대한화학회지 (Journal of the Korean Chemical Society)

  • 제29권2호
  • /
  • Pages.88-97
  • /
  • 1985
  • /
  • 1017-2548(pISSN)
  • /
  • 2234-8530(eISSN)
대한화학회 (Korean Chemical Society)
권호 표지

1-염화안트라센 술포닐의 치환아닐린과의 친핵성치환반응의 속도론적 연구

Kinetic Study on Nucleophilic Substitution of 1-Anthracenesulfonyl Chloride with Anilines

  • 김형태 (부산대학교 사범대학 화학교육과) ;
  • 여수동 (경북대학교 사범대학 화학교육과)
  • Kim Hyong Tae (Department of the Chemical Education, Busan National University) ;
  • Yoh Soo Dong (Department of Chemical Education, Kyungpook National University)
  • 발행 : 1985.04.20
PDF 다운로드
⟨ 이전 논문 다음 논문 ⟩

초록

기질로 사용한 1-염화안트라센 술포닐(융점$124^{circ}C$)을 안트라키논으로 부터 합성하여 확인한 결과, 그 융점이 문헌치($90^{circ}C$)와 상당한 차이를 나타내었다. 이 기질과 치환아닐린이 무수 아세톤 속에서 일어나는 친핵성 치환반응의 메카니즘을 전기전도도법을 써서 속도론적으로 고찰하였다. 이 반응은 무촉매 과정과 아닐린류에 의한 촉매 과정이 병행하여 일어나며 촉매작용은 친전자적임을 알았다. $Br{\phi}nsted\;{\beta}$ (0.77), Hammett ${\rho}$(-3.2) 및 무촉매반응 속도상수의 온도 의존성에서 결정한 활성화 파라미터로 부터 이 반응은 술포닐암모늄 중간체를 거치는 associative $S_N2$로 논의하는 것이 가장 적절하였다.

1-Anthracenesulfonyl chloride used as a substrate has been prepared from anthra-quinone, and its melting point ($124^{circ}C$) was confirmed to be considerably different from the literature value ($90^{circ}C$). Rates of nucleophilic substitution reactions of this substrate with some p-substituted anilines in dry acetone were determined by electroconductometric method, and their mechanism has been discussed. As a result, it has been found that these reactions proceed in parallel catalyzed by anilines together with noncatalyzed process, and that their catalytic activities are electrophilic. Judging from $Br{\phi}nsted\;{\beta}$ (0.77), Hammett ${\rho}$(-3.2), and activation parameters which were determined from the temperature dependence of noncatalyzed second order rate constants, it appears most appropriate that their mechanism should be discussed in terms of an associative $S_N2$ involving sulfonylammonium intermediate.

