Chemistry

AROMATICS

Session objectives

1. Nomenclature of aromatic hydrocarbon 2. Structure of benzene 3. Aromaticity mechanisms of electrophilic of aromatic substituents and orientation 4. Polynuclear hydrocarbons and their to icity.

Nomenclature of aromatic compound

OMe

!etho y benzene
Br

Cl O2N
Br

NO2

1" 3#$ibromobenzene %&orrect name'

1#&hloro#2" 4#dinitrobenzene %not 4#chloro#1" 3#dinitrobenzene'

Nomenclature of aromatic compound

Br Br

Br

Br

Br Br o#$ibromobenzene m#$ibromobenzene p#$ibromobenzene

Structure of benzene
Molecular formula C6H6

&).) / 3.2 &).12

4*3+,23-

(aney Ni

shows presence of three double bonds

A
1 6 2 5 4 3

A
1

B 6
5 4

1" 2 # disubstituted isomer

1" ) # disubstituted isomer

But both are same

Structure of benzene

(esonance hybrid structure of benzene

Support in favour of resonance hybrid of benzene 0 1he heat of hydro2enation of benzene is 3) 3cal4mol. 0 5en2th of carbon#carbon bond in benzene is %1.367'" 8hereas carbon#carbon sin2le bond len2th is 1.,47 and carbon#carbon double bond is 1.347.

Structure of benzene

!olecular structure of benzene

Structure of benzene

&laus structure

$e8ar

5adenbur29s prism

Armstron2#:ayer structure castric

1hiele structure

Aromaticity
&lass of compounds havin2 a characteristic stability Conditions for aromaticity 0 &omplete delocalization of p#electrons of the rin2 system. 0 Planarity; $elocalization of p#electrons is possible only if the rin2 is planar to allo8 cyclic overlap of p#orbitals. 0 .uc3el<s rule for aromaticity; Accordin2 to .uc3el<s rule for a compound to be aromatic" a molecule must have %4n / 2' electrons %n=> to any number'

Aromaticity

Benzene 6 electrons

Naphthalene 10 electrons

Anthracene 14 electrons

Phenanthracene 14 electrons

Aromaticity

.. N H Pyrrol

.. S ..

.. O .. ?ura

1hiophen

Preparation of :enzene
.ydroformation or catalytic reformin2
&.3 ( &.2 ) 4 &.3 Pt # Al2@3 ,>>A&

rom neptha
&.3 ( &.2 ) , &.3

:enzene

&).)

/ 4.2

rom neptha

Pt # Al2@3 &).,&.3 / 4.2 ,>>A& 1oluene

&.3 %&.2 ') &.3

rom neptha

Pt # Al2@3 &).4%&.3'2 / ,>>A& Bylene

Cthylbenzene

&).,&2.,

Preparation of :enzene
?rom acetylene
3CH CH red hot tube :enzene

?rom benzenediazonium chloride

! N2 Cl

2[H

SnCl2/NaOH Benzene

! HCl ! N2

Preparation of :enzene

! N2 Cl

H3PO2

C"

! H3PO3 ! HCl ! N2 :enzene

.ypophosphorous acid

$ouble distillation of coal

destructive distillation

&oal

li2ht oil fraction

i' 8ashed 8ith conc. .2S@4 ii' 8ashed 8ith Na@. iii' 8ashed 8ith .2@ iv' dried and distilled

:enzene / 1oluene /1hiophene

?ractionless distillation

:enzene %D> + D2>&'

Properties
Clectrophilic aromatic substitution reaction of benzene .alo2enation
Cl Anh#$ AlCl3 300 % 320 &

! Cl2
:enzene

! HCl
&hlorobenzene

!echanism of .alo2enation
# ?e&l3 / &l # &l ?e &l4 / &l/
H H Cl H Cl H Cl H Cl

! Cl

! slo'

! !

