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

• Published in: Journal of organic chemistry Vol. 69; no. 9; pp. 3166 - 3172
• Main Authors: Um, Ik-Hwan, Chun, Sun-Mee, Chae, Ok-Mi, Fujio, Mizue, Tsuno, Yuho
• Format: Journal Article
• Language: English
• Published: Washington, DC American Chemical Society 30.04.2004
• Subjects: Chemistry; Exact sciences and technology; Kinetics and mechanisms; Organic chemistry; Reactivity and mechanisms; Substituent effect; Nitro compound; Correlation; Regioselectivity; Reaction rate; Sulfonate; Reaction mechanism; Benzenic compound; Electronic effect; Alkalinity; Kinetics; Rate constant; Chemical reactivity; Nucleophilic substitution; Secondary amine
• ISSN: 0022-3263; 1520-6904
• DOI: 10.1021/jo049812u

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 pK a° = 9.1. The secondary amines are more reactive than primary amines of similar basicity for the S−O bond fission. The k 1 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.