Chapter 3..

Rearrangement Reactions
Contents ...
3.1 Introduction
3.2 Types of Rearrangements
3.3 Types of Reactive Intermediates involved in different Rearrangements
3.4 Beckmann Rearrangement
3.5 Baeyer-Viliger Oxidation
3.6 Favorskii Rearrangement
3.7 Curtius Rearrangement
3.8 Lossen Rearrangement
3.9 Schmidt Rearrangement
3.10 Pinacol-Pinacolone Rearrangeme
3.11 Electrocyclic Rearrangements
3.11.1 The Claisen Rearrangement
3.11.2 Cope Rearrangement
3.11.3 Mc-Lafferty Rearrangement
Exercise

3.1 Introduction
A rearrangement reaction is a broad class of organic reactions where the carbon
to give a structural isomer of the original molecule.
skeleton of a molecule is rearranged
the same
The migration of an group from one position to another within
atom or
The rearrangement involves migration of
molecule is known as molecular rearrangement.
or in some cases migration is
an atom or of atoms to an adjacent atom (L,2-shift),
group
Over longer distances.
where,
M A Migration origin
M
B Migrationterminus
AB 1.2-shift AA B M Migrating group
atom to
he atom from which migration begins is
known as the migration origin and the
moves is called migration terminus.
which migration qroup

(3.1)
 [Link]. Organic Chemistry I (Sem. V) 3.2 Rearrangement Reactions
In rearrangement reaction, migrating group shift with its lone pair of electrons clled as
nucleophilic (anionotropic) rearrangement and migrating group shift without electron
pair is called electrophilic (cationotropic) rearrangement. In the rearrangement, if the
migration of group is with one electron then it is called free radical rearrangement.

The most common migrating atoms are carbon, hydrogen or heteroatom. The
nucleophilic 1.2-shifts are more common in rearrangement reactions. The rearrangement

reaction involves two possible modes of reaction as shown below.

R R R R R R

A-8 and A -C A-B and A- C with A - B and A-C

Intermolecular rearrangement
R R R R

)A-B and A -C A- B and A-C

Intramolecular rearrangement
type of rearrangements are called as intermolecular rearrangement in which the group
Ris completely detached from group A and may end up on the B atom or C atom of
another molecule. In 'I type of rearrangement, R going from A to B in the same
molecule is called intramolecularrearrangement.
3.2 Types of Rearrangements
There are two key rearrangement reactions:
1,2-rearrangements and pericyclic reactions
(i) 1,2-Rearrangements: In this type of reaction the
migrating group carries the
electron pair with it, the
migration terminus B must be an electron deficient atom with only
Six electrons in its Outer shell. The first
step is the formation of a carbocation intermediate.
Carbocation can be formed from alcohol
(the acid treatment of an alcohol to give
carbocation from an intermediate oxonium ion), alkyl halide
(reaction with AgNO3) and
alkene (electrophilic addition to C=C).
R

A-B B

R H,O
H HH
oH H
-C-H
H H
Carbocation intermediate
 Rearrangement
[Link]. Organic Chemistry -I (Sem. V)
3.3

Lossen, Schmiat
Examples rearrangements are, Beckmann, Baeyer-Villiger,
of these

Cutius, Pinacol, Wagner-Meerwein Rearrangement

H
HO
H,O

i) Pericyclic reaction
-
A pericyclic reaction is a type of reaction with multiple carbon

carbon bond making and breaking wherein the transition state of the molecule has a cyclic
Eamples
fashion. of pericyclic
geometry and the reaction progresses in a concerted
reactions are Claisen, Cope, Diels Alder and McLafferty rearrangements
R Y (1,3)
H

(1,5)
H
R

3.3 Types
3.3 Types of
-
Reactive
H
Intermediates
(1,7)

involved in Different

Rearrangements
Pearangement reactions usually involve carbocation, carbanion, carbene and electron

ceficient nitrogen and oxygen intermediates. Carbocation intermediates are most common

ir termediates in rearrangement reactions.

earrangements involving Carbocation Intermediate

The skeletal rearrangement of carbocation which involves migration of B-alkyl. aryl or

