BENZENE

Total No.of questions in Benzene are -

In chapter Examples .................................................................. 06

Solved Examples ........................................ ............................ 18

Total No. of questions .............................................................. 24

1. INTRODUCTION (p) The number of bond angles is eighteen
(i.e. 3 on each carbon) and each of 120º.
(a) Benzene is a simplest aromatic hydrocarbon
in which alternate double bonds are present.
(b) Aromatic compounds are those which follow
Huckel's principle.
(c) According to Huckel's principle, aromatic
compounds contain (4n + 2) electrons.
(d) Aromatic compounds show characteristic (q) Carbon-carbon bond lengths are equal
smell, burn with sooty fuming flame due to due to resonance and it is 1.39 Å and
more percentage of carbon than aliphatic C – C bond order is between one and
compounds. two.
(e) Aromatic compounds mainly shows (r) The resonating energy of benzene
electrophilic substitution reactions. molecule is 36 k cal/mol.
(f) Benzene was discov ered by 'Michael
Faraday'. 2. RESONANCE IN BENZENE MOLECULE
(g) It was initially obtained from coal-tar/charcoal
by 'Hoffmann'. (a) The cloud of -electrons in benzene is
delocalised type, due to this delocalisation
(h) It's prismatic structure was giv en by
number of structures are produced in benzene
'Ledenberg'
ring and all these are helpful to explain the
(i) It's diagonal structure was given by 'claus'. property of benzene.
(j) It's centric structure was given by 'Bayer
and Armstrong'.
(k) It's parallel structure was given by 'Dewar'.
(l) It's alternate structure was given by 'Kekule'.
(m) It's partial valency structure was given by
'Thalae'.

(resonating structures of benzene)

(i) prismatic structure (ii) diagonal structure
(b) An extra stability is developed due to
resonance in benzene molecule. This is
called 'AROMATICITY'
(c) Due to this aromaticity there is no effect of
normal oxidant like acidic KMnO4, acidic
K2Cr2O7, dil H2SO 4 on benzene ring.
(iii) centric structure (iv) parallel structure (d) Benzene mainly giv es electrophilic
substitution reaction due to delocalisation
although it has three  bonds.

3. METHODS OF PREPARATION OF BENZENE

3.1 From Sodium salt of benzoic acid-
(v) alternate structure (vi) partial valency
structure
(n) Hybridisation state of carbon in benzene
+ NaOH CaO

is sp2.
(o) The geometry of carbon is trigonal, that's
why geometry of benzene molecule is
benzene
planar.
3.2 From Benzene sulphonic acid (BSA) on
hydrolysis-

CrO  Al O
 
3

2 3
+ 4H2
500 º C

benzene
benzene
NOTE - If hydrolysis is alkaline, product would be Examples
based on
phenol.
3.3 From Benzene diazonium chloride (BDC)- Ex.1 W hich of the following is not correctly
C6H5 — N = N — Cl + CH3 — CH2 — OH matched-

 
 C6H6 + N2 + HCl + CH3 — CHO (A) Hydrolysis of phenyl magnesium iodide
– benzene
benzene
(B) –Isomer of BHC– lindane
NOTE- (a) In the above reaction BDC is reduced
where as ethanol is oxidised. (C) (2n + 4)  Rule– aromaticity
(b) Instead of ethanol we can use other (D) Trimerisation of propyne– mesitylene
reducing agents like orthophosphoric acid Ans.(C)
or glacial acetic acid. Sol. The Huckel rule to account for aromaticity is
3.4 From Phenol (with Zn dust)- closed ring of (4n + 2)  electrons.
Ex.2 Benzene can be directly obtained from-

+ Zn (dust) 
 C6H6 + ZnO (A) Acetylene
300ºC
(B) Ethene and butadiene
benzene (C) Chlorobenzene
(D) All the above Ans.(A)
The reaction is called 'Deoxygenation-reaction' Sol. See Text.
3.5 From Grignard-reagent- Ex.3 In which of the following reactions benzene
C6H5 – Mg – X + H – O – H C6H6 +Mg(OH) X is obtained.
3.6 From Acetylene-

