Aromaticity

Chapter Aromtic Compounds
 5.1 Introduction,
 Benzene was first isolated by Faraday.
Hoffman was the first scientist who separated benzene from coal tar.
 Molecular formula = C6H6 & Empirical formula = CH

Molecular mass = 78 & Empirical formula mass = 13
Percentage of carbon = 93.6% & Percentage of hydrogen = 6.4
Physical state = liquid at room temperature, Melting point = 5.5oC & Boiling point = 80oC
It is highly inflammable & burns with smoke due to high percentage of carbon.
It is insoluble in water & soluble in organic solvents.
Benzene dissolves fats, sulphur, iodine and resins & many organic compounds (non polar compounds).
 It is an aromatic hydrocarbon, So readily undergo substitution reactions, thermally stable & resist
addition, oxidation & reduction reactions.
Stability of benzene
 Resonance Energy :- Benzene resists addition whereas it readily undergoes substitution reactions, like nitration,
sulphonation, halogenation etc. This indicates that benzene is more stable than the hypothetical cyclohexatriene
molecule. This has been proved by the fact that the enthalpies of hydrogenation and combustion of benzene are
lower than expected. Enthalpy of hydrogenation is the change in enthalpy when one mole of an unsaturated
compound is hydrogenated. It has been experimentally found that enthalpy of hydrogenation for cyclohexene is
28 kcal mol-1. Accordingly, the values for cyclohexene and hypothetical cyclohexa-1, 3, 5-triene were calculated &
compared with their experimental values. It should note that here negative sign for the value of ∆ H0 is
indicating that reaction is exothermic
Experiment involve following reactions & values for Hydrogenation,
+ H
2
Cyclohexene Cyclohexane
∆ H -28 kcal/mol Experiment
0
+ 3H
2
Cyclohexatriene Hypothetical Cyclohexane

∆ H0 -86 kcal/mol Calculated (if electrons are localized)
+ 3 H2
Benzene Cyclohexane
∆ H -50 kcal/mol Experiment (if electrons are delocalized)
0
Mr. M.S.Thakare, M.Sc. (Organic Chemistry) SET Dept. of Chemistry, Pratap College, Amalner. Page 1
 The ∆ H0 for the hydrogenation of cyclohexene, = ∆ H0 = -28 kcal/mol ( Experimental )

