12.

ALDEHYDES, KETONES AND CARBOXYLIC ACIDS

Can you recall ? 12.2.1 Classification of aldehydes :

• Draw the structures of the (Aldehydes are classified as aliphatic and
following compounds and aromatic aldehydes)
classify them on the basis of a. Aliphatic aldehydes : The compounds
C-O single bond and C = O double in which the –CHO group (formyl group) is
bond present in them, Ethyl alcohol, attached directly to sp3 hybridized carbon
acetaldehyde, o-nitrophenol, Diethyl atom that is saturated carbon atom are
ether, isopropyl alcohol, acetone. called aliphatic aldehydes. (Exception :
• What are carbonyl compounds? Formaldehyde, H-CHO is also classified as
aliphatic aldehyde though –CHO group is not
12.1 Introduction : In the previous chapter, attached to any carbon ). For example :
you learnt about the organic compounds
CH3 - CHO CH3 - CH2 - CHO
which contain carbon –oxygen single bond. In
this chapter, we are going to study the organic (Acetaldehyde) ( Propionaldehyde)
compounds containing carbon - oxygen double O
bond (>C=O ) called carbonyl group, which
is one of the most important functional group C
R H
in organic chemistry.
General formula
O carbonyl oxygen
(R= H or alkyl group)
C carbonyl carbon
b. Aromatic aldehydes : The compounds in
R R'
which –CHO group is attached directly to an
Both aldehydes and ketones contain aromatic ring are called aromatic aldehydes.
a carbon –oxygen double bond (-C-) as their For example :
O
functional group. Therefore they are called
H O H O H O
carbonyl compounds. In aldehydes , carbonyl
carbon is bonded to at least one hydrogen apart OH
from an alkyl or aryl group. The functional
group of aldehydes, therefore, is - CHO which NO2
is called formyl group or aldehydic carbonyl
(Benzaldehyde) (Salicylaldehyde)(p-Nitrobenzaldehyde)
group. On the other hand in ketones, carbonyl
carbon is bonded to two alkyl or aryl groups Use your brain power
either identical (R = R) or different (R ≠ R').
It is called ketonic carbonyl group. The Classify the following as aliphatic
functional group of carboxylic acids is -COOH and aromatic aldehydes.
called carboxyl group. Due to the -OH group O
bonded to (>C=O ) group, carboxylic acids are O
H
distinct from aldehydes and ketones. H
12.2 Classification of aldehydes, ketones
and carboxylic acids : Aldehydes, ketones CHO
CHO
and carboxylic acids are classified as per the
nature of carbon skeleton bonded to (>C=O ). CH3

254
12.2.2 Classification of ketones : Ketones are
classified as aliphatic and aromatic ketones: Use your brain power
• Classify the followings as
a. Aliphatic ketones : The compounds in
simple and mixed ketones.
which >C=O group is attached to two alkyl
• Benzophenone, acetone, butanone,
groups are called aliphatic ketones.
acetophenone.

O Oxo or ketonic carbonyl group

Do you know ?
C • Aldehydes and ketones are
R R'
responsible for many flavours and
General formula
(Where R , R’ = alkyl group, identical or different) odours that you will readily recognize :
CHO CHO
On the basis of types of alkyl groups bonded to
carbonyl carbon, aliphatic ketones are further
classified as simple and mixed ketones. OCH3
i. Simple or symmetrical ketones : The OH
ketones in which both the alkyl groups bonded Benzaldehyde Vanillin
to carbonyl carbon are identical, are called (Bitter almond flavour) (Vanilla flavour)
simple ketones or symmetrical ketones. For
example : CH = CH - CHO
O O
H3C - C - CH3 H5C2 - C - C2H5 O
(Dimethyl ketone) ( Acetone) (Diethyl ketone) Cinnamaldehyde Camphor
(Cinnamon flavour) (Camphor fragance)
ii. Mixed or unsymmetrical ketones : The • Structures of many important biological
ketones in which two alkyl groups bonded compounds contain carbonyl moiety. For
to carbonyl carbon are different, are called example progesterone and testosterone,
mixed ketones or unsymmetrical ketones. For the female and male sex hormones
example : respectively.
O O
H5C2 - C - CH3 H5C2 - C - CH2 - CH2 - CH3
Do you know ?
(Ethyl methyl ketone) (Ethyl n-propyl ketone)
• Butyraldehyde is used in
b. Aromatic ketones : The compounds in margarine and food for its
which a >C=O group is attached to either two buttery odour.
aryl groups or one aryl and one alkyl group are
called aromatic ketones. For example : • Acetophenone has smell of pistachio
and is used in ice-cream. Muscone has
O O musky aroma and is used in perfumes.
C C Popcorn has butter flavour which
CH3 contains butane-2,3-dione.

Benzophenone Acetophenone 12.2.3 Classification of carboxylic acids :

(Diphenyl ketone) (Methyl phenyl ketone) Carboxylic acids are classified as aliphatic
and aromatic carboxylic acids :

255
a. Aliphatic carboxylic acids : The organic
compounds in which carboxyl (-COOH) Remember...
group is bonded to an alkyl group are called The aromatic compounds in which
aliphatic carboxylic acids or fatty acids. the –COOH group is not attached
(Exception : Formic acid, H-COOH is also directly to the ring are called side-chain
classified as aliphatic carboxylic acid though aromatic acids. For example :
–COOH group is not attached to any carbon).
For example : CH2 - COOH
H3C - COOH H3C - CH2 - COOH (Phenyl acetic acid)
(Acetic acid) (Propionic acid )
Carboxylic acids are widely distributed
O
Carboxyl in nature; they are found in both the plants and
R C
OH
functional group animals. L-lactic acid is present in curd , citric
acid is found in citrus fruit (Lemons). Acetic
General formula
(R= H or alkyl group) acid is the key ingredient of vinegar.

Depending on the number of –COOH groups 12.3 Nomenclature of aldehydes, ketones

present carboxylic acids are classified as and carboxylic acids :
mono, di, tri carboxylic acids and so on. For 12.3.1 Nomenclature of aldehydes and
example : COOH carboxylic acid : The names of aldehydes
and carboxylic acids are related to each other.
H3C - CH2 - COOH COOH
There are two systems of naming aldehydes
Propionic acid Oxalic acid and carboxylic acids : trivial and IUPAC.
( a monocarboxylic acid) (a dicarboxylic
acid) a. Trivial names of aldehydes and carboxylic
CH2 - COOH acids : Trivial names of aliphatic aldehydes
HO - C - COOH are derived from the corresponding trivial
names of carboxylic acids. Here the ending
CH2 - COOH
‘ic acid’ of carboxylic acid is replaced by
Citric acid
the ending ‘aldehyde’. In case of substituted
(a tricarboxylic acid)
aliphatic carboxylic acids and aldehydes the
b. Aromatic carboxylic acids : These are the position of substituent is indicated by labeling
compounds in which one or more carboxyl the carbon serially as α, β, γ and so on. The
groups (-COOH ) are attached directly to the carbon atom adjacent to carbonyl carbon is
aromatic ring. For example : labeled as α and next one is β and so on. (See
Table 12.1).
COOH
COOH

COOH
(Benzoic acid) (Phthalic acid)

OCOCH3

COOH
(Acetyl salicylic acid) ( Aspirin)

