CHM 303 RAMAZ PRINT 34

CHEMISTRY

Alcohols, Ethers and Epoxides, Aldehydes and Ketones, Carboxylic Acids

and their Functional Derivatives

CONTENTS

Alcohols
Ethers
Epoxides
Aldehydes and Ketones
Carboxylic Acids and Their Functional Derivatives

Keywords
alcohols, ethers, epoxides, aldehydes, ketones and carboxylic acids

1
Alcohols
Alcohols are the hydroxyl derivatives of saturated hydrocarbon in which hydroxyl(-OH) group is
attached to saturated carbon atom. All the chemical properties of alcohols are due to the presence
of –OH group thus hydroxyl group is the functional group of alcohols. Alcohols can be
represented by the general formula R-OH.

Alcohols can be classified as mono, di, tri and polyhydric alcohols depending on the number of
hydroxyl groups (1, 2, 3 or more) present in a molecule. For example
CH2OH CH3
CH2OH
H3C CH2 OH CHOH (CHOH)4
ethanol
CH2OH CH2OH CH3
(Mono hydric) Sorbitol
ethylene glycol glycerol
(Dihidric) [Poly hydric]
[[Trihydric]

Monohydric alcohols [R-OH] are further subdivided into 1o, 2o and 3o alcohols depending upon
the nature of carbon atom to which –OH group is attached.
H R' R'
1oCarbon o 3oCarbon
2 Carbon
R C OH R C OH R C OH

H H R"
Primary Alcohol secondary Alcohol Tertiary Alcohol

General Methods of preparation:

1) By the Hydrolysis of alkyl halides: Alkyl halides react with aq. KOH or moist silver oxide
to give alcohols.
R-X + KOH(aq) R-OH +KX

R-X + AgOH R-OH + AgX

2) By hydration of olefins: Alkenes react with Sulphuric acid (98%) to give first addition
product, alkyl hydrogen sulphates which on hydrolysis give alcohols.

In case on unsymmetrical alkenes for addition, Markonikov’s rule is followed.

34
 OSO 3H
R CH CH2 + HOSO3H R CH CH3
Alkyl hydrogen sulhate
OSO 3H H OH

R CH CH3 + O H R CH CH3 + H2SO4

o
2 alcohol

Except ethyl alcohols primary alcohols cannot be prepared by this method. Overall reaction is
the Markonikov’s addition of water to a double bond. e.g.
OH
+
H3C CH CH2 + H2O H
H3C CH CH3
Propylene
Iso propyl alcohol

3)Hydroboration-Oxidation of Alkenes: When alkenes are treated with diborane, trialkyl

boranes are formed. In this reaction diborane adds as borane (BH3). The positive part of BH3 is
boron and negative part is hydrogen. e.g.
3 R C CH2 + 1/ 2 B 2H6 (RCH2CH2)3B

Trialkyl borane on treatment with alkaline aqueous solution of hydrogen peroxide gives
1oalcohols.
-OH
(RCH2CH2)3B + H2O 2 3RCH2CH2OH + H3BO3

1o Alcohol
The overall reaction of hydroboration-oxidation results anti- Markonikov’s addition of water to
double bond. e.g.
I)B 2H6
CH3CH=CH2 CH3CH2CH2OH
II) H 2O/-OH
n-propylalcohol
Propylene
4) Hydrolysis of Esters: Acid hydrolysis of esters yield alcohols. e.g

O +
H
H3C C CH3 + H2O RCOOH + R'OH

5)By catalytic Reduction of Carbonyl Compounds: Aldehydes on reduction give 1o alcohols

and ketones give 2o alcohols. 3o Alcohols can’t be prepared by this method.
i) Reduction by using alcoholic sodium[Bouveoult-Blanc reduction]:
O
Na/C2H5OH
R C H R-CH2OH
Aldehyde 1o alcohol

O
OH
Na/C2H5OH
R C R'
R CH R'
Ketone 2o alcohol

35
ii) Reduction by using LiAlH4 or NaBH4 :

O
Li AlH 4
R C H R-CH2OH
or
Aldehyde NaBH4 1o alcohol
O OH
Li AlH 4
R C R' R CH R'
or
Ketone
NaBH4 2o alcohol
α,β-unsaturated carbonyl compounds may also be reduced by LiAlH4 or NaBH4 to give
corresponding alcohols.

iii)Reduction with H2/Ni:

O
H2 /Ni
R C H R-CH2OH
Aldehyde 1o alcohol
O
OH
R C R' H2 /Ni
R CH R'
Ketone o
2 alcohol
6) From Grignard Reagent: Grignard Reagent (RMgX) first react with carbonyl compound to
give the addition product which on acid-hydrolysis gives corresponding alcohol.
OMgX OH
O
δ- δ +
+
H3C C CH3 + R-MgX H3C C CH3 H /H2O H3C C CH3
R R
Addition product
Unstable
Grignard reagent with formaldehyde, aldehydes other than formaldehyde and ketones leads to
the formation of 1o, 2o and 3o alcohols respectively. For example,
O OMgX
+
H C H + RMgX H C H
H /H2O
R-CH2OH

R
1o alcohol
OMgX
O +
OH
H /H2O
R' C H + RMgX R' C H
R' C H
R
R
2o alcohol
OMgX OH
O +
H /H2O
R' C R' + RMgX R' C R' R' C R'

R R

3o alcohol

36
7) By the reaction of aliphatic primary amine with nitrous acid: Primary aliphatic amines
react with nitrous acid to give alcohols.
RCH2NH2 + HONO RCH2OH + N2 + H2O
8) By Fermentation: Fermentation is the slow decomposition of complex organic compounds
into simple compound in the presence of enzymes obtained from microorganism. Fermentation
of starch and sugars under the influence of suitable microorganism gives alcohols.

For example:
C6H12O 6 Zymase
yeast
2C2H5OH + 2CO2
Glucose Ethyl alcohol

O
(C6H10O 5)n Fermentation CH CH CH CH OH
3 2 2 2 + H3C C CH3
Starch n-Butyl alocohol

Properties:
Physical properties:
1) Lower alcohols are colourless, toxic liquids while higher having more than 12 carbon are
solids. They have characteristic sweet alcoholic odour and burning taste.
2) Lower alcohols are easily soluble in water but solubility decreases with increase in molecular
weight.
Solubility of lower alcohols in water is due to the Hydrogen bonding between highly polarized –
OH groups present both in water and alcohols.

δ+ δ- δ+ δ- δ+ δ-
H O | | || || H O|| ||| H O| | || |

H R H

Figure-5: Hydrogen bonding between alcohol and water molecules.

But Higher alocohols have less tendency to form hydrogen bonds with water molecule because
of the presence of non polar long hydrocarbon chain and hence the solubility in water decreases.
3) Boiling points of alcohol increase with the increase in number of carbon atoms but their
boiling points are much higher than those of the corresponding alknaes. This is again because of
intermolecular hydrogen bonding. Highly polar –OH groups of different alcohol molecule and
partially negative oxygen in another alcohol molecule.
δ+ δ- δ+ δ- δ+ δ-
H O | | || || H O|| ||| H O|||||

H R H

4) Among isomeric alcohols boiling and melting points decreases with branching.
Primary> Secondary>Tertiary.

37
Chemical Properties:
Alcohols are chemically reactive compounds this is due to the presence of reactive functional
group, -OH group, which is polar in nature. Because of the high electronegativity of oxygen
δ+ δ- δ + δ -
atom both -C-O and -O-H bonds in alcohols are polar bonds.
Alcohols undergo following reactions.

1) Reactions involving only the hydrogen atom of the –OH group:

These reactions involve cleavage of oxygen and hydrogen bond.

i) Reaction with alkali metals: Alcohols react with sodium or potassium to form alkoxides with
the liberation of hydrogen gas.
2ROH + 2Na 2RONa + H 2
Sod.alkoxide

Their reaction shows the acidic nature of alcohols. Primary alcohols are more acidic than
secondary, which in turn is more acidic than tertiary thus order of acidic nature is as follows.
1oalcohols>2oalohols>3oalcohols

This is because of the +I effect of the alkyl groups attached. It would be maximum in tertiary
alcohols.

2)Reaction with carboxylic Acids: Alcohols react with carboxylic acids in presence of
concentrated sulphuric acid as a catalyst to give ester. The process is known as esterification.
The reaction is reversible.

O + O
H
R'OH + HO C R' R'O C R
Ester
+ H2 O
Alcohol Carboxylic acid

O +
O
H
C2H5OH +
HO C CH3 H5C2-O C CH3 + H2O
Ethyl alcohol Acetic acid Ethyl acetate

3) Reaction with Acid halides and Acid anhydrides: Alcohols can more easily esterified by
the action of acid Chloride or acid anhydride.
O O

R C Cl + HOR' R C OR' + HCl

Ester
O O
O
R C O C R + HOR' R C OR' + RCOOH
Acid anhydride Ester Carboxylic acid

38
4) Reaction with Grignard Reagent: Alcohols react with Grignard reagent to give alkanes.
This reaction is used for the estimation of alcoholic group [Zerewitnoff reaction]
R'OH
+ RMgX
alkyl magnesium
RH + R'OMgX
Alcohols Alkane Alkoxy mag.halide
halides

