Cyclohexa-1,3-diene
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Cyclohexa-1,3-diene is an organic compound with the formula (C2H4)(CH)4. It is a colorless, flammable liquid. Its refractive index is 1.475 (20 °C, D). It is one of two isomers of cyclohexadiene, the other being 1,4-cyclohexadiene.
Synthesis
Cyclohexadiene is prepared by the double dehydrobromination of 1,2-dibromocyclohexane:[1]
- (CH2)4(CHBr)2 + 2 NaH → (CH2)2(CH)4 + 2 NaBr + 2 H2
Reactions
Useful reactions of this diene are cycloadditions, such as the Diels-Alder reaction.[2]
Conversion of cyclohexa-1,3-diene to benzene + hydrogen is exothermic by about 25 kJ/mol in the gas phase.[3][4]
- cyclohexane → cyclohexa-1,3-diene + 2 H2 (ΔH = +231.5 kJ/mol; endothermic)
- cyclohexane → benzene + 3 H2 (ΔH = +205 kJ/mol; endothermic)
- cyclohexa-1,3-diene → benzene + H2 (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.[5]
Cyclohexadiene and its derivatives form (diene)iron tricarbonyl complexes. Illustrative is [(C6H8)Fe(CO)3], an orange liquid. This complex reacts with hydride-abstracting reagents to give the cyclohexadienyl derivative [(C6H7)Fe(CO)3]+.[6] Cyclohexadienes react with ruthenium trichloride to give (Benzene)ruthenium dichloride dimer.[7]
Occurrence
Cyclohexa-1,3-diene itself is rare in nature, but the cyclohexa-1,3-diene motif is fairly common.[8] 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.[9]
See also
References
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- ↑ Sanjeeva Rao Guppi, George A. O'Doherty, "1,3-Cyclohexadiene" Encyclopedia of Reagents for Organic Synthesis, 2008 John Wiley & Sons. Script error: No such module "doi".
- ↑ US National Institute of Standards and Technology, NIST Chemistry WebBook 1,3-Cyclohexadiene Benzene
- ↑ J. Sherman The heats of hydrogenation of unsaturated hydrocarbons Template:Webarchive Journal of the American Oil Chemists' Society; Volume 16, Number 2 / February, 1939
- ↑ NIST Chemistry WebBook 1,4-Cyclohexadiene
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