Anthracene and phenanthrene

C B
A B C Or
A A C
B
Anthracene Phenanthrene
Phenanthrene
(i) Systematic or substitutive or IUPAC nomenclature, and
(ii) Common nomenclature
(i) Systematic or substitutive or IUPAC nomenclature
8 9 1 9 10
8a 9a
2 8 8a 10a 1 X
7
1
6 3 7 2 6
10a 4a 4b 4a 2
5 10 4
Anthracene 6 5 4 3 5 3
Resonance energy Phenanthrene
Resonance energy 4
= 84 kcal/mol
= 92 kcal/mol

(ii) Common nomenclature

  
 
 
  
Anthracene
Resonance structures of anthracene (Resonance energy = 84 kcal/mol)
There are four resonance structures of anthracene which are shown below:

(1) (2) (3) (4)

 1.433A C1-C2 Three times double bonds
1.399A 1.366A 
and one times single bond.
9 1
C2-C3 Three times single bonds
2 and one times double bond.
1.419A
3 C9-C10 Two times double bonds
and two times single bonds.
10 4  (structures 1-2, right side double
1.436A bond and left side single bonds)
and two times single bonds
(structures 3-4, right side single
bond and left side double bonds).

Two benzenoid rings

One benzenoid ring

(1) (2) (3) (4)

Quinonoid Two benzenoid rings One benzenoid ring
ring
The resonance structures of phenanthrene are shown below (resonance energy
92kcal/mol).

(2) (3)
(1)

(5)
(4)

(2) (3)
(1)

(5)
(4)
Reactions of anthracene and phenanthrene
(a) Oxidation reaction
O
K2Cr2O7, H2SO4 9

Heat 10
Anthracene
O
9,10-Anthraquinone
O O
9 10
K2Cr2O7, H2SO4
Heat
Phenanthrene 9,10-Phenanthrenequinone
Both anthracene and phenanthrene are oxidized and reduced in the 9, 10 positions.
Attack at the 9 and 10 positions of the middle ring of anthracene and phenanthrene
leaves two benzene rings intact. Anthracene sacrifice 12 kcal/mol energy (84-2×36
=12; Phenanthrene sacrifice 20 kcal/mol energy (92-2×36=20).
CHO OHC CO2H HO2C
(i) O3 KMnO4
(ii) H2O
Phenanthrene
In phenanthrene there is an olefinic type bond between the C9-C10 bond but in the
anthracene there is no such type of olefinic type bond. So anthracene only gives this reaction.
Reduction of anthracene and phenanthrene

H H
Na, C2H5OH 9

Reflux 10
Anthracene H H
9,10-Dihydroanthracene

H H
H 9 10 H
Na, (CH3)2CHCH2CH2OH
Reflux
Phenanthrene 9,10-Dihydrophenanthracene
Electrophilic aromatic substitution reaction
Bromination of anthracene and phenanthrene take place at the position-9 (at C 9). In both cases, especially for
anthracene, there is a tendency for addition to take place with the formation of 9,10-dibromo-9,10-dihydro
derivatives.
Br
9
Br2, FeBr3
+HBr (Substitutin product)
9-Bromophenanthrene
Br Br
H 9 10 H
Phenanthrene
Br2, CCl4
(Addition product)

9,10-Dibromo-9,10-dihydrophenanthracene

H Br Br
Br2 9 Heat or OH
CCl4 10
Anthracene H Br 9-Bromoanthracene
9,10-Dibromo-9,10-dihydroanthracene (Substitution or elimination
(Addition product) product)

They also undergo nitration, sulfonation, Friedel-Crafts reactions.

 NO2
HNO3, (CH3CO)2O
(i)
15-20oC
Anthracene 9-Nitroanthracene

COCH3
CH3COCl, AlCl3
(iii)
C2H2Cl4 or CS2
Anthracene 9-Acetylanthracene

CH3COCl, AlCl3 COCH3

(iv)
C6H5NO2
Anthracene 2-Acetylanthracene

SO3H
H2SO4
(v)
Low temperature
Anthracene Anthracene-1-sulphonic acid

H2SO4 SO3H
(vi)
High temperature
Anthracene Anthracene-2-sulphonic acid
Question: How can you chemically distinguish between anthracene and phenanthrene?
O O
+ Heat
O O

O
Anthracene Maleic anhydride Anthracenemaleic anhydride O
An "endo" adduct
Not acts as a diene
O

+ O No reaction
Phenanthrene O
Synthesis of anthracene (Haworth Synthesis)
O O
O
AlCl3 H2SO4
O+ or, PPA
O
100oC
O OH O
Anthraquinone
Zn dust distillation

Anthracene
Synthesis of phenanthracene (Haworth Synthesis)
O

+ O

Napahthalene O
Succinic anhydride
AlCl3
O
HOOC
COOH
O

-(1-Naphthoyl)propionic acid -(2-Naphthoyl)propionic acid

Zn(Hg), HCl Zn(Hg), HCl
HOOC
COOH

HF or polyphosphoric acid HF or polyphosphoric acid

O

Zn(Hg), HCl Zn(Hg), HCl

Pd/C, Heat

Phenanthrene