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Bulletin of the Korean Chemical Society (BKCS)

ISSN 0253-2964(Print)
ISSN 1229-5949(Online)
Volume 22, Number 1
BKCSDE 22(1)
January 20, 2001 

Theoretical Studies on the Competitive SN2 Reactions of O-Imidomethyl Derivatives of Phenols with OH-
Chang Kon Kim, Dong Soo Chung, Chan Kyung Kim, Bon-Su Lee, Yeong-Jin Chung, Byung Choon Lee, Ikchoon Lee
Competitive SN2, AM1-SM2.1, D-Imidomethyl Derivatives, TS-Solvation.
Nucleophilic substitution reactions of O-imidomethyl derivatives of phenols with OH- were studied theoretically using the semiempirical AM1 and Solvation Model 2.1 (SM2.1) methods in the gas phase and aqueous solution, respectively. In the gas phase, the two reaction paths, in which the imide (1a) or phenol (1b) is functioning as a leaving group, can occur competitively. In contrast, in aqueous solution, path (1b) becomes more favorable than (1a) because the transition states (TS) of path (1b) are more stabilized by solvent. Differences in solvation energies are caused by the structural differences of TS, i.e., the TS via path (1b) is more dissociative than that via path (1a). Therefore we conclude that the solvent effects play an important role in the hydrolysis of O-imidomethyl derivatives of phenols. However, reactivity is dependent on the acidities of both the imide and the phenol fragments since the ρz values vary progressively from 4.2 (Z' = I) to 2.5 (Z' = IV) as the acidities of imide increase. These are in good agreement with the experimental results.
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