256
 When two –CHO groups are present at
Do you know ? the two ends of the chain the ending ‘e’of
A series of straight chain
alkane is retained and the suffix –‘dial’ is
dicarboxylic acids are
added to the name of parent aldehyde. In case
commercially known by the following
of dicarboxylic acids, ‘dioic acid’ is added
common names:
COOH COOH COOH COOH COOH to the name of the parent alkane. In IUPAC
COOH CH2 (CH2)2 (CH2)3 (CH2)4 nomenclature an alicyclic compound in
(oxalic COOH COOH COOH COOH which –CHO group is attached directly to the
acid) (malonic (succinic (glutaric (adipic
acid) acid) acid) acid)
ring is named as a carbaldehyde. The suffix
A series of lower fatty acids are commercially ‘carbaldehyde’ is added after the full name
known by the following common names. of parent cycloalkane structure. Similarly an
CH3 CH3 CH3 CH3 CH3 alicyclic compound having a carboxyl group
COOH CH2 (CH2)2 (CH2)3 (CH2)4 directly attached to alicyclic ring is named as
(Acetic COOH COOH COOH COOH cycloalkane carboxylic acid.
acid) (n-propionic (n-butyric (n-valeric (n-caproic
acid) acid) acid) acid) Substituted aromatic aldehydes and
carboxylic acids : When two or more different
b. IUPAC names of aldehydes and carboxylic functional groups are attached to a ring ,
acids : the higher priority group (std. XI Chemistry
Can you recall ? Textbook, Chapter 14, sec.14.4.7) is given
lower number. When –CHO group, appears
Which suffix do appear in the as substituent prefix ‘formyl’ is used in the
IUPAC names of aldehydes and IUPAC name.
carboxylic acids ?
CHO
According to IUPAC system, the name of an
aliphatic aldehyde is derived from the name of
the corresponding alkane by replacing ending CH3
‘e’ of alkane with ‘ al ’. Aldehyde is named OH
as alkanal (Table 12.1). The IUPAC name of
(4-Hydroxy-3-methylbenzaldehyde)
aliphatic carboxylic acid is derived from the
name of the corresponding alkane by replacing COOH
ending ‘ e’ of alkane with ‘ oic acid ’. (Refer to
Std. XI Chemistry Textbook sec. 14.4.7).
Alkane Alkanal OH
CH3
Alkane Alkanoic acid
(3-Hydroxy-4-methylbenzoic acid)
The longest chain including –CHO or –
COOH group is identified as the parent chain. CHO
Numbering of the chain is done by giving
number 1 to the –CHO or –COOH carbon. The COOH
name of substituent is included along with its (2-Formylbenzoic acid)
locant.
4
CH3-3CH2-2CH2-1CHO ; 4CH3-3CH2-2CH2-1COOH Trivial and IUPAC names of some aldehydes
and carboxylic acids are given in Table 12.1.
Aldehyde (-CHO) group and carboxyl
(-COOH) group are always present at the end
of the parent straight chain.
257
 Table 12.1 Trivial and IUPAC names of carboxylic acids and aldehydes

Carboxylic acids Aldehydes

Structure Trivial name IUPAC name Structure Trivial name IUPAC name
H - COOH Formic acid Methanoic acid H-CHO Formaldehyde Methanal
CH3 - COOH Acetic acid Ethanoic acid CH3-CHO Acetaldehyde Ethanal
CH3 - CH2 - COOH Propionic acid Propanoic acid CH3-CH2-CHO Propionaldehyde Propanal
CH3 - CH2 - CH2 - COOH n-Butyric acid Butanoic acid CH3-CH2-CH2-CHO Butyraldehyde Butanal
(CH3)2CH - COOH Isobutyric acid 2-Methylpropanoic (CH3)2CH-CHO Isobutyrlaldehyde 2 - Methylpropanal
( a - methylpropionic acid (a -
acid) methylpropionaldehyde)
CH2 = CH - COOH Acrylic acid Prop-2-enoic acid CH2=CH-CHO Acrolein Prop-2-enal
HOOC - COOH Oxalic acid Ethanedioic acid CHO-CHO Oxaldehyde (Glyoxal) Ethanedial
COOH Benzoic acid Benzoic acid CHO Benzaldehyde Benzaldehyde

258
(Benzenecarboxylic (Benzenecarbaldehyde)
acid)
COOH o-Toluic acid 2-Methylbenzoic acid CHO o-Tolualdehyde 2-Methylbenzaldehyde

CH3 CH3
COOH Salicyclic acid 2-Hydroxybenzoic acid CHO Salicylaldehyde 2-Hydroxybenzaldehyde

OH OH
COOH Phthalic acid Benzene-1,2- CHO Phthalaldehyde Benzene-1,2-
dicarboxylic acid dicarbaldehyde
COOH CHO
COOH Cyclohexylcarboxylic Cyclohexanecarboxylic CHO Cyclohexane aldehyde Cyclohexanecarbaldehyde
acid acid
 In case of substituted aliphatic ketones the
Do you know ? position of substituent is indicated by labelling
The trivial names of carboxylic the carbon serially as α, β, γ and so on. The
acids are often derived from Latin carbon atom adjacent to carbonyl carbon
names of their original natural source. is labelled as α and next one is β and so on.
For example, Formic acid is obtained Names of aromatic ketones are based on a
from red ants (Formica means ant), acetic phenone. (see Table 12.2)
acid is obtained from acetum (acetum b. The IUPAC names of aliphatic ketones are
means vinegar), propionic acid is from basic derived from the name of the corresponding
fat (propion means first fat), butyric acid is alkanes by replacing ending ‘e’ of alkane
from butter (butyrum means butter). with ‘one’. They are named as alkanone. The
longest chain of carbon atoms containing the
12.3.2 Trivial and IUPAC names of ketones:
ketonic carbonyl group is numbered from the
a. The trivial names of aliphatic ketones are end closer to the carbonyl carbon.
based on the names of alkyl groups or aryl
Alkane Alkanone
groups attached to carbonyl carbon .Names of
alkyl or aryl groups are written in alphabetical When two >C=O groups are present,
order followed by the word ketone. then ending ‘e’of alkane is retained and
the suffix –‘dione’ is added to the name of
parent ketone indicating the locants of ketonic
Table 12.2 Trivial and IUPAC names of some ketones

Sr.No. Compound Trivial name IUPAC name

1 CH3-CO-CH3 Dimethyl ketone (Acetone) Propanone
2 CH3-CO-CH2-CH3 Ethyl methyl ketone Butanone
3 CH3-CO-CH2-CH2-CH3 Methyl n-propyl ketone Pentan-2-one
4 CH3-CH2-CO-CH2-CH3 Diethyl ketone Pentan-3-one
5 CH3-CHBr-CO-CH2-CH2-CH3 α-Bromoethyln-propyl 2-Bromohexan-3-one
ketone
6 (CH3)2C=CH-CO-CH3 Mesityl oxide 4-Methylpent-3-en-2-
one
7 CH3-CO-CH2-CO-CH2-CH3 --------------------- Hexane-2,4-dione
8 CH3-CO-CH2-CHO --------------------- 3-Oxobutanal
9 O Diphenyl ketone Benzophenone
C (Benzophenone)

10 O Methyl phenyl ketone Acetophenone

CH3 (Acetophenone)

11 O ----------------------- 2-Chloro-4-
Cl methylcyclohexanone

259
carbonyl groups. In case of polyfunctional ii. By dehydrogenation of alcohols : This
ketones, higher priority group is given lower method has industrial application. Aldehydes
number. When ketonic carbonyl is a lower and ketones are prepared by passing the
priority group it is named as 'oxo', preceded vapours of primary and secondary alcohols
by the locant. In alicyclic ketones, carbonyl respectively over hot copper powder. (See
carbon is numbered as 1. (Refer Table 12.2). Chapter 11)
b. From hydrocarbons :
Use your brain power
Write IUPAC names for the Can you recall ?
following compounds.
• What is ozonolysis ?
i. H
• What is the role of zinc dust in
Br Br ozonolysis process?
O
i. By ozonolysis : Alkene reacts with ozone to
O
ii. give ozonide which on decomposition with zinc
dust and water gives aldehyde and/or ketones.
O (See Std. XI Chemistry Textbook, Chapter 15)
iii. H
ii. By hydration of alkynes : Alkynes react
O with water in presence of 40% sulfuric acid
and 1% mercuric sulfate to give aldehydes
or ketones. (See Std. XI Chemistry Textbook,
iv. CHO v. O Chapter 15)
12.4.2 Other methods of preparation of
aldehydes and ketones : Some methods of
preparation of aldehydes and ketones involve
common starting functional groups but
Try this...
different types.
Draw structures for the following
a. 2-Methylpentanal a. From acyl chlorides (Acid chlorides) :
b. Hexan-2-one Aldehydes and ketones both can be obtained
from acyl chloride, but the reactions involved
12.4 Preparation of aldehydes and ketones : are different.
12.4.1 General methods of preparation of • Preparation of aldehyde from acyl
aldehydes and ketones : chloride
a. By oxidation of alcohols : i. Aldehydes Acyl chloride is reduced to corresponding
and ketones are prepared by the oxidation of aldehyde by hydrogen using a palladium
primary and secondary alcohols respectively. catalyst poisoned with barium sulfate. This
(See Chapter 11 ) reaction is known as Rosenmund reduction.
Can you tell ? O O
H2
What is the reagent which R - C - Cl Pd-BaSO4 R - C - H + HCl
oxidizes primary alcohols to
only aldehydes and does not oxidize (Acyl chloride) (Aldehyde)
aldehydes further into carboxylic acid ?

