Generation and Reactions of 2-(1-Adamantyl)adamantene. Rearrangement to 3-(1-Adamantyl)-4-protoadamantylidene

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Abstract

The S<sub>N</sub>1 methanolysis of (1-adamantyl)(3-noradamantyl)methyl heptafluorobutyrate at 100 °C yielded (1-adamantyl)(3-noradamantyl)methyl methyl ether (<b>17</b>), 2-(1-adamantyl)-1-methoxyadamantane (<b>18</b>), and 4-(1-adamantyl)-3-methoxyprotoadamantane (<b>19</b>) in a 2 : 65 : 33 ratio. The methanolysis of (1-adamantyl)(3-noradamantyl)diazomethane (<b>7</b>) at 0 °C also yielded <b>17</b>, <b>18</b>, and <b>19</b> in a 4 : 33 : 63 ratio. On the other hand, the photolysis of <b>7</b> in 99 : 1 (v/v) hexane–methanol gave <b>17</b>, <b>18</b>, 2-(1-adamantyl)-2-methoxyadamantane (<b>25</b>), and 2-(1-adamantyl)-2,4-didehydroadamantane (<b>20</b>) in a 30 : 9 : 36 : 25 ratio. Presence of triethylamine decreased the yields of ethers <b>17</b>, <b>18</b>, and <b>25</b>, and increased the yield of <b>20</b> to 46%. The formation of a considerable amount of <b>17</b> and the absence of <b>19</b> in the photolysis products indicate the generation of (1-adamantyl)(3-noradamantyl)methylidene (<b>8</b>). The formation of <b>25</b> and <b>20</b> suggests that the generated carbene <b>8</b> rearranges to 2-(1-adamantyl)adamantene (<b>3b</b>) and then gives 3-(1-adamantyl)-4-protoadamantylildene by the subsequent retro-insertion. An attempt to isolate <b>3b</b> in the photolysis of <b>7</b> in cyclohexane failed, and the sole isolated product was <b>20</b>.

Journal

  • Bulletin of the Chemical Society of Japan

    Bulletin of the Chemical Society of Japan 69(7), 2053-2062, 1996-07-15

    The Chemical Society of Japan

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Codes

  • NII Article ID (NAID)
    10008906326
  • NII NACSIS-CAT ID (NCID)
    AA00580132
  • Text Lang
    ENG
  • Article Type
    ART
  • ISSN
    00092673
  • NDL Article ID
    4060472
  • NDL Source Classification
    ZP1(科学技術--化学・化学工業)
  • NDL Call No.
    Z53-B35
  • Data Source
    CJP  NDL  J-STAGE 
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