Lesson Eleven

O XI D A T I O N - R E DU C T I O N R EA C T I O NS
 
In an oxidation-reduction reaction, one molecule loses electrons and
one molecule gains electrons. The molecule that loses electrons is oxidised,
and the molecule that gains electrons is reduced. The loss of electrons is
oxidation and the gain of electrons is reduction.

+ 3+ 2+ 2+
Cu + Fe Cu + Fe

Here Cu + loses an electron, which means that it is oxidised; the other

reactant, Fe 3 + , is the oxidising agent Fe 3 + , gains electrons, which means that
it is reduced; Cu + is the reducing agent. Thus, oxidation is always coupled
with reduction.

It is easy to tell whether an organic compound is being oxidised or

reduced simply by looking at the change in the structure of the compound. If
the number of carbon-hydrogen bonds increases, the compound is being
reduced. If the number of carbon-hydrogen bonds decreases, or if the number
of carbon-oxygen, carbon-nitrogen, or carbon-halogen bond increases, the
compound is being oxidised.

H2
RCH=CHR RCH2CH2R
Pt
an alkene

O
1) NaBH4
RCH RCH2OH
2) H2O

O
NH2NH2
RCH - RCH2R
OH

In the above group of reactions number of carbon-hydrogen bonds

increase, thus, they are reduction reactions.

In the next reaction the number of carbon-hydrogen bonds decreases

or the number of C-O, C-N, C-X (X = halogen) bonds increase, thus, they are
oxidation reactions.
 Br2
RCH=CHR RCH CHR
CCl4
an alkene Br Br
O O
Na2Cr2O7
RCH RC OH
H2SO4
an aldehyde
OH O
Na2Cr2O7
RCHR RC R
H2SO4
an alcohol

In the following reaction:-

+
H
RCH=CHR RCH2 CHR
H2O
OH

Compared with the reactant, the product has one more carbon-
hydrogen bond, but it also has one more carbon-oxygen bond. So one carbon
is reduced and another is oxidised. The two cancel each other and the overall
reaction is neither an oxidation nor a reduction.

An organic compound is reduced by:-

a) Addition of two hydrogen
atoms.
b) Addition of an electron, a
proton, an electron, a
proton.
c) Addition of hydride ion and
proton.
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       Catalytic hydrogenation

These reactions involve addition of hydrogen in presence of metal

catalyst and called catalytic hydrogenation. Both alkenes and alkynes are
reduced to alkanes.

Pt, Pd or Ni
CH3CH2CH=CH2 + H2 CH3CH2CH2CH3
1-butene butane
Pt, Pd or Ni
CH3CH2CH2C CH + 2 H2 CH3CH2CH2CH2CH3
1-pentyne pentane

The catalytic hydrogenation of an alkyne can be stopped at a cis-

alkene if a deactivated catalyst is used.
 Lindlar's H3C CH3
CH3C CCH3 + 2 H2
catalyst C C
H H
2-butyne cis-2-butene

H2
CH=CH2 CH2CH3
Pt

The very stable benzene ring can be reduced only under special
conditions.

O OH
H2
CH3CH2CCH3 CH3CH2CH CH3
Raney Ni
ketone secondary alcohol

(Raney Ni :-is finely dispersed nickel with preadsorped hydrogen).

O O
H2
CH3CH2C Cl CH3CH2C H CH3CH2CH2 OH
Pd / C
aldehyde primary alcohol

Pt
CH3CH2CH NCH3 + H2 CH3CH2CH2 NHCH3

O O
CH3CH2C Cl H2 CH3CH2C H
deactivated
aldehyde
Pd

The CO double bonds of the carboxylic acids, amides and esters are
harder to reduce than the C O double bonds of   aldehydes and ketones.
Thus,
O O O
RCOR , RCNHR and RCOH
 can not be reduced by catalytic hydrogenation.

Relative ease of reduction of functional groups by catalytic hydrogenation

being in the order:-

O O O
RCCl RC CR RCH RCH=CHR RCR RC N RCH=NR

Reduction by Addition of an Electron, a Proton, an Electron,

      a Proton-Dissolving Metal Reduction.

This reduction is carried out using sodium in liquid ammonia. Sodium

donates electron to the compound and ammonia donates a proton. This
sequence is repeated, so the overall reduction adds two electrons and two
protons to the compound. Such a reaction is called a dissolving metal
reduction.

H3C H
Na or Li
CH3C CCH3
NH3 (liq) H CH3
2-butyne trans-2-butene
H CH3
CH3 CH3
Na or Li H
CH3 C=CHCH2C CCH3 CH3 C=CHCH2
NH3 (liq)

So, this reagent is useful for reducing a triple bond in a compound in

which there is also a double bond.

Reduction by Addition of a Hydride ion and a proton

CO double bonds are easily reduced by sodium borohydride (NaBH 4 )

and or/lithium aluminium hydride (LiAlH 4 ). These reagents are sources of
hydride ion (H - ), which is the actual reducing agent.

O OH
1) NaBH4
R C R CH
2) H2O

aldehydr or ketone                         1° or 2° alcohol

The carbonyl group is reduced by adding H - followed by H + .

LiAlH 4 , due to its more polar metal hydrogen bonds, is a stronger

reducing agent than sodium borohydride. This reagent is strong enough to
reduce carboxylic acid, esters, and amides to alcohols and amines.
 O
1) LiAlH4
CH3CH2CH2COH
2) H2O
CH3CH2CH2CH2OH + H2O
alcohol
O
1) LiAlH4
CH3CH2COCH3
2) H2O
CH3CH2CH2OH + CH3OH
alcohol
O
1) LiAlH4
CH3CH2CH2CNH2 CH3CH2CH2CH2NH2
2) H2O amine

Because NaBH4 can not reduce an ester, it can be used to reduce selectively an
aldehyde or a ketone group in a compound that also contains an ester group

O O OH O
1) NaBH4
CH3CCH2CH2COCH3 CH3CHCH2CH2COCH3
2) H2O

The multiply-bonded carbon atoms of alkenes and alkynes do not

possess a partial positive charge and therefore will not react with reagents
that reduce compounds by donating a hydride ion.

Relative ease of reduction of functional groups by addition of hydride ion are

arranged in the following order  :-

O O O O O O
RCCl RCH RCR RCOR RCOH RCNHR RC N

Oxidation of Alcohols

The reagents most commonly used for the oxidation of alcohols are
acidic solution of chromic anhydride (CrO 3 ), sodium chromate (Na 2 CrO 4 ),
sodium dichromate (Na 2 Cr 2 O 7 ), or potassium permanganate (KMnO 4 ).

OH O
CrO3 or Na2Cr2O7 or KMnO4
CH3CH2CHCH3 CH3CH2CCH3
H2SO4

OH O
KMnO4
H2SO4
 O O
Na2Cr2O 7 further
CH3CH2CH2CH2OH CH3CH2CH2CH CH3CH2CH2COH
H2SO 4 oxidation

              1° alcohol                           aldehyde                     carboxylic acid

O O
E2
CH3CH2OH + HO Cr OH CH3CH O Cr OH

O H O
H2O chromate ester
chromic acid
O
CH3CH=O + Cr OH + HO2

OH

The role of hydrates in the oxidation of primary alcohols.

O OH O
+
Na2Cr2O7 H / H2O Na2Cr2O7
CH3CH2OH CH3CH CH3C H CH3C
H2SO4 H2SO4
OH OH

the oxidation reaction can be stopped at the aldehyde if the reaction is

carried out with pyridinium chlorochromate (PCC), because PCC is used in an
anhydrous solvent. If water is not present, the hydrate can not be formed.