LECTURE NOTES

Session - 2012-13

ORGANIC CHEMISTRY
TOPIC
Reduction, Oxidation & Hydrolysis
CONTENTS :

1
2
3.

Reduction.
Oxidation
Hydrolysis

Refer sheet : Reduction, Oxidation & Hydrolysis.

JEE Syllabus [2013]
Concepts :
Reduction of alkene, Alkyne, Alcohol, Aldehyde, Ketone, Acid, Acid halide, Ester, Amide & Anhydride.
Oxidation of Alkene, Alkyne, Alcohol, Aldehyde, Ketone, Acid, Acid halide, Ester, Amide & Anhydride.
Hydrolysis reaction of Acid halide, Ester, Amide & Anhydride, Cyanide, Ether etc.

Reduction, Oxidation & Hydrolysis

LECTURE PLAN
(A). REDUCTION-1 (L-1)
A-1

Introduction :
Reduction covers both the addition of hydrogen (or deuterium) to a double bond and the replacement of an
atom or group by hydrogen (or deuterium). In other words, reduction means hydrogenation or hydrogenolysis.
Reduction can be carried out in following ways:

A-2

(i)

Catalytic hydrogenation

(ii)

Metal/proton (acid) reduction

(iii)

Metal hydrides reduction

(iv)

Miscellaneous Reductions

Catalytic hydrogenation :
Hydrogenation using H2(gas) on metal surface or other suitable catalyst is called catalytic hydrogenation. A
catalyst provides a new pathway for the reaction that involves lower free energy of activation .

Heterogeneous hydrogenation catalysts typically involve finely divided platinum,

The catalysts used can be divided into two broad classes, (a) Heterogeneous catalysts and (b) Homogeneous

catalysts, both of which mainly consist of transition metals and their compounds :
(i)

Heterogeneous catalysts : (catalysts insoluble in the reaction medium)

In heterogeneous catalytic hydrogenation catalysts are used in powdered form. Raney nickel (Ni), Palladium
on charcol (Pd/C), Platinum metal or its oxide are common Heterogeneous catalysts.
Facts of catalysis :
(i) Substrate molecules are assumed to undergo homolysis into atoms at the surface of the catalyst.
(ii) The substrate is chemisorbed on the surface of the catalyst and hydrogenation takes place.
(iii) The process is exothermic,

Note : (If H2 and D2 mixture is used with a Pt catalyst, the two isotopes quickly scramble to produce a random
mixture of HD, H2 and D2. (No scrambling occurs in the absence of the catalyst.) The product has both D and
H atoms).

RESONANCE

Catalytic Hydrogenation : [H2/Pd (C)] Raney nickel (Ni), Palladium on charcol (Pd/C), Platinum metal or
its oxide are commonly used for catalytic hydrogenation.
They reduced the organic functional groups as given in the table.

Catalytic Reduction of Functional Groups Using H2/Pd(C).

Ni or Pd

R CH = CH R + H2 R CH2 CH2 R + heat

Note : Stereochemistry of catalytic hydrogenation : The above reaction is syn addition (addition takes place
from the same face of alkene or alkyne).

(ii)

Homogeneous catalysis : (catalysts soluble in the reaction medium). It uses reactants and catalyst
in the same phase. Both hydrogen atoms usually add from the same side of the molecule. Common
example : Use of Wilkinsion catalyst.

(iii)

Lindlars catalyst : [H2/Pd (CaCO3, quinoline)]

It is a poisoned palladium catalyst. It is composed of powdered calcium carbonate coated with palladium and
poisoned with quinoline. It carry out partial reduction of alkyne to alkene and acid chloride to aldehyde.
Stereochemistry : Syn addition.

H2 Lindlar 's catalyst

CH3 CH2 C C CH3

(syn addition)

or Ni2B

(iv)

Rosenmund catalyst : [H2/Pd (BaSO4, quinoline)] Hydrogenation in presence of H2/Pd/BaSO4

is called Rosenmund Reduction. It reduces alkyne to alkene and acid halide to aldehyde. It is poisoned
palladium catalyst, composed of powdered barium sulphate coated with palladium, poisoned with quinoline
or sulphur. Stereochemistry : Syn addition.
(a)

CH3CCCH3

(b)

H2 / Pd BaSO 4

CH3 CHO

Note : Nickel boride Ni2B (P-2 catalyst) (made from sodium acetate and sodium borohidride) is an excellent alternative
catalyst for the conversion of alkyne into alkene. Stereochemistry : Syn addition.

