Abstract
N-(2,2-Dichloro-2-phenylethylidene)arenesulfonamides were synthesized by a modified procedure, and their reactions with secondary amines were studied for the first time. Reactions of imines with dialkylamines proceed at room temperature to afford α,α-dichloromethylbenzene and N,N-dialkyl-N′-(arenesulfonyl)formamidines arising from the haloform cleavage of the initially formed unstable N-(1-dialkylamino-2,2-dichloro-2-phenylethyl)arenesulfonamides. When the reaction is carried out upon cooling to 0°C, the products of the nucleophilic addition of secondary amines to azomethines, N-(1-dialkylamino-2,2-dichloro-2-phenylethyl) are formed in yields of no higher than 5%. Nonempirical calculations of 13C-1H spin-spin coupling constants and their experimental measurements for the series of the synthesized N-arenesulfonamides were performed to show that these compounds exist in solutions exclusively as E isomers. Preferable conformations of the investigated compounds and the relative energies of their E and Z isomers in the gas phase were determined by quantum-chemical calculations at the MP2/6-311G** level of theory. The NMR spectral data revealed restricted rotation of the N,N-dialkylamino group about the partially double C-NAlk2 bond in the molecules of N-arenesulfonylformamidines.
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Original Russian Text © I.B. Rozentsveig, G.N. Rozentsveig, A.N. Mirskova, K.A. Chernyshev, L.B. Krivdin, G.G. Levkovskaya, 2008, published in Zhurnal Obshchei Khimii, 2008, Vol. 78, No. 7, pp. 1135–1143.
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Rozentsveig, I.B., Rozentsveig, G.N., Mirskova, A.N. et al. N-(2,2-Dichloro-2-phenylethylidene)arenesulfonamides in reactions with secondary amines. Russ J Gen Chem 78, 1371–1379 (2008). https://doi.org/10.1134/S1070363208070141
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DOI: https://doi.org/10.1134/S1070363208070141