CH4 + C2H5OMgBr
C2H5OH + CH3MgI
methane
Ethoxy mag.bromide

(B) Reaction involving –OH group: These reaction involve cleavage of Carbon-oxygen bond
``````

-C--OH

5) Reaction with phosphorous Halides: When alcohols react with phosphorous penta
halide[PX5] or phosphorous halide [PX3], replacement of –OH group by halogen atom take place
and alkyl halides are formed.
R-OH + PX5 R-X + + HX
POX3

C2H5OH + PCl5 C2H5Cl + POCl 3 + HCl

3-R-OH + PX3 3-R-X + H3PO 3

3C2H5OH + PX3 3C2H5Br + H3PO 3

PBr3 and PI3 are usually prepared in situ.

6) Reaction with thionyl chloride: This involves replacement of –OH group by chlorine atom.

R CH3 + SOCl 2 R Cl + SO 2 + HCl

C2H5 CH3 + SOCl2 C2H5 Cl + SO2 + HCl

7) Reaction with halogen acids: Alcohols react with halogen acid to give corresponding alkyl
halides.
R OH + HX R X + H2O
The reactivity of halogen acids are in the order,
HI >HBr >HCl

No catalyst is required in case of HI and HBr but HCl reacts only in presence of anhydrous
ZnCl2 catalyst.

39
 anhydrous ZnCl2
C2H5 OH + HCl H5C2 Cl + H2O
Mechanism: Primary alcohols follow SN1 mechanism for the substitution of –OH group by
halogen atom.
Step 1: Protonation of Alcohol

.. +
.. H3CH2C O H
+
+
H3CH2C O H H
..
H
Step 2: Attach of nucleophile [X-]

.. +
H3CH2C O H + -X CH3-CH2-X + H2O
H
2o and 3o alcohols follow SN2 mechanism.

8) Reaction with sulphuric acid: The action of concentrated sulphuric acid is of great interest
as it gives different products under different conditions.
i) At room temperature, ethyl alcohol reacts with concentrated sulphuric acid to give ethyl
hydrogen sulphate.
Room Temperature C H OSO H
H5C2 OH + HOSO3H 2 5 3

Ethyl hydrogen sulphate

ii) When alcohols heated with concentrated H2SO4, dehydration takes place to give alkenes. For
example
H2SO 4
H5C2 OH
170o C
H2C CH2 + H2O
Ethyl alcohol Ethylene

Mechanism: Mechanism involve formation of carbocation.

Step 1: Protonation of alcohol.

+ +
H3C CH2 O H + H H3C CH2 O H
H
Step 2: Elimination of water molecule to give carbocation.
.. + +
H3C CH2 O H H3C CH2
+ H2O
H

Step 3: Removal of proton from carbocation:

40
 H H
+
H C C H2C CH2
H H Ethylene

The ease of dehydration of alcohols follow the following order

3o>2o>1o
This is also the order of stability of carbocation.

With secondary and tertiary alcohols, dehydration may occur in two ways, e.g.:

CH3CH2CH=CH2
1-Butene
OH
-H2O
H3C CH2 CH CH3

CH3CH=CHCH3
2-Butene
According to Saytzeff’s rule more substituted alkene is the major product.

iii) When excess of ethyl alcohol is heated with concentrated sulphuric acid at 140oC, diethyl
ether is formed.
con H2SO4
C2H5OH
+ OHC2H5 140 C o
C2H5-O-C2H5
Diethyl ether
Mechanism: Mechanism involves the following steps.

Step 1: Protonation of one Molecule.

.. .. +
H3CH2C O H
.. + H
+ H3CH2C O H
H
Step 2: Elimination of water molecule:

.. + +
H3C CH2 O H H3C CH2
+ H2O
H
Step 3: Attach of carbocation to another molecule of alcohol.

H
+
..
H3C CH2 + H O.. CH2CH3 C2H5-O-C2H5
..
+

Oxonium ion

41
Step 4: Removal of proton from Oxonium ion leads to the formation of ether.

H
-H
+ ..
+
H5C2 O C2H5 H5C2 O
.. C2H5
..
Diethyl ether

Alcohols can also be dehydrated by passing the vapours of alcohol over heated aluminia to give
ethers or alkenes e.g.
Al 2O 3 ..
2C2H5OH H5C2 O .. C2H5 + H2O
200oC diethyl ether

9) Reduction of Alcohols:
Alcohols are reduced to alkanes by concentrated HI and red phosphorous

red P
+
ROH 2HI RH + I 2 + H2O
alcohol Alkane

C2H5OH
+ 2HI
red P C2H6 + I2 + H2O
Ethane

10) Oxidation: Nature of oxidation products of alcohols depend upon the nature of alcohols,
oxidizing agent used and reaction conditions. Most commonly used oxidizing agents are acidic
KMnO4 and acidic Na2Cr2O7.

Primary alcohols are easily oxidized to aldehydes and then to carboxylic acids both with the
same number of carbon atoms as the parent alcohol. E.g.:
O
[O] [O]
CH3CH2OH H3C C H + CH3COOH
+ K2Cr2O 7/H
K2Cr2O 7/H Acetic acid
Ethyl alcohol Acetaldehye

Secondary alcohols oxidized to ketone with same number of carbon atoms, but these ketones
can’t be easily oxidized, these undergo oxidation under very drastic conditions to give mixture of
carboxylic acid with lesser number of carbon atomes than parent alcohol. Eg:
OH O
[O]
H3C HC CH3 H3C C CH3
+
K2Cr2o7 /H
Isopropyl alcohol Acetone

OH [O]
H3C CH CH3
KMnO4 /H
+
CH3COOH
+ HCOOH
Formic acid
Acetic acid

42
Tertiary alcohols are resistant to oxidation under normal conditions but under drastic conditions
they oxidized to first form ketones and then carboxylic acid both having lesser number of carbon
atoms.
CH3 O
[O] [O]
H3C C OH
+
H3C C CH3 +
CH3COOH
Acetic acid
+ Formic
HCOOH
acid
CH3 KMnO4 /H KMnO4 /H
t-Butyl alcohol Acetone
(one carbon less)

USE: The oxidation reaction may also be used to distinguish between primary, secondary
and tertiary alcohols.

11) Reaction with hot Copper: Primary and secondary alcohols dehydrogenated to form
aldehyde and ketones respectively, Tertiary alcohols are not dehydrogenated but they dehydrated
to give alkanes. e.g.
O
Cu
H3C CH2 OH H3C C H
ethanol 300oC acetaldehyde

OH O
Cu
H3C CH CH3 H3C C CH3
300oC acetone
iso propyl alcohol

CH3
CH3
Cu
H3C C OH
300oC
H3C C CH2
+ H2O
CH3
Isobutene
t-Butyl alcohol

USE: The dehydrogenation with hot copper may also be used to distinguish between
primary and secondary alcohols.

Ethers
Ethers are the organic compounds in which an oxygen atom is bonded to alkyl groups. The
functional group is [C-O-C]. If same alkyl groups are attached to central oxygen atom ethers are
classified as symmetrical ethers. While ethers containing different alkyl groups attached with
central oxygen atom are classified as unsymmetrical ethers.
.. ..
R O R R O R'
.. ..
symmetrical ethers unsymmetrical ethers

43
Ethers may be considered as derivatives of alcohol or water in which hydrogen atom /atoms have
been replaced by alkyl group or groups.
.. .. ..
H O H R O H R O R
.. .. ..
water alcohol ether

Some common examples of ethers are

.. ..
H5C2 O CH3 H5C2 O C2H5
.. ..
ethyl methyl ether diethyl ether

[methoxy ethane] ethoxy ethane

In ethers central oxygen atom is sp3 hybridized .Thus two C-O, σ-bond are formed by the
overlap of two half filled sp3 hybrid orbitals of oxygen atom with the half filled sp3 hybrid
orbitals of two carbon atoms of two alkyl groups. Remaining two sp3 hybrid orbitals of oxygen
atoms are occupied by the two unshared pairs of electrons. Here the C-O-C bond angle is about
110o which is quite close to tetrahedral angle [109.5o]
unshared
pair of
electrons
P3

SP
3
-S

-S
SP 3

110o
P

σ
3

σ
R R R R
Structure of Ether
Methods of preparation:
i) Dehydration of alcohols: By heating excess of alcohol with concentrated sulphuric acid at
140oC
Con.H2SO4
R-OH + HO-R R-O-R + H2O
140oC

Con.H2SO 4
C2H5OH + HO-C2H5 C2H5-O-C2H5 + H2O
ii) By passing alcohol vapors over Al2O3 at 250oC:

Al 2O 3
R-OH + HO-R R-O-R + H2O
2) By heating alkyl halides with silver oxide: Ethers are obtained by heating alkyl halides with
dry silver oxide.
C2H5I + Ag2O+ IC2H5 C2H5-O-C2H5
Diethyl ether

44
This method is useful for the preparation of simple ethers only.

3) Williamson Ether Synthesis: This is the most important industrial and laboratory method
of preparation ethers. It involves the treatment of sodium alkoxide with an alkyl halide.
Both symmetrical unsymmetrical ethers can be prepared by this method.

- +
R-ONa + X-R' R-O-R' + NaX
Sod. alkoxide Alkyl halide unsymmetrical ether
- +
R-ONa + X-R R-O-R + NaX
Sod. alkoxide Alkyl halide Symmetrical ether

- +
C2H5ONa + Br-C2H5 C2H5-O-C2H5
+ NaBr
Diethyl ether

- +
CH3ONa + Br-C2H5 CH3-O-C2H5
+ NaBr
Ethyl methyl ether

Tertiary and Secondary alkyl halides undergo elimination reaction with sodium alkoxide [strong
base]. Thus to introduce a tertiary group it will be better to take this group as a base, not as a
tertiary halide. For example
H3C CH3
R-ONa
H3C Cl H3C C CH2 + HCl
H3C

- +
Thus for preparing (CH3)3C-O-C2H5 , we should start with (CH 3)3C-ONa and C2H5Br.

Mechanism: It follows SN2 mechanism. Displacement of halide ion by alkoxide ion.

-+ SN2
R-ONa +R X R-O-R + NaBr

5)Action of Diazomethane on Alcohols: Ethers can be prepared by treatment of primary or

secondary alcohols with diazomethane in presence of flouroboric acid as a catalyst.
