Benzene

L.S.T.
Leung Chik Wai Memorial School

F.6 Chemistry
Chapter 32: Aromatic y!rocar"on
Benzene and other Arenes
(A) Introduction
#en$ene% C
6
6
is the simplest mem"er o& the class o& hy!rocar"on calle! aromatic hy!rocar"ons or
arenes. 't is a colourless li(ui! )ith a characteristic smell.
These aromatic compoun!s contain a ring o& sp
2
car"on atoms% )ith a !elocali$e! system o& electrons.
Aromatic compoun!s *inclu!ing aromatic hy!rocar"ons+ are sta"ili$e! "y the electron !elocali$ation.
The !elocali$e! &ormulae &or "en$ene an! other arenes are sho)n "elo):
CH
3
CH
3
CH
3
,,,,,,,,,,,,,,,,,,
,,,,,,,,,,,,,,,,,,, ,,,,,,,,,,,,,,,,,,,
NO
2
Cl
,,,,,,,,,,,,,,,,,,,
,,,,,,,,,,,,,,,,,,, ,,,,,,,,,,,,,,,,,,,
NH
2
SO
3
H OH
,,,,,,,,,,,,,,,,,,,
,,,,,,,,,,,,,,,,,,, ,,,,,,,,,,,,,,,,,,,
Chpt. 32: p.-
L.S.T. Leung Chik Wai Memorial School
F.6 Chemistry
NO
2
NO
2
NO
2
NO
2
,,,,,,,,,,,,,,,,,,,
,,,,,,,,,,,,,,,,,,,
(B) Reactions of Benzene: General consideration
The "en$ene ring is a planar he.agon )ith a clou! o& !elocali$e! electrons lying a"o/e an!
"elo) the ring. The reactions o& "en$ene coul! in/ol/e the attack o& an electrophile on the
clou! o& electrons an! un!ergo a!!ition reaction.
o)e/er% )hat is &oun! is (uite contrary to the e.pectation. The &ollo)ing ta"le compares some
reactions o& cyclohe.ane% cyclohe.ene an! "en$ene.
Chpt. 32: p.2
F.6 Chemistry
Ta"le Some 0eactions o& Cyctohe.ane% Cyclohe.ene an! #en$ene
0eagent Cyclohe.ane Cy!ohe.ene #en$ene
#r
2
1 CCl
2
*in !ark+
3Mn4
2
1
5
Conc.
2
S4
2
2
1 &inely
!i/i!e! 6i
6o reaction #r
2
!ecolorise! rea!ily% no #r 6o reaction )ith #r
2
alone% e/ol/e!% in the presence o& Fe
&ilings% #r
2
!ecolorise!
slo)ly an! #r &umes
e/ol/e!.
6o reaction Mn4
2
7

!ecolorise! rea!ily. 6o reaction
6o reaction
2
S4
2
a"sor"e! rea!ily. Slo) su"stitution reaction
)hen heate!% yello) oil
&orme!.
6o reaction 4ne mole a"sor"s one mole o&
2
4ne mole a"sor"s 3 moles
at room temperature o&
2
slo)ly at -89
9
C
'nterpretation:
#en$ene is LESS reactive than cyclohe.ene *an alkene+ though it contains it electrons as alkenes !o.
0eason :
The !elocali$ation o& it electrons in the "en$ene ring lea!s to consi!era"le aromatic
sta"ili$ation. Larger amount o& energy is re(uire! to acti/ate the ring "e&ore any reaction coul! occur.
As a result%
the benzene ring requires higher temperature and possibly catalyst before it can react due to the
resonance stabilization.
(C) Electrophilic Aromatic Sustitution of Benzene
:nlike alkenes. "en$ene un!ergoes electrophilic su"stitution rather than a!!ition.
;.amples:
Chpt. 32: p.3
F.6 Chemistry
H
Cl
2
/ AlCl
3
Cl
+ Cl H
H
conc. H
2
SO
4
SO
3
H
+
O H
2
The su"stitution reactions can preser/e the aromatic sta"ili$ation a&ter electrophilic attack.
Chpt. 32: p.2
F.6 Chemistry
The general reaction o& electrophilic aromatic su"stitution can "e represente! as &ollo):
-. Formation o& the reacti/e electrophile ;
5
.
2. Attack "y ;
5
on the clou! o& the "en$ene ring. The &orme! car"ocation interme!iate in/ol/es a
high acti/ation energy% there&ore this "ecomes the rate !etermining step.
+
E+
3. Formation o& the &inal pro!uct "y loss o& the ring proton &rom the position o& electrophilic
attack.
The aromaticity is restore! to the ring.
The energy pro&ile &or this electrophilic aromatic su"stitution is sho)n "elo) :
Chpt. 32: p.8
F.6 Chemistry
(!) "itration of Benzene
The su"stitution o& a < atom "y a <64
2
group is calle! nitration.
To o"tain nitro"en$ene. C
6
8
64
2
. "en$ene is re&lu.e! on a )ater "ath at 69=C )ith a >nitrating
mi.ture? < a mi.ture o& concentrate! nitric aci! an! sulphuric aci!.
nitro"en$ene is a pale yello) li(ui! )hich can "e separate! &rom "en$ene "y !istillation un!er
re!uce pressure.
Mechanism:
-. The generation o& the nitronium ion 64
2
5
Sulphuric aci! ser/es as a strong aci! an! !onate a proton to nitric aci! )hich acts as a
"ase.
2. The nitronium ion 64
2
5

