SN2 Type Hydrolysis of Secondary Alkyl Halides and Sulfonates in Hydrothermal Water

2004 ◽  
Vol 33 (7) ◽  
pp. 864-865 ◽  
Author(s):  
Yuki Yamasaki ◽  
Takaharu Hirayama ◽  
Koichiro Oshima ◽  
Seijiro Matsubara
Keyword(s):  
Alkyl Halides ◽  
Hydrolysis Of ◽  
Hydrothermal Water

SN2 Type Hydrolysis of Secondary Alkyl Halides and Sulfonates in Hydrothermal Water.

ChemInform ◽  
2004 ◽  
Vol 35 (46) ◽  
Author(s):  
Yuki Yamasaki ◽  
Takaharu Hirayama ◽  
Koichiro Oshima ◽  
Seijiro Matsubara
Keyword(s):  
Alkyl Halides ◽  
Hydrolysis Of ◽  
Hydrothermal Water

The Mechanism for Hydrolysis of Primary Alkyl Chlorosulfates in Water. The Kinetic Solvent Isotope Effect and the Secondary Deuterium Isotope Effect

1972 ◽  
Vol 50 (3) ◽  
pp. 434-437 ◽  
Author(s):  
E. C. F. Ko ◽  
R. E. Robertson
Keyword(s):  
Isotope Effect ◽  
Sulfonyl Chloride ◽  
Alkyl Halides ◽  
Activation Process ◽  
Deuterium Isotope Effect ◽  
Solvent Isotope Effect ◽  
Temperature Coefficients ◽  
Enthalpy Of Activation ◽  
Solvent Isotope ◽  
Hydrolysis Of

The temperature coefficients of the enthalpy of activation [Formula: see text] for the hydrolysis of the three chlorosulfates, methyl, ethyl, and β-chloro, are shown to have values of −50,−55, and −60 cal deg−1 mol−1; values in the same range as previously reported for the hydrolysis of the sulfonyl chlorides. The corresponding value for the β-methoxy isomer was −40 cal deg−1 mol−1, about the same as found for the p-methoxybenzenesulfonyl chloride. The kinetic solvent isotope effect, however, was significantly lower than reported for the sulfonyl chloride series, being about the same as found for the hydrolysis of the alkyl halides. While some degree of nucleophilic overlap is probably required in the activation process, the requirement here is reduced to about the same level as that for the primary halides, and there is no need to postulate a different mechanism on passing from the methyl to the ethyl member of the series, confirming the earlier conclusion of Buncel and Millington.

SOLVOLYSIS IN HYDROGEN AND DEUTERIUM OXIDE: III. ALKYL HALIDES

1959 ◽  
Vol 37 (9) ◽  
pp. 1491-1497 ◽  
Author(s):  
P. M. Laughton ◽  
R. E. Robertson
Keyword(s):  
Isotope Effect ◽  
Relative Stability ◽  
Rate Ratio ◽  
Deuterium Oxide ◽  
Pure Water ◽  
Relative Viscosity ◽  
Solvation Shell ◽  
Alkyl Halides ◽  
Kinetic Isotope ◽  
Hydrolysis Of

Rate data for the hydrolysis of a series of α- and β-methylated allyl, benzyl, and cycloalkyl halides in light and heavy water are compared. The major factor determining the rate ratio [Formula: see text] appears to be the relative stability of the initial solvation shell. When the relative viscosity of H2O and D2O is used as a measure of the relative stability of structure in bulk solvent, the observed kinetic isotope effect and the temperature dependence of the isotope effect can be rationalized in terms of accepted properties of aqueous solutions.Attention is drawn to the anomalous rate ratio kRBr/kRI > 1 which appears to be characteristic of solvolysis of these alkyl halides in pure water in contrast to other media.

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