Carboxylic Acids and Acid Derivatives Carbonyl - Pdfcgvdufgdyufgduyfgsdyfgsdygbxcghvyufgxdzuyfgdf

IDEAL 21ST CENTURY COMPETITIONS
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J EE ADVANCED
LEARNI NG MODULE
CHEMI STRY
1. CARBONYL COMPOUNDS
2. CARBOXYLI C ACI DS & ACI D
DERI VATI VES
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CARBONYL COMPOUNDS (Page 1 - 106)
TOPIC PAGE NO.
Theory 03 - 30
EXERCISE-I
Subjective Questions 31 - 34
Objective Questions 35 - 42
EXERCISE-II
EXERCISE-III
Mixed Type Problems 54 - 61
EXERCISE-IV
Past Year JEE/AIEEE Problems
IIT - J EE Problems (Previous Years) 62 - 67
AIEEE Problems (Previous Years) 67 - 68
ANSWRE KEY 69 - 76
MISSCELLANEOUS QUESTION BANK 77 - 99
ANSWRE KEY 100 - 106
CONTENTS
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CARBOXYLIC ACIDS & ACID DERIVATIVES (Page 107 - 181)
TOPIC PAGE NO.
Theory 109 - 138
EXERCISE-I
EXERCISE-II
Subjective Questions 148
EXERCISE-III
Mixed Type Problems 157 - 162
EXERCISE-IV
Past Year JEE/AIEEE Problems
IT - J EE Problems (Previous Years) 163 - 165
AIEEE Problems (Previous Years) 165 - 166
MISSCELLANEOUS QUESTION BANK 171 - 179
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CARBONYL COMPOUNDS | 1
CARBONYL COMPOUNDS
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PART - I : SUBJECTIVE QUESTIONS
Section (A) : Nucleophilic addition reactions
A-1. Why aldehyde are more reactive than ketones (among isomers) towards nucleophilic addition reaction.
A-2. Arrange the following compounds in decreasing order of rate of nucleophilic addition with RMgBr.
(I) PhCOCH
3
(II) PhCHO (III) CH
3
CHO (IV) CCl
3
CHO
A-3. Arrange the following compounds in decreasing orders of nucleophilic addition with semicarbazide
NH
2
NHCONH
2
i.e.,
. .
2
. .
Z H N :
(I) (II) (III) (IV)
A-4. Arrange the following compounds in decreasing orders of rate of addition of HCN.
(a) (b)
(c) (d) CH
3
CHO
A-5. Arrange the following compounds in decreasing orders of K
eq
for hydrate formation.
(a) (b) (c) (d)
A-6. Show how you would synthesis the following ?
(a) Acetophenone Acetophenone cyanohydrin
(b)

A-7. Cyclohexanone forms cyanohydrin in good yield but 2,2,6-trimethylcyclohexanone does not. Explain why ?
A-8. Give the structure of the carbonyl compound and amine used to form the following imines.
(a) (b)
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A-9. Show which alcohol and carbonyl compound react to give each of the following product.
(a) (b)
A-10. Write the product of following reaction :
(a)
H
Ph
C
O
+NaHSO
3
(b)
C =N
CH
3
OH
C H
2 5

4 2
SO H
(c)
16
3 3
O
||
CH C CH
18
2
O D
(d) +
+
H
Section (B) : Condensation reactions
B-1. Predict the product of following aldol condensation reaction :
(a) CH
3
CH
2
CHO
A
/ OH
(b) PhCH
2
CHO
A
/ OH
(c) PhCOCH
3

A
/ OH
B-2. Indicate the starting aldehyde or ketone from which each of the following compounds are formed by an aldol
condensation reaction.
(a) 2Ethyl 3hydroxy hexanal ; (b) 4Hydroxy4methyl2pentanone
B-3. When acetone is treated with excess of benzaldehyde in the presence of base, the crossed condensation
add two equivalents of benzaldehyde and expels two equivalent of water and forms [X]. Identify the structure
of [X] when [X] reacts with NH
2
OH how many stereoisomers are formed.
B-4. Predict the products of following cross condensation reaction,
(a)
O CH
|| |
H C C CH
|
CH
3
3
3
+
O
||
H C CH
3

A
O
/ OH
(b)
O
||
H C Ph
+
O
||
H C CH CH
2 3
A
O
/ OH
(c)
O
||
H C Ph
+
O
||
CH C
3
A
O
/ OH
B-5. What is the principal product of the follwoing reaction ?
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B-6. Show which esters would undergo claisen condensation to give the following |ketoester.
(a)
(b)
(c)
Section (C) : Cannizzaro's reactions
C-1. Identify the products in the following disproportionation reaction and also mention rate determining step.
+ +
C-2.
O
||
H C CH
3
+
O
||
H C H

OH
Product
excess
Section (D) : Redox reactions
D-1. Write the product of following reaction,
(a) (p)
4
LiAlH
(q) +(r)
(b)
O

acid Per
D-2. Write the product of following reaction :
(a)
HO
CHO
+Ag O
2

(b)
HO
CHO
+K Cr O / H SO
2 2 7 2 4

(c)
||
CHO
O
+Ag(NH) OH
3 2
+
-

(d)
CHO
+KMnO
(cold, dil.)
4

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D-3. Give the structure of compound A to D.
CH
2
=CHCH
2
OH A(C
3
H
4
O) B(C
5
H
10
O
2
) C(C
5
H
12
O
4
)

D
Section (E) : -Halogenation, haloform, -deuteration reactions
E-1.
||
C H
6 5
CH
3
O
Ph

O
OH /
Br
2
Products and mention stereochemical relation
E-2. Write the product of following reaction,
(a) CH
3
CH
2
OH

KOH / I
2 (b) PhCH
2
COCH
3

KOH / I
2
(c) (Me)
3
CCOCH
3

KOH / I
2
Section (F) : Miscellanious reactions
F-1. Formaldehyde and malonic ester reacts in presence of ethoxide ion to give K (C
8
H
12
O
4
) ; what is the structure
of K ? How can K be converted into L (C
2
H
5
OOC)
2
CH CH
2
CH (COOC
2
H
5
)
2
what would you get if L was
subjected to hydrolysis and heat ?
F-2. CH
3
I +Ph
3
P
benzene
Li CH CH CH CH
2 2 2 3

=O C Ph
2
F-3. Product.
F-4. Compound (X) with molecular formula C
9
H
10
O forms a semicarbazone and gives negative Tollens and Iodoform
tests. Upon reduction it gives n-propyl benzene. Deduce the structure of X.
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PART - II : OBJECTIVE QUESTIONS
* Marked Questi ons are havi ng more than one correct opti on.
A-1. Arrange the following compounds in decreasing orders of rate of exchange of O
18
with H
2
O
18
(X) CCl
3
CHO (Y) CH
3
CHO (Z) CH
3
COCH
3
(W) CF
3
CHO
(A) W >Z >X >Y (B) W >X >Y >Z (C) W >Y >Z >X (D) W >Z >Y >X
A-2. Which of the following compound has the largest equilibrium constant for the addition of water ?
(A) (B)
(C) (D)
A-3. Acetaldehyde on reaction with sodium hydrogen sulphite produces
(A) (B)
(C) (D)
A-4. Write the product of following reaction :

2 2
NH NH
(A) (B) (C) (D)
A-5.
H C CH
||
O
3
16

18
2
O D

The intermediate is :
(A) (B) (C) (D)
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A-6. Aromatic carbonyl compounds having molecular formula C
8
H
8
O react with NH
2
OH how many oximes can be
formed :
(A) 8 (B) 10 (C) 12 (D) 6
A-7.
CH OH
2
H
OH
OCH
3
CH O
3
H
H
CH OH
2

] X [
Compound (X) in the above reaction.
(A) (B) (C) (D)
A-8. The general order of reactivities of carbonyl compounds towards nucleophilic addition reactions
(A) H
2
C =O >(CH
3
)
2
C =O >Ar
2
C =O >CH
3
CHO >ArCHO.
(B) H
2
C =O >CH
3
CHO >(CH
3
)
2
C =O >ArCHO >Ar
2
C =O.
(C) ArCHO >Ar
2
C =O >CH
3
CHO >(CH
3
)
2
C=O >H
2
C =O.
(D) Ar
2
C =O >(CH
3
)
2
C =O >ArCHO >CH
3
CHO >H
2
C =O.
A-9. The correct order of reactivity of PhMgBr with following compounds will be.
PhMgBr
(C
6
H
5
)
2
CO, CH
3
CH =O , (CH
3
)
2
C =O
(1) (2) (3)
(A) 1 >2 >3 (B) 2 >3 >1 (C) 3 >2 >1 (D) 1 >3 >2
A-10. Cyanohydrin formation constant will be highest for ?
(A)
ON
2
CHO
(B)
CH O
3
CHO
(C)
CH
3
CHO
N
CH
3
(D)
COCH
3
A-11. The cyanohydrin of a carbonyl compound on hydrolysis gives lactic acid. The carbonyl compound is
(A) HCHO (B) CH
3
CHO (C) CH
3
COCH
3
(D) CH
3
COCH
2
CH
3
B-1. Which of the following will not undergo aldol condensation ?
(A) CH
3
CHO (B) CH
3
CH
2
CHO (C) CD
3
CHO (D) PhCHO
B-2. (X) is the product of cross aldol condensation between benzaldehyde (C
6
H
5
CHO) and acetone What is its
structure ?
(A) (B) C
6
H
5
CH=C(CH
3
)
2
(C) C
6
H
5
COCH
2
C=(CH
3
)
2
(D) None of these (buesa l s dksbZ ugha)
B-3. In which of the following compounds the methylene hydrogens are the most acidic ?
(A) CH
3
COCH
2
CH
3
(B) CH
3
CH
2
COOC
2
H
5
(C) CH
3
CH
2
CH(COOC
2
H
5
)
2
(D) CH
3
COCH
2
CN.
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B-4. PhCHO +(CH
3
CO)
2
O
A

, hydrolysis ) 2 (
COONa CH ) 1 (
3
A
HBr
B
The product B is :
(A) PhCH =CHCH
2
Br (B) (C) PhCH
2
CH(Br) COOH (D) PhCH =CH COBr
B-5. In the given reaction the product is :
+
A

O H
2
(A) (B)
(C) (D)
B-6.* The compounds that undergo Aldol condensation is :
(A) (B) (C) (D)
C-1. Cannizzaro reaction does not take place with
(A) (CH
3
)
3
CCHO. (B) (C) (D) CH
3
CHO.
C-2. In the reaction, (CH
3
)
3
CCHO +HCHO
heat
NaOH

A +B.
the products (A) and (B) are respectively :
(A) (CH
3
)
3
CCH
2
OH and HCOO
Na
+
. (B) (CH
3
)
3
CCOONa and CH
3
OH.
(C) (CH
3
)
3
CCH
2
OH and CH
3
OH. (D) (CH
3
)
3
COONa and HCOO
Na
+
.
C-3. +HCHO
A

KOH
(A) +(B)
(A) (B) +CH
3
OH
(C) (D) Both (A) and (B),
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C-4. In the cannizzaro's reaction the intermediate that will be the best hydride donar ?
(A) (B)
(C) (D)
C-5. Product of following reaction is
+conc. NaOH
heat
?
(A) (B) (C) (D)
C-6. In the given reaction Product is
(A) (B)
(C) (D)
D-1. (CH
3
)
2
C =
3 2 2
CCH CH CHCH
||
O

) X (

OH
|
CCH CH CHCHCH ) CH (
||
O
3 2 2 2 3

) Z (

3 2 2 2 3
CCH CH CHCCH ) CH (
|| ||
O O
x y z
(A) H
2
CrO
4
B
2
H
6
, THF/H
2
O
2
,OH
O
OH
O
/ A
(B) B
2
H
6
, THF/H
2
O
2
,OH
O
H
2
CrO
4
/ CrO
3
OH
O
/ A
(C) B
2
H
6
, THF/H
2
O
2
,OH
O
OH
O
H
2
CrO
4
/ CrO
3
(D) H
2
CrO
4
OH
O
B
2
H
6
, THF/H
2
O
2
,OH
O
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D-2.
||
O
A
O

/ H O
CHO Ph

4
LiAlH
[X], Product (X) in this reaction is :
(A) (B)
(C) (D)
D-3.*
O

OH / KMnO
. aq . dil Cold
4
(X) (Y) (Z)
The products of the above reaction is / are :
(A) (B) (C) (D)
D-4. What will be the product of the following reaction

H RCO
3
?
(A) (B) Ph
O
| |
C CH (C) PhCH(Me)OCOOMe (D) None of these
D-5. 2-Methyhlcyclohexanone is allowed to react with metachloroperbenzoic acid. The major product in the reac-
tion is
(A) (B) (C) (D)
D-6. In the following conversion

Which of the following regents is suitable ?
(A) NH
2
NH
2
,KOH, DMSO (B) NaBH
4
(C) Zn-Hg, concentrated H
2
SO
4
(D) LiAlH
4
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D-7.

Above conversion can be achieved by
(A) NH
2
NH
2
/ NaOH (B) ZnHg/HCl
(C) LiAlH
4
(D) NaBH
4
.
(A) NH
2
NH
2
/ NaOH (B) ZnHg/HCl
(C) LiAlH
4
(D) NaBH
4
.
E-1.

H / Br
2 Major Product is :
(A) (B) (C) (D) A and C both
(
) optical inactive optical active

E-2.
O

D
D
D
The above conversion is carried out
(A) KOD /D
2
O, H
/A, LiAlH
4
(B) H
/A / KOD, D
2
O, LiAlH
4
(C) KOD/ D
2
O, LiAlH
4
, H
/A (D) LiAlH
4
, H

A ,KOD/H
2
O
E-3.* Which of the following gives haloform reaction
(A) (B) (C) (D)
E-4.* In which of the following reaction deuterium exchange is observed ?
(A)
excess
OH / O D
2

O
(B)

O
OH / O D
2
(C)

O
OH / O D
2
(D)

O
OH / O D
2
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E-5.* In which of the following reaction deuterium exchange is not observed ?
(A) (B) (C) (D)
F-1. The major product formed in the reaction.
C
6
H
5
CHO +CH
3
NO
2

heat
NaOH
(X)
(A) (B)
(C) C
6
H
5
CH =CH NO
2
(D) .
F-2. What is the final product of this sequence of reactions ?

(A) (B) (C) (D)
F-3. PhCH
2
COOEt + (A) (B)
Product B is :
(A) PhCH
2
COOH (B) PhCH
2
COOEt (C) (D) None of these
F-4.*

O
EtO
(P)

O
I
H ) 2 (
OH / ) 1 (
2
(Q)

A
(R)
The products of the above reaction is / are :
(A) (B) (C) (D)
F-5. 2-pentanone can be distinguished from 3- pentanone by the reagent ?
(A) 2, 4- Dinitrophenyl hydrazine (B)Tollen's reagent
(C) I
2
and dilute NaOH (D) NaHSO
3
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F-6. +(C
6
H
5
)
3
P =CHCH
3

(A) (B) (C) (D)
F-7.* Which of the following will gives iodoform with NaOI ?
(A) (B) (C) (D)
1. Write the product of the following reaction
(a) +HO NH
2

H
(b) +NH
2
NH
2

H
(c) Ph CH
2
CH
2
CHO +
(d) +Ph NH NH
2

2. When semicarbazide reacts with a ketone (or aldehyde) to form semicarbazone. Only one nitrogen atom of
semicarbazide acts as a nucleophile and attack the carbonyl carbon of the ketone. The product of the
reaction consequently is R
2
C=NNHCONH
2
rather than R
2
C=NCONHNH
2
. What factor account for the
fact that two nitrogen atom of semicarbazide are relatively non nucleophile ?
3. Cyclopropanone exists as the hydrate in water but 2-hydroxy ethanal does not exist as its hemiacetal
expalin why ? [Claiden]
4. Show how would you accomplish the following synthesis
(a)

(b)
O
||
CH C CH CH Br
3 2 2

O
||
CH C CH CH C HC
3 2 2
(c)
CH - Br
2
O

CH - Ph
2
O
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5. (a) Cis-1, 2-Cyclopentanediol reacts with acetone in the presence of dry HCl to yield compound K, C
8
H
14
O
2
,
which is resistant to boiling alkali, but which is readily converted into the starting material by aqueous acids.
What is structure of K ?
(b) Trans-1, 2-Cyclopentanediol does not form an analogous compound. Explain why ?
6. On the basis of following reaction answer the following questions.
) mixture d (
Me
|
O CH H C Ph
*
= +
) isomer optical pure (
Me O
| ||
CH CH C NH C NH . NH
*
|
H
3 2 2

+
H
(a) How many stereoisomers will be formed.
(b) How many pair(s) of enantiomers are formed ?
7. Predict the product from claisen condensation of the following pair of esters.
(a) +
O
EtO
(b) +
O
EtO
(c) +
A
O

/ O
2
H . 2
EtO . 1
8. Write the components which on crossed claisen condensation could be used to prepare the following esters.
(a) (b) (c)
9. Predict the product for each of the following reactions,
(a) OHC CHO +
O O
|| ||
CH C O C CH
3 3

+
Na COO CH
3
excess
(b) CH
3
CHO +CH
2
CN
CN

A / Pyridine
(c) +CH
3
COCH
2
COOEt
EtOH
/ EtONa

A
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10. Predict the product for each of the following reactions.
(a) +

