Download PDF
Synlett 2003(2): 0221-0222
DOI: 10.1055/s-2003-36783
LETTER
© Georg Thieme Verlag Stuttgart · New York

A Novel and Efficient Ceric Ammonium Nitrate Catalyzed Oxidative Nuclear Chlorination of Activated Aromatic Compounds by Acetyl Chloride

Subhas Chandra Roy*, Kalyan Kumar Rana, Chandrani Guin, Biplab Banerjee
Department of Organic Chemistry Indian Association for the Cultivation of Science, Jadavpur, Calcutta - 700 032, India
e-Mail: ocscr@mahendra.iacs.res.in;
Further Information

Publication History

Received 2 December 2002
Publication Date:
22 January 2003 (online)

    Permissions and Reprints All articles of this category

Abstract

A mild and efficient oxidative chlorination of activated aromatic compounds have been achieved in excellent yields using acetyl chloride in the presence of a catalytic amount of ceric ammonium nitrate at room temperature. However, chlorination failed to occur with deactivated aromatic rings.

Key words

ceric ammonium nitrate - nuclear chlorination - acetyl chloride

    References

  • 1 For a general review of aromatic halogenation, see: Braendlin HP. McBee ET. In Friedel-Crafts and related reactions   Vol. III, part 2:  Olah GA. John Wiley and Sons, Inc.; New York: 1964.  Chap. 46.
    Google Scholar
  • 2 Krumenacker L. Ratton S. L’actualite Chimique  1986,  6:  29 
    Google Scholar
  • 3 March J. Advanced Organic Chemistry   3rd ed.:  Wiley-Interscience; New York: 1985.  p.576 
    Google Scholar
  • 4 See for example: Kharasch MS. Reinmuth O. Grignard Reactions of Nonmetallic Substances   Prentice-Hall; New York: 1954. 
    Google Scholar
  • 5 De la Mare PBD. Suzuki H. J. Chem. Soc. C  1967,  1586 
    CrossrefGoogle Scholar
  • 6 Campaigne E. Thompson W. J. Am. Chem. Soc.  1950,  72:  629 
    Google Scholar
  • 7 Chip GK. Grossert JS. Can. J. Chem.  1972,  50:  1233 
    Google Scholar
  • 8 Nonhebel DC. Org. Synth.  1963,  43:  15 
    Google Scholar
  • 9 Kovacic P. Sparks AK. J. Am. Chem. Soc.  1960,  82:  5740 
    CrossrefGoogle Scholar
  • 10 Albeck M. Shaik S. J. Chem. Soc., Perkin Trans. 1  1975,  1233 
    Google Scholar
  • 11 Juenge EC. Beal DA. Duncan WP. J. Org. Chem.  1970,  35:  719 
    CrossrefGoogle Scholar
  • 12 Yaroslavsky C. Katchalski E. Tetrahedron Lett.  1972,  5173 
    CrossrefGoogle Scholar
  • 13a Kajigaeshi S. Kakinami T. Ikeda H. Okamoto T. Chem. Express  1988,  3:  659 
    Google Scholar
  • 13b Kajigaeshi S. Shinmasu Y. Fujisaki S. Kakinami T. Chem. Lett.  1989,  415 
    Google Scholar
  • 13c Kajigaeshi S. Ueda Y. Fujisaki S. Kakinami T. Bull. Chem. Soc. Jpn.  1989,  62:  2096 
    Google Scholar
  • 13d Kajigaeshi S. Shinmasu Y. Fujisaki S. Kakinami T. Bull. Chem. Soc. Jpn.  1990,  63:  941 
    Google Scholar
  • 14 Roy SC. Guin C. Rana KK. Maiti G. Tetrahedron Lett.  2001,  6941 
    CrossrefGoogle Scholar
  • 16 Dincturk S. Ridd JH. J. Chem. Soc., Perkin Trans. 2  1982,  965 ; and references cited therein
    CrossrefGoogle Scholar
15

General Procedure. To a stirred mixture of the aromatic substrate (1.5 mmol) and freshly distilled acetylchloride (1.52 mmol) in acetonitrile (10 mL), was added ceric ammonium nitrate (0.15 mmol) in one portion under N2 at room temperature. The reaction mixture was allowed to stir for 7-8 h. After completion of the reaction (the progress of the reaction was monitored by TLC), the reaction mixture was diluted with diethyl ether (25 mL) and washed thoroughly with saturated aqueous NaHCO3 solution (3 × 10 mL), brine (3 × 10 mL) and dried (Na2SO4). Volatiles were removed under reduced pressure and the residue obtained was purified by column chromatography over silica gel (2% ethyl acetate in light petroleum) to yield the pure chlorinated product.