HBF 4
R-OH + CH2N2 R-O-CH3 + N2

HBF 4
C2H5-OH + CH2N2 C2H5-O-CH 3 + N2
But this method is only useful for the preparation of methyl ethers.

45
Properties:
Physical properties:
1) Ethers are highly volatile and inflammable substances.
2) Except dimethyl ether and ethyl methyl ether, which are gases all are pleasant
smelling colourless liquids.
3) Their boiling points gradually increase with the increase in molecular weight. But
ethers have lower boiling points than isomeric alcohols because they are
incapable of forming inter molecular hydrogen bonds due to the absence of –OH
groups.

Ethers are sparingly soluble in water since their oxygen atom is not capable of forming H-bond
with hydrogen with hydrogen atom of water molecule.

Chemical Properties:
Ethers are much less reactive compounds because they are quite stable. They do not react with
active metals, strong bases like NaOH, reducing and oxidizing agents.
1) Halogenations: When ethers react with chlorine or bromine substitution preferentially at α-
Carbon takes place.
For example:
Cl Cl Cl
Cl 2 Cl 2
CH3-CH2-O-CH 2-CH3 CH3-CH-O-CH2-CH3 CH3-CH-O-CH-CH3
dark dark
α- Chloro diethyl ether α,α1- Dichlorodiethyl ether.

The extent of substitution depends on reaction conditions.

2) Basic Nature: Ethers react with cold concentrated sulphuric acid or HCl to give oxonium salt.
Their basic nature is due to the presence of two lone pairs on oxygen atom.
H
.. cold -
R O
..
R + HCl R O
..
+
R Cl

oxonium ion

This property is used to separate ethers from ethyl bromide and to distinguish from alkanes.
Since alkanes do not react with acids.

3) Formation of peroxides (Auto oxidation): On standing in contact with air ethers combine
with oxygen to form peroxide which is highly explosive.
CH3CH2 O CH2CH3 + O2 long
(CH3CH(OOH).OC2H5
contact

These peroxides decompose violently at high temperature. Thus ethers should always be
purified before distillation. When ethers that contains peroxide is distilled, at the
end of 46
distillation residual peroxide may explode. Because of these ether should never be evaporated
to dryness.

4) Hydrolysis: Ethers when treated with dilute sulphuric acid under pressure, they hydrolyse
to give alcohols.
dil H 2SO4
R O R +H2O under pressure
2 ROH

H5C2 O C2H5 + H2O

dil H 2SO4
under pressure
2 C2H5OH

Diethyl ether Ethyl alcohol

5) Reaction with Phosphorus Penta-chloride: With PCl5 ether cleave to give alkyl chlorides

R O R + PCl5 2 R-Cl + POCl3

R O R' + PCl5 R-Cl + R'Cl + POCl3

6) Reaction with HI and HBr: Ethers react with hot concentrated HI or HBr to give an alcohol
and alkyl halide.
R O R' + HBr R-OH + R'Br

In case of mixed ethers the halogen atom attacks the smaller alkyl groups, due to the sterric
effect. e.g.
H5C6 O C2H5 + HI C6H5-OH + C2H5I
The order of reactivity of halogen acid is
HI>HBr>HCl

With the excess of acid, the alcohol initially produced is also converted to alkyl halide. e.g.

H5C2 O C2H5 +(excess)

2HI 2C2H5I + H2O
7) Reaction with acetyl chloride: Ethers react with acid chloride to give alkyl halides and
esters. For example
O O
ZnCl2
H5C2 O C2H 5 + H3C C Cl C2H5Cl + H3C C C2H5
Diethyl ether Acetyl chloride Ethyl chloride Ethyl actate

47
Epoxide
Epoxides are the cylclic ethers in which ethereal oxygen is linked with two adjacent carbon to
form three membered ring. i.e. oxiran (oxirane) ring. Epoxy compound contain oxirane ring.
Oxiran compounds are also referred to as cyclic ethers or alkene oxides.

HO OH

H3C C C CH3

O
epoxide

R HC CH2
H 2C CH2

O
O [ 1, 2 -epoxyalkane]
Ethyleneoxide[ 1, 2 -Epoxyethane]

Epoxy ethane or ethylene oxide (oxiran) is the most important member of this group.

Method of preparation: Epoxides may, in general, be prepared by epoxidation of alkenes with

peroxy acids. Perbenzoic acid C6H5COO2H, monoperphthalic acid, HOOCC6H4COO2H and P-
nitro benzoic acid have been used.
per acid
R-CH=CHR' R R'

O
Epoxide

H2C CH2
per acid
H2C CH2
O
Ethylene oxide

Ethylene oxide may be obtained:

i) By Reaction of Chlorohydrin with base:

HO-CH2-CH2-Cl + KOH H2C CH2 + KCl + H2O

48
Possibly the mechanism is:

HO - O
-
O
fast
-
-Cl
H O CH2 CH2 Cl
-H2O H2C CH2 Cl
H2C CH2

ii) By oxidation of ethylene with oxygen in the presence of silver catalyst.

Ag H2C CH2
2CH2=CH 2 + O2
2500C
2
O
Properties:
Ethylene oxide is toxic, flammable gas having b.p 10.7oC.generally epoxides are reactive
compound, this is because to release their strain they have the tendency to open their ring. These
oxygen atoms combine with the reactive hydrogen atom of various compounds to form hydroxyl
group.

H2C CH2

O + H A HO-CH2-CH2-A

Reaction with HOH

+ H2C CH 2
H2C CH2 H

O + H2O
OH OH

Ethylene glycol
Reaction with alcohols

H2C CH2 H2C CH2 OR

O + H-O-R OH
Alkoxy ethane
Reaction with Ammonia

H2C CH2 H2C CH2 NH2

O + HNH2 OH
2-Aminoethonal
Reaction with halogenated, HBr:

H2C CH2 H2C CH2 Br

O + HBr OH

49
Reaction with LiAlH4

H2C CH2
+ LiAlH 4 CH3CH2OH
O Ethyl alcohol

Unsymmetrical epoxides give the more highly substituted alcohol with main product.

OH
R H2C CH2 LiAlH 4
R-CH-CH3 + RCH2CH2OH
O main product

Reaction with HCN:

H2 C CH2

O
+ HCN HO-CH2-CH2-CN
ethylene cyanohydrin

Reaction with Grignard Reagent:

Ethylene oxide reacts with Grignard Reagent to give addition product which on hydrolysis yield
primary alcohol.
OMgX
H2C CH2 +
H / H 2O
O
+ R-MgX CH2-CH2-R HO-CH2-CH2-R

Oxidation:
Epoxides are oxidized with dimethyl sulphoxide to α-hydroxy ketones.
OH H OH O
R HC CH R +
H
O
+ Me2SO R CH C R
-Me2S
R CH C R
+-
O SMe2

Aldehydes and Ketones

Aldehydes and ketones both contain oxo or carbonyl group ( >=O ). In aldehydes carbonyl
carbon on one side attached to hydrogen atom and to carbon atom on other side, thus functional
group of aldehydes is –CHO. This group occurs at the end of a chain. In ketones carbonyl
carbon, on both sides attack to carbon atoms, thus the functional group in ketones occurs within a
O
chain. ( c c c)

50
Aldehyde and ketones are collectively called carbonyl compounds.

Like carbon-carbon double bond, double bond between carbon and oxygen in carbonyl group is
composed of one σ and one π bond. Carbonyl carbon is in a state of sp2 hybridization. The
carbon –oxygen σ bond is formed by the overlap of sp2 orbital of carbon with sp2- orbital of
oxygen atom. On the other hand the carbon oxygen π bond is formed by side wise overlap of
unhybridised p-orbital of both atoms. Two unshared pairs of electron occupy the sp-hybrid
orbitals of oxygen. since three σ-bond of carbonyl carbon utilize sp2 orbitals, they lie in one
plane. The bond angles between the attached atoms are approximately 1200.

But here π electrons are not equally shared by both carbon and oxygen atoms. This is because of
the electronegativity . Due to the high electronegativity of oxygen atom, the π electron cloud is
pulled more forward the oxygen atom. As result bond is polarized, oxygen attains a partial
negative charge and carbon a partial positive charge.

51
 .

δ+ δ-
C O

.
polarity due to inductive effect

However the high values of dipole moments of aldehydes and ketones can’t be accounted only
by inductive effect but also by the resonance effect. Following resonance structures are possible.
. .

+ -
C O C O

. .

Carboxyl group is resonance hybrid of above two structures.

Methods of Preparation:
Both Aldehydes and ketones may be prepared by the following methods.
1) Oxidation of alcohols: Aldehydes are formed by the oxidation of primary alcohols.
+
K2Cr2O7 / H
RCH2OH RCHO + H2O
Controlled Oxidation
o
1 alcohol Aldehyde

Controlled Oxidation
CH3CH2OH CH3CHO + H2O
Ethyl alcohol Acetaldehyde

Controlled oxidation can also be carried out by using CrO3- pyridine [Collin reagent] Ketones
are prepared by the oxidation of secondary alcohols.
O
+
K2Cr2O7 / H
R-CHOH R-C-R' + H2O
R' Ketone
2o alcohol
OH O
+
K2Cr2O7 / H
H3C CH CH3 H3C C CH3 + H2O

2-Propanol Acetone

Ketones are not easily oxidized further. Ketones can also be obtained by Oppenauer oxidation
of secondary alcohols, which involves refluxing of second alcohol with acetone in the presence
of aluminium tertiary butoxide, AlOC(CH3)3, catalyst.

52
 R H3C R H3C
AlOC(CH 3)3
CHOH + C O C O + CHOH
R' H3C R' H3C

2o Alcohol Acetone
Ketone Iso propyl alcohol