A
O
/ OH
(b) +

A
O
/ OH
(c)

A
O
/ OH
(d)
5 6 5 6
H CCC H C
|| ||
O O
+
5 6 2 2 5 6
H C CCH CH H C
||
O

ethanol
KOH

11. +CH
2
=CH
O
||
C
Ph
O
EtO
Product (P) is :
12. Write the product of the following reaction,
(a)
CHO
OMe
+
CDO
OMe

A
/ OH
(b)
CHO
NO
2
+
CHO

A
/ OH
13. PhCOCHBr
2

OH
A
OH
B
+
H
C
The compound 'C' is :
14. Glyoxal (CHOCHO) on being heated with concentrated NaOH forms.
15. +
COOH
|
CHO

+

A
O H ) ii (
, NaOH . conc ) i (
3
Product is :
16. The compound C
4
H
8
CI
2
(A) on hydrolysis gives a compound C
4
H
8
O, (B). The compound (B) reacts with
hydroxylamine and gives a negative test with Tollens reagent. What are (A) and (B) Support your answer
with proper reasoning and give the equations of reactions.
17. A ketone (A) which undergoes haloform reaction, gives compound (B) on reduction with LiAlH
4
. (B) on
heating with conc. H
2
SO
4
gives (C) which forms monoozonide (D). (D) on hydrolysis in presence of zinc dust
gives only acetaldehyde. Identify (A), (B and (C). Write reactions involved.
18. Compound X (C
5
H
10
O) reacts with KCN in dilute H
2
SO
4
followed by heating with dilute acid , results in
compound Y which is achiral and gives effervescence with NaHCO
3
. Reduction of X forms Z (achiral)
which gives positive Lucas test . X responds negatively to iodoform and Fehlings tests . Identify X , Y and
Z .
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(without section in class room but store sections in Main Sheet)
Single choice type
1. Products
Products obtained in the reaction is-
(A) Diastereomer (B) Racemic mixture (C) Meso compound (D) Optically pure enantiomer
2. CH
2
O

O H
Mg CHD
3
2
I
X
A

4 2
SO H Conc.
Y
In the above reaction compound X & Y respectively will be
(A) OH CH CHD
|
OH
2
, CHO CHO (B) CHD
2
CH
2
OH , CHO CHO
(C) CHD
2
CH
2
OH , CD
2
=CH
2
(D)
OH
|
OH CH CHD
2
, CD
2
=CH
2
3. For the given reaction + Mg
ether dry
A
+

O H ) ii (
CHO CH ) i (
3
3
B.
product B is :
(A) (B)
(C) (D)
4.

) 1 (

) 2 (

) 3 (

(A) (1)
H
OH CH
|
OH CH
2
2
(2) Mg / (3)
O
||
H O C H / H
+
(B) (1)
H
OH CH
|
OH CH
2
2
(2) Mg / (3)
O
||
Et O C CH
3
/ H
+
(C) (1)
H
OH CH
|
OH CH
2
2
(2) Mg / THF (3)
O
||
Et O C CH
3
/ H
+
(D) (1)
H
OH CH
|
OH CH
2
2
(2) Mg / THF (3)
O
||
H O C H
/ H
+
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5. In the given reaction, (X) (Y)
(Y) is
(A) (B)
(C) (D)
6. Product is
(A) (B)
(C) (D)
7. Consider the following sequence of reactions-.
PhC CH
4 2
4
SO H . dil
HgSO

A
OH NH
2
B +C.
The products (A), (B) and (C) are respectively,
(A) PhCHO, and
(B) PhCH
2
CHO, and
(C) , and
(D) , and
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8.
O
||
H C CH CH Ph =

MgBr CH CH ) i (
2 3

O H ) ii (
3
(X)
A , Cu
(Y)
(A) X is 1, 4-addition product ; Y is
O
||
CH CH CH CH C Ph
3 2
=
(B) X is 1, 2-addition product ; Y is
O
||
CH CH C CH CH Ph
3 2
=
(C) X is 1, 4-addition product ; Y is
O
||
CH CH C CH CH Ph
3 2
=
(D) X is 1, 2-addition product ; Y is
O
||
CH CH CH CH C Ph
3 2
=
9.
4
4 2
LiAlH ) ii (
SO H / KCN ) i (
Product is
(A)
OH
|
NH CH CH CH CH
2 2 2 3
(B) CH
3
CH
2
CH
2
NH

CH
3
(C)
OH
|
CN CH CH CH
2 3

(D)
OH
|
NH CH CH CH CH
2 2 2 3

10. Consider the following sequence of reactions :
+H
2
NOH

Heat
A A
Heat
SO H
4 2

B.
The products (A) and (B) are, respectively :
(A) and (B) and
(C) and (D) and
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11. Compound (X) C9H10O gives yellow coloured ppt with 2,4 DNP but does not give red coloured ppt with
Fehlings solution. (X) on treatment with NH
2
OH/H
+
gives compound (Y) C9H11NO. (Y) when treated with PCl5
gives isomeric compound (Z). (Z) on hydrolysis gives propanoic acid and aniline. What will be the correct
structure of (X), (Y) and (Z) ?
(A) ; ;
(B) ; ;
(C) ; ;
(D) ; ;
12. + Product
(A) (B)
(C) (D)
13. In the given reaction sequence B is
(A) (B)
(A) (B) (C) (D)
14. (A) (B)
The reactant (A) will be :
(A) (B) (C) (D)
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15.
3
2 3
3
CH
|
CCHO CCH CH
| ||
CH O

A

O
2
H , KOH
Product (C
7
H
10
O) : (mRi kn (C
7
H
10
O)
(A) (B) (C) (D)
16.
(A) (B)
(C) (D)
17. In the following reaction, A +B
A and B respectively are :
(A) + CH
3
COOC
2
H
5
(B) + CH
3
O
||
C OC
2
H
5
(C) + C
2
H
5
O
O
||
C OC
2
H
5
(D) + C
2
H
5
O
O
||
C CH
2
O
||
C OC
2
H
5
18. (X) Identify.
(A) (B) (C) (D)
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19.
O
+
CHO

A
O
/ H O
Product is
(A) (B)
Ph CH
O
(C)
Ph CH
OH
(D)
COOH
+
OH
20. The suitable reagent for the following reaction is :

(A) LiAlH
4
(B) Na / C
2
H
5
OH (C) H
2
/ Ni (D) CH
2
= O /
21. Which of the following can be the product/s of following reaction.

NaOH . Conc
(A) I, II, IV (B) III, IV (C) II, V (D) I, V
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22.
A

, O H ) ii (
Pyridine / ) H COOC ( CH ) i (
2
2 5 2 2
(P) is

A

, O H ) ii (
/ ) H COOC ( CH ) i (
2
2 5 2 2
fifjMhu
(P) gS
(A) (B)
(C) (D)
More than one choice type
23. Which of the following correctly indicate(s) the rate.
(A) CH CH
3
CN
OH ) fast very (
CHO CH
3
KCN +HCl
OH
CN
Me CH Me CH Me CH Me CH Me CH Me CH Me CH Me CH Me CH Me CH Me CH Me CH Me CH Me CH
(B) (hydrate)
) fast (
O CH CH
3

=
H
2
O/H
+
hydrate
(C) Cyanohydrin
slow
OH / HCN

O
C
2
H
5
CHO
fast
MgBr CH
3
Adduct formation
(D) All of these
24. Observe the following reaction Products.
The correct statement is
(A) The product is a mixture of two compounds
(B) The product is optically inactive
(C) The product is a mixture of two chiral and one achiral stereoisomer
(D) The product is a mixture of three stereoisomers.
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25. The following conversion is/are possible by
Ph CH
2
CH =O
(A)
O H / KCN
2

A , NH
3

A
, O H
3
(B)
Cl NH / KCN
4

A
, O H
3
(C)

NaOH / HCN

2
SOCl

3
NH

A
, O H
3
(D)
COOH CH / Br
3 2

3
NH

H / CrO
3
26. In the given reaction which one of the following statement is correct
(A) Oxime may be E/Z.
(B) Amide on hydrolysis gives a mixture acetic acid, benzoic acid, Aniline and methylamine.
(C) Preparation of oxime is nucleophilic addition followed by elimination reaction.
(D) Oxime and amides are isomers.
27. In the given reaction
CHCH (X) (Y) (Z)
(A) X is CH
3
CHO (B) Y is (C) Z is (D) Z is CH
3
COOH
28. A compound (A) C
5
H
10
O forms a phenyl hydrozone and gives negative tollen's and positive iodoform test
compound can be :
(A) (B)
(C) (D)
29. Which of the following will give 3pentanone.
(A) (CH
3
CH
2
COO )
2
Ca
A
(B) CH
3
CH
2
C N
O H ) 2 (
MgBr CH CH ) 1 (
3
2 3

(C) CH C CH CH C OC H
3 2 2 2 5
|| ||
O O

) cao ( NaOH ) 2 (
H / O H ) 1 (
2

+
(D)

A
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30. W X Y Z
Product (Y) and (Z) is / are :
(A) (B) (C) (D)
31. Which of the following reactions is / are correct to get cinnammic acid :
(A) C
6
H
5
-CH=O
COONa CH / O ) CO CH (
3 2 3
(B) C
6
H
5
-CH=O
Pyridine
) H COOC ( CH
2 5 2 2

(C) C
6
H
5
-CH=O
5 2 3
OH / H COOC CH
(D) C
6
H
5
-CH=O
A
A
+

/ H / O H ) ii (
/ Zn / H COOC BrCH ) i (
2
5 2 2
32. Identify product in the following reaction sequence
CH
3
I +(W)

2
SOCl
(X)
equivalent 1
3
MgBr CH
(Y)
) excess (
O D / OD
2

Z
(A) (B) (C) (D)
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MIXED TYPE PROBLEMS
PART - I : MATCH THE COLUMN
1. Match the column
Column I Column II
(A) MeCO(CH
2
)
4
COMe
A
+
O

/ H ) ii (
OH ) i (
(p)
(B) (CH
2
)
4

O
OEt
(q)
(C) PhCHO +

3
COO CH
(r)
OH
|
COO C ) Ph (
2
(D) PhCOCOPh

O
OH
(s)
2. Column-I Column-II
Aldol product Reactant required
(A) (p)
(B) (q) HCHO
(C) (r) PhCHO
(D) PhCH=CHCHO (s) CH
3
CHO
(A) (p) 1, 4-addition
(B) (q) Tautomerism
(C) CH
3
CH=CHCH =CH
2
(r) AgNO
3
/ NH
4
OH
(D) (s) 2, 4 DNP test
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PART - II : COMPREHENSION
Read the following passage carefully and answer the questions.
Comprehension # 1
Aldehydes and Ketones reacts with NH
2
OH to form Aldoximes and Ketoximes respectively. Configuration of
these can be determined by Beckmann rearrangement as that group migrates which is anti w.r.t OH.
R'
R
C N
OH
.
.

R'
R
C N
OH
2
.
.
) (II

R N C ' R =
) (
O H
2
III

OH
|
R N C ' R =
O
||
R NH C ' R
4. [X]
4 2
SO H

O H
2
Ph NH
2
+
Identify the configuration of [X] compound :
(A) (B) . (C) (D)
5. Which step is Rate determening step ?
(A) I (B) II (C) III (D) IV
6.

OH NH
2
(A)
hydrolysis ) 2 (
SO H ) 1 (
4 2
(B).
The product (B) is :
(A) (B) (C) (D)
Comprehension # 2
Carbonyl compound which contains oH gives aldol condenation reaction in presence of alkaline medium.
The reaction between two molecules of acetaldehyde take place as follows in presence of base.
7. Aldol condensation reaction is given by
(A) C
6
H
5
CHO (B) CX
3
CHO (C) O
2
N CHO (D) C
6
H
5
CH
2
CHO
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8. + Product (mRi kn)
(A) Ph CH =CH (CH
2
)
5
CHO (B) Ph (CH
2
)
5
CH =CH CHO
(C) (D)
9. Intramolecular aldol condensation reaction is given by
(A) 1,4 diketone (B) 1,6 diketone (C) 1,5 and 1,7 diketone (D) All of these
Comprehension # 3
The conversion of aldehyde having no alpha hydrogen to a mixture of carboxylic acid and primary alcohol is
known as cannizzaro reaction. The most important feature of this reaction is the conjugate base of hydrate
of aldehyde.
10. Which step is rate determining step
(A) step I (B) step II (C) step III (D) step I and II both
11. Aldehyde having o-Hydrogen does not give cannizzaro reaction because
(A) Such aldehyde will form enolate ion
(B) Such aldehyde will not form conjugate base of hydrate of aldehyde
(C) Such aldehyde may undergo polymerisation
(D) All of these
12. In the given reaction final product is (nh xbZ vf Hkf ; k eas vf Ur e mRi kn gaS )
(A) CH
3
OH + (B) HCOONa +
(C) HCOONa + (D) HCOONa +
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Comprehension # 4
Perkin reaction is the condensation reaction between aromatic aldehyde and aliphatic acid anhydride in the
presence of sodium or potasium salt of the acid of the corresponding anhydride to yield o, | unsaturated
aromatic acid.
PhCHO +(CH
3
CO)
2
O PhCH=CHCOOH +CH
3
COOH
Mechanism
CH
3
COONa CH
3
COO
O
+Na
CH
3
COO
O
+ CH
3
COOH +
13.

A / O H
2
Product is
(A) (B)
(C) (D)
14.

A
H ) ii (
/ O H ) i (
2
(A) (B) (C) (D)
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15. +(CH
3
CH
2
CO)
2
O
A / O H
2
Product is
(A) (B)
(C) (D)
Comprehension # 5
Ester having o-hydrogen on treatment with a strong base eg. C
2
H
5
ONa undergoes self condensation to
produce |-keto esters.This is called claisen condensation.
C
2
H
5
O
+H CH
2
COOC
2
H
5
C
2
H
5
OH +

16. +
(A) +C
2
H
5
OH (B) +C
2
H
5
OH
(C) +C
2
H
5
OH (D) None of these
17. + product is
(A) (B)
(C) (D) Ph CH
2
COOH
18.
(A) (B)
(C) (D) COOH
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Comprehension # 6
Study following mechanism of haloform reaction.
H O
| ||
H C C R
|
H
+
-
HO

a

R C C H
||
O
|
H
I I
-
b
H O
| ||
H C C R
|
X

(1) HO, (2) I
2
C
-

H O
| ||
X C C R
|
X

CHX
3
+ R C O
-
||
O
X

f

O
||
OH C R
+
CX
3
-

X O
| ||
X C C R
|
X

HO
-
e

(1) HO
(2) I
2
-
d
19. Which step is RDS
(A) a (B) b (C) c (D) f
20. Which of the following compounds gives haloform reaction ?
(A)
O O
|| ||
CH C CH C CH
3 2 3
(B)
O
||
NO CH C CH
2 2 3

(C) CH C CH CH C
3 2 2
||
||
O O
(D)
C CH
3
O
O O
21. Which step produces most acidic compound
(A) a (B) c (C) d (D) b
Comprehension # 7
CH
2
(COOEt)
2
+ CH
3
CHO K (C
9
H
14
O
4
) L (C
16
H
26
O
8
)
(M) (anhydride) (C
6
H
10
O
4
)
22. The product K is
(A) (B)
(C) (D)
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23. The product L is
(A) (B)
(C) (D)
24. The product M is
(A) (B) (C) (D)
PART - III : ASSERTION / REASONING
DIRECTIONS :
Each question has 5 choices (A), (B), (C), (D) and (E) out of which ONLY ONE is correct.
(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.
(E) Statement-1 and Statement-2 both are False.
25. Statement-1 : Aldehyde and ketone undergo nucleophilic addition reaction with carbon nucleophile and
underog nucleophilic addition-elimination reaction with nitrogen Nucleophile.
Statement-2 : Addition of nucleophile on aldehyde and ketone form tetrahedral intermediate, in case of
tetrahedral intermediate of nitrogen nucleophile non bonding electrons are present on nitrogen which cause
water molecule to eliminate while in case of carbon and hydrogen nucleophile non bonding electron are not
present.
26. Statement-1 : The rate of addition reaction of alcohol on aldehyde can be increased by adding small amount
of base.
Statement-2 : Addition of alcohols to an aldehyde form acetal.
27. Statement-1 :
Compound II is more reactive towards nucleophilic addition reaction.
Statement-2 : Cyclic ketones are more reactive than acyclic ketone due to less steric hinderance and
compact structure of cyclic ketone.
28. Statement-1 : NaHSO
3
is used in seperation and purification of aldehydes.
Statements-2 : NaHSO
3
is reducing agent.
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29. Statement -1 : Dehydration of aldol takes place by the following mechanism.

