Kinetics and mechanism of the aminolysis of aryl propanedithioates in acetonitrile?
New Journal of Chemistry Pub Date: 2000-12-22 DOI: 10.1039/B006974O
Abstract
The kinetics and mechanism of the aminolysis of aryl proanedithioates with benzylamines are investigated in acetonitrile at ?35.0?°C. A large magnitude of the Hammett (ρX and ρZ) and Br?nsted (βX and βZ) coefficients and exceptionally large cross-interaction constant ρXZ(=?3.5) are consistent with a stepwise mechanism in which leaving group expulsion from an intermediate, T±, is the rate-determining step. The faster rates observed for dithio esters (II) than for thio esters (I), and the validity of the reactivity-selectivity principle (RSP) are also in line with the mechanism proposed. The kH/kD values (=?1.0–1.8) determined with deuterated benzylamines (XC6H4CH2ND2) and the activation parameters, ΔH≠(??8 kcal mol?1) and ΔS≠(=? ?16 to ?23 e.u.), suggest that proton transfer occurs concurrently with leaving group departure in the transition state.
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Journal Name：New Journal of Chemistry
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CAS no.: 89640-58-4
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