AROMATIC
COMPOUNDS
A Lecture Presentation
Group 3
What are 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.
What is aromatic?
Criteria of aromaticity:
1 Molecule must be cyclic
2 Molecule must be planar
3 Molecule must be fully conjugated
4 4n+2 π-electrons (Hückel's Rule)
Aromatic, Non-Aromatic, & Anti- aromatic
1 Molecule must be cyclic
Violate any of
AROMATIC
2 Molecule must be planar these
= NON-aromatic
3 Molecule must be fully conjugated
4 4n+2 π-electrons (Hückel's Rule)
4a 4n π-electrons anti-aromatic
aromatic abnormally stable, unique chemical properties
anti-aromatic = very unstable
Non-aromatic = nothing special
Aromatic, Antiaromatic, Nonaromatic?
Antiaromatic Nonaromatic Aromatic
Benzene
Benzene (C6H6), is the simplest aromatic hydrocarbon (or
arene) and parent compound of numerous important aromatic
compounds.
Benzene has four degrees of unsaturation, making it highly
unsaturated hydrocarbon.
But, whereas unsaturated hydrocarbon such as alkenes,
alkynes, and dienes readily undergo addition reaction,
benzene does not.
Structure and bonding of Benzene
• It was first isolated from coal tar by Michael Faraday in 1825.
• The molecular formula: C6H6 Molecular weight: 78.
• Molecular formula of benzene indicates a high degree of unsaturation in
the molecule.
• Benzene is aromatic, six membered cyclic hydrocarbon.
• Carbon atoms of benzene are attached in planar hexagonal ring.
Kekulé's Structure
Chemist Kekulé proposed that benzene was a cyclic hydrocarbon
with a hexagon ring structure.
In Kekulé's model, each carbon atom alternates between single and
double bonds to other carbon atoms.
The IUPAC name for this structure is cyclohexa-1,3,5-triene
Problems with the Kekulé Structure
1. Bond Lengths:
The Kekulé model suggests alternating single and double bonds,
resulting in different bond lengths. However, experiments show
that all carbon-carbon bonds in benzene are of equal length,
approximately 0.139 nm.
Problems with the Kekulé Structure
2. Stability:
The predicted enthalpy change of hydrogenation for benzene (based
on three double bonds) is -360 kJ/mol. Actual measurements show
it is only -208 kJ/mol, indicating that benzene is more stable than
expected.
Problems with the Kekulé Structure
3. Reactivity:
The structure implies higher reactivity due to the presence of
double bonds, but benzene is actually less reactive than
alkenes, which contradicts the expectations from the Kekulé
model.
Resonance Structure of Benzene
• Resonance theory says that positions of double bonds in benzene molecule
are not fixed, i.e., л electrons associated with double bonds are delocalized in
benzene ring.
Aromaticity of benzene
• It has a planar molecular structure.
• All the π electrons of benzene molecule are delocalized.
• All six carbon atoms of the benzene molecule are sp² hybridized.
• Six p₂ orbitals (unhybridized) of six carbon atoms in benzene
are available for the delocalization of π electron cloud.
• It obeys Huckel's rule of aromaticity.
• If, n = 1, Then, 4n + 2 = (4 X 1) + 2 = 6 π electrons.
• The following are contributing resonance structures and
resonance hybrid.
• Benzene is an aromatic compound.
Molecular orbital structure of Benzene
• According to molecular orbital concept, all six carbon atoms of
benzene are sp² hybridized and thus each one of them forms
two sigma bonds with two carbon atoms on either side and one
sigma bond with hydrogen atom.
• Thus, all 6 carbon atoms and 6 hydrogen atoms of benzene
lie in the same plane. The angle between two adjacent
bonds is 120° as shown in Figure
Molecular orbital structure of Benzene
• Each carbon atom of benzene has an unhybridized л orbital (p₂- orbital). It
lies above and under the plane of benzene ring.
• These π orbitals of six carbon atoms overlap sidewise (above and below the
plane) to form two sets of π electron clouds.
Molecular orbital structure of Benzene
• π electrons of p₂ orbitals are delocalized and they
can move over all the six carbon atoms of benzene.
• Such delocalization of л electrons constitutes
continuous ring like electron clouds (above and
below the plane).
The final molecular orbital structure of benzene
with bond lengths and bond angle
Bonding in Benzene
Benzene's true structure involves a delocalized ring of electrons
Each carbon atom has one unbonded electron in a p-shaped orbital, which extends
above and below the carbon ring.
These p orbitals interact, creating a pi-bonding system with electron density above
and below the ring
The electrons are delocalized, meaning they aren't fixed to a single carbon atom but
can move around the entire ring
This delocalization makes benzene more stable because spreading out the electrons
lowers their energy
The delocalized electron rings create a high electron density, making benzene
susceptible to attack by electrophiles.