Statement -2 : It is due to acidity of o H and stability of conjugated double bond
30. Statement-1 : (cinnamaldehyde) fails to undergo aldol condensation
Statement 2: This is due to the fact that cinnamaldehyde does not have acidic o H
PART - IV : TRUE / FALSE
31. Acid or Base catalysed halogenations of Acetaldehyde follows the reactivity order as Cl
2
=Br
2
=I
2
32. High Alcohol and low water concentration shifts the aldehyde-hemiacetal and hemiacetal-acetal equilibria
towards acetal.
33. Conc. KOH changes PhCCPh
O O
to
O
PhCCOO
Ph
OH
34. (CH
3
)
2
CuLi changes to
PART - V : FILL IN THE BLANKS
35. Fehling solution (A) consists of aquous solution of copper sulphate, while Fehlings solution B consists of
an alkaline solution ............
36. The structure of the intermediate product, formed by the oxidation of toluene with CrO
3
and acetic anhydride,
whose hydrolysis gives benzaldehyde is ...........
37. Ethanol vapour is passed over heated copper and the product is treated with aqeuous NaOH. The final
product is ..........
38. The conversion of carbonyl compound into alkane by reduction is termed as ............
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PART - I : IIT-JEE PROBLEMS (PREVIOUS YEARS)
1. Identify (A), (B), (C), (D) and (E) in the following schemes and write their structures : [JEE 2001, 5/100]

4 2
CCl / Br
A

2
NaNH
B
4 2 4
SO H / HgSO
C
C

2 2
NHCONH H N
D
C
) excess ( O D / aOD N
2
E
2. An alkene A (C
16
H
16
) on ozonolysis gives only one product B (C
8
H
8
O). Compound B on reaction with NaOH/
I
2
yields sodium benzoate. Compound B reacts with KOH/NH
2
NH
2
yielding a hydrocarbon C. (C
8
H
10
). Write
the structure of compound B and C based on this information two isomeric structures can be proposed for
alkene A. Write their structures and identify the isomer which on catalytic hydrogenation (H
2
/Pd-C) gives a
racemic mixture. [JEE 2001, 5/100]
3. 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 [JEE 2001, 1/35]
4. 1-Propanol and 2-Propanol can be best distinguished by [JEE 2001, 1/35]
(A) oxidation with alkaline KMnO
4
followed by reaction with Fehling solution
(B) oxidation with acidic dichromate followed by reaction with Fehling solution
(C) oxidation by heating with copper followed by reaction with Fehling solution
(D) oxidation with concentrated H
2
SO
4
followed by reaction with Fehling solution
5. Write structures of the products A, B, C, D and E in the following scheme. [JEE 2002, 5/60]

3 2
FeCl / Cl
A A
HCl / Hg Na
B
4 2 3
SO H / HNO
C
E
C / Pd / H
2
D
6. Five isomeric para-disubstituted aromatic compounds A to E with molecular formula C
8
H
8
O
2
were given for
identification. Based on the following observations, give structures of the compounds.
(i) Both A and B form a silver mirror with Tollens reagent; also, B gives a positive test with FeCl
3
solution.
(ii) C gives positive iodoform test.
(iii) D is readily extracted in aqueous NaHCO
3
solution.
(iv) E on acid hydrolysis gives 1, 4dihydroxybenzene. [JEE 2002, 5/60]
7. A biologically compound Bombykol (C
16
H
30
O) is obtained from a natural source. The structure of the compound
is determined by the following reaction.
(a) On hydrogenation, bombykol gives a compound A (C
16
H
34
O). Which react with acetic anhydride to
give an ester.
(b) Bombykol also react with acetic anhydride to give another ester. Which on oxidative ozonolysis (O
3
/
H
2
O
2
) gives a mixture of butanoic acid, oxalic acid and 10 acetoxy decanoic acid.
Determine the number of double bond in Bombykol. Write the structure of compound (A) and Bombykol. How
many geometrical isomer are possible for Bombykol. [JEE 2002, 5/60]
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8. Compound 'A (molecular formula C
3
H
8
O) is treated with acidified potassium dichromate to form a product 'B'
(mol. Formula C
3
H
6
O). 'B' forms a shining silver mirror on warming with ammonical AgNO
3
. 'B' when treated
with an aqueous solution of H
2
NCONHNH
2
. HCl & sodium acetate gives a product 'C'. Identify the structure of
'C. [JEE 2002, 3/90]
(A) CH
3
CH
2
CH =NNHCONH
2
(B)
2 3
3
CONHNH N C CH
|
CH
=
(C) CH
3
CH =N.NH CONH
2
(D) CH
3
CH
2
CH =NCONHNH
2
9. Compound A of molecular formula C
9
H
7
O
2
Cl exists in ketoform and predominantly in enolic form B. On
oxidation with KMnO
4
, A gives m-chlorobenzoic acid. Identify A and B. [JEE 2003, 2/60]
10. A (C
6
H
12
)

HCl

) Cl H C (
C B
13 6
+
[JEE 2003, 4/60]
B
KOH alc
D (isomer of A)
D
ozonolysis
E (it gives negative test with Fehling solution but responds to iodoform test).
A
ozonolysis
F +G (both give positive Tollens test but do not give iodoform test.)
F +G
NaOH . conc
HCOONa +a primary alcohol.
Identify to A to G.
11.
O H / H ) ii (
C 100 / NaOH ) i (
2
+

Major Product is [JEE 2003, 3/84]
(A) (B)
(C) (D)
12. In the following reaction [JEE 2005, 3/84]

heat
COONa CH
3
, X can be :
(A)
Br
|
H O C CH
||
O
2
(B)
H O C C H
|| ||
O O

(C)
H O C CH
||
O
3

(D) O ) CO CH (
2 3
13. In conversion of 2-butanone to propanoic acid which reagent is used. [JEE 2005, 3/84]
(A) NaOH, NaI / (B) Fehling solution (C) NaOH, I
2
/ (D) Tollen's reagent
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14. 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 : [JEE 2007, 3/162]
(A)
CHO
(B)
CHO
(C)
COOH
(D)
CO H
2
CO H
2
15. Match the compounds/ions in Column I with their properties/reactions in Column II. [JEE 2007, 8/162]
Column I Column II
(A) C
6
H
5
CHO (p) gives precipitate with 2,4 dinitrophenylhydrazine.
(B) CH
3
C CH (q) gives precipitate with AgNO
3
.
(C) CN
(r) is a nucleophile.
(D) I
(s) is involved in cyanohydrin formation.

16. In the following reaction sequence, the correct structures of E, F and G are [JEE 2008, 3/163]
[E] [F] +[G]
(*implies
13
C labelled carbon)
(A) E = F = G =CHI
3
(B) E = F = G =CHI
3
(C) E = F = G =
*
CHI
3
(D) E = F = G =CH
3
I
Write Up
A tetriary 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 compound L, whereas K on reaction
with KOH gives only M.
M =
17. Compound H is formed by the reaction of [JEE 2008, 4/163]
(A) + PhMgBr (B) + PhCH
2
MgBr
(C) + PhCH
2
MgBr (D) +
18. The structure of compound I is [JEE 2008, 4/163]
(A) (B) (C) (D)
19. The structure of compounds J, K and L respecitvely, are : [JEE 2008, 4/163]
(A) PhCOCH
3
, PhCH
2
COCH
3
and PhCH
2
COO
K
+
(B) PhCHO, PhCH
2
CHO and PhCOO
K
+
(C) PhCOCH
3
, PhCH
2
CHO and CH
3
COO
K
+
(D) PhCHO, PhCOCH
3
and PhCOO
K
+
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Write Up
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.
P
A
+

, SO H . 3
O H , H . 2
MeMgBr . 1
4 2
2
Q
O H , Zn . 2
O . 1
2
3
R
A

. 2
OH . 1
S
20. The structure of the carbonyl compound P is : [JEE 2009, 4/160]
(A) (B) (C) (D)
21. The structures of the products Q and R, respectively, are : [JEE 2009, 4/160]
(A) , (B) ,
(C) , (D) ,
22. The structure of the product S is : [JEE 2009, 4/160]
(A) (B) (C) (D)
23. Match each of the compounds given in Column I with the reaction(s), that they can undergo, given in
column II. [JEE-2009, 8/160]
Column I Column II
(A) (p) Nucleophilic substitution
(B) (q) Elimination
(C) (r) Nucleophilic addition
(D) (s) Esterification with acetic anhydride
(t) Dehydrogenation
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24. In the scheme given below, the total number of intramolecular aldol condensation products formed from 'Y' is:
[JEE 2010, 3/163]

O
2
H , Zn . 2
3
O . 1

Y
heat . 2
) aq ( NaOH . 1

Comprehension
Two aliphatic aldehydes P and Q react in the presence of aqueous K
2
CO
3
to give compound R, which upon
treatment with HCN provides compound S. On acidification and heating, S gives the product shown below :
25. The compounds P and Q respectively are : [JEE 2010, 3/163]
(A) and (B) and
(C) and (D) and
26. The compound R is : [JEE 2010, 3/163]
(A) (B)
(C) (D)
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27. The compound S is : [JEE 2010, 3/163]
(A) (B)
(C) (D)
PART - II : AIEEE PROBLEMS (PREVIOUS YEARS)
1. On vigorous oxidation by permangnate solution (CH
3
)
2
C =CHCH
2
CHO gives [AIEEE-2002]
(A) (CH
3
)
2
CO and OHCCH
2
CHO (B)
OH OH
| |
CHO CHCH C ) CH (
2 2 3

(C) (CH
3
)
2
CO and OHCCH
2
COOH (D) (CH
3
)
2
CO and CH
2
(COOH)
2
2. Maximum dehydration takes place in : [AIEEE-2002]
(A)
||
O
OH
(B)
||
O
OH
(C)
||
O
OH
(D)
CH
3
OH
3. Which one of the following is reduced with Zn, Hg and HCl acid to give the corresponding hydrocarbon?
[AIEEE-2004]
(A) Ethyl acetate (B) Butan-2-one (C) Acetamide (D) Acetic acid
4. Which one of the following undergoes reaction with 50% sodium hydroxide solution to give the corresponding
alcohol and acid ? [AIEEE-2004]
(A) Phenol (B) Benzoic acid (C) Butanal (D) Benzaldehyde
5. The best reagent to convert pent-3-en-2-ol into pent-3-ene-2-one is [AIEEE-2005]
(A) Pyridinium chloro-chromate (B) Chromic anhydride in glacial acetic acid
(C) Acidic dichromate (D) Acidic permanganate
6. The reaction [AIEEE-2005]
R C + Nu
X Nu
O O
-
R C + X
-
is fastest when X is :
(A) OCOR (B) OC
2
H
5
(C) NH
2
(D) Cl
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7. Reaction of cyclohexanone with dimethylamine in the presence of catalytic amount of an acid forms a
compound if water during the reaction is continuously removed. The compound formed is generally known as
[AIEEE-2005]
(A) an amine (B) an imine (C) an enamine (D) a Schiff's base
8. The decreasing order of the ratio of HCN addition to compounds A to D is [AIEEE-2006]
(a) HCHO (b) CH
3
COCH
3
(c) PhCOCH
3
(d) PhCOPh
(A) d >b >c >a (B) d >c >b >a (C) c >d >b >a (D) a >b >c >d
9. In the following sequence of reactions, [AIEEE-2007, 3/120]
CH
3
CH
2
OH
I +
2
P
A
Ether
Mg

B
HCHO
C
O H
2
D. The compound D is is
(A) n-propyl alcohol (B) propanal (C) butanal (D) n-butyl alcohol
10. In the following sequence of reactions, the alkene affords the compound 'B' [AIEEE-2008, 3/105]
B A CHCH CH CH
Zn
O H O
3 3
2 3
= .The compound B is
(A) CH
3
COCH
3
(B) CH
3
CH
2
COCH
3
(C) CH
3
CHO (D) CH
3
CH
2
CHO
11. In Cannizzaro reaction given below [AIEEE-2009, 4/144]
2Ph CHO
O
H O :
PhCH
2
OH +PhCO
2
..
the slowest step is :
(A) the transfer of hydride to the carbonyl group (B) the abstraction of proton from the carboxylic group
(C) the deprotonation of PhCH
2
OH (D) the attack of : H O
O
at the carboxyl group
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EXERCISE - 1
PART - I
A-1. The reactivity of carbonyl group towards nucleophilic reagent depends upon the extent of positive charge
present on the carbon. In ketones two alkyl group attach to the carbon reduce the positive charge on the
carbonyl carbon due to their electron repelling nature while in aldehyde the positive charge on carbonyl
carbon is reduced to lesser extent because only one alkyl group is present.
Also, In ketones steric hinderance is more than aldehyde.
A-2. IV >III >II >I A-3. IV >III >I >II A-4. d >b >c >a
A-5. c >b >a >d
A-6. (a)
4 2
SO H . dil / KCN or
NaOH / HCN

(b)

H / O
2
H ) 2 (
NaOH / HCN ) 1 (

A-7. Cyanohydrin is formed by nucleophilic attack on carbonyl group (C=O), 2, 2, 6-trimethylcyclohexanone has
more steric crowding and three methyl groups in tri methyl cyclohexanone which nearly neutralise the
positive charge on carbon hence CN
nucleophile does not react with 2,2,6-trimethylcyclohexanone.

A-8. (a) +CH
3
CHO (b) H
2
N CH
2
CH
2
CH
2
CH
2
COCH
3
A-9. (a) CH
3
CHO + (b) +
A-10. (a)
OH
|
Na SO CH Ph
3

; (b)
O
||
NHCH C H C
3 5 2
; (c)
18
3 3
O
||
CH C CH
; (d)
B-1. (a)
3
2 3
CH
|
CHO C CH CH CH =
(b)
Ph
|
CHO C CH CH Ph
2
= (c) PhCOCH=C
Ph
CH
3
B-2. (a) CH
3
CH
2
CH
2
CHO ; (b) CH
3
COCH
3
B-3. [X] = , Four stereoisomers are formed.
B-4. (a)
O CH
|| |
H C CH CH C CH
|
CH
3
3
3
= ; (b)
3
CH
|
H C C CH Ph
||
O
= ; (c)
O
||
C CH CH Ph =
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B-5.
B-6. (a) CH
3
CH
2
CH
2
COOEt ; (b) PhCH
2
COOCH
3
; (c) (CH
3
)
2
CHCH
2
COOEt
C-1. (P) = (Q) = DCH
2
OH
C-2.
OH CH
|
OH CH C CH HO
|
OH CH
2
2 2
2
+HCOO
Na
+
D-1. (a) (p) , (q) , (r) CH
3
CH
2
CH
2
OH
(b)
O O
D-2. (a) ; (b)
|
||
COOH
O
;
(c) ; (d)
|
COOH
OH
|
OH
D-3. (A) CH
2
=CHCHO (B)
(C) (D)
E-1.
||
C H
6 5
CH
3
O
Ph
Br
+
||
C H
6 5
CH
3
O
Br
Ph
, (Diastereomer).
E-2. (a) CHI
3
+HCOO
O
Na
(b) CHI
3
+PhCH
2
COO
O
Na
(c) CHI
3
+(Me)
3
CCOO
O
Na

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F-1. (K) , Product is HOOC (CH
2
)
3
COOH.
F-2. Ph
2
C =CH
2
F-3. F-4. X .
PART - II
A-1. (B) A-2. (C) A-3. (D) A-4. (A) A-5. (B)
A-6. (B) A-7. (B) A-8. (B) A-9. (B) A-10. (A)
A-11. (B)
B-1. (D) B-2. (A) B-3. (D) B-4. (B) B-5. (D)
B-6.* (A, B, D)
C-1. (D) C-2. (A) C-3. (A) C-4. (C) C-5. (C)
C-6. (B)
D-1. (B) D-2. (A) D-3.* (A, B, C) D-4. (A) D-5. (C)
D-6. (A) D-7. (B)
E-1. (A) E-2. (C) E-3.* (A, B, C) E-4.* (A, B, C) E-5.* (A, C)
F-1. (C) F-2. (B) F-3. (A) F-4.* (A, C, D) F-5. (C)
F-6. (B) F-7.* (A, B, C)
EXERCISE - 2
PART - I
1. (a) (b)
(c) (d)
Ph C Ph
||
N NH Ph
2. Two nitrogen atoms of semicarbazide that are adjacent to the (C=O) group have their lone pair present in
conjugation so nucleophilicity decreases.
3.