G-bond is called Wagner-Meerwein rearrangement. In most of the carbocation
of atom or group occurs due to the formation of
rearrangement reactions, migration an

more stable carbocation from less stable carbocation. Neopentyl alcohol on treatment
with HCi gives the rearranged product 2-chloro-2-methyl butane.
[Link]. Organic hemistry - I (Sem. v) 3.4 Rearrangement Reaction
CH CH 1, 2-CH CH
CH, OH2
I T -HO
HC C-CH-OH HCI H,C-C-CH2 H,0H,C-- HshiftH,C--CH2
CHa CH CH, H CH3
(Neopentyl alcohol)
2, 2-dimethyl propanol
I-Carbocation III°-Carbocation
(less stable) (more stable)

CI

H,C-CCH-CH
CH
2-chloro-2-methyl butane
Rearranged product
This rearrangement occurs via carbocation intermediate and involves migration of alkR
with its lone pair of electrons to an electron deficient carbon atom. It forms more
stable carbocation which finally react with nucleophile to give rearranged product.
In another case, the addition of HCl to 3,3-dimethyl-1-butene forms 3-chloro-22. re
dimethy! butane (an expected product) and 2-chloro-2,3-dimethyl butane R
(rearrangement product). The rearranged product is the major product.

CH :CH3 H CH
HCI H,C-C 1,2-CH,shift
HCc-c=¢-H- H,CC-C-CH
CH, H H CH H
3, 3-dimethyl-1-butene II°-Carbocation III°-Carbocation
(less stable) more stable)

CI CH3
HC-C-C-CH
CH, H
2-chloro-2, 3-dimethyl butane
The order of stability of carbocations is I > I > f >
H
The carbocations rearrange only if ot
they become more stable as a result
rearrangement.
CH3 CH3 CH
HC-C-CH2 Br AgNO3
HO
HC-C 1, 2-CH, shift
H,C--C
CHa CH
1-Bromo-2, 2-dimethyl propane CH
I°-Carbocation III°-Carbocation
[Link]. Organic Chemistry I (Sem. V) 3.5 Rearrangement Reactions

CH 1,2-H shift CH3 1,2-CH, Ch 1,2-H

shift
C Sn H

CH CH CH CH CH CH
II°-Carbocation I1°-Carbocation I1°-Carbocation
more stable

CH

CH CH
III°-Carbocation
Other examples of rearangements involving carbocation intermediate are Pinacol, semi-
pinacol rearrangements.
Rearrangements involving Carbanion Intermediate
ments involving carbanion intermediates are rare. Some examples of carbanion
ntermediates in rearrangements are Favorskii, Ramberg-Bäcklund, Stevens and Wittig

earrangements.
Rearrangements involving Carbene
Rearrangement involving carbene intermediates is Wolff rearrangement.
Rearrangements involving Electron Deficient Nitrogen and Oxygen

Rearrengements to electron-deficient nitrogen are Beckmann, Neber, Hoffmann, Curtius

Schmict, Lossen and Baeyer-Villiger rearrangement.
3.4 Beckmann Rearrangement
earrangement of oximes to give N-substituted carboxylic amides, the rearrangement of
ketoxime under the influence of acidic reagents to yield N-substituted carboxylic amides
Aldoximes often are less reactive and they form
S Called the Beckmann rearrangement.
itrie.
PCl5 - R

C=N R
OH
R
H
Ris anti to OH
O

Ph PCl N P h

=NOH HC
HC
to give
the hydroxy group of the oxime is protonated
PC treaiment with a protic acid, water molecule. The
anti group migration
a XOLim derivative which can easily lose a

electrons) and loss of water proceed

h e sbstituent R (together with the bonding
[Link]. Organic Chemistry 1 (Sem. V) 3.6 Rearrangement Reactio
with water to give the imi
Simultaneously. The cationic species thus formed reacts
stable amide tautomer,
the N-substituted carbor
which tautomerizes to a more

