Generic placeholder image

Current Organic Chemistry

Author(s): Vikas Yadav, Mitushree Ghosh and Virendra Prasad*

DOI: 10.2174/1385272827666230519163647

DownloadDownload PDF Flyer Cite As
Transition Metal-Free Catalyzed Oxidative Coupling of Anilines to Azo Compounds and Thiophenols to Disulfides

Page: [435 - 443] Pages: 9

  • * (Excluding Mailing and Handling)

Explore Articles
About Journal
For Authors
For Editors
For Reviewers

Abstract

Introduction: Herein we report the efficient oxidative transformations of aryl amines to azoarenes and aryl thiols to the corresponding disulfides using diacetoxyiodobenzene and potassium iodide as transition metal-free catalysts in acetonitrile at room temperature. The developed protocols are highly efficient and employ readily accessible, inexpensive, and environmentally friendly starting.

Methods: All the reactions were carried out in a fuming hood at room temperature (approximately 25- 30°C). The chemicals used in these reactions were purchased from Avra, Aldrich and Spectrochem with a minimum of 95-99% purities and used without further purification.

Results: The reaction of DIB with KI would generate PhI(OAc)I through a partial AcO-I exchange process, and the subsequent reaction of 2PhI(OAc)I with aromatic amines should produce PhNI2 on the elimination of 2AcOH and 2PhI.

Conclusion: The protocol was applicable to a wide range of aromatic amines and aromatic thiols under mild reaction conditions and has no safety concerns, requires inexpensive chemicals and is environmentally friendly.

Keywords: Transition, oxidative, anilines, azo compounds, thiophenols, organic dyes.

