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Synthesis 2008(16): 2575-2581  
DOI: 10.1055/s-2008-1067207
PAPER
© Georg Thieme Verlag Stuttgart ˙ New York

Chemistry of Halonitroethenes, 1: First Synthesis of Functionalized 3-Chloroquinoxalin-2(1H)-one 4-Oxides

Christian Meyera, Viktor A. Zapol’skiia, Arnold E. W. Adamb, Dieter E. Kaufmann*a
a Institut für Organische Chemie, TU Clausthal, Leibnizstr. 6, 38678 Clausthal-Zellerfeld, Germany
Fax: +49(5323)722834; e-Mail: dieter.kaufmann@tu-clausthal.de;
b Institut für Anorganische und Analytische Chemie, TU Clausthal, Paul-Ernst-Str. 4, 38678 Clausthal-Zellerfeld, Germany
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Publication History

Received 29 February 2008
Publication Date:
30 July 2008 (online)

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Abstract

A one-pot annulation reaction of aniline and its ring-substituted derivatives with 1,1,2-trichloro-2-nitroethene (TCNiE) was developed delivering 3-chloroquinoxalin-2(1H)-one 4-oxides, exclusively, in good yields. The structure was proved by X-ray analysis. The C-N cyclization, a competing reaction to the double SNVin reaction of 1,1,2-trichloro-2-nitroethene with amines, can be controlled by the mode of addition. Some of the resulting quinoxalin­ones are promising candidates with respect to their prospective biological, especially pharmacological, activity.

Key words

annulation - C-N coupling - amines - halides - nitro compounds - nitrones - quinoxalinones

