A combined experimental and density functional study of 1‐(arylsulfonyl)‐2‐R‐4‐chloro‐2‐butenes reactivity towards the allylic chlorine |
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Authors: | Sergey V Bondarchuk Victor V Smalius Boris F Minaev |
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Institution: | 1. Department of Organic Chemistry, Bogdan Khmelnitsky Cherkasy National University, Cherkasy, Ukraine;2. Department of Theoretical Chemistry and Biochemistry, Royal Institute of Technology, AlbaNova, Stockholm, Sweden |
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Abstract: | Nucleophilic substitution and dehydrochlorination reactions of a number of the ring‐substituted 1‐(arylsulfonyl)‐2‐R‐4‐chloro‐2‐butenes are studied both experimentally and theoretically. The developed synthetic procedures are characterized by a general rapidity, cheapness, and simplicity providing moderate to high yields of 1‐arylsulfonyl 1,3‐butadienes (48–95%), 1‐(arylsulfonyl)‐2‐R‐4‐(N,N‐dialkylamino)‐2‐butenes (31–53%), 1‐(arylsulfonyl)‐2‐R‐2‐buten‐4‐ols (37–61%), and bis4‐(arylsulfonyl)‐3‐R‐but‐2‐enyl]sulfides (40–70%). The density functional theory B3LYP/6‐311++G(2d,2p) calculations of the intermediate allylic cations in acetone revealed their high stability occurring from a resonance stabilization and hyperconjugation by the SO2Ar group. The reactivity parameters estimated at the bond critical points of the diene/allylic moiety display a high correlation (R2 > 0.97) with the Hammett (σp) constants. 1‐Arylsulfonyl 1,3‐butadienes are characterized by a partly broken π conjugated system, which follows from analysis of the two‐centered delocalization (δ) and localization (λ) index values. The highest occupied molecular orbital energies of 1‐arylsulfonyl 1,3‐butadienes are lower than those of 1,3‐butadiene explaining their low reactivity towards the Diels–Alder condensation. Copyright © 2015 John Wiley & Sons, Ltd. |
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Keywords: | 1‐(arylsulfonyl)‐2‐R‐4‐chloro‐2‐butenes 1‐arylsulfonyl 1 3‐dienes conceptual density functional theory electrophile‐nucleophile interactions quantum theory of atoms in molecules |
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