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http://dx.doi.org/10.5012/bkcs.2002.23.10.1445

Correlation of Rates of Solvolysis of Phenyl Chlorodithioformate  

An, Sun-Kyoung (Department of Chemical Education, Gyeongsang National University)
Yang, Jin-Soon (Department of Chemical Education, Gyeongsang National University)
Cho, Jun-Mi (Department of Chemical Education, Gyeongsang National University)
Yang, Ki-yull (Department of Chemical Education, Gyeongsang National University)
Lee, Jong-Pal (Department of Chemistry, Dong-A University)
Bentley, T.W. (Department of Chemistry, University of Wales)
Lee, Ik-choon (Department of Chemistry, Inha University)
Koo, In-Sun (Department of Chemical Education, Gyeongsang National University)
Publication Information
Bulletin of the Korean Chemical Society / v.23, no.10, 2002 , pp. 1445-1450 More about this Journal
Abstract
Solvolytic rate constants at 25 $^{\circ}C$ are reported for solvolysis of chlorodithioformate (1) in binary mixtures of water with acetone, ethanol, methanol, methanol-d, 50%methanol-d/50%D2O, and 2,2,2-trifluroethanol (TFE), and also in TFE-ethanol mixtures. The Grunwald-Winstein plot shows that the three aqueous mixtures exhibit dispersions into separate line. The correlation is improved only slightly by additional parameters NT for solvent nucleophilicity and/or I for aromatic ring parameter. Rate ratios in solvents of the same $Y_cl$ value, having different nucleophilicity provide measures of the minimum extent of nucleophilic solvent assistance, and the value of 3.35 for $[$k_{40EW}$/$k_97TFE$]_Y$ (EW = ethanol-water), is consistent with an essentially SN1 reaction mechanism. This study has shown that the magnitude of l, m and h values associated with a change of solvent composition is able to predict the SN1 reaction mechanism. log(k/$k_o$) = mY + lN + hI
Keywords
Chlorodithioformate;
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