Aromatic Compounds

1. Benzene & Aromaticity

2. Chemistry of Benzene:
Electrophilic Aromatic
Substitution
Benzene & Aromaticity
Aromatic Compounds
Benzene & Aromaticity
Aromatic Compounds

Q1. Give three examples of aromatic compounds with fragrance.

Q2. Write four characteristics of aromatic compounds.
 Benzene & Aromaticity
Aromatic Compounds
The word aromatic refers to the class of compounds that contain
six-membered benzene-like rings with three double bonds.
Many naturally occurring compounds are aromatic in part, including steroids
such as estrone and well-known pharmaceuticals such as the cholesterol-
lowering drug atorvastatin, marketed as Lipitor. Benzene itself causes a
depressed white blood cell count (leukopenia) on prolonged exposure and
should not be used as a laboratory solvent.

Q1. Give modern definition of aromatic compounds.

Q2. Name two aromatic compounds.
No question on the structures on this slide in exam.
 Benzene & Aromaticity
Sources of Aromatic Compounds

Q1. What are the two main sources of simple aromatic compounds?
Q2. Draw structures of three aromatic hydrocarbons found in coal tar.
 Benzene & Aromaticity
Sources of Aromatic Compounds

http://www.engineersindia.com/petroleumrefining/m-27

http://www.worldofchemicals.com/42/chemistry-articles/vladimir-nikolayevich-ipatieff-modern-petroleum-
chemist.html

https://www.britannica.com/technology/petroleum-refining/Polymerization-and-
alkylation
Q1. How aromatic compounds are made by refining petroleum?
No question in exam from the images of this slide.
 Benzene & Aromaticity
Common Names of Aromatic Compounds

Q1. Draw structures of toluene, phenol, aniline, benzaldehyde, Benzoic acid, ortho-Xylene.
 Benzene & Aromaticity
Naming alkyl-substituted and monosubstituted Benzenes
 Benzene & Aromaticity
Naming alkyl-substituted and monosubstituted Benzenes

Q1. Draw the structures of phenyl group, benzyl group.

Q2. Name and draw the structure of a monosubstituted benzene.
Benzene & Aromaticity
Naming disubstituted Benzenes
Naming disubstituted Benzenes

Q1. Explain nomenclature of disubstituted benzenes by ortho-, meta-, para- system with examples.
 Benzene & Aromaticity
Naming of tri- or more substituted Benzenes
 Benzene & Aromaticity
Naming of tri- or more substituted Benzenes

Q1. Explain nomenclature of benzenes with more two substituents with examples.
 Benzene & Aromaticity
Structure and Stability of Benzene: Unusual properties of benzene

Q1. Discuss reaction of benzene with bromine.

 Benzene & Aromaticity
Difference in the brominations of benzene and alkenes

Alkene Addition

Benzene Substitution

Q1. Discuss how the bromination reactions differ between benzene and an alkene.
 Benzene & Aromaticity

Benzene has no double bond

All of the carbon–carbon bonds of benzene have the same length—139 pm—
intermediate between typical single (154 pm) and double (134 pm) bonds. In
addition, an electrostatic potential map shows that the electron density in all six
C-C bonds is identical. Thus, benzene is a planar molecule with the shape of a
regular hexagon.
Benzene & Aromaticity
Benzene has no double bond

Q1. Discuss the nature of carbon-carbon bonds in benzene.

Q2. How many double bonds are there in benzene?
Q3. Draw the most appropriate representation of the structure of benzene.
 Benzene & Aromaticity

Aromaticity and the Hückel 4n+2 rule

 Benzene & Aromaticity
Aromaticity and the Hückel 4n+2 rule

According to a theory devised in 1931 by the German physicist Erich

Hückel, a molecule is aromatic only if it has a planar, monocyclic system
of conjugation and contains a total of 4n+2 π electrons, where n is an
integer (n = 0, 1, 2, 3, . . .).

In other words, only molecules with 2, 6, 10, 14, 18, . . . π electrons can
be aromatic.

Q1. Write three properties of benzene.