(A) NaOH
 / CaO


red
hot Cu tube

500º C

CH 
(B) H
3O

CH CH

CH CH
CH
benzene (C) NaOH

633 K , 300 air
3.7 By Aromatisation-
 (D) H
2O
  Ans. (B) (Birch-Reduction)


Sol. C6H5MgBr  C6H6 [benzene]

cyclohexa-1, 4-diene
(b) Addition with Halogen-
4. PHYSICAL PROPERTIES

(a) Benzene is colourless with a pleasant smell. + Cl – Cl  h

/ light

(b) It is insoluble in water and soluble in organic
solvents.
(c) Vapours of benzene are poisonous in nature.
(d) It's boiling point is 80 ºC

5. CHEMICAL PROPERTIES

Chemical properties of benzene are classified in

the following four types-
5.1 Addition reactions (C6H6Cl 6)
5.2 Electrophillic substitution reactions NOTE- (a)This product is called Benzene
5.3 Oxidation reactions hexachloride (BHC).
5.4 -Complex reactions (b) BHC has nine isomers in which -isomer
is highly poisonous called 'gammaxane'.
5.1 Addition reactions-
(c) It's commercial name is lindane or 666.
(a) Reaction with Hydrogen (Reduction)- (c) Addition with Ozone-

(i) C6H6 + 3H2 Ni

, Pt or Pd
 C6H12
Catalyst

cyclohexane
+ 3O3 

HOH H C  O
(ii) C6H6 + 12HI  + + I2   3 |
Hydrolysis H C  O
glyoxal
cyclohexane methyl
cyclopentane 5.2 Electrophillic substitution reactions-
Benzene ring shows bimolecular type of
Na NH substitution reaction due to the formation of
liq. 3
(iii) C6H6 + 2H    transition state (half bond structure). So reactions
ethanol of aromatic compounds are called electrophillic
bimolecular substitution reaction. Examples of
such reactions are halogenation, nitration,
sulphonation and Friedel-Crafts reaction (FCR).
 (vap. conc.)

 
+ H2O

Wheland intermediate nitrobenzene

 complex, Benzenium ion Mechanism-

(i) H2SO 4  H+ + HS O 4

 + H+

H
|
 –
(ii) H+ + H – O  H – O 
(a) Halogenation- ..


+ Cl – Cl AlCl
 3    
180 º C H O
2

nitronium ion

+ HCl


chlorobenzene (iii) + N O2  + H+
Mechanism-
(i) Cl – Cl + AlCl3 

AlC l4 + Cl + (Chloronium ion) (iv) H+ + HS O 4  H2SO 4

(c) Sulphonation-


(ii)   + H — O — SO3H 
100ºC

fuming

+ H2O
 — + H+

benzene sulphonic acid

Mechanism-
(iii) H+ + AlC l4  AlCl3 + HCl 
H2SO 4   SO3 + H2O
(b) Nitration-
NOTE- The reacting species is SO3, which reacts
with benzene ring to form benzene sulphonic acid
2 conc . H SO
4
+ HO — NO2  60
 
C
  after the intermediate stage.
 + Cl — C —CH3 
+ H+ ||
O

(d) Friedel-Craft's reaction -

(i) In electrophillic substitution reaction of
benzene, if attacking species is carbonium
ion then reaction is called friedel craft
reaction. acetophenone

(ii) Lewis acid or halogen carrier is necessary Mechanism-

for this reaction.
CH3 — C — Cl + AlCl3 CH3 — C  + AlC l4
(iii) Temperature should be 180º – 200ºC || ||
O O
(iv) Nitrobenzene is used as a solvent in this
reaction. ex. alkylation, acetylation, acetyl carbonium ion
formylation.
(v) Alkylation (Reaction with alkyl halide)
+ CH3 — C  
AlC l ||
+ Cl — CH3  
3
O
180  200 º C

