CY 1001: Organic Chemistry

Aromaticity: (4 classes + 1 tutorial) By Dr. Beeraiah Baire

Aromatic, non-aromatic and anti-aromatic compounds. Basic concepts of NMR
spectroscopy; Annulenes.

Aromatic substitution reactions: (3 classes + 1 tutorial) By Prof. G. Sekar

Aromatic nucleophilic substitution reactions.
Applications briefly: production of Ibuprofen and paracetamol. Application of
Sangers reagent.
Definition, classifications, electrocyclic reactions of butadiene and hexatriene.

Pericyclic reactions: (4 classes + 1 tutorial) By Dr. P. Anbarasan

photochemical [2+2] and thermal [4+2] cycloadditions, Sigmatropic
rearrangements – limited to Cope and Claisen rearrangements, FMO approach –
Woodward Hoffmann rules and basic stereochemistry aspects of the above
reactions.
CY 1001: Organic Chemistry

Dr. BB
27/04/2021 (13:00-13:50) Tuesday
28/04/2021 (13:00-13:50)
29/04/2021 (11:00-11:50)
30/04/2021 (10:00-10:50, 11:00-11:50 tutorial)

Prof. G. Sekar
3/05/2021 (08:00-08:50, 09:00-09:50)
4/05/2021 (08:00-08:50, 13:00-13:50 tutorial)

Dr. Anbarasan
5/05/2021 (13:00-13:50)
6/05/2021 (11:00-11:50)
7/05/2021 (10:00-10:50, 11:00-11:50)
10/05/2021 (08:00-08:50 tutorial)
 Text Books:

1. Advanced Organic Chemistry, Part A by F. A. Cary and R. I. Sundberg, 5th

Edition, Springer, 2009.

2. Organic Chemistry by Robert Thornton Morrison and Robert Neilson Boyd, 6th
Edition, Pearson

3. Organic Chemistry by Paula Yurkanis Bruice, 3rd Edition, Pearson.

4. Introduction to spectroscopy, Pavia, 4th Edition, Science Publisher, 2015.

5. Organic Chemistry by J Clayden, N Greeves and S Warren, 2nd Edition 2012,

Oxford University Press.
 Broad Classification of Hydrocarbons

Aliphatic compounds: open-chain compounds and ring compounds

that are chemically similar to open-chain compounds.
Alkanes, alkenes, alkynes, dienes, alicyclics, etc.

Aromatic compounds: unsaturated ring compounds that are far

more stable than they should be and exhibit special chemical
properties
i.e., resist the addition reactions typical of unsaturated aliphatic
compounds.
Benzene and related compounds.
 Aromaticity and Aromatic Compounds
Aromaticity: Extra stability possessed by a molecule that meets specific
criteria
 Aromaticity and Aromatic Compounds
•In the nineteenth century, many compounds having properties
similar to those of benzene were isolated from natural sources.
Since these compounds possessed strong and characteristic
odors, they were called aromatic compounds. It should be noted,
however, that it is their chemical properties, and not their odor,
that make them special.

6
 Benzene
• Benzene (C6H6) is the simplest aromatic hydrocarbon (or
arene).
• Isolated in 1825 by Michael Faraday
• Benzene has four degrees of unsaturation by formula,
making it a highly unsaturated hydrocarbon.
• Unsaturated hydrocarbons such as alkenes, alkynes and
dienes readily undergo addition reactions, benzene does not.
 Reagent Cyclohexene Benzene

KMnO4 oxidation no reaction

Br2/CCl4 addition no reaction
HI addition no reaction
H2/Ni reduction no reaction

• Benzene does react with bromine, but only in the presence of FeBr3
(a Lewis acid), and the reaction is a substitution, not an addition.
 Reactions of benzene: substitutions

1. Nitration
C6H6 + HNO3, H2SO4  C6H5NO2 + H2O
2. Sulfonation
C6H6 + H2SO4, SO3  C6H5SO3H + H2O
3. Halogenation
C6H6 + X2, Fe  C6H5X + HX
4. Freidel-Crafts alkylation
C6H6 + RX, AlCl3  C6H5R + HX
Any Proposed structures of benzene must account for

1. a six-membered ring and three additional degrees of

unsaturation.
2. Planar.
3. From X-ray All C—C bond lengths are equal (1.39 Å) , and
intermediate in length between single (1.54 Å) and double
bonds (1.34 Å) .

