Solvolytic Reactivities of Nortricyclyl, Dehydronorbornyl and Norbornyl Halides. Possible Steric Requirements for Hyperconjugative Resonance¹

Solvolytic Displacement Reactions At Saturated Carbon Atoms

“…The reactivities of the corresponding chlorides in 80 per cent ethanol at 85°C. are >150 (529,530). Neighboring double bond participation a t the backside is geometrically favored in CCXXIII but not in CCXXIV.…”

“…The rates of solvolysis of exo isomers relative to the endo isomers are -70 for the chlorides in 80 per cent ethanol a t 7 CXLVII CXLVIII 85°C. (529,530), 350 for the brosylates in acetic acid at 25°C. (692,693), and 310…”

The crystal structure of cyclopropanecarbohydrazide

“…:~ It has been pointed out to us by Prof. Roberts that there is evidence from solvolysis rate studies indicating that a possible stabilization of the bonded amide-cyclopropane system might result from a configuration in which the planes of the amide group and the cyclopropane ring are not normal ~o one another (Roberts, Bennett & Armstrong, 1950). The nature of this stabilization might be expected to produce ~symmetry in the ring bond lengths.…”

Acid-catalyzed solvolysis: unusually rapid solvolysis of 3-fluoronortricyclene in CD3COOD – 0.1 M D2SO4

“…Similar results were obtained by Chapman and Levy (6) for the solvolysis of tert-butyl and tert-amyl fluorides in aqueous ethanol containing hydrochloric acid. The 'Converted from data (15,16) for the solvolysis rates in 80% EtOH -H 2 0 using the Winstein-Grunwald linear free energy relationship, log klk, = my, with Y = -1.64 for 100% acetic acid. The rate comparison is necessarily approximate since the rate data for l a is for fully deuterated acetic acid containing D,SO,.…”