Journal of the Korean Chemical Society (대한화학회지)

Korean Chemical Society (대한화학회)
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The Studies on The Tetrazotization of Aromatic Diamines (I). Tetrazotization of p-Phenylenediamine in Hydrochloric Acid and Perchloric Acid

방향족 디아민의 Tetrazo 화에 관한 연구 (제1보). 염산 및과염소산 중에서 p-Phenylenediamine의 Tetrazo 화

  • Woo Young Lee (Department of Chemistry, College of General Studies, Seoul National University) ;
  • Youn Young Lee (College of Liberal Arts and Sciences, Seoul National University) ;
  • Sae Hee Chang (College of Liberal Arts and Sciences, Seoul National University)
  • Published : 1973.08.30
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Abstract

p-Phenylenediamine was tetrazotized with sodium nitrite in an excess amount of concentrated hydrochloric acid media at -10$^{\circ}$C. It was also tetrazotized almost completely in 45% perchloric acid media. The two diazo groups in the tetrazonium salt were substituted by halogen, and the degree of tetrazotization reaction was observed by dihalobenzene yielded. The result of the tetrazotization was dependent upon the stability of the tetrazonium salt, and the stability was determined by concentration and quantity of the acid media. In dilute acid media the tetrazonium salt was unstable and completely decomposed. In concentrated acid media, though the tetrazonium salt was stable, tetrazotization reaction was retarded. To harmonize the two opposing tendencies it was advisable to find the optimum acidity of media at which the salt was fairly stable. About $40{\sim}45$% of the acid media was suitable. The fact that the $H^+$ ion behaved as a negative catalyst supported the assumption that the diazotization reaction is primarily a reaction between the free amine and a nitroso group. The reaction of tetrazotization is expressed with respect to the kinetics and mechanism of diazotization.

p-Phenylenediamine을 과량의 진한 염산 및 과염소산을 매질로하여 거의 완전히 tetrazo화 하였다. Tetrazonium염의 두 diazo기를 할로겐으로 치환하여 생긴 dihalobenzene의 수량으로 반응의 정도를 알아 보았다. 이 반응의 성패는 tetrazonium염의 안정도에 의하여 죄우되었으며, 그 안정도는 매질의 종류, 산도(농도) 및 그양과 밀접한 관계가 있음을 알았다. 즉 산매질의 농도가 너무 묽으면 tetrazonium염은 불안정하여 완전히 분해되었으며, 매질의 농도가 너무 진하면 tetrazonium염은 안정한 반면에 tetrazo화 반응이 방해되었다. 이 상반되는 두 경향을 조화시키기 위해서는 tetrazonium염이 안정하게 존재할 수 있는 가장 낮은 농도의 산을 매질로 써야함을 알 수 있었다. p-Phenylenediamine의 tetrazo화에서는 약$40{\sim}45$%의 산매질이 적당하였다. $H^+$이온이 부촉매로 작용하는 것으로 보아 diazo화 반응이 아민의 염의 상태에서 일어나는 것이아니고 유리상태의 아민과 nitroso group 사이에서 일어난다는 설이 타당함을 알 수 있었다. Tetrazo화 반응을 diazo화 반응의 kinetics 및 mechanism과 관련시켜서 설명하였다.

Keywords

References

  1. Ber. v.17 Griess
  2. German Patent, 60, 170
  3. Friedlander v.8
  4. Ber. v.30 Bulow;Mann
  5. Ber. v.44 Benda
  6. J. Chem. Soc. v.91 Cain
  7. J. Chem. Soc. v.91 Morgan
  8. J. Chem. Soc. v.95 Morgan
  9. J. Amer. Chem. Soc. v.55 H.A.J. Schoutissen
  10. J. Amer. Chem. Soc. v.55 H.A.J. Schoutissen
  11. Zh. Obshch. Khim. v.32 B.I. Belov;V.V. Kozlov
  12. C.A. v.56 B.I. Belov;V.V. Kozlov
  13. U.S. 2053, 745 Karl Schnitz-Spahn
  14. C.A. v.30 Karl Schnitz-Spahn
  15. Ber v.32 A. Hanztsch;M. Schumann
  16. J. Amer. Chem. Soc. v.58 H.A.J. Schoutissen
  17. C.A. v.30 H.A.J. Schoutissen
  18. J. Amer. Chem. Soc. v.73 J.H. Dusenbury;R.E. Powell
  19. Dictionary of Applied Chemistry v.9 G.T.Morgan
  20. The Aromatic Diazo Compounds and Their Application K.H. Saunders
  21. Trans. 8th Aniline Dye Conf. Voprosy Anilinokrasochnoi, Trudy VIII, Soveshchaniya Khim. i. Tekh. T.N. Vernikovskaya
  22. J. Soc. Dyers Colourists v.68 T.N. Vernikovskaya
  23. Nature v.166 E.D. Hughes;C.K. Ingold;J.H. Ridd
  24. J.Amer. Chem.Soc. v.74 A.T. Austin;E.D.Hughes;C.K. Ingold;J.H. Ridd
  25. Trans. 8th Aniline Dye Conf. Voprosy Anilinokrasochnoi Khim., Trudy IVII, Soveshchiniya Khim. i. Tekh. B.A. Porai-Koshits
  26. J. Soc. Dyers Colourists v.68 B.A. Porai-Koshits
  27. C.A. v.47 B.A. Porai-Koshits