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Polar Effects. X. Polar Substituent Effects in the Solvolysis of 3-Substituted 1-Adamantyl Bromides and Toluenesulfonates

✍ Scribed by Cyril A. Grob; Bruno Schaub

Publisher
John Wiley and Sons
Year
1982
Tongue
German
Weight
413 KB
Volume
65
Category
Article
ISSN
0018-019X

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✦ Synopsis

Abstract

The rate constants for 3‐substituted adamantyl p‐toluenesulfonates 3a‐3k in ethanol/water 80:20 correlate well with the respective inductive substituent constants σ. The reaction constant ρ for the toluenesulfonates 3 is 10% larger than for the corresponding bromides 2, indicating somewhat more charge separation in the activation of the toluenesulfonates. Evidence is presented that stabilization of the resultant 1‐adamantyl cations by induction involves graded 1,3‐bridging, which is favored when the substituent is an electrofugal group, and that stabilization by n‐electron donors involves C, C‐hyperconjugation. Rate ratios for the toluenesulfonates 3 and the bromides 1 exceed 10^3^ and are almost independent of the 3‐substituents. The implications of this are discussed in the light of current hypotheses.

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