Aldehydes and Ketones (Carbonyl Compounds)

Aldehydes and Ketones (Carbonyl Compounds)

EXERCISES-I
INTRODUCTION
Q.1 In aldehydes and ketones, carbon of carbonyl group is
(1) sp 3 hybridised (2) sp 2 hybridised (3) sp hybridised (4) Unhybridised
Ans. (2)
CO
Sol. sp2 hybridised

Q.2 Glyoxal is
CH 2 OH CHO CH 2 OH
(1) CH 2 O  CH 2 O (2) | (3) | (4) |
CH 2OH CHO CHO
Ans. (3)

Q.3 Which of the following compounds does not contain an OH group
(1) Phenol (2) Carboxylic acid (3) Aldehydes (4) Alcohols
Ans. (3)

Q.4 What is the compound called if remaining two valencies of a carbonyl group are satisfied by two alkyl groups
(1) Aldehyde (2) Ketone (3) Acid (4) Acid chloride
Ans. (2)

Q.5 Which of the following types of isomerism is shown by pentanone

(1) Chain isomerism (2) Position isomerism (3) Functional isomerism (4) All of these
Ans. (4)

Q.6 Which of the following is not a mixed ketone

(1) 3-Pentanone (2) Acetophenone (3) Benzophenone (4) Butanone
Ans. (3)

Q.7 Carbonyl compounds are usually

(1) Ethers, aldehydes, ketones and carboxylic acids (2) Aldehydes, ketones and carboxylic acids
(3) Aldehydes and ketones (4) Carboxylic acids
Ans. (3)

Method of Preparation of Carbonyl Compound

Q.8 Compound which gives acetone on ozonolysis
(1) CH 3  CH  CH  CH 3 (2) (CH 3 )2 C  C(CH 3 )2 (3) C6 H 5 CH  CH 2 (4) CH 3 CH  CH 2
Ans. (2)

(CH3 )2 C  C(CH3 ) 2  2CH3  CO  CH3

O
Sol. 3

Q.9 Which one of the following compounds is prepared in the laboratory from benzene by a substitution reaction
(1) Glyoxal (2) Cyclohexane (3) Acetophenone (4) Hexabromo cyclohexane
Ans. (3)

COCH 3
 CH3COCl 
AlCl3
Sol. +HCl

It is Friedel-Crafts reaction. Acetophenone

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Aldehydes and Ketones (Carbonyl Compounds)

(R  C  R 1 )
Q.10 Ketones || where R  R1  alkyl group. It can be obtained in one step by
O
(1) Hydrolysis of esters (2) Oxidation of primary alcohol
(3) Oxidation of secondary alcohol (4) Reaction of acid halide with alcohols
Ans. (3)

Q.11 CH 3  CH 2  C  CH 
R Butanone, R is
H 2O

(1) Hg   (2) KMnO 4 (3) KClO 3 (4) K 2 Cr2 O7

Ans. (1)
Sol. It is hydration of alkynes.

O
||
Hg 
CH 3  CH 2  C  CH  CH 3  CH 2  C  CH 3
H2O Butanone

Q.12 Acetophenone is prepared by the reaction of which of the following in the presence of AlCl 3 catalyst
(1) Phenol and acetic acid (2) Benzene and acetone
(3) Benzene and acetyl chloride (4) Phenol and acetone
Ans. (3)
COCH

 CH 3COCl  
only AlCl
Sol. 3 + HCl

Q.13 On heating calcium acetate and calcium formate, the product formed is
(1) CH 3 COCH 3 (2) CH 3 CHO (3) HCHO  CaCO 3 (4) CH 3 CHO  CaCO 3
Ans. (4)
CH 3COO OOCH
Sol. Ca  Ca 
Distill
 2CH CHO  2CaCO
CH 3COO OOCH 3 3

C6 H 6  CO  HCl     X  HCl
Anhy AlCl
Q.14 3

Compound X is
(1) C 6 H 5 CH 3 (2) C 6 H 5 CH 2 Cl (3) C 6 H 5 CHO (4) C 6 H 5 COOH
Ans. (3)

Q.15 CH 3 COCH 3
can be obtained by
(1) Heating acetaldehyde with methanol (2) Oxidation of propyl alcohol
(3) Oxidation of isopropyl alcohol (4) Reduction of propionic acid
Ans. (3)

Q.16 Which of the following on reaction with NH 3 gives urinary antiseptic compound
(1) HCHO (2) CH 3 CHO (3) C 6 H 5 CHO (4) C 6 H 5 CH 2 CHO
Ans. (1)

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 Aldehydes and Ketones (Carbonyl Compounds)

Q.17 Ketones are prepared by

(1) Clemmensen’s reduction (2) Cannizzaro reaction (3) Rosenmund’s reduction (4) Oppenaur’s oxidation
Ans. (4)

Sol.
R
R
 CH  OH  RR  C  O [(CH3 )3 CO]3 Al
Aluminium ter butoxide
Isopropyl alcohol Ketone

R  CH  CH 2  CO  H 2 High
   RCH 2 CH 2 CHO .
High Temp
Q.18 Pressure

The above reaction is

(1) Mendius reaction (2) Oxo process (3) Sandorn’s reaction (4) Stephen’s reaction
Ans. (2)

CH3
Q.19 On reductive ozonolysis yields

(1) 6-oxoheptanal (2) 6-oxoheptanoic acid (3) 6-hydroxyheptanal (4) 3-hydroxypentanal

Ans. (1)
5 7 7
5
43
2 6
1 CH3 4 6 CH3
Sol. ozonolysis

C=O
HC=O
34
6 3 1
5
1 2
2 6-oxoheptanal

Q.20 Gem dihalide on hydrolysis gives:

(1) Vic diol (2) Gem diol (3) Carbonyl compound (4) Carboxylic acid
Ans. (3)
OH – H2O
Sol. C C=O
OH

Q.21 Predict the product ‘B’ in the seuqnece of reaction

NaOH
HC  CH 30%H
 2SO 4
 A 
 B
HgSO 4

(1) CH3COONa (2) CH3COOH (3) CH3CHO (4) CH3CH(OH)CH2CHO

Ans. (4)
O
HC  CH 30%H 2SO 4
 CH3CHO   CH3–CH–CH2–C–H
NaOH
Sol. 
HgSO 4 Aldolreactions
O

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Aldehydes and Ketones (Carbonyl Compounds)

OH
|
In the given reaction : X + Y  CH 3  CH  CH  CHO
NaOH
Q.22
5 C |
CH 3

(X) and (Y) will respectively be:

(1) CH3–CH2–CHO and CH3–CH2–CHO (2) CH3–CHO and CH3–CH2–CHO

CH 3
|
(3) CH3–CHO and CH3–CHO (4) CH3–CHO and CH 3  C  CHO
|
CH 3
Ans. (2)

OH
CH3 –CHO + CH3–CH2 –CHO 
NaOH
Sol. 5C
CH3 – CH – CH – CHO
CH 3

Q.23 Compound (1) on ozonolysis gives the following compound

CH 3 — CH — CH 2 — C — (CH 2 ) 4 — CHO
| ||
CH 3 O structure of compound (1) is -

CH3 CH3
CH2–CH CH2–CH
(1) CH3 (2) CH3

CH3 CH3
CH2–CH CH2–CH2–CH
(3) CH3 (4) CH 3

Ans. (1)
CH3
CH2–CH
Sol. CH3

Physical & Chemical Properties of Carbonyl Compound

Q.24 Which of the following products is formed when benzaldehyde is treated with CH 3 MgBr and the addition product so
obtained is subjected to acid hydrolysis
(1) Secondary alcohol (2) Aprimary alcohol (3) Phenol (4) Tert-Butyl alcohol
Ans. (1)

C6 H 5 CHO 
3 CH MgBr
C6 H5 CH(OH)CH3
Sol. Benzaldehyde H  /H 2 O 2 Alcohol

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 Aldehydes and Ketones (Carbonyl Compounds)

NHNH2
Q.25
O2 N NO2
Which of the following compounds containing carbonyl group will give coloured crystalline compound with

(1) CH 3 COCl (2) CH 3 COCH 3 (3) CH 3 CO (OC 2 H 5 ) (4) CH 3 CONH 2

Ans. (2)
Sol. Among the given compounds only acetone gives crystalline coloured derivative with 2, 4 DNP.

Q.26 Which of the following compound will undergo self aldol condensation in the presence of cold dilute alkali
(1) C 6 H 5 CHO (2) CH 3 CH 2 CHO (3) CH  C  CHO (4) CH 2  CH  CHO
Ans. (2)

Q.27 Which of the following oxidation reactions can be carried out with chromic acid in aqueous acetone at 5  10 o C
O
||
(1) CH 3 (CH 2 )3 C  C  CH  CH 3  CH 3 (CH 2 )3 C C C CH 3
|
OH

(2) CH 3 (CH 2 ) 3 CH  CH  CH 2 OH  CH 3 (CH 2 )3 CH  CH  CHO

(3) C 6 H 5 CH 3  C 6 H 5 COOH
(4) All of the above
Ans. (4)

Q.28 The following reagent converts C 6 H 5 COCHO to C 6 H 5 CHOHCOONa

(1) Aq. NaOH (2) Acidic Na 2 S 2 O 3 (3) Na 2 CrO 4 / H 2 SO 4 (4) NaNO 2 / HCl
Ans. (1)

Q.29 To distinguish between formaldehyde and acetaldehyde, we require

(1) Tollen’s reagent (2) Fehling’s solution (3) Schiff’s reagent (4) Caustic soda solution
Ans. (4)

Sol. 2HCHO 

NaOH
CH3OH  HCOONa
Conc.

It is a Cannizzaro’s reaction.

OH
|
2CH 3CHO  CH3  CH  CH 2  CHO
NaOH
dil

It is aldol condensation reaction.

Q.30 The light yellow compound produced when acetone reacts with iodine and alkali, is
(1) CH 3 .CO .CH 2 I (2) CH 3 I (3) CHI 3 (4) None of these
Ans. (3)
Sol. CHI 3 is yellow compound when iodine reacts with NaOH and ketone.

Q.31 Which of the following reagent reacts differently with HCHO , CH 3 CHO and CH 3 COCH 3
(1) HCN (2) NH 2 NH 2 (3) NH 2 OH (4) NH 3
Ans. (4)

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Aldehydes and Ketones (Carbonyl Compounds)

Q.32 Treatment of propionaldehyde with dilute NaOH solution gives

(1) CH 3 CH 2 COOCH 2 CH 2 CH 3 (2) CH 3 CH 2 CHOHCH (CH 3 )CHO
(3) CH 3 CH 2 CHOHCH 2 CH 2 CHO (4) CH 3 CH 2 COCH 2 CH 2 CHO
Ans. (2)

Q.33 Aromatic aldehydes undergo disproportionation in presence of sodium or potassium hydroxide to give corresponding
alcohol and acid. The reaction is known as
(1) Wurtz’s reaction (2) Cannizzaro reaction (3) Friedel-Craft’s reaction (4) Claisen reaction
Ans. (2)

Sol.

