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 WS ' '
r

was
, .in org.anic c.icmistry meaning ‘‘fragrant ” ( Pleasant odour) and was
me
r [ .
for a special .class of compounds. These compounds have a low hydrogen to carbon
110 or high carbon to hydrogen ratio) in •their molecular formulas and have a characteristic odour. These arc
ca e aromatic compounds. It was observed that almost all the aromatic compounds have a six carbon unit in j K
their molecules like benzene. I fence, benzene was recognized as the simplest and the parent member of this class
pfeoinpounds.
I
JI
r.
However, it was soon realized that many aromatic compounds are odouriess whereas many others are fragrant I
though they are not aromatic. Further, when aromatic compounds of higher molecular mass were subjected to
various methods of degradation, they, often produced benzene or derivatives of benzene.
.
Q Aromatic compounds burn with sooty flame. Justify. I it
r
[|
jg Sooty Flame of Aromatic Compounds: . j J
Aromatic compounds have relatively high ratio of carbon to hydrogen. So. when they arc burnt, they give sooty I

flame. The sooty flame is carbon particles.

2C 6 H6 + 1502 -> 12G02 + 6 HjG
Onlhe othcrJiand, if we bum methaneJnaUira[ gasy in a normal supply of air, a blue flame with no sooty particles >i

is formed.
^

CH4 + 202 -> GG2 + 2H20

~
Reason:
|] mole of benzene requires 7.5 moles of oxygenTor complete combustion
1 mole of methane requires only 2 moles of oxygen
compounds require a much lower volume of oxygen for complete combustion . So 1,
It means that the aliphatic appear of
some .carbon remainsJn unbunU form which in the fonn I

during the burning of aromatic compounds , • I

*

sooty flame. 1
How are they classified ? •

What are aromatic hydrocarbons?' A

'

!=_
°Us"nd
^ ^
Aromatic C0 P that structurally related to benzene.
d& benzenetand all those compounds ^ ' - it
Aromatic hydro GH, Arenes are strictly
hydrocarbons. If ,

o Toluene
Biphenyl
'
Aromatic compounds
can contain other
functional groups.
.

.
J
Benzene Naphthalene
structural features It jias a regular planar hexagonal structure. A
Benzene has characteristics
Ossification of Aromatic Compounds 5
hydrocarbons can be categorized into following classes.
—————— rings aromatic • * I

Ji

J» -r
 ( b) Polycyclic Aromatic Hydrocarbons
(a ) Monocyclic AromaticTlydrbcarbons
benzene ring in their molecules are called Monoevelie
!
" “ - ——
Substituted phenyl. groups rwimivccnrrcmmen/cne. we get a phenyl groiip
symbolized
' “ Aromatic ‘ hydrocarbons containing one
_ j_lydroearbon}T . e^g. benzene and its derivatives.
Cll. OH Nil . COOH nuo . SO) JI
A
3.
'
I he second suhstiluontin
1 met a ( l. 3 ) and para
( 1.4) .
are calledran
U ! groups.
benzene Hould give rise to three i
. e.g. isomeric products designated
bv tVJ b - or Ph -.

as ortho ( I.
ClI

Oi rci ]
fo io o o o
Cll

Q:
CM

Toluene Phenol Aniline Benzoic

acid
Benzaldehyde Benzene- |
sujphonic acid CM,
O ,

r
(b ) Polycyclic Aromatic Hydrocarbons 1,2 - Dimethylbenzene CTI
,3 - Dimethylbenzene •
‘- Aromatic hydrocarbons containing two or more benzene rings iiHhcir molecules are called Polycyclic A rpinatic
i (o-Xylene) - 1
(m-Xylene)
1.4 - Dimethylbenzene i

I lydrocarbons ". .
I 4. li two or more substituents
are tlifferent. then the
number I position in the bcn/
(p-Xyleiie )
substituent that is treated as a high priority group, is given J
Thev mav be divided into two.main classes cne ring. Other groups are thei
(i) Isolated rings: Those in which benzene riims are isolated e.g. biphenvh diphenylmclhane. etc
m m

. ' which gives them the lowest •

number
numbered by counting from position l in the manner
.
I CM.
-- - •

COOH
3
G

4
5
Biphenyl Diphenylmothane
(It) Fused rings: Those in which the benzene rings are fused together at ortho positions so that the adjacent:rings have a -
.
common carbon to carbon bonds e.g naphthalene, phenantbrene anthracene etc. . '
(
2 Aminobenzaldehyde
l lie order of priority of tile groups (left -
3 Hydroxybenzoic acid
;
to right )
COOI I. - CN. - Cl IO - COCI I;. - OIi. Nl| . - OR
-
IT two substituents are different ami they are not present in priority order , 2 . - R. I
~

1 fhe last
-
named substituent will he al position l. e g. list they
. are named in alphabetical order.1
* 1
W, -
'
A .
Naphthalene Phenanthrene Anthracene
W OMENGUATililRE
'

( (Monocyclic Aromatic Hydrocarbons and their Derivatives)

Some important rules of naming arc given below .
3iGhloroiodobenzone
2 Bromonitrobenzene
1T there is a substituent on lire ring which gives a special name Io the molecule,
-
then special name is used] as parent
1. Mono-substiluted'benzcne derivatives are named by prefixing benzene with the name of the substituent IhC| . nhinO'to ihe molecule e g. .
W
.
whole name is written as one word e u
_ Cfli _L
'
. ..
ci hen .
OH

o o- T
.

~
Methylbenzene Ethylbenzene
Chlorobenzene Nitrobenzene
Nil
I There are certain monosiibslituled ' benzenc derivativesAvhieii arc givemthe speeialmames; like methy|b,t’nzt
J
4-AminophenoI ‘
4-Ghlorobenzenesulphonic acid -
2 lodotoIuene
toluene, hydroxybenzene as phenol AUC.
^
. _L_ J OGS
(!)
II Q7. compounds
(•)!!
Nil. 0 ‘
— 11 (a) Draw structural formulas for the following :
(i) rfi- Ghlorobenzoic acid Oi ) p -Hydroxybenzoic acid
v
'« ) Ethyltoluene

o; |iii) o- Bromonitirobenzene ( o-
;( ..
.. ...
v ) p-Nitroaniline (vi) 2,4,6-Trinitrotoluene

Toluene Phenol Aniline Benzoicacid Benzaldehyde (ix ) ^- Amino - vbromg- nitrobgnze

.

