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Bulletin of the Korean Chemical Society (BKCS)

ISSN 0253-2964(Print)
ISSN 1229-5949(Online)
Volume 34, Number 8
BKCSDE 34(8)
August 20, 2013 

Structure-Reactivity Correlations in Nucleophilic Displacement Reactions of Y-Substituted-Phenyl X-Substituted-Cinnamates with Z-Substituted-Phenoxides
Yu-Jin Son, Eun-Hee Kim, Ji-Sun Kang, Ik-Hwan Um*
Brønsted-type plot, Hammett plot, Concerted mechanism, Stepwise mechanism, Phenyl cinnamate
Second-order rate constants (kN) have been measured spectrophotometrically for the nucleophilic displacement reactions of 4-nitrophenyl X-substituted-cinnamates (4a-4e) and Y-substituted-phenyl cinnamates (5a-5e) with Z-substituted-phenoxide anions in 80 mol % H2O/20 mol % DMSO at 25.0 ± 0.1 oC. The Hammett plot for the reactions of 4a-4e with 4-chlorophenoxide (4-ClPhO–) consists of two intersecting straight lines, which might be taken as a change in the rate-determining step (RDS). However, it has been concluded that the nonlinear Hammett plot is not due to a change in the RDS but is caused by stabilization of the ground state of substrates possessing an electron-withdrawing group in the cinnamoyl moiety through resonance interactions, since the Yukawa-Tsuno plot exhibits an excellent linear correlation with ρX = 0.89 and r = 0.58. The Brønsted-type plot for the reactions of 4-nitrophenyl cinnamate (4c) with Z-substituted-phenoxides is linear with βnuc = 0.76. The Brønsted-type plot for the reactions of Y-substituted-phenyl cinnamates (5a-5d) with 4-chlorophenoxides (4- ClPhO–) is also linear with βlg = –0.72. The Hammett plot correlated with σ– constants for the reactions of 5a- 5d results in a much better linear correlation than that correlated with σo constants, indicating that a partial negative charge develops on the O atom of the leaving aryloxide. Thus, the reactions have been concluded to proceed through a concerted mechanism.
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