! !
(esonance hybrid structure

Cl

Cl Abstraction of ./

! ! (eCl4

! HCl ! (eCl3
&hloro benzene

Properties
Nitration
NO2

! HNO3 330)C
Nitro benzene

H2SO4

!echanism of Nitration
2.2S@4 / .N@3
/ N@2 / .3@ / 2 .S@# 4 /
H H H NO2 H NO2

! NO2
Nitronium ion

NO2

slo'

! !

NO2

!
Entermediate cation

!echanism of Nitration

NO2

NO2
HSO 4 !

A*stract+on o, H!

!
Nitrobenzene

H2SO4

Properties
Sulphonation
SO3H 330 &

!
Benzene

Conc$ H2SO4

! H2O
:enzene sulphonic acid

!echanism of Sulphonation

2.2S@4 .3@/ / S@3 / .S@# 4

H H SO 3 H SO H 3 H SO H 3 H SO H 3

! SO3

H3O

! !

H SO H 3

!
(esonance hybrid structure

!echanism of Sulphonation

H SO H 3

SO3H

HSO 4

! :enzene sulphonic acid

H2SO4

Properties
?riedel#&raft<s reaction %a' friedel+craft al3ylation
Anh-# AlCl3 CH3

! CH3Cl

! 1oluene

HCl

%a' friedel+craft acylation

Anh-# AlCl3

COCH3

! CH3COCl

HCl

Acetyl benzene %Aceto phenone'

!echanism of ?riedel+&raft<s reaction

/ &.3&@&l / Al&l3 Al&l# / &. &@ 4 3
H
+

/ &.3&l / Al&l3 Al&l# / &. 4 3

CH3 !

CH3 !

CH3

! C H3

! H CH3

! (esonance hybrid structure

!echanism of ?riedel+&raft<s reaction

CH3 ! ! AlCl4

CH3

! HCl ! AlCl3 1oluene

5imitations of ?riedel &raft al3ylation

1. 1he dan2er of poly substitution. 2. 1he possibility that the al3yl 2roup 8ill rearran2ement. 3. Aryl halides cannot ta3e place of al3yl halides. 4. An aromatic rin2 less reactive than that of the halobenzenes does not under2o the ?riedel &rafts reaction.

5imitations of ?riedel &raft al3ylation

,. Aromatic rin2s containin2 the F N.2" F N.( or F N(2 2roup do not under2o ?riedel &rafts al3ylation because the stron2ly basic nitro2en ties up the 5e8is acid. H C6H5NH2 ! AlCl3 C6H5 N ! AlCl3
H

Addition reaction of benzene

Addition of hydro2en
! 3H2
:enzene %Aromatic compound' N+ 4.5 % 500 & &yclohe ane %non aromatic compound'
Cl Cl Cl Cl :enzene .e a &hloride %:...&' Cl Cl

Addition of halo2ens
! 3Cl2
h

@ idation
CH3 COOH

! 3 [O
1oluene

&MnO4 / H2O 3.5 % 3/5 &

! H2O
:enzoic acid

CH2CH3

COOH &MnO4 / H2O 3.5 % 3/5 &

! 6 [O

! 2H2O ! CO2
:enzoic acid

@ idation
CH3 &MnO4 / H2O 3/5 &0 6[O CH3 P# ylene COOH 1erephthalic acid COOH

! H2O

CH3

CH3

COOH &MnO4 / H2O COOH

3/5 &0 6[O

@# ylene Phthalic acid

! 2H2O

@ idation

CH3 C CH3 CH3 &MnO4 CH3

CH3 C CH3 COOH

@zonolysis of benzene
1+2 O3 1++2 3n #"st/H2O CHO 3 CHO Glyo al
CH3 1+2 O3 1++2 3n #"st/'ater 2 CHO Glyo al CHO CH3 C O !ethyl 2lyo al CHO

Enfluence of Substituents on Clecrophilic Aromatic Substitution

Substituent

Cffects on reactivity

NH20 OH0 OCH3 NHCOCH3 0 C6H5 0 CH3

N ( CH3 ) 3 0 NO2 CN0 SO3H0 COOH CHO0 CO40 halo5ens
+

Activates

$eactivates

Enfluence of Substituents on Clecrophilic Aromatic Substitution

Cl

Cl

Cl Cl

Cl

&l 4?e&l3

or

Cl

or
Cl

Enfluence of Substituents on Clecrophilic Aromatic Substitution

! OH

""