 The ∆ H0 for the hydrogenation of cyclohexatriene = ∆ H0 = 3 × -28 kcal/mol = -86 kcal/mol (calculated)
 The ∆ H0 for the hydrogenation of benzene = ∆ H0 = -50 kcal/mol ( Experimental )
 Thus benzene must be more stable than cyclohexatriene by 36 kcal/mol & as This extra stability to a
compound gains from delocalized electrons, it is known as delocalization energy or resonance energy.
 Thus the resonance energy is a measure of how much more stable a compound with delocalized electrons is
than it would be if its electrons were localized hence the least stable alkene has the greatest value & vice a
versa.
X-ray studies show that it is planar molecule and that all six C-C bonds in benzene are of equal length (139 pm),
intermediate between C-C single bond (154 pm) and C=C (134 pm). All six carbons are sp2 hybridized and all
bond angles are 120o. Benzene is a hybrid of various resonating structures, the two Kekule structures A and B,
being the main contributing forms.
A B
 5.2 Aromaticity, introduction:-
The compound we know as benzene was first isolated in 1825 by Michael Faraday, he extracted the benzene
from a liquid residue obtained after heating whale oil under pressure to produce a gas used to illuminate
buildings in London. Because of its origin, chemists suggested that it should be called “pheno” from the Greek
word phainein (“to shine”). In 1834, Eilhardt Mitscherlich correctly determined benzene’s molecular formula
(C6H6) and decided to call it benzin because of its relationship to benzoic acid, a known substituted form of the
compound. Later its name was changed to benzene. Compounds like benzene, which have relatively few
hydrogens in relation to the number of carbons, are typically found in oils produced by trees and other plants.
Early chemists called such compounds aromatic compounds because of their pleasing fragrances. In this way,
they were distinguished from aliphatic compounds, with higher hydrogen-to-carbon ratios, that were obtained
from the chemical degradation of fats. The chemical meaning of the word “aromatic” now signifies certain kinds
of chemical structures. We will now examine the criteria that a compound must satisfy to be classified as
aromatic.
‘Aromatic compounds are particularly stable’. An aromatic compound is more stable than an
analogous cyclic compound with localized electrons i.e Aromaticity is characterized by stability
In order for a molecule to be aromatic, it must obey following characteristics:
1. It must be cyclic
2. It must be conjugated (i.e. all atoms around the ring must be able to participate in π-bonding through
resonance)
3. It must be flat, planner
4. And, it must contain (4n + 2) π electrons. This is known as Huckel’s rule for aromaticity. The number of π
electrons for aromaticity follows this sequence: 2 (n=o), 6 (n=1), 10 (n=2), 14 (n=3), 18 (n=4), etc….
In short The π - cloud must contain an odd number of pairs of π -electrons.
Note :- While counting electron * Consider 2 electrons for each pi bond; lone pair & negative charge.
*Consider zero or no electrons for positive charge.
Examples
A) 2 pi electron system, obey Huckle rule for Aromaticity all are Aromatic in nature, here n=0
B) 6 pi electron system, obey Huckle rule for Aromaticity all are Aromatic in nature, here n=1
N O S N
H
C) 10 pi electron system, obey Huckle rule f or Aromaticity all are Aromatic in nature, here n=2
N N
H
D) 14 pi electron system, obey Huckle rule for Aromaticity all are Aromatic in nature, here n=3
N
H
Dilfference between aromatic and aliphatic compounds.
Sr.No. Aromatic compounds Aliphatic compounds
1. Aromatic compound are closed chain compounds Aliphatic compounds are open chain compounds.
2. They contain higher percentage of carbon. They contain lower percentage of carbon.
3. They burn with sooty flame. They burn with non-sooty flame.
4. They don’t undergo addition reactions easily. They undergo addition reactions easily.
5. They undergo substitution reaction. Aliphatic compounds except alkane don’t undergo
substitution reactions.
6. Aromatic compounds are not attacked by normal Aliphatic compounds are attacked by normal
oxidizing and reducing agents. oxidizing and reducing agents.
 Antiaromaticity
An aromatic compound is more stable than an analogous cyclic compound with localized electrons. In contrast, an
antiaromatic compound is less stable than an analogous cyclic compound with localized electrons. Aromaticity
is characterized by stability, whereas antiaromaticity is characterized by instability
In order for a molecule to be antiaromatic, it must obey following characteristics:
1. It must be cyclic
2. It must be conjugated (i.e. all atoms around the ring must be able to participate in π -bonding through
resonance)
3. It must be flat, planner
4. And, it must contain (4n) π electrons. This is known as Huckel’s rule for antiaromaticity. The number of π
electrons for antiaromaticity follows this sequence: 4(n=1), 8(n=2), 12(n=3), 16(n=4), etc….
Examples
Relative stabilities
Aromatic compound > Cyclic compound with localized electrons (non aromatic) > Antiaromatic
compound
Increasing stability
 ANNULENE
 The term annulene refers to completely conjugated monocyclic polyenes OR

 Monocyclic hydrocarbons with alternating single and double bonds are called annulenes.
A prefix in brackets denotes the number of carbons in the ring e.g.
[4] -Annulene [ 6] -Annulene tub shaped (non planer)

[8 ] -Annulene
Cyclobutadiene or [4]-annulene :- 4 electrons (even number of pairs; 4n, n = 1) Cyclic, planar, uninterrupted
ring of p orbital bearing atoms (i.e fully conjugated) hence Antiaromatic
Benzene or [6]-Annulene. :- A perfect example of cyclic planar molecule with uninterrupted ring of p orbital
bearing atoms; 6 electron system (4n+2, n = 1) hence Aromatic
[8]Annulenes, 1,3,5,7-Cyclooctatetraene:- X-ray structure determination shows that the molecule is tub-
shaped, and therefore is not a planar system to which the Hückel rule applies. The bond lengths around the ring
alternate as expected for a polyene. 8 π electron system; If completely planar, this molecule will become
antiaromatic but the molecule is actually boat shaped and hence Nonaromatic. (Nonaromatic form is more
stable than an antiaromatic form)
[10]Annulenes—1,3,5,7,9-Cyclodecapentaene Isomers:- According to the Hückel rule, [10]annulene

