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Chapter 21, Benzene and and The Concept of Aromaticity
Chapter 21, Benzene and and The Concept of Aromaticity
21-1
Benzene - Kekulé
In 1872, August Kekulé proposed the following
structure for benzene.
H H
H C H H C H
C C C C
C C C C
H C H H C H
H H
21-2
Benzene - Resonance
Weoften represent benzene as a hybrid of two
equivalent Kekulé structures.
• Each makes an equal contribution to the hybrid and
thus the C-C bonds are neither double nor single, but
something in between.
21-3
Benzene - Resonance Model
Theconcepts of hybridization of atomic orbitals
and the theory of resonance, developed in the
1930s, provided the first adequate description of
benzene’s structure.
• The carbon skeleton is a planar regular hexagon.
• All C-C-C and H-C-C bond angles 120°.
H 120° H
sp2 -sp2
120° C C
120°
H C C H
109 pm C C 2
sp -1 s
H
139 pm H
21-4
The Pi System of Benzene
• (a) The carbon framework with the six 2p orbitals.
• (b) Overlap of the parallel 2p orbitals forms one torus
above the plane of the ring and another below it
• this orbital represents the lowest-lying pi-bonding
molecular orbital.
21-5
Benzene-Molecular Orbital Model
The
molecular orbital representation of the pi
bonding in benzene.
21-6
Orbitals of the pi System of Benzene
Number of
nodal surfaces
3
21-7
Benzene - Resonance
Resonance energy: The difference in energy
between a resonance hybrid in which the
electrons are delocalized
and
the most stable one of its hypothetical
contributing structures in which electrons are
localized on particular atoms and in particular
bonds.
• One way to estimate the resonance energy of benzene
is to compare the heats of hydrogenation of benzene
and cyclohexene.
21-8
Benzene- Resonance Energy
Model
Experimental
data
21-9
Concept of Aromaticity
The underlying criteria for aromaticity were
recognized in the early 1930s by Erich Hückel,
based on molecular orbital (MO) calculations.
To be aromatic, a compound must
• Be cyclic.
• Have one p orbital on each atom of the ring.
• Be planar or nearly planar so that there is continuous
or nearly continuous overlap of all p orbitals of the
ring.
• Have a closed loop of (4n + 2) pi electrons in the cyclic
arrangement of p orbitals.
21-10
Frost Circles
Frostcircle: A graphic method for determining
the relative order of pi MOs in planar, fully
conjugated monocyclic compounds.
• Inscribe in a circle a polygon of the same number of
sides as the ring to be examined such that one of the
vertices of the polygon is at the bottom of the circle.
• The relative energies of the MOs in the ring are given
by where the vertices of the polygon touch the circle.
Those MOs
• Below the horizontal line through the center of the ring
are bonding MOs.
• on the horizontal line are nonbonding MOs.
• above the horizontal line are antibonding MOs.
21-11
Frost Circles
• Frost circles describing the MOs for monocyclic,
planar, fully conjugated four-, five-, and six-membered
rings.
21-12
Relationship of hexa-1,3,5-triene to benzene
21-13
Relationship of hexa-1,3,5-triene to benzene
?
Relationship of hexa-1,3,5-triene to benzene
p3 ?
p2
Bonding,
stabilizing
Curve
around
Antibonding,
destabilizing
Aromatic Hydrocarbons
Annulene:A cyclic hydrocarbon with a
continuous alternation of single and double
bonds.
• [14]Annulene is aromatic according to Hückel’s
criteria. n=3
H
H H
H HH H
H HH H
H H
H
[14]Ann ulene
(aromatic) 21-16
Aromatic Hydrocarbons
• [18]Annulene is also aromatic.
H H
H H
H H H n=4
H H
H H
H H H
H H
H H
[18]A nnu lene
(aromatic)
21-17
Aromatic Hydrocarbons
• According to Hückel’s criteria, [10]annulene should be
aromatic; it has been found, however, that it is not.
• Nonbonded interactions between the two hydrogens
that point inward toward the center of the ring force
the ring into a nonplanar conformation in which
overlap of the ten 2p orbitals is no longer continuous.
21-18
Aromatic Hydrocarbons
• What is remarkable relative to [10]annulene is that if
the two hydrogens facing inward toward the center of
the ring are replaced by a methylene (CH2) group, the
ring is able to assume a conformation close enough to
planar that it becomes aromatic.
