Ch09 Benzene and Deriv.

WILLIAM H.
BROWN
THOMAS POON
www.wiley.com/college/brown
CHAPTER NINE
Benzene and Its

Derivatives
Copyright2014JohnWiley&Sons,Inc.Allrightsreserved.
9-1
Benzene - Kekul
The first structure for benzene was proposed by
August Kekul in 1872.
This structure, however, did not account for the unusual

chemical reactivity of benzene.
Copyright 2014 John Wiley & Sons, Inc. All rights reserved.
9-2
Benzene Orbital Overlap Model

The concepts of hybridization of atomic orbitals and
the theory of resonance, developed in the 1930s,
provided the first adequate description of benzenes
structure.
The carbon skeleton is a regular hexagon, with all C-C-C
and H-C-C bond angles 120.
9-3
Benzene - Orbital Overlap Model

(a) The carbon framework; the six parallel 2p orbitals,
each with one electron, are shown uncombined.
(b) Overlap of the six 2p orbitals forms a continuous pi
cloud, shown as one torus above the plane of the ring, the
other below it.
9-4
Benzene - Resonance Model
We often represent benzene as a hybrid of

two equivalent Kekul structures.
Each Kekul structure makes an equal
contribution to the hybrid.
The C-C bonds are neither double nor single but
something in between.
9-5
Benzene - Resonance Energy
Resonance energy: The difference in energy

between a resonance hybrid and its most
stable hypothetical contributing structure 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.
9-6
Heats of hydrogenation for both cyclohexene

and benzene are negative (heat is liberated).
These results are shown graphically on the next

slide.
9-7

Figure 9.2 The resonance energy of benzene.
9-8
Resonance Energy
Resonance energies [kJ/mol and kcal/mol] for
benzene and several other aromatic
hydrocarbons.
9-9
Concept of Aromaticity
The criteria for aromaticity were recognized in the
early 1930s by Erich Hckel.
To be aromatic, a ring must:
have one 2p orbital on each atom of the ring.
be planar or nearly planar, so that overlap of all 2p
H C CH C CH CH
orbitals of the ring is continuous
or nearly continuous.
have 2, 6, 10, 14, 18, and so forth pi electrons in the
cyclic arrangement of 2p orbitals.
3
Benzene meets these criteria

It is cyclic, planar, has one 2p orbital on each atom of the
ring, and has 6 pi electrons (the aromatic sextet) in the
cyclic arrangement of its 2p orbitals.
9-10
Huckels Rule
4n + 2 = number of pi electrons If n = integer, follows the
Huckels rule
If n is a fraction, does not follow the Huckels rule
Ex
4n + 2 = 6 pi electrons
4n = 6 2
n= 4 =1
4
4n + 2 = 8 pi electrons
n = 8 2 / 4 = 6/4 = 1
9-11
9-12
Heterocyclic Aromatics
Heterocyclic compound: A compound that
contains one or more atoms other than carbon in its
ring.
Heterocyclic aromatic compound: A heterocyclic
compound whose ring is aromatic.
Pyridine and pyrimidine are heterocyclic analogs of
benzene; each is aromatic.
9-13
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
sextet.
Pyridine has a resonance energy of 32 kcal (134 kJ)/mol,
slightly less than that of benzene.
9-14
Figure 9.3 Origin of the six pi electrons (aromatic
sextet) in furan and pyrrole.
9-15
Nature abounds in compounds with a

heterocyclic aromatic ring fused to another
aromatic ring.
9-16
Nomenclature
Monosubstituted alkylbenzenes are named

as derivatives of benzene.
Many common names are retained.
9-17
Nomenclature
Phenyl and benzyl groups
9-18
Nomenclature
Disubstituted benzenes
Locate substituents by numbering or
Use 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.
9-19
Nomenclature
Polysubstituted benzenes
With three or more substituents, number the atoms of the
ring.
If one group imparts a special name, it becomes the
parent name.
If no group imparts a special name, number to give the
smallest set of numbers, and list alphabetically.
9-20
Polynuclear Aromatic Hydrocarbons
Polynuclear aromatic hydrocarbons (PAHs)

Contain two or more fused aromatic rings.
9-21
Carcinogenic PAHs
Benzo[a]pyrene is a carcinogen.
Once absorbed, the body oxidizes it to a more soluble
compound that can be excreted.
The diol epoxide contains a reactive epoxide ring and can

bind to DNA, thereby altering the structure of DNA and
producing a cancer-causing mutation.
9-22
Benzylic Oxidation
Benzene is unaffected by strong oxidizing

agents such as H2CrO4 and KMnO4.
Halogen and nitro substituents are unaffected by
these reagents.
An alkyl group with at least one hydrogen on the
benzylic carbon is oxidized to a carboxyl group.
9-23
Benzylic Oxidation
If there is more than one alkyl group, each is
oxidized to a -COOH group.
Terephthalic acid is one of the two monomers

required for the synthesis of poly(ethylene
terephthalate), a polymer that can be fabricated
into Dacron polyester fibers and into Mylar films.
9-24
Reactions of Benzene
The most characteristic reaction of aromatic

compounds is substitution at a ring carbon.
9-25
Reactions of Benzene
9-26
Electrophilic Aromatic Substitution
Electrophilic Aromatic Substitution (EAS):

