CONTENT

1)
2)
3)

Pinacol Rearrangement
Wagner-Meerwin Rearrangement
Beckman Rearrangement

PINACOL
REARRANGEMENT
Wilhelm Rudolph Fittig
(6 December 1835 19 November 1910) was a
German chemist. Fittig discovered the
pinacol coupling reaction.

OH

OH

Pinacol are ditertiary 1,2-diols.

the simplest member of this class is Me2C(OH).C(OH)Me2.

2

When pinacol is treated with dilute moderately conc. H2SO4 a

rearrangement reaction takes place which leads to the formation
of Me3C.CO.Me(pinacolone).

CH3

CH3

CH3

OH

OH

Pinacol

CH3
CH3

CH3

CH3

CH3

Pinacolone

The acid catalysed rearrangement of vic diols (1-2 diols) to

ketone or aldehyde with elimination of water is known as Pinacol
pinacolone rearrangement.
Example shows that the migration origin and migration terminus
are the two adjacent carbon atoms.
the migrating group may be aryl group, or alkyl an H atom.
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Mechanisms:
Step1: reversible protonation to a hydroxyl group and elimination of
water molecule
R

OH2

OH

H
C

OH

OH

R
R

OH

Step2: formation of non-classical carbenium ion , a bridged intermediate.

R

R
R

R
OH

C
R
OH

Bridged intermediate

Step3:actual migration of a group to form the classical carbenium ion.

R

C
R
R

R
C

R
R
OH

C
OH

R3C

OH

Bridged intermediate

Step4: The loss of proton and the formation of oxo compound.

R

R3C

R3C
O

O
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STEREOCHEMISTRY:

Reaction is intra molecular.

When different group are present on C atom bearing the hydroxyl
groups, two question arise.

Ph

Ph

Me

HO

1.

Which of the two OH group will

1. beWhich
of the two OH group
protonated.
will be Protonated?

2.

Which of the group will

2. migrate?
Which of the group will
migrate?

Me

OH

2-methyl-1,1-diphenylpropane

Answer of
Q1

Stability order of
carbenium ion is

Ph2CH

> Ph

the carbenium ions. Decreasing stability order of

CMe > PhCH

>(CH3)2C

.CH3CH

Usually that OH receives the proton which produces the more stable
carbenium ion by elimination of water molecule.
thus in this example OH gr. On the C atom holding the phenyl gr Will
receive the proton since the stability of diphenyl carbenium ion is greater
than that OH dimethyl carbenium ion.
Stability of carbenium ion depend on the delocalization of positive charge
on the C atom either through resonance or through hyper conjugation.
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Answer of
Q2

There is no clear cut answer in so far as migratory preference is

concern.
It has found that a gr in anti or trans position with respect to the
leaving group, H2O, in the more stable conformation of the Protonated
substrate migrate preferentially.
Ph

Me

Me

H2SO4
Ph

C
HO

Me

OH

Ph

Ph

Me

2-methyl-1,1-diphenylpropane-1,2-diol
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10

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12

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Wagner-Meerwein rearrangement

OH conc. H SO
2
4

OH2

H
+

_H O
2
The Wagner-Meerwein
rearrangement is an organic
reaction used to convert an
alcohol to an olefin using an
acid catalyst.

Methyl shift
H H
_

H+

Mechanism

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BEKMANN REARRANGEMENT
The Beckmann rearrangement, named after
the
German
chemist
ERNST
OTTO
BECKMAN (18531923),
It is an acid catalyzed conversion of keto
oximes to N substituted amides usually called
the Bechmann rearrangement.

It is

reaction
R'
C
R

1.PCL5/ether
N

or H2SO4
OH

2.H2O

NHR'

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OXIMES
oIn organic chemistry, compounds containing the grouping C = N-OH,
derived from aldehyde and Ketones by condensing them with hydroxylamine.
oTwo types of oximes are known:
Aldoxime: combination of aldehyde with hydroxylamine.
Ketoxime: Combination of Ketones with hydroxylamine.