260
 hydrochloric acid which on acid hydrolysis
Use your brain power give corresponding aldehydes. This reaction
Write the structure of the is called Stephen reaction.
product formed on Rosenmund SnCl2, HCl
reduction of ethanoyl chloride and benzoyl R - C ≡ N + 2[H] R - HC = NH.HCl
(Alkane nitrile) (imine hydrochloride)
chloride.
H3O⊕
R - CHO + NH4Cl
(Aldehyde)
Can you think ?
For example,
What is the alcohol formed when SnCl2, HCl
benzoyl chloride is reduced with H3C - C ≡ N + 2[H] (reduction)
pure palladium as the catalyst ? (Ethanenitrile)
H3O⊕
CH3 - HC = NH.HCl CH3-CHO+NH4Cl
b. Preparation of ketone (aliphatic and (ethanimine hydrochloride) (Ethanal)
aromatic) from acyl chloride :
SnCl2, HCl
i. Preparation of aliphatic ketones from C6H5 - C ≡ N + 2[H]
acyl chloride: ketones are obtained from acyl (Benzonitrile)
chloride by reaction with dialkyl cadmium H3O⊕
C6H5 - HC = NH.HCl C6H5-CHO+NH4Cl
which is prepared by the treatment of cadmium
(Benzanimine hydrochloride) (Benzaldehyde)
chloride with Grignard reagent.
Alternatively, nitriles are also reduced by
2R - MgX + CdCl2 R2Cd + 2Mg(X)Cl
diisobutylaluminium hydride (DIBAl-H)
2R' - COCl + R2Cd 2 R' - CO - R or AlH (i-Bu)2 to imines followed by acid
(Acyl chloride) (Ketone) hydrolysis to aldehydes. An advantage of this
+ CdCl2 method is that double or triple bond present in
For example, the same molecule is not reduced..
AIH (i-Bu)2
2CH3 - COCl + (CH3)2Cd H3C - CH = CH - CH2 - C ≡ N H O ⊕
3

(Ethanoyl chloride) (Dimethyl cadmium)

(Pent-3-enenitrile)
2CH3-CO-CH3 + CdCl2 H3C - CH = CH - CH2 - CHO
(Pent-3-enal)
Propanone (Acetone)
• Preparation of ketones from nitriles :
2C6H5 - COCl + ( CH3)2Cd
(Benzoyl chloride) (Dimethyl cadmium) Ketones are prepared by reacting nitriles
C6H5 - CO - CH3 + CdCl2 with Grignard reagent in dry ether as solvent
(Acetophenone) followed by acid hydrolysis.
dry ether
ii. Preparation of aromatic ketones from H3C - C ≡ N + H3CMgCl
acyl chloride : Aromatic ketones are prepared (Ethanenitrile)
H3O⊕
by Friedel Craft's acylation reaction (Std. XI CH3 - C = NMgCl CH3 - CO - CH3
Chemistry Textbook, Chapter 15, sec. 15.4.6) H3C (Acetone)
b. From nitriles : Aldehydes and ketones both + NH3 + Mg(Cl)OH
can be obtained from nitriles but by different
dry ether
reaction. C6H5 - C ≡ N + C6H5 - MgBr
• Preparation of aldehydes from nitriles : (Benzonitrile)
H3O⊕
C6H5 - C = NMgBr C6H5 - CO - C6H5
Nitriles are reduced to imine hydrochloride
by stannous chloride in presence of C6H5 (Benzophenone)
+ NH3 +Mg(Br)OH
261
c. From aromatic hydrocarbons : Aromatic iii. By side chain chlorination of toluene:
aldehydes and ketones are both prepared Side chain chlorination of toluene gives
from aromatic hydrocarbons but by different benzal chloride which on acid hydrolysis at
methods. 373K gives benzaldehyde. Benzaldehyde, is
• Preparation of aromatic aldehydes from manufactured commercially by this method.
hydrocarbon CH3 CHCl2
Cl - Cl H 3O ⊕
Strong oxidizing agents transform -CH3 group hv ∆ 373K
bonded to aromatic ring into carboxyl group
(-COOH). For obtaining aromatic aldehyde (Toluene) (Benzal chloride)

from methyl arene the following special CHO

methods are used.
i. Etard reaction : Methyl group in methyl (Benzaldehyde)
benzene (or methyl arene) is oxidized by iv. Gatterman –Koch formylation of arene:
oxidizing agent chromyl chloride in carbon Benzene or substituted benzene is treated
disulfide as solvent, to form a chromium under high pressure with carbon monoxide and
complex, from which the corresponding hydrogen chloride in presence of anhydrous
benzaldehyde is obtained on acid hydrolysis. aluminium chloride or cuprous chloride to give
This reaction is known as Etard reaction. benzaldehyde or substituted benzaldehyde.
H
H CO,HCl
CHO
C
H CS2
Anhyd.AlCl3
+ CrO2Cl2 high pressure
(Benzene) (Benzaldehyde)
(Toluene) (Chromyl chloride)
• Preparation of Aromatic ketones from
CHO hydrocarbons :
H OCr(OH)Cl2 By Friedel-crafts acylation of arene : (Refer
H3O⊕
OCr(OH)Cl2 to sec. 12.4.2 (a) ii and Std. XI Chemistry
Textbook, Chapter 15, sec. 15.4.6).
(Chromium complex) (Benzaldehyde)
Use your brain power
ii. By oxidation of methyl arene using CrO3
: Methylarene is converted into a benzyllidene Name the compounds which
diacetate on treatment with chromium are used for the preparation
oxide in acetic anhydride at 273-278 K. The of benzophenone by Friedel-Crafts
diacetate derivative on acid hydrolysis gives acylation reaction. Draw their structures.
corresponding aldehyde.
12.4.3 Preparation of aldehydes only from
H
H esters : Aliphatic or aromatic esters are reduced
C to aldehydes by using diisobutylaluminium
H 273 - 283 K
+ CrO3 + (CH3CO)2O hydride DIBAl-H or AlH (i-Bu)2. The
reaction is usually carried out at 195 K to
(Methylbenzene) (Acetic anhydride) prevent further reduction of the aldehyde
CHO produced.
H OCOCH3 ∆ O O
AIH (i-Bu)
OCOCH3
H3O⊕ R - C - O - R' H O R-C-H
3
⊕
2

(Benzaldehyde) (Ester) (Aldehyde)

262
 b. Anhydrides on hydrolysis with water give
Try this...
Draw the structure of the product carboxylic acids.
formed by the combination of O O O
carbon monoxide and HCl. R - C - O - C - R + H2O 2R - C - O - H
(Anhydride) (Carboxylic acid)
Use your brain power
12.5.3 From esters : Carboxylic acids can be
Identify the reagents necessary obtained from esters either by acid hydrolysis
to achieve each of the following or alkaline hydrolysis.
transformation a. Acid hydrolysis of ester : Esters on
O O hydrolysis with dilute mineral acid like dilute
Cl H HCl or dilute H2SO4 give the corresponding
carboxylic acid .
O O O
R - C - O - R' + H2O dil.H
∆
SO 2
R -4
C -O-H
(Ester) (Carboxylic acid)

O O + R' - OH
(Alcohol)
OCH3 H
O2N b. Alkaline hydrolysis of ester using dilute
O2N
alkali like dilute NaOH or dilute KOH form
solution of water soluble sodium or potassium
12.5 Preparation of carboxylic acids : salt of the acid (carboxylate). On acidification
12.5.1 From nitriles and amides : Alkyl with concentrated HCl, free acid is formed.
nitriles or aryl nitriles on acid hydrolysis give O
amides . Amides on further acid hydrolysis give H5C2 - C - O - CH3 + dil.NaOH ∆

corresponding carboxylic acids. Hydrolysis is (Methyl propanoate)

carried out by using dilute mineral acids like O ⊕
dilute sulfuric acid or dilute hydrochloric acid. H5C2 - C - O - Na + CH3 - OH
OH (Sodium propanoate)
R - C ≡ N + H2O [R - C = NH]
O ⊕
(Nitrile) H⊕
H5C2 - C - O - Na + H2O Conc. HCl
O
H 2O (Sodium propanoate)
R - C - NH2 dil.HCl R-COOH+NH4Cl O
(Amide) (carboxylic acid) H5C2 - C - O - H + NaOH
R - C ≡ N + 2H2O + dil.HCl ∆
R - COOH (Propanoic acid)
+ NH4Cl The sodium or potassium salts of higher fatty
12.5.2 From acyl chloride and anhydrides : acids are known as soaps. Hence alkaline
hydrolysis of esters is called saponification
a. Acyl chlorides on hydrolysis with water give
(Std XI Chemistry Textbook, Chapter 16).
carboxylic acids. This method is useful for
preparation of aliphatic as well as aromatic 12.5.4 From alkyl benzene : Aromatic
acid. carboxylic acids can be prepared by oxidation
of alkyl benzene with dilute HNO3 or alkaline
R - COCl + H2O R - COOH + H - Cl
/acidic KMnO4 or chromic acid. The entire
(Acyl chloride) (Carboxylic acid)
263
alkyl chain , regardless of its length, is oxidized Internet my friend
to a carboxyl group. (Tertiary alkyl substituent
on benzene, however, is not oxidized). Collect information of dry ice and
ice from internet. Draw chemical
For example, structures of dry ice and regular ice.
H Prepare a chart of uses of dry ice.
H ⊕
C COOK
H KMnO4.KOH
∆