Q2. What is Hückel rule?
 Benzene & Aromaticity

Aromatic Heterocycles: Pyridine and Pyrrole

 Benzene & Aromaticity
Aromatic Heterocycles: Pyridine and Pyrrole

Q1. What is a
heterocycle?
Q2. Are pyridine and
pyrimidine aromatic?
Draw orbitals to
explain your answer.
 Benzene & Aromaticity

Aromatic Heterocycles: Pyridine and Pyrrole

 Benzene & Aromaticity
Aromatic Heterocycles: Pyridine and Pyrrole

Q1. Draw the structure of a five-membered heterocyclic aromatic compound.

Q2. Are pyrrole and imidazole aromatic? Draw orbitals to explain your answer.
 Benzene & Aromaticity
Aromatic Heterocycles: Pyrimidine and Imidazole rings in biological compounds

Q1. Draw structures of a biological compound

with (i) a pyrimidine, (ii) an imidazole ring.
 Benzene & Aromaticity
Polycyclic Aromatic Compounds

Polycyclic aromatic hydrocarbons (PAHs) are a group of more than 100

different chemicals that are released from burning coal, oil, gasoline,
trash, tobacco, wood, or other organic substances such as charcoal-
broiled meat.

Q1. Draw the structures of two polycyclic aromatic compounds.

 Benzene & Aromaticity
Polycyclic Aromatic Compounds: Naphthalene

Q1. Draw the resonance forms of naphthalene.

Q2. Show the bromination reaction of naphthalene.
 Benzene & Aromaticity
Polycyclic Aromatic Compounds: Naphthalene

Q1. Draw orbital structures to explain aromaticity of naphthalene.

 Benzene & Aromaticity
Heterocyclic Analogues of Naphthalene

Q1. Draw the structure of an aromatic heterocyclic analogue of naphthalene.

(Suggestion: Indole, Purine)
 Benzene & Aromaticity
Polycyclic Aromatic Compounds: Biological examples

Q1. Draw the structures of two biological compounds with polycyclic

aromatic rings. (Suggestion: Tryptophan, Adenine, Guanine)
 Chemistry of Benzene:
Electrophilic Aromatic Substitution
 Chemistry of Benzene
Electrophilic Aromatic Substitutions

Electrophilic aromatic substitution is an

organic reaction in which an atom that is
attached to an aromatic system (usually
hydrogen) is replaced by an electrophile.

Q1. What is electrophilic aromatic substitution reaction?

 Chemistry of Benzene
Electrophilic Aromatic Substitutions

Q1. Write five substituents

that can be introduced onto
an aromatic ring through
electrophilic aromatic
substitution.
 Chemistry of Benzene
Electrophilic Aromatic Substitutions: Bromination

Q1. Show the bromination of benzene.

 Chemistry of Benzene
Electrophilic Aromatic Substitutions: Mechanism of Bromination of Benzene

Q1. Show how FeBr3 facilitates bromination of benzene.

 Chemistry of Benzene
Electrophilic Aromatic Substitutions: Mechanism of Bromination of Benzene
Mechanism of bromination of benzene:

Q1. Schematically show the mechanism of bromination of benzene.

 Chemistry of Benzene
Electrophilic Aromatic Substitutions: Step-by-step Mechanism of Bromination of Benzene
Step-by-step mechanism of bromination of Benzene:

No question in the exam

from this slide.
 Chemistry of Benzene
Electrophilic Aromatic Substitutions: Why bromination is slower for benzene than alkenes?

Q1. Explain with an energy diagram why bromination of benzene is slower than the bromination of alkenes.
 Chemistry of Benzene
Electrophilic Aromatic Substitutions: Why substitution, not addition in benzene?

Q1. Explain with an energy diagram

why substitution is favored over
addition during bromination of
benzene.
 Chemistry of Benzene
Electrophilic Aromatic Substitutions: Aromatic Fluorination

Aromatic hydrocarbons react with copper(II) fluoride, in an oxygen-containing atmosphere

at temperatures above 450°C, to form fluorinated aromatic hydrocarbons. This is only
applicable for compounds that are stable enough to survive the high temperature.

Half mole of oxygen is used with 2

HF and Cu to make a mole of water
and copper(II) fluoride.
http://www.wikiwand.com/en/Copper(II)_fluoride

Q1. Show direct fluorination of benzene.

 Chemistry of Benzene
Electrophilic Aromatic Substitutions: Aromatic Fluorination

Q1. Show indirect fluorination of benzene.

