Aldehydes and Ketones

Exercise:1
Q. 1 The formation of cynohydrin from a ketone is an example of
(A) Electrophilic addition (B) Nucleophilic addition
(C) Nucleophilic substitution (D) Electrophilic substitution

Q.2 The enolic form of acetone contains :

(A) 9 sigma bonds, 1 pi bond and 2 lone pairs
(B) 8 sigma bonds, 2 pi bonds and 2 lone pairs
(C) 10 sigma bonds, 1 pi bond and 1 lone pair
(D) 9 sigma bonds, 2 pi bonds and 1 lone pair

Q.3 m-chlorobenzaldehyde on reaction with conc. KOH at room temperature gives:

(A) Potassium m-chlorobenzoate and m-hydroxybenzaldehyde
(B) m- hydroxybenzaldehyde and m- chlorobenzyl alcohol
(C) m-chlorobenzyl and m-hydroxybenzyl alcohol
(D) Potassium m-chlorobenzoate and m-chlorobenzyl alcohol

Q.4 Hydrogenation of benzoyl chloride in the presence of Pd and BaSO4 gives:

(A) Benzyl alcohol (B) Benzaldehyde
(C) Benzoic acid (D) Phenol

Q.5 An organic compound C3H6O does not give a precipitate with 2,4-Dinitrophenyl hydrazine reagent and
does not react with metallic sodium. It could be:
(A) CH3CH2CHO (B) CH3COCH3
(C) CH2= CH–CH2OH (D) CH2= CH –O –CH3

Q.6 Under Wolff Kishner reduction conditions, the conversions which may be brought about is?

(A) Benzaldehyde into Benzyl alcohol

(B) Cyclohexanol into Cyclohexane
(C) Cyclohexanone into Cyclohexanol
(D) Benzophenone into Diphenylmethane

Q.7 In the reaction, P is

CH3
SeO2
CO P + Se + H2O
CH3
(A) CH3COCHO (B) CH3COOCH3
(C) CH3COCH2OH (D) None

1
-------------------------------------------------------------------------------------------------------
G KISHORE BABU, SriChaitanya Co School, VVNAGAR
 OH – –
Q.8 In the Cannizzaro reaction given below, 2Ph –CHO   Ph –CH2OH + PhCO2 the slowest step is
:
(A) the attack of OH– at the carbonyl group
(B) the transfer of hydride to the carbonyl group
(C) the abstraction of proton from the carboxylic acid
(D) the deprotonation of Ph–CH2OH

Q.9 Among the given compounds, the most susceptible to nucleophilic attack at the carbonyl group is-

(A) MeCOCl (B) MeCHO

(C) MeCOOMe (D) MeCOOCOMe

Q.10 In a Cannizzaro reaction the intermediate which is the best hydride donor is:

H H
– –
(A) C6H5 – C – O (B) C6H5 – C – O
OH O–

H H
–
O O–
(C) O– (D) O–
O2N CH3O

Q.11 CH3CHO + H2NOH  CH3 – CH = N – OH. The above reaction occurs at :

(A) pH = 1 (B) pH = 4.5
(C) Any value of pH (D) pH = 12

Q.12 Among the following compounds, which will react acetone to give a product containing > C = N –
(A) C6H5NH2 (B) (CH3)3N
(C) C6H5NHC6H5 (D) C6H5NHNH2

Q.13 The product obtained via oxymercuration (HgSO4 – H2SO4) of 1- butyne would be
O
(A) CH3CH2 –C –CH3 (B) CH3CH2CH2CHO
(C) CH3CH2CHO + HCHO (D) CH3CH2COOH + HCOOH

Q.14 Which of the following will undergo aldol condensation:

(A) Acetaldehyde (B) Propanaldehyde
(C) Benzaldehyde (D) Trideutero acetaldehyde

Q.15 Which of the following will react with water:

(A) CHCl3 (B) Cl3CCHO
(C) CCl4 (D) ClCH2CH2Cl

2
-------------------------------------------------------------------------------------------------------
G KISHORE BABU, SriChaitanya Co School, VVNAGAR
Q.16 A new carbon-carbon bond formation is possible in:
(A) Cannizzaro reaction (B) Friedel-Crafts alkylation
(C) Clemmensen reduction (D) Reimer-Tiemann reaction

Q.17 Which of the following has the most acidic hydrogen:

(A) 3-hexanone (B) 2, 4-hexanedione
(C) 2,5-hexanedione (D) 2, 3-hexandione

Q.18 The appropriate reagent for the following transformation:

O
CH2CH3
CH3
HO HO
(A) Zn (Hg), HCl (B) NH2NH2, OH–
(C) H2/Ni (D) NaBH4

Q.19 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

Q.20 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. HCl and sodium acetate gives
a product C. Identify the structure of C.
(A) CH3CH2CH= NNHCONH2 (B) CH3 – C = NNHCONH2

CH3

(C) CH3 – C = NCONHNH2 (D) CH3CH2CH= NCONHNH2

CH3
Q.21 1- propanol and 2- propanol can be best distinguished by:
(A) Oxidation with alkaline KMnO4 followed by reaction with Fehling solution
(B) Oxidation with acedic dichromate followed by reaction with Fehling solution
(C) Oxidation by heating with copper followed by reaction with Fehling solution
(D) Oxidation with concentrated H2SO4 followed by reaction with Fehling

CHO OHC
(i) NaOH (excess) 100°C
Q.22
+
(ii) H /H2O
CHO OHC
any one of the products formed is:

3
-------------------------------------------------------------------------------------------------------
G KISHORE BABU, SriChaitanya Co School, VVNAGAR
 CH2OH
COOH HOOC CH2OH

(A) (B)
COOH HOOC CH2OH
CH2OH

CH2OH COOH O
O
(C) (D)
COOH CH2OH
O
O
OCOCH3
P Acidic
Q.23  Products formed by P & Q can be differentiated by :
 
OCOCH3 Hydrolysis
Q

(A) 2,4 DNP (B) Lucas reagent (ZnCl2) conc. HCl

(C) NaHSO3 (D) Fehlings solution
Q.24 The order of reactivity of phenyl Magnesium Bromide with the following compounds is :

O O O

H3C CH3 H3C Ph

H Ph

(I) (II) (III)

(A) II > III > I (B) I > III > II

(C) II > I > III (D) All react with the same rate

COOH
CHO CH3COONa
Q.25 + X   

MeO MeO
What is X?
(A) CH3COOH (B) BrCH2, COOH (C) (CH3CO)2O (D) CHO –COOH

Q.26 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

Q.27 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:

4
-------------------------------------------------------------------------------------------------------
G KISHORE BABU, SriChaitanya Co School, VVNAGAR
 CO2H
(A) CHO (B) CHO (C) COOH (D)
CO2H

Q.28 Statement-1 : Glucose gives a reddish-brown precipitate with Fehling's solution.

because
Statement-2 : Reaction of glucose with Fehling's solution gives CuO and gluconic acid.
(A) Statement-1 is true, Statement-2 is True; Statement-2 is a correct explanation for Statement-1
(B) Statement-1 is True, Statement-2 is True; Statement-2 is NOT a correct explanation for Statement-1.
(C) Statement-1 is True, Statement-2 is False.
(D) Statement-1 is False, Statement-2 is True.

Paragraph for Question Nos. 29 to 31(3 questions)

Reimer-Tiemann reaction introduces an aldehyde group, on to the aromatic ring of phenol, ortho to the
hydroxyl group. This reaction involves electrophilic aromatic substitution. This is a general method for
the synthesis of substituted salicylaldehydes as depicted below:


O Na OH
OH
CHO CHO
aq. HCl
(I)
(Intermediate)
CH3 CH3
CH3

(I) (II) (III)

Q.29 Which one of the following reagents is used in the above reaction? [JEE 2007]
(A) aq.NaOH + CH3Cl (B) aq. NaOH +CH2Cl2
(C) aq. NaOH + CHCl3 (D) aq. NaOH + CCl4

Q.30 The electrophile in this reaction is:

(A) : CHCl (B) +CHCl2
(C) : CCl 2 (D) : CCl3

Q.31 The structure of the intermediate I is: [JEE 2007]

   
O Na O Na O Na O Na
CH2Cl CHCl2 CCl3 CH2OH
(A) (B) (C) (D)

CH3 CH3 CH3 CH3

5
-------------------------------------------------------------------------------------------------------
G KISHORE BABU, SriChaitanya Co School, VVNAGAR
Q.32 Match the compounds/ion in column-I with their properties/reaction in Column- II. Indicate your answer
by darkening the appropriate bubbles of the 4 × 4 matrix given in the ORS.
[JEE 2007]

