Organic Chemistry II / CHEM

252
Chapter 14 – Aromatic
Compounds
Bela Torok
Department of Chemistry
University of Massachusetts Boston
Boston, MA
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 Introduction
- Historical name, based on smell, no relation to sturcture
• Nomenclature of Benzene Derivatives
• Benzene is the parent name for some monosubstituted benzenes; the
substituent name is added as a prefix

• For other monosubstituted benzenes, the presence of the substituent results

in a new parent name

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 Introduction
• When two substituents are present their position may be indicated
by the prefixes ortho, meta, and para (o, m and p) or by the
corresponding numerical positions

• Dimethyl substituted benzenes are called xylenes

3
 Introduction
• Numbers must be used as locants when more than two
substituents are present
– The lowest possible set of numbers should be given to the
substituents
– The substituents should be listed in alphabetical order
– If one of the substituents defines a parent other than
benzene, this substituent defines the parent name and
should be designated position 1

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 Introduction
• The C6H5- group is called phenyl when it is a substituent
– Phenyl is abbreviated Ph or Φ
– A hydrocarbon with a saturated chain and a benzene ring is named by
choosing the larger structural unit as the parent
– If the chain is unsaturated then it must be the parent and the benzene is
then a phenyl substituent

• The phenylmethyl group is called a benzyl (abbreviated Bz)

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 Reactions of Benzenes
• Reactions of Benzene
• Even though benzene is highly unsaturated it does not undergo any of
the regular reactions of alkenes such as addition or oxidation

• Benzene can be induced to react with bromine if a Lewis acid catalyst is

present however the reaction is a substitution and not an addition
– Benzene produces only one monobrominated compound, which
indicates that all 6 carbon-hydrogen bonds are equivalent

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 Structure of Benzene
• The Kekule Structure for Benzene
• Kekule was the first to formulate a reasonable representation of benzene

Friedrich August Kekule von Stradonitz

• The Kekule structure suggests alternating double and single bonds
– Based on the Kekule structure one would expect there to be two
different 1,2-dibromobenzenes but there is only one
– Kekule suggested an equilibrium between these compounds to explain
this observation but it is now known no such equilibrium exists

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 Structure of Benzene
• The Stability of Benzene
• Benzene is much more stable than the cyclohexatriene
– A reasonable prediction for the heat of hydrogenation of hypothetical
cyclohexatriene is -360 kJ mol-1 (3 x cyclohexene, -120 kJ mol-1 )
– The heat of hydrogenation for benzene is -280 mol-1, 152 kJ mol-1
more stable than hypothetical cyclohexatriene
– This difference is called the resonance energy

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 Structure of Benzene
• Modern Theories of the Structure of Benzene
– The Resonance Explanation of the Structure of Benzene
• Structures I and ΙΙ are equal resonance contributors to the real
structure of benzene
– Benzene is particularly stable because it has two
equivalent and important resonance structures
– Each carbon-carbon bond is 1.39 Å, which is between the
length of a carbon-carbon single bond between sp2 carbons
(1.47Å) and a carbon-carbon double bond (1.33 Å)
– Often the hybrid is represented by a circle in a hexagon
(III)

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 Structure of Benzene
– The Molecular Orbital Explanation of the Structure of Benzene
• The carbons in benzene are sp2 hybridized with p orbitals on all 6 carbons
(a)
– The p orbitals overlap around the ring (b) to form a bonding molecular
orbital with electron density above and below the plane of the ring (c)

• There are six π molecular orbitals for benzene

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 Structure of Benzene
• Huckel’s Rule: The 4n+2π Electron Rule
• Planar monocyclic rings with a continuous system of p orbitals and 4n +
2π electrons are aromatic (n = 0, 1, 2, 3 etc)
– Aromatic compounds have substantial resonance stabilization
– Benzene is aromatic: it is planar, cyclic, has a p orbital at every
carbon, and 6 π electrons (n=1)
• There is a polygon-and-circle method for deriving the relative energies of
orbitals of a system with a cyclic continuous array of p orbitals
– A polygon corresponding to the ring is inscribed in a circle with one
point of the polygon pointing directly down
– A horizontal line is drawn where vertices of the polygon touch the
circle - each line corresponds to the energy level of the π MOs at
those atoms
– A dashed horizontal line half way up the circle indicates the
separation of bonding and antibonding orbitals

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 Structure of Benzene
Benzene has 3 bonding and 3 antibonding orbitals
All the bonding orbitals are full and there are no electrons in antibonding orbitals;
benzene has a closed shell of delocalized electrons and is very stable

Cyclooctatetraene has two nonbonding orbitals each with one electron

This is an unstable configuration; cyclooctatetraene adopts a nonplanar conformation
with localized p bonds to avoid this instability