O H
2
In cyclopropanone angle strain decreases after addition of water, while cyclic hemiacetal structure of
2-hydroxy ethanal will develope angle strain.
HOCH
2
CHO

O H
2
Hemiacetal
(Not form due to angle strain)
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4. (a)

+
H
OH CH
|
OH CH
2
2

+

H ) ii (
LiAlH ) i (
4

(b)
O
||
CH C CH CH Br
3 2 2

+
H
OH CH
|
OH CH
2
2
Br CH CH C CH
2 3 2

O O
+
+

H ) ii (
Na C C H ) i (

O
||
CH C CH CH C HC
3 2 2
(c)
CH - Br
2
O

+
H
OH CH
|
OH CH
2
2

CH Br
2
O O

O H ) ii (
PhMgBr ) i (
2

CH - Ph
2
O
5. (a) (b) The OH groups in the trans isomer are too far apart for the cyclic structure to form.
6. (a) 4 (b) 2
7. (a) (b) (c) CH
3
CH
2
COOH
8. (a)
O
||
OCH C CH Ph
3 2
+
O
||
OR C H (b) +
O
||
OCH C CH Ph
3 2

(c)
O
||
OR C Ph +
O
||
H OC C CH CH
5 2 2 3

9. (a) HOOCCH=HC CH=CHCOOH
(b) CH
3
CH =C
CN
CN
(c)
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10. (a) ; (b) ; (c) ; (d)
11.
12. (a) +
CHOH
D
OMe
(b) +
CH OH
2
13. PhCH(OH)COOH 14. HO CH
2
COONa.
15. +
16. (i) (B) reacts with hydroxyl amine and thus (B) has carbonyl group, i.e., >C = O group kettonic either or
aldehyde (CH =O ) group.
(ii) (B) gives negative test with Tollens reagent and thus (B) is ketone.
(iii) (B) is obtained by hydrolysis of (A) and thus both CI atoms should be on same carbon atoms, i.e., (A)
must be gem dihalide as well as not on terminals. Thus, only possibility of (A) is CH
3
CCI
2
CH
2
CH
3
.
(i)
(ii)
(iii)
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17. (A)
(B) CH
3
CHOHCH
2
CH
2
CH
3
(Butan-2-ol )
(C) CH
3
CH =CHCH
3
(But -2- ene )
18. ,
) achiral ( ) Y (
COOH
|
H C C H C
|
OH
5 2 5 2
,
) achiral ( ) Z (
OH
|
H C CH H C
5 2 5 2

,
) ( ) Y (
COOH
|
H C C H C
|
OH
5 2 5 2
vfdjSy
,
) ( ) Z (
OH
|
H C CH H C
5 2 5 2
vfdjSy

PART - II
1. (A) 2. (C) 3. (B) 4. (C) 5. (B)
6. (B) 7. (D) 8. (B) 9. (A) 10. (D)
11. (B) 12. (A)
13. (B) 14. (B) 15. (C) 16. (A) 17. (C)
18. (C) 19. (B)
20. (D) 21. (C)
22. (A)
23. (A, C) 24. (B, C, D) 25. (A, B, C) 26. (A, B, C, D)
27. (A, B, C, D) 28. (A, D) 29. (A, B, D)
30. (B, D) 31. (Aa, B, D) 32. (A, B, C)
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EXERCISE - 3
1. (A) - q ; (B) - p ; (C) - s ; (D) - r
2. (A) - p,q ; (B) - p,r ; (C) - q,s ; (D) - r,s
3. (A) - p, q, s ; (B) - p, q, r, s ; (C) - p ; (D) - q, r, s
4. (A) 5. (B) 6. (A) 7. (D) 8. (D)
9. (D) 10. (B) 11. (D) 12. (C) 13. (A)
14. (A) 15. (A) 16. (A) 17. (D) 18. (A)
19. (A) 20. (C) 21. (B) 22. (C) 23. (C)
24. (D) 25. (A) 26. (D) 27. (A) 28. (B)
29. (A) 30. (A)
31. True 32. True 33. True 34. False
35. Sodium potassium tarterate
36. C
6
H
5
CH(OCOCH
3
)
2
37. Aldol
38. Clemmensens reduction or Wolf kishner reduction
EXERCISE - 4
PART - I
1. (A) = (B) = (C) =
(D) = (E) =
2. A = or ; k
B =
O
||
CH C H C
3 5 6
C =C
6
H
5
CH
2
CH
3
Trans isomer give racemic mixture.
3. (A) 4. (C)
5. A =
Cl
Cl
CH CH CH
2 2 3
||
O
'A'
B = C =
D = E =
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6. (A) (B) (C) (D) (E)
7. Structure of Bombykol is CH
3
CH
2
CH
2
CH =CH CH =CH(CH
2
)
8
CH
2
OH
8. (A)
9.
10. A = B = C =
D = E = F & G are
11. (B) 12. (D) 13. (C) 14. (A)
15. (A) (p, q, s) ; (B) (q) ; (C) (q, r, s) ; (D) (q, r)
16. (C) 17. (B) 18. (A) 19. (D)
20. (B) 21. (A) 22. (B)
23. (A) - p, q, t ; (B) - p, s, t ; (C) - r, s ; (D) - p
24. 1 25. (B) 26. (A) 27. (D)
PART - II
1. (D) 2. (B) 3. (B) 4. (D) 5. (A)
6. (D) 7. (C) 8. (D) 9. (A) 10. (C)
11. (A)
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PART - I : OBJECTIVE QUESTIONS
Single choice type
1. Which of the following will be product of following reactions ?
+
) excess (
3
2 2
3
CH
|
OH CH C CH HO
|
CH

acid
(A) (B) (C) (D)
2.

R
above reaction has reagents R
(A) Zn Hg/HCl (B) N
2
H
4
/HO
(C) H
2
/Ni (D) NaBH
4
3. Which of the following compounds on reaction with conc. NaOH followed by gives following cyclic ester. .
(A) (B)
(C) (D)
4.
A

O
/ excess
OH . Conc
x
A

H
y
The major product (y) in the above reaction :
(A) (B) (C) (D)
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5.

O H
3
A +B
Compound (A) and (B) can be differentiated by :
(A) 2, 4-DNP (B) Fehling solution (C) Lucas reagant (D) NaHSO
3
6. The formation of cyanohydrin from a ketone is an example of : [JEE 90]
(A) Electrophilic addition (B) Nucleophilic addition
(C) Nucleophilic substitution (D) Electrophilic substitution
7. The enolic form of acetone contains : [JEE 90]
(A) 9 sigma bonds, 1 pi bond and 2 lone pairs (B) 8 sigma bonds, 2 pi bond and 2 lone pairs
(C) 10 sigma bonds, 1 pi bond and 1 lone pairs (D) 9 sigma bonds, 2 pi bond and 1 lone pairs
8. m-chlorobenzaldehyde on reaction with conc. KOH at room temperature gives : [JEE 91]
(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.
9. Under Wolf Kishner reduction conditions, the conversions which may be brought about is ? [JEE 92]
(A) Benzaldehyde into Benzyl alcohol (B) Cyclohexanol into Cyclohexane
(C) Cyclohexanone into Cyclohexanol (D) Benzophenone into Diphenylmethane
10. Hydrogenation of benzoylchloride in presence of Pd and BaSO
4
gives [JEE 92]
(A) Benzyl alcohol (B) Benzaldehyde (C) Benzoic acid (D) Phenol
11. Among the given compounds, the most susceptible to nucleophilic attack at the carbonyl group is : [JEE 97]
(A) MeCOCl (B) MeCHO (C) MeCOOMe (D) MeCOOCOMe
12. An organic compound C
3
H
6
O does not give a precipitate with 2, 4-dinitrophenyl hydrazine reagent also does
not react with metallic sodium it could be :
(A) CH
3
CH
2
CHO (B) CH
3
COCH
3
(C) CH
2
=CHCH
2
OH (D) CH
2
=CHOCH
3
13. The product of the reaction
(X) will be :
(A) C
6
H
5
CH=CHCOOH (B)
(C) (D)
14. In the given reaction sequence PhCH
2
CHO (X)
Product (X) will be :
(A) (B)
(C) (D)
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15. (B) +
A and B are :
(A) ,
(B)
(C) Both a and b
(D) ,
[X] , [X] is :
(A) 2 Mole (B) (C) (D) All of these
17. Among the following compounds which one will react with acetone to give a product that contains carbon-
nitrogen double bond ?
(A)
5 6 5 6
H HC N H C
- -
(B) (CH
3
)
3
- -
N
(C) (D) C
6
H
5
- -
NH
- -
NH
2
.
18. The end product is :

A

H
(A) (B) (C) (D)
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19. The final product of the following reaction is :
2
. .
5 2
H N H C +
O=CH O=CH
H C
3
CH
3

acid
(A) (B)
N
..
|
C H
2 5
CH
3
+
CH
3
(C)
N
..
H C
3
CH
3
CH
CH
2
(D)
CH HC
NC H
2 5
H C N
5 2
20. In the given reaction P
P will be :
(A) (B) (C) (D)
21. A compound (X) on treatment with SOCl
2
produces another compound (Y). The latter on hydrolysis yields a
mixture of benzoic acid and methylamine. The compound (X) is :
(A) (B)
(C) (D)
22.
Above conversion is carried out :
(A) X Y (B) X Y
(C) X Y (D) (A) and (C) both
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23. Compound A given below can undergo intramolecular aldol condensation reaction.
product formed is :
(A) (B) (C) (D)
24. Consider following intramolecular aldol condensation reaction.
X
X can be :
(A) (B)
(C) (D)
25. B
final product B is :
(A) (B) (C) (D)
26. The product of given reaction is :
[X]
(A) (B)
(C) (D)
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+
A

O H
2
the major product will be
(A) (B)
(C) (D) CH
3
CH
2
CHO
28. Which of the following reaction will give |-keto aldehyde as the final product ?
(A) + (B) +
(C) + (D) All of these (mi ; qZ l HkhA)
29. An organic compound X on treatment with acidified K
2
Cr
2
O
7
gives compound Y which reacts with I
2
and
sodium carbonate to form Triodomethane. The compound X can be :
(A) CH
3
OH (B) CHCCH
3 3
O
(C) CH
3
CHO (D) CH
3
CH(OH)CH
3
.
30. C
2
H
5
CHO and (CH
3
)
2
CO can be distinguished by testing with
(A) Phenyl hydrazine (B) Hydroxylamine (C) Fehling solution (D) Sodium bisulphite.
31. Which hydrogen of the given compound is least acidic in nature
(A) 1 (B) 2 (C) 3 (D) 4
32. In the given reaction sequence
(A) (B)
Compound (B) is :
(A) (B) (C) (D)
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33. Arrange the following compound in decreasing order of K
eq
for hydrate formation.

(A) III > II > I > IV (B) I > II > III > IV (C) II > III > I > IV (D) III > IV > II > I
34.
O H
EtOH , KCN
2

Product is :
(A) (B)
(C) (D)
35. G H
The products G & H are respectively.
(A) and (B) and
(C) and (D) and
, (X) will be :
(A) (B)
(C) (D)
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37. The number of stereoisomeric products formed in the following reaction is

O H
2
(A) 1 (B) 8 (C) 4 (D) 2
38. What will be the product of the following reaction
+
3 2 2 3
CH C ) CH ( C C H
|| ||
O O

+
H
(A) (B) (C) (D)
39. In the Cannizzaro reaction given below : [JEE 1996]
2Ph CHO
O
OH
Ph CH
2
OH +PhCO
2
The slowest step is :

(A) The attack of OH
O
at the carbonyl group (B) The transfer of hydride to the carbonyl group
(C) The abstraction of proton from the carboxylic acid (D) The disproportionation of Ph CH
2
OH
40. +
(A) (B) (C) (D)
41.

HCN

O H
3
Product
The correct statement about product is
(A) The product is optical inactive (B) The product is meso compound
(C) The product is mixture of two enantiamer (D) Product exist is two diastereomer forms
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42. Which of the following reaction correct product is mention :
(A)

HCl . Con / Hg Zn

(B)

OH / NH NH
2 2
(C)

OH / NH NH
2 2
(D)

HCl . Con / Hg Zn
43. Which of the following compound gives a positive iodoform test
(A) 1 - Phenyl ethanol (B) 2-pentanone (C) 2- pentanol (D) Isopropyl alcohol
44. The sutabile reagent of the following reaction is :

(A) K
2
Cr
2
O
7
/ H
(B) N
2
H
4
/ OH
O
(C) CrO
3
/ H
, Zn-Hg/ Con. HCl (D) CrO

3
/ H
, N
2
H
4
/ OH
O
, A
45. Which of the following aldol reaction product is correctly mention :
(A) +CH
3
CH
2
CHO
O
H O

(B) PhCHO +
O
H O

(C) PhCHO +CH
3
COCH
3

(D)
A

O
H O

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46. Observe the following series of reaction.
P
3 5 2
) H OC ( Al
Q (CH
3
)
2
CHCOO
+(CH
3
)
2
CHCH
2
OH
Which of the following statement is true
(A) The reaction involved are cannizaro reaction followed by acidic hydrolysis
(B)The reaction involed are cannizaro reaction followed by alkaline hydrolysis.
(C) Compound p is isobutanal and the reaction involved are tischenko reaction followed by alkaline hydrolysis
(D) Compound (Q) have fruity smell.
47. During aldol condensation between excess of formaldehyde and acetaldehyde in basic medium we can get
(A) Trihydroxy methyl acetaldehyde (B) Sodium formate
(C) CH
2
=CH CHO (D) Tetrahydroxymethylmethane
48. Which of the following is possible combination to prepare 1 -phenyl 1,3 butadiene from Wittig reaction ?
(A) +Ph
3
P =CH CH =CH
2
(B) +
(C) +Ph
3
P =CH CH =CH
2
(D) +
49. Stability of hydrates of carbonyl compound depends on
(A) Steric hindrance (B) presence of I group on gemdiol carbon
(C) Intramolecular hydrogen bonding (D) Angle strain in carbonyl compound
50. Which one of the following pair is not correctly matched
(A) (B)
(C) CHO (D) CN CHO
51. Which one of the following -dicarbonyl-compound will not show enolisation ?
(A) (B) (C) (D)
52. o , |, unsaturated acids can be prepared by which one of the following reaction ?
(A) C
6
H
5
CHO +(CH
3
CO)
2
O (B)
(C) + (D) CH
3
CH
2
CHO +BrCH
2
COOC
2
H
5

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53. 2CH
2
=O
CH HC
P
Ni / H
2
Q

H
R
R is an ether which a good solvent for grignard reagent. Which of the following are correct.
(A) P =HOCH
2
CCCH
2
OH (B) Q =HOCH
2
CH
2
CH
2
CH
2
OH
(C) R =
O
(D) R =
O
54.
The correct statements are :
(A) R =
COOH
O
O
(B) S =
CH
3
O
O
(C) Q =
CH
3
O
(D) Q and T are homologues.
55. Which of the following will undergo aldol condensation : [JEE-98, 3M]
(A) Acetaldehyde (B) Propanaldehyde
(C) Benzaldehyde (D) Trideuteroacetaldehyde
56. Among the following compounds, which will react with acetone to give a product containing >C =N :
[JEE-98, 3M]
(A) C
6
H
5
NH
2
(B) (CH
3
)
3
N (C) C
6
H
5
NHC
6
H
5
(D) C
6
H
5
NHNH
2
57. The enol form of acetone, after treatment with D
2
O, gives : [JEE-99, 2M]
(A)
2 3
CH C CH
|
OD
= (B)
3 3
CD C CD
||
O
(C)
D CH C CH
|
OH
2 2
=
(D)
3 3
CD C CD
|
OD
=
Assertion-Reason
DIRECTIONS :
58. Statement-1 : CCl
3
CHO forms an isolable crystilline hydrate.
Statement-2 : Powerfully electron withdrawing chlorine atoms stabilise hydrate by intramolecular H-bonding.
59. Statement-1 : Carbonyl compound are more soluble in water than the corresponding alkanes
Statement-2 : H-bonding between carbonyl oxygen and water makes carbonyl compounds more water
soluble than hydrocarbon
60. Statement-1 : Acetophenone and benzophenone can be distinguished by Iodoform test.
Statement-2 : Acetophenone and benzophenone both are carbonyl compound.
61. Statement-1 : Isobutanal does not give iodoform test.
Statement-2 : It does not have ohydrogen.
62. Statement-1 : Acetylene on treatment with alkaline KMnO
4
produce acetaldehyde.
Statement-2 : Alkaline KMnO
4
is a oxidising agent.
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63. Statement-1 : Acetic acid does not undergo haloform reaction.
Statement-2 : Acetic acid has no alpha hydrogen.
64. Statement-1 : Benzaldehyde is more reactive than acetaldehyde towards nucleophilic addition reaction.
Statement-2 : In benzaldehyde >C=O group is resonance stabilised by phenyl ring.
65. Statement-1 : Acetal are easily coverted to parent carbonyl compound. This easy interconverision make
acetal attractive as protecting group to prevent carbonyl compound.
Statement-2 : Acetal are easily hydrolysed in acidic as well as basic medium.
66. Statement-1 : Acetaldehyde react with nitromethane in presence of dil. NaOH to give 1-nitro-2-propanol.
Statement-2 : The hydrogen atom of acetaldehyde are more acidic than nitromethane.
67. Statement-1 : The following conversion
can be done by using NH
2
NH
2
/KOH, A and not by Zn-Hg/con. HCl.
Statement-2 : Zn.Hg/HCl can affect OH group and shows substitution reaction.
68. Statement-1 :
Heat
OH