^ "^ "
0
^ ac d .
p Dibenzylbenzene

All the six position in benzene are exacth cquivalent

so there is only one monosubstituted benzeiu?*
 ££8

III

m - Chlorobenzoic Acid p - Hydroxybenzoic Acid

COGH COOH

o
OH
(iv) ( v)
O - Ethyltoluene p - Nitroaniline
CH NIL •

j -
CH . CH ,
0

5
4
o
NO -
( vii) ( viu)
m - Nitrophenol p - Dibenzylbenezene
Cli.— CJi.

o
. CU — C'Jh •

Q.7(b) Give names and the possible isomeric structures of the following:
(|) Xylene (ii) Trjmethylbenzene (Hi) Bromonitrotdluene
If two ( CH3) groups are allocated with a benzene ring, the compound is called as xylene.
b) Give names and possible isomers.
1. Isomers of Xvlcne
CH
GH ,

o
1,2-^Dimethylbenzene 1,3- DimethyIbtMizeno 1,4- Dimethylbenzene
(o-xylene) . (m-xylene) (p- xylcne)
ii. Isomers of Trimethylben'/cne
 r -~ -
•MESSu. aDK' . H
£fT .. =C
/
-
'

o --:.-\ -
- - • '

202
Chapter 9 ( Aromatic Hydrora, —
^^ Schohir ^ MEMflSTRY ;. (Suhjce<ivi»)
a
"A cyclic rctiulnr hrvi
Discovery
— IU1 -slrilvturc
o Benzene was discovered b \ Michael Faraday in 1825 in the gas produced by the destructive distillation of vegetable!
CM
oil. «?: ^CH
o I wenl \ vears later it was also found in coal-tar by Ilot imstiin . HC
\ >CH
CH^ ’
SWCO liesiipptirtwl l i.
Molecular Formula
elemental analysis, which is Cl I. So its
(i)
' "
' ' ""o: by
•
• the
Benzene gives only one
rolltming- argumenisj
monosubstituted product
(i) The empirical formula of benzene is determined by the empiriealllbnnula
mass is ( Cl 1 - 1 2 * 1 - 1 3 )
( ii ) . .
Its moleculur mass determined by the vapour density method is 78.108 amu. I herelbre the molecular tbriiiula
of benzene is CJ l„ .
Molecular formula - n x limpirical formula ( ii) . hen /.ene gives only three disubsiimted produelsj
Molecular mass 78.108 , ^ -1

n 6
hmpirieal formula mass 13
Molecular formula 6 x Cl 1 *

Molecular formula -- CJ I,.

( iii) flic molecular formula of benzene indicates that it is highly unsaturated compound . . Ihe.se points confirm the
Straight Chain Structure Ruled Out positions in
regular hexagonal structure fur hen /.eue in which all the carbon atoms are 1
* identical the molecule, Iherolore, benzene occupying
(i) Straight chain formulas (Hi) Hen/.ene adds three Hydrogen.molecules in the
forms only one toluene, one nitrobenzene and one phenol .
\\
fwo of the possible straight chain formulas suggested for benzene are:
presence of a catalvst
'
.
^

jj
I IC - C - Clb CM; C ~ ClI ( 1.5 I iexadiviie ) PS /

^^
:
•
• 3h nr Xh

Comparison with alkenes and alkynes

- -
ihc ci i - c e ClI - Cl b (il. 5 - I lexadiene 3 ynei . *
200 C of C.H. or
HCN
CH

A compound having a strucluic as above should behave like an alkene or alkvne. Both are oxidized:by alkaline . < iv > - Cyclohu r'inu
IK n/.citc :idds three molecules pfehloriiie in the presence of sunliglii; *

KMnO solution, while benzene is stable to KMnOj solution. It does not decolorize KMnO.j solution. H Cl
V
]

A /°
H-i
Hen /.ene gives addition reactions with hydrogen and halogens, which indicate the presence of three double bonds.
^-—
r .
Sunlignt c
' f N
-M or CM Cl
o Benzene also gives substitution reactionswith cone. UNO); and cone. IFSOj which indicate that benzene has a H r c ci
saiuralcd structure. / \
C« /\ H
(ii) Monosubstituent product H Cl
Hexachlorocyclohexane
Considering a .straight chain structure for benzene and * further assuming that each carbon carries one !I - atom, it
1
I hose two reactions eon linn the, presence of three double bonds allematiniwith three single hnmk
should be capable of forming threemono substitution products.
X X X 0-

C.C.C.C.C.C
*
CC»
C.C.C.C .. C.C.C.C.C.C Studies Of Benzene Structure H
I 1.09A
But benzene yields only one nionosubstiluent product. • 1 be X -ra\ studies of hen/ene have con firmed that: H- .e,
(iii) General formula . #
Benzene has regular hexagonal-structure . 9
‘
1 2(r G
I lie molecular formula ol benzene CJl<, does not obev any olithe open chain hydrocarbons, such as alkane * All the carbon and Hydrogen atoms are in the same plane. — 1.397A
C„l l;„.:( C„ ,
IIj ). alkene Cnl 1:„( CJ h:j or alkvne CJ \ 2u : (CJ l!o). ^1 • All the ancles are of 120° . |
.G
• H
Conclusion * All C - C and C -MI bondJengths are . U 9 7A and l 09 A,TCspeeu \e
>
^
. - ^
O H

—
i
It means benzene does not belong to open chain hydrocarbons and therefore possibility of a Slraighl chain
'

