AROMATIC HYDROCARBONS [ARENES]

Cyclic hydrocarbons with alkyl / alkenyl / alkynyl substituents that contain one or more benzene rings either fused state or isolated are called Aromatic
hydrocarbons. These compounds exhibit a phenomenon called Aromaticity. Due to the presence of double bonds in the ring these are called Aromatic
Alkenes or simply Arenes.
These compounds burn with a sooty flame due to high percentage of carbon Aromatic hydrocarbons may be benzenoid [possess benzene ring] or now
benzenoid [no benzene like structure]. but they exhibit aromatic nature.
AROMATIC
AROMATICITY:-
The characteristic behaviour of aromatic compounds is called aromaticity.
* conditions for a molecule to be aromatic:
1) It should be cyclic and planar (with sp2 hybrid carbons)
2) Alternate single and double bonds are to be present.
3) It should exhibit resonance and should have resonance energy.
4) Number of  electrons should be as per Huckel's rule i.e (4n + 2) e– where n = a natural number (0, 1, 2, 3 …...)
5) Aromatic compounds should have delocalised electron cloud of 2, 6, 10, 14  electrons as per Hackel's rule.
Ex:- I) Homocyclic and Aromatic:-

II) Heterocyclic and aromatic:-

III) Ionic species and Aromatic:-

Cyclo propenyl cation Cyclopenta dienyl anion Tropylium cation or Cyclobutene Cyclooctatetraene
(2e−) (6e−) Cyclohepta trienyl dicarbocation dianion
Cation (6e−) (2e−) (10e−)
IV) Heterocyclic and Non aromatic:-
* These cyclic compounds are non aromatic due to lack of delocalisation of 6e−

Ex:-
Piperidine Tetrahydrofuran Pyrrolidine
V) Antiaromatic: - Antiaromatic compounds have
1) cyclic structure 2) Planar structure 3) possess 4n  e− (where n = 1/2/3)
* Antiaromatic systems have 4 or 8 or 12  electrons.

Cyclobutadiene cyclopropenylanion Cyclopentadienyl cation Cycloheptatroenyl anion

(4e−) (4e−) (4e−) (8e−)
VI) Non Aromatic :- Non aromatic compounds have
1) Cyclic structure 2) no ring planarity 3) May have 4n or 4n + 2  e−

Ex:
1,3 – cyclohexadiene Tub shape Repulsion on of two 'H' makes it out of plane.
[no ring planarity] [no ring planarity]
STRUCTURE OF BENZENE:-
Benzene is a monocyclic arene and fits in a general formula CnH2n − 6. It is the parent compound of all aromatic compounds. Its earlier name is phene
Faraday isolated benzene from the condensed fumes released during the destructive distillation of whale oil.
Hoffman isolated benzene from coal tar [a pyrolysis product of coal].
Bertholet prepared benzene via cyclictrimerisation of ethyne.
Mitscherkisch proposed the name 'benzene' and fixed the molecular formula as C6 H6 .

Kekule proposed two cyclic structures for benzene with oscillating double bonds

Benzene consumes 3 H2 molecules during catalytic hydrogen. Thus kekule proposed a cyclic structure with three alternative bonds [Oscillating type]
In benzene, all the six carbons are in sp2 hybridised state [each carbon forms 3 hybrid orbitals hence in total 18 sp2 hybrid orbitals are formed]
The 18 hybrid orbitals involve in overlapping 10 form 6 c-c  bonds (sp2 - sp2) and 6 C - H  bonds (sp2 - s)
The unhybridised Pz orbital of each carbon under go lateral overlapping to form three  bonds. [Benzene molecule has 12  and 3  bonds]
In the formation of benzene molecule 18 hybrid orbitals and 12 unhybrid orbitals (six Pz & six 'S’ orbitals of H) are involved.
In benzene, all the C-C bonds are equal and bond length is 1.39 A0.
Benzene has the resonance energy of 36 KCal / mole or 150.48 kJ/mole.
Benzene molecule is highly unsaturated (presence of three double bonds) but prefers to undergo substitution reactions (like saturated compounds)
instead of addition reactions like alkenes.
To explain the unique behaviour, two different theories are put forward.
1) Resonance theory 2) M.O. Theory.
I) Resonance theory:-
The phenomenon by which a single molecule is represented by different electronic strictures but none of them explain all its properties is called
Resonance. A hybrid form of all these structures can explain all its properties and is called resonance hybrid [It is hypothetical or imaginably and cannot
be depicted on a paper or black board]
Resonance hybrid has less energy than any other canonical strictures this provides or gains stability. For benzene this value is 36 Kcal /mole.

