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http://dx.doi.org/10.5012/bkcs.2002.23.3.381

Kinetics and Mechanism for the Reaction of 4-Nitrophenyl 2-Thiophenecarboxylate with Secondary Alicyclic Amines  

Um, Ik-Hwan
Lee, Eun-Ju
Lee, Jong-Pal
Publication Information
Bulletin of the Korean Chemical Society / v.23, no.3, 2002 , pp. 381-384 More about this Journal
Abstract
Second-order-rate constants ($k_N$) have been measured spectrophotometrically for the reactions of 4-nitrophenyl 2-thiophenecarboxylate (1a) with a series of secondary alicyclic amines in H2O containing 20 mole % DMSO at 25.0 $^{\circ}C$ . The ester 1a is less reactive than 4-nitrophenyl 2-furoate (1b) but more reactive than 4-nitrophenyl benzoate (1c) except towards piperazinium ion. The Brønsted-type plots for the aminolyses of 1a, 1b and 1c are linear with a $\beta$nuc value of 0.92, 0.84 and 0.85, respectively, indicating that the replacement of the CH=CH group by a sulfur or an oxygen atom in the benzoyl moiety of 1c does not cause any mechanism change. The reaction of piperidine with a series of substituted phenyl 2-thiophenecarboxylates gives a linear Hammett plot with a large $\rho^-$ value ($\rho^-$ = 3.11) when $\sigma^- $ constants are used. The linear Brønsted and Hammett plots with large $\beta$nuc and $\rho^-$ values suggest that the aminolysis of 1a proceeds via rate-determining break-down of the addition intermediate to the products.
Keywords
Aminolysis; Rate-determining step; Mechanism; Hammett equation;
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