-
structure is ruled out.
Objections to Kekule's Fdrrnula
-
Rekute'sStructure
, f
cMiibiis a*saturated
** >
* character. Ihus%it
kn ne is alst,a very stable ebmpoimdi
*
, . , , .
I lie structure of benzene continued to
I k e k u l c at last solved the problem in ISfo.
j I
be a serious problem for chemists lor about 40 vears. A Geniiuij
kckule proposed
 w y
•
-
-\
: ~
:v r -
^•arVrp~ K .r& 9 . - ?cc
204 Chapter 9 ( AromaticWdf
^I2
*
" 1 <-
‘
*
~
M*1
.
.
"

-T _
1

AM

^
r
ns)
—
•

GHEMlSTkY - XIIYS-uhi .
1
VI
HI Scholar’s
. .
Q 10 Describe the structure of benzene on the basis of following: ! ^ 2Q5
V -
A '1
(ii) Resonance method. H C; !
'
(i) Atomic orbital treatment 1> MSV &:i JB:
7

( Atomic Orbital Treatment of Benzene )

»2

H <&.
1 '
I Benzene

r
•
i

I :
ir ,
-
The hexagonal frame- work of benzene can be conveniently explained using Cyclohexane
AH = -208' kJ / mol §fi
hybridization approach . According to atomic orbital hybridization: Calculated AH = (3x M 9:5) - - -358.5kJ/mole }
2 Observed AH i
(i ) Bach carbon in benzene is sp hybridized.
(ii) file three sp~ hybrid orbitals on each carbon arc utilized to form three a bonds,
'

two with adjacent carbon atoms and one with hydrogen .

H
a * Fromework of
benzene Diffcrei c
Stability diagram ^ -= -208 kJ/molc
150.5kJ/moIe
,
i

ii
£
tit
Y.

( iii) fhe unhybiidi /ed p, orbitals remain right

^ at angle to these sp ~ orbitals . Since

all the sp~ orbitals are in the same plane therefore all the carbon and hydrogen
„calculated It to be. ** rCprcscmi:d ll be following figure
‘ , it becomes clearlfiat benzeneis much mote stable than .
atoms arc coplanar.
( iv) All the angles are of 12 tf which confirms the regular hexagonal structure of I +. 311; Refinance Energy
I
= 150.5 UAnoIc I
benzene. !tSl )
(v.) The uiihybridi /cd 2 p, orbitals partially overlap to form a continuous sheath of
Unhybridizud 2 P , orbitals
electron cloud , cits eloping, abov e and below, the six carbon-carbon sigma; i •V
bonds of the t ing, -
A = 358.5 kJ/mote ll
( vi ) Since each 2 p . orbital A overlapped by the 2 pA orbitals of adjacent carbon
atoms therefore this overlapping
, , gives ’ diffused *
or . ’ delocalized ' electron ! Benzene +, 3H . i

cloud. \

-
Delocalized .t orbital of benzene
-
AH = 231.5 kJ /molc :
-
AH = 208 kJ/mo!c

Benzene is an extraordinary stable molecule. This stability is due to the extensive delocalization of electron | j

cloud. The extent of stability of benzene can be measured by comparing it with hypothetical ' compound
|
,
i
,
-
1 ,3,5 cycloheXalriene. Stability of benzene is determined by eslhnating the heat of hydrogenation (Al l ). • Cyclohexane
i
i
"i ,
( i ) AHfor Gyclohexene •
S ,
Gyclohexene. can be easily hydrogenated to give cyclohexane. When the AH for this reaction is measured 1 iris ^ -
Relative stabilities of Gyclohexene, i;3 Cydohexadiene, 1,3,5 Cyclohexatrlene ( hypothetical) and benzene. , i II

found to be - 119.5 kJ / molc. very much like that of any similarly hydrogenated alkene. Resonance energy r - - m

.
The difference of energy between hypothetical compound i e., (1 / 3* 5 - cyclohexatriene) and actual compound
i

• t
i.e. ( benzene)’ is called resonance energy. Indeed, benzene is more stable thanthe hypothetical 3J ey P watrien by -^
H*
Pt
> 150.5 kJ/mole. Greater the resonance energy greater the stability of the . compound ~
. If m ans benzene sKo&s the
'

phenomenon of resonance which makes it more stable than others. In benzene electrons are delocalized making it a very ^ ^ ^ ^ *
I

Gyclohexene Cyclohexane stable molecule.

• . Al 1 - -119.5 kJ / mol -
Hi
'
-
( ii ) AHfori/ 3 Gyclohexadiene Zfr ms
i* ••
ill
We would expect that hydrogeualion of 1.3 - GyeloheXadiene would liixrrate - rbogii ly nVice as'niiicivISwii a® Ate
' '

—
have AH equal to 239 k)/mol. When this experiment is done, the result iis Al l = -23 l .5kJ /inulc. I his result is quite close
to what we calculated, and the difference can be explained by taking into' aeednni the fact that coinpounds containing
meiResonaWceiMethod
Resonance
J v •
1
conjugated double bonds are usually somewhat more stable than those containing isolated double bonds. “ The possibility of different pairing schemes of valence electrons of atoms is called resonance" *

iji
i
on
Pi structures can be written butthe actual structure cannot be
:
-f- 211, i
“ The situation in which two onmore plausible is
Lewis
A
written is cal led i Resonance.” • r -r .n : ti
* *
11

-! The resonance is represented by a double headed arrow (o). .. ^ ! *

>
I

-
1,3 Cyclohexadiene
Calculated AH = 2 z (-119.5 ) = -239kJ / mole '
Observed AM ~ -23 l .5 kJ / mo!c
Cyclohexane YjAr X :4 Resonance Structures
The different structures arranged as a - -
result nr
of onance
.
„
^
dnxcalled “ Resonance structures” . _^
c|ectrons) 0fcarbon atoms are possible in
t;

if
» ii

-
(iii ) AH for 1,3,5 Gyclbhexatriene
‘
o
° lL 03 Tot would , .,
predict hat benzene vvotdd liberate approximately
WC
! iy - - ) xyhcn , l s Mrogenated: When the experiment, surprisingly
- . T

^ is chemically quite stable.

nzene »
.I ' (!

