Enhanced reactivity of an α-nucleophile in water-dimethyl sulfoxide mixtures. A transition state effect.

1984 ◽  
Vol 25 (12) ◽  
pp. 1267-1268 ◽  
Author(s):  
Marguerite Laloi-Diard ◽  
Jean-François Verchere ◽  
Patrick Gosselin ◽  
François Terrier
Keyword(s):  
Transition State ◽  
Dimethyl Sulfoxide ◽  
State Effect

The Hydrolysis of Bis(2-chloroethyl) Sulfide (Sulfur Mustard) in Aqueous Mixtures of Ethanol, Acetone and Dimethyl Sulfoxide

1993 ◽  
Vol 46 (3) ◽  
pp. 293 ◽  
Author(s):  
RI Tilley
Keyword(s):  
Transition State ◽  
Dimethyl Sulfoxide ◽  
Rate Constants ◽  
Charge Separation ◽  
Sulfur Mustard ◽  
Transition States ◽  
Aqueous Mixtures ◽  
Sulfide Sulfur ◽  
Rate Of Hydrolysis ◽  
Hydrolysis Of

The rate of hydrolysis of bis (2-chloroethyl) sulfide (sulfur mustard) in aqueous mixtures of ethanol, acetone and dimethyl sulfoxide has been measured and compared with previously reported values. Rate constants in water at 25°C for the two consecutive hydrolysis reactions undergone by sulfur mustard were estimated to be (2.93�0.15)×10-3 and (3.87�0.14)×10-3 s-1. Charge separation of 0.42 in the transition states was indicated together with significant solvation of the positive end of the transition state dipoles.

Ester Cleavage by Cyclodextrins in Aqueous Dimethyl Sulfoxide Mixtures. Substrate Binding versus Transition State Binding

1994 ◽  
Vol 59 (25) ◽  
pp. 7602-7608 ◽  
Author(s):  
Oswald S. Tee ◽  
Charles Mazza ◽  
Rafael Lozano-Hemmer ◽  
Javier B. Giorgi
Keyword(s):  
Transition State ◽  
Dimethyl Sulfoxide ◽  
Substrate Binding ◽  
Versus Transition

Kinetic solvation steric effect at the transition state of reaction between trichlorocobaltate(II) and chloride ions in N,N-dimethylformamide and dimethyl sulfoxide

2005 ◽  
Vol 119 (1-3) ◽  
pp. 177-182 ◽  
Author(s):  
Yasuhiro Umebayashi ◽  
Nobuyuki Shigeta ◽  
Yue Zhang ◽  
Morito Komiya ◽  
Yu-ichi Murakami ◽  
...  
Keyword(s):  
Transition State ◽  
Dimethyl Sulfoxide ◽  
Steric Effect ◽  
Chloride Ions

Transition state enthalpies of transfer in aqueous dimethyl sulfoxide solutions. The hydroxide catalyzed ionization of chloroform

1977 ◽  
Vol 55 (1) ◽  
pp. 99-101 ◽  
Author(s):  
John R. Jones ◽  
Richard Fuchs
Keyword(s):  
Transition State ◽  
Dimethyl Sulfoxide ◽  
Enthalpies Of Solution ◽  
Hydroxide Ion ◽  
Enthalpies Of Transfer ◽  
Aqueous Dmso

The accelerating effect of added dimethyl sulfoxide on the rate of hydroxide-catalyzed ionization of chloroform in water has been examined in terms of the solvation of reactants and transition state. Enthalpies of solution of chloroform in water, DMSO, and mixtures of the two have been measured. From these, together with enthalpies of activation for the detritiation of chloroform, and enthalpies of transfer of hydroxide ion from water to aqueous DMSO mixtures, transition state enthalpies of transfer have been calculated. The reaction is accelerated by small concentrations of DMSO because of increased transition state solvation, but by large DMSO concentrations due to reduced solvation of hydroxide ion. Transition state solvation is unlike that of the reactants, but resembles that expected for CCl3− ion.

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