Rearrangements

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Rearrangements
Rearrangements are change in structure with or without any chemical reaction.

Rearrangements are divided into two categories
1) Electrophilic Rearrangements
2) Nucleophilic Rearrangements
Nucleophilic migration are those in which migrating group migrate with bonding
pair of e.
Migration can also divided in two categories on the basis of initial & final bonding
behaviour.
Homoatomic migration- Attachment of migrating group remains with some atom.
Hetero Atomic migration- Attachment of migratory group changes.
Wagner Meerwein Rearrangement

All kind of rearrangement taking place in carbonation are regarded as WM
rearrangement.
It is rearrangement of carbocation for the stability
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WMR is unaffected by source of carbonation.
In all case carbocation formed is
Carbonation is
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Relative Migration Tendency

Depend upon Nucleophilicity bcz it is a nucleoophilie migration
i.e. Aryl with EDe > Ph > Aryl with EWG > 30 > 20 > 10 > CH3 > H.
Exceptionally high tendency of migration of Ph group. Over alkyl can be

explained on the basis of intermediate of migration.
No such extra stabilization is possible in case of alkyl.
Migrating tendency also depends upon leaving group.
L= Cl aq. KOH 62%

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L= oTs
48%
L = NH2 (HNO2)
42%
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This can be explained on the basis of reactivity & selectivity.

If L is very good like
N
2
, it will remove immediately so there is no time for
rearrangement. So, rearrangement become unselective,

But if L is poor, it take time for departure, migration require some time, & it
become selective on the basis of Nucleophilicity and stability of T.s or
intermediate.
WMR can take place more than one time.
Sometime rearrangement is so extensive, there, is no relationship between reactant
& product.
WMR is trans migration with retention of configuration in migrating group

While inversion of configuration at terminal migration.
* inversion of configuration.
In cyclic system trans migration is a rigidity.
Anti migration is general rule in WMR as for as cyclic system is concerned.

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No. of Products:
During WMR all type of product possible are formed. With only one restriction
that carbocation will always rearrange for stability.
Q. How many isomeric alkene can be formed if this reactance undergo dehydration.
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Pinacol Pinacolone Rearrangement
One pair is major product & other one is Minor & out of Major pair one is
dominant.
Mech. Step-1 Protonation-
Step -2 Removal of H2O
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Which Oh products move stable carbonation will be protonated.

Step -3 Rearrangement-
PPR is a thermodynamic Rearrangement take place due to push- pull effect in

stable carbocation followed by ketonisation of product i.e. generation of carbonyl
carbon.
Relative migrating tendency remain some as for WMR but subject to stability
carbocation.
Basic Diff between WMR & PPR WMR takes place for stability carbonation. Which PPR takes place in stable
carbocatoin.
Is PPR a general Reaction or specific Reaction any system which is capable to

give
give PPR.
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Stereochemistry of PPR remains same i.e. configuration in Transmigration with

retention of migrating group. Put inversion at migrating terminal.
In cyclic system Transmigration is rigidity.
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Dienone-Phenol Rearrangement:
Mechanism
Step -1 protonation
Step -2
Mech. of minor product-
e-& are more Nucleophilic but due to product stability 5-mem. Ring product is
never major product.
But its proportion increases as migrating tendency of R1& R2 (but never above
50%) decreases.
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Migration is a matter of 3 factors1
Initial situation
(2) Transition sate
Consider the migration of Ph -
3) Final stage
After CH3 migration
But intermediate for Ph migrant is more stable.
But in case of COOEt

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So in this case carbocation stability become imp.

.:-Ph Migration is restricted. Whenever EWG like COOEt, NO2, CN, COOR,
CONH2, COOH, SO3H, CF3, -Cll3.
These group will migrate preferentially to Ph group.
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Rearrangements

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CSIR-NET, SET

Rearrangements are change in structure with or without any chemical reaction.

Hetero Atomic migration- Attachment of migratory group changes.

Wagner Meerwein Rearrangement

It is rearrangement of carbocation for the stability

WMR is unaffected by source of carbonation.

In all case carbocation formed is

Relative Migration Tendency

Exceptionally high tendency of migration of Ph group. Over alkyl can be

No such extra stabilization is possible in case of alkyl.

Migrating tendency also depends upon leaving group.

L= Cl aq. KOH 62%

This can be explained on the basis of reactivity & selectivity.

rearrangement. So, rearrangement become unselective,

WMR is trans migration with retention of configuration in migrating group

Anti migration is general rule in WMR as for as cyclic system is concerned.

Pinacol Pinacolone Rearrangement

Step -2 Removal of H2O

Which Oh products move stable carbonation will be protonated.

PPR is a thermodynamic Rearrangement take place due to push- pull effect in

Is PPR a general Reaction or specific Reaction any system which is capable to

Stereochemistry of PPR remains same i.e. configuration in Transmigration with

Mech. of minor product-

Migration is a matter of 3 factors1

(2) Transition sate

Consider the migration of Ph -

After CH3 migration

But intermediate for Ph migrant is more stable.

But in case of COOEt

So in this case carbocation stability become imp.

These group will migrate preferentially to Ph group.

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