Organofluorosilicates in organic synthesis. XVI. Synthesis of organo-pentafluorosilicates via the Diels-Alder, ene, and Friedel-Crafts reaction. Their transformations to organic halides and alcohols.

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概要

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• Described herein are several representative examples of cleavage reactions of otherwise hardly accessible organopentafluorosilicates which are obtainable <I>via</I> the Diels-Alder reaction, ene reaction, and the Friedel-Crafts reaction of vinyl-, ethynyl-, or allyl-trichlorosilanes. The Diels-Alder reaction between vinyltrichlorosilane and <I>o</I>-xylylene generated <I>in situ</I> by debromination of α,α′-dibromo-<I>o</I>-xylene afforded (1,2,3,4-tetrahydro-2-naphthyl)trichlorosilane which was converted to the corresponding silicate. The silicate reacted with NBS and MCPBA to give the respective bromide and alcohol. The Diels-Alder reaction between ethynyltrichlorosilane and methyl coumalate gave a mixture of meta and para isomers of methyl (trichlorosilyl)benzoate in the ratio of 55/45, the silicate of which reacted with NBS to give two positional isomers of methyl bromobenzoate. The electronic effect of the methoxycarbonyl group on the Si–C bond cleavage was small. The silicate derived from 4-octenyltrichlorosilane which was obtained by the ene reaction between vinyltrichlorosilane and 1-hexene afforded, upon treatment with NBS, 4-octenyl bromide in the ratio of <I>E</I>⁄<I>Z</I>=83⁄17. The sterically crowded neophylsilicate obtainable <I>via</I> the Friedel-Crafts reaction of 2-methyl-1-propenyltrichlorosilane with benzene underwent the cleavage reaction with NBS in methanol. Neophyl bromide was formed with CuBr<SUB>2</SUB> in a low yield, no product being formed arising from rearrangement of the neophyl radical.

• 公益社団法人 日本化学会の論文

著者

• Tamao Kohei

  Department Of Synthetic Chemistry Faculty Of Engineering Kyoto University

• Yoshida Jun-ichi

  Department Of Biological Science Faculty Of Science Kumamoto University

• Kumada Makoto

  Department Of Applied Chemistry And Chemical Engineering Yamaguchi University

• Akita Munetaka

  Department of Macromolecular Science, Faculty of Science, Osaka University

• Sugihara Yoshihiro

  Department of Synthetic Chemistry, Faculty of Engineering, Kyoto University

• Iwahara Takahisa

  Department of Synthetic Chemistry, Faculty of Engineering, Kyoto University

• Akita Munetaka

  Department of Synthetic Chemistry, Faculty of Engineering, Kyoto University

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