RESONANCE

A-3

Metal/proton (acid) reduction :

Reduction by dissolving metals is based on the fact that the metal acts as a source of electrons.
Step -1 : Metals give electrons to the electrophilic species and form anion
Step-2 : Proton is abstracted from the acidic source.

H
e
A + B : or A : + B

A B
A + B H

H
e
: A B or A B :
A BH
A = B

(i)

Birch reduction [Na or Li/NH3(liq.) or (ethyl alcohol)] :

Alkyne and Aromatic Compounds are reduced by Na or Li/NH3.
Alkynes are reduced to trans alkene.
Na / NH 3
R C C R

(anti addition)

Stereochemistry : anti addition.

Benzene ring is reduced at 1, 4-position.
Typical example of reduction for aromatic system :
Presence of alkyl, alkoxy, amines reduces the benzene ring at ortho position.

Na / NH

Presence of nitro, cyano, carboxylic or aldehyded group reduces the benzene ring at ipso position.

Na / NH

(ii)

Bouvealt-Blanc reduction [Na/C2H5OH] :

Reduction of aldehydes ketones or esters by means of excess of Na/C2H5OH or n-butanol is called BouvealtBlanc reduction reduction.
CH3CHO

CH3CH2OH

Acetaldehyde

Ethanol

RESONANCE

(iii)

Stephens Reductions : [SnCl2/HCl]

When reduction of compounds is carried out with acidified stannous chloride (SnCl2/HCl) at room temperature,
imine hydrochloride is obtained which on subsequent hydrolysis with boiling water gives aldehyde. This
specific type of reduction of nitrile is called stephens reduction.

(iv)

Clemmensens Reduction : [Zn-Hg/Conc. HCl]

(Aldehyde and ketones in absence of acid sensitive groups). It is used to prepane alkanes from carbonyl
compounds.

(a)

(b)

Zn Hg / conc . HCl

RCH3 + H2O
R CHO

O
||
Zn Hg / conc . HCl
RCH2R + H2O
R C R

Note : Clemmensen reduction is not used for compounds which have acid sensitive group.
[Like Alcohol, Alkene, Alkyne, Ether, Ester, Amides & Cyanides].

RESONANCE

REDUCTION-2 (L-2)
A-4

Metal hydrides reduction

Certain complex metal and boron hydrides, are important reagents for reduction.

(i)

LiAlH4 (LAH) Lithium aluminium hydride [LiAlH4 / Ether or THF] :

LAH is most common and versatile reagent. It is sensitive to protic solvent and therefore used in ether.

LiAlH4

LiAlH4

LiAlH4

LiAlH4/Excess LiAlH4/Excess

LiAlH4

LiAlH4

LiAlH4

LiAlH4

LiAlH4

LiAlH4

Reactant Aldehyde

Ketone

Acid

Acidanhydride

Acid chloride

Ester

Cyanide

Amide

Isocyanide

Nitro

Product 1 alcohol

2 alcohol

1 alcohol

1 alcohol

1 alcohol

1 alcohol

1 amine

1 amine

2 amine

1 amine

Note : Alkene, alkyne, benzene rings are not reduced by LiAlH4 in ether but it is reported that
(*) double bond can be reduced by LiAlH4 / THF in cinnamic system.
(i) LiAlH THF

4
PhCH CH CH OH
PhCH=CHCHO
2
2
2
(ii) H O
2

(ii)

Sodium borohydride [NaBH4 / C2H5OH or Ether] :

It is more specific than LAH as a reducing agent. It reduces ketones and aldehydes to the corresponding
alcohols without affecting other functional groups, reduces acid chlorides to aldehyde. It does not reduce any
other derivative of acid. It is effective even in protic solvent like alcohol.
NaBH4

NaBH4

NaBH4

NaBH4

Reactant Aldehyde

Ketone

Acid chloride

Product 1 alcohol

2 alcohol

Aldehyde

LiAlH 4

(iii)

Diisobutyl Aluminium Hydride [DIBAL-H / Inert solvent] :

Diisobutyl aluminium hydride is parallel to LAH (Lithium aluminium hydride) as a reducing agent but it is
more selective.
DiBAL-H

(a)

DiBAL-H

DiBAL-H

DiBAL-H

DiBAL-H/Hot DiBAL-H/Cold DiBAL-H/Hydrolysis

Reactant

Aldehyde

Ketone

Acid chloride

Ester

Ester

Cyanide

Product

1 alcohol

2 alcohol

1 alcohol

1 alcohol

Aldehyde

Aldehyde

LiAlH THF

4 PhCH CH CH OH + C H OH
PhCH=CHCOOC2H5
2
2
2
2 5

H2O

PhCH=CHCH2OH
(b)

By DIBAL at ordinary temperature esters are reduced to alcohols but at low temperature esters are
reduced to aldehyde.

