Benzene PDF

Benzene - Kekul Benzene Orbital Overlap Model
The first structure for benzene was proposed by The concepts of hybridization of atomic orbitals and
August Kekul in 1872. 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.
This structure, however, did not account for the unusual

chemical reactivity of benzene.
Copyright 2014 John Wiley & Sons, Inc. All rights reserved. 1 Copyright 2014 John Wiley & Sons, Inc. All rights reserved. 2
1 2
Benzene - Resonance Model Benzene - Resonance Energy
We often represent benzene as a hybrid of Resonance energy: The difference in energy

two equivalent Kekul structures. between a resonance hybrid and its most
Each Kekul structure makes an equal stable hypothetical contributing structure in
contribution to the hybrid. which electrons are localized on particular
The C-C bonds are neither double nor single but atoms and in particular bonds.
something in between. One way to estimate the resonance energy of
benzene is to compare the heats of hydrogenation
of benzene and cyclohexene.
3 4
Benzene - Resonance Energy Resonance Energy
Figure 9.2 The resonance energy of benzene. Resonance energies [kJ/mol and kcal/mol] for
benzene and several other aromatic
hydrocarbons.
5 6
Concept of Aromaticity
The criteria for aromaticity were recognized in the Huckels Rule 4n+2= no. of electrons
early 1930s by Erich Hckel. Ex. 4n+2=2 e- aromatic if n is an integer (0,1,2..
4n=22 not aromatic if n is not a whole no.
To be aromatic, a ring must: n = 0/4 = 0 aromatic
have one 2p orbital on each atom of the ring.
4n +2 = 4 e-
be planar or nearly planar, so that overlap of all 2p n = 4-2/4 = 2/4 = 0.5 not aromatic
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.
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.
7 8
Heterocyclic Aromatics Pyridine
Heterocyclic compound: A compound that contains The nitrogen atom of pyridine is sp2 hybridized.
one or more atoms other than carbon in its ring. The unshared pair of electrons lies in an sp2 hybrid orbital
Heterocyclic aromatic compound: A heterocyclic and is not a part of the six pi electrons of the aromatic
sextet.
compound whose ring is aromatic.
Pyridine has a resonance energy of 32 kcal (134 kJ)/mol,
Pyridine and pyrimidine are heterocyclic analogs of
slightly less than that of benzene.
benzene; each is aromatic.
9 10
Concept of Aromaticity Concept of Aromaticity
Figure 9.3 Origin of the six pi electrons (aromatic Nature abounds in compounds with a
sextet) in furan and pyrrole. heterocyclic aromatic ring fused to another
aromatic ring.
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Nomenclature Nomenclature
Monosubstituted alkylbenzenes are named as Phenyl and benzyl groups

derivatives of benzene.
Many common names are retained.
13 14
Nomenclature Nomenclature
Disubstituted benzenes Polysubstituted benzenes

Locate substituents by numbering or With three or more substituents, number the atoms of the
Use the locators ortho (1,2-), meta (1,3-), and para (1,4-) ring.
If one group imparts a special name, it becomes the
Where one group imparts a special name, name the
parent name.
compound as a derivative of that molecule.
If no group imparts a special name, number to give the
smallest set of numbers, and list alphabetically.
15 16
Benzylic Oxidation Benzylic Oxidation
Benzene is unaffected by strong oxidizing If there is more than one alkyl group, each is
agents such as H2CrO4 and KMnO4. oxidized to a -COOH group.
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.
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.
17 18
Reactions of Benzene Reactions of Benzene
The most characteristic reaction of aromatic

compounds is substitution at a ring carbon.
19 20
Electrophilic Aromatic Substitution Electrophilic Aromatic Substitution
Electrophilic Aromatic Substitution (EAS): A All EAS reactions occur by a three-step

reaction in which an electrophile, E+, substitutes mechanism.
for an H on an aromatic ring. Step 1: Generation of the electrophile.
Step 2: Reaction of an electrophile and a