Benzene does not react with bromine, but only in the presence of FeBr. (a
Lewis acid). and the reaction is substitution, not an addition.
Nomenclatures of
Aromatic
Compounds
Nomenclatures of Aromatics
Compounds
The nomenclature of aromatic compounds is a systematic way to name
these substances. For benzene-based compounds, the parent ring is often
benzene itself. Monosubstituted benzenes have the substituent named as
a prefix to “benzene”. Disubstituted benzenes use prefixes like ortho -,
meta -, para - or numbering to show the substituent positions. Poly -
substituted benzenes are numbered to give the lowest set of numbers to
substituents, which are listed
. Fused - ring and heteroaromatic compounds have their own rules based on
common parent names and specific ring characteristics.
Nomenclatures of Aromatics
Compounds
Monosubstituted Derivatives of Benzene
Benzene is the “first and simplest” aromatic compound and many
monosubstituted derivatives of benzene are named systematically by
adding the name of the substituent to “benzene” which is the parent: For
examples:
Nomenclatures of Aromatics
Compounds
If the substituent is an alkyl chain with more carbon atoms than benzene,
then benzene can be treated as a substituent. The ring, in this case, is called
a phenyl group just like the methyl, ethyl, etc. The phenyl group is often
abbreviated as “Ph”.
Nomenclatures of Aromatics
Compounds
There are also monosubstituted benzene rings
that have common names. And when naming an
aromatic compound with one of these rings, you
need to use the common name as the parent
and not the “benzene”.
Nomenclatures of Aromatics
Compounds
Disubstituted Derivatives of Benzene
Some disubstituted benzene rings also have
common names, and the first thing here is to
know the relative positions of ortho, meta, and
para:
Disubsituted Derivatives of
Benzene
Disubsituted Derivatives of
Benzene
Disubsituted Derivatives of
Benzene
Disubsituted Derivatives of
Benzene
Nomenclatures of Aromatics
Compounds
For the other rings with common
names, start numbering the ring from
the substituent that is part of the
common ring such that the other groups
get the smallest possible locants:
Nomenclatures of Aromatics
Compounds
Nomenclatures of Aromatics
Compounds
Using “benzene” as the
parent can also be
encountered, even though it
is not what you’d commonly
see:
Nomenclatures of Aromatics
Compounds
In general, to name an aromatic compound, you can follow
these steps:
[Link] and name the parent. If it is not one of the
common names, then use benzene.
[Link] and name the substituents.
[Link] the ring to give the substituents the smallest
possible number.
[Link] the substituents alphabetically followed by the parent
name.
For example, in ortho-dibromobenzene, numbering from
the top Br goes clockwise to have a 1,2, instead of 1,6 locant
order:
We do the same way if there are more substituents:
If the numbering does not make a difference, then give a
smaller locant to the alphabetical priority:
If there are more than two groups, and numbering doesn’t
make a difference, start from the alphabetical priority and
number the ring toward the next alphabetical priority:
When two common names are possible for example phenol and
aniline, we need to go based on the priority of the groups. In this
case, we are comparing the amine and alcohol, and since OH stands
above NH2 in the priority chart, the parent chain should be an
alcohol (phenol) rather than aniline.
Important
Aromatic
Hydrocarbons
Important Aromatic
Hydrocarbons
Aromatic hydrocarbons, also known as arenes, are a
significant class of organic compounds characterized
by the presence of one or more benzene rings in
their molecular structure. These compounds are
ubiquitous in both natural and synthetic
environments and play crucial roles in various
industries and biological processes.
Important Aromatic
Hydrocarbons
Benzene (C₆H₆): The parent compound of
all aromatic hydrocarbons. Its unique
structure, with delocalized pi electrons,
leads to its exceptional stability and
reactivity. It's a crucial building block for
countless other chemicals. However, it's
also a known carcinogen, so its use
requires careful handling
Important Aromatic
Hydrocarbons
Toluene (Methylbenzene, C₇H₈): A methyl
derivative of benzene, toluene is a
common solvent and an important
intermediate in the synthesis of many
other compounds. It's less toxic than
benzene but still requires caution.
Important Aromatic
Hydrocarbons
Xylene (Dimethylbenzene, C₈H₁₀): With
three isomers (ortho, meta, and para),
xylenes are vital in the production of
polymers, fibers, and other materials.
They are also used as solvents.
Important Aromatic
Hydrocarbons
Naphthalene (C₁₀H₈): A bicyclic aromatic
hydrocarbon, naphthalene is famously
used in mothballs due to its strong odor
that repels insects. It also has applications
in the chemical industry.
Important Aromatic
Hydrocarbons
Phenol (C₆H₅OH): While containing a
hydroxyl group (-OH), phenol is
considered an aromatic compound due to
the benzene ring. It's a crucial starting
material for the production of resins,
plastics, and disinfectants. It's also a
significant industrial chemical.
