Synthesis and properties of bis(cyclopropylphenyl)cyclopropenones and the tris(p-cyclopropylphenyl)cyclopropenium ion.

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概要

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• The reaction of trichlorocyclopropenium tetrachloroaluminate with cyclopropylbenzene has been found to readily afford the disubstitution products, bis(<I>p</I>-cyclopropylphenyl)- (<B>1a</B>), (<I>p</I>-cyclopropylphenyl) (<I>o</I>-cyclopropylphenyl)-, and bis(<I>o</I>-cyclopropylphenyl)cyclopropenones, each of which has been separated and fully characterized spectroscopically. The tris(<I>p</I>-cyclopropylphenyl)cyclopropenium ion (<B>2</B>) could not be obtained by the direct trisubstitution of the trichlorocyclopropenium ion with cyclopropylbenzene, but has been synthesized <I>via</I> two other routes starting from cyclopropenone <B>1a</B>. The UV and <SUP>13</SUP>C NMR spectral data of the cation <B>2</B> indicated the conjugative interaction of the <I>para</I>-cyclopropyl group with the cyclopropenium ring. However, the cation-stabilizing effect of the <I>para</I>-cyclopropyl group, as shown by the p<I>K</I><SUB>R<SUP>+</SUP></SUB> value (3.23 in 23% ethanol) for <B>2</B>, is much smaller than in the case of the tris(<I>p</I>-cyclopropylphenyl)methyl cation. This has been interpreted in terms of the decrease in delocalization of the positive charge to the <I>para</I>-position of the cation <B>2</B>, when compared with the triarylmethyl analogue.

• 公益社団法人 日本化学会の論文

著者

• Komatsu Koichi

  Department Of Environmental And Biological Chemistry Fukui University Of Technology

• Okamoto Kunio

  Department of Fuel Chemistry Faculty of Engineering Kyoto University

• Tomioka Isao

  Department of Hydrocarbon Chemistry, Faculty of Engineering, Kyoto University

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