CONJUGATED DIENES

Electrophilic addition reactions on conjugated

dienes are a little different than alkenes

consider 1,3 butadiene

Cas
3 A H
A
Br H Br
41 Ct
Z

Tx
b
H
HATH
the Ve can be
Due to resonance charge
lo and I C atoms
delocalized b w
allylic
Hence there can be 2 possible products
I Br I
1,2 addition
41 product
a Stable BRO
 I H
Br Br 3
1
1,4 addition
product
i
b stable
is
Blow the carbocations ca and b Ca

a more stable carbocation

B IN the products alkenes 1,4 product

less stable carbocation
obtained from
intermediate is more stable I

i
s
4

L H
H L O

EH Br
I 1,2
Br 1,4
 BV

x
T
t

Br
4

af
Rt
t K

H IL H
I H
Br
a
H
H X
H Br
stable
5h
The product obtained with a lesser activation

energy is called kinetic product

In this reaction 1,2 addition product
lesser Ea Hence it is called
requires
kinetic product 1
RT
f k A e

The product that will be stable at high

is called thermodynamic
temperatures
product
In this reaction as 1,4 product needs
more activation it is obtained
energy
high temperatures
Edl RT f
f k Ae
Also when temperature F the 1,2 product

to revert back and

gets enough energy
eventually form more stable 1,4 product

Hence 1,4 product is called thermodynamic

product
H

HBR
I
80 C
Br

112 addition Major

HBV Br
H
room
temp 1,4 addition major
DIEL'S ALDER REACTION

conjugated
Alkene Pericyclic
diene dienophile reaction

f
it 1
till
20
8

1 IT V
31T X Et
Nu

MECHANISM

f e
x EI
Nu

state there will be deloca

In transition
2 TE Transition state
lization of cent

is aromatic for pericyclic reaction

 i1

Aromatic transition state

In Diel's alder reaction 31T bonds are

broken and 2 0 bonds and a T bond

are formed

diene is as Noi presence

since acting
of EDG on diene increases the ease

of reaction Similarly as alkene is

Et EWG increase
acting
as presence of
on alkine increases the ease of rxn

C H
HEI
f e Il
HI neut E C R
 g
FR
groups
5
D AIdwrxn
i

f
1,3 cyclopentadiene

A
HII
A
IE I
dienecahi dienophile CE'T