2) Dehydrogenation of alcohols: By passing the alcohol vapours over a copper catalyst heated
to about 300oC, aldehydes and ketones are prepared. 1o alcohols give aldehydes while 2o give
ketones.
O
Cu
RCH2OH
300 oC
R C H + H2

O
Cu
CH3CH2OH
300 oC
H3C C H + H2

Ethylalcohol Acetaldehyde
O

R-CHOH-R'
Cu
o
R C R' + H2
300 C
2o alcohol Ketone

O
OH
Cu
H3C CH CH3 o H3C CH CH3 + H2
300 C
Iso propyl alcohol Acetone

3. Dry distillation of calcium salts of Acids: Aldehydes are prepared by pyrolysis of calcium
salt of fatty acid with Calcium formate. While calcium formate alone on heating gives
formaldehyde.

53
Ketones are obtained by heating calcium salt of fatty acid other than calcium formate.

4) Hydration of alkynes: Aldehydes and ketones can be prepared by reactions of alkynes with
the water in presence of mercuric sulphate and sulphuric acid.
H
HgSO4
H3C C C CH3 + H OH
H2SO4
R C C H R C CH3

Propyne O H O
Acetone
Unstable

Acetylene give aldehyde under these conditions.

O
HgSO4
H C C H + H OH
H2SO4
H3C C H

5) Hydrolysis of gem-Dihalides: Aldehydes are prepared by the hydrolysis of gem dihalides

containing both halogen atom on terminal carbon atom.
Cl OH O
H2O - H2O
R CH Cl NaOH R CH OH R C H

54
Ketones are prepared by the hydolysis of gem-dihalides containing both halogen atoms on non
terminal carbon atom.
Cl O
H 2O
R C R' R C R'
NaOH

Cl

For example

Cl
H2O
H3C CH Cl CH3CHO
NaOH
Acetaldehyde

Cl O
H2O
H3C C CH3 H3C C CH3
NaOH
Cl

6) Catalytic decomposition of acids: Aldehydes cannot be prepared by this method. Ketones

are prepared by passing vapours of carboxylic acid over heated MnO or ThO2. For example,
O O
MnO
2 H3C C OH
300oC
H3C C CH3 + H2O + CO2
2 molecules of acetic acid Acetone

7) Reduction of Acid Chlorides: [Rosenmund Reduction]: Aldehydes can be prepared by the

reduction of acid chloride in the presence of palladium supported over barium sulphate.
O O
Pd / BaSO 4
R C Cl + H2
S or quinoline
R C H + HCl
Aldehydes can also be easily reduced to primary alcohol but the catalyst is poisoned by the
sulphur and thus aldehydes are the final product.
Ketones cannot be prepared by this method.

8) From Grignard Reagent: Aldehydes can be prepared from Grignard Reagent (RMgX) in
two ways.
i) From hydrogen cyanide:
H O
+
H / H 2O
RMgX + H C N R C NMgX R C H3
Additin product
+
MgX(NH2)

55
ii) From alkyl formates:

O O-MgX

H C OR' + RMgX H C OR'

H2O

R
OH O
-H2O
H C OH R C H

Ketones can also be prepared from Grignard reagent in two ways,

i) From alkyl cyanide:

R O
+
H / H 2O
R'-MgX +R C N R C NMgBr R C R' + MgX
ii) From acid Chlorides:

O OMgX O

H3C C Cl + R'MgX R C Cl R C R' + MgXCl

R'

Aldehyde or ketones so formed, may further react with excess of the Grignard reagents to give
alcohols.

9) Oxo process: This method is industrially important for the preparation of aldehydes. It
involves the treatment of an alkene with carbon monoxide and hydrogen in the presence of
cobalt carbonyl catalyst at high temperature and pressure.
O
[Co(CO)4
R CH CH2 + CO + H2 R CH2 CH2 C CH3

Aldehyde
Alkene

Ketones cannot be prepared by this method.

10) Wacker process: This method involves the treatment of alkene with acidified aqueous
solution of palladium chloride, PdCl2 and cupric chloride, CuCl2.

56
 O
CuCl2
H2C CH2 + PdCl2 + H2O H3C C H + Pd + 2HCl
Alkene Acetaldehyde

O
R CH CH2 + PdCl2 + H2O R C CH3 + Pd + 2HCl
Ketone

Properties:
1) Formaldehyde is gas at room temperature and other aldehydes and ketones are colourless
liquids.
2) Lower aldehydes and ketones are soluble in water due to capability of forming hydrogen
bonds with water molecules. But higher members containing more than five carbon
atoms are insoluble in water and soluble in organic solvent.
3) Since aldehydes and ketones are polar compounds. Their boiling points are higher than
corresponding non polar compounds. But these molecules are not capable of forming
intermolecular hydrogen bonds. Their boiling points are lower than corresponding
alcohols.
4) Density of aldehydes and ketones are lesser than that of water.

Chemical properties: Both aldehydes and ketones contain highly polar carbonyl group.

. .
+ -
.
δ+ δ-
C O C O C O
. .
.

Carbonyl carbon is electron deficient and carbonyl oxygen is electron rich. The electron deficient
carbon is readily attacked by electron rich nucleophiles and electron rich oxygen is attacked by
electron deficient electrophiles. The typical reaction of aldehydes and ketones is nucleophilic
addition. They undergo nucleophilic addition reaction by following general mechanism.

Nu-H + B Nu:
-
+ B-H
Neutral weak nucleophile Strong nucleophile
A: Base Catalysed Addition: Base convert weak nucleophile to strong one
Step 1: Attack of nucleophile at carbonyl carbon to form new σ-bond.

. Nu
.. ..
- O: O:
Nu: ..
. .

Step 2: Attack of electrophile ( e.g., -H+) at negatively charged oxygen to give addition product.

57
 Nu Nu
.. - ..
+ OH
O:
.. +H ..
. .
Addition product

B) Acid Catalysed Addition:

Step 1: Protonation of carbonyl group.
. .
.
.. +
+ ..
+H + O H
O:
.. .. O
.. H
. .
.
Resonance stabilised protonated carbonylgroup

Step 2: Attack of nucleophile on protonated carbonyl carbon to give addition product.

Nu
. ..
.. -
C
+
O
.. H + Nu:
O
.. H

.
. Addition product.

Addition products remains same in both acid and base catalysed reaction.

The reactivity of the carbonyl group towards the nucleophilic addition reactions depends upon
the magnitude of the positive charge on the carbonyl carbon and also on crowding around the
carbonyl carbon. (Steric factor). Alkyl groups of other electron donating that decreases the
positive charge on the carbonyl carbon will decrease its reactivity towards the nucleophilic
addition follows the following order.
O O O

H C H > R C H > R C R
Formaldehyde Aldehyde Ketone

Acidity of α-Hydrogens: A carbon atom next to carbonyl group is α-carbon atom and hydrogens
attached to this carbon are known as α – hydrogens. α- hydrogens in aldehydes and ketones are
abstractable by base i.e; acidic in nature. this is due to the fact that carbonion formed the normal
of hydrogen atom is stabilized by resonance. this ion is called Enolate ion.

58
 -
.. B
.. -..
:O H :O :O :
-..
H3C C C CH3 H3C C C CH3 H3C C C CH3

CH3 CH3 CH3

Resonance Stabilized
Enolate ion.

The negatively charged carbon of enolate ion act as a nucleophile. All condensation reaction
involved formation of enolate ion and its addition to carbonyl group.

(A) Nucleophilic Addition Reactions of Aldehydes & Ketones

(1) Addition of Hydrogen Cyanide: Aldehydes and Ketones on addition of HCN give
cyanohydrins. Reaction is carried out in the presence of basic catalyst. HCN is produced in situ
by the action of dilute H2SO4 on KCN.
O OH

+ HCN H3C C CH3

H3C CH3
CN
Cyanohydrin

O OH

H3C C H + HCN H3C C H

CN
Acetaldehyde cyanohydrin
Acetaldehyde

O
OH
H3C C CH3 + HCN H3C C CH3
CN
Acetone Acetone cyanohydrin.

(2) Addition of Grignard reagent: Aldehydes and Ketones with Grignard reagent first give the
addition product which can be hydrolysed with dilute acid to yield alcohol. Only formaldehyde
gives 10 alcohols, other aldehydes give 20 alcohol and ketones give 3o alcohols. For example
O OMgX +
RMgX H / H 2O
H C H H C H RCH2OH
o
Formaldehyde R 1 alcohol

59
 O OMgX + OH
R'MgX H / H 2O
R C H R C H R CH
R' R'
Aldehyde o
2 alcohol

O OMgX + OH
R'MgX H / H 2O
R C R R C R R C R
Ketone R' R'
3o alcohol
(3) Addition of Sodium bisulphate: Aledehydes and methyl ketones when treated with
saturated aqueous solution of sodium bisulphate, a solid addition compound is formed.
O OH

H C H + NaHSO4 H3C CH3

SO3Na
Bisulphite addition compound

O OH
H3C C H + NaHSO4 H3C H
SO3Na
Acetaldehyde bisulphite

O OH
H3C C CH3 + NaHSO4 H3C H
SO3Na
Acetone bisulphite

These bisulphites can be decomposed with dilute acids or bases to regenerate the carbonyl
compound, therefore this process of formation and decomposition of bisulphite is used for the
purification and separation of carbonyl compounds from mixtures.

(4) Addition of Ammonia: Aldehydes (except formaldehyde) form solid addition product,
aldehyde ammonia
O OH
R C H + NH3 R C H
NH2
Aldehyde ammonia

Aldehydes can also be regenerated by heating aldehyde ammonias with dilute acids. Thus the
process of formation and decomposition of these compounds can be used or the separation and