V ,v . ‘
diMcrcnt . The reaction is exotberniie but only be r 208kj/ mole. '
is actually
'
done, thc rcsul is i U

%
 ;
Kekules structures Dewar- structures \ /
CH.
Dewar' s structures
n - Hoxano Benzene
the adjacent positions 1 ?. 2 3. 3 1. 5. 5 ( > aml ( >
'
* (> arc
not CH,
.
L:\ iiiiMblc eiu- ieetic iiK . lienee the DeWar suuelure.s h »r benzene have minor contribution towards the actual structure of
beiv/cnc
eh,. -

Kekule' s structures /
'

•
.
KekuU-V micuite l i t ) ami ib) have the larger contribution in benzene sructure
I herelt'fe. benzene molecule ean be rcpicscntcd In eillu - at the two Kekule's structures
’ .
. H >c CH .
Cr Oj AhO. f SiO .
H.C OH,
Resonance Hybrid structure *
\ /
. . .
Ijilawt. the struct lire of ben/ene is a resonance lismui of all the live structures ( a), ( b) ( c ) ( dl andi(p) The three
.
CH
alternate single and double bonds in the kekule’s structures a;e called conjugate bonds or resonating bonds -
n Hoptano Toluorio

.
-
- Since the structure of benzene is a resoname hybrid, thyielbre all the C .C bond 1 lengths arc equal butdilTerent front those
4 . Preparation in the Laboratory
in alkanes, alkeues and alkynes Benzene ean be prepared in the laboratory by any one of the following methods
In alkanes the C 0' hniuMcngih is 1 .52 *V
In r*lkene> the C C bomi length is 1.3 --IA
~
. (i) By heating sodium salt of bcnzoicjidd withsodn lime
COONa
. ^
In aikvne.s the ( - bond length is I . 20 A .
'
In benzene the C ( ‘bomhlcngtii i> I A. Benzene
Conclusion
I he i C bond ienetli in benzene iuiennediaie between those in alkanes and nlkcnes.
.
I he resomuing. sir ele :md.d< >:ble bonds in- ben/ ene ean better be represenledas a complete circle insidedhe ring Sodium benzoate . Bonzone
( ii ) By distilling phenol with zinc dust.
•
OH

Preparation pf Benzene
| .Benzene and oilier aromatic - hydrocarbons are readily obtained in large quantities from coal and petroleum.
Benzene and some other hydrocarbons can also be obtained from petroleum by special cracking methods. |
Some of the methods generally used 1 for the preparation of benzene arc as follows.
Phenol
1 . Dehydrogenation of Cyclohexane ( iii ) By the hvdrolvsis ofrbcnzcncsulphonic acid
a with superheated steam or by boiling with dil . HGI .
,
When cvelohexane
•
or its derivative is dehvdroiienated
• - we
v act benzene or a substituted benzene
W
•
The .reaction
« _
is
. “SiA
*
. 7 LI

carried out in the presence of catalyst at elevated temperature.

j Pt or.Pel
250 C o
Cyclohexane Benzene
2 . From Acetylene (polymerization)
Benzene is formed by passing acetylene under pressure overai
ui organo-nickcl catalyst at 70°C;

311C
.
’ -a
Cl I
,
ongaiuvn jckcl.catalyst
7( :C I

Acetylene
Benzene
 V A

208. Chapters (Arom

aticHydr

Wum Synthesis:
2GH j“ GH2"Gh*
f GHjGHjBr + 2NaEr . 2N3
GH3-GH2-CH, GH
•
tlha Halogenation 11

Euiylbromide -3 + 2 fjjQ | 1' *

The int rod uc tio n of hal oge n group in benzene ring is called “ Halogenation
”
° Useful for the with halogen in the presence of a catalyst like FeBr3, AlClj, etc.
of symmetrical ^ 3
Benzene rcact s .
Bromobenzene Ethylbenzene alkahos '

, Chlorination and bromination arc normal reactions but fluorination is too vigorous to control
B
1

todination giv es poo r yie ld .

i W
— ————w
—
FeBr Br
0 •

REA gfiTSWSrQ BtN-ZefgH Br, *

^
' + + HBr

General Pattern of Reactivity of Benzene towards Electrophiles Bromobenzene

(anions) are nucleophiles
^ Jca
-
• Negatively charged Ions T Positively charged ions 1
Uc ns ) are eledrophtles

-
The highly stable. delocalized electrons of benzene ring are not readily available for the nuclcophiffic Similarly,
.
o g. Cf, K \ Br SO; etc
”
.
1
e.g. H CI .Br , NH*
* +

, the electrons of aikenes. Therefore, the electrons of benzene ring arc not attacked by weak electrophiles. It atta ck I ? HNeutral ' molecules in which j • Neutral molecules in whichi
1
more powerful electrophiles are required to penetrate and break the continuous sheath of electron cloud in means 12 Cl cent ral atom
I ofeledronj h3 ve
.
lone pairs cent ral atom is elec tron
«iV
be nzene + Cl , FeCI,
* HCI
. . -
. e.g. 80, PH,, So,, fiH,. .
decent. •

.
e.g. BH,. BF,; BeCl, AICI ,
|
.
« i

etc. : t ZnCI, FeCI, etc.

Electrophile in haiogenaticn Chlorobenzene i 1
• Lewis bases are usual!y •Lewis adds are usually
nucleophiles. .
Mechanism:
-
o Substitution of halogen in benzene requires iron or corresponding ferric halide as a catalyst. electrophiles
+
o Infacl iron too is first converted into FeX3 which further reacts with halogen molecule to produce The actual halqgenaring agent is Xr ( i.e. Clf or Br ) is formed by i •The molecules which contain Neutral molecules in which
i pi electrons in their stnxtures central atom contains -
a * powerful the following mechanism.
electrophile. act as nuc leop hile s. part ial pos itive char ge act as1

X, + FeXj + FeX
I
_ .
L e.g. ethene J?enzene etc. - .-
electrophiles. e.g PC!, SO,J .
2Fe 4- 3X2 2FeX3 : O i,Y r ' CO, etc.

