DIENES AND AROMATIC

COMPOUNDS
Course Name: Organic Pharmacy-I
Course Code: Phrm 1102

Prepared by:
Furhatun-Noor
Lecturer, Department of Pharmacy
Northern University Bangladesh
 DIENES
A diene is a hydrocarbon chain that has two double bonds that may or may
not be adjacent to each other.

Types of Dienes:
1. A conjugated diene contains two double bonds separated by a single
bond.
1. Isolated dienes or non-conjugated diene:
An isolated diene has the two double bonds of the molecule separated by
more than one single bond.
3. Cumulated Dienes or “Allenes”
Cumulated dienes have the double bonds sharing a common atom
 Example:

CH2= CH-CH2-CH=CH2 CH2=CH-CH=CH-CH3 CH2=C=CH-CH2-CH3

1,4- Pentadiene 1,3- Pentadiene 1,2- Pentadiene

Isolated Diene Conjugated Diene Cumulated Diene
 Conjugated diene 1,2 and 1,4-addition reactions

Addition of Halogen:

Addition of 1mole of Br2 to butadiene at -15°C gives a mixture of two

constitutional isomers we account for the formation of these 1,2- and 1,4-
addition products following by two steps mechanism.
Addition of Halogen acid:

Addition of 1 mole of HBr to butadiene at -78°C also gives a mixture of

two constitutional isomers we account for these products by the same
mechanism.
 Conjugated diene 1,2 and 1,4-addition reactions

https://www.youtube.com/watch?v=X5QSKx_97wA&t=212s
 Aromatic compounds

Aromatic compounds are benzene and compounds that resemble benzene in

chemical behavior. This particular behavior is known as aromaticity.
 Structure of Benzene

The Kekule Structure for Benzene:

• Kekule was the first to formulate a reasonable
representation of benzene.
• August Kekulé proposed that benzene was a rapidly
equilibrating mixture of two compounds, each Friedrich August Kekule

containing a six-membered ring with three

alternating  bonds.
• In the Kekulé description, the bond between any
two carbon atoms is sometimes a single bond and
sometimes a double bond (alternating single bond
and double bond).
• But these does not satisfy the criteria of structure of benzene. Because
having three alternating π bonds means that benzene should have three
short double bonds alternating with three longer single bonds. Instead of
alternating single and double bonds, all of the C—C bonds are the same
length.
• Kekule also suggested that, an equilibrium exists between two equivalent
compounds, but in reality it is now known no such equilibrium exists.
 UNUSUAL BEHAVIOUR OF BENEZENE

Benzene does not undergo addition reactions typical of other highly unsaturated
compounds (e.g., alkene, alkyne), including conjugated dienes.

Benzene does react with bromine, but only in the presence of FeBr 3 (a Lewis
acid), and the reaction is a substitution, not an addition.
 Resonance Structures of Benzene

Combined
Resonance representation representation/hybrid

Resonance is the phenomenon in which two or more structures can be

written for the same compound which involve identical positions of atoms.
The actual structure is called resonance hybrid and the alternative structures
are contributing forms.
Benzene is actually a resonance hybrid between the two Kekulé structures.
The C—C bond lengths in benzene are 1.39 A which is shorter than typical
single-bond lengths (1.54 A), but longer than typical double-bond lengths
(1.34 A).
Each sp2 hybridized C in the ring has an unhybridized p orbital
perpendicular to the ring which overlaps around the ring.
This resonance stabilizes the aromatic system so much that normal reactions
of double bonds do not happen for aromatic compounds.
So, Benzene does not prefer addition.
 Criteria for Aromaticity 

The four general requirements for a compound to be aromatic are:

1. The compound must be cyclic.

To be aromatic, each p orbital must overlap with p orbitals on adjacent atoms.

2. A molecule must be planar.
All adjacent p orbitals must be aligned so that the electron density can
be delocalized.

Benzene- A Planar Molecule

Since cyclooctatetraene is non-planar, it is not aromatic, and it undergoes
addition reactions just like those of other.
3. Every atom in the ring must be conjugated.
Aromatic compounds must have a p orbital on every atom.

4. The compound must follow Hückel's Rule and contain a particular

number of  electrons.
 Aromaticity—Hückel’s Rule

Hückel’s Rule:
• An aromatic compound must contain 4n+2  electrons (“n” = 0, 1, 2, 3, 4… ).
• Cyclic, planar and completely conjugated compounds that contain 4n 
electrons are specially unstable and are said to be antiaromatic.

