Concerted solvent processes for common sulfonyl chloride precursors used in the synthesis of sulfonamide-based drugs.
Specific rates of solvolysis in hydroxylic solvents available for the solvolysis of 2-thiophenesulfonyl chloride and phenylmethanesulfonyl chloride are supplemented by determining the values in fluoroalcohol-containing solvents. The data sets are then correlated using the extended Grunwald-Winstein equation. For both substrates, it is found that a single correlation controls the influence of solvent over the full range of solvent composition. The sensitivities to solvent nucleophilicity and solvent ionizing power are compared to values available for other substrates. Three of these previous studies are upgraded by the incorporation of additional specific rate values from the recent literature. With a methyl, isopropyl, benzyl, aromatic or heteroaromatic group as the R group of RSO(2)Cl, a concerted S(N)2 mechanism is proposed for the solvolysis.
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.
Mlynarski
Stacey L
SL
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.