CH2
21-19
Antiaromatic Hydrocarbons
Antiaromatic hydrocarbon: A monocyclic, planar,
fully conjugated hydrocarbon with 4n pi
electrons (4, 8, 12, 16, 20...).
• An antiaromatic hydrocarbon is especially unstable
relative to an open-chain fully conjugated hydrocarbon
of the same number of carbon atoms.
Cyclobutadiene is antiaromatic.
• In the ground-state electron configuration of this
molecule, two electrons fill the p1 bonding MO.
• The remaining two electrons lie in the p2 and p3
nonbonding MOs.
21-20
Cyclobutadiene
• The ground state of planar cyclobutadiene has two
unpaired electrons, which make it highly unstable and
reactive.
21-21
Cyclooctatetraene
• Cyclooctatetraene, with 8 pi electrons is not aromatic;
it shows reactions typical of alkenes.
• X-ray studies show that the most stable conformation
is a nonplanar “tub” conformation.
• Although overlap of 2p orbitals occurs to form pi
bonds, there is only minimal overlap between sets of
2p orbitals because they are not parallel.
21-23
Heterocyclic Aromatics
Heterocyclic
compound: A compound that
contains more than one kind of atom in a ring.
• In organic chemistry, the term refers to a ring with one
or more atoms that differ from carbon.
Pyridine
and pyrimidine are heterocyclic analogs
of benzene; each is aromatic.
4 3 4
3 5 N 5
2 6 2 6
1 N 1N
•• ••
Pyridine Pyrimidine
21-24
Pyridine
• The nitrogen atom of
pyridine is sp2
hybridized.
• The unshared pair of
electrons lies in an sp2
hybrid orbital and is not
a part of the six pi
electrons of the
aromatic system (the
aromatic sextet).
• Resonance energy of
pyridine is134 kJ (32
kcal)/mol.
21-25
Furan and Pyrrole
• The oxygen atom of furan is sp2 hybridized.
• one unshared pairs of electrons on oxygen lies in an
unhybridized 2p orbital and is a part of the aromatic
sextet.
• The other unshared pair lies in an sp2 hybrid orbital
and is not a part of the aromatic system.
• The resonance energy of furan is 67 kJ (16 kcal)/mol.
21-26
Other Heterocyclics
CH 2 CH2 NH 2
HO
N N
H H
Indole Serotonin
(a neurotransmitter)
O CH3
N H3 C N
N N
N O N N
N
H CH 3
Purine Caffeine
21-27
Aromatic Hydrocarbon Ions
Anyneutral, monocyclic, unsaturated
hydrocarbon with an odd number of carbons
must have at least one CH2 group and, therefore,
cannot be aromatic.
CH2 CH2 CH2
21-28
Cyclopropenyl Cation
• If, however, the CH2 group of cyclopropene is
transformed into a CH+ group in which carbon is sp2
hybridized and has a vacant 2p orbital, the overlap of
orbitals is continuous and the cation is aromatic.
H H H
+ H +
H H
+
H H H
Cycloprop enyl cation represented as a h yb rid
of three equ ivalen t contributin g s tru ctures
21-29
Cyclopropenyl Cation
• When 3-chlorocyclopropene is treated with SbCl5, it
forms a stable salt.
H
-
+ Sb Cl 5 + H Sb Cl 6
Cl
3-Chloro- Antimony(V) Cyclopropenyl
cyclopropene chloride hexachloroantimonate
(a Lewis acid)
21-30
Cyclopentadienyl Cation
H
+ A gBF4 + -
H BF4 + Ag Cl
Cl
5-Chloro-1,3- Cyclopentadienyl
cyclopentadiene tetrafluoroborate
21-31
Cyclopentadienyl Anion, C5H5-
To convert cyclopentadiene to an aromatic ion, it
is necessary to convert the CH2 group to a CH
group in which carbon becomes sp2 hybridized
and has 2 electrons in its unhybridized 2p orbital.
H • H H
•
H H
H • • H : H H
H H H
H H H
th e origin of th e 6 pi electrons Cyclopentad ienyl anion
in the cyclopen tadienyl anion (aromatic)
n=1
21-32
Cyclopentadienyl Anion, C5H5-
• As seen in the Frost circle, the six pi electrons of
cyclopentadienyl anion occupy the p1, p2, and p3
molecular orbitals, all of which are bonding.
21-33
Cyclopentadienyl Anion, C5H5-
The pKa of cyclopentadiene is 16.
