Bulletin of the Korean Chemical Society

Korean Chemical Society (대한화학회)
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Kinetics and Mechanism for the Reaction of 4-Nitrophenyl 2-Thiophenecarboxylate with Secondary Alicyclic Amines

  • Published : 2002.03.20
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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.

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References

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