are concentrated sulfuric acid, hydrochloric acid, liquid sulfur dioxin

amide As reagents
e v e n silica gel MoO, on sil
zinc oxide and
thionyl chionde phosphorus pentachloride,
POCl, BiCl3, heat
with FeCl3, and polyphospho
gel RuCl Y(OT) HCI-HOAc AcO, like phosphoruS pentachlori
acid can be used for Becknmann rearrangement. Reagents
chloride and others) first
convert the hydroxy group of the oxime ir
as
well thionyl
as

a good leaving group enlargement and form lactam

The reaction with oximes of cyclic ketones leads to ring
reaction is pertormed
on an industrial sca
enlargement. This particular
-caprolactam is used as a monomer for polymerization
to polyamide for the productic
of synthetic fibers
R
c a=N = N1 , 2 -R shift R-C

HO
N- R CN-R N-R
H-O

H,0
OH
N

N-H
HN-OH
HO
Example of Beckmann rearrangement:

NH,OH
HSO. H.O, A
N O
O
H

N-OH O H

(HPO )n
N
N-OH O H
Anthrancene-9.10-dioxime dibenzofb.f[1,4]diazocine
6,11 (5H,12H)dione
[Link]. Organic Chemistry I (Sem. V) 3.7 Rearrangement Reactions

3.5 Baeyer Villiger Oxidation

.The treatment of ketones with peroxy acids or with hydrogen peroxide, in the presence
of acid catalysts, a formal insertion of oxygen followed by migration of alkyl or aryl group
can take place to yield a carboxylic ester. This reaction is called the Baeyer-Villiger
rearrangement.

H,0. H
or
O - R
R - C

R oO, RR--OH
R
ina first step, the carbonyl group is taking the proton from acid and protonated to form
carbocation intermediate.
In the second step, the peracid adds to the carbocation to form Criegee intermediate
n the third step, migration of alkyl or aryl takes place with the elimination of carboxylic

Oo-H O-H R

-R

R ~oH
The ease of migration of substituents R, Rz depends on their ability to stabilize a positive
cnerge in the transition state. For unsymmetrical ketones the approximate order of
igration is RC > R,CH> Ar > RCH,> [Link] CH3 group has a low migrating ability,
ara the migrating ability of aryl groups is decreased by electron-withdrawing and
ncreased by electron-donating substituents. The Baeyer-Villiger oxidation of
unsymmetrical ketones is regioselective.
o-H
Bu
FC-COOH
- 0-0-C-CH
Bu
Bu

1 -HH

O
+CFC
Bu
[Link]. Organic Chemistry I (Sem. V)
3.8
Rearrangement React
tO yield lactones (cyclic esterc Y.B.S
Cychc ketones react through ring expansion sters). Hydro
ketones to lacTones
using a catalytic arm eact
peroxide has been used to convert cyclic Ourt

MeReO
mCPBA -O

OBn
OBn
CI
C
mCPBA

NaHCO3. CH2Cl2 BnO

BnO
OBn OBn

Examples of Baeyer Villiger Oxidation :

OH OH OH
H mCPBA OH Hydrolysis OH

CH2Cl2 O

CF COOOH
HC
CH H c H CH

3.6 Favorskii Rearrangement

2-Halo ketones (chloro, bromo, or iodo) possessing at least one a-hydrogen
reated with a base (NaOH or NaOEt reac
or NaNH2), Can undergo a
rearrangeme
Via a Cyciopropanone intermediate to give a carboxylic acid or an ester
or a
depending on the base used. This reaction
is called the Favorskii rearrangeme
the first step,
In
the u-halo ketone is deprotonated by the base at
n to g
the the d-Lau
carbanion, which
undergoes a ring-closure reaction by an intramolecuid
substitut
give the
cyclopropanone
to

derivative. The nucleophilic addition of the base to

Cyciopropanone intermediate leads to the
of the Substitule

ring a openinq. With symmetricduyoduct I

ically
cyciopropanone, leavage of
either Cu CO bond leads to
the same P
unsymmetrical cyclopropanone, that bond is which leadk
broken preferentially wne
thermodynamically more stable carbanion. The carbanion protonate0

give the final product. intermediate p

is
[Link]. Organic chemistry -I (Sem. V) 3.9 Rearrangement Reactions

Reaction mechanism

CH3 CH 1
CH, Na0CH, H,c C CH H,C ,cH
CH HOC,H OCH H,C CH
CI

Protons a' to ketone is acidicc Cl is a leaving group Cyclopropanones are

and sodium ethoxide is strong Carbanion attack on the particularly susceptible
base that easily abstract the a carbon atom and substitution to nucleophilic addition
proton to formm cabanion as reaction takes place to give due to ring strain
nucleophie cyclopropanone
Addition elimination reaction at the carbonyl and cyclopropanone ring opening takes
place to generate a stabilised enolate product.

