AROMATICITY

OBJECTIVES
At the end of this presentation. The class should be able to:
 Define Aromaticity
 Understand the Orbital Picture of Aromaticity
 Understand the structure of aromatic hydrocarbons
 Understand the general conditions for aromaticity and its
prediction in simple molecules (Huckels and Mobious rules)
 Be able to correctly identify aromatic, anti-aromatic and non-
aromatic compunds
 OUTLINE
 History
 Definition
 Structure and stability of benzene: molecular orbital theory
 Generalconditions for aromaticity and its prediction in
simple molecules – Huckel’s and Mobious rules
 Polygon Method
 Aromatic Ions
 Aromatic Heterocycles
 Examples
 References
 HISTORY

 1825 - Michael Faraday isolates “bicarburetted hydrogen” (C12H6) from liquid

residue in a cylinder of illuminating gas. [C = 6, H = 1]
 1834 - Mitscherlich prepares benzene (C6H6) from benzoic acid by heating
with CaO. Benzoic acid was prepared from gum benzoin resin from Styrax
benzoin.
 1865 - August Kekulé Proposes a cyclic structure for benzene with alternating
single and double bonds
 1869 - Ladenburg, a former student of Kekulé’s, objects to his mentor’s
formula for benzene because only one o-dibromobenzene is known, not two.
 1872 - Kekulé revises his theory, suggesting that the single bonds are changing
places with the double bonds.
 DEFINITION

 The property of certain planar cyclic conjugated

molecules, esp benzene, of behaving like unsaturated
molecules and undergoing substitution reactions rather
than addition as a result of delocalization of electrons in
the ring

https://www.chemcentral.com/aromaticity">aromaticity</a>
STRUCTURE AND STABILITY
OF BENZENE: MOLECULAR
ORBITAL THEORY
 Benzene reacts slowly with Br2 to give bromobenzene
(where Br replaces H)
 This is substitution rather than the rapid addition reaction
common to compounds with C=C, suggesting that in
benzene there is a higher barrier
McMURRY J. (2016).
CONT.

 The addition of H2 to C=C normally gives off about 118

kJ/mol – 3 double bonds would give off 356kJ/mol
 Two conjugated double bonds in cyclohexadiene add 2
H2 to give off 230 kJ/mol
 Benzene has 3 unsaturation sites but gives off only 206
kJ/mol on reacting with 3 H2 molecules
 Therefore it has about 150 kJ more “stability” than an
isolated set of three double bonds
 CONT.

McMURRY J. (2016).
CONT.

 All its C-C bonds are the same length: 139 pm — between
single (154 pm) and double (134 pm) bonds
 Electron density in all six C-C bonds is identical
 Structure is planar, hexagonal
 C–C–C bond angles 120°
 Each C is sp2 and has a p orbital perpendicular to the plane
of the six-membered ring
McMURRY J. (2016).
SOLOMONS G. AND FRYHLE C. (2011).
GENERAL CONDITIONS FOR AROMATICITY
AND ITS PREDICTION IN SIMPLE
MOLECULES – HUCKEL’S AND MOBIOUS
RULES

Rules:
 The carbons must be trigonal planar (sp2 hybridized)
 All
the bonds must be conjugated i.e alternating single and
double bonds
 The number of delocalized electrons must obey Huckel’s
rules
 Huckel’s Rule

 Hückel’s rule is concerned with compounds containing

one planar ring in which each atom has a p orbital as
in benzene. His calculations show that planar monocyclic
rings containing 4n + 2 π electrons, where n 0, 1, 2, 3,
and so on (i.e., rings containing 2, 6, 10, 14, . . . , etc., p
electrons), have closed shells of delocalized electrons like
benzene and should have substantial resonance energies
(Solomons G. and Fryhle C., 2011).
CONT.

 In other words, Hückel’s rule states that planar

monocyclic rings with 2, 6, 10, 14, . . . , delocalized
electrons should be aromatic.
CONT.

