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Synthesis 2006(17): 2927-2933  
DOI: 10.1055/s-2006-950187
PAPER
© Georg Thieme Verlag Stuttgart · New York

Chemistry of Polyhalogenated Nitrobutadienes, 2: Synthesis of N-Tetrachloro­allylidene-N′-arylhydrazines by a Formal Synproportionation Reaction

Viktor A. Zapol’skiia, Eva Nutza, Jan C. Namysloa, Arnold E. W. Adamb, Dieter E. Kaufmann*a
a Institut für Organische Chemie der 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 der TU Clausthal, Paul-Ernst-Str. 4, 38678 Clausthal-Zellerfeld, Germany
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Publication History

Received 3 March 2006
Publication Date:
15 August 2006 (online)

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Abstract

The reaction of 2-nitropentachlorobuta-1,3-diene with a variety of anilines substituted with electron-withdrawing groups generates, contrary to expectations, N-tetrachloroallylidene-N′-arylhydrazines instead of 1,1-bisaminated substitution products. The imidoyl-type chlorides are capable of undergoing nucleophilic substitution with amines or hydrides. The resulting compounds should exhibit physiological activity, especially for use in crop science.

Key words

nitro compounds - halides - hydrazones - N-N couplings - nucleophilic substitutions

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6

X-ray crystallographic analysis of C10H7Cl4N3O2 was performed at 223 (2) K by using a STOE IPDS II diffractometer with Mo Kα radiation (λ= 0.71073 Å) and a graphite monochromator. Crystal system: orthorhombic, SG Pbca (No. 61), Z = 8, a = 738.22 (9) pm, b = 1551.6 (3) pm, c = 2399.4 (3) pm, VEZ = 2748.3 (7) 106 pm3. The structure was solved by direct methods (SHELXS-97 [7a] ) using 2093 independent reflections. Structure refinement: full matrix least-squares methods on F2 using SHELXL-97 [7b] all non-hydrogen 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 = 0.0878 for 2093 unique reflections and R1 = 0.0429 for 1563 observed reflections [I0 > 2s(I0)] and 200 refined parameters with a goodness-of-fit of 1.052. Crystallographic data have been deposited with the Cambridge Crystallographic Data Centre as supplementary publication no. CCDC-245642. 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]