Heterocyclic Chemistry and

Spectroscopy

C 22022/CHE 22022

Course Lecturer: Dr. Dinusha Udukala

• Explain the following statement.

"Naphthalene nitration with nitric acid in acetic anhydride at 60 0C gives 1-

nitronaphthalene and 2-nitronaphthalene in the ratio 10:1".

for the alpha substitution intermediate, two contributions in which one benzenoid ring
remains intact. For beta substitution, the intermediate has only one such contribution
 Anthracene

• n=3; 14 πe
satisfies HUCKEL’s RULE;
Aromatic compound
 Synthesis of Anthracene

• Can be synthesized in several ways

(1)
Benzene reacted with phthalic anhydride and aluminium
trichloride, o-benzoylbenzoic acid is formed, which on treatment
with sulphuric acid affords 9,10 anthraquinone (anthraquinone),
one of the more important anthracene derivatives. Distillation of
anthraquinone with zinc dust yields anthracene.
 Synthesis of Anthracene

(2)
A Diels-Alder approach can also be adopted, and if 1,4-
naphthoquinone is reacted with 1,3-butadiene a
tetrahydroanthraquinone is produced. This can be oxidized to
anthraquinone by treatment with chromium trioxide in acetic acid.
 Structure of Anthracene
• The major contributors to the valence bond description of
anthracene.
• As for naphthalene, these reveal that is not possible for all the rings to
be benzenoid simultaneously.

• A four carbon atom fragment of the central ring terminated on either

side by C-9 and C-10 has a high degree of “dienic” character.

• This is manifested in much of the chemistry of anthracene, where

additions across the 9,10-positions are commonplace giving 9,10-
disubstituted dihydroanthracenes in which two outside rings are fully
benzenoid.

• It was this special reactivity of anthracene which caused early

chemists to emphasize the reactive sites of the molecule and to
adopt the unusual numbering system for anthracene which persists to
this day.
 Reactions of Anthracene

• Oxidation yields 9,10-anthraquinone .

• Why?

• Reduction yields 9,10-dihydroanthracene.

• Electrophiles react preferentially at C-9 since the carbocationic
intermediate thus formed is stabilized by resonance with both of the
flanking benzene nuclei.

• The same intermediate can also readily trap available nucleophiles

(X-) at C-10.

• In this case overall result is an addition process.

• Chlorine and Bromine, in carbon disulfide at 0 0C, give dihalides
initially, but if the temperature is allowed to rise dehydrohalagonation
occurs to yield 9-halegenoanthracenes.

• Some dehydrogenation also takes place and the product is

contaminated with the appropriate 9,10-dihaloanthracene
• Concentrated nitric acid oxidizes anthracene to anthraquinone

• Dilute nitric acid or nirtic acid in acetic acid (ROH=CH3CO2H), affords

10-hydroxy-or 10-acetoxy-9-nitro-9,10-dihydroanthracenes,
respectively.

• These compounds lose water or acetic acid, respectively, on

treatment with alkali to yield 9-nitroanthracene.
• Large groups at C-9 suffer steric hindrance from both the hydrogen
atoms at positions 1 and 8 (peri positions). Thus, although attack at C-
9 is the kinetic preference, sulphonation with sulphuric acid at 200C
occurs to give mainly 1,5- and 1,8-anthracene disulphonic acids.

• Even so, these products still suffer adverse non-bonded interactions

between the sulphonic acid functions and the peri-hydrogen atoms.

• When the reaction is repeated at 1300C the more thermodynamically

stable 2-anthracene sulphonic acid is obtained, together with 2,6-
and 2,7-anthracene disulhonic acids.
• .
Anthracene with benzyne yields triptycene

+
 Phenanthrene

• Phenanthrene is a polycyclic aromatic hydrocarbon composed of

three fused benzene rings.

• The name phenanthrene is a composite of phenyl and anthracene.

• In its pure form, it is found in cigarette smoke and is a known irritant,

photosensitizing skin to light.

• Phenanthrene appears as a white powder having blue fluorescence.

 Synthesis of Phenanthrene

• Naphthalene undergoes the Haworth succinoylation reaction to

afford 1-naphthyl-4-oxobutanoic acid, which can be reduced
under Clemmensen conditions (Zn/HgCl) to afford the
corresponding butanoic acid.

• This product is then cyclized to 1,2,3,4-tetrahydro-1-

oxophenanthrene by treatment with sulphuric acid.

• Reduction, dehydration, and dehydrogenation of the

tetrahydrophenanthrene affords phenanthrene, whereas
reactions with alkyl Girgnard reagents, prior to dehydration and
oxidation gives 1-alkylphenanthrenes.
Synthesis of Phenanthrene
 Synthesis of Phenanthrene

• Trans-stilbene when irradiated with ultraviolet light gives a trans-

dihydrophenanthrene which readily aromatizes to phenanthrene
in the presence of an oxidizing agent such as iodine or oxygen.

• Then reaction can be used to cyclize derivatives of stilbene,

although its application is limited to compounds which bear
electronically similar groups in the two rings.
 Structure of Phenanthrene

• The resonance description of phenanthrene shows that the bond

between C-9 and C-10 has a high degree of double bond
character.

• In line with this prediction, the chemistry of phenanthrene shows

many similarities to that of anthracene.
Structure of Phenanthrene
 Reactions of Phenanthrene
• Addition reactions across the 9,10-bond are common, but rather
less easily effected. This can be accounted for since initial attack
of an electrophile (Y+) produces a singly benzylic carbocation,
which can either be deprotonated or quenched with available
nucleophiles (X-)
Reactions of Phenanthrene
 Reactions of Phenanthrene
• Chlorine in acetic acid solution gives cis- and trans- 9,10-dichloro-
9,10-dihydrophenanthrenes.

• Both the dihalides and the acetoxychloro derivatives eliminate

hydrogen chloride to form 9-chlorophenanthrene or 9-
acetoxyphenanthrene respectively.

• The acetoxychloro compounds may also lose acetic acid and

give 9-chlorophenanthrene.
Reactions of Phenanthrene
 Reactions of Phenanthrene
• Oxidation of phenanthrene with chromic acid gives 9,10-
phenathraquinone, which on reduction with lithium aluminium
hydride affords trans-9,10-dihydroxy-9,10-dihydrophenanthrene
plus 9,10-dihydroxyphenanthrene.