Aldehydes, Ketones and Carboxylic Acids

The general formulas of these classes of compounds

are given below:

STRUCTURE

COMMON
NAME

I U P AC N AM E

HCHO

Formaldehyde

Methanal

CH3CHO

Acetaldehyde

Ethanal

(CH3)2CHCHO

Isobutyraldehy
de

2Methypropanal

CH3CH(OCH3)CHO

-Methoxy
2propionaldehyd Methoxypropa
e
nal

CH2=CHCHO

Acrolein

Prop-2-enal

Phthaldehyde

Benzene-1,2dicarbaldehyde

m-Bromo
benzaldehyde

3Bromobenzene
carbaldehyde
or3Bromobenzald
ehyde

12.1.1 Nomenclature

by replacing the ending ic of acid with aldehyde.

CH3COCH2CH2CH3

the simplest dimethyl ketone is called acetone.

Alkyl phenyl ketones are usually named by adding the

Methyl n-propyl Pentan-2-one

ketone

(CH2)2C=CHCOCH3 Mesityl oxide

acyl group as prefix to phenone. For example

-Methyl
cyclohexanone

4-Methyl
pent-3-en-2-one
2-Methylcyclo
hexanone

Common and IUPAC Names of Some Aldehydes and

Ketones
(b) IUPAC names
When the aldehyde group is attached to a ring, the suffix
carbaldehyde is added after the full name of the
cycloalkane.

The numbering of the ring carbon atoms start from the

carbon atom attached to the aldehyde group.

The name of the simplest aromatic aldehyde carrying

the aldehyde group on a benzene ring is
benzenecarbaldehyde.

Other aromatic aldehydes are hence named as

substituted benzaldehydes
The carbon-oxygen double bond is polarised

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In Structure of the carbonyl carbon is an electrophilic

(Lewis acid), due to + charge and carbonyl oxygen, a
nucleophilic (Lewis base) centre.

Intext Questions
12.1 Write the structures of the following compounds.
(i) -Methoxypropionaldehyde (ii) 3-Hydroxybutanal

(ii) By hydration of alkynes:

(iii) 2-Hydroxycyclopentane carbaldehyde

(iv) 4-Oxopentanal (v) Di-sec. butyl ketone
(vi) 4-Fluoroacetophenone
12.2 Preparation of Aldehydes and Ketones
12.2.1 Preparation of Aldehydes and Ketones1. By
oxidation of alcohols

only for aldehydes

1. Rosenmund reduction.
From acyl chloride (acid chloride)

2. (i)From nitriles by Stephen reaction.

Alternatively, nitriles are selectively reduced by

diisobutylaluminium hydride, (DIBAL-H):

3 From esters. Reduction by By DIBAL-H.

Similarly, esters are also reduced to aldehydes with

4. From hydrocarbons
Aromatic aldehydes (benzaldehyde and its derivatives) (i)

3. From hydrocarbons

By oxidation of methylbenzene

(i) By ozonolysis oalkenes:

(a) Etard reaction. Use of chromyl chloride (CrO2Cl2):

Chromyl chloride oxidises methyl group to a chromium
complex, which on hydrolysis gives corresponding
benzaldehyde. This reaction is called Etard reaction.

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(vi) But-2-ene to ethanal

Solution
+

(i) C5H5NH CrO3Cl (PCC) (ii) K2Cr2O7 in acidic medium

(iii) CrO3 in the presence of acetic anhydride/ 1. CrO2Cl22.
(b) Use of chromic oxide (CrO3):

HOH,(iv) (Diisobutyl)aluminium hydride (DIBAL-H)

(v) PCC,(vi) O3/H2O-Zn dust
Intext Question
12.2 Write the structures of products of the following

(ii) By side chain chlorination followed by hydrolysis

reactions;

chlorination at benzylic of toluene gives benzal chloride,

which on hydrolysis gives benzaldehyde..

(iii) By Gatterman Koch reaction.

12.3 Physical properties
Methanal is a gas at room temperature. Ethanal is a
volatile liquid.
Boiling points:
Due to dipoledipole interactions in aldehydes and
ketones, they have higher boiling points than
hydrocarbons and ethers of comparable molecular
masses.
Due to the presence of intermolecular H-bonding in
alcohols, the boiling points of aldehydes and ketones
are higher than those of alcohols of comparable
molecular masses.
Solubility: The solubility of aldehydes and ketones in water
decreases with increase in the length of the alkyl chain.
The lower members of aldehydes and ketones such
as methanal, ethanal and propanone are miscible with
water in all proportions, because they form hydrogen
bond with water.

