A New Method for the Synthesis of 2-Substituted Benzoxazoles from 2-Nitrophenol Derivatives and Aldehydes
Main Article Content
Abstract
Benzoxazole derivatives are one of those compounds with many interesting biological activities. Conventional methods are often performed under complex conditions using strong acids, expensive metal catalysts, requiring high pressure, high temperature, and under microwave irradiation. In this study, we reported a new method of benzoxazole synthesis with Fe/S redox catalyst using FeCl3.6H2O and sulfur. This is a suitable, efficient, readily available and environmentally friendly catalyst system for redox and condensation reactions in one step at 100oC. Applying this new method, we have synthesized 8 benzoxazole derivatives with high yields (calculated according to 2-nitrophenol). This research is an important step forward in the synthesis of biologically active compounds containing the benzoxazole framework from readily available starting materials in a single reaction.
Keywords
2-arylbenzoxazole, 2-nitrophenol, sulfur, aldehyde, FeCl3.6H2O
Article Details
References
[1] Khaled R. A. Abdellatif, Noha H., Amin Asma, A. Mohammed., Synthesis of some benzoxazole derivatives and their anti-inflammatory evaluation, Journal of Chemical and Pharmaceutical Research, 8(4), (2016), 1253-1261.
[2] D.D. Kumar, R. Jacob, B. Renolds, M. Kerwin, Synthesis and evaluation of anticancer benzoxazoles and benzimidazoles related to UK-1. Bioorg. Med. Chem. 10 (12), (2002) 3997-4004.
https://doi.org/10.1016/S0968-0896(02)00327-9
[3] I.H. Hall, N.J. Peaty, J.R. Henry, J. Easmon, G. Heinisch, G. Purshinger, Investigations on the mechanism of action of the novel antitumor agents 2‐benzothiazolyl, 2‐benzoxazolyl, and 2‐benzimidazolyl hydrazones derived from 2‐acetylpyridine, Arch. Pharm., 332 (4), (1999), 115-123.
https://doi.org/10.1002/(SICI)1521-4184(19994)332:4<115::AID-ARDP115>3.0.CO;2-G
[4] S. Rajasekhar, B. Maiti, K. Chanda, A decade update on benzoxazoles, a privileged scaffold in synthetic organic chemistry, Synlett 28, (2017), 521-541.
https://doi.org/10.1055/s-0036-1588671
[5] Y. Riadiad, R. Mamouni, R. Azzaloua, M. E. Haddad, S. Routier, G. Guillaumet, S. Lazar, An efficient and reusable heterogeneous catalyst animal bone meal for facile synthesis of benzimidazoles, benzoxazoles, and benzothiazoles, Tetrahedron Lett. 52, (2011), 3492.
https://doi.org/10.1016/j.tetlet.2011.04.121
[6] T. B. Nguyen, L. Ermolenko, A. Almourabit, Sodium sulfide: a sustainable solution for unbalanced redox condensation reaction between o-nitroanilines and alcohols catalyzed by an iron-sulfur system, Synthesis, 47, (2015), 1741.
https://doi.org/10.1055/s-0034-1380134
[7] T. B. Nguyen, L. Ermolenko, M. Corbin, A. Almourabit, Fe/S-catalyzed decarboxylative redox condensation of arylacetic acids with nitroarenes, Org. Chem. Front. 1, (2014), 1157.
https://doi.org/10.1039/C4QO00221K
[8] T. B. Nguyen, P. Retailleau, A. AlMourabit, A simple and straightforward approach to quinoxalines by iron/sulfur-catalyzed redox condensation of o-nitroanilines and phenethylamines, Org. Lett. 15, (2013), 5238.
https://doi.org/10.1021/ol402435c
[9] T. B. Nguyen, L. Ermolenko, A. Almourabit, Nitromethyl redox coupling: efficient approach to 2-hetarylbenzothiazoles from 2-halonitroarene, methylhetarene, and elemental sulfur, Org. Lett. 15, (2013), 4218.
https://doi.org/10.1021/ol401944a
[10] T. B. Nguyen, L. Ermolenko, A. Almourabit, Iron sulfide catalyzed redox/condensation cascade reaction between 2-amino/hydroxy nitrobenzenes and activated methyl groups: a straightforward atom economical approach to 2-hetaryl-benzimidazoles and -benzoxazoles, J. Am. Chem. Soc. 135, (2013), 118.
https://doi.org/10.1021/ja311780a
[11] W. Kong, B. Li, X. Xu, Q. Song, Fe-catalyzed aerobic oxidative c-cn bond cleavage of arylacetonitriles leading to various esters, J. Org. Chem. 81, (2016), 8436.
https://doi.org/10.1021/acs.joc.6b01594
[12] Nguyen, T. B., Cheung-Lung, Iron‐catalyzed sulfur‐promoted decyanative redox condensation of o‐nitrophenols and arylacetonitriles: an unprecedented route to 2‐arylbenzoxazoles, J. Eur. J. Org. Chem. 3, (2018), 5815.
https://doi.org/10.1002/ejoc.201701607
[13] Wu, M., Hu, X., Liu, J., Liao, Y., & Deng, G.-J. Iron catalyzed 2-arylbenzoxazole formation from o-nitrophenols and benzylic alcohols. Organic Letters 14, (2012), 2722-2725.
https://doi.org/10.1021/ol300937z
[14] H Beinert, R H Holm, E Münck. Iron-sulfur clusters: nature's modular, multipurpose structures. Science 277, (1997), 653-659.