키워드

참고문헌

  1. Zh. Prickl. Khim. Mosk. v.21 Z.G. Linetskaya;N.V. Sapozhnikova
  2. C.R. Acad. Sci. USSR v.86 Z.G. Linetskaya;N.V. Sapozhnikova
  3. J. Korean Chem. Soc. v.20 T.S. Uhm;I. Lee;J.R. Kim
  4. J. Korean Chem. Soc. v.21 T.S. Uhm;I. Lee;E.S. Lee
  5. J. Korean Chem. Soc. v.22 T.S. Uhm;I. Lee;E.S. Lee
  6. J. Org. Chem. v.38 A. Arcoria;E. Maccarone;G. Musumarra;G. A. Tomaselli
  7. J. Org. Chem. v.39 A. Arcoria;E. Maccarone;G. Musumarra;G. A. Tomaselli
  8. J. Hetero. Chem. v.12 A. Arcoria;E. Maccarone;G. A. Tomaselli
  9. Tetrahedron v.33 A. Arcoria;V. Librando;E. Maccarone;G. Musumarra;G.A. Tomaselli
  10. Tetrahedron v.34 A. Arcoria;F.P. BalIistreri;G.A. Tomaselli
  11. J. Chem. Soc. Perkin II A. Arcoria;F.P. Ballistreri;G. Musumarra;G.A. Tomaselli
  12. J. Korean Chem. Soc. v.18 W.K. Kim;I. Lee
  13. Bull. Korean Chem. Soc. v.2 I. Lee;I.S. Koo;H.K. Kang
  14. J. Chem. Soc. (B) O. Rogne
  15. J. Chem. Soc. O. Rogne
  16. J. Chem. Soc. Perkin II E. Ciuffarin;L. Senatore;M. Isola
  17. J. Chem. Soc. Perkin II L.J. Stangeland;L. Senatore;E. Ciuffarin
  18. J. Amer. Chem. Soc. v.92 L. Senatore;E. Ciuffarin;A. Fava
  19. J. Chem. Soc. Perkin II O. Rogne
  20. J. Chem. Soc. (B) v.727 O. Rogne
  21. J. Chem. Soc. (B) O. Rogne
  22. Dokl. Akad. Nauk SSSR v.160 L.M. Litvinenko;A.F. Popov
  23. Zh. O. Kh. v.36 L.M. Litvinenko;V.A. Savelova
  24. Zh. O. Kh. v.36 L.M. Litvinenko;A.F. Popov
  25. J. Gen. Chem. USSR v.41 L.M. Litvinenko;N.T. Maleeva;V.A. Savelova;T.D. Kovach
  26. Ukr, Khim. Zh. v.33 L.M. Litvinenko;A.F. Popov;V.A. Savelova
  27. Chemisch Berichte v.28 Heffter
  28. Dictionary of Organic Compounds(4th Ed.) v.1 I. Heilbron;A.H. Cook;H.M. Bunbury;D.H. Hey(ed.)
  29. Dictionary of Organic Compounds(5eh Ed.) v.1 J. Buckingham(ed.)
  30. Phil. Mag. v.2 E.A. Guggenheim
  31. The Organic Chemistry of Sulfur C.M. Suter
  32. Elementary Practical Organic Chemistry A.I. Vogel
  33. Rates and Equilibria of Organic Reactions J.E. Leffier;E. Grunwald
  34. Chem. Rev. v.69 A.J. Parker
  35. Chimia v.16 R.F. Hudson
  36. J. Amer. Chem. Soc. v.90 W. P. Jencks;M. Gilchrist
  37. J. Chem. Soc. (B) E. Ciuffarin;L. Senatore
  38. J. Chem. Soc. (B) E. Ciuffarin;L. Senatore;M. Isola
  39. Proc. Chem. Soc. J.R. Knowless;R.O.C. Norman;J.H. Prosser
  40. J. Chem. Soc. (B) G. Biggi;F. Pietra
  41. J. Chem. Soc. R.F. Hudson;G. Klopman
  42. J. Chem. Soc. R.F. Hudson;G. W. Loveday
  43. J. Amer. Chem. Soc. v.92 H.J. Brass;J.O. Edwards;M.J. Biallas
  44. J. Amer. Chem. Soc. v.89 E. R. Thornton
  45. J. Amer. Chem. Soc. v.92 J. C. Harris;J.L. Kurtz
  46. J. Amer. Chem. Soc. v.92 A. Streitwieser, Jr.;H. A. Hammond;R. H. Jagow;R. M. Williams;R. G. Jesaitis;C. J. Chang;R. Wolf
  47. The Molecular Orbital Theory of Organic Chemistry M.J.S. Dewar
  48. J. Chem. Soc. (B) R.A. More O'Ferrall
  49. J. Amer. Chem. Soc. v.97 D.A. Winey;E.R. Thornton
  50. Chem. Rev. v.72 W. P. Jencks
  51. J. Amer. Chem. Soc. v.101 P.R. Young;W.P. Jencks
  52. J. Amer. Chem. Soc. v.101 J.M. Harris;S.G. Shafer;J.R. Moffatt;A.R. Becker
  53. Quart. Rev.(London) v.16 A.J. Parker
  54. J. Amer. Chem. Soc. v.90 R. Alexander;E.C.F. Ko;A.J. Parker;T.J. Broxton