(Toluene) (Potassium benzoate)

COOH
H3O⊕

(Benzoic acid)
Use your brain power
CH3
H3C ⊕ Predict the products (name and
C COOK
H KMnO4.KOH structure) in the following reactions.
∆ ∆
CH3CH2CN dil. HCl ?
(Cumene) (Potassium benzoate) ∆
CH3-CONH2 dil. HCl ?
COOH
H3O⊕ alk.KMnO4
C6H5-CH2-CH3 ∆ ?
∆
(Benzoic acid) C6H5-COO-C2H5 dil. H2SO4 ?
12.5.5 From alkenes : Carboxylic acids can CH3MgBr
(i) dry ice/dry ether
?
(ii) dil. HCl
also be prepared by the oxidation of alkenes
by KMnO4 in dilute H2SO4. 12.6 Physical properties :
KMnO4.dil.H2SO4
H5C6 - CH = CH2 ∆ H5C6 - COOH 12.6.1 Nature of intermolecular forces :
(Phenyl ethene) (Benzoic acid) The carbonyl bond ( C=O) in aldehydes and
ketones is a polar covalent bond. As a result,
KMnO4.dil.H2SO4 COOH these compounds contain dipole-dipole forces
∆ COOH
of attraction. (Fig. 12.1) The molecules orient
(Cyclohexene) (Adipic acid) in such a way as to have oppositely polarized
atoms facing each other.
12.5.6 From Grignard reagent : Grignard δ δ⊕
reagent in dry ether solvent is added to solid O C
carbon dioxide (dry ice) to give a complex
C O
which on acid hydrolysis gives corresponding δ⊕ δ
carboxylic acid.
Fig. 12.1 Dipole-dipole attraction in carbonyl
dry ether
R - Mg - X + O = C = O R - COOMgX compounds
(Alkyl (dry ice) (complex) Carboxyl group of carboxylic acid contains
magnesium halide) O-H bond which is responsible for formation
HOH of hydrogen bonding. Thus, carboxylic acids
dil.HCl R - COOH + Mg(X)OH have the strongest intermolecular forces of
(carboxylic acid) attraction. (Fig.12.3 in section 12.6.4).

264
 Table 12.4 Boiling points of aldehydes and ketones
Number of carbon atoms Aldehyde Boiling point Ketone Boiling point
1 Methanal 252 K ----- --------
2 Ethanal 294 K ------- ---------
3 Propanal 319 K Propanone 329 K
4 Butanal 348 K Butan -2-one 353 K
5 Pentanal 376 K Pentan-2-one 375 K
6 Hexanal 392 K Hexan-2-one 400 K

12.6.2 Physical state and boiling points of 12.6.4 Physical state, boiling points and
aldehydes and ketones : solubilities of carboxylic acids : Lower
Formaldehyde is a gas at room temperature aliphatic carboxylic acids upto nine carbon
and has irritating odour. Acetaldehdye is atoms are colourless liquids with irritating
extremely volatile, colourless liquid. Higher odours. The higher homologues are colourless,
aldehydes have pleasant odour. Acetone is a odourless wax like solids, have low volatility.
liquid at room temperature and has pleasant Boiling points of lower carboxylic acids are
odour but most of the higher ketones have listed in Table 12.5.
bland odours. Carboxylic acids have higher boiling
Increasing boiling points in the homologous points than those of alkanes, ethers, alcohols
series of aldehydes and ketones are listed in aldehydes and ketones of comparable mass
Table 12.4. (Table 12.6). The reason is that , in liquid
phase, carboxylic acids form dimer in which
12.6.3 Solubility of aldehydes and ketones : two molecules are held by two hydrogen
The oxygen atom of ( C=O) can involve bonds. Acidic hydrogen of one molecule form
in hydrogen bonding with water molecule hydrogen bond with carbonyl oxygen of the
(Fig 12.2). As a result of this, the lower other molecule (Fig.12.3). This doubles the
aldehydes and ketones are water soluble (For size of the molecule resulting in increase in
example : acetaldehyde, acetone). As the intermolecular van der Waals forces, which in
molecular mass increases, the proportion of turn results in high boiling point. In the case of
hydrocarbon part of the molecule increases acetic acid dimers exist even in the gas phase
which cannot form hydrogen bond; and the (Fig.12.3).
water solubility decreases. δ δ⊕
O H O
δ δ⊕ δ H3 C - C C - CH3
δ⊕ C = O H -O δ⊕
H O H O
Fig. 12.2 : Hydrogen bonding in carbonyl δ⊕ δ
compound and water Fig. 12.3 : Dimer of acetic acid (Two molecules
held by two hydrogen bonds)
Table 12.5 Increasing boiling points of carboxylic acids
Name Formula Boiling point in K
Formic acid HCOOH 373 K
Acetic acid CH3COOH 391 K
Propionic acid CH3CH2COOH 414 K
Butyric acid CH3CH2CH2COOH 437 K
Valeric acid CH3CH2CH2CH2COOH 460 K

265
 Table 12.6 : Variation of boiling point with functional group
Compound Family Molecular mass Boiling point Strength of intermolecular
forces
CH3-CH2-CH2-CH3 Alkane 58 272 K
CH3-O-CH2-CH3 Ether 60 281 K

increases
CH3-CH2-CHO Aldehyde 58 322 K
CH3-CO-CH3 Ketone 58 329 K
CH3-CH2-CH2-OH Alcohol 60 370 K
CH3-COOH Carboxylic acid 60 391 K

Remember... solubility of carboxylic acids in water decreases

Relative strength of with increase in molecular mass. Higher
intermolecular force : H-Bond carboxylic acids are practically insoluble
> dipole-dipole attraction > van der in water due to the increased hydrophobic
Waals force. Hence, Boiling points : (water hating) interaction of hydrocarbon part
Carboxylic acids > Alcohols > Ketones > with water. Aromatic acids like benzoic acid
Aldehydes > ether > Alkanes are also practically insoluble in water at room
temperature. Water insoluble carboxylic acids
Do you know ? are soluble in less polar organic solvents like
Commercially available forms of ether, alcohol, benzene, and so on.
formaldehyde and acetaldehyde: 12.7 Polarity of carbonyl group : The
i. Formaldehyde is available commercially polarity of a carbonyl group originates from
as solid polymer called paraformaldehyde higher electronegativity of oxygen relative to
HO [CH2 - O]n H and trioxane (CH2O)3 carbon as well as resonance effects as shown
(Trioxane has cyclic structure). These are in Fig. 12.4.
convenient for use in chemical reactions as O Oδ
source of formaldehyde.
C C δ⊕
ii. Aqueous solution of formaldehyde
gas is called formalin, which is used for (A)
preservation of biological and anatomical
specimens.
O O
iii. When dry formaldehyde is required, it
is obtained by heating paraformaldehyde C C
or trioxane. ⊕
major minor
iv. Acetaldehyde is also conveniently used (B) (C)
as solid trimer (paraldehyde) and tetramer
(metaldehyde).
Oδ
Lower aliphatic carboxylic acids C δ⊕
containing upto four carbons are miscible resonance
with water due to formation of intermolecular hybrid
hydrogen bonds between carboxylic acid (D)
molecules and solvent water molecules. The Fig. 12.4 : Polarity of carbonyl group

266
 The carbonyl carbon has positive polarity
Try this...
(see structures (A) and (D)). Therefore, it is
electron deficient. As a result, this carbon Draw structure of propanone and
atom is electrophilic (electron loving) and is indicate its polarity.
susceptible to attack by a nucleophile (Nu: ).
12.8 Chemical properties of aldehydes and
12.7.1 Reactivity of aldehydes and ketones ketones :
: Reactivity of aldehydes and ketones is
due to the polarity of carbonyl group which 12.8.1 Laboratory tests for aldehydes and
results in electrophilicity of carbon. In general, ketones : Aldehydes are easily oxidized to
aldehydes are more reactive than ketones carboxylic acids and therefore, act as reducing
toward nucleophilic attack. This can be well agents toward mild oxidizing agents. Ketones,
explained in terms of both the electronic effects do not have hydrogen atom directly attached to
and steric effect. carbonyl carbon. Hence, they are not oxidized
by mild oxidizing agents. On the basis of this
1. Influence of electronic effects : Alkyl difference in the reactivity, aldehydes and
groups have electron donating inductive effect ketones are distinguished by the following
(+I). A ketone has two electron donating alkyl tests:
groups bonded to carbonyl carbon which are
responsible for decreasing its positive polarity a. Tests given by only aldehydes :
and electrophilicity. In contrast, aldehydes 1. Schiff test : When alcoholic solution of
have only one electron donating group bonded aldehyde is treated with few drops of Schiff 's
to carbonyl carbon. This makes aldehydes reagent, pink or red or magenta colour appears.
more electrophilic than ketones. This confirms the presence of aldehydic
2. Steric effects : Two bulky alkyl groups (-CHO) group.
in ketone come in the way of incoming 2. Tollens' test or silver mirror test : When
nucleophile. This is called steric hindrance to an aldehyde is boiled with Tollens' reagent
nucleophilic attack. (ammonical silver nitrate), silver mirror
On the other hand, nucleophile can easily is formed. The aldehyde is oxidized to
attack the carbonyl carbon in aldehyde because carboxylate ion by Tollens' reagent and Ag⊕
it has one alkyl group and is less crowded or ion is reduced to Ag.
sterically less hindered . Hence aldehyde are R - CHO + 2 Ag (NH3)2⊕ + 3OH ∆

more easily attacked by nucleophiles.