12.2.3 Preparation of Ketones

1. From acyl chlorides

2. From nitriles

Example 12.2
3. Friedel-Crafts acylation reaction.

Arrange the following compounds in the increasing order

of their boiling points:
CH3CH2CH2CHO, CH3CH2CH2CH2OH, H5C2-O-C2H5,
CH3CH2CH2CH2CH3
Solution

Example 12.1
Give names of the reagents to bring about the following

Hence increasing order of boiling points of the given

compounds is as follows:

transformations:
(i) Hexan-1-ol to hexanal (ii) Cyclohexanol to

CH3CH2CH2CH2CH3 < H5C2-O-C2H5 < CH3CH2CH2CHO <

CH3CH2CH2CH2OH

cyclohexanone
(iii) p-Fluorotoluene to p-fluorobenzaldehyde
(iv) Ethanenitrile to ethanol (v) Allyl alcohol to propenal

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Intext Question
12.3 Arrange the following compounds in increasing order

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of their boiling points.

CH3CHO, CH3CH2OH, CH3OCH3, CH3CH2CH3
12.4 Chemical Reactions
Since aldehydes and ketones both possess the carbonyl
functional group, they undergo similar chemical reactions.
Nucleophilic addition reactions

Contrary to electrophilic addition reactions observed in

alkenes

the aldehydes and ketones undergo nucleophilic

addition reactions.

Reason :-The positively charged carbon is readily

attacked nucleophiles.

The negatively charged oxygen is attacked by electron

deficient electrophiles.

During addition reaction nucleophilic attack followed by

Example 12.3
Would you expect benzaldehyde to be more reactive or
less reactive in nucleophilic addition reactions than
propanal? Explain your answer.
Solution
The carbon atom of the carbonyl group of benzaldehyde is
less electrophilic than carbon atom of the carbonyl group
present in propanal. The polarity of the carbonyl group is
reduced in benzaldehyde due to resonance as shown
below and hence it is less reactive than propanal.
(iii) Some important examples of nucleophilic addition
and nucleophilic addition-elimination reactions:
(a) Addition of hydrogen cyanide (HCN):

the electrophilic attack because the anion produced is

more stable than the cation.
(i) Mechanism of nucleophilic addition reactions

The net result is addition of Nu and H across the carbon

oxygen double bond as shown in

(b)Addition of sodium hydrogensulphite: .

The hydrogensulphite addition compound is water

soluble and can be converted back to the original
carbonyl compound

these are useful for separation and purification of

aldehydes.

(ii) Reactivity
Due to steric and electronic reasons, aldehydes are
more reactive than ketones towards nucleophilic
addition reactions.
Electronically, aldehydes are more reactive than
ketones because in ketones two alkyl groups reduce
the (+ve charge )electrophilicity of the carbonyl more
effectively than in aldehyde

(c) Addition of Grignard reagents:

Formaldehyde forma a primary alcohol,

Higher aldehydes give secondary alcohols and

Ketones give tertiary alcohols.

(d) Addition of alcohols:

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(ii) Reduction to hydrocarbons: The carbonyl group of

aldehydes and ketones is reduced to CH2 group on
treatment with zinc- amalgam and concentrated
hydrochloric acid [Clemmensen reduction] or with
hydrazine followed by heating with sodium or potassium
hydroxide in high boiling solvent such as ethylene glycol
(Wolff-Kishner reduction).

.(e) Addition of ammonia and its derivatives:

Nucleophiles, such as ammonia and its derivatives

H2N-Z add to the carbonyl group of aldehydes and
ketones.

3. Oxidation
with common oxidising agents like nitric acid, potassium

The equilibrium favours the product formation due to

rapid dehydration of the intermediate to form >C=N-Z.
Z = Alkyl, aryl, OH, NH2, C6H5NH, NHCONH2, etc.

REAGENT
NAME

CARBONYL
DERIVATIVE

-H

Ammonia

Imine

-R

Amine

imine(Schiffs base)

-OH

Hydroxylam
ine

Oxime

permanganate, potassium dichromate, etc. Even mild

oxidising agents, mainly Tollens reagent and Fehlings
reagent also oxidise aldehydes to carboxylic acids on

PRODUCT NAME

The mild oxidising agents given below are used to

-NH2

Hydrazine

Hydrazone

distinguish aldehydes from ketones:

(i) Tollens test: ammoniacal silver nitrate solution
(Tollens reagent), forms a bright silver mirror is produced

Phenylhydr
azine

Phenylhydrazone

2,4Dinitrophen
ylhydrazine

2,4-Dinitrophenyl
hydrazone

Semicarbaz
ide

due to the formation of silver metal.

