06

ALDEHYDES AND KETONES

Chapter 06

Aldehydes and Ketones

1. Introduction 2.1 Alkanes

Aldehydes and Ketones are organic compounds belonging to Controlled oxidation of alkanes under high temperature and
the class of carbonyl compounds. Aldehydes have a general pressure in the presence of a catalyst gives carbonyl compounds.
formula of RCHO and ketones have a general formula of RCOR' . Example:
Carbonyl compounds have a common group >C=O. Molybdenum Oxide
CH 4 +O 2 
 HCHO+H 2 O

2.2 Alkenes
2.2.1 Ozonolysis
Alkenes can be oxidized to aldehydes and ketones if reacted with
“Aldehydes and ketones play an important role in biochemical O3 and then reduced with Zn or dimethyl sulphide, (CH3 )2S . If a
processes of life. They add fragrance and flavour to nature, for reducing agent is not used, the aldehyde formed cannot be isolated
example, vanillin (from vanilla beans), salicylaldehyde (from as it is further oxidized to carboxylic acids.
meadow sweet) and cinnamaldehyde (from cinnamon) have very
Example:
pleasant fragrances.They are used in many food products and
pharmaceuticals to add flavours. Some of these families are
manufactured for use as solvents (i.e., acetone) and for preparing
materials like adhesives, paints, resins, perfumes, plastics, fabrics,
etc.“

2. Preparation of Carbonyl
Compounds

2.2.2 Oxidative Cleavage

Strong oxidizing agents such as acidic K 2 Cr2 O7 or alkaline
KMnO 4 cause oxidative cleavage of double bond to form ketones
and carboxylic acids.
Example:

Fig. 6.1 :Preparation of Carbonyl Compounds

Aldehydes and Ketones

10 ALDEHYDES AND KETONES

1
NOTE :
CH 2  CH 2  O 2 
PdCl2 .CuCl2
H2O
 CH 3 CHO 1. Hydration of an internal alkyne always yields a ketone.
2 (Wacker Process)
2. Acid catalyzed hydration of acetylene yields acetaldehyde.
All other terminal alkynes yield ketone.
3. Hydroboration oxidation of terminal alkynes always yields
an aldehyde.

2.4 Alkyl Halides

(Oxo Process)
Alkaline hydrolysis of geminal dihalides yields carbonyl
NOTE : compounds.
1. Wacker Process is the industrial method to prepare Example:
acetaldehyde.
2. Product formed in Oxo process mixture of isomeric chain
(predominant) and branched chain aldehydes.

2.3 Alkynes
2.3.1 By Acid Catalyzed Hydration in presence of
Mercuric Salt
This reaction follows Markovnikov addition
2.5 Alkyl Cyanides
2.5.1 Reduction of Cyanides (Stephen’s Reduction)

Only aldehydes are prepared by this method.

2.5.2 Grignard Reagent

2.3.2 Hydroboration Oxidation Grignard reagents give aldehydes with hydrogen cyanide (HCN)
This reaction follows Anti-Markonikov addition. The reagent that and ketones with alkyl cyanides (RCN).
can be used are BH 3 or Sia 2 BH (Disiamylborane).
Example:

2.6 Alcohols
Primary alcohols (1° ) are oxidized to aldehydes whereas

secondary alcohols (2° ) are oxidized to ketones using suitable

reagents. Tertiary alcohols (3° ) cannot be oxidized.

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ALDEHYDES AND KETONES 11
2.6.1 PCC/PDC/Collin’s Reagent 2.6.4 Periodic Acid/Lead Tetraacetate
Pyridinium chlorochromate (PCC) and Pyridinium Oxidation of vicinal diols can be carried out with oxidizing agents
dichromate(PDC) oxidize (1° ) alcohols and (2° ) alcohols to such as periodic acid, HIO 4 and lead tetra acetate,
aldehydes and ketones respectively.  CH3COO 4 Pb .These oxidizing agents also cleave vicinal
Example: diketo compounds to carboxylic acids.
Example:

NOTE :
1. Collin’s Reagent-Dipyridine Chromium (VI) oxide.
CrO3 .2C 2 H 5 N in CH 2 Cl 2 .

2. Corey’s Reagent - PCC in CH 2 Cl 2 .

3. Cr (VI) oxidizes 1 alcohols to aldehydes in anhydrons
medium and to carboxylic acids in aqueous medium.
2.6.5 Oppenauer Oxidation
Secondary Alcohols are oxidized to ketones by refluxing them
2.6.2 MnO2 with aluminium tert-butoxide and then acetone is added. The
Allylic, benzylic and propargylic alcohol are oxidized to aldehydes reaction is selective and is particularly used to oxidize unsaturated
and ketones by MnO 2 . secondary alcohols.
Example: Example:

2.6.3 Cu,  - Vapour Phase Dehydrogenation

Vapours of alcohol are passed over heated copper to
convert them into aldehydes and ketones. 3 alcohols are 2.7 Carboxylic Acids and Derivatives
oxidized to alkenes.
2.7.1 Decarboxylation of Ca Salts
Example:
A calcium salt of monocarboxylic acids on heating gives ketone.
If heated with calcium salt of formic acid, the product is an
aldehyde. If calcium salt of alkanoate is heated, the product is
ketone.
Example:


 RCOO 2 Ca   R 'COO 2 Ca  2RCOR ' 2CaCO3

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12 ALDEHYDES AND KETONES

2.7.2 Rosenmund’s Reduction Example:

Acid chloride is reduced in boiling xylene using palladium catalyst
supported on barium sulphate. Small amounts of quinoline and
sulphur are also added to increase poisoning. Lithium tri-t-
butoxyaluminium hydride can also reduce acid chloride to
aldehyde.
Example:
2.9.2 Gattermann Aldehyde Synthesis
Benzene on treatment with hydrogen cyanide and hydrogen
chloride in the presence of aluminium chloride initially gives imine
which is hydrolysed into benzaldehyde.
Example:
2.7.3 Acid Derivatives and Grignard Reagent

2.9.3 Etard Reaction

Toluene on treatment with chromyl chloride in CCl 4 , and on
following hydrolysis gives benzaldehyde.
Example:

2.8 Nitro Alkanes - NEF Carbonyl

Synthesis
Nitro compounds dissolve in aqueous sodium hydroxide to form
salts. When this salt is acidified with 50% H 2SO4 , aldehydes
(from 1o) and ketones (from 2o) are formed. Toluene on treatment with CrO3 in acetic anhydride also gives
Example: benzaldehyde. The formation of benzalidene acetate as
intermediate prevents further oxidation to acid.

3. Physical Properties Of
Carbonyl Compounds
2.9 Aromatic Aldehydes
The carbonyl carbon atom is sp 2 -hybridized and bonded to three
2.9.1 Gattermann Koch Aldehyde Synthesis
Carbon monoxide and HC1 are passed through benzene solution other atoms through coplanar sigma bonds oriented about 120
in ether in the presence of AlC1 3 , (catalyst) to produce apart. The unhybridized p-orbital overlaps with a p-orbital of
benzaldehyde. oxygen to form a pi-bond.

Aldehydes and Ketones

ALDEHYDES AND KETONES 13

3.2 Boiling Point

Ketones and aldehydes have no O—H or N—H bonds, however,
so their molecules cannot form hydrogen bonds with each other.
Their boiling points are therefore lower than those of alcohols of
similar molecular weight. The ketone and the aldehyde are more
polar and higher boiling point than the ether and the alkane, but
lower-boiling point than the hydrogen- bonded alcohol.

3.1 Dipole Moment

The double bond of the carbonyl group has a large dipole moment
because oxygen is more electronegative than carbon, and the
bonding electrons are not shared equally. In particular, the less
tightly held pi electrons are pulled more strongly toward the
oxygen atom, giving ketones and aldehydes larger dipole
moments than most alkyl halides and ethers. We can use
resonance forms to symbolize this unequal sharing of the pi
electrons.

3.3 Solubility
Although pure ketones and aldehydes cannot engage in
hydrogen bonding with each other, they have lone pairs of
electrons and can act as hydrogen bond acceptors with other
The first resonance form is more important because it involves
compounds having O—H or N—H bonds. For example, the —
more bonds and less charge separation. The contribution of the
OH group of water or an alcohol can form a hydrogen bond with
second structure is evidenced by the large dipole moments of
the unshared electrons on a carbonyl oxygen atom.
the ketones and aldehydes shown here.

The positively polarized carbon atom acts as an electrophile

(Lewis acid), and the negatively polarized oxygen acts as a Because of this hydrogen bonding, ketones and aldehydes are
nucleophile (Lewis base). good solvents for polar hydroxyl substances such as alcohols.
Acetaldehyde and acetone are miscible (soluble in all proportions)
with water. Other ketones and aldehydes with up to four carbon
atoms are fairly soluble in water. There solubility properties are
similar to those of ethers and alcohols, which also engage in
hydrogen bonding with water.

Aldehydes and Ketones

14 ALDEHYDES AND KETONES

4. Chemical Properties of
Carbonyl Compounds

Important examples of nucleophilic addition & elimination

reactions:

4.1.2 Addition of H2O - Hydrate Formation

Hydrate is a geminal diol, which is usually unstable, that’s why it
cannot be isolated from the aqueous solution. Formation depends
on the equilibrium constant, which reflects the stability of the
corresponding hydrate.

Electron withdrawing groups stabilize the hydrate.

4.1.3 Addition of ROH - Hemiacetal/Acetal Formation

Addition of one alcohol gives hemiacetal and two alcohol
molecules gives acetal. Acetal formation involves - acid-catalysed
nucleophilic addition to the carbonyl and following unimolecular
substitution ( SN 1 ) - protonation, loss of OH and attack of
Fig. 6.2 :Chemical Reactions of Carbonyl Compounds
alcohol. Usually reactions are reversible. Simple aldehydes favour
the formation of acetal but the hindered aldehydes and most of
4.1 Nucleophilic Addition Reactions the ketones do not favour such a formation.
4.1.1 Mechanism of Nucleophilic Addition Reactions
Trigonal carbonyl compound gets converted into a tetrahedral
product. Electronic as well as steric factor suggest that aldehyde
is more reactive in comparison to ketone. Racemisation may
proceed.

Example:

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ALDEHYDES AND KETONES 15

4.1.4 Addition of NaHSO3- Bisulphite formation increases reactivity of carbonyl group while OH  increases
Aldehydes and ketones add on sodium hydrogen sulphite to reactivity of CN  , but in both the conditions, the reaction is a
form a bisulphite compound (hydroxy sulphonic acid salts). Most nucleophilic addition. Reaction is usually reversible, cyanohydrin
of ketones, especially hindered ketones have very less tendency formation depends on the extent of equilibrium (equilibrium
to form bisulphites. Bisulphite compounds are usually crystalline constant).
solids insoluble in sodium hydrogen sulphite solution
Example:
Example:

4.1.6 Addition of NH3 and Its Derivatives

4.1.5 Addition of HCN - Cyanohydrin formation

Addition of HCN to aldehyde or ketone gives cyanohydrin (  -
hydroxynitrile). HCN (Hydrocyanic acid) is a weak Nu provider,,
Usually, the reaction is acid catalysed.
reaction is usually acid or base catalysed. Presence of H 
The product can demonstrate geometrical isomerism is a
crystalline solid.

Table 6.1 :N-Substituted Derivatives of Aldehydes and Ketones

Reagent Reagent Name Product Product Name

NH2- R Primary (1o) Amine Imine (Schiff Base)

NH2- OH Hydroxylamine Oxime

NH2- NH2 Hydrazine Hydrazone

NH2- NHPh Phenyl Hydrazine Phenyl Hydrazone

2,4-Dinitrophenyl 2,4-Dinitrophenyl
Hydrazine Hydrazone
(Brady’s Reagent)

Semicarbazide Semicarbazone

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16 ALDEHYDES AND KETONES

NOTE : 4.2.2 Clemmensen Reduction

The reaction with Brady’s reagent is known as DNP Test and is Aldehydes and ketones which are not acid sensitive when heated
used as a test for detection of carbonyl compounds. with excess of amalgamated zinc (Zn-Hg) and HCl give the
corresponding alkanes.
Example: Example:

4.1.7 Addition of Grignard Reagent-Alcohol

Formation 4.2.3 Reduction to Alcohols(Metal Hydrides and
A Grignard reagent (a strong nucleophile resembling a carbanion Hydrogenation)
R  ) attacks on an aldehyde or a ketone, the subsequent
Aldehydes and ketones are reduced to 10 and 20 alcohols
protonation gives the alcohol.
respectively by various reagents, e.g., H2/Ni, B2H6, LiAlH4, NaBH4
HCHO  10 alcohol
, etc.Usually LiAIH 4 doesn’t affect the double and triple bonds.
RCHO  20 alcohol
It selectively reduces carbonyl group but reduces even the double
RCOR’  30 alcohol bond in the cinnamyl system.
Example: Example:

4.2.4 Meerwein-Ponndorf-Verley Reduction

Carbonyl compound is heated with aluminium isopropoxide in
isopropanol. Isopropoxide is oxidised to acetone. Without
affecting double or triple bonds and some other functional
groups, selectively carbonyl group is reduced to the
corresponding alcohol.
4.1.8 Addition of PCl5 Example:

On reaction with PC15 , carbonyl compounds give gem-dihalide.

4.2 Reduction Reactions

4.2.1 Wolff-Kishner Reduction

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ALDEHYDES AND KETONES 17

4.3 Oxidation Reactions 4.4 Alpha Substitutions

Aldehydes are easily oxidised and hence, are powerful reducing Alpha (α) substitutions involve the replacement of a hydrogen
agents. Aldehydes reduce Fehling’s solution (alkaline solution
atom at the α carbon atom (the carbon next to he carbonyl group)
of Cu2+ with tartaric acid) to red cuprous oxide and Tollen’s reagent
by some other group.The α hydrogen is more acidic because the
(ammonical silver nitrate) to metallic silver. Benzaldehyde do not
enolate ion that results from its removal is resonance-stabilized,
reduce Cu2+ salt (Fehling solution). Ketones (except  -hydroxy
with the negative charge delocalized over the α carbon atom and
ketones) don’t reduce Tollen’s reagent and the Fehling solution.
the carbonyl oxygen atom.
Benzaldehyde gives positive Tollen’s test. All aldehydes and
ketones are oxidised by permanganate, acid dichromates etc.
These strong oxidising agents oxidise adjacent carbon atom of Mechanism :
ketonic carbonyl and the carbonyl group remains chiefly with Step 1: Deprotonation of α carbon to form an enolate.
smaller alkyl group. (Popoff’s rule) Step 2: Nucleophilic attack on an electrophile.
Example:

4.4.1 Keto-Enol Tautomerism

(A) Base-Catalyzed Mechanism
Step 1: Deprotonation of  C.
Step 2: Reprotonation on O.

4.3.2 Baeyer-Villiger Oxidation of Ketones

Ketones on treatment with peracids such as perbenzoic acid or
peracetic acid or with other peroxy compounds in the presence
of acid catalysts, give carboxylic esters by insertion of oxygen.
The reaction involves rearrangement at electron deficient oxygen.
For unsymmetrical ketones the approximate order of migratory
aptitude is:
3o alkyl >2 o alkyl> phenyl>1o alkyl
Example:

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18 ALDEHYDES AND KETONES
(B) Acid-Catalyzed Mechanism 4.4.2  -Deutration
Step 1: An acid protonates the carbonyl oxygen. Example:
Step 2: Deprotonation on C gives the enol form.

4.4.3  -Alkylation
Example:

NOTE

NOTE :
4.4.4  -Halogenation
1. Acid catalyzed mechanism is slower than the base catalyzed
Chlorine or bromine replaces one or more α- hydrogen atoms in
mechanism.
aldehydes and ketones. Acetone may be brominated in glacial
2. If an asymmetric carbon atom has an enolizable hydrogen acetic acid to give monobromoacetone. Reaction occurs by
atom, a trace of acid or base allows that carbon to invert its electrophilic attack of the halogen on the carbon-carbon double
configuration, with the enol serving as the intermediate. A bond of the enol form. The halogenation is catalysed by acids
racemic mixture (or an equilibrium mixture of diastereomers) is and bases.
the result.

4.4.5 Haloform Reaction

Methyl ketones are cleaved on reaction with excess halogen in
the presence of a base. The products are a trihalomethane
(haloform) and a carboxylate salt. In aqueous sodium hydroxide,
the rate has been shown to be independent of the halogen
concentration. The reaction is used for structural determinations.
The positive iodoform (bright yellow ppt) confirms
CH3CO  group usually..

Aldehydes and Ketones

ALDEHYDES AND KETONES 19
Example: Example:

(B) Cross-Aldol Condensation (Claisen-Schmidt Reaction)

A mixed aldol condensation, more precisely the condensation of
4.5. Reactions Due to  -Hydrogen aromatic aldehyde (or aldehyde without α -Hs) with an enolisable
4.5.1 Aldol Condensation aldehyde and ketone, which is most suitable.
Example:

(C) Intramolecular Aldol Condensation

Dicarbonyl compounds give this reaction and undergo cyclization.
The formation of the product depends upon the size of the ring
Fig. 6.3 :Types of Aldol Condensation
(usually 5 or 6 membered rings are formed).
Example:
(A) Self-Aldol Condensation

The enolisable carbonyl compound in the presence of H  or

OH (at or below room temp.) undergoes dimerisation, producing
aldol. The following dehydration gives α,β -unsaturated aldehyde
or ketone. Actually reaction involves nucleophilic addition of an
enolate ion to the carbonyl group. Aldehydes are more suitable
for aldol condensation than ketones.

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20 ALDEHYDES AND KETONES

4.5.2 Claisen Condensation (C) Intramolecular-Claisen Condensation Dieckmann

Esters having α- hydrogens on treatment with a strong base such Condensation)
as C 2 H5 ONa undergo condensation reactions to produce β -keto Example:
esters.

Fig. 6.4 :Types of Claisen Condensation

(A) Self-Claisen Condensation
Example:

4.6 Cannizzaro Reaction

It is a characteristic of aldehydes having no α hydrogens e.g.,
aromatic aldehydes, formaldehydes, etc. It involves oxidation
and reduction of molecuels in the presence of highly concentrated
OH   50%  . Reaction is intermolecular. The hydride transfer is
the rate determining step.

(B) Cross-Claisen Condensation

Example:
Fig. 6.5 :Types of Cannizzaro Reaction
(A) Self-Cannizzaro Reaction
Example:

(B) Cross-Cannizzaro Reaction

In cross-cannizzaro reaction, acid is formed from that molecule
which has more electron deficient carbon.

Aldehydes and Ketones

ALDEHYDES AND KETONES 21
Example: 4.7.3 Wittig Reaction
Carbonyl compounds react with phosphorus ylides
(phosphoranes) to yield alkenes and triphenyl phosphine oxide.
Reaction involves : First, SN2 attack of triphenyl phosphine (PPh3)
over 1 ° and 2° alkyl halide - alkyltriphenyl phosphonium salt.
Second, alkyl lithium or phenyl lithium removes a proton (acid-
base reaction) from salt to give ylide. Third, the combination of
ylide with carbonyl group. Mixture of E and Z forms are observed.
Example:

(C) Intramolecular Cannizzaro Reaction

Example:

4.7 Other Important Name Reactions

4.7.1 Beckmann Rearrangement 4.7.4 Benzoin Condensation
It is the rearrangement of oximes to form substituted amides in Benzaldehyde on treatment with aqueous ethanolic potassium
the presence of acid catalyst such as H2SO4, PCl5, H3PO4 etc. cyanide gives benzoin. Mixture of aldehydes give mixed benzoins.
Aliphatic aldehydes do not undergo the benzoin condensation.
Benzoin is an  -hydroxyketone, hence it reduces Fehling’ss
solution.
Example:

4.7.5 Knoevenagel Condensation

Compounds containing active CH 2 group condense with
NOTE : aldehydes and ketones. It proceeds like aldol condensation and
The alkyl group that migrates must be anti to the HO group. usually aldehydes and ketones do not have  -hydrogens. A
CH2 group is active if it is adjacent to the C=O group.
4.7.2 Schmidt Reaction
The reaction involves treatment of hydrazoic acid ( HN 3 ) with
carbonyl compounds, in the presence of concentrated sulphuric
acid. It is a rearrangement at electron deficient nitrogen and is
intramolecular in nature.
Example:

Aldehydes and Ketones

22 ALDEHYDES AND KETONES

Example: aluminium ethoxide. Acetaldehyde gives ethyl acetate and

propionaldehyde gives propylpropionate.

4.7.8 Darzen’s Glycidic Ester Condensation

The reaction involves the condensation of an aldehyde or ketone
with an  -halogen-ester to produce an ,  (5-epoxy-ester
(glycidic ester) in the presence of sodium ethoxide or sodamide.
Example:

4.7.6 Reformatsky Reaction

The addition of an organozinc reagent to the carbonyl group.
Actually the intermediate in the reaction appears to be an
organozinc that adds to the carbonyl group in a manner analogous
to that of a Grignard reagent.
Example:
4.7.9 Benzil-Benzilic Acid Rearrangement
 -diketones on treatment with base rearrange to give the salts
of  -hydroxyacids. Most known examples are aromatic but can
also be applied to aliphatic diketones and to  -keto aldehydes.
Example:

4.7.10 Michael Addition

The strong Nu (nucleophile) gives 1,2-addition (across carbonyl
group) and weaker nucleophile gives 1, 4-addition. Active
methylene carbanion is considered a weak nucleophile. The
conjugate addition of cnolatc anions to ,  -unsaturated
carbonyl compounds is known as Michael Additions.

4.7.7 Tischenko Reaction

All aldehydes undergo disproportionation giving ester as the
final product (instead of acid and alcohol) in the presence of

Aldehydes and Ketones

ALDEHYDES AND KETONES 23
Example: 5. Some Important Compounds
of Aldehydes and Ketones
5.1 Formaldehyde - HCHO
It is present in green leaves of plants where its presence is
supposed to be due to the reaction of CO, with water in presence
of sunlight and chlorophyll.
CO 2  H 2 O  HCHO  O 2
Traces of formaldehyde formed when incomplete combustion of
wood, sugar, coal. etc., occurs.
4.7.11 Perkin Addition
Formaldehyde is prepared in laboratory by catalytic oxidation of
It is the condensation of an aromatic aldehyde with an acid methyl alcohol.
anhydride to form ,  -unsaturated carboxylic acids. Excess of methyl alcohol is removed by fractional distillation.
Example: The resulting mixture is called formalin which contains 40%
formaldehyde. 8% methyl alcohol and 52% water.

5.1.1 Important Reactions

Reaction with ammonia
Formaldehyde does not form addition product with ammonia but
crystalline compound, hexamethylene tetramine (Urotropine).

4.7.12 Reduction with Metals (Pinacol-Pinacolone

rearrangement).
The reduction of ketones with magnesium amalgam gives pinacol. It is used as medicine in case of urinary troubles under the name
Similarly, benzaldehyde on treatment with zinc and hydrochloric of Urotropine or hexamine. Nitration of urotropine under
acid or with sodium amalgam gives hydrobenzoin. controlled conditions gives an explosive RDX (Research and
Example: Development Explosive).
Condensation with phenol
Formaldehyde condenses with phenol to give a synthetic plastic,
bakelite. The condensation occurs in presence of dilute sodium
hydroxide or ammonia at 80°-90°C. Bakelite is used for preparing
electrical insulators, electric switches and toys, etc.

Aldehydes and Ketones

24 ALDEHYDES AND KETONES

It is a pleasant smelling liquid (B.P. 124°C). It has cyclic structure

and when heated with dilute sulphuric acid, it changes again into
acetaldehyde. It is used in the medicine as a hypnotic and
soporific (sleep producing).

5.2.2 Uses
Acetaldehyde is used :
(i) In the preparation of acetic acid, acetic anhydride, ethyl
acetate, chloral, buta-1,3-diene (used in rubbers), dyes and
5.1.2 Uses drugs.
(i) The 40% solution of formaldehyde in water (formalin) is used (ii) As an antiseptic inhalant in nose troubles.
as disinfectant, germicide and antiseptic. It is used for the (iii) In the preparation of paraldehyde (hypnotic) and
preservation of biological specimens. metaldehyde (solid fuel).
(ii) It is used in the preparation of hexamethylene tetramine (iv) In the preparation of acetaldehyde ammonia (a rubber
(urotropine) which is used as an antiseptic and germicide. accelerator).
(iii) It is used in silvering of mirror and decolouring vat dyes. (v) As a reducing agent in silvering of mirror.
(iv) It is employed in the manufacture of synthetic dyes such as
para-rosaniline, indigo, etc.
(v) It is used in the manufacture of formamint (by mixing
5.3 Acetone - CH3COCH3
formaldehyde with lactose) - a throat lozenge. 5.3.1 Important Reactions

5.2 Acetaldehyde - CH3CHO

5.2.1 Important Reactions
Polymerisation : Acetaldehyde undergoes polymerisation forming
different products under different conditions.
Paraldehyde : It is formed, when anhydrous acetaldehyde is
treated with a few drops of conc. sulphuric acid.

Aldehydes and Ketones

ALDEHYDES AND KETONES 25
When acetone is distilled with concentrated sulphuric acid it 5.3.2 Uses
forms mesitylene. (i) As a solvent for cellulose acetate, cellulose nitrate, celluloid,
lacquers, resins, etc.
(ii) For storing acetylene.
(iii) In the manufacture of cordite—a smokeless powder explosive.
(iv) In the preparation of chloroform, iodoform, sulphonal and
chloretone.
(v) As a nail polish remover.
(vi) In the preparation of an artificial scent (ionone), plexiglass (a
tough transparent plastic) and synthetic rubber.

6. Tests Of Aldehydes And Ketones

Table 6.2 : Tests for Characterizing Aldehydes & Ketones

Test Reaction Confirmation

Aldehydic group
Tollen’s test RCHO + 2[Ag(NH3)2]OH  RCOONH4 + 3NH3 + Formation of silver
H2O + 2Ag(s) mirror along the sides of
silver mirror the test tube.

Fehling’s test RCHO  2Cu 2  5OH   Cu 2 O   RCOO   3H 2 O A red ppt. is formed (only
Re d ppt. by aliphatic aldehydes).
Schiff’s test RCHO + p-rosaniline hydrochloride in saturated solution of Appearance of pink colour.
SO2 in water (colourless olution)

Ketonic group

Iodoform test R  CO  CH3  3I 2  4NaOH  Formation of yellow ppt of

CHI3 (for methyl ketones
3NaI  CHI3   RCOONa  3H 2 O only).
Yellow ppt.

Sodium RCOR + sodium nitroprusside solution + NaOH Appearance of wine-red

nitroprusside colour (for methyl ketones
test only).

