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Aromatic hydrocarbon - Wikipedia https://en.wikipedia.


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An aromatic hydrocarbon or arene[1] (or sometimes aryl hydrocarbon)[2] is a hydrocarbon with sigma bonds
and delocalized pi electrons between carbon atoms forming a circle. In contrast, aliphatic hydrocarbons lack this
delocalization. The term 'aromatic' was assigned before the physical mechanism determining aromaticity was
discovered; the term was coined as such simply because many of the compounds have a sweet or pleasant
odour. The configuration of six carbon atoms in aromatic compounds is known as a benzene ring, after the
simplest possible such hydrocarbon, benzene. Aromatic hydrocarbons can be monocyclic (MAH) or polycyclic

Some non-benzene-based compounds called heteroarenes, which follow Hckel's rule (for monocyclic rings:
when the number of its -electrons equals 4n + 2, where n = 0, 1, 2, 3,), are also called aromatic compounds.
In these compounds, at least one carbon atom is replaced by one of the heteroatoms oxygen, nitrogen, or sulfur.
Examples of non-benzene compounds with aromatic properties are furan, a heterocyclic compound with a
five-membered ring that includes a single oxygen atom, and pyridine, a heterocyclic compound with a
six-membered ring containing one nitrogen atom.[3]

1 Benzene ring model

2 Arene synthesis
3 Arene reactions
3.1 Aromatic substitution
3.2 Coupling reactions
3.3 Hydrogenation
3.4 Cycloadditions
4 Benzene and derivatives of benzene
5 Polycyclic aromatic hydrocarbons
6 See also
7 References
8 External links

Benzene, C6H6, is the simplest aromatic hydrocarbon, and it was the first one named as
such. The nature of its bonding was first recognized by August Kekul in the 19th century.
Each carbon atom in the hexagonal cycle has four electrons to share. One goes to the
hydrogen atom, and one each to the two neighbouring carbons. This leaves one electron to
share with one of the same two neighbouring carbon atoms, thus creating a double bond
with one carbon and leaving a single bond with the other, which is why the benzene
molecule is drawn with alternating single and double bonds around the hexagon.
The structure is alternatively illustrated as a circle around the inside of the ring to show six
electrons floating around in delocalized molecular orbitals the size of the ring itself. This
depiction represents the equivalent nature of the six carboncarbon bonds all of bond order 1.5; the equivalency

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Aromatic hydrocarbon - Wikipedia https://en.wikipedia.org/wiki/Aromatic_hydrocarbon

is explained by resonance forms. The electrons are visualized as floating above and below the ring with the
electromagnetic fields they generate acting to keep the ring flat.

General properties of aromatic hydrocarbons:

1. They display aromaticity

2. The carbonhydrogen ratio is high
3. They burn with a strong sooty yellow flame because of the high carbonhydrogen ratio
4. They undergo electrophilic substitution reactions and nucleophilic aromatic substitutions

The circle symbol for aromaticity was introduced by Sir Robert Robinson and his student James Armit in 1925[4]
and popularized starting in 1959 by the Morrison & Boyd textbook on organic chemistry. The proper use of the
symbol is debated; it is used to describe any cyclic system in some publications, or only those systems that
obey Hckel's rule in others. Jensen[5] argues that, in line with Robinson's original proposal, the use of the circle
symbol should be limited to monocyclic 6 -electron systems. In this way the circle symbol for a six-center
six-electron bond can be compared to the Y symbol for a three-center two-electron bond.

A reaction that forms an arene compound from an unsaturated or partially unsaturated cyclic precursor is simply
called an aromatization. Many laboratory methods exist for the organic synthesis of arenes from non-arene
precursors. Many methods rely on cycloaddition reactions. Alkyne trimerization describes the [2+2+2]
cyclization of three alkynes, in the Dtz reaction an alkyne, carbon monoxide and a chromium carbene complex
are the reactants. DielsAlder reactions of alkynes with pyrone or cyclopentadienone with expulsion of carbon
dioxide or carbon monoxide also form arene compounds. In Bergman cyclization the reactants are an enyne plus
a hydrogen donor.