+ HCl
+ H+

Mechanism-


CH3Cl + AlCl3  CH3 + AlC l4 H+ + AlC l4  HCl + AlCl3

carbonium (vii) Formylation (Reaction with CO & HCl)-

ion Insertion of –CHO group in a compound is
called formylation. For formylation, formylating
 agent is CO and HCl.
+ CH3  + H+

+ Cl — C — H 
H+ + AlC l4  HCl + AlCl3 ||
O
Very Important- In the above reaction if we take
n-propyl chloride as reagent, then product will be
isopropyl benzene (cumene), because
intermediate 1º carbocation formed rearranges
itself and changes into 2º carbocation (more
stable) benzaldehyde
(vi) Acetylation (Reaction with acetyl NOTE- The reaction is called 'Gattermann - koch -
chloride)- Aldehyde - Synthesis'.
 (e) Formation of benzoic acid

AlCl / CO —COOH
3 2
  

+ CO 2 + H2O
benzoic acid
(f) Formation of benzoyl chloride

AlCl / COCl —COCl

 
3

2

L
M
 O maleic anhydride
N P
C OCl
Q
benzoyl chloride VO
(C)  
2 5
 C H OH
300 º C 6 5
(g) Formation of Benzamide

AlCl / ClCONH —CONH2 phenol

 
3 2

5.4 - Complex Reactions -
benzamide When benzene is heated in the presence of
(h) Formation of Benzophenone chromic chloride, aluminium chloride and alumina
then a product is formed, which gives dibenzene
AlCl / C H COCl —CO— chromium on reduction.
3 6 5
  
L
M
C H

CO
O
P This reaction is called charge transfer reaction.
N 6 5
Q
benzophenone
(i) Formation of Benzyl chloride

( i) CrCl  AlCl  Al O ,
3 3 2 3
HCHO /HCl
—CH2Cl   
  (ii) reduction
ZnCl2

benzyl chloride
(j) Formation of Acetoxy mercury benzene
benzene dibenzene
bCH COO gHg
3 2
  
—HgOOCCH3 chromium

Examples
based on Chemical reaction
acetoxy mercury benzene
Ex.4 Which of the following is used as a solvent
5.3 Oxidation reactions-
in Friedel Craft's reaction -

air
(A) Aniline (B) Nitrobenzene
(a) + O2   CO 2 + H2O (C) Toluene (D) Benzene

(Ans.B)

VO Sol. Nitrobenzene is used as a solvent in Friedel-

+ [O]  
2 5
(b) Craft's reaction. It itself does not undergo
400  500 º C
Friedel -Craft's reaction. The Friedel Craft's
reaction is an electrophillic substitution reaction
 Ex.6 Ozonolysis of benzene yields -
(A) Glyoxal (B) Glycerine
(C) Glycol (D) Glycerol
(Ans.A)
Sol. Ozonolysis of benzene yields glyoxal. Benzene
nitro benzene
adds three molecules of ozone and forms
Ex.5 The resonance of the electron cloud in benzene triozonide which on decomposition
the benzene ring was confirmed after ozo- with water gives three molecules of glyoxal
nolysis of -
C6H6 + 3O3  C6H6 O9
(A) Benzene (B) Toluene
benzene ozone benzene triozonide
(C) o-Xylene (D) None of these
(Ans.C)
Sol. Benzene is an aromatic hydrocarbon having H–C=O
C6H6 O9 
H 2O
 3 |
carbon atom in sp2 hybridized and, one H–C=O

p-orbital of carbon remains unhybridized benzene triozonide glyoxal

,which overlaps colaterally to f orm a
continuous electron cloud both above and
below the plane of the benzene ring .There
are two resonating structures of benzene

