Lewis Acid Catalyzed Highly Selective Halogenation of Aromatic Compounds

Abstract

A simple and efficient procedure for the halogenation of aromatic compounds with NCS, NBS, NIS and NFSI in the presence of catalytic amount of ZrCl₄ is described. Chlorination, bromination, iodination and fluorination of various aromatic compounds are performed with high selectivity under mild reaction conditions.

Key words

halogenation - aromatic compounds - N-halo reagents - zirconium tetrachloride - Lewis acid catalysis

References

• 1a Ullmann’s Encyclopedia of Industrial Chemistry   6th ed:  Wiley-VCH; Weinheim: 2002. 
• 1b Davids SGM. Organotransition Metal Chemistry: Application to Organic Synthesis   Pergamon Press; Oxford: 1982. 
• 2 Diederich F. Stang PJ. Metal-Catalyzed Cross-Coupling Reactions   Wiley-VCH; Weinheim: 1998. 
• 3a Dewkar GK. Narina SV. Sudalai A. Org. Lett.  2003,  5:  4501 
• 3b Vyas PV. Bhatt AK. Ramachanraiah G. Bedekar AV. Tetrahedron Lett.  2003,  44:  4085 
• 3c Taylor R. Electrophilic Aromatic Substitution   John Wiley; New York: 1990. 
• 3d De la Mare PB. Electrophilic Halogenation   Cambridge University Press; Cambridge: 1976.  Chapt. 5.
• 4a Park MY. Yang SG. Jadhav V. Kim YH. Tetrahedron Lett.  2004,  45:  4887 
• 4b Esakkidurai T. Kumarraja M. Pitchumani K. Catal. Lett.  2004,  92:  169 
• 4c Zhao J. Jia X. Zhai H. Tetrahedron Lett.  2003,  44:  9371 
• 4d Firouzabadi H. Iranpoor N. Shiri M. Tetrahedron Lett.  2003,  44:  8781 
• 4e Sasson Y. In The Chemistry of Functional Groups   Patai S. Rappoport Z. John Wiley and Sons; New York: 1995. Suppl. D2: The Chemistry of Halides, Pseudo-Halides and Azides, Part 1
• 5a Prakash GKS. Mathew T. Hoole D. Esteves PM. J. Am. Chem. Soc.  2004,  126:  15770 
• 5b Tanemura K. Suzuki T. Nishida Y. Satsumabayashi K. Horaguchi T. Chem. Lett.  2003,  32:  932 
• 5c Zanka A. Kubota A. Synlett  1999,  1984 
• 6 Zhang Y. Shibatomi K. Yamamoto H. J. Am. Chem. Soc.  2004,  126:  15038 
• 7 Schmid H. Helv. Chim. Acta  1946,  29:  1144 
• 8a Joshi AV. Baidossi M. Mukhopadhyay S. Sasson Y. Org. Process Res. Dev.  2004,  8:  568 
• 8b Chiappe C. Leandri E. Pieraccini D. Chem. Commun.  2004,  2536 
• 8c Narender N. Srinivasu P. Prasad MR. Kulkarni SJ. Raghavan KV. Synth. Commun.  2002,  32:  2313 
• 9a Olah GA. Wang Q. Sandford G. Prakash GKS. J. Org. Chem.  1993,  58:  3194 
• 9b Kondradssor P. Mottoo DR. McDevitt RE. J. Chem. Soc., Chem. Commun.  1990,  1270 
• 9c Kondradssor P. Udong VE. Frazer-Reid B. Tetrahedron Lett.  1990,  31:  1331-4313  
• 10 Firouzabadi H. Iranpoor N. Jafarpour M. Tetrahedron Lett.  2004,  45:  7451 

11

Structure of the product was determined by comparison of ¹H NMR and ¹³C NMR with reported data.