PDF herunterladen
Synlett 2002(10): 1653-1656
DOI: 10.1055/s-2002-34231
LETTER
© Georg Thieme Verlag Stuttgart · New York

A Highly Active Ytterbium(III) Methide Complex for Truly Catalytic Friedel-Crafts Acylation Reactions

Anthony G. M. Barrett*a, Nathalie Bouloca, D. Christopher Braddocka, David Chadwickb, David A. Hendersona
a Department of Chemistry, Imperial College of Science, Technology and Medicine, South Kensington, London SW7 2AY, UK
e-Mail: agmb@ic.ac.uk;
b Department of Chemical Engineering, Imperial College of Science, Technology and Medicine, South Kensington, London SW7 2AY, UK
Weitere Informationen

Publikationsverlauf

Received 15 August 2002
Publikationsdatum:
23. September 2002 (online)

    Lizenzen und Reprints Alle Artikel dieser Rubrik

Abstract

The Friedel-Crafts acylation of anisole with acetic anhydride using ytterbium(III) tri[tris(nonafluorobutanesulfonyl)methide] was studied with respect to catalyst loading. A strong inhibitory effect due to the product became apparent from doping experiments and from examination of the kinetic data. This understanding allowed catalyst loadings to be reduced to as little as 0.1 mol% for effective acylation under a suitable temperature and pressure regime.

Key words

Friedel-Crafts - acylation - catalytic - ytterbium(III) methide - inhibition

    References

  • 1a Olah GA. Friedel-Crafts Chemistry   Wiley-Interscience; London: 1973. 
  • 1b Heaney H. In Comprehensive Organic Synthesis   Vol. 2:  Trost BM. Fleming I. Pergamon Press; Oxford: 1991.  p.733 
    Suche in Google Scholar
  • 2a Kawada A. Mitamura S. Kobayashi S. J. Chem. Soc., Chem. Commun.  1993,  1157 
    Crossref
  • 2b Kawada A. Mitamura S. Kobayashi S. Synlett  1994,  545 
    Crossref
  • 2c Hachiya I. Moriwaki M. Kobayshi S. Bull. Chem. Soc. Jpn.  1995,  68:  2053 
    CrossrefSuche in Google Scholar
  • 2d Kobayashi S. Iwamoto S. Tetrahedron Lett.  1998,  39:  4697 
    CrossrefSuche in Google Scholar
  • 3a Desmur JR. Labrouillere M. Le Roux C. Gaspard H. Laporterie A. Dubac J. Tetrahedron Lett.  1997,  38:  8871 
    CrossrefSuche in Google Scholar
  • 3b Repichet S. LeRoux C. Dubac J. Desmurs JR. Eur. J. Org. Chem.  1998,  2743 
    Crossref
  • 4 Mikami K. Kotera O. Motoyama Y. Sakaguchi H. Maruta M. Synlett  1996,  171 
    Thieme Connect
  • 5 Fürstner A. Voightlander D. Schrader W. Giebel D. Reetz MT. Org. Lett.  2001,  3:  417 
    CrossrefSuche in Google Scholar
  • 6 Waller FJ. Barrett AGM. Braddock DC. Ramprasad D. McKinnell RM. White JP. Williams DJ. Ducray R. J. Org. Chem.  1999,  64:  2910 
    CrossrefPubMedSuche in Google Scholar
  • 7 Barrett AGM. Braddock DC. Ducray R. McKinnell RM. Waller FJ. Synlett  2000,  57 
    Thieme Connect
  • 8a Barrett AGM. Braddock DC. Catterick D. Chadwick D. Henschke JP. McKinnell RM. Synlett  2000,  847 
    Crossref
  • 8b Barrett AGM. Bouloc N. Braddock DC. Catterick D. Chadwick D. White AJP. Williams DJ. Tetrahedron  2002,  58:  3835 
    CrossrefSuche in Google Scholar
  • 10a Mikami K. Mikami Y. Matsumoto Y. Nishikido J. Yamamoto F. Nakajimi H. Tetrahedron Lett.  2001,  42:  289 
    CrossrefSuche in Google Scholar
  • 10b Mikami K. Mikami Y. Matsuzawa H. Matsumoto Y. Nishikido J. Yamamoto F. Nakajima H. Tetrahedron  2002,  58:  4015 
    CrossrefSuche in Google Scholar
  • 11 For experimental details for the preparation of these complexes see: Barrett AGM. Bouloc N. Braddock DC. Catterick D. Chadwick D. White AJP. Williams DJ. Tetrahedron  2002,  58:  3835 
    CrossrefSuche in Google Scholar
9

