1.

Wittig Reaction:
The reaction between Carbonyl compound and triphenyl phosphonium ylide to give an
alkene is known as Wittig reaction. The Wittig reagent triphenylphosphonium ylide is also
known as phosphorus ylide, which contains a carbon covalently bonded to a positive charge
Phosphorus. Eg.

R'' R R''
R + Ph3PO
C O + Ph3P C
R'
R''' R' R'''

O
H2 CH2CH3 H3CH2CH2C CH2CH3
C C +
H3C C CH3 Ph3P C C + Ph3PO
H2
CH3 H3C CH3

CH2CH3
O
CH2CH3 C
+ CH3
Ph3P C
CH3

The Wittig reagent is prepared by treating triphenyl phosphorus with alkyl halide

PhLi
Ph3P + CH3Br Ph3P+CH3 Br(-) Ph3 = CH2
Et2O
Mechanism:
Step-1: NÜ attack to e` deficient carbonyl carbon to form a betain as intermediate
R'
R'' R'' O
(+) (-) R O(-)
Ph3P C Ph3P C + R C R' R'' P+Ph3
R''' R'''
R'''
(betain)

Step-2: Formation of P-O bond through cyclic TS

 R' R' R'

R O(-) R O R O

R'' P+Ph3 R'' PPh3 R'' PPh3

R''' R''' R'''

cyclic TS

Step-3: Breaking of C-O & C-P bonds and formation of C-C π-bond through a cyclic TS

R' R' R'

R O R O R
+ Ph3PO
R'' PPh3 R'' PPh3 R''
R''' R''' R'''
TS

2. Heck Reaction:
The Heck reaction is the coupling reaction between alkene with an organic halide (alkyl or
aryl) or triflate or vinyl halide in presence of base and palladium catalyst. Here the alkyl group
may be aryl, vinyl or any alkyl gr without β- H on sp3 carbon. This palladium catalyst reaction
has one of the most important synthetic usefulness.
Eg.
H Pd (0) R
R-X + R' R' + H-X
base
I PdCl2
+ CH3COOK, CH3OH, 12O0C

O
I O
Pd(OAc)2 , Ph3P
+
R

Mechanism:
The mechanism of Heck reaction involves the oxidative addition of the halide , insertion
of olefin and elimination of product by a β- hydride elimination. A base is then regenerates
palladium (0) catalyst. The whole process is catalytic cycle.
 BHX

ad ive
PdL2

dn
at
RX

eli n tive

id
ox
uc
B Pd(0)

red
H R

L2Pd Pd(II) Pd(II) L2Pd

X X

id e
dr Pd(II) H

lation
- hy n R'
B li R L2 Pd X
e

metal
R

carbo
R' H R'

Reactions of alkene:
The reaction of alkenes are the addition of electrophile, nucleophile or free radicals to
C=C bond. Since C=C bonds are formed by loosely held π- electrons, electrophilic addition
reaction takes place by breaking of one weak π- bond and formation of two strong σ- bonds.
Such type reaction is called addition reaction.

+ YZ
Y Z
In case of nucleophilic addition reaction the π- electron cloud tends to shield the molecule
from attacking nucleophile. Therefore, such reaction are difficult to take place. However such
reaction may be initiated by electron withdrawing substituent, which polarizes π- electron cloud
in such as way that β- carbon become electron deficient, and nucleophile can easily attached to
the C- atom.

1. Electrophilic addition reaction of helogen:

When alkene is treated with halogene it undergo electrophilic addition reaction to give
1,2- dihaloalkane.
Br
CCl4
H2C CH2 + Br2 H2C CH2

Br
Br
CCl4 H
H3C C CH2 + Br2 H3C C CH2
H
Br
Mechanism:
Step-I: electrophilic addition to C=C bond to form cyclic bromonium ion intermediate

Step-II: Nucleophilic addn to cyclic bromonium ion

(+) Br
Br
H
R C CH R R C C R
H H

Br

Br(-)

Stereochemistry: The addition reaction of X2 is highly stereospecific. Eg. Cis- butene form dl-
2,3-dibromobutane and trans-butene gives meso- 2,3-dibromobutane when treated with Br2.
Br
H H
(-)
a
Br C C