RESONANCE

O
||
DIBAL
C6H5 C OCH3 C6H5CH2OH
toluene 25 C

C6H5CHO
(c)

LAH reduce RCN to amine but DIBAL is found to be reduce it to aldehyde.

LiAlH THF

4 CH CH NH
CH3CN
3
2
2

H2O

CH3CHO

A-5

Miscellaneous Reductions :

(i)

Wolff-kishner reduction [NH2NH2 / KOH] :

Used to prepane alkane from carbonyl compounds

NH2NH2 / KOH
RCH3
RCHO

Note : Wolff-kishner reduction is not used for compounds which have base sensitive groups used to reduce carbonyl
& carbonyl group. [Halogens, Acid halide, Esters, Anhydride, Cyanide]

(ii)

By Red P & HI :
Used to prepare alkane from acid, acid derivatives and carbonyl compounds.
Red P & HI

Red P & HI

Red P & HI

Red P & HI

Red P & HI

Reactant

Aldehyde

Ketone

Acid chloride

Acidanhydride

Ester

Product

Alkane

Alkane

Alkane

Alkane

Alkane

(a)

(c)

Re d P HI
R CH3

Re d P HI
R CH3

Re d P HI
(e) CH3CH=O CH3CH3

(iii)

Red P & HI

(b)

Re d P HI
R CH3

(d)

Re d P HI
R CH R
2

(f)

Red P HI
CH CH CH
3
2
3

Meerwein-Pondorf-Verley reduction (Reduction by isopropyl alcohol and aluminium

isopropoxide) : It is selective reduction of ketones to alcohol, even in presence of other functional groups
using Aluminium isopropoxide in isopropyl alcohol.

eg.

RESONANCE

(B). Oxidation-1 (L-3)

B-1.

INTRODUCTION
1.

2.

3.

oxidation is defined as the addition of oxygen (electronegative) element to a substance or removal of

hydrogen (electropositive) element from a substance.
or
Oxidation of an organic molecule usually corresponds to increasing its oxygen content or decreasing
its hydrogen content.

Oxidation of an organic compound may be more broadly defined as a reaction that increases its
content of any element more electronegative than carbon.
Replacing hydrogen atoms by chlorine atoms is an oxidation
Ar CH3

ArCH2 Cl

ArCHCl2

ArCCl3

When organic compound is oxidised, something else the oxidising agent is reduced. When an
organic compound is reduced, something else - the reducing agent must be oxidized.

B-2.

OXIDATION OF ALKANES
Different products are formed by the use of different oxidising agents or different reaction conditions.

(i)

Chemical oxidation with KMnO4 or K2Cr2O7 : Alkanes are usually not affected by oxidising
agents like KMnO4 or K2Cr2O7. However, alkanes having tertiary hydrogen are oxidised by these oxidising
agents to an alcohol.
KMnO 4
(CH3)3CH
(CH3)3COH
(Isobutane)
(Tertiary butyl alcohol)

B-3.
(i)

OXIDATION OF ALKENES AND ALKYNES

Bayer reagent [cold dilute alkaline KMnO4 solution] :
Bayer
Reagent

Bayer
Reagent

Bayer
Reagent

Reactant

Alkene

Alkyne

Product

Vicinal diol

Diketone

Stereochemistry : syn addition.

Both OH groups add from same stereochemical side.
General Reaction

C=C

+ KMnO4 + OH, H2O

(or OsO4, H2O2)

RESONANCE

|
|
CC
|
|
OH OH
(syn addition)

Ex.1

(ii)

OH
H2O

+ MnO2 + H2O

Osmium tetraoxide in alkaline medium [OsO4 / H2O2] :

Similar to Bayer reagent.
OsO4 /H2O2 OsO4 /H2O2 OsO4 /H2O2
Reactant

Alkene

Alkyne

Product

Vicinal diol

Diketone

Stereochemistry : syn addition.