In addition,
Its lack of reactivity towards electrophilic addition.

11
• August Kekulé 1866 proposed that benzene was a rapidly
equilibrating mixture of two compounds, each containing a six-
membered ring with three alternating  bonds.
• In the Kekulé description, the bond between any two carbon atoms
is sometimes a single bond and sometimes a double bond.

• These structures are known as Kekulé structures.

Drawbacks
• Although benzene is still drawn as a six-membered ring with
alternating  bonds, in reality there is no equilibrium between the
two different kinds of benzene molecules.
The Kekulé structures satisfy the first two criteria but not the third,
because having three alternating  bonds means that benzene
should have three short double bonds alternating with three longer
single bonds.

Kekulé di-Substituted benzenes

13
 New representation
• Later he proposed the structure of benzene as a resonance hybrid
of the two Lewis structures, with the dashed lines of the hybrid
indicating the delocalization of the  bonds. This fits well with the
requirements
• We will use one of the two Lewis structures and not the hybrid in
drawing benzene. This will make it easier to keep track of the
electron pairs in the  bonds (the  electrons).
• Because each  bond has two electrons, benzene has six 
electrons.

15
• In benzene, the actual bond length (1.39 Å) is intermediate
between the carbon—carbon single bond (1.53 Å) and the
carbon—carbon double bond (1.34 Å).

16
Stability of Benzene and Aromaticity
• Consider the heats of hydrogenation of cyclohexene, 1,3-
cyclohexadiene and benzene, all of which give cyclohexane when
treated with excess hydrogen in the presence of a metal catalyst.

17
 Delocalization Energy

• The low heat of hydrogenation of benzene means that benzene is

especially stable—even more so than conjugated polyenes. This
unusual stability is characteristic of aromatic compounds.

18
 Delocalization Energy

The huge difference between the hypothetical and observed heats of

hydrogenation for benzene cannot be explained solely on the basis
of resonance and conjugation but by delocalization.

19
Delocalization Energy

20
The Criteria for Aromaticity—Hückel’s Rule
Four structural criteria must be satisfied for a compound to be
aromatic.

[1] A molecule must be cyclic.

To be aromatic, each p orbital must overlap with p orbitals on

adjacent atoms.
21
The Criteria for Aromaticity—Hückel’s Rule
Four structural criteria must be satisfied for a compound to be
aromatic.

[1] A molecule must be cyclic.

To be aromatic, each p orbital must overlap with p orbitals on

adjacent atoms.
22
[2] A molecule must be planar.

All adjacent p orbitals must be aligned so that the  electron

density can be delocalized.

Since cyclooctatetraene is non-planar, it is not aromatic, and it

undergoes addition reactions just like those of other alkenes.

23
[3] A molecule must be completely conjugated.
Aromatic compounds must have a p orbital on every atom.

24
[4] A molecule must satisfy Hückel’s rule, and contain
a particular number of  electrons.
Hückel's rule:

Benzene is aromatic and especially stable because it contains

6  electrons. Cyclobutadiene is antiaromatic and especially
unstable because it contains 4  electrons.

25
Note:
Hückel’s rule refers to the number of  electrons, not the
number of atoms in a particular ring.

Eg. Furan, thiophene, pyrrole, cyclopentadienylanion,

cycloheptatrienyl cation
26
Considering aromaticity, a compound can be classified in one
of three ways:

1. Aromatic—A cyclic, planar, completely conjugated compound

with 4n + 2  electrons.
2. Antiaromatic—A cyclic, planar, completely conjugated compound
with 4n  electrons.
3. Not aromatic (nonaromatic)—A compound that lacks one (or
more) of the following requirements for aromaticity: being cyclic,
planar, and completely conjugated.

27
Note the relationship between each compound type and a similar open-
chained molecule having the same number of  electrons.

28
 Benzene and Aromatic Compounds
The Basis of Hückel’s Rule:

• Why does the number of  electrons determine whether a

compound is aromatic?
• The basis of aromaticity can be better understood by
considering orbitals and bonding.