Another set of methods is the aromatization of cyclohexanes and other aliphatic rings: reagents are catalysts
used in hydrogenation such as platinum, palladium and nickel (reverse hydrogenation), quinones and the
elements sulfur and selenium.[6]

Arenes are reactants in many organic reactions.

Aromatic substitution

In aromatic substitution one substituent on the arene ring, usually hydrogen, is replaced by another substituent.
The two main types are electrophilic aromatic substitution when the active reagent is an electrophile and
nucleophilic aromatic substitution when the reagent is a nucleophile. In radical-nucleophilic aromatic
substitution the active reagent is a radical. An example of electrophilic aromatic substitution is the nitration of
salicylic acid:[7]

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Aromatic hydrocarbon - Wikipedia https://en.wikipedia.org/wiki/Aromatic_hydrocarbon

Coupling reactions

In coupling reactions a metal catalyses a coupling between two formal radical fragments. Common coupling
reactions with arenes result in the formation of new carboncarbon bonds e.g., alkylarenes, vinyl arenes,
biraryls, new carbonnitrogen bonds (anilines) or new carbonoxygen bonds (aryloxy compounds). An example
is the direct arylation of perfluorobenzenes [8]


Hydrogenation of arenes create saturated rings. The compound 1-naphthol is completely reduced to a mixture of
decalin-ol isomers.[9]

The compound resorcinol, hydrogenated with Raney nickel in presence of aqueous sodium hydroxide forms an
enolate which is alkylated with methyl iodide to 2-methyl-1,3-cyclohexandione:[10]


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Cycloaddition reaction are not common. Unusual thermal DielsAlder reactivity of arenes can be found in the
Wagner-Jauregg reaction. Other photochemical cycloaddition reactions with alkenes occur through excimers.

Benzene derivatives have from one to six substituents attached to the central benzene core. Examples of
benzene compounds with just one substituent are phenol, which carries a hydroxyl group, and toluene with a
methyl group. When there is more than one substituent present on the ring, their spatial relationship becomes
important for which the arene substitution patterns ortho, meta, and para are devised. For example, three
isomers exist for cresol because the methyl group and the hydroxyl group can be placed next to each other
(ortho), one position removed from each other (meta), or two positions removed from each other (para).
Xylenol has two methyl groups in addition to the hydroxyl group, and, for this structure, 6 isomers exist.

Representative arene compounds

Toluene Ethylbenzene p-Xylene m-Xylene

Mesitylene Durene 2-Phenylhexane Biphenyl

Phenol Aniline Nitrobenzene Benzoic acid

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Aspirin Paracetamol Picric acid

The arene ring has an ability to stabilize charges. This is seen in, for example, phenol (C6H5OH), which is
acidic at the hydroxyl (OH), since a charge on this oxygen (alkoxide O) is partially delocalized into the
benzene ring.

Polycyclic aromatic hydrocarbons (PAHs) are aromatic

hydrocarbons that consist of fused aromatic rings and do not
contain heteroatoms or carry substituents.[11] Naphthalene is the
simplest example of a PAH. PAHs occur in oil, coal, and tar
deposits, and are produced as byproducts of fuel burning (whether
fossil fuel or biomass). As pollutants, they are of concern because
some compounds have been identified as carcinogenic, mutagenic,
and teratogenic. PAHs are also found in cooked foods. Studies have
shown that high levels of PAHs are found, for example, in meat
cooked at high temperatures such as grilling or barbecuing, and in
smoked fish.[12][13][14] An illustration of typical polycyclic aromatic
hydrocarbons. Clockwise from top left:
They are also found in the interstellar medium, in comets, and in
benz(e)acephenanthrylene, pyrene and
meteorites and are a candidate molecule to act as a basis for the
earliest forms of life. In graphene the PAH motif is extended to
large 2D sheets.

