Cyclohexa-1,3-diene explained

Cyclohexa-1,3-diene (also known as Benzane) 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 H2H = +231.5 kJ/mol; endothermic)

cyclohexane → benzene + 3 H2H = +205 kJ/mol; endothermic)

cyclohexa-1,3-diene → benzene + H2H = -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 [(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>]+.[6] Cyclohexadienes react with ruthenium trichloride to give (Benzene)ruthenium dichloride dimer.[7]

Occurrence

Cyclohexa-1,3-diene is a fairly common motif in nature.[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.

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

Notes and References

  1. John P.. Schaefer. Leland . Endres. 1967. 1,3-Cyclohexadiene. 31. Organic Syntheses. 47. 10.15227/orgsyn.047.0031.
  2. Sanjeeva Rao Guppi, George A. O'Doherty, "1,3-Cyclohexadiene" Encyclopedia of Reagents for Organic Synthesis, 2008 John Wiley & Sons.
  3. US National Institute of Standards and Technology, NIST Chemistry WebBook 1,3-Cyclohexadiene Benzene
  4. J. Sherman The heats of hydrogenation of unsaturated hydrocarbons Journal of the American Oil Chemists' Society; Volume 16, Number 2 / February, 1939
  5. NIST Chemistry WebBook 1,4-Cyclohexadiene
  6. Cyclohexadieneiron Tricarbonyl. Anthony J.. Pearson. Huikai. Sun. 2008. 10.1002/047084289X.rn00791. E-EROS Encyclopedia of Reagents for Organic Synthesis. 978-0471936237 .
  7. Book: Bennett. M. A.. Huang. T. N.. Matheson. T. W.. Smith. A. K.. (η-Hexamethylbenzene)ruthenium Complexes. 16. (η6 -Hexamethylbenzene)Ruthenium Complexes . Inorganic Syntheses. 1982. 21. 74–78. 10.1002/9780470132524.ch16. 9780470132524 .
  8. Book: 10.1016/B978-044453347-0.50066-5 . Natural Products Containing a Cyclohexane, Cyclohexene, or Cyclohexadiene Subunit . Second Supplements to the 2nd Edition of Rodd's Chemistry of Carbon Compounds . 1991 . Gribble . G.W. . 375–445 . 978-0-444-53347-0 .
  9. 24767428 . 2014 . Porter . A. W. . Young . L. Y. . Benzoyl-CoA, a Universal Biomarker for Anaerobic Degradation of Aromatic Compounds . Advances in Applied Microbiology . 88 . 167–203 . 10.1016/B978-0-12-800260-5.00005-X . 978-0-12-800260-5 .