Cairo University

Faculty of Science
Chemistry Department

Basic Organic Chemistry

Chemistry of Arenes and Polycyclic
Aromatic Hydrocarbons

Chem. 242

For Second Year Students

Table of Contents

Content

Page

Introduction

Chapter 1: Chemistry of Benzene

Chapter 2: Alkyl and Alkenylbenzenes

24

Chapter 3: Halobenzenes

30

Chapter 4: Phenols

36

Chapter 5: Aromatic Carbonyl Compounds

42

Chapter 6: Aromatic Carboxylic Acids and Acid Derivatives

Chapter 7: Aromatic Amines

Chapter 8: Polycyclic Aromatic Hydrocarbons

Introduction
The classification of organic compounds is based on the structure of molecules.

Aromatic Compounds
Unsaturated cyclic molecules which have additional stability due to the arrangement
of - electrons

Chapter 1
Chemistry of Benzene
Stable organic compound with M.F. C6H6, it reacted by substitution reaction rather
than addition reaction.
A) Kekules structure of benzene [Postulates]
Benzene is a cyclic hexagonal planer structure of six carbon atoms with
alternating single and double bonds.

Benzene can be considered as 1,3,5-cyclohexatriene.

Benzene is existed in two resonating structures.

In the light of the proposed structure of benzene, it should give two orthodisubstituted isomers and in reality only one isomer is observed.

B) The Resonance Theory

The benzene ring can be represented by two equivalent resonating structures
and the truly structure is the hybrid one The hybrid structure can explain the
formation of single ortho-disubstituted isomer.

The resonance theory also explained why the six carbon-carbon bond lengths are
equivalent; the value of each (C-C) bond is shorter than normal single bond (C-C)
and longer than the double bond (C=C).

The resonance theory also explained the high stability of benzene ring due to the
delocalization of -electrons.

C) The Molecular Orbital Theory

The hybridization of carbon atom in benzene ring is SP2 in which three hybrid
orbitals form three bonds (2 C-C and one C-H) with bond angle = 120 o, and there is a
p-orbital containing one electron above and below the plane of benzene ring as
shown. The six p-orbitals are overlapping leads to a delocalization of - cloud above
and below the plane of the ring.

Criteria for Aromaticity

The features of Aromatic compounds
1) Cyclic, planar, and contain conjugated system of -electrons (double, single,
double, single, .)
2) The aromatic compounds must contain (4n+2) -electrons (n = integer
number, 0, 1, 2, ..) according to Huckels rule

Aromatic Ions
Monocyclic species that bear either a positive or a negative charge on the ring.

Comment: Cyclopentadiene is more acidic than cycloheptadiene?

The features of Antiaromatic compounds
1) Cyclic, planar, and contain conjugated system of -electrons (double, single,
double, single, .)
2) The antiaromatic compounds must contain (4n) -electrons (n = integer
number 1, 2, 3, ..).

Annulenes: Monocyclic hydrocarbons with conjugated system. A prefix in brackets

indicates the number of carbons in the ring.
If the compounds did not fulfill the requirements of aromatic or antiaromatic
characters it will be Non-aromatic compounds
7

Nomenclature of monosubstituted benzene

i) Name of substituent followed by the word of benzene
ii) Some monosubstituted benzenes have common names which you should
memorize

iii) When a benzene ring is a substituent, it is called a phenyl group. A benzene ring
with a methylene group is called benzyl group

Nomenclature of disubstituted benzene

If the two substituents in positions 1,2 they named as ortho (o-)

If the two substituents in positions 1,3 they named as meta (m-)

If the two substituents in positions 1,4 they named as para (p-)

If the two substituents are different, they are listed in alphabetical order. The
group with lower alphabet will take position no. 1

If the two substituents are different and one of these groups has common name,
this group will take position no. 1

If the two substituents are different and both of them have common name, apply
the priority rule to choose the group which will take position no. 1

COOH (Acid) > COOR (Ester) > CN (Nitrile) > CHO (Aldehyde) > C=O
(Ketone) > OH (Alcohol) > SH (Thioalcohol) > O- (Ether) > S- (Thioether) >
C=C (Alkene) > CC (Alkyne) > R-X (Alkyl halide) > R (Alkyl group)

Nomenclature of Polysubstituted benzene

i) The substituents are numbered with the lowest possible numbers
ii) The group of common name will take position no. 1

10

Electrophilic substitution Reactions of benzene

Benzene ring undergoes electrophilic substitution reactions rather than addition
reactions in order to preserve the delocalized system. These reactions are
accelerated by lewis acids to generate the electrophile.

1- Halogenation

Mechanism

11

2- Nitration

3- Sulfonation

12

4) Friedel Crafts Alkylation

Limitation of Friedel Crafts Reaction

1) If the alkyl group is long (at least 3-carbons) it will carry out rearrangement.
Primary carbocation (R-CH2)+ will convert into secondary carbocation (R2CH)+.
Also, the secondary carbocation (R2CH)+ will convert into tertiary carbocation (R3C)+

13

Mechanism

Q: How do you account for fact that: benzene in the presence of AlCl3 react with
isobutyl bromide to yield tert-butylbenzene?

2) Friedel Crafts Reaction could not occurred when the benzene ring have strong
Electron-withdrawing groups (EWG) because these groups decrease the electron
density on the ring.

3) Friedel Crafts Reaction could not occurred when the benzene ring have NH2NHR- or NR2 groups because the lone pair of electron on nitrogen atom of these
14

groups will react with Lewis acid (AlCl3) and the group will become strong EWG so
the reaction will not proceeded.

