Chapter–12

Aldehydes, Ketones
and Carboxylic Acids

1. The Carbonyl Group, C O : The functional group C O is called carbonyl group. Organic
compounds containing carbonyl group are aldehydes, ketones, carboxylic acids and their derivatives. The
general formulae of these compounds are given below:
O O O
R—C—H R—C—R ' R—C—OH
Aldehyde Ketone Carboxylic acid
(where R may be H or any alkyl, (where R and R' may be (where R may be H or any alkyl,
aryl or aralkyl group) same or different alkyl, aryl or aralkyl group)
aryl or aralkyl group)

Derivatives of Carboxylic Acids:

O O O O O
R—C—X R—C—O—C—R′ R—C—O—R′ R—C—NH2
Acyl halide Acid anhydride Ester Acid amide
X = Halogen (where R and R′ may be (where R and R′ may be (where R may be H
same or different groups) same or different groups) or any group)

The carbon atom of the carbonyl group is sp2 hybridised. The structure of carbonyl group is shown in
Fig. 12.1.
π

σ σ π σ
120°
σ
+ δ–
120° C σ O 120° C O 120° C O
120°
σ σ π σ

Fig. 12.1 Structure of Carbonyl Group ( C O)

+ –
The C O bond is polar due to higher electronegativity of oxygen atom as compared to carbon.

2. Common and IUPAC Names of Some Aldehydes and Ketones:

Table 12.1: Common and IUPAC Names of Some Aldehydes and Ketones
Common Name Structural Formula IUPAC Name
Formaldehyde HCHO Methanal
Acetaldehyde CH3—CHO Ethanal

Aldehydes, Ketones and Carboxylic Acids 465

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 a
CH3 —CH 2 —CH—CHO
a-Methylbutyraldehyde 2-Methylbutanal
|
CH3

CH3
|
Isobutyraldehyde 2-Methylpropanal
CH3 — CH —CHO
Valeraldehyde CH3—CH2— CH2 —CH2—CHO Pentanal
Acrolein CH2— CH—CHO Prop-2-enal
a
CH3 — CH—CHO
a-Methoxypropionaldehyde | 2-Methoxypropanal
OCH3

H3C CHO
g-Methylcyclohexane 3-Methylcyclohexanecarbaldehyde

CHO
Phthaldehyde Benzene-1, 2-dicarbaldehyde
CHO

CHO 3-Bromobenzenecarbaldehyde
m-Bromobenzaldehyde     or
Br 3-Bromobenzaldehyde

Crotonaldehyde CH3—CH—CH—CHO But-2-enal

CH CH CHO
Cinnamaldehyde 3-Phenyl prop-2-enal

Acetone CH3COCH3 Propanone

CH3 O CH3
Diisopropyl ketone | || | 2, 4-Dimethylpentan-3-one
CH3—CH—C—CH—CH3

CH3
Mesityl oxide | 4-Methylpent-3-en-2-one
CH3 — C == CH—COCH3

O
a-Methylcyclohexanone 2-Methylcyclohexanone
CH3

CHO
CHO O
—C—CH2—CH3
Cyclohexanecarbaldehyde NO2 1-Phenyl propanone
4-Nitrobenzenecarbaldehyde
or 4-Nitrobenzaldehyde
O O

CH3—CH2—C—CH2—CHO
CH3
3-Oxopentanal 3-Methylcyclopentanone

466 Xam idea Chemistry–XII

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 OHC—CH 2 —CH—CH 2 —CHO CH3 —C—CH 2 —C—CH3
| || ||
CHO O O
Propane - 1, 2, 3 - tricarbaldehyde Pen tan e - 2, 4 - dione

3. Preparation of Aldehydes
(a) By oxidation of primary alcohols
K2 Cr2 O 7 /H2 SO 4
R—CH2 —OH + [O] R—CHO + H2 O
or KMnO 4
1° Alcohol Aldehyde
(distilled out as soon
as formed)
2 2 PCC/CH Cl
R—CH2 —OH R—CHO
1° Alcohol Aldehyde
PCC/CH2 Cl2
CH3— CH == CH—CH2—OH CH3 —CH == CH—CHO
But-2-en-1-ol But-2-en-1-al

(b) By dehydrogenation of primary alcohols

Cu

R—CH 2 —OH R—CHO + H 2
573 K
1° Alcohol Aldehyde

(c) From hydrocarbons

(i) By ozonolysis of alkenes
O
H2O, Zn
R—CH—CH—R′ + O3 R—CH CHR′ R—CHO + R′—CHO
–ZnO
O O

(ii) By hydration of alkynes
RS V
H2 SO 4 /HgSO 4 SS OH WWW Rearrangement
CH // CH + H 2 O SS | W CH3 —CHO
Acetylene
333 K SSCH 2 == CH WWW Acetaldehyde
T Unstable X
(d) From acyl chloride
O O
|| ||
Pd - BaSO 4
R—C—Cl + H 2 _ Rosenmund reduction i
R—C—H + HCl
Aldehyde
O O
|| ||
Pd - BaSO 4
CH3 —C—Cl + H 2
CH3 —C—H + HCl
Acetyl chloride Acetaldehyde

(e) From nitriles and esters

SnCl 2 + 2HCl
SnCl 4 + 2 [H]
+H2 O
R—C // N + HCl + 2 [H]
R—CH == NH.HCl R—CHO
– NH 4 Cl Aldehyde
This reaction is called Stephen reaction
1. AlH (i - Bu) 2

R—CN R—CHO
2. H2 O
Aldehyde
1. AlH (i - Bu) 2
CH3 —CH == CH—CH 2 —CH 2 —CN
CH3 —CH == CH—CH 2 —CH 2 —CHO
2 2. H O
Hex-4-enenitrile Hex-4-en-1-al

O O
|| ||
1. DIBAL - H
—
CH3 (CH 2) 9 —C—O—CH 2 —CH3 CH3 (CH 2) 9 —C—H
2. H2 O
Ethyl undecanoate Undecanal

Aldehydes, Ketones and Carboxylic Acids 467

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 4. Preparation of Benzaldehyde
(a) By oxidation of toluene
OCr(OH)Cl2
CH3 HC CHO
OCr(OH)Cl2 +
CrO2Cl2 H3O
CS2

Toluene Chromium complex Benzaldehyde

This reaction is called Etard reaction.
OCOCH3
CH3 HC CHO
OCOCH3 +
CrO 3 H3O
O
+ 2CH3COOH
Toluene CH3—C Benzylidene Benzaldehyde
O diacetate
CH3—C

(b) By side chain chlorination followed by hydrolysis

CH3 CHCl2 CHO
+
+ Cl2 H 3O
hν 373 K

Toluene Benzal chloride Benzaldehyde

(c) By Gatterman–Koch reaction

CHO
CO, HCl
Anhyd. AlCl3/CuCl
Benzaldehyde

5. Preparation of Ketones
(a) By oxidation of secondary alcohols
R K2Cr2O7/H2SO4
R
CH—OH + [O] C—O + H2O
or CrO3
R′ R′
2°Alcohol Ketone

(b) By dehydrogenation of secondary alcohols

R R
Cu
CH—OH C—O + H2
573 K
R′ R′
2°Alcohol Ketone

(c) From hydrocarbons

(i) By ozonolysis of alkenes
O
R R R R R
H2O, Zn
C—C + O3 C C 2 C—O
–ZnO
R R R R R
O O Ketone

(ii) By hydration of alkynes
RS VW O
SS OH WW ||
H2 SO 4 /HgSO 4
CH3 —C // CH SS | W CH3 —C—CH3
Propyne
Markovnikov’s SSCH —C == CH WWW Acetone
addition 3 2
T Unstable X

468 Xam idea Chemistry–XII

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 (d) From acyl chlorides
2R—MgX + CdCl 2
R 2 Cd + 2MgXCl
O O
|| ||
2Rl —C—Cl + R2 Cd
2Rl —C—R + CdCl 2
Acyl chloride Dialkyl Ketone
Cadmium

(e) From nitriles

CH3—CH2—MgBr + CH3—C≡N CH3—C—NMgBr

Ethyl magnesium bromide Methyl cyanide CH2—CH3

+H3O+

O
NH2
CH3—C—CH2—CH3 + Mg
Ethyl methyl ketone Br

6. Preparation of Aromatic Ketones
(a) By Friedel-Crafts acylation
O
C R
O
Anhyd. AlCl3
+ R C Cl + HCl
   
O O
C Cl C
Anhyd. AlCl3
+ + HCl

    Benzyl chloride Benzophenone

(b) From nitriles
NMgBr
ether
CH3—CH2—C≡N + C6H5MgBr CH3—CH2—C—C6H5
Ethyl cyanide Phenyl
Magnesium bromide +H3O+

O
NH2
CH3—CH2—C—C6H5 + Mg
Propiophenone Br
  
7. Physical Properties of Aldehydes and Ketones
(a) Physical state: Most of the aldehydes (except formaldehyde which is a gas) are liquids at room
temperature. The lower ketones are colourless liquids and have a pleasant smell. The higher members
are colourless solids. Aromatic ketones are usually solids with a pleasant smell.
(b) Boiling points: Aldehydes and ketones have relatively high boiling points as compared to hydrocarbons
of comparable molecular masses. It is due to the reason that aldehydes and ketones contain polar
carbonyl group and therefore, they have stronger dipole–dipole interactions between the opposite ends
of C — O dipoles.
These dipole–dipole interactions are however, weaker than intermolecular H-bonding in alcohols.
Consequently, boiling points of aldehydes and ketones are relatively lower than the alcohols of
comparable molecular masses.

Aldehydes, Ketones and Carboxylic Acids 469

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 (c) Solubility: The lower members of aldehydes and ketones (up to four carbon atoms) are soluble in water. It
is due to their capability to form hydrogen bonds with water molecules. The solubility of these compounds
in water decreases with the increase in the size of alkyl group. It is because of the increase in the magnitude
of non-polar part in the molecule. However, higher homologues are soluble in organic solvents.
O R
R
C — O.....H H.....O — C
R R
8. Chemical Properties
Aldehydes and ketones are highly reactive compounds. Both aldehydes and ketones undergo nucleophilic
addition reactions.
Explanation: The reactive nature of aldehydes and ketones is because of the presence of a polar carbonyl
group. As the oxygen atom is more electronegative, therefore, it pulls the electron around itself acquiring a
partial negative charge (d– ) whereas a partial positive charge (d+ ) is developed on the carbon atom.
– + –
+
[ C O C O] C O
Resonating forms
The positively charged carbon atom of carbonyl group is then readily attacked by the nucleophilic species
for initiation of the reaction. This leads to the formation of an intermediate anion which further undergoes
the attack of (H+) ion or other positively charged species to form the final product. The nucleophilic
reactions may be catalysed by acids or bases. The reaction in general, may be represented as:
– Nu Nu
Nu
a +
H
+ – Slow Fast
C O C –
C
Step 1 a O Step 2 a OH
b b b
Planar Tetrahedral intermediate Addition product
Relative Reactivity of Aldehydes and Ketones
In general, ketones are less reactive than aldehydes on account of the following facts:
Aldehydes are generally more reactive than ketones in nucleophilic addition reactions due to steric and
electronic reasons. Sterically, the presence of two relatively large substituents in ketones hinders the approach
of nucleophile to carbonyl carbon than in aldehydes having only one such substituent. Electronically,
aldehydes are more reactive than ketones because two alkyl groups reduce the electrophilicity of the
carbonyl carbon more effectively than in former.
H R R
C—O > C—O > C—O
H H R
Formaldehyde Aldehyde Ketone
Some Important Nucleophilic Addition Reactions
(a) (i) Addition of hydrogen cyanide (HCN)
– –
HCN + OH CN + H2O
O– H+
OH
— O + CN –
C— C C
CN CN
Aldehyde Tetrahedral Cyanohydrin
or Ketone intermediate
OH
H3O+
—C—COOH
OH
α-Hydroxy acid
—C—CN
OH
Cyanohydrin LiAlH4
—C—CH2—NH2
β-amino alcohol