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26 ALDEHYDES AND KETONES

Summary
 Preparation of Aldehyde:

 Preparation of Ketones :

Aldehydes and Ketones

ALDEHYDES AND KETONES 27
 Properties of Aldehydes and Ketones :

 Properties of Benzaldehyde :

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28 ALDEHYDES & KETONES

Solved Examples
Example-1 (d) It can show optical isomerism
Name the following compounds according to IUPAC system Ans. (b)
of nomenclature:
Sol. It has 1º and 2º alcoholic group, but not 3º
(a) CH3CH(CH3)CH2CH2CHO
 It is isomer of 1, 3-dihydroxypropanone.
(b) CH3CH2COCH(C2H5)CH2CH2Cl
HOH2C – CO – CH2OH
(c) CH3CH= CHCHO
 It has same empirical formula as Glucose i.e. CH2O
(d) CH3COCH2COCH3
 The molecule has asymmetric centre. Hence, it shows
(e) CH3CH(CH3)CH2C(CH3)2COCH3
optical isomerism.
Sol. (a) 4-methylpentanal
Example-5
(b) 6-Chloro-4-ethylhexan-3-one
Trioxane is a trimer of
(c) But-2-en-1-al
(a) acetaldehyde (b) formaldehyde
(d) Pentane-2, 4-dione
(c) benzaldehyde (d) salicylaldehyde
(e) 3, 3, 5-Trimethylhexan-2-one
Ans. (b)
Example-2
Sol.
In aldehydes and ketones, carbon of the carbonyl group is
(a) sp3-hybridized (b) sp2-hybridized CH2

(c) sp-hybridized (d) unhybridized O O

Ans. (b) H2C CH2

Sol. Aldehydes and ketones have C = O in which C is sp 2 O
hybridised. Trioxane
Example-3
Example-6
Which of the following types of isomerism is exhibited by
pentanone? Ozonolysis of an organic compound ‘A’ produces acetone
and propionaldehyde in equimolar mixture. Identify ‘A’ from
(a) Chain isomerism
the following compounds:
(b) Position isomerism
(a) 1 – Pentene
(c) Functional isomerism
(b) 2 – Pentene
(d) All of these
(c) 2 – Methyl – 2 – pentene
Ans. (d)
(d) 2 – Methyl – 1 – pentene
Sol.
Ans. (c)
CH 3 Sol. From the products formed it is clear that the compound has
| 5 carbon atoms with a double bond and methyl group on
CH 3 COCH 2 CH 2 CH 3 and CH 3 COCHCH 3 2nd carbon atom.
are chain isomers CH3COCH2CH2CH3 and Example-7
CH3CH2COCH2CH3 are position isomers or metamers
The following reaction
CH3COCH2CH2CH3 and CH3CH2CH2CH2CHO are
functional isomers.
Example-4
Which one of the statements about HOH2CCH(OH)CHO is
not correct?
(a) It is an isomer of 1, 3-dihydroxypropanone is known as
(b) It contains a tertiary alcoholic group
(c) It has the same empirical formula as glucose
ALDEHYDES & KETONES 29

(a) Perkin reaction

(b) Gattermann aldehyde synthesis
(c) Kolbe’s reaction
(d) Gattermann-Koch reaction
Ans. (b)
Sol. Example-9
The reaction of C6H5CH = CHCHO with NaBH4 gives
(a) C6H5CH2CH2CH2OH (b) C6H5CH = CHCH2OH
(c) C6H5CH2CH2CHO (d) C6H5CH2CHOHCH3
Ans. (b)
Sol. Normally NaBH4 as well as LiAlH4 reduce only –CHO group
without effecting carbon-carbon double bond, however when
it is present in conjugation with benzene ring and aldehydic
group in presence of LiAlH4, it is also reduced along with
the reduction of –CHO group.
LiAlH
4  C H CH CH CH OH
C6 H5CH  CHCHO  6 5 2 2 2

But in presence of NaBH4, double bond remains intact.

NaBH
4  C H CH  CH CH OH
C6 H5 CH  CHCHO  6 5 2

Example-10
Give the product of the following reaction:

Example-8
Draw the structure of the following compounds:
(a) 3-Methylbutanal (a) (b)
(b) p-Nitropropiophenone
(c) p-Methylbenzaldehyde
(d) 4-Methylpent-3-en-2-one (c) (d)
(e) 4-Chloropentan-2-one
Sol. Ans. (b)
Sol.

Example-11
Which of the following compounds will undergo self aldol
condensation in the presence of cold dilute alkali?
(a) CH2 = CH – CHO (b) CH  C-CHO
(c) C6H5CHO (d) CH3CH2CHO
30 ALDEHYDES & KETONES

Ans. (d) (iii) Taking one molecule each of propanal and butanal in
Sol. Aldol condensation is given by only those aldehydes or which propanal acts as a nucleophile and butanal acts as an
ketones which have -hydrogen atom on a saturated carbon; electrophile.
-H present on unsaturated carbon atom cannot be easily OH CH3
removed by a base. dil NaOH
CH3CH2CH2CHO + CH3CH2CHO CH3CH2CH2 – CH – CH – CHO
(a) Butanal Propanal 3– Hydroxy – 2 – methylpentanal
(Electrophile) (Nucleophile)

(iv) Taking one molecules each of propanal and butanal in

which propanal acts as an electrophile and butanal acts as a
nucleophile.
OH CH2CH3
dil NaOH
(b) CH3CH2CHO + CH3CH2CH2CHO CH3CH2 – CH – CHCHO
Propanal Butanal 2– Ethyl – 3 – hydroxyhexanal
(Electrophile) (Nucleophile)

Example-13
Predict the product in the given reaction.

(c)

(d) (a)

(b)
Example-12
Write structural formulas and names of four possible aldol
condensation products from propanal and butanal. In each
case, indicate which aldehydes acts as nucleophile and which
as electrophile. (c)
Sol. (i) Taking two molecules of propanal, one which acts as a
nucleophilic and the other as an electrophile.
OH CH3

2 CH3CH2CHO dil NaOH CH3CH2 – CH – CH – CHO (d)

Propanal 3 – hydroxy – 2 – methylpentanal

(ii) Taking two molecules of butanal, one which acts as a

Ans. (c)
nucleophile and the other as an electrophile.
Sol. Cannizzaro reaction - when an aldehyde containing no -H
OH CH2CH3 undergo reaction in presence of 50% KOH. It
2 CH3CH2CH2CHO
dil NaOH
CH3CH2CH2 – CH – CH – CHO
disproportionates to form a molecule of carboxylic salt and
Butanal 2– Ethyl – 3 – hydroxyhexanal
a molecule of alcohol.
ALDEHYDES & KETONES 31

contain -hydrogens, four compounds are obtained as

products.
For example, ethanal and propanal react to give four
products.

Example-14

Reduction of C = O to > CH2 can be carried out with

(a) catalytic reduction (b) Na/C2H5OH

(c) Wolf-Kishner reduction (d) LiAlH4
Ans. (c)
Sol. Catalytic reduction, Na/C2H5OH and LiAlH4 reduce

C = O group to CHOH and not CH2

Example-15
Describe the following:
(a) Acetylation (b) Cannizzaro reaction
(c) Cross aldol condensation (d) Decarboxylation
Sol. (a) Acetylation: The introduction of an acetyl functional
group into an organic compound is known as acetylation. It
is usually carried out in the presence of a base such as
pyridine, dimethylaniline, etc. This process involves the
substitution of an acetyl group for an active hydrogen atom. (d) Decarboxylation: Decarboxylation refers to the reaction
Acetyl chloride and acetic anhydride are commonly used in which carboxylic acids lose carbon dioxide to form
as acetylating agents. hydrocarbons when their sodium salts are heated with soda-
For example, acetylation of ethanol produces ethyl acetate. lime.
Pyridine
CH 3 CH 2 OH  CH 3 COCl  CH 3COOC 2 H 5
Ethanol Acetyl Ethylacetate
Chloride  HCl

(b) Cannizzaro reaction: The self oxidation-reduction

(disproportionation) reaction of aldehydes having no  -
hydrogens on treatment with concentrated alkalis is known Example-16
as the Cannizzaro reaction. Arrange the following compounds in increasing order of
their property as indicated:
Acetaldehyde, Acetone, Di-tert-butyl ketone, Methyl tert-
butyle ketone (reactivity towards HCN)
Sol. More the electron deficient carbonyl carbon more will be
reactivity toward nucleophilic addition reaction
Hence, the given compounds can be arranged according to
(c) Cross-aldol condensation: When aldol condensation is their increasing reactivities towards HCN as:
carried out between two different aldehydes, or two different Di-tert-butyl ketone < Methyl tert-butyl ketone < Acetone <
ketones, or an aldehyde and a ketone, then the reaction is Acetaldehyde
called a cross-aldol condensation. If both the reactants
32 ALDEHYDES & KETONES

(f)

(g)

Sol. (a)
O
C6H5CHO + H2NCONHNH2 C6H5CH=NNHC–NH2 + H2O
Benzaldehyde Semicarbazide Benzaldehyde semicarbazone

(b)
Example-17
How will you convert ethanal into the following compounds?
(a) Butane-1, 3-diol
(b) But-2-enal
Sol. (a) On treatment with dilute alkali, ethanal produces 3-
hydroxybutanal gives butane-1, 3-diol on reduction.
OH OH
dil NaOH NaBH4
CH3CHO CH3–CH–CH2–CHO (Reduction) CH3–CH–CH2–CH2–OH
Ethanal 3-hydroxybutenal Butane-1, 3-diol

(b) On treatment with dilute alkali, ethanal gives 3-

hydroxybutanal which on heating produces but-2-enal.
OH
dil NaOH 
CH3CHO CH3–CH–CH2–CHO –H2O
CH3–CH–CH–CHO (c)
Ethanal 3-hydroxybutenal Butane-2 enal

Example-18
Complete each synthesis by giving missing starting material,
reagent or products.
2 2 H NCONHNH
(a) C6 H5 CHO 
(d)

(b)

(c)

C 6 H5 CHO (e)
 dil.NaOH 

(d)
CH 3 CH 2 CHO

(e)
ALDEHYDES & KETONES 33

(f) (c)

(g) (d)

Example-19
How will you bring about the following conversions in not
more than two steps?
(a) Propanone to Propene
(b) Ethanol to 3-Hydroxybutanal
(c) Benzene to m-Nitroacetophenone
(d) Bromobenzene to 1-Phenylethanol
(e) Benzaldehyde to 3-Phenylpropan-1-ol
(e)
Sol. (a)

(b)
34 ALDEHYDES & KETONES

Example-20
Which of the following reagents reacts differently with
HCHO, CH3CHO and CH3COCH3?
(a) HCN (b) NH2NH2
(c) NH2OH (d) NH3
Ans. (d)
Sol. 6HCHO  4NH3   CH 2 6 N 4  6H 2 O

Both give a yellow precipitate of CHI3 (iodoform) with iodine

and alkali.
Acid derivatives donot show iodoform test.
2CH3COCH3  NH3   CH3  2 C  NH 2  CH 2 COCH 3 Example-23
Example-21 An organic compound ‘A’ has the molecular formula C3H6O.
Which of the following reagents cannot be used to It undergoes iodoform test. When saturated with HCl it gives
distinguish between hexanal and 2-hexanone? ‘B’ of molecular formula C9H14O. ‘A’ and ‘B’ respectively are
(a) Tollen’s reagent (b) Br2 in CCl4 (a) Propanal and mesitylene
(c) I2 in NaOH (d) Fehling solution (b) Propanone and mesityl oxide
Ans. (b) (c) Propanone and 2,6-dimethyl-2, 5-heptadien-4-one
Sol. (d) Propanone and mesitylene oxide
Test C 4H 9CH 2CHO CH 3COC 4H 9 Ans. (c)
Sol. Since compound A (C3H6O) undergoes iodoform test, it must
(hexanal) (2-hexanone)
be CH3COCH3 (propanone). Further the compound B
Tollen’s reagent Positive Negative
obtained from A has three times the number of carbon atoms
Br2 in CCl4 Negative Negative in A (propanone), B must be phorone, i.e., 2, 6-dimethyl-2, 5-
I2 in NaOH Negative Positive heptadien -4- one.
Fehling Sol. Positive Negative (CH3)2C= O + H3CCOCH3 + O = C(CH3)2
HCl

A, propanone (3 molecules)
Example-22 (CH3)2C= CHCOCH = C(CH3)2
2. 6-dimethyl-2.5 –heptadiene - 4- one
Which of the following compounds will give a yellow
precipitate with iodine and alkali ? Example-24
(i) Acetophenone (ii) Acetamide What is meant by the following terms? Give an example of
(iii) Methyl acetate (iv) 2-Hydroxypropane the reaction in each case.
(a) (i), (ii) and (iii) (b) (i) and (iv) (a) Cyanohydrin (b) Acetal
(c) (ii) and (iv) (d) (i), (iii) and (iv) (c) Semicarbazone (d) Aldol
Ans. (b) (e) Hemiacetal (f) Oxime
Sol. It is iodoform reaction. Acetophenone (g) Ketal (h) Imine
(i) 2, 4-DNP-derivative (j) Schiff’s base
Sol. (a) Cyanohydrin: Cyanohydrins are organic compounds
having the formula RRC(OH)CN, where R and R can be
alkyl or aryl groups.
ALDEHYDES & KETONES 35

molecules of the same or one molecule each of two different

aldehydes or ketones in the presence of a base.
Reaction:
 CH3  CH 2  CH  CH 2  CH 2  CHO
dil NaOH
2CH3CH 2  CHO 
Propanal
OH
4-Hydroxyhexanal(Aldol)
Reaction:
(e) Hemiacetal: Hemiacetals are -alkoxyalcohols

(b) Acetal: Acetals are gem-dialkoxy alkanes in which two

alkoxy groups are present on the terminal carbon atom. One
bond is connected to an alkyl group while the other is
connected to a hydrogen atom.
OR’
“RO Aldehyde reats with one molecule of a monohydric alcohol
in the presence of dry HCl gas.
Reaction:
R H
OR`
Reaction:

R `OH,dryHClgas
 R – CH
RCHO  
OH
Hemiacetal

(f) Oxime: Oximes are a class of organic compounds having

the general formula RR CNOH, where R is an organic side
chain and R is either hydrogen or an organic chain. If Ris
H, then it is known as aldoxime and if R is an organic side
chain, it is known as ketoxime.
OH OH

N N
(c) Semicarbarbanzone: Semicarbazones are derivatives of
aldehydes and ketones produced by the condensation
R H R R`
reaction between a ketone or aldehyde and semicarbazide.
Aldoxime Ketoxime
Reaction:
On treatment with hydroxylamine in a weakly acidic medium,
aldehydes or ketones form oximes.
(g) Ketal: Ketals are gem-dialkoxyalkanes in which two alkoxy
groups are present on the same carbon atom within the
chain. The other two bonds of the carbon atom are
connected to two alkyl groups.

‘“RO OR”

R R’
(d) Aldol: A -hydroxy aldehyde or ketone is known as an
aldol. It is produced by the condensation reaction of two
36 ALDEHYDES & KETONES

Reaction: Reaction:
R O – CH2 +
R CH2OH R – CH = O + H2 – N – R` Trace of H R – CH = N – R` + H2O
C=O+ 
HClgas
  C + H2O Aldehyde 1 amine Schiff’s base
R` CH2OH dil.HCl
R` O – CH2
ketane Ethyl glycol Ethylene glycol ketal Example-25
(h) Imine: Imines are chemical compounds containing a Give simple chemical tests to distinguish between the
carbon nitrogen double bond. following pairs of compounds.
(a) Propanal and Propanone
(b) Acetophenone and Benzophenone
(c) Ethanal and Propanal
Sol. (a) Propanal and propanone can be distinguished by the
Tollen’s test.
Tollen’s test: Propanal is an aldehyde. Thus, it reduces
Reaction: Tollen’s reagent. But, propanone being a ketone does not
OH reduce Tollen’s reagent.
C= O + H2 N–Z ⇌ C C= N – Z + H2O
NHZ C6H5CHO = 2 [Ag (NH3)2 ]+ + 30H– C6H5COO– Ag + 4NH3 + 2H2O
Benzaldehyde Tollen’s reagent Benzoate ion Silver mirror
(i) 2, 4–DNP–derivative: 2,4-dinitrophenylhydragones are
2, 4-DNP–derivatives, which are produced when aldehydes
or ketones react wth 2, 4-dinitrophenylhydrazine in a weakly (b) Acetophenone and Benzophenone can be distinguished
acidic medium. using the iodoform test.
Reaction: Iodoform test: Methyl ketones are oxidized by sodium
NO2 hypoiodite to give yellow ppt. of iodoform. Acetophenone
being a methyl ketone responds to this test, but bezophenone
C= O + H2 –NNH NO2 does not.

2. 4 - Dinitrophenylhydrazone NO2 C6H5COCH3 + 3 NaOl C6H5COONa + CHI3 + 2 NaOH

Acetophenone Sodium Sodium Iodoform
H2O + hypoiodite benzoate (yellow ppt)
C = NNH – NO2
C6H5COCH3 + NaOl No yellow ppt of CHI3
2. 4 - Dinitrophenylhydrazone

(i) Schiff’s base: Schiff’s base (or azomethine) is a chemical (c) Ethanal and propanal can be distinguished by iodoform
compound containing a carbon-nitrogen double bond with test:
the nitrogen atom connected to an aryl or alkyl group-but Iodoform test: Aldehydes and ketones having at least one
not hydrogen. They have the general formula R1R2C = NR3. methyl group linked to the carbonyl carbon atom responds
Hence, it is an imine. It is named after a scientist, Hugo to the iodoform test. Ethanal having one methyl group linked
Schiff. to the carbonyl carbon atom responds to this test. But
propanal does not have a methyl group linked to the carbonyl
carbon atom thus, it does not respond to this state.

CH3CHO + 3NaOl HCOONa + CHI3 + 2 NaOH

Ethanal Sodium Iodoform
methanoate (yellow ppt)
ALDEHYDES AND KETONES 37

EXERCISE – 1: Basic Objective Questions

Carbonyl Compounds-Introduction 12. When enolate A is compared with enolate B
1. The IUPAC name of Cl3CCH2CHO is :
(a) chloral
(b) 3,3,3-trichloropropanal
(c) 1,1,1-trichloropropanal
(d) 2,2,2-trichloropropanal
2. The IUPAC name of CH3COCH(CH3)2 is :
(A) (B)
(a) isopropyl methyl ketone
Which of the following statements is true?
(b) 2-methyl-3-butanone
(a) A is more stable than B
(c) 4-methyl-isopropyl ketone
(b) B is more stable than A
(d) 3-methyl-2-butanone
(c) A and B have the same stability
3. The general formula of both aldehydes and ketones is:
(d) No comparison of stability can be made
(a) CnH2n + 2O (b) CnH2nO
13. Which of the compound shown is (are) correctly named
(c) CnH2n – 2O (d) CnH2n + 4O
as pentane derivates, either as pentanals or pentanones?
4. Aldehydic group can occur :
(a) anywhere in the carbon chain
(b) in the middle of carbon chain
(c) only at the second carbon atom of the chain
(d) only at the end carbon atom of the carbon chain
5. The formula of chloral is (a) 1 only (b) 2 only
(a)𝐶𝐻3 𝐶𝐻 = 𝑁𝐻𝐶6 𝐻5 (b) CH2ClCHO (c) 3 only (d) 1 and 3
(c) CCl3CHO (d) CHCl2CHO 14. Which of the following forms an enol to the greatest
6. A strong base can abstract an alpha-hydrogen from extent?
(a) amide (b) amine
(c) ketone (d) alkane
7. Formalin is an aqueous solution of : (a) (b)
(a) formic acid (b) fluorescein
(c) formaldehyde (d) furfuraldehyde
8. Acetals are (c) (d)
(a) ketones (b) diethers
(c) aldehyde (d) hydroxy aldehydes Preparation Of Aldehydes & Ketones

15. Which of the following compound will yield 2,5-

9. The structure would be best classified as dimethylhexan-1,6-dial upon ozonolysis?
a(n) (a) 3, 6-dimethyl cyclohexene
(a) Acetal (b) Hemiacetal (b) 3,4-dimethyl cyclohexene
(c) 4,6-dimethyl cyclohexene
(c) Hydrate (d) Cyanohydrin
(d) 3,5-dimethyl cyclohexene
10. Ethanedial has which functional group ?
(a) One ketonic (b) Two aldehydic
(c) One double bond (d) Two double bond
11. Which of the following is paradehyde?
16. On reductive ozonolysis yields
(a) HCHO (b) (CH3CHO)3
(a) 6-oxoheptanal (b) 6-oxoheptanoic acid
(c) (CH3CHO)4 (d) CH3COOH
(c) 6-hydroxyheptanal (d) 3-hydroxypentanal
38 ALDEHYDES AND KETONES

17. Which of the following yield 2 moles of formaldehyde (b) CH3 CH2CHO+C2 H5 OH
on ozonolysis? (c) CH3 CH2CHO+CH3 CHO
(a) CH  CH (b) CH2  CH2 (d) CH3 CH2 CH2 CHO + CH3 CHO
24. Complete the reaction:
(c) CH3  CH  CH2 (d) C6H6
PhMgBr/H O+
18. Which compound would give 5 – keto – 2 – methyl Ph  CH  CH  CHO 
3  Product
hexanal upon ozonolysis? Ph  CH  CHO
(a) |
Ph
Ph  CH  CH 2  CHO
(b) |
Ph
Ph  CH  CH  CHO
(c) | |
(a) (b) OH Ph
Ph  CH  CH 2  CH 2  OH
|
(d)
Ph
25. Which of the following is the industrial method of
preparation of acetaldehyde?
(a)
(c) (d) SnCl H O
CH3CN 
2  CH CH  NH 
HCl 3
3  CH CHO
3
19. Which of the compounds with molecular formula C5H10
yields acetone on ozonolysis? (b)
Pd
(a) 2-methyl-2-butene CH 3 COCl  H 2   CH 3 CHO  HCl
BaSO
(b) 3-methyl-1-butene 4
(c) Cyclopentane Pd 2
(c) CH2=CH2 + H2O  CH3CHO
(d) 2-methyl-1-butene
(d) None of the above
20. Which of the following gases when passed through
warm dilute solution of H2SO4 in presence of HgSO4
gives acetaldehyde?
Physical And Chemical Properties Of Aldehydes
(a) CH4 (b) C2H6
& Ketones
(c) C2H4 (d) C2H2 26. Arrange the following compounds in decreasing order
21. When but-2-yne is treated dil.H2SO4/HgSO4 the product of their boiling points.
formed is : CH3CHO, CH3CH2OH, CH3OCH3, CH3CH2CH3
(a) butan-1-ol (b) butan-2-ol (a) CH3CH2CH3>CH3OCH3> CH3CHO > CH3CH2OH
(c) acetone (d) 2-butanone (b) CH3CH2CH3> CH3CHO > CH3OCH3> CH3CH2OH
22. Which of the following on heating with aqueous KOH, (c) CH3CH2CH3> CH3CHO > CH3CH2OH> CH3OCH3
produces acetaldehyde ? (d) CH3CH2OH> CH3CHO > CH3OCH3> CH3CH2CH3
(a) CH3COCl (b) CH3CH2Cl 27. Ketones
(c) CH2ClCH2Cl (d) CH3CHCl2
23.

O where R = R1 = alkyl group. It can be obtained in one

|| (i) DIBAL H(1eq) (ii) H O step by
CH3 CH 2  C  O  C2 H5  3 
(a) Hydrolysis of esters
AB (b) Oxidation of primary alcohol
A and B are respectively. (c) Oxidation of secondary alcohol
(a) CH3 CH2 CH2OH+C2 H5 OH (d) Reaction of acid halide with alcohols
ALDEHYDES AND KETONES 39

28. Aldehydes are the first oxidation product of 36. Consider the following statement Acetophenone can be
(a) primary alcohol (b) secondary alcohol prepared by
(c) tertiary alcohol (d) dihydric alcohol (1) Oxidation of 1-phenyethanol
29. An organic compound X on treatment with pyridinium (2) Reaction of 1-phenylethanol with methyl
chloro chromate in dichloromethane gives compound magnesiumbromide
Y. Compound Y reacts with I2 and alkali to form (3) Friedel Craft’s reaction of benzene with acetyl
triiodomethane. The compound ‘X’ is chloride
(a) C2H5OH (b) CH3CHO (4) Distillation of calcium benzoate
(c) CH3COCH3 (d) CH3COOH (a) 1 and 2 (b) 1 and 4
30. Oxidation reactions can be carried out with chromic (c) 1 and 3 (d) 3 and 4
acid in aqueous acetone at 5–10°C.Which of following 37. Dry heating of calcium acetate gives
is incorrect in this respect (a) Acetaldehyde (b) Ethane
(a) (c) Acetic acid (d) Acetone
38. On heating calcium acetate and calcium formate, the
product formed is
(a) CH3COCH3 (b) CH3CHO
(c) HCHO + CaCO3 (d) CH3CHO + CaCO3
(b) 39. In the following reaction, product P is

(a) RCH2OH (b) RCOOH

(c) RCHO (d) RCH3
(c) CH3  CH2 3 CH2 OH  CH3  CH2 3 COOH
40. Catalyst used in Rosenmund reduction is
(a) Pd/BaSO4 (b) Zn-Hg couple
(d) None of these (c) LiAlH4 (d) Ni/H2
31. The oxidation product of 2-propanol with hot conc. 41. What reagent is used in the Rosenmund reduction?
HNO3 is (a) H2/Pd-BaSO4
(a) Ethanoic acid (b) Propanone (b) LiAlH4
(c) Propanal (d) None of these (c) NH2NH2/KOH/CH2OH-CH2OH
32. Methyl ethyl ketone is prepared by the oxidation of (d) Zn-Hg/HCl
(a) 2-propanol (b) 1-butanol 42. Reduction of acetonitrile in presence of SnCl2/HCl,
(c) 2-butanol (d) t-butyl alcohol followed by hydrolysis gives :
33. Which one of the following can be oxidised to the (a) HCHO (b) CH3CHO
corresponding carbonyl compound? (c) CH3CH2CHO (d) CH3COCH3
(a) 2-hydroxy-propane 43. The reagent used in Gattermann Koch aldehyde
(b) ortho-nitro-phenol synthesis is
(c) Phenol (a) Pb/BaSO4 (b) alkaline KMnO4
(d) 2-methyl-2-hydroxy-propane (c) acidic KMnO4 (d) CO + HCl
34. The oxidation of toluene to benzaldehyde by chromyl
chloride is called
Chemical Reactions Of Carbonyl Compounds
(a) Cannizzaro reaction
(b) Wurtz reaction
44. Arrange the following compounds in increasing order
(c) Etard reaction
of their reactivity in nucleophilic addition reactions.
(d) Reimer-Tiemann reaction
Ethanal (I), Propanal (II), Propanone (III), Butanone
35. Acetone on distillation with conc. H2SO4 forms
(IV)
(a) phorone (b) acrolein
(a) III < II < I < IV (b) II < I < III < IV
(c) mesitylene (d) mesityl oxide
(c) IV < III < II < I (d) I < II < III < IV
40 ALDEHYDES AND KETONES

45. A carbonyl compound reacts with hydrogen cyanide to 51. Correct order of reactivity of CH 3CHO, C2H5COCH3
form cyanohydrin which on hydrolysis forms a racemic and CH3COCH3 is
mixture of a α-hydroxy acid. The carbonyl compound (a) CH3CHO > CH3COCH3>CH3COC2H5
is (b) C2H5COCH3> CH3COCH3> CH3CHO
(a) acetaldehyde (b) acetone (c) CH3COCH3> CH3CHO > C2H5COCH3
(c) diethyl ketone (d) formaldehyde (d) CH3COCH3> C2H5COCH3> CH3CHO
46. The increasing order of the rate of HCN addition to 52. The most reactive compound towards formation of
compounds A-D is cyanohydrin on treatment with HCN followed by
(A) HCHO (B) CH3COCH3 acidification is
(C) PhCOCH3 (D) PhCOPh (a) benzaldehyde (b) p-nitrobenzaldehyde
(a) A < B < C < D (b) D < B < C < A (c) phenylacetaldehyde (d) p-hydroxybenzaldehyde
(c) D < C < B < A (d) C < D < B < A 53. A and B in the following reactions are
47. Nucleophilic addition reaction will be most favoured in
(a) CH3CH2CHO
(b) CH3CHO

(a)
(c)
(d) (CH3)2C = O
48. Which of the aldehyde is most reactive towards
nucleophilic addition reaction ? (b)
(a) C6H5–CHO
(b) CH3CHO
(c) HCHO
(d) All are equally reactive
49. (c)

Product may be (d) A = RR’CH2CN, B = NaOH

(a) Meso 54. Reaction of acetaldehyde with HCN followed by
(b) Racemic hydrolysis gives a compound which shows
(c) Inversion (a) Optical isomerism
(d) All of these (b) Geometrical isomerism
50. Which of the following carbonyl oxygen will form (c) Metamerism
strongest hydrogen bond with 𝐻2 𝑂 molecule? (d) Tautomerism
55. Which one of the following does not form sodium
bisulphite addition product with sodium bisulphite
solution
(a) CH2O (b) C6H5COCH3
(a) (b) (c) C6H5CHO (d) CH3CHO
56. Benzaldehyde condenses with N,N-dimethylaniline in
presence of anhydrous ZnCl2 to give
(a) Michler’s ketone (b) azo-dye
(c) malachite green (d) buffer yellow

(c) (d)
ALDEHYDES AND KETONES 41

57. Which of the following species is the conjugate acid of 63. Clemmensen reduction involves > C = O to > CH2 in
the hemiacetal formed by reaction of benzaldehyde presence of
with methanol containing a trace of acid ? (a) Zn/Hg (b) Alcohol
(c) Zn dust (d) Zn/alcohol
64. Clemmensen's reduction will convert cyclohexanone
into:
(a) (b) (a) Cyclopentanone (b) Cyclohexane
(c) n-Hexane (d) Benzene
65. Clemensen’s reduction of ketones is carried out in
(a) H2 with Pd catalyst (b) Glycol with KOH
(c) LiAlH4 in water (d) Zn–Hg with HCl
(c) (d) 66. Aldehydes and ketones can be reduced to
58. Grignard reagent on reaction with acetone forms corresponding hydrocarbons by
(a) Tertiary alcohol (b) Secondary alcohol (a) Refluxing with water
(c) Acetic acid (d) Acetaldehyde (b) Refluxing with strong acids
59. Product in following reaction is CH3MgI + HCHO → (c) Refluxing with soda amalgam and water
Product (d) Refluxing with zinc amalgam and concentrated HCl
(a) CH3CHO (b) CH3OH 67. In Wolf-Kishner reduction, the carbonyl group of
(c) C2H5OH (d) CH3– O – CH3 aldehydes and ketones is converted into
(a) > CH2 group (b) – CH3 group
60. Identify the reactant X and the product Y (c) – CH2OH group (d) > CHOH group
68. Wolff-Kishner reduction is :
(a) reduction of carbonyl compounds into hydrocarbons
(b) reduction of carbonyl compounds into alcohols
(c) reduction of nitrobenzene into aniline
(d) reduction of carbohydrates into alcohols
(a) X = MgCl2 ; Y = CH3CH = CH2 69.
(b) X = CH3MgCl ; Y = C2H5COCH3
(c) X = CH3MgCl ; Y = (CH3)3C – OH
(d) X = C2H5MgCl ; Y = (CH3)3C – OH
61. The order of reactivity of phenyl magnesium bromide
with the following compounds is
A is
(a) Zn −Hg/HCl (b) NH2 − NH2 /OH −
(c) Both (a) and (b) (d) NaBH4
70. Which one of the following pairs is not correctly
matched
(a) (II) > (III) > (I) Clemmenson
(a) > C = O → > CH2
(b) (I) > (III) > (II) Wolf−kishner
(c) (II) > (I) > (III) (b) > C = O → > CHOH
(d) All react with the same rate R osenmund′ sreduction
(c) – COCl → CHO
62. Which of the following reagents converts both
Stephenreduction
acetaldehyde and acetone to alkanes? (d) – C ≡ N → CHO
(a) Ni/H2 (b) LiAlH4 71. For C6H5CHO which of the following is incorrect?
(c) I2/NaOH (d) Zn-Hg/conc.HCl (a) On oxidation it yields benzoic acid
(b) It is used in perfumery
(c) It is an aromatic aldehyde
(d) On reduction yields phenol
42 ALDEHYDES AND KETONES

72.
81. O
|| Conc. HNO
CH 3  C  CH 2  CH 3  3  Product

The product is
(a) CH3COOH
The product predominates is (b) CH3CH2 COOH  HCOOH
(c) CH3CH2 CH2 COOH
(d) No reaction
(a) (b) 82.