OsO 4 , H2O 2

Ex.

(iii)

Oxidation with acidic KMnO4 [KMnO4/H+] : Stereochemistry : syn addition.

When alkene & alkyne heated with KMnO4 in acidic or in alkaline medium; following changes takes place.
KMnO4/H+

KMnO4/H+

KMnO4/H+

Reactant

.= CH2 group

.= CH R group

.= CR1R2 group

Product

CO2

RCOOH

O.= CR1R2 group CO2

Carbon dioxide Carboxylic acid

Ex.-1

KMnO4/H+

Ketone

KMnO4/H+
. CH group

KMnO4/H+
. CR group
RCOOH

Carbon dioxide Carboxylic acid

O]
RCH= CH2 [
CO2 + H2O + RCOOH

Ex.-2

O]
RC CH [
CO2 + H2O + RCOOH

Ex.-3

O]
RC C R [
2RCOOH

KMnO4
Warm
conc.

Ex.4

KMnO4
Warm
conc.

Ex.5

RESONANCE

OH

+
O

COOH

+ CO2 + H2O

COOH
O

Ex.6

O
O
||
||
CH3 C C CH2CH3 CH3 C OH + HO C CH2CH3
(1) KMnO 4 , NaOH,
( 2 ) H

Ex.7

O
||
CH3CH2CH2 C CH CH3 CH2CH2 C OH + CO2 + H2O

(1) KMnO 4 , NaOH,

(2) H

Oxidation with peroxyacids :

An alkene is converted to an epoxide by a peroxyacid.
[a carboxylic acid that has an extra oxygen atom in a O O (peroxy) linkage].

General Reaction

C=C

O
||
+R C O

O
||
+ R C O H (acid)

The epoxidation of an alkene is clearly an oxidation, since in oxidation, an oxygen atom is added. Peroxyacids
are highly selective oxidizing agents. Some simple peroxyacids (sometimes called peracids) are shown
below :

RCO3H = Peroxy acid

HCO3H = PFA (Performic acid)
CH3CO3H = PAA (Peracetic acid)
PhCO3H = PBA (Per benzoic acid)
CO H
3

= MCPBA (Metachloro perbenzoic acid)

(iv)

Cl

CF3CO3H = TFPAA (Trifluoro peracetic acid)

Stereochemistry : anti addition in diol formation.

H , H O

General Reaction

RESONANCE

10

Note : The more highly substituted olifinic bond is more nucleophilic and therefore reacts faster with the peroxyacid
than the less susbstituted double bond.

HCO3H

HCO2H

Ex.7

(v).

+ Enantiomer Ex.8

Oxidation with ozone (ozonolysis) :

Alkene & Alkyne
Like permanganate ozone cleaves double bonds to give Ketones and aldehydes. However, ozonolysis is
milder, and both Ketones and aldehydes can be recovered without further oxidation.
Reductive Ozonolysis Products (O 3 / Zn, H 2 O)
O3/ Zn, H2O

O3/ Zn, H2O

O3/ Zn, H2O

O3/ Zn, H2O

.= CR1R2 group

O3/ Zn, H2O

O3/ Zn, H2O

Reactant

.= CH2 group

.= CH R group

Product

HCHO

O.= CH R group O.= CR1R2 group HCOOH

RCOOH

Formaldehyde

Aldehyde

Carboxylic acid
or diketone

Ketone

. CH group

Formic acid

. CR group

Oxidative Ozonolysis Products

O3/H2O2

O3/H2O2

O3/H2O2

Reactant

.= CH2 group

.= CH R group

.= CR1R2 group

Product

CO2

RCOOH

O.= CR1R2 group CO2

Carbon dioxide Carboxylic acid

O3/H2O2

Ketone

O3/H2O2

O3/H2O2

. CH group

. CR group
RCOOH

Carbon dioxide Carboxylic acid

Ex.16

O 3 , H2 O
C8H10 (A)
Acid (B) Identify (A) and (B) in the above reaction

Sol.

(A)

Ex.17

A certain hydrocarbon has the formula C16H26. Ozonolysis followed by hydrolysis gives CH3(CH2)4CO2H and
succinic acid as the only product. What is hydrocarbon
DU = 4

Molecular structure must be :

CH3(CH2)4CCCH2CH2CC(CH2)4CH3

Sol.