This reaction is called as Cannizzaro’s reaction.

Q.34 Correct order of reactivity of CH 3 CHO , C 2 H 5 COCH 3 and CH 3 COCH 3 is

(1) CH 3 CHO  CH 3 COCH 3  CH 3 COC 2 H 5 (2) C 2 H 5 COCH 3  CH 3 COCH 3  CH 3 CHO
(3) CH 3 COCH 3  CH 3 CHO  C 2 H 5 COCH 3 (4) CH 3 COCH 3  C 2 H 5 COCH 3  CH 3 CHO
Ans. (1)
Sol. Increasing alkyl group the reactivity decreases.

Q.35 Which of the following does not turn Schiff’s reagent to pink
(1) Formaldehyde (2) Benzaldehyde (3) Acetone (4) Acetaldehyde
Ans. (3)

Q.36 Acetaldehyde and acetone differ in their reaction with

(1) Sodium bisulphite (2) Ammonia
(3) Phosphorus pentachloride (4) Phenyl hydrazine
Ans. (2)

OH
|

Sol. CH3  C  H  NH3  CH3  C  H

|| |
O NH2

O CH3
|| |
2CH 3  C  CH 3  NH 3  CH3  C  CH 2 C  CH3
|| |
O NH2

Q.37 The compound obtained by the reduction of propionaldehyde by amalgamated zinc and concentrated HCl is
(1) Propanol (2) Propane (3) Propene (4) All of these
Ans. (2)

Sol. CH3CH 2 CHO  4H 

Zn/Hg
CH 3CH 2 CH 3  H 2 O
HCl

This reaction is called clemmenson’s reduction.

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 Aldehydes and Ketones (Carbonyl Compounds)

Q.38 The typical reactions of aldehyde is

(1) Electrophilic addition (2) Nucleophilic substitution
(3) Nucleophilic addition (4) Nucleophilic elimination
Ans. (3)
Sol. Nucleophilic as addition of HCN , NaHSO 3 etc.

Q.39 The product formed by the reaction of chlorine with benzaldehyde in the absence of a catalyst is
(1) Chlorobenzene (2) Benzyl chloride (3) Benzoyl Chloride (4) o-Chlorobenzaldehyde
Ans. (3)
C6 H5 CHO  Cl2  C6 H5 COCl  HCl
Sol. Benzaldehyde Benzoylchloride

Q.40 In which of the following reactions aromatic aldehyde is treated with acid anhydride in presence of corresponding salt
of the acid to give unsaturated aromatic acid
(1) Friedel-Craft’s reaction (2) Perkin reaction (3) Wurtz reaction (4) None of these
Ans. (2)

Q.41 Cinnamic acid is formed when C6 H 5  CHO condenses with (CH 3 CO )2 O in presence of

(1) Conc. H 2 SO 4 (2) Sodium acetate (3) Sodium metal (4) Anhydrous ZnCl 2
Ans. (2)

C6 H5 CHO  (CH3CO) 2 O   C6 H 5 CH  CHCO 2 H

CH 3CO 2 Na
Sol.
It is Perkin’s reaction.

O O
||
H  or OH  ||
Q.42 The reaction, CH 3  C  OCH 3  C 2 H 5 OH     CH 3  C  OC 2 H 5  CH 3 OH is called
(1) Perkin’s reaction (2) Claisen Schmidt reaction
(3) Esterification (4) Trans-esterification
Ans. (4)
Sol. The substitution of alkoxy group of ester by an alcohol, is called trans-esterification. It occurs in presence of either
an acid or base.

Q.43 Aldol condensation will not take place in

(1) HCHO (2) CH 3 CH 2 CHO (3) CH 3 CHO (4) CH 3 COCH 3
Ans. (1)
Sol. In HCHO because -Hydrogen atom is absent.

Q.44 Action of hydrazine on aldehydes and ketones gives compound of the general structure
(1)  C  N  NH 2 (2)  C  N  OH
(3)  C  N  NH  CONH 2 (4)  C  N  NH  C 6 H 5
Ans. (1)

Q.45 Bakelite is a polymer of

(1) HCHO  phenol (2) HCHO  aldehyde (acetaldehyde)
(3) Phenol  H 2 SO 4 (4) HCHO  acetone
Ans. (1)

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Aldehydes and Ketones (Carbonyl Compounds)

Q.46 Enol content is highest in

(1) Acetone (2) Acetophenone (3) Acetic acid (4) Acetyl acetone
Ans. (4)
Sol. The amount of enolic form is highest (76%) in acetyl acetone because keto group is a much better electron-withdrawing
group.

O O O — H....O O....H — O
|| || | ||

 CH 3C  CH  CCH 3  CH C  CH  C  CH
|| |
CH 3CCH 2 CCH 3  3 3
acetyl acetone enolic form (76%)
(keto form, 24%)

Q.47 During reaction of benzaldehyde with alkali one of the product is

(1) Phenol (2) Benzyl alcohol (3) Benzene (4) Benzophenone
Ans. (2)

Sol.

Q.48 The reaction C 6 H 5 CHO  CH 3 CHO  C 6 H 5 CH  CH  CHO is known as

(1) Perkin’s reaction (2) Claisen condensation (3) Benzoin condensation (4) Cannizzaro’s reaction
Ans. (2)

Sol.

Q.49 Acetaldehyde on treatment with dil. NaOH followed by heating gives

(1) CH 3 CH 2 CH 2 CH 2 OH (2) CH 3 CH 2 CH 2 CHO (3) CH 3  CH  CHCHO
(4) CH 3  CH  CHCH 2 OH
Ans. (3)

 CH 3  CH  CH 2  CHO   CH 3  CH  CH  CHO  H 2 O

Heat
Sol. CH 3CHO 
dil NaOH
|
OH
Aldol

Q.50 Benzaldehyde on reaction with acetophenone in the presence of sodium hydroxide solution gives
(1) C 6 H 5 CH  CHCOC 6 H 5 (2) C 6 H 5 COCH 2 C 6 H 5 (3) C 6 H 5 CH  CHC 6 H 5 (4) C 6 H 5 CH (OH )COC 6 H 5
Ans. (1)

O
||
Sol. C6 H5 CHO  CH3 COC6 H 5 
NaOH C6 H5  CH  CH  C  C6 H5
 H 2O Benzyl acetophenone

Q.51 Identify the organic compound which, on heating with strong solution of NaOH , partly converted into an acid salt and
partly into alcohol
(1) Benzyl alcohol (2) Acetaldehyde (3) Acetone (4) Benzaldehyde
Ans. (4)
Sol. 2C6 H 5 CHO 
50% NaOH
 C6 H5 COONa  C6 H 5 CH 2 OH
It is Cannizzaro’s reaction
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 Aldehydes and Ketones (Carbonyl Compounds)

Q.52 CH 3 CHO  CH 3 MgBr  Product   A

H 2O

What is A ?
(1) Primary alcohol (2) Secondary alcohol (3) Tertiary alcohol (4) Ketone
Ans. (2)

CH 3
|
Sol. CH 3  C  O  CH 3 MgBr  CH 3  C  OH
| |
H H
(2o alcohol)

Q.53 CH 3 CHO react with aqueous NaOH solution to form

(1) 3-hydroxy butanal (2) 2-hydroxy butanal (3) 4-hydroxy butanal (4) 3-hydroxy butanol
Ans. (1)
Sol. This reaction is aldol condensation

2CH3CHO 
dil NaOH
 CH3  CH  CH 2  CHO
|
OH
3 hydroxy butanal

Q.54 Only an aldehyde having..... can undergo the aldol condensation

(1) At least one beta H atom (2) At least one alpha H atom
(3) An aromatic ring (4) No alpha H atom
Ans. (2)

Q.55 What is the name of reaction when benzaldehyde changes into benzyl alcohol
(1) Friedel-Craft’s reaction (2) Kolbe’s reaction (3) Wurtz reaction (4) Cannizzaro reaction
Ans. (4)
Sol. Cannizzaro’s reaction involve self oxidation and self reduction.

Q.56 Which one is used in the manufacture of mirror

(1) Red lead (litharge) (2) Ammoniacal AgNO 3
(3) Ammoniacal AgNO 3  Red lead (4) Ammoniacal AgNO 3  HCHO
Ans. (4)

Q.57 Which of the following would undergo aldol condensation

CH 3
|
(1) CCl 3 .CHO (2) CH 3  C  CHO (3) CH 3 .CH 2 .CHO (4) HCHO
|
CH 3

Ans. (3)
 
Sol. CH 3  CH 2  CHO aldehydes having   H atom can participate in aldol condensation. The H  atom attached to 
carbon atom are called -hydrogen.

Q.58 When acetaldehyde is heated with Tollen’s reagent, following is obtained

(1) Methyl alcohol (2) Silver acetate (3) Silver mirror (4) Formaldehyde
Ans. (3)

Sol. CH 3CHO  2[Ag(NH 3 ) 2 ]OH  CH 3COONH 4  2Ag  3NH 3  H 2 O

Tollen's reagent Silver mirror

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Aldehydes and Ketones (Carbonyl Compounds)

Q.59 Urotropine is
(1) Hexamethylene tetramine (2) Hexaethylene tetramine
(3) Hexamethylene diamine (4) None of these
Ans. (1)
Sol. It is used as a medicine to treat urinary infections.

Q.60 Cannizzaro reaction is not shown by

(1) HCHO (2) C 6 H 5 CHO (3) CH 3 CHO (4) All of these
Ans. (3)
Sol. Cannizzaro’s reaction is shown by aldehydes in which -H atom is absent. CH 3 CHO contains 3,  -H atoms thus, does
not show this reaction.

Q.61 Benzaldehyde and acetaldehyde can be differentiated by

(1) HCN (2) NH 2 OH (3) Hydrazine (4) NaOH solution
Ans. (4)
Sol. Benzaldehyde gives cannizaro’s reaction whereas acetaldehyde gives aldol condensation.

Q.62 Base catalysed aldol condensation occurs with

(1) Benzaldehyde (2) 2, 2-dimethyl propionaldehyde
(3) Acetaldehyde (4) Formaldehyde
Ans. (3)

Q.63 Glucose + Tollen’s reagent  Silver mirror shows

(1) Presence of acidic group (2) Presence of alkaline group
(3) Presence of ketonic group (4) Presence of aldehyde group
Ans. (4)

Q.64 Which of the following on reaction with conc. NaOH gives an alcohol
(1) Methanal (2) Ethanal (3) Propanal (4) Butanal
Ans. (1)
Sol. HCHO  HCHO 
NaOH
 CH 3OH  HCOONa
Conc

Q.65 Which one of the following on oxidation will not give a carboxylic acid with the same number of carbon atoms
(1) CH 3 COCH 3 (2) CCl 3 CH 2 CHO (3) CH 3 CH 2 CH 2 OH (4) CH 3 CH 2 CHO
Ans. (1)
O
||
Sol. CH 3  C CH 3 
K 2 Cr2 O 7
 CH 3COOH  HCOOH
H 2SO 4

one carbon atom is less in the ketone group

Q.66 Which of the following is used in the manufacture of thermosetting plastics

(1) Formaldehyde (2) Acetaldehyde (2) Acetone (4) Benzaldehyde
Ans. (1)

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 Aldehydes and Ketones (Carbonyl Compounds)

Q.67 Which does not react with Fehling solution

(1) Acetaldehyde (2) Benzaldehyde (3) Glucose (4) Formic acid
Ans. (2)
Sol. Fehling solution is a weak oxidising agent therefore unable to oxidise benzaldehyde.

