Download PDF
Synlett 2003(10): 1419-1422
DOI: 10.1055/s-2003-40850
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

Silica-Alumina Catalyst Support, an Efficient Catalyst for Synthesis of Halogen Substituted 2,6-Bis(imino)pyridines

Changtao Qian*, Feifeng Gao, Yaofeng Chen, Lijun Gao
State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 354 Fenglin Road, Shanghai 200032, China
Fax: +86(21)64166148; e-Mail: qianct@mail.sioc.ac.cn;
Further Information

Publication History

Received 3 March 2003
Publication Date:
24 July 2003 (online)

    Permissions and Reprints All articles of this category

Abstract

Silica-alumina catalyst support was found to be an efficient catalyst for the condensation reaction of 2,6-, 2,5-, and 2,4-difluoroaniline and ortho-halogen-aniline with 2,6-diacetylpyridine to afford corresponding 2,6-bis(imino)pyridines in 56-75% isolated yields under extremely mild reaction conditions. The catalyst can be recovered and reused

Key words

silica-alumina catalyst support - halogen substituted 2,6-bis(imino)pyridine - condensation reaction

    References

  • 1 Small BL. Brookhart M. Polym. Prepr. (Am. Chem. Soc., Div. Polym. Chem.)  1998,  39:  213 
    Google Scholar
  • 2 Small BL. Brookhart M. Bennett AMA. J. Am. Chem. Soc.  1998,  120:  4049 
    CrossrefGoogle Scholar
  • 3 Small BL. Brookhart M. J. Am. Chem. Soc.  1998,  120:  7143 
    CrossrefGoogle Scholar
  • 4 Britovsek GPJ. Gibson VC. Kimberley BS. Maddox PJ. McTavish SJ. Solan GA. White AJP. Williams DJ. Chem. Commun.  1998,  849 
    CrossrefGoogle Scholar
  • 5 Britovsek GPJ. Bruce M. Gibson VCB. Kimberley S. Maddox PJ. McTavish SJ. Redshaw C. Solan GA. Strömberg S. White AJP. Williams DJ. J. Am. Chem. Soc.  1999,  121:  8728 
    Google Scholar
  • 6 Chen RF. Qian CT. Sun J. Chin. J. Chem.  2001,  19:  866 
    Google Scholar
  • 8 Chen YF. Qian CT. Sun J. Organometallics  2003,  22:  1231 
    CrossrefGoogle Scholar
  • 9 Sonovskikh VY. Usachev BI. Röschenthaler GV. Tetrahedron  2002,  58:  1375 
    CrossrefGoogle Scholar
  • 10 Sevennard D. Khomotutov O. Koryakova O. Sattarova V. Kodess M. Stelten J. Loop I. Lork E. Pashkevich KI. Röeschenthaler GV. Synthesis  2000,  1738 
    Article in Thieme ConnectGoogle Scholar
  • 11a Suga K. inventors; JP  2002037841, A2, 6. 
  • 11b Kusuda S. inventors; JP  2002146328, A2. 
  • 11c Tanaka A, and Ohzeki Y. inventors; Ger. Offen. DE  2835289. 
  • 11d Hiroyuki O. Tomoya K. Mitukazu O. Hidekazu T. Neltowaku Porima  2002,  23:  11 
    Google Scholar
  • 12 Grammaticakis MP. Bull. Soc. Chim. Fr.  1949,  761 
    Google Scholar
  • 13a Petrova TD. Lolesnikova IV. Mamatyuk VI. Vetohinov VP. Platonov VE. Russ. Chem. B1.  1993,  42:  1540 
    Google Scholar
  • 13b Krishna JC. Renuka J. Pooran C. Saroj G. J. Indian. Chem. Soc.  1983,  60:  760 
    Google Scholar
  • 13c Matsui M. Fukuyasu K. Shibata K. Muramatsu H. J. Chem. Soc., Perkin Trans. 2  1993,  6:  1107 
    Google Scholar
  • 13d Kayakova LA. Erzhanov KB. Umarova ZN. J. Org. Chem. USSR (Engl. Transl.)  1988,  24:  111 
    Google Scholar
  • 13e Kayaukova LA. Chermova NV. Manchuk ZN. Erzhanov KB. J. Org. Chem. USSR (Engl. Transl.)  1990,  26:  1389 
    Google Scholar
  • 13f Brook GM. Matthews RS. J. Fluorine Chem.  1988,  40:  109 
    Google Scholar
  • 13g Okamoto H. Kato S. Ogasawara M. Konnai M. Takematsu T. Agric. Biol.  1991,  55:  2733 
    Google Scholar
  • 14a Denmark SE. Rivera I. J. Org. Chem.  1994,  59:  6887 
    CrossrefGoogle Scholar
  • 14b Weingarten H. Chupp JP. White WA. J. Org. Chem.  1967,  32:  3246 
    CrossrefGoogle Scholar
  • 16a Kobayashi S. Chem. Rev.  2002,  102:  2227 
    CrossrefGoogle Scholar
  • 16b Ma Y. Qian CT. Wang L. Yang M. J. Org. Chem.  2000,  65:  3864 
    CrossrefGoogle Scholar
  • 17 Hanamoto T. Sugimoto Y. Jin YZ. Inanaga J. Bull. Chem. Soc. Jpn.  1997,  70:  142 
    Google Scholar
  • 20 Bellabarba RM. et al. 20th International Conference on Organometallic Chemistry, Book of Abstract   Corfu; Greece: 2002.  p.230 
    Google Scholar
  • 21a

