Download PDF
Synlett 2006(3): 0472-0474  
DOI: 10.1055/s-2006-926242
LETTER
© Georg Thieme Verlag Stuttgart · New York

New Polynitrogen Materials Based on Fused 1,2,4-Triazines

Ethel Garniera,b, Franck Suzeneta, Didier Poullainb, Bruno Lebretb, Gérald Guillaumet*a
a Institut de Chimie Organique et Analytique (ICOA), UMR-CNRS 6005, FR CNRS 2708, LRC CEA M09, Université d’Orléans, Rue de Chartres, BP 6759, 45067 Orléans Cedex 2, France
Fax: +33(2)38417281; e-Mail: gerald.guillaumet@univ-orleans.fr;
b CEA Le Ripault, BP 16, 37260 Monts, France
Further Information

Publication History

Received 13 October 2005
Publication Date:
06 February 2006 (online)

    Permissions and Reprints All articles of this category

Abstract

The synthesis of several novel polynitrogen materials based on fused 1,2,4-triazines is described. A powerful palladium-catalyzed N-heteroarylation strategy followed by a cyclization provides a straightforward one-pot reaction to these tricyclic materials.

Key words

N-arylation reactions - palladium - energetic materials - 1,2,4-triazines

    References and Notes

  • 1a Millar RW. Philbin SP. Claridge RP. Hamid J. Propellants, Explos., Pyrotech.  2004,  81 
    CrossrefGoogle Scholar
  • 1b Sikder AK. Sikder N. J. Hazard. Mater.  2004,  A112:  1 
    CrossrefGoogle Scholar
  • 1c Singh G. Singh Kapoor IP. J. Hazard. Mater.  1999,  A68:  155 
    CrossrefGoogle Scholar
  • 1d Chapman RD. Wilson WS. Thermochim. Acta  2002,  384:  229 
    CrossrefGoogle Scholar
  • For C-C bond formation, see:
  • 2a Alphonse F.-A. Suzenet F. Keromnes A. Lebret B. Guillaumet G. Synlett  2002,  447 
    Google Scholar
  • 2b Alphonse F.-A. Suzenet F. Keromnes A. Lebret B. Guillaumet G. Org. Lett.  2003,  5:  803 
    Google Scholar
  • 2c Alphonse F.-A. Suzenet F. Keromnes A. Lebret B. Guillaumet G. Synthesis  2004,  2893 
    Google Scholar
  • 2d For general chemistry, see: Neunhoffer H. Comprehensive Chemistry II   Vol. 6:  Katritzky AR. Rees CW. Scriven EFW. Pergamon Press; Oxford UK: 1996.  p.507 
    Google Scholar
  • For inverse-electron-demand Diels-Alder reaction, see:
  • 2e Lipinska T. Tetrahedron Lett.  2002,  43:  9565 
    Google Scholar
  • 2f Lahue B. Wan Z.-K. Snyder JK. J. Org. Chem.  2003,  68:  4345 
    Google Scholar
  • 2g Lahue BR. Lo S.-M. Wan Z.-K. Woo GHC. Snyder JK. J. Org. Chem.  2004,  69:  7171 
    Google Scholar
  • 2h Branowska D. Synthesis  2003,  2096 
    Google Scholar
  • 2i Bilbao ER. Alvarado M. Masguer CF. Ravina E. Tetrahedron Lett.  2002,  43:  3551 
    Google Scholar
  • For fused 1,2,4-triazine derivatives, see:
  • 2j Garnier E. Guillard J. Pasquinet E. Suzenet F. Poullain D. Jarry C. Léger J.-M. Lebret B. Guillaumet G. Org. Lett.  2003,  5:  4595 
    Google Scholar
  • 2k Mojzych M. Rykowski A. Heterocycles  2004,  63:  1829 
    Google Scholar
  • 2l Chupakhin ON. Rusinov GL. Beresnev DG. Charushin VN. Neunhoeffer H. J. Heterocycl. Chem.  2001,  38:  901 
    Google Scholar
  • 2m Nagai S.-I. Miyachi T. Nakane T. Ueda T. Uozumi Y. J. Heterocycl. Chem.  2001,  38:  379 
    Google Scholar
  • 3a Pesson M. Antoine M. Benichon J.-L. de Lajudie P. Horvath E. Leriche B. Patte S. Eur. J. Med. Chem.  1980,  15:  269 
    CrossrefGoogle Scholar
  • 3b Huang JJ. J. Org. Chem.  1985,  50:  2293 
    CrossrefGoogle Scholar
  • 3c Taylor EC. McDaniel KF. Warner JC. Tetrahedron Lett.  1987,  28:  1977 
    CrossrefGoogle Scholar
  • 3d Piazza GA, and Pamukcu R. inventors; Am. Pat. Appl.  US6060477.  ; Chem. Abstr. 2000, 132, 321870
    Crossref
  • 4a Jonckers THM. Maes BUW. Lemière GLF. Dommisse R. Tetrahedron  2001,  57:  7027 
    CrossrefGoogle Scholar
  • 4b Komrlj J. Maes BUW. Lemière GLF. Haemers A. Synlett  2000,  1581 
    CrossrefGoogle Scholar
  • 4c De Riccardis F. Johnson F. Org. Lett.  2000,  2:  293 
    CrossrefGoogle Scholar
  • 4d Schoffers E. Olsen PD. Means JC. Org. Lett.  2001,  3:  4221 
    CrossrefGoogle Scholar
  • 4e Yin J. Zhao MM. Huffman MA. McNamara JM. Org. Lett.  2002,  4:  3481 
    CrossrefGoogle Scholar
  • 5 Garnier E. Audoux J. Pasquinet E. Suzenet F. Poullain D. Lebret B. Guillaumet G. J. Org. Chem.  2004,  69:  7809 
    CrossrefGoogle Scholar
  • For reviews about metal-catalyzed C-N bond formation, see:
  • 6a Culkin DA. Hartwig JF. Acc. Chem. Res.  2003,  36:  234 
    CrossrefGoogle Scholar
  • 6b Baranano D. Mann G. Hartwig JF. Curr. Org. Chem.  1997,  1:  287 
    CrossrefGoogle Scholar
  • 6c Muci AR. Buchwald SL. Cross-Coupling Reactions, In Topics in Current Chemistry   Vol. 219:  Springer-Verlag; Berlin / Heideberg: 2002.  p.131 
    CrossrefGoogle Scholar
  • 6d Wolfe JP. Wagaw S. Marcoux J.-F. Buchwald SL. Acc. Chem. Res.  1998,  31:  805 
    CrossrefGoogle Scholar
  • 7 For chemical shift assignment, see: Martin ML. Gouesnard J.-P. In 15 N-NMR Spectrometry   Diehl P. Fluck E. Kosfeld R. Springer-Verlag; New York: 1981.  p.4 
    Google Scholar
  • 8 Garratt PJ. Comprehensive Chemistry II   Vol. 4:  Katritzky AR. Rees CW. Scriven EFW. Pergamon Press; Oxford UK: 1996.  p.127 
    Google Scholar
9