(c) (d)
73. CH3CHO  LiAlH4  CH3CH2 OH
Nucleophile added in this reaction is
(a) AlH 4 (b) Li 
(a) (b)
(c) H  (d) H 

74.
In the above sequence X can be
(a) H2/Ni (b) NaBH4
(c) (d)
(c) K2Cr2O7 (d) Both (a) and (b) 83. Oxidation of acetaldehyde with selenium dioxide
75. The compound which is not reduced by 𝐿𝑖𝐴𝑙𝐻4 is produces:
(a) Cyclohexanone (b) 2-Methyl-1-butanol (a) ethanoic acid (b) methanoic acid
(c) Ethyl benzoate (d)  -caprolactam (c) glyoxal (d) oxalic acid
76. If pentan-2-one is reacted with NaBH4, followed by 84. The product obtained in the following reaction is
hydrolysis with D2O, the product will be :
(a) CH3CD(OD)CH2CH2CH3
(b) CH3CD(OH)CH2CH2CH3
(c) CH3CH(OH)CH2CH2CH3
(d) CH3CH(OD)CH2CH2CH3
77. The reaction of acetaldehyde with conc. KMnO4 gives
(a) CH3COOH (b) CH3CH2OH (a)
(c) HCHO (d) CH3OH
78. An aldehyde on oxidation gives
(a) An alcohol (b) An acid
(c) A ketone (d) An ether (b)
79. Aldehydes are first oxidation products of:
(a) primary alcohols (b) secondary alcohols
(c) tertiary alcohols (d) none of these
(c)
80. Isopropyl alcohol on oxidation forms:
(a) acetone (b) ether
(c) acetaldehyde (d) ethylene
(d)
ALDEHYDES AND KETONES 43

85. When dihydroxy acetone reacts with HIO4, the product 92. Aldol condensation will not take place in
is/are (a) HCHO
(a) HCHO (b) HCOOH (b) CH3CH2CHO
(c) HCHO and HCOOH (d) HCHO and CO2 (c) CH3CHO
86. Aldol condensation will not be observed in (d) CH3COCH3
(a) Chloral (b) Phenyl acetaldehyde 93. Acetophenone when reacted with a base, C2H5ONa,
(c) Hexanal (d) Ethanal yields a stable compound which has the structure
87. Which of the following will not undergo aldol
condensation
(a) Acetaldehyde (b) Propanaldehyde (a)
(c) Benzaldehyde (d) Trideuteroacetaldehyde
88. Treatment of propionaldehyde with dilute NaOH
solution gives
(a) CH3CH2COOCH2CH2CH3
(b) CH3CH2CHOHCH(CH3)CHO (b)
(c) CH3CH2CHOHCH2CH2CHO
(d) CH3CH2COCH2CH2CHO
89. Aldol condensation is
(c)
(a) self condensation of aldehydes only having atleast
(d) none of these
one alpha hydrogen
(b) self condensation of ketones only having atleast one 94. Which of the products is formed when acetone is
alpha hydrogen reacted with barium hydroxide solution?
(c) self condensation of both aldehydes and ketones
having atleast one alpha hydrogen
(d) self condensation of both aldehydes and ketones
having no alpha hydrogen (a)

(b)

90. does not show aldol condensation

because :
(c)
(a) carbon is bounded by 3-heavy methyl groups
(b) due to the absence of α-hydrogen
(c) it is a neutral molecule
(d) due to hindrance created by methyl group for (d)
carbanion 95. 3-hydroxy butanal is formed when X reacts with Y in
91. Predict the product ‘B’ in the sequence of reaction dilute Z solution. What are X, Y and Z?
X Y Z
(a) CH3CHO, (CH3)2CO, NaOH
(a) CH3COONa
(b) CH3CHO, CH3CHO, NaCl
(b) CH3COOH
(c) (CH3)2CO, (CH3)2CO, HCl
(c) CH3CHO
(d) CH3CHO, CH3CHO, NaOH
96. Which of the following compound will undergo self
(d) aldol condensation in the presence of cold dilute alkali
(a) C6H5CHO (b) CH3CH2CHO
(c) CH  C  CHO (d) CH2  CH  CHO
44 ALDEHYDES AND KETONES

97. 103. The correct sequence of step involved in the mechanism

of Cannizzaro’s reaction is
(a) nucleophilic attack, transfer of H– and transfer of
H+.
(b) transfer of H–, transfer of H+ and nucleophilic
attack.
(c) transfer of H+, nucleophilic attack and transfer of
(a) H–.
(d) electrophilic attack by OH–, transfer of H+ and
transfer of H–.
104. Which one of the following undergoes reaction with
(b) 50% sodium hydroxide solution to give the
corresponding alcohol and acid
(a) Butanal (b) Benzaldehyde
(c) Phenol (d) Benzoic acid
NaOH
(c) 105. 2C6 H5 CHO   C6 H5 CH 2 OH  C6 H5 COONa
The similar reaction can take place with which of the
following aldehyde?
(a) CH3 CHO
(d) (b) CH3CH2CHO
98. In the scheme given below, the total number of (c) (CH3 )3 CCHO
intramolecular aldol condensation products formed (d) CH3 CH2CH2CHO
from ′′𝑌 ′′ is 106. Which one does not give Cannizzaro’s reaction?
(a) Benzaldehyde
(b) propanal
(c) p-methoxybenzaldehyde
(a) 1 (b) 2 (d) 2, 2-dimethyl propanal
(c) 3 (d) 4 107. The key step in cannizzaro’s reaction is the
99. Benzaldehyde + NaOH→ intermolecular shift of
(a) Benzyl alcohol (b) Benzene (a) Proton
(c) Hydrobenzamide (d) Cinnamic acid (b) Hydride ion
100. Cannizzaro’s reaction is not given by : (c) Hydronium ion
(a) CH3CHO (b) HCHO (d) Hydrogen bond
(c) benzaldehyde (d) triethyl acetaldehyde 108. m-chlorobenzaldehyde on reaction with conc. KOH at
room temperature gives
(a) potassium m-chlorobenzoate and m-chlorobenzyl
alcohol
101. shows Cannizzaro’s reaction due to (b) m-hydroxybenzaldehyde and m-chlorobenzyl
alcohol
(a) carbon is bounded by 3 methyl groups (c) m-chlorobenzyl alcohol and m-hydroxy benzyl
(b) absence of α-hydrogen atom alcohol
(c) due to steric effect (d) potassium m-chlorobenzoate and m-
(d) None of the above Hydroxybenzaldehyde

102. The following reagent converts C6H5COCHO to

C6H5CHOHCOOH
(a) Aq. NaOH/H+ (b) Acidic Na2S2O3
(c) Na2CrO4/H2SO4 (d) NaNO2/HCl
ALDEHYDES AND KETONES 45

109. Trichloroacetaldehyde was subjected to Cannizaro’s (c)

reaction by using NaOH. The mixture of the products
contains sodium trichloroacetate ion and another
compound. The other compound is
(a) 2, 2, 2-trichloroethanol
(b) trichloromethanol (d)
(c) 2, 2, 2-trichloromethanol
(d) chloroform
110.

112. The number of aldol reaction(s) that occurs in the given

transformation is
(a)

(a) 1 (b) 2
(b)
(c) 3 (d) 4
113.

(c)
The reaction given is
(a) Aldol condensation (b) Knoevenagel reaction
(c) Cannizzaro reaction (d) None of these
(d) 114. Which of the following is obtained when chloral is
boiled with NaOH
(a) CH3Cl (b) CHCl3
(c) CCl4 (d) None of these
111.
115. Acetone is mixed with bleaching powder to give
(a) chloroform (b) acetaldehyde
(c) ethanol (d) phosgene
116. Ketones reacts with Mg-Hg over water gives
(a) pinacolone (b) pinacols
(c) alcohols (d) None of these
Undergo Cannizaro reaction give product as 117.
(a)

(b)
The compound 𝑥is
(a) CH3 COOH (b) BrCH2 − COOH
(c) (CH3 CO)2 O (d) CHO − COOH
118. Acetaldehyde reacts with chlorine to give
(a) CCl4 (b) CHCl3
(c) CCl3.COCH3 (d) CCl3.CHO
46 ALDEHYDES AND KETONES

Test Of Carbonyl Compounds 130. Benedict's solution and Fehling’s solution are similar in
all of the following except:
119. Silver mirror is a test for (a) Both consist of a solution of CuSO4
(a) Aldehydes (b) Thio alcohols (b) Both contain NaOH and complexing reagent
(c) Amines (d) Ethers (c) Both contain Cu2+ ion as the oxidising agent
120. Aldehydes and ketones are differentiated by using (d) Sodium citrate is used in Benedict's solution and
(a) NaOH/I2 (b) NaHSO3 Rochelle salt in Fehling's solution
(c) AgNO3/NH4OH (d) NH2.NH2 131. Acetaldehyde cannot show
121. Which is not true about acetophenone? (a) Iodoform test (b) Lucas test
(a) Reacts to form 2, 4-dinitrophenyl hydrazine gives (c) Benedict’s test (d) Tollen’s test
coloured ppt. 132. The reagent used for the separation of acetaldehyde
(b) Reacts with Tollen’s reagent to form silver mirror from acetophenone is
(c) Reacts with I2/NaOH to form iodoform (a) NaHSO3 (b) C6H5NHNH2
(d) On oxidation with alkaline KMnO4 followed by (c) NH2OH (d) NaOH–I2
hydrolysis gives benzoic acid 133. Brady’s reagent is
122. The compound which reacts with hydroxyl amine but (a) 2,4-DNP (b) conc. HCl + ZnCl2
does not react with Tollen’s reagent is (c) DMSO (d) None of these
(a) CH3CHO (b) HCHO 134. The reagent that gives an orange-coloured precipitate
(c) C2H5OH (d) CH3COCH3 with acetaldehyde
123. Benedict’s solution is not reduced by (a) NH2OH (b) NaHSO3
(a) formaldehyde (b) acetaldehyde (c) Iodine (d) 2, 4-DNP
(c) glucose (d) acetic anhydride 135. An aromatic compound ′𝑋 ′ with molecular formula
124. Fehling’s test is positive for C9 H10O gives the following chemical tests
(a) Acetaldehyde (b) Benzaldehyde (i) Forms 2,4-DNP derivative
(c) Ether (d) Alcohol (ii) Reduce Tollens reagent
125. C2H5CHO and (CH3)2CO can be distinguished by (iii) Undergoes Cannizzaro reaction and
testing with (iv) On vigorous oxidation, 1,2-benzenedicarboxylic
(a) Phenyl hydrazine (b) Hydroxylamine acid is obtained
(c) Fehling solution (d) none of these The compound
126. Which of the following does not give brick red
precipitate with Fehling solution
(a) Acetone (b) Acetaldehyde
(c) Formalin (d) D-glucose
127. Which does not react with Fehling’s solution?
(a) CH3CHO (b) C6H5CHO (a) (b)
(c) CH3CH2CHO (d) Glucose
128. When acetaldehyde is heated with Fehling’s solution, it
gives a precipitate of
(a) Cu (b) CuO
(c) Cu2O (d) Cu + Cu2O + CuO
129. Which of the following is incorrect (c) (d)
(a) FeCl3 is used in the detection of phenols 136. Schiff’s solution is obtained when
(b) Fehling solution is used in the detection of glucose (a) sulphurous acid is passed through magenta dye
(c) Tollen’s reagent is used in detection of unsaturation (b) chlorine is passed through magenta dye
(d) NaHSO3 is used in the detection of carbonyl (c) Both (a) and (b)
compounds (d) None of the above
ALDEHYDES AND KETONES 47

137. Which of the following compounds containing carbonyl 145. Which of the following will not give iodoform test ?
group will give coloured crystalline compound with (a) Isopropyl alcohol (b) Ethanol
(c) Ethanal (d) Benzyl alcohol
146. Which compound undergoes iodoform reaction?
(a) HCHO (b) CH3CHO
(c) CH3OH (d) CH3COOH
(a) CH3COCl (b) CH3COCH3 147. Which of the following will not give iodoform test?
(c) CH3CO(OC2H5) (d) CH3CONH2 (a) Acetone (b) Ethanol
138. Which of the following does not give iodoform test? (c) Ethanal (d) Butanal
(a) CH3CH2OH (b) CH3OH 148. Among the following the one that gives positive
(c) CH3CHO (d) PhCOCH3 iodoform test upon reaction with I2 and NaOH is
139. Which of the following will not give iodoform test? (a) CH3CH2CH(OH)CH2CH3
(a) Ethanal (b) Ethanol (b) C6H5CH2CH2OH
(c) 2-propanone (d) 3-pentanone
140. Which compound does not gives yellow ppt. with (c)
iodine and alkali
(a) 2-hydroxy propane (b) Acetophenone (d) PhCHOHCH3
(c) Methyl ketone (d) Acetamide
141. A compound that gives a positive iodoform test is
(a) 1-pentanol (b) 3-pentanone
(c) 2-pentanone (d) pentanal 149. The compound can be exclusively
142. Which compound does not form iodoform with alkali
and iodine
(a) Acetone (b) Ethanol oxidized into by
(c) Diethyl ketone (d) Isopropyl alcohol (a) NaCN followed by hydrolysis
143. Which compound gives iodoform test? (b) NaOI followed by H3 O+
(a) CH3CHO (b) CH3CH2CH2OH (c) KMnO4 hot followed by hydrolysis
(c) C6H5CH2CH3 (d) C6H5CH2OH (d) K2Cr2O7 followed H3O+
144. Which is necessary for the conversion of butan-2-one 150. Which of the following reagents can be used to
into propanoic acid? distinguish Benzaldehyde from acetophenone?
(a) Tollen reagent (b) Fehling solution (a) Tollen’s reagent
+
(c) NaOH/I2/H (d) NaOH/NaI/H+ (b) Sodium hypoiodite
(c) 2,4-Dinitrophenyl hydrazone
(d) Both a and b
48 ALDEHYDES AND KETONES

EXERCISE – 2: Previous Year Questions

1. Assertion (A): 2-butenal lacks enolisable H-atom, α to 8. Identify the reaction which is used to obtain -hydroxy
carbonyl group, still it has sufficient acidic character. ketone? (Guj CET 2010)
Reason (R): The conjugate base of 2-butenal is
(a) Condensation reaction
stabilized by resonance. (AIIMS 2009)
(b) Aldol condensation
(a) Both A and R are correct and R is the correct
(c) Cross aldol condensation
explanation of A
(d) Cannizaro reaction
(b) Both A and R are correct but R is not the correct
9. Which of the following reaction will not result in the
explanation of A
formation of carbon-carbon bonds?
(c) A is correct but R is incorrect
(CBSE AIPMT 2010)
(d) Both A and R are incorrect
(a) Friedel-Crafts’ acylation
2. The compound, with which ethanal does not react, is.
(b) Reimer-Tiemann reaction
(AFMC 2009)
(c) Cannizzaro reaction
(a) HCl (b) Cl2
(d) Wurtz reaction
(c) PCl5 (d) aq.NaHSO3
10. Name the reagent used to bring about the following
3. The most reactive of the following is
transformation : But-2-ene to ethanol (AMU 2010)
(J&K CET)
(a) K2Cr2O7 in acidic medium
(a) acetone
(b) CrO2Cl2/H3O+
(b) benzophenone
(c) PCC
(c) benzaldehyde
(d) O3/H2O–Zn dust
(d) acetaldehyde
11. When ethanal is treated with Fehling’s solution, it gives a
4. If heavy water is taken as solvent instead of normal
precipitate of
water while performing Cannizzaro reaction, the
(a) Cu2O (b) Cu
products of the reaction are (AIIMS 2009)
(c) Cu3O (d) CuO
(a) RCOO– + RCH2OH
12. The major product formed from the following reaction
(b) RCOO– + RCH2OD
(c) RCOOD + RCD2OD
(d) RCOO– + RCD2OD
5. Aldehydes and ketones are differentiated by using is
(UP CPMT 2010) (AFMC 2010)
(a) NaOH/I2
(b) NaHSO3
(a)
(c) AgNO3/NH4OH
(d) NH2.NH2
6. In the following reaction seqsuence,
Cl C H NH
CH 3CHO 
2  X 
6 5 2  Y Y is
(b)
Ca(OH) 2 Alc.KOH

(MHT CET 2010)

(a) CH3CH = NHC6H5 (b) C6H5NHCH3
(c) C6H5NC (d) C6H5NCO
7. Ethyl methyl ketone is obtained by heating calcium (c)
salts of (MHT CET 2010)
(a) formic acid + propionic acid
(b) acetic acid + propionic acid
(c) acetic acid only (d)
(d) acetic acid + methanoic acid
ALDEHYDES AND KETONES 49

13. An organic compound A burns with a sooty flame. It is 21. Clemmensen reduction of a ketone is carried out in the
negative towards Tollen’s reagent test and positive for presence of which of the following?
Brady’s reagent test. The compound A is (KCET 2011) (CBSE AIPMT 2011)
(a) acetophenone (b) acetone (a) H2 and Pt as catalyst
(c) salicylic acid (d) benzaldehyde (b) Glycol with KOH
14. Which of the following pairs can be distinguished by (c) Zn—Hg with HCl
sodium hypoiodide? (d) LiAlH4
(Kerala CEE 2011) 22. Which of the following pairs can be distinguished by
(a) CH3CHO and CH3COCH3 iodoform test? (Kerala CEE 2012)
(b) CH3CH2CHO and CH3COCH3 (a) CH3CHO and CH3COCH3
(c) CH3CH3OH and CH3CH2CHOHCH3 (b) CH3CH2CHO and C2H5OH
(d) CH3OH and CH3CH2CHO (c) CH3CH2OH and CH3CH2CHOHCH3
15. The compound that neither forms semicarbazone nor (d) CH3OH and CH3CH2 CH2CHO
oxime is (Kerala CEE 2011) 23. CH3CHO and C6H5CH2CHO can be distinguished
(a) HCHO (b) CH3COCH2Cl chemically by (AIPMT 2012)
(c) CH3CHO (d) CH3CONHCH3 (a) Benedict test (b) Iodoform test
16. The reagent with which both acetaldehyde and acetone (c) Tollen’s reagent test (d) Fehling solution test
react is (KCET 2011) 24. Which of the following compounds undergoes both
(a) Fehling’s solution (b) I2/NaOH Cannizzaro and aldol reaction?
(c) Tollen’s reagent (d) Carbonic acid (CBSE AIPMT/AMU 2012)
17. Which of the following gives an aldehyde on dry (a) (CH3)2CH.CHO (b) HCHO
distillation? (KCET 2011) (c) C6H5CHO (d) CH3CHO
(a) Calcium formate calcium acetate 25. The product formed when acetone reacts with nitro
(b) Calcium formate calcium benzoate methane in the presence of a base is (AFMC 2012)
(c) Calcium acetate
(d) Calcium benzoate
18. Which of the following reactions convert acetone into
hydrocarbon having same number of carbons atoms? (a) (b)
(Guj CET 2011)
(a) Wolff-Kishner reaction
(b) Hofmann reaction (c) (d) CH3COCH=CHNO2
(c) Grignard reaction 26. Aldehydes and ketones can be distinguished by
(d) Reduction with LiAlH4 (AIIMS 2013)
19. In Tollen’s test, aldehydes (DUMET 2011) (a) ammonia (b) H2SO4
(a) are oxidised (c) alkaline KMnO4 (d) Fehling solution
(b) are reduced to alcohol 27. Which of the following organic compounds answers
(c) neither reduced to alcohol both iodoform test Fehling’s test? (KCET 2013)
(d) precipitate Ag+ as AgCl (a) Methanal (b) Ethanol
20. In the conversion of (c) Propane (d) Ethanal
28. Which of the follwing reactions cannnot be used to
increase the number of carbon atoms in a organic
comound? (UK PMT 2014)
(a) Grignard reaction
(b) Cannizzaro’s reaction
(c) Aldol condensation
X is (DUMET 2011)
(d) All of these
(a) H2/Pt (b) Zn–Hg/HCl
(c) Li/NH3 (d) NaBH4
50 ALDEHYDES AND KETONES

C H CO H 35. Reaction of carbonyl compound with one of the

29. CH3COC2H5 
6 5 Tishchenko B
3  A 
reaction following reagents involves nucleophilic addition
Identify A and B in this reaction. followed by elimination of water. The reagent is
(UK PMT 2014) (AIPMT 2015)
(a) CH3COOC2H5,CH3CH2OH (a) hydrocyanic acid
(b) CH3COOC2H5,CH3CHO (b) sodium hydrogen sulphite
(c) CH3CHO,CH3COOC2H5 (c) a Grignard reagent
(d) None of the above (d) hydrazine in presence of feebly acidic solution.
30. Schiff’s reagent’s pink colour is restored in 36. An organic compound ‘X’ having molecular formula
(UK PMT2014) C5H10O yields phenyl hydrazone and gives a negative
(a) caboxylic acid (b) ketones response to the iodoform test and Tollen’s test. It
(c) ethers (d) aldehydes produces n-pentane on reduction. ‘X’ could be
Ozonolysis
31. X 
(Reductive)
Y  Z (AIPMT 2015)
(a) 2-pentanone (b) 3-pentanone
Y can be obtained by Etard’s reaction, Z undergoes
(c) n-amyl alcohol (d) pentanal
disproportion reaction with concentrated alkali ,
37. The correct statement regarding a carbonyl compound
X could be (KCET 2014)
with a hydrogen atom on its alpha-carbon is
(a)
(NEET 2016)
(a) a carbonyl compound with a hydrogen atom on its
alpha-carbon never equilibrates with its
corresponding enol.
(b)
(b) a carbonyl compound with a hydrogen atom on its
alpha-carbon never equilibrates with its
corresponding enol and this process is known as
carbonylation.
(c)
(c) a carbonyl compound with a hydrogen atom on its
alpha-carbon rapidly equilibrates with its
corresponding enol and this process is known as
carbonylation.
(d) (d) a carbonyl compound with a hydrogen atom on its
alpha-carbon rapidly equilibrates with its
corresponding enol and this process is known as
keto-enol tautomerism.
38. The IUPAC name of the compound (NEET 2017)

(i)CH MgBr (i)Dil.NaOH

32. P 
3

 R 

(ii)H3O (ii) 

4-methylpent-3-en-2-one compound P is (KCET 2014) is

(a) propanone (b) ethanamine (a) 3-keto-2-methylhex-4-enal
(c) ethane nitrile (d) ethanal (b)5-formylhex-2-en-3-one
33. Which one of the following compounds do not give a (c) 5-methyl-4-oxohex-2-en-5-al
primary alcohol on reduction? (Guj CET 2014) (d) 3-keto-2-methylhex-5-enal
(a) Propanal (b) Propanoic acid 39. Cannizzaro reaction is not shown by (JIPMER 2017)
(c) Methyl propanoate (d) Propan-2-one
34. Name the catalyst [X] for the reaction,
CO(g)  H 2 (g) X
 HCHO(g) (Guj CET 2014) (a) (b)
(c) CH3CHO (d) HCHO
(a) Cu (b) Ni
(c) Cu/ZnO (d) Cu/Cr2O3
ALDEHYDES AND KETONES 51

40. Consider the following equation (a) Nucleophilic attack, Transfer of H– and transfer of
H+
(b) Transfer of H–, transfer of H+ and nucleophilic
attack
The end product fo the given sequence of reaction is (c) Transfer of H+, nucleophilic attack and transfer of
(AIIMS 2017) H–
(d) Electrophilic attack by OH–, transfer of H+ and
transfer of H–
(a) 45. In the reaction, (JIPMER2018)

