John E.

McMurry

[Link]/chemistry/mcmurry

Chapter 15
Benzene and Aromaticity

Paul D. Adams • University of Arkansas

Aromatic Compounds
 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
 Why this Chapter?
 Reactivity of substituted aromatic compounds is
tied to their structure

 Aromatic compounds provide a sensitive probe

for studying relationship between structure and
reactivity
15.1 Sources and Names of
Aromatic Hydrocarbons
 From high temperature distillation of coal tar
 Heating petroleum at high temperature and pressure over
a catalyst
 Naming Aromatic Compounds
 Many common names (toluene = methylbenzene; aniline =
aminobenzene)
 Monosubstituted benzenes systematic names as
hydrocarbons with –benzene
 C6H5Br = bromobenzene
 C6H5NO2 = nitrobenzene, and C6H5CH2CH2CH3 is
propylbenzene
The Phenyl Group
 When a benzene ring is a substituent, the term
phenyl is used (for C6H5?)
 You may also see “Ph” or “” in place of “C6H5”
 “Benzyl” refers to “C6H5CH2?”
 Disubstituted 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”)

 Naming Benzenes with More Than
Two 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)
15.2 Structure and Stability of
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
 Heats of Hydrogenation as
Indicators of Stability
 The addition of H2 to C=C
normally gives off about 118
kJ/mol – 3 double bonds
would give off 354kJ/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
 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
 Drawing Benzene and Its
Derivatives
 The two benzene resonance forms can be represented by a single
structure with a circle in the center to indicate the equivalence of the
carbon–carbon bonds
 This does not indicate the number of  electrons in the ring but
reminds us of the delocalized structure
 We shall use one of the resonance structures to represent benzene
for ease in keeping track of bonding changes in reactions
Molecular Orbital Description of
Benzene
 The 6 p-orbitals combine to give
 Three bonding orbitals with 6  electrons,
 Three antibonding with no electrons
 Orbitals with the same energy are degenerate
15.3 Aromaticity and the Hückel
4n+2 Rule
 Unusually stable - heat of hydrogenation 150 kJ/mol less
negative than a hypothetical 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
Aromaticity and the 4n + 2
Rule
 Hückel’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
The Hückel 4n+2 Rule
 Compounds with 4n  Electrons Are
Not Aromatic (May be Antiaromatic)
 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
 15.4 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
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•
generate nonaromatic 4
and 5 electron systems
 Relatively acidic (pKa =
16) because the anion is
stable
 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
15.5 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
 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
 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
15.6 Polycyclic Aromatic
Compounds
 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
Naphthalene Orbitals
 Three resonance forms and delocalized electrons
15.7 Spectroscopy of Aromatic
Compounds
 IR: Aromatic ring C–H stretching at 3030 cm 1
and peaks 1450 to 1600 cm1 (See Figure 15-13)
 UV: Peak near 205 nm and a less intense peak in
255-275 nm range
 1
H NMR: Aromatic H’s strongly deshielded by ring
and absorb between  6.5 and  8.0
 Peak pattern is characteristic of positions of

substituents
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
 C NMR of Aromatic
13

Compounds
 Carbons in aromatic ring absorb at  110 to 140
 Shift is distinct from alkane carbons but in same
range as alkene carbons
Let’s Work a Problem

Cycloheptatrienone is stable, but

cyclopentadienone is so reactive that it can’t be
isolated. Explain, taking the polarity of the carbonyl
group into account?
Answer

Draw the resonance forms of the molecules in

which both carbonyl electrons are on the oxygen.
The cycloheptatrienone ring possesses 6
electrons and is aromatic according to Hückel’s
rule. When we do this with the cyclopentadienone
ring, we see that it contains 4 electrons and thus
is antiaromatic and does not obey Hückel’s rule,
resulting in its extreme reactivity.
HW
 18
 19
 23
 34
 39
 40
 47