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Organotellurium Chemistry: Synthesis and Properties of 2-Acylamino- and 2-Arylamino-1,3-benzotellurazoles

Received: 6 December 2018     Accepted: 10 July 2019     Published: 30 July 2019
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Abstract

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.

Published in American Journal of Heterocyclic Chemistry (Volume 5, Issue 3)
DOI 10.11648/j.ajhc.20190503.11
Page(s) 49-54
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This is an Open Access article, distributed under the terms of the Creative Commons Attribution 4.0 International License (http://creativecommons.org/licenses/by/4.0/), which permits unrestricted use, distribution and reproduction in any medium or format, provided the original work is properly cited.

Copyright

Copyright © The Author(s), 2019. Published by Science Publishing Group

Keywords

Tellurium, Tellurazoles, Self-Assembly

References
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    Whitney Elisabeth Smith, Donna Victoria Franklin, Kourtni Lynn Goutierrez, Frank Robert Fronczek, Franz Andreas Mautner, et al. (2019). Organotellurium Chemistry: Synthesis and Properties of 2-Acylamino- and 2-Arylamino-1,3-benzotellurazoles. American Journal of Heterocyclic Chemistry, 5(3), 49-54. https://doi.org/10.11648/j.ajhc.20190503.11

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    Whitney Elisabeth Smith; Donna Victoria Franklin; Kourtni Lynn Goutierrez; Frank Robert Fronczek; Franz Andreas Mautner, et al. Organotellurium Chemistry: Synthesis and Properties of 2-Acylamino- and 2-Arylamino-1,3-benzotellurazoles. Am. J. Heterocycl. Chem. 2019, 5(3), 49-54. doi: 10.11648/j.ajhc.20190503.11

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    Whitney Elisabeth Smith, Donna Victoria Franklin, Kourtni Lynn Goutierrez, Frank Robert Fronczek, Franz Andreas Mautner, et al. Organotellurium Chemistry: Synthesis and Properties of 2-Acylamino- and 2-Arylamino-1,3-benzotellurazoles. Am J Heterocycl Chem. 2019;5(3):49-54. doi: 10.11648/j.ajhc.20190503.11

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  • @article{10.11648/j.ajhc.20190503.11,
      author = {Whitney Elisabeth Smith and Donna Victoria Franklin and Kourtni Lynn Goutierrez and Frank Robert Fronczek and Franz Andreas Mautner and Thomas Junk},
      title = {Organotellurium Chemistry: Synthesis and Properties of 2-Acylamino- and 2-Arylamino-1,3-benzotellurazoles},
      journal = {American Journal of Heterocyclic Chemistry},
      volume = {5},
      number = {3},
      pages = {49-54},
      doi = {10.11648/j.ajhc.20190503.11},
      url = {https://doi.org/10.11648/j.ajhc.20190503.11},
      eprint = {https://article.sciencepublishinggroup.com/pdf/10.11648.j.ajhc.20190503.11},
      abstract = {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.},
     year = {2019}
    }
    

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  • TY  - JOUR
    T1  - Organotellurium Chemistry: Synthesis and Properties of 2-Acylamino- and 2-Arylamino-1,3-benzotellurazoles
    AU  - Whitney Elisabeth Smith
    AU  - Donna Victoria Franklin
    AU  - Kourtni Lynn Goutierrez
    AU  - Frank Robert Fronczek
    AU  - Franz Andreas Mautner
    AU  - Thomas Junk
    Y1  - 2019/07/30
    PY  - 2019
    N1  - https://doi.org/10.11648/j.ajhc.20190503.11
    DO  - 10.11648/j.ajhc.20190503.11
    T2  - American Journal of Heterocyclic Chemistry
    JF  - American Journal of Heterocyclic Chemistry
    JO  - American Journal of Heterocyclic Chemistry
    SP  - 49
    EP  - 54
    PB  - Science Publishing Group
    SN  - 2575-5722
    UR  - https://doi.org/10.11648/j.ajhc.20190503.11
    AB  - 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.
    VL  - 5
    IS  - 3
    ER  - 

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Author Information
  • Department of Chemistry, University of Louisiana at Lafayette, Lafayette, USA

  • Department of Chemistry, University of Louisiana at Lafayette, Lafayette, USA

  • Department of Chemistry, University of Louisiana at Lafayette, Lafayette, USA

  • Department of Chemistry, Louisiana State University, Baton Rouge, USA

  • Institute for Physical and Theoretical Chemistry, Technical University Graz, Graz, Austria

  • Department of Chemistry, University of Louisiana at Lafayette, Lafayette, USA

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