29
 Benzene and Aromatic Compounds
Molecular Orbitals:
• Molecular orbital (MO) theory permits a better explanation of
bonding in aromatic systems.
• When forming molecular orbitals from atomic orbitals, keep in
mind that a set of n atomic orbitals forms n molecular orbitals.
• If two atomic orbitals combine, two molecular orbitals are
formed.
• Recall that aromaticity is based on p orbital overlap.
• Also note that the two lobes of each p orbital are opposite in
phase, with a node of electron density at the nucleus.
• When two p orbitals combine, two molecular orbitals should
form.

30
 Benzene and Aromatic Compounds
Molecular Orbitals:
• The combination of two p orbitals can be
• constructive: with like phases reinforcing, or
• destructive: with opposite phases cancelling.

• When two p orbitals of similar phase overlap side-by-side, a 

bonding molecular orbital results.
• When two p orbitals of opposite phase overlap side-by-side, a
* antibonding orbital results. 31
 Benzene and Aromatic Compounds
Molecular Orbitals:

32
 Benzene and Aromatic Compounds
Molecular Orbitals of Benzene:

• Since each of the six carbon atoms of benzene has a p orbital,

six atomic p orbitals combine to form six  molecular orbitals

• The six MOs are labeled 1- 6, with 1 being the lowest energy
and 6 being the highest.

• A greater number of bonding interactions gives a lower MO

energy.

• A greater number of nodes, gives a higher MO energy.

33
 Benzene and Aromatic Compounds
Molecular Orbitals of Benzene:

• Three of the MOs are lower in energy than the starting p

orbitals, and are bonding MOs, whereas three of the MOs are
higher in energy than the starting p orbitals, and are antibonding
MOs.
• The two pairs of MOs with the same energy are called
degenerate orbitals.

• The highest energy orbital that contains electrons is called the

highest occupied molecular orbital (HOMO).

• The lowest energy orbital that does not contain electrons is

called the lowest unoccupied molecular orbital (LUMO).
34
 Benzene and Aromatic Compounds
Molecular Orbitals of Benzene:

To fill the MOs, the six

electrons are added,
two to an orbital. The
six electrons completely
fill the bonding MOs,
leaving the anti-bonding
MOs empty.

All bonding MOs (and

HOMOs) are completely
filled in aromatic
compounds. No  electrons
occupy antibonding MOs.

35
 6

4 5

six p-orbitals 2 3

1

Degenerate orbitals:
orbitals that have the 1: zero nodes
Bonding
same energy 2 and 3: one node

4 and 5: two nodes

Anti-bonding
6: three node

36
36
 Benzene and Aromatic Compounds
The Inscribed Polygon Method of Predicting Aromaticity

37
 Benzene and Aromatic Compounds
The Inscribed Polygon Method of Predicting Aromaticity

38
 Benzene and Aromatic Compounds
The Inscribed Polygon Method of Predicting Aromaticity

• This method works for all monocyclic completely conjugated

systems regardless of ring size.
• The total number of MOs always equals the number of vertices of
the polygon.
• This method is consistent with Hückel's 4n + 2 rule, there is always
one lowest energy bonding MO that can hold two  electrons and
the other bonding MOs come in degenerate pairs that can hold a
total of four  electrons. 39
 Benzene and Aromatic Compounds
The Inscribed Polygon Method of Predicting Aromaticity

The inscribed polygon method for five- and seven-membered rings

40
For the compound to be aromatic, these bonding MOs must be
completely filled with electrons, so the “magic numbers” for aromaticity
fit Hückel’s 4n + 2 rule.

MO patterns for cyclic, completely conjugated systems

41
Cyclopropenyl cation

H 2 3
4n+2=2
1 n=0
H H
aromatic
cyclopropenyl cation
2 -electrons
Cyclopentadienyl cation
H
4 5
H H 4n=4
2 3 n=1
H H
anti-aromatic
cyclopentadienyl cation 1
4 -electrons

Cycloheptatrienyl cation
6 7
H H
4 5 4n+2=6
H H
n=1
2 3
H H aromatic
H 1
cycloheptatrienyl cation
6 -electrons 42
Cyclopropenyl anion
H H H
+ B: + B:H
4n=4
H H H H
n=1
cyclopropenyl anion
anti-aromatic
4 -electrons

2 3

1

Cyclopentadienyl anion
H H H
H H H H
+ B: + B:H
4n+2=6
H H H H
n=1
p Ka ~ 16 cyclopentad ienyl anion
aromatic
6 -electrons
4 5