RCHO

+
R2CO

NH2OH

RHC=NOH

R2C=NOH
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MECHANISM
Step1) Formation of a better leaving group
R
C

OH
H2SO4

OH2
C

R'

R'

Step2) Ionization step

migration of anti group (w.r.t.leaving group) loss of leaving group
R

C
R'

OH2

OH2
N

R.D.step

R'

R'

R'

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Step3) Nucleophilic attach by water molecule to carbenium ion

R'

H2 O

OH2
C
R

R'

-H
R'

NHR

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20

GRIGNARD REACTION
Franois Auguste Victor Grignard (May 6,
1871 in Cherbourg - December 13, 1935 in Lyon)
was a Nobel Prize-winning French chemist.

RX + Mg

Introduction

Formula RMgX.it is prepared by the reaction

of metallic magnesium with the appropriate
organic halide.(R=ALKYL/ARYL/ALKENYL)
halied in order of reactivity (I> Br> Cl>> F).

Anhydrous ether

RMgX
Grignard
reagent

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Organolithium compound:
Less prone to unwanted side reaction. Lithium is more
electropositive than magnesium. Carbon lithium bond are more
polar than carbon magnesium bond. This are more reactive than
Grignard reagent.
halide.(R=ALKYL/ARYL/ALKENYL) halide in order of reactivity
(I> Br> Cl>> F).

RX + 2Li

Anhydrous ether

RLi +LiX
Grignard reagent

WHY GRIGNARD SYNTHESIS IS SO IMPORTANT?

because it enable us to take two organic molecules and convert
them in to bigger one.
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Reaction:
C

O + RMgX

OH

Mg(OH)X

Mechanism:

Alcohol

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STEREOCHEMISTRY
the reaction of carbonyl group can establish a steriocenter.if the
reactant are symmetric ,equal amount of the two enantiomers are
formed,

Me

1)MeMgI

Ph

Et

2)H

HO

OH

Me

+
Ph

Ph

Et

1Parts

Et

1 part

If one of the reactant are asymmetric, there is a predominance of the

one of the two possible diastereomers
H
H

Me

Mr

1)MeMgI
Ph

Me

CHO

2)H

Ph
HO

2 PART

Me
Mr

Ph
H

1 PART

OH

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REACTIONS:
reactions are classified with reference to the type of
compound which is obtained.
Hydrocarbons:
XMg

R +

CH3

CH3

+ MgX2

Grignard reagent react with alkyl halides and related compounds in the
SN2manner.the reaction with saturated halide are slow and the yields poor ,but
allyl and benzyl halide(more reactive than alkyl halide)react Efficiently.
oAlcohol:
R'

XMg

+
"R

R'
O

R
"R

H
O

MgX

R'
R

OH

"R

Grignard reagent react at the carbonyl carbon of aldehyde and ketone to give
alcohols.

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Aldehyde:

The reaction of Grignard reagent with ethyl orto format gives

an acetal which is converted by mild acid hydrolysis into
the aldehyde
EtO

EtO
OEt + RMgX

OEt + RMgOEt + X

EtO

EtO

oKetones:
Three methods are available
1)from nitriles.

RMgX +

R
O
R

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2)from N-substituted amides.

R
RMgX +

R'
MgX

R"2NH

N2"R

O+

3)from acid chlorides

1)PhCOCl

C6H11

Ph

C6H11MgBr
2)H
O

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Reaction at element other than carbon:

Grignard reagent may be used to attach various other

element to carbon. The following type of compound can be
obtained.

1) hydro peroxide
Me3C

O2
MgX

Me3C

MgX

Mg3C

CO2H

2) Thiols

RMgX

+ S

MgX
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3) sulfinic

acids
O

RMgX

+ SO2

H
MgX

OH
R

S
O

4)iodide.
RMgX + I

I +

MgXI

5)amines
RMgX + NH2

OCH3

NH2 + MgX(OCH3)
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Limitation:

Solvent must be scrupulously dried and freed of the alcohol from

which it was very probably made.
Grignard reagent will not even form in the presence of water.
Apparatus must be complelty dry before start. Protect reaction
from reaction from water vapors.
Grignard reagent can not prepare from a compound
(HOCH2CH2Br) that contain addition halogen/some other group (OH) that will react with a Grignard reagent.
In preparation of aryl magnesium halide substituent present on
benzene ring like COOH.-OH,-NH2,-SO3H contain hydrogen
attach to O or N are so acidic that they decompose Grignard
reagent .

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