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Synthesis 2004(14): 2386-2390  
DOI: 10.1055/s-2004-831183
PAPER
© Georg Thieme Verlag Stuttgart · New York

Hydrodediazoniation of Dry Arenediazonium o-Benzenedisulfonimides with Hydrogen Peroxide

Margherita Barbero, Iacopo Degani, Stefano Dughera*, Rita Fochi*
Dip.to di Chimica Generale ed Organica Applicata dell’Università , C.so M. D"Azeglio 48, 10125 Torino, Italy
e-Mail: rita.fochi@unito.it;
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Publication History

Received 19 May 2004
Publication Date:
19 August 2004 (online)

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Abstract

This report describes the hydrodediazoniation of dry arenediazonium o-benzenedisulfonimides 1 with hydrogen peroxide (2) in THF at reflux. The new procedure is general, giving positive results in the presence of both electron-donating and electron-withdrawing substituents. Furthermore, it does not suffer from steric effects and always gives the pure reduction products 3 in excellent yields (15 examples, average yield = 93%). All the reactions show over 90% recovery of o-benzenedisulfonimide (4) that can be reused to prepare the salts 1. The collateral proofs we performed led us to hypothesize, for this reaction, a free-radical chain mechanism in which 2 is the exclusive hydrogen source in the arenes Ar-H 3.