(aldehyde) Tollens reagent
Oδ Oδ
R - COO + 2 Ag↓ + 4NH3↑ + 2H2O
(carboxylate) (Silver mirror)
C C
R δ⊕ R R δ⊕ H
(Ketone) (Aldehyde)
3. Fehling test : When a mixture of an aldehyde
and Fehling solution is boiled in hot water, a
Remember... red precipitate of cuprous oxide is formed.
Aromatic aldehydes are less An aldehyde is oxidized to carboxylate ion
reactive than aliphatic aldehydes by Fehling solution and Cu2⊕ ion is reduced
in nucleophilic addition reactions. This is to Cu⊕ ion. It may be noted that α-hydroxy
due to electron-donating resonance effect ketone also gives this test positive.
of aromatic ring which makes carbonyl
carbon less electrophilic.

267
R - CHO + 2Cu2⊕ + 5OH boil a. Addition of hydrogen cyanide (H-CN) :
Hydrogen cyanide (weak acid) adds across
(Aldehyde) (Fehling solution) the carbon-oxygen double bond in aldehydes
R - COO + Cu2O↓ + 3H2O and ketones to produce compounds called
(carboxylate ion) red ppt
Do you know ?
Can you tell ?
1. Schiff 's reagent is a colourless
Simple hydrocarbons, ethers, solution obtained by passing sulfur
ketones and alcohols do not dioxide gas (oxidant) through magenta
get oxidized by Tollens' reagent. coloured solution of p-rosaniline
Explain, Why ? hydrochloride .

Use your brain power NH2⊕Cl

Why is benzaldehyde NOT oxidized
by Fehling solution ?

b. Laboratory test for ketonic group : H2N NH2

Sodium nitroprusside test : (p-rosaniline hydrochloride)
When a freshly prepared sodium nitroprusside
solution is added to a ketone, mixture is shaken aldehyde SO2/H2O

well and basified by adding sodium hydroxide

solution drop by drop, red colour appears in NH2
the solution, which indicates the presence of
ketonic ( >C=O) group.
CH3 - CO - CH3+ OH CH3 - CO - CH2 SO3H
(Acetone)
+ H2O
[Fe( CN)5NO]2 + CH3- CO- CH2 H2N NH2
(Nitroprusside ion) (Schiff 's reagent)
2. Tollens' reagent is prepared by mixing
[Fe(CN)5 NO (CH3- CO- CH2)]3
a few drops of AgNO3 solution and a few
Red colouration
mL of dilute sodium hydroxide solution.
The anion of ketone formed by alkali reacts A brown precipitate is formed which is
with nitroprusside ion to form a red coloured then dissolved by adding dilute ammonium
complex which indicates the presence of hydroxide.
ketonic group.
3. Fehling solution is a mixture of two
12.8.2 Chemical reactions of aldehydes solutions Fehling A and Fehling B. Fehling
and ketones with nucleophile : In all these A is prepared by dissolving crystals of
reactions the nucleophilic reagent brings about copper sulfate in concentrated sulfuric
reactions by attacking on positively polarized acid. Fehling B is prepared by dissolving
electrophilic carbonyl carbon in aldehydes sodium potassium tartarate in sodium
and ketones. hydroxide solution.

268
cyanohydrins. The negative part of the reagent H3C CH3
( CN) attacks the electrophilic carbon of C = O + NaHSO3 H3C − C − OH
carbonyl group. The reaction requires either H3C SO3Na
acid or base as catalyst. (Acetonesodium
(Acetone)
R R bisulfite adduct)
C = O + HCN R' − C − OH
Use your brain power
R' CN
(Aldehyde when R' = H
Sodium bisulfite is sodium salt
(cyanohydrin)
Ketone : R' = alkyl/aryl group) of sulfurous acid, write down its
detailed bond structure .
For example ,
H3C H Do you know ?
C = O + H - CN H3C − C − OH Sodium bisulfite addition product
H CN so formed can be split easily to
(Acetaldehyde) (acetaldehyde cyanohydrin) regenerate aldehydes and ketones on
treatment with dilute acid or base. Thus,
H3C CH3 this reaction is used to separate and purify
C = O + H - CN the aldehydes and ketones from other
H3C − C − OH
H3C organic compounds.
CN
(Acetone) (Acetone cynohydrin) c. Addition of alcohols : Aldehyde reacts
with one molecule of anhydrous monohydric
Remember... alcohol in presence of dry hydrogen chloride
i. Cyanohydrin formation is a to give alkoxyalcohol known as hemiacetal,
'step-up' reaction as a new carbon which further reacts with one more molecule
- carbon single bond is formed. of anhydrous monohydric alcohol to give a
geminaldialkoxy compound known as acetal
ii. The - C ≡ N group can be converted to as shown in the reaction.
–COOH, - CH2 - NH2 and so on.
Step 1 :
iii. Therefore, cyanohydrins are used as
intermediate in step up synthesis. R H
dry HCl
C = O +R' - OH R − C − OR'
dil. HCl
b. Addition of NaHSO3 (Sodium bisulphite) H OH
: Aldehydes and ketones react with saturated
(Aldehyde) (Hemiacetal) unstable
aqueous solution of sodium bisulfite to give
crystalline precipitate of sodium bisulfite
Step 2 :
adduct (addition compound). For example ,
H H
dry HCl
H3C H R − C − OR' +R' - OH R − C − OR'
dil. HCl
C = O + NaHSO3 H3C − C − OH OH OR'
H SO3Na (Hemiacetal) (Acetal) stable

(Acetaldehyde) (Acetaldehyde + H2O

sodium bisulfite
adduct)

269
For example ,
Do you know ?
Step 1 :
Cyclic ketal is used as protecting
H3C
group for ketone in reactions of
C=O + H5C2 - OH
multifunctional compound to which
H
ketone is sensitive.
(Acetaldehyde)
H
dry HCl
H3C − C − OC2H5 Use your brain power
dil. HCl
OH Predict the product of the
(Hemiacetal) unstable following reaction :
O HO-CH2-CH2-OH
Step 2 : Br
Mg in dry ether
H
dry HCl
H3C − C − OC2H5 + H5C2 - OH Acetals and ketals are hydrolysed with
dil. HCl
OH aqueous mineral acids to give corresponding
(Hemiacetal) (unstable) aldehydes and ketones respectively.
H
H3C − C − OC2H5 + H2O Remember...
OC2H5 Organic molecule containing
(1,1-Diethyoxyethane) an alcohol and carbonyl group can
(stable) undergo intramolecular reaction with dry
HCl to form cyclic hemiacetals/hemiketals.
Similarly, Ketones react with alcohol in
presence of acid catalyst to form hemiketal
and ketal. d. Addition of Grignard reagent : Aldehydes
and ketones on reaction with alkyl magnesium
Ketones react with 1,2- or 1,3- diols in halide followed by acid hydrolysis give
presence of dry hydrogen chloride to give five- alcohols.(Refer to Chapter 11, sec. 11.4.1 d.)
or six -membered cyclic ketals .
e. Nucleophilic addition –elimination of
R HO -CH2 aldehydes and ketones with ammonia
C=O + derivatives : Aldehydes and ketones undergo
R HO -CH2
addition elimination with some ammonia
(ketone) (ethane-1,2-diol)
derivatives (NH2-Z ) to give product
dry HCl R O CH2 containing C = N bonds (imines). The reaction
dil. HCl C is reversible and takes place in weakly acidic
R O CH2 medium. The substituted imine is called a
(cyclic ketal) Schiff 's base.

