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Effect of Amine Nature on Reaction Rate and Mechanism in Nucleophilic Substitution Reactions of 2,4-Dinitrophenyl X-Substituted Benzenesulfonates with Alicyclic Secondary Amines

Title
Effect of Amine Nature on Reaction Rate and Mechanism in Nucleophilic Substitution Reactions of 2,4-Dinitrophenyl X-Substituted Benzenesulfonates with Alicyclic Secondary Amines
Authors
Um I.-H.Chun S.-M.Chae O.-M.Fujio M.Tsuno Y.
Ewha Authors
엄익환
SCOPUS Author ID
엄익환scopusscopus
Issue Date
2004
Journal Title
Journal of Organic Chemistry
ISSN
0022-3263JCR Link
Citation
Journal of Organic Chemistry vol. 69, no. 9, pp. 3166 - 3172
Indexed
SCIE; SCOPUS WOS scopus
Document Type
Article
Abstract
Second-order rate constants have been measured for reactions of 2,4-dinitrophenyl X-substituted benzenesulfonates with a series of alicyclic secondary amines. The reaction proceeds through S-O and C-O bond fission pathways competitively. The S-O bond fission occurs more dominantly as the amine basicity increases and the substituent X in the sulfonyl moiety becomes more strongly electron withdrawing, indicating that the regioselectivity is governed by the amine basicity as well as the electronic nature of the substituent X. The S-O bond fission proceeds through an addition intermediate with a change in the rate-determining step at pKa° = 9.1. The secondary amines are more reactive than primary amines of similar basicity for the S-O bond fission. The k1 value has been determined to be larger for reactions with secondary amines than with primary amines of similar basicity, which fully accounts for their higher reactivity. The second-order rate constants for the S-O bond fission result in linear Yukawa-Tsuno plots while those for the C-O bond fission exhibit poor correlation with the electronic nature of the substituent X. The distance effect and the nature of reaction mechanism have been suggested to be responsible for the poor correlation for the C-O bond fission pathway.
DOI
10.1021/jo049812u
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자연과학대학 > 화학·나노과학전공 > Journal papers
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