• In aqueous NaOH, it is in equilibrium with its sodium
salt. H
H
CH2 + NaOH : H Na+ + H2 O
H pK a 15.7
p K a 16.0 H
21-34
Cycloheptatrienyl Cation, C7H7+
Cycloheptatriene forms an aromatic cation by
conversion of its CH2 group to a CH+ group with
its sp2 carbon having a vacant 2p orbital.
H H
H H
H H
+ H + H
H H
H H
H H
Cyclohep tatrien yl cation
(Tropylium ion )
(aromatic)
21-35
Nomenclature
Monosubstituted alkylbenzenes are named as
derivatives of benzene.
• Many common names are retained.
21-36
Nomenclature
Benzyl and phenyl groups
CH3
CH2
Benzene Phenyl group, Ph- Toluene Benzyl group, Bn-
O O
H 3 CO
Ph
21-37
Disubstituted Benzenes
Locatetwo groups by numbers or by the
locators ortho (1,2-), meta (1,3-), and para (1,4-).
• Where one group imparts a special name, name the
compound as a derivative of that molecule.
Cl
CH3
Br
4-Bromotolu ene 3-Chloroan iline 2-N itrobenzoic acid m-Xylene
(p-Bromotoluen e) (m-Chloroan iline) (o-N itrob enzoic acid )
21-38
Disubstituted Benzenes
• Where neither group imparts a special name, locate
the groups and list them in alphabetical order.
CH2 CH3 NO2
4 2
Br
3 1
2
1
Cl
1-Chloro-4-ethylben zene 1-Bromo-2-nitrob enzene
(p-Ch loroethylbenzen e) (o-Bromon itroben zene)
21-39
Polysubstituted Derivatives
• If one group imparts a special name, name the
molecule as a derivative of that compound.
• If no group imparts a special name, list them in
alphabetical order, giving them the lowest set of
numbers.
CH3 OH N O2
1 2 1 4
N O2 Br 6 2 Br
2
4 4 1 Br
Cl Br CH2 CH3
4-Chloro-2-nitro- 2,4,6-Tribromo- 2-Bromo-1-ethyl-4-
toluene phenol nitrobenzene
21-40
Phenols
The
functional group of a phenol is an -OH group
bonded to a benzene ring.
OH OH OH OH
OH
CH3
OH
Phenol 3-Methylphenol 1,2-Benzenediol 1,4-Benzenediol
(m- Cresol) (Catechol) (Hydroquinone)
21-41
Acidity of Phenols
Phenols are significantly more acidic than
alcohols.
OH + H2 O O- + H3 O+ pK a = 9.95
- +
CH3 CH2 OH + H2 O CH3 CH2 O + H3 O pK a = 15.9
21-43
Acidity of Phenols
Separationof water-
insoluble phenols
from water-insoluble
alcohols.
21-44
Acidity of Phenols (Resonance)
• The greater acidity of phenols compared with alcohols
is due to the greater stability of the phenoxide ion
relative to an alkoxide ion.
O O O O O
H H
H
These 2 Kekulé These th ree con trib utin g s tru ctures
s tru ctures are delocalize th e negative charge
equivalent on to carb on atoms of th e rin g
21-45
Phenol Subsitituents (Inductive Effect)
Alkyland halogen substituents effect acidities by
inductive effects:
• Alkyl groups are electron-releasing.
• Halogens are electron-withdrawing.
OH OH OH OH OH
CH3 Cl
CH3 Cl
Phen ol m-Cres ol p-Cres ol m-Chlorop henol p-Chororophen ol
pK a 9.95 p Ka 10.01 pK a 10.17 pK a 8.85 p Ka 9.18
21-46
Phenol Subsitituents(Resonance, Inductiion)
• Nitro groups increase the acidity of phenols by both an
electron-withdrawing inductive effect and a resonance
effect.
OH OH OH
NO2
NO2
Ph e no l m - N itrop h e n ol p- N itrop h e n ol
p K a 9.95 p K a 8.28 p K a 7.15
21-47
Acidity of Phenols
• Part of the acid-strengthening effect of -NO2 is due to
its electron-withdrawing inductive effect.
• In addition, -NO2 substituents in the ortho and para
positions help to delocalize the negative charge.
