Chapter 6

Aromatic Carboxylic Acids

Organic compounds, in which, the carboxyl group (COOH) is directly attached to
aromatic ring (Ar-COOH).
Common names of aromatic acids

Acidity of aromatic carboxylic acids

The acidic character of aromatic carboxylic acids is due to removal of proton and the
stability of conjugate base as shown.

Presence of electron-withdrawing groups (EWG) on benzene ring will facilitate the

removal of proton so it will increase the acidic character (Ka will increase and pKa
will decrease). The strength of acidity is depending on the position of EWG. When
EWG is present on para-position (resonance effect) its effect will be stronger than on
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meta- position (inductive effect) so the arrangement of acidic character as the

following.

Presence of electron-donating groups (EDG) on benzene ring will not facilitate the
removal of proton so it will decrease the acidic character (Ka will decrease and pKa
will increase). The strength of acidity is also depending on the position of EDG.
When EDG is present on para-position (resonance effect) its effect will be stronger
than on meta- position (inductive effect) so the arrangement of acidic character as the
following.

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The strength of acidic character in case of EWG and EDG as the following order

Carboxylic Acid Derivatives

Aromatic acid derivatives are less reactive than aliphatic acid derivatives
towards nucleophilic acyl substitution reactions

General mechanism for nucleophilic acyl substitution reactions

The nucleophilic acyl substitution reactions involved two steps: i) nucleophilic attack
at carbonyl group to give tetrahedral addition intermediate; and ii) elimination of
leaving group to give substitution product as shown from the given mechanism.
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As the basic character of leaving group (L) decrease, the reactivity of acid
derivatives will increase.

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A) Acid Chlorides

B) Acid Anhydrides

The acid anhydride derivatives can also undergo nucleophilic substitution reactions
but it less reactive than acid chlorides. So they can not react with NaCl, this is
because the incoming chloride ion is a weaker base than the leaving ion.

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Formation of Asprine and Vicks

C) Esters

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Reactions of esters

Acid catalyzed hydrolysis of esters

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Base catalyzed hydrolysis of esters

The rate of basic hydrolysis is depending on the nature of substituents on aryl group
(EWG will be more reactive than EDG)

D) Acid Amides

Acid catalyzed hydrolysis of amides

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Base catalyzed hydrolysis of amides

Amides don't react with halide ions, alcohols or carboxylate because; in each case the
incoming nucleophile is weaker base than the leaving group (NH2) of the amide.
Reduction of acid amides

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Chapter 7
Aromatic Amines
Organic compounds, in which, the aromatic ring is directly attached into amino group
(NH2) as a functional group. They can be classified into
Primary aromatic amines (Ar-NH2)

Secondary aromatic amines [Ar-NH-R(Ar)]

Tertiary aromatic amines [Ar-NR2(Ar)2]

Preparation of amines
1- Reduction of nitro compounds

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2- Hoffmann degradiation of amides

Structure and Basic Characters of Amines

The hybridization of nitrogen atom in amine compounds is SP3 (tetrahedral structure
with bond angle close to 109o) in which three orbitals are overlapped and the fourth
orbital contain lone pair of electron as shown.

Amines are weak bases (the basic character is due to the presence of lone pair of
electron on nitrogen atom). They are stronger bases than water but weaker bases than
hydroxide ions, alkoxide ions.
Aliphatic amines are more basic than aromatic amines because the lone pair of
electrons on nitrogen atom will participate in the resonance structures (in case
of aromatic amines) as shown.

For both aliphatic and aromatic amines as the number of alkyl groups on
nitrogen atom increase the basic character will also increase.
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 In case of aromatic amines, the presence of electron-withdrawing groups

(EWG) on benzene ring will decrease the electron density and pull-down the
lone pair of electrons from nitrogen atom so the basic characters will decrease.
On the other hand, the presence of electron-donating groups (EDG) on benzene
ring will increase the electron density on nitrogen atom so the basic characters
will increase.

The presence of EDG (which has I such as, OH, OR, X) on meta-position will
decrease the basic character (it will have lower basic character than aniline).
Reactions of aromatic amines
1- Hinsberg reactions: can be used to differentiate between primary, secondary, and
tertiary aromatic amines

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2- Action of Nitrous Acid (HNO2)

2a) 1ry Aromatic Amines

2b) 2ry Aromatic Amines

2c) 3ry Aromatic Amines

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3- Sandmeyer Reaction

4- Azodye Formation
Benzene diazonium chloride can be coupled with different aromatic compounds (with
high electron density) to give the respective dyes.

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Chapter 8
Polycyclic Aromatic Hydrocarbons
Aromatic compounds contain more than one benzene ring(s). They can be classified
into
Biaryls (Isolated System): benzenoid compounds in which two rings are linked
together by a single bond.
Condensed (Fused System): benzenoid compounds are characterized by two or
more benzene rings are fused (pair of rings share two carbons in ortho- position).

Naphthalene
Colorless crystalline aromatic hydrocarbon, m.p. = 80 oC with molecular formula
C10H8. The method of numbering of two fused benzene rings as the following.

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Structure of naphthalene
Planer molecule with high degree of unsaturation. It resists the addition reactions and
undergoes electrophilic substitution reactions easily. X-ray proved that C1-C2, C3C4, C5-C6 and C7-C8 bonds are double bonds

Haworth synthesis of naphthalene (Conversion of benzene into naphthalene)

A) Synthesis of unsubstituted naphthalene

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B) Synthesis of -substituted naphthalene

C) Synthesis of -substituted naphthalene

D) Synthesis of 1,7-disubstituted naphthalene

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Reactions of naphthalene
1- Electrophilic Substitution Reactions
The electrophile can attack -position (C1) or -position (C2) depending on number
and stability of resonating structures.

If the electrophile attacks -position (C1) it will give 5-resonating structures, two
resonating structures are stable (I), (II) (because they have benzenoid structure) and
other resonating structures (IIIV) are unstable (do not have benzenoid structure).

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If the electrophile attacks -position (C2) it will give 5-resonating structures, one
resonating structure is stable (I) (has benzenoid structure), and other resonating
structures (IIV) are unstable (do not have benzenoid structure).
So the electrophilic substitution reactions will take place at position 1

Sulfonation under low temperature gives 1-naphthalenesulfonic acid as kinetic

product but at higher temperature it will give 2-naphthalenesulfonic as
thermodynamic product. This is due to sulfonic group (SO3H) is bulky group (steric
hinderence) so, 1-naphthalenesulfonic will become more hindered than 2naphthalenesulfonic.
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2- Oxidation

3- Reduction

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Anthracene: Linear tricyclic benzenoid hydrocarbons with M.F. C14H10. It has

different isomeric structures

Haworth synthesis of anthracene (Conversion of benzene into anthracene)

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Reactions of Anthracene
Electrophilic substitution reactions will take place at position C-9 and C-10
Anthracene undergoes oxidation to the corresponding quinones at position C-9
and C-10
Anthracene undergoes reduction to the corresponding dihydro derivatives at
position C-9 and C-10

Phenanthrene: Angular tricyclic benzenoid hydrocarbons with M.F. C14H10. It has

different isomeric structures

The method of numbering of phnanthrene as the following

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Haworth synthesis of phenanthrene (Conversion of naphthalene into

phenanthrene)

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Reactions of phenanthrene
Electrophilic substitution reactions will take place at position C-9 and C-10
Phenanthrene undergoes oxidation to the corresponding quinones at position
C-9 and C-10
Phenanthrene undergoes reduction to the corresponding dihydro derivatives at
position C-9 and C-10

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