著者

大前 巌

出版者

The Society of Synthetic Organic Chemistry, Japan

雑誌

有機合成化学協会誌 (ISSN:00379980)

巻号頁・発行日

vol.36, no.2, pp.133-145, 1978-02-01 (Released:2009-11-13)

参考文献数

99

被引用文献数

2 2

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1, 4-Cyclohexadiene (1, 4-CHD) is easily prepared by the Birch reduction using an alkali metal and a proton source in liquid ammonia or by the electrolytic reduction, and the 1, 4-CHD can be isomerized to 1, 3-CHD and disproportionated to benzene and cyclohexene or cyclohexane. While the addition reaction of one double bond in the 1, 4-CHD occurs easily, the reactivity of the other double bond is lowered. As the disproportionation and the hydrogenation are carried out using the same catalyst, it seems reasonable that the reaction of the 1, 4-CHD with the catalyst forms once a π-complex, the 1, 4-CHD moiety of the π-complex is eliminated as benzene by heating, the remaining catalyst moiety having two hydrogen atoms of the complex reacts with the other 1, 4-CHD molecule to form the hydrogenated π-complex, which gives cyclohexene. The 1, 4-CHD forms the 1, 4-, 1, 3-CHD of phenyl-π- complexes depending upon various kinds of metals of the catalyst, and the mass spectra of the 1, 3-π- complex indicates the presence a metastable ion during the cource from the molecular ion to the dehydrogenated phenyl-π-complex ion. The polymerizability of 1, 4-CHD monomer is low and poly-1, 3-CHD-, polymer of a low molecular weight is formed after the isomerization to 1, 3-CHD in the polymerization. Its oxidation affords diepoxide and tetraol which can be used as polymers and modifiers, and its reaction with metal cyanide and phosgene affords tetracyanoquinodimethane which can be also used as conductive polymers and super conduction materials.