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Development and Application of New Steric Protection Group for Stabilization of Highly Reactive Organic Species

Research Project

Project/Area Number 01470020
Research Category

Grant-in-Aid for General Scientific Research (B)

Allocation TypeSingle-year Grants
Research Field 有機化学一般
Research InstitutionThe University of Tokyo

Principal Investigator

OKAZAKI Renji  Faculty of Science, University of Tokyo Professor, 理学部, 教授 (70011567)

Project Period (FY) 1989 – 1990
Project Status Completed (Fiscal Year 1990)
Budget Amount *help
¥5,700,000 (Direct Cost: ¥5,700,000)
Fiscal Year 1990: ¥1,300,000 (Direct Cost: ¥1,300,000)
Fiscal Year 1989: ¥4,400,000 (Direct Cost: ¥4,400,000)
KeywordsHighly reactive species / Kinetic stabilization / Silicon / Germanium / Tin / Sterically protecting group / Polysulfide / Polyselenide / 不安定化学種 / 立体保護 / DNMR / 分子力場計算
Research Abstract

In recent years much attention has been paid to a new methodology for isolation of highly reactive chemical species which takes advantage of kinetic stabilization by sterically bulky groups. In the present study new bulky groups for stecric protection , i. e., benzene derivatives bearing (Me_3Si)_3C, (Me_3Si)_2CH, (Me_3Si)_2CMe at their o-positions, have been developed and various new compounds having this group have been prepared. Among them, 2, 4, 6-tris[bis (trimethylsilyl) methyl] phenyl group (Tb group) is especially useful baeuse it can be easily synthesized from mesitylene by chlorination and subsequent trimethylsilation and found to be bulkier than often used 2, 4, 6-tri-t-butylphenyl group. TbLi, obtained through bromination of TbH followedd by lithiation with t-BuLi, were converted into very sterically bulky compounds Tb (Mes) MX_2 (Mes = mesityl ; M=Si, Ge, Sn ; X=CL, H). New polysulfides and polyselenides Tb (Mes) MS_4 (Y=S or Se) were obtained from Tb (Mes) MX_2 and their structures were establised by X-ray structural analysis. These compounds are considered to be excellent precursors of compounds having M=Y bonds (M=Si, Ge, Sn : Y=S, Se) and indeed Tb (Mes) MS_4 (M=Ge, Sn) readily reacted with hexamethyl phosphorous triamide to give products which were considered to be formed via germanethione (Ge=S) and stannanethione (Sn=S). The polyselenides Tb (Mes) MSe_4 behaved similarly.

Report

(3 results)
  • 1990 Annual Research Report   Final Research Report Summary
  • 1989 Annual Research Report
  • Research Products

    (37 results)

All Other

All Publications (37 results)