Typical Procedure for the Pd-Catalyzed N-Arylation Cyclization. A three-necked flask was flushed with N2 and charged with xantphos (20 mol%) and dry dioxane (5 mL). After degassing, Pd(OAc)2 (10 mol%) was added and the mixture was stirred under N2 for 10 min. In another three-necked round-bottom flask, compound 1 (0.100 g, 1.0 equiv), heteroarylamine (1.2 equiv) and K2CO3 (20 equiv) were poured into dry dioxane (7 mL). Then, the Pd(OAc)2/xantphos solution was added via cannula. The resulting mixture was subsequently heated to reflux and vigorously stirred until 1 has disappeared. After cooling down, the solid material was filtered off and washed with CH2Cl2 (20 mL) and MeOH (20 mL). The solvent was evaporated and the resulting crude product was purified by flash column chromatography using CH2Cl2-MeOH (99:1 v/v) as eluent.
Characterization of Compounds 3a and 3b.
Compound 3a: 1H NMR (200 MHz, DMSO): δ = 2.10 (s, 3 H, CH3), 11.97 (br s, 1 H, NH) ppm. 13C NMR (50 MHz, DMSO): δ = 13.1 (CH3), 144.8 (C10a), 153.7 (C5a), 154.1 (C10), 154.6 (C4a), 165.5 (C7), 178.1 (C3) ppm. 15N NMR (30 MHz, DMSO): δ = -296, -258 (NH), -133, -154, -54, -49, 5, 12 (NO2) ppm. IR: ν = 3223, 2975, 1652, 1521, 1352, 1023 cm-1. MS: m/z = 281 [M + 1]. Anal. Calcd for C7H4N8O3S: C, 30.00; H, 1.44; N, 39.99. Found: C, 30.11; H, 1.48; N, 40.05.
Compound 3b: 1H NMR (200 MHz, DMSO): δ = 1.30 (t, J = 8.1 Hz, 3 H, CH3), 2.37 (s, 3 H, SCH3), 4.14 (q, J = 8.1 Hz, 2 H, CH2), 7.03 (dd, J 2 ′,4 ′ = 1.1 Hz, J 3 ′,4 ′ = 7.4 Hz, 1 H, H4 ′), 7.43 (dd, J 2 ′,3 ′ = 7.9 Hz, J 3 ′,4 ′ = 7.4 Hz, 2 H, H3 ′ and H5 ′), 7.93 (dd, J 2 ′,4 ′ = 1.1 Hz, J 2 ′,3 ′ = 7.9 Hz, 2 H, H2 ′ and H6 ′), 11.43 (br s, 1 H, NH) ppm. 13C NMR (50 MHz, DMSO): δ = 12.1 (CH3), 14.07 (CH3), 62.0 (CH2), 122.9 (C4 ′), 123.5 (C2 ′ and C6 ′), 126.6 (C3 ′ and C5 ′), 140.5 (C6), 149.4 (C1 ′), 155.6 (C5), 163.8 (C=O), 188.1 (C3) ppm. IR: ν = 3188, 2932, 1726, 1663 cm-1. MS: m/z = 291 [M + 1]; mp 85-87 °C. Anal. Calcd for C13H14N4O2S: C, 53.78; H, 4.86; N, 19.30. Found: C, 54.01; H, 4.54; N, 19.12.