(b)
The major product formed is
(a) C6H5CH2CHO
(b) C6H5COOH
(c) C6H5CH=CH-COOH
(c)
(d) C6H5CH=CH-COCH3
46. Suitable reagent for conversion of following reaction
CH 2  CH  CHO  ?
 CH 2  CH  CH 2  OH ?
(JIPMER 2019)
(d)
(a)NaBH4 (b) Ni/H2
41. The product formed by the reaction of an aldehyde with
(c) Zn-Hg/HCl (d) Red P + Hl
a primary amine is (NEET 2017)
47. Write IUPAC name of the following (JIPMER 2019)
(a) Schiff base (b) Ketone
(c) Carboxylic acid (d) Aromatic acid
42. The correct IUPAC name of the given compound is (AIIMS 2018)

(a) 2-bromo-2-ethyl hexanal

(b) 3-bromo-2-methyl hexanal
(c) 2-methyl-3-bromo hexanal
(a) 7-hydroxy cyclohex -5-en-1-one (d) 3-bromo-2-formyol hexanal
(b) 3-hydroxy cyclohex -5-en-1-one O
(c) 8-hydroxy cyclohex -3-en-1-one ||
Conc.NaOH
(d) 5-hydroxy cyclohex -3-en-1-one H  C  H  CH 3  CH  O 
48.
43. Which of the following compound does not undergo Find out the products of reaction (AIIMS 2019)
aldol condensation? (AIIMS 2018) (a) CH3CO2 Na and CH3OH
CH3 (b) CH3OH and HCO2Na
| (c) CH3CH2OH and HCO2Na
(a) CH3  C  CHO (b) CH3  CHO
| (d) CH3CO2Na+HCO2Na
CH3 49. Reaction between benzaldehyde and acetophenone in
presence of dilute NaOH is known as: (NEET 2020)
(a) Cross Cannizzaro’s reaction
(c) (d) CH3CH2CHO (b) Cross Aldol condensation
(c) Aldol condensation
44. Which of the following is the correct sequence of step (d) Cannizzaro’s reaction
involved on the mechanism of Cannizzaro reaction?
(JIPMER 2018)
52 ALDEHYDES AND KETONES

50. Identify compound X in the following sequences of

reactions : (NEET 2021)

(a) (b)

(c) (d)
ALDEHYDES AND KETONES 53

EXERCISE – 3: Achiever’s Section

Single Choice Questions
1. The IUPAC name of the following structure is

(a) (b)

(a) 1-hydroxy 4-methyl 3-pentanone

(b) 2-methyl 5-hydroxy 3-pentanone
(c) 4-methyl 3-oxo 1-pentanol
(d) Hexanol-1, one-3 (c) (d)
2. The end product in the following sequence of reaction is 6. When a nucleophile encounters a ketone, the site of
attack is
1% HgSO CH MgX O  (a) The carbon atom of the carbonyl
 
HC  CH  4  A  3  B   (b) The oxygen atom of the carbonyl
20% H SO
2 4 (c) Both the carbon and oxygen atoms, with equal
(a) Acetic acid (b) Isopropyl alcohol probability
(c) Acetone (d) Ethanol (d) No attack occurs ketones do not react with
3. Cyclohexene on ozonolysis followed by reaction with nucleophiles.
zinc dust and water gives compound E. Compound E on 7. Which of the following compound gives a ketone with
further treatment with aqueous KOH yields compound F. Grignard reagent:
Compound F is (a) Formaldehyde (b) Ethyl alcohol
(c) Methyl cyanide (d) Methyl iodide
8. Which one of the following will most readily be
dehydrated in acidic condition ?
(a) (b)

(a) (b)
(c) (d)
4. What reagent is used in the Rosenmund’s reduction ?
(a) H2/Pd-BaSO4
(b) LiAlH4
(c) NH2NH2/KOH/CH2OH-CH2OH (c) (d)
(d) Zn-Hg/HCl 9. The smallest ketone and its next homologue are reacted
5. The major product obtained in the following reaction is : with NH2OH to form oxime
(a) two different oximes are formed
(b) three different oximes are formed
(c) two oximes are optically active
(d) all oximes are optically active
10. A mixture of benzaldehyde and formaldehyde on heating
with aqueous NaOH solution gives
(a) benzyl alcohol and sodium formate
(b) sodium benzoate and methyl alcohol
(c) sodium benzoate and sodium formate
(d) benzyl alcohol and methyl alcohol
54 ALDEHYDES AND KETONES

11. Aldol reaction involving CH3CHO + CH3CHO gives the

product
(a) CH3CHOHCH2CHO (b) CH3COCH2CH3
(c) (d) None of these
12. Which of the following species is (are) not intermediates
in the aldol condensation of acetaldehyde (ethanal) in
(c)
aqueous base ?

(1) (2)

(d)
(3) (4) 16. m-chlorobenzaldehyde on reaction with conc. KOH at
(a) 1 and 2 (b) 3 only room temperature gives
(c) 4 only (d) 3 and 4 (a) potassium m-chlorobenzoate and m-chlorobenzyl
13. The aldehyde having α-hydrogen which gives alcohol
Cannizzaro’s reaction is : (b) m-hydroxybenzaldehyde and m-chlorobenzyl
alcohol
(c) m-chlorobenzyl alcohol and m-hydroxy benzyl
(a) (b) alcohol
(d) potassium m-chlorobenzoate and m-
hydroxybenzaldehyde
(c) (d)
17. Which of the following compounds gives internal
14. The aldehyde which shows Cannizzaro’s reaction is
crossed Cannizzaro’s reaction ?
(a) HCHO
(b) C6H5CHO
(c) CCl3–CHO
(d) All of these
(a) (b)
15.

(c) (d)

18. The product formed in the following reaction will be:

major product is

(a) (b)
(a)

(c) (d) all of these

(b)
ALDEHYDES AND KETONES 55

19. The major product of the following reaction sequence is and sodium acetate gives a product C. Identify the
structure of C.
(a) CH3CH2 CH  N.NHCONH2
(b)

(c)

(a) (b)

(d) CH3CH2 CH  N.CONHNH2

24. A compound has a vapour density of 29. On warming an
aqueous solution of alkali, it gives a yellow precipitate.
The compound is
(c) (d)
(a) CH3CH2CHO (b) CH3CHOHCH3
20.
(c) CH3COCH3 (d) CH3CH2COOH
25. In the following reaction sequence, the correct structures
of E, F and G are

the compound (X) is

(* implies 13C labelled carbon)
(a) CH3COOH (b) BrCH2 – COOH
(c) (CH3CO)2O (d) CHO – COOH
21. Acetone and acetaldehyde are differentiated by
(a) NaOH + I2 (b) [Ag(NH3)2] ⊕ (a)
(c) HNO2 (d) I2
22. The correct sequence of reagents for the following
conversion will be : (b)

(c)


(a) CH 3 MgBr, H  / CH 3OH,  Ag  NH 3 2  OH 
(d)

(b) CH3 MgBr,  Ag  NH 3 2  OH  , H  / CH 3OH

(c)  Ag  NH 3 2  OH  , CH 3 MgBr, H  / CH 3OH Assertion- Reason Type Questions
(A) If both assertion and reason are correct and reason is the

(d)  Ag  NH 3 2  OH  , H  / CH 3OH, CH 3 MgBr correct explanation of assertion.
23. Compound A (molecular formula C3H8O) is treated with (B) If both assertion and reason are true but reason is not the
acidified potassium dichromate to form a product B correct explanation of assertion.
(molecular formula C3H6O). B forms a shining silver (C) If assertion is true but reason is false.
mirror on warming with ammonical silver nitrate. B (D) If reason is true but assertion is false.
when treated with an aqueous solution of H2NCONHNH2
56 ALDEHYDES AND KETONES

26. Assertion (A): Aldehydes form stable hydrates. 29. Assertion (A): Reimer-Tiemann reaction is used to
Reason (R): Aldehydic carbonyl is more electron prepare benzaldehyde from benzene.
deficient than the ketone. Reason (R): Reimer-Tiemann reaction involves
(a) A (b) B electrophilic substitution.
(c) C (d) D (a) A (b) B
27. Assertion (A) : Lower aldehydes and ketones are soluble (c) C (d) D
in water but the solubility decreases as the molecular 30. Assertion (A): Isobutanal does not give iodoform tests.
mass increases. Reason (R): It does not have α-hydrogen
Reason (R) : Distinction between aldehydes and ketones (a) A (b) B
can be made by tollen’s reagent. (c) C (d) D
(a) A (b) B
(c) C (d) D
28. Assertion (A): Hydroxyketones are not directly used in
Grignard reaction.
Reason (R): Grignard reagents react with hydroxyl
group.
(a) A (b) B
(c) C (d) D
ALDEHYDES AND KETONES 57

Notes:

Find Answer Key and Detailed Solutions at the end of this book

ALDEHYDES AND KETONES

ANSWER KEY 225

Answer Key
CHAPTER - 6: ALDEHYDES AND KETONES

Exercise - 1: Basic Objective Questions

DIRECTIONS FOR USE-

Scan the QR code and check detailed solutions.
1. (b) 2. (d) 3. (b) 4. (d) 81. (a) 82. (a) 83. (c) 84. (b)
5. (c) 6. (c) 7. (c) 8. (b) 85. (d) 86. (a) 87. (c) 88. (b)
9. (b) 10. (b) 11. (b) 12. (a) 89. (c) 90. (b) 91. (d) 92. (a)
13. (c) 14. (c) 15. (a) 16. (a) 93. (a) 94. (a) 95. (d) 96. (b)
17. (b) 18. (d) 19. (a) 20. (d) 97. (c) 98. (a) 99. (a) 100. (a)
21. (d) 22. (d) 23. (b) 24. (b) 101. (b) 102. (a) 103. (a) 104. (b)
25. (c) 26. (d) 27. (c) 28. (a) 105. (c) 106. (b) 107. (b) 108. (a)
29. (a) 30. (d) 31. (b) 32. (c) 109. (a) 110. (a) 111. (b) 112. (c)
33. (a) 34. (c) 35. (c) 36. (c) 113. (c) 114. (b) 115. (a) 116. (b)
37. (d) 38. (d) 39. (c) 40. (a) 117. (c) 118. (d) 119. (a) 120. (c)
41. (a) 42. (b) 43. (d) 44. (c) 121. (b) 122. (d) 123. (d) 124. (a)
45. (a) 46. (c) 47. (b) 48. (c) 125. (c) 126. (a) 127. (b) 128. (c)
49. (b) 50. (b) 51. (a) 52. (b) 129. (c) 130. (d) 131. (b) 132. (a)
53. (a) 54. (a) 55. (b) 56. (c) 133. (a) 134. (d) 135. (a) 136. (a)
57. (c) 58. (a) 59. (c) 60. (c) 137. (b) 138. (b) 139. (d) 140. (d)
61. (c) 62. (d) 63. (a) 64. (b) 141. (c) 142. (c) 143. (a) 144. (c)
65. (d) 66. (d) 67. (a) 68. (a) 145. (d) 146. (b) 147. (d) 148. (d)
69. (b) 70. (b) 71. (d) 72. (b) 149. (b) 150. (d)
73. (d) 74. (b) 75. (b) 76. (d)
77. (a) 78. (b) 79. (a) 80. (a)
226 ANSWER KEY

Exercise - 2: Previous Year Questions Exercise - 3: Achiever’s section

DIRECTIONS FOR USE- DIRECTIONS FOR USE-

Scan the QR code and check detailed solutions. Scan the QR code and check detailed solutions.

1. (a) 2. (a) 3. (d) 4. (b) 1. (a) 2. (c) 3. (a) 4. (a)

5. (c) 6. (c) 7. (b) 8. (b) 5. (a) 6. (a) 7. (c) 8. (a)
9. (c) 10. (d) 11. (a) 12. (b) 9. (b) 10. (a) 11. (a) 12. (d)
13. (a) 14. (b) 15. (d) 16. (b) 13. (b) 14. (d) 15. (d) 16. (a)
17. (a) 18. (a) 19. (a) 20. (d) 17. (c) 18. (b) 19. (a) 20. (c)
21. (c) 22. (b) 23. (b) 24. (a) 21. (b) 22. (d) 23. (a) 24. (c)
25. (c) 26. (d) 27. (d) 28. (b)
25. (c) 26. (d) 27. (b) 28. (a)
29. (b) 30. (d) 31. (b) 32. (c)
29. (d) 30. (c)
33. (d) 34. (a) 35. (d) 36. (b)
37. (d) 38. (a) 39. (c) 40. (b)
41. (a) 42. (d) 43. (a) 44. (a)
45. (c) 46. (a) 47. (b) 48. (c)
49. (b) 50. (a)
1 Aldehydes and Ketones

Exercise – 1: Basic Objective Questions

Carbonyl Compounds-Introduction (d) only at the end carbon atom of the carbon chain
1. The IUPAC name of Cl3CCH2CHO is : Ans. (d)
(a) chloral Sol. The functional group that represents the aldehyde group
(b) 3,3,3-trichloropropanal is 𝐶𝐻𝑂, in which the carbon atom is joined to the
(c) 1,1,1-trichloropropanal oxygen atom with the double bond and carbon atom is
(d) 2,2,2-trichloropropanal joined to the hydrogen atom by the single bond. So,
Ans. (b) only one bond is there for the attachment of the carbon
Sol. The IUPAC name is given by taking the longest chain of chain, therefore, the aldehyde group can be present only
the carbon atoms. There are three carbon atoms in the at the terminal carbon atoms in the chain.
given compound and there are two functional groups in
the compound, and these are aldehyde and chlorine. 5. The formula of chloral is
The numbering will start from aldehyde. So, the name (a)𝐶𝐻3 𝐶𝐻 = 𝑁𝐻𝐶6 𝐻5 (b) CH2ClCHO
of the compound will be 3,3,3 Trichloropropanal. (c) CCl3CHO (d) CHCl2CHO
Ans. (c)
2. The IUPAC name of CH3COCH(CH3)2 is : Sol. The IUPAC name of chloral is 3,3,3-Trichloroethanal.
(a) isopropyl methyl ketone There are two carbon atoms in the given compound and
(b) 2-methyl-3-butanone there are two functional groups in the compound, these
(c) 4-methyl-isopropyl ketone are aldehyde and chlorine. So, the formula of chloral
(d) 3-methyl-2-butanone is𝐶𝐶𝑙3 𝐶𝐻𝑂.
Ans. (d)
Sol. 6. A strong base can abstract an alpha-hydrogen from
(a) amide (b) amine
(c) ketone (d) alkane
Ans. (c)
Sol. Aldehydes and ketones react very easily with base to
give alpha hydrogen atom. This is due to the fact that,
The IUPAC name of this structure is 3-Methyl-2- both aldehydes and ketones are strong electron
butanone. withdrawing groups. So, ketone is the correct answer.

3. The general formula of both aldehydes and ketones is: 7. Formalin is an aqueous solution of :
(a) CnH2n + 2O (b) CnH2nO (a) formic acid (b) fluorescein
(c) CnH2n – 2O (d) CnH2n + 4O (c) formaldehyde (d) furfuraldehyde
Ans. (b) Ans. (c)
Sol. Let us take an aldehyde, ethanal. The formula of Sol. Aldehydes can be dissolved in water to make an
ethanal is 𝐶𝐻3 𝐶𝐻𝑂, so the number of carbon atoms is 2 aqueous solution. One such important solution is
and the number of hydrogen atoms is 4, and the formalin which is the aqueous solution of
number of oxygen atom is one. Now let us take a formaldehyde, specifically 40% aqueous solution of
ketone, acetone. The formula of acetone is𝐶𝐻3 𝐶𝑂𝐶𝐻3 , formaldehyde. Or we can say that in 100 ml of solution
so the number of carbon atoms is 3, the number of 40 ml is formaldehyde and 60 ml is water.
hydrogen atoms is 6, and the number of oxygen atom is
one. So, from this we can conclude the general formula 8. Acetals are
of aldehydes and ketones as 𝐶𝑛 𝐻2𝑛 𝑂. (a) ketones (b) diethers
4. Aldehydic group can occur : (c) aldehyde (d) hydroxy aldehydes
(a) anywhere in the carbon chain Ans. (b)
(b) in the middle of carbon chain Sol. Acetals are geminal-diether derivatives of aldehydes or
(c) only at the second carbon atom of the chain ketones.
Aldehydes and Ketones 2

9. The structure would be best classified as

a(n)
(a) Acetal (b) Hemiacetal
(c) Hydrate (d) Cyanohydrin
Ans. (b)
Sol. The compound given here is classified as
hemiacetals.Hemiacetals are also known as hemiketals
and these compounds with the general formula
R’R”C(OH)OR.

10. Ethanedial has which functional group ?

(a) One ketonic (b) Two aldehydic
(c) One double bond (d) Two double bond In the enolate A, the negative charge can be delocalised
Ans. (b) over the two oxygen atoms and thus giving 2 canonical
Sol. Ethanedial or Glyoxal has two aldehyde group. forms and hence is more stable.
Therefore, the correct answer is option (a) A is more
stable than B.

11. Which of the following is paradehyde? 13. Which of the compound shown is (are) correctly named
(a) HCHO (b) (CH3CHO)3 as pentane derivates, either as pentanals or pentanones
(c) (CH3CHO)4 (d) CH3COOH ?
Ans. (b)
Sol.

(a) 1 only (b) 2 only

(c) 3 only (d) 1 and 3
Ans. (c)
Sol. Pentanes are compounds containing a five carbon chain.
12. When enolate A is compared with enolate B Here, only the third structure has five carbon atoms and
thus can be named as pentane derivatives like
pentanone or pentanal.
Therefore, the correct answer is option (c) 3 only.

14. Which of the following forms an enol to the greatest

(A) (B) extent ?
which of the following statements is true ?
(a) A is more stable than B
(b) B is more stable than A (a) (b)
(c) A and B have the same stability
(d) No comparison of stability can be made.
Ans. (a) (c) (d)
Sol. Ans. (c)
Sol. Here, the compound in the third option is a
2,4-dione compound.
3 Aldehydes and Ketones

Here, the stability of the enol formed is higher due to

resonance compared to the other keto forms.
Also, due to possibility of intra-molecular hydrogen
bonding, extra stability is obtained in this structure
hence will prefer enol form more than the keto form.
17. Which of the following yield 2 moles of formaldehyde
on ozonolysis?
(a) CH CH (b) CH2 CH2
(c) CH3—CH CH2 (d) C6H6
Ans. (b)
Sol. When the alkene is subjected to ozonolysis, the double
Therefore, the correct answer is option (c)
bond of the alkene will break and there will be
formation of ozonide. This ozonide on reaction with
Preparation of Aldehydes & Ketones zinc dust forms carbonyl compound. So, if we want 2
15. Which of the following compound will yield 2,5-
moles of formaldehyde or methanal, ethene must be the
dimethylhexan-1,6-dial upon ozonolysis?
reactant.
(a) 3, 6-dimethyl cyclohexene
(b) 3,4-dimethyl cyclohexene
(c) 4,6-dimethyl cyclohexene
(d) 3,5-dimethyl cyclohexene
Ans. (a)
Sol. 3,6-Dimethyl cyclohexene, will give 2,5-
18. Which compound would give 5 – keto – 2 – methyl
dimethylhexan-1, 6-dial. The double bond of the
hexanal upon ozonolysis?
cyclohexene will break and the both the carbon atoms
will convert into aldehyde group. The reaction is given
below:

(a) (b)

𝐶𝐻3 𝐶𝐻3
| |
(c) (d)
𝐶𝐻𝑂 − 𝐶 − 𝐶𝐻2 − 𝐶𝐻2 − 𝐶 − 𝐶𝐻𝑂
Ans. (d)
Sol. Among the given compounds the compound (d)
gives 5-keto-2-methyl hexanal on ozonolysis.

16. On reductive ozonolysis yields

(a) 6-oxoheptanal (b) 6-oxoheptanoic acid
(c) 6-hydroxyheptanal (d) 3-hydroxypentanal
Ans. (a)
Sol. When the alkene undergoes reductive ozonolysis, it will
form aldehydes, ketones or the compounds having both Hence, the correct answer is option (d)
aldehyde and ketone. So, in the reactant given when the
double bond breaks, then at first position aldehyde 19. Which of the compounds with molecular formula C5H10
group will form and at the sixth position ketone group yields acetone on ozonolysis?
will form. Hence, there will be formation of 6- (a) 2-methyl-2-butene
oxoheptanal. The reaction is given below:
Aldehydes and Ketones 4

(b) 3-methyl-1-butene
(c) Cyclopentane
(d) 2-methyl-1-butene
Ans. (a)
Sol. Ozonolysis is a process in which the double bond of the
alkene will break and then convert into carbonyl
compounds. So, from the given options, 2-methyl-2-
butene will form ethanal and acetone on ozonolysis.
The reaction is given below:

22. Which of the following on heating with aqueous KOH,

produces acetaldehyde ?
(a) CH3COCl
(b) CH3CH2Cl
(c) CH2ClCH2Cl
(d) CH3CHCl2
Ans. (d)
Sol. Among the given options, option (d) on heating with
aqueous KOH produces acetaldehyde.
20. Which of the following gases when passed through
warm dilute solution of H2SO4 in presence of HgSO4
gives acetaldehyde? Hence, the correct answer is option (d)
(a) CH4 (b) C2H6
(c) C2H4 (d) C2H2 23.
Ans. (d)
Sol. When acetylene reacts with dilute sulphuric acid in
presence of mercuric sulphate, an aldehyde is formed. A and B are respectively.
𝐻𝑔𝑆𝑂4 /𝐻2 𝑆𝑂4
The reaction is- 𝐻𝐶 ≡ 𝐶𝐻 → 𝐶𝐻3 𝐶𝐻𝑂 (a) CH3 CH2 CH2 OH + C2 H5 OH
Acetylene is a gas and it forms acetaldehyde. (b) CH3 CH2 CHO + C2 H5 OH
Therefore, the correct answer is option (d) 𝐶2 𝐻2 . (c) CH3 CH2 CHO + CH3 CHO
(d) CH3 CH2 CH2 CHO + CH3 CHO
21. When but-2-yne is treated dil.H2SO4/HgSO4 the product Ans. (b)
formed is : Sol.
(a) butan-1-ol
(b) butan-2-ol
(c) acetone
(d) 2-butanone
Ans. (d)
Sol. But-2-yne is the compound in which four carbon atoms
are present and the second carbon atom has a triple
bond. So when the but-2-yne is treated with 𝐻𝑔𝑆𝑂4 , the
addition of hydroxyl group at the second carbon atom.
Now, this secondary alcohol will convert into ketone.
So, the product will be Butanone. The reaction is given
below:
5 Aldehydes and Ketones

24. Complete the reaction: 26. Arrange the following compounds in decreasing order
PhMgBr/H3 O+ of their boiling points.
Ph − CH = CH − CHO → Product
CH3CHO, CH3CH2OH, CH3OCH3, CH3CH2CH3
(a) Ph − C H − CHO
| (a) CH3CH2CH3>CH3OCH3> CH3CHO > CH3CH2OH
Ph
(b) Ph − C H − CH2 − CHO (b) CH3CH2CH3> CH3CHO > CH3OCH3> CH3CH2OH
| (c) CH3CH2CH3> CH3CHO > CH3CH2OH> CH3OCH3
Ph
(c) Ph − C H − C H − CHO (d) CH3CH2OH> CH3CHO > CH3OCH3> CH3CH2CH3
| |
OH Ph
Ans. (d)
(d) Ph − C H − CH2 − CH2 − OH Sol. The boiling point of alcohols is the highest among the
|
Ph given compound, because of the formation of hydrogen
Ans. (b) bonding which is a strong bond. Then comes the
Sol. aldehydes which have higher boiling point than
hydrocarbons and ethers, since they are polar
compounds and have higher dipole –dipole interactions.
Among ethers and hydrocarbons, ethers have the higher
boiling point and the hydrocarbons have the least
boiling point due to weak vander Waals interactions. So
the correct order of compounds on the decreasing order
of boiling points is as follows:
𝐶𝐻3 𝐶𝐻2 𝑂𝐻 > 𝐶𝐻3 𝐶𝐻𝑂 > 𝐶𝐻3 𝑂𝐶𝐻3 >
𝐶𝐻3 𝐶𝐻2 𝐶𝐻3
27. Ketones
25. Which of the following is the industrial method of
preparation of acetaldehyde?
where R = R1 = alkyl group. It can be obtained in one
step by
(a) Hydrolysis of esters
𝑃𝑑 2+
(b) Oxidation of primary alcohol
(c) CH2=CH2 + H2O→ 𝐶𝐻3CHO (c) Oxidation of secondary alcohol
(d) None of the above (d) Reaction of acid halide with alcohols
Ans. (c) Ans. (c)
Sol. Acetaldehyde is an organic compound having formula Sol. Secondary alcohols are those compounds in which the
𝐶𝐻3 𝐶𝐻𝑂 and industrially it is prepared from Wacker alcohol group is present at the carbon atom which is
process, in which the alkene is treated with water in the further attached to 2 carbon atoms. So, when this
presence of palladium chloride or copper chloride. secondary alcohol is oxidized, there is formation of
Acetaldehyde is easily prepared from ethene. Since ketone. The reaction is given below:
palladium chloride is an expensive catalyst so, copper [𝑂]
𝑅 − 𝐶𝐻(𝑂𝐻) − 𝑅1 → 𝑅 − 𝐶𝑂 − 𝑅1
chloride is mostly used. so copper chloride is used for
regeneration of palladium.
𝐶𝑢𝐶𝑙2 𝑂2
28. Aldehydes are the first oxidation product of
𝐶𝐻2 = 𝐶𝐻2 + 𝑃𝑑𝐶𝑙2 + 𝐻2 𝑂 → 𝐶𝐻3 𝐶𝐻𝑂 + 𝑃𝑑 + 2𝐻𝐶𝑙 (a) primary alcohol
[𝑃𝑑 + 2𝐻𝐶𝑙 → 𝑃𝑑𝐶𝑙2 + 𝐻2 ] (b) secondary alcohol
[𝑃𝑑 + 2𝐶𝑢𝐶𝑙2 → 𝑃𝑑𝐶𝑙2 + 2𝐶𝑢𝐶𝑙] (c) tertiary alcohol
1
[2𝐶𝑢𝐶𝑙 + 𝑂2 + 2𝐻𝐶𝑙 → 2𝐶𝑢𝐶𝑙2 + 𝐻2 𝑂] (d) dihydric alcohol
2
Ans. (a)
Sol. Aldehydes are the primary oxidation product of primary
alcohols. The primary alcohols are first oxidized to
Physical and chemical properties of Aldehydes &Ketones form aldehydes which on further oxidations can be
Aldehydes and Ketones 6

converted into carboxylic acid. Ketones are formed Sol. Conc. HNO3 act as an oxidizing agent, thus oxidises -
from oxidation of secondary alcohols and this cannot be OH to > = O in 2-propanol i.e. CH3CH(OH)CH3 + [O]
further oxidized to form carboxylic acids. → CH3COCH3 conversion takes place

29. An organic compound X on treatment with pyridinium 32. Methyl ethyl ketone is prepared by the oxidation of
chloro chromate in dichloromethane gives compound (a) 2-propanol (b) 1-butanol
Y. Compound Y reacts with I2 and alkali to form (c) 2-butanol (d) t-butyl alcohol
triiodomethane. The compound ‘X’ is Ans. (c)
(a) C2H5OH (b) CH3CHO Sol. In methyl ethyl ketone, the ketone group is attached to
(c) CH3COCH3 (d) CH3COOH methyl group on one side and to ethyl group on the
Ans. (a) other side. So, there are total 4 carbon atoms in the
Sol. From the given information, X reacts with compound. Since it is a ketone, it can be prepared only
pyridiniumchloro chromate in dichloromethane to form from secondary alcohol. So, butan-2-ol will give methyl
Y. PCC is a weak oxidizing agent and it is used to ethyl ketone on oxidation. The reaction is given below:
oxidize alcohol to aldehyde. So from the given options
only 𝐶2 𝐻5 𝑂𝐻 is alcohol and when it is treated with
PCC ethanal is formed which on reaction with iodine
gives triiodomethane.