A reaction in which an electrophile, E +,
substitutes for an H on an aromatic ring.
We study
several common types of electrophiles.
how each is generated.
the mechanism by which each replaces hydrogen.
9-27
All EAS reactions occur by a three-step

mechanism.
Step 1: Generation of the electrophile.
Step 2: Reaction of an electrophile and a
nucleophile to form a new covalent bond.
9-28

Step 3: Take a proton away. Proton transfer
regenerates the aromatic ring.
9-29
Chlorination and Bromination

Step 1: Formation of the electrophile (a
chloronium ion).
9-30

Step 2: Reaction of an electrophile and a
nucleophile to form a new covalent bond.
9-31

Step 3: Take a proton away. Proton transfer to
FeCl4 forms HCl, regenerates the Lewis acid
catalyst, and gives chlorobenzene.
9-32
Nitration
The electrophile, NO2+, generated in two steps.
Step 1: Add a proton.
Step 2: Break a bond to form a stable molecule or ion.
9-33
Friedel-Crafts Alkylation
Friedel-Crafts alkylation forms a new C-C

bond between an aromatic ring and an alkyl
group.
9-34
Step 1: Formation of an electrophile.
9-35
Step 2: Reaction of an electrophile and a nucleophile
to form a new covalent bond.
Step 3: Take a proton away. Proton transfer regenerates

the aromatic ring.
9-36
Friedel-Crafts Alkylations
There are two major limitations on F-C alkylations.
It is practical only with stable carbocations, such as 2
and 3 carbocations.
It fails on benzene rings bearing one or more of these
strongly electron-withdrawing groups.
9-37
Friedel-Crafts Acylations
Treating an aromatic ring with an acid

chloride in the presence of AlCl3.
Acid (acyl) chloride: a derivative of a carboxylic
acid in which the -OH is replaced by a chlorine.
9-38
Friedel-Crafts Acylations
Step 1: Formation of the electrophile.
9-39
Other Benzene Alkylations

Generation of carbocations
Treating an alkene with a protic acid, most commonly
H2SO4 or H3PO4.
9-40
Other Benzene Alkylations

Generation of carbocations
Treating an alcohol with H2SO4 or H3PO4.
9-41
Di- and Polysubstitution
Existing groups on a benzene ring influence

further substitution in both orientation and
rate.
Orientation
Certain substituents direct new substitution
preferentially toward ortho-para positions, others
direct preferentially toward meta positions.
Rate
Certain substituents are activating toward further
substitution, others are deactivating toward
further substitution.
9-42

-OCH3 is ortho-para directing.
9-43

-NO2 is meta directing.
9-44
9-45
Generalizations
1. Alkyl groups, phenyl groups, and substituents in
which the atom bonded to the ring has an
unshared pair of electrons are ortho-para directing;
all other substituents are meta directing.
2. All ortho-para directing groups are activating
toward further substitution; the exceptions to this
generalization are the halogens, which are weakly
deactivating.
3. All meta directing groups carry either a partial or
full positive charge on the atom bonded to the ring.
9-46
Draw the structure of the compounds and number them in

increasing order of reactivity towards SarE
Benzene
toluene
aminobenzene
chlorobenzene
nitrobenzene
9-47
Give the structure of the major product:

1
SO 3H
+ Br2 FeBr3
O
Br + CH3CH2CCl AlCl3
3
NH2 + HNO 3
H2SO 4
9-48
CH3
CCH3 + CH3CHCl
AlCl3
O 2N
CH3 + KMnO 4
H2O
OH
6
+ SO 3
H2SO 4
O 2N
9-49
The order of steps is important.
9-50
Theory of Directing Effects
The rate of electrophilic aromatic substitution

The rate of EAS is determined by the slowest
step in the reaction.
For almost every EAS, the rate-determining step
is attack of E+ on the aromatic ring to give a
resonance-stabilized cation intermediate.
The more stable this cation intermediate, the
faster the rate-determining step and the faster the
overall reaction.
9-51
For ortho-para directors, ortho-para attack

forms a more stable cation than meta attack.
Ortho-para products are formed faster than meta
products.
For meta directors, meta attack forms a more

stable cation than ortho-para attack.
Meta products are formed faster than ortho-para
products.
9-52

-OCH3; assume meta attack.
9-53

-OCH3; assume para (or ortho) attack.
9-54

-NO2; assume meta attack.
9-55

-NO2; assume para attack.
Contributor (e) places positive charge on adjacent atoms.

