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Correlation of Rates of Solvolysis of Phenyl Chlorodithioformate
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  • Correlation of Rates of Solvolysis of Phenyl Chlorodithioformate
  • Correlation of Rates of Solvolysis of Phenyl Chlorodithioformate
저자명
An. Sun-Kyoung,Yang. Jin-Soon,Cho. Jun-Mi,Yang. Ki-yull,Lee. Jong-Pal,Bentley. T.W.,Lee. Ik-choon,Koo. In-Sun
간행물명
Bulletin of the Korean Chemical Society
권/호정보
2002년|23권 10호|pp.1445-1450 (6 pages)
발행정보
대한화학회
파일정보
정기간행물|ENG|
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이 논문은 한국과학기술정보연구원과 논문 연계를 통해 무료로 제공되는 원문입니다.
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기타언어초록

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$]_Y$</TEX> (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