Graphical Abstract

[1]
Anderson, R.G.; Nickless, G. Heterocyclic azo dyestuffs in analytical chemistry. A review. Analyst, 1967, 92(1093), 207-238.
[http://dx.doi.org/10.1039/an9679200207] [PMID: 4859975]
[2]
Androvič L.; Bartáček, J.; Sedlák, M. Recent advances in the synthesis and applications of azo initiators. Res. Chem. Intermed., 2016, 42(6), 5133-5145.
[http://dx.doi.org/10.1007/s11164-015-2351-4]
[3]
DiCesare, N.; Lakowicz, J.R. New color chemosensors for monosaccharides based on azo dyes. Org. Lett., 2001, 3(24), 3891-3893.
[http://dx.doi.org/10.1021/ol016813p] [PMID: 11720562]
[4]
Naser, N.A.; Kahdim, K.H.; Taha, D.N. Synthesis and characterization of an organic reagent 4-(6-bromo-2-benzothiazolylazo) pyrogallol and its analytical application. J. Oleo Sci., 2012, 61(7), 387-392.
[http://dx.doi.org/10.5650/jos.61.387] [PMID: 22790169]
[5]
Sandborn, W.J. Rational selection of oral 5-aminosalicylate formulations and prodrugs for the treatment of ulcerative colitis. Am. J. Gastroenterol., 2002, 97(12), 2939-2941.
[http://dx.doi.org/10.1111/j.1572-0241.2002.07092.x] [PMID: 12492172]
[6]
Jain, A.; Gupta, Y.; Jain, S.K. Azo chemistry and its potential for colonic delivery. Crit. Rev. Ther. Drug Carrier Syst., 2006, 23(5), 349-400.
[7]
Cisnetti, F.; Ballardini, R.; Credi, A.; Gandolfi, M.T.; Masiero, S.; Negri, F.; Pieraccini, S.; Spada, G.P. Photochemical and electronic properties of conjugated bis(azo) compounds: An experimental and computational study. Chemistry, 2004, 10(8), 2011-2021.
[http://dx.doi.org/10.1002/chem.200305590] [PMID: 15079841]
[8]
Yang, Y.; Hughes, R.P.; Aprahamian, I. Visible light switching of a BF2-coordinated azo compound. J. Am. Chem. Soc., 2012, 134(37), 15221-15224.
[http://dx.doi.org/10.1021/ja306030d] [PMID: 22954379]
[9]
Wang, Y.F.; Wang, C.J.; Feng, Q.Z.; Zhai, J.J.; Qi, S.S.; Zhong, A.G.; Chu, M.M.; Xu, D.Q. Copper-catalyzed asymmetric 1,6-conjugate addition of in situ generated para -quinone methides with β-ketoesters. Chem. Commun., 2022, 58(46), 6653-6656.
[http://dx.doi.org/10.1039/D2CC00146B] [PMID: 35593224]
[10]
Yao, W.; Wang, J.; Zhong, A.; Wang, S.; Shao, Y. Transition-metal-free catalytic hydroboration reduction of amides to amines. Org. Chem. Front., 2020, 7(21), 3515-3520.
[http://dx.doi.org/10.1039/D0QO01092H]
[11]
Yang, Q.; Wen, Y.; Zhong, A.; Xu, J.; Shao, S. An HBT-based fluorescent probe for nitroreductase determination and its application in Escherichia coli cell imaging. New J. Chem., 2020, 44(38), 16265-16268.
[http://dx.doi.org/10.1039/D0NJ03286G]
[12]
Yao, W.; Wang, J.; Lou, Y.; Wu, H.; Qi, X.; Yang, J.; Zhong, A. Chemoselective hydroborative reduction of nitro motifs using a transition-metal-free catalyst. Org. Chem. Front., 2021, 8(16), 4554-4559.
[http://dx.doi.org/10.1039/D1QO00705J]
[13]
Takeda, Y.; Okumura, S.; Minakata, S. Oxidative dimerization of aromatic amines using tBuOI: Entry to unsymmetric aromatic azo compounds. Angew. Chem. Int. Ed., 2012, 51(31), 7804-7808.
[http://dx.doi.org/10.1002/anie.201202786] [PMID: 22740244]
[14]
Zhu, Y.; Shi, Y. Facile Cu(I)-catalyzed oxidative coupling of anilines to azo compounds and hydrazines with diaziridinone under mild conditions. Org. Lett., 2013, 15(8), 1942-1945.
[http://dx.doi.org/10.1021/ol4005917] [PMID: 23545123]
[15]
Hu, L.; Cao, X.; Shi, L.; Qi, F.; Guo, Z.; Lu, J.; Gu, H. A highly active nano-palladium catalyst for the preparation of aromatic azos under mild conditions. Org. Lett., 2011, 13(20), 5640-5643.
[http://dx.doi.org/10.1021/ol202362f] [PMID: 21939197]
[16]
Dabbagh, H.A.; Teimouri, A.; Chermahini, A.N. Green and efficient diazotization and diazo coupling reactions on clays. Dyes Pigments, 2007, 73(2), 239-244.
[http://dx.doi.org/10.1016/j.dyepig.2005.12.002]
[17]
Boyer, J. The Chemistry of the Nitro and Nitroso Groups, Part 1; Feuer, H., Ed.; Interscience Publishers: New York, 1969.