30. Oxidation reactions can be carried out with chromic

acid in aqueous acetone at 5–10°C.Which of following 33. Which one of the following can be oxidised to the
is incorrect in this respect corresponding carbonyl compound?
(a) (a) 2-hydroxy-propane
(b) ortho-nitro-phenol
(c) Phenol
(d) 2-methyl-2-hydroxy-propane
Ans. (a)
(b)
Sol. Carbonyl compounds are the either aldehydes or
ketones. From primary and secondary alcohols carbonyl
compounds are obtained. When primary alcohol is
(c) 𝐶𝐻3 (𝐶𝐻2 )3 𝐶𝐻2 𝑂𝐻 → 𝐶𝐻3 (𝐶𝐻2 )3 𝐶𝑂𝑂𝐻 oxidized, there is formation of aldehyde and when
(d) None of these secondary alcohol is oxidized, there is formation of
Ans. (d) ketone. So, from the options given, 2-hydroxy propane
Sol. A solution of chromic acid in the presence of acetone is will give a ketone.
known as Jones reagent. This reagent is mostly used for
the conversion of most of the primary alcohols to 34. The oxidation of toluene to benzaldehyde by chromyl
carboxylic acids and the secondary alcohols to ketones. chloride is called
Since this reagent is very selective and sensitive, it does (a) Cannizzaro reaction
not attack the double or triple bond so it used to oxidize (b) Wurtz reaction
the allylic or benzylic alcohols to aldehydes. (c) Etard reaction
(d) Reimer-Tiemann reaction
31. The oxidation product of 2-propanol with hot conc. Ans. (c)
HNO3 is Sol. Benzaldehyde can be prepared by oxidizing the toluene
(a) Ethanoic acid with a solution of chromyl chloride. In this reaction, the
(b) Propanone toluene is first converted into a brown chromium
(c) Propanal complex, which on hydrolysis forms benzaldehyde. The
(d) None of these reaction is given below:
Ans. (b)
7 Aldehydes and Ketones

Sol.

So this reaction is known as Etard reaction.

35. Acetone on distillation with conc. H2SO4 forms

(a) phorone (b) acrolein
(c) mesitylene (d) mesityl oxide 38. On heating calcium acetate and calcium formate, the
Ans. (c) product formed is
Sol. Acetone is a compound having formula 𝐶𝐻3 𝐶𝑂𝐶𝐻3 and (a) CH3COCH3 (b) CH3CHO
when it reacts with concentrated sulphuric acid it forms (c) HCHO + CaCO3 (d) CH3CHO + CaCO3
a cyclic compound. 3 moles of acetone on distillation Ans. (d)
with concentrated sulphuric acid will form mesitylene. Sol.
The reaction is given below: 𝐶𝐻3 𝐶𝑂𝑂𝐶𝑎𝑂𝑂𝐶𝐶𝐻3 + 𝐻𝐶𝑂𝑂𝐶𝑎𝑂𝑂𝐶𝐻 →
2𝐶𝐻3 𝐶𝐻𝑂 + 2𝐶𝑎𝐶𝑂3
39. In the following reaction, product P is

(a) RCH2OH (b) RCOOH

(c) RCHO (d) RCH3
36. Consider the following statement Acetophenone can be Ans. (c)
prepared by Sol. The reactant given in the reaction is acid chloride, and
(1) Oxidation of 1-phenyethanol it is reacted with hydrogen in the presence of palladium
(2) Reaction of 1-phenylethanol with methyl supported over barium sulfate, so the formation of
magnesiumbromide aldehyde will take place and hydrochloric acid is also
(3) Friedel Craft’s reaction of benzene with acetyl produced. This reaction is known as Rosenmund
chloride reduction. So, the reaction is given below:
𝐻2 +𝑃𝑑−𝐵𝑎𝑆𝑂4
(4) Distillation of calcium benzoate 𝑅 − 𝐶𝑂 − 𝐶𝑙 → 𝑅 − 𝐶𝐻𝑂
(a) 1 and 2 (b) 1 and 4
(c) 1 and 3 (d) 3 and 4 40. Catalyst used in Rosenmund reduction is
Ans. (c) (a) Pd/BaSO4
Sol. The most common method used for the preparation of (b) Zn-Hg couple
acetophenone is Friedel Craft’s reaction in which the (c) LiAlH4
benzene is reacted with acetyl chloride and the product (d) Ni/H2
formed is acetophenone and hydrogen chloride. The Ans. (a)
reaction is given below: Sol. The Rosenmund reaction is a hydrogenation process
𝐶6 𝐻6 + 𝐶𝐻3 𝐶𝑂𝐶𝑙 → 𝐶6 𝐻5 𝐶𝑂𝐶𝐻3 + 𝐻𝐶𝑙 where molecular hydrogen reacts with acyl chloride in
The other process from which we can produce the presence of palladium/barium sulfate catalyst.
acetophenone is oxidation of 1-Phenyl ethanol. The Barium sulfate reduces the activity of palladium due to
reaction is given below: its low surface area, thereby preventing over reduction.
[𝑂] 𝐻2 +𝑃𝑑−𝐵𝑎𝑆𝑂4
𝐶6 𝐻5 𝐶𝐻𝑂𝐻𝐶𝐻3 → 𝐶6 𝐻5 𝐶𝑂𝐶𝐻3 𝑅 − 𝐶𝑂 − 𝐶𝑙 → 𝑅 − 𝐶𝐻𝑂
37. Dry heating of calcium acetate gives
(a) Acetaldehyde (b) Ethane 41. What reagent is used in the Rosenmund reduction?
(c) Acetic acid (d) Acetone (a) H2/Pd-BaSO4
Ans. (d) (b) LiAlH4
Aldehydes and Ketones 8

(c) NH2NH2/KOH/CH2OH-CH2OH Sol. The order of the reactivity towards the Nucleophilic
(d) Zn-Hg/HCl addition reaction can be decided on the factor of
Ans. (a) electron density on the carbonyl compound. So, as the
Sol. Rosenmund reaction or Rosenmund reduction is a alkyl group increases the +I-effect increases and the
chemical reaction in which the acid chlorides are electron density on the carbonyl group increases, this
converted into aldehydes. The reactant in the makes difficult for the nucleophile to attack. So, the
Rosenmund reaction is acid chloride, and it is reacted order of reactivity will be Ethanal > Propanal >
with hydrogen in the presence of palladium supported Propanone > Butanone.
over barium sulfate so, the formation of aldehyde will
take place and hydrochloric acid is also produced. The 45. A carbonyl compound reacts with hydrogen cyanide to
reaction is given below: form cyanohydrin which on hydrolysis forms a racemic
𝑅 − 𝐶𝑂 − 𝐶𝑙 →
𝐻2 +𝑃𝑑−𝐵𝑎𝑆𝑂4
𝑅 − 𝐶𝐻𝑂 mixture of a α-hydroxy acid. The carbonyl compound
is
42. Reduction of acetonitrile in presence of SnCl2/HCl, (a) acetaldehyde (b) acetone
followed by hydrolysis gives : (c) diethyl ketone (d) formaldehyde
(a) HCHO (b) CH3CHO Ans. (a)
(c) CH3CH2CHO (d) CH3COCH3 Sol. The carbonyl compound will be acetaldehyde, so when
Ans. (b) the acetaldehyde reacts with hydrogen cyanide, then
Sol. In Stephen reduction, the aldehyde is formed from there is formation of cyanohydrin, (𝐶𝐻3 𝐶𝐻(𝑂𝐻)(𝐶𝑁))
nitriles, by reacting the nitriles with stannous chloride and when it is hydrolyzed the cyanide group will
in the presence of hydrochloric acid. convert into carboxylic group 𝐶𝐻3 𝐶𝐻(𝑂𝐻)(𝐶𝑂𝑂𝐻).
𝐶𝐻3 − 𝐶 ≡ 𝑁 + 𝑆𝑛𝐶𝑙2 + 𝐻𝐶𝑙 So, in this product the carbon atom is joined to all
𝐷𝑟𝑦 𝐸𝑡ℎ𝑒𝑟 different compounds, hence it will give racemic mixture
→ 𝐶𝐻3 𝐶𝐻 = 𝑁𝐻. 𝐻𝐶𝑙
of alpha-hydroxy acid.
→ 𝐶𝐻3 𝐶𝐻𝑂 + 𝑁𝐻4 𝐶𝑙
46. The increasing order of the rate of HCN addition to
43. The reagent used in Gattermann Koch aldehyde
compounds A-D is
synthesis is
(A) HCHO (B) CH3COCH3
(a) Pb/BaSO4 (b) alkaline KMnO4
(C) PhCOCH3 (D) PhCOPh
(c) acidic KMnO4 (d) CO + HCl
(a) A < B < C < D
Ans. (d)
(b) D < B < C < A
Sol. Gattermann-Koch reaction is a process in which the
(c) D < C < B < A
benzene is converted into benzaldehyde. When benzene
(d) C < D < B < A
is reacted with carbon mono oxide and hydrochloric
Ans. (c)
acid, there is formation of benzaldehyde. The reaction
Sol. We know that HCN is a good nucleophile so here the
is given below:
rate of the reaction will depend upon two main factors
i.e. inductive effect and the steric factor. The low
reactivity of the ketones over the aldehydes is due to the
presence of +I group i.e. the alkyl group and the steric
hindrance.
Chemical Reactions of Carbonyl compounds The aromatic aldehydes and ketones are less reactive
44. Arrange the following compounds in increasing order than the aliphatic aldehydes due to the presence of +R
of their reactivity in nucleophilic addition reactions. effect of the benzene ring.
Ethanal (I), Propanal (II), Propanone (III), Butanone Hence, the correct answer is option (c)
(IV)
(a) III < II < I < IV (b) II < I < III < IV 47. Nucleophilic addition reaction will be most favoured in
(c) IV < III < II < I (d) I < II < III < IV (a) CH3CH2CHO
Ans. (c) (b) CH3CHO
9 Aldehydes and Ketones

(c)
(d) (CH3)2C = O
Ans. (b) (a)
Sol. Both aldehydes and ketones are very reactive towards
the Nucleophilic addition reaction, because carbonyl
group is a very reactive group. So, the reactivity of the
carbonyl group can be decided the magnitude of the
positive charge on the carbonyl group. So, the (b)
compounds that have least methyl group will have the
highest positive charge and will have highest reactivity.
So, CH3CHO will have highest reactivity.
(c)
48. Which of the aldehyde is most reactive towards
nucleophilic addition reaction ?
(a) C6H5–CHO
(b) CH3CHO
(c) HCHO
(d) All are equally reactive (d)
Ans. (c) Ans. (b)
Sol. Both aldehydes and ketones are very reactive towards Sol.
the Nucleophilic addition reaction, because carbonyl
group is a very reactive group. So, the reactivity of the
carbonyl group can be decided the magnitude of the
positive charge on the carbonyl group. So, the
compounds that have least +I and +R group will have
forms strongest hydrogen bond with 𝐻2 𝑂 molecule
the highest positive charge and will have highest
because in this case carbonyl readily attains +𝑣𝑒 charge
reactivity. So, the HCHO doesn’t have any +I and +R
to aromaticity
group, therefore, it will have the highest reactivity.
49.
51. Correct order of reactivity of CH 3CHO, C2H5COCH3
and CH3COCH3 is
(a) CH3CHO > CH3COCH3>CH3COC2H5
(b) C2H5COCH3> CH3COCH3> CH3CHO
Product may be (c) CH3COCH3> CH3CHO > C2H5COCH3
(a) Meso (d) CH3COCH3> C2H5COCH3> CH3CHO
(b) Racemic Ans. (a)
(c) Inversion Sol. Both the aldehydes and ketones are very reactive
(d) All of these towards the Nucleophilic addition reaction, because
Ans. (b) carbonyl group is a very reactive group. So, the
Sol. Product may be racemic, because carbonyl is reactivity of the carbonyl group can be decided the
𝑠𝑝2 hybridized and has planar shape. So, 𝑁𝑢− attacks on magnitude of the positive charge on the carbonyl group.
front as well as back side. So, the compounds that have least +I effect and stearic
hinderance group will have the highest positive charge
50. Which of the following carbonyl oxygen will form and will have highest reactivity. So, the order will be:
strongest hydrogen bond with 𝐻2 𝑂 molecule? 𝐶𝐻3 𝐶𝐻𝑂 > 𝐶𝐻3 𝐶𝑂𝐶𝐻3 > 𝐶𝐻3 𝐶𝑂𝐶2 𝐻5 .
Aldehydes and Ketones 10

52. The most reactive compound towards formation of (c) Metamerism

cyanohydrin on treatment with HCN followed by (d) Tautomerism
acidification is Ans. (a)
(a) benzaldehyde Sol.
(b) p-nitrobenzaldehyde
(c) phenylacetaldehyde
(d) p-hydroxybenzaldehyde
Ans. (b)
Sol. Cyanohydrin will be formed easily by those compounds
in which electron withdrawing group is present.
Electron withdrawing will have –I-Effect which will
have more positive charge on the carbonyl carbon atom
decreasing the electron density and increasing the
tendency of the HCN to attack. So, from the given
options in p-nitrobenzaldehyde, nitro group is electron
withdrawing group.
53. A and B in the following reactions are 55. Which one of the following does not form sodium
bisulphite addition product with sodium bisulphite
solution
(a) CH2O (b) C6H5COCH3
(c) C6H5CHO (d) CH3CHO
Ans. (b)
(a) Sol. All aldehydes (aliphatic and aromatic) can react with
sodium bisulphite and will give addition products. In
ketones only methyl ketones react with sodium sulphite
to form addition products. So, from the given options,
(b)
acetophenone has bulkier groups on the carbonyl group,
hence it will not react with sodium bisulfite
(c)
(d) A = RR’CH2CN, B = NaOH 56. Benzaldehyde condenses with N,N-dimethylaniline in
Ans. (a) presence of anhydrous ZnCl2 to give
(a) Michler’s ketone (b) azo-dye
Sol. The compound given in the reactant is a ketone. So,
(c) malachite green (d) buffer yellow
when the HCN group attacks the ketone and the
Ans. (c)
hydrogen group will get attached to the oxygen atom.
The cyanide group will attach to the carbon atom. So, Sol. Benzaldehyde is an aromatic compound having formula
this compound is reduced using a strong reducing agent 𝐶6 𝐻5 𝐶𝐻𝑂 and the formula of N,N-Dimethylaniline is
like 𝐿𝑖𝐴𝑙𝐻4 , the cyanide group will convert into 𝐶6 𝐻5 𝑁(𝐶𝐻3 )2 . When they both react, there is
𝐶𝐻2 𝑁𝐻2 . formation of Malachite green which is a dye. The
reaction is given below:

54. Reaction of acetaldehyde with HCN followed by

hydrolysis gives a compound which shows
(a) Optical isomerism
(b) Geometrical isomerism
11 Aldehydes and Ketones

(c) Acetic acid (d) Acetaldehyde

Ans. (a)
Sol.

57. Which of the following species is the conjugate acid of

the hemiacetal formed by reaction of benzaldehyde
with methanol containing a trace of acid ?
59. Product in following reaction is CH3MgI + HCHO →
Product
(a) CH3CHO (b) CH3OH
(a) (b) (c) C2H5OH (d) CH3– O – CH3
Ans. (c)
Sol. Here, 𝐶𝐻3 𝑀𝑔𝐼is a Grignard reagent. This reagent is
used for alkylation. Upon addition of water, an alcohol
is obtained.
The reaction is-
(c) (d)
𝐶𝐻3 𝑀𝑔𝐼 + 𝐻𝐶𝐻𝑂 → 𝐶𝐻3 𝐶𝐻2 𝑂𝐻
Ans. (c)
Therefore, the correct answer is option (c) 𝐶2 𝐻5 𝑂𝐻
Sol. Benzaldehyde is an aromatic aldehyde and methanol is
an alcohol. The reaction of formation of hemiacetal of
60. Identify the reactant X and the product Y
these two is given as-

(a) X = MgCl2 ; Y = CH3CH = CH2

(b) X = CH3MgCl ; Y = C2H5COCH3
(c) X = CH3MgCl ; Y = (CH3)3C – OH
(d) X = C2H5MgCl ; Y = (CH3)3C – OH
Ans. (c)
Thus, the hemiacetal formed is PhCH(OH)(OMe) and Sol. In the given reaction the reactant is acetone and the first
its conjugate acid is formed by adding a proton to the R product formed is (𝐶𝐻3 )3 𝐶 − 𝑂𝑀𝑔 − 𝐶𝑙, so in this
i.e. Me here. product there is addition of a methyl group and
Therefore, the correct answer is option (c) magnesium chloride, hence the X will be 𝐶𝐻3 𝑀𝑔𝐶𝑙,
and 𝐶𝐻3 𝑀𝑔𝐶𝑙is a Grignard reagent. When this
compound is hydrolyzed, there is formation of tertiary
alcohol, so the product will be (𝐶𝐻3 )3 𝐶 − 𝑂𝐻and
(𝐶𝐻3 )3 𝐶 − 𝑂𝐻is Y.

61. The order of reactivity of phenyl magnesium bromide

58. Grignard reagent on reaction with acetone forms
with the following compounds is
(a) Tertiary alcohol (b) Secondary alcohol
Aldehydes and Ketones 12

(c) n-Hexane
(d) Benzene
Ans. (b)
Sol.

(a) (II) > (III) > (I)

(b) (I) > (III) > (II)
(c) (II) > (I) > (III) 65. Clemensen’s reduction of ketones is carried out in
(d) All react with the same rate (a) H2 with Pd catalyst
Ans. (c) (b) Glycol with KOH
Sol. The order of the reactivity of the phenyl magnesium (c) LiAlH4 in water
bromide that is PhMgBr with the following compounds (d) Zn–Hg with HCl
will be represented as II > I > III because as the number Ans. (d)
of the alkyl group increase or we can say that the size of Sol. Clemmensen’s reduction is a common reaction which
the alkyl group increases the steric crowding also includes reduction of carbonyl compounds.
increases and the ease of the nucleophilic attack also Here, zinc amalgam (which is nothing but a binary
decreases. solution i.e. liquid in solid solution of zinc and
Hence, the correct answer is option (c) mercury) along with concentrated hydrochloric acid
is used for the reduction of ketones to give the
62. Which of the following reagents converts both corresponding hydrocarbon.
acetaldehyde and acetone to alkanes? Therefore, the correct answer is option (d) Zn–Hg
(a) Ni/H2 (b) LiAlH4 with HCl.
(c) I2/NaOH (d) Zn-Hg/conc.HCl
Ans. (d) 66. Aldehydes and ketones can be reduced to
Sol. Alkanes can be formed from both aldehydes and corresponding hydrocarbons by
ketones with zinc amalgam and concentrated (a) Refluxing with water
hydrochloric acid. The acetaldehyde will form ethane (b) Refluxing with strong acids
and the acetone will form propane. This reaction is (c) Refluxing with soda amalgam and water
known as Clemmensen reduction. So, the reagent that (d) Refluxing with zinc amalgam and concentrated HCl
can be use to convert both acetaldehyde and acetone is Ans. (d)
Zn-Hg/conc.HCl Sol. Reduction of aldehydes and ketones to their
corresponding hydrocarbons is carried out by a reaction
63. Clemmensen reduction involves > C = O to > CH2 in named Clemmenson’s reduction.
presence of Here, zinc amalgam (which is nothing but a binary
(a) Zn/Hg (b) Alcohol solution i.e. liquid in solid solution of zinc and
(c) Zn dust (d) Zn/alcohol mercury) along with concentrated hydrochloric acid is
Ans. (a) used for the reduction of ketones to give the
Sol. In Clemmensen reduction reaction, reduction of corresponding hydrocarbon.
carbonyl groups to alkane groups takes place. This Therefore, the correct answer is option (d) refluxing
reaction required the reagent known as zinc amalgam. with zinc amalgam and concentrated HCl
Zinc amalgam is nothing but a binary solution i.e.
liquid in solid solution of zinc and mercury. 67. In Wolf-Kishner reduction, the carbonyl group of
Therefore, the correct answer is option (a) Zn/Hg. aldehydes and ketones is converted into
(a) > CH2 group (b) – CH3 group
64. Clemmensen's reduction will convert cyclohexanone (c) – CH2OH group (d) > CHOH group
into: Ans. (a)
(a) Cyclopentanone Sol. In Wolff-Kishner reduction, hydrazine is used alone
(b) Cyclohexane with a base. Here, the carbonyl functional group is
13 Aldehydes and Ketones

converted to the methylene group by addition of 𝑁𝐻2 − Ans. (b)

𝑁𝐻2 by which we get hydrazone by the attack of the Sol. In Clemmensen’s reduction, alkanes are formed from
group to the carbonyl group. It is further reduced to an aldehyde or ketone with zinc amalgam and
alkane by addition of ethylene glycol and heating. concentrated hydrochloric acid. So, the option (a) is
Therefore, the correct answer is option (a) > CH2 group correct.
In Wolf- Kishner reduction, alkanes are formed from
68. Wolff-Kishner reduction is : aldehyde or ketone when they are heated with
(a) reduction of carbonyl compounds into hydrocarbons hydrazine and KOH. So, the option (b) is incorrect.
(b) reduction of carbonyl compounds into alcohols In Rosenmund’s reduction, the aldehyde is formed from
(c) reduction of nitrobenzene into aniline acid chloride, when acid chloride is treated with
(d) reduction of carbohydrates into alcohols hydrogen in the presence of boiling xylene solution and
Ans. (a) over Pd or 𝐵𝑎𝑆𝑂4 surface which is used as the catalyst
Sol. Wolff-Kishner is one of the method in which the and they are also called as the Rosenmund’s catalyst.
aldehydes or ketones are converted into alkanes or So, option (c) is correct.
hydrocarbons. This reaction takes place in the presence In Stephen reduction, the aldehyde is formed from
of hydrazine and potassium hydroxide. The reaction is nitriles, by treating the nitriles with stannous chloride in
given below: the presence of hydrochloric acid. So, option (d) is
correct.
71. For C6H5CHO which of the following is incorrect?
(a) On oxidation it yields benzoic acid
(b) It is used in perfumery
(c) It is an aromatic aldehyde
(d) On reduction yields phenol
69. Ans. (d)
Sol. The compound given in the question is benzaldehyde
having formula 𝐶6 𝐻5 𝐶𝐻𝑂 . Since, it has aldehyde
functional group, so, on oxidation the aldehyde will
convert into carboxylic acid. So, on oxidation of
A is
benzaldehyde will give benzoic acid. Since it is an
(a) 𝑍𝑛 −Hg/HCl (b) 𝑁𝐻2 − 𝑁𝐻2 /𝑂𝐻 − aromatic aldehyde, it is used in perfumery. When the
(c) Both (a) and (b) (d) 𝑁𝑎𝐵𝐻4 benzaldehyde is reduced, there is formation of benzyl
Ans. (b) alcohol having formula 𝐶6 𝐻5 𝐶𝐻2 𝑂𝐻 . The reaction is
Sol.
given below:

In this reaction, 𝑍𝑛 − 𝐻𝑔/𝐻𝐶𝑙 is not used because in

acidic medium, −𝑁𝐻2 group is affected. 72.

70. Which one of the following pairs is not correctly

matched
𝐶𝑙𝑒𝑚𝑚𝑒𝑛𝑠𝑜𝑛
(a) > 𝐶 = 𝑂 → > 𝐶𝐻2
𝑊𝑜𝑙𝑓−𝑘𝑖𝑠ℎ𝑛𝑒𝑟
(b) > C = O → > CHOH The product predominates is
𝑅 𝑜𝑠𝑒𝑛𝑚𝑢𝑛𝑑 ′ 𝑠𝑟𝑒𝑑𝑢𝑐𝑡𝑖𝑜𝑛
(c) – COCl → CHO
𝑆𝑡𝑒𝑝ℎ𝑒𝑛𝑟𝑒𝑑𝑢𝑐𝑡𝑖𝑜𝑛
(d) – C ≡ N → CHO
Aldehydes and Ketones 14

Sol. Alcohols can’t be reduced by 𝐿𝑖𝐴𝑙𝐻4 . Only carbonyl

compound, carboxylic acid and acid derivatives are
reduced by 𝐿𝑖𝐴𝑙𝐻4
(a)
76. If pentan-2-one is reacted with NaBH4, followed by
hydrolysis with D2O, the product will be :
(b) (a) CH3CD(OD)CH2CH2CH3
(b) CH3CD(OH)CH2CH2CH3
(c) CH3CH(OH)CH2CH2CH3
(d) CH3CH(OD)CH2CH2CH3
Ans. (d)
(c) Sol. Pentan-2-one is the compound of five carbon atoms and
the ketone group is present at the second carbon atom.
So, when this compound is treated with 𝑁𝑎𝐵𝐻4 , the
(d) ketone group will convert into alcohol group. So, when
Ans. (b) this compound is treated with 𝐷2 𝑂, the hydrogen atom
Sol. of the alcohol group will be replaced with D atom.
So the product will be 𝐶𝐻3 𝐶𝐻(𝑂𝐷)𝐶𝐻2 𝐶𝐻2 𝐶𝐻3 .

𝐿𝑖𝐴𝑙𝐻4 does not reduce bond. If double bond is

conjugated with phenyl system then double bond is 77. The reaction of acetaldehyde with conc. KMnO4 gives
reduced by 𝐿𝑖𝐴𝑙𝐻4 . (a) CH3COOH (b) CH3CH2OH
73. 𝐶𝐻3 𝐶𝐻𝑂 + 𝐿𝑖𝐴𝑙𝐻4 → 𝐶𝐻3 𝐶𝐻2 𝑂𝐻 (c) HCHO (d) CH3OH
Nucleophile added in this reaction is Ans. (a)
(a) 𝐴𝑙𝐻4− (b) 𝐿𝑖 + Sol. When the aldehydes or ketones are oxidized, there is
+
(c) 𝐻 (d) 𝐻 − formation of carboxylic acid. Concentrated 𝐾𝑀𝑛𝑂4 is
Ans. (d) strong oxidizing agent. So, it will oxidize the
Sol. Hydride act as nucleophile in this reaction. acetaldehyde to acetic acid in single step. The reaction
is given below:
𝑐𝑜𝑛𝑐.𝐾𝑀𝑛𝑂4
74. 𝐶𝐻3 𝐶𝐻𝑂 → 𝐶𝐻3 𝐶𝑂𝑂𝐻
In the above sequence X can be
(a) H2/Ni (b) NaBH4 78. An aldehyde on oxidation gives
(c) K2Cr2O7 (d) Both (a) and (b) (a) An alcohol (b) An acid
Ans. (b) (c) A ketone (d) An ether
Sol. In the given reaction, the aldehyde is converted into Ans. (b)
alcohol, but the double bond is not attacked. So, the Sol. When the aldehydes or ketones are oxidized, there is
aldehyde must be reacted with a compound that will formation of carboxylic acid. Or we can say that the
only reduce the aldehyde and not the double bond. carbonyl group of the aldehydes and ketones are
Hence we can use 𝑁𝑎𝐵𝐻4 . So, the option (b) is correct. converted into acid group in carboxylic acid. The
reaction is:
[𝑂]
75. The compound which is not reduced by 𝐿𝑖𝐴𝑙𝐻4 is 𝑅 − 𝐶𝐻𝑂 → 𝑅 − 𝐶𝑂𝑂𝐻
(a) Cyclohexanone (b) 2-Methyl-1-butanol
(c) Ethyl benzoate (d) 𝜔 -caprolactam 79. Aldehydes are first oxidation products of:
Ans. (b) (a) primary alcohols (b) secondary alcohols
(c) tertiary alcohols (d) none of these
Ans. (a)
15 Aldehydes and Ketones

Sol. Aldehydes are the first oxidation product of primary

alcohols. The primary alcohols are first oxidized to
form aldehydes which on further oxidations can be
converted into carboxylic acid. Ketones are formed
from oxidation of secondary alcohols and this cannot be (b)
further oxidized to form carboxylic acids.