  • [Publications] R.OKazaki,M.Unno,N.Inamoto,and G.Yamamoto: "A Conformational Study on Highy Crowded 1,3,5ーTris[bis(trimethylsilyl)methy1]benzene Derivatives." Chem.Lett.1989. 493-496 (1989)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1990 Final Research Report Summary
  • [Publications] R.Okazaki,M.Unno,and N.Inamoto: "Estimation of Bulkiness of a Highly Sterically Demanding 2,4,6ーTris[bis(trimethylsilyl)meth1]pheny1 Group." Chem.Lett.1989. 791-792 (1989)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1990 Final Research Report Summary
  • [Publications] R.Okazaki,N.Kumon,and N.Inamoto: "2,4,6ーTriーtertーbutylselenobenzaldehyde,the First Stable SelenoAldehyde." J.Am.Chem.Soc.111. 5949-5951 (1989)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1990 Final Research Report Summary
  • [Publications] R.Okazaki,M.Takahashi,N.Inamoto,T.Sugawara,and H.Iwamura: "Photoreaction of 3ーAzidoー5,7ーdiーtーbuty1ー2,1ーbenzisothiazole. Spectroscopic Detection of a Thionitroso Intermediate." Chem. Lett.1989. 2083-2076 (1989)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1990 Final Research Report Summary
  • [Publications] M.Takhashi,R.Okazaki,and N.Inamoto: "New Reactions of Thionitrosoarenes." Chem.ett.1989. 2087-2090 (1989)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1990 Final Research Report Summary
  • [Publications] M.A.Cremonini,L.Lunazzi,G.Placucci,R,Okazaki,and G.Yamamoto: "Conformation and Stereodynamics of Highly Hindered Ethane,1,2ーBis(2,4,6ーtriーtertーbutylphenyl)ethane, and of the Corresponding Ethyl Radical." J.Am.Chem.Soc.112. 2915-2921 (1990)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1990 Final Research Report Summary
  • [Publications] T.Kawashima,S.Nakayama,M.Yoshifuji,R.Okazaki,and N.Inamoto: "Revised Structure of 2ーCyclohexy1ー3,4ーdipheny1ー1,2ーoxaphphetane 2ーOxide." Bull.Chem.Soc.Jpn.64. 711-712 (1991)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1990 Final Research Report Summary
  • [Publications] N.Tokitoh,T.Matsumoto,H.Suzuki,and R.Okazaki: "Unusual 1,3ーRearrangement of Trimenthylsilyl Group in the Reaction of 2,4,6ーTris[bis(trimethylsily)methy1]phenyllithium." Terrahedron Lett.32. (1991)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1990 Final Research Report Summary
  • [Publications] M.A.Cremonini,L.Lunazzi,G.Placucci,N.Kumon,A.Ishii,T.Kawashima,and R.Okazaki: "Photoreaction of a Stable Thioaldehyde,2,4,6ーTriーtertーbutylーthiobenzaldehyde." J.Chem.Soc.Perkin 2. (1990)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1990 Final Research Report Summary
  • [Publications] N.Tokitoh,M.Takahashi,T.Matsumoto,H.Suzuki,Y.Matsuhashi,and R.Okazaki: "Synthesis and Reactions of Novel Organosulfur Compounds Having a Highly Sterically Sterically Bulky Group,2,4,6ー[Bis(trimethylsilyl)methy1]phenyl." Phosphorus,Sulfur,and Silion,and Related Elemnts. (1991)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1990 Final Research Report Summary
  • [Publications] N.Tokitoh,H.Suzuki,T.Matsumoto,Y.Masuhashi,and R.Okazaki: "1,2,3,4ーTetrathiametallolanes of Group 14 Metals,RR'MS_4 (S=Si,Ge,and Sn): Synthesis and Crystal Structures." J.Am.Chem.Soc.