The reaction can be reversed by treating the C = O + NH2 Z C N Z

-H2O
cyclic ketal with aqueous HCl to regenerate (Aldehyde OH H
the ketone. or Ketone)
C N Z + H2O
(imine)

270
 Table 12.7 Nucleophilic addition – elimination reactions of aldehydes and ketones with
ammonia derivatives
Sr. Aldehyde(R'=H)/ + NH2 - Z imine (a crystalline
-H2O
No. Ketone(R'≠H) derivative)
R NH2 OH R
1. C=O + Hydroxyl amine -H2O R' C N OH
R' oxime
R NH2 NH2 R
2. C=O + Hydrazine -H2O R' C N NH2
R' hydrazone
R NH2 NH   C6H5 R
3. C=O + Phenyl hydrazine -H2O R' C N NH C6H5
R' phenylhydrazone
R NH2 NH   CONH2 R
4. C=O + Semicarbazide -H2O R' C N NH CONH2
R' semicarbazone
NO2 NO2
H R H
R
+H2N N NO2 C=N N NO2
5. C=O -H2O
R
R' 2, 4 - Dinitrophenyl 2, 4 -
hydrazine Dinitrophenylhydrazone

Where Z = -R, -Ar, -NH2, -NHC6H5,

-NHCONH2 , -NHC6H3(NO2)2 Remember...

For example, In strong acidic medium,

nitrogen atom of ammonia
H3C derivative H2N-Z is protonated to form
H3C C N OH
C = O + NH2 OH (H3N+ – Z) ion which is no longer a
HO H
H (Hydroxyl nucleophile.
(Acetaldehyde)
amine)
H Use your brain power
-H2O
H3C C N OH
(Acetaldoxime) Draw the structures of
i. The semicarbazone of cyclohexanone
All aldehydes and ketones give similar
reactions .Some important reactions are ii. The imine formed in the reaction
listed in Table 12.7. The resulting products between 2-methylhexanal and ethyl
have high molecular mass and are crystalline amine
solids. These reactions are, therefore, useful iii. 2, 4 - dinitrophenylhydrazone of
for characterization of the original aldehydes acetaldehyde.
and ketones.

271
f. Haloform reaction : This reaction is g. Aldol condensation :
given by acetaldehyde, all methyl ketones
(CH3-CO-R) and all alcohols containing CH3- Try this...
(CHOH)- group. When an alcohol or methyl When acetaldehyde is treated
ketone is warmed with sodium hydroxide and with dilute NaOH, the following
iodine, a yellow precipitate is formed. Here reaction is observed.
the reagent sodium hypoiodite is produced
dil. NaOH
in situ. During the reaction, sodium salt of 2CH3-CHO CH3 -CH-CH2-CHO
carboxylic acid is formed which contains OH
one carbon atom less than the substrate. The • What are the functional groups in the
methyl group is converted in to haloform. product ?
For example : Acetone is oxidized by sodium • Will there be another product formed
hypoiodite to give sodium salt of acetic acid during the same reaction ? (Deduce
and yellow precipitate of iodoform. the answer by doing atomic audit of
reactant and product)
O • Is this an addition reaction or
NaOH, I2
H3C C CH3 + 3 Na OI condensation reaction ?
∆
(Acetone) (Sodium
hypoiodite)
Aldehydes containing at least one
O α –hydrogen atom undergo a reaction in
⊕
CHI3 ↓ + H3C   C ONa + 2 NaOH presence of dilute alkali ( dilute NaOH, KOH
(Iodoform) (Sodium acetate) or Na2CO3) as catalyst to form β-hydroxy
aldehydes (aldol). This reaction is known
as aldol reaction. Formation of aldol is an
Remember...
addition reaction. Aldol formed from aldehyde
1. If C=C bond is present in a given having α-hydrogens undergoes subsequent
aldehyde or ketone or methyl elimination of water molecule on warming,
ketone, it is not attacked by hypohalite. giving rise to a, b - unsaturated aldehyde.
2. Non methyl ketones do not give a aq. NaOH
R-CH2-CH-CH-CHO
2R-CH2-CHO
positive iodoform test.
OH R
3. Secondary alcohols having CH3- (aldehyde) (aldol)
CHOH- group give positive iodoform -H2O
test because the reagent first oxidizes it R-CH2-CH-CHR-CHO R-CH=C CHO
warm
to a CH3-CO- group which subsequently OH R
forms iodoform. (aldol) (a, b - unsaturated aldehyde)

For example :
Try this...
(i)
Write chemical reactions taking H
place when propan-2-ol is treated α dil. NaOH
H C C H + H CH2 C H
with iodine and sodium hydroxide.
H O O
(Ethanal) (Ethanal)

272
 b a ∆ b a
H3C CH CH CHO-H O H3C CH CH CHO Use your brain power
2

OH H • Observe the following

(But-2-enal)
(3-Hydroxybutanal) reaction.
(an Aldol)
O O
The overall reaction is called aldol
condensation. It is a nuclephilic addition- C C
H H 3C
elimination reaction. +
Ketones containing at least two a- hydrogen (1-Phenylethanone)
(Benzaldehyde)
also undergo aldol condensation reaction (acetophenone)
and give an a, b - unsaturated ketone. For O
example:
CH C
dil.base
(ii) CH3 CH
CH3 O ∆
Ba(OH) 2 β a
2 H3C C H3C C CH C CH3 (1,3-Diphenylprop-2-en-1-one)
O OH H (Benzal acetophenone)
(Propanone) (4-Hydroxy-4-methylpentan-2-one) • Will this reaction give a mixture of
(a Ketol) products like a cross aldol reaction ?
CH3 O
∆ β a
H3C C CH C CH3 α-hydrogen atom. Aldehydes undergo self
-H2O
(4-methylpent-3-en-2-one) -oxidation and reduction reaction on heating
with concentrated alkali. This is an example of
Cross aldol condensation : Cross aldol disproportionation reaction. In cannizzaro
condensation refers to the aldol condensation reaction one molecule of an aldehyde is
that takes place in between two different reduced to alcohol and at the same time second
aldehydes or ketones . If both aldehydes or molecule is oxidized to carboxylic acid salt.
ketones contain two α-hydrogen atoms each, For example, Formaldehyde and benzaldehyde
then a mixture of four products, is formed.
(i) O
For example, a mixture of ethanal and propanal ∆
2H C H + NaOH
on reaction with dilute alkali followed by
(Formaldehyde) (sodium hydroxide)
heating gives a mixture of four products (50%)
(Fig.12.5). O H
Ketones can also be used as one of the H C O Na⊕ + H C OH
components in cross aldol condensation .
(Sodium formate) H
h. Cannizzaro reaction : This reaction (Methanol)
is given only by aldehydes having no

O H H O H3C O
Self
H3C- C-H condensation
H3C - C = C - C - H + H3C - CH2 - CH = C - C - H
(Ethanal) i. dil.NaOH (Crotonaldehyde / But-2-enal) (2-Methylpent-2-enal)
+ ii. heat
O H3C O H H O
H3C-CH2-C-H Cross H3C - CH = C - C- H + H3C - CH2 - C = C - C - H
condensation
(Propanal) (2-Methylbut-2-enal) (Pent-2-enal)

Fig. 12.5 : Cross aldol condensation

273
(ii) H K2Cr2O7
R CHO dil. H2SO4
R COOH
C (Aldehyde)
O (Carboxylic acid)
2 KOH in MeOH
∆
Ketones resist oxidation due to strong
(Benzaldehyde) CO-C bond ,but they are oxidized by strong
oxidizing agents such as CrO3, alkaline
O
KMnO4 or hot concentrated HNO3 to a mixture
C CH2 OH of carboxylic acids having less number of
O K⊕
+ carbon atoms than the starting ketone. Thus,
Oxidation of ketones is accompanied by
(Potassium benzoate) (Phenylmethanol / breaking C - C bond.
benzyl alcohol) O
CrO3
Use your brain power R C R' R COOH + R' COOH
(Ketone) (Carboxylic acids)
Can isobutyraldehyde undergo
Cannizzaro reaction ? Explain.
For example,
Cross Cannizzaro reaction : When a mixture O
of formaldehyde and non-enolisable aldehyde CrO3
(aldehyde with no α-hydrogen) is treated with (i) H 3C C CH3 H3C COOH
a strong base, formaldehyde is oxidized to (Acetone) (Acetic Acid)
formic acid while the other non-enolisable is
reduced to alcohol. Formic acid forms sodium O
formate with NaOH. On acidification sodium CrO3
(ii) H3C C C2H5 H3C COOH
formate is converted into formic acid. For
(Ethanonic acid)
example : (Butan-2-one)
H + H5C2 COOH
O (Propanoic acid)
C
H C H + O i. conc. NaOH b. Clemmensen and Wolf-Kishner
ii. H3O⊕
reduction: The carbonyl group of aldehydes
(Formaldehyde) (Benzaldehyde)
and ketones is reduced to methylene group
(-CH2- ) on treatment with zinc –amalgam and
CH2 OH O concentrated hydrochloric acid (Clemmensen
+ H C OH reduction) or hydrazine followed by heating
with sodium or potassium hydroxide in high
(Phenylmethanol) (formic acid) boiling solvent like ethylene glycol (Wolf-
Kishner reduction).
12.8.3 Oxidation and reduction reactions of
aldehydes and ketones ; In both the reactions, oxygen is replaced by
two hydrogen atoms.
a. Oxidation of aldehydes and ketones
by dilute HNO3, KMnO4 and K2Cr2O7 : Clemmensen reduction :
Aldehydes are oxidized to the corresponding
Zn-Hg, conc. HCl
carboxylic acids by oxidant such as dilute nitric C O + 4[H] C H2 + H2O
∆
acid, potassium permanganate and sodium or (Carbonyl group
potassium dichromate in acidic medium. in aldehydes and (Methylene group)
ketones)