Q.68 Schiff’s reagent gives pink colour with

(1) Aldehydes (2) Ethers (3) Ketones (4) Carboxylic acid
Ans. (1)

Sol. Aldehyde  Schiff's reagent  Pink colour

(Colourless)

Ketone do not give this test.

Q.69 The compound which reacts with Fehling solution is

(1) C 6 H 5 COOH (2) HCOOH (3) C 6 H 5 CHO (4) CH 2 ClCH 3
Ans. (2)

Q.70 Which one of the following is reduced with zinc and hydrochloric acid to give the corresponding hydrocarbon
(1) Acetamide (2) Acetic acid (3) Ethyl acetate (4) Butan–2–one
Ans. (4)
Sol. Butane 2-one will get reduced into butane when treated with Zinc and hydrochloric acid following Clemmensen reduction,
whereas Zn/HCl do not reduce ester, acid, amide

Q.71 Aldehydes and ketones can be reduced to corresponding hydrocarbons by

(1) Refluxing with water (2) Refluxing with strong acids
(3) Refluxing with soda amalgam and water (4) Refluxing with zinc amalgam and concentrated HCl
(e) Passing the vapour under heated PbO 2
Ans. (4)
Zn  Hg/ HCl
Sol. RCHO  4H  R  CH 3  H 2 O

Q.72 Which of the following is used to detect aldehydes

(1) Million’s test (2) Tollen’s reagent
(3) Neutral ferric chloride solution (4) Molisch’s test
Ans. (2)
Sol. Tollen’s reagent is used to detect aldehydes. Aldehyde reduce Tollen’s reagent to give Silver mirror while these are
oxidised to acid.

Q.73 A (CH 3 ) 2 C  CHCOCH 3 A is

(1) Acetone (2) Acetaldehyde (3) Propionaldehyde (4) Formaldehyde
Ans. (1)
Sol. Two molecules of acetone condense in presence of dry HCl gas to form mesityl oxide.

(CH 3 ) 2 C  CH.COCH 3
Mesityl oxide

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Aldehydes and Ketones (Carbonyl Compounds)

Q.74 In Wolf-Kishner reduction, the carbonyl group of aldehydes and ketones is converted into
(1) > CH2 group (2) – CH3 group (3) – CH2 OH group (4) > CHOH group
Ans. (1)
Sol. Wolf kischner reduction : Hydrazine ( NH 2  NH 2 ) followed by reaction with strong base like KOH reduce carbonyl
group into alkyl group.

Q.75 Fehling solution is

(1) CuSO 4 + lime (2) CuSO 4  NaOH (aq) (3) CuSO 4  Na 2 CO 3 (4) None of these
Ans. (4)
Sol. Fehling’s solution is the solution of CuSO 4  NaOH + Roschel salt (Sodium potassium tartarate). Aldehyde give red
precipitate with Fehling’s solution.

Q.76 A compound has a vapour density of 29. On warming an aqueous solution of alkali, it gives a yellow precipitate. The
compound is
(1) CH 3 CH 2 CHO (2) CH 3 CHOHCH 3 (3) CH 3 COCH 3 (4) CH 3 CH 2 COOH
Ans. (3)
Sol. Molecular weight of the compound
 2  Vapour density
 2  29  58
Molecular weight of CH 3 CH 2 CHO , CH 3 CHOHCH 3 , CH 3 COCH 3 and CH 3 CH 2 COOH are 58, 60, 58 and 74 respectively..
Both CH 3 CH 2 CHO and CH 3 COCH 3 have molecular weight 58 but only aldehyde i.e., CH3COCH3 on warming with
aqueous alkali gives yellow precipitate.

Q.77 The pair of compounds in which both the compounds give positive test with Tollen’s reagent is
(1) Glucose and Sucrose (2) Fructose and Sucrose
(3) Acetophenone and Hexanal (4) Glucose and Fructose
Ans. (4)
Sol. Tollen’s reagent oxidizes the compound having aldehyde group like glucose and also oxidizes -hydroxy ketones having
COCH 2 OH group as in fructose.

Q.78 Paraldehyde is used as a

(1) Medicine (2) Poison (3) Polymer (4) Dye
Ans. (1)

Q.79 Which of the following does not give Fehling solution test?
(1) Acetone (2) Propanal (3) Ethanal (4) Butanal
Ans. (1)

Q.80 CH 3  CHO  HCN  A ; Compound

A on hydrolysis gives
(1) CH 3  CH 2  COOH (2) CH 3  CH 2  CH 2  NH 2
(3) CH 3  CO  COOH (4) CH 3  CH  COOH
|
OH
Ans. (4)

OH OH
|
H3O  |
Sol. CH3 CHO  HCN  CH 3C  C  CN  CH 3  C  COOH
| |
OH H
(A)

72
 Aldehydes and Ketones (Carbonyl Compounds)

OH
Q.81 In the Cannizzaro reaction : 2PhCHO  PhCH2OH + PhCOO– the slowest step is
(1) The attack of OH– at the carboxyl group
(2) The transfer of hydride to the carbonyl group
(3) The abstraction of proton from the carboxylic acid
(4) The deprotonation of PhCH2OH
Ans. (2)
Sol. Hyride transfer is slowest step.

Q.82 2-Methylcyclohexanone is allowed to react with metachloroperoxobenzoic acid. The major product formed in the reaction
is

(1) (2) (3) (4)

Ans. (3)

O O
O –C–O–O–C– O
CH3 CH3
Sol. Cl O

Q.83 The product formed in the following reaction will be -

CHO NaOH
| product -
CHO
(1) CH2OH (2) CH2OH (3) COONa (4) All of these
| | |
CH2OH COONa COONa
Ans. (2)
CHO NaOH CH2OH
Sol. Cannizaro
CHO reaction COONa

Q.84 Compound formed by the reaction of furfural ( ) with ethanol is

(1) an aldol (2) an acetal (3) a ketal (4) a hemiacetal

Ans. (4)
Sol. Aldehydes reacts with alcohol; in the precence of dry HCl to give dialkoxy compounds known as acetal a hemiacetal is
formed first.

dry
O CH=O + C2H5OH HCl OC2H5
O CH
Hemiacetal OH

73
Aldehydes and Ketones (Carbonyl Compounds)

Q.85 Cannizzaro reaction does not take place with -

(1) (CH3)3CCHO (2) CHO (3) CHO (4) CH3CHO

O
Ans. (4)
Sol. CH3CHO gives aldol reaction.

Q.86 Which of the following is an example of aldol condensation ?

NaOH
(1) C6H5CHO + HCHO  
 C H CH OH
6 5 2 heat

1. C H ONa
(2) 2CH3COOC2H5    CH3COCH2COOC2H5
2 5

2.H3O

CH3 CH3

(3) CH3COCH3 + (CH3)2NH  CH3 – C –– N – CH3

OH

Ba(OH)
(4) 2CH3COCH3   CH3C(OH)(CH3)CH2COCH3
2

Ans. (4)
OH O

CH3COCH3     CH3–C–CH2–C–CH3
Ba(OH)
Sol.
CH3


/
H  [X]
O
Q.87 In the reaction : +

[X] will be :

(1) (2)

(3) (4)

Ans. (4)

O
OH


OH /  O
Sol. + 

74
 Aldehydes and Ketones (Carbonyl Compounds)

Q.88 In a Cannizzaro reaction the intermediate which is the best hydride donor is –

H H H H
| | –
O O–
(1) C6H5– C – O– (2) C6H5– C – O– (3) (4)
| O– O–
| O2 N CH3O
OH O–
Ans., (4)
   
Sol. –OCH
  3 is an electron releasing group this group (–OCH
   3 ) facilitates the release of hydride ion. Therefore option (4) is


correct.

Q.89 A + B forms A and B are –

N

NH2 CH 2  NH 2 CHO
(1) , CH3– CHO (2) CH3CHO, CH3 - NH2 (3) | , | (4) HCHO, CH3NH2
NH2 CH 2  NH 2 CHO

Ans. (3)
Sol.

N–H2 + O = CH
CH 2 –2H2O
|
CH 2 O = CH
N–H2 + O = [B]
[A]
N

CH 2 CH
|
CH 2
CH
N

Therefore option (3) is correct.

75
Aldehydes and Ketones (Carbonyl Compounds)

GRIGNARD REAGENT

Q.90 Identify the reactant X and the product Y

CH 3  CO  CH 3  X  (CH 3 )3 C  OMg  Cl

Hydrolysis

Y  Mg (OH) Cl
(1) X  MgCl 2 ; Y  CH 3 CH  CH 2 (2) X  CH 3 MgCl ; Y  C 2 H 5 COCH 3
(3) X  CH 3 MgCl ; Y  (CH 3 )3 C  OH (4) X  C 2 H 5 MgCl ; Y  (CH 3 )3 C  OH
Ans. (3)
CH 3COCH3  CH3 MgCl  (CH3 )3 C  OMgCl 
hydrolysis
(CH 3 )3 C  OH  Mg(OH)Cl
Sol. (X) (Y)

Q.91 Product in following reaction is CH 3 MgI  HCHO  Product

(1) CH 3 CHO (2) CH 3 OH (3) C 2 H 5 OH (4) CH 3  O  CH 3
Ans. (3)

Sol. H  CHO  CH 3MgI  CH 3  CH 2  OH  Mg


Q.92 Identify the product Y in the sequence CH 3 CHO  CH 3 Mgl   X 
Ether

H 2O / H
 Y

(1) CH 3 OH (2) CH 3 CH 2 OH (3) (CH 3 )2 CHOH (4) (CH 3 )3 COH

Ans. (3)

 OMgI 
 |  H O
CH 3 MgI  CH 3CHO  CH 3  C  H  
3
 (CH 3 ) 2 CHOH
Sol.
 
|
2  Propanol
 CH 3 

Q.93 The correct order of reactivity of PhMgBr with

O O O
|| ||
||
CH 3  C  H CH 3  C  CH 3
is
Ph  C  Ph
(I) (II) (III)
(1) (I) > (II) > (III) (2) (III) > (II) > (I) (3) (II) > (III) > (I) (4) (I) > (III) > (II)
Ans. (3)
Sol. In nucleophilic addition reaction, the carbonyl compound will respond in preference which is sterically more exposed
and electronically have intact positive charge over carbonyl carbon. So reactivity order towards reaction with phMgBr
is (II) > (III) > (I).4

Q.94 The correct order of reactivity of PhMgBr with

O O O
|| ||
|| is
Ph  C  Ph CH 3  C  H C2H5  C  C2H5
(I) (II) (III)
(1) (I) > (II) > (III) (2) (III) > (II) > (I) (3) (II) > (III) > (I) (4) (I) > (III) > (II)
Ans. (3)

76
 Aldehydes and Ketones (Carbonyl Compounds)

Sol. In nucleophilic addition reaction, the carbonyl compound will respond in preference which is sterically more exposed
and electronically have intact positive charge over carbonyl carbon. So reactivity order towards reaction with phMgBr
is (II) > (III) > (I).