a!!s to the "en$ene ring to &orm the short7li/e! interme!iate% in
)hich "oth the entering 764
2
group an! the lea/ing < atom are "on!e! to the ring.
3. The interme!iate rapi!ly loses a proton% restoring the symmetry an! sta"ility o& the
"en$ene ring. The proton is imme!iately picke! up "y a hy!rogen sulphate ion.
6ote @-A The 2n! step is the rate !etermining step.
0eason:
@2A '& the temperature is raise! to B8=C% an! the &uming nitric aci! is use!. -%3<
!initro"en$ene is &orme!.
Chpt. 32: p.6
F.6 Chemistry
Chpt. 32: p.C
F.6 Chemistry
(E) #alo$enation of enzene
The a!!ition o& halogens to the "en$ene ring takes place un!er con!itions )hich &a/our the &ormation
o& &ree ra!icals% i.e.% sunlight or high temperature. The &irst step in the a!!ition is the homolysis o& the
halogen molecule% e.g.
Cl
2
2Cl
A !i&&erent type o& reaction takes place at room temperature in the presence o& a Frie!el<Cra&ts
catalyst Su"stitution then occurs.
e.g.
Mechanism o& halogenation
0eaction : #en$ene reacts )ith "romine to &orm "romo"en$ene *)ith the presence o& Fe#r
3
+
- The electron clou! interacts )ith the "romine molecule% the #r<#r "on! "ecomes polarise!
2. The &rie!el<Cra&ts catalyst accepts a pair o& electrons &rom the 6<#r atom in the polarise! #r
2
molecule% an! ena"les the #r<#r "on! to split. A "romonium ion an! a Fe#r
2
7
comple. ion are
&orme!.
Br Br FeBr
3
3. The "romonium ion rapi!ly loses a proton to &orm "romo"en$ene% )ith the generation o& the
catalyst% Fe#r
3
.
Chpt. 32: p.D
F.6 Chemistry
6ote:
lo!ination o& "en$ene !oes not occur "ut some "en$ene !eri/ati/es% containing acti/ating su"stituents%
are io!inate!.
Chpt. 32: p.B
F.6 Chemistry
(%) Sulphonation of Benzene
Sulphonation is the su"stitution o& a < atom "y an <S4
3
group. #en$enesulphonic aci!%
C
6
8
S4
3
. is o"taine! "y re&lu.ing "en$ene )ith concentrate! sulphuric aci! &or many hours.
or )arming )ith &uming sulphuric aci! *)hich contain S4
3
+ at 29
9
C &or 29739 minutes.
H
+
H
2
SO
4
reflux with conc. H
2
SO
4
Mechanism.
-. Sulphur trio.i!e is pro!uce! in the &ollo)ing e(uili"rium in )hich sulphuric aci! acts as
"oth an aci! an! a "ase.
2
2
S4
2
S4
3
5
3
4
5
5 S4
2
7
2. Sulphur trio.i!e is a po)er&ul electrophile an! react )ith the aromatic n system to &orm
a neutral "ut !ipolar interme!iate.
S
O
O
O
3. The interme!iate is attacke! "y the hy!rogen sulphate ion S4
2
7
to &orm the pro!uct.
6ote : @-A :nlike nitration% halogenation% etc. sulphonation is re/ersi"le. #y heating an
9
a(ueous
solution o& "en$enesulphonic aci! a"o/e -99
9
C% "en$ene an! sulphuric aci! are &orme!.
So% the choice o& con!itions !etermines the !irection o& the reaction.
@2A The <S4
3
group in the pro!uct can "e replace! "y hy!rolysis to gi/e an <4 group.
#en$enesulphonic aci! is con/erte! to phenol. C
6
8
4. This is the easiest )ay o&
preparing phenol in the la"oratory.
Chpt. 32: p.-9
F.6 Chemistry
@3A Sulphonation is important in the manu&acture o& !etergents "ecause !etergents contain
<S4
3
groups that they lather
e/en in har! )ater% as the calcium an! magnesium salts o& sulphonic aci! are solu"le.
(G) Al&'lation of enzene
An alkyl group can "e intro!uce! into the "en$ene ring "y the reaction o& a halogenoalkane
)ith "en$ene.
Such type o& reaction is calle! Frie!el7Cra&ts reaction. The reaction takes place un!er the
in&luence o& a catalyst% such as aluminium chlori!e *AlCl
3
+ % aluminium "romi!e *Al#r
3
+ an!
iron*'''+ "romi!e *Fe#r
3
+
Such catalysts &unction as Le)is aci! since the central atom can accept a pair o& electrons. e.g.
AlC-
3
can accept a pair o& electrons &rom a chlori!e ion.
AlCl
3

