Presentation Topic

A POLYNUCLEAR AROMATIC HYDROCARBON

PHENANTHRENE

Presented By

Basanta Rajkhowa
 Conditions necessary for aromaticity

Any compound to be aromatic , it must be

1.Cyclic & Planner 2. All C-atoms must be Sp2

3. All double bonds must be conjugated

4..Obey Huckle rule which state that any aromatic compound must
contain 4n+2 pi electrons where n =
0,1,2,3,…
 Polynuclear Hydrocarbons

Benzenoid Non- Benzenoid

Isolated Fused rings

Linear Angular
 Fused Ring Aromatic Hydrocarbons

* Fused or condensed aromatic hydrocarbons contain

more than one ring and have two carbons shared by
two(or more) rings.

* Phenanthrene a member of this class. Phenanthrene

have two pairs of carbon atom shared by two rings, each
pair being shared by separate pair of rings. This is solid
at room temperature.
 What is Phenanthrene?

*Phenanthrene is an isomer of anthracene. It is obtained along with

anthracene from green oil fraction of coal-tar.

On cooling this fraction we get a solid mass which contains

phenanthrene anthracene and carbazole, treatment of this with
solvent naphtha dissolves phenathrene.

Evaporation of this solution yields crude phenanthrene, purified by

recrystallization of the picrate from ethanol.
 Structure of Phenanthrene

*Phenanthrene is a planer molecule .All fourteen

carbon are Sp2 hybridized. The sp2 hybrid orbitals
overlap with each other and 10-hydrogen atoms
forming C-H and C-C sigma bonds.

* Each carbon atom also possesses a p orbital and this are perpendicular
to the plane containing the sigma bonds. Lateral overlap of these p
orbitals produces a pi-molecular orbital containing 14 electrons.

* Phenanthrene shows aromatic properties because the resulting pi-

molecular orbitals satisfies Huckel’s rule(n=3,in 4n+2)
Position of the Double Bond
 Numbering System
In naming the phenanthrene derivatives , the numbering systems
shown below is used; the no used to determine the position of
substituent on the ring should be as small as possible:
3
4 2 9 10

5 8 1
1
6
7 2
7 10
6 5 4 3
8 9
 Synthesis of Phenanthrene
1.Haworth Method

COOH
2.Pschorr Synthesis

Cu
 3.Bardhan –Sengupta Synthesis
Br MgBr CH2CH2OH CH2CH2Br
O
Mg 1.H2C CH2 HBr
ether 2,H3O +

O
O O O O
OC2H5
+
CO2C2H5 CH3CH2ONa - CO OC2H5
CO2C2H5 -EtO-
O

CH2Br CO2C2H5
H2C
H 1.KOH
2,HCl
C2H5O2C K 3.heat Na
+
O
SN2 O Moist ether
O

P2O5
Se
OH cyclisation
 Physical Properties Chemical Properties

*Colorless solid. *Undergoes oxidation

*Insoluble in water ,addition and
dissolves readily in electrophilic
ethanol , benzene and substitution reaction.
ether. *Occur at the C-9 and
* Gives fluoroscence C-10 positions
in benzene solution
 Chemical reactions of Phenanthrene
1.Halogenation:

Phenanthrene reacts with chlorine in carbon tetrachloride solution at room

temperature to give 9,10-dichloro-9,10-dihydrophenanthrene (an adduct). On
heating, this loses a molecule of HCl to give 9-chlorophenanthrene (a
substituent product).
Cl Cl
H H Cl

Cl2
in CCl4 -HCl

9,10-Dichloro-9,10-
Dihydrophenathrene 9=Chlorophenanthrene
2.Friedel Crafts Acylation
Phenanthrene undergoes acylation on treatment with acetyl chloride in
presence of aluminium chloride at 273 K to give 9-acetylphenanthrene

O
H3C C
O
AlCl3
+ H3C C Cl
273 K
Acetyl chloride

9-Acetylphenanthrene
3.Nitration:

Phenanthrene undergoes nitration with concentrated nitric acid and sulphuric

acid to yield 9-nitrophenanthrene

O2N

HNO3

H2SO4

9=Nitrophenanthrene
4.Sulphonation:

Phenanthrene reacts with concentrated sulphuric acid at 393 K to give a

mixture of 2-phenanthrenesulphonic acid and 3-phenanthrenesulphonic acid.

conc. H2SO4
SO3H +

SO3H
2-Phenanthrenesulfonic acid
3-Phenanthrenesulfonic acid
Oxidation:

Phenanthrene undergoes oxidation with potassium dichromate and sulphuric

acid to form 9,10-phenanthraquinone. Further oxidation of this with hydrogen
peroxide gives diphenic acid.

O
K2Cr2O7 H2O2 COOH

H2SO4 CH3COOH COOH

O

9,10-phenanthrenaquinone Diphenic acid

Reduction:

Phenanthrene undergoes reduction with sodium and isopentanol to form 9.10-

dihydrophenanthrene.
H H

H H
Na/C5H11OH

9,10-dihydrophenanthrene
 Preparation of Derivatives
1.Preparation of 1-alkylphenanthrene
O
O
COOH
AlCl3 Zn-Hg/HCl
+ O

Naphthalene O

COOH 1) RMgX OH
conc.H2SO4 O 2) H2O

R
Se
2.Preparation of 4-alkylphenanthrene
O
O
HO
HO
O AlCl3
+ Zn/Hg + HCl
O O
O
succinic anhydride

CH3
O
IMgO

conc. H2SO4 CH3MgI H3O+

Cyclisation

H3C

Pd-C
3.Preparation of 2 or 3-alkylphenanthrene:
. By using alkyl succinic anhydride instead of succinic anhydride, an alkyl group
can be introduced into the 2- or 3- position. For example, preparation of 2-
derivative
O R
O
R COOH
AlCl3 Zn-Hg/HCl
+ O

Naphthalene O

R R R

COOH
conc.H2SO4 O Zn-Hg/HCl

Se
Uses:

1.Phenathrene can produce phenanthrequinone, polyester resin,

benzene anhydride,

2.In papermaking it is an antifogging agent of pulp;

3.In medicine, it can produce alkaloid.

4.Phenanthrene can be used in the production of fuel of jet plane

 Conclusion

In this presentation, we have studied about a polynuclear aromatic

hydrocarbon called Phenanthrene , having the formula C14H10 . We
have studied its structure , its processes of synthesis and its chemical
reactions etc.
THANK YOU FOR
HAVING YOUR
ATTENTION