WEEK 3:

Reaction of Alkenes
REACTION OF ALKENES
❖Alkenes are generally more reactive than alkanes due to the electron density available in their
pi bonds.
❖In particular, these molecules can participate in a variety of addition reactions and can be used
in polymer formation.
❖Alkenes participate in a variety of addition reactions.
❖Since sigma bonds are stronger than pi bonds, double bonds tend to react to convert the double
bond into sigma bonds.
❖Alkenes undergo addition reactions, in which two molecules combine to form a larger one.
❖Addition takes place across the double bond (C=C) where the weaker pi bond is broken in
favour of the formation of stronger sigma bonds.
❖After looking at some of the common addition reactions of alkenes, we'll take a look at the
most common mechanism for these types of reactions, the electrophilic addition mechanism. 
TYPES OF ALKENE REACTIONS

1.Hydrohalogenation Reaction
2.Hydration Reaction
3.Halogenation Reaction
4.Hydrogenation Reaction
5.Oxidation Reaction
1. HYDROHALOGENATION
⮚ Addition of HX (Hydrogen + Halogen) compound to an alkene.
⮚Addition is regioselective.
❑Regioselective reaction: A reaction in which one direction of bond-
forming or bond-breaking occurs in preference to all other directions.

❑Markovnikov’s rule: In additions of HX to a double bond, H adds to the

carbon with the greater number of hydrogens bonded to it.
⮚ Markovnikov's Rule: 
�When HX is added to an unsymmetrical alkene, the hydrogen
becomes attached to the carbon with the most hydrogens
attached to it already.
� The proton of an acid adds to the carbon in the double bond
that already has the most H’s. “Rich get richer.”
Addition of HCl to 2-butene
❑ A two-step mechanism

- Step 1: Formation of sec-butyl cation, a 2o carbocation intermediate

- Step 2: Reaction of the sec-butyl cation (an electrophile) with chloride ion (a
nucleophile) completes the reaction.
Addition of HBr to 2-
methylbutene
2. HYDRATION REACTION
⮚ addition of H2O to an alkene is called hydration
🡪 acid-catalyzed hydration of an alkene is regioselective, hydrogen adds
preferentially to the less substituted carbon of the double bond. Thus, H-OH adds
to the alkenes in accordance with Markovnikov’s Rule.
Mechanism of Hydration of Propene
Mechanism of
Hydration of 2-
methylpropene
Hydration of Ethylene
Mechanism of Hydration of Ethylene
3. HALOGENATION
⮚ addition of halogen (X-X) to an alkene: most common are Cl2 and Br2
⮚ carried out with either the pure reagents or an inert solvent such as CH2Cl2
⮚ Addition is stereoselective.
⮚ Stereoselective reaction: A reaction in which one stereoisomer is
formed or destroyed in preference to all others that might be formed
or destroyed.
⮚Addition to a cycloalkane, for example, gives only a trans product.
The reaction occurs with anti stereoselectivity.
Mechanism of Addition of Br2
- Step 1: Formation of a bromonium ion intermediate

- Step 2: Halide ion opens the three-membered ring.

4. HYDROGENATION
⮚ Alkenes react with H2 in the presence of a transition metal catalyst to give
alkanes.
⮚ The most common used catalysts are Pd, Pt, Ni and Rh.
⮚ The reaction is called catalytic reduction or catalytic hydrogenation.
⮚ The most common pattern is syn addition of hydrogens;
both hydrogens add to the same face of the double bond.
⮚ Catalytic reduction is syn stereoselectivity.
5. OXIDATION REACTION
❑Oxidation and reduction plays an important role in organic chemistry.
❑We say that a substance has undergone oxidation reaction if it gains
oxygen or loses hydrogen.
❑Similarly, we say that a substance has undergone reduction if it loses
oxygen or gains hydrogen.
❑In oxidation reaction of alkenes, the double bond between C atoms
beaks and oxygen is added to those carbon atom.
❑Types of Oxidation Reaction
a. Hydroxylation
b. Epoxidation
c. Ozonolysis
d. Polymerization
A. HYDROXYLATION

FORMATION OF 1,2 DIOLS

✔Alkenes are oxidized with certain oxidizing agents such as
potassium permanganate to add hydroxyl groups at double
bonds of alkenes.
✔This addition of hydroxyl groups is called hydroxylation and
it gives vicinal diols. This is an important reaction for the
synthesis of diols.

Ethylene glycol
Ethylene glycol
▪ Another example is the oxidation of propene that turns into
Propane-1,2-diol

▪ In this reaction KMnO4 gives MnO4-. This react with the alkene as
shown below
▪ Thus, an intermediate
compound is formed.

▪ Now, an OH- attacks the

intermediate like this. In
the 3rd step, H shifts from
O on Mn to O on the
alkene.
▪ Similarly, another
OH- will attack the
intermediate.

▪ So due to the presence of

OH- in this alkaline
solution, the intermediate
is converted into
Propane-1,2-diol.
▪ However, we do not need to write the mechanism to get to the
product. We can easily identify the product in such reaction using a
trick.
▪ For the trick, we have to suppose the emerging O from KMnO4
combines with water to give two OH.
▪ The double bond between two carbon atoms of alkene
breaks. The two OH get attached to those two carbons.
▪ Thus, the product diol is formed from alkenes e.g.
Propane-1,2-diol from propene.
B. EPOXIDATION
✔Three membered ring containing oxygen are called epoxide (oxiranes).
✔The epoxide formation is a major organic reaction.
✔They are formed by the reaction of alkenes with a source of electrophilic oxygen.
✔ The most important epoxide at industrial scale is actually the simplest of all, ethylene
oxide (oxacyclopropane).
✔ It has numerous industrial applications and is formed by catalytic oxidation of ethene
by air. 
C. OZONOLYSIS
✔Ozone (O3) is a triatomic molecule and is a powerful
electrophile.
✔It undergoes reaction with alkenes cleaving both sigma and pi
carbon-carbon bonds.
✔This reaction is known as ozonolysis or ozonation and the
products are called ozonides. 
✔Ozone is passed through alkene solution in an inert solvent.
The reaction leaves viscous ozonide that cannot be purified as it
is unstable and explosive in nature.
✔Ozonide is immediately treated with water and in the presence
of a reducing agent to form carbonyl compounds (ketone or
aldehyde).
D. POLYMERIZATION
✔Polymerization is a chemical reaction where small units or groups
combine together to make a bigger molecular material.
✔The small sub-units (or building blocks) are called monomers while the
resultant bigger molecular weight material is called polymer and the
process is called polymerization.
✔During polymerization, thousands of monomer unite together to make a
very large molecule. 
✔Ethene is an important feedstock for the synthesis of various polymers in
chemical industry. PVC and PE are commonly known words in our
everyday life. PVC stands for polyvinyl chloride while PE is
polyethylene. Both are plastics and are in use around us. 
✔Polyethylene is made up by the polymerization of numerous
ethylene units. The reaction proceeds via free radical
mechanism where oxygen or peroxide is used to initiate the
chemical reaction.
✔Another good example of polymerization is synthesis of
polyvinyl chloride. Here, ethene undergoes halogenation first and
then subsequent polymerization to form our popular plastic. 
GENERALIZATION
1. Why are alkenes reactive?
2. What are the general types of alkene reaction?
3. Define or describe each type.
4. What about the types of oxidation reaction?
5. Define or describe each type.
6. What is Markovnikov’s Rule?
EN
D
Thank you!