Download PDF
Synthesis 2011(13): 2154-2158  
DOI: 10.1055/s-0030-1260046
PAPER
© Georg Thieme Verlag Stuttgart ˙ New York

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

Marina E. Trusovaa, Elena A. Krasnokutskayaa, Pavel S. Postnikova, Younghwa Choib, Ki-Whan Chi*b, Victor D. Filimonov*a
a Department of Organic Chemistry, National Research Tomsk Polytechnic University, Tomsk 634050, Russian Federation
e-Mail: filimonov@tpu.ru;
b Department of Chemistry, University of Ulsan, Ulsan 680-749, Republic of Korea
e-Mail: kwchi@ulsan.ac.kr;
Further Information

Publication History

Received 7 April 2011
Publication Date:
13 May 2011 (online)

   Permissions and Reprints All articles of this category
Preview

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 
    Search in Google Scholar
  • 1c Bellina F. Carpita A. Rossi R. Synthesis  2004,  2419 
  • 1d Prajapati D. Gohain M. Tetrahedron  2004,  60:  815 
    Search in Google Scholar
  • 1e Tour JM. J. Org. Chem.  2007,  72:  7477 
    Search in Google Scholar
  • 1f Ila H. Baron O. Wagner AJ. Knochel P. Chem. Commun.  2006,  583 
  • 1g Hopf H. Tetrahedron  2008,  64:  11504 
    Search in Google Scholar
  • 1h Darses S. Genet J.-P. Chem. Rev.  2008,  108:  288 
    Search in Google Scholar
  • 2a Volkert WA. Hoffman TJ. Chem. Rev.  1999,  99:  2269 
    Search in Google Scholar
  • 2b Yu S.-B. Watson AD. Chem. Rev.  1999,  99:  2353 
    Search in Google Scholar
  • 2c Nilsson M. Exp. Clin. Endocrinol. Diabetes  2001,  109:  13 
    Search in Google Scholar
  • 2d Pleiss U. J. Labelled Compd. Radiopharm.  2007,  50:  818 
    Search in Google Scholar
  • 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 
    CrossrefSearch in Google Scholar
  • 6 Zarei A. Hajipour AR. Khazdooz L. Synthesis  2009,  941 
    Thieme Connect
  • 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, 
    Search in Google Scholar
  • 7d Gorlushko DA. Filimonov VD. Semenishcheva NI. Krasnokutskaya EA. Tret’yakov AN. Chi K.-W. Russ. J. Org. Chem.  2008,  44:  1243 
    Search in Google Scholar
  • 7e Lee YM. Moon ME. Vajpayee V. Filimonov VD. Chi K.-W. Tetrahedron  2010,  66:  7418 
    Search in Google Scholar
  • 7f Moon ME. Choi Y. Lee YM. Vajpayee V. Trusova M. Filimonov VD. Chi K.-W. Tetrahedron Lett.  2010,  51:  6769 
    Search in Google Scholar
  • 8 Filimonov VD. Trusova ME. Postnikov PS. Krasnokutskaya EA. Lee YM. Hwang HY. Kim H. Chi K.-W. Org. Lett.  2008,  10:  3961 
    CrossrefPubMedSearch in Google Scholar
  • 9a Caldarelli M. Baxendale IR. Ley SV. Green Chem.  2000,  2:  43 
    Search in Google Scholar
  • 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 
    Search in Google Scholar
  • 13b Hünig S. Fleckenstein E. Liebigs Ann. Chem.  1970,  738:  192 
    Search in Google Scholar
  • 14 Aldrich Handbook of Fine Chemicals and Laboratory Equipment   Aldrich; Milwaukee: 2006-2007. 
  • 15 Zielinska A. Skulski L. Molecules  2005,  10:  1307 
    CrossrefSearch in Google Scholar
  • 16 Barbero M. Degani I. Diulgheroff N. Dughera S. Fochi R. Synthesis  2001,  2180 
    Thieme Connect
  • 17 Yu B.-C. Shirai Y. Tour JM. Tetrahedron  2006,  62:  10303 
    CrossrefSearch in Google Scholar
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