    References

  • 1a Kaberdin RV. Potkin VI. Zapol’skii VA. Russ. Chem. Rev. (Engl. Transl.)  1997,  66:  827 
    Google Scholar
  • 1b Potkin VI. Zapol’skii VA. Knizhnikov VA. Kaberdin RV. Yanuchok AA. Petkevich SK. Russ. J. Org. Chem. (Engl. Transl.)  2001,  37:  727 
    Google Scholar
  • 2a Zapol’skii VA. Namyslo JC. Adam AEW. Kaufmann DE. Heterocycles  2004,  1281 
    Google Scholar
  • 2b Zapol’skii VA. Namyslo JC. Blaschkowski B. Kaufmann DE. Synlett  2006,  3464 
    Google Scholar
  • 2c Zapol’skii VA. Namyslo JC. Gjikaj M. Kaufmann DE. ARKIVOC  2007,  i:  76 ; http://www.arkat-usa.org/home
    Google Scholar
  • 2d Zapol’skii VA. Namyslo JC. Gjikaj M. Kaufmann DE. Synlett  2007,  1507 
    Google Scholar
  • 2e Zapol’skii VA. Namyslo JC. Altug C. Gjikaj M. Kaufmann DE. Synthesis  2008,  304 
    Google Scholar
  • 3a Li Z, Qian X, Shao X, Xu X, Tian Z, and Huang Q. inventors; WO  2007,101,369. 
  • 3b Volynskii VE. Sopova AS. J. Org. Chem. USSR (Engl. Transl.)  1982,  2215 
    Google Scholar
  • 3c Wilkendorf R. Trenel M. Ber. Dtsch. Chem. Ges.  1924,  306 
    Google Scholar
  • 3d Eremenko LT. Oreshko GV. Bull. Acad. Sci. USSR, Div. Chem. Sci. (Engl. Transl.)  1969,  660 
    Google Scholar
  • 3e Ott E. Bossaller W. Ber. Dtsch. Chem. Ges.  1943,  88 
    Google Scholar
  • 3f Nef JU. Justus Liebigs Ann. Chem.  1901,  50:  1 
    Google Scholar
  • 3g Biltz H. Ber. Dtsch. Chem. Ges.  1897,  1206 
    Google Scholar
  • 3h Kaberdin RV. Nikolaeva EE. Potkin VI. Ol’dekop YA. J. Org. Chem. USSR (Engl. Transl.)  1990,  1918 
    Google Scholar
  • 3i Buevich VA. Grineva VS. Perekalin VV. J. Org. Chem. USSR (Engl. Transl.)  1971,  2723 
    Google Scholar
  • 3j Jia Z. Yao C. Jingxi Huagong Zhongjianti  2004,  26 
    Google Scholar
  • 3k Scribner RM. J. Org. Chem.  1965,  30:  3657 
    Google Scholar
  • 4 Johnston H. inventors; US  3,054,828.  ; Chem. Abstr. 1963, 58, 20392
  • 5 Barrett AG. Chem. Soc. Rev.  1991,  20:  95 
    CrossrefGoogle Scholar
  • 6a Buevich VA. Rudchenko VV. Grineva VS. Perekalin VV. J. Org. Chem. USSR (Engl. Transl.)  1978,  2031 
    Google Scholar
  • 6b Tiemann CH, Kollmeyer WD, and Roman SA. inventors; US  3,971,774.  ; Chem. Abstr. 1976, 86, 5460
  • 6c Buevich VA. Nakova NZ. Kempter G. Perekalin VV. J. Org. Chem. USSR (Engl. Transl.)  1977,  2430 
    Google Scholar
  • 7a Buevich VA. Rudchenko VV. Perekalin VV. Chem. Heterocycl. Compd. (Engl. Transl.)  1976,  1185 ; Chem. Abstr. 1977, 86, 72357
    Google Scholar
  • 7b Buevich VA. Deiko LI. Volynskii VE. J. Org. Chem. USSR (Engl. Transl.)  1980,  2055 
    Google Scholar
  • 8 Francotte E. Verbruggen R. Viehe HG. van Meerssche M. Germain G. Declercq JP. Bull. Soc. Chim. Belg.  1978,  693 
    Google Scholar
  • 10a Sheldrick GM. SHELXS-97   University of Göttingen; Germany: 1997. 
    Google Scholar
  • 10b Sheldrick GM. SHELXL-97   University of Göttingen; Germany: 1997. 
    Google Scholar
  • 11 Krowczynski A. Kozerski L. Bull. Pol. Acad. Sci., Ser. Sci. Chim.  1986,  341 
    Google Scholar
  • 12a Brown DJ. The Quinoxalines: Supplement II, In The Chemistry of Heterocyclic Compounds   Vol. 61:  Taylor EC. Wipf P. John Wiley & Sons; New York: 2004. 
    Google Scholar
  • 12b Tennant G. J. Chem. Soc.  1964,  2666 
    Google Scholar
  • 12c Toman J. Klicnar J. Collect. Czech. Chem. Commun.  1984,  976 
    Google Scholar
  • 12d Romanenko VD. Kul’chitskaya NE. Burmistrov SI. J. Org. Chem. USSR (Engl. Transl.)  1972,  669 
    Google Scholar
  • 12e Argilagos DM. Linden A. Heimgärtner H. Helv. Chim. Acta  1999,  82:  238 
    Google Scholar
  • 13a Awad I. Hassan K. Collect. Czech. Chem. Commun.  1990,  2715 
    Google Scholar
  • 13b Mashkovski MD. Lekarstvennye sredstva   Gamta; Vilnius: 1993. 
    Google Scholar
  • 13c Gazit A. App H. McMahon G. Chen J. Levitzki A. Bohmer FD. J. Med. Chem.  1996,  39:  2170 
    Google Scholar
  • 13d Carta A. Paglietti G. Nikookar MER. Sanna P. Sechi L. Zanetti S. Eur. J. Med. Chem.  2002,  37:  355 
    Google Scholar
  • 13e Carta A. Loriga M. Zanetti S. Sechi LA. Farmaco  2003,  58:  1251 
    Google Scholar
  • 13f Loev B. Musser JH. Brown RE. Jones H. Kahen R. Huang F.-C. Khandwala A. Sonnino-Goldman P. Leibowitz M. J. Med. Chem.  1985,  28:  363 
    Google Scholar
  • 13g Zarranz B. Jaso A. Aldana I. Monge A. Maurel S. Deharo E. Jullioan V. Sauvain M. Drug Res.  2005,  55:  754 
    Google Scholar
9

X-ray crystallographic analysis of C21H32N2O3S was performed at 223(2) K by using a STOE IPDS II diffractometer with MoKα radiation (λ = 0.71073 Å) and a graphite monochromator. Crystal system: triclinic, P1 (No. 2), Z = 1, a = 632.32(13) pm, b = 900.7(2) pm, c = 1935.2(4) pm, α = 84.236(19), β = 83.827(17), γ = 77.126(18), VEZ = 1064.9(4) 106 pm³. The structure was solved by direct methods (SHELXS-97)¹0a using 3704 independent reflections. Structure refinement: full matrix least-squares methods on F² using SHELXL-97¹0b all nonhydrogen atoms with anisotropic displacement parameters. All hydrogen atoms were taken from a difference Fourier synthesis and were isotropically refined. The refinement converged to a final wR2 = 0.1223 for 3704 unique reflections and R1 = 0.0540 for 2420 observed reflections [I 0 > 2σ(I 0)] and 373 refined parameters with a goodness-of-fit of 1.053. Crystallographic data have been deposited with the Cambridge Crystallographic Data Centre as supplementary publication no. CCDC-679570. Copies of the data can be obtained free of charge on application to CCDC, 12 Union Road, Cambridge CB2 1EZ, UK [fax: +44(1223)336033, e-mail: deposit@ccdc.cam.ac.uk].