Reactivity of <I>exo</I>- and <I>endo</I>-Tricyclo[3.2.1.0<SUP>2,4</SUP>]octan-8-ylidenes and 7-Norbornenylidene

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概要

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• <I>endo</I>-Tricyclo[3.2.1.0<SUP>2,4</SUP>]octan-8-ylidene (<B>2</B>) generated by the thermolysis of sodium salt of <I>endo</I>-tricyclo[3.2.1.0<SUP>2,4</SUP>]octan-8-one tosylhydrazone (<B>5</B>) gave toluene (3.9%), cyclohepta-1,4-diene(<B>6</B>, 14%), cyclohepta-1,3-diene(<B>7</B>, 3.5%), bicyclo[3.3.0]octa-1,6-diene(<B>8</B>, 4.8%), bicyclo[3.3.0]octa-1,7-diene(<B>9</B>, 9.0%), and <I>endo</I>-tricyclo[3.2.1.0<SUP>2,4</SUP>]octane (<B>10</B>, 21%). In sharp contrast, <I>exo</I>-tricyclo[3.2.1.0<SUP>2,4</SUP>]oct-8-ylidene (<B>1</B>) gave toluene (1.5%) and tricyclo[5.1.0<SUP>1,7</SUP>]oct-5-ene (<B>14</B>, 57%). The results indicate significant homoconjugative interaction between the p-orbital of the divalent carbon and the symmetric Walsh orbital of the cyclopropane. This is in line with the results of 7-norbornenylidene (<B>3</B>) in which the interaction between the divalent carbon and the carbon-carbon double bond stabilizes the nonclassical methylene. Thermolysis of sodium salt of 7-norbornenone tosylhydrazone (<B>18</B>) gave rise to cyclohexa-1,3-diene (3%), norbornene (6%), toluene (5%), spiro[2.4]hepta-4,6-diene (<B>19</B>, 10%), and bicyclo[3.2.0]hepta-1,6-diene (<B>21</B>, 56%).

• 公益社団法人 日本化学会の論文

著者

• Murahashi Shun-ichi

  Department Of Applied Chemistry Okayama University Of Science

• Sonoda Akio

  Department of Chemistry Faculty of Science Osaka University

• MAEDA Yusuke

  Department of Applied Chemistry, Graduate School of Engineering, Osaka City University

• Moritani Ichiro

  Department of Chemistry, Faculty of Engineering Science, Osaka University

• Okumura Kazuo

  Department of Chemistry, Faculty of Engineering Science, Osaka University

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