274
For example : Wolf-Kishner reduction is used to
CH3 synthesize straight chain alkyl substituted
Zn-Hg, conc. HCl benzenes which is not possible by Friedel-
(i) H3C C O + 4[H] ∆
Crafts alkylation reaction.
(Acetone) CH3
12.8.4 Electrophilic substitution reactions:
H3C C H2 + H2O Aromatic aldehydes and ketones undergo
(propane) electrophilic substitution reactions such as
Zn-Hg, conc. HCl
nitration ,sulfonation and halogenation. The
(ii) CH3 CH2 CHO + 4[H] ∆ aldehydic ( -CHO) and ketonic (>C=O)
(Propanal) groups are electron-withdrawing by inductive
CH3 CH2 CH3 + H2O as well as resonance effects. They deactivate
(Propane) the benzene ring at ortho- and para- positions.
This results in the formation of meta-product.
Wolf-Kishner reduction : For example ,
H2N-NH2 CHO
C O -H2O
C N NH2 conc. H2SO4
+ HO NO2
(Carbonyl group (conc. HNO3)
(Hydrazone)
in aldehydes and (Benzaldehyde)
ketones)
CHO
KOH, HO-CH2-CH2-OH + H2O
∆ CH2 + N2
(Methylene group)
NO2
For example : (m-Nitrobenzaldehyde)
12.9 Chemical properties of carboxylic
H2N-NH2
(i) C2H5 CHO acids :
-H2O C2H5 CH N NH2
12.9.1 Acidic character of carboxylic acids:
(Propanal) (Hydrazone)
The carboxyl group (- COOH) imparts acidic
KOH, HO-CH2-CH2-OH
character to carboxylic acids. A carboxyl
CH3 CH2 CH3 + N2 group is made of -OH group bonded to a
∆
(Propane) carbonyl group. In aqueous solution the H
atom in OH of carboxyl group dissociates as
proton and carboxylate ion is formed as the
C2H5 conjugate base,
H2N-NH2
(ii) C O R - COOH + H2O R - COO + H3O⊕
-H2O
(carboxylate ion)
(Ethyl phenyl ketone) Carboxylate ion is resonance stabilized by
C2H5 two equivalent resonance structures as shown
KOH, HO-CH2-CH2-OH below.
C N-NH2 ∆

(Hydrazone) O O
C2H5 O
R C R C R C
CH2 + N2 O O O
(n-Propyl benzene) (i) (ii) resonance
hybrid

275
Carboxylate ion has two resonance structures Table 12.8 : pKa values of haloacetic acids
(i) and (ii) and both of them are equivalent to
Acid pKa Acid
each other (Refer to Std. XI Chemistry Textbook
strength
Chapter 14). This gives good resonance
F-CH2-COOH 2.56
stabilization to carboxylate ion, which in turn
Cl-CH2-COOH 2.86

decreases
gives acidic character to carboxylic acids.
Br-CH2-COOH 2.90
Can you recall ?
I-CH2-COOH 3.18
What is the numerical parameter
to express acid strength? CH3-COOH 4.76

Halogens are electronegative atoms and exert

Remember... electron withdrawing inductive effect (-I
Lower Ka value, higher pKa: effect). The negatively charged carboxylate ion
Weaker acid. in the conjugate base of haloacetic acid gets
Higher Ka value, lower pKa : stronger acid. stabilized by the -I effect of halogen. Which is
responsible to diffuse the native charge.
Influence of electronic effects on acidity O
of carboxylic acids : All the carboxylic X CH2 C
acids do not have the same pKa value. The O
structure of 'R' in R-COOH has influence on Higher the electronegativity of halogen greater
the acid strength of carboxylic acids. Various is the stabilization of the conjugate base,
haloacetic acids illustrate this point very well stronger is the acid and smaller is the pKa
(Tables 12.8 and 12.9). value.
Problem 12.1
Alcohols (R-OH), phenols (Ar-OH) and carboxylic acids (R-COOH) can undergo ionization
of O-H bond to give away proton H⊕; yet they have different pKa values, which are 16, 10 and
4.5 respectively. Explain
Solution : pKa value is indicative of acid strength. Lower the pKa value stronger the acid.
Alcohols, phenols and carboxylic acids, all involve ionization of an O-H bond. But their
different pKa values indicate that their acid strength are different. This is because the resulting
conjugate bases are stabilized to different extent.
Acid(HA) Conjugate base(A ) Electronic effect Stabilization/destabilization
R-O-H R O +I effect of R destabilization of conjugate base
group
Ar-O-H Ar-O -R effect or Ar stabilization of conjugate base is
group moderate because all the resonance
structures are not equivalent to each
other
O O -R effect of C = O stabilization is good because all the
R - C - O-H R-C-O group resonance structures are equivalent
to each other
As the conjugate base of carboxylic acid is best stabilized, among the three, carboxylic acids
are strongest and have the lowest pKa value. As conjugate base of alcohols is destabilized,
alcohols are weakest acids and have highest pKa value. As conjugate base of phenols is
moderately stabilized phenols are moderately acidic and have intermediate pKa value.

276
 Try this... ring exerts electron withdrawing inductive
effect (-I effect) which stabilizes the conjugate
Compare the following two base and increases the acid strength of
conjugate bases and answer. aromatic acids.
O O Table 12.9 illustrates that more the number of
CH3 C Cl - CH2 C electron withdrawing substituents higher is the
O O acid strength.
(a) (b)
Try this...
• Indicate the inuctive effects of CH3 -
Arrange the following acids in
group in (a) and Cl - group in (b) by
order of their decreasing acidity.
putting arrowheads in the middle of
appropriate covalent bonds. CH3-CH-CH2-COOH, CCl3-CH2-COOH,
• Which species is stabilized by Cl
CH3COOH
inductive effect, (a) or (b) ?
• Which species is destabilized by Electron–withdrawing groups like -Cl, -CN,
inductive effect, (a) or (b) ? and -NO2 increase the acidity of substituted
benzoic acids while electron –donating group
like –CH3, - OH , - OCH3 and -NH2 decrease
Use your brain power the acidity of substituted benzoic acids .
• Compare the pKa values and COOH COOH COOH
arrange the following in an
increasing order of acid strength.
Cl3CCOOH, ClCH2COOH, CH3COOH,
Cl2CHCOOH
NO2 CH3
• Draw structures of conjugate bases
of monochloroacetic acid and (4-Nitrobenzoic (Benzoic acid) (4-Methylbenzoic
acid) (pKa = 4.2) acid)
dichloroacetic acid. Which one is more (pKa = 3.41) (pKa = 4.4)
stabilized by -I effect ?
Try this...
Acidity of aromatic carboxylic acids :
Benzoic acid is the simplest aromatic acid. Arrange the following carboxylic
From the pKa value of benzoic acid (4.2) we acids in order of increasing acidity.
understand that it is stronger than acetic acid m-Nitrobenzoic acid, Trichloroacetic acid,
(pKa 4.76). The sp2 hybrid carbon of aromatic benzoic acid, α-Chlorobutyric acid.