FeXi + Xj FeX “ 4 Cl, + FeCI, cf + FeCI

'

4 + X (Kalogcrionium ion)
Tctra halofermtc ion (III)
o The halogenonium ion X + thus produced attacks as a powerful electrophile on the electrons of benzene ring. H
^
u +
+X

Berizanonium ion
^

T
+
—
X
H

2. Nitration:
HCI 4 FeCI,
• !

.I :y

.. >
The introduction of nitro group (N 02 ) in ben zen e ring is cal led " Nit rati on .
v v
.x I . of con e. HN Qj and con c. H 2 04
S at 50-1
*

tak es pla ce wh en it is hea ted . wit h a 1: 1 mix tur e

+ PeX3 +
9 The nitration of benzene : *
' *

HX
55°C.
Benzenonium ion •
Sulphuric acid reac ts with nitric acid to generate nit ron ium ion ( NO ). ,
o
frhc addition product is not favourable because in its formation the characteristic, stability' of benzene u NO,
lost. The only possible product is the substitution produc
t in which the stability of benzene is retained. . |
*
1 + HNO
+ HjO
v•
* »

Q . Write down general mechanism of electrophilic substitution

reactions of benzene? Mechanism:
SSSj The general pattern of the chemical reactivity of benzene tow
ards electrophiles can be shown as follows.
r . '
+
i
+' E
. Electrophile

“
+ B
Base
 z .-
i
K'*
• '
i r 1L
• "

, • . • -« .
r uv] •

-XL
»ns
Chapter 9 ( Aromatic Hydro
)
Scholar's © MEW1BSTRY- -
^
jcc tivc)

.
3 Sulphonation:
is called
— —

Sulphonation
—

\
—

|
— — — i Mechanism:
The introduction of sulphonic acid group in benzene ring “

When benzene is heated with fuming Il>S0 j or cone. H 2 SO 4 it .

yields benzene sulphonic
_SO>H
acid
_
.
_ _
i

— — — — — — — S'
j
*
80*‘
G
+ HjSO, + H,0 -

Benzencsulphonic acid

.
SO H

.
H,SO .
^ SO 25°G

Mechanism:
sulphuric acid alone is used the actual electrophile in this .reaction is SO3
When ,
-1
11:S04 + H.S ©4 H,0 + SO, + MSO4
(b) Acylation:
O
1
flic introduction of an acyl group R G- in the '
AlCI; is called Friedel Crafts acylation orvAcvIation.
—
benzene ring in the presence of an aeyMialide and ‘a cataKsi
G 0
II .1
R 0 GI + AlCI,
- -
Acid Halide
R —G + AI0I,
:uci . ;• V r iJi
f 1
!

- 1
*

factions in which Benzei ,e,

Addition Reactions! ^ ^^ Mga

(a ) Reduction:
«
u
Itigh temperature with hydrogen in the presence of H 111 an
1

on heating at
benzene is reduced to cyclohexane acatalysl ,
acidic solvent (acetic acid) or Ni at *200.°Cas
 . v 'P '
1
J fcJ

- • i± — ^ “ * J
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< warn .
£ * £9S|
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i* .
-
J
•
ar -
Ghapter 9 (Aromatic Hydroc,; onj
r’s <gW EW II8 TR V --
xl i. „Kj<w.Mi.r)
r

^' scho la fS > i

) ,

21 3 ' frt
- ?4 2 ‘
i
i
tf
&r \ s o V
\ v
•ii
-
j ’
!r f
*V -
(i) si de ch ai n su b st it u ti o n i

Cyclohoxano When alkyl benzenes are treated. with

. chlorine'or bromine in the presence of sunlight; only I

substituted the alkyl groups are

(b) Halogenation: ?H,CI i

bro mi ne in the pr es en ce of su nli gh t to giv e ad di tio n pro du cts

Benzene reacts with chlorine an d
or he xa bro mo be nz en e. Flo uri na tio n is too vig oro us wh ile iod ina tio n is slo w.’
’ . + HC!
hcxachlorobenzene
Benzyl chtorkJo

Sunlight ‘ /v

C ,H,,Br
( 6 or
i
I

Benzal chlorido
H Br :* 'M f . *

.
1 aiSAS -Hoxabromocyclohexanp
^ ' + HCI I i

- (c) Combustion:
‘
Bcnzotrichlorido •

H O.

-^
GO an d
When benzene is burnt in Tree; supply of air, it is co ze d to

--
mp let ely ox idi 2
I
2 •
(ii) Side chain oxidation
, I >
*

,
I 1
I t
»
* 1

2C6H6 + 150, 12GO, + 6H20 by c

“ “ ***
' "°d'
‘ « « •
“ » w are
1
!t
i;
(d)iOwidation: • j ' r% •
> ’At J,
1 1

»
eooH •

(i) Catalytic Oxidation: ‘\ 4

•/ *
I*
I

ox idi ze d by KM n 04 or K G O at roo m tem pe rat ure. Th e rin g is de str oy ed wh en be nz en e is

•Benzen

strongly heated
e
wi
is
th
no
air
t
in the pre sen ce of V 2O5 as ^
a ca tal
?
ys t . ^ + H2O
.*

r 0
IIr - 1
TIG— - Toluene Benzole acid
VA
O + 4 G0-. + 4H,0 Whatev er the len gth of an alk yl gro up ma y be it giv es on ly. on e car bo xy l gro up M or eo ve r, the co lou r of KM n 04 *
.
.
— is discharged. Therefore- this reaction is used as a test - foralkvll>enzenes
I
450*C
HC - C IT I I !
f 1

,;a
II GITGHj COOH
-
- . ir
. 1

Benzene ; O i
-1
. A.'
Maleic anhydride ii Ir
" I - Ji
,1 !
o .
.1 J I
^ ill *
+ 6 [0] — +;2HiO>ca
_*4T , — ^Ty. -> . I «

—
’
.

