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

Whitney Elisabeth Smith; Donna Victoria Franklin; Kourtni Lynn Goutierrez; Frank Robert Fronczek; Franz Andreas Mautner; Thomas Junk

doi:doi:10.11648/j.ajhc.20190503.11

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

Whitney Elisabeth Smith, Donna Victoria Franklin, Kourtni Lynn Goutierrez, Frank Robert Fronczek, Franz Andreas Mautner, Thomas Junk

Published in American Journal of Heterocyclic Chemistry (Volume 5, Issue 3)

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
Creative Commons	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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ACS Style

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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AMA Style

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

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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APA Style

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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ACS Style

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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AMA Style

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

Copy | Download

@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}
}

Copy | Download

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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