Download PDF
Synlett 2011(6): 862-868  
DOI: 10.1055/s-0030-1259910
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

Novel Synthesis of 1,4-Dialkoxy-5,6,7,8-multisubstituted-2,3-dicyanonaphthalenes through Electron Transfer from Mg Metal and Efficient Development of New Naphthalocyanines

Takeshi Miyazaki, Aiko Harada, Hirofumi Maekawa*, Yoshimasa Yamamoto, Ikuzo Nishiguchi*
Department of Chemistry, Nagaoka University of Technology, 1603-1 Kamitomioka-cho, Nagaoka, Niigata 940-2188, Japan
Fax: +81(258)479300; e-Mail: nishiiku@vos.nagaokaut.ac.jp;
Further Information

Publication History

Received 28 December 2010
Publication Date:
15 March 2011 (online)

    Permissions and Reprints All articles of this category

Abstract

Novel methods for efficient synthesis of 1,4-diamyloxy-5,6,7,8-multisubstituted-2,3-dicyanonaphthalenes were successfully developed, starting from easily available 2,3-dicyanohydroquinone as a common single compound through only three steps, the first dibromination of 2,3-dicyanohydroquinone, the second Mitsunobu dialkylation of 2,3-dicyano-5,6-diboromo-1,4-hydroquinone, and the last Diels-Alder-type of cycloaddition between 1,4-alkoxy-2,3-dicyano-5,6-diboromobenzenes and multisubstituted furans, followed by reductive deoxygenation with Mg turning. The obtained 1,4-diamyloxy-5,6,7,8-multisubstituted-2,3-dicyanonaphthalenes were easily transformed into the corresponding naphthalocyanines in 20-45% yields which showed their λmax at 867-892 nm.

Key words

multisubstituted-2,3-dicyanonaphthalenes - Mg metal naphthalocyanines - benzyne - νmax at 867-892 nm

    Reference and Notes

  • 1a Wagner HJ. Loutfly RO. Hsiao CK. J. Mater. Sci.  1982,  17:  2281 
    Google Scholar
  • 1b Moser FH. Thomas AL. The Phthalocyanines   Vol. 1:  CRC Press; Boca Raton / FL: 1983. 
    Google Scholar
  • 1c Schichiri T. Suezaki M. Inoue T. Chem.Lett.  1992,  1717 
    Google Scholar
  • 1d Shirai O. Kobayashi T. Phthalocyanines - Chemistry and Functions   IPC Publisher; Tokyo: 1997. 
    Google Scholar
  • 2a Liljeroth P. Lepp J. Meyer G. Science  2007,  317:  1203 
    Google Scholar
  • 2b Nakamura Y. Katagiri Y. Tonomoto Y. Technical Reports of Fuji Xerox Co. Ltd.  2006,  16:  20 
    Google Scholar
  • 2c . inventors; JP  211174. 
  • 3a . inventors; JP  78307. 
  • 3b . inventors;  JP-A-67826. 
  • 3c Shirai O. inventors; JP-A-  118273. 
  • 5 Nakamori T. Chiba T. Kasai T. Nippon Kagaku Zasshi  1981,  12:  1916 
    Google Scholar
  • Recent studies on Mitsunobu Reaction, see:
  • 6a Anne-Sophie F. Sebastien D. Jacques B. Regis V. Claude D. Axelle A. Brigitte J. Tetrahedron  2008,  64:  10741 
    Google Scholar
  • 6b Wang G. Ella-Menye J.-R. St. Martin M. Yang H. Williams K. Org. Lett.  2008,  10:  4203 
    Google Scholar
  • 6c Vintonyak VV. Kunze B. Sasse F. Maier ME. Chem. Eur. J.  2008,  14:  11132 
    Google Scholar
  • 7 Cook MJ. Heeney MJ. Chem. Eur. J.  2000,  21:  39587 
    Google Scholar
  • 8a Forgione P. Wilson PD. Fallis AG. Tetrahedron Lett.  2000,  41:  17 
    Google Scholar
  • 8b Yoshina S. Yamamoto K. Yakugaku Zasshi  1974,  94:  1312 
    Google Scholar
  • 8c Nakano M. Tsurugi H. Satoh T. Miura M. Org. Lett.  2008,  10:  1851 
    Google Scholar
  • 8d Li ZF. Zheng YM. Liu YK. J. Indian Chem. Soc.  2002,  79:  188 
    Google Scholar
  • 9a Berson JA. Swidler R. J. Am. Chem. Soc.  1953,  75:  1721 
    Google Scholar
  • 9b Morton GE. Barrett AGM. J. Org. Chem.  2005,  70:  3525 
    Google Scholar
  • 9c Biland-Thommen AS. Raju GS. Blagg J. Whitea AJP. Barretta AGM. Tetrahedron Lett.  2004,  45:  3181 
    Google Scholar
  • 10 Repine JT. Johnson DS. White AD. Favor FD. Stier MA. Maiti SN. Tetrahedron Lett.  2007,  48:  5539 
    CrossrefGoogle Scholar
  • 11a Yamamoto Y. Kawano S. Maekawa H. Nishiguchi I. Synlett.  2004,  30 
    Google Scholar
  • 11b Maekawa H. Sakai M. Uchida T. Kita Y. Nishiguchi I. Tetrahedron Lett.  2004,  45:  607 
    Google Scholar
  • 12a Cook MJ. Dunn AJ. Howe SD. Thomson AJ. J. Chem. Soc., Perkin Trans. 1  1988,  2453 
    Google Scholar
  • 12b . inventors; JP  39378. 
4

Substitution of activated chlorine groups of 6-nitro-2,3-dichloronaphthalene to cyano groups by sodium cyanide was reported,5 although the yield was inadequate (46%) and application to preparation of many various derivatives may be difficult.