C C

RESONANCE

(B)

COOH

11

Oxidation-2
B-4.

(L-4)

Oxidation Reaction of Alcohols :

Oxidation Product of Alcohol-1

Weak oxidising agent
PCC*

X2 + NaOH***

PDC**

Strong oxidising agent

CrO3/Inert
medium

CrO3 in water
or H2CrO4

KMnO4/H

1 alcohol
or Primary alcohol

Aldehyde

Carboxylic acid

2 alcohol or Secondary alcohol

Ketone

Ketone

3 alcohol or tertiary alcohol

Not oxidised

Not oxidised

K2Cr2O7/H

PCC* = (Pyridinium Chloro Chromate) in CH2Cl2

Non aquous solvent
+ HCl + CrO3

.Cl.CrO3

PDC** = Collin's Reagent (2C6H5N.CrO3)

X2 + NaOH*** = (NaOX sodium hypohalide)
Oxidation Product of Alcohol-2
Very-Very Strong oxidising agent
KMnO4/H+/Heat

Copper & heat

as oxidising agent

Oppenaurs
oxidation**

1 alcohol
or Primary alcohol

Carboxylic acid

Aldehyde

Aldehyde

2 alcohol or Secondary alcohol

Mixture of
Carboxylic acid

Ketone

Ketone

3 alcohol or tertiary alcohol

Mixture of
Carboxylic acid

Dehydrate to alkene

*MnO2 (Selectively oxidised allylic and benzylic alcohol into aldehyde and ketone).
**Oppenaur's oxidation
Base + Ketone (solvent)
K(CH3)3CO / [Al(CH3)3CO]3 + (CH3)2CO / CH3COC2H5 /

Selectively oxidised secondary alcohol into ketone.

(i)

Acidic KMnO4 & K2Cr2O7 as oxidising agent :

Aldehydes are oxidised to carboxylic acid having same number of C atoms as aldehyde.
HCHO + [O] HCOOH

RCHO + [O] RCOOH

Ketones are oxidised with difficulty. They are oxidised only on heating with a strong oxidising agent.
2

Cr2 O 7 H
CH3COOH + CO2 + H2O
+ [O]
or KMnO4 H
In case of mixed or unsymmetrical ketones the >C = O group remains with the smaller alkyl group.
(Popoffs rule)
[O]
CH3COCH2CH3 2 CH3COOH ;

RESONANCE

[O] CH COOH + CH CH COOH

CH3COCH2CH2CH3

3
3
2

12

Mechanism (with Cr+6 oxidising agents) :

(i) CrO3 + H2O

H2CrO4 =

H2 O

(ii) R C OH + H O Cr OH

..
H2O

O
OH
OH
H2 CrO 4
rds
R C OH R C O Cr OH R C = O + H2CrO3
OH
H
H
O
Acid
Gemdiol
unstable

(iii) R C = O
H

rds
R C = O + H2CrO3

Remarks :
(1) Primary alcohol forms a chromate ester with chromic acid.
(2) The chromate ester decomposes in 2nd slow step with the elimination of -hydrogen. So the first
oxidation product, an aldehyde is obtained.
(3) In aqueous medium, aldehyde forms a gemdiol (hydrated aldehyde). It is further oxidised to an
acid by similar mechanism.
(4) The following reactivity orders can be explained by this mechanism :
Rate of Oxidation
(a) RCH2OH > R2CHOH > R3C OH (inert)

(b) CH3OH > CH3 CH2 OH >

(c) R CH2OH > R CD2OH (Bond Energy : C H < C D )
(d) RCHO > RCH2OH
(e) RCHO > RCDO

(ii)

With Tollen's reagent :

RCHO (aldehydes) can be easily oxidised to RCOOH (except HCHO that can be oxidised to CO2) by weak
oxidising agents like ammonical AgNO3 (Tollens reagent) hence they are better reducing agents.

Aldehydes reduce Tollens reagent to Ag and appears in the form of silver mirror is called silver-mirror test.
It is given by all aldehydes and reducing sugars.

RCHO + 2[Ag(NH3)2+ ] + 3OH RCOO + 2Ag + 4NH3 + 2H2O

(iii)

With Fehling Solution :

Aldehydes (except benzaldehyde) reduce Fehlings solution (Cu2+ reduced to Cu+) which is an alkaline
solution of cupric (Cu2+) ion complexed with tartrate ion.

