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Cyclohexa-1,3-diene

Cyclohexa-1,3-diene is an organic compound with the formula (C<sub>2</sub>H<sub>4</sub>)(CH)<sub>4</sub>. It is a colorless, flammable liquid. Its refractive index is 1.475 (20&nbsp;°C, D). It is one of two isomers of cyclohexadiene, the other being 1,4-cyclohexadiene. It is commonly referred to as "benzane" due to the structural similarities to benzene and benzyne.

Synthesis

Cyclohexadiene is prepared by the double dehydrobromination of 1,2-dibromocyclohexane:

(CH<sub>2</sub>)<sub>4</sub>(CHBr)<sub>2</sub> + 2 NaH → (CH<sub>2</sub>)<sub>2</sub>(CH)<sub>4</sub> + 2 NaBr + 2 H<sub>2</sub>

Reactions

Useful reactions of this diene are cycloadditions, such as the Diels-Alder reaction.

Conversion of cyclohexa-1,3-diene to benzene + hydrogen is exothermic by about 25 kJ/mol in the gas phase.

cyclohexane → cyclohexa-1,3-diene + 2 H<sub>2</sub> (ΔH = +231.5 kJ/mol; endothermic)
cyclohexane → benzene + 3 H<sub>2</sub> (ΔH = +205 kJ/mol; endothermic)
cyclohexa-1,3-diene → benzene + H<sub>2</sub> (ΔH = -26.5 kJ/mol; exothermic)

Compared with its isomer cyclohexa-1,4-diene, cyclohexa-1,3-diene is about 1.6 kJ/mol more stable.

Cyclohexadiene and its derivatives form (diene)iron tricarbonyl complexes. Illustrative is [(C<sub>6</sub>H<sub>8</sub>)Fe(CO)<sub>3</sub>], an orange liquid. This complex reacts with hydride-abstracting reagents to give the cyclohexadienyl derivative [(C<sub>6</sub>H<sub>7</sub>)Fe(CO)<sub>3</sub>]<sup>+</sup>. Cyclohexadienes react with ruthenium trichloride to give (Benzene)ruthenium dichloride dimer.

Occurrence

Cyclohexa-1,3-diene itself is rare in nature, but the cyclohexa-1,3-diene motif is fairly common. One example is chorismic acid, an intermediate in the shikimic acid pathway. Of the several examples of the terpenoids and terpenes, a prominent example is phellandrene. An unusual derivative is cis-1,2-dihydrocatechol.

Coenzyme A-conjugated to the 2-position of cyclohexadiene-2-carboxylic acid is an intermediate in the biodegradation of aromatic carboxylic acids.

See also

References