Statement-2 :Polyccarbonyl compound with o-H give intramolecular aldol condensation in alkaline medium.
69. Statement-1 : The addition of ammonia derivative to a carbonyl compound is carried out in weakly acidic
medium.
Statement-2 : In weakly acidic medium attacking nucleophile is also protonated.
70. Statement-1 : HCHO is always oxidized in the crossed cannizzaro reaction.
Statement-2 : HCHO is the most reactive aldehyde, it exist in aquous OH
O
solution as the conjugate base
of its hydrate , there is also a statistical factor because HCHO has two aldehydic hydrogen
available for transfer while in other aldehyde hydrate anion has only one such hydrogen atom.
71. Statement-1 : Cannizzaro reaction is given by aldehyde having no o-hydrogen atom.
Statement-2 : Cannizzaro reaction is redox reaction.
COMPREHENSION
Comprehensi on # 1
P is an alcohol which on heating with Al
2
O
3
forms an alkene Q. Q on ozonolysis produces R and S. When the
mixture of R and S is heated with NaOH, a redox reaction takes place and a mixture of an acid salt and
alcohol is formed.
72. The alcohol (P) is obtained by :
(A) +CH
3
MgBr (B) +CH
3
MgBr
(C) +CH
2
=O (D) +CH
3
MgCl
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73. The compound (Q) is :
(A) (B)
(C) (D)
74. The compounds R and S are :
(A) , CH
2
=O (B) , CH
3
CH =O
(C) +CH
2
=O (D) +CH
2
=O
Comprehensi on # 2
Aldehyde and ketone undergo nucleophilic addition reaction because of polarity betwen >C=O group. The
reactivity of carbonyl groups toward nucleophile depends upon the nature of inductive effect of group present
at carbonyl carbon.
75. Which among the following is most reactive towards nucleophilic addition reaction.
(A) FCH
2
CHO (B) ClCH
2
CHO (C) Br CH
2
CHO (D) I CH
2
CHO
76. Which of the following is least reactive for nucleophilic addition reaction
(A) (B) (C) (D)
77. Nucleophilic addition reaction over carbonyl compound is shown by :
(A) HCN +dil. NaOH (B) NaHSO
3
(C) CH
3
OH +HCl (D) All of these
Comprehensi on # 3
The conversion of aldehyde having no alpha hydrogen to a mixture of carboxylic acid and primary alcohol is
known as cannizzaro reaction. The most important features of this reaction is the conjugate base of hydrate
of aldehyde.
78. Order of the above reaction is :
(A) 1 (B) 2 (C) 3 (D) 4
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79. Write order of best hydride ion donar in cannizzaro reaction
(I) (II)
(III) (IV)
(A) III >II >I >IV (B) II >IV >III >I (C) II >III >I >IV (D) III >I >II >IV
80. Which of the following cannot undergo intramolecular cannizzaro reaction ?
(A)
O O
|| ||
H C C H (B)
O O
|| ||
Ph C C H (C)
O O
|| ||
Ph C C Ph (D)
O O
|| ||
H C C C PhC
Comprehensi on # 4
In presence of excess base and excess halogen a methyl ketone is converted first into a trihalo substituted
ketone and then into a carboxylic acid. After the trihalo substituted ketone is formed hydroxide ion attacks
the carboxyl carbon because the trihalo methyl ion is the group more easily expelled from the tetrahedral
intermediate. The conversion of a methyl ketone to a carboxylic acid is called a haloform reaction because
one of the product is haloform (CHCI
3
) or CHI
3
or CHBr
3
.
R C CH
3
||
O
) excess (
) excess ( H O
2
I

O

R C OH +C I
3
||
O

R C O +CH I
3
||
O
81. Which of the following compound show haloform reaction and racemisation in OD
/ D
2
O.
(A) CH
3
CH
2
OH (B)
Me
O
Me
Et Ph
(C) (D)
82.
Et
Ph C C C CH
3
O O Me
|
| || ||
A
I

) 3 (
H ) 2 (
OH / ) 1 (
2
product is
(A)
Et
Ph C C COOH
O
Me
|
| ||
(B)
Et
Ph C CH Me
O
| ||
(C)
Ph C O CH Et
O
Me
| ||
(D) Ph C CH OEt
O
Me
| ||
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83.
O
O
Ph

A
I

, H ) 2 (
O Na ) 1 (
product is
(A) O (B)
O
HOOC Ph
(C) (D)
Comprehensi on # 5
Following is the mechanism of Benzoin condensation reaction. Answer the following based on it
H C Ph
||
O
+
CN
-

a

Ph C H
-
|
CN
|
O

b

Ph C
-
|
C N
|
OH

Ph C H
O
||
c

Ph C C Ph
-
| |
O OH
|
H
|
CN
O H O
|| |
Ph C C Ph
|
H

e

Ph C C Ph
-
| |
OH O
|
H
|
CN

d
84. Rate of reaction is given by :
(A) r =k [PhCHO]
2
[CN
O
]
1
(B) r =k [PhCHO]
1
[CN
O
]
1
(C) r =k [PhCHO]
1
[CN
O
]
0
(D)

r =k [PhCHO]
2
[CN
O
]
0
85. Which step involves Bronsted lowery acid base reaction
(A) b, d (B) c, d (C) b, e (D) c, e
86. The benzoin obtained in above reaction when oxidised with Cu / 573 K followed by treatment wth ethanolic
KOH gives
(A) (B)
O O
|| ||
OH C C Ph +
O
||
OH CH C Ph
2

(C)
-
Ph CH COO
2
(D)
OH OH
| |
Ph CH CH Ph
Comprehensi on # 6
Observed the following reaction sequences :
(P)

2
) OH ( Ca
(Q)

4
LiAlH
(R) (chiral carbon)

I NaOH /
2 CHI
3
+S (acid)

CaO / NaOH
(T)

2 2
Cl CrO
(U)
COONa CH
) V (
3
3-phenyl propenoic acid.
87. What is the structure of (T) :
(A)
CH
3
(B)
CH CHO
2
(C)
CHO
CH
3
(D)
O
CH CH
2 3
C CH
3
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88. Which of the following structures is not correct.
(A) (Q) = (B) (V) =CH
3
O
||
C O
O
||
C CH
3
(C) (S) = (D) (R) =
89. What is the structure of (P).
(A) (B) (C)
CH
3
CH
3
CCl
2
(D)
CI
CH
3
CI
CH CH
2
Comprehensi on # 7
Observe the following reactions and its mechanistic steps and intermediate products.
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Reaction -2
+ +ACO
O

90. The intermediate product similar to (IV) following in the reaction-(2) :
(A) (B) (C) (D)
91. The leaving group of step (V) in reaction-2 :
(A) CH
3
COO
O
(B) CO
2
(C) PhCOO
O
(D) PhCH=CHCOOH
92. If PhCH=O
18
is used then O
18
is traced in reaction -2 :
(A)
O
||
H O C Ph
18
(B)
O
||
H O C CH
18
3
(C)
O
||
H O C CH CH Ph
18
= (D)
O
||
H O C O H
18
PART - II SUBJECTIVE QUESTIONS
1. Identify A, B, C and D in the following scheme and write their strucute.
2. Identify A, B, C, D and E in the following scheme and write their strucute. [5 marks]
A A B
4 2
4
SO H . dil
HgSO

3. CH
3
Cl A B C D .
Give the structures from A to D. [2 marks]
4. Give structure for compound A to E.
Cyclohexanol

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5. Give the structure of compound K to M ?
Ethanal Butanol
6. Compounds (A) and (B) on reaction in ether medium and subsequent acidififcation and oxidation give
2,5-dimethyl-3-hexanone. What are (A) and (B) ?
7. An organic compound C
8
H
12
decolourised the bromine water and Baeyers reagent. On complete bromination,
it gave a tetrabromo derivative C
8
H
12
Br
4
having three asymmetric carbon atoms. On ozonolysis, (A) gives
, and HCOOH. What is 'A'
8.
9. (A) on hydration gives (B) which gives positive iodoform test. Also (A) gives white precipitate with Tollen's
reagent. (B) is also obtained from acetyl chlori de on treating with benzene in the presence of anhydrous
AlCl
3
.
10. An alkene C
6
H
12
after ozonolysis yielded two products. One of these gave a positive iodoform reaction but a
negative Tollen's test. The other gave a positive Tollen's test but negative iodoform test. The structure of C
6
H
12
is.
11. Compound (A) C
5
H
10
O forms phenyl hydrozone and gives negative Tollens and Iodoform tests. Compound
(A) on reduction gives n-pentane. Give structure of (A). Explain the reactions.
12. The calcium salt of an acid A (C
6
H
10
O
4
) on dry distillation produced B (C
5
H
8
O). When B is reacted with Bromine
solution in acetic acid, C (C
5
H
7
OBr) is obtained. C is reacted with anhydrous acidic glycol (HOCH
2
CH
2
OH)
solution and PhMgBr is added to this solution carefully and then its is subjected to dilute HCl solution then
compound D (C
11
H
12
O) is formed. D reacted with hydroxylamine hydrochloride to give E and F having
molecular formula (C
11
H
13
NO). E on heating with small amount of H
2
SO
4
produced G which on hydrolysis
produced H. F under the same treatment yields I and J compounds respectively. E, F, G and I all are
isomeric and have molecular formula (C
11
H
13
NO). H have two o hydrogen atom while J have only one o
hydrogen atom. Identify compounds A to J . H on reaction with SOCl
2
followed by treatment with anhydrous
AlCl
3
gives the following compound X.
X =
13. A compound has two isomers (A) and (B) of formula C
5
H
10
O. Isomer (A) on treating with NaOH (aq.) gives 2,
2-dimethylpropan-1-ol and 2, 2-dimethylpropanic acid salt. The isomer (B) on treating with NaOH (aq.) gives
3-hydroxy, 2-propylheptanal. What are A and B ?
14. A
OH / O H ) 2 (
B
) 1 (
2 2
6 2
H

B
2
ZnCl , HCl
C
O Et / Mg
2
CH
3
CH
2
CH
2
MgCl
A

, O H ) 2 (
CHO Ph ) 1 (
3
D
15. An organic compound (A) C
4
H
9
Cl on reaction with aqueous KOH gives (B). (A) on reaction with alcoholic
KOH gives (C) which is also formed on passing the vapours of (B) over heated copper. The compound (C)
readily decolourise bromine water. Ozonolysis of (C) gives two compounds (D) and (E). Compound (D) reacts
with NH
2
OH to give (F) and compound (E) reacts with NaOH to give an alcohol (G) and sodium salt (H) of an
acid. (D) can also be prepared from propyne on treatment with water in presence of Hg
+2
and H
2
SO
4
. Indentify
(A) to (H) with proper reasoning.
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16. An alkene (A) on passing through Br
2
/ CCl
4
gives a compound (B) which on dehydrobromination in the
presence of NaNH
2
gives a hydrocarbon (C). Compound (C) yield. (D) when warmed with dil H
2
SO
4
in the
presence of HgSO
4
. (D) gives a yellow ppt. of (E) on treatment with I
2
and NaOH and also forms sodium salt
of 3, 4-dimethylpentanoic acid. Give structure of (A) to (E) with reason.
17. An organic compound (A) contains 40% carbon and 67% Hydrogen. Its vapour density is 15. (A) on reaction
with a concentrated solution of KOH gives two compound (B) and (C). When (B) is oxidised original compound
(A) is obtained. When C is treated with concentrated HCl, it gives a compound (D) which reduces ammonical.
AgNO
3
solution and also gives effervescences with sodium bicarbonate solution. Write structure (A), (B), (C)
and (D).
18. CH
3
CH=CHCHO

OH
HCN
A
hydrolysis Alkaline

+
) O H (
3
B
19. CH
3
CHO
HMgBr C CH ) i (
|
CH
3
3

+
H / O H ) ii (
2
A
A

4 2
SO H . Conc
B

C
+
H / O H
18
2
D
20.
21. Me
2
C =O +HCN

OH
A
+
O H
3
B
A

4 2
SO H
C
OH , O H . 2
THF / BH . 1
2 2
3
D.
9
H
10
O reacts with NH
2
OH to give two isomers B & C with same moleculer formula
C
9
H
10
ON.The compound B and C isomerizes to D and E respectively on treating with small amount of H
2
SO
4
.
Compound (F) C
8
H
8
O
2
is formed either by (A) on treating with I
2
/KOH followed by acidification or by acid
hydrolysis of (D). Hydrolysis of (E) gives orthomethylaniline. identify the structure from (A) to (E).
23. Compound A to D do not gives tollens test however compound C does. Give the structure of A to D.
4-bromobutanal
HA
OH CH CH HO
2 2

(C
6
H
11 1
O
2
Br)

O Et / Mg
2
(C
6
H
11 1
MgO
2
Br)
A B

(C
7
H
14
O
2
)

HA , OH CH
3 (C
6
H
12
O
2
) [Solomon]
D C
24. Acetophenone on reaction with hydroxylamine hydrochloride can produce two isomeric oximes. Write structure
of the oximes. [JEE-97, 2M]
25. Complete the following giving the structures of the principal organic products. [JEE-97, 8M]
(a) +Ph
3
P =CH
2
E (b)
(c) ClCH
2
CH
2
CH
2
COPh +KOH +MeOH I (d) H
3
CCOCOC
6
H
5
+ NaOH / H
3
O
+
J
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26. How many asymmetric cabon atoms are created during the complete reduction of benzil (PhCOCOPh) with
LiAlH
4
? Also write the number of possible stereoisomer of the possible product. [JEE 97, 3M]
27.

MeMgBr
[JEE 97, 2M]
28. +(COOEt)
2
+EtONa [JEE 97, 2M]
29. An aldehyde (A) (C
11
H
8
O), 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 compound
(A) and (B). [JEE-98, 2M]
30. Write the intermediate steps for each of the following reactions [JEE-98, 2M]
C
6
H
5
CH(OH)C CH

+
O H
3
C
6
H
5
CH =CHCHO
31.
A

A
+

, H ) ii (
LiAlH ) i (
4
B [JEE 98, 2M]
32. The compound X does not show any stereoisomerism. On oxidative ozonolysis it produces Formic acid and
Y. With HIO
4
oxidation, Y forms only acetic acid. X on reaction with 1 mole of Br
2
(with moderate heating)
forms most stable major product Z. Report molecular weight of X and report whether Z will show
stereoisomerism or not.
32. Compound A (C
8
H
8
O) on treatment with NH
2
OH . HCl gives B and C . B and C rearrange to give D and
E respectively on treatment with acid . B , C , D , and E are all isomers of molecular formula C
8
H
9
NO
. When D is boiled with alcoholic KOH , an oil F (C
6
H
7
N) separates out . F reacts rapidly with CH
3
COCl to
give back D . E on boiling with alkali , followed by acidification gives a white solid G (C
7
H
6
O
2
) Identify A
to G. [JEE-99, 7M]
33. Carry out the following transformation in not more than three steps : [JEE 99, 2M]
CH
3
CH
2
C C H CH
3
CH
2
CH
2

C
||
O
CH
3
34. [JEE 99, 3M]
35. Two different Grignard reagents, (X) and (Y) produce C
6
H
5
CH
2
C(CH
3
)
2
OH on reaction with (P) and (Q)
respectively. Give structures of (X), (Y), (P) and (Q). [REE 2000, 2M]
36.
+
H
A A [JEE 2000, 2M]
37.

Base
[JEE 2000, 1M]
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38. Identify A, B & C and give their structures : [JEE 2000, 3M]

A

, NaOH
Br
2
A +B
A

+
H
C (C
7
H
12
O)
39. An organic compound (A), C
8
H
4
O
3
, in dry benzene in the presence of anhydrous AlCl
3
gives compound (B).
The compound (B) on treatment with PCl
5
, followed by reaction with H
2
/ Pd(BaSO
4
) gives compound (C),
which on reaction with hydrazine gives a cyclised compound (D) (C
14
H
10
N
2
). Identify (A), (B), (C) and (D).
Explain the formation of (D) from (C). [JEE 2000, 5M]
40. An organic compound A, C
6
H
10
O, on reaction with CH
3
MgBr followed by acid treatment gives compound B.
The compound B on ozonolysis gives compound C, which in presence of a base gives 1-acetyl cyclopentene
D. The compound B on reaction with HBr gives compound E. Write the structures of A, B, C and E. Show
how D is formed from C. [JEE 2000, 5M]
Matching :
41. Match the compounds/ ions in column I with their properties/reactions in column II.
Column-I Column-II
(A) CH
3
CH =O (p) Redox-reaction
(B) (q) Precipitate with Tollen`s reagent
(C) CI
(r) Nucleophile
(D) (C
2
H
5
O)
3
AI (s) condensation
42.
Reacti on Commonl y used Reagent
(A) Perkin reaction (p) CHCl
3
/ KOH
(B) Aldol reaction (q) CH
3
COOK / (CH
3
CO)
2
O
(C) Cannizzaro reaction (r) dil. KOH
(D) Riemer Tiemann reaction (s) conc. KOH
(A) (p) Aldol condensation
(B) (q) Benzoin condensation
(q) Perkin reaction
(C) PhCH=CHCOOH
(D) (s) Claisen schmith reaction
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44.
45. Column I Column II
(A) (p) Iodoform test
(B) CH
3
.CHO (q) Fehling test
(C) HCHO (r) Tollen's test
(D) (s) FeCl
3
test
(A) (p) Decolourise Br
2
water
(B) (q) 2, 4-DNP
(C) (r) NaHCO
3
(D) (s) FeCl
3
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Reaction Nature of product or intermediate
(A) HCHO +H
+
(p) Carbocation intermediate
(B) +
H O
O
(q) Carbanion intermediate
(C) CH
3
COCH
3

alcohol / Na
(r) Free radical intermediate
(D) PhCOCH
3
+ H O
O
(s) Aldol reaction
(A) +
N C
O