The resonance of the  - electron cloud in

the benzene ring was confirmed after
ozonolysis of o-xylene
 SOLVED EXAMPLES
Ex.1 An aromatic compound contains ....  electrons Ex.4 Number of  electrons present in
(A) 4n (B) 4n + 1 naphthalene is-
(C) 4n + 2 (D) 4n + 3 (Ans.C) (A) 2 (B) 4
Sol. An aromatic compound contains (4n + 2)  (C) 10 (D) 14 (Ans.C)
electrons. It is according to Huckel's rule, Sol. Note that naphthalene has 5 bonds and thus
which represents the aromaticity of the the number of  electrons is 5 x 2 = 10.
molecules. Aromatic compounds possess a
sweet smell which is characteristic and
different from other fragments.
The term aromatic compounds is now used
for benzene and the compounds structurally Ex.5 Benzene can be obtained from trimerization
related to benzene, even if they do not of -
possess a sweet smell. (A) Hexane (B) Ethyne
Ex.2 Which of the following will show aromatic (C) Cyclohexane (D) Cyclopropane
character - (Ans.B)
Sol. When ethyne is passed through a red hot tube
at 500º-600ºC it trimerises to form benzene
o
3H – C  C – H 500  600 C
 C6H6
I II III IV ethyne benzene
(A) I, II and III (B) II and III Benzene is an aromatic hydrocarbon which
(C) II and IV (D) All the four possess a characteristic pleasant smell.
(Ans.C) Ex.6 Which aromatic compound is obtained when
Sol. Benzene has 6 electrons (2 from each double n-octane undergoes catalytic hydroforming -
bond) present in cyclic continous form. (A) Toluene (B) m-Methylbenzene
(C) o-Xylene (D) Benzene
(Ans.C)
Sol. By dehydrogenation of n-octane, o-xylene is
obtained.
benzene furan Ex.7 Which of the following is not the property of
Furan also has 6 electrons present in benzene -
continous cyclic cloud, note that one of the (A) Characteristic smell (B) Inflammable
pair of electrons present in sp2 orbital does (C) Unsaturation (D) Colourless
not involve in overlapping of the sextet; while (Ans.C)
the unused pair of electrons present in p Sol. Unsaturation is not the property of benzene .
orbital is involved in overlapping forming sextet. It is quite stable and remains unaffected by
Ex.3 How many  electron are there in the following alkalies, hydrochloric acid, oxidising agents
species- like acid dichromate and acid permanganate
.This shows that unsaturation is not present
in benzene. Benzene does not decolourize
Br2 water, which indicates that it has no
unsaturation.
(A) 2 (B) 4 (C) 6 (D) 8 Ex.8 Benzene undergoes substitution reaction
(Ans.C) more easily than addition because-
Sol. 2 electron for each double bond and one (A) It has a cyclic structure
(B) It has three double bonds
lone pair of electrons of carbon. These six
electrons are forming a continous cyclic (C) It has six hydrogen atoms
cloud (aromatic sextet). (D) Of resonance (Ans.D)
Sol. If there were no resonance in benzene,  Sol. Chlorination of benzene is carried out by
electrons would have not delocalised and chlorine in presence of halogen carrier like
hence easily available to undergo addition AlCl3.
reactions as in ethylene. Further the Ex.13 Which order is correct for the decreasing
substituted benzene is stable due to reactivity to ring monobromination of the
resonance. following compounds-
Ex.9 The order of reactivity of following compounds - C6H5CH3, C6H5COOH, C6H6, C6H5NO 2
–CH3–CH2 – CH3 –CH(CH3)2 -C(CH3)3
I II III IV
(I) (II) (III) (IV) (A) I > II > III > IV (B) I > III > II > IV
towards electrophilic substitution will be- (C) II > III > IV > I (D) III > I > II > IV
[where  = C6H5] (Ans.B)
(A) I > II > III > IV
(B) IV > III > II > I Sol. C 6 H 5 CH 3 is most reactive due to the
(C) II > I > III > IV
(D) III > II > I > IV presence of -CH3 group (a + I group), followed
(Ans.A)
