CITY COLLEGE OF CALAMBA

DALUBHASAAN NG LUNGSOD NG CALAMBA

Organic Chemistry

Name: Midterm
Year&Section: 2-SEDS1 Prof. Nazareth

INTRODUCTION
Delocalized electrons play such as an important role in organic chemistry.
This lesson starts by showing you how delocalized electrons are depicted. Then
you will see how they affect things that are now familiar to you, such as pKa
values, the stability of carbocations, and the products form from electrophilic
addition reactions. You will also find out what it means for a compound. To be
aromatic and how aromaticity causes a compound with carbon-carbon double
bonds to undergo substitution reaction rather than addition reactions.

LESSON OBJECTIVES
At the end of the lesson, the students should be able to:
1. Discuss the structure of benzene and the effects of delocalized electron on
stability
2. Analyze the chlorination and bromination of alkanes
3. Explain the low reactivity of alkanes radical reaction in biological system
LESSON 1:
Delocalized Electrons and their effect on stability and reactivity
Delocalized electrons explain benzene structure
 Benzene's structure puzzled early chemists due to lack of knowledge on
delocalized electrons.
 Benzene has a molecular formula of C6H6 and forms four total rings and pi
bonds.
 Monosubstitution yields one product, and disubstitution yields three
products.
 Friedrich Kekule proposed interconverting 1,2-distributed products.
 In the 1930s, analytical techniques revealed benzene is planar with
uniform carbon-carbon bond lengths of 1.39 Å.
 Benzene does not have alternating single and double bonds.
 The pi electrons in benzene are delocalized around the ring.

Friedrick August Kukule

 Friedrich August Kekule von Stradonitz (1829–1896) was born in Germany.
 Initially studied architecture, switched to chemistry at the University of
Giessen.
 Held professorships at the University of Heidelberg, University of Ghent,
and University of Bonn.
 In 1890, he shared his dream-inspired discovery of benzene's cyclic
structure.
 He dreamed of carbon atoms forming a snake that bit its own tail, creating
a ring.
 In 1895, Kekule was made a nobleman and added "von Stradonitz" to his
name.
 Three of his students won the first Nobel Prizes in chemistry.
 In 1965, the German chemist Friedrich Kekule suggested a way of
resolving this dilemma. He proposed that there are actually four
distributed products, but the two 1,2-distributed products interconvert too
rapidly to be separated from each other.
The bonding in benzene
 Benzene’s six carbon atoms are sp2 hybridized.
 Each sp2 hybridized carbon has 120° bond angles, forming a planar
hexagon.
 Two sp2 orbitals bond with other carbons; the third bonds with hydrogen.
 Each carbon has a p orbital at right angles to the sp2 orbitals.
 The six parallel p orbitals overlap side-to-side, forming a continuous
electron cloud above and below the benzene ring.
 This electron cloud creates equal electron density across all carbon-carbon
bonds.

a. Each of the carbons in benzene uses two sp2 orbitals to bond to two
other carbons; its third sp2 orbital overlaps the s orbital of a
hydrogen
b. Each carbon has a p orbital at right angles to the sp2 orbitals. The
parallel p orbitals are close enough for side to side overlap, so each
p orbital overlaps the p orbitals on both adjacent carbons.
c. The overlapping p orbitals form two continuous doughnut-shaped
clouds of electrons – one above the plane of the benzene ring and
one below it.
d. The electrostatic potential map shows that all the carbon-carbon
bonds have the same electron density

A. Benzene’s six pi electrons are not localized to any single carbon or bond.
B. Each pi electron is shared by all six carbon atoms.
C. The pi electrons are delocalized, moving freely within the doughnut-
shaped electron clouds above and below the ring.
D. Benzene is often represented by a hexagon with dashed lines or a circle to
symbolize the six delocalized pi electrons.

The difference between a resonance contributor and a resonance hybrid

  Resonance contributors are like imaginary creatures, such as unicorns and
dragons.
 These contributors do not exist in reality or switch back and forth.
 They are used to describe the real structure, similar to how a rhinoceros is
described.
 The resonance hybrid is the actual structure, just as the rhinoceros is the
real animal.
 Contributors help visualize the resonance hybrid, which is the true form.

