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
Further Information

Publication History

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

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.

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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].