470 Xam idea Chemistry–XII
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 (ii) Addition of sodium hydrogensulphite (NaHSO3)
OSO2H OSO2Na
Proton
C—O + NaHSO3 C transfer
C
Aldehyde ONa OH
Bisulphite
or
addition compound
Ketone
(crystalline)
This reaction is useful for separation and purification of aldehydes and ketones.
(iii) Addition of Grignard reagent

H2O
C—O + R—MgX C—OMgX C—OH
Aldehyde R R
or Alcohol
Ketone
(iv) Addition of alcohols
R +R′—OH
R OH +R′—OH
R OR′
C—O HCl gas
C HCl gas
C + H2O
H H OR′ H OR′
Aldehyde Hemiacetal Acetal
Ketones do not react with monohydric alcohols but react with dihydric alcohols to give ketals.
R CH2—OH HCl gas
R O—CH2
C—O + | C | + H2O
dil. HCl
R CH2—OH R O—CH2
Ketone Ethylene glycol Ethylene glycol
ketal
(b) Addition of ammonia and its derivatives
OH
C—O + H2—N—Z C C—NZ + H2O
Aldehyde NHZ
or
Ketone
+NH3
(ammonia)
C—NH + H2O
Imine
+NH2—NH2
Hydrazine
C—N—NH2 + H2O
Hydrazone
C6H5NH—NH2
C—O (Phenylhydrazine) C—N—NHC6H5 + H2O
Aldehyde Phenylhydrazone
or O 2N O2N
Ketone NH2—HN— —NO2
C—N—NH— —NO2
(2, 4-Dinitrophenylhydrazine)
2, 4-Dinitrophenylhydrazone
+NH2—OH
(Hydroxylamine)
C—N—OH + H2O
Oxime
O O
H2N—HN—C—NH2
(Semicarbazide) C—N—NH—C—NH2
Semicarbazone
+R—NH2
C—N—R + H2O
(Amine)
Substituted imine
(Schiffs base)

Aldehydes, Ketones and Carboxylic Acids 471

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 (c) Reduction
(i) Reduction to alcohols: Aldehydes and ketones are reduced to primary and secondary alcohols,
respectively, by LiAlH4 or NaBH4 or H2 in the presence of Ni or Pt.
LiAlH 4
      R—CHO + 2 [H] R—CH 2 —OH
or NaBH 4
1° Alcohol

R Ni or Pt
R
C—O + H2 CH—OH
R Ketone R 2°Alcohol

(ii) Reduction to hydrocarbons
(Clemmensen reduction)
Zn-Hg/conc. HCl
C—O + 4[H] CH2 + H2O
Aldehyde
or Hydrocarbon
Ketone
O
C CH3 CH2 CH3
Zn-Hg
+ 4 [H] + H 2O
HCl (conc.)
Acetophenone Ethyl benzene

(Wolff–Kishner reduction)
+ NH2—NH2 KOH
C—O C— N—NH2 Ethylene glycol
CH2 + N2
– H2O
Aldehyde Hydrocarbon
or
Ketone
(d) Oxidation: Aldehydes are easily oxidised to carboxylic acids on treatment with common oxidising
agents or mild oxidising agent like Tollens’ reagent or Fehling’s solution.
K2Cr2O7/H2SO4
R—CHO + [O] or
R—COOH
Aldehyde KMnO4/H2SO4 Carboxylic acid

Ketones undergo oxidation under vigorous conditions with cleavage of carbon–carbon bond.
O
conc. HNO3
CH3—C—CH3 + 3[O] HCOOH + CH3—COOH
Methanoic Ethanoic acid
Acetone acid
C1—C2 bond
HCOOH + CH3—CH2—CH2COOH
O cleavage
Methanoic acid Butanoic acid
1 2 3 K2Cr2O7 (Carbonyl group stays (Minor products)
CH3—C—CH2—CH2—CH3 H2SO4 preferentially with the
smaller alkyl group)
Pentan-2-one C2—C3 bond
cleavage
CH3—COOH + CH3—CH2—COOH
Ethanoic acid Propanoic acid
(Major products)

As ketones are not oxidised by mild oxidising agents such as Tollens’ reagent and Fehling’s solution,
these reagents are used to distinguish aldehydes from ketones.
Electrophilic substitution reactions:
O O
   ||        ||
As, —C—H or —C—R group are electron-withdrawing and, therefore they are deactivating and
m-directing.

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 Nitration:
CHO CHO
conc. H2SO4
+ HNO3 (conc.) NO2 + H 2O

Benzaldehyde m-Nitrobenzene

O O
C CH3 C CH3
conc. H2SO4
+ HNO3 (conc.) NO2 + H 2O

  Acetophenone m-Nitroacetophenone

9. Uses of Aldehydes and Ketones

(i) A 40% aqueous solution of formaldehyde is known as formalin and is used to preserve biological
specimens and to prepare bakelite.
(ii) Acetaldehydes are used as a starting material in the manufacture of acetic acid, ethyl acetate,
vinyl acetate, polymers and drugs.
(iii) Benzaldehyde is used in perfumery and in dye industries.
(iv) Acetone and ethyl methyl ketone are common industrial solvents.
10. Carboxylic Acid
O
Organic compounds containing carboxyl group —C possess sufficient acidic character and are called
OH
carboxylic acids. The carboxyl group is made up of carbonyl, C O and hydroxyl, —OH group, hence,
its name is carboxyl group (carb from carbonyl and oxyl from hydroxyl). Carboxylic acids may be aliphatic
(R—COOH) or aromatic (Ar—COOH) depending upon whether —COOH group is attached to aliphatic
alkyl chain or aryl groups, respectively.
Aliphatic monocarboxylic acids are known as fatty acids because some of their higher members (C12—C18)
like palmitic acid (C15H31COOH) and stearic acid (C17H35COOH) exist in natural fats as esters of glycerol
and are obtained by their hydrolysis.
Structure of Carboxyl Group
In carboxylic acids, the bonds to the carboxyl carbon lie in one plane and are separated by about 120°. The
carboxylic carbon is less electrophilic than carbonyl carbon because of the possible resonance structure
shown below:

– –
O +
O O
—C —C —C +
O—H O—H O—H

11. In IUPAC system, the name of carboxylic acid is derived by replacing terminal e of the alkane with oic
acid. For example,

1
O COOH
3 2 1 4 3 2 1 2 3 4
CH3CH2COOH CH3 — C — CH2—COOH CH3—CH—CH2—COOH
Propanoic acid 3-Oxobutanoic acid 2-Methyl butane-1, 4-dioic acid

Aldehydes, Ketones and Carboxylic Acids 473

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 Table 12.2: Common and IUPAC Names of Some Carboxylic Acids
Common Name Structural Formula IUPAC Name
O
Formic acid || Methanoic acid
H—C—O—H
Acetic acid CH3—COOH Ethanoic acid

CH3
Isobutyric acid | 2-Methyl propanoic acid
CH3 —CH—COOH
Oxalic acid HOOC—COOH Ethanedioic acid
3 2 1
Malonic acid HOOC—CH2—COOH Propane-1, 3-dioic acid
Succinic acid HOOC—(CH2)2—COOH Butane-1, 4-dioic acid
Glutaric acid HOOC—(CH2)3—COOH Pentane-1, 5-dioic acid
Adipic acid HOOC—(CH2)4—COOH Hexane-1, 6-dioic acid
OH
Lactic acid | 2-Hydroxy propanoic acid
CH3 —CH—COOH
Acrylic acid CH2==CH—COOH Prop-2-enoic acid
Crotonic acid CH3—CH==CH—COOH But-2-enoic acid

COOH
Benzoic acid Benzene carboxylic acid(Benzoic acid)

CH2COOH
Phenyl acetic acid 2-Phenylethanoic acid

COOH
Phthalic acid COOH Benzene-1, 2-dicarboxylic acid

CH 2 —COOH
|
CH—COOH
|
CH 2 —COOH
Propane - 1, 2, 3 - tricarboxylic acid

12. Methods of Preparation of Carboxylic Acids

(a) By oxidation of primary alcohols and aldehydes.
(i) Alk. KMnO 4
R—CH 2 —OH +
R—COOH
1° Alcohol (ii) H3 O Carboxylic acid
K2 Cr2 O 7 /H2 SO 4

R—CHO + [O] or R—COOH
Aldehyde CrO3/H2SO4 Carboxylic acid
(Jones reagent)

(b) From alkyl cyanides and amides.
O O
+ – || + – ||
H or OH H or OH
R—C // N R—C—NH 2 R—C—O—H
H2 O D
    Alkyl cyanide Acid amide Carboxylic acid

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 O
+ – || + –
H or OH H or OH

CH3 —C // N CH3 —C—NH 2 CH3 —COOH
H2 O D
Acetonitrile Acetamide Acetic acid
–NH3

(c) From Grignard reagent
O O O
Dry ether H3O+
R—Mg—X + C—O R—C—OMgX R—C—OH
Carboxylic acid

O O
Dry ether H3O+
C—O + CH3—MgBr CH3—C—OMgBr CH3—COOH
Acetic acid

(d) By hydrolysis of acyl halides and acid anhydrides
H2O –
R—COOH + Cl
O
R—C—Cl
Acyl chloride O +
O
OH/H2O – H3O
R—C—O R—C—O—H
Carboxylic acid
H2 O

(C6 H5 CO) 2 O 2C6 H5 —COOH
   Benzoic anhydride Benzoic acid
O
CH3—C H2O
O C6H5—COOH + CH 3—COOH
H5C6—C Benzoic acid Ethanoic acid
O
Benzoic ethanoic anhydride
(e) By hydrolysis of esters
NaOH
CH3—CH2—CH2—COOCH2—CH3
Ethyl butyrate – +
CH3—CH2—CH2—COONa + CH3—CH2—OH
H3O+

CH3—CH2—CH2—COOH
Butanoic acid

Preparation of benzoic acid

(i) From alkyl benzene
CH3 COO– K+ CH2 CH2 CH3
KMnO4–KOH KMnO4–KOH

Toluene 1-Phenyl propane

H3O+

COOH

Benzoic acid

Aldehydes, Ketones and Carboxylic Acids 475

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 (ii) From nitriles and amides
C N CONH2 COOH
+ +
H2O/H H2O/H

