Engineering Chemistry III

Prof. Santosh Gharpure

Polar Reactions
Important points to be discussed in this module:
1. Chemistry of Carbocations with respect to:
a. 1,2-shifts of carbocations
b. Pinacol-pinacolone rearrangement
c. Semipinacolone rearrangement
2. Chemistry of Carbanions:
a. Alkylation and acylation of enolates
b. Aldol condensation
c. Michael reaction
d. Claisen and Dieckman condensation reactions
Chemistry of Carbocations
During the Friedel-Crafts alkylation, we saw that n-propyl cation (CH3CH2CH2+)
undergoes rearrangement to give rise to a more stable secondary carbocation
(CH3+CH2CH3). The driving force for this reaction is generation of a more stable
carbocation it is estimated that approximately 16 kcal/mol (67 kJ/mol) is gained by
conversion of a primary to a secondary or a secondary to tertiary carbocation. These
types of rearrangements are broadly classified as Wagner-Meerwein rearrangements and
involve 1,2-shift of an adjacent group. These types of reactions are common to all the
reactions which involve carbocation intermediate and the fate of the carbocation
intermediate is dependent of the reaction conditions. The reaction of neopentylic alcohol
with a mineral acid such as HCl can nicely illustrate this point. In this reaction,
depending on the exact reaction conditions, varying amounts 2-methyl-2-butene and 2chloro-2-methylbutane are formed and neopentyl chloride is conspicuous by its absence!
CH3 OH
H3 C

CH3 OH2

HCl

CH3

-H 2O

H 3C

H3 C
CH3

CH3

neopentyl
alcohol

1,2-shif t
H3C

CH 3

H 3C

-H+

CH3

CH3
CH3

2-methyl-2-butene

+Cl-

H 3C
Cl

CH3
CH 3

2-chloro-2-methylbutane

1
Indian Institute of Technology Madras

CH 2
CH3

Engineering Chemistry III

Prof. Santosh Gharpure

What happens in this transformation then? The answer to this question could be obtained
by writing the mechanism for this transformation. In the first step, the HCl protonates the
hydroxyl group of the neopentyl alcohol which leads to dehydration and subsequent
formation of neopentylic carboaction. This intermediate is extremely short lived and
rearranges via the migration of a methyl group along with its pair of bonding electrons to
generate a more stable tertiary carbocation. This process of intramolecular migration is
considerably faster than the intermolecular trapping of the carbocation with solvent or
chloride nucleophile. The migration of a group from one carbon to an adjacent
carbocation is commonly encountered when the reactive intermediate involved is
carbocations and is commonly referred to as 1,2-shift.
Pinacol Rearrangement:
1,2-diols, known as pinacols, also undergo a similar type of dehydration reaction when
treated with acid to furnish a ketone or aldehyde which have rearranged structure
compared to the initial diol. This transformation is commonly referred to as Pinacol
Rearrangement. Lets take an example when pinacol reacts with an acid, it leads to the
formation of pincolone. It is believed that this reaction also involves the formation of a
tertiary carbocation in the first step which is followed by 1,2-shift of the methyl group.
Now, the question will be if we already have a stable carbocation, why should it undergo
rearrangement? The answer is - the oxygen lone pair - which can stabilize the newly
formed carbocation by donating its lone pair to carbocation, thereby completing octet for
all the atoms involved. In fact, one could view this reaction as a push-pull reaction! The
carbocation pulls the alkyl group along with its bonding electrons towards itself while
the oxygen lone pair pushes the alkyl group away.
HO OH
H3C
CH3
H3C CH3

H+

HO OH2
H3C
CH3
H3C CH3

-H2O

OH
H3C
CH3
H3C CH3

pinacol

O
H3C

CH3
CH3
CH3

-H+

HO
H3C

CH3
CH3
CH3

pinacolone

2
Indian Institute of Technology Madras

HO CH3
H3C
CH3
CH3

Engineering Chemistry III

Prof. Santosh Gharpure

It is clear now that there are two important steps involved in pinacol rearrangement: (1)
loss of water from the protonated diol to form the carbocation; and (2) rearrangement of
the carbocation by a 1,2-shift to give rise to the protonated ketone.
OMe
HO OH
MeO

OMe
Ph Ph

H+
O
OMe
Ph

Ph

The next question that arises is what happens when the pinacol is unsymmetrical? In such
situations, the product obtained is determined (a) by which OH group is lost in step (1)
and then (b) by which group migrates in step (2) to the electron deficient carbon thus
formed. The OH group is usually lost from the carbon atom that will form the more
stable carbocation. The rate of migration of the groups in the second step is referred to as
the migratory aptitude of the group. Since the rearrangement involves movement of the
migrating group with its bonding electrons to an electron deficient centre, migratory
aptitudes are greatest for groups in which the migrating atom is most electron rich. It
should be kept in mind though that the direction of the rearrangement is largely
determined by the relative ease of removal of a OH group (first step) and rearrangement
may not necessarily involve the group of highest migratory aptitude.
HO OH
Et
H
H3C H

H+

HO OH
Ph
CH3
H H

H+

Et

CHO

H3C

H
Ph

H3C

A general order of migratory aptitudes for the pinacol rearrangements is:

p-anisyl > p-tolyl > phenyl > tert.-alkyl > primary alkyl > H
It should be noted however, that even though the migratory aptitudes generally follow the
order given above, the absolute comparison depends on the actual reaction and condition.
Semipinacol rearrangement:
The pinacol type of rearrangement is not limited only to vicinal diols. Deamination of aamino alcohols also leads to a reaction which closely resembles the pinacol

3
Indian Institute of Technology Madras

Engineering Chemistry III

Prof. Santosh Gharpure

rearrangement and is often called the semipinacol rearrangement. In this reaction, nitrous
acid is used to form an alkanediazonium ion which readily looses nitrogen to give the
intermediate carbocation.
Ph

HO NH2
CH3
Ph H

O
Ph

HO N2

HNO2
Ph

OH

-N2

Ph

CH3

Ph H

Ph H

CH3
H
Ph

-H+

CH3
H
Ph

HO
Ph

CH3

Ph

HO CH3
H
Ph

This reaction can be used for expansion as well as the contraction of medium sized rings.
NH2

HNO2

CHO

N2

N2

OH
NH2

HNO2

OH

4
Indian Institute of Technology Madras

Engineering Chemistry III

Prof. Santosh Gharpure

Assignment
A.

Suggest a suitable mechanism for the following reactions. Write each step and
show the rearrangement clearly by means of arrow.

1.
Cl

OH

HCl

Me

Me

2.
OH

Me

H+

Me
Me

Me

3.
OH

H+

OH

4.
Me
Me

H+

OH
OH

CHO

Me

Me

5.
OH Me
Me
OH

H+

Me
Me
O

6.
OH

HBr

Br

5
Indian Institute of Technology Madras

Me
+

Me
O

Engineering Chemistry III

B.

Prof. Santosh Gharpure

Identify the products of the following reactions and suggest a mechanism for the
reaction.

1.
OMe
H+

Ph
MeO

Ph
HO OH

2.
OH

H+

HO

3.
Ph Ph
Me

H+

Me
HO OH

4.
Ph
Me

HNO 2
CH 2NH2

HO

5.
Ph Me
Ph

HNO 2

Me
HO NH 2

6.
OMe
HNO 2
Ph
MeO

Ph
HO NH 2

6
Indian Institute of Technology Madras