—II
'
• \4

.
H
•
• » • '
‘

HG r -Q . HCs GOOH ii c \

—
11 1
1* f : ; . 1 . ;

H;o
»

;o +
1. •

I '
Benzole acid
r
- ; - 'FP '

— —
.
t • 1
>' i:
rEthylhferizenb
• 1 ' /
*
*w
1
r
HC C
II
: HC ‘
. ,1
GOOI.I •

ac id? -ii .
Q* How would your convertbenzene int o be nz oi c >
* h - J n ,
O
Maleic anhydride ' Maleic acid -
Q Distinguish between benzene and tojuene. : i . * i .

> 1
..
I
r - • -
I

(ii).OzonoIysis:
Benezene reacts with ozone and gives; glvoxal through benzene triozonide . fi What Happens When : 0
C
j
1

(a) Benzene is heated with cone. H2 04

•j at 25 0
GHO
4
—
r - -
> -w — ^• r. S
su nl ig ht. ’

-
3H,0
13
T-
1
•

t .
1
(b) Chlorine is passed through benzene in
,
pa as se d ov er he at ed va na di um pe nt ao xid e. 1 '
GfHA .>
(?) A mixture of benzene vapours an d air ar e
GHO a
^^ ^ I f1 ;
* J
» (d) prn rnr r hurnt in
~ frA ag llp P ‘ —

Benzene triozonide Glyoxal 1

'.nr. '
JltjS

a . ir:
 "
_
. A Ghapter 9 (Aromatic Hydi .
-
:
*-
:r
r •*
-
i »'
r . *
u “ - - --
22
214

a s STi 0. 0 0
^ ; 1.7;
5)
Scholar s
’

;
GHEMHSTRV 1 11 (Subijcctivc
f he electron • releasing
^ )
J 4
\ -V *
'1 effect of wgroup
methyl
;
Substituted benzene product increased reactivity , more
nitro groups can is significant and iit makes
, we get only one the ring a good nucleophile. Due to this
When an elcctorphiiic substitution reaction takes place on benzene ring monosubstitiited - hc enter the ring.
because all the six position
three isomeric disubstituted
— — — — —
in the ring
products
—
are equivalent . However
, ortho, meta and para.
x
, the introduction of a second group into the ring ma ' ^
.
+2H 0

2,6 -Dlnitrotoluone
Benzene
2,4rDinitrotolueno
.
* Disubstituted Bonzonos
ortho 40 % meta and 20% para disubstituted products arc expected. But the actual
l chance basis
On 40 % ,

disubstitution of benzene docs not follow this principle ofchance .

Examples
(i) Chlorination of nitrobenzene
m-Chloronilro benzene is the main product of the following halpgcnation reaction.
2 2,4.6-Trinitrotoluene (TNT)
Other examples of ortho and pam
groups:
i 4 n N(C1lj)j. - Nl!;. - OH. - OGH,. - Gl. - Br
+ HGI .- I|
i *

Mrjj§tiDlitjgj]Qut)s
2-amftt|
Gl • M
,
(ii) nitration of chlorobenzene
m-Ghloronitro benzene
|
° h
, ’fC f T !MZlhc CClronL
r
C 0llllC bcnzcne
.to the electrophiles, f bis results m the
1
rine towards lliemselv.es. thereby dccrcasinu their availability
decreased chemical rcactivitv of benzene.
A mixture of o- Chloronitrobcnzne and p- Chloronitrobenzcne is obtained from the nitration of chlorobenzene. O Due to the electron withdrawing clfcct of such substituents, the ortho and para
positions arc become more
electron deficient than the meta position. Thus the incoming electrophile will prefer to attack on
meta position
rather than ortho and para positions. These groups arc called meta-directing groups.
Example: Nitration of nitrobenzene
2(llN.0i *HjS0.i>

• 1* • v
o-Ghioronitro benzene 7 t '2 *13
:
\
p-Chloronitro benzene

Conclusion
It means that the groujftpresent iivthc mono-substituted benzene ring has the . directive effect and thus detennines
position orientation for the new incoming groups . Therefore there are two . tvpes of groups :!
I the or ,
m - dirntrobonzcno
1 . ortho- and para- directing groups 2. meta - directing groups
The substitution of ihird nitro group is not possible.
. : o ,

jL ' o.rttip andiRaraiBirecting..QfOijps o Other examples nf incla dinTtin°.gruups are:

o
^
These groups release electrons to
, the benzene ring, thereby facilitating the availability of electrons to the
- N* R;.. - G -N
electrophiles at ortho and paratpositions. J %1
r
'This results in the increased chemical reactivity of benzene ring towards electrophiles.. . . f
I4 .
o
:L
flic benzene ring can offer more than one positions (ortho and para) to the new incoming groups ,
rn6afisdfi@(Rea'otivitiesOf AlKanes,.AIkenesAndjBe n£
^ ^
o

.
;
o These groups are called ortho and para directinggroups. - ' of compounds and their unrcactivily
' is due to their non-polar
We have studied that alkalies arc un a VveTdass .
3
^ '

^^
,i *

substitution reactions relatively easily

Example: Nitration of toluene
CMi CM , ! ' J
1

; n\
. nature and the inertness of of ^ ver they undergo and these
J ;

i . NO, nsti;. i.;oT < : l ' • 11 reactions involve free radicals.

class f compounds and thcir - ixactivatyds-due tq thc inherent weakness i
D IriJ
^
* Alkcncs. on the other hand, are very reactivv electrophilic reagents: They undergo electrophilic addition '
. >- .
4

