The chemistry of phenalenium systems. XXXI. The synthesis, dimerization, and trapping of 6-methylenebenzo[cd]pyrene.
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概要
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The acetolysis of 6-mesyloxymethyl-6<I>H</I>-benzo[<I>cd</I>]pyrene (<B>6</B>) gave 7,7a-dihydrospiro[benzo[<I>ghi</I>]perylene-5-(6<I>H</I>),6′-[6<I>H</I>]benzo[<I>cd</I>]pyrene] (<B>13</B>), whereas, on formolysis, <B>6</B> gave spiro[benzo[<I>ghi</I>]perylene-5(6<I>H</I>),6′-[6<I>H</I>]benzo[<I>cd</I>]-pyrene], 6-hydroxymethyl-6<I>H</I>-benzo[<I>cd</I>]pyrene, and 6-methyl-6<I>H</I>-benzo[<I>cd</I>]pyrene as well as <B>13</B>. It might reasonably be supposed that the formation of <B>13</B> proceeds in a process involving four steps: (i) the formation of the intermediate 6<I>H</I>-6-benzo[<I>cd</I>]pyren-6-ylmethyl cation (<B>8</B>); (ii) the conversion of <B>8</B> into the reactive 6-methylenebenzo[<I>cd</I>]pyrene (<B>5</B>) by the loss of a proton; (iii) the head-to-head self-Diels-Alder dimerization of <B>5</B> to the initial dimer, 6,7-dihydrospiro[benzo[<I>ghi</I>]perylene-5(4a<I>H</I>),6′-[<I>cd</I>]benzo[<I>cd</I>]pyrene], and (iv) a 1,3-hydrogen shift to form <B>13</B>. When 6-methylbenzo[<I>cd</I>]pyren-6-yl tetrafluoroborate (<B>7</B>) was treated with triethylamine in chloroform, the spiro-dimer, <B>13</B>, was also obtained. The reaction of <B>7</B> with triethylamine in the presence of dimethyl acetylenedicarboxylate resulted in the formation of dimethyl benzo[<I>ghi</I>]perylene-5,6-dicarboxylate. These results strongly suggest the intermediate formation of <B>5</B> as a reactive compound.
- 公益社団法人 日本化学会の論文
著者
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Murata Ichiro
Department Of Cardiovascular Medicine Graduate School Of Medicine
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Yamamoto Kagetoshi
Department Of Chemistry Graduate School Of Science Osaka University
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Hara Osamu
Department Of Applied Biological Sciences Nagoya University:(present Address)faculty Of Pharmaceutic
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- The chemistry of phenalenium systems. XXXI. The synthesis, dimerization, and trapping of 6-methylenebenzo[cd]pyrene.
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