Important Aromatic
Hydrocarbons
Aniline (C₆H₅NH₂): Aniline is an aromatic
amine, crucial in the production of dyes,
pharmaceuticals, and rubber chemicals.
PREPARATION OF
AROMATIC
HYDROCARBONS
Aromatic hydrocarbons, especially benzene and its derivatives,
are essential in organic chemistry and industry. These stable
compounds feature conjugated double bonds and are widely
used in pharmaceuticals, plastics, dyes, and fuels.
-They can be synthesized through various methods, including
aromatization of aliphatic hydrocarbons, polymerization of
ethyne, decarboxylation of sodium benzoate, and reduction of
phenol. Alkylbenzenes are also produced via Friedel-Crafts
alkylation and Wurtz-Fittig reactions.
Key preparation methods include:
i. Aromatization of aliphatic hydrocarbons
ii. Polymerization of ethyne
iii. Decarboxylation of sodium benzoate
iv. Reduction of phenol
v. Reduction of Benzenediazonium Salts
vi. Hydrolysis of sulphonic acid
vii. Hydrodealkylation of Toluene
Alkylbenzenes are synthesized using:
Friedel-Crafts alkylation
Wurtz-Fittig reaction
The Wurtz-Fittig reaction can also take place with metals other
than sodium, like potassium, iron, copper, and lithium. In
presence of lithium, it gives good yield but under ultrasonic
irradiation.
The reaction works best for forming asymmetrical products.
Typically the reaction is used for the alkylation of aryl halides.
However, with the use of ultrasound, the reaction can also be
made useful for the production of biphenyl compounds
Like Wurtz reaction, Wurtz-Fittig reaction also gives some
undesired side products, which limits its applications.
ORIENTATION ON DI-
SUBSTITUTION OF BENZENE
Presented by Charles Adrian Bucasas
ELECTROPHILIC AROMATIC SUBSTITUTION
Due to the benzene ring containing six delocalized pi electrons, it is
especially stable. The loosely held pi electrons make the benzene ring
electron-rich, thus, it reacts with electrophiles
Electrophilic Aromatic Substitution (EAS) is the reaction of benzene
where a hydrogen atom is replaced by an electrophile
The reaction is endothermic because benzene loses aromaticity when it
attacks an electrophile, forming a resonance-stabilized carbocation called
a sigma complex. Aromaticity is then regained through the loss of a
proton.
GENERAL MECHANISM
SUBSTITUENT EFFECTS IN AROMATIC RINGS
Substituents can cause a compound to be more or less reactive than
benzene and can affect the orientation of the reaction. When a benzene
ring already has a substituent (X), the following electrophilic
substitution can occur at different positions relative to the existing
substituent:
Ortho (o): Adjacent to the existing substituent.
Meta (m): One carbon atom away from the existing substituent.
Para (p): Directly opposite the existing substituent.
CLASSIFICATION OF SUBSTITUENT GROUPS
ACTIVATING ORTHO-PARA DIRECTORS
All activating groups are ortho-para directors
These groups donate electron density to the ring, making it more reactive
towards electrophiles
The methyl group of toluene is an ortho-para director, which makes it react
more readily than benzene
Amino and hydroxyl groups are also activating and ortho-para directors
CLASSIFICATION OF SUBSTITUENT GROUPS
META DIRECTORS
Meta directing substituents are deactivating groups
These groups withdraw electron density from the ring, making it less
reactive
Strong electron-withdrawing groups such as nitro, carboxyl, and sulfonate
are deactivators and meta directors
CLASSIFICATION OF SUBSTITUENT GROUPS
DEACTIVATING ORTHO-PARA DIRECTORS
They are weakly deactivating due to their electronegativity, but their lone
pairs can participate in resonance
Chloro and bromo groups are weakly deactivating but are also ortho-para
directors
CLASSIFICATION OF SUBSTITUENT GROUPS
DISUBSTITUTED BENZENES
WHEN THERE ARE TWO (OR MORE)
SUBSTITUENTS, THE RELATIVE POSITION OF
THE SUBSITUENTS MUST BE DEFINED.
There are two methods used based on either
numerical locants or specific words for the three
possible forms:
•THE WORDS CAN ALSO BE SHORTENED TO THEIR
FIRST LETTER, I.E. O-, M- AND P-
•THE TERMS ORTHO-, META- OR PARA- (OR THEIR
SINGEL LETTER EQUIVALENTS) ARE USED AS PREFIXES.
•THESE TERMS ARE ONLY USED FOR BENZENE
SYSTEMS.
•WHEN USING NUMERICAL LOCANTS, THE PRINCIPAL
FUNCTIONAL GROUP IS DEFINED TO BE AT C1.
•THE NUMERICAL LOCANT METHOD IS ALSO
APPLICABLE TO OTHER AROMATIC SYSTEMS.