Markovnikov's rule (1870)

This is an empirical rule based on Markovnikov's experimental observations on the addition of hydrogen halides to alkenes.
The rule states that :

"when an unsymmetrical alkene reacts with a hydrogen halide to give an alkyl halide, the hydrogen adds to the carbon of the
alkene that has the greater number of hydrogen substituents, and the halogen to the carbon of the alkene with the fewer
number of hydrogen substituents"

This is illustrated by the following example: Br H

H3C C CH 2 + HBr
H H3 C C CH 2
H
(Look at the position of the H and the Br in relation to the statement of Markovnikovs rule given above.)

Why does this happen? Current knowledge indicates that the reaction occurs via protonation to give the more stable
carbocation (an ion with a positively-charged carbon atom). The general stability order of simple alkyl carbocations is:

H 3C CH 3 H 3C H H H H H
C+ C+ C+ C+

CH 3 CH 3 CH 3 H

(most stable) 3° > 2° > 1° > methyl (least stable).

On the previous example, there could be two “possible” ways in which the reaction happens; notice the different carbocations
that form in every case:
H
Br H
A)
H 3C C CH 2 + H Br H 3C C+ CH 2 + Br-
H 3C C CH 2
H
H H
Secondary carbocation.

H
H Br
B)
H 3C C CH 2 + H Br H 3C C +CH 2 + Br-
H 3C C CH 2
H
H H
Primary Carbocation

Since reaction A is the one that leads to the formation of the most stable carbocation (secondary), 2-bromopropane is the
product of the reaction and 1-bromo propane will not be formed.

Keep in mind that:

- The rule applies to molecules with the formula H–X, like H–Cl, H–Br, H–OH and H–HSO4.
- The rule can also be used with alkynes.
- Some alkenes are symmetric at the double bond, but they have an unsymmetrical structure and you
will get two products from the reaction. Look at the following example:
H Cl
H2
H3 C C C C CH 3
H H Using Markovnikov’s rule there is
3-chloropentane no preference, but the fact that the
H2
H3 C C C C CH 3 + HCl
H H
Cl H
alkene is unsymmetrical leads to
H2
these two different products.
Both C’s at the double bond have H3 C C
H
C
H
C CH 3

the same # of H’s. So H could bond 2-chloropentane

to any of the two.
Reyes 1
Markovnikov's rule (The hydrogen from HX goes to the carbon with the greatest number of H atoms in the double bond.)

Using Markovnikov’s rule, find the reaction product given by the following reactions. Make sure to check if you could get
different products from the reaction.

a. H H2
C C
H+
H 3C C CH3 + H 2O

CH 3

b.

H2 H H2
C C C H CH 3
H3 C C C C + HBr
H2 H
CH3

c. H2
H3C C C CH + 2HCl

d. H3 C C C CH3 HI
+
CH3 CH3

e.
H+
+ H 2O

Reyes 2