Polynuclear Hydrocarbons Naphthalene

Polynuclear
Hydrocarbons:
Naphthalene
Presentation by Dr. Gulshan Kumar

Assistant Professor-I, AIP
Pharmaceutical Organic Chemistry-II
 Polycyclic aromatic hydrocarbon (PAH) is a class of organic compounds that is composed of multiple aromatic rings
Biphenyl
Diphenylmethane
Triphenylmethane
Polynuclear aromatic hydrocarbon (PHA)
 PHA are organic compounds composed of hydrogen and carbon atoms. Two or more benzene
rings are fused together and share at least one side and possesses delocalized electrons.
 PAHs are ubiquitous environmental pollutants generated primarily during the incomplete
combustion of organic materials (e.g. coal, oil, petrol, and wood)
 Sources of PAHs include residential heating, coal gasification and liquefying plants,
carbon black, coal-tar pitch and asphalt production, coke and aluminum
production, catalytic cracking towers and related activities in petroleum refineries
as well as and motor vehicle exhaust
 PAHs observed in the environment are molecules having two to seven rings.
Properties
 Polynuclear aromatic hydrocarbons are lipophilic, nonpolar molecules. They tend to persist in
the environment because PAHs are not very soluble in water. While 2- and 3-ring PAHs are
somewhat soluble in aqueous solution, the solubility decreases nearly logarithmically as
molecular mass increases.
 2-, 3-, and 4-ring PAHs are sufficiently volatile to exist in the gas phases, while larger
molecules exist as solids. Pure solid PAHs may be colourless, white, pale yellow, or pale
green
Health effects:
 PAHs have toxic, mutagenic and/or carcinogenic and teratogenic properties

 Metabolism of PAHs occurs via the cytochrome P450-mediated mixed function oxidase system with
oxidation or hydroxylation as the first step.
 PAHs are toxic to aquatic life
Polyneuclear hydrocarbons Classification
Nomenclature for nitro, hydroxy and quinoid
derivatives of PAHs
Napthalene:
Naphthalene (C10H8) is an aromatic hydrocarbon in which two benzene rings are fused in
ortho
positions. For the purposes of naming its derivatives ,the positions are indicated by figures.
Properties:
Physical:-Naphthalene is a white solid which crystallizes in shining plates., m.p.-80 °C, b.p.-
218°,having a strong odor. It is very volatile and sublimes readily on warming. Naphthalene is
insoluble in water, but dissolves easily in organic solvents, particularly in ether and benzene.
Chemical:-The reactions of naphthalene are essentially the same as those of benzene .It undergoes
substitution readily. However it is somewhat less aromatic than benzene. Thus the double
bonds in naphthalene exhibit in part the reactivity of alkenes and it forms addition compounds
more readily than does benzene. As soon as one of the ring is fully saturated by addition of
hydrogen or halogen.
Resonance structure of naphthalene:
x-ray diffraction studies show that ,unlike benzene, all carbon –carbon bonds in naphthalene
are not of the same length. In particular the C1-C2 bond is considerably shorter (1.36A°) than
the C2-C3 bond (1.40A°). This difference can be understood if we examine the three resonance
forms. Notice that the C1-C2 bond is double in two structures (A and B) and single in only
one (C) ;where as the C2-C3 bond is single in two structures (A and B) and double in only
one (C). We would, therefore , expect the C1-C2 bond to have more double-bond character
(shorter bond length ), and the C2-C3 bond to have more single-bond character (longer
bond length). The resonance energy of naphthalene is about 61 kcal/mole. This value is less than
twice the amount
of a single benzene ring (36 kcal/mole).As a result, naphthalene is somewhat less aromatic (more
reactive) than benzene.
Synthesis of
Naphthalene
1). From petroleum:
 Heating petroleum fraction at 680 oC using copper catalyst, two products

