AbstractThe solvolysis rates and products of the tertiary 2‐methyl‐2‐exo‐ and ‐2‐endo‐norbornyl 2,4‐dinitrophenyl ethers1and2, (X = 2,4‐(NO2)22C6H3O) have been determined. The different sensitivities of the rates of these ethers to the inductive effect of substituents at C(6) indicate that graded bridging of C(2) by C(6) occurs in the ionization of theexo‐ethers1, not, however, in the ionization of theendo‐ethers2.In both cases hydrolysis leads to 2‐methyl‐2‐exo‐norbornanols only. Consequently, substitution takes place with retention at C(2) in theexo‐series1and with inversion at C(2) in theendo‐series2.It is concluded that stereoelectronic and polar effects, rather than steric bulk effects, determine the highexo/endorate ratios of the pa