Phenyl cyanide Benzamide Benzoic acid

(iii) By hydrolysis of esters

COOCH2 CH3 COOH
H3 O+ + C2H5OH
Ethanol

Ethyl benzoate Benzoic acid

(iv) From Grignard reagent

O O
H3O+
C—O + C6H5MgBr C6H5—C—OMgBr C6H5—COOH
Benzoic acid

13. Physical Properties of Carboxylic Acids
(a) Physical state: The first three aliphatic acids are colourless liquids with pungent smell. The next six
are oily liquids with an odour of rancid butter while the higher members are colourless, odourless,
waxy solids. Benzoic acid is a crystalline solid.
(b) Solubility: Carboxylic acid molecules are polar, like alcohols, and can form intermolecular hydrogen
bonds. The first four acids are miscible with water, the C5H11COOH is partly soluble and the higher
acids are insoluble. It is because of the increase in the magnitude of non-polar part in the molecule.
Benzoic acid is practically insoluble in water.
Carboxylic acids are soluble in less polar solvents like ether, benzene, alcohol, etc.
(c) Boiling points: Because of their ability to form intermolecular hydrogen bonding, carboxylic acids
have high boiling points. The hydrogen bonds formed by the carboxylic acids are stronger than those
in alcohols because O—H bond in COOH is strongly polarised due to the presence of electron-
withdrawing carbonyl group in adjacent position than the O—H bond of alcohols. Therefore, the
boiling points of carboxylic acids particularly lower members are higher than alcohols of comparable
molecular masses.
O...H—O
R—C C—R
O—H ...O

Intermolecular hydrogen bonding in carboxylic acids
14. Chemical Properties of Carboxylic Acids
Carboxylic acids are resonance hybrid of the following structures:
–
O O O
R—C R—C + == R—C
O—H O—H O—H
I II Carboxylic acid

From these structures, it is clear that the carbonyl parts of the carboxyl group have a reduced double
bond character. Thus, it does not give the reactions of the carbonyl group. Also it is evident that the two
contributing structures of carboxylic acid are not equivalent, therefore, they are less resonance stabilized.
Moreover, oxygen atom of —OH group has positive charge in structure II, this indicates its electron
deficient nature. Hence, the shared pair of electrons of O—H bond will be strongly pulled towards oxygen
and this makes the O—H bond quite polar. Thus, the reactions of carboxylic acids are characteristic of the
carboxyl group and alkyl group.

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 Acidic Nature
Carboxylic acids are quite strong acids because of the presence of polar O—H group. They ionise to give
hydrogen ions and hence behave as acids.

O O
– +
R—C—O—H R—C—O + H
Carboxylic acid Carboxylate ion

Carboxylic acids behave as fairly strong acids: This can be explained as follows:
Carboxylic acids as well as carboxylate ion both are stabilised by resonance. However, carboxylate ion is
more stabilised by resonance because its contributing structures are exactly identical. On the other hand,
the contributing structures of carboxylic acid involve charge separation. Since carboxylate ion is more
stabilised by resonance than carboxylic acid, therefore, equilibrium lies very much in forward direction,
i.e., in favour of ionised form. Hence, carboxylic acids behave as fairly strong acids.

O O O
+
R—C—OH R—C—OH R—C—O—H
Carboxylic acid
Less stabilised

–
O O O
R—C—O R—C—O R—C—O
Carboxylate ion
More stabilised

Acidity of carboxylic acids: Both carboxylic acid and carboxylate ion are resonance stabilised but
stabilisation is far greater for the carboxylate ion than for the acid. Thus, carboxylic acids get ionised due
to gain in the stability in going from carboxylic acid to the more stable carboxylate ion. Any factor that
stabilises the carboxylate ion more would facilitate the release of protons and increase the acidity. Thus,
electron-withdrawing substituents (Cl, NO2, CN, etc.) in a carboxylic acid would disperse the negative
charge of the COO–, stabilise it and thus enhance the acid strength. On the other hand, the presence of an
electron-donating substituent such as alkyl group, would intensify the negative charge on the COO– ion and
thus destabilise it, making the carboxylic acid less acidic.
The effect of some substituents is as follows:
(i) Effect of electron withdrawing substituents: The electron withdrawing substituents decrease the
electron density on the O—H bond thus facilitating the release of H+ ions and also stabilise the
carboxylate anion by dispersal of negative charge. Thus, an electron-withdrawing group increases the
strength of the acid.
(ii) Effect of electron releasing substituents—alkyl groups: The presence of electron releasing substituent
intensifies the electron density in O—H bond. As a result, it adversely affects the release of H+ ions
and thus decreases the acidic character.
(iii) Acidity decreases with larger alkyl groups as the +I effect of the alkyl group increases with size of
alkyl group. For example, Formic acid > Acetic acid > Propanoic acid.
(iv) Acidity increases with increasing number of electron-withdrawing substituents on the a-carbon. For
example, Acetic acid < Chloroacetic acid < Dichloroacetic acid (Cl2CH—COOH) < Trichloroacetic
acid (Cl3C—COOH).
(v) Acidity increases with increasing electronegativity of substituents. Thus,
Iodoacetic acid (ICH2—COOH) < Bromoacetic acid (BrCH2—COOH) < Chloroacetic acid
(ClCH2—COOH) < Fluoroacetic acid (FCH2—COOH).

Aldehydes, Ketones and Carboxylic Acids 477

13
 (vi) Acidity declines with increasing distance between electron-withdrawing group and COOH group. For
example, 2-Chlorobutanoic acid > 3-Chlorobutanoic acid > 4-Chlorobutanoic acid.
(vii) Unsubstituted aromatic carboxylic acids are stronger acids than unsubstituted aliphatic carboxylic
acids. Benzoic acid is a stronger acid than acetic acid. Further, since formic acid does not contain any
alkyl group, therefore, it is a stronger acid than benzoic acid. Thus,
Formic acid > Benzoic acid > Acetic acid
Effect of substituents on the acidic strength of benzoic acid.
(i) The electron-releasing groups such as, —CH3, —OH, —NH2, etc., tend to decrease the acid strength
of benzoic acid. The electron-withdrawing groups such as —Cl, —NO2, etc., tend to increase the
strength of benzoic acid.
(ii) Ortho isomer of benzoic acid is the strongest of all the isomers irrespective of the nature of the substituent.
This is called ortho effect. This effect may be due to a combination of steric and electronic factors.
(iii) The acid-strengthening effect of electron-withdrawing group (e.g., —Cl, —NO2, etc.) is more
pronounced at p-position than at m-position.
(iv) The acid-weakening effect of an electron-releasing substituent (e.g., —OH, —CH3, —NH2, etc.) is
more pronounced at p-position than at m-position.
15. Chemical Reactions
The reaction of carboxylic acids are classified as follows:
(a) Reactions involving cleavage of O—H bond: Reaction with metals and alkalis.
– +
2R—COOH + 2Na 2R—COONa + H 2
Sodium carboxylate
– +
R—COOH + NaOH R—COONa + H 2 O
– +
R—COOH + NaHCO3 R—COONa + H 2 O + CO 2 -

(b) Reactions involving cleavage of C—OH bond

(i) Formation of anhydride
O
O
H+,
R—C
2R—C—OH O + H2O
or P2O5,
R—C
O
Acid anhydride

O
O
H+,
CH3—C
2CH3—C—OH O + H2O
or P2O5,
Acetic acid CH3—C
O
Acetic anhydride

(ii) Esterification:
+
H
R—COOH + Rl —OH R—COORl + H 2 O
+
H
CH3 —COOH + CH3 —CH 2 —OH CH3 —COOCH 2 —CH3 + H2 O
Acetic acid Ethyl acetate

478 Xam idea Chemistry–XII

14
 (iii) Reactions with PCl5, PCl3 and SOCl2
R—COOH + PCl5 RCOCl + POCl3 + HCl
Acyl chloride

3R—COOH + PCl3 3RCOCl + H3 PO3

R—COOH + SOCl RCOCl + SO 2 + HCl
2

(iv) Reaction with ammonia:

+ D
R—COOH + NH3 R—COO – NH 4 R—CONH 2
–H2 O
Acid amide

COOH COONH+4 CONH2

+ NH3 + H2O
Benzoic acid Benzamide

– +
COOH COONH4
+ NH3 –+
COOH COONH4
Pthalic acid
O –H2O

C Strong heating CONH2

NH
C –NH 3 CONH2

O
Phthalimide

(c) Reaction involving —COOH group

(i) Reduction:
(i) LiAlH 4 /ether or B2 H6
R—COOH +
R—CH 2 —OH
(ii) H3 O 1° Alcohol

(ii) Decarboxylation:
– + NaOH and CaO
R—COONa R—H + Na 2 CO3
D
Sodium carboxylate

– +
COONa
NaOH and CaO
+ Na2CO3
∆

Sodium benzoate Benzene

(iii) Halogenation:
(Hell-Volhard Zelinsky reaction)

X
(i) X2/Red P
R—CH2—COOH R—CH—COOH (X = Cl, Br)
(ii) H2O
α-Halocarboxylic acid

(d) Ring substitution reaction: Aromatic carboxylic acids undergo electrophilic substitution reactions in
which —COOH group acts as a deactivating and meta-directing group. They however do not undergo
Friedel–Crafts reaction because the carboxyl group is deactivating and the catalyst AlCl3 (Lewis acid)
gets bonded to the carboxyl group.

Aldehydes, Ketones and Carboxylic Acids 479

15
 COOH
conc. HNO3/conc. H2SO4
(Nitration) NO2
m-Nitrobenzoic acid

COOH COOH
Br2/FeBr3
(Bromination) Br
Benzoic acid m-Bromobenzoic acid

COOH
conc. H2SO4
(Sulphonation) SO3H
m-Sulphobenzoic acid

16. Uses of Carboxylic acids:

(i) Formic acid is used in rubber, textile, dyeing, leather and electroplating industry.
(ii) Acetic acid is used as solvent and as vinegar in food industry.
(iii) Adipic acid is used in the manufacture of nylon-6, 6.
(iv) Sodium benzoate is used as preservative.
(v) Higher fatty acids are used for the manufacture of soaps and detergents.
(vi) Esters of benzoic acid are used in perfumery.
17. Some Important Name Reactions
(a) Rosenmund Reduction:
Acid chloride are converted to corresponding aldehydes by catalytic reduction. The reaction is carried
out by passing H2 gas through a hot solution of acid chloride in the presence of Pd deposited over
BaSO4 (partially poisoned with sulphur or quinoline).
O O
|| ||
Pd/BaSO 4
R—C—Cl + H 2 R—C—H + HCl
Acyl chloride Aldehyde
O O
|| ||
Pd/BaSO 4
CH3 —C—Cl + H 2 CH3 —C—H + HCl
Acetyl chloride Acetaldehyde

O O
C Cl C H
Pd/BaSO4
+ H2 + HCl
Benzoyl chloride Benzaldehyde

(b) Stephen reaction: Nitriles are reduced to corresponding imines with SnCl2 in the presence of
hydrochloric acid, which on hydrolysis give corresponding aldehyde.
      SnCl 2 + 2HCl SnCl 4 + 2 [H]
H2 O (boil)
CH3 —C // N + 2 [H] + HCl
CH3 —CH == NH.HCl CH3 —CHO + NH 4 Cl
Ethanenitrile Acetaldoxime hydrochloride Acetaldehyde

C N CH—NH.HCl CHO
H 2 O (boil)
+ 2[H] + HCl + HCl
Phenyl cyanide Benzaldoxime Benzaldehyde
hydrochloride