by benzene due to absence of any -I group,
Sol. More are the number of -hydrogen present followed by benzoic acid due to -COOH group
in the alkyl group attached to the benzene
(a weaker -I group) and then nitrobenzene
ring more pronounced will be the hyper
conjugation and the benzene ring will be more (having -NO2, a strong -I group).
electron rich and easily be attacked by an Ex.14 Benzene on treatment with a mixture of conc.
electrophile. -Hydrogen in –CH3, – CH2 –CH3, HNO3 and conc. H2SO 4 at 100ºC gives-
– CH(CH3)2 and – C(CH3)3 respectively are (A) Nitrobenzene (B) m-Dinitrobenzene
three, two, one and zero. (C) p-Dinitrobenzene (D) o-Dinitrobenzene
Ex.10 Which one of the following is the most basic (Ans.B)
compound- Sol. At high temperature (100ºC), nitrobenzene is
(A) C6H5 - NH2 (B) C6H5-NHCH3 formed, at low temperature it undergoes further
(C) C6H5 - N(CH3)2 (D) C6H5N(C2H5)2 nitration forming m-dinitrobenzene.
(Ans.D) Ex.15 Which of the following structures correspond
to the product expected, when excess of
C6H6 reacts with CH2Cl 2 in presence of
Sol.
anhydrous AlCl3 -
Due to + I effect of ethyl group the availability
of lone pair of electron on N atom is more, (A) CH
thereby making it more basic. |
Cl
Ex.11 Find odd man out -
(A) Lindane (B) Gammexane (B) CHCl 2
(C) 666 (D) Nonane
(Ans.D)
Sol. The odd man out is nonane. It is a saturated Cl
|
hydro carbon with C9H20 configuration Lindane, (C) C
gammexane and 666 are all the names of |
the same compound benzene hexa chloride Cl
(B.H.C.). It is a powerful insecticide.
(D) CH2 (Ans.D)
+ 3Cl2  C6H6 Cl 6
Sol. The reaction takes place as follows :
benzene benzene hexa chloride
Ex.12 Which of the following reagents and conditions + ClCH2Cl + 
convert benzene to chloro-benzene-
(A) Cl2, sunlight, heat (B) HCl, heat
(C) HCl, sunlight, heat (D) Cl2, AlCl 3, cold CH2
(Ans.D)
Ex.16 For preparing monoalkyl benzene, acylation Ex.17 Benzene reacts with n-propyl chloride in the
process is preferred than direct alkylation presence of anhydrous AlCl 3 to giv e
because- predominantly-
(A) In alkylation, a poisonous gas is evolved (A) n-Propylbenzene
(B) In alkylation, large amount of heat is (B) Isopropylbenzene
evolved (C) 3-Propyl-1-chlorobenzene
(C) In alkylation, polyalkylated product is (D) No reaction (Ans.B)
formed 
(D) Alkylation is very costly (Ans.C) Sol. Propyl carbonium ion, CH 3 CH 2 CH2 is
Sol. For preparing monoalkylbenzene, acylation primary carbonium ion, it rearranges to the
route is preferred rather than direct alkylation. more stable secondary carbonium ion
This is because of the fact that during 
CH3 CH CH3 , which then reacts to form
alkylation, alkyl group is introduced, which isopropylbenzene.
being activating group, accelerates further
alkylation to form di-tri- and tetra-alkylated  

products CH3 - CH - CH2  CH3 - CH - CH3

|
H
propyl carbonium isopropyl carbonium
C H Cl C H Cl ion (1º) ion (2º)
 
2 5
  
2 5

AlCl3 AlCl3 Ex.18 Which of the following reactions of benzene
does not account for the three ‘C = C’ bonds
in the molecule-
FeBr
 
(a) Benzene + Br2 conH
3

C2H5 Cl . 2SO4
 
AlCl3
bromobenzene + HBr
(b) Benzene + HNO3  nitrobenzene + H2O
On the other hand, during acylation we get (c) Benzene + 3O3  Triozonide
acylbenzene (e.g. acetylbenzene); acyl Ni
(d) Benzene + 3H2   cyclohexane
group, being deactivating group does not
Code is :
allow further acylation easily. Hence the
reaction stops at the monoacyl stage which (A) a, c (B) b, d
then can be reduced to alkylbenzene easily. (C) b, c, d (D) a, b
(Ans.D)
Sol. a and b are the electrophilic substitution
reactions and do not account for the C = C
CH COCl
 
3
 reduction
  bond reactions.
AlCl3

benzene acetylbenzene

ethylbenzene