Fast and Easy Halide Exchange in Aryl Halides

Abstract

We report here the rapid halide exchange in aryl halides facilitated by microwave and conventional heating using nickel(II) halides as reagents. The methodology can be used for conversion of aryl chlorides to bromides, aryl iodides to bromides and chlorides and aryl bromides to chlorides. Reactions are fast (5 minutes reaction time for microwave heating and 4 hours for conventional heating) and can be performed without the need for exclusion of air and water.

Key words

aryl halide - nickel - water - microwave

References

• 1 Metal-Catalysed Cross-Coupling Reactions   Diederich F. Stang PJ. Wiley-VCH; New York: 1998. 
• For recent reviews see:
• 2a Hassan J. Sévignon M. Gozzi C. Schulz E. Lemaire M. Chem. Rev.  2002,  102:  1359 
• 2b Suzuki A. J. Organomet. Chem.  1999,  576:  147 
• 2c Miyaura N. Suzuki A. Chem. Rev.  1995,  95:  2457 
• 3 See for example: Kashiyama E. Hutchinson I. Chua M.-S. Stinson SF. Phillips LR. Kaur G. Sauville EA. Bradshaw TD. Westwell AD. Stevens MFG. J. Med. Chem.  1999,  42:  4172 
• 4 Leadbeater NE. Marco M. Org. Lett.  2002,  4:  2973 
• 5 Leadbeater NE. Marco M. J. Org. Chem.  2003,  68:  888 
• 6 Bacon RGR. Hill HAO. J. Chem. Soc.  1964,  1097 
• 7 Clark JH. Denness JE. McClinton MA. Wynd AJ. J. Fluorine Chem.  1990,  50:  411 
• 8 Bozell JJ. Vogt CE. J. Am. Chem. Soc.  1988,  110:  2655 
• 9 Yang SH. Li CS. Cheng CH. J. Org. Chem.  1987,  52:  691 
• 10 Takagi K. Hayama N. Inokawa S. Bull. Chem. Soc. Jpn.  1980,  53:  3691 
• 11 O’Connor KJ. Burrows CJ. J. Org. Chem.  1991,  56:  1344 
• 12a Arnold JT. Bayraktaroglu TO. Brown RG. Heiermann CR. Magnus WW. Ohman AB. Landolt RG. J. Org. Chem.  1992,  57:  391 
• 12b Bayraktaroglu TO. Gooding MA. Khatib SF. Lee H. Kourouma M. Landolt RG. J. Org. Chem.  1993,  58:  1264 
• 13a Vol S. Vivier L. Pérot G. J. Mol. Catal. A.: Chem.  2001,  172:  241 
• 13b Imhaoulene S. Vivier L. Guisnet M. Pérot G. Tetrahedron  1994,  50:  12913 
• 14 Meyer G. Rollin Y. Perichon J. Tetrahedron Lett.  1986,  27:  3497 
• 15 Bonnichon F. Grabner G. Guyot G. Richard C. J. Chem. Soc., Perkin Trans. 2  1999,  1203 
• 16 Klapars A. Buchwald SL. J. Am. Chem. Soc.  2002,  124:  14844 
• For recent reviews on the area, see:
• 17a Larhed M. Moberg C. Hallberg A. Acc. Chem. Res.  2002,  35:  717 
• 17b Lew A. Krutzik PO. Hart ME. Chamberlin AR. J. Comb. Chem.  2002,  4:  95 
• 17c Lindström P. Tierney J. Wathey B. Westman J. Tetrahedron  2001,  57:  9225 
• 18 For a review on the concepts, see: Gabriel C. Gabriel S. Grant EH. Halstead BS. Mingos DMP. Chem. Soc. Rev.  1998,  27:  213 

19

Yields for the transformation with other solvents: H₂O, 0%, PEG-400, 8%, DME, 0%.

20

CAUTION: The DMF is heated above its boiling point so all necessary precautions should be taken when performing such experiments. Vessels designed to withhold elevated pressures must be used. The microwave apparatus used here incorporates a protective metal cage around the microwave vessel in case of explosion. After completion of an experiment, the vessel must be allowed to cool to a temperature below the boiling point of the solvent before removal from the microwave cavity and opening to the atmosphere.

21

CAUTION: A blast shield should be in place and vessels designed to withhold elevated pressures must be used. After completion of an experiment, the vessel must be allowed to cool before opening to the atmosphere.