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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Authors
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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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.
Keywords
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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This article is an open access article distributed under the Creative Commons Attribution License (http://creativecommons.org/licenses/by/4.0/) which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.
References
[1]
A. F. Cozzolino, P. S. Whitfield and I. Vargas-Baca (2010). Supramolecular Chromotropism of the Crystalline Phases of 4,5,6,7-Tetrafluorobenzo-2,1,3-telluradiazole. Am. Chem. Soc. 132, 17265–17270.
[2]
A. F. Cozzolino, Q. Yang, and I. Vargas-Baca (2010). Engineering Second-Order Nonlinear Optical Activity by Means of a Noncentrosymmetric Distortion of the [Te-N]2 Supramolecular Synthon. Cryst. Growth Des. 10, 4959–4964.
[3]
P. C. Ho, P. Szydlowski, J. Sinclair, P. J. W. Elder, J. Kübel, C. Gendy, L. M. Lee, H. A. Jenkins, J. F. Britten, D. R. Morim and I. Vargas-Baca (2016), Supramolecular Macrocycles Reversibly Assembled by Te…O Chalcogen Bonding. Nat. Commun. 7, 11299; doi: 10.1038/ncomms11299.
[4]
G. Sanford, K. E. Walker, F. R. Fronczek and T. Junk (2017). Novel Organotellurium Heterocycles Derived From Bis (2-Aminophenyl) Ditelluride. J. Heterocycl. Chem. 54, 575–579. doi: 10.1002/jhet.2624.
[5]
A. Kremer, A. Fermi, N. Biot, J. Wouters and D. Bonifazi (2016), Supramolecular Wiring of Benzo-1,3-chalcogenazoles Through Programmed Chalcogen Bonding Interactions. Chem. Eur. J. 22, 5665–5675.
[6]
T. Junk, Chapter “Recent Advances in the Preparation and Characterization of Te, N-Containing Heterocycles”, in “Tellurium: Properties, Uses and Research”, Ed. D. Grey, Nova Science Publishers, ISBN 978-1-53610-555-1, 2017 pp. 107-136.
[7]
T. Junk, N. C. McMullen and F. R. Fronczek (2013). Organotellurium Chemistry: Remarkably Facile Preparation of Benzo-1,3-tellurazoles. J. Heterocycl. Chem. 50 (1), 120–124.
[8]
S.-I. Fujiwara, Y. Asanuma, T. Shin-Ike and N. Kambe (2007). Copper(I)-Catalyzed Highly Efficient Synthesis of Benzoselenazoles and Benzotellurazoles. J. Org. Chem. 72 (21), 8087-8090.
[9]
H. Ogura, S. Mineo and K. Nakagawa (1981). Studies on Heterocyclic Compounds XXXIV. Synthesis of 2-Substituted Aminobenzoxazoles with Nickel Peroxide. Chem. & Pharm. Bull. 29 (6), 1518-1524.
[10]
J. Sam and J. N. Plampin (1964). Benzoxazoles: Potent Skeletal Muscle Relaxants. J. Pharm. Sci. 53 (5), 538-544.
[11]
M. D. Uher, J. Berkes, J. Lesko and L. Floch (1983). Reactions of Carbonyl Isothiocyanates with Nucleophilic Bifunctional Reagents. Coll. Czechoslovak Chem. Comm. 48 (6), 1651-1658.
[12]
K. J. Irgolic, Houben-Weyl: Methods of Organic Chemistry, vol. E12b, Organotellurium Compounds, D. Klamann, Ed., Georg Thieme, Stuttgart, 1990, 152-153.
[13]
A. Wroblewska and G. Mloston (2013). Synthesis of New Enantiopure Thioureas Derived from (S)-Proline. Phosphorus, Sulfur Silicon Relat. Elem. 188 (4), 509-511.
[14]
A. S. Kuzovlev, E. V. Savinkina, V. V. Chernyshev, M. S. Grigoriev and A. N. Volov (2016). Copper and Palladium Complexes with Substituted Pyrimidine-2-thiones and 2-Thiouracils: Syntheses, Spectral Characterization and X-ray Crystallographic Study. J. Coord. Chem. 69 (3), 508-552.
[15]
F. Asghar, S. Rana, S. Fatima, A. Badshah, B. Lal and I. S. Butler (2018). Biologically Active Halo-Substituted Ferrocenyl Thioureas: Synthesis, Spectroscopic Characterization and DFT Calculations. New J. Chem. 42 (9), 7154-7165.
[16]
L.-P. Duan J. Xue, L.-L. Xu and H.-B. Zhang (2010). Synthesis of 1-Acyl-3-(2'-aminophenyl) Thioureas as Anti-Intestinal Nematode Prodrugs. Molecules 15, 6941-6947.
[17]
A. Rana, N. Siddiqui, S. A. Khan, S. Ehtaishamul Haqueand and M. A. Bhat (2008). N-{[(6-Substituted-1,3-benzothiazol-2-yl)amino]carbonothioyl}-2,4-substituted Benzamides: Synthesis and Pharmacological Evaluation. Eur. J. Med. Chem. 43 (5), 1114-1122.
[18]
M.-J. Wang, X. Nan, G. Feng, Y. Gang, H.-T. Yu, G.-F. Hu and Y.-Q. Liu (2014). Design, Synthesis and Bioactivity Evaluation of Novel Acylthiourea Derivatives of Cantharidin. Ind. Crops Prod. 55, 11-18.
[19]
E. S. Lang, R. A. Zan, C. C. Gatto, R. A. Burrow and E. M. Vazquez-Lopez (2002). Syntheses and Structures of New Tellurium-Mercury Clusters with Twelve- and Six-Membered Rings. Eur. J. Inorg. Chem. 2, 331-333.
[20]
Y. Okamoto and Y. Takefumi (1971). The Reaction of Dioorganyl Diselenides and Ditellurides with Organic Mercury Compounds. A Convenient Method for the Synthesis of Unsymmetrical Organic Selenides and Tellurides. J. Organomet. Chem. 29 (1), 99-103.
[21]
G. Sanford, K. E. Walker, F. R. Fronczek and T. Junk (2016). CCDC 1423100: Experimental Crystal Structure Determination, DOI: 10.5517/ccdc.csd.cc1jrvgl.
[22]
Mautner, F. A. and T. Junk, unpublished.
[23]
V. Bertini, P. Dapporto, F. Lucchesini, A. Sega, A. DeMunno (1984). Actra Cryst. C 40, 653-655.
[24]
A. F. Cozzolino and I. Vargas-Baca (2007). J. Organomet. Chem. 692 (13) 13, 2654-2657.
[25]
G. Sanford, K. E. Walker, F. R. Fronczek and T. Junk (2017). Novel Organotellurium Heterocycles Derived from bis(2-Aminophenyl) Ditelluride. J. Heterocycl. Chem. 54, 575–579. doi: 10.1002/jhet.2624.
[26]
J. P. Myers, F. R. Fronczek and T. Junk (2015). The First Crystal Structures of Six- and Seven-Membered Tellurium- and Nitrogen-Containing (Te-N) Heterocycles: 2H-1,4-Benzo-tellurazin-3(4H)-one and 2,3-Dihydro-1,5-benzotellurazepin-4(5H)-one. Acta Cryst. C72, 1-5.
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