A Green Alternative for Aryl Iodide Preparation from Aromatic Amines

Author(s): Zohreh Shahnavaz, Lia Zaharani, Mohd Rafie Johan, Nader Ghaffari Khaligh*.

Journal Name: Current Organic Synthesis

Volume 17 , Issue 2 , 2020

Become EABM
Become Reviewer

Graphical Abstract:


Abstract:

Background: In continuation of our previous work and the applications of saccharin, we encouraged to investigate the one-pot synthesis of the aryl iodides by the diazotization of the arene diazonium saccharin salts.

Objective: Arene diazonium salts play an important role in organic synthesis as intermediate and a wide variety of aromatic compounds have been prepared using them. A serious drawback of arene diazonium salts is their instability in a dry state; therefore, they must be stored and handled carefully to avoid spontaneous explosion and other hazard events.

Methods: The arene diazonium saccharin salts were prepared as active intermediates in situ through the reaction of various aryl amines with tert-butyl nitrite (TBN) in the presence of saccharin (Sac–H). Then, in situ obtained intermediates were used into the diazotization step without separation and purification in the current protocol.

Results: A variety of aryl iodides were synthesized at a greener and low-cost method in the presence of TBN, Sac–H, glacial acetic acid, and TEAI.

Conclusion: In summary, a telescopic reaction is developed for the synthesis of aryl iodides. The current methodology is safe, cost-effective, broad substrate scope, and metal-free. All used reagents are commercially available and inert to moisture and air. Also, the saccharine and tetraethylammonium cation could be partially recovered from the reaction residue, which reduces waste generation, energy consumption, raw material, and waste disposal costs.

Keywords: Green chemistry, halogenation, one-pot synthesis, saccharin, stable intermediate, aromatic amines.

