REDUCTIO

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Definition:- An increase in
hydrogen content or decrease in oxygen
content
an organic
of compound is usually
described an its reduction.

The reductive process fall into

three categories:-
The removal of oxygen
The addition of hydrogen and
The gain of electrons
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 Types of reduction reaction

1. Reduction by desolving metals

2. Reduction by reductive cleavage

3. Reductive deoxygenation of carbonyl group

4. Reduction by hydride transfer reagent

5. Reduction by borane and dialkylborane as a

hydride source

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 Catalytic Hydrogenation

Definition :- The addition of hydrogen to unsaturated

system in the presence of catalyst OR addition of
molecular hydrogen, as an reduction on metal.

Almost all the alkenes can be saturated in very high

yield by treatment with hydrogen and a metal catalyst.

The hydrogenation of alkenes is an exothermic

reaction.
Mostly hydrogenation reactions are having high free
energies of activation.

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 CH3
CH3
Ni
CH + H2 CH2

CH3 CH3
Propane
Propene

Catalytic hydrogenation

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What is the need of catalyst?

The reduction of alkenes with molecular hydrogen

does not occur at room temperature without a catalyst
but often take place at room temperature if metal
catalyst is added.

Also the catalyst is able to provide a new pathway for

the reaction with a lower free energy of activation.

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Catalyst used in catalytic hydrogenation
reaction are of following :-
1. Palladium
2. Adam’s catalyst
3. Raney nickel
4. Copper chromite
5. Transfer hydrogenation
6. Rhodium
7. Ruthenium
8. Triethylamine

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 Types
1. Heterogeneous Catalytic Hydrogenation

•It is possible in that alkanes which are strained can be

reduced catalytically by rupturing C-C cleavage would
relieve the strain.

•The catalysts is not soluble in the reaction media,

thus this process is referred to as a heterogenous
catalysis.

•The catalyst assists in breaking the π-bond of the

alkene and the H-H σ-bond.

•The reaction takes places on the surface of the

catalyst. Thus, the rate of the reaction is proportional
to the surface area of the catalyst.
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 Heterogeneous Catalysis

•Heterogeneous catalysts dominate chemical and petrochemical

industry: ~ 95% of all chemical processes use heterogenous catalysts.

•Carbon-carbon π-bond of alkenes and alkynes can be reduced to the

corresponding saturated C-C bond. Other π-bond bond such as C=O
(carbonyl) and C≡N are not easily reduced by catalytic hydrogenation.
The C=C bonds of aryl rings are not easily reduced.

Ziegler-Natta Catalysis
The German chemist Karl Ziegler (1898-1973) discovered in 1953 that
when TiCl3(s) and AlEt3 are combined together they produced an
extremely active heterogeneous catalyst for the polymerization of
ethylene at atmospheric pressure.

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1. Palladium
An active form of palladium obtained from
palladium chloride more commonly the palladium
chloride reduce in presence of charcoal or any other
solid support on which the metal is deposited in a
very finely divided state.
Example

H H
Pd
R R C C +
2 R +
C C 2 R
R
R R R
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2. Adam’s catalyst
Chloroplastinic acid is fused with sodium nitrate to
give a brown platinum oxide which can be stored. When
required , it is treated with hydrogen to give a very
finely divided black suspension of the metal.
OH
O
O C
C OH H2-Pt C O

C OH OH

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 2. Homogeneous Catalytic Hydrogenation

1. Wilkinson`s Catalyst : Olefin Hydrogenation :-

RhCl(PPh3)3 was the first highly active homogeneous
hydrogenation catalyst and was discovered by
Geoffrey Wilkinson (Nobel prize winner for
Ferrocene) in 1964.

2. Hydroformylation :- The reaction of an alkene with

carbon monoxide and hydrogen, catalyzed by cobalt or
rhodium salts to form an aldehyde is called
hydroformylation. Hydroformylation was discovered
by Otto Roelen in 1938.

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3. Monsanto Acetic acid Process:- Monsanto
developed the rhodium catalyzed process for the
carbonylation of methanol to produce acetic acid.

4.Wacker Process:-This is one of the earliest industrial

processes developed in Germany for the conversion
of ethylene into acetaldehyde. Wacker process is
more complex than other catalytic processes
described above.

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 • Catalytic steps in homogeneous reactions
 Most catalytic process can be built up from a
small number of different types of step
–Association / dissociation of a ligand
requires labile complexes
– Insertion and elimination reactions
– Nucleophilic attack on a coordinated
ligand
– Oxidation and reduction of a metal
center
– Oxidative addition / reductive
elimination
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 Mechanism of Catalytic Hydrogenation:
STEP 1:

Hydrogen molecules react with the metal atoms at the catalyst surface.

The relatively strong H-H sigma bond is broken and replaced with two
weak metal-H bonds.
H
H B Y H
H

C C

A
X

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STEP 2:

The pi bond of the alkene interacts with the metal catalyst weakening the
bond.

A hydrogen atom is transferred from the catalyst surface to one of the

carbons of the double bond. B Y
C C
A
X

H H
H

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STEP 3:
The pi bond of the alkene interacts with the metal catalyst
weakening the bond.

B
Y
A X
H H
H
C C

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A second hydrogen atom is transferred from the
catalyst surface forming the alkane.
The alkane is released from the catalyst's
surface allowing the catalyst to acced pt
additional hydrogen anBd alkene m olecules.
Y
A

X
H H
H H
C

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Advantages :

 Relatively high specificity

 Relatively low reaction temperatures

 Generally far more selective for a

single product
 far more easily studied from chemical &
mechanistic aspects
 far more active

Disadvantages :

o far more difficult for

achieving product/catalyst
separations
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Applications

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1. Reduction of aldehyde to alkane

2. Reduction of acid

3. Reduction of acyl chloride

4. Reduction of ester

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5.Reduction of ketone

6.Reduction of amide

7.Reduction of unhydride

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Reference
s•Norman, Coxon ,“Principles of organic synthesis”, nelson
thornes, Third edition, page no. 631-634.

•P.S. Kalsi, “ Organic Reaction and their mechanisms”, New age

publication, Second edition, page no.453-462.

•G. R. Chatwal, “Reaction Mechanism and Reagents in Organic

Chemistry”, Himalaya publishing house, page no. 1002-1006.

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Thank you

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