76542-11-5Relevant academic research and scientific papers
Rapid and convenient thioester synthesis under phase-transfer catalysis conditions
Simion, Cristian,Hashimoto, Iwao,Mitoma, Yoshiharu,Simion, Alina Marieta,Egashira, Naoyoshi
experimental part, p. 2480 - 2488 (2011/02/23)
Various thioesters were obtained through an efficient phase-transfer catalysis method, by treating several thiophenols with different acyl chlorides, in a biphasic system composed of 10% aqueous NaOH and dichloromethane in the presence of tetrabutylammonium chloride. The thiolation reaction was complete in only 5 minutes, at 0C. Taylor & Francis Group, LLC.
Kinetics and mechanism of the aminolysis of aryl propanedithioates in acetonitrile
Hyuck Keun Oh,Sun Kyung Kim,Hai Whang Lee,Lee
, p. 313 - 317 (2007/10/03)
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 Broensted (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 (I1) 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.