would be aromatic if it has planar structure. However, all the 1,3,5,7,9-cyclodecapentaene isomers suffer serious
steric strain that prevents the planar geometry & hence all isomers of [10]annulene are Nonaromatic.
Both internal hydrogen

disturb the plannarity
H
H
[12]Annulenes:- [12]Annulene is a very unstable compound. This feature is characteristic of the [4n] annulenes
(n=3) i.e. theoretically Antiaromatic
[14],Annulenes:- [14]Annulene is a Nonaromatic as steric interactions associated with internal hydrogens

disturb the plannarity
[12] Annulenes Z,E,E,Z,E,Z,E Z,E,Z,E,Z,Z,
[14] Annulenes
[16]annulene :- [16]annulene indicate that there are several conformations that differ in relative placement of
the internal hydrogens.These structural data are consistent with regarding [16]annulene as being nonaromatic.
Experimental combustion data indicate that [16]annulene is less stable than cyclooctatetraene. [16] annulene
o o
shows significant bond alteration, characteristic of a polyene structure (C-C, 1.46A ; C=C, 1.34 A ). It is
nonplanar and is Nonaromatic.
[18]Annulene and Larger Annulenes :- [18]Annulene offers a particularly significant test of the Hückel rule.
The internal cavity in [18]annulene is large enough to minimize steric interaction between the internal hydrogens
in a geometry that is free of angle strain. The properties of [18]annulene are consistent with its being
Aromatic.
H
H H
H H
H
[16] Annulenes [18] Annulenes
 Fused Benzene Ring Compounds

Benzene rings may be joined together (fused) to give larger polycyclic aromatic compounds. A few examples are
drawn below, together with the approved numbering scheme for substituted derivatives.
 Fused nonbenzenoid systems
Azulene (A) is one of the few nonbenzenoid hydrocarbons that appear to have appreciable aromatic
stabilization.An interesting structural question involves the contribution of a dipolar structure (B) that pictures the
molecule as the fusion of a cyclopentadienide anion and a cycloheptatrienyl cation. Azulene does have an
appreciable dipole moment (0.8 D).
A B
The significant resonance stabilization of azulene can be contrasted with pentalene C and heptalene D both of
which are indicated to be destabilized relative to a reference polyene.
(C) Very Unstable (D) Very Unstable

8 π electrons 12 π electrons
 Aromaticity in Charged Rings :- Conjugated Cyclic Cations and Anions
A is non aromatic as one of the carbon is sp3 hybridized
B is aromatic & obey all the necessary condition required for

aromaticity.
C
C is antiaromatic & obey all the necessary condition required
A B
for antiaromaticity.
D is non aromatic as one of the carbon is sp 3 hybridized
E is antiaromatic & obey all the necessary condition required for

antiaromaticity
E F F is aromatic & obey all the necessary condition required for

D
aromaticity.
G is non aromatic as one of the carbon is sp 3 hybridized
H is aromatic & obey all the necessary condition required for

aromaticity.
I is nonaromatic as being not flat.

G H I
+ .. + .. .. + ..
+
D E F
A B C
+ .. + + .. .. ..
G H I J K
Hückel’s Rule Relationships for Charged Species
Sr. Compound No. of π Value of n Nature