Drawing resonance contributors

 The resonance hybrid shows the nitrogen’s p orbital overlapping with both
oxygen p orbitals.
The two π electrons are shared among the three atoms (nitrogen and two
oxygens).
 Both nitrogen-oxygen bonds are identical, with the negative charge shared
between the two oxygen atoms.
 Visualizing both resonance contributors helps to understand the actual
structure, the resonance hybrid.
Rules for drawing resonance contributors
To draw resonance contributors, the electrons in one resonance contributor are
moved to generate the next resonance contributor. As you draw resonance
contributors, keep in mind the following constraints:
1. Only electrons move. The nuclei of the atoms never move.
2. The only electrons that can move are π electrons (electrons in π bonds)
and lone-pair electrons
3. The total number of electrons in the molecule does not change. Therefore,
each of the resonance contributors for a particular compound must have
the same net charge. If one has a net charge of zero, all the others must
also have net charges of zero. (A net charge of zero does not necessarily
mean that there is no charge on any of the atoms: a molecule with a
positive charge on one atom and a negative charge on another atom has a
net charge of zero.
Rules for drawing resonance contributors
Features that decrease the predicted stability
We can summarize the features that decrease the predicted stability of a
resonance contributor as follows:
1. An atom with an incomplete octet
2. A negative charge that is not on the most electronegative atom
3. A positive charge that is on an electronegative atom
4. Charge separation
The effect of Delocalized Electrons on stability
 In isolated dienes, π electrons are localized between two carbons.
 In conjugated dienes, π electrons are delocalized.
 Delocalization stabilizes the molecule, making conjugated dienes more
stable than isolated dienes.
 Without an electronegative atom, electrons in conjugated dienes can
move in both directions.CH2 -- CH == CH – CH2+ ↔ CH2 == CH – CH ==
CH2 ↔ CH2+ -- CH ==CH –CH2-
 An allylic cation has a positive charge on a carbon adjacent to an sp2
carbon of an alkene. A benzylic cation has a positive charge on a carbon
adjacent to an sp2 carbon of a benzene ring.

CH2 == CHCH2+
 An allylic cation has two resonance contributors. The positive charge is not
localized on a single carbon but is shared by two carbons

CH2 == CH – CH2+ ↔ CH2+ -- CH == CH2

 A benzylic cation has five resonance contributors. Notice that the positive
charge is shared by four carbons.

 Because allylic and benzylic cation have delocalized electrons, they are
more stable than other primary carbocations with localized electrons.
(Indeed, they have about the same stability as secondary alkyl
carbocations.) we can add allylic and benzylic cations to the group of
carbocations.

Relative stabilities of carbocations

Not all allylic and benzylic carbocations have the same stability. A tertiary allylic
cation is more stable that a secondary allylic cation, which in turn is more stable
than a primary allylic cation. Similarly, a tertiary benzylic cation is more stable
than a secondary benzylic cation, which is more stable than a primary benzylic
cation.

The compound known as benzene was first isolated in 1825 by Michael Faraday.
He extracted it form the liquid residue obtained after heating whale oil under
pressure to produce the gas that was being used to illuminate buildings in
London. Many substituted benzenes are found in nature. A few that have
physiological activities are shown:

Criteria for Aromaticity

The cloud must contain an odd number of pairs of electrons Benzene is an
aromatic compound because it is cyclic and planar, every carbon in the ring has
a p orbital, and the cloud contains three parts of electrons.
Aromatic Hydrocarbons
Cyclobutadiene has two pairs of electrons, and cyclooctatetraene has four pairs
of electrons. Unlike benzene, these compounds are not aromatic because they
have an even number of pairs of electrons. There is an additional reason why
cyclooctatetraene is not aromatic – it is not planar. Because cyclobutadiene are
cyclooctatetraene are not aromatic, they do not have the unusual stability of
aromatic compounds.

Each carbon has exactly one-fifth of the negative charge associated with the
anion

The criteria for determining whether a monocyclic hydrocarbon compound is

aromatic can also be used to determine whether a polycyclic hydrocarbon
compound is aromatic. Naphthalene (five pairs of electron), phenanthrene
(seven pairs of electron) and chrysene (nine pairs of electron) are aromatic.

Reactions of benzene
The following are four most common electrophilic aromatic substitution
reactions:
1. Halogenation. Benzene reacts with bromine in the presence of iron and
forms the substitution product, bromobenzene or phenyl bromide.
2. Further treatments causes the successive substitution of other bromine
atoms for hydrogen atoms. With complete substitution,
hexabromobenzene is produced.
3. Nitration. Nitrobenzene is produced by treating benzene with concentrated
nitric and sulfuric acids.
4. Sulfonation. Benzenesulfonic acid is produced at room temperature by
treating benzene with fuming sulfuric acid (fuming sulfuric acid contains
an excess of sulfur trioxide.
 5. Friedel-crafts reaction. An alkyl group may be introduced into the benzene
ring by using an alkyl halide in the presence of anhydrous aluminum
chloride.

