The chlorination of norbornene by metal chlorides and the product isomerization.
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概要
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The reaction of norbornene with CuCl<SUB>2</SUB>, TlCl<SUB>3</SUB>·4H<SUB>2</SUB>O, PbCl<SUB>4</SUB>, SeCl<SUB>4</SUB>, SbCl<SUB>5</SUB>, and VCl<SUB>4</SUB> in CCl<SUB>4</SUB>, CH<SUB>2</SUB>Cl<SUB>2</SUB>, or CH<SUB>3</SUB>CN gave a mixture of nortricyclyl chloride (<B>1</B>), and six isomeric dichloronorbornanes [<I>trans</I>-2,3-(<B>2</B>), <I>exo</I>-2-<I>anti</I>-7-(<B>3</B>), <I>trans</I>-2,5-(<B>4</B>), <I>exo</I>-<I>cis</I>-2,5-(<B>5</B>), <I>exo</I>-<I>cis</I>-2,3-(<B>6</B>), and <I>exo</I>-2-<I>syn</I>-7-(<B>7</B>)], the product distribution depending very much on metal chlorides and reaction conditions. The reactions did not show any participation of a chlorine molecule which may be released from metal chlorides. The ability of SeCl<SUB>4</SUB> and VCl<SUB>4</SUB> to chlorinate olefins was found for the first time. From a synthetic viewpoint CuCl<SUB>2</SUB> was a good reagent for obtaining <B>2</B>, while TlCl<SUB>3</SUB>·4H<SUB>2</SUB>O and SbCl<SUB>5</SUB> were recommended for either <B>3</B> or <B>7</B>. The reactions with the following metal chlorides did not give any dichloronorbornanes; SnCl<SUB>4</SUB>, BiCl<SUB>3</SUB>, TiCl<SUB>4</SUB>, FeCl<SUB>3</SUB>, NbCl<SUB>5</SUB>, TaCl<SUB>5</SUB>, and WCl<SUB>6</SUB>. It was revealed that isomerization of <B>2</B> or <B>7</B> to a mixture of <B>3</B>, <B>4</B>, and <B>5</B> occurred very rapidly by SbCl<SUB>5</SUB> and smoothly by TlCl<SUB>3</SUB>·4H<SUB>2</SUB>O. The chlorination of norbornene and their products isomerization were mainly explained by assuming a chloronorbornyl cation as an intermediate.
- 公益社団法人 日本化学会の論文
著者
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Okano Masaya
Institute for Chemical Research, Kyoto University
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Uemura Sakae
Institute for Chemical Research, Kyoto University
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Onoe Akira
Institute for Chemical Research, Kyoto University
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