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Bulletin of the Korean Chemical Society (BKCS)

ISSN 0253-2964(Print)
ISSN 1229-5949(Online)
Volume 23, Number 10
BKCSDE 23(10)
October 20, 2002 

 
Title
Correlation of the Rates of Solvolysis of Phenyl Chlorodithioformate
Author
Sun Kyoung An, Jin Soon Yang, Jun Mi Cho, Kiyull Yang, Jong Pal Lee, T. W. Bentley, Ikchoon Lee, In Sun Koo
Keywords
Chlorodithioformate, Ionizing power, Nucleophilicity, Solvolysis
Abstract
Solvolytic rate constants at 25 ℃ 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 YCl value, having different nucleophilicity provide measures of the minimum extent of nucleophilic solvent assistance, and the value of 3.35 for [k40EW/k97TFE]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/ko) = mY + lN + hI
Page
1445 - 1450
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