pcHs ROH
CH O
CH OCHs H3C CH3 H,C -C-ocH,
H,C H,C
cH
H CH
C-OCH
Hc
CHa

CH,OPh-CH
Pr-CHË-CH2 CH Ph-

H
CI
OH

H O Ph-CH-CH-C-O - Ph-CH-CHC-OH
Ph-CH-CH-C-OH contraction as shown in the
yclic -halo ketones on treatment with base give ring
cllowing reaction
aocHs

CH,OH

C-OEt Eto-C=0
[Link]. Organic Chemistry - I (Sem. V) .10 Rearrangement Reactio
Reac
aree
The two important variations of Favorskii rearrangement
the reactin.
of nucleophile
B-halo ketones treated with base, in presence on
1 When are
This reaction takes place via
a a cyclobutanor
called Homo-Favorskii arrangement.

intermediate
R
R
R ROH
Base R R
R-
RR
R R 0
RO
R alkyl/hydrogen

does not have any enolizable hydrogen then the reaction is called :
Ia-haloketone

Quasi-Favorskii rearrangement.

Oo) oR R
R

R RO
OR R R R R
R

Examples of Favorskii rearrangement:

HC-CH-C-CH2-CH 4 CH-CHCH-C-OH

Br HHO CH3

(1) KOH, HO
MeOH COOH
(2) dil. HCI
-CI

3.7 The Curtius Rearrangement

involves the thermal decomposition of
an acyl azide to yie s
The Curtius rearrangement
loss of N2. Isocyanate on hydrolysis gives amine. The cu
an isocyanate by amines.
can thus be applied to convert carboxylic acids into primary
rearrangement

CICO,Et R O OEt
NaN3
Mixed anhydride

SOCl2 NaN3 R--N, R-N=C=O

R-OH R- CI
Acid chloride Acyl azide
-N Isocyanate
TMSN
(PhO)P(O)N
Diphenyl phosphoryl azide (DPPA)
 I (Sem. V)
[Link]. Organic Chemistry 3.11
Rearrangement Reactions
This reaction can be applied to almost any carboxylic acids such as aliphatic, aromatic,
alicyclic. heterocyclic, unsaturated, and containing many functional groups. The required
acyl azide can be prepared from the corresponding acyl chloride and azide ion (e.g. with
sodium azide) or alternatively from an acyl hydrazine by treatment with nitrous acidd or
from mixed anhydride.
Acyl azide can be synthesized from carboxylic acid by using diphenyl phosphoryl azide
(DPPA)
HO
O=C=0R 10 Amine
NH

R-N=C=0- RNH2 C NHR

H
Urea derivative

R-OH R
OR

Carbamate
Loss of N; and migration of the group R is likely to be a concerted process, since
evidence for a free acyl nitrene RCON in the thermal reaction has not been found.

NaN3
R-C-C+
or TMSN
R Na
Alkali azide
Trimethyl slylazide
Nitrous acid

-NHNH2 +HNO, RN
O
RoOEt NaNa
P-C-OH+CI-CO,Et R N
Mixed anhydride

OEt
0 OEt NaN3
N'PrEt

N PhCH,OH ph
N00

H
ihe Curtius rearrangement is catalyzed by Lewis or protic acids, but good yields of
product are often obtained also without a catalyst. Isocyanates are highly reactive and
they immediately react with water and form amine. When alcohol is used as a solvent, the
isocyanate reacts with alcohol to form carbamate. From reaction in an inert solvent
e.g. benzene, chloroform) in the absence of water, the isocyanate can be isolated.
[Link]. Organic Chemistry I (Sem. V) 3.12 Rearrangement Reacti
The examples of Curtius rearrangement are:

-C-CI
NaN,/ a
HC H,O
H,C-NH

R C N ,Ero, R-N- -OEt

R-C NHNH, HNO

COOH
ODPPA. EL,N OCH,Ph
benrene reflux

CM,CH,OH LX
DPPA IS prepared from the corresponding acyl chloride and azide 1on (e.g. with soditn

azide) or alternatively from an acylhydrazine by treatment with nitrous acid.

