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Organotellurium Chemistry: Synthesis and Properties of 2-Acylamino- and 2-Arylamino-1,3-benzotellurazoles
American Journal of Heterocyclic Chemistry
Volume 5, Issue 3, September 2019, Pages: 49-54
Received: Dec. 6, 2018; Accepted: Jul. 10, 2019; Published: Jul. 30, 2019
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Whitney Elisabeth Smith, Department of Chemistry, University of Louisiana at Lafayette, Lafayette, USA
Donna Victoria Franklin, Department of Chemistry, University of Louisiana at Lafayette, Lafayette, USA
Kourtni Lynn Goutierrez, Department of Chemistry, University of Louisiana at Lafayette, Lafayette, USA
Frank Robert Fronczek, Department of Chemistry, Louisiana State University, Baton Rouge, USA
Franz Andreas Mautner, Institute for Physical and Theoretical Chemistry, Technical University Graz, Graz, Austria
Thomas Junk, Department of Chemistry, University of Louisiana at Lafayette, Lafayette, USA
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Synthetic methods have been developed to prepare novel 1,3-benzotellurazoles carrying acylamino and arylamino moieties in position 2, in order to investigate their propensity to self-assemble to supramolecular structures. The targeted compounds were obtained in yields ranging from 44% to 67%, by reacting bis(2-aminophenyl) ditelluride with acyl- and aryl isothiocyanates, respectively, and subsequent reductive cyclization of the resulting thiourea derivatives. Seven novel 1,3-benzotellurazole derivatives were prepared: 2-benzoylamino-1,3-benzotellurazole, 2-(4-chlorobenzoylamino)-1,3-benzotellurazole, 2-(2-bromobenzoylamino)-1,3-benzotellurazole, 2-(4-bromobenzoylamino)-1,3-benzotellurazole, 2-(4-methoxybenzoylamino)-1,3-benzotellurazole, 2-phenylamino-1,3-benzotellurazole, and 2-(4-chlorophenylamino-1,3-benzotellurazole. A simplified protocol was employed to synthesize all acyl isothiocyanates needed for their preparation from benzoyl halide derivatives and potassium thiocyanate. The reductive cyclization of the intermediate thioureas was challenging, only the use of hydroxymethanesulfinate in the presence of elemental mercury provided synthetically useful product yields. A mechanism was proposed, consisting of the insertion of mercury into the Te-Te bond, followed by intramolecular nucleophilic attack of the thiocarbonyl moiety by the resulting insertion product. All 2-acylamino-1,3-benzotellurazoles are crystalline solids, which are stable to ambient light, air and moderate heat. A characterization of selected samples by X-ray crystallography indicated that they form dimers in solid state, resulting from hydrogen bonding between the exocyclic and endocyclic nitrogen atoms of two adjacent molecules. This sets them apart from 2-alkyl- and 2-aryl-1,3-benzotellurazoles, which are known to self-assemble into supramolecular wires.
Tellurium, Tellurazoles, Self-Assembly
To cite this article
Whitney Elisabeth Smith, Donna Victoria Franklin, Kourtni Lynn Goutierrez, Frank Robert Fronczek, Franz Andreas Mautner, Thomas Junk, Organotellurium Chemistry: Synthesis and Properties of 2-Acylamino- and 2-Arylamino-1,3-benzotellurazoles, American Journal of Heterocyclic Chemistry. Vol. 5, No. 3, 2019, pp. 49-54. doi: 10.11648/j.ajhc.20190503.11
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