O O
delocalization of negative
charge onto oxygen further
increases the resonance
stabilization of phenoxide ion
N+ N+
O O O O
21-48
Synthesis: Alkyl-Aryl Ethers
Alkyl-aryl
ethers can be prepared by the
Williamson ether synthesis:
• but only using phenoxide salts and haloalkanes.
• haloarenes cannot be used because they are
unreactive to SN2 reactions.
X + RO - N a+ no reaction
21-51
Synthesis: Alkyl-Aryl Ethers
N aOH, H2 O, CH2 Cl 2
OH + CH2 = CHCH2 Cl
Phenol 3-Chloropropene
(Allyl chloride) OCH2 CH= CH2
O
N aOH, H2 O, CH2 Cl 2
OH + CH3 OSOCH3
O
Phenol D imethyl sulfate
OCH3 + N a2 SO 4
21-53
Mechanism: Kolbe Carboxylation
• The mechanism begins by nucleophilic addition of the
phenoxide ion to a carbonyl group of CO2.
O O OH O
O
O C keto-enol
O C
tautomerism O
+ C
(1) H (2)
O
Sodium A cyclohexadienone Salicylate anion
phenoxide intermediate
Go back to aromatic
structure
21-54
Synthesis: Quinones
Because of the presence of the electron-donating
-OH group, phenols are susceptible to oxidation
by a variety of strong oxidizing agents.
OH O
H2 Cr O 4
O
Phenol 1,4-Benzoquinone
(p-Quinone)
21-55
Quinones
OH O
OH K2 Cr2 O7 O
H2 SO4
1,2-Benzen ediol 1,2-Benzoquin on e
(Catechol) (o-Qu inone)
OH O
K2 Cr2 O7
H2 SO4
OH O
1,4-Ben zenediol 1,4-Benzoquin on e
(Hydroquin on e) (p-Qu inone)
21-56
Quinones
Readily reduced to hydroquinones.
O OH
Na2 S2 O4 , H2 O
(reduction )
O OH
1,4-Benzoqu inone 1,4-Benzen ediol
(p-Qu inone) (Hydroq uinone)
21-57
Coenzyme Q
Coenzyme Q is a carrier of electrons in the
respiratory chain.
O OH
MeO MeO
reduction
MeO H oxidation MeO H
n n
O OH
Coenzyme Q Coenzyme Q
(oxid ized form) (redu ced form)
21-58
Benzylic Oxidation
Benzene is unaffected by strong oxidizing agents
such as H2CrO4 and KMnO4
• Halogen and nitro substituents are also unaffected by
these reagents.
• An alkyl group with at least one hydrogen on its
benzylic carbon is oxidized to a carboxyl group.
CH3 COOH
H2 Cr O4
O2 N Cl O2 N Cl
2-Chloro-4-nitrotoluene 2-Chloro-4-nitrobenzoic acid
21-60
Benzylic Oxidation
• If there is more than one alkyl group on the benzene
ring, each is oxidized to a -COOH group.
O O
K2 Cr 2 O 7
H3 C CH3 HOC COH
H2 SO 4
1,4-Dimethylbenzene 1,4-Benzenedicarboxylic acid
(p-xylene) (terephthalic acid)
21-61
Benzylic Chlorination
Chlorination
and bromination occur by a radical
chain mechanism.
CH3 h eat CH2 Cl
+
or ligh t +
Cl2 HCl
Toluen e Benzyl ch loride
Br
NBS
( PhCO2 ) 2 , CCl4
Ethylbenzen e 1-Bromo-1-p henylethan e
(racemic)
21-62
Mechanism: Benzylic Reactions
Benzylicradicals (and cations also) are easily
formed because of the resonance stabilization of
these intermediates.
• The benzyl radical is a hybrid of five contributing
structures.
C C
C C C
21-63
Benzylic Halogenation
• Benzylic bromination is highly regioselective.
Br
NBS
(PhCO2 ) 2 , CCl4
Eth ylb enzene 1-Bromo-1-phen yleth ane
(the only product formed )
this bond
is cleaved
Pd/ C Me
O + H2 OH +
21-65
Synthesis, Protecting Group: Benzyl Ethers
Thevalue of benzyl ethers is as protecting
groups for the OH groups of alcohols and
phenols.
• To carry out hydroboration/oxidation of this alkene,
the phenolic -OH must first be protected; it is acidic
enough to react with BH3 and destroy the reagent.
OH H2 OH
Pd/ C
O Ph OH
2-(3-Hyd roxyprop yl)p henol
21-66