80. Isopropyl alcohol on oxidation forms:

(a) acetone (b) ether
(c)
(c) acetaldehyde (d) ethylene
Ans. (a)
Sol. Isopropyl alcohol is the compound in which the alcohol
group is present at the second carbon atom. The
(d)
formula of isopropyl alcohol is 𝐶𝐻3 − 𝐶𝐻𝑂𝐻 − 𝐶𝐻3 . It
Ans. (a)
will form ketone on oxidation. Since a ketone can be Sol.
prepared only from secondary alcohol. Secondary
alcohols are those compounds in which the alcohol
group is present at the carbon atom which is further
attached to 2 carbon atoms. So, when this secondary
alcohol is oxidized, there is formation of ketone. So, the
isopropyl alcohol will form acetone. Tertiary alcohols
83. Oxidation of acetaldehyde with selenium dioxide
can't be oxidized.
produces:
𝑂
(a) ethanoic acid (b) methanoic acid
|| 𝐶𝑜𝑛𝑐.𝐻𝑁𝑂3 (c) glyoxal (d) oxalic acid
81. 𝐶𝐻3 − 𝐶 − 𝐶𝐻2 − 𝐶𝐻3 → Product Ans. (c)
The product is Sol. When the aldehyde is oxidized with selenium dioxide,
(a) 𝐶𝐻3 𝐶𝑂𝑂𝐻 the methyl group of the acetaldehyde will convert into
(b) 𝐶𝐻3 𝐶𝐻2 𝐶𝑂𝑂𝐻 + 𝐻𝐶𝑂𝑂𝐻 aldehyde group and the aldehyde group of the reactant
(c) 𝐶𝐻3 𝐶𝐻2 𝐶𝐻2 𝐶𝑂𝑂𝐻 will not be affected. So, the reactant given is
(d) No reaction acetaldehyde having formula 𝐶𝐻3 𝐶𝐻𝑂. So, when it is
Ans. (a) oxidized, glyoxal will be formed. The reaction will be:
𝑂
|| 𝐶𝑜𝑛𝑐.𝐻𝑁𝑂3
𝐶𝐻3 𝐶𝐻𝑂 + 𝑆𝑒𝑂2 → 𝑂𝐻𝐶 − 𝐶𝐻𝑂 + 𝑆𝑒 + 𝐻2 𝑂
Sol. 𝐶𝐻3 − 𝐶 − 𝐶𝐻2 − 𝐶𝐻3 → 𝐶𝐻3 𝐶𝑂𝑂𝐻
According to Popoff’s rule, carbonyl group goes with 84. The product obtained in the following reaction is
less complex alkyl group.

82.

(a)

(a)

(b)
Aldehydes and Ketones 16

(b) Propanaldehyde
(c) Benzaldehyde
(d) Trideuteroacetaldehyde
(c) Ans. (c)
Sol. Aldol condensation is a chemical property of the
aldehydes in which two molecules of the aldehydes
combines to form a compound in which alcohol and
(d)
aldehyde groups are present. But the requirement for
Ans. (b)
the aldehyde to show aldol condensation is that, the
Sol. When the reactant is treated with 𝐻𝐼𝑂4 , the ketone
aldehyde must have 𝛼 − 𝐻𝑦𝑑𝑟𝑜𝑔𝑒𝑛 . So, the
group will convert into carboxylic acid group and the
alcohol group will convert into aldehyde group. The benzaldehyde whose formula is 𝐶6 𝐻5 𝐶𝐻𝑂 doesn’t have
reaction is given below: 𝛼 − 𝐻𝑦𝑑𝑟𝑜𝑔𝑒𝑛 so, it cannot show aldol condensation.

88. Treatment of propionaldehyde with dilute NaOH

solution gives
(a) CH3CH2COOCH2CH2CH3
(b) CH3CH2CHOHCH(CH3)CHO
85. When dihydroxy acetone reacts with HIO4, the product
(c) CH3CH2CHOHCH2CH2CHO
is/are
(d) CH3CH2COCH2CH2CHO
(a) HCHO (b) HCOOH
Ans. (b)
(c) HCHO and HCOOH (d) HCHO and CO2
Sol. Aldol condensation is a chemical property of the
Ans. (d)
aldehydes in which two molecules of the aldehydes
Sol. This reaction of dihydroxyacetone with 𝐻𝐼𝑂4 is known
combines to form a compound in which alcohol and
as Malaparade oxidation. So, when dihydroxyacetone
aldehyde groups are present. But the requirement for
reacts with 𝐻𝐼𝑂4 , there is formation of formaldehyde
the aldehyde to show aldol condensation is that, the
and carbon dioxide. The reaction is given below:
aldehyde must have 𝛼 − 𝐻𝑦𝑑𝑟𝑜𝑔𝑒𝑛 . So, the
propionaldehyde with dilute NaOH will give 𝐶𝐻3 −
𝐶𝐻2 − 𝐶𝐻(𝑂𝐻) − 𝐶𝐻(𝐶𝐻3 ) − 𝐶𝐻𝑂. The reaction is
given below:

86. Aldol condensation will not be observed in

(a) Chloral (b) Phenyl acetaldehyde
(c) Hexanal (d) Ethanal
Ans. (a)
Sol. Aldol condensation is a chemical property of the
aldehydes in which two molecules of the aldehydes
89. Aldol condensation is
combines to form a compound in which alcohol and
(a) self condensation of aldehydes only having atleast
aldehyde groups are present. But the requirement for
one alpha hydrogen
the aldehyde to show aldol condensation is that, the
(b) self condensation of ketones only having atleast one
aldehyde must have 𝛼 − 𝐻𝑦𝑑𝑟𝑜𝑔𝑒𝑛 . So, the chloral
alpha hydrogen
whose formula is 𝐶𝑙3 𝐶𝐶𝐻𝑂 doesn’t have 𝛼 − (c) self condensation of both aldehydes and ketones
𝐻𝑦𝑑𝑟𝑜𝑔𝑒𝑛 so, it cannot show aldol condensation. having atleast one alpha hydrogen
(d) self condensation of both aldehydes and ketones
87. Which of the following will not undergo aldol having no alpha hydrogen
condensation Ans. (c)
(a) Acetaldehyde
17 Aldehydes and Ketones

Sol. Aldol condensation is a chemical property of the

aldehydes and ketones in which two molecules of the
aldehydes combines to form a compound in which
alcohol and aldehyde groups are present. But the
requirement for the aldehyde to show aldol
condensation is that, the aldehyde and ketone must have
𝛼 − 𝐻𝑦𝑑𝑟𝑜𝑔𝑒𝑛.
92. Aldol condensation will not take place in
(a) HCHO
(b) CH3CH2CHO
(c) CH3CHO
90. does not show aldol condensation (d) CH3COCH3
because : Ans. (a)
(a) carbon is bounded by 3-heavy methyl groups Sol. no alpha hydrogen atom is present and thus it cannot go
(b) due to the absence of α-hydrogen aldol condensation reaction.
(c) it is a neutral molecule Therefore, the correct answer is option (a) HCHO.
(d) due to hindrance created by methyl group for
carbanion
Ans. (b)
Sol. Aldol condensation is a chemical property of the
aldehydes and ketones in which two molecules of the
aldehydes combines to form a compound in which
alcohol and aldehyde groups are present. But the
requirement for the aldehyde to show aldol
condensation is that, the aldehyde and ketone must
have 𝛼 − 𝐻𝑦𝑑𝑟𝑜𝑔𝑒𝑛. So, in the given compound there
is no 𝛼 − 𝐻𝑦𝑑𝑟𝑜𝑔𝑒𝑛, hence it will not give aldol
condensation reaction.

91. Predict the product ‘B’ in the sequence of reaction

(a) CH3COONa
(b) CH3COOH
(c) CH3CHO

(d)
Ans. (d)
Sol. The reactant is ethyne so, when the ethyne is reacted in
the presence of dil.𝐻2 𝑆𝑂4 and 𝐻𝑔𝑆𝑂4 to form
acetaldehyde. Hence, acetaldehyde is the product A.So
this product A on the reaction with 𝑁𝑎𝑂𝐻 will undergo
aldol condensation to form 3-hydroxybutanal. The
reaction is given below:
Aldehydes and Ketones 18

93. Acetophenone when reacted with a base, C2H5ONa,

yields a stable compound which has the structure

(d)
Ans. (a)
(a)
Sol.

(b)

95. 3-hydroxy butanal is formed when X reacts with Y in

(c) dilute Z solution. What are X, Y and Z?
(d) none of these X Y Z
Ans. (a) (a) CH3CHO, (CH3)2CO, NaOH
Sol. 𝐶2 𝐻5 𝑂𝑁𝑎 is a strong base and acetophenone is a (b) CH3CHO, CH3CHO, NaCl
ketone. And when aldehydes and ketones react with a (c) (CH3)2CO, (CH3)2CO, HCl
strong base, then they undergo self-aldol condensation (d) CH3CHO, CH3CHO, NaOH
reaction. The aldol condensation of acetophenone is Ans. (d)
given below: Sol. 3-Hydroxy butanal is a product formed when the
ethanal or acetaldehyde. When 2 moles of ethanal or
acetaldehyde react with each other in the presence of
strong base to undergo self aldol condensation reaction.
The reaction is given below:

Aldol compound having two functional groups.

96. Which of the following compound will undergo self

aldol condensation in the presence of cold dilute alkali
(a) C6H5CHO (b) CH3CH2CHO
(c) (d)
Ans. (b)
94. Which of the products is formed when acetone is Sol. Aldol condensation is a chemical property of the
reacted with barium hydroxide solution? aldehydes in which two molecules of the aldehydes
combines to form a compound in which alcohol and
aldehyde groups are present. But the requirement for
(a) the aldehyde to show aldol condensation is that, the
aldehyde must have saturated 𝛼 − 𝐻𝑦𝑑𝑟𝑜𝑔𝑒𝑛 . In
𝐶𝐻3 𝐶𝐻2 𝐶𝐻𝑂 there is 𝛼 − 𝐻𝑦𝑑𝑟𝑜𝑔𝑒𝑛 so, it will give
self-aldol condensation reaction.
(b) 97.

(c)
19 Aldehydes and Ketones

benzene ring. So there is no 𝛼 − Hydrogen in the

compound, hence, they will give Cannizzaro reaction.
(a) So, this compound will give two products, one by
reduction will form benzyl alcohol and one by
oxidation form benzoic acid. The reaction is given
below:
(b)

(c)

100. Cannizzaro’s reaction is not given by :

(a) CH3CHO (b) HCHO
(c) benzaldehyde (d) triethyl acetaldehyde
(d)
Ans. (a)
Sol. Cannizzaro’s reaction is a chemical property of the
Ans. (c)
aldehydes. The aldehydes that do not have 𝛼 −
Sol.
𝐻𝑦𝑑𝑟𝑜𝑔𝑒𝑛 can undergo disproportionation reaction,
i.e., self oxidation and reduction reaction. This reaction
is Cannizzaro reaction. So, from the given options,
𝐶𝐻3 𝐶𝐻𝑂 has 𝛼 − 𝐻𝑦𝑑𝑟𝑜𝑔𝑒𝑛 so, it will not give
98. In the scheme given below, the total number of Cannizzaro’s reaction.
intramolecular aldol condensation products formed
from ′′𝑌 ′′ is

101. shows Cannizzaro’s reaction due to

(a)1 (b)2
(c)3 (d)4 (a) carbon is bounded by 3 methyl groups
Ans (a) (b) absence of α-hydrogen atom
(c) due to steric effect
Sol.
(d) None of the above
Ans. (b)
Sol. The aldehydes that do not have𝛼 − 𝐻𝑦𝑑𝑟𝑜𝑔𝑒𝑛 can
undergo disproportionation reaction, i.e., self oxidation
and reduction reaction. This reaction is Cannizzaro
reaction. So, the given compound should not have
alpha-hydrogen. Hence in the given compound the
alpha carbon have methyl groups so, it will show
Cannizzaro’s reaction.

99. Benzaldehyde + NaOH→ 102. The following reagent converts C6H5COCHO to

(a) Benzyl alcohol (b) Benzene C6H5CHOHCOOH
(c) Hydrobenzamide (d) Cinnamic acid (a) Aq. NaOH/H+ (b) Acidic Na2S2O3
Ans. (a) (c) Na2CrO4/H2SO4 (d) NaNO2/HCl
Sol. In the given reaction, benzaldehyde is reacting with Ans. (a)
sodium hydroxide, and we know in benzaldehyde an
aldehyde group is present at the carbon atom of the
Aldehydes and Ketones 20

Sol. The aldehydes that do not have 𝛼 − 𝐻𝑦𝑑𝑟𝑜𝑔𝑒𝑛 can

undergo disproportionation reaction, i.e., self oxidation
and reduction reaction. This reaction is Cannizzaro
reaction. So, the given compound 𝐶6 𝐻5 𝐶𝑂𝐶𝐻𝑂 when
treated with aqueous solution of NaOH will be
converted into 𝐶6 𝐻5 𝐶𝐻𝑂𝐻𝐶𝑂𝑂𝐻. The reaction is given
below:

103. The correct sequence of step involved in the mechanism 104. Which one of the following undergoes reaction with
of Cannizzaro’s reaction is 50% sodium hydroxide solution to give the
(a) nucleophilic attack, transfer of H– and transfer of corresponding alcohol and acid
H+. (a) Butanal (b) Benzaldehyde
(b) transfer of H–, transfer of H+ and nucleophilic (c) Phenol (d) Benzoic acid
attack. Ans. (b)
(c) transfer of H+, nucleophilic attack and transfer of Sol. Benzaldehyde does not have any alpha hydrogen atoms
H –. in it. Benzaldehyde will undergo Cannizzaro reaction
(d) electrophilic attack by OH–, transfer of H+ and when treated with aqueous base, 50% sodium
transfer of H–. hydroxide and give the corresponding acid and alcohol
Ans. (a) i.e. benzoic acid and benzyl alcohol respectively. The
Sol. Cannizzaro’s reaction is a chemical property of the reaction is-
aldehydes. The aldehydes that do not have 𝛼 −
𝐻𝑦𝑑𝑟𝑜𝑔𝑒𝑛 can undergo disproportionation reaction,
i.e., self oxidation and reduction reaction. The
mechanism involved in the Cannizzaro’s reaction is
first Nucleophilic attack (fast reaction), then hydride Therefore, the correct answer is option (b)
transfer (slow step), and then 𝐻 + transfer. benzaldehyde.

𝑁𝑎𝑂𝐻
105. 2𝐶6 𝐻5 𝐶𝐻𝑂 → 𝐶6 𝐻5 𝐶𝐻2 𝑂𝐻 + 𝐶6 𝐻5 𝐶𝑂𝑂𝑁𝑎
The similar reaction can take place with which of the
following aldehyde?
(a) 𝐶𝐻3 𝐶𝐻𝑂
(b) 𝐶𝐻3 𝐶𝐻2 𝐶𝐻𝑂
(c) (𝐶𝐻3 )3 𝐶𝐶𝐻𝑂
(d) 𝐶𝐻3 𝐶𝐻2 𝐶𝐻2 𝐶𝐻𝑂
Ans. (c)
Sol. No 𝛼 – hydrogen in this compound.

106. Which one does not give Cannizzaro’s reaction?

21 Aldehydes and Ketones

(a) Benzaldehyde
(b) propanal 109. Trichloroacetaldehyde was subjected to Cannizaro’s
(c) p-methoxybenzaldehyde reaction by using NaOH. The mixture of the products
(d) 2, 2-dimethyl propanal contains sodium trichloroacetate ion and another
Ans. (b) compound. The other compound is
Sol. The Cannizzaro reaction is the disproportionation in (a) 2, 2, 2-trichloroethanol
concentrated base of an aldehyde lacking an α- (b) trichloromethanol
hydrogen atom to form a carboxylic acid and a alcohol. (c) 2, 2, 2-trichloromethanol
propanal has three α-hydrogen, so it will not undergo (d) chloroform
the Cannizzaro reaction Ans. (a)
𝑁𝑎𝑂𝐻
Sol. 2𝐶𝐶𝑙3 𝐶𝐻𝑂 → 𝐶𝐶𝑙3 𝐶𝑂𝑂𝑁𝑎 + 𝐶𝐶𝑙3 𝐶𝐻2 𝑂𝐻
Cannizzaro reaction is a type of disproportionation
107. The key step in cannizzaro’s reaction is the reaction in which the aldehyde molecules get oxidized to
intermolecular shift of the carboxylic acid salt and the other compound get
(a) Proton (b) Hydride ion reduced to alcohols. IUPAC name for the compound is
(c) Hydronium ion (d) Hydrogen bond 2,2,2-Trichloroethanol.
Ans. (b) Hence, the correct answer is option (a)
Sol. Cannizzaro reaction is a disproportionation reaction
induced by a base. This reaction is useful for the 110.
conversion of two molecules of an aldehyde into a
primary alcohol as well as an acid. But the aldehyde
should not be enolizable and aldehydes with no alpha
hydrogen atoms are non-enolizable. (a)
In this reaction, shift of hydride ion takes place.
Therefore, the correct answer is option (b) Hydride ion.
(b)
108. m-chlorobenzaldehyde on reaction with conc. KOH at
room temperature gives
(a) potassium m-chlorobenzoate and m-chlorobenzyl
(c)
alcohol
(b) m-hydroxybenzaldehyde and m-chlorobenzyl
alcohol
(c) m-chlorobenzyl alcohol and m-hydroxy benzyl
alcohol (d)
(d) potassium m-chlorobenzoate and m- Ans. (a)
hydroxybenzaldehyde Sol. This is example of Cannizaro reaction.
Ans. (a)
Sol. The given reaction is a Cannizzaro reaction therefore
the products for the m-chlorobenzaldehyde in the
Cannizzaro reactions are potassium m-chlorobenzoate
and m-chlorobenzyl alcohols.

111.

Hence, the correct answer is option (a)

Aldehydes and Ketones 22

Undergo Cannizaro reaction give product as

(a)

(b)

(c)
∴ Number of aldol reactions = 3

113.

(d) The reaction given is

(a) Aldol condensation (b) Knoevenagel reaction
(c) Cannizzaro reaction (d) None of these
Ans. (c)
Sol. When a compound containing no alpha hydrogen atoms
Ans. (b) undergoes a self-oxidation and self-reduction reaction
Sol. induced by a base, the reaction is named as Cannizzaro
reaction.
Cannizzaro reaction is a disproportionation reaction
induced by a base. This reaction is useful for the
conversion of two molecules of an aldehyde into a
alcohol as well as an acid.
Therefore, the correct answer is option (c) Cannizzaro
reaction.
112. The number of aldol reaction(s) that occurs in the given
transformation is
114. Which of the following is obtained when chloral is
boiled with NaOH
(a) CH3Cl (b) CHCl3
(c) CCl4 (d) None of these
(a) 1 (b) 2
Ans. (b)
(c) 3 (d) 4
Sol. Chloral is an organic compound whose formula
Ans. (c)
is𝐶𝐶𝑙3 𝐶𝐻𝑂, and when it is treated with sodium
Sol. hydroxide, the hydrolysis will take place and there is
23 Aldehydes and Ketones

formation of chloroform, whose formula is 𝐶𝐻𝐶𝑙3 and

sodium formate whose formula is 𝐻𝐶𝑂𝑂𝑁𝑎.

115. Acetone is mixed with bleaching powder to give The compound 𝑥is
(a) chloroform (b) acetaldehyde (a) 𝐶𝐻3 𝐶𝑂𝑂𝐻 (b) 𝐵𝑟𝐶𝐻2 − 𝐶𝑂𝑂𝐻
(c) ethanol (d) phosgene
(c) (𝐶𝐻3 𝐶𝑂)2 𝑂 (d) 𝐶𝐻𝑂 − 𝐶𝑂𝑂𝐻
Ans. (a)
Ans. (c)
Sol. When acetone is reacted with bleaching powder then
Sol.
there is formation of chloroform. The formula of
chloroform is 𝐶𝐻𝐶𝑙3 . The series of reaction is given
below:
𝐶𝑎𝑂𝐶𝑙2 + 𝐻2 𝑂 → 𝐶𝑎(𝑂𝐻)2 + 𝐶𝑙2
𝑂 𝑂
∥ ∥
𝐶𝐻3 − 𝐶 − 𝐶𝐻3 + 3𝐶𝑙2 → (𝐶𝑙)3 𝐶 − 𝐶 − 𝐶𝐻3 + 3𝐻𝐶𝑙
Acetone
2𝐶𝑙3 𝐶𝐶𝑂𝐶𝐻3 + 𝐶𝑎(𝑂𝐻)2 → 2𝐶𝐻𝐶𝑙3 + 118. Acetaldehyde reacts with chlorine to give
Chloroform
(a) CCl4 (b) CHCl3
(𝐶𝐻3 𝐶𝑂𝑂)2 𝐶𝑎
(c) CCl3.COCH3 (d) CCl3.CHO
Ans. (d)
116. Ketones reacts with Mg-Hg over water gives
Sol. Acetaldehyde has alpha hydrogen atom show it will
(a) pinacolone (b) pinacols
show tautomerism, and it will convert into enol form.
(c) alcohols (d) None of these
Now when this enol form is treated with chlorine then
Ans. (b)
there is formation of 2, 2, 2-Trichloroacetadehyde and
Sol. When ketones react with Mg-Hg over water, there is
hydrochloric acid. The reaction is given below:
formation of pinacols. Pinacols are those compounds in
which the two adjacent carbon atoms have alcohol
group. So, in this reaction two moles of ketones are
required. The reaction is given below:

Test of carbonyl compounds

119. Silver mirror is a test for
(a) Aldehydes
(b) Thio alcohols
(c) Amines
(d) Ethers
Ans. (a)
Sol. Tollen’s test is known as silver mirror test and it is used
for the detection of aldehyde in the compound.
.
Ammonical solution of silver nitrate is known as
117.
Tollen’s reagent, and when an aldehyde reacts with
Tollen’s reagent then there is formation of silver mirror.
So, only aldehydes can give this test.

120. Aldehydes and ketones are differentiated by using

Aldehydes and Ketones 24

(a) NaOH/I2 (b) NaHSO3 anhydride is not an aldehyde therefore, it will not
(c) AgNO3/NH4OH (d) NH2.NH2 give the benedict’s test.
Ans. (c)
Sol. Tollen’s test is known as silver mirror test and it is used 124. Fehling’s test is positive for
for the detection of aldehyde in the compound. (a) Acetaldehyde (b) Benzaldehyde
Ammonical solution of silver nitrate is known as (c) Ether (d) Alcohol
Tollen’s reagent, and when an aldehyde reacts with Ans. (a)
Tollen’s reagent then there is formation of silver mirror. Sol. Fehling’s test is used for the presence of aliphatic
The reactant used in Tollen’s test is AgNO3/NH4OH. aldehyde in the compound. Alkaline solution of
Since this test is only given by the aldehydes, it can be 𝐶𝑢𝑆𝑂4 containing some Rochelle salt is known as
used to differentiate between aldehyde and ketone. Fehling’s solution. When the aliphatic aldehyde is
treated with Fehling’s solution, red ppt. is formed. So,
121. Which is not true about acetophenone? from the given options acetaldehyde is the aliphatic
(a) Reacts to form 2, 4-dinitrophenyl hydrazine gives aldehyde and will give positive Fehling’s test.
coloured ppt.
(b) Reacts with Tollen’s reagent to form silver mirror 125. C2H5CHO and (CH3)2CO can be distinguished by
(c) Reacts with I2/NaOH to form iodoform testing with
(d) On oxidation with alkaline KMnO4 followed by (a) Phenyl hydrazine (b) Hydroxylamine
hydrolysis gives benzoic acid (c) Fehling solution (d) none of these
Ans. (b) Ans. (c)
Sol. Acetophenone is a methyl ketone. Its chemical formula Sol. 𝐶2 𝐻5 𝐶𝐻𝑂is an aldehyde and(𝐶𝐻3 )2 𝐶𝑂 is a ketone, so
is PhCOMe. from the given options Fehlings solution can be used to
Aldehydes give Tollen’s test but ketones do not give differentiate between the aldehyde and ketone.
Tollen’s test. Aldehyde or 𝐶2 𝐻5 𝐶𝐻𝑂will give a positive for the
Ketones do not reduce the Tollen’s reagent to show the Fehling’s test but ketone will give a negative test for the
silver mirror. Fehling’s solution.
Therefore, the correct answer is option (b) reacts with
Tollen’s reagent to form silver mirror. 126. Which of the following does not give brick red
precipitate with Fehling solution
122. The compound which reacts with hydroxyl amine but (a) Acetone (b) Acetaldehyde
does not react with Tollen’s reagent is (c) Formalin (d) D-glucose
(a) CH3CHO (b) HCHO Ans. (a)
(c) C2H5OH (d) CH3COCH3 Sol. Fehling solution contains two separate solutions namely
Ans. (d) – Fehling solution A and Fehling solution B. Fehling A
Sol. Both the aldehydes and ketones can react with hydroxyl is basically an aqueous solution of copper sulphate and
amine to form oximes. Tollen’s reagent is used to detect Fehling B is a solution of potassium sodium tartrate.
the presence of aldehyde in the compound, but ketones Fehling solution is used to distinguish between
do not give the Tollen’s test. So, if the compound can aldehydes and acetone.
react with hydroxyl amine but don’t give Tollen’s test, Therefore, the correct answer is option (a)acetone.
then it is a ketone.
127. Which does not react with Fehling’s solution?
123. Benedict’s solution is not reduced by (a) CH3CHO (b) C6H5CHO
(a) formaldehyde (b) acetaldehyde (c) CH3CH2CHO (d) Glucose
(c) glucose (d) acetic anhydride Ans. (b)
Ans. (d) Sol. Fehling’s test is used for the presence of aliphatic
Sol. Benedict’s solution is a test for the presence of aldehyde in the compound. Alkaline solution of
aldehyde group in the compound. It works same as 𝐶𝑢𝑆𝑂4 containing some Rochelle salt is known as
Fehling’s solution. So, from the given options, acetic Fehling’s solution. When the aldehyde is treated with
25 Aldehydes and Ketones

Fehling’s solution, red ppt. is formed. So, from the Sol. Acetaldehyde is a compound having formula 𝐶𝐻3 𝐶𝐻𝑂,
given options C6H5CHO is an aromatic aldehyde will so this is compound having aldehyde functional group.
be the correct answer, since the ketones and aromatic So, the aldehydes can give Benedict’s test, Tollen’s test
aldehydes will not give positive results for Fehling’s and since it has 𝐶𝐻3 𝐶𝑂 −group so it can give Iodoform
test also. But it cannot give Lucas test because this test
128. When acetaldehyde is heated with Fehling’s solution, it is used to detect the presence of primary, secondary,
gives a precipitate of and tertiary alcohols in the compound.
(a) Cu (b) CuO
(c) Cu2O (d) Cu + Cu2O + CuO 132. The reagent used for the separation of acetaldehyde
Ans. (c) from acetophenone is
Sol. When acetaldehyde is treated with the Fehling solution (a) NaHSO3 (b) C6H5NHNH2
which is tartaric complex of the cuprous ions, a red (c) NH2OH (d) NaOH–I2
precipitate of 𝐶𝑢2 𝑂 is obtained. The reaction involved Ans. (a)
is: Sol. Acetaldehyde is an aliphatic aldehyde having formula
𝐶𝐻3 𝐶𝐻𝑂 + 2𝐶𝑢+ + 5𝑂𝐻 − → 𝐶𝐻3 𝐶𝑂𝑂 − + 𝐶𝑢2 𝑂 + 𝐶𝐻3 𝐶𝐻𝑂and acetophenone is aromatic ketone having
3𝐻2 𝑂 formula 𝐶6 𝐻5 𝐶𝑂𝐶𝐻3 . So, when the acetaldehyde reacts
Hence, the correct answer is option (c) with 𝑁𝑎𝐻𝑆𝑂3 , the addition reaction takes place. But
when acetophenone reacts with 𝑁𝑎𝐻𝑆𝑂3 , there is no
129. Which of the following is incorrect formation of product because of the presence of bulkier
(a) FeCl3 is used in the detection of phenols groups.
(b) Fehling solution is used in the detection of glucose
(c) Tollen’s reagent is used in detection of unsaturation 133. Brady’s reagent is
(d) NaHSO3 is used in the detection of carbonyl (a) 2,4-DNP (b) conc. HCl + ZnCl2
compounds (c) DMSO (d) None of these
Ans. (c) Ans. (a)
Sol. Tollen’s test is known as silver mirror test and it is used Sol. 2, 4-Dinitrophenylhydrazine is a compound known as
for the detection of aldehyde in the compound. Brady’s reagent. It is written as 2, 4-DNP. It is used to
Ammonical solution of silver nitrate is known as detect the carbonyl group in the molecule because when
Tollen’s reagent, and when an aldehyde reacts with the carbonyl groups react with Brady’s reagent,
Tollen’s reagent then there is formation silver mirror. coloured precipitate is formed.
So, it is not used for the unsaturation in the compound. 134. The reagent that gives an orange-coloured precipitate
with acetaldehyde
130. Benedict's solution and Fehling’s solution are similar in (a) NH2OH (b) NaHSO3
all of the following except: (c) Iodine (d) 2, 4-DNP
(a) Both consist of a solution of CuSO4 Ans. (d)
(b) Both contain NaOH and complexing reagent Sol. With acetaldehyde which is a simple aldehyde, 2, 4 –
(c) Both contain Cu2+ ion as the oxidising agent DNP gives an orange coloured precipitate. DNP stands
(d) Sodium citrate is used in Benedict's solution and for dinitrophenylhydrazine and it is also known as
Rochelle salt in Fehling's solution Brady’s reagent.
Ans. (d) It is used for the identification of aldehydes and
Sol. Sodium citrate is used in Benedict's solution and ketones.
Rochelle salt in Fehling's solution Therefore, the correct answer is option (d) 2, 4 – DNP.
135. An aromatic compound ′𝑋 ′ with molecular formula
131. Acetaldehyde cannot show 𝐶9 𝐻10 𝑂 gives the following chemical tests
(a) Iodoform test (b) Lucas test (i) Forms 2,4-DNP derivative
(c) Benedict’s test (d) Tollen’s test (ii) Reduce Tollens reagent
Ans. (b) (iii) Undergoes Cannizzaro reaction and
(iv) On vigorous oxidation, 1,2-benzenedicarboxylic
Aldehydes and Ketones 26

acid is obtained Schiff’s reagent or Schiff’s Solution. So, the option (a)
The compound is correct.