no. Electrons according to by
(4n +2) rule
1 Cyclopropenylium cation (A) 2 0 Aromatic
2 Cyclopropenide anion (B) 4 0.5 Antiaromatic
3 Cyclobutadiene dication (C) 2 0 Aromatic
4 Cyclobutadiene dianion (D) 6 1 Aromatic
5 cyclopentadienyl cation (E), 4 0.5 Antiaromatic
6 Cyclopentadienide anion (F) 6 1 Aromatic
7 cycloheptatrienyl cation (tropylium ion) (G) 6 1 Aromatic
8 cycloheptatrienyl anion (H) 8 1.5 Nonaromatic
9 Cyclooctatetraene dication (I) 6 1 Aromatic
10 Cyclooctatetraene dianion (J) 10 2 Aromatic
11 cyclononatetraenide anion (K). 10 2 Aromatic
 Aromaticity of heterocycles
Many heterocyclic compounds are aromatic. A heterocyclic compound is a cyclic compound in which one or
more of the ring atoms is an atom other than carbon. A ring atom other than carbon is called a heteroatom.
The name comes from the Greek word heteros, which means “different.” The most common heteroatoms found
in heterocyclic compounds are N, O, and S.
1. Five-membered ring systems containing aromatic sextet: The degree of aromaticity is easily
described by the resonance energy. In this compounds one unshareded paired lone pair of electron is engaged in
delocalization to complete aromatic sextet & is parallel to pi orbital of double bond as shown
.. .. ..
S N O
.. ..
H
Thiophene Pyrrole Furan
Orbital structure of pyrrole Orbital structure of furan
2. Six-membered systems containing aromatic sextet

The nitrogen-containing heterocycles: the unshared pair of electrons is not part of the aromatic sextet & . In this
copounds unshareded paired or lone pair of electron is not engaged in delocalization to complete aromatic sextet
& is perpendicular to pi orbital of double bond as shown.
N
N
.. N ..
..
pyridine quinoline isoquin
Orbital structure of pyridine
3. Other Aromaticity of heterocycles
N
N N
N
N N N N
H N
Indole Pyrimidine Pyrazine Purine
Nomenclature
Nomenclature of Monosubstituted Benzenes
Some monosubstituted benzenes are named simply by stating the name of the substituent, followed by the word
“benzene.”
Br I CH2CH3 O
F Cl +
N
O
Flurobenzene iodobenzene ethylbenzene nitrobenzene

chlorobenzene bromobenzene
Some monosubstituted benzenes have names that incorporate the name of the substituent. Unfortunately, such
names have to be memorized
NH2 OH OMe SO3 H CH CH2

CH3
toluene styrene
aniline phenol anisole benzene sulfonic acid
O H
O OH C N
benzaldehyde benzoic acid benzonitrile
With the exception of toluene, benzene rings with an alkyl substituent are named as alkyl-substituted benzenes or
as phenyl-substituted alkanes.
CH3
CH3CHCH3 CH3CHCH2CH3 H3C CCH3
Isopropylbenzene sec-butylbenzene tert-butylbenzene

cumene
When a benzene ring is a substituent, it is called a phenyl group. A benzene ring with a methylene group is
called a benzyl group.
H2C
a phenyl group a benzyl group
H3C CHCH2CH2CH2CH3 H3CH2C CH2CH2CH2CH3
2-phenylhexane 3-phenylhexane diphenyl ether
H2C OH H2C Cl
CH2OCH2
benzyl chloride benzyl chloride dibenzyl ether
Nomenclature of Disubstituted Benzenes
When more than one substituent is present on a benzene ring, the relative locations of the substituents must be
designated by numbering the ring carbons or by some other notation.
In the case of disubstituted benzenes,
 the prefixes ipso is used for 1 position where substituent is attached
 the prefixes ortho is used for 2,6 position
 the prefixes meta is used for 3,5 position
 the prefixes para is used for 6 position
ipso position
X
ortho
ortho position
meta position
meta
para position
CH3 OH OH
CH3
CH3 OH
o-xylene CH3 pyrocatechol

