Bulletin of the Korean Chemical Society

Korean Chemical Society (대한화학회)
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Anion Effects on the Aminolysis of Carboxyl-Containing Esters by Triamines in Dimethyl Sulfoxide

  • Suh Junghun (Department of Chemistry, Seoul National University) ;
  • Kim Yongho (Department of Chemistry, Seoul National University) ;
  • Chang Sae Hee (Department of Chemistry, Seoul National University)
  • 서정훈 (서울대학교 자연과학대학 화학과) ;
  • 김용호 (서울대학교 자연과학대학 화학과) ;
  • 장재희 (서울대학교 자연과학대학 화학과)
  • Published : 19890200
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Abstract

Aminolysis of various carboxyl-containing ester substrates by triamines was kinetically studied in dimethyl sulfoxide (DMSO) in the presence of p-toluenesulfonic acid (TSA) or in the presence of sulfuric acid and potassium iodide (KI). In the presence of TSA or KI, the pseudo-first-order rate constants ($k_o$) were proportional to the total amine concentration ($N_o$). This stands in marked contrast with the corresponding reactions carried out with sulfuric acid added as the sole additive, in which saturation kinetic behavior of ko with respect to No was manifested. This indicates that complex formation between the ester substrate and the amine is greatly suppressed by the addition of TSA or KI. The second-order rate constants obtained in the presence of TSA or KI were substantially greater than those measured in the absence of any additive. These kinetic features were explained in terms of tight interaction between the protonated amines with I- or TSA-. Thus, the results were related to the hydrogen bonding that involves DMSO, bisulfate ion, I-, TSA-, and the protonated forms of triamines.

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References

  1. Bioorg. Chem. v.14 Suh, J.;Kim, Y.;Lee, E.;Chang, S. H.
  2. J. Org. Chem. v.49 Bordewell, F. G.;McCallum, R. J.;Olmstead, W. N.
  3. Inorg. Chem. v.1 Kolthoff, I. M.;Reddy, T. B.
  4. J. Am. Chem. Soc. v.90 Kolthoff, I. M.;Chantooni, M. K., Jr.
  5. J. Am. Chem. Soc. v.90 Kolthoff, J. M.;Chantooni, M. K., Jr.;Bhowmik, S.
  6. J. Am. Chem. Soc. v.93 Kolthoff, I. M.;Chantooni, M. K. Jr.