Column-I Column-II
(A) C6H5CHO (P) gives precipitate with
2,4- dinitrophenylhydrazine
(B) CH3C CH (Q) gives precipitate with AgNO3
(C) CN– (R) is a nucleophile
(D) I– (S) is involved in cyanohydrin formation

Paragraph for Question No.33 to 35

In the following reaction sequence, products I, J and L are formed. K represents a reagent.
1. Mg / ether Cl
Hex-3-ynal 1 . NaBH 4
  I  2. CO2


K
 J  Me 
H2
 L
2. PBr3 3. H3O Pd / BaSO 4
O quinoline

Q.33 The structure of the product I is:

Me
(A) Me Br (B) Br

(C) Me Br (D) Me Br

Q.34 The structures of compounds J and K, respectively, are:

(A) Me COOH & SOCl2 (B) Me O & SO2Cl2

Me
(C) COOH & SOCl2 (D) Me COOH & CH3SO2Cl

Q.35 The structure of product L is:

(A) Me CHO (B) Me CHO

CHO
(C) Me (D) Me CHO

6
-------------------------------------------------------------------------------------------------------
G KISHORE BABU, SriChaitanya . Co School, VVNAGAR
Paragraph for Question No.36 to 38

A tertiary alcohol H upon acid catalysed dehydration gives a product I. Ozonolysis of I leads to
compounds J and K. Compound J upon reaction with KOH gives benzyl alcohol and a compound L,
whereas K on reaction with KOH gives only M.
O
H3C
Ph
M=
H
Ph

Q.36 Compound H is formed by the reaction of :

O O
(A) + PhMgBr (C) + PhCH2MgBr
Ph CH3 Ph CH3
O O Me
(C) + PhCH2 MgBr (D) +
Ph H Ph H Ph MgBr

Q.37 The structure of compound I is:

Ph CH3 H3C Ph
(A) (B)

H Ph H Ph
Ph CH3 H3C CH3
(C) (D)

H CH2Ph Ph H

Q.38 The structures of compounds J, K and L, respectively are :

(A) PhCOCH3, PhCH2COCH3 and PhCH2COO– K+
(B) PhCHO, PhCH2CHO and PhCOO– K+
(C) PhCOCH3, PhCH2CHO and CH3COO– K+
(D) PhCHO, PhCOCH3 and PhCOO– K+

Paragraph for Question Nos. 39 to 41

A carbonyl compound P, which gives positive iodoform test, undergoes reaction with MeMgBr
followed by dehydration to give an olefin Q. Ozonolysis of Q leads to a dicarbonyl compound R, which
undergoes Intramolecular aldol reaction to give predominantly S.

7
-------------------------------------------------------------------------------------------------------
G KISHORE BABU, SriChaitanya Co School, VVNAGAR
 
1. O 3 1. OH
P 1
. MeMgBr
  Q  

 R   S
2. H , H2O 2. Zn,H2O 2. 
3. H2SO 4 , 
Q.39 The structure of the carbonyl compound P is:
Me
(A) (B)

O Me O Me
O

(C) (D)

O Et Me

Q.40 The structure of the products Q and R, respectively, are

O

Me H
(A) , COMe
Me
Me Me Me
O

(B) H
,
COMe
Me
Me
Me Me
O

H
(C) ,
CHO
Et
Me
Me Et
Me O

CH3
(D) ,
CHO
Me
Me Et

Q.41 The structure of the product S is :

(A) (B)
O
Me Me Me
8
-------------------------------------------------------------------------------------------------------
G KISHORE BABU, SriChaitanya Co School, VVNAGAR
 O
O
Me
(C) (D)

Me Me

EXERCISE-2

NaOC 2H5
Q.1 C6H5 –CHO + CH3 –COOC2H5    (D).
C2H5OH and heat

CH3CH2
(i) KCN/H2SO4
Q.2 C=O D
H (ii) LiAlH4

Q.3 Acetophenone on reaction with hydroxylamine- hydrochloride can produce two isomeric oximes. Write
structure of the oximes.

