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1990 Fiscal Year Final Research Report Summary

A Novel Synthesis of Indole and Quinoline Derivatives from Aniline and 1, 2- or 1, 3-Diols

Research Project

Project/Area Number 01850192
Research Category

Grant-in-Aid for Developmental Scientific Research (B).

Allocation TypeSingle-year Grants
Research Field Synthetic chemistry
Research InstitutionKyoto University

Principal Investigator

WATANABE Yoshihisa  Kyoto University, Hydrocarbon Chemistry, Professor, 工学部, 教授 (70025956)

Co-Investigator(Kenkyū-buntansha) HONDA Tadatoshi  Mitsui Toatsu Chemicals, Inc., Senior Research Scientist, 技術研究部, 主席研究員
KONDO Teruyuki  Kyoto University, Hydrocarbon Chemistry, Instructor, 工学部, 助手 (20211914)
MITSUDO Takeaki  Kyoto University, Hydrocarbon Chemistry, Associate Professor, 工学部, 助教授 (90026344)
Project Period (FY) 1989 – 1990
KeywordsIndole / Quinoline / Ruthenium catalyst / Homogeneous catalyst / Dehydrogenation / Heterocyclization
Research Abstract

1. (1) Syntheses of Indole Derivatives from 2- (2-Aminophenyl) ethanol and 2- (2-Nitrophenyl) ethanol : When 2- (2-aminophenyl) ethanols (3), which were easily prepared by condensation between the corresponding 2-nitrotoluene (1) and aldehydes followed by reduction, were treated with a catalytic amount of RuCl_2(PPh_3)_3 (2 mol%) under reflux in toluene for 6 h, the corresponding indoles (4) were readily obtained in high to excellent yields (73-100 %).
1. (2) Plots of -ln vs time were linear over 70 % conversions of (3), where x is the amount of indoles (4) formed and a_0 is the amount of (3) charged. Furthermore, a straight line with a zero intercept was obtained on plotting the observed rate constants against the different initial catalyst concentrations ([RuCl6.10 x 10-2.44 x 10 mol dm^<-3>). Thus the rate law for the present indole synthesis is expressed by the following equation.
d[(4)]/dt=kappa_<obs>[RuCl_2(PPh_3)_3]_0[(3)]
1. (3) With a heterogeneous (Pd/C or Rh/C) and homogeneous (RuCl_2(PPh_3)_3 binary catalyst system, indoles were afforded in one pot from 2- (2-nitrophenyl) ethanols (2) under a hydrogen atmosphere.
2. (1) Synthesis of Indole from Aniline and Ethylene Glycol : When the reaction of aniline with ethylene glyol was performed (aniline/ethylene glycol=1.0/1.5) in the presence of a catalytic amount of RuCl, 1.4-diphenylpiperazine was mainly obtained. However, when the molar ration of aniline/ethylene glycol was increased from 1.0/1.5 to 10/1.0, indole was obtained in 8 % yield together with a considerable amount of N, N'-diphenylethylenediamine. At this stage, RuClO - dppe is the most suitable catalyst system for the synthesis of indole from aniline and ethylene glycol (18 % yield).
2. (2) N- (Trimethylsilyl) aniline and acetanilide, which were protected compounds of aniline, did not react with ethylene glycol and the corresponding indoles were not obtained at all.

  • Research Products

    (4 results)

All Other

All Publications (4 results)

  • [Publications] 渡部 良久: "VIII族金属錯体を用いる新規合成反応の開発" 有機合成化学協会誌. 47. 1132-1145 (1989)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Yasushi Tsuji: "RutheniumーCatalyzed Dehydrogenative NーHeterocyclization:Indoles from 2ーAminophenethyl Alcohols and 2ーNitrophenethyl Alcohols" The Journal Organic Chemistry. 55. 580-584 (1990)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Yoshihisa Watanabe: "Novel Organic Syntheses Using Group VIII Metal Complexes" Journal of Synthetic Organic Chemistry, Japan. Vol. 47. 1132-1145 (1989)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Yasushi Tsuji: "Ruthenium-Catalyzed Dehydrogenative N-Heterocyclization : Indoles from 2-Aminophenethyl Alcohols and 2-Nitrophenethyl Alcohols" The Journal of Organic Chemistry. Vol. 55. 580-584 (1990)

    • Description
      「研究成果報告書概要(欧文)」より

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Published: 1993-08-12  

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