(ii) Fehlings test: Fehling reagent comprises of two

solutions, Fehling solution A[copper sulphate] and Fehling

semicarbazone

solution B[ alkaline sodium potassium tartarate (Rochelle

Some N-Substituted Derivatives of Aldehydes and Ketones (>C=N-Z)

salt)].. On heating an aldehyde with Fehlings reagent, a

2. Reduction (i) Reduction to alcohols:

reddish brown precipitate is obtained. Aldehydes are

Reduction to alcohols Reagent LiAlH4, NaBH4 and

oxidised to corresponding carboxylate anion.

Aromatic aldehydes do not respond to this test.

(iii) Oxidation of methyl ketones by haloform

reaction:
Aldehydes and ketones having at least one methyl
group linked to the carbonyl carbon atom (methyl

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ketones) are oxidised by sodium hypohalite to sodium

known as Aldol reaction.

salts of corresponding carboxylic acids having one

carbon atom less than that of carbonyl compound.

The methyl group is converted to haloform.

This oxidation does not affect a carbon-carbon double

bond, if present in the molecule.

Iodoform reaction with sodium hypoiodite is also used

for detection of CH3CO group or CH3CH(OH) group
which produces CH3CO group on oxidation.
In this reaction new C-C bond is formed between C and
C=O carbon
(ii) Cross aldol condensation: When aldol condensation
is carried out between two different aldehydes and / or
ketones,

Example 12.4 An organic compound (A) with molecular

formula C8H8O forms an orange-red precipitate with 2,4DNP reagent and gives yellow precipitate on heating with
iodine in the presence of sodium hydroxide. It neither
reduces Tollens or Fehlings reagent, nor does it
decolourise bromine water or Baeyers reagent. On drastic
oxidation with chromic acid, it gives a carboxylic acid (B)
having molecular formula C7H6O2. Identify the compounds
(A) and (B) and explain the reactions involved.
Solution

5. Other reactions
(i) Cannizzaro reaction:

Aldehydes which do not have an -hydrogen atom,

undergo self oxidation and reduction
(disproportionation) reaction on treatment with
concentrated alkali.

4. Reactions due to a-hydrogen

In this reaction, one molecule of the aldehyde is

reduced to alcohol while another is oxidised to

The acidity of -hydrogen atoms of carbonyl

carboxylic acid salt.

compounds is due to the strong electron withdrawing

effect of the carbonyl group and resonance
stabilisation of the conjugate base.

(i) Aldol condensation: Aldehydes and ketones having at

least one -hydrogen undergo a reaction in the presence

(ii) Electrophilic substitution reaction: Aromatic

of dilute alkali as catalyst to form -hydroxy aldehydes

aldehydes and ketones undergo electrophilic substitution

(aldol) or -hydroxy ketones (ketol), respectively. This is

at the ring in which the carbonyl group acts as a

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deactivating and meta-directing group.

HOOC-CH2CHCOOH-CH2-COOH

Propane-1,2,3-tricarboxylic

Benzoic acid

Benzenecarboxylic acid(Ben

Phenylacetic
acid

2-Phenylethanoic acid

Phthalic acid

Benzene-1,2- dicarboxylic a

Intext Questions
12.4 Arrange the following compounds in increasing order
of their reactivity in nucleophilic addition reactions.
(i) Ethanal, Propanal, Propanone, Butanone.
(ii) Benzaldehyde, p-Tolualdehyde, p-Nitrobenzaldehyde,
Acetophenone.
Hint: Consider steric effect and electronic effect.

