A New, One-Step, Effective Protocol for the Iodination of Aromatic and Heterocyclic Compounds via Aprotic Diazotization of Amines

Abstract

We have developed a convenient one-step preparation of aromatic and some heterocyclic iodides by the sequential diazotization-iodination of the aromatic amines with a KI/NaNO₂/p-TsOH system in acetonitrile at room temperature. This method has general character and allows aryl iodides with either donor or acceptor substituents in various positions to be obtained from the corresponding amines in 50-90% yield.

Key words

aromatic iodides - aromatic amines - diazotization - potassium iodide - sodium nitrite

References

• 1a Li JJ. Gribble GW. Tetrahedron Organic Chemistry Series   Vol. 20:  Pergamon; Oxford: 2000. 
• 1b Soderberg BC. Coord G. Chem. Rev.  2004,  248:  1085 
• 1c Kotha S. Lahiri K. Kashinath D. Tetrahedron  2002,  58:  9633 
• 1d Bellina F. Carpita A. Rossi R. Synthesis  2004,  2419 
• 1e Guiry P. Kiely D. Curr. Org. Chem.  2004,  8:  781 
• 1f Prajapati D. Gohain M. Tetrahedron  2004,  60:  815 
• 1g de Vries JG. Can. J. Chem.  2001,  79:  1086 
• 1h Cacchi S. Fabrizi G. Goggiomani A. Heterocycles  2002,  56:  613 
• 2a Volkert WA. Hoffman TJ. Chem. Rev.  1999,  99:  2269 
• 2b Yu S.-B. Watson AD. Chem. Rev.  1999,  99:  2353 
• 3a The Chemistry of Diazonium and Diazo Groups   Patai S. Wiley; New York: 1978. 
• 3b Godovikova TI. Rakitin OA. Khmelnitskii LI. Russ. Chem. Rev.  1983,  52:  440 
• 3c Galli C. Chem. Rev.  1988,  88:  765 
• 4a Friedman L. Chlebowsky JF. J. Org. Chem.  1968,  33:  1636 
• 4b Smith WB. Ho OC. J. Org. Chem.  1990,  55:  2543 
• 5 Baik W. Luan W. Lee HJ. Yoon CH. Koo S. Kim BH. Can. J. Chem.  2005,  83:  213 
• 6 Furniss BS. Hannaford AJ. Smith PWG. Tatchell AR. Vogel’s Textbook of Practical Organic Chemistry   5th ed.:  Longman; London: 1989. 
• 7 Smith WB. Ho OC. J. Org. Chem.  1990,  55:  2543 
• 8 Wilgerodt W. Ber. Dtsch. Chem. Ges.  1910,  43:  2747 
• 9 Mattern DL. Chen X. J. Org. Chem.  1991,  56:  5903 
• 10 Bunnett JF. Conner RM. J. Org. Chem.  1958,  23:  305 
• 11 Ogata Y. Urasaki I. Ishibashi T. J. Chem. Soc., Perkin Trans. 1  1972,  2:  180 
• 12 Chaikovskii VK. Kharlova TS. Filimonov VD. Russ. Chem. Bull.  1999,  48:  1291 
• 13 Goldstein AE. J. Am. Chem. Soc.  1939,  61:  1600 
• 14 Brown HC. McDaniel DH. J. Am. Chem. Soc.  1955,  77:  3752 
• 15 Marzi E. Bigi A. Schlosser M. Eur. J. Org. Chem.  2001,  7:  1371 
• 16 Van den Hoven BG. Alper H. J. Am. Chem. Soc.  2001,  123:  1017