(p) Nucleophilic addition
(B) +NH
2
NH
2

HCl
(q) Nucleophilic addition elimination
(C) +NH
2
NH
2

KOH
(r) Reduction
(D) + D O
O
Excess
O D
2

(s) o-substitution
(A) (p) Nucleophilic addtion
(B) (q) Aliphatic nucleophilic substitution
(C) (r) Elimination
(D) (s) Electrophilic addition reaction
(t) Electrophilic substitution reaction
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MISSCELLANEOUS QUESTION BANK
1. (A) 2. (A) 3. (B) 4. (C) 5. (B)
6. (B) 7. (A) 8. (D) 9. (D) 10. (B)
11. (A) 12. (D) 13. (D) 14. (B) 15. (A)
16. (B) 17. (D) 18. (D) 19. (A) 20. (A)
21. (A) 22. (A) 23. (C) 24. (D) 25. (B)
26. (A) 27. (D) 28. (A) 29. (D) 30. (C)
31. (B) 32. (A) 33. (A) 34. (A) 35. (B)
36. (C) 37. (D) 38. (B) 39. (B) 40. (D)
41. (A, D) 42. (A, B, C, D) 43. (A, B, C, D) 44. (C, D) 45. (A,B,C)
46. (C, D) 47. (A, B, C, D) 48. (A, B) 49. (A, B, C, D) 50. (B, D)
51. (B, C, D) 52. (A, B, C) 53. (A, B, D) 54. (A, B, C, D)
55. (A, B, D) 56. (A, D) 57. (A)
58. (A) 59. (A) 60. (B) 61. (C) 62. (D)
63. (C) 64. (D) 65. (C) 66. (C) 67. (A)
68. (A) 69. (C) 70. (A) 71. (B)
72. (C) 73. (D) 74. (C)
75. (A) 76. (A) 77. (D)
78. (B) 79. (A) 80. (C)
81. (D) 82. (B) 83. (A)
84. (A) 85. (A) 86. (A)
87. (A) 88. (A) 89. (C)
90. (B) 91. (C) 92. (A)
1. (A) (B)
(C) (D) (Succinic acid )
2. (A) (B) (C)
(D) (E)
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3. (A)
2 2 3
NO CH CH (B)
(C) (D)
4. (A) (B) (C)
(D) (E)
5. (K) (L) CH
3
CH=CHCOOEt (M) CH
3
CH=CHCH
2
OH
6.
8. A =Propyne B = C = (aldol product)
D =CH
3
C C CH
3
E = F =
G =
9. (A) C
6
H
5
C C H (B)
11. (1) (A) forms phenyl hydrazone and thus carbonyl compound, i.e., an aldehyde or ketone.
(2) (A) give s negative Tollens reagent test and thus (A) is ketone.
(3) (A) also does not respond Iodoform test and thus it is not methyl ketone.
(4) (A) on reduction gives n-pentane and thus, (A) is straight chain compound.
(5) Keeping in view of above facts and the formula of (A), i.e., C
5
H
10
O, (A) is
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12.
COOH CH CH
|
COOH CH CH
2 2
2 2

on distillati Dry

COOH CH / Br
3 2
(A) (B) (C)

HCl / OH NH
2 +
(D) (E) (F)

4 2
SO H

O H
2
Ph
|
NH CH CH CH CH HOOC
2 2 2 2

(E) (G) (H)

4 2
SO H

O H
2
Ph
|
COOH CH CH CH CH N H
2 2 2 2

(F) (I) (J )
13. (A)
nal ethylpropa dim 2 , 2
3 3
CCHO ) CH (
(B)
) al 1 tan Pen (
3 2 2
2 2 2 2 3
CH CH CH O
| ||
CHO CH CH CH CH CH CH

14. (A) CH
3
CH =CH
2
(B) CH
3
CH
2
CH
2
OH (C) CH
3
CH
2
CH
2
Cl (D) PhCH =CHCH
2
CH
3
15. (A) , (B) , (C) , (D)
(E) HCHO, (F) , (G) CH
3
OH, (H) HCOONa
16. (A) (B)
(C) (D)
(E) CHI
3
17. (A) 2HCHO, (B) CH
3
OH, (C) HCOONa, (D) HCOOH
18. (A)
OH
|
CN CH CH CH CH
3

, (B)
OH
|
COOH CH CH CH CH
3

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21. (A)
3
3
CH
|
CN C CH
|
OH

(B)
3
3
CH
|
COOH C CH
|
OH

(C)
3
2
CH
|
COOH C CH
(D)
3
2
CH
|
COOH CH HOCH
22. (A) (B) (C)
(D) (E)
CH
3
O
CH C NH
3
23. (A) (B)
(C) (D)
24.
O H
HCl
2

It shows two isomers which are geometrical isomers to each other and represented as follow :
(i)
C H
C =N
CH OH
6 5
3
Syn-methyl anti-Syn-phenyl
Ketoxime
(ii)
C H OH
C =N
CH
6 5
3
Syn-phenyl anti Syn-methyl
Ketoxime
Their configuration may be identified with the help of Backmanns Rearrangement

anhydride Acid or
PCl
or
acid of esence Pr
5

acetamide phenyl N
H C NH C CH
||
O
5 6 3

anhydride Acid
or
PCl or
acid of esence Pr
5

acetamide phenyl N
CH C NH H C
||
O
3 5 6

Therefore both isomers give different product with different configturation.
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25. (a) CH
2
+Ph
3
P=O (b)
(c) (d)
26.
OH OH
| |
Ph H
*
C H
*
C Ph
two chiral C atoms ; total 3 isomers :
27. 28.
29. A =
Ozonolysis
+

moles Two
COOH COOH
| |
CHO CHO
B =
) B (
COOH
|
CHO

O Ag
2

COOH
|
COOH
oxalic acid
30.
CH C CH H C
|
OH
5 6

O H
3

O H
2
C
6
H
5
H C
C CH C
6
H
5
CH =C = H C

OH
O
C
6
H
5
CH =C =CHOH C
6
H
5
CH =CH CHO
Enol-form (less stable) Keto form (more stable)
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31.
Base
) A (
) CHO H C (
5 6

4
LiAlH ) i (

Rearrangement

32. X

3
O
HCOOH +Y

4
HIO
CH
3
COOH
So Y = CH C C CH
3 3
O O
X = CH C C CH
3 3
CH
2
CH
2
Z = CH C C CH
3 3
CH Br
2
CH Br
2
(1,4 Addition)
Yes, It will show geometrical Isomerism.
M.W. (X) =82
32. So compound are
A = B =
C = D =
5 6 3
H C NH C CH
||
O

E =
3 5 6
CH NH C H C
||
O
F =C
6
H
5
NH
2
G = H O C H C
||
O
5 6

33. CH
3
CH
2
C CH
Na
CH
3
CH
2
C CNa
X CH
3
CH
3
CH
2
C CCH
3

OH , O H
THF / BH
2 2
3

3 2 2 3
CCH CH CH CH
||
O
CH
3
CH
2
CH
2
CH =O
3 2 2 3
CCH CH CH CH
||
O
34.
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35. (X) C
6
H
5
CH
2
MgX (Y) CH
3
MgX (P) (Q)
+
OH
|
H C CH C CH
|
CH
5 6 2 3
3

OH
|
H C CH C CH
|
CH
5 6 2 3
3

36. (A) (Beckmann's rearrangement) 37.
38. (A) CHBr
3
(B) (C)
39. (A) (B) (C) (D)
40. A = , B =
41. (A) (q, s) ; (B) (q) ; (C) (q, r) ; (D) (p)
42. (A) - (q) ; (B) - (r) ; (C) - (s) ; (D) - (p)
43. (A) - (q) ; (B) - (s) ; (C) - (r) ; (D) - (p)
44. (A) - s ; (B) - p ; (C) - q ; (D) - r
45. (A) - q, r ; (B) - p, q, r ; (C) - q, r ; (D) - s
46. A p, q B r C p, q, s D p, q, s
47. A p B q, s C q, r D q, s
48. A p, B q, C r D s
49. A p, t B q, r, t C q, r, s D s, t
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CARBOXYLIC ACIDS & ACID DERIVATIVES | 107
CARBOXYLIC ACIDS & ACID DERIVATIVES
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Section (A) : Carboxylic acid
A-1. Describe the preparation of acetic acid from acetylene.
A-2. In what way can acetic acid can be distinguished from acetone ?
Section (B) : Acid Halide
B-1. Give the IUPAC names of the following compounds.
(a)
O O
|| ||
Cl C CH C Cl
2

(b) (c) Cl C CH Ph
||
O
2
(d)
O
||
Cl C Ph
B-2. Observe the following reactions.
F C CH
||
O
3
1
2
r
O H

Cl C CH
||
O
3
2
2
r
O H

Br C CH
||
O
3
3
2
r
O H

I C CH
||
O
3
4
2
r
O H

Identify the order of the rate of reaction r
1
, r
2
, r
3
and r
4
, give reason.
B-3. Predict the products of the following reactions
(i) +
(ii) Cl C Ph
||
O
+
(iii) Cl C CH CH
||
O
2 3
+Ph H

3
AlCl
(iv)
fDouksyhu Quinoline
C / Pd / H
2

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Section (C) : Ester
C-1. The boiling point of esters are always less than the corresponding carboxylic acids. Why ?
Ans. Because esters do not form hydrogen bonds
C-2. Explain the order of the rate of esterification of the following acid with MeOH :
MeCH
2
COOH >Me
2
CHCOOH >Me
3
CCOOH >Et
3
CCOOH >>(i-Pr)
2
CHCOOH
Section (D) : Amide
D-1. Predict the products of following reaction
(a)
O H
NaOH
2

(b)

heat
(c) +H
2
SO
4

O H
2
(d) +

D-2. Write balanced equation, having all the organic product , for the reaction of phenylacetamide with
(a) hot HCl (aq) (b) hot NaOH (aq)
D-3. What products would you expect from acidic & basic hydrolysis of each of the following amides ?
(a) N,N - Diethylbenzamide
(b)
(c)
Section (E) : Anhydride
E-1. Predict the products of the following reaction
(a) Phenol +acetic anhydride in presence of lewis acid.
(b) Aniline +phthallic anhydride on heating.
(c) Anisole +succinic anhydride & aluminium chloride
(d) Benzaldehyde +acetic anhydride in presence of acetate ion.
E-2. Predict the products of the following reactions
(a) +
A

+
H
(b) +CH
3
NH
2

A
(c) +CH
3
CH
2
OH
A

+
H
(d) +

3
AlCl
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A-1. Which of the following acids has the smallest dissociation constant ?
(A) (B) O
2
NCH
2
CH
2
COOH
(C) ClCH
2
CH
2
COOH (D) NCCH
2
CH
2
COOH
A-2.* In the following ester there are three carbon oxygen bonds denoted by x , y and z
Their lengths are in order
(A) x =y =z (B) x <y (C) y <z (D) x <z
A-3.
heat SO H
acid acetic , O H
4 2
2

Product is :
(A) (B) (C) (D)
A-4. X Y
In the above reaction sequence X & Y are :
(A) Identical (B) Homologs (C) Structural isomers (D) Stereoisomer
A-5. End product of this reaction is :

(A) (B) (C) (D)
A-6.
O H ) ii (
Br / P ) i (
2
2
X, X is :
(A) (B) (C) (D)
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A-7.
A
A, A is : A A gS :
(A) (B) (C) (D)
A-8. + x +y the organic products x and y are
(A) Enantiomers (B) Diastereomers (C) Metamers (D) achiral molecules
A-9. For the following acids the rate of decarboxylation on heating would be :
I. II.
III. NO
2
CH
2
COOH IV. HOOCCH
2
COOH
(A) III >I >IV >II (B) I >III >IV >II (C) III >IV >I >II (D) I >IV >III >II
Section (B) : Acid Halide
B-1.* The correct order/s of decreasing reactivity of the given compound towards hydrolysis under identical condition
is/are :
(A) CH
3
COCl >CH
3
CONH
2
(B) CH
3
COCl >(CH
3
CO)
2
O
(C) CH
3
COOCH
3
>CH
3
COCl (D) (CH
3
CO)
2
O >CH
3
CONH
2
B-2. Phosgene (COCl
2
) +1 mol C
2
H
5
OH
3
NH
X, X is
(A)
O
||
NH C NH
2 2

(B) NH =C =O (C)
O
||
Cl C NH
2

(D)
O
||
NH C EtO
2

B-3. Cl C C ) CH (
||
O
3 3
+LiAlH
4
(excess) (vkf / kD; )
+
O H
3
X, X is : (X gS :)
+LiAlH
4
X,
(A) H C C ) CH (
||
O
3 3
(B)
3
2 3
3
CH
|
OH CH C CH
|
CH

(C)
3
2 2 3
CH
|
OH CH CH CH CH (D) CH
3
CH
2
CH
2
CH
2
CH
2
OH
B-4. For the given reaction
A is gSA
(A) CH
2
=CHOCH
3
(B) CH
2
=CHOH (C) (CH
2
=CH)
2
CuLi (D) (CH
2
=CH)
2
Cl
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B-5. SH CH CH Cl C PhCH
||
O
2 3 2
+

X, X is
(A)
3
3
CH
|
CH CH S C Ph
||
O
(B)
5 2 2
H C S C CH Ph
||
O

(C)
Ph S C CH CH CH
||
O
2 2 3

(D)
3
3
CH
|
Ph S C CH CH
||
O

B-6. + Cl C Cl
||
O
X, X is gSA
(A) (B) (C) (D)
C
NH
||
O
O
C
O
Section (C) : Ester
C-1. List the following esters in order of decreasing reactivity in the second step of a nucleophilic acyl substitution
reaction .
(A) IV >I >III >II (B) IV >III >I >II (C) III >IV >I >II (D) II >I >III >IV
C-2. Which one of the following is least reactive for hydrolysis reaction?
(A) (B)
(C) (D)
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C-3. Which one of the following esters is most reactive for saponification ?
(A) (B) (C) (D)
C-4.* Which of the following is not the correct order of esterification of following acids with CH
3
OH :
HCOOH , CH
3
COOH , CH
3
CH
2
COOH , , is
I II III IV
(A) I =II =III =IV (B) I >II >III >IV (C) I <II <III <IV(D) I >IV >III >II
C-5.
4 2
SO H , ethanol
X, X is :

4 2
SO H , ethanol
X, X gS %
(A) (B)
(C) (D)
C-6. In the given reaction
, [X] is gSA
(A) (B)
(C) (D) No reaction is possible
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C-7.
OH CH
OCH
3
3
X, X is
(A)
OH ) CH ( C CO H
||
O
5 2 3

(B)
3
2 2 2 3
CH
|
OH CH CH CH CH C CO H
||
O

(C)
3
2 2 2 3
CH
|
||
O
(D)
3
2 2 2 3
CH
|
||
O

C-8. Ease of esterification of following alcohol with HCOOH is
CH
3
CH
2
OH (CH
3
)
2
CH OH (CH
3
)
3
C OH
I II III
(A) III >II >I (B) I >II >III (C) II >I >III (D) II >III >I
C-9.
heat
NH CH
2 3
X, X is
(A) (B)
(C) (D)
C-10. In the given reaction
[P] will be
(A) (B)
(C) (D)
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Section (D) : Amide
D-1.
O H ) 2 (
LiAlH ) 1 (
2
4
X, X is
(A) (B) (C) (D)
D-2. Consider the following compounds :
I II
III IV
The decreasing order of reactivity towards hydrolysis by aqueous NaOH is :
(A) I >II >III >IV (B) III >II >IV >I (C) IV >I >II >III (D) I >IV >II >III
D-3.* C NH
2
O
+ CH C NH
2 2
O
15
OH, Br , heat
2
-
X +Y
Product X &Y can not be :
(A)
NH
2
&
CH NH
2 2
15
(B)
CH NH
2 2
15
&
CH NH
2 2
(C)
CH NH
2 2
&
NH
2
15
(D)
NH
2
&
NH
2
15
D-4. In the given reaction sequence
(A) (B)
(A) and (B) respectively are :
(A) and (B) and
(C) and (D) and
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Section (E) : Anhydride
E-1.* Which of the following will yield a cyclic compound on heating :
(A) (B) (C) (D)
E-2. In the following reaction X Y. .
X is the lowest molecular weight optically active dicarboxylic acid. What is the structure of Y.
(A) (B) (C) (D)
E-3. + X, X is
(A) (B) (C) (D)
E-4.