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 Annulenes
– The Annulenes
• Annulenes are monocyclic compounds with alternating double and single
bonds
– Annulenes are named using a number in brackets that indicates the
ring size
– Benzene is [6]annulene and cyclooctatetraene is [8]annulene
– An annulene is aromatic if it has 4n+2π electrons and a planar
carbon skeleton
• The [14]and [18]annulenes are aromatic (4n+2, where n= 3,4)
– The [16] annulene is not aromatic

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 Annulenes
• The [10]annulenes below should be aromatic but none of them can be
planar
– 4 is not planar because of steric interaction of the indicated
hydrogens
– 5 and 6 are not be planar because of large angle strain in the flat
molecules

– Cyclobutadiene is a [4]annulene and is not aromatic

– It does not follow the 4n+ 2 rule and is highly unstable

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 Evidence of Electron Delocalization
NMR Spectroscopy: Evidence for Electron Delocalization in Aromatic Compounds

UV-Vis Spectroscopy

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 Aromatic Ions
• Cyclopentadiene is unusually acidic (pKa = 16) because it becomes the
aromatic cyclopentadienyl anion when a proton is removed
– Cyclopentadienyl anion has 6 π electrons in a cyclic, continuous π-
electron system, and hence follows the 4n + 2 rule for aromaticity

• Cycloheptatriene is not aromatic because its π electrons are not

delocalized around the ring (the sp3-hybrid CH2 group is an “insulator”)
– Lose of hydride produces the aromatic cycloheptatrienyl cation
(tropylium cation)

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Aromatic Ions

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Aromatic Ions

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 Anti- and Nonaromatic Compounds
– Aromatic, Antiaromatic, and Nonaromatic Compounds
• A comparison of cyclic annulenes with their acyclic counterparts provides
a measures of the stability conferred by aromaticity
– ring has lower π-electron energy than the open chain: aromatic
– ring has the same π-electron energy as the open chain: nonaromatic
– ring has higher π-electron energy than the open chain: antiaromatic
• Benzene and cylcopentadientl anion are aromatic
• Cyclobutadiene is antiaromatic
– Cyclooctatetraene, if it were planar, would be antiaromatic

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 Other Aromatic Compounds
• Other Aromatic Compounds
– Benzenoid Aromatic Compounds
• Polycyclic benzenoid aromatic compounds have two or more benzene
rings fused together

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Other Aromatic Compounds

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Alkadienes and Polyunsaturated Hydrocarbons
• Naphthalene can be represented by three resonance structures
– The most important resonance structure is shown below
– the 10 π electrons are delocalized; it has substantial resonance energy

• Pyrene has 16 π electrons, a non-Huckel number, yet is known to be

aromatic
– Ignoring the central double bond, the periphery of pyrene has 14 π
electrons, a Huckel number, and on this basis it resembles the aromatic
[14]annulene

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 Nonbenzenoid Aromatic Compounds
• Nonbenzenoid aromatic compounds do not contain benzene rings
– Examples are cyclopentadienyl anion and the aromatic annulenes
(except [6] annulene)
• Azulene has substantial resonance energy and also substantial separation
of charge, as shown in the electrostatic potential map

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 Fullerenes
– Fullerenes
• Buckminsterfullerene is a C60 compound shaped like a soccer ball with
interconnecting pentagons and hexagons
– Each carbon is sp2 hybridized and has bonds to 3 other carbons
– Buckminsterfullerene is aromatic
• Analogs of “Buckyballs” have been synthesized (e.g. C70)

Bioshpere

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Richard Buckminster Fuller
 Carbon Forms
• Forms of Carbon
Charcoal Graphite Diamond

• Fullerenes

Sir Harold W. Kroto Robert F. Curl Jr

Nobel Prize in Chemistry

1996

Richard E. Smalley 25
 Heterocyclic Aromatic Compounds
• Heterocyclic compounds have an element other than carbon in the ring
• Example of aromatic heterocyclic compounds are shown below
– Numbering always starts at the heteroatom

• Pyridine has an sp2 hybridized nitrogen

– The p orbital on nitrogen is part of the aromatic π system of the ring
– The nitrogen lone pair is not part of the aromatic system
– The lone pair on nitrogen is available to react so pyridine is basic

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 Heterocyclic Aromatic Compounds
• The nitrogen in pyrrole is sp2 hybridized and the lone pair is in the p
orbital
– This p orbital contains two electrons and is in the aromatic system
– The lone pair of pyrrole is part of the aromatic system and not
available for protonation; pyrrole is therefore not basic

• In furan and thiophene an electron pair on the heteroatom is also in a p

orbital which is part of the aromatic system

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Heterocyclic Aromatic Compounds

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