Can I read Ab initio GB study of chemical intermediates in solution; Ethylenesulfonium ion in hydrolysis of 2-chloroethyl methyl sulfide on EtoBox?

Ab initio GB study of chemical intermediates in solution; Ethylenesulfonium ion in hydrolysis of 2-chloroethyl methyl sulfide by Osamu Kikuchi; Naoyuki Tomisawa; Ohgi Takahashi; Kenji Morihashi is a Chemistry article available to read on EtoBox.

What is Ab initio GB study of chemical intermediates in solution; Ethylenesulfonium ion in hydrolysis of 2-chloroethyl methyl sulfide about?

Ab initio MO theory including solvent effects has been applied to the structure and reactivity of methyl ethylenesulfonium ion, 1, in aqueous solution as a model of the three-membered cyclic sulfonium intermediate expected in the toxic action of sulfur mustard. The 6-31 ‫ם‬ G\* geometry optimization of the cyclic sulfonium ion 1 suggested that the ring size of 1 is expanded slightly by solvation. The contour lines map of the interaction energy between 1 and Cl ‫מ‬ has a very shallow and wide well at 5-6 A ̊distance from 1. This is the solvent-separated ion pair, and the contact ion pair was not found between 1 and Cl ‫מ‬ . The calculated energy diagrams for the S N 2-type reactions of 1 with Cl ‫מ‬ , H 2 O, and OH ‫מ‬ that give ring-opened compounds indicated the following: (1) The energy of the 1 ‫ם‬ Cl ‫מ‬ system is similar to that of chloroethyl methyl sulfide (CEMS, 2), and the interconversion between 1 ‫ם‬ Cl ‫מ‬ and 2 occurs easily in aqueous solution. The 3-21 ‫ם‬ G(\*) and 6-31 ‫ם‬ G\* activation energies for the 2 r 1 ‫ם‬ Cl ‫מ‬ reaction, 20-22 kcal/mol, agree well with the experimental enthalpy of activation for the hydrolysis of 2. (2) The reaction of 1 with OH ‫מ‬ give

Who reads Ab initio GB study of chemical intermediates in solution; Ethylenesulfonium ion in hydrolysis of 2-chloroethyl methyl sulfide?

Author

Osamu Kikuchi; Naoyuki Tomisawa; Ohgi Takahashi; Kenji Morihashi

Publisher

John Wiley and Sons; Hindawi Limited; John Wiley & Sons Inc.; Wiley (ISSN 1042-7163)

Published

1998

Language

CY

Field

Chemistry (Physical Sciences)