21 I 1NO . - II SO i t\ j ' : . ' '

C, • i1
V
9f he jt-boml and the availability. of It
)
O:
2H»0 polymerization reactions and they are also readily
• PL •
l l r t f - 4)r t:
'
' ‘ 'r .
’ ‘
«>
.• •v 'i
fir '
I reactions easily. Being relatively
* unstable , alkcm - s dc
- ' t
* » T •
;
* 1

o - Nitrbfoluenb
lI

oxidized, J
NO 'r

p - Nitrotoluono
 / :
Chapter 9 ( Aromatic Hyd
-
ii
r m
'
— i

217
^-
t

216
com pou nd and at the sam e tim e it is ver y ( ii ) Benzene'llas a pentagonal structure!
uni que in its beh avi our. It is highly uns atu rat ed |
° Ben zen e is
e as des cri bed ear lier, is due to the ext ens ive del oca liza tion of TC electrons
\ - ( iii ) The C-C bond length in benzene I O

.
molecule. The stab
resembles alkenes when
ility of
it
ben
giv
zen
es
,
add itio n rea ctio
radicals. These arc electrophilic substitution reactions
ns. The
and
sub stit
inv
uti
olv e
on of
elec
ben
trop
zen
hile
e
s
, how eve r,
.
doe s not inv olv e t *
rec • L ^
,
(iv )
(v)
'The state of hybridization of
fheirc arc
mo lec ule is l .397 A ;
carbon in benzene molecule iis sp3.
six sigma bonds in benzene molecule. i

for alk ene s.

-
Its addition reactions require more drastic conditions than tho
resi
se
stan t to oxi dat ion . , ] ( vi )
( vii )
ITalogenonium ion produced in electrophilic
substitution reactions is a powerfu
in electrophilic substitution reactions, addition products are
l elec trop hile.1

Benzene does not undergo polymerization and it is also * favourable. i

Be nze neJ > Alk ane s (viii) Sulphonation is carried out whcn benzene is heated with cone. HNO .
— — — — — Alk ene s > ^

"
( IX ')
>

In ozonolvsis benzene directly gives glyoxal.

3
.
1

*
1
( N) Benzene has five resonance contributing structures. 1

Answer Key.
KEY POINTS
Aromatic hydrocarbons include benzene and all tho se com pou nds tha t are stru ctur ally rela ted to ben zen e .
one ben zen e ring in the ir mo lec ule s arc call ed mo noc ycl ic aro ma tic \

I Aromatic hydrocarbons con tain ing

hydrocarbons.
mo lec ule s are call ed pol ycy clic Q3 . Multiple choice questions. Encircle the correct.answer .
con tain ing two or mo re ben zen e ring s in the ir aro ma tic The benzene molecule cohtains
Aromatic hydrocarbons ( i)
hydrocarbons. (a ) Three double bonds (b) Two double bonds
Benzene was disc ove red by Mi cha el Far ada y in 182 5 . ( c) One double bond (d) Delocalized 7C - electron charge
ctro ns in benzene arc loo sely hel d and the ring acts as a sou rce of elec tron s. He nce ben zen e is rea dily
I The ele 1» ) Aromatic hydrocarbons are tlic derivatives of
.
y
#

attacked by ele ctro phi les in the pre sen ce of a cata lyst . ( b) alkcnc
( a ) Normal series of paraffins
*

Since electrophilic substitutions reaction lea d to res ona nce sta bili zed ben zen e der iva tive s so sub stit utio ns are the I (d ) cyclohexane
( o) benzene
main reactions of benzene. "
' '
7 ( iii) Which of the following acid can be use d as a cata lyst in Fric del Gra fts reac tion -
s?
. -
' * '* '

Resonance energy of benzene is 150 .5 kJ / mo le ( b) HNO3 (c) Bee i •

(d ) 'NaGI

Structure of benzene is the resonance hyb rid of two Kck ule ’ s

4

stru ctu res and thre e De wa r’ s stru ctu res . • ( a ) A 1GK 2

Groups like NH2, NHR, - OR, -SH, - OCOR - , X , - OH , etc . wh ich inc rea se the ele ctro n den
.
sity in the nuc leu s (iv)
9

Benzene cannot undergo:

( b) add itio n rea ctio ns - — —
and facilitate further electrophilic sub stit utio ns arc kno wn as orth o - and par a -
dire ctin g gro ups '
(a) Substitution reaction I
d elim ina tion rea ctions
-
Groups like CN, GHO, NH 3, NR3, CGI3 which hin der furt her sub stit utio n in tlie ben zen e nuc leu s are kno wn as (c) oxidation reactions
the foll owi ng the com
,

pou ndt
,
hat
(
^
'eanbe most ' readily sulphonatedis:
-
'

meta directing groups.

'
. (v) Am ong st chl oro ben zen e
11
(a ) tolu ene ( b) ben zen e
nitr atin
(
g
c ) nitr
age nt
obe
is:
nzc ne (d )
• p
_l; : . * *• \

SOLVED OBJECTIVE EXERCISE ve 1

( vi) During nitration of benzene the acti

,' ( 0 ) NO ,' ( d ) HN O 3 -Y
( b ) NO
Fill in the blanks.
meaning
,
(
| vii)
(a)
Wh ich
NG
*

com pou nd is ^
the mo st rea ctiv
eth ene
e one :
(c ) eth ane (d ) ethy ne
(i ) The term aromatic was derived from Greek word (a ) Ben zen e-. ( b ) _

to ben zen e. I -
aro ma tics ulp hon atio nis j
Aromatic hydrocarbons include benzene and all tho se com pou nds wh ich are rela ted (viii) _ Thcclectrophile in
•

( ii )
ple st me mb er of the clas s of Aro ma tic Hy dro carb ons. (c) SO3 (d) so|
( iii ) is rec ogn ize d as the sim
(a) H,S04 ( b) HSG3
( iv) Benzene has structure. soo ty flam e bec aus e:
rad ical . The rad ica ls are cal led (ix) Aromatic compounds bur nw ilh
( b) The y hav e a ring stru ctu re. 1

hyd roc arb ons giv es a

( v) The removal of hydrogen atom fro
*
m aro ma tic
^ (a) iltey have high
' per cen tag e of hyd rog en
( c) The y res ist, reaction with air

