Presentation of Polynuclear Compounds

POLYCYCLIC
AROMATIC
HYDROCARBONS
Made by-Loveleen Kumar and Toheed Mushtaq
Roll No. 18390451015,18390451040
Semester 8th
Department:-School of Pharmacy
Poly-nuclear aromatic hydrocarbons are composed
by two or more benzene rings
Polynuclear Hydrocarbons
Benzenoid Non- Benzenoid
Isolated Fused rings
Linear Angular
 Benzenoid: Similar to benzene in structure or
linkage; having an aromatic ring system.
 Fused or condensed ring system: When
two rings share a pair of carbon atoms, the rings
are said to be fused rings.
Isolated ring
m o o m
3 2 2 3
1 1
p 4 4 p
5 6 6 5
m o o
m
Biphenyl or diphenyl
NAPTHALENE
(C10H8)
 Shows aromatic properties

 Satisfy Huckel’s rule (4n+2)
=(4*2+2)=10
 All C=C are not same (X-ray diffraction study)
C1=C2=1.36 Å
C2=C3=1.40 Å
 Resonance energy of naphthalene is 61 Kcal/mol
Benzene, 36 Kcal/mol
 2ndaromatic ring is less stable (61-
36)=25
Kcal/mol
 Naphthalene is less aromatic (more reactive) than
benzene because it has less resonance stabilizing
energy as compared to 2 individual benzene
molecules.
Structure elucidation of naphthalene
1. Molecular Formula: C10H8
2.
So naphthalene contains the skeleton

3.
 So nitro group is present in benzene ring.
Nitration basically means reaction with
HNO3/H2SO4
4.
 The ring in phthalic acid

benzene by oxidation of amino-
produced
naphthalene is not the same ring is that
obtained by oxidation of nitro
naphthalene.
 i.e. Naphthalene contains two benzene
rings and we can explain this by this equation
The structure of naphthalene is
confirmed by method of its synthesis
Howarth method
Other way of cyclization
 The reaction occurs if R is o- or p-
directing group such as NH2, NHR, OH, OR, R,
halogen.
 If R is m- directing group (e.g. NO2, CN, COOH,
COCH3, SO3H) no reaction occur.
 The above reaction gives -

substituted naphthalene.
Synthesis of 1-alkyl naphthalene
From -benzylidene – propenoic acid
Reduction
Oxidation
Addition of Cl2 / Br2
Electrophilic substitution reaction
Naphthalene undergoes ES mostly at alpha-position

Resonance forms determine higher reactivity at C-1
 C-1 attack has 2 resonance structures with benzene rings
 C-2 attack has only 1 resonance structure with a benzene ring
 The most stable intermediate (C-1 attack) gives faster reaction
Attack at C-1
Attack at C-2
At position 1; carbocation intermediate stabilize by two
resonance within one benzene ring.
So carbocation is more stable position 1 than 2

Sulfonation
 The lower stability of 1-S is attributed to the steric

interaction between the sulfonic group and the hydrogen
atom in the 8-position.
Summary of naphthalene reactions
Medicinal uses of Naphthalene
🠶 Preparation of beta blocker drugs.

🠶 To synthesize synthetic dyes.
🠶 Useful insecticide.
🠶 Veterinary medicine – dusting powder.
🠶 Polyethylene naphthalene to prepare plastic bottles.
🠶 Naphthalene sulfonic acids are used to prepare plasticizers,
natural rubbers etc.
🠶 Naphthalene drugs to cure cough, urine infection, eye
trouble etc.
Anthracene (C14H10)

8 9
7 2
1
6 3
5 10 4

Anthracene (C14H10)

1 9 8
2 7
3 6
4 10 5

 monosubstitution (C14H9X) = 3 isomers
 Disubstitution (C14H8X2) = 15
isomers
Anthracene (C14H10)
 C1-C2 bond to have more double bond

character (shorter bond length)
 C2-C3 bond to have more single bond
character (longer bond length)
 From X-ray diffraction study: C1-C2 bond = 1.37 Å
C2-C3 bond = 1.42 Å
 Resonance 84 kcal mol-1, average 28, less
energy
Synthesis of Anthracene
(i) By Friedel Crafts reaction

(a)
(b)
(c)
(ii) By Haworth synthesis
Synthesis of anthracene
(iii) By Diels-Alder reaction
Chemical reactions
Attack at C-1
Leaves naphthalene intact

Loss of RE=84-61=23 kcal
Attack at C-2
Chemical reactions
Attack at C-9
Leaves two benzene intact

Loss of RE=84-72 =12 kcal
Substitution product
Addition product
Reactions preferentially occur at C-9 & C-10
Chemical reactions
Diels Alder reaction
Addition of one molecule of O2

[HNO3+H2SO4 is not used, leads formation
of 9,10 anthraqunone by oxidation]
Medicinal uses of Anthracene
🠶 Anthracene glycosides are oxygenated derivatives of

pharmacological importance that are used as laxatives or
cathartics, antineoplastic agent, polycystic kidney.
🠶 Anti-inflammatory, antibacterial, antifungal and anti-
proliferative activity.
🠶 As natural dyes.
🠶 Hepato-protective, nephron-protrctive, antioxidant.
Phenanthrene C14H10
6
5 7
4
8
3
2 9
1 10
Phenanthrene C14H10
 monosubstitution
(C14H9X) = 5 isomers
3
4 2 Disubstitution (C14H8X2)
5 = 25 isomers
1
6
9 10
7 10
8 1
8 9
7 2
6 5 4 3
Position of double bond
3
2
4
1
5
6 10
7 9
8
 C9-C10 bond to have more double bond character

 RE 92 kcal/mole, 92-72=20 Kcal/mole to remove
the aromaticity of the middle ring
Preparation of phenanthrene
1) Howrth method
2) Posher synthesis
Preparation of 1- alkyl phenanthrene:
Preparation of 2- alkyl phenanthrene:

Oxidation:
Reduction:
 EAS in anthracene or phenanthrene yields
mixtures and is not generally useful. For
example, in sulfonation:
44 Medicinal uses of
Phenanthrene
🠶 Steroid moiety contain phenanthrene nucleus which is
present in sex hormones
🠶 Codeine has phenanthrene moiety
54 Triphenylmethane
🠶 Triphenylmethane (C6H6)3CH is the chromogen of a large
number of dyes. The common chromophore is the p- quinoid
structure and the auxochromes are OH,NH2 and NR2.
🠶 Triphenylmethane dyes are very brilliant intense colors but
fade quickly in light. Therefore, they are no longer much
used on textiles. However, they are used in large quantities

for coloring paper and typewriter ribbons.
🠶 Synthesis:-
🠶 Derivatives examples- crystal violet, malachite green

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POLYCYCLIC

Benzenoid Non- Benzenoid

Isolated Fused rings

 Shows aromatic properties

1. Molecular Formula: C10H8

So naphthalene contains the skeleton

 The ring in phthalic acid

 The above reaction gives -

Naphthalene undergoes ES mostly at alpha-position

So carbocation is more stable position 1 than 2

 The lower stability of 1-S is attributed to the steric

🠶 Preparation of beta blocker drugs.

 C1-C2 bond to have more double bond

(i) By Friedel Crafts reaction

Leaves naphthalene intact

Leaves two benzene intact

Addition of one molecule of O2

🠶 Anthracene glycosides are oxygenated derivatives of

 C9-C10 bond to have more double bond character

Preparation of 2- alkyl phenanthrene:

used on textiles. However, they are used in large quantities

🠶 Derivatives examples- crystal violet, malachite green

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