137. Which of the following compounds containing carbonyl

group will give coloured crystalline compound with

(a)

(a) CH3COCl (b) CH3COCH3

(c) CH3CO(OC2H5) (d) CH3CONH2
Ans. (b)
(b) Sol. When aldehydes or ketones react with 2, 4-DNP, there
is a formation of DNP derivative and this derivative is
a colored compound. So, from the options given the
question, we have option (b)- acetone which has
carbonyl group, therefore, it will give colored
crystalline compound.
(c)

(d)
Ans. (a)
Sol. 138. Which of the following does not give iodoform test?
All test are valid for (a) CH3CH2OH (b) CH3OH
(c) CH3CHO (d) PhCOCH3
Ans. (b)
Sol. Iodoform test is a chemical test that is used for detecting
the presence of 𝐶𝐻3 𝐶𝑂 − 𝑜𝑟 𝐶𝐻3 𝐶𝐻(𝑂𝐻) −group in
the molecule. So, in the given options 𝐶𝐻3 𝑂𝐻, doesn’t
(i) Forms 2,4-DNP derivative have 𝐶𝐻3 𝐶𝑂 −group, so it will not give iodoform test.
(ii) Reduce Tollens reagent
(iii) Undergoes Cannizzaro reaction and 139. Which of the following will not give iodoform test?
(iv) On vigorous oxidation, 1,2-benzenedicarboxylic acid (a) Ethanal (b) Ethanol
is obtained (c) 2-propanone (d) 3-pentanone
Ans. (d)
136. Schiff’s solution is obtained when Sol. Iodoform test is a chemical test that is used for detecting
(a) sulphurous acid is passed through magenta dye the presence of 𝐶𝐻3 𝐶𝑂 − 𝑜𝑟𝐶𝐻3 𝐶𝐻(𝑂𝐻) −group in
(b) chlorine is passed through magenta dye the molecule. So, in the given options 3-pentanone
(c) Both (a) and (b) whose formula is 𝐶𝐻3 𝐶𝐻2 𝐶𝑂𝐶𝐻2 𝐶𝐻3 , doesn’t have
(d) None of the above 𝐶𝐻3 𝐶𝑂 −group, so it will not give iodoform test.
Ans. (a)
Sol. A colorless solution obtained when the sulfur dioxide 140. Which compound does not gives yellow ppt. with
gas is passed over the magneta coloured solution of p- iodine and alkali
rosaniline hydrochloride. This solution is known as (a) 2-hydroxy propane (b) Acetophenone
27 Aldehydes and Ketones

(c) Methyl ketone (d) Acetamide (c) NaOH/I2/H+ (d) NaOH/NaI/H+

Ans. (d) Ans. (c)
Sol. Iodoform test is a chemical test that is used for Sol. The formula of Butan-2-one is 𝐶𝐻3 𝐶𝐻2 𝐶𝑂𝐶𝐻3 , so it
detecting the presence of 𝐶𝐻3 𝐶𝑂 − has methyl keto group, hence it will give the iodoform
𝑜𝑟 𝐶𝐻3 𝐶𝐻(𝑂𝐻) −group in the molecule. But test. So, when the butan-2-one is reacted with sodium
acetamide does not give yellow precipitate. hydroxide and iodine there is formation of iodoform
Acid or its derivatives like CH3CONH2, ester, and sodium salt of propanoic acid. Now this sodium salt
anhydride do not give haloform test because they have on reaction with hydrogen ions, formation of propanoic
resonance. acid will take place. The reaction is given below:
𝐶𝐻3 𝐶𝐻2 𝐶𝑂𝐶𝐻3 + 3𝐼2 + 𝑁𝑎𝑂𝐻 → 𝐶𝐻𝐼3 +
141. A compound that gives a positive iodoform test is 𝐻+
𝐶𝐻3 𝐶𝐻2 𝐶𝑂𝑂𝑁𝑎 → 𝐶𝐻3 𝐶𝐻2 𝐶𝑂𝑂𝐻
(a) 1-pentanol (b) 3-pentanone
(c) 2-pentanone (d) pentanal
145. Which of the following will not give iodoform test ?
Ans. (c)
(a) Isopropyl alcohol
Sol. The reaction of the bases and iodine with the methyl
(b) Ethanol
ketones is known as the iodoform test. This test is used
(c) Ethanal
to identify the presence of the methyl ketone group in a
(d) Benzyl alcohol
compound. Among all the compounds only 2-
Ans. (d)
pentanone gives iodoform test.
Sol. Upon addition of iodine and sodium hydroxide to a
Hence, the correct answer is option (c).
compound containing a methyl ketone or any secondary
alcohol with a –Me group in the alpha position,
142. Which compound does not form iodoform with alkali
formation of a yellow iodine precipitate takes place due
and iodine
to the formation of triiodomethane.
(a) Acetone (b) Ethanol
Iodoform test is generally used for the detection of
(c) Diethyl ketone (d) Isopropyl alcohol
aldehydes and ketones containing an alpha methyl
Ans. (c)
group and compounds containing CH3CO or
Sol. Iodoform test is a chemical test that is used for
𝐶𝐻3 𝐶𝐻(𝑂𝐻) gives the iodoform test.
detecting the presence of 𝐶𝐻3 𝐶𝑂 − 𝑜𝑟 𝐶𝐻3 𝐶𝐻(𝑂𝐻) −
The only aldehyde which gives iodoform test is
group in the molecule. So, in the given options Diethyl
acetaldehyde and ethanol that shows positive iodoform
ketone whose formula is 𝐶𝐻3 𝐶𝐻2 𝐶𝑂𝐶𝐻2 𝐶𝐻3 , doesn’t
test.
have 𝐶𝐻3 𝐶𝑂 − group, so it will not give iodoform test.
Therefore, the correct answer is option (d) benzyl
alcohol.
143. Which compound gives iodoform test?
(a) CH3CHO (b) CH3CH2CH2OH
146. Which compound undergoes iodoform reaction?
(c) C6H5CH2CH3 (d) C6H5CH2OH
(a) HCHO (b) CH3CHO
Ans. (a)
(c) CH3OH (d) CH3COOH
Sol. Iodoform test is a chemical test that is used for
Ans. (b)
detecting the presence of 𝐶𝐻3 𝐶𝐻𝑂𝐻 − 𝑜𝑟𝐶𝐻3 𝐶𝑂 −
Sol. Upon addition of iodine and sodium hydroxide to a
group in the molecule. When the compound is treated
compound containing a methyl ketone or any alcohol
with iodine in the presence of sodium hydroxide, if
with a –Me group in the alpha position, formation of a
there is formation of yellow precipitate, i.e., 𝐶𝐻𝐼3 , then
yellow iodine precipitate takes place due to the
the compound is having 𝐶𝐻3 𝐶𝑂 − group. So, in the formation of tri-iodomethane.
given options, 𝐶𝐻3 𝐶𝐻𝑂group, therefore, it will give the Therefore, the correct answer is option (b) 𝐶𝐻3 𝐶𝐻𝑂.
iodoform test.
147. Which of the following will not give iodoform test ?
144. Which is necessary for the conversion of butan-2-one (a) Acetone (b) Ethanol
into propanoic acid? (c) Ethanal (d) Butanal
(a) Tollen reagent (b) Fehling solution Ans. (d)
Aldehydes and Ketones 28

Sol. Upon addition of iodine and sodium hydroxide to a The above conversion is known as iodoform reaction.
compound containing a methyl ketone or any secondary 150. Which of the following reagents can be used to
alcohol with a –Me group in the alpha position, distinguish Benzaldehyde from acetophenone?
formation of a yellow iodine precipitate takes place due (a) Tollen’s reagent
to the formation of triiodomethane. (b) Sodium hypoiodite
Iodoform test is generally used for the detection of (c) 2,4-Dinitrophenyl hydrazone
aldehydes and ketones containing an alpha methyl (d) Both a and b
group and compounds containing Ans. (d)
𝐶𝐻3 𝐶𝑂 𝑜𝑟 𝐶𝐻3 𝐶𝐻(𝑂𝐻) gives the iodoform test. Sol. Benzaldehyde reduces Tollen’s reagent while
The only aldehyde which gives iodoform test is acetophenone is not while acetophenone reacts with
acetaldehyde and ethanol is the only alcohol that shows sodium hypoiodite and give iodoform reaction while
positive iodoform test. benzaldehdye is not.
Therefore, the correct answer is option (d) Butanal

148. Among the following the one that gives positive

iodoform test upon reaction with I2 and NaOH is
(a) CH3CH2CH(OH)CH2CH3
(b) C6H5CH2CH2OH

(c)
(d) PhCHOHCH3
Ans. (d)
Sol. The reaction of the bases and iodine with the methyl
ketones is known as the iodoform test. This test is use
to identify the presence of the methyl ketone group in a
compound. Among all the compounds
only𝑃ℎ𝐶𝐻𝑂𝐻𝐶𝐻3 gives iodoform test.
Hence, the correct answer is option (d)

149. The compound can be exclusively

oxidized into by
(a) NaCN followed by hydrolysis
(b) NaOl followed by H3 O+
(c) KMnO4 hot followed by hydrolysis
(d) K 2 Cr2 O7 followed H3 O+
Ans. (b)
Sol.
29 Aldehydes and Ketones

Exercise – 2: Previous Year Questions

1. Assertion(A) 2-butenal lacks enolisable H-atom, α to Sol. Relative reactivity of aldehydes and ketones depend
carbonyl group, still it has sufficient acidic character. upon (i) inductive effect (ii) steric effect.
Reason(R) The conjugate base of 2-butenal is Large number of alkyl groups on carbonyl carbon atom
stabilized by resonance. (AIIMS 2009) decreases their reactivity due to both +I-effect (these
(a) Both A and R are correct and R is the correct groups decreases polarity of carbonyl group) and steric
explanation of A effect. As ketones possess large number of alkyl
(b) Both A and R are correct but R is not the correct groups, therefore they are less reactive than aldehydes.
explanation of A Aromatic aldehydes are less reactive than
(c) A is correct but R is incorrect corresponding aliphatic aldehydes and ketones because
(d) Both A and R are incorrect of the resonance effect (+R-effect) of the benzene ring
Ans. (a) which increases electron density on carbonyl carbon,
Sol. 2-butenal contains γ-H atoms and the conjugate base thereby, repelling nucleophiles and hence, reactivity
obtained after the removal of γ-H-atom, is stabilized by decreases.
resonance. Hence, 2-butenal is sufficiently acidic. Hence, among the given, acetaldehyde is the reactive
However it lacks enolisable H-atom, α to carbonyl compound.
group.
4. If heavy water is taken as solvent instead of normal
water while performing Cannizzaro reaction, the
products of the reaction are (AIIMS 2009)
(a) RCOO– + RCH2OH
(b) RCOO– + RCH2OD
(c) RCOOD + RCD2OD
2. The compound, with which ethanal does not react, is. (d) RCOO– + RCD2OD
(AFMC 2009) Ans. (b)
(a) HCl (b) Cl2 Sol. Cannizzaro’s reaction is a chemical property of the
(c) PCl5 (d) aq.NaHSO3 aldehydes. The aldehydes that do not have
Ans. (a)   Hydrogen can undergo disproportionation reaction,
Sol. HCl is a strong inorganic acid, hence it does not react i.e., self oxidation and reduction reaction. The
with ethanal whereas, with other given reagents, it mechanism involved in the Cannizzaro’s reaction is,
reacts in the following manner. first is the nucleophilic attack which is fast reaction,
CH 3CHO  Cl2  CCl3CHO then is the hydride transfer which is the slow step i.e.
Ethanal Chloral
the rate determining step, and then comes the H 
CH 3CHO  PCl5  CH 3CHCl2  POCl3 transfer.
The mechanism is as follows:

3. The most reactive of the following is (J&K CET)

(a) acetone
(b) benzophenone
(c) benzaldehyde
(d) acetaldehyde
Ans. (d)
Aldehydes and Ketones 30

Only the hydrogen ion of the alcohol is taken from the Sol. Ethyl methyl ketone is an unsymmetric ketone, so two
solvent, so if the solvent is D 2 O , the product will be different acids (in the form of calcium salts) are used.
The structure of ethyl methyl ketone is C2H5COCH3.
RCH2 OD .
The structure shows the presence of four carbon atoms,
5. Aldehydes and ketones are differentiated by using
thus the calcium salts must be acetic acid and propionic
(UP CPMT 2010)
acid to form C2H5COCH3.
(a) NaOH/I2
Distill
(b) NaHSO3 (C2 H5COO)2 Ca  (CH3COO)2 Ca 
(c) AgNO3/NH4OH 2C2 H5COCH3  2CaCO3
(d) NH2.NH2
Ans. (c) 8. Identify the reaction which is used to obtain -hydroxy
Sol. With NaOH/I2, NaHSO3 and NH2.NH2(hydrazine), ketone? (Guj CET 2010)
aldehydes as well as ketones can react while with (a) Condensation reaction
AgNO3/NH4OH, (i.e. ammoniacal silver nitrate or (b) Aldol condensation
Tollen’s reagent) only aldehydes react. Thus, (c) Cross aldol condensation
AgNO3/NH4OH is used to distinguish aldehydes and (d) Cannizaro reaction
ketones. Ans. (b)

RCHO  2[Ag(NH3 )2 ]  3OH  
 Sol. Aldehydes and ketones containing α-hydrogen atom
undergo self condensation in the presence of a dilute
RCOO  2Ag  4NH3  2H 2O
alkali to form β-hydroxy aldehyde or β-hydroxy ketone.
This reaction is called aldol condensation.
6. In the following reaction sequence,
Cl C H NH
CH 3CHO 
2  X 
6 5 2Y
Y is
Ca(OH) 2 Alc.KOH

(MHT CET 2010)

(a) CH3CH = NHC6H5 (b) C6H5NHCH3
(c) C6H5NC (d) C6H5NCO
Ans. (c)
Sol.
Cl Ca(OH)
CH3CHO  
2  CCl CHO 
3
2
3HCl Hydrolysis
Acetaldehyde

 
CHCl3  HCO O N a
Chloroform 9. Which of the following reaction will not result in the
(X)
formation of carbon-carbon bonds?
(CBSE AIPMT 2010)
(a) Friedel-Crafts’ acylation
(b) Reimer-Tiemann reaction
(c) Cannizzaro reaction
(d) Wurtz reaction
Ans. (c)
7. Ethyl methyl ketone is obtained by heating calcium Sol. Cannizzaro’s reaction is a chemical property of the
salts of (MHT CET 2010) aldehydes. The aldehydes that do not have 𝛼 −
(a) formic acid + propionic acid 𝐻𝑦𝑑𝑟𝑜𝑔𝑒𝑛 can undergo disproportionation reaction, i.e.,
(b) acetic acid + propionic acid self oxidation and reduction reaction. So by oxidation,
(c) acetic acid only sodium salts of carboxylic acid are formed and by
(d) acetic acid + methanoic acid reduction, alcohols are formed. So, the products formed
Ans (b)
31 Aldehydes and Ketones

by the Cannizaro’s reaction does not involve carbon-

carbon bond.

10. Name the reagent used to bring about the following (a)
transformation : But-2-ene to ethanal (AMU 2010)
(a) K2Cr2O7 in acidic medium
(b) CrO2Cl2/H3O+
(b)
(c) PCC
(d) O3/H2O–Zn dust
Ans. (d)
Sol. The alkenes can be converted into aldehydes and ketones
(c)
by reacting the given aldehydes and ketones with ozone
in the presence of Zn dust and water. So, when the but-
2en is reacted with ozone, there is formation of ozonide,
which on reduction with zinc dust and water gives 2 (d)
moles of ethanal or acetaldehyde. The reaction is given Ans. (b)
below: Sol. When the compound in the reactant reacts with methyl
amine, there is loss of water molecule and the product
will be further reduced by the lithium aluminium
hydride, the product will be formation of secondary
amine. The reaction is given below:

13. An organic compound A burns with a sooty flame. It is

11. When ethanal is treated with Fehling’s solution, it gives
negative towards Tollen’s reagent test and positive for
a precipitate of (AFMC 2010)
Brady’s reagent test. The compound A is (KCET 2011)
(a) Cu2O (b) Cu
(a) acetophenone (b) acetone
(c) Cu3O (d) CuO
(c) salicylic acid (d) benzaldehyde
Ans. (a)
Ans. (a)
Sol. Fehling’s test is used for the presence of aliphatic
Sol.
aldehyde in the compound. Alkaline solution of CuSO4
containing some Rochelle salt is known as Fehling’s
solution. When the aliphatic aldehyde like ethanal, is
treated with Fehling’s solution, red ppt. is formed. And
this red precipitate is formed by the compound cuprous
oxide having formula ( Cu2O ).

12. The major product formed from the following reaction

is
(AFMC 2010)
Aldehydes and Ketones 32

Since, the given compound A burns with sooty flame, (b) Calcium formate calcium benzoate
thus, it must be aromatic compound. Again when it (c) Calcium acetate
reacts with Brady’s reagent(2,4-dinitrophenyl hydrazine (d) Calcium benzoate
solution), it yields orange precipitate but gives no Ans. (a)
precipitate or silver mirror with Tollen’s reagent. Sol. Calcium formate and calcium acetate gives aldehyde on
Therefore, A must be an aromatic ketone. dry distillation.
Hence, A is acetophenone.

14. Which of the following pairs can be distinguished by

sodium hypoiodide? (Kerala CEE 2011) 18. Which of the following reactions convert acetone into
(a) CH3CHO and CH3COCH3 hydrocarbon having same number of carbons atoms?
(b) CH3CH2CHO and CH3COCH3 (Guj CET 2011)
(c) CH3CH3OH and CH3CH2CHOHCH3 (a) Wolff-Kishner reaction
(d) CH3OH and CH3CH2CHO (b) Hofmann reaction
Ans. (b) (c) Grignard reaction
Sol. CH3CH2CHO and CH3COCH3 can be distinguished by (d) Reduction with LiAlH4
sodium hpoiodide, i.e. iodoform reaction as CH3COCH3 Ans. (a)
contains CH3CO–group. Sol.
CH3COCH3 gives yellow precipitate of iodoform when
heated with NaOl whereas CH3CH2CHO does not give
iodoform.

15. The compound that neither forms semicarbazone nor

oxime is (Kerala CEE 2011)
(a) HCHO (b) CH3COCH2Cl The reaction is known as Wolff-Kishner reduction.
(c) CH3CHO (d) CH3CONHCH3 Hofmann reaction is given by amides to yield amines.
Grignard reaction is used to increase the number of C-
Ans. (d)
Sol. CH3CONHCH3 is an amide. Aldehydes and ketones atoms and to yield alcohols. LiAlH4 reduces aldehydes
give semicarbazone and oxime, whereas amides do not. or ketones into alcohols.

16. The reagent with which both acetaldehyde and acetone 19. In Tollen’s test, aldehydes (DUMET 2011)
react is (KCET 2011) (a) are oxidised
(a) Fehling’s solution (b) I2/NaOH (b) are reduced to alcohol
(c) Tollen’s reagent (d) Carbonic acid (c) neither reduced to alcohol
(d) precipitate Ag+ as AgCl
Ans. (b)
Sol. Aldehydes and ketones containing CH3 – CO group on Ans (a)
treatment with an excess of I 2 in the presence of NaOH Sol. When aldehydes are treated with Tollen’s reagent
produce a haloform [iodoform]. (ammoniacal solution of silver nitrate), these are oxidised
𝑁𝑎𝑂𝐻 to carboxylate ion while Tollen’s reagent reduces to
𝐶𝐻3 − 𝐶𝐻𝑂 + 3𝐼2 → 𝐶𝐼3 𝐶𝐻𝑂 + 3𝐻𝐼 metallic silver which gives a shiny appearance of silver
𝑁𝑎𝑂𝐻
→ 𝐶𝐻𝑙3 ↓ + 𝐻𝐶𝑂𝑂𝑁𝑎 mirror.
(𝐼𝑜𝑑𝑜𝑓𝑜𝑟𝑚

𝑦𝑒𝑙𝑙𝑜𝑤𝑝𝑝𝑡.) RCHO  2[Ag(NH3 ) 2 ]  3OH  

𝑁𝑎𝑂𝐻 (Aldehyde) Tollen 's reagent
𝐶𝐻3 𝐶𝑂𝐶𝐻3 + 3𝐼2 → 𝐶𝐼3 𝐶𝑂𝐶𝐻3 + 3𝐻𝐼

𝑁𝑎𝑂𝐻 RCOO  2 Ag  4NH3  2H 2O
→ 𝐶𝐻𝑙3 ↓ +𝐶𝐻3 𝐶𝑂𝑂𝑁𝑎 Carboxylateion Silver
mirror
17. Which of the following gives an aldehyde on dry 20. In the conversion of
distillation? (KCET 2011)
(a) Calcium formate calcium acetate
 33 Aldehydes and Ketones

(CBSE AIPMT/AMU 2012)

(a) (CH3)2CH.CHO (b) HCHO
(c) C6H5CHO (d) CH3CHO
Ans (a)
Sol. 2-methylpropanal contains one  -H-atom. Hence, it
undergoes aldol condensation. It also undergoes
X is (DUMET 2011) Cannizzaro’s reaction. Aldol reaction proceeds via
(a) H2/Pt (b) Zn–Hg/HCl formation of carbanion. In 2-methylpropanal, due to + I-
(c) Li/NH3 (d) NaBH4 effect of the two alkyl groups attached to alpha-carbon,
Ans. (d) the carbanion of 2-methylpropanal is not stable. Thus, it
Sol. NaBH4 does not reduce olefin(alkene) double bond, it prefers to undergo nucleophilic attack of OH– ion at the
only reduces C=O groups. Thus, the reagent (X) is aldehyde leading to the formation of Cannizzaro
NaBH4. products.

21. Clemmensen reduction of a ketone is carried out in the 25. The product formed when acetone reacts with nitro
presence of which of the following? methane in the presence of a base is (AFMC 2012)
(CBSE AIPMT 2011)
(a) H2 and Pt as catalyst
(b) Glycol with KOH
(c) Zn—Hg with HCl
(a) (b)
(d) LiAlH4
Ans. (c)
Sol. Alkanes can be formed from both aldehydes and ketones
(c) (d) CH3COCH=CHNO2
with zinc amalgam and concentrated hydrochloric acid.
Ans (c)
Sol.
22. Which of the following pairs can be distinguished by
iodoform test? (Kerala CEE 2012)
(a) CH3CHO and CH3COCH3
(b) CH3CH2CHO and C2H5OH
(c) CH3CH2OH and CH3CH2CHOHCH3
(d) CH3OH and CH3CH2 CH2CHO
Ans. (b)
Sol. Ethanol gives iodoform test but propanal not.

23. CH3CHO and C6H5CH2CHO can be distinguished

chemically by (AIPMT 2012)
(a) Benedict test (b) Iodoform test
(c) Tollen’s reagent test (d) Fehling solution test
Ans. (b)
Sol. Both the compounds CH3CHO and C6 H5 CH 2 CHO are Hence, the product formed when acetone reacts with
aliphatic aldehydes, so both will give positive test for nitromethane in the presence of a base is
Benedict’s test, Tollen’s reagent test, and Fehling
solution test. So, they both can be distinguished with
Iodoform test. Since, in CH3CHO,CH3CO  group is
present, so it will give yellow precipitate with iodine, but
C6 H5 CH 2 CHO will not give the iodoform test. 26. Aldehydes and ketones can be distinguished by
24. Which of the following compounds undergoes both (AIIMS 2013)
Cannizzaro and aldol reaction? (a) ammonia
Aldehydes and Ketones 34

(b) H2SO4 Identify A and B in this reaction. (UK PMT2014)

(c) alkaline KMnO4 (a) CH3COOC2H5,CH3CH2OH
(d) Fehling solution (b) CH3COOC2H5,CH3CHO
Ans. (d) (c) CH3CHO,CH3COOC2H5
Sol. Aldehydes and ketone can be distinguished by Fehling’s (d) None of the above
reagent [alkaline solution of CuSO4 containing Rochelle Ans. (b)
salt (sodium potassium tartarate), mild oxidising agent]. Sol. Tishchenko reaction is a disproportional reaction that
Fehling reagent
Aldehydes  Red  brown ppt. allows the preparation of esteres from two equivalents of
Fehling reagent an aldehyde. In actual, aldehydes with or without  -
Ketones  No reaction hydrogens can made to undergo Cannizzaro reation on
Besides this, Tollens’s reagent and Benedict’s reagent treatment with aluminum alkoxide. However, undergo
can also be used as they give positive test with aldehydes these conditions, the alcohol and acid produced combine
but not with ketones. togther to form esters. Thus, Tishchenko reaction is a
modified form of Cannizzaro reaction.
27. Which of the following organic compounds answers
both iodoform test Fehling’s test? (KCET 2013)
(a) Methanal
(b) Ethanol
(c) Propane
(d) Ethanal
Ans. (d) So, here the compound A is CH3COOC2H5 and
Sol. Iodoform test is given by those compounds which compound B is CH3CHO.
Other given reaction is given as below:
CH3  C  CH3  CH
contains || group or |
O OH
groups while Fehling’s test is given by only aldehydic
group. Thus, iodoform test and Fehling’s test are
performed by only ethanal. 30. Schiff’s reagent’s pink colour is restored in
2
CH3CHO  2Cu  50H  fehling 's

(UK PMT2014)
Ethanal Fehling 's
dest
(a) caboxylic acid
solution (b) ketones
CH3COO   3H 2O  Cu 2O
Acetateion Cuprous oxide (c) ethers
(red ppt.)
O (d) aldehydes
|| Ans. (d)
 
NaOH
CH3CHO 
 H  C  O N a  CHI3  Sol. Schiff’s reagent is an aqueous solution of pink coloured
rosaniline hydrochloride which had been decolourised by
28. Which of the follwing reactions cannnot be used to passing SO2. When aldehydes are treated with
increase the number of carbon atoms in a organic decolourised solution of Schiff’s reagent, its pink colour
comound? (UK PMT2014) is restored.
(a) Grignard reaction
(b) Cannizzaro’s reaction
(c) Aldol condensation
(d) All of these
Ans. (b)
Sol. Cannizzro reaction cannot be used to increase the
number of carbon atoms in an organic compound.