RCHO + 2Cu2+ + 3OH RCOO + Cu2O + 2H2O

red ppt.

Aldehydes also reduce Benedicts solution (Cu2+ complexed with citrate ion) to Cu+

RESONANCE

13

B-5 Oxidation reaction of diols

(i)

HIO4 oxidation :
(Oxidation by lead acetate is similar to HIO4 oxidation)
Mechanism

R
|
RC
+
||
O18

R
|
CR
||
18 O

2H O

Remarks
(1) HIO4 (periodic acid) oxidises vicinal diols (1, 2-diols).
(2) It brings about oxidative cleavage of vicinal diol.
(3) It can also oxidise -hydroxy carbonyl compound, -dicarbonyl compound and -hydroxy acid.
(4) HIO4 forms a cyclic periodate ester as an intermediate. So the two OH groups should have synconformation.
(5) In cyclic diols only cis-vicinal diols are oxidised. Trans isomers are not oxidised.
Ex.1

General reaction
HIO

HIO

4
4

R CHO + HCOOH + R CHO

Ex.25 (1)

HIO

RESONANCE

14

Oxidation Product of 1, 2 and 3 alcohol

Write the product of (X).

CH3 CH = CH CH CH2 CH2 OH
OH
(X)
O
K 2 Cr2 O 7
X CH3 C OH + HOOC C CH2 C OH
(1) H 2SO 4
O
O

Ex.22

PCC

CH CH = CH C CH CHO
X
3
2
( 2)
O
Oppenau er oxidation

X
CH3 CH = CH C CH2 CHO
(3)

CrO3 / aq.

CH CH = CH C CH COOH
X (
3
2
4) acetone
O
MnO

2
X CH3 CH CH C CH2 CH2 OH
(5 )
||
O

RESONANCE

15

Common Oxidising Agents In Organic Chemistry

S.No.
1.

Oxidising Agent
Beyer Reagent

2.

Jones Reagent

3.

Collins Reagent
Used in (CH2Cl2)
Without overoxidation
Corey-Reagent
Used in (CH2Cl2)
Without overoxidation

4.

5.
6.

PCC (Pyridinium
Chloro Chromate)
MnO2

1% very dilute, cold and

alkaline KMnO4 solution
CrO3 + H2O or H2CrO4
aq.
CrO3+Pyridine or
CrO3.2py
Na2Cr2O7 + Pyridine
and HCl

Reactant
Alkene
Alkyne
1Alcohol
2 Alcohol
1Alcohol
2 Alcohol

Product
Cis-diol
1, 2-Diketones
Acid
Ketones
Acid
Ketones

Allylic 1Alcohol

unsaturated
aldehyde

unsaturated
Ketones
Aldehyde
Ketones

unsaturated
aldehyde

unsaturated
Ketones
Epoxides

R3N-O
Ester
Lactones
Diketones

Allylic 2Alcohol

CrO3 + 6M HCl + Py or
+

(pyH CrO3 Cl )
MnO2
cis & trans allylic
alcohols are oxidized at
the same rate without
isomerisation

1Alcohol
2 Alcohol
Allylic 1Alcohol

Alkene
R3N
Ketone
Cyclic Ketone
Electron deficient carbon
of aldehyde/ ketones
Cis diol

Allylic 2Alcohol

7.

Peroxides & Peracids

m-chloroperbenzoic
acid, Peracetic acid,
Hydrogen peroxide

8.

SeO2

SeO2 + H2O

9.

Lead Tetraacetate

Pb (CH3COO)4

10.

Per Iodate ion or

per iodic acid

IO4 or HIO4

Cis diol

11.

Tollens Reagent

Aldehyde

12.

Fehling Solution

13.

Benedict Solution

Ammonical AgNO3
solution
CuSO4 + SodiumPotassium tartrate
solution
CuSO4 + Potassium
citrate solution

14.