4
LiAlH
A

PCC
B

2 2
NH NH
C, Product (C) is
(A) (B) (C) (D)
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Section (A) : Carboxylic Acid
1. How will you convert acetaldehyde into but 2enoic acid.
2.
14
CH
3
I +Na
14
CN X

+
O H
3
Y
heat ) OH ( Ca ,
2
Z
Identify compound X, Y and Z.
3. In case of aldehydes and ketones there is nucleophilic addition but in case of acyl compound there is
Section B: Acid Halide
4. Show how would you prepare the following compounds with the help of appropriate acid chlorides?
(A) N, Ndimethylacetamide (B) Ethyl propanoate
(C) (D) Benzyl benzoate
5. (a) List three reagents for converting a carboxylic acid to its acyl chloride.
(b) Select the most convenient of the three reagents, give a reason for your choice and write a balanced
equation for its reaction with RCOOH.
6. CH
3
COOH
O H (ii)
(excess) PCl (i)
2
3
(X)
2
SOCl
(Y)

4 2
BaSO / Pd / H
(Z)
OH
W +S
write the structure of X,Y,Z,W and S
7. (a) Why cannot HCl convert RCOOH to RCOCl ? (b) Why is it more efficient to prepare an ester by the
sequence : acid acyl chloride ester, rather than acid ester ?
Section C : Ester
8. Where would you expect to find the labelled oxygen if you carried out an acid catalyzed hydrolysis of methyl
benzoate in
18
Olabeled water ? Write detailed mechanism to supports your answer.
9. A +B, find A and B.
Section D : Amide
10. The respective boiling points and molecular weights (in/gmol) of the following amides are : MeCONH
2
, 221C
and 59; MeCONHMe, 204C and 73 ; MeCONMe
2
, 165C and 87. Explain.
4
H
7
N does not react with acetyl chloride or nitrous acid. (A) when boiled with
acetic acid gave another compound B (C
6
H
11
O
2
N) and on reduction with lithium aluminium hydride formed C
(C
4
H
11
N). Compound (C) liberates nitrogen with nitrous acid. Identify compound (A) , (B) and (C).
12. Both cis- and trans-1,2-cyclohexanedicarboxylic acids form anhydrides on heating, but the anhydride formed
from the cis-1,2-cyclopentanedicarboxylic acid only. explain.
Section E: Anhydride
13. Complete the folliowing reaction
(a) Toluene +phthalic anhydride +AlCl
3
(b) Product from (a) +Conc. H
2
SO
4
+ A
14. Give the product of each of the following reactions :
(a) succinic anhydride +MeOH A
3
PCl
B
2
MeNH
C,
(b) phthalic acid +NH
3

D
C 300
E ,
(c) MeCH(CH
2
COOH)
2

O ) CO CH (
2 3 F. .
4
H
4
O
3
3
gives compound B.
The compound B on treatment with PCl
5
, followed by reaction with H
2
/Pd(BaSO
4
) gives compound C, which
on reaction with hydrazine gives a cyclised compound D (C
10
H
10
N
2
). Identify A,B,C and D. Explain the forma-
tion of D from C.
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(without section in class room but store sections in Main Sheet)
Single choice type
Section A: Carboxylic Acid
1. Which compound should have zero dipole moment ?
(A) (B)
(C) (D)
2. When picric acid is treated with aqueous sodium bicarbonate a gas is liberated with effervesence.
The gas evolved would be :
(A) H
2
(B) CO
2
(C)
14
CO
2
(D) NO
2
3.
(C O) bond lengths designated by A, B, C are in order :
(A) A =C <B =D (B) A <B <C =D (C) A <C =D <B (D) All equal l Hkh l eku
4.
+

O H . 3
CO . 2
ether diethyl Mg . 1
3
2
product is :
(A) (B)
(C) (D)
5. In the reaction sequence
(A) Compound A will be optically active
(B) Product is racemic mixture of o-hydroxyacid
(C) Product is optically active containing o-hydroxy acid.
(D) Product is optically active contaning o-hydroxy amide.
6. Identify X in the reaction sequence
X HOOC CH
2
CH
2
COOH
(A) CH
3
CH
3
(B) CH
2
=CH
2
(C) H C C H (D) CH
3
CH =CH CH
3
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7. The final product of the following reaction sequence is

(A) (B) (C) (D)
8. In the reaction sequence X & Y are
(A) Homologs (B) Identical (C) Structural isomers (D) Enantiomers
9. A racemic mixture of carboxylic acid having one chiral centre is treated with enantiomerically pure amine. the
products formed are :
(A) diastereomers (both optically active) (B) diastereomers (only one is optically active)
(C) Racemic mixture (D) two optically inactive ammonium salts of acid.
10. The product P of the following reaction is
CH
3
COOH P
(A) CH
3
COOH (B) (C) (D)
11. For the following conversion

The effective method is :
(A)
(B)
(C)
(D)
12. Q.
In the above reaction Q is.
(A) (B) (C) (D)
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13. For the following conversion the correct sequence of reagents is

(A) (B)
(C) (D)
CH
3
COOH [X], [X] will be
(A) CH
3
COOH (B) HOOCCH
2
CH
2
COOH (C) (D)
15. In the reaction sequence CH
3
CH
2
COOH x y
(A) x is (B) y is
(C) z is (D) all are correct
16.
excess
HI . Conc
P the producet P is.
(A) (B) (C) (D)
17. The correct sequence of reagents for the following conversion.
is
(A)
+

O H ) ii (
KCN ) i (
3

(B)
(C)
(D)
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Section (B) : Acid halide
18. Nucleophilic substitution at acyl carbon of a carboxylic acid derivative generally proceeds by :
(A) Addition-elimination mechanism (B) Elimination-addition mechanism
(C) S
N
1 mechanism (D) S
N
2 mechanism
19. Which of the following proposed reactions would take place most quickly under mild conditions ?
(A) CH
3
CONH
2
+NaCl CH
3
COCl +NaNH
2
(B) C
6
H
5
COCl +CH
3
NH
2

(C) CH
3
COCl +CH
3
NH
2
CH
3
CONHCH
3
(D) CH
3
COOC
2
H
5
+HOH CH
3
COONa +C
2
H
5
OH
20. In the given reaction sequence :
C
6
H
5
CN A B C, (C) is
(A) (B) (C) (D)
21.
) excess ( Cl C Ph NH N H
||
O
2 2
+

NaOH
X, X is
(A) Ph NH C H
||
O
(B) OH NH C Ph
||
O
(C)
2
NH C Ph
||
O

(D) Ph C NH NH C Ph
|| ||
O O

22. +
Pyridine
X, X is
(A) (B)
(C) (D)
23. + CH
3
CH
2
CH
2
CH
2
NH
2

C 140
X,
(A) (B) (C) (D)
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Section (C) : Ester
24. Consider the following statements for hydrolysis reaction :
(I) is more reactive than C
6
H
5
COOC
2
H
5
(II) is more reactive than
(III) is more reactive than
Of these the correct statements are
(A) I and II (B) I, II and III (C) II and III (D) I and III
A

O
O H / H
2
[P], [P] will be :
(A) (B) (C) (D)
, [X] is
(A) (B) (C) (D)
27.
EtOH
EtO

X
(A) X is (B) X is
(C) X is (D) X is
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28. The product x in the above reaction is
x
(A) (B)
(C) (D)
29. x , x is
(A) (B) (C) (D)
30. Identify the end product in the following reaction

(A) (B) (C) (D)
31. The product X in the following reaction is
acetaldehyde +X.
(A) (B) (C) (D)
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32.
x in the above reaction is
(A) (B) (C) (D)
33.
O H
/ NaOH
2

A
X, X is gSA
(A) (B) (C) (D)
34. X
A / NH
3
B
A

KOBr
C
2
HNO
(CH
3
)
3
C OH, X is:
(A) (CH
3
)
3
C COOH (B) (CH
3
)
3
C CH
2
O (C) (CH
3
)
3
C CONH
2
(D) none is true
35.
2 2 2
3
NH C CH CH PhCH
|| |
O CH

NaOH , Br
2
X, X is
(A)
Ph NH CH CH CH
|
CH
2 3
3

(B)
OH
|
NH CH CH CH Ph
|
CH
2 2
3

(C)
2 2 2
3
NH CH CH CH Ph
|
CH

(D)
O
||
NH C CH CH Ph
| |
CH CH
2
3 3

36. Urea (H
2
NCONH
2
) +hot dilute NaOH X +NH
3
, X is
(A)
O
||
Na . NH C NaNH
(B)
O
||
Na NH C N H
2
(C) Na
2
CO
3
(D)
O
||
NH C H
2

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37. X, X is :
(A) (B) (C) (D)
38. Correct water solubility order/s amongst the following pairs is/are
(A) CH
3
CH
2
CH
2
CH
2
OH >
3
3
3
CH
|
OH C CH
|
CH
(B)
OH
COOH
<
OH
COOH
(C)
Cl
Cl
<
Cl
Cl
(D) C C
HC
3
COOH H
H
> C C
H C
3
COOH
H
H
39. The correct reagent sequence for the following conversion
, is
(A) (B)
(C) (D)
40. The correct order/s for the given pair of isomers is / are
(A) > (Melting point)
(B) > (Dipole moment) (
(C) > (Boiling point)
(D) > (Water solubility)
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MIXED TYPE PROBLEMS
PART - I : MATCH THE COLUMN
Match the column
(A) (p) Hydrolysis
(B) (q) Esterification
(C) (r) Saponification
(D) (s) Acid base reaction
(t) S
N
2 Th reaction
2. If compound in column I is heated then select the correct match from column II for product obtained.
Column-I Column-II
Reaction product formed
(A) (p) Diastereomers
(B) (q) Racemic mixture
(C) (r) Meso compound
(D) (s) CO
2
gas will evolve
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PART - II : COMPREHENSION
Comprehension - 1
Observe the esterification mechanisms for primary and tertiary alcohols.
Type.1 CH
3
COOH +CH CH CH OH
3 2 2
Propyl =Pr

4 2
SO H . Conc
CH COCH CH CH
3 2 2 3
O
Mechanism
CHC
3
O
OH

. 1 Step
H

CHC
3
OH
OH
+

CHC
3
OH
OH
+ Pr
Step 2
O
H
. .
CHCOH
3
+
OH
O
Pr
H

O H
H
3 Step
2
CH COCH CH CH
3 2 2 3
O
Type. 2
CHC
3
O
OH
+
CHCOH
3
CH
3
CH
3

4 2
SO H . Conc
CHCOCCH
3 3
CH
3
CH
3
O
Mechanism
CHCOH
3
CH
3
CH
3

. 1 Step
H

+
. .
CHC
3
CH
3
CH
3
+H O
2
CH C
3
OH
O

CHCOCCH
3 3
CH
3
CH
3
O
3. CH
3
COOH +C HOH
2 5
18

4 2
SO H . Conc
(P)
CH
3
COOH +(CH ) COH
3 3
18

4 2
SO H . Conc
(Q)
In the above reaction (P) and (Q) are respectively :
(A) CHCOC H
3 2 5
O
,
CH
3
CHCOCCH
3 3
O
CH
3
18
(B)
CH COC H
3 2 5
O
18
,
CH
3
CHCOCCH
3 3
O
CH
3
(C) C HCOCH
2 5 3
O
18
,
CH
3
CHCOCCH
3 3
O
CH
3
(D)
CH COC H
3 2 5
O
18
,
CH
3
CHCOCCH
3 3
O
CH
3
18
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4. CH
3
COOH +
H
CH
3
OH D

4 2
SO H . Conc
(X)
CH
3
COOH +
CH
3
C H
2 5
PhCOH

4 2
SO H . Conc
(Y)
(A) (X) is optically active while (Y) is optically inactive (B) Both (X) and (Y) are optically active
(C) Both (X) and (Y) are optically inactive (D) (X) is optically inactive while (Y) is optically active.
5. (+) Octan-2-ol esterifies with Acetic acid to give optically inactive racemised product. It must have gone by
(A) Type I mechanism (B) Type II mechanism
(C) Mix type I and type II mechanism (D) More by type I and less by type II mechanism
Comprehension - 2
Observe the following sequence of reaction and answer the questions based on it
Phenylacetylene x y z w
6. Compound z is
(A) (B)
(C) (D)
7. Which of the following statement is not correct
(A) y decolourises Br
2
/H
2
O solution (B) on heating z CO
2
is liberated
(C) w on reaction with NaOI gives yellow ppt (D) x liberates H
2
gas with Na metal
8. Which of the following compound give benzoic acid on KMnO
4
oxidation
(A) w (B) y (C) z (D) all.
Comprehension - 3
Hoffmann rearrangement
In the Hofmann rearrangement an unsubstituted amide is treated with sodium hydroxide and bromine to give
a primary amine that has one carbon lesser than starting amide.
General reaction :
+NaOH +Br
2
R N =C =O R NH
2
isocyanate
Mechanism :

O
OH

CO
2
|+R
O
NH

R NH
2
If the migrating group is chiral then its cofiguration is retained. Electron releasing effects in the migrating
group increases reactivity of Hofmann rearrangement.
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9. Which of the following compound(s) cannot give Hoffmann rearrangement :
(A) (B)
(C) (D)
10. Arrange the following amides according to their relative reactivity when reacted with Br
2
in excess of strong
base
(A) IV >I >II >III (B) II >I >III >IV (C) II >IV . III >I (D) II >I >IV > III
11. + Products
(A) & (B) &
(C) & (D) B & C both are correct
Comprehension - 4
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12. Which reagent (X) is used to convert I to II
(A) NaOBr (B) Br
2
/CCl
4
(C) Br
2
/H
2
O (D) Na
2
CO
3
with H
2
SO
4
13. Which is true for the above reaction
(A) is formed during the reaction
(B) The rate determining step is migration of para tollyl group.
(C) Formation of II is R.D.S
(D) All are correct
14. +
Under Hoffmans condition above compounds gives respectively.
(A) (B) &
(C) + (D) +
PART - III : ASSERTION / REASONING
DIRECTIONS :
15. Statement-1 : (CH
3
)
3
CCH
2
COOH is more acidic than (CH
3
)
2
SiCH
2
COOH.
Statement-2 : Si is electropositive element than carbon and therefore has an electron donatingl (+I) induc-
tive effect.
16. Statement-1 : The Reactions of acids are quite different from aldehydes & ketones
Statement-2 : In acids one nucleophile replaces another on the acyl carbon atom but aldehyde & ketone
give simple nucleophilic addition reaction .
17. Statement-1 :

A

Statement-2 : Decarboxylation takes place readily at |-keto acid.
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18. Statement-1 : Acyl chloride undergo nucleophilic attack more rapidly than an alkyl chloride.
Statement-2 : The transition state of the acid derivative leading to the tetrahedral intermediate is less
sterically hindered than transition state in S
N
2 reaction of alkyl halide.
19. Statement-1 : The reaction of CH
3
SO
2
Cl with optically active 2-butanol gives an active methanesulphonate
which is treated with aq.NaOH giving back 2-butanol but having opposite configuration.
Statement-2 : attacks with inversion at the chiral carbon displacing .
20. Statement-1 : Unsubstituted or mono substituted amides are water soluble.
Statement-2 : The dipole moments of most amides are very high.
21. Statement-1 : Phthallimide has less acidic H attached to N as compared to benzamide.
Statement-2 : Former has two groups to stabilize the amide anion.
22. Statement-1 : The base catalysed hydrolysis of ester order is
(1) CH
3
COOCH
3
>CH
3
COOC
2
H
5
>CH
3
COOCH(CH
3
)
2
.
(2) > > >
Statement-2 : S
N
2 Th is sterically as well as electronically controlled reaction.
23. Statement-1 : CO bond length is shorter in an ester as compared with an anhydride.
Statement-2 : A degree of cross conjugation exist in the anhydride which decreases the delocalisation to
each carbonyl oxygen.
24. Statement-1 : Acid catalysed hydrolysis of ester is reversible while base catalysed hydrolysis is irriversible.
Statement-2 : In acid catalysed ester hydrolysis carboxylic acid is formed on which nucleophilic attack of
alcohol is possible but in base catalysed ester hydrolysis carboxylate anion is formed on which nucleophilic
attack is not possible.
PART - IV : TRUE / FALSE
25._ The characteristic reaction of acid derivatives is S
N
2Th.
26._ Amides have higher boiling points than corresponding carboxylic acids.
27._ Acid catalysed hydrolysis of esters is known as saponification.
28._ Carboxylic acids and amides liberate hydrogen gas on reaction with alkali metals.
29._ Acid catalysed hydrolysis of esters is a reversible reaction while base catalysed hydrolysis of esters
is an irreversible reaction.
PART - V : FILL IN THE BLANKS
30._ Acetic acid 100% free of water is known as .................. acetic acid.
31._ Aromatic carboxylic acids are ........................... acids than aliphatic carboxylic acids.
32._ On heating malonic acid forms .................. while succinic acid, forms ...........................
33._ Benzoic acid and phenol can be separated by the use of ........................... solvent.
34._ Phthalamide is ........................... acidic than benzamide.
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PART - I : IIT-JEE PROBLEMS (PREVIOUS YEARS)
1. CH
3
CH
2
COOH
e min bro
and P

A A
A
+

H . 2
) excess ( KOH alcoholic . 1
B [JEE 95, 2M]
2. Which of the following carboxylic acids undergoes decarboxylation easily. Explain briefly. [JEE 95, 2M]
(A) C
6
H
5
CO CH
2
COOH (B) C
6
H
5
CO COOH
(C)
OH
|
COOH CH H C
5 6

(D)
2
5 6
NH
|
COOH CH H C
3. The molecular weight of benzoic acid in benzene as determined by depression in freezing point method
corresponds to : [JEE 96]
(A) ionization of benzoic acid (B) dimerization of benzoic acid
(B) trimerization of the benzoic acid (D) solvation of benzoic acid
4. A compound D(C
8
H
10
O) upon treatment with alkaline solution of iodine gives a yellow precipitate. The filtrate
on acidification gives a white solid E (C
7
H
6
O
2
). Write the structures of D.E and explain the formation of E.
[JEE 96]
5. Complete the following giving the structures of the principal organic products. [JEE 97]
6. An ester A (C
4
H
8
O
2
), on treatment with excess methylmagnesium chloride followed by acidification, gives an
alcohol as the sole organic product. Alcohol B, on oxidation with NaOCl followed by acidification, gives
acetic acid. Deduce the structures of A and B. Show the reaction involved. [JEE 98]
7. Following reactions gives two products. Write the structure of the products.
8. Explain briefly the formation of the products giving the structures of the intermediates.