purification of aldehydes.
Formaldehyde and ketones do not form addition product with ammonia. They yield complex
condensation product with ammonia. For example

60
 N
O CH2
N
CH2 CH2
6H C H + 4 NH3
N N

Hexamethylene tetramine.
(Urotropine)

Urotropine is used as urinary antiseptic.

O CH3 O
2 H3C C CH3 + NH3 H3C C CH2 C CH3
NH2
Acetone Diacetone amine.

B) Reactions Involving addition followed by removal of water:

5) Reaction with Ammonia Derivatives: Reactions of Aldehyde and Ketones with ammonia
derivatives are very important and characteristic reactions of carbonyl compounds. They react
with ammonia derivatives (H2N-Y) to form compounds containing carbon-nitrogen double bond
(C=N-), with the elimination of water.
H3C H3C
O + H2N Y C N Y
+ H2O

H3C H3C

General mechanism of the reaction involve following steps.

Step 1: Attack of nucleophile on carbonyl carbon to give unstable addition product.

- H3C OH
H3C H3C O
δ+ δ- .. +
+
H transfer C N Y
O + H2N Y C NH Y
H3C H
H3C H3C H

[ unstable]
Step 2: Removal of water to give the final product.

H3C OH H3C
-H2O
C N Y C N Y
H3C H H3C

61
All the ammonia derivatives follow the same mechanism. The ammonia derivatives are
hydrazine, phenyl hydrazine, 2,4-dinitrophenyl hydrazine, hydroxylamine, and semicarbazide.

a) Reaction with Hydrazine: Aldehydes and ketones form hydrazones with hydrazine
(NH2NH2)
H

H3C C O + H2N NH2 CH3CH=N-NH2

acetaldehyde Acetaldehyde hydrazone
CH3 CH3

H3C C O + H2NNH2 H3C C N NH2

Acetone Acetone hydrazone

b) Reaction with phenyl hydrazine: Aldehydes and ketones form phenyl hydrazone with
phenyl hydrazine.

c) Reaction with 2,4-Dinitro phenyl hydrazine: Aldehydes and ketones react with 2,4-
dinitrophenyl hydrazine to form 2,4-dinitrophenyl hydrazone.

d) Reaction with Hydroxylamine: Aldehydes and ketones form oxime with

hydroxylamine(NH2OH).

62
e) Reaction with Semicarbazide: Aldehydes and ketones give Semicarbazone with
semicarbazide
H O H O

H3C C O + H2N NH C NH2 H3C C NH NH C NH2 +H2O

Acetaldehyde Acetaldehyde oxime.

CH3 O CH3 O

H3C C O + H2N NH C NH2 H3C C NH NH C NH2 +H2O

Acetone Acetone Semicarbazone.

6) Reaction with alcohols: Aldehyde react with alcohol in the presence of dry HCl gas to form
Acetals e.g:
R R OH R OR'
dry HCl R'OH
C O + R'OH C
HCl
C

H H OR' H OR'
Hemi acetal Acetal

Acetals are readily cleaved by acids to give acetaldehydes, and are stable towards base. Ketones
however, do not form ketals with monohydric alcohols, they react with dihydric alcohols to give
cyclic ketals. e.g

(C) Condensation Reactions: These reactions involve formation of enolate ion which attack on
carbonyl carbon of another molecule to give condensation product.

7) Aldol condensation: Aldehydes containing at least one α- hydrogen atom. When treated with
dilute base like NaOH undergo condensation reaction to give products called Aldols. The
reaction is known as aldol condensation. Aldols are the compounds containing both aldehydic
and Alcoholic functional groups. For example two molecules of acetaldehyde combine in
presence of dilute NaOH to form 3-hydroxy butanal.
O H OH

H 3C C H + H 2C CHO H 3C CH CH 2 CHO

2-hydroxy butanal (Aldol)

Mechanism:
Following steps are involved in the mechanism of aldol condensation reaction.
Step 1: Formation of enolate ion

63
 O O
-
-
H CH2 C H :CH2 C H + H2O
HO Acetaldehyde Enolate ion

Step 2: Attack of enolate ion (nucleophile) on carbonyl carbon of another molecule of

acetaldehyde.
δ- O O
-
O
O
-
H3C C H + :CH2 C H H3C CH CH2 C H
δ+

Step 3: Abstraction of proton from water molecule to give final product Aldol.

HO H - OH O
O O

H3C CH CH2 C H
H3C CH CH2 C H + - OH

Aldol

Aldol when heated easily loses a molecule of water to form α,β-unsaturated compound. For
example
OH H O O
-H2O
H3C CH CH C H H3C CH CH C H
Crotonaldehyde
Ketones containing α-hydrogens also undergo condensation to give ketols. For examples, two
molecule of acetone condense together in the presence of barium hydroxide to form diacetone
alcohol ( Ketol)
O H O OH O
Ba(OH)2
H3C C CH3 + H2C C CH3 H3C C CH2 C CH3
CH3

Diacetone alcohol on heating loses one molecule of water to form mesityl oxide.

Mixed Aldol Condensation: Condensation that take place between two different molecules, one
of which must have an α-hydrogen, in the presence of base is known as mixed aldol
condensation. For example condensation of acetaldehyde with benzaldehyde.

64
 O H CH3 OH O
- +
HO H or
C H + H2C C CH3 CH CH2 C H

CH CH C H + H2O
Cinnamaldehyde

(D) Reduction Reactions:

8) Reduction to Alcohols: Aldehydes and ketones are reduced to the primary and secondary
alcohols respectively by catalytic hydrogenation (H2/ Ni or Pt), nascent hydrogen (Na-Hg or
Na/C2H2OH), LiAlH4 or NaBH4
RCHO + H2 or 2[H] RCH2OH
Aldehyde o
1 alcohol

O OH

R C R + H2 or 2[H] R
o
CH R

Ketone
2 alcohol
Reduction of both aldehydes and ketones to alcohols may be effected by means of Merwein-
Ponndrof-Verley Reduction which involves the reduction by means of aluminum iso propoxide
in isopropanol.
O
[CH3CH-O]2Al
RCHO + (CH3)2CHOH RCH2OH + H3C C CH3
O OH O

+ (CH3)2CHOH [CH3CH-O] 2Al

R C R R CH R +H3C C CH3

The reduction occurs by hydride ion transfer from aluminium isopropoxide to the carbonyl
compound via a cyclic transition state.

65
9) Reduction to Alkanes: Aldehydes and ketones are reduced to corresponding alkanes by
means of zinc amalgam and hydrochloric acid [ Clemensen reduction] or alkaline solution of
hydrazine.[Wolf Kishner Reduction]

Clemmensen Reduction: This involves the use of zinc- mercury amalgam in hydrochloric acid
as the reducing agent.

O
Zn-Hg
R C H R-CH3
HCl
O
Zn-Hg
R C R R-CH2-R
HCl

Wolf Kishner Reduction : This involves the use of basic solution of hydrazine as the reducing
agent
O
NH2 -NH2
R C H R-CH3
NaOH

O
NH2 -NH2
R C R' R-CH2-R'
NaOH

(E) Oxidation Reactions:

10) Aldehydes are easily oxidized to carboxilc acid by acidic Na2Cr2O7 or K2Cr2O7 or acidic
KMnO4.
+
K2Cr2O 7 / H
R-CHO + [O] RCOOH

Aldehydes can also be oxidized by another oxidizing agents such as Tollen’s reagent, Fehling’s
solution and Benedicts solution and thus act as a strong reducing agents.

Tollen’s Reagent:[Ammonical Silver nitrate Solution] : When Tollen’s reagent is used to

oxidize an aldehyde, the Silver ion is reduced to metallic form and deposits as a mirror on clean
test tube. This reaction is used as a test of aldehyde and known as Silver mirror test.
O
O
-+
R C H
+ Ag(NH3)2OH R C ONH 4 + 2Ag
+ H2O + 3 NH3
silver mirror

Fehling solution: Blue coloured alkaline solution of cupric ion [Fehling Solution A] complexed
with sodium potassium tarterate (Fehling Solution B) is also reduced by Aldehyde. The
complexed cupric ion (deep blue) is reduced to Cuprous oxide.

66
Benedict solution (alkaline solution of cupric ion complexed with citrate ions) reacts in the same
way as Fehling Solution.

Ketones are not oxidized by milder oxidizing agents thus they do not reduce Tollen’s reagent,
Fehling solution and Benedicts solutions. However, ketones can be oxidized by stronger
oxidizing agents such as acid dichromate, alkaline KMnO4 and hot con. HNO3 to form
carboxylic acids with fewer carbon atoms that the original ketones. For example
O
+
K2Cr2O7 / H
H3C C CH3 CH3COOH + HCOOH
O
HNO3
H3C CH2 C CH3 CH3CH2COOH + HCOOH
(F) Other important Reactions of Aldehydes and Ketones.
(11) Cannizzaro reaction: Aldehydes which do not have α-hydrogen atom, when treated with
concentrated solution of NaOH undergo dis proportionation reaction. One half of the aldehydes
are oxidized to carboxylic acid and other half are reduced to alcohol. This reaction is known as
Cannizzaro reaction.
2HCHO + NaOH HCOONa + CH3OH
Formaldehyde Sodium formate Methyl alcohol

Mechanism: Following steps are involved

Step 1: Attack of the –OH on the carbonyl group.
δ- O
-
O
-
H
δ+
C H + HO H C H

OH

Step 2: Hydride transfer:

-
O O O
H +
-
+ CH3OH
- H transfer
H C H
OH
O
δ+ δ-
H C + CH3O H C O
H OH

Ketones do not give this reaction.

12) Reformatsky Reaction: Reaction of aldehydes and ketones with α-bromoester in the
presence of metallic zinc and ether to give β-hydroxy ester is known as Reformatsky reaction.
e.g.

67
 O OH
i) Zn.ether
H3C C H + Br-CH2COOC 2H5
ii) H 2O / H
+ H3C C CH2 COOC 2H5
H
O OH