4) Aryl and vinyl halides could not react with benzene ring through Friedel Crafts
reaction because they could not form the respective carbocation (electrophile).

5) Polyalkylation often occur in Friedel Crafts reaction because introducing of alkyl

group into benzene ring will activate the ring towards further alkylation

15

5) Friedel Crafts Acylation

Mechanism

Acylbenzenes have many uses in organic chemistry as precursors for the preparation
of n-alkylbenzenes without rearrangement

Starting from benzene, show how can you prepare

i) iso-propyl benzene

ii) n-propyl benzene

16

Disubstituted Benzenes
Monosubstituted benzenes are capable of undergoing further electrophilic substitution
reactions to give three possible isomeric compounds as shown

The reactivity of benzene ring towards the electrophilic substitution reactions and the
orientation of the second group are depending on the nature of (Y) group.

If (Y) is Electron-Donating Group (EDG) such as [NH2, NHR, NR2, OH, OR, R,
and X] it will increases the electron density on benzene ring so the rate of
electrophilic substitution reaction will increase.

If (Y) is Electron-Withdrawing Group (EWG) such as [C=O, NO2, SO3H and

COOH] it will decreases the electron density on benzene ring so the rate of
electrophilic substitution reaction will decrease.

17

Substituent

Orientation effect

Effect on reactivity

-NH2, -NHR, -NR2

-OH, -OR

ortho-para
directing

Strongly activating

-NHCOR, -OCOR,

ortho-para
directing

Moderatley activating

-R, -Ar, -CH=CR2

ortho-para
directing

Weakly activating

-F, -Cl, -Br, -I

ortho-para
directing

Weakly deactivating

-CHO, -COR, -COCl

-COOH

meta
directing

Moderately deactivating

-CN, -+SO3H, -+NH3

-+NH2R, -+NHR2, -+NR3
-NO2

meta
directing

Strongly deactivating

Effect of substituent on the orientation in benzene ring

Electron-Donating Group (EWG) will increase the electron density on the benzene
ring especially on ortho and para positions so, it will be (ortho and para directing
group).

18

The attacking of electrophile into positions ortho- , meta-, or para- will give three
resonating structures (I), (II), (III) (as the number of resonating structures increase,
the stability of intermediates will increase and vice-versa). In case of attacking the
electrophile into ortho- and para- positions one case, in which the positive charge was
located at the same carbon atom which carry out EDG (form (I) in ortho-attack and
form (II) in para-attack) which give extra stability for these intermediates, so the
electrophile will be directed into ortho- and para- positions.

19

Electron-Withdrawing Group (EWG) will decrease the electron density on the

benzene ring especially on ortho and para positions so, it will be (meta directing
group).

The attacking of electrophile into positions ortho- , meta-, or para- will give three
resonating structures (I), (II), (III). In case of attacking the electrophile into orthoand para- positions one case, in which the positive charge was located at the same
carbon atom which carry out EWG (form (I) in ortho-attack and form (II) in paraattack) which give lower stability for these intermediates, so the electrophile will be
directed into meta- position.

20

Q: How can you prepare the following compounds from benzene (assuming that
a pure para isomer can be separated from an ortho, para mixture)?
1) p-nitrotoluene
2) p-bromonitrobenzene
3) m-bromobenzenesulfonic acid

21

Orientation of Disubstituted benzenes

When a disubstituted benzene undergoes electrophilic substitution reaction, the
orientation of the electrophile will be determined as follow:
1) When two groups are located on benzene ring, one group is (ortho & para
directing group) and another group is (meta directing group).
i) These two groups in positions 1,2 or 1,4 they will reinforce the orientation of
electrophile.

ii) These two groups in positions 1,3 so, the ortho & para directing group will
determine the orientation of the electrophile.

22

2) When two groups which located on benzene ring, are (ortho & para
directing group), the more powerful activating group will determine the
orientation of the electrophile.

23

Chapter 2
Alkyl and Alkenylbenzenes
1) Alkyl benzene: Aromatic hydrocarbons, in which saturated alkyl chain was
attached to benzene ring.
2) Alkenyl benzene: Aromatic hydrocarbons, in which unsaturated alkyl chain was
attached to benzene ring.
1) Alkyl benzene

Preparation of alkyl benzene

1) Friedel Crafts Alkylation

2) Friedel Crafts Acylation

24

Reactions of alkyl benzene

1- Halogenation of alkyl side-chain: If the halogenation took place in the presence
of Lewis acid it will give substituted benzene. On the other hand, if the halogenation
took place in the presence of sunlight, it will undergo substitution on alkyl side-chain
via radical mechanism.

Q: Covert toluene into phenylacetic acid

In case of ethyl benzene (more than one carbon atom in alkyl group): The
halogenation will take place at a-carbon atom adjacent to benzene ring.

25

2- Oxidation of alkyl side-chain

Oxidation of alkyl group which contains at least one hydrogen atom on -carbon
atom will convert into COOH group

26

2) Alkenyl benzene

Preparation of alkenyl benzene via elimination reactions

Q: Convert benzene into p-chlorostyrene

27

Addition reactions of alkenyl benzene

Addition of HBr into 1-phenylpropene in absence of peroxide gave the respective 1bromo-1-phenylpropane in which the bromine atom attacks -carbon adjacent to
benzene ring as shown. The mechanism is proceeded by formation of carbocation.

Mechanism

On the other hand, addition of HBr into 1-phenylpropene in the presence of peroxide
gave the respective 2-bromo-1-phenylpropane in which the bromine atom attacks 28

carbon adjacent to benzene ring as shown. The mechanism is proceeded by formation

of radical.

Mechanism

29

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