5 Cl
7
AlCl
2
7

Mechanism o& alkylation
When a Frie!el<Cra&ts catalyst *e.g. A-#r
3
+ is !issol/e! in a halogenoalkane%
-. A-#r
3
can accept the "romi!e ion &rom C
2
8
#r% &orming a car"ocation% C
2
8
5
.
C
2
8
#r 5 Al#r
3
C
2
8
5
5 Al#r
2
75
2. The attack on the it electron clou! o& the "en$ene ring "y the C
2
8
5
or "y the comple.
C
2
8
5
A-#r
2
7
% &orming an interme!iate.
C
2
H
5
+
3. The reacti/e interme!iate (uickly loses a proton to &orm the pro!uct% ethyl"en$ene. The catalyst%
Al#r
3
is regenerate!% an! hy!rogen "romi!e is e/ol/e!:
6ote:
Alkylation can also "e a&&ecte! "y the use o& an alkene an! a Frie!el<Cra&ts catalyst together )ith an!
aci! such as Cl or
3
E4
2
:
Chpt. 32: p.--
F.6 Chemistry
The &irst step in the reaction is protonation o& the alkene "y the aci! to &orm a car"ocation )hich
attacks the "en$ene ring.
Chpt. 32: p.-2
(#) (eth'lenzene ()oluene)
CH
3
Methyl"en$ene *or toluene+ C
6
8
C
3
. resem"les "en$ene. 'ts physical properties are similar :
the "oiling tegiperature is higher *---
9
C+ an! the melting temperature lo)er *7B8
9
C+
0eactions o& the ring : ;lectrophilic su"stitution
Methyl"en$ene is more reacti/e than "en$ene to)ar!s the electrophilic reagents )hich
su"stitute in the ring.
0eason : The methyl group can pushes electrons into the ring through positive inductive effect.
Mil!er con!itions are employe! than in the reactions o& "en$ene.
@-A Suiphonation : &uming
2
S4
2
*containing S4
3
+
@2A 6itration : Conc. 64
3
5 conc.
2
S4
2
at 39=C
A mi.ture o& -%2< an! -.2<su"stitute! %rnethyl"en$enes o"taine! in each case.
CH
3
H
+
NO
2
+
'& the temperature is raise!% t)o groups or three groups are intro!uce!.
CH
3
NO
2
CH
3
NO
2
NO
2
CH
3
NO
2
NO
2
O
2
N

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Leung Chik Wai Memorial School

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