Dr.
Hala Fouad Labib
Organic Chemistry
Aromaticity
Benzene
• Colorless liquid immiscible and lighter than water
and miscible with most organic solvents
• BP 80° and freezing points 5.5°C
• Benzene is a very stable compound and resists
electrophilic addition
Br2/CCl4
No reaction
Huckel’s rule for Aromatic compounds:-
• Planar monocyclic rings with a continuous systems of P-orbitals and 4n+2 =
p electrons are aromatic (where n= integer number 0,1,2,3….)
Requirements for a compound to be aromatic:
1) Should be planar
2) contains Sp2 hybridized carbons
3) 4n+2= p electrons (Obeys Huckel's rule)
4) contains continuous resonance (conjugation) = -=- =-
Example Sp2 hybridization
Planar
4n+2=6 4n=4 n=1
benzene
Conjugated
Therefore > Aromatic
Sp2 carbons
Example
Planar
4n+2=10 4n=8 n=2
naphthalene Conjugated
obeys huckel's rule
Therefore > Aromatic
not all Sp2 carbons
4n+2=4 4n=2 n=1/2
not Conjugated
H H Doesn't obeys huckel's rule
cyclopentadiene Not Aromatic
Sp2 carbons Sp2 carbons
Planar Planar
Conjugated Conjugated
obeys huckel's rule phenanthrene obeys huckel's rule
anthracene
4n+2=14 4n=12 n=3 4n+2=14 n=3
Therefore > Aromatic Therefore > Aromatic
Doesn't obey huckel's rule
4n+2=4 n=1/2
cyclobutadiene Not aromatic
The following rules are applied for nomenclature
1) Number 1 is given to the principal functional group which is usually
chosen according to the following order
COOH>SO3H>CHO>C=O>OH>NH2
2) Functional group is given number (1) as suffix
3) Other groups are named as prefixes and are arranged alphabetically.
COOH CH3 OH
NO 2 CH3
Br
OH NH2 I
3-bromo-4-hydroxybenzoic acid 4-amino-2-nitrotoluene 4-iodo-2-methylphenol
CH3 H2C CH3 H2C CH2 CH3 H3C CH3
CH
benzene methylbenzene ethylbenzene propylbenzene Isopropylbenzene
CH3
CH3 CH3
CH3 CH3
CH3
CH3
CH3 H3C CH3 CH3
CH3
1,2-dimethylbenzene 1,3-dimethylbenzene 1,4-dimethylbenzene 1,3,5-trimethylbenzene 1,2,3-trimethylbenzene
O-Xylene m-Xylene p-Xylene Sym-trimethyl benzene Viscinal-trimethyl benzene
CH2 CH
H2C CH CH2 HC CH CH3
HC C
Vinylbenzene Alkyl benzene 1-phenyl propene phenyl acetylene
Styrene 3-phenyl propene
NO 2 F
CH2
CH
biphenyl diphenyl methane
Br nitrobenzene fluorobenzene
Cl OH NH2
triphenylmethane
I Cl
M-chloroiodobenzene 1-bromo-4-chlorobenzene phenol aniline
OH Cl COCH 3 SO 3H CHO COOH
NO 2 Cl
2-nitrophenol 1,2-dichlorobenzene Acetophenone benzenesulfonic acid benzaldehyde benzoic acid
CH3
O 2N NO 2 NH2
NO 2 NH2
2,4,6-trinitrotoluene M-phenylene diamine
NO 2
NH2
Br
NO 2
2-bromoaniline
1,3-dinitrobenzene
Reactions of Aromatic compounds
Substitution reactions →Nucleophilic (Rare)
→ Electrophilic (Very common)
Electrophilic aromatic substitution reactions
General mechanism:
Step1: electrophile reacts with the 2 p e’s from the aromatic ring to form an
Arenium ion which is stabilized by resonance..
H E H E H E
Slow step + +
+
+E
Rate Determining Step
+
H E
Resonance hybrid
+
arenium ion ( complex)
Step2: Proton is removed and aromatic system regenerated
H E E
+ Fast step
+ H+
Exothermic
NO 2
C. HNO3
C. H2SO4 Nitro benzene "Nitration"
SO 3 H
F.H2SO4
(oleum) Benzene Sulfonic acid "Sulfonation"
Br
Electrophilic
Br2/FeBr3
Lewis acid Bromo benzene "Halogenation" Substitution
R-Cl
R Reactions
Alkyl benzene "Friedel-craft alkylation"
AlCl3
CH3COCl COCH 3
AlCl3 Acetophenone "Friedel-craft acylation"
O 2N
Nitration Irreversible HNO3
H2SO4
nitrobenzene
Mechanism H2SO4
+
H + HSO4
-
H NO 2 H NO 2
+ + -H2O +
O +H O NO2 "Nitronium Cation"
: H
Oxonium ion
"protonated HNO3"
O 2N H O 2N H O 2N H NO 2
+ +
NO2 + +
-H
Addition Elimination
+
Electrophilic Substitution of Substituted Benzene
G
EWG EDG
Negativity of benzene ring ↓ Negativity of benzene ring↑
Reactivity of benzene ring ↓ Reactivity of benzene ring↑
∴EWG are deactivating groups ∴EDG are activating groups
∴More concentration and higher
Temperature (drastic conditions)
EX: CHO, CO, COOH, NO2, SO3H EX: :NH 2, :OH, :NHCOCH3, :OCOCH3, R
M-directing groups O- and P- directing groups
CH3 CH3
CH3
HNO3 NO 2
1) +
H2SO4
Toluene
NO 2 OCH 3 OCH 3
OCH 3
O-Nitrotoluene P-Nitrotoluene
HNO3 NO 2
2) +
H2SO4
Anisole
NO 2 NO 2
NO 2
O-Nitro anisole P-Nitroanisole
H2SO4
3)
COCH 3
SO 3H COCH 3
Nitrobenzene
M-nitrobenzenesulfonic acid Cl2/AlCl3
4)
Acetophenone Cl
M-Chloroacetophenone
Thank You
