,4-thiatriazol mit Chlorameisensäureethylester führt zu 3,5-bis-(ethoxycarbonylamino)-1,2,4-thiadiazolen, während mit Chlorthioameisensäureethylester 2,5-bis(phenoxy)-1,6,6a,Δ4-trithia-3,4-diazapentalene erhalten werden. Ohne Pyridin entsteht bei letzterer Reaktion ein wenig stabiles, aber isolierbares Zwischenprodukt: 2-Phenoxy-1-aza-3,4-dithiolium-5-imid. Die Bis(phenoxy)trithiadiazapentalene reagieren leicht mit nukleophilen Reagenzien und tauschen dabei schrittweise eine oder beide Phenoxygruppen aus.
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Graubaum H., Seeboth H. (in press) J. Prakt. Chem.
Freund P., Schwarz H. P. (1896) Ber. Chem. Ges.29: 2491
Graubaum H., Seeboth H., Zalupsky P. (in press) Z. Chem.
L'Abbe G., Verhelst G., Vermeulen G. (1977) Angew. Chem. Int., Ed. Engl.16: 403
Beer R. J. S., Hart I. (1977) J. Chem. Soc. Chem. Commun.: 143
Martin D., Graubaum H., Kulpe S. (1985) J. Org. Chem.50: 1296
Kurzer P. (1955) J. Chem. Soc.: 2288
Nagano M., Oshige M., Matsui T., Tobitsuka J., Yamada K. (1973) Chem. Pharm. Bull. Jpn.21: 2396
L'Abbe G., Toppet S., Willcox A., Mathys G. (1977) J. Heterocyclic Chem.14: 1417
Graubaum H., Seeboth H. (1987) J. Prakt. Chem.329: 409
L'Abbe G., Timmermann A., Metens C., Toppet S. (1978) J. Org. Chem.43: 4951
Behringer H., Weber D. (1964) Chem. Ber.97: 2567
Graubaum H., Seeboth H. (1989) GDR patent pending
Stelander E., Viehe H. G., van Muroschke M., Germain G., Declercq J. P. (1977) Bull. Soc. Chim. Belg.86: 291
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Graubaum, H., Seeboth, H. & Zalupsky, P. 5-Amino-1,2,3,4-thiatriazole: Its acylation with chloroformates and chlorothioformates as a route to 1,2,4-thiadiazoles and 1,6,6a,Δ4-trithia-3,4-diazapentalenes. Monatsh Chem 120, 997–1002 (1989). https://doi.org/10.1007/BF00808771
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DOI: https://doi.org/10.1007/BF00808771