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Polar Effects. Part 14. Inductive Charge Dispersal in Bicyclo[2.2.2]oct‐1‐yl Cations
Author(s) -
Bielmann Rolf,
Grob Cyril A.,
Küry Dieter,
Yao Guo Wei
Publication year - 1985
Publication title -
helvetica chimica acta
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.74
H-Index - 82
eISSN - 1522-2675
pISSN - 0018-019X
DOI - 10.1002/hlca.19850680810
Subject(s) - chemistry , solvolysis , bicyclic molecule , substituent , ion , reaction rate constant , polar , charge (physics) , inductive effect , medicinal chemistry , stereochemistry , organic chemistry , kinetics , hydrolysis , physics , quantum mechanics , astronomy
The rate constants (log k ) for solvolysis of 2‐, 3‐, and 4‐substituted bicyclo[2.2.2]octyl p ‐nitrobenzenesulfonates 10, 11 and 12 , respectively, correlate linearly with the corresponding inductive substituent constants s̀ I q . The formation of the ion pairs 9 is, therefore, controlled by the I effect of neighboring substituents. It follows from the corresponding reaction constants ρ 1 of −1.54, −1.12, and −1.22 that inductivity is highest at the positions α to C(1). It is lower and practically equal at the β‐ and γ‐positions. Therefore, charge dispersal is similar to that previously observed in the quinuclidinium ion 7 .