Azulene

Chembox new
ImageFile = Azulene-numbers.png ImageSize = 200px
IUPACName = bicyclo [5.3.0] decapentaene
OtherNames =
Section1 = Chembox Identifiers
CASNo = 275-51-4
PubChem =
SMILES = C12=CC=CC=CC1=CC=C2
Section2 = Chembox Properties
C=10|H=8
Appearance =
Density =
MeltingPt = 99 - 100 °C
BoilingPt = 242 °C
Solubility =
Section3 = Chembox Hazards
MainHazards =
FlashPt =
Autoignition =

Azulene is an organic compound and a monoterpene. It is an isomer of naphthalene but its physical properties are quite different. Naphthalene is a white crystalline solid whereas azulene, whose name is derived from the Spanish word azul, meaning "blue", is a dark blue crystalline solid used in many cosmetics. Azulene has a long history dating back to the 15th century as the azure-blue distillate obtained by steam distillation of Chamomile. The compound was discovered and named in 1863 by Septimus Piesse in azure-blue distillates from other sources such as yarrow and wormwood. Lavoslav Ružička solved the structure for this compound and the first organic synthesis followed in 1937 by Placidus Plattner.

Derivatives

Vetivazulene or 4,8-dimethyl-2-isopropylazulene is obtained from vetiver oil. Guaiazulene or 1,4-dimethyl-7-isopropylazulene occurs naturally as a constituent of guaiac wood oil.

Structure

Azulene consists of a fused cyclopentadiene ring and a cycloheptatriene ring and is an isomer of naphthalene. Azulene is 10 pi electron system just like cyclodecapentaene and does have aromatic properties even though it is not a single ring system like benzene. The peripheral bonds have similar lengths and only the shared bond in the middle is a single bond. The stability gain from aromaticity is half of that of naphthalene. The molecule can be considered a fusion product of a 6 pi electron cyclopentadienyl anion which is aromatic and the likewise aromatic 6 pi electron tropylium cation. The observed dipole moment of 0.8 Debye (very different from naphthalene, which has zero dipole moment) is consistent with this picture.

Organic synthesis

For many years not many synthetic routes existed to azulene and the compound was therefore expensive. A recent contribution takes cycloheptatriene as starting material ["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 [http://www3.interscience.wiley.com/cgi-bin/abstract/110567907/ABSTRACT Abstract] ] .

[
cycloheptatriene 2+2 cycloaddition with dichloro ketene step 2: diazomethane insertion reaction step 3: dehydrohalogenation reaction with DMF step 4: carbonyl 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 ]

In naphth [a] azulenes, a naphthalene ring is condensed with the 1,2-position of an azulene ring. In one such system ["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 [http://pubs3.acs.org/acs/journals/doilookup?in_doi=10.1021/jo051409f Abstract] ] deformation from planarity is found similar to that of tetrahelicene.

External links

* MSDS [http://physchem.ox.ac.uk/MSDS/AZ/azulene.html Website]
* MSDS [http://www.chemicalland21.com/lifescience/foco/AZULENE.htm Website]

References