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Correlation of the Rates of Solvolyses of 4-Methylthiophene-2-carbonyl Chloride Using the Extended Grunwald-Winstein Equation

  • Choi, Ho-June (Department of Chemistry, Research Instituted of Natural Science, Gyeongsang National University) ;
  • Koo, In-Sun (Department of Chemistry Education, and Research Instituted of Natural Science, Gyeongsang National University)
  • Received : 2011.11.10
  • Accepted : 2011.12.06
  • Published : 2012.02.20
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Abstract

The specific rates of sovolysis of 4-methylthiophene-2-carbonyl chloride (1) have been determined in 26 pure and binary solvents at $25.0^{\circ}C$. Product selectivities are reported for solvolyses of 1 in aqueous ethanol and methanol binary mixtures. Comparison of the specific rates of solvolyses of 1 with those for p-methoxybenzoyl chloride (2) in terms of linear free energy relationships (LFER) are helpful in mechanistic considerations, as is also treatment in terms of the extended Grunwald-Winstein equation. It is proposed that the solvolyses of 1 in binary aqueous solvent mixtures proceed through an SN1 and/or ionization (I) pathway rather than through an associative $S_N2$ and/or addition-elimination (A-E) pathway.

Keywords

References

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