Key words

reductions - diazonium compounds - radical reactions - sulfur

    References

  • 1a Barbero M. Degani I. Dughera S. Fochi R. Synthesis  2003,  1225 ; and references cited therein
    Article in Thieme ConnectGoogle Scholar
  • 1b Barbero M, Degani I, Fochi R, and Perracino P. inventors; PCT  EP9801145.  ; Chem. Abstr. 1998, 129, 244942
    Article in Thieme Connect
  • 1c Barbero M. Crisma M. Degani I. Fochi R. Perracino P. Synthesis  1998,  1171 
    Article in Thieme ConnectGoogle Scholar
  • For a general survey see:
  • 2a Kornblum N. Org. React.  1944,  262-339  ; and references cited therein
    Google Scholar
  • 2b Wulfman DS. In The Chemistry of Functional Groups: The Chemistry of Diazonium and Diazo Groups   Part 1:  Patai S. Wiley; New York: 1978.  Chap. 8. p.286-287  ; and references cited therein
    Google Scholar
  • 2c Zollinger H. In The Chemistry of Functional Groups: The Chemistry of Triple-Bonded Functional Groups   Part 1:  Patai S. Rappaport Z. Wiley; New York: 1983.  Chap. 15. p.642 ; and references cited therein
    Google Scholar
  • 2d Saunders KH. Allen RLM. In Aromatic Diazo Compounds   3rd ed.:  Edward Arnold; London: 1985.  Chap. 10. p.537-555  ; and references cited therein
    Google Scholar
  • 2e Zollinger H. Diazo Chemistry I   VCH; Weinheim: 1994.  Chap. 10. p.222-225  ; and references cited therein
    Google Scholar
  • 2f Zollinger H. In The Chemistry of Functional Groups: The Chemistry of Amino, Nitroso, Nitro and Related Groups   Suppl. F2, Part 1:  Patai S. Wiley; New York: 1996.  Chap. 13. p.650-651  ; and references cited therein
    Google Scholar
  • 2g A list of reducing agents: Larock RC. In Comprehensive Organic Transformations   2nd ed.:  Wiley; New York: 1999.  p.40-41  
    Google Scholar
  • 2h Smith MB. March J. In March’s Advanced Organic Chemistry   5th ed.:  Wiley-Interscience; New York: 2001.  Chap. 14. p.934-935  ; and references cited therein
    Google Scholar
  • 3 Griess P. Phil. Trans. Roy Soc. London, Ser. A  1864,  683 
    Google Scholar
  • Typical examples are:
  • 4a Bigelow LA. Johnson JR. Sandborn LT. Organic Syntheses Coll. Vol. I   Wiley; New York: 1941.  p.133-134  
    Google Scholar
  • 4b Wallingford VH. Krueger PA. Organic Syntheses Coll. Vol. II   Wiley; New York: 1943.  p.353-355  
    Google Scholar
  • 4c Coleman GH. Talbot WF. Organic Syntheses Coll. Vol. II   Wiley; New York: 1943.  p.592-593  
    Google Scholar
  • 5a Kornblum N. Iffland Don C. J. Am. Chem. Soc.  1949,  71:  2137 
    CrossrefGoogle Scholar
  • 5b Kornblum N. Cooper GD. Taylor JE. J. Am. Chem. Soc.  1950,  72:  3013 
    CrossrefGoogle Scholar
  • 5c Kornblum N. Kelley AE. Cooper GD. Taylor JE. J. Am. Chem. Soc.  1952,  74:  3074 
    CrossrefGoogle Scholar
  • 5d Kornblum N. Organic Syntheses Coll. Vol. III   Wiley; New York: 1953.  p.295-299  
    CrossrefGoogle Scholar
  • 6a Hendrickson JB. J. Am. Chem. Soc.  1961,  83:  1251 
    CrossrefGoogle Scholar
  • 6b Bloch M. Musso H. Zahorszky UI. Angew. Chem.  1969,  81:  370 
    CrossrefGoogle Scholar
  • 6c Nakayama J. Yoshida M. Simamura O. Tetrahedron  1970,  26:  4609 
    CrossrefGoogle Scholar
  • 7 Shono T. Matsumura Y. Tsubata K. Chem. Lett.  1979,  1051 
    Google Scholar
  • 8 Park KH. Cho YH. Jang EJ. Bull. Korean. Chem. Soc.  1996,  17:  179 
    Google Scholar
  • 9 Rutherford KG. Redmond WA. J. Org. Chem.  1963,  28:  568 
    CrossrefGoogle Scholar
  • 10 Lormann M. Dahmen S. Brase S. Tetrahedron Lett.  2000,  41:  3813 
    CrossrefGoogle Scholar
  • 11 Geoffroy OJ. Morinelli TA. Meier GP. Tetrahedron Lett.  2001,  42:  5367 
    CrossrefGoogle Scholar
  • 12a Cadogan JIG. Molina GA. J. Chem. Soc., Perkin Trans. 1  1973,  541 
    CrossrefGoogle Scholar
  • 12b Itoh T. Matsuya Y. Nagata K. Ohsawa A. Tetrahedron Lett.  1996,  37:  4165 
    CrossrefGoogle Scholar
  • 12c Li F. Yang SI. Ciringh Y. Seth J. Martin CH. Singh DL. Kim D. Birge RR. Bocian DF. Holten D. Lindsey JS. J. Am. Chem. Soc.  1998,  120:  10001 
    CrossrefGoogle Scholar
  • 13a Doyle MP. Dellaria JF. Siegfried B. Bishop SW. J. Org. Chem.  1977,  42:  3494 
    CrossrefGoogle Scholar
  • 13b Wassmund FW. Kiesman WF. J. Org. Chem.  1995,  60:  1713 
    CrossrefGoogle Scholar
  • 14 Threadgill MD. Gledhill AP. J. Chem. Soc., Perkin Trans. 1  1986,  873 
    CrossrefGoogle Scholar
  • 15 Newman MS. Hung WM. J. Org. Chem.  1974,  39:  1317 
    CrossrefGoogle Scholar
  • 16 Dictionary of Organic Compounds on CD-ROM, Version 10.2 [CD-ROM]   Chapman & Hall, Electronic Publishing Division; London: 2003. 
    Google Scholar
  • 17 Bulman Page PC. Klair SS. Brown MP. Smith CS. Maginn SJ. Mulley S. Tetrahedron  1992,  48:  5933 
    CrossrefGoogle Scholar
  • 18 Bunnet JF. Acc. Chem. Res.  1978,  11:  413 
    CrossrefGoogle Scholar
  • 19 Wassmund FW. Kiesman WF. J. Org. Chem.  1997,  62:  8304 
    CrossrefGoogle Scholar
  • 20a Barbero M. Degani I. Dughera S. Fochi R. Perracino P. Synthesis  1999,  90 
    Article in Thieme ConnectGoogle Scholar
  • 20b Barbero M. Degani I. Diulgheroff N. Dughera S. Fochi R. Migliaccio M. J. Org. Chem.  2000,  65:  5600 
    Article in Thieme ConnectGoogle Scholar
  • 20c Barbero M. Degani I. Diulgheroff N. Dughera S. Fochi R. Synthesis  2001,  2180 
    Article in Thieme ConnectGoogle Scholar