DAMIETTA

UNIVERSITY

CHEM-323:
Polynuclear Aromatic
Hydrocarbon

LECTURE 1

Dr Ali El-Agamey 1
 LEARNING OUTCOMES
LECTURES 1-2

 Understand the principles of biphenyl nomenclature and the different

methods used in its synthesis.
 Understand the various methods involved in the synthesis of the
different isolated polynuclear aromatic compounds.
 Appreciate the effect of phenyl group on the stability of various
intermediates.
 Appreciate the steric effect of phenyl and benzyl groups.
 Understand the role of phenyl and benzyl groups in electrophilic
substitution reactions.

2
 Lecture 1-2: -Nomeclature, synthesis and reactions of biphenyl.
-Synthesis and reactions of diphenylmethane,
triphenylmethane, triphenylmethyl chloride, triphenylmethanol, trans-
stilbene and benzoin.
-Nomenclature of fused systems.
 Lecture 3-6: -Aromatic character of fused systems.
-Structure elucidation of naphthalene
-Reactions of naphthalene.
 Lecture 7-11: - Synthesis of naphthalene.
- Synthesis and reactions of anthracene and
phenanthrene.
 Lecture 12: -General revision for the whole course.

Reading
RT Morrison and RN Boyd, Organic Chemistry, Allyn and Bacon, Inc., 1987.
Mundy, BP et al, Name reactions and reagents in organic synthesis, Wiley, 2005
H Meislich et al, Organic Chemistry, McGraw-Hill Book Company, 1980.
3
IL Finar, Organic Chemistry, Volume 1 (1985) and Volume 2 (1977).
Polynuclear Aromatic Hydrocarbons
Isolated rings
(1) Biphenyl

Nomenclature

4
Homework: Give name for the
following compounds
Cl
Br Br

(b)
(a)
CO2H Cl

(H3C)2N N(CH3)2

(c)

5
 (1) Biphenyl
Synthesis

(a) Fittig’s reaction

(b) Gattermann reaction

(c) Gomberg reaction

More examples 6
(d) Ullmann coupling reaction More examples

(e) Benzidine rearrangement

7
 (1) Biphenyl
Reactions

Although –NO2 is m-directing group, p-O2NC6H4 is p-directing!!

According to the charge distribution approach, a p-nitro group

would have been expected to direct to the m-position in the other ring.

O O

N N

O O

O
N
O
8
 (1) Biphenyl
Reactions

However, the stabilities of the carbocation intermediates generated

following o- and p-substitutions are greater than that generated from
m-substitution due to the greater dispersal of charge in the former
substitutions. Therefore, o-and p-substitutions are preferred.

O2N NO2 O2N NO2

p–substitution

NO2 NO2

O2N O2N

m–substitution
9
 (2) Diphenylmethane
Synthesis and reactions

(3) Triphenylmethane (Tritane)

Synthesis and reactions

10
Homework: write the product of the
following reaction

11
 DAMIETTA
UNIVERSITY

CHEM-323:
Polynuclear Aromatic
Hydrocarbon

LECTURE 2

Dr Ali El-Agamey 12
 (3) Triphenylmethyl chloride
(Trityl chloride)

Ag Dimer
2 Ph3CCl 2 Ph3C (White solid)
C6H6, no air
Yellow colour

was believed to be

Actually
Ph3C
Ph3C–CPh3
H
Hexaphenylethane

Real dimer product

13
 (4) Triphenylmethanol
(Triphenylcarbinol)

Synthesis and reactions

(5) trans-Stilbene
(trans-1,2-Diphenylethene)

Synthesis and reactions

(6) Benzoin

Synthesis and reactions

14
Homework: Complete the following equation

Homework: Write the mechanism of the following reaction

15
 Fused rings
Naphthalene

 Naphthalene, anthracene and phenanthrene are obtained

from coal tar, naphthalene being the most abundant
(5%) of all constituents of coal tar.
 Uses: moth balls, which contain naphthalene, are used as
insect repellants (naphthalene is very volatile).
 Many synthetic dyes contain naphthalene moiety.

16
 Fused rings
Nomenclature of naphthalene, anthracene and
phenanthrene

 How many isomers for monosubstitution of naphthalene

(C8H7X)?
 How many isomers for monosubstitution of anthracene
(C14H9X)?
 How many isomers for monosubstitution of phenanthrene
(C14H9X)? 17
 Homework
 How many isomers for disubstitution of naphthalene
(C8H6X2)?
 How many isomers for disubstitution of naphthalene
(C8H6XY)?

 How many isomers for disubstitution of anthracene

(C14H8X2)?
 How many isomers for disubstitution of phenanthrene
(C14H8X2)?

 In each case write the name of each isomer?

18
Nomenclature of naphthalene, anthracene and
phenanthrene

19
Homework: Give names for the following
compounds

20
 DAMIETTA
UNIVERSITY

CHEM-323:
Polynuclear Aromatic
Hydrocarbon

LECTURE 3

Dr Ali El-Agamey 21
 Aromatic character of naphthalene, anthracene
and phenanthrene
Naphthalene, anthracene and phenanthrene are classified as
aromatic because of their properties, which resemble those
of benzene.
(i) Experimental point of view

 Undergo electrophilic substitution reactions.

 Like benzene, they are unusually stable as indicated from
their low heats of hydrogenation and combustion.

