Reactivities of Stable Rotamers. XXXV. Diazotization of 2-(1,4-Dimethyl-9-triptycyl)-2-methylpropylamine Rotamers

• Michinori Oki

  Department of Chemistry, Faculty of Science, Okayama University of ScienceRidaicho, Okayama 700

• Yasushi Taguchi

  Department of Chemistry, Faculty of Science, Okayama University of ScienceRidaicho, Okayama 700

• Tsutomu Miyasaka

  Department of Chemistry, Faculty of Science, Okayama University of ScienceRidaicho, Okayama 700

• Mika Kitano

  Department of Chemistry, Faculty of Science, Okayama University of ScienceRidaicho, Okayama 700

• Shinji Toyota

  Department of Chemistry, Faculty of Science, Okayama University of ScienceRidaicho, Okayama 700

• Toshimasa Tanaka

  Department of Chemistry, Faculty of Science, The University of TokyoHongo, Bunkyo-ku, Tokyo 113

• Katsumi Yonemoto

  Department of Chemistry, Faculty of Science, The University of TokyoHongo, Bunkyo-ku, Tokyo 113

• Gaku Yamamoto

  Department of Chemistry, Faculty of Science, The University of TokyoHongo, Bunkyo-ku, Tokyo 113

抄録

The title amine rotamers were prepared from the corresponding carboxylic acids and were diazotized with isopentyl nitrite in the presence of acetic acid in benzene. The ap rotamer affords, as main products, olefins that are derived by deprotonation after rearrangement of the intervening carbocation and small amounts each of the corresponding acetate and a cyclized product, both of which are derived from the unrearranged cation. By contrast, the olefins are minor products and a cyclized product, which is formally derived by insertion of the intervening cation to a C–H bond of the 1-methyl group before rearrangement, is main in the case of the sc isomer. This cyclic product was synthesized independently. The yield of the corresponding acetate is increased to a considerable extent in the case of the sc relative to the ap. These results in the reaction of the sc are discussed in terms of stabilization of the intervening cation by the C–H bond.

収録刊行物

• Bulletin of the Chemical Society of Japan

  Bulletin of the Chemical Society of Japan 68 (5), 1485-1496, 1995-05-01

  Oxford University Press (OUP)

キーワード

• General Chemistry

詳細情報

• CRID: 1360846644034275072
• NII論文ID: 10008890051
• NII書誌ID: AA00580132
• DOI: 10.1246/bcsj.68.1485
• ISSN: 13480634
• ISSN: 00092673
• Web Site: https://academic.oup.com/bcsj/article-pdf/68/5/1485/56195478/bcsj.68.1485.pdf
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