480 Xam idea Chemistry–XII

16
 (c) Etard reaction: Chromyl chloride oxidises toluene to chromium complex which on hydrolysis gives
benzaldehyde.
OCr(OH)Cl2
CH3 HC CHO
OCr(OH)Cl2
CS2 H3O+
+ CrO2Cl2
Toluene Benzaldehyde

(d) Gatterman–Koch reaction: When benzene or its derivative is treated with carbon monoxide and
hydrogen chloride in the presence of anhydrous AlCl3 and CuCl, it gives benzaldehyde or substituted
benzaldehyde.
CHO
CO, HCl
anhyd. AlCl3/CuCl
Benzene Benzaldehyde

(e) Friedel–Crafts reactions:

Friedel–Crafts alkylation: Benzene and other aromatic compounds react with alkyl halides in the
presence of anhydrous AlCl3 to form alkyl benzenes.
CH3
anhyd. AlCl3
+ CH3 Cl + HCl
Benzene Toluene

CH3 CH3 CH3

anhyd. AlCl3 CH3
+ CH3 Cl +

Toluene o-Xylene
(Minor) CH3
p-Xylene
(Major)

Friedel–Crafts acylation: Benzene and other aromatic compounds react with acylchlorides or acid
anhydrides in the presence of anhyd. AlCl3 to form aromatic ketone.
COCH3
anhyd. AlCl3
+ CH3 CO Cl + HCl
Benzene
Acetyl chloride Acetophenone

O
C
COCl anhyd. AlCl3
+ + HCl

Benzoyl chloride Diphenyl ketone

O COCH3
CH3 C anhyd. AlCl3
+ + CH3—COOH
CH3 C O
O Acetophenone
Acetic anhydride

Aldehydes, Ketones and Carboxylic Acids 481

17
 (f) Clemmensen reduction: The carbonyl group of aldehydes and ketones is reduced to CH2 group on
treatment with zinc amalgam and concentrated hydrochloric acid.
Zn-Hg
C—O + 4[H] CH2 + H2O
HCl (conc.)

Zn-Hg
CH3—CH2—CH2—CHO + [H] CH3—CH2—CH2—CH3 + H2O
HCl (conc.)
Butyraldehyde n-Butane

COCH3 CH2 CH3

Zn-Hg
+ 4[H] + H2O
HCl (conc.)

Acetophenone Ethyl benzene

(g) Wolff–Kishner reduction: The carbonyl group of aldehydes and ketones is reduced to —CH2 group
on treatment with hydrazine followed by heating with potassium or sodium hydroxide in a high boiling
solvent such as ethylene glycol.
+ NH2—NH2 KOH
C—O C— N—NH2 Ethylene glycol,
CH2 + N2
– H2O
Hydrazone
CH3 CH3
+ NH2—NH2 KOH
C—O C— NNH2 CH3—CH2—CH3 + N2
Ethylene glycol,
– H2O
CH3 CH3 Propane
Acetone
(h) Aldol condensation: Two molecules of aldehydes or ketones containing at least one a-hydrogen
atom on treatment with dilute alkali undergo condensation to form b-hydroxy aldehydes (aldol) or
b-hydroxy ketones (Ketol).
O OH
dil. NaOH
CH3—C—H + H—CH2—CHO CH3—CH—CH2—CHO
Ethanal 3-Hydroxy butanal
(aldol)

–H2O
CH3—CH—CH—CHO
But-2-enal

O O OH O
Ba(OH)2
CH3—C + H—CH2—C—CH3 CH3—C—CH2—C—CH3
Acetone
CH3 CH3
4-Hydroxy-4-methyl
-pentan-2-one
(Ketol)
O

–H2O
CH3—C—CH—C—CH3
CH3
4-Methyl pent-3-en-2-one

(i) Cross aldol condensation: When aldol condensation is carried out between two different aldehydes
and/or ketones, it is called cross aldol condensation.
O O O OH O
dil NaOH
H—C—H + H—CH2—C—H HO—CH2—CH2—C—H + CH3—CH—CH2—C—H
Formaldehyde Acetaldehyde (Cross aldol product) (Simple aldol product)

482 Xam idea Chemistry–XII

18
 O OH O
C H CH CH2 C H CH CH CHO
O
NaOH
+H CH2 C H – H2O
Benzaldehyde Ethanal Cinnamaldehyde

O O
alc. NaOH
CHO + CH 3 C CH—CH C + H 2O
293 K
Benzaldehyde Acetophenone Benzalacetophenone
(1, 3-Diphenyl prop-2-en-1-one)
(Major product)

j) Cannizzaro reaction: Aldehydes which do not have an a-hydrogen, undergo self oxidation and
( 
reduction (disproportionation) reaction on treatment with concentrated alkali. In this reaction, one
molecule of the aldehyde is reduced to alcohol while another is oxidised to carboxylic acid salt.
conc. KOH +

2HCHO CH3 —OH + HCOO – K
Formaldehyde Methyl alcohol Potassium formate

–+
CHO CH2 OH COO Na
conc. NaOH
2 +
Benzaldehyde
Benzyl alcohol Sodium benzoate

CH3 CH3 CH3

| | | – +
NaOH (50%)

2CH3 — C—CHO CH3 — C—CH 2 —OH + CH3 — C—COONa
| | |
CH3 CH3 CH3
2,2-Dimethylpropanal 2, 2 - Dimethylpropanol Sodium 2, 2 - dim ethylpropanoate

(k) Hell-Volhard-Zelinsky reaction: Carboxylic acids having an a-hydrogen are halogenated at the
a-position on treatment with chlorine, or bromine in the presence of red phosphorus to give a-halo-
carboxylic acids.
(i) X2 /Red P a
R—CH 2 —COOH R—CH—COOH (X = Cl, Br)
(ii) H2 O
|
X
a - Halocarboxylic acid
(i) Cl2 /Red P a
CH3 —CH2 —COOH CH3 —CH—COOH
(ii) H2 O
|
Propanoic acid Cl
2 - Chloropropanoic acid

18. Chemical Tests for Aldehydes and Ketones

(a) Test for carbonyl group (2, 4-Dinitrophenyl hydrazine test): Both aldehydes and ketones contain
carbonyl group. Hence, they react with 2, 4-dinitrophenyl hydrazine to form yellow, or orange
precipitate of 2, 4-dinitrophenyl hydrazone.

O2 N O2N
C—O + H2NNH NO2 C—NNH NO2
2, 4-Dinitrophenylhydrazine 2, 4-DNP-derivative
   (Yellow, orange ppt.)

Aldehydes, Ketones and Carboxylic Acids 483

19
 (b) (i) Tollens’ test: When aldehydes are heated with Tollens’ reagent (ammoniacal silver nitrate
solution), they form silver mirror on the inner side of the test tube. Ketones do not respond to this
test.
+
R—CHO + 2 [Ag (NH3) 2] + 3OH – R—COO – + 2Ag . + 2H 2 O + 4NH3
Tollens’ reagent (Silver mirror)

(ii) Fehling’s test: Aliphatic aldehydes when warmed with a few drops of Fehling’s solution give a

reddish brown precipitate of cuprous oxide. Ketones do not respond to this test.
+
R—CHO + 2Cu 2 + 5OH – R—COO – + Cu 2 O . + 3H 2 O
Fehling solution Red brown ppt.

(iii) Iodoform test: Acetaldehyde, acetone or any ketone having at least one —CH3 group when
heated with alkaline solution of iodine form yellow coloured precipitate of iodoform.

2NaOH + I 2 NaOI + NaI + H 2 O

+3NaOI +
NaOH
R—COCH3 R—COCI3 R—COO – Na + CHI3 .
–NaOH
Iodoform
(Yellow ppt.)

(c) Tests for Carboxylic Acids
(i) Litmus test: Aqueous solutions of carboxylic acids turn blue litmus red. Phenols also give this
test. Alcohols do not respond to this test.
(ii) Sodium bicarbonate test: When carboxylic acid is added to an aqueous solution of sodium
bicarbonate, brisk effervescence of CO2 is evolved.
   RCOOH + NaHCO3 RCOONa + H2 O + CO2 -
Carboxylic acid Sodium

carboxylate
Phenols and alcohols do not give this test.
(iii) Ester formation test: On warming carboxylic acids with an alcohol (e.g., ethanol) in presence of
a small amount of sulphuric acid, a fruity smell of ester is obtained.
H2 SO 4
   RCOOH + Rl OH RCOORl + H 2 O
Carboxylic acid Alcohol Ester
(Fruity smell)

(iv) Distinction between formic acid and acetic acid.

Tollens’ reagent test: Formic acid reduces Tollens’ reagent to metallic silver but acetic acid does
not.
+
   HCOOH + 2 [Ag (NH3) 2] + 2OH – 2Ag . + CO 2 - + 2H 2 O + 4NH3
Formic acid (Silver
mirror)

HgCl2 test: Formic acid reduces HgCl2 to give white ppt. of Hg2Cl2 while acetic acid does not
give this test.
   HCOOH + 2HgCl 2 Hg 2 Cl 2 . + 2HCl + CO 2 -
Formic acid Mercuric Mercurous
chloride chloride
   (white ppt.)

484 Xam idea Chemistry–XII

20
NCERT Textbook Questions

NCERT Intext Questions

Q. 1. Write the structures of the following compounds:
(i) a-Methoxypropionaldehyde (ii) 3-Hydroxybutanal
(iii) 2-Hydroxycyclopentane carbaldehyde
(iv) 4-oxopentanal (v) Di-sec. butyl ketone
(vi) 4-Fluoroacetophenone
CH3 O O OH O
| || | ||
Ans. (i) H3 C—CH—C—H (ii) H3 C—CH—CH 2 —C—H
O
||
(iii) CHO (iv) CH3 —C—CH 2 —CH 2 —CHO

OH
CH3 O CH3 O
| || |
(v) CH3 CH 2 CH—C—CH—CH2 CH3 (vi) F C CH3

Q. 2. Write the structures of products of the following reactions:

O
anhyd. AlCl3
(i) + C
CS2
C2H5 Cl

(ii) (C 6 H 5 CH 2) 2 Cd + 2CH 3 COCl

CH3
2+
Hg , H 2 SO 4 1. CrO2Cl2
(iii) H 3 C—C / C—H   (iv)
2. H3O+

NO2
O

O C—C2H5
anhyd. AlCl 3
+ C + HCl
Ans. (i) CS 2
C 2H 5 Cl
Benzene Propanoyl chloride Propiophenone
O
O
CH2—C—CH3
Dry
(ii) (C6H5CH2)2Cd + 2CH3—C—Cl ether 2 + CdCl2
Dibenzyl cadmium Acetyl chloride
1-Phenylpropan-2-one

SRS OH WWW
V
O
SS | W ||
Hg2 ,
+ SS W Tautomerises
(iii) H3 C—C / C—H
dil. H2 SO 4
SSCH3 —C == CH 2 WWW CH3 —C—CH3
 Propyne SS WW Propanone
SS WW
T X
2CrO2Cl2 OCrCl2OH H3O
+
(iv) O2N CH3 O2N CH O2N CHO
CS2 OCrCl2OH
(Etard reaction)
p-Nitrotoluene p-Nitrobenzaldehyde

Aldehydes, Ketones and Carboxylic Acids 485

21
 Q. 3. Arrange the following compounds in increasing order of their boiling points.
CH3CHO, CH3CH2OH, CH3OCH3, CH3CH2CH3
Ans. CH3CH2CH3 < CH3OCH3 < CH3CHO< CH3CH2OH
Q. 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
Ans. (i) The reactivity in nucleophilic addition reactions increases in the order:
Butanone < Propanone < Propanal < Ethanal
(ii) Acetophenone is a ketone. All the other three compounds are aldehydes. Hence, acetophenone is least
reactive.
p-Tolualdehyde has an electron-donating methyl group at the para position of the benzene ring
whereas p-nitrobenzaldehyde has an electron-withdrawing nitro group at the para position. Thus,
p-tolualdehyde is less reactive and p-nitrobenzaldehyde is more reactive than benzaldehyde.
Therefore, the required order is as follows:
Acetophenone < p-Tolualdehyde < Benzaldehyde < p-Nitrobenzaldehyde
Q. 5. Predict the products of the following reactions:
O +
H
(i) + HO—NH2
O 2N
O
(ii) + NH2 NH NO2
O
|| +
H
(iii) R—CH == CH—CHO + NH 2 — C —NH—NH 2
O
C +
(iv) CH3 + CH CH NH H
3 2 2

O2N
N OH NNH NO2
Ans. (i) (ii)

O
||
(iii) R—CH == CH—CH == N—NH—C—NH 2
H3C
C N CH2CH3
(iv)

Q. 6. Give the IUPAC names of the following compounds:

(i) PhCH2CH2COOH (ii) (CH3)2C==CHCOOH
CH3 NO2

COOH (iv) COOH

(iii)
O2N NO2
Ans. (i) 3-Phenylpropanoic acid
(ii) 3-Methylbut-2-enoic acid
(iii) 2-Methylcyclopentanecarboxylic acid
(iv) 2, 4, 6-Trinitrobenzoic acid.