[18]
Thorwirth, R.; Bernhardt, F.; Stolle, A.; Ondruschka, B.; Asghari, J. Switchable selectivity during oxidation of anilines in a ball mill. Chemistry, 2010, 16(44), 13236-13242.
[http://dx.doi.org/10.1002/chem.201001702] [PMID: 20922723]
[19]
Ortiz, B.; Villanueva, P.; Walls, F. Silver(II) oxide as a reagent. Reactions with aromatic amines and miscellaneous related compounds. J. Org. Chem., 1972, 37(17), 2748-2750.
[http://dx.doi.org/10.1021/jo00982a028]
[20]
Huang, H.; Sommerfeld, D.; Dunn, B.C.; Lloyd, C.R.; Eyring, E.M. J. Chem. Soc., Dalton Trans., 2001, 8, 1301.
[http://dx.doi.org/10.1039/b008934f]
[21]
Kanda, Y.; Fukuyama, T. Total synthesis of (+)-leinamycin. J. Am. Chem. Soc., 1993, 115(18), 8451-8452.
[http://dx.doi.org/10.1021/ja00071a066]
[22]
Bischoff, L.; David, C.; Martin, L.; Meudal, H.; Roques, B.P.; Fournié-Zaluski, M.C. 2, 4-Dinitrophenyl 4-methoxybenzyl disulfide: A new efficient reagent for the electrophilic sulfenylation of β-amino ester enolates. J. Org. Chem., 1997, 62(14), 4848-4850.
[http://dx.doi.org/10.1021/jo9623853]
[23]
Balmer, Y.; Vensel, W.H.; Cai, N.; Manieri, W.; Schürmann, P.; Hurkman, W.J.; Buchanan, B.B. A complete ferredoxin/thioredoxin system regulates fundamental processes in amyloplasts. Proc. Natl. Acad. Sci. USA, 2006, 103(8), 2988-2993.
[http://dx.doi.org/10.1073/pnas.0511040103] [PMID: 16481623]
[24]
Singh, S.J.; Devi, N.S. Diacetoxyiodobenzene mediated oxidative transformation of thione to disulfides. Tetrahedron Lett., 2016, 57(52), 5941-5943.
[http://dx.doi.org/10.1016/j.tetlet.2016.11.091]
[25]
Firouzabadi, H.; Abbassi, M.; Karimi, B. Highly efficient oxidative coupling of thiols by active manganese dioxide (AMD) and barium manganate (BM) under solvent-free conditions at room temperature. Synth. Commun., 1999, 29(14), 2527-2531.
[http://dx.doi.org/10.1080/00397919908086260]
[26]
Noureldin, N.A.; Caldwell, M.; Hendry, J.; Lee, D.G. Heterogeneous permanganate oxidation of thiols. Synthesis, 1998, 1998(11), 1587-1589.
[http://dx.doi.org/10.1055/s-1998-2190]
[27]
Tajbakhsh, M.; Hosseinzadeh, R.; Shakoori, A. 2,6-Dicarboxypyridinium chlorochromate: An efficient and selective reagent for the oxidation of thiols to disulfides and sulfides to sulfoxides. Tetrahedron Lett., 2004, 45(9), 1889-1893.
[http://dx.doi.org/10.1016/j.tetlet.2004.01.006]
[28]
Iranpoor, N.; Zeynizadeh, B. Air oxidative coupling of thiols to disulfides catalyzed by Fe (III)/NaI. Synthesis, 1999, 1999(1), 49-50.
[http://dx.doi.org/10.1055/s-1999-3693]
[29]
Patel, S.; Mishra, B.K. Cetyltrimethylammonium dichromate: A mild oxidant for coupling amines and thiols. Tetrahedron Lett., 2004, 45(7), 1371-1372.
[http://dx.doi.org/10.1016/j.tetlet.2003.12.068]
[30]
Joshi, A.V.; Bhusare, S.; Baidossi, M.; Qafisheh, N.; Sasson, Y. Oxidative coupling of thiols to disulfides using a solid anhydrous potassium phosphate catalyst. Tetrahedron Lett., 2005, 46(20), 3583-3585.
[http://dx.doi.org/10.1016/j.tetlet.2005.03.040]
[31]
Montazerozohori, M.; Karami, B.; Azizi, M. Molybdate sulfuric acid (MSA): A novel and efficient solid acid reagent for the oxidation of thiols to symmetrical disulfides. ARKIVOC, 2007, 2007(1), 99-104.
[http://dx.doi.org/10.3998/ark.5550190.0008.111]
[32]
Shah, S.T.A.; Khan, K.M.; Fecker, M.; Voelter, W. A novel method for the syntheses of symmetrical disulfides using CsF–Celite as a solid base. Tetrahedron Lett., 2003, 44(35), 6789-6791.
[http://dx.doi.org/10.1016/S0040-4039(03)01402-3]
[33]
Shaabani, A.; Behnam, M.; Rezayan, A.H. Tungstophosphoric acid (H3PW12O40) catalyzed oxidation of organic compounds with NaBrO3. Catal. Commun., 2009, 10(7), 1074-1078.
[http://dx.doi.org/10.1016/j.catcom.2008.12.059]
[34]
