Learning Guide Module

Subject Code Chem 3 Reactions and Interactions of Organic and Inorganic

Compounds
Module Code 2.0 Organic Reactions I
Lesson Code 2.7 Electrophilic Addition (Regioselectivity)
Time Limit 30 mins.

Components Tasks TAa ATAb

Target By the end of this module, the students will have been able to: 30 s
• Apply Markovnikov’s rules in predicting the products
of addition reactions
• Determine reactants given the addition products
Hook Check-up Drill (non-graded) 3 mins
Synthetic organic chemists design processes by which
compounds can be prepared in the most efficient way to yield
the highest volume and the purest form attainable. Explain why
substrate (a) is a better starting point than substrate (b) when
preparing the required product.

substrate (b).
one product is formed unlike with the unsymmetrical
the substitution of the alkene is symmetrical. Hence, only
Answer: Substrate (a) is the better starting point because

Ignite The mechanism of Electrophilic addition of hydrogen halides 15 mins

(or hydrohalogenation) in alkenes and alkynes is
characterized by the formation of a planar carbocation
intermediate. In substrates where the carbons forming the
double bond (or triple bond) vary in their degree of
substitution, the relative stability of the carbocation
intermediate formed determines which product among a
variety of possible products, will be formed in the greatest
amount (most favored) and is referred to as the major
product.

Chemistry 3 Electrophilic Addition (Regioselectivity) │ 1 of 6

 Consider the following examples. Determine the degree of
substitution for each of them. (non-graded)

Figure 1. Examples of alkenes with varying degrees of

substitution.

When these alkenes undergo electrophilic substitution, the

corresponding carbocation(s) are formed:

Figure 2. In compound (i), an unsubstituted alkene, only one

carbocation is formed leading to the formation of one
addition product. Unlike compound (i), two
carbocations can be formed from each of compounds
(ii), a disubstituted alkene, and (iii), a trisubstituted
alkene.

Variety in carbocations formed from a single substrate leads to

variations in products formed and to regioselectivity. Smith
(2017) defines a regioselective reaction to be one that yields
predominantly if not exclusively one constitutional [structural]
isomer when more than one constitutional isomer is possible.
The electrophilic addition of hydrogen halides HX in
unsymmetrical alkenes is a regioselective reaction which obeys
Markovnikov’s Rule:
_______________________________________

When HX adds to an unsymmetrical alkene, the H atom from

HX adds to the carbon with more hydrogens initially attached
to it- the less substituted carbon.

Chemistry 3 Electrophilic Addition (Regioselectivity) │ 2 of 6

 _______________________________________
In consequence, the more substituted and more stable
carbocation is formed.

❖ Indicate the degree of substitution (primary,

secondary, or tertiary) on each carbocation shown and
encircle the more stable carbocation in each pair (non-
graded).

than iiia
tertiary; iib is more stable than iia, iiib is more stable
Answer: iia-primary, iib-tertiary, iiia-secondary, iiib-

__________________________________________

Supplemental Activity
Are you curious about how the substitution of a carbocation
carbon affects its stability? Here’s a short video to help us
understand it better.

Knowbee (2015) Carbocation Stability and

Hyperconjugation in Organic Chemistry
https://youtu.be/_mEJ1aYmYo4

__________________________________________

When compound (iii) undergoes an electrophilic addition with

hydrogen chloride, the following distribution of products is
expected:

Figure 3. Electrophilic addition of HCl to 2-methylbut-2-ene.

The formation of product (iiib), a tertiary alkyl halide is

Chemistry 3 Electrophilic Addition (Regioselectivity) │ 3 of 6

 favored over (iiia) – a secondary alkyl halide.

It is worth noting that NOT ALL electrophilic addition

reactions in alkenes exhibit the Markovnikov rule or trend.
Among these is the addition of halogens X2 which proceeds
through a halonium ion intermediate and the addition of
water through hydroboration-oxidation which exhibits the
opposite or anti-Markovnikov rule.
Navigate Let’s see how we’re doing so far… 10 mins
CAN WE ALREADY:

Draw the product(s) for each of the following sets of

substrate and reagent and where multiple products are
formed, identify the major product?

2.7.1 (non-graded)

2.7.2 (graded)

2.7.3 (non-graded)

2.7.4 A hydration reaction (Markovnikov

electrophilic addition of water) (graded)

KNOT The mechanism of the hydrohalogenation of alkenes proceeds 1.5 mins

through electrophilic addition and involves the formation of a (wrap-
carbocation intermediate. The stability of the carbocation up)
intermediate, in consonance with the Markovnikov’s rule
determines the major product formed with an unsymmetrical
alkene. Many other types of electrophilic addition reactions
occur in alkenes and these do not necessarily involves the
formation of a carbocation intermediate nor obey the
Markovnikov’s rule.

Chemistry 3 Electrophilic Addition (Regioselectivity) │ 4 of 6

 Continues…
EXERCISES:
To tie things together even better, let’s work on the following
Supply the missing substrate and/ or reagent with which the
following compounds can be formed through electrophilic
addition:

a suggested time allocation set by the teacher

b actual time spent by the student (for information purposes only)

Answer key
NAVIGATE (Formative)

(2.7.1)

(2.7.3)

Chemistry 3 Electrophilic Addition (Regioselectivity) │ 5 of 6

 References

Discussion:
McMurry, J. (2017) Organic Chemistry. Cengage Learning Asia Pte. Ltd.

Smith, J.G. (2017) 5th Ed. Organic Chemistry. McGraw Hill Education, New York

Solomons, T.W.G., Fryhle, C.B., Snyder, S.A. 11th Ed. Organic Chemistry. John Wiley
& Sons, Inc.

Prepared by: Fiona U. Paredes Reviewed by: Erika Eunice Salvador

Position: Special Science Teacher (SST) II Position: Special Science Teacher (SST) III
Campus: PSHS-CAR Campus: PSHS-WVC

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