Heteroaromatic N-oxide rearrangements. Reinvestigation of 1,3 tosyloxy migration in the reaction of isoquinoline N-oxide with tosyl chloride
Isoquinoline N-oxide (2) reacts with 18O-enriched tosyl chloride to furnish 18O-labeled 4-tosyloxy-isoquinoline (4), which was assessed for oxygen isotopic enrichment by NMR and mass spectrometry. The 30-45% 18O incorporation at the bridging oxygen is inconsistent with a high level of the intramolecular tight-ion-pair ('sliding') mechanism. A combination of two intramolecular mechanisms is probably operative.
Ion pairs in the solvolysis of secondary systems. Salt effect, 18O-labeling, and polarimetric studies of 1-(4′-tolyl)-2,2,2-trifluoroethyl tosylate
The effect of added trifluoroacetate and Inflate salts on the trifluoroacetolysis of 1-(4′-tolyl)-2,2,2-trifluoroethyl tosylate has been studied, including reactions of optically active and 18O-labeled substrates. With no added salt the polarim
Dynamics for reactions of ion pairs in aqueous solution: Reactivity of tosylate anion ion paired with the highly destabilized 1-(4-methylphenyl)-2,2,2- trifluoroethyl carbocation
The sum of the rate constants for solvolysis and scrambling of carbon bridging and nonbridging oxygen-18 at 4-MeC6H4CH(CF 3)OS(18O2)Tos in 50/50 (v/v) trifluoroethanol/water, (ksolvRki