R--OH (Pho),P-N= N=N R N==R

Diphenyl phosphoryl azide (DPPA)

The example of Curtius rearrangement

OH OH
OBn O=C= OBn HN OBn

DPPA EtgN
Toiuene, heat
OMe OMe OMe

3.8 Lossen Rearrangement

The Lossen rearrangement is the conversion of a hydroxamate ester to an isocyanate
Typicaly, O-acyl, sulfonyl, or phosphoryl 0-derivative are employed. The isocyanate can
be used further to generate ureas in the presence of amines or generate amines in the

presence of H;O.

R N=C=0
Mechanism
I n the first step an
O-acylated hydroxamic acid derivative is first converted to
conjugate base by abstraction of a
hydrogen by a base. Spontaneous rearrangee
releases a
carboxylate anion to produce the isocyanate intermediate.
[Link]. Organic Chemistry I (Sem. V) 3.13 Rearrangement Reactions
In the second step the isocyanate is hydrolyzed in the presence of H,O.
In the final step, the respective amine and CO, are generated by abstraction of a proton
with a base and decarboxylation.

H,O
R
R OH

R-CO2
R
=O=0 CO2
R-NH2

-CO2
OH H,O B:

R
R
-R-CO2
R
N=Ö=0 R
Examples of Lossen Rearrangement

CH3 NH2
NaOH
-H%O
ON ON
4-Nitroaniline
N-acetoxy-4-nitrobenzamide

N
CH3 KOH
NH2
H -HO
N-acetoxyfuran-2-carboxyamide Furan-2-amine

3.9 The Schmidt Rearrangement

An azide when reacts with a carbonyl derivative, usually a aldehyde, ketone, or carboxylic

under acidic conditions give amide, with the expulsion of nitrogen is

an amine or
acid,
known as Schmidt rearrangement. It is named after Karl Friedrich Schmidt, who first
reaction of benzophenone and hydrazoic acid.
reported the synthesis of benzanilide from
The reaction is effective with carboxylic acids to give amines, and with ketones to give

amides.

R
HH-N-NEN HNH
H,O

H+H-N-NENN R N-H

R HO
R
[Link]. Organic Chemistry I (Sem. V) 3.14 Rearrangement Reactions
T.

Mechanism:
that in this reactin
Ihe reaction is closely related to the Curtius rearrangement except
with hydrazoic acid via t.
produced by reaction
the acyt azide is of the carboxylic acid he
protonated carboxylic acid, in a process similar to a Fischer esterification. An alternatiue
tive,
becomes more important when the reactin
involving the formation of an acylium ion, bn
takes place in concentrated acid (>90% sulfuric acid). (In the Curtius rearrangement

sodium azide and an acyl chloride are combined to quantitatively generate the acyl azida

of the reaction takes place under neutral conditions.)

intermediate, and the rest
This mechanism begins with the formation of an acylium ion 1 from the protonation of

the carboxylic acid followed by the removal of water.

This acylium ion is now reacted with hydrazoic acid, leading to the formation of a
protonated azido ketone 2.
Now. the protonated azido ketone 2 and the R group undergo a rearrangement reaction,
resulting in the migration of the carbon-nitrogen bond and the removal of dinitrogen

eading to the formation of a protonated isocyanate 3.

