Dr.Maysoon .A.

Aljuraisy
 Aromatic Compounds
• Aromatic compounds are chemical compounds that consist of
conjugated planar ring systems accompanied by delocalized pi-
electron clouds in place of individual alternating double and single
bonds.
They are also called aromatics or arenes. The best examples are toluene
and benzene. Aromatics require satisfying Huckel’s rule. Plants and
micro-organisms have an exclusive route to benzene-ring compounds.
The great majority of aromatic compounds in nature, therefore, are
produced by plants and micro-organisms, and animals are dependant
upon plants for many aromatic compounds either directly or indirectly.
• Aromatic compounds have the following general properties:
• Typically unreactive
• Often non polar and hydrophobic.
• High carbon-hydrogen ratio
• Burn with a strong sooty yellow flame, due to high C:H ratio.
• Undergo electrophilic substitution reactions and nucleophilic aromatic
substitutions

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• Any hydrocarbon can be classified as an
aromatic compound provided they follow
the Huckel rule. According to Huckel rule, for a
ring to be aromatic it should have the
following properties:
• Planarity
• Complete delocalization of the π electrons in
the ring
• Presence of (4n + 2) π electrons in the ring
where n is an integer (n = 0, 1, 2, . . .)

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Benzene, C6H6, is the least complex aromatic hydrocarbon.
Each carbon atom in the hexagonal cycle has four electrons to share.
One electron forms a sigma bond with the hydrogen atom, and one is
used in covalently bonding to each of the two neighboring carbons. This
leaves six electrons, shared equally around the ring in delocalized pi
molecular orbitals the size of the ring itself.
This equivalency can also 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.

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 Huckel’s Rule of Aromaticity
• Huckel’s rule states that only planar, fully conjugated monocyclic
polyenes having 4n + 2 π electrons, where n is an integer, that is, n
= 0, 1, 2, 3, 4, etc., should possess aromatic stability. An aromatic
compound must be planar and contain a cyclic cloud of π
electrons below and above the plane of the molecule. It contains
sp2 hybridized carbon atoms and must obey the Huckel rule.
• According to this rule, the ring system must have (4n+2) π
electrons, where n is any whole number (0, 1, 2, 3, etc). On this
basis the ring systems which have 2(n=0), 6(n=1), 10(n=2), 14(n=3)
etc pi electrons are aromatic. Typical examples of aromatic
compounds are benzene, naphthalene, and anthracene.

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 Benzene derivatives
• 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.

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 IUPAC Nomenclature of Aromatic Compounds
1. For the substituted aromatic compounds, the
substituent name is placed as a prefix to the name of
aromatic compounds. For example, a benzene ring
attached to a one-nitro group is named as
nitrobenzene.

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2. When more than one similar substituent
group is present in the ring, they are labelled
with the Greek numerical prefixes such as di,
tri, tetra to denote the number of similar
substituent groups attached to the ring

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3. When different substituted groups are attached to the aromatic compounds, the
substituent of the base compound is assigned number one and then the direction
of numbering is chosen such that the next substituent gets the lowest number.
Substituents are named in alphabetical order. For example: when chloro and nitro
groups are attached to the benzene ring, we first locate the chloro group then nitro
groups.
sometimes terms like ortho (o), meta (m) and para (p) are also used as prefixes to
indicate the relative positions 1,2-; 1,3- and 1,4- respectively. For example, 1,2-Di-
bromo-benzene can be named as o-di-bromo-benzene.

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H.W. Name each compound using both the common
name and the IUPAC name.

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Electrophilic Aromatic Substitution
The most common reaction of aromatic compounds is electrophilic aromatic
substitution, in which an electrophile (E+) reacts with an aromatic ring and
substitutes for one of the hydrogens. The reaction is characteristic of all
aromatic rings, not just benzene and substituted benzenes.

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Exampels on Electrophilic Aromatic Substitution

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Aromatic heterocyclic compounds
aromatic heterocyclic compounds are analogous of benzene. The aromatic
heterocyclic compounds also follow the Huckel’s rule. According to Huckel’s rule
an aromatic compounds must be cyclic in nature with planar geometry due to
conjugate double bonds and must have (4n+2)π electrons.
Examples of aromatic heterocyclic compounds.
1. Heterocyclic compounds with one hetero atom

2. Heterocyclic compounds with more than one hetero atom

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 Aromatic compounds in Nature
•Derivatives of aromatic aldehydes occur naturally in the seeds of plants. For
example, amygdalin is a substance occurring in the seeds of the bitter
almond.

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•The flavoring vanillin occurs naturally as a glucovanillin (a glucoside) in the
vanilla bean

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