Benzene in the form of resonance hybrid possess less energy by 36 k cals/mole thus gains stability and resists to undergo addition reactions but prefers
to undergo substitution reactions.
II) Molecular orbital theory:-
In benzene formation six carbons form 18 hybrid orbitals via sp2 hybridisation [Six Pz orbitals of all carbons remain unhybridised and lie perpendicular
to Hybrid orbitals]
18 Hybrid orbitals form six C-H  bonds via linear overlap.

Unhybridised 'Pz' orbital of each carbon under go lateral overlapping in two ways to form three  bonds [corresponding to two Kekule structures]

If all the Pz orbitals undergo equal overlapping both above and below the plane then a  election ring is formed.
delocalised ring of sextet of  electrons.
Delocatisation of  electrons in benzene ring leads to
1) decrease in potential energy of benzene to an extent of 36 Kcal / mole.
2) it gains stability due to lesser energy thus do not undergo addition reactions like alkenes but undergoes substitution reactions.
3) no C – C bond is with complete double bond nature and complete single bond native. All C-C bonds are of same length 1.39 A0
4) Each carbon becomes electron rick for a while and favours an electrophile to attack to under go electrophilic substitution reactions:
5) Benzene molecule becomes e− rich and exhibits nucleophilicity.
Methods of preparation of Benzene:-
I) Laboratory methods of preparation:-
1) Decarboxylation of sodium benzoate with Sodalime:-

2) Reduction of phenol with Zinc:-

3) Cyclic trimerisation of acetylene:-

4) Acidic hydrolysis of benzene sulphonic acid with steam:-

5) Reduction of benzene diazonium chloride with H3PO2 :

6) Aromatisation of n-hexane:-

II) Commercial method :- [Coal tar distillation]

Coal tar is one of the products formed during the destructive distillation of coal. [heating coal in the absence of air at high temperature is called
destructive distillation]
Coal tar on fractional distillation gives light oil at 1700 C. It contains Benzene Toluene and xylene. Fractional distillation of light oil at 800 C gives
Benzene.
Physical properties :-
1) It is a colourless liquid with characteristic aromatic smell
2) Its B.P is 800 C and M.P is 5.50
3) It is immiscible with water
4) It is a good solvent for many nonpolar organic compounds.
CHEMICAL PROPERTIES:-
Delocalisation of e− makes benzene molecule electron rich-(nucleophile). It favours electrophilic reagents [electron deficient species] to attack so as to
form a substituted product.
Benzene and its derivatives thus undergo characteristic reactions called
Electrophilic substitution reactions. (SE)
Electrophilic substitution reactions involve 3 steps.
1) Generation of electrophile
2) Attack of electrophile [formation of arenium ion as intermediate]
3) Removal of H+ from arenium, [a Carbocation]
* When electrophile (E+) attacks benzene ring  complex (arenium ion) is formed in which electrophile linked carbon is in sp3 hybridisation stale.
* The arenium ion is stabilised by resonance. In the sigma complex or arenium ion no aromatic character is observed.
* Aromatic character is regained with the removal of H+

Electrophilic substitution reactions of Benzene types

1) Halogenation 2) Nitration 3) Sulphonation 4) Freidal-Craft’s alkylation / acylation / benzoylation.

I) Halogenation:-
* In the presence of Lewis acids like FeX3 or AlCl3 benzene reacts with Cl2 or Br2 to form chlorobenzene or bromobenzene.
*
* FeCl3 /FeBr3 act as electrophile generator. E + is halonium ion [Cl / Br  ]

a)

b)
c) H + + FeCl−4 → FeCl3 + HCl

* In the presence of anhydrous AlCl3 (in dark) if excess Cl2 is used then further substitution occurs such that all ‘H’ are replaced by 'Cl' atoms.

*
II) Nitration:-
Benzene undergoes nitration with a mixture of con HNO3 + con H2SO4 [Called nitration mixture] to form nitrobenzene
* Con H 2SO4 behave as acid and con HNO3 behave as base to generate the electrophile called nitronium ion  NO+2 
III) Sulphonation:- [Replacement of ‘ H ’ by −SO3H group]

* Benzene reacts we it con H 2 SO4 or oleum ( H 2 S2 O 7 ) to form benzene suphonic acid

* The electrophile is SO3 and is formed from the given reaction.

2H 2 SO4 SO3 + H3O+ + HSO4−

IV) Freidal- Craft's reaction:-

* Aromatic substitution reactions which takes place in the presence of anhydrous AlCl3 are called Freidral-Crafts reactions. These are of 3 types.