486 Xam idea Chemistry–XII

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 Q. 7. Show how each of the following compounds can be converted to benzoic acid:
(i) Ethylbenzene (ii) Acetophenone
(iii) Bromobenzene (iv) Phenylethene (Styrene)
CH2CH3 COOK COOH
KMnO4– KOH H3O +
Ans. (i) Heat

Ethylbenzene Benzoic acid

COCH3 COOK COOH
+
KMnO4/KOH H 3O
(ii)
Heat
Acetophenone Benzoic acid
O
COOH
Br Mg
MgBr C HOH
O—C—O OMgBr
(iii) Dry ether

Bromobenzene Phenylmagnesium Benzoic acid

bromide

COOH
CH—CH2 COOK
KMnO4 / KOH H3O+
(iv) + HCOOK + HCOOH
Methanoic
Phenylethene Benzoic acid acid

Q. 8. Which acid of each pair shown here would you expect to be stronger?
(i) CH3CO2H or CH2FCO2H (ii) CH2FCO2H or CH2ClCO2H
(iii) CH2FCH2CH2CO2H or CH3—CHF—CH2CO2H

(iv) F3C COOH or H3C COOH

O O
O O
Ans. (i) CH3 — C — O — H F — CH2 — C — O — H CH3 — C – F — CH2 — C –
The release of a proton is difficult The release of a proton is easier O O
because +I-effect of CH3 group because –I-effect of F decreases By intensifying the negative By dispersing the negative
increases the electron density in the electron density in the charge , +I-effect destabilises charge, –I-effect stabilises
the O—H bond. O—H bond. the carboxylate ion. the carboxylate ion.

Therefore, due to lesser electron density in the O—H bond and greater stability of FCH2COO– ion
over CH3COO– ion, FCH2COOH is a stronger acid than CH3COOH.
(ii) The FCH2COO– ion is much more stable than ClCH2COO– ion due to much stronger –I effect of
F than Cl and thus FCH2COOH is a stronger acid than ClCH2COOH.
O CH3 O
(iii) F — CH2 — CH2 — CH2 — C — O — H F — CH — CH2 — C — O — H
4-Fluorobutanoic acid 3-Fluorobutanoic acid

Inductive effect decreases with distance, therefore, –I effect of F is somewhat stronger in

3-fluorobutanoic acid than in 4-fluorobutanoic acid. Hence, CH3CHFCH2COOH is a stronger acid
than FCH2CH2CH2COOH.
O O
(iv) F3C C – CH3 C –
O O
CF3 has a strong –I-effect, CH3 has a weak +I-effect,
it stabilises the carboxylate it destabilises the carboxylate
ion by dispersing the –ve charge ion by intensifying the –ve charge

Hence, due to greater stability of F3C—C6H4—COO– (p) ion than CH3—C6H4COO– (p) ion,
F3C—C6H4—COOH (p) is a much stronger acid than CH3—C6H4—COOH (p).

Aldehydes, Ketones and Carboxylic Acids 487

23
NCERT Textbook Exercises
Q. 1. What is meant by the following terms? Give an example of the reaction in each case.
(i) Cyanohydrin (ii) Acetal (iii) Semicarbazone
(iv) Aldol (v) Hemiacetal (vi) Oxime
(vii) Ketal (viii) Imine (ix) 2, 4-DNP derivative
(x) Schiff’s base
Ans. (i) gem-Hydroxynitriles, i.e., compounds possessing hydroxyl and cyano groups on the same carbon
atom are called cyanohydrins. Aldehydes and ketones react with hydrogen cyanide (HCN) to
yield cyanohydrins. It is catalysed by a base and the generated cyanide ion (CN–) being a stronger
nucleophile readily adds to carbonyl compounds to yield corresponding cyanohydrin.
–
HCN + OH– CN + H2O

– O– H+ CN
C—O + CN C C
CN OH
Tetrahedral intermediate Cyanohydrin
(ii) gem-Dialkoxy compounds in which the two alkoxy groups are present on the terminal carbon atom are
called acetals. These are produced by the action of an aldehyde with two equivalents of a monohydric
alcohol in the presence of dry HCl gas.

CH3 H—OCH2CH3 Dry HCl gas CH3 OCH2CH3

C— O + C + H2O
H H—OCH2CH3 H OCH2CH3
Acetaldehyde Ethyl alcohol Acetaldehyde
diethyl acetal
These are easily hydrolysed by dilute mineral acids to regenerate the original aldehydes. Therefore,
these are used for the protection of aldehydic group in organic synthesis.
(iii) Semicarbazones are derivatives of aldehydes and ketones and are produced by the action of
semicarbazide on them in weak acidic medium.
O
CH3 pH 3.5 CH3
C—O + H2NNH—C—NH2 – H O C—NNHCONH2 + H2O
CH3 2 CH3
Acetone Semicarbazide Acetone semicarbazone
These are used for identification and characterisation of aldehydes and ketones.
(iv) Aldols are b-hydroxy aldehydes or ketones and are produced by the condensation two same or
different molecules of aldehyde or ketones.
dil. NaOH
2CH3 —CHO CH3 —CH—CH 2 —CHO
Ethanal |
OH
3 - Hydroxybu tan al
(Aldol)
  
CH3
Ba (OH) 2
|
2CH3 —CO—CH3 CH3 — C—CH 2 —CO—CH3
Propanone |
OH
4 - Hydroxy - 4 - methylpen tan - 2 - one
(v) gem-Alkoxyalcohols are called hemiacetals. These are produced by addition of one molecule of a
monohydric alcohol to an aldehyde in presence of dry HCl gas.
CH3 Dry HCl gas H3C OH
C—O + H—OCH3 C
H H OCH3
Ethanal Methyl alcohol 1-Hydroxy-1-methoxyethane
(A hemiacetal)

488 Xam idea Chemistry–XII

24
 (vi) Oximes are produced when aldehydes or ketones react with hydroxylamine in weak acidic medium.
CH3 CH3
pH 3.5
C—O + H2 NOH C—NOH + H2O
H H
   Acetaldehyde Hydroxylamine Acetaldoxime
(vii) gem-Dialkoxyalkanes are called ketals. In ketals, the two alkoxy groups are present on the same
carbon within the chain. These are produced when a ketone is heated with ethylene glycol in presence
of dry HCl gas or p-toluenesulphonic acid (PTS).
Dry HCl gas
CH3 H—O—CH2 or PTS ∆ H3C O—CH2
C— O + | C | + H2O
CH3 H—O—CH2 H3C O—CH2
Acetone Ethylene glycol Acetone ethylene ketal
These are easily hydrolysed by dilute mineral acids to regenerate the original ketones. Therefore,
ketals are used for protection of keto groups in organic synthesis.
(viii) Compounds containing C N— group are called imines. These are produced when aldehydes and
ketones react with ammonia derivatives.
C O + H2N—Z C N—Z + H 2O
Aldehyde/Ketone Ammonia Imines
   derivative
Z = H, Alkyl, aryl, —NH2 , —OH, —C6H5NH, —NHCONH2, etc.
(ix) 2, 4-Dinitrophenylhydrazones ( 2, 4-DNP derivatives) are produced when aldehydes or ketones react
with 2, 4-dinitrophenylhydrazine in weakly acidic medium.
NO2 NO2
CH3 pH 3.5 CH 3
C O + H2 NNH NO2 C NNH NO2
–H2O
CH3 CH3
2, 4-Dinitrophenyl Acetone 2, 4-dinitrophenylhydrazone
hydrazine
2, 4-DNP derivatives are used for identification and characterisation of aldehydes and ketones.
(x) Aldehydes and ketones react with primary aliphatic or aromatic amines to form azomethines or
Schiff’s bases.
+
Trace of H
 R—CH == O + H 2 N—Rl R—CH == N—Rl + H 2 O
Heat
Aldehyde 1° Amine Schiff’s base

Q. 2. Name the following compounds according to IUPAC system of nomenclature.

(i) CH3CH(CH3)CH2CH2CHO (ii) CH3CH2COCH(C2H5)CH2CH2Cl
(iii) CH3CH—CHCHO [CBSE 2019(56/5/2)]
(iv) CH3COCH2COCH3 (v) CH3CH(CH3)CH2C(CH3)2COCH3
(vi) (CH3)3CCH2COOH (vii) OHCC6H4CHO-p
Ans. (i) 4-Methylpentanal (ii) 6-Chloro-4-ethylhexan-3-one
(iii) But-2-en-1-al (iv) Pentane-2, 4-dione
(v) 3, 3, 5-Trimethylhexan-2-one (vi) 3, 3-Dimethylbutanoic acid
(vii) Benzene-1, 4-dicarbaldehyde
Q. 3. Draw the structures of the following compounds:
(i) 3-Methylbutanal (ii) p-Nitropropiophenone
(iii) p-Methylbenzaldehyde (iv) 4-Methylpent-3-en-2-one
(v) 4-Chloropentan-2-one (vi) 3-Bromo-4-phenylpentanoic acid
(vii) p-p'-Dihydroxybenzophenone (viii) Hex-2-en-4-ynoic acid
CH3 O
| ||
Ans. (i) CH3 —CH—CH 2 —C—H (ii) O2N COCH2CH3

Aldehydes, Ketones and Carboxylic Acids 489

25
 (iii) CH3 CHO (iv) CH3 —C—CH == C—CH3
|| |
O CH3
(v) CH3 —C—CH 2 —CH—CH3 (vi) CH3 —CH — CH —CH2 —COOH
|| | | |
O Cl C6 H5 Br
O
(vii) HO C OH (viii) CH3—C ≡ C—CH—CH—COOH

Q. 4. Write the IUPAC names of the following ketones and aldehydes. Wherever possible, give also
common names.
(i) CH3CO(CH2)4CH3 (ii) CH3CH2CHBrCH2CH(CH3)CHO
(iii) CH3(CH2)5CHO (iv) Ph—CH—CH—CHO
CHO
(v)       (vi) PhCOPh
Ans.
S.No. IUPAC Name Common Name
(i) Heptan-2-one Methyl n-pentyl ketone
(ii) 4-Bromo-2-methylhexanal g-Bromo-a-methylcaproaldehyde
(iii) Heptanal —
(iv) 3-Phenylprop-2-enal b-Phenylacrolein
(v) Cyclopentanecarbaldehyde Cyclopentanecarbaldehyde
(vi) Diphenylmethanone Benzophenone

Q. 5. Draw structures of the following derivatives:

(i) The 2, 4-dinitrophenylhydrazone of benzaldehyde
(ii) Cyclopropanone oxime
(iii) Acetaldehydedimethylacetal
(iv) The semicarbazone of cyclobutanone
(v) The ethylene ketal of hexan-3-one
(vi) The methyl hemiacetal of formaldehyde.
N OH
NO2
Ans. (i) CH—NNH NO2 (ii)
O
CH3 OCH3
(iii) C (iv) NNH C NH2
H OCH3

H2C CH2
O O
H OH
(v) CH3—CH2—C—CH2—CH2—CH3 (vi) C
H OCH3

Q. 6. Predict the products formed when cyclohexanecarbaldehyde reacts with following reagents:
(i) PhMgBr and then H3O+

(ii) Tollens’ reagent
(iii) Semicarbazide and weak acid
(iv) Excess ethanol and acid
(v) Zinc amalgam and dilute hydrochloric acid.