12.6.2 Structure of Carboxyl Group

12.5 Predict the products of the following reactions:

Intext Question
12.6 Give the IUPAC names of the following compounds:

12.5 Uses of Aldehydes and Ketones

12.7 Methods of Preparation of Carboxylic Acids

formalin (40%) Formaldehyde is well known as

1. From primary alcohols and aldehydes.

formalin (40%) solution used to preserve biological

specimens

. Carboxylic Acids12.6 Nomenclature and Struture

of Carbonyl Group

STRUCTURE

COMMON
NAME

IUPAC NAME

HCOOH

Formic acid

Methanoic acid

CH3COOH

Acetic acid

Ethanoic acid

CH3CH2COOH

Propionic acid

Propanoic acid

CH3CH2CH2COOH

Butyric acid

Butanoic acid

(CH3)2CHCOOH

Isobutyric acid

2- Methylpropanoic acid
3. From nitriles and amides

HOOC-COOH

Oxalic acid

Ethanedioic acid

HOOC-CH2-COOH

Malonic acid

propanedioic acid

HOOC-(CH2)2-COOH

Succinic acid

Butanedioic acid

HOOC-(CH2)3COOH

Glutamic acid

pentanedioic acid

HOOC-(CH2)4-COOH

Adipic acid

Hexanedioic acid

2. From alkylbenzenes

Nitriles are hydrolysed to amides and then to acids in the

+

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presence of H or OH as catalyst. Mild reaction conditions

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are used to stop the reaction at the amide stage.

(vi) Butanal to butanoic acid.

4. From Grignard reagents

Grignard reagents react with carbon dioxide (dry ice) to
form carboxylic acids

5. From acyl halides and anhydrides

6. From esters
Acidic hydrolysis of esters gives directly carboxylic acids
Intext Question
12.7 Show how each of the following compounds can be
converted to benzoic acid. (i) Ethylbenzene(ii)
Acetophenone (iii) Bromobenzene (iv) Phenylethene
(Styrene)
12.8 Physical Properties

Example 12.5

Carboxylic acids are higher boiling liquids than

Write chemical reactions to affect the following

aldehydes, ketones and even alcohols of comparable

transformations:

molecular masses. This is due to more extensive

(i) Butan-1-ol to butanoic acid

association of carboxylic acid molecules through

(ii) Benzyl alcohol to phenylethanoic acid

intermolecular hydrogen bonding.

(iii) 3-Nitrobromobenzene to 3-nitrobenzoic acid

The hydrogen bonds are not broken completely even

(iv) 4-Methylacetophenone to benzene-1,4-dicarboxylic

in the vapour phase. In fact, most carboxylic acids

acid

exist as dimer in the vapour phase aprotic solvent or in

(v) Cyclohexene to hexane-1,6-dioic acid

the aprotic solvents.

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12.9 Chemical Reactions

oxygen atom and less electronegative carbon atoms in

The reaction of carboxylic acids are classified as follows:

phenoxide ion (Unit 11, Class XII).

12.9.1 Reactions Involving Cleavage of OH Bond

Thus, the carboxylate ion is more stabilised than

Acidity

phenoxide ion, so carboxylic acids are more acidic

Reactions with metals and alkalies

than phenols.

Effect of substituents on the acidity of carboxylic acids:

Substituents may affect the stability of the conjugate
base and thus, also affect the acidity of the carboxylic
acids.

Carboxylic acids dissociate in water to give resonance

Electron withdrawing groups increase the acidity of

carboxylic acids by stabilising the conjugate base

stabilised carboxylate anions and hydronium ion.

through delocalisation of the negative charge by

For the above reaction:

inductive and/or resonance effects.

Conversely, electron donating groups decrease the

acidity by destabilising the conjugate base.

for the above reaction:

where Keq, is equilibrium constant and Ka is the acid

The effect of the following groups in increasing acidity

dissociation constant.

order is

For convenience, the strength of an acid is generally

Ph < I < Br < Cl < F < CN < NO2 < CF3

indicated by its pKa value rather than its Ka value.

Thus, the following acids are arranged in order of

pKa = log Ka.

increasing acidity (based on pKavalues):

Smaller the pKa, the stronger the acid ( the better it is

as a proton donor).

Carboxylic acids are weaker than mineral acids, but

they are stronger acids than alcohols and many simple
phenols (pKa is ~16 for ethanol and 10 for phenol).

The higher acidity of carboxylic acids as compared to

phenols can be understood similarly. The conjugate

Direct attachment of groups such as phenyl or vinyl to the

base of carboxylic acid, a carboxylate ion, is stabilised

carboxylic acid, increases the acidity of corresponding

by two equivalent resonance structures in which the

carboxylic acid, contrary to the decrease expected due to

negative charge is at the more electronegative oxygen

resonance effect shown below:

atom.

The conjugate base of phenol, a phenoxide ion, has

non-equivalent resonance structures in which the

negative charge is at the less electronegative carbon

This is because of greater electronegativity of sp

atom. Therefore, resonance in phenoxide ion is not as

hybridised carbon to which carboxyl carbon is attached.

important as it is in carboxylate ion.

