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FUNDAMENTAL SCIENCE –
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Topic 2.2 - Aromaticity
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Topic 2.2 - Aromaticity
• Aromatic Compounds - Introduction
• Structure of Benzene
• Nomenclature with Examples for aromatic
compounds and aromatic ions.
• The criterion for aromaticity including Huckel rule.
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Aromatic Compounds
• The term, Aromatic was used to described some
fragrant compounds in early 19th century
– Not correct: later they are grouped by chemical
behavior (unsaturated compounds that undergo
substitution rather than addition)
• Current: distinguished from aliphatic compounds
by electronic configuration
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Sources of Aromatic Hydrocarbons
• From high temperature distillation of coal tar
• Heating petroleum at high temperature and
pressure over a catalyst
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Benzene
First isolated by Michael Faraday in 1825
H
H C H
C C
C C
H C H
H
General Formula: C6H6
First isolated by Michael Faraday in 1825
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Resonance Structure
Each sp2 hybridized C in the ring has an
unhybridized p orbital perpendicular to
the ring which overlaps around the ring.
=>
Benzene’s Unusual Structure
• 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
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• Because each bond has two electrons, benzene has six
electrons.
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• 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).
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Reactions with Benzene
• Benzene (C6H6) is the simplest aromatic hydrocarbon (or
arene).
• Benzene is a highly unsaturated hydrocarbon.
• Whereas unsaturated hydrocarbons such as alkenes,
alkynes and dienes readily undergo addition reactions,
benzene does not.
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Reactions with Benzene
• 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
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Recall: Key Ideas on Benzene
• Unusually stable - heat of hydrogenation 150 kJ/mol less
negative than a cyclic triene
• Planar hexagon: bond angles are 120°, carbon–carbon
bond lengths 139 pm
• Undergoes substitution rather than electrophilic addition
• Resonance hybrid with structure between two line-bond
structures
• One more important factor is the number of electrons in
the cyclic orbital
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Naming Aromatic Compounds
• Many common names (toluene = methylbenzene;
aniline = aminobenzene)
• Mono-substituted benzenes systematic names as
hydrocarbons with –benzene
– C6H5Br = bromobenzene
– C6H5NO2 = nitrobenzene, and
C6H5CH2CH2CH3 is propylbenzene
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The Phenyl Group
• When a benzene ring is a substituent, the term
phenyl is used (for C6H5 )
– You may also see “Ph” or “f” in place of “C6H5”
• “Benzyl” refers to “C6H5CH2 ”
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Di-substituted Benzenes
• Relative positions on a
benzene ring
– ortho- (o) on adjacent
carbons (1,2)
– meta- (m) separated by
one carbon (1,3)
– para- (p) separated by
two carbons (1,4)
• Describes reaction
patterns (“occurs at the
para position”)
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Naming Benzenes With >2 Substituents
• Choose numbers to get lowest possible values
• List substituents alphabetically with hyphenated numbers
• Common names, such as “toluene” can serve as root
name (as in TNT)
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Naming Benzenes With >2 Substituents
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When is a Molecule Aromatic?
• For a molecule to be aromatic it must:
– Be cyclic, Be planar
– Have a p-orbital on every atom in ring
– Posses 4n+2 electrons (n = number of rings) i.e. 6,
10, 14 π electrons are aromatic
benzene naphthalene
Erich Hückel
phenanthrene
Aromaticity and the 4n + 2 Rule
• Huckel’s rule, based on calculations – a planar
cyclic molecule with alternating double and
single bonds has aromatic stability if it has 4n+ 2
electrons (n is 0,1,2,3,4)
• For n=1: 4n+2 = 6; benzene is stable and the
electrons are delocalized
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Aromatic Hydrocarbons
Aromatic Molecules?
• Are the following structures aromatic?
• Cyclic? P-Orbital? Planar? 4n+2 electrons?
Cycloheptarienyl Cycloheptarienyl
cation H anion H
+
C C
[14]-Annulene
Cyclobuta-
diene
No Yes No Yes
Compounds With 4n Electrons Are Not
Aromatic (May be Antiaromatic)
• Planar, cyclic molecules with 4 n
electrons are much less stable than
expected (anti-aromatic)
• They will distort out of plane and cyclobutadiene
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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
Aromatic
• Removal of H- or H• (very stable)
generate nonaromatic 4 and
5 electron systems
• Relatively acidic (pKa = 16)
because the anion is stable
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Cyclopentadienyl Anion
Acidic H
1,3-Cyclopentadiene
contains conjugated C=C’s
joined by a CH2 that blocks
delocalization
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Cycloheptatrienyl Cation
3 conjugated C=C’s
joined by a CH2
Removal of “H-”
leaves the cation
The cation has 6e-s
and is aromatic
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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
• Cyclic compounds that contain only carbon
are called carbocycles (not homocycles)
• Nomenclature is specialized
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Pyridine
• A six-membered heterocycle with a nitrogen atom
in its ring
• electron structure resembles benzene (6
electrons)
• The nitrogen lone pair electrons are not part of the
aromatic system (perpendicular orbital)
• Pyridine is a relatively weak base compared to
normal amines but protonation does not affect
aromaticity
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Pyrrole
• A five-membered heterocycle with one nitrogen
• 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
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Why 4n +2?
• When electrons fill various molecular orbitals, it
takes two electrons (one pair) to fill the lowest-
lying orbital and four electrons (two pairs) to fill
each of n succeeding energy level
• This is a total of 4n + 2
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Polycyclic Aromatic Compounds:
Naphthalene etc.
• Aromatic compounds can have rings that share
a set of carbon atoms (fused rings)
• Compounds from fused benzene or aromatic
heterocycle rings are themselves aromatic
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Naphthalene Orbitals
• Three resonance forms and delocalized electrons
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Aromatic Compounds in
Pharmaceuticals
HO O
CO 2H Me
N N
OH OEt HN
N Cl Cl
N
N
F
O
N
S
H O N
N O
N
O Me Cl
Cl
atorvastatin sildenafil miconazole
(Lipitor®) (Viagra®)
Spectroscopy of Aromatic
Compounds
• IR: Aromatic ring C–H stretching at 3030 cm1
and peaks 1450 to 1600 cm1
• UV: Peak near 205 nm and a less intense peak
in 255-275 nm range
• 1H NMR: Aromatic H’s strongly deshielded by
ring and absorb between a chemical shift () of
6.5 and 8.0
– Peak pattern is characteristic positions of
substituents
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Ring Currents
• Aromatic ring oriented perpendicular to a strong
magnetic field, delocalized electrons
producing a small local magnetic field
– Opposes applied field in middle of ring but
reinforces applied field outside of ring
– Results in outside H’s resonance at lower
field See spectrum in Figure
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13C NMR of Aromatic
Compounds
• Carbons in aromatic ring absorb at 110 to 140
• Shift is distinct from alkane carbons but in same
range as alkene carbons
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