* 1) Alkylation 2) Acylation 3) Benzoylation.

+
* Anhy AlCl3 act as Lewis acid to generate the electrophiles like R + / RCO
1) Alkylation with R - Cl and AlCl3 :- [electrophile is R + = alkyl Carbonium ion]

* With CH3Cl & anhydrous AlCl3 the product is Methyl benzene or Toluene
* With C2 H5Cl & anhydrous AlCl3 the product is Ethyl benzene

* With CH3 − CH2 − CH2Cl & anhydrous AlCl3 in the product is isopropyl benzene.
+
2) Acylation with RCOCl & anhy AlCl3 [Electrophile is RCO = acyl Carbonium]

acetophenone or methyl phenyl ketone.

* In the place of acetyl chloride [CH3COCl] one can use acetic anhydride = ( CH 3CO )2 O
+
3) Benzoylation with C6 H5COCl & anhy AlCl3 :- [Electrophile is C6 H5 CO ]

II) Addition reactions:-

* Benzene do not undergo addition reactions under normal conditions but under special conditions like catalyst or Sunlight or Pressure it undergoes
addition reactions.
1) Catalytic hydrogenation:-

or C6 H12 i.e cyclohexane.

2) Addition of Cl2:-
Hexachlorocyclohexane
Benzene hexachloride [BHC]
Gamaxene
Lindane or 666
* If is an insecticide.

3) OZONOLYSIS:-
* Benzene consumes 3 ozone molecules to form benzenetriozonide [ C6 H6O9 ]

which on reaction with Zn / H 2O , gives 3 molecules of glyoxal [Ethan-1,2-dial]

* Benzene [a trimer of acetylene] gives glyoxal similar to acetylene.

4) Combustion
1
C6 H6 + 7 O2 → 6CO2 + 3H2O + heat
2
* DIRECTIVE INFLUENCE OF FUNCTIONAL GROUPS IN MONO SUBSTITUTED BENZENE
In benzene all the six carbons are equivalent. Hence on monosubstitution only one compound is formed.
* Mono substituted benzene on further substitution forms three isomeric di substituted products
* All the three isomeric products are not formed in equal amounts. If ortho & para are formed as major products then meta isomer is a minor.
* If meta isomer is a major product then o & p-are minor products.
Position allotment to the second electrophile depends on the nature of first substituent. It is called orientation.
The first substituent may act as ortho, para directing or meta directing group.
1) Ortho and para directing groups :-
•• •• •• •• ••
* Groups like − OH , − O CH 3 , − N H 2 , − N H R, − N H COCH 3 − CH 3 − C2 H 5 act as ortho and para directing group. [Ring activating groups]
•• ••

* They pump the electron cloud of lone pair into benzene ring and increases electron density. Benzene ring gets activated and becomes more
susceptable to the attack of electrophiles.
Ex:- If -NH2 is the first substituent on benzene

* Due to +M effect lone pair is pumped into benzene ring. e− cloud density gets increased at ortho & para positions. Hence on further substitution it
forms ortho & para products. [Para product is a major product due to less steric repulsions]
•• ••
* Groups like − Cl :, − Br : do act as ortho & para directing groups but the dominant – I effect make them to act as ring deactivating groups.
•• ••
2) meta directing groups:-
* Unsaturated groups like − NO2 , −CN, −COOH, −CHO, −COR, −SO3H act as metadirecting groups.

* These groups with draw the electron cloud from the benzene ring thus it gets deactivated and benzene becomes less susceptible for electrophile
attack.
* Though e− cloud density of ring decreases it is relatively more at meta position this forms a meta product (a major) on second substitution
Ex:- If − NO2 is the first substituent on benzene

* Reactivity order of different aromatic compounds towards substitution

Ex:-
CARCINOGENITY AND TOXICITY OF POLY NUCLEAR HYDROCARBONS:
The hydrocarbons which contain two or more benzene rings in fused state are called Polynuclear Hydro Carbons. (PNHC)
PNHC are toxic and carcinogenic in nature [Cancer producing property]
PNHC are formed on incomplete combustion of organic materials like tobacco, coal and petroleum. They under go different biochemical reactions in
the human body and damage DNA formally causing cancer.
Ex:
1,2-benzanthracene 3-methyl cholanthrene 1,2-benz pyrene 1,2,5,6-di benzanthracene 9,10-dimethyl
1,2-benzanthracene

Fused benzene rings = 4 Fused benzene rings = 4 Fused Benzene rings = 5 Fused Benzene rings = 5 Fused Benzene rings = 4