Activation and reaction volumes of the reactions of <Emphasis Type="Italic">o</Emphasis>-and <Emphasis Type="Italic">p</Emphasis>-nitrophenylsulfenyl chlorides with styrene and cyclohexene in some solvents |
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Authors: | V D Kiselev E A Kashaeva L N Potapova A I Konovalov |
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Institution: | (1) A. M. Butlerov Chemical Institute, Kazan State University, 18 ul. Kremlevskaya, 420008 Kazan, Russian Federation |
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Abstract: | The effect of hydrostatic pressure below 1000 kg cm−2 on the rate of reactions of o-and p-nitrophenylsulfenyl chlorides with styrene and cyclohexene was studied. The activation and reaction volumes (cm3 mol−1) for the reactions of o-nitrophenylsulfenyl chloride with styrene in acetonitrile (−23.1 and −23.6), 1,2-dichloroethane (−29.2 and −24.7), chlorobenzene
(no, −20.2), and anisole (−25.1 and −21.2) and for the reaction of p-nitrophenylsulfenyl chloride with styrene in carbon tetrachloride (−39.5±1.5 and −22.0) were determined. In carbon tetrachloride
the activation volumes for the reactions of cyclohexene with o-and p-nitrophenylsulfenyl chlorides (−37.7±2.0 and −40.9±1.2 cm3 mol−1, respectively) are almost the same and coincide with the data for the reactions with styrene. The considerable decrease in
the volume of the transition state in the nonpolar solvent is considered as a consequence of the enhanced electrostriction
of carbon tetrachloride in the solvate sphere of the transition state of the reaction, which excludes the nonpolar transition
state of the sulfuran type.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 477–480, March, 2007. |
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Keywords: | o-nitrophenylsulfenyl chloride styrene activation volumes reaction volumes solvent effect mechanism |
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