2 3
1 43
 Benzene and Aromatic Compounds
The Inscribed Polygon Method of Predicting Aromaticity

44
Resonance Energy (Kcal/mol)
 Aromatic compounds and Ions
2 - pi electron system

Cyclopropenyl
cation

6- pi electron system

14 - pi electrons system
Cyclopentadienyl Benzene cycloheptatrienyl
anion cation (tropylium ion)

N O S Phenanthrene
N H
Pyridine pyrrole furan thiophene
18 - pi electrons system

10 - pi electrons system

N
H
Naphtheline Azulene Indole Chrysene
 Anti-aromatic compounds and Ions
4 – pi electron system

cyclobutadiene cyclopropenyl
anion Cyclopentadienyl
cation

8 – pi electron system

cyclooctatetraene cycloheptatrienyl Pentalene

anion

12 – pi electron system

heptalene
Some common observations on compounds
H Cl H
+ AgBF4 BF4 + AgCl
H H H H

H Cl H

H H H H
+ AgBF4 BF4 + AgCl
H H H H

H H H
pKa ~ 16
H H H H
+ H 2O + H 3O +
H H H H

H
H Br
H H H H

H H Br -
H H
H H 48
H H
 Benzene and Aromatic Compounds
Examples of Aromatic Rings:
• Heterocycles containing oxygen, nitrogen or sulfur, can also
be aromatic.
• With heteroatoms, one must determine whether the lone
pair is localized on the heteroatom or part of the
delocalized  system.
• An example of an aromatic heterocycle
is pyridine.

49
 Benzene and Aromatic Compounds
Examples of Aromatic Rings:
• Pyrrole is an aromatic heterocycle that contains a five-
membered ring with two  bonds and one nitrogen
atom.
• Pyrrole has a p orbital on every ring atom that overlaps,
so it is completely conjugated.
• Pyrrole has six  electrons—four from the  bonds and
two from the lone pair (obeys Huckel’s Rule).
• It is aromatic since it is cyclic, planar, completely
conjugated, and has 4n + 2  electrons.

50
 Benzene and Aromatic Compounds
Examples of Aromatic Rings:
• Imidazole is an aromatic heterocycle with two N atoms,
one which is similar to the N atom of pyridine, and the
other which is similar to the N atom of pyrrole. It is a
component of histidine
and histamine.

51
 Benzene and Aromatic Compounds
Examples of Aromatic Rings:
Both negatively and positively charged ions can be
aromatic if they possess all the necessary elements.

One can draw five equivalent resonance structures for the

52
cyclopentadienyl anion.
 Benzene and Aromatic Compounds
Examples of Aromatic Rings:
• Having the “right” number of electrons is necessary for a
species to be unusually stable by virtue of aromaticity.
• Thus, although five resonance structures can also be drawn
for the cyclopentadienyl cation and radical, only the
cyclopentadienyl anion has 6  electrons, a number that
satisfies Hückel’s rule.

53
 Benzene and Aromatic Compounds
Examples of Aromatic Rings:
• Cyclopentadiene is more acidic than many hydrocarbons
because its conjugate base is aromatic.
• The pKa of cyclopentadiene is 15, much lower (acidic) than
the pKa of any C—H bond discussed thus far.
• The cyclopentadienyl anion is both aromatic and
resonance stabilized, so it is a very stable base.
• Cyclopentadiene itself is not aromatic because it is not fully
conjugated.

54
 Benzene and Aromatic Compounds
Examples of Aromatic Rings:
• The tropylium cation is a planer carbocation with three
double bonds and a positive charge contained in a
seven-membered ring.
• Because the tropylium cation has three  bonds and no
other nonbonded electron pairs, it contains six 
electrons, thereby satisfying Hückel’s rule.

55
 Benzene and Aromatic Compounds
Examples of Aromatic Rings:
• Two or more six-membered rings with alternating double
and single bonds can be fused together to form
polycyclic aromatic hydrocarbons (PAHs).
• There are two different ways to join three rings together,
forming anthracene and phenanthrene.

56
 Benzene and Aromatic Compounds
Examples of Aromatic Rings:
• Completely conjugated rings larger than benzene are also
aromatic if they are planar and have 4n + 2  electrons.
• An annulene is a monocyclic hydrocarbon with alternating
double and single bonds.
• To name an annulene, indicate the number of atoms in the
ring in brackets and add the word annulene.