Catalytic Compounds and Processes. UK Patent Application No 9919583.6.

12

These plots were obtained using a Mettler-Toledo REACT-IR 4000 system with a dicomp probe scanning every 60 s
(25 °C, 50 °C) or 45 s (70 °C) for the first two hours followed by one scan every five min for the remaining time. The profiles are generated by following the peak area between 1672 and 1685 wave numbers to a constant baseline point.

13

General Experimental Procedure: A stirred solution of arene (0.6 mmol), anhydride (1.2 mL) and catalyst 1 (16 mg, 0.006 mmol) in PhCF3 (1.2 mL) was heated to 150 °C in a sealed tube for 20 h. The resulting mixture was allowed to cool, diluted with Et2O (10 mL), washed with water (2 × 10 mL), sat. aq sodium hydrogen carbonate solution (2 × 10 mL), sat. aq sodium chloride solution (2 × 10 mL), dried (MgSO4), concentrated in vacuo and chromatographed.

14

IR and ¹ H NMR for Friedel-Crafts Acylation Products: 4-Methoxyacetophenone: IR (KBr): 1676 cm-1. 1H NMR (300 MHz, CDCl3): δ = 2.58 (s, 3 H), 3.84 (s, 3 H), 6.96 (d, 2 H, J = 9.0 Hz), 7.95 (d, 2 H, J = 9.0 Hz). 4-Methoxy-isobutyrophenone: IR (KBr): 1675 cm-1. 1H NMR (300 MHz, CDCl3): δ = 1.20 (d, 6 H, J = 7.0 Hz), 3.53 (septet, 1 H, J = 7.0 Hz), 3.87 (s, 3 H), 6.94 (d, 2 H, J = 8.5 Hz), 7.95 (d, 2 H, J = 8.5 Hz). 4-Methoxybenzophenone: IR (KBr): 1650 cm-1. 1H NMR (300 MHz, CDCl3): δ = 3.91 (s, 3 H), 6.98 (d, 2 H, J = 8.0 Hz), 7.47-7.59 (m, 3 H), 7.78 (d, 2 H, 7.0 Hz), 7.85 (d, 2 H, J = 8.0 Hz). 4-Thiomethylace-tophenone: IR (KBr): 1673 cm-1. 1H NMR (300 MHz, CDCl3): δ = 2.55 (s, 3 H), 2.59 (s, 3 H), 7.28 (d, 2 H, J = 8.0 Hz), 7.89 (d, 2 H, J = 8.0 Hz). 4-Thiomethyl-isobutyro-phenone: IR (KBr): 1670 cm-1. 1H NMR (300 MHz, CDCl3): δ = 1.21 (d, 6 H, J = 7.0 Hz), 2.53 (s, 3 H), 3.51 (septet, 1 H, J = 7.0 Hz), 7.27 (d, 2 H, J = 8.5 Hz), 7.87 (d, 2 H, J = 8.5 Hz). 4-Thiomethylbenzophenone: IR (KBr): 1649 cm-1. 1H NMR (300 MHz, CDCl3): δ = 2.56 (s, 3 H), 7.28-7.32 (2 H, m), 7.48-7.65 (3 H, m), 7.72-7.80 (m, 4 H). 