OH
p -xylene hydroquinone
 Electrophilic Aromatic Substitution

In electrophilic aromatic substitution, the benzene ring acts as an electron donor (Lewis base or
nucleophile, ArH) and reacts with an electron acceptor (Lewis acid or electrophile, Y+ or E+). The result
of electrophilic aromatic substitution reactions is that an aromatic hydrogen (ArH) is replaced by some
other atom or functional group (ArY).
ArH + Y+ ArY + H+
Benzene is very unreactive 1) It combines only with very reactive (usually cationic) electrophiles
2) It gives substitution and not addition products
Like an alkene, the double bonds of benzene are nucleophilic and will react with electrophiles (e.g., X2, NO2+,
SO3, RX+, and RCO+). But unlike alkene reactions, the outcome is a substitution and not an addition.
Reaction of benzene with an electrophile- Because the aromatic product is more stable, the reaction
proceeds as (a) an electrophilic substitution reaction rather than (b) an electrophilic addition reaction.
H
+ H
H
Slow E
+ E+
E -H+
Fast
Sigma Intermediate
H H H
+ H H H
E E E
+ +
Resonating structures of sigma complex (carbocation)
Reaction coordinate diagrams for electrophilic substitution of benzene and electrophilic addition to benzene is
shown below.
Because electrophilic substitution of benzene involves the reaction of an electrophile with an aromatic compound,
it is more precisely called an electrophilic aromatic substitution reaction. In an electrophilic aromatic
substitution reaction, an electrophile substitutes for a hydrogen of an aromatic compound.
An electrophilic aromatic substitution reaction

The following are the five most common electrophilic aromatic substitution reactions:
1. Halogenation: A bromine (Br), a chlorine (Cl), or an iodine (I) substitutes for a hydrogen.
2. Nitration: A nitro (NO2) group substitutes for a hydrogen.
3. Sulfonation: A sulfonic acid (SO3H) group substitutes for a hydrogen.
4. Friedel–Crafts acylation: An acyl (RCO) group substitutes for a hydrogen
5. Friedel–Crafts alkylation: an alkyl (R) group substitutes for a hydrogen.
All of these electrophilic aromatic substitution reactions take place by the same way & involve two-step
mechanism. In the first step, benzene reacts with an electrophile (E +) forming a carbocation intermediate called
as σ-complex or Wheland intermediate or arenium ion. The structure of the σ-complex formed
(carbocation intermediate) is stabilized by three resonance contributors. However it is not as stable as the initial
aromatic system.
In the second step of the reaction, a conjugate base in the reaction mixture pulls off a proton from the
carbocation intermediate, and the electrons that held the proton move into the ring to reestablish its aromaticity.
Notice that the proton is always removed from the carbon that has formed the new bond with the electrophile.
H
+ H
H
Slow E
+ E+
E -H+
Fast
Sigma Intermediate
H H H
+ H H H
E E E
+ +
Resonating structures of sigma complex (carbocation)
The first step is relatively slow and endergonic because an aromatic compound is being converted into a much
less stable nonaromatic intermediate The second step is fast and strongly exergonic because this step restores
the stability enhancing aromaticity.
We will look at each of these five electrophilic aromatic substitution reactions individually.
As you study them, notice that they differ only in how the electrophile needed to start the reaction. Once the
electrophile is formed, all five reactions follow the same two-step mechanism for electrophilic aromatic
substitution.
Cl NO2
Cl2 + AlCl3 HNO3 + H2 SO4
SO3 + H2 SO4 SO3H
Br
Br2 + AlCl3
COR
RCOCl + AlCl3
OR (CH3 CO)O + AlCl3
I I2 + HNO3 RCl + AlCl3 R
OR I2 + CuCl2 OR ROH + H2 SO4
Reaction Reagents Electrophile Product
Br2 / FeBr3 Br+

