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Synlett 2007(11): 1699-1702  
DOI: 10.1055/s-2007-982576
LETTER
© Georg Thieme Verlag Stuttgart · New York

Strong-Acids-Promoted Protiodeacylation of Sterically Nonhindered Alkyl Aryl Ketones

Matjaž Koželj, Andrej Petrič*
Faculty of Chemistry and Chemical Technology, University of Ljubljana, Ljubljana 1000, Slovenia
Fax: +386(1)2419220; e-Mail: Andrej.Petric@fkkt.uni-lj.si;
Further Information

Publication History

Received 30 April 2007
Publication Date:
25 June 2007 (online)

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Abstract

In the presence of strong acids in aqueous and anhydrous media alkyl aryl ketones bearing a strong electron-releasing group in the aromatic ring undergo protiodeacylation. In a reaction with triflic acid in aromatic solvents, the transfer of the liberated acyl group to aromatic solvent molecules is observed. The effects of the nature and the position of the activating group and the strength of the acid and the solvent, on the course of this ipso-substitution were investigated.

Key words

protiodeacylation - transacylation - ketones - retro-Friedel-Crafts reaction - ipso-electrophilic-aromatic substitution

    References and Notes

  • 1a Shogi-Jadid K. Small GW. Agdeppa ED. Kepe V. Ercoli LM. Siddhart P. Read S. Satyamurthy N. Petrič A. Huang S.-C. Barrio JR. Am. J. Geriatr. Psychiatry  2002,  24 
    CrossrefGoogle Scholar
  • 1b Liu J. Kepe V. abjek A. Petrič A. Padgett HC. Satyamurthy N. Barrio JR. Mol. Imaging Biol.  2007,  9:  6 
    CrossrefGoogle Scholar
  • 1c Škofic P. Dambrot C. Ko˛elj M. Golobič A. Barrio JR. Petrič A. Acta Chim. Slov.  2005,  52:  391 
    CrossrefGoogle Scholar
  • 1d abjek A. Petrič A. Tetrahedron Lett.  1999,  40:  6077 
    CrossrefGoogle Scholar
  • 2 Taylor R. Electrophilic Aromatic Substitution   John Willey and Sons Ltd.; Chichester: 1990.  p.130 
    Google Scholar
  • 3a Luise E. Ann. Chim. Phys.  1885,  6:  210 
    Google Scholar
  • 3b Klages A. Lickroth G. Ber. Dtsch. Chem. Ges.  1899,  32:  1549 
    Google Scholar
  • 3c Weiler M. Ber. Dtsch. Chem. Ges.  1899,  32:  1908 
    Google Scholar
  • 4a Schubert WM. J. Am. Chem. Soc.  1949,  71:  2639 
    CrossrefGoogle Scholar
  • 4b Schubert WM. Latourette HK. J. Am. Chem. Soc.  1952,  74:  1829 
    CrossrefGoogle Scholar
  • 5a Farooqi J. Gore PH. Tetrahedron Lett.  1977,  2983 
    Google Scholar
  • 5b Gore PH. Nassar AG. Saad EF. J. Chem. Soc., Perkin Trans. 2  1982,  983 
    Google Scholar
  • 5c Al-Ka’bi J. Farooqi J. Gore PH. Nassar AG. Saad EF. Short EL. Waters DN. J. Chem. Soc., Perkin Trans. 2  1988,  943 
    Google Scholar
  • 5d Gore PH. Moonga BS. Short EL. J. Chem. Soc., Perkin Trans. 2  1988,  485 
    Google Scholar
  • 5e Al-Ka’bi J. Gore PH. Moonga BS. J. Chem. Res., Synop.  1993,  82 
    Google Scholar
  • 6a Keumi T. Morita T. Inui Y. Teshima N. Kitajima H. Synthesis  1985,  979 
    CrossrefGoogle Scholar
  • 6b Keumi T. Morita T. Shimada T. Teshima N. Kitajima H. Prakash GKS. J. Chem. Soc., Perkin Trans. 2  1986,  847 
    CrossrefGoogle Scholar
  • 6c Keumi T. Morita T. Ozawa Y. Kitajima H. Bull. Chem. Soc. Jpn.  1989,  62:  599 
    CrossrefGoogle Scholar
  • 7a Giordano C. Villa M. Annunziata R. Synth. Commun.  1990,  20:  383 
    Google Scholar
  • 7b Fromentin E. Coustard J.-M. Guisnet M. J. Mol. Catal. A: Chem.  2000,  159:  377 
    Google Scholar
  • 7c Hwang K.-Y. Rhee H.-K. React. Kinet. Catal. Lett.  2003,  79:  189 
    Google Scholar
  • 9a Olah GA. Laali K. Mehrotra AK. J. Org. Chem.  1983,  48:  3360 
    CrossrefGoogle Scholar
  • 9b Hwang JP. Prakash GKS. Olah GA. Tetrahedron  2000,  56:  7199 
    CrossrefGoogle Scholar
  • 10 1H NMR: δ = 2.09 (q, 2 H, J = 6.2 Hz, 3-CH2), 2.67 (t, 2 H, J = 6.2 Hz, 5-CH2), 2.90 (t, 2 H, J = 6.1 Hz, 2-CH2), 6.70 (dd, 1 H, J 1 = 8.4 Hz, J 2 = 0.9 Hz, 5-H), 6.79 (d, 1 H, J 1 = 8.4 Hz, 7-H), 7.35 (t, 1 H, J = 8.4 Hz, 6-H), 12.43 (s, 1 H, 8-OH). GC-MS: [M+] = 162; [M] = 162.185 g/mol; spectrum is identical to the literature. See: Couche E. Fkyerat A. Tabacchi R. Helv. Chim. Acta  2003,  86:  210 
    CrossrefGoogle Scholar
  • 11 Effenberger F. Eberhard JK. Maier AH. J. Am. Chem. Soc.  1996,  118:  12572 
    CrossrefGoogle Scholar
8

General Procedure for the Reaction with Aqueous Acid
A ketone (100 mg) was dissolved in the appropriate cosolvent (toluene, xylene, 3 mL); an acid (3 mL of 48% or 62% HBr in H2O or 1 mL of 50% TfOH in H2O) was added, and refluxed for 48 h. The reaction mixture was cooled, diluted with H2O (20 mL) and extracted with CH2Cl2 (4 × 5 mL); the combined organic phases were washed with a sat. aq solution of NaHCO3, dried over anhyd Na2SO4, and evaporated. The products were identified by 1H NMR spectroscopy and GC-MS.

12

General Procedure for the Reaction with Anhydrous Acid A ketone (100 mg) was dissolved in dry aromatic solvent (5 mL), TfOH (0.2 mL) was added, and the mixture was refluxed under argon. After 72 h the mixture was cooled, diluted with H2O (15 mL), and the organic layer was separated. The water layer was extracted with CH2Cl2 (2 × 10 mL); combined organic phases were washed with a sat. aq solution of NaHCO3, dried over anhyd Na2SO4, and evaporated. The mixture of compounds was analyzed by means of GC-MS.