Q.95 Consider the following sequence of reactions.

1.C H MgBr H SO heat 1.O

Ketone A  
2 5  B 2  
3
4,
 C
2.H O 2 H O 2 2.Zn,H2O

The ketone (A) is

(1) (2) (3) (4)

Ans. (2)

OH
CH3 –CH2
CH3–CH2 –C–CH2 –CH3
C=CH–CH3
Sol. O CH2–CH3 CH3 –CH2
(A) (B) (C)

OXIDATION & REDUCTION

Q.96 Catalyst SnCl 2 / HCl is used in

(1) Stephen’s reduction (2) Cannizzaro reaction
(3) Clemmensen’s reduction (4) Rosenmund’s reduction
Ans. (1)

Q.97 Benzaldehyde can be prepared by oxidation of toluene by

(1) Acidic KMnO 4 (2) K 2 Cr2 O7 (3) CrO 2 Cl 2 (4) All of these
Ans. (3)
CH3 CHO COOH


acidic K 2 Cr2O7
 
Sol. CrO Cl
2 2
or KMnO 4

This is Etard’s reaction

Q.98 The oxidation product of 2-propanol with hot conc. HNO 3 is

(1) Ethanoic acid (2) Propanone (3) Propanal (4) None of these
Ans. (2)

Q.99 Reduction of  C  O to CH 2 can be carried out with

(1) Catalytic reduction (2) Na / C 2 H 5 OH (3) Wolf-Kischner reduction (4) LiAlH 4
Ans. (3)
Sol. Reduction of  C  O to CH 2 can be carried out with Wolf Kischner reduction.

CHO CH2OH

Benzaldehy Benzylalcoh
77
Aldehydes and Ketones (Carbonyl Compounds)

Q.100 Which one of the following pairs is not correctly matched

(1)  C  O        CH 2
Clemenson' s reduction
(2)  C  O        CHOH
Wolf - Kishner reduction

(3)  COCl       CHO

Rosenmund' s reduction (4)  C  N      CHO
Stephen reduction

Ans. (2)
Sol. Wolf-Kishner reduction does not convert  CO to CHOH but converts it to  CH 2 .

Q.101 Aldehydes can be oxidised by

(1) Tollen’s reagent (2) Fehling solution (3) Benedict solution (4) All of these
Ans. (4)
Sol. All test for Aldehyde because ketone require strong oxidising agent.
2[Ag(NH3 )2 ]  RCHO  RCOOH  2Ag  4NH3  H2 O

Q.102 For the reaction RCH = O + 2[H]  RCH2OH

the catalyst is-
(1) Ni only (2) Pd. only (3) Pt. only (4) Any of the above
Ans. (4)
Sol. Aldehyde are reduced by all three catalysts (Ni / Pd / Pt)

Q.103 The conversion CH3CHO ––– OHC –– CHO can be effected by:
(1) CrO3 (2) SeO2 (3) Br2/NaOH (4) KMnO4
Ans. (2)

SeO
Q.104 In the given reaction : 2  [X]; [X] will be:

(1) (2) (3) (4)

Ans. (2)

SeO
Sol. 2 

78
 Aldehydes and Ketones (Carbonyl Compounds)

2  Q     R. The product R is –

KMnO CH COONa
In the reaction series : CH3CHO dil
. HSO P SOCl
4 3
Q.105 Heat
2 4

(1) (CH3CO) 2O (2) Cl. CH2COOCOCH3

(3) CH3COCH2COOH (4) Cl2. CHCOOCOCH3
Ans. (1)
CH 3  C  Cl
||
O
[Q]

O
CH 3  C  OH | CH 3COONa
KMnO 4 ||
    SOCl
CH3 C
Sol. CH3CHO + dil. H SO O  
 2 O +NaCl
2 4
[ P] CH3– C
|
O
(R)
Therefore optioin (1) is correct.

79
Carbonyl Compounds, Grignard Reagent , Oxidation and Reduction

EXERCISES-II

CARBONYL COMPOUNDS
Method of preparation of aldehyde &ketone and Nucleophilic addition reaction
Q.1 Arrange the following compounds in decreasing orders of rate of exchange of O18 with H2O18
(X) CCl3CHO (Y) CH3CHO (Z) CH3COCH3 (W) CF3CHO
(1) W > Z > X > Y (2*) W > X > Y > Z (3) W > Y > Z > X (4) W > Z > Y > X
Ans. (2)
Sol. > > >

Q.2 The correct order of reactivity of PhMgBr with following compounds will be.
(C6H5)2CO, CH3 – CH = O , (CH3)2 C = O
(1) (2) (3)
(1) 1 > 2 > 3 (2*) 2 > 3 > 1 (3) 3 > 2 > 1 (4) 1 > 3 > 2
Ans. (2)
Sol As the positive charge decreases and steric hinderance increases on carbonyl group the rate of nucleophilic addition
reaction decreases.

Q.3 Arrange these compounds in decreasing order of reactivity for the nucleophilic addition reaction:
(I) Acid chloride (II) Aldehyde (III) Ketone (IV) Ester
Select the correct answer from the codes given below:
(1) I > II> III > IV (2) IV > III > II > I (3) III > II > I > IV (4) I > IV > II > III
Ans. (1)
Sol. CH3 – C – Cl CH3 – C – H CH3 – C – CH3 CH3 – C – oet
O O O O
Decreasing Order of reactivity towards N.A.R.

Q.4 (x) OH

  -hydroxy ketone
H 2O

(x) can’t be
O
O O O O

(1) (2) O (3) (4)

H—C—H
O
Ans. (4)
H – C – H have no  – H so do not show aldol Rx
n
Sol.

dil.KOH
Q.5   (x) major product structure of (x) is
O O 

O O HO
COH
OH CHO CHO
(1) (2) (3) (4)

80
 Carbonyl Compounds, Grignard Reagent , Oxidation and Reduction

Ans. (4)

dil KOH
Sol. O O O O
H

CHO CHO CHO

OH O
O
H H
– H2O

Q.6 Which of the following will not undergo aldol condensation ?

(1) CH3CHO (2) CH3CH2CHO (3) CD3CHO (4*) PhCHO
Ans. (4)
Sol. -hydrogen absent.

Q.7 Compound which gives cannizaro reaction?

O
(1)CD3CHO (2) C6H5CHO (3) CH3COCH3 (4)

Ans. (2)
Sol. Corbonyl Comp having no  – H gives cannizaro Rxn

dil. H SO
Q.8 This is an example of an intramolecular aldol reaction: 
2 4
 (1),

O

Product (1) is:

O O O

(1) (2) (3) (4)

Ans. (1)

O O

H2SO4
Sol. H2O

(Intramolecular aldol Reaction)

81
Carbonyl Compounds, Grignard Reagent , Oxidation and Reduction

Q.9 (X) is the product of cross aldol condensation between benzaldehyde (C6H5CHO) and acetone What is its structure ?

(1)
(2) C6H5–CH=C–(CH3)2
(3) C6H5–CO–CH2–C=(CH3)2
(4) None of these
Ans. (1)

(CH3)3CCHO + HCHO  
 A+ B.
NaOH
Q.10 In the reaction, heat

the products (1) and (2) are respectively :

(1*) (CH3)3CCH2OH and HCOO– Na+. (2) (CH3)3CCOONa and CH3OH.
(3) (CH3)3CCH2OH and CH3OH. (4) (CH3)3COONa and HCOO– Na+.
Ans. (1)

Sol.

Q.11 In the given reaction Product is

(1) (2*) (3) (4)

Ans. (2)

82
 Carbonyl Compounds, Grignard Reagent , Oxidation and Reduction

Sol.

Q.12 
O3
(1) 
KOH
Zn 

(2)Major product (2) is:

O O O
O

(1) (2) (3) (4)

Ans. (2)

O O

O3 o KOH
Zn
Sol.
o

OH

Other name reactions

Q.13 Product of Perkin reaction is :
(1) ,  -unsaturated aldehyde (2)  -cyclohexyl ,  -unsaturated aldehyde

(3)  -Aryl- ,  -unsaturated acid (4) All of these

Ans. (3)

Sol. CH3COO Na
Ph – C – H + CH3 – C – O – C – CH 3 Ph – CH = CH – COOH
O O O -Aryl- -unsaturated Acid
or
Cinnemic Acid

83
Carbonyl Compounds, Grignard Reagent , Oxidation and Reduction

COOH
CHO

Q.14 (CHOH) 4 (CHOH) 4

CH2OH
CH2OH

Reagent responsible for given conversion will be

(1)Ag2O,NH4OH (2)Br2,H2O (3) Cu+2 (4)All
Ans. (4)

Oxidising agent
Sol. CHO COOH
Br 2, H 2O
(CH – OH)4 (CH – OH)4
Ag 2O, NH 4OH
CH2 – OH Cu
+2
CH2 – OH

Q.15 Schiff’s reagent is used for the differentiation between:

(1) HCHO and CH3CHO (2) CH3COCH3 and CH3CHO
O O

(3) C6H5 – CH2 – C – CH3 and C6H5 – C –CH2–CH3 (4) HCHO and C6H5CHO
Ans. (2)
Sol. Schiff’s reagent is [P rosanilline + HCl + SO2] which is used for different b/w Aldehyde or Ketone.

Q.16 In the reaction sequence[X] is ketone:


OH / 
[X] KMnO
 4 /  HOOC – (CH2)3–CH2–COOH; [X] will be:
O O O O

CH3 CH3 H 3C CH 3
(1) (2) (3) (4)

Ans. (1)
O

Sol. Kmno4 / OH / 
HOOC – (CH2)3 – CH2 – COOH

Q.17 Which will give silver mirror test with Tollens reagent:
(1)C6H5CHO (2) CH3–CHO (3) HCOOH (4) All of these
Ans. (4)
+ –
Sol. CH6H5 – CHO [Ag (NH3)2] OH C6H5 – COOH + Agl

CH3 – CHO H Ch 3 CH 3COOH + Agl

H COOH H H 2O + CO2 + Agl

84
 Carbonyl Compounds, Grignard Reagent , Oxidation and Reduction

Mixed/miscellaneous
Q.18 In which of the following compounds the methylene hydrogens are the most acidic ?
(1) CH3COCH2CH3 (2) CH3CH2COOC2H5
(3) CH3CH2CH(COOC2H5)2 (4*) CH3COCH2CN.
Ans. (4)
Sol.