H3C C CH3 + Br-CH2COOC 2H5 i) Zn.ether
+
H3C C CH2 COOC 2H5
ii) H 2O / H CH3

Mechanism: Three steps are involved.

Step 1: Formation of zinc salt of enol of the ester.
O OZnBr
Br CH2 C OC2H5 H2C C OC2H5

Step 2: The zinc salt reacts with the carbonyl compound.

- O O ZnBr OZnBr O

H3C
+
C + H2C C OC2H5 H3C C CH2 C OC2H5

CH3 H

Step 3: Acid hydrolysis

OZnBr O + OH O
H / H 2O
H3C C CH2 C OC 2H5 H3C C CH2 C OC 2H5
H H

13) Haloform Reaction: Acetaldehyde and methyl ketones react rapidly with halogen(Cl2,Br2 or
I2) in the presence of alkali to give haloform. This reaction is known as Haloform reaction.
O O
-+
R C CH3 + Br2 + 4NaOH R ONa + CHBr3 + 3H2O + 3NaBr
Bromoform
Methyl ketone

The reaction takes place in two steps.

O O

1. R C CH3 + 3Br2 + 3NaOH R C CBr3 + 3H2O + 3NaBr

O O

2. R C CBr3 + NaOH R C ONa + CHBr3

Bromoform

68
Haloform reaction is used as a diagnostic test for detecting the presence of –COCH3 group in a
compound. This reaction can also be used to distinguish methyl ketones. Ketone not containing
(-CO-CH3) do not give this reaction.

14) Wittig Reaction: Reaction between aldehydes and ketones with triphenyl phosphine
alkylidenes or phosopourous ylide (Ph3P=CR2) to form alkene is known as Wittig reaction.

H3C H3C
- +
O + R2C-PPh3 CR2 + O=PPh3
H3C ylide H3C Alkene

Mechanism: Attack of negative carbon of ylide on carbonyl carbon to form betaine,

- O + - +
PPh3 O PPh3
+ C + - C
:
H3C CH3 H3C R
R R R
CH3

Betaine undergo elimination to give the alkene.

- + O PPh3
O PPh3 H3C
CR2 + O=PPh 3

H3C R H3C
H3C CH3 CH3 R
CH3H3C
Betaine
Example:
CH3 CH3
+
+
-
H3C C O H2C PPh3 H3C C CH2 + O=P-Ph3

2-methyl propene

15)Reaction with PCl5: Aldehydes and ketones react with PCl5 to give gem-dihalides.e.g.

O Cl

R C H + PCl5 R C H + POCl3
Cl

O Cl

R C R + PCl5 R C R + POCl3
Cl
Gem.dihalide

69
16) Tischenko Reaction: Aldehydes having α-hydrogen atom can also be made to undergo
cannizzaro type reaction, if reaction is carried out in presence of aluminum ethoxide. But in such
case, acid and alcohol react together to form ester as the final product.
Al(OC 2H5)3
2CH3CHO CH3COOH + CH3CH2OH CH3COOC 2H5
Ethyl acetate

17) Polymerization: Lower aldehydes undergo polymerization to form different products under
different conditions. Ketones however, are not much susceptible to polymerization.

Carboxylic Acids and Their Functional Derivatives

Organic compounds containing carboxyl group (-COOH) are known as carboxylic acids. They
can be represented by the general formula.
O

R COOH Or H3C C OH

They are further classified as mono, di, tri etc., carboxylic acids, according to the number of
carboxylic groups present in their molecules. The long chain monocarboxylic acids are also
called fatty acids because many of them are obtained from fats.

Methods of Preparation
1) By the oxidation of primary alcohols or Aldehydes: Primary alcohols or aldehydes are
oxidized by acidic K2Cr2O7 or Na2Cr2O7 to give carboxylic acids.
+ +
K2Cr2O 7 / H K2Cr2O 7 / H
RCH2OH RCHO RCOOH
o
1 alcohol Aldehyde Carboxylic acid

[O] [O]
CH3CH2OH CH3CHO CH3COOH
Ethyl alcohol Acetaldehyde Acetic acid

2) By the hydrolysis of alkyl cyanides or nitriles: Alkyl cyanide on acid hydrolysis give
carboxylic acids.
+
H / H 2O
R C N RCOOH
carboxylic acid
+ NH3

Alkyl cyanide

+
CH3CN
H / H 2O CH3COOH + NH3

Methyl cyanide Acetic acid

3) By the Hydrolysis of Ester: When esters are hydrolysed by alkali NaOH or KOH, sodium or
potassium salt of carboxylic acids are formed which on treatment with dil HCl gives the
corresponding carboxylic acids.

70
 O O
-+
H3C C OC2H5 + NaOH H3C C ONa + C2H5OH
ethyl acetate Sodium acetate Ethyl alcohol

O O

H3C C
-+
ONa + HCl H3C C OH + NaCl

4) By the Reaction of Grignard Reagents with CO2: Grignard reagent with CO2 first give
addition product which on hydrolysis yield carboxylic acid.
O O
+
H / H 2O
R-MgX
Alkyl
C + O R C OMgX RCOOH
carboxylic acid
Magnesium halide

O O
+
H / H 2O
C2H5MgBr + C O C2H 5 C OMgX C2H5-COOH
Ethyl
Propionic acid.
Magnesium bromide

Organo lithium compounds can also be used in place of Grignard Reagent.

5) By Malonic Ester Synthesis: Alkyl halide react with sodium derivative of diethyl malonate
to give substituted malonic ester. This is hydrolysed and decarboxylated to yield an acid.
COOC 2H5 COOC 2H5
+
H / H 2O
R X + NaHC
-NaX
R HC

COOC 2H5 COOC 2H5

COOH

R HC RCH2COOH
-CO2
COOH Carboxylic acid

In this method two more carbons are added to alkyl group of starting alkyl halide.

6) By Carboxylation of Alkenes: This is a recent industrial method of preparation of carboxylic

acids and is called Koch Reaction. This involves treatment of alkene with carbon monoxide and
steam under pressure with phosphoric acid, H3PO3 at 400oC.

71
 H 3 PO 4
H 2C CH 2 + CO + H 2O 400 C o
CH 3 CH 2 COOH
Propionic acid

Properties:
1) The lower carboxylic acids ( C1 to C10) are colourless pungent smelling liquids. Higher
members are wax like solids and almost colourless.
2) First four members are freely soluble in water due to hydrogen bonding with water molecule.
H O C O IIIIIII H O IIIIIIII H O C O IIIIIII H O IIIIIII

R H R H
But the solubility of higher members decreases rapidly with the increase in the size of the alkyl
group due to increased influence of the non-polar and hydrophobic hydrocarbon chain.

3)Melting points of carboxylic acids increase irregularly with increase in the molecular weight.
The even members have markedly higher boiling points than the odd members.

4) Boiling points of the carboxylic acids, particularly lower members higher than the alcohols of
same molecular weight. e.g.
Acetic acid (CH3COOH) MW = 60 b.p. = 118oC
1-Propanol(CH3CH2CH2OH) MW = 60 b.p = 97oC

This is due to the strong hydrogen bonding in carboxylic acids than those in alcohols.
O IIIIIIIH O
C R
R C
O H IIIIIIIIO
5) Acidity of Carboxylic Acids: Carboxylic acid are acidic in nature but they are weak acids as
compared to inorganic acids (e.g. HCl or H2SO4). They can donate a proton and form salts with
strong bases and they are only partially ionized in aqueous solution.
O O

+
+
+ H2O
-
R C OH R C O H3O

The acidic character of carboxylic acids decreases with increase in molecular weight. Formic
acid is strongest of all fatty acids.

The acidic character of carboxylic acid is due to the resonance. The carboxylic ion form by
ionization is stabilized by resonance.

72
Hence carboxylic ion is more stabilized than the acid itself. The equilibrium of the ionization of
acids shifts to the right hand side. X-ray studies also support the existence of carboxylate ion as
resonance hybrid for example bond lengths of carboxy oxygen have different values in formic
acid. Where as in sodium formate the two carbon-oxygen bond lengths are identical.

The stability of carboxylate ion can also be explained on the basis of its molecular orbital
structure. The carbon atom of carboxyl group in sp2 hybridised. In carboxylate ion the
unhybridised P orbital of carbon overlaps with P orbital of both oxygen atom to form stable
delocalized molecular orbital.

Effect of substituents on Acidity: Acidic character of carboxylic acid is due to the stabilization
of carboxylate ion. So any factor which can enhance the dispersal of negative charge of the
carboxylate ion will increase the acidity and vise versa. Inductive effect of the substituent on the
α-carbon play very important role. Electron withdrawing substitutents like Cl, Br, F, NO2, OH,
CN etc. would disperse the negative charge and hence stabilize the carboxylic ion. On the other
hand electron releasing substituents would increase the negative charge destabilizes the
carboxylate ion and thus decrease acidity of the acid.

73
Alkyl groups are electron releasing group thus their presence in the molecule will decrease the
acidity . Longer the lengths of alkyl chain, lower will the acidity of the acid. Since formic acid
has no alkyl group, it is the strongest of all fatty acids. It is ten times stronger than acetic acid.
HCOOH>> CH3COOH >CH3CH2COOH

Similarly Chloroacetic acid is hundred times stronger than acetic acid because of the electron
withdrawing nature of Cl group following order is observed in Chloro acetic acid.
Cl3-C-COOH > Cl2-CH-COOH >Cl-CH2COOH> CH3COOH

Trichloroacetic acid is almost as strong as a mineral acid.