Q2. Write the name and structure of the compound that is
Selectfluor or 1-Chloromethyl-4-fluoro-1,4-diazoniabicyclo[2.2.2]octane bis(tetrafluoroborate)
used for the indirect fluorination of aromatic compounds.
 Chemistry of Benzene
Electrophilic Aromatic Substitutions: Aromatic Chlorination

http://chem-guide.blogspot.com/2010/04/preparation-of-haloarenes.html

Q1. Show the chlorination of benzene.

Q2. Show the product(s) after reaction of benzene with excess chlorine.
 Chemistry of Benzene
Electrophilic Aromatic Substitutions: Aromatic Iodination

http://askthenerd.com/ocol/CH15/F3.HTM

Mechanism:

Q1. Discuss the iodination of benzene.

 Chemistry of Benzene
Electrophilic Aromatic Substitutions: Aromatic Nitration

Q1. Show the nitration of benzene.

 Chemistry of Benzene
Electrophilic Aromatic Substitutions: Aromatic Sulfonation

Q1. Show the sulfonation of benzene.

 Chemistry of Benzene
Electrophilic Aromatic Substitutions: Friedel-Crafts Reactions
The Friedel–Crafts reactions are a set of reactions developed by Charles Friedel and James Crafts in 1877
to attach substituents to an aromatic ring.
There are two main types of Friedel–Crafts reactions:
1. Friedel–Crafts alkylation reactions and 
2. Friedel–Crafts acylation reactions.
Both proceed by electrophilic aromatic substitution.

Alkylation of
Benzene:

http://slideplayer.com/slide/6878189/

Acylation of
Benzene:

Q1. What are Friedel-Crafts reactions?

Q2. Show Friedel-Crafts alkylation and acylation reactions of benzene.
 Chemistry of Benzene
Electrophilic Aromatic Substitutions: Friedel-Crafts Alkylation of Aromatic Rings
Mechanism of Friedel-Crafts alkylation reaction:

Q1. Schematically show the

mechanism of Friedel-Crafts
alkylation reaction of benzene
with 2-chloropropane.
 Chemistry of Benzene
Electrophilic Aromatic Substitutions: Friedel-Crafts Alkylation of Aromatic Rings

Q1. Discuss the significance of carbocation rearrangements

in Friedel-Crafts alkylation reactions with examples.
 Chemistry of Benzene
Electrophilic Aromatic Substitutions: Friedel-Crafts Acylation of Aromatic Rings

Mechanism:

Q1. Discuss the mechanism of Friedel-Crafts acylation of benzene to acetophenone.

 Chemistry of Benzene
Electrophilic Aromatic Substitutions: Effect of Substituents on Nitration

Q1. Discuss how substituents can affect nitration of aromatic ring.

Q2. Explain what is meant by the effect of substituents on the
orientation of reaction in aromatic ring.
No question on the values of nitration in exam.
 Chemistry of Benzene
Electrophilic Aromatic Substitutions: Substituent Effects
 Chemistry of Benzene
Electrophilic Aromatic Substitutions: Substituent Effects

Q1. Digrammatically show the classification of substituent effects in electrophilic aromatic substitution.
 Chemistry of Benzene
Electrophilic Aromatic Substitutions: Activating- & Deactivating Groups

Q1. What makes a group either activating or deactivating in electrophilic aromatic substitution.
 Chemistry of Benzene
Electrophilic Aromatic Substitutions: Inductive Effects of Substituents

Q1. What is the “inductive effect of substituents” in aromatic rings?

Q2. Give one example of substituents that show “inductive electron withdrawal”
and “inductive electron donation” in aromatic rings.
 Chemistry of Benzene
Electrophilic Aromatic Substitutions: Resonance Effects of Substituents

Q1. What is “resonance effects of substituents” in aromatic rings?

Q2. Give an example of resonance electron withdrawing group in aromatic rings.
 Chemistry of Benzene
Electrophilic Aromatic Substitutions: Resonance Effects of Substituents

Q1. Give an example of resonance electron donating group in aromatic rings.