Aromatic substituents: Aryl, Aryloxy and Arenediyl

Simple aromatic rings
Rhodium-platinum oxide, a catalyst used to hydrogenate aromatic compounds.

1. Definition IUPAC Gold Book Link (http://goldbook.iupac.org/A00435.html)

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Aromatic hydrocarbon - Wikipedia https://en.wikipedia.org/wiki/Aromatic_hydrocarbon

2. Mechanisms of Activation of the Aryl Hydrocarbon Receptor (http://diss.kib.ki.se/2003/91-7349-549-2

/thesis.pdf) by Maria Backlund, Institute of Environmental Medicine, Karolinska Institutet
3. HighBeam Encyclopedia: aromatic compound (http://www.encyclopedia.com/doc/1E1-aromatic.html)
4. Armit, James Wilkins; Robinson, Robert (1925). "Polynuclear heterocyclic aromatic types. Part II. Some
anhydronium bases". J. Chem. Soc. Trans. 127: 16041618.
5. Jensen, William B. (April 2009). "The circle symbol for aromaticity" (http://www.che.uc.edu/jensen
/W.%20B.%20Jensen/Reprints/157.%20Aromaticity%20Circle.pdf) (PDF). J. Chem. Educ. 86 (4):
423424. Bibcode:2009JChEd..86..423J (http://adsabs.harvard.edu/abs/2009JChEd..86..423J).
doi:10.1021/ed086p423 (https://doi.org/10.1021%2Fed086p423).
6. March, Jerry (1985), Advanced Organic Chemistry: Reactions, Mechanisms, and Structure (3rd ed.),
New York: Wiley, ISBN 0-471-85472-7
7. Webb, K.; Seneviratne, V. (1995). "A mild oxidation of aromatic amines". Tetrahedron Letters. 36 (14):
23772378. doi:10.1016/0040-4039(95)00281-G (https://doi.org
8. Lafrance, M.; Rowley, C.; Woo, T.; Fagnou, K. (2006). "Catalytic intermolecular direct arylation of
perfluorobenzenes.". Journal of the American Chemical Society. 128 (27): 87548756.
CiteSeerX (https://citeseerx.ist.psu.edu/viewdoc/summary?doi= .
PMID 16819868 (https://www.ncbi.nlm.nih.gov/pubmed/16819868). doi:10.1021/ja062509l
9. Meyers, A. I.; Beverung, W. N.; Gault, R. "1-Naphthol" (http://www.orgsyn.org
/demo.aspx?prep=CV6P0371). Org. Synth. 51: 103.; Coll. Vol., 6
10. Noland, Wayland E.; Baude, Frederic J. "Ethyl Indole-2-carboxylate" (http://www.orgsyn.org
/demo.aspx?prep=CV5P0567). Org. Synth. 41: 56.; Coll. Vol., 5
11. Fetzer, J. C. (2000). "The Chemistry and Analysis of the Large Polycyclic Aromatic Hydrocarbons".
Polycyclic Aromatic Compounds. New York: Wiley. 27 (2): 143. ISBN 0-471-36354-5.
doi:10.1080/10406630701268255 (https://doi.org/10.1080%2F10406630701268255).
12. "Polycyclic Aromatic Hydrocarbons Occurrence in foods, dietary exposure and health effects"
(http://ec.europa.eu/food/fs/sc/scf/out154_en.pdf) (PDF). European Commission, Scientific Committee on
Food. December 4, 2002.
13. Larsson, B. K.; Sahlberg, GP; Eriksson, AT; Busk, LA (1983). "Polycyclic aromatic hydrocarbons in
grilled food". J. Agric. Food Chem. 31 (4): 867873. PMID 6352775 (https://www.ncbi.nlm.nih.gov
/pubmed/6352775). doi:10.1021/jf00118a049 (https://doi.org/10.1021%2Fjf00118a049).
14. "Polycyclic Aromatic Hydrocarbons (PAHs)" (http://www.atsdr.cdc.gov/toxfaqs/tf.asp?id=121&tid=25).
Agency for Toxic Substances and Disease Registry. 1996.

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