Chemical Properties:
A) Reactions involving hydrogen atom of the –COOH group
1) Reaction with metals and alkalies: Carboxylic acids react with strongly positive metals with
the liberation of hydrogen and form salt.
-+
RCOOH + Na RCOONa + 1/ 2 H2

Carboxylic acids also from salts with metal hydroxides, carbonates and bicarbonates. For
example

2) Reaction with Alcohols: Monocarboxylic acids react with alcohols in the presence of strong
acid catalyst like sulphuric acid to form esters. The reaction is known as Esterification.
O O
+
H
R C OH + HO R R C OR + H2O
carboxylic acid

O O
+
H
H3C C OH +HO C2H5 H3C C OC2H5
+ H2O

Acetic acid Ethyl acetate

Ethanol

Following mechanism is suggested for the esterification

Step 1: Protonation of carboxylic acid.

δ -O OH
+
+
+
H3C C OH H H3C C OH
δ+

74
 OH H OH H

H3C C
+
OH + :O.. C2H5 H3C O
+
C2H5

OH

Step III: Hydrogen ion transfer

OH +
OH2
H
+ H3C O-C2H5
H3C O C2H5
O H
O H

Step IV: Elimination of water and proton.

+
OH2 O

+
H3C O-C2H5 H3C C O-C2H5
+ H2O + H

O H

B) Reaction involving –OH part of the –COOH group

3) Reaction with Phosphorous Halides and ThIonyl Chloride: Carboxylic acids react with
phosphorous halides and thionyl chloride to form acid halides. For example.
O

3 R C OH + PCl 3 3 RCOCl + H3PO 3

R C OH + PCl5 RCOCl + POCl3 + HCl

O

R C OH + SOCl2 RCOCl + SO2 + HCl

4)Reaction with ammonia: Carboxylic acid react with ammonia to form ammonium salt which
on strong heating give acid amides with the elimination of water.
O O O
-+
R C OH + NH3 R C ONH4
-H2O
R C NH2

Carboxylic acid Ammonium salt Acid amide

75
 O O O
-+
H3C C OH + NH3 H3C C ONH4
-H2O
H3C C NH2

Acetic acid Ammonium acetate Acetamide

5) Dehydration: Carboxylic acid on dehydration with P2O5 (dehydrating agents) give acid
anhydride.

O H3C C
P 2O 5
2 H3C C OH O
+ H2O
H3C C
Acetic acid
O
Acetic anhydride

Acid anhydrides can also be prepared by heating sodium salt of acids with halides.

O O H3C C
-+
R C ONa + Cl C CH3 O
+ NaCl
H3C C

O
C) Some Other Reactions:
6) Reduction: Reduction of carboxylic acids depends on the nature of reducing agents. On
reduction with LiAlH4, carboxylic acid gives primary alcohol.
LiAlH 4
RCOOH R CH2OH
Carboxylic acid o
1 alcohol

Heating with HI / red Phosphorous, under pressure, or with hydrogen under pressure at elevated
temperature in the presence of a nickel catalyst, produces an alkane.

76
 H2 / Ni
RCOOH R CH3
or
Carboxylic acid HI / red P Alkane

7) Oxidation: All the acids, except formic acid , are extremely resistant to oxidation, but
prolonged heating with oxidizing agents produces carbon dioxide and water.

(D) Reactions Involving alkyl group of the acid:

(8) α-Halogenation: Carboxylic acids containing α-hydrogen atoms. When treated with Cl2 or
Br2 in the presence of phosphorous as a catalyst, substitution of α-halogenated acids are formed.
The reaction is known as the Hell-Volhard Zelinsky (HVZ) reaction.
Cl

R CH2 COOH + Cl2 P

R CH COOH + HCl

Carboxylic acid α - halogenated acid

H3C COOH + Cl2 P

Cl CH2 COOH + HCl
Acetic acid Chloro acetic acid

Br

H3C CH2 COOH + Br2 P

Cl CH COOH + HBr
Acetic acid 2-Bromo propionic acid.

(E) Reacations of salts of carboxylic acids:

(9) Heating of Sodium salt: When sodium salt of carboxylic acid are heated with soda lime
[NaOH + CaO] alkanes are formed.
O
- + CaO
H3C C ONa + NaOH CH4 + Na2CO3
Sod. acetate Methane

10) Heating of Ammonium salt: When ammonium salts are heated, amides are formed.

O
- +
H3C C ONH4
Ammonium acetate
CH3CONH2 + H2O
Acetamide

When ammonium salts are heated with P2O5, alkyl nitriles are formed.

O
P 2O 5
H3C C ONH4 H3C C N + 2 H 2O
Ammonium acetate methyl cyanide

77
11) Heating of Calcium salt: Calcium salts of carboxylic acids on heating give aldehydes and
ketones.
a) Calcium formate gives formaldehyde.

b)Calcium salt of any carboxylic acid other than formic acid gives ketones.

(R-COO) 2Ca R C R
+ 2CaCO3
O

(CH3-COO) 2Ca H3C C CH3 + 2CaCO3

c) Calcium salt of any carboxylic acid. when heated with calcium formate gives aldehyde.

(R-COO)2Ca + (HCOO)2Ca 2R-CHO + 2CaCO3

(CH3-COO)2Ca + (HCOO)2Ca 2CH3CHO + 2CaCO3

12)Electrolysis: Electrolysis of concentrated aqueous solution of sodium or potassium salts

gives alkanes. (Kolbe’s electrolysis)
electrolysis
2RCOONa + 2H2O R R + 2CO2 + 2NaOH + H2
At anode At cathode

electrolysis
2CH3COONa + 2H2O H3C CH3 + 2CO2 + 2NaOH + H2
Sodium acetate Ethane

13) Reaction of silver salts with halogens: When silver salt of carboxylic acids are heated with
chlorine or bromine, alkyl halides are formed. The reaction is known as Hunsdiecker Reaction.

78
 O
-+
H3C C OAg + Br2 CH3Br + 2AgBr + CO2

Carboxylic Acid Derivatives (Acid Derivatives): The compounds derived from the carboxylic
acids by the replacement of –OH function of Carboxyl group by another group are known as
acid derivatives. All such derivatives upon hydrolysis generate the parent acid.

Different Acid derivatives are:

Name Formula
O

i) Acid halides
H3C C X X = Cl,Br or I
O O
ii) Acid anhydride
R C O C R
O
iii) Ester
R C OR
O

iv) Amide R C NH2

1. Acid Halides: Acid halides are the derivatives of acids in which the –OH function of carboxyl
group is replaced by a halogen atom. Acid halides are also known as acyl halides. Acid chlorides
are most important of all the acid halides.
O

They are represented as R C Cl , some examples are,

O

H3C C Cl - Acetyl Chloride(Ethanoyl chloride)

H5C2 C Cl - Propionyl chloride (Propanoyl chloride)

Methods of Preperation:
1) By the reaction of carboxylic acids with phosphorous halides
O O

3R C OH + PCl 3 R C Cl + H3PO 3

O O

R C OH + PCl 5 R C Cl + POCl 3 + HCl

2) By the reaction of Carboxylic acids with thionyl chloride

79
 O O

R C OH + SOCl 2 R C Cl + SO2

O O

H3C C OH + SOCl 2 H3C C Cl + SO2

Properties:
Physical Properties:
i) All simple acid chlorides are pungent smelling colourless liquids of lower boiling points than
the corresponding acid. They also have tear producing property. i.e lachrymators.
ii) They are insoluble in water but slowly start to dissolve in it because of hydrolysis.

Chemical properties: Acid chlorides are very reactive compounds as they are more readily
attacked by nucleophile because of the electron withdrawing effect of highly electronegative,
chlorine atom attached to carbonyl carbon. This further diminishes the electron density on the
carbonyl carbon. Cl atom is replaced by the nucleophile.
..
δ-O O
-
O
δ -
R +C Cl + :Nu R C Cl R C Nu + Cl:

Some important reactions of acid chloride are following.

1)Hydrolysis: The acyl chlorides are readily hydrolysed by water to reform the original acid.

O O

R C Cl + H2O R C OH HCl +
Acid chloride Carboxylic acid

O O

H3C C Cl + H2O H3C C OH + HCl

Acetyl chloride Acetic acid

2) Acylation: Acid chlorides are important acylating reagent. Thus usually react rapidly with
compounds containing active hydrogen atoms i.e. hydrogen attached to oxygen, nitrogen or
O

sulphur. This active hydrogen is replaced by acyl group ( R C . ) of acid chloride.

a) Reaction with alcohols (Alcohalysis): Esters are formed

80
b) Reaction with Ammonia (Ammonolysis): Amides are formed.

O O

R C Cl + H-NH2 R C NH2 + HCl

Acid chloride

c) Reaction with Primary and Secondary Amines: N-substituted amides are formed.

O O

R C Cl + HNHR' R C NHR' + HCl

Acid chloride Primary amine N-Alkyl amide

O O

R C Cl + HNHR'2 R C NR'2 + HCl

N,N-dialkyl amide
d)Reaction with hydrazine and hydroxylamine: Hydrazides are formed.

O O

R C Cl + H2N NH2 R C NHNH2 + HCl

O O

R C Cl + H2N OH R C NHOH + HCl

Acetic anhydride
3)Reaction with salt of carboxylic acids: Anhydrides are formed.
O O O
+ -
R C Cl + NaOOCR R C O C R + NaCl
Acid anhydride

O O O O
+ -
H3C C Cl + NaO C CH3 H3C C O C CH3 + NaCl
Acetic anhydride

81
4) Reduction:
a) Acyl chlorides may be reduced catalytically to aldehydes or to alcohols.
O O
H2
H2
R C Cl R C H RCH2OH
Pd
Aldehyde Alcohol

When reduced in presence of poisoned Palladium Catalyst, they form aldehyde. This reaction is
called Rosenmund Reduction.
O O
H2 / Pd
R C Cl R C OH
BaSO4 Aldehyde
O
H2 / Pd
H3C C Cl H3C C H
BaSO4
O
Acetaldehyde

b) When reduced with LiAlH4, they form primary alcohols.

O
LiAlH 4
R C Cl R CH2 OH
o
O 1 Alcohol
LiAlH 4
H3C C Cl H3C CH2 OH
Ethanol