[1]
Liu, L.; Frohn, M.; Xi, N.; Dominguez, C.; Hungate, R.; Reider, P.J. A soluble base for the copper-catalyzed imidazole N-arylations with aryl halides. J. Org. Chem., 2005, 70(24), 10135-10138. Available at
[http://dx.doi.org/10.1021/jo051640t] [PMID: 16292856]
[2]
Nicolaou, K.C.; Bulger, P.G.; Sarlah, D. Palladium-catalyzed cross-coupling reactions in total synthesis. Angew. Chem. Int. Ed. Engl., 2005, 44(29), 4442-4489. Available at
[http://dx.doi.org/10.1002/anie.200500368] [PMID: 15991198]
[3]
Maluenda, I.; Navarro, O. Recent developments in the Suzuki-Miyaura reaction: 2010-2014. Molecules, 2015, 20(5), 7528-7557. Available at
[http://dx.doi.org/10.3390/molecules20057528] [PMID: 25919276]
[4]
Lin, H.; Sun, D. Recent synthetic developments and applications of the Ullmann reaction. A review. Org. Prep. Proced. Int., 2013, 45(5), 341-394. Available at
[http://dx.doi.org/10.1080/00304948.2013.816208] [PMID: 24223434]
[5]
Volkert, W.A.; Hoffman, T.J. Therapeutic radiopharmaceuticals. Chem. Rev., 1999, 99(9), 2269-2292. Available at
[http://dx.doi.org/10.1021/cr9804386] [PMID: 11749482]
[6]
Khaligh, N.G. A facile and sustainable protocol to the preparation of aryl iodides using stable arenediazonium bis(trifluoromethylsulfonyl)imide salts via the telescopic process. Heteroatom Chem., 2018, 29(2), e21418 Available at
[http://dx.doi.org/10.1002/hc.21418]
[7]
Khaligh, N.G.; Johan, M.R.; Ching, J.J. Saccharin: A cheap and mild acidic agent for the synthesis of azo dyes via telescoped dediazotization. Green Proc. Synth., 2019, 8(1), 24-29. Available at
[http://dx.doi.org/10.1515/gps-2017-0133]
[8]
Khaligh, N.G.; Johan, M.R.; Ching, J.J. Saccharin and tert-butyl nitrite: Cheap and efficient reagents for the synthesis of 1, 2, 3-benzotriazine-4-(3H)-ones from 2-aminobenzamides under metal-free conditions. Aust. J. Chem., 2018, 71(3), 186-189. Available at
[http://dx.doi.org/10.1071/CH17590]
[9]
Khaligh, N.G.; Mihankhah, T.; Johan, M.R.; Ching, J.J. Saccharin: An efficient organocatalyst for the one-pot synthesis of 4-amido-cinnolines under metal and halogen-free conditions. Monatsh. Chem., 2018, 149(6), 1083-1087. Available at
[http://dx.doi.org/10.1007/s00706-018-2174-2]
[10]
Khaligh, N.G. Recent advances and applications of tert-butyl nitrite (TBN) in organic synthesis. Mini Rev. Org. Chem., 2019, 16, 1-22. Available at
[http://dx.doi.org/10.2174/1570193X15666181029141019]
[11]
Khaligh, N.G. Recently applications of tert-butyl nitrite in organic synthesis-Part I. Curr. Org. Chem., 2018, 22, 1120-1138. Available at
[http://dx.doi.org/10.2174/1385272822666180430124840]
[12]
Yu, S.B.; Watson, A.D. Metal-based X-ray contrast media. Chem. Rev., 1999, 99(9), 2353-2378. Available at
[http://dx.doi.org/10.1021/cr980441p] [PMID: 11749484]
[13]
Serjeant, E.P.; Dempsey, B. Ionisation constants of organic acids in aqueous solution. International Union of Pure and Applied Chemistry (IUPAC). IUPAC Chemical Data Series No. 23; Pergamon Press, Inc.: New York, 1979.
[14]
Larsen, J.C. Artificial sweeteners. ‎. Nutrafoods, 2012, 11(1), 3-9. Available at
[http://dx.doi.org/10.1007/s13749-012-0003-5]
[15]
Weihrauch, M.R.; Diehl, V. Artificial sweeteners--do they bear a carcinogenic risk? Ann. Oncol., 2004, 15(10), 1460-1465. Available at
[http://dx.doi.org/10.1093/annonc/mdh256] [PMID: 15367404]
[16]
Jakopin, Z.; Dolenc, M.S. Advances in the chemistry of saccharins: from synthetic novelties towards biologically active compounds. Curr. Med. Chem., 2010, 17(7), 651-671. Available at
[http://dx.doi.org/10.2174/092986710790416236] [PMID: 20088762]
[17]
Whitehead, C.; Traverso, J.J. The reaction of saccharin with amines. N-Substituted-3-amino-1,2-benzisothiazole-1,1-dioxides. J. Org. Chem., 1960, 25, 413-416. Available at
[http://dx.doi.org/10.1021/jo01073a027]
[18]
Rode, H.B.; Sprang, T.; Besch, A.; Loose, J.; Otto, H.H. Pseudosaccharin amine derivatives: synthesis and elastase inhibitory activity. Pharmazie, 2005, 60(10), 723-731.
[PMID: 16259117]
[19]
Baik, W.; Luan, W.; Lee, H.J.; Yoon, C.H.; Koo, S.; Kim, B.H. Efficient one-pot transformation of aminoarenes to haloarenes using halodimethylisulfonium halides generated in situ. Can. J. Chem., 2005, 83(2), 213-219. Available at
[http://dx.doi.org/10.1139/v05-026]
[20]
Krasnokutskaya, E.A.; Semenischeva, N.I.; Filimonov, V.D.; Knochel, P. A new, one-step, effective protocol for the iodination of aromatic and heterocyclic compounds via aprotic diazotization of amines. Synth., 2007, 2007(1), 81-84. Available at
[http://dx.doi.org/10.1055/s-2006-958936]
[21]
Hajipour, A.; Mohammadsaleh, F. A Simple and effective protocol for one-pot diazotization-Iodination of aromatic amines by acidic ionic liquid [H-NMP]HSO4 at room temperature. Iran. J. Chem. Chem. Eng., 2011, 30, 23-28.
[22]
Nemati, F.; Elhampour, A. Green and efficient diazotization-iodination of aryl amines using cellulose sulfuric acid as a biodegradable and recyclable proton source under solvent-free condition. Sci. Iran., 2012, 19, 1594-1596. Available at
[http://dx.doi.org/10.1016/j.scient.2012.10.015]


Rights & PermissionsPrintExport Cite as

Article Details

VOLUME: 17
ISSUE: 2
Year: 2020
Page: [131 - 135]
Pages: 5
DOI: 10.2174/1570179417666200203121437
Price: $65

Article Metrics

PDF: 11
HTML: 1