• Number of  electron is [4n+2], where (“n” = 0, 1, 2, 3, 4… )

• Huckel series [2, 6, 10, 14, 18, 22…] .

When, n = 0 , [4 (0) + 2] = 2

n = 1 , [4 (1) + 2 ] = 6
n = 2, [4 (2) + 2 ] = 10
n = 3, [4 (3) +2 ] = 14
• Benzene is aromatic and especially stable because it contains 6  electrons.
• Cyclobutadiene is antiaromatic and especially unstable because it contains
4 electrons.

Note: Hückel’s Rule refers to the number of  electrons, not the number of
atoms in a particular ring.
Considering aromaticity, compounds can be classified into 3 categories:

1. Aromatic— A cyclic, planar, completely conjugated compound with

[4n + 2]  electrons.
2. Antiaromatic—A cyclic, planar, completely conjugated compound
with 4n  electrons.
3. Not aromatic (nonaromatic)—A compound that lacks one (or more)
of the following requirements for aromaticity: being cyclic, planar, and
completely conjugated.
 Aromatic Character of benzene

1. It has a cyclic, planar and hexagonal structure.

2. All C-C bond lengths are identical and in between normal C-C and C=C
bonds.
C-C C-C C=C
All C-C 1.39 A bond
1.54 A 1.34 A
length for benzene

3. It does not have alternative single and double bonds.

4. All hydrogens in benzene are equivalent. Every time same product is
formed no matter which hydrogen is replaced.
5. Typical reaction of benzene include substitution reaction although addition
and oxidation can occur under special conditions.
 Nomenclature of benzene derivatives

For many of these derivatives we simply prefix the name of the substituent
group to the word –benzene.

Some derivatives have special names which may show no resemblance to the
name of the attached substituent group.
The three possible isomers of a di-substituted benzene are differentiated by the
use of the names ortho, meta, and para. For example:
If one of the two groups is the kind that gives a special name to the
molecule, then the compound is named as a derivative of that special
compound, as, for example, nitrotoluene, bromophenol etc.
If more than two groups are attached to the benzene ring, numbers are used to
indicate their relative positions. For example:
 Physical Properties of Benzene

1. Benzene and its homologues are colorless, mobile liquids having a

characteristic odor.
2. They are lighter than and insoluble in water but re-miscible in all
proportions with organic solvents such as alcohol, ether, petrol, etc.
3. They dissolve fats and many other organic substances which are insoluble
in water.
4. Their boiling points show a gradual rise with increasing MW.

Boiling point of Benzene, C6H6 : 80.40°C

Boiling point of Toluene, C6H6-CH3 : 110.6°C
 
5. They have a pronounced toxic character, the continued breathing of their
vaporous being attended with danger.
 Simple Aromatic Compound
1. Toluene
 Preparation of Toluene: Friedel-Crafts reaction:
In this reaction, benzene reacts with methyl chloride in the presence of
anhydrous aluminum chloride to form toluene. This is called as  Friedel crafts
alkylation reaction.

 Physical Properties of Toluene:

Toluene is a colorless liquid with boiling point 110.6°C. It has a similar odor like
benzene. It is insoluble in water but highly soluble in benzene, ether and alcohol
(organic solvent).
 Chemical Properties of Toluene

1. Halogenation: The reaction of toluene with chlorine in the presence of iron

and carried out in absence of light, so the substitution occurs in the benzene
ring. The -CH3 group of toluene is o and p-directing then product is the
mixture of ortho-chlorotoluene and para-chlorotoluene.

Ortho-Chlorotolune Para-Chlorotolune
2. Nitration: Nitration of toluene generates a mixture of products. The major
products are those with substitution at the ortho and para positions. (This
preference for o/p substitution makes the methyl group an ortho/para director).

3. Sulfonation:
4. Friedel crafts alkylation:

Toluene reacts at room temperature with a chloroalkane (for example,

chloromethane or chloroethane) in the presence of aluminium chloride as a
catalyst.

CH3Cl HCl

Chloromethane
 5. Friedel crafts acylation:
Toluene is treated with a mixture of ethanoyl chloride, CH 3COCl, and aluminium
chloride as the catalyst. The mixture is heated to about 60°C for about 30
minutes.