Now, a carbamate 4 is formed when water is introduced to attack the protonated
isocyanate.
e carbamate 4 is now deprotonated. The subsequent removal of CO2 yields the
recuired amine.
O

. H
H
-HO
H
oEN
H

-N2

-H
R H H 3
R-NH2 H
5 4
do
In the reaction mechanism for the Schmidt reaction of the carbonyl grou.
activated by protonation for nucleophilic addition by theketone,
azide, forming azidonyn
azidohydrir
3
which loses water in an elimination reaction ary
to diazoiminium 5. One of the alkyi
groups migrates from carbon to nitrogen with loss of nitrogen to give a n
intermediate 6, as in the Beckmann rearrangement.
to

Attack by water conv c acid

protonated imidic acid 7, which arid
undergoes loss of proton to arrive at the imia
tautomer of the final amide 8.
. In an alternative mechanism, the migration occurs at 9,
ter protonation o
directly after protonded
intermediate 3, in a manner Similar to the
amide 10. Loss of a proton again furnishes the amide
Baeyer-Villiger reaction to give
give
protonat

8
[Link]. Organic Chemistry-I (Sem. V) 3.15 Rearrangement Reactions
It has been proposed that the dehydration to 3 to give 5 (and, hence, the Beckmann
pathway) is favored by nonaqueous acids like conc. H,SOa, while aqueous acids like conc.
HCI favor migration from 9
(the Baeyer-Villiger pathway).
These possibilities have been used to account for the fact that, for certain substrates like
a-tetralone. the group that migrates can sometimes change, depending on the
conditions used, to deliver either of the two possible amides.
H
N
HO N RNH
N RR B-V 10
2
pathway HO
9
I
N RNH
R - N g eckmann
H2NO N
pathway R
R'

R
6 5 4

Tautomerize

HO -H
R-N=R R-N R-N
7 OH OH

Examples of Schmidt Rearrangement:

ON N ON
O -OH O
HSO4. 80-100°C, 15 min.

-OH
63%

N
MeAICl2
CHCl2 96%

3.10 The Pinacol Rearrangement

When vicinal diol is treated with a catalytic amount of acid, it can rearrange to give an
aldehyde or ketone by migration of an alkyl or aryl group which is called as Pinacol
Rearrangement. The pinacol-pinacolone rearrangement reaction or 1,2- migration can be
viewed as a special case of the Wagner-Meerwein rearrangement.
 3.16
[Link]. Organic Chemistry I (Sem. V)

OH O
Rearrangement Rears.
OH
R R
R
R

OH

OH
CH3
HC CH HC CH3
HC CH CH
When Me-COHCOHMez (pinacol) on treatment with acid gives
MeCOHCMe which
migration of Me to yield Me,CCOCH3 is called as pinacolone.
CH3 CH3 CH3 CH3
-CH3 -HO 1,2-CH
HC- C-CH HC CH Shit
OHOH HO OH

Pinacol
CH CH3
-CH -
HCHC-C CHs1 HC-C CCH
- H CH,
CH
Mechanism Pinacolone
I n the first step
one
hydroxy group is protonated, and
group. The elimination of water thus converted into a goo leaving
from the molecule i
stable carbocation proceeds in such a way that the
intermediate is formed.
OH
H,C-C- -H
OH2
H
OH OH OH
HC-C-
CH, CH
III° Carbocation CH CH
H,C--
more stable CH CH3

OH A
Pot OH
HC- H
CH3 CH
HC-
CH CH
Ir Carbocation
less stable
[Link]. Organic Chemistry - I (Sem. V) 3.17
Rearrangement Reactions
In the second step, 1,2-shift of a R group to the more stable (lIl°) carbocation takes
place
to give a more stable hydroxyl carbocation intermediate. The reaction is intramolecular;
the migrating
group R is never completely released from the substrate. The driving force
is the formation of the more stable rearranged carbocation, which is stabilized
by the
hydroxy group. In the third step, loss of a proton yields the carbonyl compound.