Br
Halogenation Cl2 / FeCl3 Cl+

Cl
I2 / CuCl2 I+
I
Nitration HNO3/H2SO4 NO2+

NO2
Sulfonation SO3/ H2SO4 SO3

SO3H
Alkylation R-Cl / AlCl3 R+

R
Acylation RCOCl / AlCl3 RCO+ O

C R
A) Nitration of benzene:-
Nitration converts aromatic compounds (ArH) into nitrobenzenes (ArNO2) using NO2+ from HNO3 + H2SO4 .
Benzene undergo nitration when it is heated with nitrating mixture at about 50 0C to give nitrobenzene.( Nitrating
mixture consist of HNO3 & H2SO4 in the 1:2 proportion.) Nitration of benzene firstly involves the formation of a
very powerful electrophile, the nitronium ion (NO2+ ), which is linear. Second step involves loss of proton to
retain aromatisation of benzene.
Reaction:-
NO2
Conc. H2SO4
+ HNO3 + H2O
Conc.
Benzene Nitrobenzene
Mechanism:-
B) Sulfonation of benzene:-
Sulfonation with H2SO4 or SO3 in H2SO4 converts aromatic compounds (ArH) into aromatic sulfonic acids
(ArSO2OH). Benzene undergoes sulphonation when it is heated with fuming sulphuric acid or oleum (SO3
dissolved in concentrated H2SO4) at 373K to give benzene sulphonic acid.
The electrophile is SO3 or SO3H+. Benzene reacts slowly with sulfuric acid alone to give benzenesulfonic acid.
Second step involves loss of proton to retain aromatisation of benzene
Reaction:-
SO3H
fuming H 2SO4
+ H2SO4
+ H2O
Benzene Benzene sulphonic acid
Mechanism:-
Sulfonation of benzene is a reversible reaction. If benzenesulfonic acid is heated in dilute acid, the reaction
proceeds in the reverse direction.
+ 0
SO3H H3O 100 C H
C) Halogenation of Benzene:- Halogenation converts aromatic compounds (ArH) into halobenzenes (ArX)
using X+ from X2 & Lewis acid (bromination or chlorination). The bromination or chlorination of benzene
requires a Lewis acid such as ferric bromide or ferric chloride. Chlorination of benzene occur by same mechanism
as bromination as shown below
Br
FeBr3
+ Br2 + HBr + FeBr3
Benzene Bromobenzene
Cl
AlCl3
+ Cl2 + HCl + AlCl3
Benzene Chlorobenzene
Role of Lewis acid (AlCl3 , FeCl3 , FeBr3 etc ) in Halogenation of Benzene:- Without lewis acid benzene
do not react with halogen because halogens alone are weak electrophiles & to convert them into strong
electrophile, it needs lewis acid as a catalyst as shown below.
Ferric bromide and other Lewis acids enhance the electrophilic strength of bromine by forming a complex anion ,
in this case FeBr4 . At the same time, this complexation creates the strongly electrophilic bromine cation, (Br+)
which react with nucleophile (Benzene).
Iodination :- Iodination differ than bromination or chlorination of benzene. Iodine is unreactive and requires
an oxidizing agent such as CuCl2 or nitric acid for the generation of the electrophilic iodine cation I+.
HNO3 OR CuCl2
+ I2
HNO3 OR CuCl2
+
I2 2I
Mech:-
+ H
+ I
+ I -H
+ I
D) Friedel-Crafts acylation
Friedel–Crafts acylation converts aromatic compounds (ArH) into aryl ketone (ArCOR) using stable acylium ion
(RCO+) from acid chlorides (RCOCl) or acid anhydride [(RCO)2O] & Lewis acid (usually AlCl3). In second step
halide ion removes the proton from the cationic intermediate restoring aromaticity.
H3C O
O AlCl3
+ H3C Cl + HCl + AlCl3
H3C O
O O
AlCl3
+ H3C O CH3
+ CH3COOH + AlCl3
Mech-
Because the product of a Friedel–Crafts acylation reaction contains a carbonyl group that can complex with AlCl 3
so Friedel–Crafts acylation reactions must be carried out with more than one equivalent AlCl 3 of When the
reaction is over, water is added to the reaction mixture to liberate the product from the complex
AlCl3
+O O
R 3 H2O R
+ Al(OH)3 + 3 HCl
E) Friedel-Crafts alkylation:-
Friedel-Crafts alkylation converts aromatic compounds (ArH) into an alkyl benzene (ArR) like methyl benzene,
ethyl benzene etc. using (R+) (i.e. carbocation intermediate , which can rearrange) obtain from an alkyl halide &
Lewis acid (usually AlCl3)
anhydrous AlCl3
+ R Cl + HCl + AlCl3
Benzene Alkyl benzene
CH3
anhydrous AlCl3
+ CH3Cl + HCl + AlCl3
Benzene Toluene
CH2CH3
anhydrous AlCl3
+ CH3 CH2 Cl
+ HCl + AlCl3
Benzene Ethyl chloride

Ethyl benzene
CH3
H3CCCH3
CH3
anhydrous AlCl3
+ H3C Cl + HCl + AlCl3
CH3
Benzene t-butyl chloride

t-butyl benzene
In addition to this, carbocations can be generated from the reaction of an alkene or an alcohol with an acid as
shown below
F) Alkylation of benzene by an alkene