9-56
Synthesize the compound below starting from benzene

and provide all the necessary reagents needed (a-d)
and the intermediate product (e).
SO 3H
(b)
+
(a)
(c)
(e)
(d)
CH3
9-57
Activating-Deactivating
Any resonance effect such as those of -NH2,

OH, and OR, which delocalizes the
positive charge on the cation intermediate,
lowers the activation energy for its formation
and activates the ring toward further EAS.
Any resonance or inductive effect such as
those of NO2, C=O, -SO3H, NR3+, CCl3,
and CF3, which decreases electron density
on the ring, deactivates the ring toward further
EAS.
9-58
Halogens
Halogens: the resonance and inductive effects
operate in opposite directions.
The inductive effect: halogens have an electronwithdrawing inductive effect; therefore, aryl halides react
more slowly in EAS than benzene.
The resonance effect: a halogen ortho or para to the site
of electrophilic attack stabilizes the cation intermediate by
delocalizing the positive charge; halogen, therefore, is
ortho-para directing.
9-59
Phenols
The functional group of a phenol is an -OH

group bonded to a benzene ring.
9-60
Phenols
Some phenols
9-61
Acidity of Phenols
Phenols are significantly more acidic than

alcohols.
9-62
Acidity of Phenols
The greater acidity of phenols compared with
alcohols is the result of the greater stability of the
phenoxide ion relative to an alkoxide ion.
9-63
Acidity of Phenols
Ring substituents, particularly halogens and nitro
groups, increase the acidity of phenols by a
combination of resonance and inductive effects.
9-64
Acidity of Phenols
Phenols are weak acids.

They react with strong bases to form watersoluble salts.
They do not react with weak bases, such as

sodium bicarbonate.
9-65
Acidity of Phenols
Separations
9-66
Phenols as Antioxidants
Autoxidation
An oxidation requiring O2 and no other reactant.
A radical chain process.
Converts an R-H to R-O-O-H, a hydroperoxide.
We are concerned with allylic autoxidation.

Allylic carbon: A carbon adjacent to a C=C.
9-67
Step 1: Chain initiation: Formation of radicals
from nonradicals.
9-68
Steps 2a & and 2b Chain propagation:

Reaction of a radical to form a new radical.
Step 2a
Step 2b:
9-69
Vitamin E is a
natural antioxidant.
BHT and BHA are

synthetic antioxidants.
9-70
Benzene and its Derivatives
End Chapter 9
9-71

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WILLIAM H.

Benzene and Its

This structure, however, did not account for the unusual

Benzene Orbital Overlap Model

Benzene - Orbital Overlap Model

Benzene - Resonance Model

We often represent benzene as a hybrid of

Benzene - Resonance Energy

Resonance energy: The difference in energy

Benzene - Resonance Energy

Heats of hydrogenation for both cyclohexene

These results are shown graphically on the next

Benzene - Resonance Energy

Benzene meets these criteria

Nature abounds in compounds with a

Monosubstituted alkylbenzenes are named

Phenyl and benzyl groups

Where one group imparts a special name, name the

Polynuclear Aromatic Hydrocarbons

Polynuclear aromatic hydrocarbons (PAHs)

The diol epoxide contains a reactive epoxide ring and can

Benzene is unaffected by strong oxidizing

Terephthalic acid is one of the two monomers

The most characteristic reaction of aromatic

Electrophilic Aromatic Substitution

Electrophilic Aromatic Substitution (EAS):

Electrophilic Aromatic Substitution

All EAS reactions occur by a three-step

Electrophilic Aromatic Substitution

Chlorination and Bromination

Chlorination and Bromination

Chlorination and Bromination

Step 2: Break a bond to form a stable molecule or ion.

Friedel-Crafts alkylation forms a new C-C

Step 3: Take a proton away. Proton transfer regenerates

Treating an aromatic ring with an acid

Other Benzene Alkylations

Other Benzene Alkylations

Di- and Polysubstitution

Existing groups on a benzene ring influence

Di- and Polysubstitution

Di- and Polysubstitution

Di- and Polysubstitution

Di- and Polysubstitution

Draw the structure of the compounds and number them in

Give the structure of the major product:

Di- and Polysubstitution

The order of steps is important.

Theory of Directing Effects

The rate of electrophilic aromatic substitution

Theory of Directing Effects

For ortho-para directors, ortho-para attack

For meta directors, meta attack forms a more

Theory of Directing Effects

Theory of Directing Effects

Theory of Directing Effects

Theory of Directing Effects

Contributor (e) places positive charge on adjacent atoms.

Synthesize the compound below starting from benzene

Any resonance effect such as those of -NH2,

The functional group of a phenol is an -OH

Phenols are significantly more acidic than

Phenols are weak acids.

They do not react with weak bases, such as