https://doi.org/10.1126/science.277.5326.653
[15] Mingyue Wu, Xiong Hu, Juan Liu, Yunfeng Liao, Guo-Jun Deng. Iron-catalyzed 2-arylbenzoxazole formation from o-nitrophenols and benzylic alcohols. Org. Lett. 14, (2012), 2722-2725.
https://doi.org/10.1021/ol300937z
[16] Francesco Ferlin, Mitchell K. van der Hulst, Daniela Lanarib, Luigi Vaccaro. Continuous flow/waste-minimized synthesis of benzoxazoles catalysed by heterogeneous manganese systems. Green Chem., 21, (2019), 5298-5305.
https://doi.org/10.1039/C9GC01641D
[2] D.D. Kumar, R. Jacob, B. Renolds, M. Kerwin, Synthesis and evaluation of anticancer benzoxazoles and benzimidazoles related to UK-1. Bioorg. Med. Chem. 10 (12), (2002) 3997-4004.
https://doi.org/10.1016/S0968-0896(02)00327-9
[3] I.H. Hall, N.J. Peaty, J.R. Henry, J. Easmon, G. Heinisch, G. Purshinger, Investigations on the mechanism of action of the novel antitumor agents 2‐benzothiazolyl, 2‐benzoxazolyl, and 2‐benzimidazolyl hydrazones derived from 2‐acetylpyridine, Arch. Pharm., 332 (4), (1999), 115-123.
https://doi.org/10.1002/(SICI)1521-4184(19994)332:4<115::AID-ARDP115>3.0.CO;2-G
[4] S. Rajasekhar, B. Maiti, K. Chanda, A decade update on benzoxazoles, a privileged scaffold in synthetic organic chemistry, Synlett 28, (2017), 521-541.
https://doi.org/10.1055/s-0036-1588671
[5] Y. Riadiad, R. Mamouni, R. Azzaloua, M. E. Haddad, S. Routier, G. Guillaumet, S. Lazar, An efficient and reusable heterogeneous catalyst animal bone meal for facile synthesis of benzimidazoles, benzoxazoles, and benzothiazoles, Tetrahedron Lett. 52, (2011), 3492.
https://doi.org/10.1016/j.tetlet.2011.04.121
[6] T. B. Nguyen, L. Ermolenko, A. Almourabit, Sodium sulfide: a sustainable solution for unbalanced redox condensation reaction between o-nitroanilines and alcohols catalyzed by an iron-sulfur system, Synthesis, 47, (2015), 1741.
https://doi.org/10.1055/s-0034-1380134
[7] T. B. Nguyen, L. Ermolenko, M. Corbin, A. Almourabit, Fe/S-catalyzed decarboxylative redox condensation of arylacetic acids with nitroarenes, Org. Chem. Front. 1, (2014), 1157.
https://doi.org/10.1039/C4QO00221K
[8] T. B. Nguyen, P. Retailleau, A. AlMourabit, A simple and straightforward approach to quinoxalines by iron/sulfur-catalyzed redox condensation of o-nitroanilines and phenethylamines, Org. Lett. 15, (2013), 5238.
https://doi.org/10.1021/ol402435c
[9] T. B. Nguyen, L. Ermolenko, A. Almourabit, Nitromethyl redox coupling: efficient approach to 2-hetarylbenzothiazoles from 2-halonitroarene, methylhetarene, and elemental sulfur, Org. Lett. 15, (2013), 4218.
https://doi.org/10.1021/ol401944a
[10] T. B. Nguyen, L. Ermolenko, A. Almourabit, Iron sulfide catalyzed redox/condensation cascade reaction between 2-amino/hydroxy nitrobenzenes and activated methyl groups: a straightforward atom economical approach to 2-hetaryl-benzimidazoles and -benzoxazoles, J. Am. Chem. Soc. 135, (2013), 118.
https://doi.org/10.1021/ja311780a
[11] W. Kong, B. Li, X. Xu, Q. Song, Fe-catalyzed aerobic oxidative c-cn bond cleavage of arylacetonitriles leading to various esters, J. Org. Chem. 81, (2016), 8436.
https://doi.org/10.1021/acs.joc.6b01594
[12] Nguyen, T. B., Cheung-Lung, Iron‐catalyzed sulfur‐promoted decyanative redox condensation of o‐nitrophenols and arylacetonitriles: an unprecedented route to 2‐arylbenzoxazoles, J. Eur. J. Org. Chem. 3, (2018), 5815.
https://doi.org/10.1002/ejoc.201701607
[13] Wu, M., Hu, X., Liu, J., Liao, Y., & Deng, G.-J. Iron catalyzed 2-arylbenzoxazole formation from o-nitrophenols and benzylic alcohols. Organic Letters 14, (2012), 2722-2725.
https://doi.org/10.1021/ol300937z
[14] H Beinert, R H Holm, E Münck. Iron-sulfur clusters: nature's modular, multipurpose structures. Science 277, (1997), 653-659.
https://doi.org/10.1126/science.277.5326.653
[15] Mingyue Wu, Xiong Hu, Juan Liu, Yunfeng Liao, Guo-Jun Deng. Iron-catalyzed 2-arylbenzoxazole formation from o-nitrophenols and benzylic alcohols. Org. Lett. 14, (2012), 2722-2725.
https://doi.org/10.1021/ol300937z
[16] Francesco Ferlin, Mitchell K. van der Hulst, Daniela Lanarib, Luigi Vaccaro. Continuous flow/waste-minimized synthesis of benzoxazoles catalysed by heterogeneous manganese systems. Green Chem., 21, (2019), 5298-5305.
https://doi.org/10.1039/C9GC01641D