22
Resonance Energy

23
 Aromatic character of naphthalene, anthracene
and phenanthrene

 Resonance energy of A = 61 kcal mol-1

 Resonance energy of B = 84 kcal mol-1
 Resonance energy of C = 92 kcal mol-1
 Resonance energy of benzene = 36 kcal mol-1

24
 Aromatic character of naphthalene, anthracene
and phenanthrene

(ii) Theoretical point of view: they have the structure required for
aromatic compounds
 Flat (sp2-hybidized); cyclic
 p-cloud above and below the plane due to ???
 HÜckel`s rule ???

25
 Resonance structures and bond lengths of
naphthalene, anthracene and phenanthrene
There are n+1 principal resonance structures for polynuclear
aromatic hydrocarbon containing n benzene rings fused
together in a linear manner.

Double bond character

Bond length

The different carbon-carbon bond lengths reveal the

decreased aromaticity of fused polynuclear aromatic
hydrocarbons.

Phenanthrene is an angular polynuclear aromatic

hydrocarbon.

26
 Fused rings

(1) Naphthalene
(C10H8)

Naphthalene, anthracene and phenanthrene are obtained from

coal tar.
Naphthalene being the most abundent (5%) of all constituents
of coal tar.
(a) Uses
 In moth balls as insect repellants.
 Many synthetic dyes contain naphthalene moiety.
(b) Structure Elucidation 27
 Reactivity of naphthalene as compared to benzene
In naphthalene, two fused rings share a pair of p–electrons,
therefore the aromaticity and the resonance energy per ring
is less than that of benzene itself.

 Resonance energy of naphthalene = 61 kcal mol-1

 Resonance energy per ring = 30.5 kcal mol-1
 Resonance energy of benzene = 36 kcal mol-1

Reactivity Stability of the

As R.E. increases
decreases compound increases

Resistance to destroy
aromatic character
increases 28
 Reactivity of naphthalene as compared to benzene

What happened when aromatic character of one ring of

naphthalene is destroyed?

Therefore, naphthalene undergoes oxidation or reduction more

readily than benzene but only to the stage where a substituted
benzene is formed; further oxidation or reduction requires
more vigorous conditions.

29
 Reactions of naphthalene

(1) Oxidation

30
 Reactions of naphthalene

(1) Oxidation

 Oxidation by V2O5 is important industrial process (naphthalene is

available from coal tar).

 Vitamins K1 and K2 are derivatives of 1,4-naphthoquinone.

 Because of this tendency to form quinones, it is not always feasible

to prepare naphthalenecarboxylic acids by oxidation of methyl side
chains.

31
 Reactions of naphthalene

(2) Reduction

32
 Reactions of naphthalene

(3) Electrophilic susbstitution reactions

Fries rule: The most stable arrangement of a polynuclear
compound is that form which has the maximum number
of rings in the benzenoid condition.

1-Substitution versus 2-substitution

Number of resonance structures Aromatic sextet is retained

(benzene has large R. E.)
Carbocation and T.S. resulting from attack at the 1-position
are much more stable than those resulting from attack
at the 2-position . Therefore, 1-susbstitution will be 33
preferred.
 Reactions of naphthalene

(i) Nitration

34
 DAMIETTA
UNIVERSITY

CHEM-323:
Polynuclear Aromatic
Hydrocarbon

LECTURE 4

Dr Ali El-Agamey 35
 LEARNING OUTCOMES
LECTURE 4

 Reactions of naphthalene: Nitration; Halogenation;

Chloromethylation; Friedel-Crafts reactions (alkylation and
acylation).
 Sulfonation.
 Naphthols and naphthylamines.
 Synthesis of 1-substituted naphthalenes.
 Synthesis of 2-substituted naphthalenes.
 Summary of naphthalene reactions.
36
 Reactions of naphthalene

(i) Nitration

37
 Reactions of naphthalene

(ii) Halogenation

Introduction of NO2 and X groups opens the way to the

preparation of a series of 1-substituted naphthalenes.
38
 Reactions of naphthalene

(iii) Chloromethylation

(iv) Friedel-Crafts reactions

Friedel-Crafts reactions is carried out under mild conditions.

Friedel-Crafts alkylation is of little use because (1) polyalkylation
and (2) side reactions.

Alkylnaphthalenes can be prepared via acylation or ring closure.

39
 Reactions of naphthalene

(iv) Friedel-Crafts reactions

Acetylation affords access to the preparation of a series of

2-substituted naphthalenes.
40
 Reactions of naphthalene

(v) Sulfonation

41
 Reactions of naphthalene

(v) Sulfonation

42
 E2 > E1 k1 > k2

Δ H2 > Δ H1 E-2 (E2 + Δ H2) >> E-1 (E1 + Δ H1) k-1 >> k-2

At low T, 1-S is formed faster than 2-S

Therefore, 1-S is called kinetically controlled product

However, at high T, which speeds up a reaction, or if the reaction is left for

long time, 2-S becomes the main product.

1-S reforms N much faster than does 2-S and hence 2-S accumulates at the
expense of 1-S i.e. the equilibrium is established in favor of the formation 43
of 2-S,
which is called the thermodynamically controlled product.
 (v) 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.

44
Reactions of naphthalene

45
 Reactions of naphthalene

Naphthols and naphthylamines

Bucherer reaction

46
 Reactions of naphthalene

Naphthols and naphthylamines

47
Synthesis of 1-substituted naphthalenes

48
 Synthesis of 2-substituted naphthalenes

Acetylation and sulfonation affords access to the

preparation of a series of 2-substituted naphthalenes.
Summary of naphthalene reactions

50