4-methylacetophenone/ P-methylacetophenone
6. Catalytic addition:
 Aromatic Halogen Compound
 Chlorobenzene

Preparation: Raschig Process:

A mixture of benzene vapor is passed over cupric chloride as a catalyst, with
hydrogen chloride and air at 525k.

 Physical Properties of Chlorobenzene:

Chlorobenzene is a colorless pleasant smelling liquid with boiling point 132°C.
It is insoluble in water but soluble in diethyl ether and ethanol (organic
solvents). It is heavier than water. It is steam volatile.
 Chemical Properties
1. Halogenation
2. Nitration
3. Sulfonation
4. Friedel-crafts alkylation.
5. Wutz-fitting reaction: This reaction mechanism can be explained either
via the organo-alkali mechanism or the radical mechanism. The chemical
reaction of aryl halides with alkyl halides and sodium metal with dry ether
present to yield substituted aromatic compounds.
Chlorobenzene couple with chloromethane when heated with sodium in
ether to form toluene.
 Wurtz-Fittig Reaction Mechanism
The Organo Alkali Mechanism

When the aryl halide is reacted with sodium

metal, an intermediate organo-alkali
compound is formed, which is followed by
a nucleophilic attack of the alkyl halide as
shown in the figure. Thus, the required
alkyl-aryl is formed.

The Radical Mechanism

The sodium atom acts as a moderator for the

formation of alkyl radicals and aryl radicals.
These alkyl and aryl radicals now combine to
form a substituted aromatic compound as
shown in the figure.
6. Ullman reaction (also known as Ullman coupling): This reaction that
involves the coupling of two aryl halides in the presence of copper to yield a
biaryl as the product. This  coupling reaction is named after the German
chemist Fritz Ullmann. 

∆
2 + 2 Cu

Chlorobenzene Biphenyl

7. Reduction Chlorobenzene:
Chlorobenzene on reduction with Na/Alcohol or Ni-Al alloy gives benzene.
7. Reaction with magnesium: This reaction completes in two steps.
In step-I, Chlorobenzene reacts with magnesium in presence of dry ether to
give Phenyl magnesium chloride (also Grignard's reagent).
In step-2, Phenyl magnesium chloride reacts with ethanol to form benzene.
 Aromatic Amino Compound

 Aniline:

Aniline

 Preparation of Aniline:
Aniline is prepared by the reaction of nitrobenzene and Sn / concentrated HCl /
excess NaOH with nitrobenzene. In this reaction, nitrobenzene is reduced to
aniline salt by Sn / concentrated HCl. Then aniline is recovered by adding
NaOH.
 
 Physical Properties of Aniline:

i. Pure aniline is a colorless oil with boiling point 184.4C. Its density is 1.002 at
20°C.
ii. On exposure to air, it becomes pale yellow and then rapidly darkens owing to
oxidation.
iii. It has a faint characteristic odor.
iv. It is sparingly soluble in water but dissolves rapidly in ethanol, diethyl ether
and chloroform.
v. It is steam-volatile.
vi. Aniline is toxic.
 Chemical Properties of Aniline

1. Halogenations:
-NH2 group in aniline is a nucleophile (electron donating group) and is o- and p-
directing towards electrophilic substitution reaction.
When aniline reacts with bromine water, the bromine molecule develops a
polarity within itself and bromine with a slightly positive charge acts as an
electrophile (electron seeking) and attacks the electron rich ortho and para
positions of aniline. A white colored precipitate of 2,4,6-tribromoaniline is
obtained at room temperature.
2. Nitration:

In case of nitration in aniline, the Nitric Acid protonates the aniline to form
the Anilinium ion. Anilinium ion is meta directing. That is why besides
the ortho and para derivatives, significant amount of meta derivative is also
formed.

Meta-nitroaniline Ortho-nitroaniline
Para-nitroaniline

Attack for the electrophile was para>meta>ortho.