 Planar, cyclic molecules with 4 n  electrons are much

less stable than expected (antiaromatic). They will distort
out of plane and behave like ordinary alkenes
 4- and 8-electron compounds are not delocalized (single
and double bonds)
 Cyclobutadiene is so unstable that it dimerizes by a self-
Diels-Alder reaction at low temperature
 Cyclooctatetraene has four double bonds, reacting with
Br2, KMnO4, and HCl as if it were four alkenes
McMURRY J. (2016).
Aromatic
 Obeys all the rules

Anti-aromatic
Meetsthe first two rules but does not meet
Huckel’s Rule

Non-Aromatic
 Does not meet the first two rules but meets
Huckels rules
How to Diagram the Relative Energies of π
Molecular Orbitals in Monocyclic Systems Based
on Hückel’s Rule

Polygon Method
 We start by drawing a polygon corresponding to the number of carbons in the
ring, placing a corner of the polygon at the bottom.
 Next we surround the polygon with a circle that touches each corner of the
polygon.
 At the points where the polygon touches the circle, we draw short horizontal
lines outside the circle. The height of each line represents the relative energy of
each p molecular orbital.
 Next we draw a dashed horizontal line across and halfway up the circle. The
energies of bonding p molecular orbitals are below this line. The energies of
antibonding p molecular orbitals are above, and those for nonbonding orbitals are
at the level of the dashed line.
 Based on the number of π electrons in the ring, we then place electron arrows on
the lines corresponding to the respective orbitals, beginning at the lowest energy
level and working upward. In doing so, we fill degenerate orbitals each with one
electron first, then add to each unpaired electron another with opposite spin if it is
available.
SOLOMONS G. AND FRYHLE C. (2011).
 AROMATIC IONS
 The 4n + 2 rule applies to ions as well as neutral species
 Both the cyclopentadienyl anion and the
cycloheptatrienyl cation are aromatic
 The key feature of both is that they contain 6  electrons
in a ring of continuous p orbitals

McMURRY J. (2016).
Aromaticity of the
Cyclopentadienyl Anion
 1,3-Cyclopentadiene contains conjugated double bonds
joined by a CH2 that blocks delocalization
 Removal of H+ at the CH2 produces a cyclic 6-electron
system, which is stable
 Removal of H- or H• generates nonaromatic 4 and 5
electron systems
 Relatively acidic (pKa = 16) because the anion is stable
McMURRY J. (2016).
 Cycloheptatriene
 Cycloheptatriene has 3 conjugated double bonds joined
by a CH2
 Removal of “H-” leaves the cation
 The cation has 6 electrons and is aromatic

McMURRY J. (2016).
AROMATIC HETEROCYCLES:
PYRIDINE AND PYRROLE
 Heterocyclic compounds contain elements other than
carbon in a ring, such as N,S,O,P
 Aromatic compounds can have elements other than
carbon in the ring
 There are many heterocyclic aromatic compounds and
many are very common
 Pyridine
 A six-membered heterocycle with a nitrogen atom in its ring 27
  electron structure resembles benzene (6 electrons)
 The nitrogen lone pair electrons are not part of the aromatic system
(perpendicular orbital)

McMURRY J. (2016).
 Pyrrole
 A five-membered heterocycle with one nitrogen
28
  electron system similar to that of cyclopentadienyl anion
 Four sp2-hybridized carbons with 4 p orbitals perpendicular to the ring and 4 p
electrons
 Nitrogen atom is sp2-hybridized, and lone pair of electrons occupies a p orbital
(6  electrons)
 Since lone pair electrons are in the aromatic ring, protonation destroys
aromaticity, making pyrrole a very weak base

McMURRY J. (2016).
 EXAMPLES
Cyclodecapentaene

4n + 2, non-planar; non-aromatic!
 Naphthalene and Azulene

4n + 2, planar; aromatic
 H H

H •• H
–

Furan, aromatic Thiophene, aromatic H

Cyclopentadienide Anion, Aromatic

Cyclopropenium cation, Aromatic

 REFERENCES
1. SOLOMONS G. AND FRYHLE C. (2011); ORGANIC CHEMISTRY, 10TH EDITION,
JOHN WILEY AND SONS INC., NEW JERSEY. PAGES 671 – 690.
2. McMURRY J. (2016); ORGANIC CHEMISTRY, 9TH EDITION, CENGAGE LEARNING,
BOSTON. PAGES 629 – 655.
QUESTIONS?