nucleophile to form a new covalent bond.
We study
several common types of electrophiles.
how each is generated.
the mechanism by which each replaces hydrogen.
21 22
Electrophilic Aromatic Substitution Chlorination and Bromination
Step 3: Take a proton away. Proton transfer Step 1: Formation of the electrophile (a
regenerates the aromatic ring. chloronium ion).
23 24
Chlorination and Bromination Chlorination and Bromination
Step 2: Reaction of an electrophile and a Step 3: Take a proton away. Proton transfer to
nucleophile to form a new covalent bond. FeCl4 forms HCl, regenerates the Lewis acid
catalyst, and gives chlorobenzene.
25 26
Nitration Friedel-Crafts Alkylation
The electrophile, NO2+, generated in two steps. Friedel-Crafts alkylation forms a new C-C
Step 1: Add a proton. bond between an aromatic ring and an alkyl
group.
Step 2: Break a bond to form a stable molecule or ion.
27 28
Friedel-Crafts Alkylation Friedel-Crafts Alkylation
Step 1: Formation of an electrophile. 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.
29 30
Friedel-Crafts Alkylations Friedel-Crafts Acylations
There are two major limitations on F-C alkylations. Treating an aromatic ring with an acid chloride
It is practical only with stable carbocations, such as 2 and in the presence of AlCl3.
3 carbocations.
It fails on benzene rings bearing one or more of these Acid (acyl) chloride: a derivative of a carboxylic
strongly electron-withdrawing groups. acid in which the -OH is replaced by a chlorine.
31 32
Friedel-Crafts Acylations Other Benzene Alkylations
Step 1: Formation of the electrophile. Generation of carbocations

Treating an alkene with a protic acid, most commonly
H2SO4 or H3PO4.
33 34
Other Benzene Alkylations Di- and Polysubstitution
Generation of carbocations Existing groups on a benzene ring influence

Treating an alcohol with H2SO4 or H3PO4. 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.
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Di- and Polysubstitution Di- and Polysubstitution
-OCH3 is ortho-para directing. -NO2 is meta directing.
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Di- and Polysubstitution Di- and Polysubstitution
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.
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Di- and Polysubstitution Theory of Directing Effects
The order of steps is important. 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.
41 42
Theory of Directing Effects Theory of Directing Effects
For ortho-para directors, ortho-para attack -OCH3; assume meta 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.
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Theory of Directing Effects Theory of Directing Effects
-OCH3; assume para (or ortho) attack. -NO2; assume meta attack.
45 46
Theory of Directing Effects Activating-Deactivating
-NO2; assume para attack. 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
Contributor (e) places positive charge on adjacent on the ring, deactivates the ring toward further
atoms. EAS.
47 48
Halogens Phenols
Halogens: the resonance and inductive effects The functional group of a phenol is an -OH
operate in opposite directions. group bonded to a benzene ring.
The inductive effect: halogens have an electron-
withdrawing 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.
49 50

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Benzene - Kekul Benzene Orbital Overlap Model

This structure, however, did not account for the unusual

Benzene - Resonance Model Benzene - Resonance Energy

We often represent benzene as a hybrid of Resonance energy: The difference in energy

Concept of Aromaticity Concept of Aromaticity

Monosubstituted alkylbenzenes are named as Phenyl and benzyl groups

Disubstituted benzenes Polysubstituted benzenes

Reactions of Benzene Reactions of Benzene

The most characteristic reaction of aromatic

Electrophilic Aromatic Substitution (EAS): A All EAS reactions occur by a three-step

Step 2: Reaction of an electrophile and a

Electrophilic Aromatic Substitution Chlorination and Bromination

Nitration Friedel-Crafts Alkylation

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

Step 1: Formation of an electrophile. Step 2: Reaction of an electrophile and a nucleophile

Step 3: Take a proton away. Proton transfer regenerates

Friedel-Crafts Alkylations Friedel-Crafts Acylations

Step 1: Formation of the electrophile. Generation of carbocations

Other Benzene Alkylations Di- and Polysubstitution

Generation of carbocations Existing groups on a benzene ring influence

-OCH3 is ortho-para directing. -NO2 is meta directing.

Di- and Polysubstitution Di- and Polysubstitution

The order of steps is important. The rate of electrophilic aromatic substitution

Theory of Directing Effects Theory of Directing Effects

For ortho-para directors, ortho-para attack -OCH3; assume meta attack.

Theory of Directing Effects Activating-Deactivating

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