Benzene was discovered ' by Michael Faraday in car bon

'

(vi ) c
() The y hav e hig h per cen tag e of pre sen ce of Pt is call ed:
cou ld . by hea ting in the
- n "

(vii ) The unhybridized 2 pz orb ital s in ben zen e par tial ly ove rlap to for m a of ele ctro ( x) of n hex -
ane into ben zen e (d ) Rea rran gem ent
The conversion (c) Dealkylation
(viii) The introduction of halogen group in benzene ring is called . ( a) Isomerization (b ) Ar om ati zat ion
The molecular formula of G6H 6 vindicatcd that it is highly compound .
( ix)
_ Solved Exercise M CQ’ s ~

(x) On oxidation . in the presence of V2O5 benzene.giyes «I

Answe r Key. r-V -

— 3 A
• i
( j). Aroma, fragrant ( ii ) I Structurally ( d ) Delocalized •
« - electron
r charge -l
( i'i ) Benzene ( i v) JR eg ul ar hexagonal planar
,
V

(V). 1 Aryl - groups - i

A . (vj) 1825 :
; (yii) . Continuous sheath . (viii) : Tlalogenation
7T» V
L (ix) Unsaturated (x) \ Malei canhydride
'

Indicate True or false.

( i ) . Benzene is more reactive than alkene and less reactive than alkane.
 - • --
I
=“ ja
gafopy >: ? -
^^
-- > i
u - '- r:

^
-
JS= r
218 Chapter 9 (Aromatic Hvdrn *^ f
^
^2?$) •
S EW 8 ^
( » )• (c) benzene >
^ ti!iilirS
/ cj Bcnzaildchyde
^ !Igy
^^ (s» ctivc)
219

(0 Phenol
(iii). (a) AlClj

- IIBr
(iv ). (d) Elimination reaction Benzene gives substitution reactions, oxidation reactions as well
reactions. As it is very stable so elimination s not possible.
'
, /.ui ( k* h \ de
IK n m -ltroniobciizaldclivdf I’hcnnl ii *l ( rmni > )iTivooI j»
S'
- nronxiplu-nirl
(a) Toluene Toluene is electron donating group and increase the availability of electrons
ato
and 7i- positions. Therefore, the rate of reaction is very high, Qiz. How will you prepare the
following compounds from benzene in two steps.
( b) NQ; N(X is strong electrophile and attacks on benzene ring' first * ( a) m - Ghloronitrobenzene
(b) p - Chloronitrobenzene .
( b) Ethene -
I thcnc (CM, = CH,) has more diffused and loosely held TC - electrons and gives Ans. a)
addition reactions quickly. (a) iii-Chloroiiitrobciizciie
(b) < p-ChIor6nitrobenzcne
(c) S03
o Nitration of Benzene

V
(c).Theyhave high 2CA + I 5Q, Ucn/iuv (.'hlnr
percentage of carbon ^lKii/uiiY
Due to high percentage of carbon they give sooty llame’dtie to uribumt Ikn/i'iu' MinilK’H / rnir
carbon. .
Cl
0 Chlorinalion of Nitrobenzene
(b) Aroniatizution The conversion of Aliphatic compounds into aromatic compounds is NO .
.
aromalizalion.e g. 2 l \S( ); >
II O,

-
n Mcptane > Toluene • lv< T
Thisprocess is used to increase octane number

SOLVED ANSWERS TO EXERCISE '

\ On. Predict the major products of bromination of the following compounds.

 rr
U / 7fr »cjage
r

Chapter 9 (Aromatic HVrir

Ly ScholailH
220

o Combustion: u .
^ |

*» I>
“^ I LaSubjectivc)
so
^
221

+ soj -ik§Qj
25' C
.
12GO + 6H,0
BenzenesulDhonic acic
. GH
o Catalytic Oxidation:
O ,
AICI
•
II : + GH GI
^ + HGI
vo,
HC Q
2 I 0 + 4CO: + 4H2© 1 Toluene
45OX*
HC — rC Benzene as unsntura ted hydrocarbon :

Benzene O
Maleic anhydride w
Si at IQOX '

O Mi'
urlH'HO

HC e HC — COOH Cyclohexane
:o
—
• ^ HO
— Cl
V Cl
HC C
II
m '
HC C0OH Sunlight H

H
— f NdI —
'C''

— /CXC^C\— Cl
.
H
Or .
C HA

Maleic anhydride Maleic acid Cl /A H

' . /• -
/ rl
H Cl
Benzene hexachloride

GHG
3H.0
* 30, C;HrO
•
> CHO
*
Benzene trlozonide Glypxal
1
-
~ 7~ rTi
Previous Board Questions
of benzene vapours and air are passed over heated vanadium
What happens when a mixture
pentaoxide? Give equation. )
.
How ,
Write mechanism of
00
Alkylation

What are the two main -

of Benzene
? ph/P pnuatioris

. . a unsaturated compound.
showing that benzene is
Write dov;n two reactions
Prepare m-hitroto.luene from benzene .
a d wnte ein e names * >

Make two Isomers of Xylene

° yje ) ds meta -
^
chloro nitrobenz ene
^
as the main

Detail out three reactions in which benzene behaves as if it is - a saturated hydrocarbon aricMti r #
product. Why? . en .- turated compound.
• '
.
. Give two reactions whiGh showlha

^
9
ofbenzene?
10. What information are obtains following form benzene
11. prepara tion of
Write equations for the
x

^
y
(a) Maleic anhydride (b ) G
ne.|°
12- Write two rules for second substitution
13 . Convert ethylbenzene into benzoic 1
ancj benzotrichloride. I

14. Draw structural formula of tripheny . o{ benzene, why?

15 . Ortho para directing groups as meta ^
direcling, why ?
16- Nitro group when present on the benzene