57
 Benzene and Aromatic Compounds
Examples of Aromatic Rings:
• [10]-Annulene has 10  electrons, which satisfies
Hückel's rule, but a planar molecule would place the two
H atoms inside the ring too close to each other. Thus, the
ring puckers to relieve this strain.
• Since [10]-annulene is not planar, the 10  electrons can’t
delocalize over the entire ring and it is not aromatic.

58
Which of the following is aromatic?

C is aromatic 10 pi electrons, 4(2)+2=10 and completely conjugated b/c lone

pair is in a p orbital.

59
Which of these is antiaromatic?

A B

D
C

B 8 pi electrons 4(2)=8

C and D as well, 8 and 4 respectively

60
11.23: Heterocyclic Aromatic Compounds (please read)
Heterocycle: any cyclic compound that contains ring atom(s)
other than carbon (N, O, S, P). Cyclic compounds that contain
only carbon are called carbocycles

N
N N
N N
N H O S S O
H
pyridine pyrrole imidazole furan thiophene thiazole oxazole

11.24: Heterocyclic Aromatic Compounds and Hückel's Rule

Pyridine: -electron structure resembles benzene (6 -electrons)
The nitrogen lone pair electrons are not part of the aromatic
system.

pyridine
61
Pyrrole: 6 -electron system similar to that of cyclopentadienyl
anion. There are four sp2-hybridized carbons with 4 p orbitals
perpendicular to the ring and 4 -electrons and a lone pair of
electrons in an unhybridized p2 orbital that is part of the
aromatic sextet

N
H

pKa ~ 5.2
+ H2O + H3O+
N N
H

pKa ~ -4
+ H2O + H3O+
N N
H H H
62
 Nomenclature of Benzene Derivatives
• To name a benzene ring with one substituent, name the
substituent and add the word benzene.

• Many monosubstituted benzenes have common names

which you must also learn.

64
• There are three different ways that two groups can be
attached to a benzene ring, so a prefix—ortho, meta, or
para—can be used to designate the relative position of the
two substituents.

ortho-dibromobenzene meta-dibromobenzene para-dibromobenzene

or or or
o-dibromobenzene m-dibromobenzene p-dibromobenzene
or 1,2-dibromobenzene or 1,3-dibromobenzene or 1,4-dibromobenzene
65
• If the two groups on the benzene ring are different,
alphabetize the names of the substituents preceding the
word benzene.
• If one substituent is part of a common root, name the
molecule as a derivative of that monosubstituted benzene.

66
For three or more substituents on a benzene ring:
1. Number to give the lowest possible numbers around the ring.
2. Alphabetize the substituent names.
3. When substituents are part of common roots, name the molecule as
a derivative of that monosubstituted benzene. The substituent that
comprises the common root is located at C1.

67
• A benzene substituent is called a phenyl group, and it can be
abbreviated in a structure as “Ph-”.

• Therefore, benzene can be represented as PhH, and phenol would be

PhOH.

68
• The benzyl group, another common substituent that contains a
benzene ring, differs from a phenyl group.

• Substituents derived from other substituted aromatic rings are

collectively known as aryl groups.

69
Give the IUPAC name for each compound.

PhCH(CH3)2 isopropylbenzene
OH

m-butylphenol

Br

2-bromo-5-chlorotoluene
Cl

70
Which structure matches the given name?

o-dichlorobenzene

Cl

Cl Cl Cl Cl
Cl

Br Cl
A B
C D

Cl

Cl

71
4-chloro-1,2-diethylbenzene

Cl Cl
Cl

Cl
A B C D

Cl

72
 R
E
S
O
N
A
N
C
E

For reading
 Conjugation For reading
a) The special stability provided by three or more adjacent,
parallel, overlapping p orbitals in same plane.

b) Aromatic molecules, by default, have conjugation. As it takes

a minimum of three, adjacent, overlapping p orbitals for
planarity, aromaticity requires a minimum of this for
conjugation. Aromaticity is like conjugation, but extra stable.

Aromaticity cannot exist without conjugation

However, conjugation can exist in a molecule without being aromatic.

Conjugation For reading
Conjugation For reading
Frequently asked Questions
Frequently asked Questions
Frequently asked Questions