Br / H
Q.19 2  Major Product is :

(1*) (2) (3) (4) A and C both

Ans. (1)

Sol.

O
D D
Q.20  The above conversion is carried out
D

(1) KOD /D2O, H/, LiAlH4 (2) H// KOD, D2O, LiAlH4
(3*) KOD/ D2O, LiAlH4, H/ (4) LiAlH4, H,KOD/H2O
Ans. (3)

O
KOH / D O LiAlH H / 
Sol. 2 
4
  


O


Q.21 CH3 – C –OH CaO

  (2) D
 (1) KOH
  (3)
2 O / DO

  prolonged treatment 
How many hydrogen is replaced by Deuterium
(1) 2 (2) 10 (3) 7 (4) 8
Ans. (2)

CD 3
KOH D2O/OD
CH3–C–OH CaO CH3–C–CH3 CH–C–CH3 C–C–CD3
Sol. || || || CD 3 ||
O O O D O

85
Carbonyl Compounds, Grignard Reagent , Oxidation and Reduction

GRIGNARD REAGENT, REDUCTION & ALKANE

Orgenometallic compound

Q.22 The reaction

BrCH2CH2CH2Br + Mg Et2O

Product mainly
(1) CH3CH2CH3 (2) BrMgCH2CH2CH2MgBr

(3) (4) CH3CH=CH2

Ans. (3)
Sol. Br–CH2–CH2–CH2–

Et2O  
Br+Mg   BrMgCH 2–CH 2–CH2–Br

+ MgBr2

Q.23 Br–CH2–C  C–CH2–Br

Mg
BrMg–CH2–C  C–CH2–MgBr
(excess)
Et2O

Mg(1 eq.)
Product
Et2O

The major product is :

(1) Br–Mg–CH2–C=C–CH2–Br (2) Cyclobutyne
(3) –(CH2–C=C–CH2)n (4) CH2=C=C=CH2
Ans. (4)
Mg
Sol. Br–CH2–CC–CH2–Br  BrMgCH2–CC–CH2MgBr
(excess)
Et2O

Mg(1eq)
et2O

 
BrMgCH2–C C–CH2–Br

CH2=C=C=CH2

86
 Carbonyl Compounds, Grignard Reagent , Oxidation and Reduction

Q.24 Consider the given organometallic compound.

(I) (CH3)2Hg (II) (CH3)2Zn (III) (CH3)2Mg (IV) CH3Li
The correct decreasing order of ionic character is
(1) I > II > III > IV (2) II > I > III > IV (3) I > III > II > IV (4) IV > III > II > I
Ans. (4)
Sol. decreasing order of ionic character in following organo metallic compond
CH3–Li > (CH3)2 Mg > (CH3)2 Zn > (CH3)2Hg
[ionic character  difference between E.N.]

Reaction of grignard

Q.25 C6H5COOH + CH3MgI  ?

(1) C6H5COOMgI (2) CH4 (3*) Both A & B (4) none
Ans. (3)

Sol. (1) C6H5COOH + CH3MgI 

(i)
Et 2O
Q.26 + (CH3)2CH Mg Br  
(ii ) H O 2

What will be the product :

(1) CH3 – (CH2)4 – CH2 – OH (2) CH3  CH  CH  CH  CH3
|
CH3

(3*) (4) CH3  CH  CH2  CH3

|
CH (CH3 )2
Ans. (3)

Et 2O(i)
Sol. (3) + (CH3)2CH Mg Br  
( ii ) H O 2

Q.27 The reactivity order of CH3MgBr with the following compounds is:
OH
CH3 CH3
C CH3 C Cl
(I) (II) (III) CH3 – Cl (IV)
O O
(1) I > IV > II > III (2) II > I > IV > III (3) I > II > IV > III (4) IV > II > I > III
Ans. (1)

OH
CH3 CH3 CH3 – C – Cl
C CH3–Cl
Sol. O O
(III) (IV)
(II)
(I)

reactivity order of CH3MgBr with following compound.

I > IV > II > III
87
Carbonyl Compounds, Grignard Reagent , Oxidation and Reduction

Q.28 (CH3)3 CMgCI on reaction with D2O, produces :

(1*) (CH3)3 CD (2) (CH3)3 COD (3) (CD3)3 CD (4) (CD3)3 COD
Ans. (1)
Sol. (CH3)3 CMgCI + D2O  (CH3)3CD

O
||
Q.29 Ph  MgBr + (CH3 )2  CH  C  Cl [X] 
Zn Hg / HCl
  [Y]
1 mole
Identify strucutre of [Y].

(1*) Ph  CH2  CH  CH3 (2) Ph  CH  CH2  CH3

| |
CH3 CH3

CH3
|
(3) Ph  C  CH3 (4)
|
CH3
Ans. (1)
O O
|| ||
Sol. Ph  MgBr + (CH3 )2  CH  C  Cl  (CH3 )2  CH  C  Ph    Ph  CH2  CH  CH3
Zn Hg / HCl

1 mole |
CH3

Q.30 One conversion into Grignard followed by treatment with ethanol, how many alkyl halides (excluding stereoisomers)
would yeild 2-methyl butane.
(1) 2 (2) 3 (3) 4 (4) 5
Ans. (3)
Mg ether
Sol. (1) CH3– CH  CH2 –CH2–x     CH3– CH  CH2  CH3
| C2H5OH |
CH3 CH3

Mg ether
(2) CH3– CH  CH  CH3     CH3– CH  CH2  CH3
| | C2H5OH |
CH3 x CH3

X
| Mg ether
(3) CH3– C  CH2  CH3     CH3– CH  CH2  CH3
| C2H5OH |
CH3 CH3

Mg ether
(4) CH2  CH  CH2  CH3     CH3– CH  CH2  CH3
| | C2H5OH |
X CH3 CH3

Q.31 How many litres of ethene would be produced when 2.62 g of vinyl magnesium bromide is treated with 224 ml of ethyne at
STP.
(1) 0.224 litre (2) 0.08 litre (3) 0.448 litre (4) 1.12 litre
Ans. (3)

88
 Carbonyl Compounds, Grignard Reagent , Oxidation and Reduction

 
Sol. CH2 = C H M gBr + CH  CH  CH2  CH2
2 mole 1 mole 2 mole

2.62 224 ml
= .02 = .01 .02
131 22400
CH2=CH2 (in liter)  .02 × 22.4  0.448 liter

Q.32 In which one of the following reaction products are not correctly matched in
(1) RMgX +CO2 + Carboxylic acid
(2)H
(2) RMgX + C2H5OH Alkane
(3) RMgX + CH3CH2Cl Alkene

(4) RMgX + Cl O Ether

Ans. (3)
  H
Sol. (1) RMgx + CO2  R– C – O M gx   R– C –OH
|| ||
O O
X
(2) RMgx + C2H5OH  R–H + Mg
OCH
2 5

X
(3) RMgx + CH3–CH2–Cl  R–CH2–CH3 + Mg
Cl
(4) RMgx +

Cl O R O +MgxCl

O
Br2 Mg CH3–C–CH3 H
+

Q.33 CH3 – CH = CH2 (X) (Major)

Dry ether NH4Cl

End product of above reaction is :

CH2
(1) CH2 = CH – CH2 – C – CH 3 (2) CH 2 = CH – CH = C – CH 3
CH 3
OH

(3) CH2 = CH – CH2 – C – CH3 (4) CH2 = CH – CH2 – CH – CH 2 – OH

CH3 CH3
Ans. (2)
Br
CH3–CH=CH2   CH2  CH  CH2
2
Sol.
 |
Br

CH–CH=CH
2 2

MgBr O
CH–C–CH
3 3

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Carbonyl Compounds, Grignard Reagent , Oxidation and Reduction

CH3 CH3
H / 
CH–C–CH–CH=CH
3 2 2
    CH–C–CH–CH=CH
3 2 2


OH O Mgx

CH3

CH–C=CH–CH=CH
3 2

CH3MgX
Q.34 O Product is
NH4Cl

(1) Enantiomer (2) Diastereisomer (3) Meso (4) Achiral

Ans. (1)

 CH3 CH3
CH3Mgx
Sol. O +
NH4Cl
OH OH

(2)
O OH
C
O (3)
H RMgX(2moles)
H
Q.35 S
C
CH
(4)
Deprotonation will occur from the following positions:
(1) 1,2 (2) 1,3 (3) any two positions (4) 1,4
Ans. (1)


O OH O OMgx
C C
O O
H RMgx (2 mole) H
Sol. 

H  
S XMgS
C C

CH CH
More Acidic H react with R Mgx and gives Alkane.

90
 Carbonyl Compounds, Grignard Reagent , Oxidation and Reduction

H3O
+
RMgX
Q.36 RMgX + CH3CN (1) H3O
+ (2) will be
(1) 1ºROH (2) 2ºROH (3) 3ºROH (4) Alkene
Ans. (3)

R R
+
CH—C=N Mgx NH 4Cl
R Mgx + CH3 CN 3 CH3 —C=O
R Mgx
R R
Sol.
NHCl
4 +
CH3 —C—OH CH3 —C—O Mgx

R R

Q.37 How many moles of Grignard reagent will be required by one mole of given compound?
O
SH
HO C – OEt

C – Cl
CH2– CH2
O
Cl
(1) 7 (2) 6 (3) 8 (4) 5
Ans. (1)

1 mole of R Mgx
Sol. 1 mole of R Mgx
SH
O
2 mole of RMgx
NH2
C—oet

C—Cl

O
CH 2—CH2
2 mole of RMgx
Cl

1 mole of RMgx

Total No. of R Mgx consumed in above comp = 7

91
Carbonyl Compounds, Grignard Reagent , Oxidation and Reduction

Reduction

Q.38 A, A is :

(1) (2*)

(3) Both (1) and (2) (4) None of these

Ans. (2)

Sol.

x
Q.39  , X can be

(1) NH2 – NH2/ KOH (2) Zn – Hg/ HCl (3) Red P + HI (4*) All
Ans. (4)
Sol. All reagents are used to convert > C = O to > CH2

Q.40 In which case the reaction is most exothermic with H2 / Ni.

(1) (2*) (3) (4)

Ans. (2)

Sol. has maximum heat of hydrogenation and unstabiliity..

Misc /mixed
Q.41 The product formed in the reaction

is

(1) (BrCH2)3CCH2CH2C(CH2Br)3 (2)

(3) (4*)
92
 Carbonyl Compounds, Grignard Reagent , Oxidation and Reduction

Ans. (4)

Sol.

OXIDATION AND REDUCTION

Oxidation of organic compunds

Q.42 Which of the following can not be obtained when alkenes are oxidised with KMnO4 and then followed by acid hydrolysis?
(1) alkanoic acids (2*) alkanals (3) alkanones (4) carbon dioxide
Ans. (2)

Q.43 Which of the following will decolorise alkaline KMnO4 solution ?

