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Synthesis 2005(11): 1771-1774  
DOI: 10.1055/s-2005-865336
PAPER
© Georg Thieme Verlag Stuttgart · New York

Practical and Efficient Synthesis of Tris(4-formylphenyl)amine, a Key Building Block in Materials Chemistry

Thomas Mallegol, Said Gmouh, Mohamed Aït Amer Meziane, Mireille Blanchard-Desce, Olivier Mongin*
Synthèse et ElectroSynthèse Organiques (CNRS, UMR 6510), Université de Rennes 1, Campus de Beaulieu, Bât. 10A, 35042 Rennes Cedex, France
Fax: +33(1)223236955; e-Mail: olivier.mongin@univ-rennes1.fr;
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Publikationsverlauf

Received 26 January 2005
Publikationsdatum:
25. April 2005 (online)

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Abstract

A short, practical and efficient preparation of tris(4-formylphenyl)amine, a key building block in materials chemistry, is described. It involves a two-flask synthesis from triphenylamine, which requires shorter overall time than the direct one-flask threefold Vilsmeier-Haack formylation, while giving higher yields. The reaction levels off at the disubstitution stage, due to the deactivation of the bis-iminium intermediate, but hydrolysis of the latter into a less deactivated dialdehyde allows the third formylation to occur. The simple experimental protocol makes this method more convenient than the previously reported procedures.

Key words

materials chemistry - building block - aldehydes - electrophilic aromatic substitutions - Vilsmeier-Haack reaction

    References

  • 1 Suzuki H, and Matsumoto M. inventors; Jpn. Kokai Tokkyo Koho,  63163361. 
  • 2 Goto S, Abe N, and Sasaki O. inventors; Jpn. Kokai Tokkyo Koho,  01044452. 
  • 3 Kushibiki N, Takeuchi K, Kobayashi H, and Masatomi T. inventors; Eur. Pat. Appl.,  771809. 
  • 4 Nam H. Kang DH. Kim JK. Park SY. Chem. Lett.  2000,  1298 
    CrossrefGoogle Scholar
  • 5 Jiang KJ. Sun YL. Shao KF. Yang LM. Chem. Lett.  2004,  33:  50 
    CrossrefGoogle Scholar
  • 6 Meng FS. Yao QH. Shen JG. Li FL. Huang CH. Chen KC. Tian H. Synth. Met.  2003,  137:  1543 
    CrossrefGoogle Scholar
  • 7 Meng F. Liu C. Hua J. Cao Y. Chen K. Tian H. Eur. Polym. J.  2003,  39:  1325 
    CrossrefGoogle Scholar
  • 8 Elandaloussi EH. Spangler CW. Polym. Prepr. (Am. Chem. Soc., Div. Polym. Chem.)  1998,  39:  1055 
    Google Scholar
  • 9 Holmberg SE. Spangler CW. Polym. Mater. Sci. Eng.  2001,  84:  717 
    Google Scholar
  • 10 Stadler S. Feiner F. Bräuchle C. Brandl S. Gompper R. Chem. Phys. Lett.  1995,  245:  292 
    CrossrefGoogle Scholar
  • 11 Lambert C. Gaschler W. Schmalzlin E. Meerholz K. Brauchle C. J. Chem. Soc., Perkin Trans. 2  1999,  577 
    CrossrefGoogle Scholar
  • 12 Elandaloussi EH. Spangler CW. Dirk C. Casstevens M. Kumar D. Burzynski R. Mater. Res. Soc. Symp. Proc.  1999,  561:  63 
    CrossrefGoogle Scholar
  • 13 Drobizhev M. Karotki A. Rebane A. Spangler CW. Opt. Lett.  2001,  26:  1081 
    CrossrefGoogle Scholar
  • 14 Yoo J. Yang SK. Jeong M.-Y. Ahn HC. Jeon S.-J. Cho BR. Org. Lett.  2003,  5:  645 
    CrossrefGoogle Scholar
  • 15 Drobizhev M. Karotki A. Dzenis Y. Rebane A. Suo Z. Spangler CW. J. Phys. Chem. B  2003,  107:  7540 
    CrossrefGoogle Scholar
  • 16 Spangler CW. Suo Z. Drobizhev M. Karotki A. Rebane A. Proc. SPIE-Int. Soc. Opt. Eng.  2003,  4797:  146 
    Google Scholar
  • 17 Spangler CW. Suo Z. Drobizhev M. Karotki A. Rebane A. NATO Sci. Ser. II  2003,  100:  139 
    Google Scholar
  • 18 Mongin O. Porrès L. Katan C. Pons T. Mertz J. Blanchard-Desce M. Tetrahedron Lett.  2003,  44:  8121 
    CrossrefGoogle Scholar
  • 19 Lee HJ. Sohn J. Hwang J. Park SY. Choi H. Cha M. Chem. Mater.  2004,  16:  456 
    CrossrefGoogle Scholar
  • 20 Yang WJ. Kim DY. Kim CH. Jeong M.-Y. Lee SK. Jeon S.-J. Cho BR. Org. Lett.  2004,  6:  1389 
    CrossrefGoogle Scholar
  • 21 Mongin O. Charlot M. Katan C. Porrès L. Parent M. Pons T. Mertz J. Blanchard-Desce M. Proc. SPIE-Int. Soc. Opt. Eng.  2004,  5516:  9 
    Google Scholar
  • 22 Hua JL. Li B. Meng FS. Ding F. Qian SX. Tian H. Polymer  2004,  45:  7143 
    CrossrefGoogle Scholar
  • 23 Wilson CD. inventors; US Patent,  2558285. 
  • 24 Lai G. Bu XR. Santos J. Mintz EA. Synlett  1997,  1275 
    Artikel in Thieme ConnectGoogle Scholar
  • 26 Jin S.-H. Jung J.-E. Yeom I.-S. Moon S.-B. Koh K. Kim S.-H. Gal Y.-S. Eur. Polym. J.  2002,  38:  895 
    CrossrefGoogle Scholar
25

This could explain why DMF is often used in larger amounts than POCl3.24 To overcome this problem, other authors tried to use high boiling chlorinated solvents, such as 1,2-dichloroethane, but the yields remained low.19,26