Correlation of the rates of solvolysis of two arenesulfonyl chlorides and of trans-beta-styrenesulfonyl chloride - precursors in the development of new pharmaceuticals.
Additional specific rates of solvolysis have been determined, mainly in fluoroalcohol containing solvents, for benzenesulfonyl chloride (1) and p-nitrobenzene-sulfonyl chloride (2). For trans-beta-styrenesulfonyl chloride (3), a study has been carried out in 43 pure and binary solvents, covering a wide range of hyroxylic solvent systems. For the specific rates of solvolyses of each of the three substrates, a good correlation was obtained over the full range of solvents when the extended Grunwald-Winstein equation was applied. The sensitivities to changes in solvent nucleophilicity and solvent ionizing power are similar to values determined earlier and an S(N)2 process is proposed. For 3, kinetic solvent isotope effects of 1.46 for k(H(2)O)/k(D(2)O) and 1.76 for k(MeOH)/k(MeOD) were determined. These are also compared to literature values for other sulfonyl chlorides.
Ryu
Zoon Ha
ZH
Department of Chemistry, Dong-Eui University, 24 Kaya-dong, Busan-Jin-Gu, Busan 614-714, Korea.
Lee
Sang Wok
SW
Department of Chemistry, Dong-Eui University, 24 Kaya-dong, Busan-Jin-Gu, Busan 614-714, Korea.
D'Souza
Malcolm J
MJ
Department of Chemistry, Wesley College, 120 N. State Street, Dover, Delaware 19901-3875, USA.
Yaakoubd
Lamia
L
Department of Chemistry, Wesley College, 120 N. State Street, Dover, Delaware 19901-3875, USA.
Feld
Samantha E
SE
Department of Chemistry, Wesley College, 120 N. State Street, Dover, Delaware 19901-3875, USA.
Kevill
Dennis N
DN
Department of Chemistry and Biochemistry, Northern Illinois University, DeKalb, Illinois 60115- 2862, USA.