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Synthesis 2002(16): 2421-2425
DOI: 10.1055/s-2002-35227
PAPER
© Georg Thieme Verlag Stuttgart · New York

Observation of O→N Type Smiles Rearrangement in Certain Alkyl Aryl Nitro Compounds [1]

Natesan Selvakumar*, Deekonda Srinivas, Azagarsamy Malar Azhagan
Department of Discovery Chemistry, Discovery Research, Dr. Reddy’s Laboratories Ltd., Miyapur, Hyderabad 500 050, India
Fax: +91(40)3045438; e-Mail: selvakumarn@drreddys.com;
Further Information

Publication History

Received 15 July 2002
Publication Date:
04 November 2002 (online)

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Abstract

Smiles rearrangements on some alkyl aryl nitro compounds having NH2 group as the nucleophile and oxygen as the leaving group are reported.

Key words

rearrangement - nucleophilic addition - cyclization - isomerization - nitro compound

1

DRF Publication No. 212.

    References

  • 2a Truce WE. Kreider EM. Brand WW. Org. React.  1971,  18:  99 
    CrossrefGoogle Scholar
  • 2b Bunnett JF. Zahler RE. Chem. Rev.  1951,  49:  273 
    CrossrefGoogle Scholar
  • 3a Bayles R. Johnson MC. Maisey RF. Turner RW. Synthesis  1977,  31 
    CrossrefGoogle Scholar
  • 3b Baker WR. J. Org. Chem.  1983,  48:  5140 
    CrossrefGoogle Scholar
  • 3c Neumeyer JL. Gao Y. Kula NS. Baldessariu RJ. J. Med. Chem.  1990,  33:  3124 
    CrossrefGoogle Scholar
  • 4 Davies SG. Hume WE. Tetrahedron Lett.  1195,  36:  2673 
    Google Scholar
  • 5 Soukri M. Lazar S. Akssira M. Guillaumet G. Org. Lett.  2000,  2:  1557 
    CrossrefGoogle Scholar
  • 6 For example see: Cao B. Park H. Joullie MM. J. Am. Chem. Soc.  2002,  124:  520 ; during the preparation of the compound 26 the authors report the formation of an unidentified aryl amine. We believe that the undesired aryl amine is presumably the structure 28 a product of Smiles rearrangement via the intermediate 27 (Figure 2)
    CrossrefGoogle Scholar
  • 7 Bischofberger N. Waldmann H. Saito T. Simon ES. Lees W. Bednarski MD. Whitesides GM. J. Org. Chem.  1988,  53:  3457 
    CrossrefGoogle Scholar
  • Similar studies on primary acyclic amines have been reported although under different conditions:
  • 8a Knipe AC. Sridhar N. Synthesis  1976,  606 
    Google Scholar
  • 8b Mutai K. Kobayashi K. Bull. Chem. Soc. Jpn.  1981,  54:  462 
    Google Scholar
  • A similar amino-ethanol substrate undergoing Smiles rearrangement in a polyfunctional vinylthiohalobenzene substrate has been reported:
  • 9a Amosova SV. Gostevsgaya VI. Gavrilova GM. Afonin AV. Toryashinova DD. Zh. Org. Khim.  1993,  29:  2416 
    Google Scholar
  • 9b Yilmaz I. Shine HJ. Gazz. Chim. Ital.  1989,  119: 
    Google Scholar
1

DRF Publication No. 212.