CH3
CHCH2CH3
HF
+ H3CCH CHCH3
Alkylation of benzene by an alcohol

CH3
H2SO4 CHCH3
+ H3CCHCH3
OH
Limitations to Friedel-Crafts alkylation
1. Only alkyl halides can be used (i.e., not vinyl or aryl halides).
2. Polyalkylation :- It is difficult to stop at monosubstitution. Because unlike Nitration, Sulfonation, Halogenation &
Friedel–Crafts acylation the Friedel–Crafts alkylation reaction involve substitution of alkyl group which electron
donating in nature & make more reactive towards electrophile & hence alkyl-substituted benzene is more reactive
than benzene & hence further alkylation is also possible leading to formation of poly alkylated products i.e.
polyalkylation. Therefore, to prevent further alkylation of the alkyl-substituted benzene, a large excess of benzene
is used in Friedel–Crafts alkylation reactions. This approach ensures that the electrophile is more likely to
encounter a molecule of benzene than a molecule of alkyl-substituted benzene.
3. Rearrangement :- Since a carbocation is involved, rearrangements may occur, particularly if primary alkyl
halides are involved. These carbocation rearrangements can occur either by hydride shifts or alkyl shifts. When
the carbocation can rearrange in a Friedel–Crafts alkylation reaction, the major product will be the product with
the rearranged alkyl group on the benzene ring.
E.g of Rearrangement of carbocation Friedel–Crafts alkylation
Unrearranged product( 35% ) Rearranged product ( 65% )
CH3
0 CH2CH2CH2CH3
AlCl3 , 0 C CHCH2CH3
+ CH3CH2CH2CH2Cl
+
Benzene 1 -chlorobutane
1 -phenylbutane 2 -phenylbutane
AlCl3 ,
+ 1,2 hydride shift +

CH3CH2CHCH2 CH3CH2CHCH3
H
primary carbocation secondary carbocation
CH3
CH3
CH3 0
CH2CCH3
AlCl3 , 0 C CCH2CH3
+ CH3CCH2Cl +
CH3
CH3
CH3
Unrearranged product ( 0 % ) Rearranged product ( 100 % )

AlCl3 ,
CH3 CH3
+ 1,2 -methyl shift
CH3 C CH2 CH3 C CH2CH3
+
CH3
primary carbocation tertiary carbocation
 Diazotization
Nucleophilic substitution on Benzene is quite difficult but it can be easily carried out by Arenediazonium Salts this
is because a very stable N2 gas is leaving group of Arenediazonium Salts can be easily displaced by wide variety
of nucleophiles.
+
N N Cl Nu
Nu
+ N2 + Cl
Benzenediazonium
chloride
A primary amine can be converted into a diazonium salt by treatment with nitrous acid (HNO2). Because nitrous
acid is unstable, it is formed in situ, using an aqueous solution of sodium nitrite and HCl or HBr; indeed N2, is
such a good leaving group so far that the diazonium salt is synthesized at 0 °C and used immediately without
isolation
+
NH2 N N Cl
NaNO2,HCL
O
O C
Nucleophiles such as Br- , Cl- and -C N-, will replace the diazonium group if the appropriate cuprous salt is added
to the solution containing the arenediazonium salt. The reaction of an arenediazonium salt with a cuprous salt is
known as a Sandmeyer reaction.
Sandmeyer reaction.
+
N N Cl Br
CuBr + N2
Bromobenzene
+
N N Cl Cl
CuCl + N2
Chlorobenzene
+
N N Cl CN
CuCN + N2
Benzonitrile
Note:- KCl and KBr cannot be used in place of CuCl and CuBr in Sandmeyer reactions.
But iodo substituent will replace the diazonium group if potassium iodide (KI) is added to the solution containing
the diazonium ion.
+
N N Cl I
KI
+ N2 + KCl
Iodobenzene
Fluoro substitution occurs if the arenediazonium salt is heated with fluoroboric acid (HBF4). This reaction is
known as the Schiemann reaction.
+
N N Cl F
HBF4 + N2 + HCl + BF3
Flurobenzene
Some other Reaction of Arenediazonium Salts
+ NaHSO3
N N Cl NHNH2 synthesis of phenylhydrazine
Reduction
+ KSH
N N Cl SH synthesis of Thiophenol
+
CH3OH
N N Cl OMe synthesis of Ether
+ OH
N N Cl N N OH
+ Y Diazo coupling
N N Cl N N Y Reaction
Where Y= -NH2 , -NHR, -NR2