(1) C3H8 (2) CH4 (3) CCl4 (4*) C2H4
Ans. (4)

Q.44 The best reagent to convert pent-3-en-2-ol into pent -3-en- 2-one is
(1) Acidic permanganate (2) Acidic dichromate
(3) Chromic anhydride in glacial acetic acid (4) Pyridinium chloro-chromate
Ans. (3)

Q.45 Secondary alcohols on heating with copper at 300ºC give

(1) Alkenes (2) Aldehydes (3*) Ketones (4) tert-alcohols
Ans. (3)
Sol. 2º alcohol on oxidation with Cu gives ketone.

KMnO / 
1-Butyne   X + Y
4
Q.46
Identify X and Y ?
(1) CH3CH2CH2COOH + O2 (2) CH3CH2COOH
(3*) CH3CH2COOH + CO2 + H2O (4) CH3CH2COCH3 + HCOOH
Ans. (3)
KMnO / H
Sol. CH3 – CH2 – C  CH   
4 
 CH3CH2COOH + CO2 + H2O

Reduction of organic compounds

Q.47 Which reducing agent, would you use to carry out the following transformation.



(1) LiAlH4 (2*) NaBH4 (3) Na/NH3 (4) DIBAL-H

Ans. (2)
Sol. NaBH4 can not reduces ester.

93
Carbonyl Compounds, Grignard Reagent , Oxidation and Reduction

Q.48 The reactivity order towards hydrogenation of the following compounds is

(I) CH3 – C  C – CH3 (II)

(III) (IV)

(1*) I > II > III > IV (2) II > III > IV > I (3) III > IV > II > I (4) IV > III > II > I
Ans. (1)
Sol. Rate of hydrogenation will decreases on increasing steric hinderance at  bond.

LiAlD
The product of the reaction Ph2C=O    is
4
Q.49 
H3O
(1*) Ph2CD(OH) (2) Ph2CH(OD) (3) Ph2CD(OD) (4) None
Ans. (1)

Q.50 Hydrogenation of benzoyl chloride in the presence of Pd / BaSO4 gives

(1) benzyl alcohol (2*) benzaldehyde (3) benzoic acid (4) phenol
Ans. (2)

Q.51 Which of the following reagent not convert carbonyl compound into alcohol ?
(1) DiBAL—H (2*) NH2—NH2/KOH (3) Na—Hg/HCl (4) LiAlH4
Ans. (2)
Sol. Wolf-kishwner reduction (NH2—NH2/KOH) give alkane after reduction of carbonyl compound.

Q.52 Which of the following reagents converts both acetaldehyde and acetone to alkanes ?
(1) Ni/H2 (2) LiAlH4 (3) I2/NaOH (4*) Zn–Hg/conc.HCl
Ans. (4)
Sol. It is fact.

Q.53 Stephen reduction (SnCl2 / HCl) converts cyanides to

(1*) Aldehydes (2) Ketones (3) Amines (4) Acids
Ans. (1)

Q.54 When benzoic acid is treated with LiAlH4, it forms

(1) Benzaldehyde (2*) Benzyl alcohol (3) Benzene (4) Toluene
Ans. (2)
LiAlH 4
Sol. Ph–COOH    Ph–CH2OH
Re duction

Q.55 In the following reaction C2H5OC2H5 + 4H 2X + H2O, X is

(1*) Ethane (2) Ethylene (3) Butane (4) Propane
Ans. (1)

Q.56 Reduction of an isonitrile gives a

(1) primary amine (2*) secondary amine
(3) tertiary amine (4) quaternary ammonium salt.
Ans. (2)

94
 Carbonyl Compounds, Grignard Reagent , Oxidation and Reduction

Q.57 Methane may be obtained from monochloromethane by

(1*) reduction with nascent hydrogen (Zn + HCI) (2) reduction with hydrogen (H2)
(3) heating with sodium metal in dry ether (4) hydrolysis with aqueous NaOH.
Ans. (1)

Q.58 The compound which does not react with lithium aluminium hydride is
(1) 3-penten-2-one (2) methyl benzoate (3*) 2 -pentanol (4) propanenitrile
Ans. (3)

Q.59 Reduction of methylbenzoate (C6H5COOCH3) to benzyl alcohol (C6H5CH2OH) can be accomplished using
(1) H2/Pd (2*) LiAIH4 (3) NaBH4 (4)Zn-Hg/HCI
Ans. (2)

Q.60 To reduce a nitroaldehyde to a nitroalcohol the reducing agent of choice is

(1) LiAlH4 (2*) NaBH4 (3) Molecular H2 (4) SnCl2
Ans. (2)

Q.61 An isocyanide on reduction with hydrogen in the presence of plantinum gives :

(1) amide (2) primary amine (3*) secondary amine (4) alcohol
Ans. (3)
H / Pt
Sol. R – NC 2 
 R – NH – CH3

Hydrolysis
Q.62 If 2-pentanone is reacted with NaBH4 followed by hydrolysis with D2O the product will be
(1*) CH3CH(OD) CH2CH2CH3 (2) CH3CD (OH) CH2CH2CH3
(3) CH3CH (OH) CH2CH2CH3 (4) CH3CD (OD) CH2CH2CH3
Ans. (1)

Q.63 In the reaction

CH3CN + 2H X Y, Y is

(1*) acetaldehyde (2) ethanamine (3) dimethylamine (4) acetone

Ans. (1)

Q.64 The substance that gives a primary amine on hydrolysis is

(1) nitroparaffin (2) alkyl cyanide (3) oxime (4*) alkyl isocyanide.
Ans. (4)

Mixed/Miscellaneous
Q.65 Identify a reagent from the following list which can easily distinguish between 1-butyne and 2-butyne.
(1) bromine, CCl4 (2) H2, Lindlar catalyst
(3) dilute H2SO4, HgSO4 (4*) ammonical Cu2Cl2 solution
Ans. (4)

Sol. CH3–CH2–CCH + NH4Cl + H2O

95
Carbonyl Compounds, Grignard Reagent , Oxidation and Reduction

EXERCISES-III
The following questions given below consist of an “Assertion” (A) and “Reason” (R) Type questions. Use the following
Key to choose the appropriate answer.
(1) If both assertion and reason are true and reason is the correct explanation of assertion.
(2) If both assertion and reason are true but reason is not the correct explanation of assertion.
(3) If Assertion is true but reason is false.
(4) If both assertion and reason are false.

Q. 1 Assertion: Bakelite is a phenol-formaldehyde resin formed from the base catalysed reaction.
Reason :.Basic nature increases the electrophicity of HCHO
Ans. (3)

Q.2 Assertion : Acetaldehyde undergoes aldol condensation instead of hydrate formation in the presence of
OH–/H2O.
Reason : Enolate of aldehyde is better nucleophile than OH–.
Ans. (1)
O– O
| ||
Sol. CH2=CH CH2–CH(better nucleophile)

Q.3 Assertion : The addition of ammonia derivatives on carbonyl compounds is carried in weakly acidic medium.
Reason : In weakly acidic medium attacking nucleophile is also protonated.
Ans. (3)

Q.4 Assertion : Acetaldehyde undergoes aldol condensation with dilute NaOH.

Reason : Aldehyde which do not contain -hydrogen undergoes aldol condensation.
Ans. (3)

Q.5 Assertion : Chloral forms a stable hydrate.

Reason : On treatment with an aqueous solution of NaOH, chloral undergoes hydrolysis to give chloroform and sodium
formate.
Ans. (2)
Sol. Hydrate of Chloral is more stable due to Intra-molecular H-bonding.
C
CCl3CHO NaOH || –ONa–
  CHCl3
+ H
O
Chloroform Sodium Formate
Therefore option (B) is correct.

Q.6 Assertion : CH3– adds to >C=O group irrevesibly but CN– ion adds reversibly.
Reason : CH3– ion is much stronger nucleophile than CN– ion.
Ans. (1)
Sol. CH3– ion is much stronger nucleophile than CN– ion CH3– add to >C = O group irreversible.

96
 Carbonyl Compounds, Grignard Reagent , Oxidation and Reduction

CH 3
(+) (–) |
Or – C – + CH3  – C –
|| |
O O

CN
– |
– C – + CH 3 – C–
|| |
O O

Therefore option (A) is correct.

Q.7 Assertion : Acetaldehyde reduces Fehling’s solution but benzaldehyde does not.
Reason : Acetaldehyde is a stronger reducing agent than benzaldehyde.
Ans. (1)
Sol. Acetaldehyde is a stronger reducing agent than benzaldehyde so acetaldehyde reduces Fehling’s solution but
benzaldehyde does not. Therefore option (A) is correct.

Q.8 Assertion : Both Grignard reagents and dialkylcadmium react with acid chlorides to form tert-alcohols.
Reason : Grignard reagents are more reactive than dialkyl cadmium.
Ans. (2)
Sol. Grignard reagents react with acid chloride to form test-alcohols. but dialkyl cadmium react with acid chloride to form
ketone. Reactivity of organometallic compounds on the electro positive character of the metal Mg metal is more
electropositive than so the grignard reagent (RMgx) are more reactive than dialkyl-cadmium.
Therefore Assertion is false but reason is true option (D) is correct.

Q.9 Assertion : Benzonitrile is prepared by the reaction of chlorobenzene with potassium cyanide.
Reason : Cyanide (CN–) is a strong nucleophile.
Ans. (3)

Q.10 Assertion : Acetaldehyde on treatment with alkaline gives aldol.

Reason : Acetaldehyde molecules contains  hydrogen atom.
Ans. (1)
Sol. Carbonyl compounds having -hydrogen atom condenses to produce aldol in presence of alkali.

CH 3  C H  HCH 2 CHO   
dil. NaOH
||
O
Acetaldehy de

Q.11 Assertion : Aldol condensation can be catalysed both by acids and bases.
Reason : -Hydroxy aldehydes or ketones readily undergo acid catalysed dehydration.
Ans. (2)
Sol. Both carbanions (formed in presence of base) and enol form (formed in presence of an acid) act as nucleophiles and
hence add on the carbonyl group of aldehydes and ketones to give aldols.

Q.12 Assertion : Acetylene on treatment with alkaline KMnO4 produce acetaldehyde.

Reason : Alkaline KMnO4 is a reducing agent.
Ans. (4)

Q.13 Assertion : R  C  0  is more stable than R  C   0 .

Reason : Resonance in carbonyl compound provides C+ and O–.
Ans. (2)

97
Carbonyl Compounds, Grignard Reagent , Oxidation and Reduction

Sol. Both carbon and oxygen are nonmetals and try to complete their octet. In R  C  O  each has complete octet
whereas in R  C   O, carbon atom has in complete octet.

Q.14 Assertion : CH 3 CHO reacts with NH 3 to form urotropine.