H3C CH3
H H H b aH Br
H3C CH3 dl-2.3-
dibromo
C C
butane
- Br(-)
H3C CH3 (+)
Br
Br H H
Br
b
C C
Br CH3
H3C Br
 Br
H CH3
(-)
a
Br C C

H3C H
H CH3 H b a CH3 Br
H3C H meso-2.3-
dibromo
C C
butane
- Br(-)
H3C H (+)
Br
Br H CH3
Br
b
C C
Br H
trans-butene H3C Br

H/W- Write the product of the following reaction and suggest suitable mechanism:

+ Br2

2. Addition of HX to alkene:
i. Addition of HX to symmetrical alkene:
When alkene is treated with hydrogen halide it gives alkyl halide. The reactivity order
among different hydrogen halide is : HI > HBr > HCl. This order can be explain on the basis of
bond dissociation energy. As the H-I bond is weaker than H-Br, it can easily dissociate and I(-)
can easily added to alkene. So HI is highly reactive.
H

+ HX
X
Eg.
H
H3C CH3 H
+ HBr H3C C C CH3
H
H H Br

Mechanism: the addition of HX to C=C bond takes place through a cyclic bridge hydronium
ion intermediate followed by back side attack by bromide ion.
Step-I:
 C C C C + X(-)
(+)
H
H X
Step-II:
X(-)
X

C C
(+) H
H

ii. Addition of HX to unsymmetrical alkene

(a). Markovnikov’s Rule:
It states that addition of HX to unsymmetrical alkene take place in such a way that the H-
atom of HX adds to the carbon having already greater number of H-atoms.

CH3CH = CH2 + HX CH3 - CH - CH3 + CH3 - CH2 - CH2 - X

X
Major product minor product

Eg.
CH3CH = CH2 + HBr CH3 - CH - CH3 + CH3 - CH2 - CH2 - Br
Br
Major product minor product
Mechanism:
Step-I
(+)
H3C HC CH2 H3C HC CH3 + Br(-)

H Br
Step-II
Br(-)
Br
H H3C C CH3
H3C C CH3 H
(+)

The reaction is highly regioselective. The formation of product depends on the stability of
the carbocation intermediate step. As we know that 30 carbocation is more stable than 20 and 10,
the H atom get attached to that carbon atom which produce more stable carbocation and
accordingly the product is formed.
 It is also observed that the addition of HX to alkene may follow rearrangement reaction
on the basis of stability of the intermediate.
CH3 CH3 CH3
H H
H3C C C CH2 + HBr H3C C C CH3 + H3C C C CH3
H
Br CH3 CH3 Br
CH3
+
(Major product) normal
Rearranged product CH3 product
H2
H3C C C CH2 - Br

CH3

(b). Anti- Markovnikov’s Rule:

It states that in presence the addition of HX to unsymmetrical alkene take place in such a
way that the H-atom of HX adds to the carbon having already less number of H-atoms.
H2O2
CH3CH = CH2 + HX CH3 - CH - CH3 + CH3 - CH2 - CH2 - X
X
major pruduct
minor pruduct

CH3 CH3 CH3

H2O2
CH3 - C = CH - CH3 + HBr CH3 - C - CH2 - CH3 + CH3 - CH - CH -CH3
Br Br
minor pruduct major pruduct

Mechanism: Free radical mechanism

Chain Initiation:
.
R-O-O-R 2 RO

. + .
RO + H - Br ROH Br

Chain Propagation:

.
CH3CH = CH2 . CH3 - CH - CH2 - Br
+ Br
20 -radical
(more stable)

. .
CH3 - CH - CH2 - Br + H - Br CH3 - CH2 - CH2 - Br + Br
Chain Termination:
 . + .
Br Br Br2

.
CH3 - CH - CH2 - Br + Br . CH3 - CH(Br) - CH2 - Br

. .
CH3 - CH - CH2 - Br + CH3 - CH - CH2 - Br Br - CH2 - CH(CH3) - CH(CH3) - CH2 -Br

The peroxide effect is observed only in case of HBr but not in case of HF, HCl and HI, as
the ∆H value of Br-C bond formation and H-Br breaking is exothermic and suitable for the
reaction. But in case of HF, HCl and HI the ∆H are not suitable for the reaction as given below:
∆H value for ∆H value for
X-C formation H-X breaking
˙
F -210 +160
˙
Cl -100 +30
˙
Br -40 - 30
˙
I + 10 - 100