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11. Separate samples of the three halogenoalkanes given in question 10 were shaken
thoroughly with a mixture of AgNO3(aq) and the mixtures allowed to stand for some
time. Describe and explain the observations that were made.

Solution
CH3I readily gave a yellow precipitate (of AgI).
CH3Br gave a thinner and yellow precipitate (of AgBr) after a longer time.
CH3Cl gave no precipitate, or gave a very thin white precipitate ( of AgCl) after a much
longer time.
These observations are explained in terms of the bond energy (strength) of the C-Hal bond
and hence the tendency of the halogenoalkane to release the halogen atom in solution. The
bond energy is smallest in iodomethane, that is the C-I bond is the weakest. The iodine atom
is readily released in solution, and it immediately combines with Ag+ ions to form the yellow
AgI. The C-Cl bond is strongest and formation of AgCl is less likely.

Electrophilic reactions
These reactions involve the participation of a reactive particle known as an electrophile.

An electrophile is an electron deficient species which is therefore

attracted to an electron rich centre.

Electrophiles are positively charged ions which are usually generated insitu from
electrophilic reagents. The term insitu means that the species is not readily
available as a reagent, but it is produced during the course of a reaction. (It is too
unstable to be isolated and stored as a reagent).
A clear distinction should be made between an electrophile and an electrophilic
reagent. For example, Br2 is an electrophilic reagent, and it can give rise to the
Br+ electrophile (bromonium ion), for example, during the electrophilic addition
of bromine to the C to C double bond.
Since electrophiles are positively charged, they are naturally attracted to electron
rich centres, particularly the C to C double bond and the benzene ring. The C to C
double bond in alkenes is electron rich due to the presence of a pi bond. The pi
bond, being further form the nuclei of the two atoms of the bond, is weaker and
more diffuse than a sigma bond. The pi bond is therefore weaker and is easily
attacked by electrophiles.
The benzene ring has six delocalized electrons, which makes it electron rich and
prone to attack by electrophiles.
There are two types of electrophilic reactions, namely electrophilic addition and
electrophilic substitution.

Electrophilic addition occurs to the C to C double bond in alkenes. Electrophilic

substitution occurs in the benzene ring.

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Electrophilic reactions

electrophilic addition electrophilic substitution

The following questions, answers and discussions are based on electrophilic addition and
substitution reactions.

1. a) Outline the mechanism for the reaction between ethene and bromine. Why
should water not be used as the solvent in this reaction?
b) Write down two observations that are made during this reaction.

Solutions
1. a)

H H H H
+ +
C C C C Br
H H H H
Br

Br Br

H H

H C C H

Br Br
1,2- dibromoethane

a) The presence of water results in the formation of a mixture of 1, 2-

dibromoethane and 1- bromoethanol, CH2BrCH2OH.
b) Bromine is decolourized and an oily liquid (1, 2-dibromoethane) is formed.

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Notes
The reaction between ethene and bromine involves the bromonium electrophile, Br+. This species
has no independent existence and it is generated insitu from the polarization of bromine
molecules. The carbon to carbon double bond, being electron rich, repels the valence electrons in
bromine, causing one end of the bromine molecule to become electron deficient relative to the
other. The electron deficient atom on bromine becomes the Br + electrophile and attacks one
carbon atom of the C to C double bond. A C to Br bond is formed using the two π electrons of the
double bond. Breaking of the π bond results in one of the carbon atoms of the double bond
becoming electron deficient (has three bonds only).
The fact that the presence of water results in the formation of bromoethanol proves that the
reaction proceeds via a carbocation. This carbocation reacts with whatever nucleophile is present,
for example the hydroxide ion present in water.

H H H + H
Br2
C C C C Br
H H H H

OH- from water Br- from bromine

H H H
H
HO C C Br Br C C Br
H H H
H

1- bromoethanol 1,2-dibromoethanol

2. Predict the products formed when compound X below reacts with the given
reagents under the stated conditions.

Br
H3C
CH3
NaOH(aq)/reflux

Br
H3C
CH3
Cl2 / CCl4

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Br OH
H3C H3C
CH3 CH3
i) NaOH(aq)/reflux

Br Br
H3C CH3 H3C
CH3
ii)
Cl2 / CCl4 Cl

Cl

Notes
Reaction (i) : nucleophilic substitution.
Reaction (ii) : Electrophilic addition. CCl4 serves as the solvent.