Reason : Urotropine is used as medicine in case of urinary troubles.
Ans. (4)
Sol. HCHO reacts with NH 3 to form urotropine 6 HCHO  4 NH 3  (CH 2 )6 N 4  6 H 2 O

Q.15 Assertion : 2, 2–Dimethyl propanal undergoes Cannizzaro reaction with concentrated NaOH.
Reason : Cannizzaro is a disproportionation reaction.
Ans. (2)
Sol. Aldehydes which do not contain -hydrogens undergo Cannizzaro reaction.

CH 3
|
H 3 C  C   CHO
|
CH 3
2, 2 dimethyl p ropanal (no  hydrogen)

GRIGNARD REAGENT

Q.16 Assertion : In the bromination of propane and 2-Methyl propane. 2-Methyl propane gives more stable transition state.
Reason : 3° C–H bond is weaker than 2° C – H bond.
Ans. (1)
Sol. Bromine is more selective and reactivity of bromine towards hydrogen is 3º H > 2º H > 1º H.

Q.17 Assertion : The preparation of G.R. occurs in solution phase.

Reason : The reaction will be explosive in solid phase. G.R. is stable only in solution phase.
Ans. (1)
Sol. The preparation of G.R. occurs in solution phase because reaction of G.R. will be explosive in solid phase. G.R. is stable
only in solution phase.

Q.18 Assertion : n-butane on heating in presence of AlCl3 gives Isobutane

Reason : n-butane and isobutane are isomers.
Ans. (2)

Q.19 Assertion : Alkanes undergo free radicals substitution reaction

Reason : Alkanes undergo homolytic fission.
Ans. (2)

Q.20 Assertion : CH3MgBr is prepared in cold aqueous solution.

Reason : Water molecule stablise grignard molecule by H–Bonding.
Ans. (4)
Sol. G.R. can not prepared in aqueous solution due to acid base reaction.

98
 Aldehydes and Ketones (Carbonyl Compounds)

EXERCISES-IV

Q.1 Which of the following reactions will not result in the formation of carbon-carbon bonds? [CBSEAIPMT 2010]
(1) Friedal - crafts Acylation (2) Reimer - Tiemann reaction
(3) Cannizzaro reaction (4) Wurtz reaction
Ans. (3)
Sol. In Cannizzaro reaction oxidation and reduction both taken place

Q.2 Aldehydes and ketones are differentiated by using : [CPMT 2010]

(1) NaOH/I2 (2) NaHSO3 (3) AgNO3/NH4OH (4) NH2·NH2
Ans. (3)
Sol. Aldehydes and ketones are differentiated by AgNO | NH4OH

Q.3 Arrange the following compounds in increasing order of their reactivity in nucleophilic addition reactions. Ethanol (I),
Propanol (II), Propanone (III), Butanone (IV) [AFMC 2010]
(1) Cu2O (2) Cu (3) Cu3O (4) CuO
Ans. (1)

Q.4 The major organic product formed from the following reaction. [AFMC 2010]

O
(i) CH3NH2
? is :
(ii) LiAlH4 (iii) H2O

O–NHCH3 NHCH3 NHCH3

(1) (2) (3) (4)
NHCH3 OH H
Ans. (2)
O N–CH3 NH–CH3
 3 2 


 ii LiAlH 4 
i CH NH
Sol.
 iii H 2O

Q.5 Clemmensen reaction of a ketone is carried out in the presence of which of the following?
(1) H2 and Pt as catalyst (2) Glycol with KOH [CBSEAIPMT 2011]
(3) Zn-Hg with HCl (4) LiAlH4
Ans. (3)
Sol. Clemmensen reaction of a ketone is carried out in the presence of Zn-Hg with HCl

99
Aldehydes and Ketones (Carbonyl Compounds)

Q.6 Which one is a nucleophilic substitution reaction among the following? [CBSEAIPMT 2011]
(1) CH3CHO + HCN  CH3CH(OH)CN

(2) CH3– CH = CH2 – H2O H CH 3  CH  CH 3
|
OH

(3) RCHO + R’MgX  R  CH  R '

|
OH

CH 3 CH 3
| |
(4) CH3  CH 2  CH  CH 2 Br  NH 3  CH 3  CH 2  CH  CH 2 NH 2

Ans. (4)
Sol. In substitution reaction one group is substituted by another group.

Q.7 The order of reactivity of phenyl magnesium bromide (PhMgBr) with the following compounds :
[CBSEAIPMT 2011]

CH3 CH3 Ph
C= O , C= O and C=O
H H3C Ph
(1) I > III > II (2) I > II > III (3) III > II > I (4) II > I > III
Ans. (2)
Sol. order of reactivity towards Ni–
CH3 – CHO > (CH3)2CO > (Ph)2CO

Q.8 Predict the product in the given reaction. [CBSE AIPMT 2012]

CHO

50
% 
KOH

Cl

CH2OH CH2OO¯ CH2OH OH

(1) + (2) +

Cl Cl OH OH

CH2OH COO¯ CH2OH COO¯

(3) + (4) +

Cl Cl OH OH
Ans. (3)

CHO COOK CH2OH

Sol. 
50% KOH
cannizzaro R n
 +
x

Cl Cl Cl
100
 Aldehydes and Ketones (Carbonyl Compounds)

Q.9 Acetone is treated with excess of ethanol in the presence of hydrochloric acid. The product obtained is:
[CBSEAIPMT 2012]
O O

(1) CH 3CH2CH2 – C – CH3 (2) CH3CH2 CH2 – C – CH2CH2CH3

OH OC2H5
(3) (CH3)2C (4) (CH3)2C
OC2H5 OC2H5
Ans. (4)
CH3 CH3 O – C2H5
Sol. C=O 
C2 H5OH|HCl
 C
CH3 CH3 O – C2H5

Q.10 Acetone is treated with excess of ethanol in the presence of hydrochloric acid. The product obtained is :
[JIPMER-2013,AIPMT 2012]
O O

(1) CH3CH2CH2 – C – CH3 (2) CH3CH2CH2 – C – CH2CH2CH3

OH OC2H5
(3) (CH3)2 C (4) (CH3)2 C
OC2H5 OC2H5
Ans. (4)
OC 2H 5
H OC2H 5 HCl
(CH3)2 C = O + (CH 3) 2 C
Sol. OC 2H 5
Acetone H OC 2H 5
Acetal

Q.11 In the following reaction : [NEET Karnataka 2013]

H2SO4
HC CH Hg 2+
'P'
Product ‘P’ will not give
(1) Tollen’s reagent test (2) Brady’s reagent test (3) Victor Meyer test (4) Iodoform test.
Ans. (3)

CH2 CH3
Tautomerises
H2SO4
Sol. HC CH Hg2+ CHOH CHO
Vinyl alcohol (P)
Acetaldeyde

Q.12 Arrange the following compounds in increasing order of reactivity towards nucleophilic addition reaction.
[AIIMS 2013]
(I) C6H5COCH3 (II) CH3CO – C2H5
(III) C6H5CHO (IV) Cl – CH3– CHO
(1) IV > III > II > I (2) IV > II > III > I (3) I > II > III > IV (4) III > IV > II > I
Ans. (1)
Sol. Two electron releasing alkyl groups in ketons make the carbon less electron deficient in comparison to aldehydes.
Therefore, ketones are less reactive than aldehyde towards nucleophilic addition reactions.
Aromatic aldehydes and ketones are less reactive than corresponding aliphatic aldehyde and ketones due to +R effect of
benzene ring.
Aromatic aldehyde are more reactive than alkyl aryl ketones which in turn are more reactive than diarly ketones.
Since – Cl is more electronegative than carbon, it increases the reactivity.

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Aldehydes and Ketones (Carbonyl Compounds)

So the order is
(IV) Cl – CH3– CHO > (III) C6H5CHO > (II) CH3CO – C2H5 > (I) C6H5COCH3

Q.13 Assertion : Mixture of Benzaldehyde and acetaldehyde in hot alkaline medium gives cinnamaldehyde.
Reason : Benzaldehde is strong electrophile than acetaldehyde. [AIIMS 2013]
(1) Both assertion and reason are true statements and reason is the correct explanation of assertion
(2) Both assertion and reason are true statements and reason is not the correct explanation of assertion
(3) Assertion is true but reason is a false statement
(4) Both assertion and reason are false statement
Ans. (1)
Sol. This is a Claisen - Schmidt reaction.

C6H5 – C – H + CH2CHO
Benzaldehyde Acetaldehyde
(Electrophile (Nucleophile
as it does not as it contains
-hydrogen) -hydrogen)

OH H
C6H5 – CH – CH + CHO
Aldol (unstable)
+
,H
– H2O

C6H5 CH = CHCHO
Cinnamaldehyde

Q.14 If acetyl chloride is reduced in the presence of BaSO4 and Pd, then [JIPMER 2013]
(1) CH3CHO is formed (2) CH3CH2OH is formed (3) CH3COOH is formed (4) CH3COCH3 is formed
Ans. (1)
H2–Pd/BaSO4
Sol. CH3COCl (Rosenmund
CH3CHO + HCl
reduction)

Q.15 Which one is most reactive towards nucleophilic addition reaction? [AIPMT 2014]

CHO CHO
CHO COCH3
(1) (2) (3) (4)

CH3 NO2

Ans. (4)
Sol. Aromatic aldehydes are more reactive than alkyl aryl ketones. Electron withdrawing group (–NO2) increases the reactivity
towards nucleophilic addition reactions whereas, electron donating group (–CH3) decreases the reactivity towards
necleophilic addition reactions. Therefore, the order is

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 Aldehydes and Ketones (Carbonyl Compounds)

CHO CHO CHO COCH3

> > >

NO2 CH3

Q.16 Which does not give Cannizzaro reaction ? [AIIMS 2014]

(1) HCHO (2) C6H5C – CHO (3) Ph – CHO (4) Ph–CH2–CHO
O
Ans. (2)
Sol. Aldehydes having no. -H atoms undergo Cannizzaro reaction. Hence, all the given compounds (except PhCH2CHO has
-H atom) will undergo Cannizzaro reaction.

Q.17 In Clemmensen reduction, carbonyl compound is treated with : [AIIMS 2014]

(1) zinc amalgam + HCl (2) sodium amalgam + HCl
(3) zinc amalgam + HNO3 (4) sodium amalgam + HNO3
Ans. (1)

Sol. In Clemmensen reduction, the carbonyl group of aldehydes and ketons is reduced to CH2 group on treatment with zinc

zinc amalgam and concentrated hydrochloric acid.

