Structure, Synthesis, and Properties of Some Persubstituted 1,2‐Dintroethanes. In Quest of Nitrocyclopropyl‐Anion Derivatives
摘要：
Attempts to deprotonate nitrocyclopropane led to solutions which showed strong ESR. signals (Fig. 1)and from which 1-nitro- l′-nitroso-bicyclopropyl (3) and 1,1′-dinitro-bicyclopropyl (2) were isolated. The activation energy for rotation about the central C, C-bond of 2 is estimated to be about 12 kcal/mol (1 H-NMR. spectra in Fig. 2). In contrast, the oven-chain analogue 2,3-dimethyl-2,3-dinitrobutane (1) shows a methyl singlet down to 70° C. Low-temperature X-ray analyses of 1, 2, 3, and also of 1,1′-dinitro-bicyclobutyl (4) show that all four molecules have gauche-conformations but reveal striking structural differences between the openchain and the cyclic derivatives (Fig. 4–6): the central C, C-bond is long in 1 (1.575 A), short in 2 (1.479 A); the C, N-bonds are long in 1 (1.549 A), short in 2 (1.488 A); the orientation of the nitro groups is bisected in 2 and perpendicular in 1. The crystal structure of the nitro-nitroso compound 3 is isomorphous with that of the dinitro compound 2 and thus disordered (Fig. 15–16). The effect of the nitro group as π-electron acceptor on the molecular conformations and bond lengths is discussed. From analysis of the anisotropic vibrational parameters of 2 the root-mean-square librational amplitude of the nitro groups about their C, N-bonds is estimated to be about 5.8° at 95 K, corresponding to a rotational barrier of about 9 kcal/mol, i. e. the same order of magnitude as the NMR. estimate of about 12 kcal/mol for C, C-rotation.
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DOI：
10.1002/HLCA.19820650114
年份：
1982
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