CH3COC2H5   A  B

C H CO H
Tishchenko
29. 6 5 3
reaction
 35 Aldehydes and Ketones

31. X 
Ozonolysis
(Re ductive)
Y  Z (a) propanone (b) ethanamine
(c) ethane nitrile (d) ethanal
Y can be obtained by Etard’s reaction, Z undergoes
Ans. (c)
disproportion reaction with concentrated alkali ,X could
Sol.
be (KCET 2014)
(a)

(b)

(c)

(d)

33. Which one of the following compounds do not give a

primary alcohol on reduction? (Guj CET 2014)
Ans. (b)
(a) Propanal (b) Propanoic acid
Sol. The substance containing C=C double bond on
(c) Methyl propanoate (d) Propan-2-one
ozonolysis using O3 followed by reductive cleavage
Ans. (d)
using Zn/H2O produces two carbonyl compounds.
Sol. Ketone always produce secondary or tertiary alcohols on
Carbonyl compound obtained after reductive ozonolysis
reduction. Thus, propan-2-one does not give a primary
of (b) , (c) and (d) are as follows
alcohols on reduction.
𝐿𝑖𝐴𝐼𝐻4 2[𝐻]
(𝑎)𝐶𝐻3 𝐶𝐻2 𝐶𝐻𝑂 → 𝐶𝐻3 𝐶𝐻2 𝐶𝐻2 𝑂𝐻
Propana𝑙 Propano𝑙
(1°𝑎𝑙𝑐𝑜ℎ𝑜𝑙)
𝐿𝑖𝐴𝐼𝐻4 4[𝐻]
(𝑏)𝐶𝐻3 𝐶𝐻2 𝐶𝑂𝑂𝐻 → 𝐶𝐻3 𝐶𝐻2 𝐶𝐻2 𝑂𝐻
(Propanoic acid) Propano𝑙
(1°𝑎𝑙𝑐𝑜ℎ𝑜𝑙)
LiAIH
(c) CH3CH 2COOCH 3 
4

Methyl
propanoate
CH3CH 2 CH 2OH  CH3OH
Propanol (Methanol
(1alcohol) 1alcohol)

LiAIH
In each case, benzaldehyde is produced as one of the (d) CH3  C  CH3 
4  CH CHCH
3 3
|| |
product but on the other hand formaldehyde, acetaldehyde O OH
and acetone are produce as other products. Thus, in order Propan-2-one Propan-2-ol
(2°alcohol)
to select to correct choice, the concept of Cannizzaro
reaction (disproportionation reaction)
34. Name the catalyst [X] for the reaction,
X
32.
(i)CH MgBr
P 
3  R 

(i)Dil.NaOH CO(g)  H 2 (g)  HCHO(g) (Guj CET 2014)
 (ii) 
(ii)H3O

4-methylpent-3-en-2-one compound P is (KCET 2014) (a) Cu

Aldehydes and Ketones 36

(b) Ni information, we can say that the ‘X’ compound is 3-

(c) Cu/ZnO Pentanone.
(d) Cu/Cr2O3
Ans. (a) 37. The correct statement regarding a carbonyl compound
X
Sol. CO(g)  H 2 (g)  HCHO(g) with a hydrogen atom on its alpha-carbon is
(NEET 2016)
Here, X is copper (Cu) which acts as a good reductant
(a) a carbonyl compound with a hydrogen atom on its
and gives formaldehyde in this reaction. The reaction
alpha-carbon never equilibrates with its
infact occurs in the following manner.
corresponding enol.
Cu(X)
CO(g)  H 2 (g)  CH3OH 
 HCHO(g) (b) a carbonyl compound with a hydrogen atom on its
alpha-carbon never equilibrates with its
35. Reaction of carbonyl compound with one of the corresponding enol and this process is known as
following reagents involves nucleophilic addition carbonylation.
followed by elimination of water. The reagent is (c) a carbonyl compound with a hydrogen atom on its
(AIPMT 2015) alpha-carbon rapidly equilibrates with its
(a) hydrocyanic acid corresponding enol and this process is known as
(b) sodium hydrogen sulphite carbonylation.
(c) a Grignard reagent (d) a carbonyl compound with a hydrogen atom on its
(d) hydrazine in presence of feebly acidic solution. alpha-carbon rapidly equilibrates with its
Ans. (d) corresponding enol and this process is known as
Sol. When the carbonyl compound reacts with hydrazine, the keto-enol tautomerism.
nucleophile will gets attached and there is elimination of Ans. (d)

water molecule. The formula of hydrazine is NH 2  NH 2

Sol. If the carbonyl compound has a hydrogen atom which
is present on the alpha carbon atom, then this hydrogen
. The ketone is a carbonyl compound, so its reaction with
atom can change its position within the molecule and
hydrazine is given below:
creates equilibrium.
keto–enol tautomerism refers to a chemical equilibrium
between a carbonyl compound (a ketone or an
aldehyde) and an enol (an alcohol). The keto and enol
forms are said to be tautomers of each other.
36. An organic compound ‘X’ having molecular formula
C5H10O yields phenyl hydrazone and gives a negative
response to the iodoform test and Tollen’s test. It
produces n-pentane on reduction. ‘X’ could be
(AIPMT 2015)
(a) 2-pentanone
(b) 3-pentanone
(c) n-amyl alcohol
(d) pentanal
Ans. (b)
Sol. So, we are given the information that the ‘X’ compound
can yield phenyl hydrazone, so it means that the ‘X’
compound is a carbonyl compound. And this compound
gives negative result for iodoform test. So, there is
absence of methyl keto group. The compound ‘X’ also
gives negative results for Tollen’s test, hence the
compound is not an aldehyde. So, by combining the
 37 Aldehydes and Ketones

38. The IUPAC name of the compound (NEET 2017)

is
(a) 3-keto-2-methylhex-4-enal
(b)5-formylhex-2-en-3-one 41. The product formed by the reaction of an aldehyde with
(c) 5-methyl-4-oxohex-2-en-5-al a primary amine is (NEET 2017)
(d) 3-keto-2-methylhex-5-enal (a) Schiff base (b) Ketone
Ans. (a) (c) Carboxylic acid (d) Aromatic acid
Sol. Ans. (a)
Sol. Azomethines are formed when the aldehyde or ketones
react with primary amine. This reaction can only occur in
the presence of catalytic amount of acid. The
azomethines are known as Schiff’s bases. The reaction of
aldehyde with primary amine is given below:
–CHO group gets higher RCHO  H 2 NR '  RCH  NR ' H 2O

39. Cannizzaro reaction is not shown by (JIPMER2017)

42. The correct IUPAC name of the given compound is
(AIIMS 2018)
(a) (b)
(c) CH3CHO (d) HCHO
Ans. (c)
Sol. The aldehyde/ketone,which do not contain  - H atom
(a) 7-hydroxy cyclohex -5-en-1-one
shows Cannizaro reaction.
(b) 3-hydroxy cyclohex -5-en-1-one
In CH3CHO, carbonyl group is attached to C-atom
(c) 8-hydroxy cyclohex -3-en-1-one
having  - H; Hence, CH3CHO does not show
(d) 5-hydroxy cyclohex -3-en-1-one
Cannizzaro reaction.
Ans. (d)
Sol. The correct IUPAC name of the given compound is 5-
40. Consider the following equation
hydroxy cyclohex -3-en-1-one.

The end product fo the given sequence of reaction is

(AIIMS 2017)

43. Which of the following compound does not undergo

aldol condensation? (AIIMS2018)
(a) (b) CH3
|
(a) CH3  C  CHO (b) CH3  CHO
|
CH3

(c) (d)
Ans. (b) (c) (d) CH3CH2CHO
Sol.
Ans. (a)
Aldehydes and Ketones 38

Sol. Necessary condition for aldol condensation is the

presence of at least one  - H atom. Thus, among the
given options,
CH3
|
CH3  C  CHO does not undergo aldol condensation as
|
CH3
it does not contain any  - hydrogen atom.
Thus, the correct option is (c)
44. Which of the following is the correct sequence of step 46. Suitable reagent for conversion of following reaction
?
involved on the mechanism of Cannizzaro reaction? CH2  CH  CHO 
CH2  CH  CH2  OH?
(JIMPER2018)
(JIPMER 2019)
(a) Nucleophilic attack, Transfer of H– and transfer of H+
(a)NaBH4 (b) Ni/H2
(b) Transfer of H–, transfer of H+ and nucleophilic attack
(c) Zn-Hg/HCl (d) Red P + Hl
(c) Transfer of H+, nucleophilic attack and transfer of H–
Ans. (a)
(d) Electrophilic attack by OH–, transfer of H+
Sol. The suitable reagent for the conversion
and transfer of H– ?
Ans. (a) CH2  CH  CHO 
CH2  CH  CH2  OH is
Sol. Considering the following Cannizzaro reaction, \
NaBH4. It is as selective reagent that reduce CO
/
group to – OH does not reduce carbon–carbon double
bond. Thus, unsaturated alcohols can be prepared.

47. Write IUPAC name of the following (JIPMER 2019)

(a) 2-bromo-2-ethyl hexanal

(b) 3-bromo-2-methyl hexanal
(c) 2-methyl-3-bromo hexanal
(d) 3-bromo-2-formyol hexanal
Ans. (b)
Sol. The priority order of functional group is CHO  Br
45. In the reaction, (JIPMER2018)
therefor, IUPAC name of the given compound is as
follows

The major product formed is

(a) C6H5CH2CHO
(b) C6H5COOH O
(c) C6H5CH=CH-COOH 48. ||
Conc.NaOH
H  C  H  CH 3  CH  O 
(d) C6H5CH=CH-COCH3
Ans. (c) Find out the products of reaction (AIIMS 2019)
Sol. (a) CH3CO2 Na and CH3OH
(b) CH3OH and HCO2Na
(c) CH3CH2OH and HCO2Na
(d) CH3CO2Na+HCO2Na
 39 Aldehydes and Ketones

Ans. (c)
Sol.

49. Reaction between benzaldehyde and acetophenone in

presence of dilute NaOH is known as: (NEET 2020)
(a) Cross Cannizzaro’s reaction
(b) Cross Aldol condensation
(c) Aldol condensation
(d) Cannizzaro’s reaction
Ans. (b)
Sol.

Two different carbonyl compound is treated with base

known as cross-aldol condensation.

50. Identify compound X in the following sequences of

reactions : (NEET 2021)

(a)

(b)

(c)

(d)
Ans. (a)
Sol.
Aldehydes and Ketones 40

Exercise – 3: Achievers Section

Single choice questions
1. The IUPAC name of the following structure is
(a) (b)

(a) 1-hydroxy 4-methyl 3-pentanone

(b) 2-methyl 5-hydroxy 3-pentanone
(c) (d)
(c) 4-methyl 3-oxo 1-pentanol
Ans. (a)
(d) Hexanol-1, one-3
Sol. The reaction involved in the following reaction is
Ans. (a)
mentioned below:
Sol.

So, the IUPAC name of the compound will be 1-

Hydroxy-4-methyl-3-pentanone

2. The end product in the following sequence of reaction is

Hence, the correct answer is option (a)

4. What reagent is used in the Rosenmund’s reduction ?

(a) H2/Pd-BaSO4
(b) LiAlH4
(a) Acetic acid (b) Isopropyl alcohol (c) NH2NH2/KOH/CH2OH-CH2OH
(c) Acetone (d) Ethanol (d) Zn-Hg/HCl
Ans. (c) Ans. (a)
Sol. The reactant in the given reaction is ethyne, so when Sol. Rosenmund reaction or Rosenmund reduction is a
ethyne is reacted with HgSO4 there will be formation of chemical reaction in which the acid chlorides are
ethanal. Now when this ethanal is reacted withCH3MgX converted into aldehydes. The reactant in the
, then there is formation of a secondary alcohol, propan- Rosenmund reaction is acid chloride, and it is reacted
2-ol. We know that secondary alcohol on oxidation with hydrogen in the presence of palladium supported
forms ketone, so propan-2-ol on oxidation will form over barium sulfate so, the formation of aldehyde will
acetone. The reaction is given below: take place and hydrochloric acid is also produced. The
reaction is given below:
H 2  Pd  BaSO4
R  CO  Cl   R  CHO

5. The major product obtained in the following reaction is :

3. Cyclohexene on ozonolysis followed by reaction with

zinc dust and water gives compound E. Compound E on
further treatment with aqueous KOH yields compound F.
Compound F is
41 Aldehydes and Ketones

7. Which of the following compound gives a ketone with

Grignard reagent:
(a) Formaldehyde (b) Ethyl alcohol
(a)
(c) Methyl cyanide (d) Methyl iodide
Ans. (c)

(b) Sol. The formula of Grignard reagent is RMgX and when it

reacts with different organic compounds to give
different products. So, when it reacts with
formaldehyde there is formation of primary alcohol.
(c) When it reacts with ethyl alcohol, methane is formed
and later ethyl alcohol is also formed. When it reacts
with methyl cyanide it forms ketone. With methyl
iodide it forms alkane.
(d)
Ans. (a)
Sol. Dibal-H is an electrophilic reducing agent. Hence, it
reduces the cyanide, esters, lactone, amide, carboxylic
acid into the corresponding aldehydes which is a partial
reduction of the given groups.

3)

Hence, the correct answer is option (a)

6. When a nucleophile encounters a ketone, the site of

attack is
(a) The carbon atom of the carbonyl
(b) The oxygen atom of the carbonyl
(c) Both the carbon and oxygen atoms, with equal
probability 4) CH 3  I  R  MgBr  CH 3  R  MgBrI
(d) No attack occurs ketones do not react with (methyliodide) (Alkane)
nucleophiles.
Ans. (a) 8. Which one of the following will most readily be
Sol. Nucleophilic attack is by nucleophiles i.e. electron rich dehydrated in acidic condition ?
species.
These species tend to donate their electron density by
attacking the electron poor centre.
In a ketone, a – CO group is present which is known as (a) (b)
the carbonyl carbon.
The nucleophiles attack on the carbon centre of the
carbonyl as it is electro positive.
Therefore, the correct answer is option (a) the carbon (c) (d)
atom of the carbonyl Ans. (a)
Aldehydes and Ketones 42

Sol. Dehydration reaction is the reaction which involves the Sol. This reaction is a cross-Cannizzaro reaction and the
removal of water molecule. From an alcohol, water reaction involved will be
molecule is removed to form the corresponding alkene C6 H 5CHO  HCHO 
NaOH ( conc.)
 C6 H 5CH 2OH  HCOONa
and this is called as the dehydration reaction of The mechanism of the reaction is:
alcohols. Molecule which has more conjugation, greater In the mechanism, the OH- in NaOH will attack the
will be the stability and the easier will be the formaldehyde molecule. Since we know that in the
dehydration cross-Cannizzaro reaction, the compound with lesser
Hence, in the acidic conditions the compound (a) will bulky groups will form the acid and the compounds
be most readily dehydrated. with bulky group will produce the alcohol.
Hence, the correct answer is option (a) The mechanism of the reaction is as follows:

9. The smallest ketone and its next homologue are reacted

with NH2OH to form oxime
(a) two different oximes are formed
(b) three different oximes are formed
(c) two oximes are optically active
(d) all oximes are optically active
Ans. (b)
Sol. The smallest ketone and it is next homologous are
reacted with NH 2OH which leads to the formation of
three types of oxime. The three types of oximes are:

Hence, the correct answer is option (a)

The smallest ketone is acetone and its next homologue 11. Aldol reaction involving CH3CHO + CH3CHO gives the
is butanone product
Hence, the correct answer is option (b) (a) CH3CHOHCH2CHO (b) CH3COCH2CH3
10. A mixture of benzaldehyde and formaldehyde on heating (c) (d) None of these
with aqueous NaOH solution gives Ans. (a)
(a) benzyl alcohol and sodium formate Sol. Aldol condensation is a reaction in which an enolate ion
(b) sodium benzoate and methyl alcohol reacts with carbonyl compounds (aldehydes or ketones)
(c) sodium benzoate and sodium formate to form beta-hydroxyaldehyde or beta-hydroxyketone.
(d) benzyl alcohol and methyl alcohol Upon dehydration, it forms a conjugated enone.
Ans. (a) Here, ethanal undergoes self aldol condensation. The
reaction is –
43 Aldehydes and Ketones

13. The aldehyde having α-hydrogen which gives

Cannizzaro’s reaction is :

(a) (b)

(c) (d)
Ans. (b)
Sol. Compound containing alpha hydrogen atoms do not
undergo Cannizaro’s reaction. However, there are
exceptions to this. Since there are two alkyl group
Therefore,
the correct answer is option is (a) attached to the alpha C and the alkyl group has +I
CH3CHOHCH2 CHO effect. The two alkyl groups decreases the acidic nature
and of alpha H and the compound can undergo intra-
12. Which of the following species is (are) not intermediates molecular Cannizzaro reaction.
in the aldol condensation of acetaldehyde (ethanal) in The reaction is as follows:
aqueous base ?

(1) (2)

Therefore, the correct answer is option (b)

(3) (4)
(a) 1 and 2 (b) 3 only
(c) 4 only (d) 3 and 4
Ans. (d)
Sol. Aldol condensation is a reaction in which an enolate ion
reacts with carbonyl compounds (aldehydes or ketones) 14. The aldehyde which shows Cannizzaro’s reaction is
to form beta-hydroxyaldehyde or beta-hydroxyketone. (a) HCHO
Upon dehydration, it forms a conjugated enone. (b) C6H5CHO
The aldol condensation reaction of ethanal with an (c) CCl3–CHO
aqueous base is given by- (d) All of these
Ans. (d)
Sol. In Cannizzaro reaction, the same compound undergoes
self-oxidation as well as self-reduction. Cannizzaro
reaction is a disproportionation reaction induced by a
base. This reaction is useful for the conversion of two
molecules of an aldehyde into a primary alcohol as well
as an aldehyde. But the aldehyde should not be
enolizable and aldehydes with no alpha hydrogen atoms
are non-enolizable.
This reaction is given by compounds which have no
alpha hydrogen.

15.
Therefore, the correct answer is option (d) 3 and 4.
Aldehydes and Ketones 44

major product is Hence, the correct answer is option (a)

17. Which of the following compounds gives internal

crossed Cannizzaro’s reaction ?
(a)

(a) (b)
(b)

(c) (d)
Ans. (c)
(c) Sol. In Cannizzaro reaction, the same compound undergoes
self-oxidation as well as self-reduction.
In cross-Cannizzaro, instead of using two molecules of
the same aldehyde, formaldehyde is used along with
(d) any other aldehyde in presence of a base. The product
Ans. (d) obtained is sodium formate and an alcohol.
Internal Cannizzaro will be given by compound where
hydride shift is possible internally i.e. within the
molecule.

Sol.
Therefore, the correct answers are options (c)
16. m-chlorobenzaldehyde on reaction with conc. KOH at
room temperature gives 18. The product formed in the following reaction will be:
(a) potassium m-chlorobenzoate and m-chlorobenzyl
alcohol
(b) m-hydroxybenzaldehyde and m-chlorobenzyl
alcohol
(c) m-chlorobenzyl alcohol and m-hydroxy benzyl (a) (b)
alcohol
(d) potassium m-chlorobenzoate and m-
hydroxybenzaldehyde (c) (d) all of these
Ans. (a) Ans. (b)
Sol. The given reaction is a Cannizzaro reaction therefore Sol. The given compound here is known as Glyoxal.
the products for the m-chlorobenzaldehyde in the Here, in presence on NaOH, the given compound will
Cannizzaro reactions are potassium m-chlorobenzoate undergo Cannizaro reaction.
and m-chlorobenzyl alcohols. The reaction is-
45 Aldehydes and Ketones

the compound (X) is

(a) CH3COOH (b) BrCH2 – COOH
(c) (CH3CO)2O (d) CHO – COOH
Ans. (c)
Sol.

Therefore, the correct answer is option (b)

19. The major product of the following reaction sequence is

Hence, the correct answer is option (c)

21. Acetone and acetaldehyde are differentiated by
(a) (b) (a) NaOH + I2 (b) [Ag(NH3)2] ⊕
(c) HNO2 (d) I2
Ans. (b)
Sol. Tollen’s test is also known as the silver mirror test and
(c) (d) in this the given compound is treated with ammoniacal
Ans. (a) silver nitrate to give a silver coloured mirror like
Sol. This given reaction is aldol condensation and the solution. It is used to determine the presence of
product formed will undergo cannizzaro reaction since aldehyde and aromatic aldehydes and for the detection
excess amount of HCHO is present, then the product of some alpha-hydroxy ketones which undergoes
formed undergoes nucleophilic attack and finally forms tautomerisation to form an aldehyde.
the acetal. The reaction involved is: Here, acetaldehyde is an aldehyde and acetone is not so
this test can be used to distinguish between the two.

Therefore, the correct answer is option (b) Ag ( NH 3 ) 2

22. The correct sequence of reagents for the following

conversion will be :


CH 3 MgBr , H  / CH 3OH ,  Ag  NH 3 2  OH 
(a)

CH 3 MgBr ,  Ag  NH 3 2  OH  , H  / CH 3OH
(b)

 Ag  NH 3 2  OH  , CH 3 MgBr , H  / CH 3OH
Hence, the correct answer is option (a) (c) 

 Ag  NH 3 2  OH  , H  / CH 3OH , CH 3 MgBr
(d) 
20.
Aldehydes and Ketones 46

24. A compound has a vapour density of 29. On warming an

Ans. (d) aqueous solution of alkali, it gives a yellow precipitate.
Sol. The correct sequence of the reagents is The compound is
   (a) CH3CH2CHO (b) CH3CHOHCH3
[ Ag ( NH 3 ) 2 ] OH , CH 3 MgBr , H / CH 3 MgBr . the
(c) CH3COCH3 (d) CH3CH2COOH
reaction involved is mentioned below:
Ans. (c)
Sol. Multiplying by 2 the vapour density gives the molecular
weight of the compound. Here, vapour density given is
29. So, its molecular weight is 58.
Formation of yellow precipitate upon warming with
aqueous solution of alkali gives a yellow precipitate
means it shows positive iodoform test. Thus, it will be a
methyl ketone.
The molecular weight of MeCOMe is 58 and when it is
heated with the reagents, it gives triiodomethane and
thus the yellow precipitate.
Therefore, the correct answer is option (c) CH3COCH3

Hence, the correct answer is option (d) 25. In the following reaction sequence, the correct structures
of E, F and G are
23. Compound A (molecular formula C3H8O) is treated with
acidified potassium dichromate to form a product B
(molecular formula C3H6O). B forms a shining silver
mirror on warming with ammonical silver nitrate. B
when treated with an aqueous solution of H2NCONHNH2 (* implies 13C labelled carbon)
and sodium acetate gives a product C. Identify the
structure of C.
(a) (a)
(b)

(b)
(c)

(c)

(d)
Ans. (a)
Sol. A is an alcohol and the oxidation product gives the (d)
Tollen’s test and the compound B must be an aldehyde Ans. (c)
Sol. The reaction involved in the following reaction is
i.e. CH3CH2 CHO . mentioned below:
CH3CH 2 CH 2 OH  A  
Acidified K 2 Cr2 O7
 CH3CH 2 CHO  B 

H2 NHNCONH 2
 CH3CH 2 CH  N  NHCONH 2
Hence, the correct answer is option (a)

Hence, the correct answer is option (c)

47 Aldehydes and Ketones

(c) C (d) D
Assertion- Reason Type Questions Ans. (a)
Sol. Hydroxy ketones are not directly used in Grignard
26. Assertion : Aldehydes form stable hydrates. reaction. Grignard reagents reacts with hydroxyl group.
Reason :Aldehydic carbonyl is more electron deficient Hence, the hydroxyl group of hydroxy ketones should
than the ketone. be protected by using suitable protecting group. Thus,
(a) A (b) B Both Assertion and Reason are correct and Reason is
(c) C (d) D the correct explanation for Assertion.
Ans. (d)
Sol. Aldehydes do not form stable hydrides as the hydride
formed is not stable and eventually revert back to the
original aldehyde.
Aldehydes have only one alkyl groups whereas ketones
have more Thus the partial positive charge of carbonyl
group is compensated by the electron donating nature of 29. Assertion : Reimer-Tiemann reaction is used to prepare
the alkyl groups in ketone. Whereas in aldehydes, the benzaldehyde from benzene.
alkyl group cannot compensate for the same factor thus Reason : Reimer-Tiemann reaction involves
it is more reactive. electrophilic substitution.
Therefore, the correct answer is option (d) i.e. (D) (a) A (b) B
reason is true but assertion is false. (c) C (d) D
Ans. (d)
27. Assertion (A) : Lower aldehydes and ketones are soluble Sol. In Reimer – Tiemann reaction, when phenol is treated
in water but the solubility decreases as the molecular with chloroform and aqueous hydroxide, introduction
mass increases. of an aldehyde group –CHO takes place in the aromatic
Reason (R) : Distinction between aldehydes and ketones ring.
can be made by tollen’s reagent. The reaction proceeds through electrophilic substitution
(a) A (b) B pathway.
(c) C (d) D Therefore, the correct answer is option (d) i.e. (D)
Ans. (b) reason is true but assertion is false.
Sol. Aldehydes have oxygen atoms that can form hydrogen
bonds in aqueous medium and thus are soluble. But, 30. Assertion: Isobutanal does not give iodoform tests.
with the increase in the chain length, the solubility Reason: It does not have α-hydrogen
decreases as the hydrophobic part dominates over the (a) A (b) B
hydrophilic part. Thus, higher aldehydes and ketones (c) C (d) D
are insoluble. Ans. (c)
Tollen’s test is known as the silver mirror test and it is Sol. The structure of isobutanal is given below:
used to determine the presence of aldehyde and
aromatic aldehydes as well as the detection of some
alpha-hydroxy ketones which undergoes
tautomerisation to form an aldehyde.
Therefore, the correct answer is option (b) i.e. (B) So, as you can see that, there is an alpha-hydrogen
assertion and reason are true but reason is not the present. But it doesn’t give the iodoform test because
correct explanation of assertion. there is absence of methyl keto group. So, the assertion
is true but the reason is incorrect.
28. Assertion Hydroxyketones are not directly used in
Grignard reaction.
Reason Grignard reagents react with hydroxyl group.
(a) A (b) B