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Solvation and Conformational Effects in Heterolysis of 1-Methylcycloalkyl Halides

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Abstract

In the series of substrates 1-bromo-1-methylcyclopentane, 1-bromo-1-methylcyclohexane, 1-methyl-1-chlorocyclopentane, 1-methyl-1-chlorocyclohexane, the heterolysis rate in acetone at 25 °C is reduced by four orders of magnitude; v = k[RX], E1 mechanism. The decrease in reaction rate as we go from a cyclopentyl compound to a cyclohexyl compound is due to the decrease in entropy of activation as a result of rapid solvation of the transition state as the conformational barrier is overcome.

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Authors and Affiliations

  1. National Technical University of Ukraine "Kyiv Polytechnical Institute,", 37 Peremogy Prospekt, 03056, Kyiv, Ukraine

    G. F. Dvorko, I. V. Koshchii & É. A. Ponomareva

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  1. G. F. Dvorko
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  2. I. V. Koshchii
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  3. É. A. Ponomareva
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Dvorko, G.F., Koshchii, I.V. & Ponomareva, É.A. Solvation and Conformational Effects in Heterolysis of 1-Methylcycloalkyl Halides. Theoretical and Experimental Chemistry 39, 99–103 (2003). https://doi.org/10.1023/A:1024025708837

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  • DOI: https://doi.org/10.1023/A:1024025708837

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