5)Friedel-Craft Acylation: Acyl chlorides react with aromatic hydrocarbon in presence of

AlCl3 catalyst. The reaction is known as F.C.acylation. e.g.
O CH3
C
O

+ H3C Cl
AlCl 3 + HCl

Benzene Acetophenone

2. Acid Anhydrides: The compound derived from an acid by the removal of one water molecule
from two molecule of the acid are called anhydrides.
O O
-H2O
2 R-COOH R C O C R

Anhydrides derived from two molecule of different acids are called mixed anhydride.

R-CO-O-CO-R'

82
Methods of preparation:
Acid anhydrides may be prepared.
1) By reaction of acid halide with carboxylic acid or its Sodium salt.
O
Pyridine
R C OH + Cl-CO-R R-CO-O-CO-R + HCl
O
Pyridine
R C ONa + Cl-CO-R R-CO-O-CO-R + NaCl
2) By dehydration of Carboxylic acids in presence of P2O5.

O
P2O 5
2 R C OH R-CO-O-CO-R + H2O

Properties:
Physical properties:
i) The lower simple anhydrides are colourless liquids with an irritating smell.
ii) They are in soluble in water but dissolve slowly because of the slow hydrolysis. They are
soluble in ether and benzene.
iii) They have higher boiling points than the corresponding acids because of large size of
molecule and enhanced van der Waals interactions.

Chemical Properties: In anhydrides –OCOR group is replaced by nucleophile like acid

chlorides but they are less reactive than acid chlorides because –OCOR group is not as
electronegative as Cl atom.
-
O O O O
-
R C O C R + :Nu R C O C OH

Nu

O
O
-
-R C O
R C Nu
The anhydrides give all the nucleophilic substitution reaction given by acid chlorides but with
less vigour.
i) Hydrolysis:

Acetic anhydride Acetic acid

83
ii) Reaction with Alcohols:

iii) Reaction with Ammonia:

Acetamide Acetic acid

iv) Reaction with Amines:

+ CH3COOH
N-Alkylacetamide Acetic acid

v) Friedel Crafts Reacation:

O
C CH3

+ (CH3CO)2O AlCl 3
+ CH3COOH

Benzene Acetic acid anhydride Acetic Acid

Acetophenone

3.Acid Amides: These are the derivatives of carboxylic acids in which the –OH function of
carboxylic group is replaced by –NH2 group.
O O
-OH
R C OH R C NH2
+ NH2
Carboxylic acid Amide

84
Functional group of amides is –CONH2.

O O

H C NH2 H3C C NH2

Formamide Acetamide

Methods of Preparation: Amides are prepared-

i) By the action of Ammonia on Acid Chlorides:
O O

H3C C Cl + 2NH3 H3C C NH2 + NH4Cl

Acetamide

ii) By heating of Ammonia salts of Carboxylic acid:

O O
-+
H3C C ONH4 H3C C NH2 + H2O
Ammonium acetate
Acetamide

iii) By the action of ammonia on Anhydrides:

(CH3CO)2O + NH3 H3C C NH2 + CH3COOH

Acetamide Acetic acid

Properties:
Physical Properties:
i) All amides are white, odourless, crystalline solids.
ii) Among the four derivatives of acids, only acid amides are capable of forming intermolecular
hydrogen bonds due to which they have sharp melting points that are higher than those of
corresponding acids.
iii) Simple amides (up to C6) are soluble in water but solubility in water decreases as we ascend
the series.

Chemical Properties: Amides are stabilized by resonance.

-
O O
.. +
R C NH2 R C NH2

Since the electron pair on N-atom is not readily available to an acid amides are less basic than
amines. Amides are least reactive of the acid derivatives. Important reactions of amides are given
below.

85
i) Hydrolysis: Amides are hydrolyzed by acid or alkali on prolonged heating.
O O
+-
+ -
H3C C NH2 + H2O + HCl H3C C OH + NH4Cl
O O
-+
H3C C NH2 + NaOH H3C C ONa + NH3

ii) Reaction with Nitrous Acid (HONO): Amides when heated with Nitrous acid (NaNO2 +
HCl) give carboxylic acids.

iii) Reduction: Amides reduces to amines by LiAlH4.

O
LiAlH 4 R-CH2-NH2
R C NH2
1o amine
Amide

iv) Dehydration: When heated with strong dehydrating agent such as phosphorous pentoxide,
they form nitriles.
O
P 2O 5
R C NH2 R C N
-H2O
Amide Alkane nitrile
(Alkyl cyanide)
v) Hofmann’s Degradation: Amides when treated with bromine and sodium hydroxide, they
produces primary amine, which is one carbon less than the amide.
O

R C NH2 + Br2 + 4NaOH RNH2 + 2NaBr+ Na2CO3 + 2H2O

o
O 1 amine

H3C C NH2 + Br2 + 4NaOH CH3NH2 +

2NaBr + Na2CO3 + 2H2O
Acetamide Methyl amine

This reaction is also called Hoffmann’s rearrangement.

Mechanism: The Hofmann’s degradation of amides involves the following steps.

86
 +-
2NaOH
+ Br2 NaOBr + NaBr+ H2O
O H O H
I -
R C N
.. H + O
-
Br R C N + OH

Br

O
II .. III
R-N=C=O NaOH
-H2O ,Br
R C N:
iso cyanate
R-NH2
o
+ Na2CO3
1 amine
4. Esters: Esters are carboxylic acid derivatives in which the –OH group has been replaced by
alkoxy (-OR) group. They can be represented as,
O

R C OR' Or R-COOR'
They are named as the alkyl salts of the acid e.g

HCOOC2H5 – Ethyl formate

CH3COO C2H5 – Ethyl acetate.

A large number of esters occur in flowers, fruits of the plants and provide the fragrance to
flowers and fruits.

Method of Preparation: Generally esters are prepared by carboxylic acids and their other
derivatives.
i) By the reaction of carboxylic acid with alcohols in presence of acid
(Fischer’sEsterification method).
O O
H2SO 4
R C OH + HOR' R C OR'
+ H2O

O O
H2SO 4
H3C C OH + HOC2H5 H3C C OC2H5 + H2O

ii) By the reaction of Acid Chlorides with Alcohols.

iii) By the reaction of Carboxylic salts with alkyl halide.

87
 O O
-+ +-
R C ONa + XR' R C OR'
+ NaX
Ester
Sodium carboxylate

iv) By the reaction of carboxylic acid with Diazomethane.

O O

R C OH + CH2N2 R C OCH3
+ N2

But only methyl esters are formed by this method.

v) Transformation.

O O
+
H
R C R' + R"OH
or OH-
R C OR"
+ R'OH
vi) By the reaction of alkyl halide with silver salt of carboxylic acid.

R-COOAg + Br-R' RCOOR'

+ AgBr

Properties:
Physical Properties:
1) The carboxylic esters are pleasant smelling liquids or solids.
2) The boiling points of the strongest chain isomers are higher than those of branched chain
isomers. The boiling points of methyl and ethyl esters are lower than those of
corresponding acid, this is due to their inability to form intermolecular hydrogen bonds.
3) They are generally insoluble in water and soluble in most organic solvents.

Chemical Properties: Esters give nucleophilic substitution reaction similar to acids halides
because of the electron withdrawing effect of the –OR| group.
- -
O O O
+ -
R C OR' + :Nu R C OR'
-OR'
H3C C Nu

Nu

But esters are also stabilized by resonance thus they undergo nucleophilic substitution less
readily than do acid halides.

88
 -
O O
.. +
R C OR'
.. + H OH R C OR

General reactions of esters are given below.

1) Hydrolysis:
a) Acid hydrolysis: Esters are hydrolyzed in presence of acid catalyst (H2SO4) or HCl) to give
parent carboxylic acid and alcohol.
O O
+
R C OR' + H2O H
reflux
R C OH + R'OH
Ester Carboxylic acid Alcohol

b) Alkaline hydrolysis: The alkaline hydrolysis of ester to form sodium or potassium salt of
carboxylic acid and alcohol is referred to as Saponification.
O O

R C OR' + NaOH R C
- +
ONa + R'OH
Ester Sodium carboxylate Alcohol
O

CH3COOC2H5 + NaOH H3C C

-+
ONa + C2H5OH
Ethyl acetate Sodium acetate Ethyl alcohol

2) Reaction with Ammonia:

O O

R C OR' + H NH2 R C NH2 + R'OH

Ester Amide
Alcohol

O
CH3COOC2H5 +H NH2 H3C C NH2 + C2H5OH
Ethyl acetate Acetamide

3) Reduction:

O
LiAlH 4 / Ether
R C OR'
or
R-CH2OH + R'OH
Na / C2H5OH Alcohols

89
 O
LiAlH 4 / Ether
H3C C OCH3 or
CH3-CH2OH + CH3OH
Na / C2H5OH Ethyl alcohol Methyl alcohol
4) Reaction with Grignard Reagent: Esters with Grignard reagent first gives ketone which on
further reacting with another molecule of the G.R gives tertiary alcohol.
O OMgX O
R"-MgX -OR'
R C OR' R C OR' R C R"
R" Ketone

OMgX OH
R"MgX H2 O
R C R" R C R"
R" R"
3o alcohol

5) Claisen Condensation: Esters containing α-hydrogen atom undergo condensation reactions to

form β-ketoesters, in the presence of strong base. This reaction is known as .
O O O O
C2H5ONa
H3C C OC2H5 + H CH2 C OC2H5
-C2H5OH
H3C C CH2 C OC2H5

Ethyl acetoacetate
Mechanism: Following steps are involved.

H3C C OC2H5
O O
-
H CH2 C OC2H5 H2C C OC2H5

C2H5O
-
-
O O O O
-
-C2H5O
H3C C CH2 C OC 2H5 H3C C CH2 C OC2H5
Ethyl acetoacetate
OC 2H5

(β-keto ester)

Suggested Readings:
• Organic Chemistry by I. L. Finar, vol. 1, 6thedition
• Organic Chemistry by Paula Yurkanis Bruice, 3rd edition.
• Organic Chemistry by Robert T. Morrison and Robert Neilson Boyd, 6th edition.
• Organic Chemistry by K. Peter C. Vollhardt and Neil E. Schore, 4th edition.

90