Zn-Hg
CH = O CH 2 + H 2O
HCl

Q.18 When aniline reacts with oil of bitter almonds (C6H5CHO) condensation takes place and benzal derivative if removed. This
is known as : [JIPMER 2014]
(1) Schiff’s base (2) Benedict’s reagent (3) Millon’s base (4) Schiff’s reagent
Ans. (1)
Sol. Benzaldehyde reacts with primary aromatic amines to form Schiff’s base.
C6H5 CH = O + C 6H 5CH2 C 6H 5CH = NC6 H5 + H2 O
Benzaldehyde Aniline Schiff's base

Q.19 Reaction of a carbonyl compound with one of the following reagents involves nucleophilic addition followed by elimination
of water. The reagent is : [AIPMT 2015]
(1) Hydrazine in presence of feebly acidic solution
(2) Hydrocyanic acid
(3) Sodium hydrogen sulphite
(4) a Grignard reagent
Ans. (1)
Sol. Carbonyl compounds react with ammonia derivative in weakly acidic medium as follows:

OH
C = O + H 2N – Z C
Ammonia NHZ
Derivative
+
H – H2O

C=N–Z

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Aldehydes and Ketones (Carbonyl Compounds)

Q.20 The following conversion : [AIIMS 2015]

H
Dil. NaOH
CH3– C = O+ H – CH2 CHO
H
CH 3– C – CH2CHO

OH

is known as
(1) Cannizzaro reaction (2) Aldol condensation (3) polymerisation (4) benzoin condensation
Ans. (2)

Q.21 Which can be used to distinguish aldehydes and ketons? [JIPMER 2015]
(1) Fehling’s solution (2) H2SO4 solution (3) NaHSO3 (4) NH3
Ans. (1)
Sol. All aldehydes give red ppt. with Fehling’s solution but ketones do not reduce Fehling’s solution.

Q.22 Nucleophilic attack on carbonyl carbon changes its hybridisation form: [JIPMER 2015]
(1) sp to sp2 (2) sp2 to sp3 (3) sp3 to sp2 (4) sp to sp3
Ans. (2)

sp3
:

Nu– H+
C=O C – O– C – OH
Sol.

sp2 Nu Nu

Q.23 The correct structure of the product A formed in the reaction. [NEET-II 2016]

  A is :
2H (gas,1atm.)
Pd/carbon,ethanol

OH OH OH
O
+
(1) (2) (3) (4)

Ans. (2)

O
O

 
2H (gas,1atm.)
Sol. Pd/carbon,ethanol

C = C bond is reduced faster than C = O bond with H2(Pd – C).

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 Aldehydes and Ketones (Carbonyl Compounds)

Q.24 The correct order of strengths of the carboxylic acids. [NEET -II 2016]

COOH COOH COOH

O
O
I II III
is :
(1) I > II > III (2) II > III > I (3) III > II > I (4) II > I > III
Ans. (2)
Sol. Acidic strength  – I effect
As oxygen is more electronic withdrawing (II) and (III) show greater –I effect than (I). Thus (I) is least acidic. Out of (II)
and (III), (II) is more acidic than (III) as distance of O increases form – COOH group and acidic strength decreases.

Q.25 Ease of nucleophilic addition in the given compounds is : [AIIMS 2016]

COCH3
O O

CH3–C–H CH3–C–CH3
I II III
(1) I > III > II (2) II > III > I (3) II > I > III (4) III > I > II
Ans. (2)
Sol. Aromatic aldehydes and ketons are less reactive than the corresponding aliphatic analogues towards nucleophilic addition
reactions due to the +R effect of benzene ring. Further, aldehydes are more reactive than ketones due to +I effect and steric
effect of alkyl group.
Therefore, the ease of nucleophilic addition will follow the order.
COCH3
O O
CH3–C–H > CH3–C–CH3 >

Preparation ofAldehydes and Ketones.

Q.26 Benzaldehyde can be prepared from : [AIIMS 2016]
O
(1) Pd/BaSO4
C – Cl + H2

O
(2) C – NH2 + Br2 + KOH

Sn/HCl
(3) C N + H2

(4) N2+Cl– + H2 O

Ans. (1)

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Aldehydes and Ketones (Carbonyl Compounds)

O
Sol. Pd/BaSO4 CHO + HCl
C – Cl + H2

C – NH2 + Br2 + KOH NH2 + K2CO3 + 2KBr + 2H2O

Sn/HCl
C N + H2 CH2NH2

N2+Cl– + H2 O OH + N2 + HCl

Q.27 Consider the reactions. [NEET 2016]

+
X Cu [Ag(NH3)2 ]
A Siliver mirror
(C2H6O) 573K –OH, Observed

–OH,
Y
NH2NHCONH2
Z

Identify, A, X, Y and Z.
(1) A- Methoxymethane, X - Ethanol, Y-Ethanoic acid, Z-semicarbazide.
(2) A- Ethanal, X-Ethanol, Y-But-2-enal, Z-semicarbazone.
(3) A-Ethanol, X-Acetaldehyde, Y-Butanone, Z- Hydrazone.
(4) A-Methoxymethane, X-Ethanoic acid, Y-Acetate ion, Z-Hydrazine.
Ans. (2)

+
[Ag(NH3)2]
– Silver mirror
(OH )
Cu,573K
Sol. CH3CH2OH CH3CHO
Ethanol Ethanal
Aldol
(X) (A)
condensation
(OH–)
OH
CH3–CH–CH2CHO

CH3–CH=CH–CHO
But-2-enal
(Y) O
CH3C = O + H2 N–NH–C–NH2

H –H2O
O
CH3– CH= N–NH–C–NH2
Semicarbazone
(Z)

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 Aldehydes and Ketones (Carbonyl Compounds)

Nomenclature and Structure of Carbonyl Group

Q.28 The correct statement regarding a carbonyl compound with a hydrogen atom on its alpha-carbon, is
[NEET Phase I-2016]
(1) carbonyl compound with a hydrogen atom on its alph-carbon rapidly equilibrates with its corresponding enol and
this process is known as carbonylation.
(2) 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.
(3) a carbonyl compound with a hydrogen atom on its alpha-carbon never equilibrates with its corresponding enol.
(4) a carbonyl compound with a hydrogen atom on its alpha-carbon rapidly equilibrates with its corresponding enol and
this process is known as aldehyde-ketone equilibration.
Ans. (2)
Sol. Keto-enol tautomerism :

O OH
–C–C– –C=C–
H enol - form
Keto-form

Q.29 Which of the following reagents would distinguish cis-cyclopenta-1,2-diol form the trans-isomer?
[NEET Phase 1-2016]
(1) MnO2 (2) Aluminium isopropoxide (3) Acetone (4) Ozone
Ans. (3)

OH CH3
+O=C
Sol. O H CH3
Acetone
cis-Cyclopneta-1,2-diol
O CH3
C
O CH3

Trans-isomer does not react with acetone.

Q.30 Of the following, which is the product formed when cyclohexanone undergoes aldol condensation followed by heating?

(1) (2) (3) (4)

OH
O OH O O
[NEET-2017]
Ans. (2)

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Aldehydes and Ketones (Carbonyl Compounds)

O O
H
OH + H2O
H
O

O O
OH O
H2O

Sol.
–H2O
O

Q.31 The compound C7H8 undergoes the following reactions:

C7H8 3Cl2 /
 A 
Br2 /Fe B 
Zn /HCl
C
The product 'C' is [NEET - 2018]
(1) 3-bromo-2,4,6-trichlorotoluene (2) o-bromotoluene
(3) m-bromotoluene (4) p-bromotoluene
Ans. (3)

CH3 CCl3 CCl3

Sol. 3Cl2 Br2
Fe
Br
(C7H8 ) (A) (B)

Zn HCl

CH3

Br
(C)

So, the correct option is (3).

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 Aldehydes and Ketones (Carbonyl Compounds)

Q.32 Compound A, C8H11O, is found to react with NaOI (produced by reacting Y with NaOH) and yields a yellow precipitate with
characteristic smell. A and Y are respectively [NEET - 2018]

CH–CH 3 and I 2
(1) (2) CH2–CH2–OH and I2
OH

CH3

(3) H3C CH 2–OH and I 2 (4) CH OH and I2

3

Ans. (1)
Sol. Option (1) is secondary alcohol which on oxidation gives phenylmethyl ketone (Acetophenone). This on reaction with I2
and NaOH form iodoform and sodium benzoate.
2NaOH + I2  NaOI + NaI + H2O

NaOI
CH–CH3 CH–CH3

OH O
Acetopehnone
I2 NaOH

COONa + CHI3
Iodoform
Sodium benzoate (Yellow ppt.)

Q.33 CH3 – CH=CH –CH = N – CH3 LiAIH 4

[AIIMS - 2018]
What is final product
(1) CH3– CH2 – CH 2– CH2– NH – CH3 (2) CH3– CH = CH – CH 2– NH – CH 3
(3) CH3 – CH2 – CH2 – CH – N – CH3 (4) CH3– CH = CH – CH2– OH
Ans. (2)
LiAIH
Sol. CH3–CH=CH –CH=N–CH3 CH3–CH=CH –CH2 –NH –CH3
4

LiAIH4 reduces imine into Amine but does not reduces C=C double bond.

Q.34 Na/NH3 Cl2/hv [AIIMS - 2018]

Ph – CH 2 – CH 2 – C C – CH 3
Ph – CH(Cl) – CH2 H
(1) Ph – CH(Cl) – CH 2 CH3 (2)
C=C
C=C
H CH 3
H H
(3) Ph – CH2 – CH(Cl) – CH = CH – CH 3 (4) None of these
Ans. (2)
Sol.

Na/NH3
Ph – CH2– CH2– C C – CH2 Ph – CH(Cl) – CH 2 CH3
C=C
H H
Cl2/h

Ph – CH(Cl) – CH2 H
C=C
H CH

109
Aldehydes and Ketones (Carbonyl Compounds)

O
C
Br 2 product
Q.35 NaOH [AIIMS - 2018]

O O O O
C CH2 Br C C Br C
(1) (2) (3) (4)
Br
CH2 Br

Ans. (1)
Sol.

O O O
C C CH2 +Br–Br C CH2–Br
Br2
NaOH

-Halogenation of carbonyl compound by Br2 in presence of alkali medium

H2/Pd/C
Q. 36 CH3 C No. of stereoisomerism [AIIMS - 2018]
O
(1) 2 (2) 4 (3) 8 (4) 6
Ans. (1)
Sol.
CH3 CH C H2/Pd/C
CH3 C
O OH
Total number of stereo isomer = 2

Q.37 Give correct sequences of raction for following conversion : [AIIMS -2018]

O O
C OCH3 C H

(1) DIBAL– H, NaBH4, H3O/ (2) H3O/, NaBH4, DIBAL – H

(3) NaBH4, DIBAL– H, H3O/ (4) DIBAL–H, H3O/, NaBH4
Ans. (3)

O O O O
C OCH3 C OCH3 C H C H

NaBH4 DIBAC–H

O OH OH OH

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 Aldehydes and Ketones (Carbonyl Compounds)

Q.38 What are the suitable reagent for following conversion ? [AIIMS - 2018]

CH3 COOH

NO2
Br
(1) Br2/FeBr3, KMnO4, HNO3 / H2SO4 (2) KMnO4, Br2 / FeBr3, HNO3
(3) HNO3, Br2 / FeBr3, KMnO4 (4) HNO3, KMnO4, Br2 / FeBr3
Ans. (1)
Sol.

CH3 CH3 COOH COOH5

Br2/FeBr3 KMnO4 HNO3

NO2
Br Br Br

111