Dehydrohalogenation: this is another elimination reaction like the dehydration reaction.

Recall that we have studied the dehydration reaction. In that reaction, an alcohol is heated with a strong acid catalyst to
produce an alkene and water.

OH acid


+ H2O

Notice that in this reaction, a hydroxyl group (OH) is removed from the α (alpha) carbon and a hydrogen atom (H) is
removed from the β (beta) carbon which produces a π (pi) bond between the α and β carbons.

OH acid


+ H2O

beta carbon
alpha carbon
alpha carbon
beta carbon
beta carbon

We must also recall that a compound might have several different β carbons, and therefore more than one product may
form since removing a hydrogen from one of the β positions might lead to a product that is different than removing a
hydrogen from the other β position(s). For example, consider the alcohol 2-butanol.

HO
This alcohol has an α carbon, two different β carbons, and it has a γ (gamma) carbon. (the gamma carbon isn’t
important to know about, its just the next carbon and if the chain continued we would label those carbons with the next
letters in the Greek alphabet).

 

 

HO
So, when 2-butanol is heated with an acid catalyst, 2 different alkene products are produced. (example at the top of the
next page)
 

 acid


+
  
HO
MAJOR MINOR
PRODUCT PRODUCT
We have learned that the more substituted double bond is more stable, and that this reaction produces a major product
according to stability so therefore the major product here is the one which creates that α to β1 double bond and the
other product which is the α to β2 double bond is the minor product. Zaitsev’s rule helps us find this major product,
since this rule says that we should remove the hydrogen from the β carbon which has the fewest hydrogen atoms
bonded. Looking at the reactant alcohol, β1 has 2 hydrogen atoms, while β2 has 3 hydrogen atoms and according to
Zaitsev’s rule the major product should therefore be the one with a double bond between α and β1.

The dehydrohalogenation reaction is similar, except instead of removing the OH from the alpha carbon and H from
the beta carbon, a halogen atom is removed from the α carbon and hydrogen is removed from the β carbon. In the
example below, X represents a halogen atom, which can be Cl or Br or I.. it cannot be F because F won’t work. If you are
curious about why all halogens work except F, it has to do with basicity and the fact that Cl, Br and I are all conjugate
bases of strong acids while F is not.

 

  +

 
X
MAJOR MINOR
PRODUCT PRODUCT
The same Zaitsev rule applies to find the major product. There is however a MAJOR difference between the dehydration
reaction and the dehydrohalogenation reaction, and that is the reagent that is needed to affect the conversion. The
dehydration reaction is carried out by heating the alcohol in strong acid, where the strong acid is a catalyst. The
dehydrohalogenation reaction is carried out by heating the alkyl halide in strong base, where the strong base is a
reagent and not a catalyst.

HO 
+ HCl
+ H2O + HCl

Br 
+ NaOH + NaBr + H2O
There is, however, one aspect of the dehydrohalogenation reaction which makes it complicated and that is the fact that
it is an anti- elimination. This stereochemical aspect of the reaction makes it slightly tricky. Remember that Br2 or Cl2
addition to the double bond was an anti- addition reaction.

Br Br

Br2 Br Br

Similarly, the dehydrohalogenation reaction is an anti-elimination which means that the halogen and the hydrogen must
be anti to one another otherwise the reaction cannot happen. So, in the example below,

Br
H3C 
 

according to Zaitsev’s rule we would assume that the elimination would occur between α and β1 (which has only 1
hydrogen atom) rather than between α and β2 (which has 2 hydrogen atoms) but the hydrogen atom on β1 is NOT anti
to the halogen and therefore it cannot be eliminated. Therefore, there is only 1 product formed.

Br
H3C  
NaOH H3C
   

ONLY
PRODUCT

In our class, I am not going to make a big deal out of the stereochemical aspect of this reaction, because for alkanes we
usually don’t have to consider this anti aspect of the reaction. This reaction is going to be very useful in synthesis as we
will see shortly.