1,2 CH HOH CH O H
shift
HC- HC- -H
H,C-C- - H

CH CH3 CH3
T Carbocation Carbocation stabilised by
hydroxyl group CH
HC-C-
CH
Reaction with an unsymmetrical diol as starting material may give rise to formation of a
mixture of products. Mixtures are product formed, may depend on the reaction
conditions which group preferentially migrates as well as on the nature of the substrate.
The order of migration is R,C > R2CH > RCH2 > CH3 > H.
1,2-CH3
CsHs CH CoH CH shift CH CH
-H,O
HC -¢-CH H,--CH H,-¢-
OH OH Cot
More stable,
CEHO
stabilized by two
-c-CH Ph groups

1,2-Ph shift
CoH CH CeHs CH3 CeHs
-H0 -H
H,C- -CH CH3 HC-C--CH
[Link]
a trace of H2SO4 OHOH2 :OH CH3
Less stable

The action of cold, conc. H,SO on A produces mainly the ketone B (-CH3 migration)
while treatment of A with acetic acid containing a trace of H,SO gives mostly C (pheny
migration). If one hydrogen, aldehydes can be produced as well as ketones.
R is

Generally, aldehyde formation is favored by the use of mild conditions (lower

temperatures, weaker acids).
Ph Ph Ph
Ph
Ph-C- C-CH Ph-C-C-Ph
Ph-C -CH
OH OH Ph CH
Major Minor
 Rearrangement Reaction.
3.18
[Link] Chemistry - 1 (Sem. V)
Examples of Pinacol Rearrangement
- CH

P h --C CCH HPh-CH2

OH OH

OH OH

OH OH CH

o
HO
-C-CH Ph
Ph
CH, CH3 CH
AgNO
HC--¢-H HC-C-C-CHa3
OH Br

CH CH3 CH3

HC---H NaNO2 H C-CH

HO NH2
3.11 Electrolytic Rearrangements
An electrocyclic reaction is a type of pericyclic rearrangement where the net result is
one pi bond being converted into one sigma bond or vice versa. These reactions are usualy
categorized by the following criteria
Reactions can be either photochemical or CH3
thermal. CH3 170°C
Reactions can be either ring-opening or ring-
closing (electrocyclization). CIS cis, trans
Depending on the type of
of reaction
(photochemical or thermal) and the number of pi
electrons, the reaction can happen through
CH3 170°c
either a conrotatory or disrotatory mechanism.
H
The type of rotation determines whether the cis
ortrans isomer of the product will be formed. trans trans, trans
System Thermally induced Photochemically induced
(ground state) (excited state)
Even number of conjugation
Odd number of conjugation | Conrotatory
Disrotatory
Disrotatory
3.11.1 The Claisen Conrotatory
Rearrangement
.Allylic aryl ethers, when heated,
Claisen rearrange to
rearrangement. If both ortho positions ortho-allylphenols, this reaction is callea t e

para position (para-Claisen are filled, the allylic group

rearrangement). migrates to
 3.19 Rearrangement Reactions
[Link]. Organic Chemistry -I(Sem.
V)

concerted pericyclic 3.3] sigmatropic

The Claisen rearrangement reaction is a
bond is
bond is cleaved and a carbon-carbon
rearrangement reaction. A carbon-oxygen
formed followed by tautomerization to the stable aromatic allyl phenol.

OH

o 13, 3]
Allyl phenyl ether Sigmatropic Ortho
rearrangement allyl
phenol
P

10 O

3, 3] Sigmatropic
rearrangement
y-o unsaturated
Allyl vinyl ether
carbonyl compound

OH

2x [3, 3]
Sigmatropic
Substituted rearrangement
allyl
pheny Para allyl phenol
ether
also undergo the Claisen rearrangement.
Allylic ethers of enols (allylic vinylic ethers)
OH
H

3,3

A .. - C
13,3

R R R

O.
13, 3 [Link]
COOEt
R
 3.20
Rearrangement Reacti
[Link]. Organic Chemistry I (Sem. V)
an allylic shift. Whereas in .
migration, the allylic group always undergoes
n the ortho is f
an allylic shift. The alylic group toun
para-Claisen rearrangement there
is never

exactlyas it was in the oniginal ether

O OH ste
Me Me Me Me
Me Me
Me Me
Me
13..31
3
3. 3

3.11.2 The Cope Rearrangement

T h e Cope Rearangement is the thermal isomerization of leading to
a 1,5-diene
more stab
regioisomeric 15-diene. The main product is the thermodynamically
recioisomer. R- R

The Oxy-Cope has a hydroxyl substituent on an sp°-hybridized carbon of the starting

Somer.