Chauhan, S.M.S.; Kumar, A.; Srinivas, K.A. Oxidation of thiols with molecular oxygen catalyzed by cobalt(ii) phthalocyanines in ionic liquid. Chem. Commun. (Camb.), 2003, (18), 2348-2349.
[http://dx.doi.org/10.1039/b305888c] [PMID: 14518908]
[35]
Khodaei, M.; Mohammadpoor-Baltork, I.; Nikoofar, K. Bismuth(Ⅲ) nitrate pentahydrate Bi(NO3)3•5H2O: An inexpensive and mild reagent for the efficient and clean oxidation of thiols to disulfides. Bull. Korean Chem. Soc., 2003, 24(7), 885-886.
[http://dx.doi.org/10.5012/bkcs.2003.24.7.885]
[36]
Karimi, B.; Zareyee, D. Hexamethyldisilazane (HMDS) promotes highly efficient oxidative coupling of Thiols by DMSO under nearly neutral reaction conditions. Bull. Korean Chem. Soc., 2002, 2002(2), 346.
[37]
Demir, A.S.; Cigdem Igdir, A.; Mahasneh, A.S. Novel conversion of thiols into disulfides, via S-nitrosothiol intermediates using trichloronitromethane. Tetrahedron, 1999, 55(42), 12399-12404.
[http://dx.doi.org/10.1016/S0040-4020(99)00722-X]
[38]
Hajipour, A.R.; Mallakpour, S.E.; Adibi, H. Selective and efficient oxidation of sulfides and thiols with benzyltriphenylphosphonium peroxymonosulfate in aprotic solvent. J. Org. Chem., 2002, 67(24), 8666-8668.
[http://dx.doi.org/10.1021/jo026106p] [PMID: 12444655]
[39]
Ali, M.H.; McDermott, M. Oxidation of thiols to disulfides with molecular bromine on hydrated silica gel support. Tetrahedron Lett., 2002, 43(35), 6271-6273.
[http://dx.doi.org/10.1016/S0040-4039(02)01220-0]
[40]
Kesavan, V.; Bonnet-Delpon, D.; Bégué, J.P. Oxidation in fluoro alcohols: Mild and efficient preparation of disulfides from thiols. Synthesis, 2000, 2000(2), 223-225.
[http://dx.doi.org/10.1055/s-2000-6262]
[41]
Hayashi, M.; Okunaga, K.; Nishida, S.; Kawamura, K.; Eda, K. Oxidative transformation of thiols to disulfides promoted by activated carbon–air system. Tetrahedron Lett., 2010, 51(51), 6734-6736.
[http://dx.doi.org/10.1016/j.tetlet.2010.10.070]
[42]
Vandavasi, J.K.; Hu, W.P.; Chen, C.Y.; Wang, J.J. Efficient synthesis of unsymmetrical disulfides. Tetrahedron, 2011, 67(46), 8895-8901.
[http://dx.doi.org/10.1016/j.tet.2011.09.071]
[43]
Leino, R.; Lönnqvist, J.E. A very simple method for the preparation of symmetrical disulfides. Tetrahedron Lett., 2004, 45(46), 8489-8491.
[http://dx.doi.org/10.1016/j.tetlet.2004.09.100]
[44]
Naimi-Jamal, M.R.; Hamzeali, H.; Mokhtari, J.; Boy, J.; Kaupp, G. Sustainable synthesis of aldehydes, ketones or acids from neat alcohols using nitrogen dioxide gas, and related reactions. ChemSusChem, 2009, 2(1), 83-88.
[http://dx.doi.org/10.1002/cssc.200800193] [PMID: 19115303]
[45]
Li, X.B.; Li, Z.J.; Gao, Y.J.; Meng, Q.Y.; Yu, S.; Weiss, R.G.; Tung, C.H.; Wu, L.Z. Mechanistic insights into the interface-directed transformation of thiols into disulfides and molecular hydrogen by visible-light irradiation of quantum dots. Angew. Chem. Int. Ed., 2014, 53(8), 2085-2089.
[http://dx.doi.org/10.1002/anie.201310249] [PMID: 24470069]
[46]
García Ruano, J.L.; Parra, A.; Alemán, J. Efficient synthesis of disulfides by air oxidation of thiols under sonication. Green Chem., 2008, 10(6), 706-711.
[http://dx.doi.org/10.1039/b800705e]
[47]
Hong, K.B.; Johnston, J.N. Alkene diamination using electron-rich amines: Hypervalent iodine-promoted inter-/intramolecular C-N bond formation. Org. Lett., 2014, 16(14), 3804-3807.
[http://dx.doi.org/10.1021/ol501693j] [PMID: 24981419]
[48]
de Souza, G.F.P.; von Zuben, T.W.; Salles, A.G. Jr A metal-catalyst-free oxidative coupling of anilines to aromatic azo compounds in water using bleach. Tetrahedron Lett., 2018, 59(42), 3753-3755.
[http://dx.doi.org/10.1016/j.tetlet.2018.08.053]
[49]
Bettanin, L.; Saba, S.; Galetto, F.Z.; Mike, G.A.; Rafique, J.; Braga, A.L. Solvent- and metal-free selective oxidation of thiols to disulfides using I2/DMSO catalytic system. Tetrahedron Lett., 2017, 58(50), 4713-4716.
[http://dx.doi.org/10.1016/j.tetlet.2017.11.009]