Transition state enthalpies of transfer in aqueous dimethyl sulfoxide solutions. Alkaline hydrolysis of ethyl acetate

1974 ◽  
Vol 78 (15) ◽  
pp. 1509-1511 ◽  
Author(s):  
Richard Fuchs ◽  
C. Patrick Hagan ◽  
Randolph F. Rodewald
Keyword(s):  
Transition State ◽  
Ethyl Acetate ◽  
Dimethyl Sulfoxide ◽  
Alkaline Hydrolysis ◽  
Enthalpies Of Transfer ◽  
Hydrolysis Of

The Alkaline Hydrolysis of Ethyl Acetate from the Standpoint of Ion-Dipole Theory

1949 ◽  
Vol 71 (6) ◽  
pp. 2112-2116 ◽  
Author(s):  
James Edward. Potts ◽  
Edward S. Amis
Keyword(s):  
Ethyl Acetate ◽  
Alkaline Hydrolysis ◽  
Hydrolysis Of

Effect of Medium on Reactivity for Alkaline Hydrolysis of p-Nitrophenyl Acetate and S-p-Nitrophenyl Thioacetate in DMSO-H2O Mixtures of Varying Compositions: Ground State and Transition State Contributions

2021 ◽  
Author(s):  
Ik-Hwan Um ◽  
Seungjae Kim
Keyword(s):  
Transition State ◽  
Alkaline Hydrolysis ◽  
Ground State ◽  
Rate Constants ◽  
Kinetic Data ◽  
Reaction Medium ◽  
Stepwise Mechanism ◽  
Rate Determining Step ◽  
Leaving Group ◽  
Hydrolysis Of

Second-order rate constants (kN) for reactions of p-nitrophenyl acetate (1) and S-p-nitrophenyl thioacetate (2) with OH‒ have been measured spectrophotometrically in DMSO-H2O mixtures of varying compositions at 25.0 ± 0.1 oC. The kN value increases from 11.6 to 32,800 M‒1s‒1 for the reactions of 1 and from 5.90 to 190,000 M‒1s‒1 for those of 2 as the reaction medium changes from H2O to 80 mol % DMSO, indicating that the effect of medium on reactivity is more remarkable for the reactions of 2 than for those of 1. Although 2 possesses a better leaving group than 1, the former is less reactive than the latter by a factor of 2 in H2O. This implies that expulsion of the leaving group is not advanced in the rate-determining transition state (TS), i.e., the reactions of 1 and 2 with OH‒ proceed through a stepwise mechanism, in which expulsion of the leaving group from the addition intermediate occurs after the rate-determining step (RDS). Addition of DMSO to H2O would destabilize OH‒ through electronic repulsion between the anion and the negative-dipole end in DMSO. However, destabilization of OH‒ in the ground state (GS) is not solely responsible for the remarkably enhanced reactivity upon addition of DMSO to the medium. The effect of medium on reactivity has been dissected into the GS and TS contributions through combination of the kinetic data with the transfer enthalpies (ΔΔHtr) from H2O to DMSO-H2O mixtures for OH‒ ion.

scholarly journals Heterogeneity of the reaction system of alkaline hydrolysis of ethyl acetate in a batch stirred tank.

1981 ◽  
Vol 14 (6) ◽  
pp. 499-500
Author(s):  
YASUHIRO MURAKAMI ◽  
MASAHARU TAKAO ◽  
HIDEAKI INOUE
Keyword(s):  
Ethyl Acetate ◽  
Alkaline Hydrolysis ◽  
Reaction System ◽  
Stirred Tank ◽  
Hydrolysis Of

Mass transfer enhancement by the alkaline hydrolysis of ethyl acetate in a single droplet system

2011 ◽  
Vol 17 (4) ◽  
pp. 782-787 ◽  
Author(s):  
Sang Jun Jeon ◽  
Alexander Pawelski ◽  
Matthias Kraume ◽  
Won Hi Hong
Keyword(s):  
Mass Transfer ◽  
Ethyl Acetate ◽  
Alkaline Hydrolysis ◽  
Single Droplet ◽  
Transfer Enhancement ◽  
Mass Transfer Enhancement ◽  
Hydrolysis Of

Solvent Effect of Dimethyl Sulfoxide on Alkaline Hydrolysis of Amide

1974 ◽  
Vol 22 (4) ◽  
pp. 864-870 ◽  
Author(s):  
ITARU KOJO ◽  
SHOJI AWAZU ◽  
MANABU HANANO
Keyword(s):  
Solvent Effect ◽  
Dimethyl Sulfoxide ◽  
Alkaline Hydrolysis ◽  
Hydrolysis Of
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