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1990 Final Research Report Summary
  • [Publications] R. Okazaki, M. Unno, N, Inamoto, and G. Yamamoto: "A Conformational Study on Highly Crowded 1, 3.5-Tris [bis (trimethylsilyl) methyl] benzene Derivatives" Chem. Lett.,. 493-496 (1989)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1990 Final Research Report Summary
  • [Publications] R. Okazaki, M. Unno, and N. Inamoto,: "Estimation of Bulkiness of a Highly Sterically Demanding 2, 4, 6-Tris[bis (trimethylsilyl) methyl] phenyl Group" Chem. Lett.,. 791-792 (1989)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1990 Final Research Report Summary
  • [Publications] R. Okazaki, N. Kumon, and N. Inamoto,: "2, 4, 6-Tritert-butylselenobenzaldehyde, the First Stable Selenoaldehyde" J. Am. Chem. Soc.111,. 5949-5951 (1989)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1990 Final Research Report Summary
  • [Publications] R. Okazaki, M. Takahashi, N. Inamoto, T. Sugawara, and H. Iwamura: "Photoreaction of 3-Azido-5, 7-dit-butyl-2, 1-benzisothiazole. Spectroscopic Detection of a Thionitroso Intermediate" Chem. Lett.,. 2083-2076 (1989)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1990 Final Research Report Summary
  • [Publications] M. Takahashi, R. Okazaki, and N. Inamoto,,: "New Reactions of Thionitrosoarenes" Chem. Lett.,. 2087-2090 (1989)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1990 Final Research Report Summary
  • [Publications] M. A. Cremonini, L. Lunazzi, G. Placucci, R. Okazaki, and G. Yamamoto,: "Conformation and Stereodynamics of a Highly Hindered Ethane, 1, 2-Bis (2, 4, 6-tri-tert-butylphenyl) ethane, and of the Corresponding Ethyl Radical" J. Am. Chem. Soc.112,. 2915-2921 (1990)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1990 Final Research Report Summary
  • [Publications] T. Kawashima, S. Nakayama, M. Yoshifuji, R, Okazaki, and N. Inamoto,: "Revised Structure of 2-Cyclohexy1-3, 4-diphenyl-1, 2-oxaphos-phetane 2-Oxide" Bull. Chem. Soc. Jpn.,. 64,. 711-712 (1991)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1990 Final Research Report Summary
  • [Publications] N. Tokitoh, T. Matsumoto, H. Suzuki, and R. Okazaki,: "Unusual 1, 3-Rearrangement of Trimethylsilyl Group in the Reaction of 2, 4, 6-Tris [bis (trimethylsilyl) methyl] pheny-lithium" Tetrahedron Lett.32,. (1991)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1990 Final Research Report Summary
  • [Publications] M. A. Cremonini, L. Lunazzi, G, Placucci, N, Kumon, A. Ishii, T. Kawashima, and R. Okazaki,: "Photoreaction of a Stable Thioaldehyde, 2, 4, 6-Tritert-butylthiobenzaldehyde" J. Chem. Soc., Perkin. 2,. (1991)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1990 Final Research Report Summary
  • [Publications] N. Tokitoh, M. Takahashi, T. Matsumoto, H. Suzuki, Y. Matsuhashi, and R. Okazaki,: "Synthesis and Reactions of Novel Organosulfur Compounds Having a Highly Sterically Bulky Group, 2, 4, 6- [Bis (trimethylsiulyl) -methyl] phenyl" Phosphorus, Sulfur, and Silicon, and Related Elements. (1991)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1990 Final Research Report Summary
  • [Publications] R.Okazaki,M.Unno,N.Inamoto,and G.Yamamoto: "A Conformational Study on Highly Crowded 1,3,5ーTris[bis(trimethylーsilyl)methyl]benzene Derivatives." Chem.Lett.1989. 493-496 (1989)

    • Related Report
      1990 Annual Research Report
  • [Publications] R.Okazaki,M.Unno,and N.Inamoto: "Estimation of Bulkiness of a Highly Sterically Demanding 2,4,6ーTris[bis(trimethylsilyl)methyl)methyl]pheny Group." Chem.Lett.1989. 791-792 (1989)

    • Related Report
      1990 Annual Research Report
  • [Publications] R.Okazaki,N.Kumon,and N.Inamoto: "2,4,6ーTriーtertーbutylselenobenzaldehyde,the First Stable Selenoaldehyde." J.Am.Chem.Soc.111. 5949-5951 (1989)

    • Related Report
      1990 Annual Research Report
  • [Publications] R.Okazaki,M.Takahashi,N.Inamoto,T.Sugawara,and H.Iwamura: "Photoreaction of 3ーAzidoー5,7ーdiーtーbutylー2,1ーbenzisothiazole.Spectroscopic Detection of a Thionitroso Intermediate." Chem.Lett.1989. 2083-2076 (1989)

    • Related Report
      1990 Annual Research Report
  • [Publications] M.Takahashi,R.Okazaki,and N.Inamoto: "New Reactions of Thionitrosoarenes." Chem.Lett.1989. 2087-2090 (1989)