Q.4 An aldehyde (A) (C11H8O), which does not undergo self aldol condensation, gives benzaldehyde and
two mole of (B) on ozonolysis. Compound (B), on oxidation with silver ion, gives oxalic acid. Identify
the compounds (A) and (B).
O
O CHC6H5
(C)
(i)LiAlH
Q.5   
4
 (D)
(ii) H ,heat

Q.6 What would be the major product in each of the following reaction?
Ph
Base
O

Q.7 Identify (A), (B) and (C), and give their structures.
O
CH3
CH3 Br2
A+B
NaOH
O +
H C(C7H12O)

Q.8 Five isomeric para-disubstituted aromatic compounds A to E with molecular formula C8H8O2 were
given for identification. Based on the following observations, give structure of the compounds.
(i) Both A and B form a silver mirror with Tollen's reagent; also, B gives a positive test with FeCl3
solution
(ii) C gives positive iodoform test.
(iii)D is readily extracted in aqueous NaHCO3solution.
9
-------------------------------------------------------------------------------------------------------
G KISHORE BABU, SriChaitanya Co School, VVNAGAR
 (iv) E on acid hydrolysis gives 1,4-dihydroxybenzene.

Q.9 Write structures of the products A, B, C, D and e in the following scheme.

O
Cl2/FeCl3 Na-Hg HNO3/ H2SO4
CH2CH2CH3 A B C
HCl
– +
Cl CH2= CHCH2O Na H2/ Pd/C
D E
HCl
Q.10 C6H12 C6H13Cl + (C)
(B)
ozonolysis
(D) (E)
ozonolysis NaOH
(A)    (F) + (G)    NCOONa + 1°alcohol
(D) is isomer A. E gives negative test with Fehling solution but gives iodoform test. F and G gives
Tollen's test but do not give iodoform test. Identify A to G.

Q.11 Which of the following disaccharide will not reduce. Tollen's reagent?

CH2OH CH2OH HOH2C CH2OH

HO O H H O HO OH O H H O OH
(A) (B)
H HO OH H HO OH H
H O H H O H

OH H OH H OH H H H

(Q) (P)

EXERCISE-1

Q.No. 1 2 3 4 5 6 7 8 9 10
Ans. B A D B D D A B A D
Q.No. 11 12 13 14 15 16 17 18 19 20
Ans. B A,D A A,B,D B B, D B B A A
Q.No. 21 22 23 24 25 26 27 28 29 30
Ans. C C D C C B A C C C
Q.No. 31 A B C D 33 34 35 36
32
Ans. B P, S Q Q,R, S Q,R D A C B
Q.No. 37 38 39 40 41
Ans. A D B A B
EXERCISE-2

10
-------------------------------------------------------------------------------------------------------
G KISHORE BABU, SriChaitanya Co School, VVNAGAR
 CH3CH2 OH

C
C6H5CH = CHCOOC2H5
Q. 1 Q.2
(D) H CH2NH2

(a racemic mixture)

Q.3 C6H5 – C – CH3 C6H5 – C – CH3

N – OH and HO – N
syn anti (isomers)

CH= CH –C C – CHO

Ozonolysis
CHO CHO Ag
+
COOH
Q.4 +2
COOH COOH

(A) (B) (Oxalic acid)

Ph Ph
CHC6H5
Q.5 C6H5CHO Q.6 Base
+ Base O O
(C) (D) Br
O O O
CH3 CH3 CH3
C –CH3 Br2 + NaOH COONa + CHBr3
Q.7 O

(A) (B) (C)

O
CHO CHO CH2CHO C – CH3 COOH O – CH = CH2

Q.8 (A) or (B) (C) (D) (E)

OCH3 CH2OH OH OH CH3 OH

11
-------------------------------------------------------------------------------------------------------
G KISHORE BABU, SriChaitanya Co School, VVNAGAR
 O NO2
C – Pr Bu Bu
Q.9 (A) (B) (C)

Cl Cl Cl
Cl Cl Cl

NO2 NH2
Bu Bu
(D)
(E)
Cl Cl
O –CH2 –CH = CH2 O –Pr

Q.10 Me3C – CH = CH2 Me2C – CHMe2 + Me3C – CH–Me

Cl Cl
(A) (B) (C)
alc.KOH

Ozonolysis NaOH
(A) HCHO + Me3C – CHO
(F) (G)

HCOONa + Me3C – CH2OH (1° alcohol)

Q.11 In structure (P) both the rings are present in acetyl form therefore it will not hydrolyse in solution that's
why Fehling solution cannot react with this.
In structure (Q) one ring present in the form of hemiacetal. This will hydrolysed in solution it can reduce
Fehling solution.

12
-------------------------------------------------------------------------------------------------------
G KISHORE BABU, SriChaitanya Co School, VVNAGAR