Question 3
Predict the major product for the reaction between compound P below and HCl in a non -
aqueous solvent.

Br
H3C CH3

P
Solution

Br Br
H3C H3C
CH3 CH3
1 HCl
2
Cl

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Notes
This is electrophilic addition to the double bond. The electrophile is H+, generated from HCl. The first
step involves attack of either carbon 1 or carbon 2 by the electrophile. The positive charge of the
carbocation intermediate develops on the carbon atom that has not bonded to the electrophile.
According to Markownikoff’s rule, the hydrogen atom attacks that carbon atom of the double bond
which already has the greater number of hydrogen atoms, in this case carbon 1.

4. Describe the mechanism of the reaction between benzene and bromine. Why is a
catalyst needed for this reaction?

Solution
The reaction occurs by electrophilic substitution. The electrophile is the bromonium ion, Br +
generated insitu from bromine.

Br

AlBr3
+ HBr
(catalyst)

Br

H
Al
Br Br
Br + Br + H+
Br Br
+

Br

Al
Br Br
Br

Br

Al + HBr
Br
Br
catalyst regenerated

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The reaction requires a catalyst because the benzene ring is relatively stable and it
reluctantly participates in chemical reactions. The reaction has high activation energy.

5. Describe the catalytic role of AlBr3 in the reaction between bromine and benzene.
Name another catalyst that could be used in this reaction. What is the reason for using
this catalyst?

Solution
The reaction depends on the production of the Br+ electrophile from bromine. For this to
happen, the bromine molecule must first be polarized by the π electrons in benzene. However,
these electrons are delocalized and so are not readily available for polarizing the bromine
molecules. The catalyst helps to polarize bromine so that the Br+ electrophiles are readily
produced. Al in AlBr3 has only six valence electrons, two less than an octet. It is therefore
electron deficient and easily withdraws electrons from bromine, leading to polarization of the Br-
Br bond. Any catalyst used in this reaction must have the ability to withdraw electrons from
bromine molecules. Both iron powder and FeBr3 can be used to catalyze the reaction because
iron has vacant d orbitals to attract electrons from bromine molecules.

6. Augustus Kekule proposed the following structure, now known as Kekule’ structure, for
benzene

a) What is the bond angle marked x.

b) What does the bond angle x indicate about the bonding in benzene?
c) Construct equations for the complete hydrogenation of benzene and cyclohexene.
The enthalpy change of hydrogenation of cyclohexene and benzene are -120 and -
208Kj/mol respectively. What information does this provide about the relative
stabilities of benzene and Kekule’s structure?

Solutions
a) 1200
b) Each carbon atom is sp2 hybridized. It has three hybrid orbitals which it uses to form
three sigma bonds to three neighbouring carbon atoms. Thus each carbon atom uses
three out of its four valence electrons in sigma bonding, leaving one electron in a p z
orbital to be used in pi bonding. There are therefore six pz orbitals that overlap to form
one delocalized pi bond, containing six electrons.

c)
+ H2(g)

+ H2(g)

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d) If benzene had three double bonds as proposed by Kekule, then its enthalpy of
hydrogenation would be three times that of cyclohexene, that is, 320 x 3 = 360. The
actual enthalpy of hydrogenation is -208Kj/mol, which is 152 Kj less than the expected
value . This value of 152Kj/mol is known as the resonance energy of benzene. It
represents the extra energy associated with the benzene ring, relative to Kekule’s
structure.

Notes
Kekule received great accolade for figuring out that the structure of a compound with the molecular
formula C6H6 (benzene) should have six carbon atoms in a ring, with three double bonds. However, a
few years after this discovery of the structure of benzene, scientists began to think that Kekule’s
structure had to be modified because it was inconsistent with the known facts about benzene.

All bonds in benzene have the same bond length. If Benzene had three localized
double bonds and three single bonds as proposed by Kekule, then it would have
shorter and longer bonds.
If benzene had three double bonds, its enthalpy change of hydrogenation would be
three times that of cyclohexene, as discussed above.
If benzene had three double bonds it would have been an alkene and so would
decolorize bromine. The fact is that benzene has no reaction with bromine except
in the presence of a halogen carrier (catalyst).

