Theoretical studies on the competitive S(N)2 reactions of O-imidomethyl derivatives of phenols with OH-

Title
Theoretical studies on the competitive S(N)2 reactions of O-imidomethyl derivatives of phenols with OH-
Authors
Kim, C.K.; Lee, B.S.
Keywords
D-imidomethyl derivatives, TS-solvation
Issue Date
2001-01
Publisher
BULLETIN OF THE KOREAN CHEMICAL SOCIETY
Abstract
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 rho (Z) 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.
URI
http://dspace.inha.ac.kr/handle/10505/20188
ISSN
0253-2964
Appears in Collections:
College of Natural Science(자연과학대학) > Chemistry (화학) > Journal Papers, Reports(화학 논문, 보고서)
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