Dn. Kevill et Mj. D'Souza, Correlation of the rates of solvolysis of phenyl chlorothionoformate and phenyl chlorodithioformate, CAN J CHEM, 77(5-6), 1999, pp. 1118-1122
Citations number
18
Categorie Soggetti
Chemistry
Journal title
CANADIAN JOURNAL OF CHEMISTRY-REVUE CANADIENNE DE CHIMIE
The specific rates of solvolysis of phenyl chlorothionoformate (PhOCSCl) ar
e remarkably similar to those previously reported for phenyl chlorothioform
ate (PhSCOCl). When analyzed using the extended Grunwald-Winstein equation
over the usual range of solvent types, these solvolyses show essentially id
entical divisions into the solvents favoring the addition-elimination chann
el and those favoring the ionization channel. The introduction of one sulfu
r caused a partial shift away from the addition-elimination pathway, which
was dominant over the full range of solvents for phenyl chloroformate (PhOC
OCl). Consistent with these results, introduction of the second sulfur with
in phenyl chlorodithioformate (PhSCSCl) leads to a completion of this shift
, such that an extended Grunwald-Winstein treatment of the specific rates o
f solvolysis now shows the ionization pathway to be dominant over the full
range of solvents.