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Dynamic Stereochemistry of N-Acyl-9-triptycylamine derivatives.

Research Project

Project/Area Number 09640645
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeSingle-year Grants
Section一般
Research Field Organic chemistry
Research InstitutionKitasato University

Principal Investigator

YAMAMOTO Gaku  Kitasato University, Department of Chemistry, , School of Science, Kitasato University professor, 理学部, 教授 (70011632)

Project Period (FY) 1997 – 1998
Project Status Completed (Fiscal Year 1998)
Budget Amount *help
¥2,200,000 (Direct Cost: ¥2,200,000)
Fiscal Year 1998: ¥1,000,000 (Direct Cost: ¥1,000,000)
Fiscal Year 1997: ¥1,200,000 (Direct Cost: ¥1,200,000)
Keywordsamide / triptycenes / nitrogen inversion / stereochemistry / dynamic NMR / X-ray crystallography / internal rotation
Research Abstract

Dynamic stereochemistry of N-9-triptycylacetamide (1) and its N-methyl-, N-ethyl-, N-benzyl-, and N-phenyl derivatives was studied. These compounds were synthesized by alkylation of 9-triptycylamine followed by acetylation. X-Ray crystallographic analysis of all the compounds were made, and revealed that the nitrogen atom is significantly pyramidalized in any compound except for the parent one 1. For the N-ethyl compound, both Z- and E-isomers exist in a single crystal, while the other compounds adopt Z-configuration in crystal. In solution, 1 and the N-phenyl compound exist almost exclusively as the Z-isomer as for the amide bond, while the other compounds exist as an equilibrium mixture of Z- and E-isomers. The equilibrium constant (Z/E) tends to increase with the solvent polarity in any compound. Rotation of the amide bond was studied by dynamic NMR spectroscopy. The barrier to rotation also tends to increase with the solvent polarity. At low temperatures, the methylene protons of the N-ethyl and N-benzyl compounds are nonequivalent to each other, indicating the pyramidality of the nitrogen atom in solution. Stereomutation of the Tp-N bond was measured and discussed.

Report

(3 results)
  • 1998 Annual Research Report   Final Research Report Summary
  • 1997 Annual Research Report
  • Research Products

    (11 results)

All Other

All Publications (11 results)

  • [Publications] 山本 学: "Structure and Stereodynamics of N-Methyl-N-9-triptycylacetamide : Pyramidal Amide Nitrogen in the Crystalline State." Chemistry Letters. (7). 605-606 (1997)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] 山本 学: "Structure and Stereodynamics of N-Ethyl-N-9-triptycylacetamide : Co-existence of Z-and E-Isomers in a Single Crystal and Pyramidal Amide Nitrogen Both in Crystal and in Solution." Chemistry Letters. (12). 1295-1296 (1997)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] 山本 学: "Dynamic Stereochemistry of N-Phenyl-9-triptycylamine and its N-Alkyl Derivatives." Bulletin of the Chemical Society of Japan. 71 (5). 1241-1248 (1998)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] G.Yamamoto, H.Murakami, N.Tsubai, and Y.Mazaki: "Structure and Stereodynamics of N-Methyl-N-9-triptycylacetamide : Pyramidal Amide Nitrogen in the Crystalline State" Chem.Lett.(7). 605-606 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] G.Yamamoto. N.Tsubai, H.Murakami, and Y.Mazaki: "Structure and Stereodynamics of N-Ethyl-N-9-triptycylacetamide : Co-existence of Z- and E-Isomers in a Single Crystal and Pyramidal Amide Nitrogen Both in Crystal and in Solution" Chem.Lett.(12). 1295-1296 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] G.Yamamoto, K.Inoue, H.Higuchi, M.Yonebayashi, Y.Nabeta, and J.Ojima: "Dynamic Stereochemistry of N-Phenyl-9-triptycylamine and its N-Alkyl Derivatives" Bull.Chem.Soc.Jpn.71 (5). 1241-1248 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] 山本 学: "Strucutre and Stereodynamics of N-Methyl-N-9-triptycylacetamide : Pyramidal Amide Nitrogen in the Crystalline State." Chemistry Letters. (7). 605-606 (1997)

    • Related Report
      1998 Annual Research Report
  • [Publications] 山本 学: "Strucutre and Stereodynamics of N-Ethyl-N-9-triptycylacetamide : Co-existence of Z-and E-Isomers in a Single Crystal and Pyramidal Amide Nitrogen Both in Crystal and in Solution." Chemistry Letters. (12). 1295-1296 (1997)

    • Related Report
      1998 Annual Research Report
  • [Publications] 山本 学: "Dynamic Stereochemistry of N-Phenyl-9-triptycylamine and its N-Alkyl Derivatives." Bulletin of the Chemical Society of Japan. 71(5). 1241-1248 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] 山本 学: "Strucutre and stereodynamics of N-methyl-N-9-triptycylacetamide:Pyramidal amide nitrogen in the crystalline sate." Chemistry Letters. (7). 605-606 (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] 山本 学: "Strucutre and stereodynamics of N-ethyl-N-9-triptycylacetamide:Co-existence of Z-and E-isomers in a single crystal and pyramidal amide nitrogen both in crystal and in solution." Chemistry Letters. (12). 1295-1296 (1997)

    • Related Report
      1997 Annual Research Report

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Published: 1997-04-01   Modified: 2016-04-21  

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