The chemical properties of benzene are a result of the delocalization of pi electrons. Since the pi
bonds are not localized, it is found that they are intermediate between being double and being single,
and they have equal bond lengths.

7a) Write down a balanced equation for the mono-nitration of benzene by electrophilic
substitution.
b) The mono-nitration of benzene is a very slow process. It is made faster by
adding concentrated sulphuric acid

i) Write down the formula of the electrophile during this reaction.

ii) Briefly explain the role of sulphuric acid in the reaction.

c) Briefly describe the mechanism of the nitration of benzene.

d) Why is it important to make sure that temperature does not rise above600C?

Solutions
a) C6H6 + HNO3  C6H5NO2 + H2O
b (i) NO2+
(ii) Sulphuric acid acts as a catalyst. It serves as a proton donor, giving a hydrogen ion to
nitric acid. This causes nitric acid to decompose, releasing the nitronium ion (NO2+).

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 H H
O-H O O
H-O H +
S + N O N O O N=O + H2O
O
O O O NO2+
H2SO4 HNO3 +
HSO4-
c)

NO2 NO2
NO2+ + H + H+

d) To prevent polysubstitution/formation of polysubstituted compounds such as 1.3-

dinitrobenzene.

8. Benzene can be converted to compound X as shown below.

O
step 1 step 2

What are the reagents and conditions required for steps 1 and 2?

Solution
Step 1- CH3Br/CH3Cl
Step 2-CH3COCl

Notes
Step 1 is a type of electrophilic substitution known as Friedel-Crafts alkylation. This is an important
reaction because it introduces an alkyl group to the benzene ring. The mechanism is shown below.

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CH3
+ CH3
CH3 Br H + HBr

The C-Br bond in CH3Br is polarized, making the carbon atom is a centre of relative positive charge. It is
this centre that is attacked by the pi electrons in benzene, resulting in the formation of a bond between a
carbon atom on the benzene ring and the electron deficient C in the haloalkane. This reaction occurs in
the presence of a halogen carrier catalyst, for example AlBr 3, which increases polarity of the C-Br bond,
causing it to break and release the CH3+ electrophile insitu.
Reaction 2 is a special type of electrophilic substitution known as Friedel-Crafts acylation. The
mechanism is shown below. Once more, a halogen carrier catalyst is required to assist in the production
of the electrophile, which is the CH3CO+ ion.

-
O
HO
CH3C
Cl
C + HCl
+
CH3

a) What is the product of the reaction between phenol and bromine?

b) What type of reaction occurs in this reaction?
c) Write down observations made during this reaction.
d) Why is a catalyst not necessary in this reaction?

Solutions
a) 2,4,6-tribromophenol

OH
Br Br

Br

b) Electrophilic substitution.
c) Bromine is decolourised.
A white precipitate is formed.
d) The ring is activated by the –OH group.

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Notes
Halogenation of the benzene ring by electrophilic substitution depends on the polarization of the
halogen by electrons delocalized in the benzene ring. In a non- activated benzene ring, the pi electrons
are not effective in polarizing the halogen. Groups that push electrons into the benzene ring (ring
activators) for example the –OH and the –NH2 groups, activate the ring by increasing the size of
delocalized electron density required to polarize the halogen molecule. For this reason, a catalyst is
not required. The effect of a ring activator is summarized below.

Naming positions on the benzene ring

X
1 The substituent X occupies position 1.
2 2
3 Carbon 2 ortho(o-)
3
4
Carbon 3 meta(m-)
Carbon 4 para(p-)

If X is a ring activator
1. The incoming group is directed to the ortho or para positions.
2. No catalyst is required.
3. Polysubstitution occurs, that is more than one hydrogen atoms are replaced by the electrophile.

(Ring deactivators, such as the –NO2 and –SO3 groups tend to withdraw electrons from the benzene ring.
This makes the ring less reactive towards electrophiles. A catalyst is required and polysubstitution is
not likely unless if temperature is very high. In addition, substitution occurs at C3 (meta-))

comparing the reaction of benzene and phenol with

bromine.

AlBr3 Br
+ Br2 + HBr
benzene(non-activated)
OH OH
B Br
+ Br2 r
2,4,6-tribromophenol(white
Phenol(activated) Br
precipitate)

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