The presence of electron withdrawing group on the

Further, the negative charge is delocalised over two

phenyl of aromatic carboxylic acid increases their

electronegative oxygen atoms in carboxylate ion

acidity while electron donating groups decrease their

whereas it is less effectively delocalised over one

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acidity.

12.9.2 Reactions Involving Cleavage of COH Bond

1. Formation of anhydride
Carboxylic acids on heating with mineral acids such as
H2SO4 or with P2O5 give corresponding anhydride.

12.9.3 Reactions Involving COOH Group

1. Reduction, By LIAlH4
Sodium borohydride does not reduce the carboxyl group.

2. Esterification
Carboxylic acids are esterified with alcohols or phenols in
the presence of a mineral acid such as concentrated
H2SO4 or HCl gas as a catalyst.

2. Decarboxylation

Mechanism of esterification of carboxylic acids:

3 Kolbe electrolysis
2RCOONa- R-R +2CO2+ H2+2NaOH

12.9.4 Substitution Reactions in the Hydrocarbon Part

1. Hell-Volhard-Zelinsky reaction. -Halogenation
Carboxylic acids having an -hydrogen are halogenated at
the -position

3. Reactions with PCl5, PCl3 and SOCl2

RCOOH + PCl5 RCOCl + POCl3 +HCl
3RCOOH + PCl3 3RCOCl + H3PO3

2. Ring substitution

RCOOH + SOCl2 RCOCl + SO2 +HCl

Aromatic carboxylic acids undergo electrophilic

4. Reaction with ammonia

substitution reactions in which the carboxyl group acts as a

Carboxylic acids react with ammonia to give ammonium

deactivating and meta-directing group.

salt which on further heating at high temperature give

amides. For example:

They however, do not undergo Friedel-Crafts reaction

(because the carboxyl group is deactivating and the
catalyst aluminium chloride (Lewis acid) gets bonded
to the carboxyl group).

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10

ans Fehlings solution

Problems
Formaldehyde
and
acetaldehyde
Pentane -3-one
and
pentane-2-one
Acetophenone
and
benzophenone
Phenol and
acetic acid
[carboxylic acid]

Iodoform
test[NaOH+I2]

Yellow ppt with

acetaldehyde

Iodoform
test[NaOH+I2]

Yellow ppt with

pentane-2-one

Iodoform
test[NaOH+I2] or
NaOI
Sodium
bicarbonate

Yellow ppt with

Acetophenone

Propanal
and Propanone

Tollens test or
Fehlings test

Silver mirror with

Propanal or red
ppt with FT
Violet colour with
phenol
Effervescence of
CO2 with acetic
acid
Silver mirror with
Benzaldehyde

Phenol and
Benzoic acid
Benzoic acid
and Ethyl
benzoate
Benzaldehyde
and
Acetophenone
Ethanal and
Propanal

Neutral FeCl3
Sodium
bicarbonate
Tollens test or
Fehlings test
Iodoform
test[NaOH+I2] or
NaOI

Effervescence of
CO2 with acetic
acid

6. Cannizaros reaction is not given by _____________

(iii) HCHO (iv) CH3CHO Ans iv

7. Which product is formed when the benzaldehyde is

treated with concentrated aqueous KOH solution?

Ans
8

ans (iv) Prop-1-en-2-ol, tautomerism

9. Compounds A and C in the following reaction are
__________.

Yellow ppt with

ethanol
ans positional isomers

1The correct ncreasin order of reactivity towards

10. In Clemmensen Reduction carbonyl compound is

nucleophilic addition reactions?

treated with _____________.Ans (i) Zinc amalgam + HCl

. Match the example given in Column I with the name of
the reaction in Column II.

Ans i>iii>ii>iv.
2Which is the most suitable reagent for the following
conversion?

(iii)iodoform test I2 and NaOH solution

3. The correct order of increasing acidic strength is
Phenol, Ethanol , Chloroacetic acid , Acetic acid
ans Ethanol < Phenol < Acetic acid < Chloroacetic acid

4. Compound

can be prepared by the

reaction of _____________.
Ans Phenol and benzoyl chloride in the presence of
5. The reagent which does not react with both, acetone
and benzaldehyde.(i) Sodium hydrogensulphite
(ii) Phenyl hydrazine iii) Fehlings solution (iv) Grignard
reagent

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11