! OH

""

OH

OH

OH

Enfluence of Substituents on Clecrophilic Aromatic Substitution

O N O$ O N

$
N

$
N

# #

O N

@rtho+Para and meta directors

Ortho-para directors (0 Cl0 Br0 6 OH OCH30 O4 NH2 NH40 N42 NHCOCH3 CH30 C 2H5 Meta directors NO2 SO3H CN COOH CHO N! 1CH323 O 77 C 8 O4

Polynuclear .ydrocarbon and their 1o icity

Naphthalene

Anthracene

Phenanthracen e

CH3 1" 2#benzanthracene 2>#methyl cholanthracene

Class e%ercise

&lass e ercise 1
In the reaction of C).,H" the major product %I )>J' is m#isomer" so the 2roup H is %a' F &@@. %c' F @. Solution; %b' F &l %d' F N.&@&.3

F &@@. is m#directin2 2roup.

.ence" the ans8er is %a'

&lass e ercise 2
Khich of the follo8in2 is the stron2est o" p#directin2 2roupL %a' +@. %c' +@&.3 Solution; :ecause the lone pair of electrons of @&.3 ta3es part in resonance 8ith benzene rin2. .ence it is stron2er ortho-para directin2 2roup. %b' +&l %d' +&.3

.ence" the ans8er is %c'

&lass e ercise 3
Aromatic compounds burn 8ith a sooty flame because 1. they have a rin2 2. they have a relatively hi2h percenta2e of hydro2en 3. they have a relatively hi2h percenta2e of carbon 4. @f structure of carbon atoms Solution; Aromatic compounds have relatively hi2h percenta2e of carbon. .ence" the ans8er is %c'

&lass e ercise 4
:enzene is less reactive than ethene and ethyne to8ards addition reactions due to 1. the presence of 3#bonds 2. the cyclic nature 3. the sp2 hybridization of carbon atoms 4.the delocalization of #electrons Solution; $elocalization of #electrons reduce the reactivity of benzene. .ence" the ans8er is %d'

&lass e ercise ,
Khich of the follo8in2 has the hi2hest meltin2 pointL %a' o# ylene %c' p# ylene Solution; p# ylene bein2 symmetrical pac3s closely in the crystal lattice. %b' m# ylene %d' toluene

.ence" the ans8er is %c'

&lass e ercise )
Khich of the follo8in2 types of compounds are e pected to have the hi2hest octane numberL %a' Strai2ht chain al3anes %b' &ycloal3anes %c' :ranched chain al3anes %d' Aromatic hydrocarbons Solution; Aromatic hydrocarbons have hi2h octane number. .ence" the ans8er is %d'

&lass e ercise *
1he chemical system that is non#aromatic is &a'

&b'

&c' Solution;

&d'

1he compound : has no #electrons but other are aromatic compounds. .ence" the ans8er is %b'

&lass e ercise D
Khat is the ratio of and bonds in benzeneL %a' 1 ; 4 %c' 1 ; 1 Solution; In ben(ene Number of #bonds = 3 Number of s#bonds = 12 (atio = 3 ; 12 = 1 ; 4 %b' 2 ; 1 %d' 2 ; 2

.ence" the ans8er is %a'

&lass e ercise 6
Khich one of the follo8in2 is not compatible 8ith arenesL %a' Greater stability %b' $elocalization of #electrons %c' Clectrophilic addition %d' (esonance Solution; Arenes do not 2ive electrophilic addition because they have stable compounds. .ence" the ans8er is %c'

&lass e ercise 1>

Khich one of the follo8in2 is not aromaticL %a' :enzene %b' &yclopentadienyl anion %c' 1ropyllium cation %d' &yclopentadienyl cation Solution; &yclopentadienyl cation has only four #electrons . .ence" the ans8er is %d'

Than) you