 Chemistry of Benzene
Electrophilic Aromatic Substitutions: Substituent Effects

Inductive effects and resonance effects don’t necessarily act in the same direction.
Halogen, hydroxyl, alkoxyl, and amino substituents, for instance, have
electron-withdrawing inductive effects because of the electronegativity
of the -X, -O, or -N atom bonded to the aromatic ring but have
electron-donating resonance effects because of the lone-pair electrons
on those -X, -O, or -N atoms.
When the two effects act in opposite directions, the stronger
effect dominates.
Thus, hydroxyl, alkoxyl, and amino substituents are activators because their stronger
electron-donating resonance effect outweighs their weaker electron-withdrawing
inductive effect.
Halogens, however, are deactivators because their stronger electron-withdrawing
inductive effect outweighs their weaker electron-donating resonance effect.

Q1. Explain why hydroxyl group is an activator but halogen group is

deactivator for substitution in an aromatic ring.
 Chemistry of Benzene
Electrophilic Aromatic Substitutions: Substituent Effects

Q1. Draw the structures of the

carbocation intermediates in the
nitration of toluene.
 Chemistry of Benzene
Electrophilic Aromatic Substitutions: Substituent Effects

Q1. Draw the structures of the carbocation intermediates in the nitration of phenol.
 Chemistry of Benzene
Electrophilic Aromatic Substitutions: Substituent Effects

Q1. Draw the structures of the carbocation

intermediates in the nitration of
chlorobenzene.
 Chemistry of Benzene
Electrophilic Aromatic Substitutions: Substituent Effects

In general, any substituent that has a positively polarized atom (δ+)

directly attached to the ring will make one of the resonance forms of the
ortho and para intermediates unfavorable and will thus act as a meta
director.

Q1. What is the general characteristic of

meta-directing substituents of aromatic
rings?
Q2. Draw the structure of the major
product of nitration of benzaldehyde.
 Chemistry of Benzene
Electrophilic Aromatic Substitutions: Substituent Effects

Q1. Draw the structures of

carbocation intermediates in
the nitration of
benzaldehyde.
 Chemistry of Benzene
Electrophilic Aromatic Substitutions: Substituent Effects

Q1. Summarize substituent effects in electrophilic aromatic substitution using a table.

 Chemistry of Benzene
Electrophilic Aromatic Substitutions: Tri-substituted benzenes

Q1. How many rules govern the electrophilic substitution of a disubstituted benzene?
 Chemistry of Benzene
Electrophilic Aromatic Substitutions: Tri-substituted benzenes
 Chemistry of Benzene
Electrophilic Aromatic Substitutions: Tri-substituted benzenes
 Chemistry of Benzene
Electrophilic Aromatic Substitutions: Tri-substituted benzenes

Q1. Discuss the three general rules for electrophilic aromatic substitution of disubstituted aromatic rings.
 Chemistry of Benzene
Nucleophilic Aromatic Substitution

Q1. Give an example of nucleophilic aromatic substitution reaction.

 Chemistry of Benzene
Nucleophilic Aromatic Substitution
Mechanism:

Q1. Explain why nucleophilic aromatic substitution cannot happen through S N1 or SN2 mechanism.
 Chemistry of Benzene
Nucleophilic Aromatic Substitution
Mechanism:

Q1. Show the mechanism of a nucleophilic aromatic substitution reaction.

 Chemistry of Benzene
Nucleophilic Aromatic Substitution

Q1. Which factor determines nucleophilic aromatic substitution?

 Chemistry of Benzene
Nucleophilic Aromatic Substitution

Q1. Discuss the mechanism of the nucleophilic aromatic substitution of

nitrochlorobenzenes with hydroxide ion at high temperature.
Chemistry of Benzene
Reduction of the Aromatic Ring

Q1. Give two examples of

the hydrogenation of
http://nptel.ac.in/courses/104103071/module7/lec19/4.html aromatic rings.
 Chemistry of Benzene
Preparing Benzene in the Lab

http://www.chemgapedia.de/vsengine/vlu/vsc/en/ch/2/vlu/oxidation_reduktion/aroma_ringe.vlu/Page/vsc/en/ch/2/oc/reaktionen/
formale_systematik/oxidation_reduktion/oxidation/entfernen_wasserstoff/aromatisierung_6_ringe/dehydrierung_aromatisierung.vscml.html

Q1. Show the reactions to prepare benzene in lab by

dehydrogenation reactions.