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2005 Fiscal Year Final Research Report Summary

Synthesis of Novel, Highly Reactive Sulfur-containing Species by Taking Advantage of Steric Protection

Research Project

Project/Area Number 16550045
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeSingle-year Grants
Section一般
Research Field Organic chemistry
Research InstitutionJapan Women's University

Principal Investigator

OKAZAKI Renji  Japan Women's University, Faculty of Science, Professor, 理学部, 教授 (70011567)

Co-Investigator(Kenkyū-buntansha) TAKENAKA Keiko  Japan Women's University, Faculty of Science, Research Associate, 理学部, 助手 (00130740)
Project Period (FY) 2004 – 2005
Keywordssteric protection / thioaldehyde / thioacyl halide / thiophilic reaction / carbon monosulfide / carbanion / carbene
Research Abstract

We have synthesized two types of highly reactive organosulfur species by taking advantage of steric protection due to bulky substituents such as 2,4,6-tri-t-butylphenyl (Mes^*) and 4-t-butyl-2,6-bis[(2,2",6,6"-tetrametyl-m-terphenyl-2'-yl)methyl]phenyl(Bmt). Reaction of stable thioaldehyde Mes^*CHS, synthesized by us as the first stable thioaldehyde, with N-bromo- or N-chlorosuccinimide gave the corresponding thioacyl halides Mes^*C(=S)X(X=Br,Cl), which reacted with alcohols, thiols or amines to afford thioesters, dithioesters or thioamides. BmtLi attacked on the sulfur of CS_2 (thiophilic reaction) to produce highly reactive anionic species having carbene character, (BmtS)(LiS)C : (1),which was in equiliprium with dimeric species, (BmtS)(LiS)C=C(SLi)(SBmt) (2).Anionic species 1 and 2 were also formed when HC(=S)(SBmt) was deprotonated with lithium tetramethylpiperidide and quenched with a variety of alkyl halides. Anion 1 was stabe at -78℃ but decomposed into C=S and BmtSLi at -30℃. This represents a novel method for the generation of C=S.

  • Research Products

    (4 results)

All 2005 2004

All Journal Article (4 results)

  • [Journal Article] Deprotonation of Aryl Methanedithioate by Lithium Amides : Formation of Lithium Arylthio(thioxo) methanide Having Unique Reactivity2005

    • Author(s)
      K.Mogi
    • Journal Title

      Chem. Lett. 34

      Pages: 1674-1675

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Deprotonation of Aryl Methanedithioate by Lithium Amide : Formation of Lithium Arylthio(thioxo)methanide Having Unique Reactivity2005

    • Author(s)
      K.Mogi
    • Journal Title

      Chem.Lett. 34

      Pages: 1674-1675

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Tin-Chalcogen Double-Bond Compound, Stannanethione and Stannaneselone : Synthesis, Structure, and Reactivities2004

    • Author(s)
      M.Saito
    • Journal Title

      J. Am. Chem. Soc. 126

      Pages: 15572-15582

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Tin-Chalcogen Double-Bond Compounds, Stannanethione and Stannaneselone : Synthesis, Structure, and Reactivities2004

    • Author(s)
      M.Saito
    • Journal Title

      J.Am.Chem.Soc. 126

      Pages: 15572-15582

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

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Published: 2007-12-13  

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