    • Related Report
      1990 Annual Research Report
  • [Publications] M.A.Cremonini,L.Lunazzi,G.Placucci,R.Okazaki,and G.Yamamoto: "Conformation and Stereodynamics of a Highly Hindered Ethane,1,2ーBis(2,4,6ーtriーtertーbutylphenyl)ethane,and of the Corresponding Ethyl Radical." J.Am.Chem.Soc.112. 2915-2921 (1990)

    • Related Report
      1990 Annual Research Report
  • [Publications] T.Kawashima,S.Nakayama,M.Yoshifuji,R.Okazaki,and N.Inamoto: "Revised Structure of 2ーCyclohexy1ー3,4ーdiphenylー1,2ーoxaphosphetane 2ーOxide." Bull.Chem.Soc.Jpn.64. 711-712 (1991)

    • Related Report
      1990 Annual Research Report
  • [Publications] N.Tokitoh,T.Matsumoto,H.Suzuki,and R.Okazaki: "Unusual 1,3ーRearrangement of Trimethylsilyl Group in the Reaction of 2,4,6ーTris[bis(trimethylsily)methyl]phenyllithium." Tetrahedron Lett.32. (1991)

    • Related Report
      1990 Annual Research Report
  • [Publications] M.A.Cremonini,L.Lunazzi,G.Placucci,N.Kumon,A.Ishii,T.Kawashima,and R.Okazaki: "Photoreaction of a Stable Thioaldehyde,2,4,6ーTriーtertーbutylーthiobenzaldehyde." J.Chem.Soc.Perkin2. (1990)

    • Related Report
      1990 Annual Research Report
  • [Publications] N.Tokitoh,M.Takahashi,T.Matsumoto,H.Suzuki,Y.Matsuhashi,and R.Okazaki: "Synthesis and Reactions of Novel Organosulfur Compounds Having a Highly Sterically Bulky Group,2,4,6ー[Bis(trimethylsilyl)ーmethyl]phenyl." Phosphorus,Sulfur,and Silicon,and Related Elements. (1991)

    • Related Report
      1990 Annual Research Report
  • [Publications] N.Tokitoh,H.Suzuki,T.Matsumoto,Y.Matsuhashi,and R.Okazaki: "1,2,3,4ーTetrathiametallolanes of Group 14 Metals,PR'MS_4 (S=Si,Ge,and Sn):Synthesis and Crystal Structures." J.Am.Chem.Soc.

    • Related Report
      1990 Annual Research Report
  • [Publications] R.Okazaki: "A conformational study on highly crowded 1,3,5-tris-[bis(trimethylsilyl)methyl]benzene derivatives" Chem.Lett.1989. 493-496 (1989)

    • Related Report
      1989 Annual Research Report
  • [Publications] R.Okazaki: "Estimation of bulkiness of a highly sterically demanding 2,4,6-tris[bis(trimethylsilyl)methyl]phenyl group" Chem.Lett.1989. 791-792 (1989)

    • Related Report
      1989 Annual Research Report
  • [Publications] R.Okazaki: "2,4,6-Tri-tert-butylselenobenzaldehyde,the first stable selenoaldehyde" J.Am.Chem.Soc.111. 5949-5951 (1989)

    • Related Report
      1989 Annual Research Report
  • [Publications] R.Okazaki: "Photoreaction of 3-azido-5,7-di-t-butyl-2,1-benziso-thiazole. Spectroscopic detection of a thionitroso intermediate" Chem.Lett.1989. 2083-2086 (1989)

    • Related Report
      1989 Annual Research Report
  • [Publications] M.Takahashi: "New reactions of thionitrosoarenes" Chem.Lett.1989. 2087-2090 (1989)

    • Related Report
      1989 Annual Research Report

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Published: 1989-04-01   Modified: 2016-04-21  

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