    Zeolite H-Beta Si/Al = 19.98, specific surface area 554.4 m2/g, average pore size 6.6-6.7, 5.6-5.6 Å.

  • 21b

    Zeolite H-Y Si/Al = 3.35, specific surface area 739.3 m2/g, average pore size 7.4 Å, cage diameter 12 Å.

  • 21c

    Si-Al(II) Si/Al = 1.0, specific surface area 240.4 m2/g.

7

We applied a China patent (CN1322717A) in January 2001. BASF Company promulgated a WO Patent (01/07491) in February, 2001, in which two halogen substituted 2,6-bis(imino)pyridyl iron complexes, 2,6-bis-diacetyl-pyridinebis(2,6-dibrom-4-methylanil)FeCl2 and 2,6-bis-diacetyl pyridinebis(2,6-dichloroanil)FeCl2, appeared, but there was no characterization of the complexes.

15

The condensation reaction of 2,6-dibromoaniline with 2,6-diacetylpyridine catalyzed by p-TsOH in refluxing toluene, with removing water by azeotropic distillation gave corresponding 2,6-bis(imino)pyridine in 58% yield if purified by recrystallization, However, it gave 30% yield when purified by flash column. See ref. [6]

18

Silica-alumina catalyst support (Grade 135) was purchased from Aldrich. Si/Al = 5.62, its specific surface area is 421.3 m2/g, average pore size 61.0545 Å. In our study, silica-alumina catalyst support (Grade 135) combined with 4 Å MS is found to be excellent catalyst for the condensation reaction of arylaldehydes with anilines, which gave almost quantitative yield.

19

Typical Experimental Procedure: Under an argon atmosphere, a mixture of 2,6-difluoroaniline (0.77 g, 6.0 mmol), 2,6-diacetylpyridine (0.41 g, 2.5 mmol), silica-alumina catalyst support (0.2 g) and molecular sieves 4 Å (0.5 g) in 8 mL toluene was stirred at 30-40 °C for 24 h. The reaction mixture was filtered and the filtration was condensed in vacuo. Anhydrous MeOH (5 mL) was added to the residue. A yellow solid was collected by filtration to yield 1a in 65% yield. 1H NMR (300 MHz, CDCl3): d = 8.39 (d, 2 H, J = 8.0 Hz), 7.93 (t, 1 H, J = 7.9 Hz), 7.07 (m, 4 H,), 6.99 (t, 2 H, J = 7.6 Hz), 2.46 (s, 6 H). IR (KBr): n = 1636, 1576, 1465, 1369, 1277, 1237, 1215, 1126, 1032, 1002, 827, 789, 759 cm-1. MS (EI): m/z 349 (M+). Anal. Calcd for C21H15F4N3: C, 72.19; H, 4.90; N, 12.03. Found: C, 71.88; H, 4.96; N, 11.96.