Aromatic compounds 

are those chemical compounds (most commonly organic) that contain

one or more rings with pi electrons delocalized all the way around them. In contrast to
compounds that exhibit aromaticity, aliphatic compounds lack this delocalization. The term
"aromatic" was assigned before the physical mechanism determining aromaticity was discovered,
and referred simply to the fact that many such compounds have a sweet or pleasant odour;
however, not all aromatic compounds have a sweet odour, and not all compounds with a sweet
odour are aromatic compounds. Aromatic hydrocarbons, or arenes, are aromatic organic
compounds containing solely carbon and hydrogen atoms. The configuration of six carbon atoms
in aromatic compounds is called a "benzene ring", after the simple aromatic compound benzene,
or a phenyl group when part of a larger compound.
Not all aromatic compounds are benzene-based; aromaticity can also manifest in heteroarenes,
which follow Hückel's rule (for monocyclic rings: when the number of its π electrons equals
4n + 2, where n = 0, 1, 2, 3, ...). 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.[1]

Contents

 1Benzene ring model

 2Arene synthesis
 3Reactions
o 3.1Aromatic substitution
o 3.2Coupling reactions
o 3.3Hydrogenation
o 3.4Cycloadditions
o 3.5Dearomatization
 4Benzene and derivatives of benzene
o 4.1Other monocyclic aromatic hydrocarbon
 5Polycyclic aromatic hydrocarbons
 6See also
 7References
 8External links

Benzene ring model[edit]

Benzene

Main article: Aromaticity
Benzene, , is the least complex aromatic hydrocarbon, and it was the first one named as such.
The nature of its bonding was first recognized by August Kekulé in the 19th century. Each carbon
atom in the hexagonal cycle has four electrons to share. One goes to the hydrogen atom, and
one to each of the two neighbouring carbons. This leaves one electron to share with one of the
two neighbouring carbon atoms, thus creating a double bond with one carbon and leaving a
single bond with the other, which is why some representations of the benzene molecule portray it
as a hexagon with alternating single and double bonds.
Other depictions of the structure portray the hexagon with a circle inside it, to indicate that the six
electrons are floating around in delocalized molecular orbitals the size of the ring itself. This
represents the equivalent nature of the six carbon–carbon bonds all of bond order 1.5; the
equivalency 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 carbon–hydrogen ratio is high
3. They burn with a strong sooty yellow flame because of the high carbon–hydrogen 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[2] and popularized starting in 1959 by the Morrison & Boyd textbook on organic
chemistry. The proper use of the symbol is debated: some publications use it to any cyclic π
system, while others use it only for those π systems that obey Hückel's rule. Jensen[3] argues that,
in line with Robinson's original proposal, the use of the circle symbol should be limited to
monocyclic 6 π-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.

Arene synthesis[edit]
A reaction that forms an arene compound from an unsaturated or partially unsaturated cyclic
precursor is simply called 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 Dötz reaction an alkyne, carbon monoxide and a chromium carbene complex are the
reactants. Diels–Alder 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.[4]

Reactions[edit]
Aromatic ring systems participate in many organic reactions.

Aromatic substitution[edit]
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:[5]
Coupling reactions[edit]
In coupling reactions a metal catalyses a coupling between two formal radical fragments.
Common coupling reactions with arenes result in the formation of new carbon–carbon
bonds e.g., alkylarenes, vinyl arenes, biraryls, new carbon–nitrogen bonds (anilines) or
new carbon–oxygen bonds (aryloxy compounds). An example is the direct arylation
of perfluorobenzenes[6]

Hydrogenation[edit]
Hydrogenation of arenes create saturated rings. The compound 1-naphthol is completely
reduced to a mixture of decalin-ol isomers.[7]

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:[8]

Cycloadditions[edit]
Cycloaddition reaction are not common. Unusual thermal Diels–Alder reactivity
of arenes can be found in the Wagner-Jauregg reaction. Other photochemical
cycloaddition reactions with alkenes occur through excimers.
Dearomatization[edit]
In dearomatization reactions the aromaticity of the reactant is permanently lost.

Benzene and derivatives of benzene[edit]

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
 

Aspirin
 

Paracetamol
 

Picric acid
The arene ring has an ability to stabilize charges. This is seen in, for example,
phenol (C6H5–OH), which is acidic at the hydroxyl (OH), since a charge on this
oxygen (alkoxide –O−) is partially delocalized into the benzene ring.

Other monocyclic aromatic hydrocarbon[edit]

Other monocyclic aromatic hydrocarbon
include Cyclotetradecaheptaene or Cyclooctadecanonaene.
Polycyclic aromatic hydrocarbons[edit]

Hexabenzocoronene is a large polycyclic aromatic hydrocarbon.

Main article: Polycyclic aromatic hydrocarbon

Polynuclear aromatic hydrocarbons (PAHs) are aromatic hydrocarbons that
consist of fused aromatic rings and do not contain heteroatoms or
carry substituents.[9] 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.[10][11][12]
They are also found in the interstellar medium, in comets, and in 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.

See also[edit]
 Aromatic substituents: Aryl, Aryloxy and Arenediyl
 Asphaltene
 Hydrodealkylation
 Simple aromatic rings
 Rhodium-platinum oxide, a catalyst used to hydrogenate aromatic
compounds.