490 Xam idea Chemistry–XII

26
 OMgBr OH
CH—O Ph–MgBr C H 3O + C
Ans. (i) H H
Dry ether Ph Hydrolysis Ph
Cyclohexane Cyclohexylphenyl carbinol
carbaldehyde

CH—O + –
COO–
(ii) + 2[Ag(NH3)2] + 3OH + 2Ag + 4NH3 + 2H2O
Silver
Cyclohexane Tollens’s reagent Cyclohexane Mirror
carbaldehyde carboxylate ion

O
O
CHO CH—NNH C NH2 + H2O
(iii) + H2NNH C NH2 Weak acid
Cyclohexane Semicarbazide Cyclohexanecarbaldehyde
carbaldehyde semicarbazone

OC2H5
CH O H OC2H5 H+ C
(iv) OC2H5 + H2O
+ H
H OC2H5
Cyclohexane Cyclohexanecarbaldehyde
carbaldehyde Ethanol (excess) diethyl acetal

CHO Zn / Hg – HCl CH3

(v) (Clemmensen reduction)
Cyclohexane Methylcyclohexane
carbaldehyde

Q. 7. Which of the following compounds will undergo aldol condensation, which the Cannizzaro reaction
and which neither? Write the structures of the expected products of aldol condensation and
Cannizzaro reaction.
(i) Methanal (ii) 2-Methylpentanal
(iii) Benzaldehyde (iv) Benzophenone
(v) Cyclohexanone (vi) 1-Phenylpropanone
(vii) Phenylacetaldehyde (viii) Butan-1-ol
(ix) 2, 2-Dimethylbutanal.
Ans. (i) Methanal does not contain a-hydrogen and hence undergoes cannizzaro reaction.
conc. NaOH
2HCHO CH3 OH + HCOONa
Methanal Methanol Sodium methanoate

(ii) 2-Methylpentanal, contains a-hydrogens and hence undergo aldol condensation.

CH3
7 6 5 |4 3 2
dil. NaOH
2CH3 CH 2 CH2 —CH—CHO CH3 CH3 CH 2 CH —CH— C — CH 2 CH 2 CH3
| | | 1|
CH3 CH3 OH CHO
2-Methylpentanal
3-Hydroxy-2,4-dimethyl-2-propylheptanal

(iii) Benzaldehyde does not contain a-hydrogen and hence undergoes cannizzaro reaction.
conc. NaOH
2 CHO CH2OH + COONa
Benzaldehyde Benzyl alcohol Sodium benzoate
(iv) Benzophenone is a ketone having no a-hydrogen. It neither undergoes aldol condensation nor
Cannizzaro reaction.

Aldehydes, Ketones and Carboxylic Acids 491

27
 (v) Cyclohexanone contains a-hydrogens and hence undergo aldol condensation.
O
Dil. NaOH
2 O 1 2

Cyclohexanone OH
2-(1-Hydroxy-1-cyclohexyl)
cyclohexan-1-one
(vi) 1-Phenylpropanone contains a-hydrogens and hence undergo aldol condensation.
HO CH3
3 1
Dil. NaOH 2

2 COCH2CH3 C CH C
5 4
1-Phenylpropanone H3C—CH2 O
3-Hydroxy-2-methyl-1,3-diphenylpentan-1-one
(vii) Phenylacetaldehyde contains a-hydrogen and hence undergoes aldol condensation.
1
OH CHO
Dil. NaOH
2 CH2CHO CH2 CH CH
4 3 2
Phenylacetaldehyde
3-Hydroxy-2, 4-diphenylbutanal
(viii) Butan-1-ol is an alcohol, so it neither undergoes aldol condensation nor Cannizzaro reaction.
(ix) 2, 2-dimethylbutanal does not contain a-hydrogen and hence undergo Cannizzaro reaction.
CH3 CH3 CH3
| | |
conc. NaOH
CH3 CH 2 —CH—CHO CH3 CH 2 — C—CH 2 OH + CH3 CH 2 — C—COONa
| | |
CH3 CH3 CH3
2, 2-Dimethylbutanal 2, 2-Dimethylbutan-1-ol Sodium 2, 2-Dimethylbutanonate
Q. 8. How will you convert ethanal into the following compounds?
(i) Butane-1, 3-diol (ii) But-2-enal (iii) But-2-enoic acid.
Dil. NaOH 4 3 2 1 NaBH 4 4 3 2 1
Ans. (i) 2CH3 CHO CH3 CHOH—CH 2 —CHO CH3 —CHOH—CH 2 CH 2 OH
(Aldol condensation) (Reduction)
Ethanal 3 - Hydroxybu tan al Bu tan e - 1. 3 - diol

Dil. NaOH 4 3 2 1 +
H3 O /Heat
(ii) 2CH3 CHO CH3 —CHOH—CH 2 —CHO CH3 —CH == CH—CHO
(Aldol condensation) – H2 O
Ethanal 3 - Hydroxybu tan al But - 2 - enal
+
(i) dil. NaOH [Ag (NH3) 2] OH –
(iii) 2CH3 CHO +
CH3 CH == CHCHO CH3 CH == CHCO 2 H
(ii) H , D Tollens’ reagent
Ethanal But - 2 - enal But - 2 - enoic acid
Q. 9. Write structural formula and names of four possible aldol condensation products from propanal and
butanal. In each case indicate which aldehyde acts as nucleophile and which as electrophile.
Ans. (i) Propanal serves as nucleophile and also as electrophile.
OH CH3
5 4 3| 2| 1
CH3 CH 2 CHO + CH3 CH 2 CHO CH3 CH 2 CH— C— CHO
Propanal Propanal 3 - Hydroxy - 2 - methylpen tan al
(Nucleophile) (Electrophile)

(ii) Butanal serves both as nucleophile and an electrophile.

OH CH 2 —CH3
6 5 2| 41 3|
CH3 CH 2 CH 2 CHO + CH3 CH 2 CH 2 CHO CH3 CH 2 CH 2 —CH—CHCHO
Butanal Butanal 2 - Ethyl - 3 - hydroxyhexanal
(Electrophile) (Nucleophile)

(iii) Butanal as electrophile and propanal as nucleophile.

CH3 OH
6 5 | 14 3| 2
CH3 CH 2 CH 2 CHO + CH3 CH 2 CHO
CH3 CH 2 CH 2 —CH—CH—CHO
Butanal Propanal 3 - Hydroxy - 2 - methylhexanal
(Electrophile) (Nucleophile)

492 Xam idea Chemistry–XII

28
 (iv) Propanal as electrophile and butanal as nucleophile.
CH 2 CH3
OH
5 4 2| 3|
1
CH3 CH 2 CHO + CH3 CH 2 CH 2 CHO CH3 CH 2 —CH—CHCHO
Propanal Butanal 2 - Ethyl - 3 - hydroxypentanal
(Electrophile
  ) (Nucleophile)

Q. 10. An organic compound with molecular formula C9H10O forms 2, 4-DNP derivative, reduces Tollens’
reagent and undergoes Cannizzaro reaction. On vigorous oxidation, it gives 1, 2-benzenedicarboxylic
acid. Identify the compound. [HOTS]
Ans. (i) The given compound with molecular formula C9H10O forms a 2, 4-DNP derivative and reduces
Tollens’ reagent, it must be an aldehyde.
(ii) As it undergoes Cannizzaro reaction, therefore, CHO group is directly attached to the benzene ring.
(iii) On vigorous oxidation, it gives 1,  2-benzenedicarboxylic acid, therefore, it must be an
ortho-substituted benzaldehyde. The only o-substituted aromatic aldehyde having molecular formula
C9H10O is o-ethylbenzaldehyde. All the reactions can be explained on the basis of this structure.

COO– [Ag(NH3 )2]+ OH– CHO [O]

COOH
Ag +
Tollens’ reagent
Silver C2H5 C 2 H5 COOH
mirror
2-Ethylbenzoate o-Ethylbenzaldehyde 1, 2-Benzenedicarboxylic acid
(M.F. C9H10O)

2, 4-DNP

NO2
CH—NNH NO2 + H2O

C2H5
2, 4-DNP derivative

Q. 11. An organic compound (A) (molecular formula C8H16O2) was hydrolysed with dilute sulphuric acid
to a carboxylic acid (B) and an alcohol (C). Oxidation of (C) with chromic acid produced (B). (C) on
dehydration gives but-1-ene. Write equations for the reactions involved.
[CBSE Delhi 2010; (AI) 2009] [HOTS]
Ans. As the organic compound (A) with molecular formula C8H16O2 upon hydrolysis gives carboxylic acid (B)
and the alcohol (C) therefore (A) must be an ester and oxidation of (C) with chromic acid produces the acid
(B), therefore, both the carboxylic acid (B) and alcohol (C) must contain the same number of carbon atoms.
Now ester (A) contains eight carbon atoms, therefore, both the carboxylic acid (B) and the alcohol (C) must
contain four carbon atoms each.
As the alcohol (C) on dehydration gives but-1-ene, therefore, (C) must be a straight chain alcohol, i.e.,
butan-1-ol.
If C is butan-1-ol, then the acid (B) which it gives on oxidation must be butanoic acid and the ester (A) must
be butyl butanoate.
The relevant equations for all the reactions involved may be explained as follows:
O O
|| ||
Dil. H2 SO 4
CH3 CH 2 CH 2 —C— OCH 2 CH 2 CH 2 CH3 CH3 CH 2 CH 2 —C—OH + CH3 CH 2 CH 2 CH 2 OH
Hydrolysis
Butyl butanoate, (A) Butanoic acid, (B) Butan - 1 - ol, (C)
(M.F. = C8 H16 O2)
O
||
CrO3 /CH3 COOH Dehydration
CH3 CH 2 CH 2 —C—OH CH3 CH 2 CH 2 CH 2 OH CH3 CH 2 CH == CH 2
(Oxidation) (– H 2 O )
Butanoic acid, (B) Butan - 1 - ol, (C) But - 1 - ene

