Journal of the Korean Chemical Society (대한화학회지)

Korean Chemical Society (대한화학회)
권호 표지

Dehydropolycondensation of Aminophenols under the Catalytic Action of Metallic Chelate Compounds (II) Effects of the Ligands, Structures of the Mixed Complexes, and Side Reactions

金屬킬레이트 化合物의 觸媒作用에 依한 Aminophenol 類의 酸化的 重縮合反應 (Ⅱ) Ligands 種의 效果, 混合錯物의 構造및 副反應

  • Published : 19680900
Download PDF
⟨ Previous Next ⟩

Abstract

In the oligomerization of p-aminophenol under the catalytic action of the metallic complexes, the effects of the ligands are studied. When the initial velocity of $O_2$ uptake at pH 8 using Fe(Ⅲ) as the central metal and N-hydroxylethylethylenediaminetriacetic acid (HEDTA), ethylenediaminetetraacetic acid (EDTA), diethylenetriaminepentaacetic acid (DTPA), 1,2-cyclohexanediaminetetraacetic acid(CyDTA) as the ligands respectively are compared, the velocities are as the following order: HEDTA > EDTA > DTPA > CyDTA. Further when the effect of the ligands, nitrilotriacetic acid (NTA), HEDTA, EDTA, and DTPA, on the yields of oligomers are compared, the result shows as the following order: NTA > HEDTA > EDTA > DTPA. These are nearly reverse order of the stability constants of the complexes. In order to determine the composition of the mixed complexes at the initial step, the method of continuous variation is used, and it is found that the composition ratio of Fe-EDTA complex to monomer in the mixed complexes is one at pH 5-8 range. It is also found that at pH 9 or in the more alkaline range, side reactions occur to form water soluble dimer of quinone type and the catalytic action of the metallic complex markedly decreases on account of the hydrolysis of the central metal by the $OH^-$ ion.

Keywords

References

  1. J. Am. Chem. Soc. v.70 J.E. LuValle;D.B. Glass;A. Weissberger
  2. J. Am. Chem. Soc. v.69 J. E. LuValle;A. Weissberger
  3. J. Am. Chem. Soc. v.48 J.B. Conant;M.F. Pratt
  4. Chem. Ber. v.96 L. Horner;J. Dehnert
  5. J. Am. Chem. Soc. v.84 G.A. Russell
  6. J. Allg. Chem. (USSR) v.28 A.P. Terentjew
  7. Zh. Obsh. Khim. v.32 V.A. Simanov(et al.)
  8. J. Am. Chem. Soc. v.81 A.S. Hay;H.S. Blanchard
  9. J. Org. Chem. v.28 G.F. Endres;A.S. Hay
  10. Advanced Organic Chemistry L.F. Fieser;M. Fieser
  11. 大韓化學會誌 v.12 no.3 崔奎碩
  12. Vysokomolekul. Soedin. v.5 Y.V. Kissin;G.M. Pshenitsyna
  13. Vysokomolekul. Soedin. v.7 B. I. Liogonkii;A. V. Ragimov;Y. G. Aseev;A. A. Berlin