A Green Procedure for the Diazotization-Iodination of Aromatic Amines under Aqueous, Strong-Acid-Free Conditions

Abstract

A convenient and mild one-pot method for the synthesis of iodoarenes in high yields by the sequential diazotization-iodination of aromatic amines with a reusable polymeric diazotization agent in the presence of p-toluenesulfonic acid at room temperature in water was developed. The method is general and is the greenest alternative of the known diazotization-iodination methods. The method is also effective for the preparation of 1H-benzo[d][1,2,3]triazole and benzo[d][1,2,3]thiadiazole.

Key words

diazotization - halogenation - iodination - heterocycles - amines

References

• 1a Diederich F. Stang PJ. Metal-Catalyzed Cross-Coupling Reactions   Wiley-VCH; Weinheim: 1998. 
• 1b Kotha S. Lahiri K. Kashinath D. Tetrahedron  2002,  58:  9633 
• 1c Bellina F. Carpita A. Rossi R. Synthesis  2004,  2419 
• 1d Prajapati D. Gohain M. Tetrahedron  2004,  60:  815 
• 1e Tour JM. J. Org. Chem.  2007,  72:  7477 
• 1f Ila H. Baron O. Wagner AJ. Knochel P. Chem. Commun.  2006,  583 
• 1g Hopf H. Tetrahedron  2008,  64:  11504 
• 1h Darses S. Genet J.-P. Chem. Rev.  2008,  108:  288 
• 2a Volkert WA. Hoffman TJ. Chem. Rev.  1999,  99:  2269 
• 2b Yu S.-B. Watson AD. Chem. Rev.  1999,  99:  2353 
• 2c Nilsson M. Exp. Clin. Endocrinol. Diabetes  2001,  109:  13 
• 2d Pleiss U. J. Labelled Compd. Radiopharm.  2007,  50:  818 
• 3a Hanson JR. J. Chem. Res.  2006,  277 
• 3b Stavber S. Jereb M. Zupan M. Synthesis  2008,  1487 
• 4 Zollinger H. Diazo Chemistry I: Aromatic and Heteroaromatic Compounds   VCH; Weinheim: 1994. 
• 5 Tundo P. Loris A. Selva M. Green Chem.  2007,  9:  777 
• 6 Zarei A. Hajipour AR. Khazdooz L. Synthesis  2009,  941 
• 7a Filimonov VD. Semenischeva NI. Krasnokutskaya EA. Tretyakov AN. Hwang HY. Chi K.-W. Synthesis  2008,  185 
• 7b Krasnokutskaya EA. Semenischeva NI. Filimonov VD. Knochel P. Synthesis  2007,  81 
• 7c Gorlushko DA. Filimonov VD. Krasnokutskaya EA. Semenischeva NI. Go BS. Hwang HY. Cha EH. Chi K.-W. Tetrahedron Lett.  2008,  49:  1080, 
• 7d Gorlushko DA. Filimonov VD. Semenishcheva NI. Krasnokutskaya EA. Tret’yakov AN. Chi K.-W. Russ. J. Org. Chem.  2008,  44:  1243 
• 7e Lee YM. Moon ME. Vajpayee V. Filimonov VD. Chi K.-W. Tetrahedron  2010,  66:  7418 
• 7f Moon ME. Choi Y. Lee YM. Vajpayee V. Trusova M. Filimonov VD. Chi K.-W. Tetrahedron Lett.  2010,  51:  6769 
• 8 Filimonov VD. Trusova ME. Postnikov PS. Krasnokutskaya EA. Lee YM. Hwang HY. Kim H. Chi K.-W. Org. Lett.  2008,  10:  3961 
• 9a Caldarelli M. Baxendale IR. Ley SV. Green Chem.  2000,  2:  43 
• 9b Merrington J. James M. Bradley M. Chem. Commun.  2002,  140 
• 11 Vogel’s Textbook of Practical Organic Chemistry   5th ed.:  Furniss B. S. Hannaford A. J. Smith P. W. G. Tatchell A. R. Longman; London: 1989. 
• 12 Kryska A. Skulski L. J. Chem. Res., Synop.  1999,  590 
• 13a Damschroder RE. Peterson WD. Org. Synth.  1955,  3:  106 
• 13b Hünig S. Fleckenstein E. Liebigs Ann. Chem.  1970,  738:  192 
• 14 Aldrich Handbook of Fine Chemicals and Laboratory Equipment   Aldrich; Milwaukee: 2006-2007. 
• 15 Zielinska A. Skulski L. Molecules  2005,  10:  1307 
• 16 Barbero M. Degani I. Diulgheroff N. Dughera S. Fochi R. Synthesis  2001,  2180 
• 17 Yu B.-C. Shirai Y. Tour JM. Tetrahedron  2006,  62:  10303 

10

For several examples, the resulting diazonium tosylates can be partially isolated from the aqueous solution by extraction with ethyl acetate, followed by pouring the organic solution in diethyl ether. Properties and spectral data of these salts were identical to those previously obtained by diazotization in acetic acid.⁸