Table 12.9 pKa values of chloroacetic acids

Name Structure pKa Acid strength

Monochloroacetic acid Cl - CH2 - COOH 2.86
Cl - CH - COOH
increases

Dichloroacetic acid 1.26

Cl
Cl
Trichloroacetic acid Cl C - COOH 0.6
Cl

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12.9.2 Laboratory tests for carboxyl 12.9.3 Formation of acyl chloride
(-COOH) group : The presence of -COOH Reaction with PCl3, PCl5, SOCl2 : Carboxylic
group in carboxylic acids is identified by the acids on heating with PCl3, PCl5, SOCl2 give
following tests: the corresponding acyl chlorides. Thionyl
a. Litmus test : (valid for water soluble chloride (SOCl2) is preferred because the
substances) byproducts formed are in gaseous state so they
Aqueous solution of Organic compound can easily escape from the reaction mixture.
containing –COOH group turns blue litmus In this reaction –OH group of –COOH is
red which indicates the presence of acidic replaced by –Cl .
functional group. (It may be noted that ∆
R COOH + SOCl2 R - COCl + SO2↑
aqueous solutions of water soluble phenols (Carboxylic acid) (acyl chloride)
also turn blue litmus red.) +HCl ↑
∆
b. Sodium bicarbonate test : 3 R COOH + PCl3 3 R - COCl + P(OH)3
∆
When sodium bicarbonate is added to an R COOH + PCl5 R - COCl + POCl3
organic compound containing –COOH + HCl
group, a brisk effervescence of carbon
dioxide gas is evolved. Water insoluble acid
goes in solution and gives precipitate on Use your brain power
acidification with conc.HCl. This indicates
Fill in the blanks and rewrite the
the presence of –COOH group.
-CO2
balanced equations.
R - COOH + NaHCO3(aq) -H2O ∆
(water insoluble)
• CH3COOH + thionyl chloride
HCl + +
R - COONa(aq) R - COOH↓
∆
+ NaCl(aq) • CH3-CH2-COOH +
+ + H3PO3
(Phenol does not evolve CO2 gas with
∆
sodium bicarbonate. Hence, carboxylic • C6H5-COOH + +
acid and phenol are distinguished by this phosphorous oxylchloride + HCl
test.) • CH3-COOH + phosphorous trichloride
∆
c. Ester test : One drop of concentrated +
NH3
sulfuric acid is added to a mixture of given • CH3-COOH ∆

organic compound containing –COOH

NH3 ∆
group and one mL of ethanol, the reaction • C6H5-CONH2
mixture is heated for 5 minutes in hot water
bath. After this , hot solution is poured in 12.9.4 Reaction with ammonia : Formation
a beaker containing water, fruity smell of of amide : Carboxylic acids react with
ester confirms the presence of carboxylic ammonia to from ammonium carboxylate
acid. salt which on further strong heating at high
H⊕ temperature decomposes to give acid amide.
R - COOH + C2H5OH warm
R - COO - C2H5 + H2O ⊕
R COOH + NH3 R COONH4
(ester)
(Carboxylic acid) (ammonium carboxylate)
∆
-H2O R CONH2
(Acid amide)

278
 Acyl chloride and sodium salt of acid
Do you know ? are prepared by reacting carboxylic acid
separately with thionyl chloride and sodium
hydroxide respectively.
COOH COONH4
+ 2NH3
COOH COONH4 SOCl2
Phthalic acid R COOH R COCl
O ∆
CONH2 C ⊕
∆ -NH3 R COOH NaOH R COONa
-2H2O NH
CONH2 C
O O
O
Phthalimide R C O C   R + NaCl
(Anhydride)
b. Acid amides can also be prepared by
reacting acid chloride with ammonia. Can you recall ?
R COCl + NH3 R CONH2 + HCl Which molecule is eliminated in a
(Acyl chloride) (Acid amide) decarboxylation ?
12.9.5 Formation of acid anhydride :
12.9.6 Decarboxylation of carboxylic acids :
Can you tell ?
Sodium salts of carboxylic acids on heating
What is the term used for
with soda lime give hydrocarbons which
elimination of water molecule ?
contain one carbon atom less than the
Mono carboxylic acids on heating with carboxylic acid. For example,
⊕ CaO
strong dehydrating agent like P2O5 concentrated R COONa + NaOH R H + Na2CO3
∆
H2SO4 give acid anhydrides. The reaction is
reversible. Anhydrides are readily hydrolyzed
back to acids on reaction with water. ⊕ CaO
CH3 COONa + NaOH ∆ CH4 + Na2CO3
O O (Sodium acetate) (Methane)
R C R C
O H ∆ P2O5
+ O
+H2O
R C 12.9.7 Reduction of carboxylic acids :
R C O H
O Carboxylic acids are reduced to primary
O alcohols by powerful reducing agent like
(Carboxylic acid) (Acid anhydride) lithium aluminium hydride. Carboxylic acid
Better yield of acid anhydride is obtained can also be reduced by diborane (diborane
by heating sodium carboxylate with acyl does not reduce –COOR , -NO2 , -X).
chloride. (Note : Sodium borohydride (NaBH4 )does
⊕
R COONa + R COCl not reduce-COOH group).
(sodium carboxylate) (acyl chloride) dry
R COOH + LiAlH4 R CH2OH
ether
O O
∆ R C O C   R + NaCl
(acid anhydride)

279
 Exercises

1. Choose the most correct option. d. COOH

i. In the following resonating structures
A and B, the number of unshared
electrons in valence shell present on
oxygen respectively are OCH3
O O v. Diborane reduces
C C⊕ a. ester group b. nitro group

(A) (B) c. halo group d. acid group

a. 2, 4 b. 2, 6 vi. Benzaldehyde does NOT show positive
c. 4, 6 d. 6, 4 test with

ii. In the Wolf -Kishner reduction, alkyl a. Schiff reagent

aryl ketones are reduced to alkyl b. Tollens' ragent
benzenes. During this change, ketones c. Sodium bisulphite solution
are first converted into
d. Fehling solution
a. acids b. alcohols
2. Answer the following in one sentence
c. hydrazones d. alkenes
i. What are aromatic ketones?
iii. Aldol condensation is
ii. Is phenyl acetic acid an aromatic
a. electrophilic substitution reaction carboxylic acid ?
b. nucleophilic substitution reaction iii. Write reaction showing conversion of
c. elimination reaction ethanenitrile into ethanol.
d. addition - elimination reaction iv. Predict the product of the following
iv. Which one of the following has lowest reaction:
acidity ?
i. AlH (i-Bu)2
CH3 CH2 COOCH3 ?
a.
COOH ii. H3O⊕

v. Name the product obtained by reacting

toluene with carbon monoxide and
NO2 hydrogen chloride in presence of
anhydrous aluminium chloride.
b.
COOH vi. Write reaction showing conversion of
Benzonitrile into benzoic acid.
Cl vii.Name the product obtained
by the oxidation of
c.
COOH 1,2,3,4-tetrahydronaphthalene with
acidified potassium permanganate .
viii.What is formalin ?

280
 ix. Arrange the following compounds in the 4. Answer the following
increasing order of their boiling points : i. Write a note on –
Formaldehyde, ethane, methyl alcohol. a. Cannizaro reaction
x. Acetic acid is prepared from methyl b. Stephen reaction.
magnesium bromide and dry ice
in presence of dry ether. Name the ii. What is the action of the following
compound which serves not only reagent reagents on toluene ?
but also as cooling agent in the reaction. a. Alkaline KMnO4 , dil. HCl and heat
3. Answer in brief. b. CrO2Cl2 in CS2
i. Observe the following equation of c. Acetyl chloride in presence of
reaction of Tollens' reagent with anhydrous AlCl3.
aldehyde. How do we know that a redox
iii. Write the IUPAC names of the following
reaction has taken place. Explain.
structures :
∆
R CHO + 2 Ag(NH3)2+ + OH- a. O b. COOH
R COO- + 2 Ag + 4 NH3 + 2 H2O
COOH
ii. Formic acid is stronger than acetic acid.
Explain. iv. Write reaction showing conversion
iii. What is the action of hydrazine on of p- bromoisopropyl benzene into
cyclopentanone in presence of ---. p-Isopropyl benzoic acid ( 3 steps).
KOH in ethylene glycol ? v. Write reaction showing aldol
condensation of cyclohexanone.
iv. Write reaction showing conversion
of Acetaldehyde into acetaldehyde
dimethyl acetal. Activity :
v. Aldehydes are more reactive toward Draw and complete the
nucleophilic addition reactions than following reaction scheme which
ketones. Explain. starts with acetaldehyde. In each empty
vi. Write reaction showing the action of the box, write the structural formula of
following reagent on propanenitrile – the organic compound that would be
formed.
a. Dilute NaOH
HCN reduction
b. Dilute HCl ? CH3CHO
vi. Arrange the following carboxylic acids dilute H2SO4, heat Tollens' reagents
with increasing order of their acidic
strength and justify your answer.

COOH COOH Conc. H2SO4 heat

O Cold dilute KMnO4/H+

CH2 = CHCO2H

COOH

281