The Ethanolysis of Allyl Benzenesulfonate

Solvolytic Displacement Reactions At Saturated Carbon Atoms

“…Formation of the less reactive rearranged halides was also shown by the drifting instantaneous rate constants obtained in kinetic measurements of cyclopropylcarbinyl chloride in aqueous ethanol (535). It is pertinent that the solvolysis of cyclopropylcarbinyl benzenesulfonate in absolute ethanol gives good fist-order rate constants without drift (83).…”

Reaction Kinetics

“…Bergstrom & Siegel (164) found the rate of solvolysis of cyclopropyl methyl benzene sulfonate to be independent of the concentration of NaOH. On this and other evidence they conclude that an SN l mechanism operates, explaining it on the basis of the stability of an ion of the type['�17"J + Clra .…”

Neighboring‐Group Effects and Rearrangements in Reactions of Cyclopropylmethyl, Cyclobutyl, and Homoallyl Systems

“…found that the cyclopropylmethyl system (19), X = C1, is solvolysed 107.4 times as rapidly as the homoallyl system ( I S ) , X = C1; the hydrolysis of (19) is only about 10 times as fast as that of the stereoisomeric 6a product, despite the less favorable position of the three-membered ring with respect to the leaving substituent in the latter case [371. Winstein interprets the rearrangements and its kinetics on the basis of a common non-classical intermediate (22), in which the charge is delocalized by "homoallyl resonance" …”

“…The i-steroid rearrangement [Id], which has been known for some time, is stereospecific in that only the 3P-cholesteryl derivatives (18) three-membered ring with respect to the leaving substituent in the latter case [371. Winstein interprets the rearrangements and its kinetics on the basis of a common non-classical intermediate (22), in which the charge is delocalized by "homoallyl resonance" (20) f-t (21) […”