Other aromatic hydrocarbons

Toluene

 Toluene is used to produce benzene.

 Xylenes (dimethylbenzenes) are a mixture of three isomers used to make
polyester fibers, plasticizers, and resins.
 Ethylbenzene, when treated with a catalyst, produces styrene, used for
SBR synthetic rubber.
 Styrene can be polymerized into polystyrene, a tough, transparent plastic,
or Styrofoam, used for packaging and insulation.
 Naphthalene, made from coal-tar or petroleum, consists of two benzene
rings and is used in crystalline form.
 Anthracene, composed of three benzene rings, is obtained from coal tar
and used in synthetic dye production.

Nomenclature of Monosubstituted Benzenes

Some monosubstituted benzenes are named simply by stating the name of the
substituent,

Some monosubstituted benzenes have names that incorporate the name of the
substituent. When a benzene ring is a substituent, it is called a phenyl group. A
benzene ring with a methylene group is called a benzyl group.

An aryl group (Ar) is the general term for either a phenyl group or a substituted
phenyl group, just as an alkyl group (R) is the general term for a group derived
from an alkane. In other words, ArOH could be used to designate any of the
following phenols:

Halogenation of Benzene
The bromination or chlorination of benzene requires a Lewis acid catalyst such as
ferric bromide or ferric chloride. Recall that a Lewis acid is a compound that
accepts a share in an electron pair.

Bromination
The bromination or chlorination of benzene requires a Lewis acid catalyst such as
ferric bromide or ferric chloride. Recall that a Lewis acid is a compound that
accepts a share in an electron pair.

Chlorination
Why does the reaction of benzene with Br2 or Cl2 require a catalyst when the
reaction of an alkene with these reagents does not require a catalyst? Benzene,
because of its stability, is much less reactive than an alkene; therefore, it
requires a better electrophile. Donating a lone pair to the Lewis acid and
weakens the Br – Br (or Cl – Cl) bond, which makes Br2 (or Cl2) a better
electrophile.

To make the mechanism easier to understand, only one of the three resonance
contributors of the carbocation intermediate is shown in this and subsequent
mechanism. Bear in mind, however, that each carbonation intermediate actually
has the three resonance contributors. In the last step of the reaction, a base from
the reaction mixture removes a proton from the carbonation intermediate.

Mechanism for bromination

Chlorination of benzene occurs by the same mechanism as bromination.

Mechanism for chlorination

Nitration of Benzene
Nitration of benzene with nitric acid requires sulfuric acid as a catalyst.

To generate the necessary electrophile, sulfuric acid protonates nitric acid. Loss
of water from protonated nitric acid forms a nitronium ion, the electrophile
required for nitration.

Remember that any base present in the reaction mixture can remove the proton
in the second step of the aromatic substitution reaction.

Mechanism for nitration

Halogenation of Benzene
Fuming sulfuric acid (a solution of SO3 in sulfuric acid) or concentrated sulfuric
acid is used to sulfonate aromatic rings

Take a minute to note the similarities in the mechanism for forming the +SO3H
electrophile for sulfonation and the +NO2 electrophile for nitration.

Take a minute to note the similarities in the mechanism for forming the +SO3H
electrophile for sulfonation and the +NO2 electrophile for nitration.

Mechanism for Sulfonation

Friedel-Crafts Acylation of Benzene
Two electrophilic substitution reactions bear the names of chemist Charles Friedel
and James Crafts. Friedel-Crafts acylation places an acyl group on a benzene
ring.

Friedel-Crafts acylation

The electrophile (an acylium ion) required for a Friedel-Crafts acylation is formed
by the reaction of an acyl chloride with AlCl3, a Lewis acid. An acyl chloride has a
chlorine in place of the OH group of carboxylic acid.
 Mechanism for Friedel-Crafts acylation

Nomenclature of distributed benzenes

The relative positions of two substituents on a benzene ring can be
indicated either by numbers or by the prefixes, ortho, meta, and para.
Adjacent substituents are called ortho, substituents separated by one
carbon are called meta, and substituents located opposite one another are
designated para. Often, only their abbreviations (o, m, p) are used in
naming compounds.

If the two substituents are different, they are listed in alphabetical order. The first
stated substituents is given the 1-position, and the ring is numbered in the
direction that gives the second substituent the lowest possible number.

If one of the substituents can be incorporated into a name, that name is used
and the incorporated substituent is given the 1-position.