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

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 S_NVin 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

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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 pm^³. The structure was solved by direct methods (SHELXS-97)^¹0a using 3704 independent reflections. Structure refinement: full matrix least-squares methods on F^² using SHELXL-97^¹0b 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: [phone], e-mail: [e-mail]].