are formed. Naphthalene and methyl naphthalene
 After separating methyl naphthalene further converted into naphthalene
by heating under pressure of Hydrogen referred as dealkylation.
2). From 4-phenyl-1-butene:
Heating 4-phenyl-1-butene using red hot calcium oxide
3) Haworth
synthesis
Step I: Formation of 3-benzoyl propanoic acid by the treatment of benzene with
succinic anhydride.
Step II: 3 benzoyl propanoic acid is treated with amalgamated zinc to produce 4-phenyl
butanoic acid.
Step III: 4- phenyl butanoic acid is heated with conc. Sulphuric acid to form Tetralone and water
(ring closer reaction) Conc. H SO
2 4
Heating
HOOC
O
Tetralone
Step IV: Tetralone is again heated with amalgamated zinc and HCl to give
tetraline.
Step V: Tetraline is heated with palladium to yield
naphthalene
4) From 4-Phenyl-3-butanoic acids
Heating phenyl-3-butanoic acid in conc. H2SO4 provides

1-naphthol, which on further heating with Zinc dust Conc. H2SO4
+ H2O
(reduction) give naphthalene OH
Heating
O
O
4-Phenyl-3-butenoic acid Unstable
ZnO + Zn, Heating
OH
1-Naphthol
Reactions of Naphthalene: Naphthalene ,like benzene, undergoes
electrophilic substitution reactions. substitution occurs primarily at C1(α-position). This
can be understood if we examine the intermediate carboniumion. Two resonsnce forms
can be written for the intermediate carbonium ion obtained from the attack at C-
1(without involving the other ring), whereas only one form is possible for substitution at
Consequently the former
C-2. E+ in the following intermediate
equations is more
represents anstable and the product with a substituent
electrophile.
at C-1 predominates. Substitution at C-2 (ß-position) occurs only when the
reactions are carried at higher temperatures or when bulkier solvents are
used.
1). Nitration of Naphthalene: Naphthalene nitrates with a mixture of nitric acid and sulphuric
acid at low temperature to form mainly the α-nitronaphthalene
NO2
HNO3/H2SO4
60 oC
2). Friedel-Craft acylation of Naphthalene: Naphthalene undergoes Friedel-crafts reaction with

acetyl chloride to form the α or β products depending on the conditions
3). Friedel-craft alkylation:
Friedel craft alkylation at low temperature is carried out for naphthalene using lewis acid AlCl3 or
FeCl3, which reacting with iodomethane to produce 1-methyl naphthalene as major product and 2-
methyl naphthalene as minor product
4) Sulphonation: Sulphonation of Napthalene at low temperature (80oC) using SO3/H2SO4

produces naphthalene-1-sulfonic acid while at higher temperature (120 oC) it produces
naphthalene -2-sulfonic acid.
5). Halogenation of Naphthalene:
Cl
Cl2/ Fe
Medicinal uses of Napthalene:
1) Production of naphthol
2) Production of Dyes, Phenyl azo-beta-nahpthol red dye
3) Preparing of beta blocker drugs, Propranolol
4) Usefull insecticide.
5)Veterinary medicine – dusting powder.
6.Polyethylene naphthalene to prepare plastic bottles.
7.Naphthalene sulfonic acids are used to prepare plasticizers,
natural rubbers etc.
8.Naphthalene drugs to cure cough, urine infection, eye trouble
etc.
Naphthalene is more reactive than benzene. It undergoes several reactions like oxidation,
reduction, addition, nitration, halogenations, acylation etc.
1) Oxidation of Naphthalene: 2). Reduction of

Naphthalene:
3). Addition Reaction:
Addition of bromine or chlorine to naphthalene gives naphthalene dibromide or
naphthalene dichloride.
Further addition of bromine or chlorine results in formation of naphthalene tetra bromide or
naphthalene tetra chloride.

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Polynuclear

Presentation by Dr. Gulshan Kumar

 PAHs have toxic, mutagenic and/or carcinogenic and teratogenic properties

 Heating petroleum fraction at 680 oC using copper catalyst, two products

Heating 4-phenyl-1-butene using red hot calcium oxide

4) From 4-Phenyl-3-butanoic acids

Heating phenyl-3-butanoic acid in conc. H2SO4 provides

ZnO + Zn, Heating

2). Friedel-Craft acylation of Naphthalene: Naphthalene undergoes Friedel-crafts reaction with

4) Sulphonation: Sulphonation of Napthalene at low temperature (80oC) using SO3/H2SO4

Medicinal uses of Napthalene:

1) Oxidation of Naphthalene: 2). Reduction of

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