Aldehydes, Ketones and Carboxylic Acids 493

29
 Q. 12. Arrange the following compounds in increasing order of their property as indicated:
(i) Acetaldehyde, Acetone, Di-tert-butyl ketone, Methyl tert-butyl ketone (reactivity towards HCN).
(ii) CH3CH2CH(Br)COOH, CH3CH(Br)CH2COOH, (CH3)2CHCOOH, CH3CH2CH2COOH (acid
strength).
(iii) Benzoic acid, 4-nitrobenzoic acid, 3, 4-dinitrobenzoic acid, 4-methoxy benzoic acid (acid strength).
Ans. (i) The reactivity towards HCN addition decreases as the +I-effect of the alkyl group/s increases and/or
the steric hindrance to the nucleophilic attack by CN– at the carbonyl carbon increases. Hence, the
reactivity decreases in the order:
CH3 O CH3 O CH3
CH3 CH3
C— O > C — O > CH3 — C — C — CH3 > CH3 — C — C — C — CH3
H CH3
CH3 CH3 CH3
Acetaldehyde Acetone
Methyl tert-butyl ketone Di-tert-butyl ketone
+ I-effect increases
Steric hindrance increases

Thus, di-tert-butyl ketone < methyl tert-butyl ketone < Acetone < Acetaldehyde.
(ii) As we know + I-effect decreases while – I-effect increases the acid strength of carboxylic acids. As
+I-effect of isopropyl group is more than that of n-propyl group, therefore, (CH3)2CHCOOH is a
weaker acid than CH3CH2CH2COOH.
Now –I-effect decreases with distance, therefore, CH3CH2CH(Br)COOH is a stronger acid than
CH3CH(Br)CH2COOH.
Therefore, the overall acid strength increases in the order:
CH3
|
CH3 —CH—COOH < CH3 CH 2 CH 2 —COOH < CH3 —CH—CH 2 —COOH
|
Br
< CH3 —CH 2 —CH—COOH
|
Br
(iii) As electron-donating groups decrease the acid strength, therefore 4-methoxybenzoic acid is a weaker
acid than benzoic acid.
Now electron-withdrawing groups increase the acid strength, therefore, both 4-nitrobenzoic acid and
3, 4-dinitrobenzoic acids are stronger acids than benzoic acid. Further due to the presence of an
additional NO2 groups at m-position w.r.t. COOH group, 3, 4-dinitrobenzoic acid is a little stronger
acid than 4-nitrobenzoic acid. Therefore, the overall acid strength increases in the following order:
4-methoxybenzoic acid < benzoic acid < 4-nitrobenzoic acid < 3, 4-dinitrobenzoic acid.
Q. 13. Give simple chemical tests to distinguish between the following pairs of compounds:
 [CBSE 2019(56/2/1)]
(i) Propanal and Propanone (ii) Acetophenone and Benzophenone
(iii) Phenol and Benzoic acid (iv) Benzoic acid and Ethyl benzoate
(v) Pentan-2-one and Pentan-3-one (vi) Benzaldehyde and Acetophenone
(vii) Ethanal and Propanal
Ans. (i) Propanal and propanone:
Iodoform test: This test is given by propanone and not by propanal. Propanone on reacting with hot
NaOH/I2 gives a yellow precipitate of CHI3 while propanal does not.
2NaOH + I 2 NaI + NaOI + H 2 O

CH3 —C—CH3 + 3NaOI CHI3 . + CH3 COONa + 2NaOH
|| Sodium Yellow Sodium acetate
hypo - iodite ppt.
O

494 Xam idea Chemistry–XII

30
 (ii) Acetophenone and benzophenone: Acetophenone responds to iodoform test, but benzophenone
does not.
COCH3 I2 /NaOH
COONa
+ 3NaOI + CHI3 + 2NaOH
Heat
Yellow ppt.
Sodium (Iodoform)
Benzoate

(iii) Phenol and benzoic acid: Benzoic acid reacts with NaHCO3 giving CO2 gas with effervescence,
whereas phenol does not.
COOH COONa

+ NaHCO3 + H2O + CO2

Benzoic acid Sodium benzoate
(iv) Benzoic acid and ethyl benzoate: Benzoic acid on reaction with sodium hydrogencarbonate gives
out CO2 gas with effervescence, while ethyl benzoate does not.
COOH COONa
+ NaHCO3 + H2O + CO2

(v) Pentan-2-one and Pentan-3-one: Pentan-2-one when treated with NaOI (I2/NaOH) gives yellow
precipitate of iodoform but pentan-3-one does not give this test.
CH3 —CH 2 —CH 2 —COCH3 + 3NaOI
CH3 CH 2 CH 2 COONa + CHI3 . + 2NaOH
Pen tan - 2 - one Sodium Iodoform
hypoiodite (Yellow ppt.)
(vi) Benzaldehyde and Acetophenone: Benzaldehyde being an aldehyde gives silver mirror with

Tollens’ reagent but acetophenone being a ketone does not give this test.
+
C6 H5 CHO + 2 [Ag (NH3) 2] + 3OH –
C6 H5 COO – + 2Ag . + 4NH3 + 2H 2 O
Benzaldehyde Tollens’ reagent Silver mirror

(vii) Ethanal (CH3CHO) and propanal (CH3CH2CHO): Ethanal responds to iodoform test, while
propanal does not.
NaOH/I2
CH3 CHO + 3NaOI
CHI3 . + HCOONa + 2NaOH
D
(Yellow ppt.)
Q. 14. How will you prepare the following compounds from benzene? You may use any inorganic reagent
and any organic reagent having not more than one carbon atom.
(i) Methyl benzoate (ii) m-nitrobenzoic acid
(iii) p-nitrobenzoic acid (iv) Phenylacetic acid
(v) p-nitrobenzaldehyde
Br MgBr COOH COOCH3
CH 3OH(excess);
Br2/FeBr3 Mg, dry ether CO 2 conc. H2SO 4,
Ans. (i) + (Esterification)
(Bromination) (Grignard H3 O
reaction)
Benzene Methyl
benzoate
COOH COOH
Conc. HNO3/
As in ( i ) above conc. H2SO4,
(ii)
Nitration NO2
Benzene Benzoic acid m-Nitrobenzoic acid

CH3 CH3 COOH

Conc. HNO3 /
CH 3 Cl/Anhyd. AlCl 3 conc. H2SO4, (i) KMnO4/KOH,
(iii) (F.C. alkylation) (Nitration) ( ii ) H2SO4
Benzene Toluene
NO2 NO2
p-Nitrotoluene p-Nitrobenzoic acid
(Major product)

Aldehydes, Ketones and Carboxylic Acids 495

31
 CH3 CH2Br
CH3Cl/Anhyd. AlCl3 NBS, hv or Br2, and hv Alc. KCN, ∆
(iv)
(Side chain, bromination) (Nucleophilic substitution)
Benzene Toluene Benzyl bromide

CH2CN CH2COOH
H+ / H2O
Hydrolysis
Benzyl cyanide Phenylacetic acid

CH3 CHO
As in (iii) (i) CrO3 /(CH3 CO)2 O
(v)
(above) (ii) H3 O +
Benzene
NO2 NO2
p-Nitrobenzaldehyde

Q. 15. How will you bring about the following conversions in not more than two steps?
(i) Propanone to Propene (ii) Benzoic acid to Benzaldehyde
(iii) Ethanol to 3-Hydroxybutanal (iv) Benzene to m-Nitroacetophenone
(v) Benzaldehyde to Benzophenone (vi) Bromobenzene to 1-Phenylethanol
(vii) Benzaldehyde to 3-Phenylpropan-1-ol
(viii) Benzaldehyde to a-Hydroxyphenylacetic acid
(ix) Benzoic acid to m-Nitrobenzyl alcohol
Ans. (i) Propanone to Propene
H2 /Ni conc. H2 SO 4
CH3 —C—CH3 CH3 —CH—CH3 CH3 —CH == CH 2
443 K
|| | Propene
O OH
Propanone 2 - propanol
(ii) Benzoic acid to Benzaldehyde
SOCl 2 H 2/Pd-BaSO4
COOH COCl CHO
–SO2 , –HCl boiling xylene
Benzoic acid Benzoyl chloride Benzaldehyde

(iii) Ethanol to 3-Hydroxybutanal

OH
– |
Mild Oxidation OH
—CH
CH3 2 —OH CH3 —CHO CH3 —CH—CH2 —CHO
KMnO 4 /dil. H2 SO 4 Dil. NaOH
Ethanol Acetaldehyde 3-hydroxybutanal
(Two molecules)
(iv) Benzene to m-Nitroacetophenone
COCH3 COCH3
(CH3CO2)2O/ conc. HNO3/
anhyd. AlCl3 conc. H2SO4
(Friedel Crafts Acylation) Nitration NO2
Acetophenone m-nitroacetophenone

(v) Benzaldehyde to Benzophenone

O
(i) K2Cr2O7/H2SO4 dry distil.
C O (C6H5 COO)2Ca –CaCO3
C
(ii) CaCO3
H Calcium benzoate
Benzaldehyde
Benzophenone

496 Xam idea Chemistry–XII

32
 (vi) Bromobenzene to 1-phenylethanol:
Mg ( i ) CH3—CHO
Br Mg Br CH CH3
Dry ether ( ii ) H 2O/H+
(Phenyl Magnesium OH
bromide) 1-Phenyl ethanol

(vii) Benzaldehyde to 3-phenylpropan-1-ol:

CH—CHCHO
H
OH – H2O
C O + HCH2CHO (Cross aldol
C CH2CHO
H Acetaldehyde condensation)
OH 3-phenyl-prop-2-enal
Benzaldehyde
H2 /Ni
CH2 CH2CH2OH
3-Phenylpropanol
(viii) Benzaldehyde to a-Hydroxyphenylacetic acid
CN H
HO—C—H HO—C—COOH
H2O/H+
C O + HCN
(Complete hydrolysis)
H Hydrogen α-Hydroxyphenyl
Benzaldehyde cyanide acetic acid

(ix) Benzoic acid to m-nitrobenzyl alcohol:
COOH COCl CH2 OH
(i) Conc. HNO 3 ( i ) NaBH4
Conc. H 2SO 4 NO2 ( ii ) H 3O + NO2
(ii) SOCl2
Benzoic acid m-nitrobenzoyl m-nitrobenzyl
chloride alcohol

Q. 16. Describe the following:

(i) Acetylation (ii) Cannizzaro reaction
(iii) Cross aldol condensation (iv) Decarboxylation
Ans. (i) Acetylation: The replacement of an active hydrogen of alcohols, phenols or amines with an acyl
(RCO) group to form the corresponding esters or amides is called acetylation. This replacement
is carried out by using acid chloride or an acid anhydride in the presence of a base like pyridine or
dimethylaniline.
Pyridine
CH3 COCl + C2 H5 OH CH3 COOC2 H5 + HCl
Ethyl acetate

Pyridine
(CH3CO)2 + OH CH3COC6H5 + CH3COOH
Phenyl acetate

CH3 COCl + C2 H5 NH 2
CH3 CONHC 2 H5 + HCl
N - Ethylacetamide

(ii) Cannizzaro reaction: Refer to Basic Concepts Point 17( j).