2-Acetylthiophene: IR (KBr): 1662 cm-1. 1H NMR (270 MHz, CDCl3): δ = 2.59 (s, 3 H), 7.15 (1 H, t, J = 4.0 Hz) 7.65 (d, 1 H, J = 4.0 Hz), 7.71 (d, 1 H, J = 4.0 Hz). 2-Isobutyryl-thiophene: IR (KBr): 1662 cm-1. 1H NMR (300 MHz, CDCl3): δ = 1.27 (d, 6 H, J = 7.0 Hz), 3.41 (septet, 1 H, J = 7.0 Hz) 7.15 (t, 1 H, J = 4.5 Hz) 7.65 (d, 1 H, J = 5.0 Hz), 7.75 (d, 1 H, J = 4.5 Hz). 2-Benzoylthiophene: IR (KBr): 1632 cm-1. 1H NMR (300 MHz, CDCl3): δ = 7.19 (t, 1 H, J = 3.5 Hz), 7.52-7.68 (m, 6 H), 7.87 (d, 2 H, J = 3.0 Hz). 5-Acetyl-3-methylthiophene: IR (KBr): 1662 cm-1. 1H NMR (270 MHz, CDCl3): δ = 2.29 (s, 3 H), 2.53 (s, 3 H), 7.22 (d, 1 H, J = 1.0 Hz), 7.49 (d, 1 H, J = 1.0 Hz). 2-Acetyl-3-methylthiophene: IR (KBr): 1662 cm-1. 1H NMR (270 MHz, CDCl3): δ = 2.29 (s, 3 H), 2.55 (s, 3 H), 6.93 (d, 1 H, J = 5.0 Hz), 7.39 (d, 1 H, J = 5.0 Hz). 2- and 5-Isobutyryl-3-methylthiophene: IR (KBr): 1660 cm-1. 1H NMR (300 MHz, CDCl3): δ = 1.23 (d, 6 H, J = 7.0 Hz), 2.13 (s, 1.05 H), 2.59 (s, 1.95 H), 3.32 (m, 1 H), 6.97 (d, 0.65 H, J = 5.0 Hz), 7.38 (s, 0.35 H), 7.40 (d, 0.65 H, J = 5.0 Hz), 7.55 (s, 0.35 H). 2- and 5-Benzoyl-3-methylthiophene: IR (KBr): 1633 cm-1. 1H NMR (300 MHz, CDCl3): δ = 2.34 (s, 1.2 H), 2.51 (s, 1.8 H), 7.03 (d, 0.6 H, J = 5.0 Hz), 7.34 (s, 0.4 H), 7.46-7.61 (m, 4 H), 7.86 (m, 2 H). 9-Benzoylanthracene: IR (KBr): 1656 cm-1. 1H NMR (300 MHz, CDCl3): δ = 7.39-7.61 (m, 7 H), 7.74 (d, 2 H, J = 8.5 Hz), 7.84 (d, 2 H, J = 7.0 Hz), 8.09 (d, 2 H, J = 8.5 Hz), 8.56 (s, 1 H). α- and β- Benz-oylnaphthalene: IR (KBr): 1659 cm-1. 1H NMR (300 MHz, CDCl3): δ = 7.46-7.65 (m, 7 H), 7.88-8.05 (m, 4 H), 8.11 (d, 0.65 H, J = 7.5 Hz), 8.29 (s, 0.35 H). 2,4-Dimethyl-benzophenone: IR (KBr): 1662 cm-1. 1H NMR (300 MHz, CDCl3): δ = 2.35 (s, 3 H), 2.41 (s, 3 H), 7.07 (d, 1 H, J = 7.0 Hz), 7.13 (s, 1 H), 7.25 (d, 1 H, J = 7.5 Hz), 7.47 (m, 2 H), 7.58 (m, 1 H), 7.81 (d, 2 H, J = 7.0 Hz). 2- and 4-Methyl-benzophenone: IR (KBr): 1658 cm-1. 1H NMR (300 MHz, CDCl3): δ = 2.36 (s, 0.4 H, 2-CH3), 2.45 (s, 2.6 H, 4-CH3), 7.29-7.82 (m, 9 H).