Aromaticity

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Aromaticity

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Chapter Aromtic Compounds

 Molecular formula = C6H6 & Empirical formula = CH

Experiment involve following reactions & values for Hydrogenation,

Cyclohexatriene Hypothetical Cyclohexane

 The ∆ H0 for the hydrogenation of cyclohexene, = ∆ H0 = -28 kcal/mol ( Experimental )

 5.2 Aromaticity, introduction:-

In order for a molecule to be aromatic, it must obey following characteristics:

Dilfference between aromatic and aliphatic compounds.

Sr.No. Aromatic compounds Aliphatic compounds

 The term annulene refers to completely conjugated monocyclic polyenes OR

[4] -Annulene [ 6] -Annulene tub shaped (non planer)

[10]Annulenes—1,3,5,7,9-Cyclodecapentaene Isomers:- According to the Hückel rule, [10]annulene

Both internal hydrogen

[14],Annulenes:- [14]Annulene is a Nonaromatic as steric interactions associated with internal hydrogens

[12] Annulenes Z,E,E,Z,E,Z,E Z,E,Z,E,Z,Z,

[16] Annulenes [18] Annulenes

 Fused Benzene Ring Compounds

 Fused nonbenzenoid systems

(C) Very Unstable (D) Very Unstable

 Aromaticity in Charged Rings :- Conjugated Cyclic Cations and Anions

A is non aromatic as one of the carbon is sp3 hybridized

B is aromatic & obey all the necessary condition required for

D is non aromatic as one of the carbon is sp 3 hybridized

E is antiaromatic & obey all the necessary condition required for

E F F is aromatic & obey all the necessary condition required for

G is non aromatic as one of the carbon is sp 3 hybridized

H is aromatic & obey all the necessary condition required for

I is nonaromatic as being not flat.

Hückel’s Rule Relationships for Charged Species

Sr. Compound No. of π Value of n Nature

Orbital structure of pyrrole Orbital structure of furan

2. Six-membered systems containing aromatic sextet

Orbital structure of pyridine

3. Other Aromaticity of heterocycles

Flurobenzene iodobenzene ethylbenzene nitrobenzene

NH2 OH OMe SO3 H CH CH2

benzaldehyde benzoic acid benzonitrile

CH3CHCH3 CH3CHCH2CH3 H3C CCH3

Isopropylbenzene sec-butylbenzene tert-butylbenzene

a phenyl group a benzyl group

H3C CHCH2CH2CH2CH3 H3CH2C CH2CH2CH2CH3

2-phenylhexane 3-phenylhexane diphenyl ether

benzyl chloride benzyl chloride dibenzyl ether

Nomenclature of Disubstituted Benzenes

o-xylene CH3 pyrocatechol

 Electrophilic Aromatic Substitution

An electrophilic aromatic substitution reaction

4. Friedel–Crafts acylation: An acyl (RCO) group substitutes for a hydrogen

5. Friedel–Crafts alkylation: an alkyl (R) group substitutes for a hydrogen.

SO3 + H2 SO4 SO3H

OR (CH3 CO)O + AlCl3

I I2 + HNO3 RCl + AlCl3 R

OR I2 + CuCl2 OR ROH + H2 SO4

Reaction Reagents Electrophile Product

Br2 / FeBr3 Br+

Halogenation Cl2 / FeCl3 Cl+

Nitration HNO3/H2SO4 NO2+

Sulfonation SO3/ H2SO4 SO3

Alkylation R-Cl / AlCl3 R+

Acylation RCOCl / AlCl3 RCO+ O

Benzene Benzene sulphonic acid

Benzene Alkyl benzene

Benzene Ethyl chloride