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Azulene

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Azulene
Names
IUPAC name
bicyclo[5.3.0]decapentaene
Identifiers
3D model (JSmol)
ChEBI
ChemSpider
ECHA InfoCard 100.005.449 Edit this at Wikidata
KEGG
UNII
  • InChI=1S/C10H8/c1-2-5-9-7-4-8-10(9)6-3-1/h1-8H checkY
    Key: CUFNKYGDVFVPHO-UHFFFAOYSA-N checkY
  • InChI=1/C10H8/c1-2-5-9-7-4-8-10(9)6-3-1/h1-8H
    Key: CUFNKYGDVFVPHO-UHFFFAOYAT
  • c1cccc2cccc2c1
Properties
C10H8
Molar mass 128.174 g·mol−1
Melting point 99–100 °C
Boiling point 242 °C
0.02 g/l[1]
Thermochemistry
-1266.5 kcal/mol[2]
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
checkY verify (what is checkY☒N ?)

Azulene is an organic compound and an isomer of naphthalene. Whereas naphthalene is colourless, azulene is dark blue. Its name is derived from the Spanish word azul, meaning "blue". Two terpenoids, vetivazulene (4,8-dimethyl-2-isopropylazulene) and guaiazulene (1,4-dimethyl-7-isopropylazulene), that feature the azulene skeleton are found in nature as constituents of pigments in mushrooms, guaiac wood oil, and some marine invertebrates.

Azulene has a long history, dating back to the 15th century as the azure-blue chromophore obtained by steam distillation of German chamomile. The chromophore was discovered in yarrow and wormwood and named in 1863 by Septimus Piesse. Its structure was first reported by Lavoslav Ružička, followed by its organic synthesis in 1937 by Placidus Plattner.

Structure and bonding

The blue color of the mushroom Lactarius indigo is due to the azulene derivative (7-isopropenyl-4-methylazulen-1-yl)methyl stearate.[3]

Azulene is usually viewed as resulting from fusion of cyclopentadiene and cycloheptatriene rings. Like naphthalene and cyclodecapentaene, it is a 10 pi electron system. It exhibits aromatic properties: (i) the peripheral bonds have similar lengths and (ii) it undergoes Friedel-Crafts-like substitutions. The stability gain from aromaticity is estimated to be half that of naphthalene.

Its dipole moment is 1.08 D,[4] in contrast with naphthalene, which has a dipole moment of zero. This polarity can be explained by regarding azulene as the fusion of the aromatic 6 π-electron cyclopentadienyl anion and aromatic 6 π-electron tropylium cation. In order to achieve the stable aromatic sextet in both rings, one electron from the seven-membered ring is transferred to the five-membered ring. Reactivity studies confirm that seven-membered ring is electrophilic and the five-membered ring is nucleophilic. The dipolar nature of the ground state is reflected in its deep colour, which is unusual for small unsaturated aromatic compounds. Another notable feature of azulene is that it violates Kasha's rule by exhibiting fluorescence from an upper-excited state (S2 → S0).[5]

Organic synthesis

Synthetic routes to azulene have long been of interest because of its unusual structure. In 1939 the first method was reported by St. Pfau and Plattner [6] starting from indane and ethyl diazoacetate.

An efficient one-pot route entails annulation of cyclopentadiene with unsaturated C5-synthons.[7] The alternative approach from cycloheptatriene has long been known, one illustrative method being shown below.[8]

Azulene procedure. step 1: cycloheptatriene 2+2 cycloaddition with dichloro ketene step 2: diazomethane insertion reaction step 3: dehydrohalogenation reaction with DMF step 4: Luche reduction to alcohol with sodium borohydride step 5: elimination reaction with Burgess reagent step 6: oxidation with p-chloranil step 7: dehalogenation with PMHS, palladium(II) acetate, potassium phosphate and the DPDB ligand

Organometallic complexes

In organometallic chemistry, azulene serves as a ligand for low-valent metal centers, which otherwise are known to form π-complexes with both cyclopentadienyl and cycloheptatrienyl ligands. Illustrative complexes are (azulene)Mo2(CO)6 and (azulene)Fe2(CO)5.[9]

In naphth[a]azulene, a naphthalene ring is condensed at the 1,2-positions of azulene. In one such system[10] deformation from planarity is found similar to that of tetrahelicene.

References

  1. ^ http://deepblue.lib.umich.edu/bitstream/2027.42/42354/1/128-58-2-268_58n2p268.pdf
  2. ^ Carl Salter, James B. Foresman (1998). "Naphthalene and Azulene I: Semimicro Bomb Calorimetry and Quantum Mechanical Calculations". Journal of Chemical Education. 75 (10): 1341. doi:10.1021/ed075p1341.
  3. ^ Harmon AD, Weisgraber KH, Weiss U. (1979). "Preformed azulene pigments of Lactarius indigo (Schw.) Fries (Russulaceae, Basidiomycetes)". Cellular and Molecular Life Sciences. 36 (1): 54–56. doi:10.1007/BF02003967. ISSN 1420-682X.{{cite journal}}: CS1 maint: multiple names: authors list (link)
  4. ^ Anderson, A. G., Jr.; Stecker, B. M. (1959). J. Am. Chem. Soc. 81 (18): 4941. doi:10.1021/ja01527a046. {{cite journal}}: Missing or empty |title= (help)CS1 maint: multiple names: authors list (link)
  5. ^ Tétreault, N.; Muthyala, R.S.; Liu, R.S.H.; Steer, R.P. Control of the Photophysical Properties of Polyatomic Molecules by Substitution and Solvation: The Second Excited Singlet State of Azulene. J. Phys. Chem. A. 1999, 103, 2524-2531.
  6. ^ Zur Kenntnis der flüchtigen Pflanzenstoffe VIII. Synthese des Vetivazulens Alexander St. Pfau , Pl. A. Plattner Helvetica Chimica Acta Volume 22 Issue 1, Pages 202 - 208 1939 doi:10.1002/hlca.19390220126
  7. ^ Klaus Hafner and Klaus-Peter Meinhardt (1990). "Azulene". Organic Syntheses; Collected Volumes, vol. 7, p. 15.
  8. ^ Approach to the Blues: A Highly Flexible Route to the Azulenes Sébastien Carret, Aurélien Blanc, Yoann Coquerel, Mikaël Berthod, Andrew E. Greene, Jean-Pierre Deprés Angewandte Chemie International Edition Volume 44, Issue 32 , Pages 5130 - 5133 2005 Abstract
  9. ^ Melvyn R. Churchill "Transition Metal Complexes of Azulene and Related Ligands" Progress in Inorganic Chemistry 1970, volume 11. doi:10.1002/9780470166123.ch2
  10. ^ Novel Synthesis of Benzalacetone Analogues of Naphth[a]azulenes by Intramolecular Tropylium Ion-Mediated Furan Ring-Opening Reaction and X-ray Investigation of a Naphth[1,2-a]azulene Derivative Kimiaki Yamamura, Shizuka Kawabata, Takatomo Kimura, Kazuo Eda, and Masao Hashimoto J. Org. Chem.; 2005; 70(22) pp 8902 - 8906; (Article) doi:10.1021/jo051409f Abstract
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