Concentrated sulphuric

Dehydration acid
of (H
alcohols
2SO4) or
phosphoric acid
(H3PO4) : as acidic
alcohols
catalysts and
dehydrating agents.
C

OH

H2 SO4 (conc.)

H2 O

The major product is the MOST

STABLE ALKENE, which has greater
number of alkyl group attach to C=C is
follow SAYTZEFFS RULE.

Mechanism of dehydration of alcohols

3 step of mechanism

Protonati
on of
alcohols

Step
1

Step
2

Formation of
carbocation

Formatio
n of
alkenes

Step
3

Step 1 : Protonation of alcohols

H
H has form
A bond
+
as
aOresult
from
H C C CH CH
:
H
+
is
3
2 What
3
protonation
Why
it has +
:OH
H
..
protonation? (nucleophile

(nucleophile
charge?
reacts with acid,
attacking
atom
OxygenHhas
loss
+
from
H
0
3 H of
Electron
its pair
H
+
+
move
to
electron
(make a
H
or
H
0
3
Nucleophile
(lone
pair
at
+
H
C
C
CH
CH
O HH
:
Oxygen (look
bond with
3atom)
2
3
..
O
attack
+
at arrow
atom) and it also
:
OH
electrophile
movement) (H atom
has +1 formal
H acid)
form
charge

Step 2 : Formation of carbocation

How to neutralize
the
H
H
+ charge?
+
H C C CH CH Move the electron
H
C
C
CH
CH
form
3
2
3
2
3
3
+
:OH
Carbon to Oxygen (look
carbocation
at
arrow
movement).
H
This will results a
H
carbocation
formation.
0
3
Redraw the
+
:O H
carbocati
previous
..
on
structure from
step 1

Step 3 : Formation of alkenes

H H H
H C C+ C CH

a
OR

In order to form
an alkenes, all
the bond
surrounded
carbocation
has
Lets
look at these
twopossibilities
possibilitiesto
form
a double
1.Root
a
a
bond
2.Root
b
(Look at arrow
movement)

Step 3 : Formation of alkenes

Root b

alkene
a

Root a

H
H H H
H
H C C+ C CH + : O H
C
..
3
H C
H
H
H2O alkene
+
(determine
b
Hfrom step 1)
H
asH
a
: Onucleophile
H
C C

..

CH2CH3

H
C
+

H
+
:O
H

CH
3

How to determine major and

minor product?
H
H H H Saytzeffs
rule H
H
+
An
elimination
the
: O H gives
H C C C CH +usually
C
C
..
3
most stable
alkene
product,
b
H highly
C
CH
a the most
H commonly
H
3
3
+
+ substituted alkene.major
H
H

:O
H
..

C
H

+
+ :O
C
CH2CH3 H

minor

Rearrangement During Dehydration of Alcohol

Example 1:
CH H
HC
3

CH OH

CH

H SO (conc.)
2

You might predict

the structure
beside but the
answer is wrong.
But WHY?

CH H
HC
3

CH
3

CH
2

Rearrangement During Dehydration of Alcohol

Example 1:
CH H
HC
3

CH OH

CH
3

H SO (conc.)
2

This is because CH
CH3
3
rearrangement
H C C CH CH
+ actual
H 3C
C occurs.
C C H 3The
2
3
is.
C Hproduct
CH
3
3
(major product)
(minor product)

Step 1 : Protonation of alcohols

CH H
HC
3

CH +

CH :OH
..

H
+
:O H
H

CH H
H

:O
..

+
H

HC
3

C CH
3
+
CH :OH
3

Step 2 : Formation of carbocation

The rearrangement
CH
H through the
occurs
CH H
3
migration of an alkyl
3
H Cgroup
C C
CH from theH C C C+ CH
(methyl)
2 1
3
3
4
+ atom adjacent to 3 0
3
0
carbon
0
CH :OH
CH
the one
3 with the positive
2
3
H charge.
carbocation
Rearrangement
0

1,2-methy shift

Because
group
CHa H
3 the one
migrates from
H Cto the
C next,
C CH
carbon
this
3
+
kind of3 rearrangement
is
3 carbocation
CH
often
called
a
1,23 shift.
More stable
0

Less stable

Step 3 : Formation of alkenes

(a)

H CH H
H- C
H

C
+

CH
HC
3

:O H
..

(b)

CH

Major
product

CH

CH

CH

3
C CH

H
:O H
..

HC
2

C
CH

3
CH CH
3

Minor
product

Try this!
CH H
3
H C C C CH
3
3
H OH

H2SO4 (conc)

CH
3
H C C CH CH
3
3

CH
3
H C C CH CH
2
2 3