Abstract
AbstractVarious tert‐butyl perbenzoates were prepared according to the known methods. The mixtures of tert‐butyl perbenzoate and dimethyl sulfide underwent thermolysis at several temperatures (T °C: 80, 90, 100, and 110). The rates of consumption of the peresters (kobs) were obtained from ln C0/Ct = kobs × t where C0 and Ct are the concentration of the perester at time 0 and t, respectively. For example: The decrease of the perester satisfied pseudo first order kinetics, and kobswere determined. kHom. and kET were obtained from kobs = kHom. + kET[CH3SCH3] where [CH3SCH3]/[perester] > 10. kET and its relative rates are produced from plot of kobs against [CH3SCH3]. Hammett correlation are plotted against σ and σ+ in which σ is better correlated than σ+. Hammett ρ could be considered selectivity which stays constant irrespective of temperature. The phenomenon is not consistent with reactivity/selectivity principle. The differential activation entropies linearly increase with substituent constant σ to give slope of 2.63 while the similar slope for differential enthalpies shows much lower value of 0.892. The dominance of differential entropic terms clearly indicates the entropy control of the rates. Copyright © 2006 John Wiley & Sons, Ltd.
Sign-in/Register to access full text options 
Talk to us
Join us for a 30 min session where you can share your feedback and ask us any queries you have
Schedule a callDisclaimer: All third-party content on this website/platform is and will remain the property of their respective owners and is provided on "as is" basis without any warranties, express or implied. Use of third-party content does not indicate any affiliation, sponsorship with or endorsement by them. Any references to third-party content is to identify the corresponding services and shall be considered fair use under The CopyrightLaw.
