Download PDF
Synthesis 2005(11): 1801-1806  
DOI: 10.1055/s-2005-869974
PAPER
© Georg Thieme Verlag Stuttgart · New York

An Easy Access to Aryl Azides from Aryl Amines under Neutral Conditions

Jagattaran Das*, Santoshkumar N. Patil, Riti Awasthi, C. Prasad Narasimhulu, Sanjay Trehan
Discovery Research, Dr. Reddy’s Laboratories Ltd., Miyapur, Hyderabad 500 049, India
Fax: +91(40)23045438; e-Mail: jagat@drreddys.com;
Further Information

Publication History

Received 13 December 2004
Publication Date:
27 June 2005 (online)

    Permissions and Reprints All articles of this category

Abstract

A variety of substituted aryl amines were transformed into aryl azides using t-BuONO and moist NaN3 in t-BuOH in good to excellent yields. Smooth transformation was observed with anilines, having electron withdrawing and donating groups. Both acid- and base-sensitive groups survived the reaction conditions.

Key words

amines - azides - anilines - diazo compounds - sodium azide

    References

  • 1 Scriven EFV. Turnbull K. Chem. Rev.  1988,  88:  297 
    CrossrefGoogle Scholar
  • 2a Rostovsev VV. Green LG. Fokin VV. Sharpless KB. Angew. Chem. Int. Ed.  2002,  41:  2596 
    CrossrefPubMedGoogle Scholar
  • 2b Wang Q. Chan TR. Hilgraf R. Fokin VV. Sharpless KB. Fin MG. J. Am. Chem. Soc.  2003,  125:  3192 
    CrossrefPubMedGoogle Scholar
  • 2c Tornoe CW. Christensen C. Meldal M. J. Org. Chem.  2002,  67:  3057 
    CrossrefPubMedGoogle Scholar
  • 3a Biffin MEC. Miller J. Paul DB. In The Chemistry of the Azido Groups   Patai S. Interscience; London/ New York: 1971.  p.147-176  
    Google Scholar
  • 3b The Chemistry of Functional Groups, The Chemistry of Halides, Pseudo Halides and Azides   Suppl. D:  Patai S. Rappoport Z. Wiley; Chichester UK: 1983.  Part 1, 2.
    Google Scholar
  • 3c Hassner A. In Houben-Weyl, Organische Stickstoffverbindungen   Vol. E16q:  Klamann D. Thieme; Stuttgart/ New York: 1990.  Part I/2. p.1234 
    Google Scholar
  • 4a Fischer W. Anselme J.-P. J. Am. Chem. Soc.  1967,  89:  5284 
    CrossrefGoogle Scholar
  • 4b Nakajima M. Anselme J.-P. Tetrahedron Lett.  1976,  4421 
    CrossrefGoogle Scholar
  • 5 Smith PAS. Rowe CD. Bruner LB. J. Org. Chem.  1969,  34:  3430 
    CrossrefGoogle Scholar
  • 6 Liu Q. Tor Y. Org. Lett.  2003,  5:  2571 
    CrossrefGoogle Scholar
  • 7 Zhu W. Ma D. Chem. Commun.  2004,  888 
    CrossrefGoogle Scholar
  • 8 Diazotization of aryl amines in the presence of alkyl nitrite has been discussed in: Frieman F. Chlebowski JF. J. Org. Chem.  1968,  33:  1633 
    CrossrefGoogle Scholar
  • Rate enhancement of a reaction by addition of minute quantities of H2O has been observed before:
  • 10a Liotta CL. Burgess EM. Ray CC. Black ED. Fair BE. Phase Transfer Catalysis New Chemistry Catalysts and Applications   Starks CM. ACS Symposium Series 326;American Chemical Society; Washington DC: 1987.  p.15 
    CrossrefGoogle Scholar
  • 10b Liotta CL. Burgess EM. Ray CC. Black ED. Fair BE. Prepr. - Am. Chem. Soc., Div. Pet. Chem.  1985,  30:  367 
    CrossrefGoogle Scholar
  • Similar was the observation by Chandrasekaran’s group in heterogeneous permanganate oxidation of olefins in presence of small quantities of t-BuOH and H2O:
  • 10c Baskaran S. Das J. Chandrasekaran S. J. Org. Chem.  1989,  54:  5182 
    CrossrefGoogle Scholar
  • 13a Brickner SJ. Hutchinson DK. Barbachyn MR. Manninen PR. Ulanowicz DA. Garmon SA. Grega KC. Hendges SK. Toops DS. Ford CW. Zurenko GE. J. Med. Chem.  1996,  39:  673 
    CrossrefGoogle Scholar
  • 13b Genin MJ. Allwine DA. Anderson DJ. Barbachyn MR. Emmert DE. Garmon SA. Graber DR. Grega KC. Hester JB. Hutchinson DK. Morris J. Reischer RJ. Ford CW. Zurenko GE. Hamel JC. Schaadt RD. Stapert D. Yagi BH. J. Med. Chem.  2000,  43:  953 
    CrossrefGoogle Scholar
  • 14 Leffler JE. Temple RD. J. Am. Chem. Soc.  1967,  89:  5235 
    CrossrefGoogle Scholar
  • 15 Di Nunno L. Scilimati A. Tetrahedron  1986,  42:  3913 
    CrossrefGoogle Scholar
  • 16 Kita Y. Tohma H. Hatanaka K. Takada T. Fujita S. Mitoh S. Sakurai H. Oka S. J. Am. Chem. Soc.  1994,  116:  3684 
    CrossrefGoogle Scholar
  • 17 Dyall LK. Kemp JE. Aust. J. Chem.  1967,  20:  1395 
    CrossrefGoogle Scholar
  • 18 Takabatake T. Miyazawa T. Hasegawa M. J. Heterocycl. Chem.  1996,  33:  1057 
    CrossrefGoogle Scholar
  • 19 Hagedorn M. Sauers RR. Eichholz A. J. Org. Chem.  1978,  43:  2070 
    CrossrefGoogle Scholar
9

GC analysis showed the presence of ca. 40% t-BuOH in t-BuONO. This reagent could be stored in the refrigerator (4 °C) for one week. However, t-BuONO stored more than a week was not as effective and larger excess of reagent was needed for completion of the reaction. The amount of t-BuONO was calculated on the basis of 60% purity.

11

Isoamyl nitrite was purchased from Aldrich Chemical.

12

2-Aminobenzoxazole did not undergo transformation to corresponding azide under the reaction conditions.