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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 2-
chloro-2-methylbutane are formed and neopentyl chloride is conspicuous by its absence!
CH3 OH CH3 OH2 CH3
HCl -H 2O
H3 C H3 C H 3C CH 2
CH3 CH3 CH3
neopentyl
alcohol 1,2-shif t

H3C -H+ H 3C +Cl- H 3C


CH 3 CH3 CH3
Cl
CH3 CH3 CH 3
2-methyl-2-butene 2-chloro-2-methylbutane

Indian Institute of Technology Madras


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. Let’s 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 HO OH2 OH
H+ -H2O
H3C CH3 H3C CH3 H3C CH3
H3C CH3 H3C CH3 H3C CH3
pinacol

O CH3 CH3 HO CH3


-H+ HO
CH3 CH3 H3C CH3
H3C CH3 H3C CH3
CH3
pinacolone

Indian Institute of Technology Madras


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
H+
MeO OMe
O
Ph Ph
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 CHO
H+
Et H
H3C H H3C

HO OH O H
H+
Ph CH3 Ph
H H H3C H

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 a-
amino alcohols also leads to a reaction which closely resembles the pinacol

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.
HO NH2 HO N2 -N2 OH
HNO2
Ph CH3 Ph CH3 Ph CH3
Ph H Ph H Ph H

O CH3 CH3 HO CH3


-H+ HO
H H Ph H
Ph Ph Ph Ph
Ph

This reaction can be used for expansion as well as the contraction of medium sized rings.
NH2 HNO2
CHO + N2
OH

NH2 HNO2 O
+ N2
OH

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+
O
OH

4.

Me OH H+ CHO
Me
Me OH
Me
5.
Me Me
OH Me
H+ Me Me
Me +
O
OH O

6.
OH HBr
Br

Indian Institute of Technology Madras


Engineering Chemistry III Prof. Santosh Gharpure

B. 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
H+
Me Me
HO OH
4.
Ph HNO 2
Me CH 2NH2
HO
5.
Ph Me HNO 2
Ph Me
HO NH 2

6.
OMe

HNO 2
Ph
MeO Ph
HO NH 2

Indian Institute of Technology Madras

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