(iii) Cross aldol condensation: When aldol condensation is carried out between two different aldehydes
and/or ketones, it is called cross aldol condensation. If both of them contain a-hydrogen atoms, it gives
a mixture of four products. This is illustrated below by aldol reaction of a mixture of benzaldehyde
and acetophenone.
O
OH –
CHO + C CH3 CH CH C
293 K
O 1, 3-Diphenylprop-2-en-1-one
(Benzalacetophenone)
(Major product)

Aldehydes, Ketones and Carboxylic Acids 497

33
 (iv) Decarboxylation: Carboxylic acids lose carbon dioxide to form hydrocarbons when their sodium
salts are heated with sodalime (NaOH and CaO in the ratio of 3 : 1). The reaction is known as
decarboxylation.
NaOH & CaO
R—COONa R—H + Na 2 CO3
Heat

Q. 17. Complete each synthesis by giving missing starting material, reagent or products.
CH2CH3 KMnO4 COOH SOCl 2
(i) KOH, heat
(ii) Heat
COOH
O
C
H 2 NCONHNH 2
(iii) C 6 H 5 CHO (iv)

O [Ag(NH 3) 2]
+ CHO NaCN/HCl
(v) (vi)
CHO COOH
dil. NaOH
(vii) C 6 H 5 CHO + CH 3 CH 2 CHO
D
(i) NaBH 4 CrO3
(viii) CH 3 COCH 2 COOC 2 H 5 +
(ix) OH
(ii) H
(i) O3
(x) CH2 CHO (xi) 2 O
(ii) Zn–H2O

CH2CH3 KMnO4
COOK
Ans. (i) KOH, heat
Ethylbenzene Potassium benzoate

COOH SOCl 2
COCl
(ii) Heat
COOH COCl
Phthalic acid Phthaloyl chloride
(iii) C6 H5 CHO + H 2 NNHCONH 2 C6 H5 CH == NNHCONH2 + H 2 O
Benzaldehyde Semicarbazide Benzaldehyde semicarbazone
O
COCl C
Anhyd. AlCl3
(iv) + + HCl
F.C. acylation
Benzene Benzoyl chloride Benzophenone

(v) Only aldehydes are oxidised by Tollens’ reagent.

O [Ag(NH ) ] + O
32
Oxidation –
CHO COO
4-Oxocyclohexanecarbaldehyde 4-Oxocyclohexanecarboxylate anion
(vi) Cyanohydrin formation occurs at the aldehyde group
OH
CHO NaCN/HCl CH CN
COOH COOH
2-Formylbenzoic acid 2-[1-Hydroxycyanomethyl]
benzoic acid

CH3 CH3
dil. NaOH 3 2 1
(vii) C6H5CH O + H2 C—CHO Claisen-Schmidt condensation
C6H5CH—C—CHO
Benzaldehyde Propanal 2-Methyl-3-phenyl-prop-2-enal

498 Xam idea Chemistry–XII

34
 (viii) Only keto group is reduced by NaBH4.
O OH
|| |
(i) NaBH 4
CH3 —C—CH 2 COOC2 H5 +
CH3 —CH—CH 2 COOC2 H5
(ii) H
Ethyl - 3 - oxobutanoate Ethyl - 3 - hydroxybutanoate

CrO3
(ix) OH O
H2SO4
Cyclohexanol Cyclohexanone

B2H6/ H2O2 PCC

(x) CH2 CH2 B CH2OH CHO
THF NaOH
3 Cyclohexane
Methylenecyclohexane carbaldehyde
(i) O3
(xi) 2 O
(ii) Zn-H2O
Cyclohexylidenecyclohexane Cyclohexanone

Q. 18. Give plausible explanation for each of the following:

(i) Cyclohexanone forms cyanohydrin in good yield but 2,2,6-trimethylcyclohexanone does not.
(ii) There are two —NH2 groups in semicarbazide, only one is involved in the formation of semicarbazone.
(iii) During the preparation of esters from a carboxylic acid and an alcohol in the presence of an
acid catalyst, the water or the ester should be removed as soon as it is formed.
O HO CN
Ans. (i) HCN

Cyclohexanone Cyclohexanone cyanohydrin

O HO CN
H3 C 2 CH3 H3C CH3
6 CH3 HCN CH3
2,2,6-trimethylcyclohexanone
Due to the presence of three methyl groups at a-position with respect to the C—O group, the
nucleophilic attack by the CN– ion does not occur due to steric hindrance. As there is no such steric
hindrance in cyclohexanone, hence, nucleophilic attack by the CN– ion occurs readily and hence
cyclohexanone cyanohydrin is obtained in good yield.
– –
O O O
+ +
(ii) H2 N—C—NHNH2 H2 N — C—NH—NH2 H2 N— C NH—NH2
Semicarbazide
Semicarbazide has two –NH2 groups but one of them (i.e., directly attached to C—O) is involved in
resonance as shown above. Thus, electron density on this NH2 group decreases hence it does not act
as a nucleophile. In contrast, the lone pair of electrons on the other NH2 group (i.e., attached to —NH)
is not involved in resonance and hence is available for nucleophilic attack on the C—O group of
aldehydes and ketones.
(iii) The formation of esters from a carboxylic acid and an alcohol in presence of an acid catalyst is a
reversible reaction.
H2 SO 4
     RCOOH + Rl OH RCOORl + H 2 O
Carboxylic acid Alcohol Ester
To shift the equilibrium in the forward direction, the water or the ester formed should be removed as
fast as it is formed.
Q. 19. An organic compound contains 69.77% carbon, 11.63% hydrogen and rest oxygen. The molecular
mass of the compound is 86. It does not reduce Tollens’ reagent but forms an additional compound
with sodium hydrogensulphite and gives a positive iodoform test. On vigorous oxidation, it gives
ethanoic acid and propanoic acid. Write the possible structure of the compound.
[CBSE Delhi 2009; (AI) 2009] [HOTS]

Aldehydes, Ketones and Carboxylic Acids 499

35
 Ans.
Element Percentage Atomic mass No. of moles Simplest molar ratio
C 69.77 12 69.77 5.81
= 5.81 =5
12 1.16
11.63 11.63
H 11.63 1 = 11.63 = 10
1 1.16
O (100 – 81.4) = 18.60 16 18.60 1.16
= 1.16 =1
16 1.16

Empirical formula of the compound A = C5H10O

Molecular formula of the compound A = n (Empirical formula)
Molecular mass of compound A
            n =
Empirical formula mass of compound A
Molecular mass of compound A = 86
Empirical formula mass of compound A = 5 × 12 + 1 × 10 + 1 × 16 = 60 + 10 + 16 = 86
86
             n = =1
86
Molecular formula of the compound A = 1 (C5H10O) = C5H10O
As the compound A forms addition compound with NaHSO3 therefore it must be either an aldehyde or ketone.
As it does not reduce Tollens’ reagent and give positive iodoform test therefore it must be a methyl ketone.
As on oxidation the compound A gives a mixture of ethanoic acid and propanoic acid, therefore compound A is
O
||
CH3 —C—CH 2 —CH 2 —CH3
Pentan - 2 - one

The chemical reactions are:

O OH
|| |
CH3 —C—CH2 —CH2 —CH3 + NaHSO3
CH3 — C—CH2 —CH 2 —CH3
Pentan - 2 - one |
–+
SO3 Na
Sodium hydrogen sulphite _ addition product i
O
||
CH
3 — C —CH 2 —CH2 —CH3 + 3I 2 + 4NaOH
Pentan - 2 - qne
Iodoform – +
CHI3 . + CH3 —CH 2 —CH 2 —COONa + 3NaI + 3H 2 O
reaction
(Iodoform yellow ppt.)

O
||
K2 Cr2 O 7

CH3 —C—CH 2 —CH 2 —CH3 CH3 —COOH + CH3 —CH 2 —COOH
H2 SO 4
Pentan - 2 - qne Ethanoic acid Propanoic acid

Q. 20. Although phenoxide ion has more number of resonating structures than carboxylate ion, carboxylic
acid is stronger acid than phenol. Why?
Ans. Consider the resonating structures of carboxylate ion and phenoxide ion.
–
O O
R—C – R—C
O O

I II

500 Xam idea Chemistry–XII

36
 – –
O O O O O
– –

–
III IV V VI VII
In the resonating structures IV, V, VI of phenoxide ion carry a negative charge on the less electronegative
carbon atom. Therefore, their contribution towards the resonance stabilisation of phenoxide ion is very
small and hence can be rejected.
In structures I and II of carboxylate ion the negative charge on the carboxylate ion is delocalised over two
electronegative oxygen atoms while in structures III and VII of phenoxide ion, the negative charge on
electronegative oxygen atom remains localised while the electrons of the benzene ring only are delocalised.
As the delocalisation of benzene electrons contributes little towards the stability of phenoxide ion, therefore,
carboxylate ion is much more resonance stabilised than phenoxide ion. Thus, the release of proton from
carboxylic acid is much easier than from phenol. Hence, carboxylic acid is a stronger acid than phenol.

Multiple Choice Questions [1 mark]

Choose and write the correct option(s) in the following questions.
1. Which of the following compounds will give butanone on oxidation with alkaline KMnO4 solution?
[NCERT Exemplar]
(a) Butan-1-ol (b) Butan-2-ol (c) Both of these (d) None of these
2. Addition of water to alkynes occurs in acidic medium and in the presence of Hg2+ ions as a catalyst.
Which of the following products will be formed on addition of water to but-1-yne under these condition?
 O O [NCERT Exemplar]
|| ||
(a) CH3 —CH 2 —CH 2 —C—H (b) CH3 —CH 2 —C—CH3
O O O
|| || ||
(c) CH3 —CH 2 —C—OH + CO 2 (d) CH3 —C—OH + H—C—H
40%H 2 SO 4 Isomerisation
3.
CH 3 —C // CH A
CH 3 —C —CH 3
1%HgSO 4
||
O
Structure of ‘A’ and type of isomerism in the above reaction are respectively. [NCERT Exemplar]
(a) Prop–1–en–2–ol, metamerism (b) Prop–1–en–1–ol, tautomerism
(c) Prop–2–en–2–ol, geometrical isomerism (d) Prop–1–en–2–ol, tautomerism
4. Which of the following compounds is most reactive towards nucleophilic addition reactions?
[NCERT Exemplar]
O O O
|| || O
(a) CH3 —C—H (b) CH3 —C—CH3 (c) (d)
—C—H —C—CH3

5.
The formation of cyanohydrin from propanone is which type of reaction?
(a) Electrophilic substitution (b) Nucleophilic substitution
(c) Electrophilic addition (d) Nucleophilic addition
6. Compounds A and C in the following reaction are _____________. [NCERT Exemplar]
Hydroboration
(i) CH 3 MgBr H 2 SO 4, D oxidation

CH 3 CHO (A) (B) (C)
(ii) H 2 O
(a) identical (b) positional isomers (c) functional isomers (d) optical isomers
7. The reagent which does not react with both, acetone and benzaldehyde is [NCERT Exemplar]
(a) Sodium hydrogensulphite (b) Phenyl hydrazine
(c) Fehling’s solution (d) Grignard reagent

Aldehydes, Ketones and Carboxylic Acids 501

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