HO

The driving force for the neutral or anionic Oxy-Cope Rearrangement is that the prodiu3
is an enol or enolate (resp.), which can tautomerize to the corresponding carbon,
compound. This product will not equilibrate back to the other regioisomer. The Oxy-Cope
Rearrangement proceeds at a much faster rate when the starting alcohol is deprotonatec
e.g. with KH. The reaction is then up to 10* times faster, and may be conducted at roo
emperature. Aqueous work up then gives the carbonyl compound.

HO O HO O
HO
Mechanism:
- R R
N

R R
[Link]. Organic Chemistry I (Sem. V) 3.21
Rearrangement Reactions
Two transition states are possible, and the outcome of the reaction can be predicted on
the basis of the most favorable overlap of the orbitals of the double bond, as influenced by
stereoelectronic factors:

OH OH

-
--
H
H
Examples of Cope and Oxy-Cope Rearrangement:

Heat
2

3.11.3 The McLafferty Rearrangement

The McLafferty-Rearrangement is observed in compounds in which at least one
abstractable gamma (y) hydrogen is present with respect to a pi (T) bond. When such
compounds are ionized as molecular ions, in mass spectrometer, usually by the Electron
lonization (ED method. The resultant molecular ion undergoes a special type of

rearrangement. The hydrogen gamma (y) position transfers to the carbonyl functional
at
group followed by the hemolytic cleavage of the Ca-Cp sigma bond. This rearrangement

Tinally results in the formation of an olefin without any charge and an enol radical cation
as products
Ihis rearrangement is widely observed in Aldehydes, Ketones, Carboxylic acids, Esters,
Amides, Imines, Cyanides, Alkenes, and Alkynes. The McLafferty Rearrangement is helpful
in the identification and characterization of various organic molecules.

Mechanism:
R- H

Z,Y = C, N, O
 3.22
Rearrangement Reactio-
I (Sem. V
[Link]. Organic Chemistry
Rearrangement
Examples of McLafferty OH
OH OH

R CH2
R

Exercisse
(A) State True or False Questions
its lone pair of electror
in rearrangement reaction, migrating group shift with
(1)
called as electrophilic rearrangement.
The skeletal rearrangement of carbocation which involves migration of B-alkyl, ar

or d-bond is called Wagner-Meerwein rearrangement.

Rearrangement involving carbanion is Favorskii rearrangement.
Vicinal diol on treatment with a catalytic amount of acid, rearrange to give
aldehyde or ketone is called as Baeyer Villiger rearrangement.
5) Allylic aryl ethers, when heated, rearrange to ortho-allylphenols, this reaction
called the Cope rearrangement.
6) The McLafferty-rearrangement is observed in compounds in which at least or
stractable gamma (7) hydrogen is present with respect to a pi (7) bond.
(7) Allylic ethers of enols (allylic vinylic ethers) also undergo the Claisen rearrangemer
8) The Cope rearrangement is the thermal
isomerization of a 1,5-diene.
9) In Pinacol rearrangement, the order of migration is R,C < RCH < RCH2 < CH3 < H
(10) In Lossen rearrangement, azide reacts with a
carbonyl derivative, usually
aldehyde, ketone, or carboxylic acid, under acidic conditions to
amide
an amine give
(11) When B-halo ketones are
treated with base, in the
reaction is called presence of nucleophile
(12) In pericyclic
Quasi-Favorskii rearrangement
rearrangement the net result is one pi bond being
Sigma bond or vice
versa.
converted into
(13) In Baeyer Villiger rearrangement, for
ofmigration is R3C >R,CH> Ar unsymmetrical ketones the approximate ord
(14) In Beckmann RCH,> CH.
>

rearrangement,
they form nitrile. aldoximes often are more
reactive than ketox1me
1. False
[Link] [Link] ANSWERS
8. True 4. False 5.
9. False 10. False 11. False
False 6. True 7 . Tru
12. True 13. True 1 4 Fals