Explanation:
In nitration of aniline in strong acid (HNO 3, H2SO4) aniline changes to
anillium ion. Anillium withdraws electron density. Its effect (inductive effect)
is felt maximum at ortho followed by meta and then para position.
Consequently, very little of ortho nitrated product is formed.
Since electron withdrawing inductive effects are minimum at para position,
maximum nitration occurs here.
Or we can say that the position farthest from the nitrogen substituted carbon
will have the highest electron density.
3. Sulfonation:
Sulphuric acid reacts vigorously with aniline to form anilinium hydrogen
sulphate which on heating produces sulphanilic acid which in turn also has a
resonating structure with zwitter ion.
4. Acetylation:
In reaction of Aniline (basic in nature) with acetic anhydride to form
Acetanilide, aniline acts as the nucleophile and acyl (CH 3CO-) group from acetic
anhydride acts as the electrophile. Hydrogen atom of -NH 2 group is replaced by
the acyl group. This is a nucleophilic substitution reaction.

Mechanism
5. Salt formation:

7. Reaction with benzaldehyde

 Aromatic Nitro Compound

Preparation of Nitrobenzene: Nitration of benzene:

Nitrobenzene is prepared in laboratory and industry by heating with
concentrated nitric and sulphuric acid at 50.
 The mechanism for nitration of benzene:

Step 1: Nitric acid accepts a proton from sulphuric acid and then dissociates to
form nitronium ion.

Step 2: The nitronium ion acts as an electrophile in the process which further reacts
with benzene to form an arenium ion.
Step 3: The arenium ion then loses its proton to Lewis base forming nitrobenzene.

Physical Properties:
Nitrobenzene is a pale-yellow liquid with boiling point 211°C having odor of
bitter almonds. It is insoluble in water but dissolves in most organic solvents. It is
steam volatile. Nitrobenzene is highly toxic.
 
 Chemical Properties

1. Electrophilic substitution

Nitrobenzene

1,2-Dinitrobenzene 1, 4-Dinitrobenzene 1,3-Dinitrobenzene

Here, NO2 group being electron withdrawing reduces electron density at ortho
and para-positions. Hence, now the meta-position becomes electron rich on
which the electrophile (nitronium ion) attacks during nitration.
 2. Nucleophilic substitution: When nitro benzene is heated with potassium
hydroxide, a mixture of ortho and para nitro phenol is obtained.
In this reaction hydrogen of benzene ring is substituted by hydroxyl group.
Hydroxide ion acts as a nucleophile. Hence, this reaction is an aromatic
nucleophilic substitution reaction.

3. Reduction:

Nitrobenzene Aniline
 Aromatic Alcohol

 Preparation of Phenol: Dow process

In Dow process, the reactant chlorobenzene is heated with aqueous sodium

hydroxide at temperature 623K and 300atm to get sodium phenoxide ion. Then
in the next step sodium phenoxide ion is treated with Dilute HCl which gives
the final product as phenol.
 Physical Properties of Phenol

1. Phenol is a colorless, hygroscopic, crystalline solid with melting point at

42° C.
2. Below 65.8°C, Phenol is only partially miscible with water but above this
temperature it is miscible in all proportions.
3. It is readily soluble in ethanol and other organic solvents.
4. It turns pink on exposure to air and light.
5. It has a distinctive odor.
6. Phenol is a poison when taken orally and with skin it produces painful
blisters.
 Chemical Properties of Phenol

1. Ester formation:
When phenol is reacted with acetyl chloride in the presence of sodium
hydroxide, it leads to the formation of phenyl esters and this reaction will lead
to the formation of phenyl ethanoate/phenyl acetate.

2. Salt formation:

Phenol
3. Ether formation:
O-C2H5

C2H5Cl

Ethoxy benzene

4. Reaction with Zinc-dust: Distillation of phenol with Zn-dust gives benzene

and ZnO as by product.

Phenol Benzene
 Aromatic Acid

Benzoic acid is an organic compound which is described

by the chemical formula C6H5COOH. It consists of a
carboxyl group attached to a benzene ring.
Benzoic Acid

Preparation of benzoic acid:

The commercial production of benzoic acid is done via the partial oxidation of 
toluene with oxygen, catalyzed by manganese or cobalt naphthenates. 
 Physical Properties of benzoic acid

Benzoic acid is a colorless solid with melting point of 122° C. It is soluble in

hot water, ether, ethanol and benzene. It is steam volatile. Benzoic acid is
slightly stronger than acetic acid.

 Chemical Properties of benzoic acid

1. Ester formation: This is also known as Fisher esterification
2. Salt Formation

3. Aryl halide Formation:

When benzoic acid is treated with PCl 5, benzoyl chloride is obtained, including
POCl3 and HCl as by product.

Phosphorus
trichloride
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