Cu/

RESONANCE

Aldehyde

Aldehyde
1Alcohol
2 Alcohol
3 Alcohol

Cleaves to
aldehyde,
keone/acid
Cleaves to
aldehyde,
keone/acid
Carboxylic
acids
Carboxylic
acids
Carboxylic
acids
Aldehyde
Ketones
Alkene

16

(C). HYDROLYSIS (L-5)

(i)

Introduction :
Hydrolysis is a chemical reaction or process in which a molecule splits into two parts by reacting with a
molecule of water,(H2O). One of the parts gets OH- from the water molecule and the other part gets H+ from
the water.Such reactions are endothermic.
This is distinct from a hydration reaction, in which water molecules are added to a substance, but no
fragmentation of molecule/species occurs.Such a process is exothermic.

(ii)

Hydrolysis of an ester :
Hydrolysis of an ester involves breaking off an ester link. It can takes place in

(a) Mild acidic medium : Dilute H2SO4, dilute HCl.

(b) Strong alkaline medium : Aqueous NaOH or KOH and heat.
one hydrolysis product contains a hydroxyl functional group, while the other contains a carboxylic acid
functional group.

(iii)

Hydrolysis of an anhydride :
The hydrolysis of acid anhydride produces two carboxylic acids.

(iv)

Hydrolysis of acid halide :

Hydrolysis of an acidhalide results into a carboxylic acid and hydrogenhalide. Only the carboxylic acid
product has a hydroxyl group derived from the water. Hydrohalic acid product gains the remaining hydrogen
ion.

+ HCl

(v)

Hydrolysis of acid amide :

Hydrolysis of an amide results into a carboxylic acid and an amine product or ammonia, only the carboxylic
acid product has a hydroxyl group derived from the water. The amine product (or ammonia) gains the remaining
hydrogen ion.

+ NH3

RESONANCE

17

(vi)

Hydrolysis of cyanides :
Cyanides has 30 nitrogen bonded with SP carbon.On hydrolysis C-N bond dissociates to produce ammonia
and carboxylc acids.It is carried out in acidic medium.

+ NH3

(vii)

Hydrolysis of isocyanides :
IsoCyanides has 40 nitrogen bonded with SP carbon and one of the alkyl/aryl group.On hydrolysis C-N bond
dissociates to produce Primary amines and formic acids.It is carried out in acidic medium.

+ RNH2

(viii) Hydrolysis of Ethers :

Ethers has R-O-R group.In strong acidic medium (HI or HBr) in hydrolysis to produce 2 equivalent of
alcohols.

(ix)

Hydrolysis of Hemiacetals and Acetals :

Hemiacetals and Acetals has R-O-R group.
Hemiacetals are unstable and get hydrolysed to aldehyde/ketones even in aq medium. However acetals /
Ketals are stable and hydrolyse only in strong acidic medium (HI or HBr) to produce 2 equivalent of alcohols.
and one equivalent of aldehyde/ketone. Acetals are often used as protecting groups.

(x)

Hydrolysis of Alkylhalides :
10 and 20 Alkyl halides in aq basic medium hydrolyses to alcohol and hydrahalic acids.30 alkyl halides are
hydrolysed in aq medium only.

(xi)

Hydrolysis of Grignard reagents and metal alkyls :

Grignard reagents and metal alkyls are very strong bases and hydrolyse violently even with a trace of water
to gives hydrocarbons and metal hydroxides.

RESONANCE

18

HYDROLYSIS OF COMMON FUNCTIONAL GROUPS

Functional Groups

Reactant

Bond

Products

Products

Catalysis

Broken
Alkyl Halides

C-Hal

Cl

Ethers

O
R

C-O

O
R

R
HC

O
H

and

Alcohols

Basic

Acidic

Acids and

NH3

Basic

or

basic

acidic HI
and

Acids

HO

Strong

Hydrogen Halides

O
OH

or

Phenols

HCl

Nitriles/Cyanides

OH

C-O

Alcohol

Acids

Cl

Cl

Acid Anhydrides

C-Hal

Hydrogen Halides

Acid Halides

OH

Acidic

Ammonia

OH
Esters

C-O

O
R

Amides

R
O

O
R

NH

Isonitriles/isocyanid
es

HC

H +

NH

Acids and

Strong

Ammonia or

Acidic

Amines

R
Formic acid and

NH2

Acidic
basic

C-N

Amides and Nsubstituted

Acids and Alcohols

Acidic

Primary amines

+
HO

Metal Alkyl Halides

Mg

Br

M-C

RH

Hydrocarbons

H 2O

and Metal
Hydroxides
Metal Alkyls

M-C

Li

RH

Hydrocarbons

H 2O

and Metal
Hydroxides

RESONANCE

19

or