+

A
H . ii
/ OH . i

O
||
OH C CH
|
OH C CH C H
||
O
2
3

[JEE 99,5/120]
9. When propionic acid is treated with aqueous sodium bicarbonate, CO
2
is liberated. The C of CO
2
comes
from : [JEE 99, 2/80]
(A) methyl group (B) carboxylic group (C) methylene group (D) bicarbonate
8
H
4
O
3
3
gives compound B. The
compound B treatment with PCl
5
, following by reaction with H
2
/ Pd(BaSO
4
) gives compound C, which on the
hydrazine gives a cyclised compound D (C
14
H
10
N
2
). Identify A, B, C and D. Explain the formation of D from C.
[JEE 2000, 5/100]
11. Which of the following acids has the smallest dissociation constant ? [JEE 2002, 1/35]
(A) CH
3
CHFCOOH (B) FCH
2
CH
2
COOH (C) BrCH
2
CH
2
COOH (D) CH
3
CHBrCOOH
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12. There is a solution of p-hydroxy benzoic acid and p-amino benzoic acid. Discuss one method by which we
can separate them and also write down the confirmatory test of the functional groups present.
13. Statement-1 : Acetate ion is more basic than the methoxide ion.
Statement-2 : The acetate ion is resonance stabilized. [JEE-2004, 3/84]
(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
14. In conversion of 2-butanone to propanoic acid which reagent is used. [JEE-2005, 3/84]
(A) NaOH, NaI / (B) Fehling solution (C) NaOH, I
2
/ (D) Tollen's reagent
Passage

X

15. Which reagent (X) is used to convert I to II [JEE 2006, 5/184]
(A) KBr / NaOH (B) Br
2
/ NaOH (C) NaHCO
3
(D) N-Bromo succinamide
16. Which step is rate determining step [JEE 2006, 5/184]
(A) Formation of II (B) Formation of III (C) Formation of V (D) Formation of IV
17. + under Hofmann conditions will give : [JEE 2006, 5/184]
(A) + (B) +
(C) + (D) +
18. Statement-1 : p-Hydroxybenzoic acid has a lower boiling point that o-hydroxybenzoic acid.
Statement-2 : o-Hydroxybenzoic acid has intramolecular hydrogen bonding.
(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. [JEE 2007,3/162]
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19. In the reaction T, the strucutre of the Product T is :
(A) (B)
(C) (D)
PART - II : AIEEE PROBLEMS (PREVIOUS YEARS)
1. Compound A given below is : [AIEEE-2002]
OCOCH
3
COOH
(A) antiseptic (B) antibiotic (C) analgesic (D) pesticide
2. End product of the following reaction is : [AIEEE-2002]
CH
3
CH
2
COOH
P red
Cl
2

KOH alcoholic
(A)
OH
|
CHCOOH CH
3 (B)
OH
|
COOH CH CH
2 2
(C) CH
2
=CHCOOH (D)
OH Cl
| |
CHCOOH CH
2
3. Rate of the reaction is fastest when Z is : [AIEEE-2004]
RC
Z
O
+Nu RC
Nu
O
+Z
(A) Cl (B) OCOCH
3
(C) OC
2
H
5
(D) NH
2
4. Consider the acidity of the carboxylic acids : [AIEEE-2004]
(a) PhCOOH (b) o-NO
2
C
6
H
4
COOH
(c) p-NO
2
C
6
H
4
COOH (d) m-NO
2
C
6
H
4
COOH
which of the following order is correct ?
(A) a >b >c >d (B) b >c >d >a (C) b >d >a >c (D) b >d >c >a
5. On mixing ethyl acetate with aqueous sodium chloride, the composition of the resultant solution is :
[AIEEE-2004]
(A) CH
3
COOC
2
H
6
+NaCl (B) CH
3
Cl +C
2
H
5
COONa
(C) CH
3
COCl +C
2
H
5
OH +NaOH (D) CH
3
COONa +C
2
H
5
OH
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6. p-cresol reacts with chloroform in alkaline medium to give the compound A which adds hydrogen cyanide to
form, the compound B. The latter on acidic hydrolysis gives chiral carboxylic acid. The structure of the
carboxylic acid is : [AIEEE-2005]
(A)
OH
CH
3
CH COOH
2
(B)
OH
CH
3
CH COOH
2
(C)
OH
CH
3
CH(OH)COOH
(D)
OH
CH
3
CH(OH)COOH
7. An organic compound having molecular mass 60 is found to to contain C =20%, H =6.67% and N =46.67%
while rest is oxygen. On heating it gives NH
3
alongwith a solid resdue. The solid residue give violet colour with
alkaline copper sulphate solution. The compound is : [AIEEE-2005]
(A) CH
3
CH
2
CONH
2
(B) (NH
2
)
2
CO (C) CH
3
CONH
2
(D) CH
3
NCO
8. A liquid was mixed with ethanol and a drop of concentrated H
2
SO
4
was added. A compound with a fruity smell
was formed. The liquid was : [AIEEE-2009]
(A) HCHO (B) CH
3
COCH
3
(C) CH
3
COOH (D) CH
3
OH
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Exercise - 1
PART : I
B-3. (i) (ii) (iii) (iv)
C-1. Because esters do not form hydrogen bonds
D-1. (a) (b)
(c) +CH
3
NH
2
(d) +C
2
H
5
OH
E-1. (a) +CH
3
COOH (b)
(c) (d) PhCH=CHCOOH +CH
3
COOH
E-2. (a) +CH
3
COOH (b)
3 3
CH C NH CH
||
O
+CH
3
COOH
(c) (d)
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PART - II
A-1. (C) A-2.* (B, C, D) A-3. (A) A-4. (B) A-5. (A)
A-6. (D) A-7. (A) A-8. (B) A-9. (D)
B-1.* (A, B, D) B-2. (D) B-3. (B) B-4. (C) B-5. (B)
B-6. (D)
C-1. (A) C-2. (B) C-3. (A) C-4.* (A, B, D) C-5. (C)
C-6. (C) C-7. (A) C-8. (B) C-9. (C) C-10. (B)
D-1. (A) D-2. (B) D-3.* (B, C, D) D-4. (B)
E-1.* (B, C, D) E-2. (C) E-3. (A)
E-4.

4
LiAlH
A

PCC
B

2 2
NH NH
C, Product (C) is
(A) (B) (C) (D)
EXERCISE - 2
PART - I
2. X
CN CH
14
3
14
y
H COO CH
14
3
14
z
3
14
3
14
||
O
H C C CH
6. X = , Y = , Z =
O
||
H C C Cl
3
, W =CHCl
3
, S =
9. (A) =PhCOOH, (B) =
11. (A) C
3
H
7
CN (B) C
3
H
7
CONHCOCH
3
(C) C
3
H
7
CH
2
NH
2
14. (a) A =HOOCCH
2
CH
2
COOMe : B =ClCOCH
2
CH
2
COOMe ; C =MeNHCOCH
2
CH
2
COOMe
(b) D = E = (c) F =
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PART - II
1. (C) 2. (C) 3. (C) 4. (C) 5. (B)
6. (B) 7. (D) 8. (A) 9. (A) 10. (B)
11. (C) 12. (B) 13. (C) 14. (A) 15. (D)
16. (B) 17. (A) 18. (A) 19. (C) 20. (A)
21. (D) 22. (C) 23. (C) 24. (A) 25. (D)
26. (C) 27. (B) 28. (A) 29. (D) 30. (C)
31. (C) 32. (C) 33. (A) 34. (A) 35. (C)
36. (C) 37. (B) 38. (C, D) 39. (B, D) 40. (B, D)
EXERCISE - 3
1. (A) - (s) ; (B) - (q, s) ; (C) - (p, s) ; (D) - (p, r, s)
2. (A) - (p,s) ; (B) - (q,s) ; (C) - (p, s) ; (D) - (r)
3. (B) 4. (A) 5. (B) 6. (C) 7. (D)
8. (D) 9. (B) 10. (D) 11. (B) 12. (A)
13. (B) 14. (C) 15. (A) 16. (A) 17. (A)
18. (A) 19. (A) 20. (B) 21. (D)
22. (A) 23. (A) 24. (A)
25._ (T) 26._ (T) 27._ (F) 28._ (T) 29._ (T)
30._ Glacial 31._ Weaker de
32._ Acetic acid, Succinic anhydride
33._ aq. NaHCO
3
34._ more
EXERCISE - 4
PART - I
2. (A) 3. (B)
8. First, anion of Malonic ester is formed which attacks as a nucleophile on the other reagent.
9. When propionic acid is treated with aqueous sodium bicarbonate, CO
2
is liberated. The C of CO
2
comes
from : [JEE 99, 2/80]
(A) methyl group (B) carboxylic group (C) methylene group (D) bicarbonate
11. (C)
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12. +
These can be separated by aq. HCl.
Test : (1)
3
FeCl Neutral
Violet blue ppt.
Test : (2)
KOH / Naphthol HCl / NaNO
2
Red Orange dye.
13. (D) 14. (C) 15. (B) 16. (D) 17. (A)
18. (D) 19. (C)
PART - II
1. (C) 2. (C) 3. (A) 4. (B) 5. (A)
6. (C) 7. (B) 8. (C)
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Single choice type
1.
5 2
2 5 2 3
5 2
H OC
|
O H H OC C C H
|
H OC
+

) catalyst (
HCl . dil
X + Y (Alcohol)
(A) X =
5 2 3
H C O C CH
||
O

(B) X =
3 2 3
CH O C CH CH
||
O

(C) X =CH
3
COOH (D) Y =CH
3
OH
2.

A
X,
(A) (B) (C) (D)
3.
5 2 5 2
H OC C O H C
||
O

+EtMgBr (large excess)
+
O H
3
X, X is
(A)
OH
|
H C C H C
|
H C
5 2 5 2
5 2

(B)
OH
|
H C C CH
|
H C
5 2 3
7 3

(C) (D)
OH
|
CH C CH
|
H C
3 3
9 4

4. In the reaction sequence [X] will be
(A) (B) CH
2
CHCOOH (C) (D)
5. Which acid can be oxidised by Fehling solution.
(A) Malonic acid (B) Acetic acid (C) Oxalic acid (D) Formic acid
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6.
KOH

Cl PhCH
2
X, X is,
(A) (B)
(C) (D)
7. OH C CH CH
||
O
2 3

.) equiv 1 ( KOH
X, X is, gS
(A) (B)
(C) (D)
8.
O H . 2
LiAlD . 1
2
4
X, X is gS
(A) (B) (C) (D)
9. + BrMgCH
2
CH
2
CH
2
CH
2
MgBr
+

O H . 2
THF . 1
3
X,
(A) (B)
(C) (D)
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10.

= ? R

CHOH
2
HO
(A) NaBH
4
(B) LiAlH
4
(C) MPV (D) H
2
/ Ni
11.
.) cat ( SO H
4 2
X,
(A)
3
2
CH
|
Ph C O CH CH Ph
||
O

(B)
3
3
CH
|
Ph C O C Ph
|| |
O CH

(C)
3
3
CH
|
CH C O C Ph
|| |
O Ph
(D)
3 2
CH C O CH CH Ph
|| |
O Ph

12.
O H ) 2 (
PhMgBr excess ) 1 (
2

X,
(A) (B) (C) (D)
13.
CN ) CH ( C O H C
||
O
2 2 5 2

) excess (
LiAlH
4

OH ) 2 (
, O H ) 1 (
3

A
+
X,
(A) (B) (C) (D)
14. H
2
C =CHCH
2
CN
+

H . 2
PhMgBr . 1
X,
(A) CHO CH C CH
|
Ph
3
= (B) CHO CH CH CH
|
Ph
2
=
(C) H
2
C =CHCH
2
COPh (D) CH
3
CH =CH COPh
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O

H / O H ) ii (
) equiv 1 ( MgBr CH ) i (
2
3
P, ,
(A) (B)
(C) (D)
16.
A

10 4
O P
P
+

O H
MeMgBr
3
Q
2 2
I , ) OH ( Ca
R, compound R is
(A) (B) (C) (D)
17. Which gives unsaturated acid on heating ?
(A) (B) (C) (D) All l Hkh
18.

+
O H
3
Select the correct statement :
(A) Alkyl CO bond breaks and O
18
is contained in acid
(B) Alkyl CO bond breaks and O
18
is contained in alcohol
(C) Acyl CO bond breaks and O
18
is contained in alcohol
(D) Acyl CO bond breaks and O
18
is contained in acid
19. An optically active compound X has molecular formula C
4
H
8
O
3
. It evolves CO
2
with aq. NaHCO
3
. X reacts
with LiAlH
4
to give achiral compound X is
(A) (B) (C) (D)
20.
2 2
3
OH . O H
THF . BH

+

H
NaOH / I
2

A
X,
(A) (B) (C) (D)
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21. Consider following compounds
Which of the above compounds reacts with NaHCO
3
giving CO
2
:
(A) I, II and III (B) I and III (C) II and IIII (D) I and II
22. The carboxylic acid which has maximum solubility in water is :
(A) Phthalic acid (B) Succinic acid (C) Malonic acid(D) Salicylic acid
23. Peroxyacetic acid (CH
3
CO
3
H) is a weaker acid than acetic acid (CH
3
CO
2
H) since :
(A) negative charge in cant be delocalised into the carbonyl group
(B) CH
3
group in CH
3
CO
3
H shows +I effect
(C) both are correct
(D) none is correct
24.

A
A,
(A) (B) (C) (D) None
25. In case of Hoffmann bromamide degradation reaction, intermdediate RNCO is formed by :
(A) intramolecular migration (B) Intermolecular migration
(C) hydrolysis is RCONH
2
(D) none is correct
26. When RCOOH reacts with NaHCO
3
, CO
2
is formed. CO
2
contains carbon of
(A) RCOOH (B) NaHCO
3
(C) Both (D) none
27. Consider following reactions
I

4 2
BaSO / Pd . H
, II
4
LiAlH
, III

3
) BuO t ( LiAlH
is obtained from RCOCl using
(A) I, II and III (B) I and II (C) I and III (D) II and III
28. . +
O

H ) ii (
O CH CH ) i (
2 3
A, A,
(A) (B) (C) (D)
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29.

Reactivity order of different nucleophiles (NH
2
CH
3
COO
,
OH) is in order :
(A) NH
2
<CHC
-
OO
<OH
(B) CH
3
COO
<OH
<NH
2
(C) NH
2

<OH
<CH
3
COO
(D) CH
3
COO
<NH
2
<OH
30. +KOH +Br

2

Intermediates of this reactions is/are expect to be :
(A) RN=C=O (B) (C) (D) A, C
31.
OH CH
3
A, A is gSA
(A) (B) (C) both are correct (D) None is correct
32. Give the structure of the expected product of the following reaction :
+CH
3
NH
2

A
(A) (B) (C) (D) None
33. Consider the following reaction :
CH
3
NHCH
2
CH
2
CH
2
OH + produt in the above reaction
(A) is the only product
(B) is the only product
(C) is a major product and is a minor product
(D) is a major product and is a minor
product.
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34. In the given reaction :
+
) excess (
OH CH
3

H
[X] is :
(A) (B) (C) (D) Mixture of all
C
6
H
5
CH
3

u

h
NBS
A
NaCN
B
A

O H
3
C
C is gSA
(A) C
6
H
5
CH
2
Br (B) C
6
H
5
CH
2
CN (C) (D) C
6
H
5
CH
2
COOH
36. Consider the following reaction
CH
3
CH
2
+CH
3
MgBr (1 equiv) Product
The product will be :
(A) CH
3
CH
2
(B) CH
2
CHO
(C) CH
2
(D) CH
2
CHO
Pyridine
SOCl
2
A
Cd ) CH CH (
2 2 3
B
B will be :
(A) (B) (C) (D)
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38. Find out the possible products in the following reaction.
H O N
O
O
O O
O
Cl

4
LiAlH
?
(A)
O
HO
O
CH OH
2
NH
2
(B)
NH
2
CH OH
2
OH
OH
CH OH
2
(C) CH
3
CH
2
OH (D)
NH
2
CHOH
2
OH
O
O
CH OH
2
H
H
39. Benzoyl chloride is less reactive than acetyl chloride for nucleophilic acyl substitution reaction because :
(A) group of benzoyl chloride is in conjugation with benzene ring. This makes benzoyl chloride more
stable than acyl chloride.
(B) CH
3
group of acetyl chloride makes CCl bond stronger due to the +I effect.
(C) C
6
H
5
group of benzoyl chloride makes CCl bond weaker due to +R effect.
(D) CH
3
group makes CCl bond weaker due to +I effect and C
6
H
5
group makes CCl bond stronger due to
I effect.
1. Complete the following by supplying (A) to (F)
[A]
2
Br / P
CH
3
CH
2
CH
2
Br
A

KOH Alcoholic
[B]
4
2
CCl
Br

[C]
2
NaNH by Followed
.) alc ( KOH

[D]
4 2
2
SO H . dil
Hg

+
[E]
+

H
OH NH
2
[F]
2. Bring out the following conversions :
(i) Ethanal to 2-Hydroxypropanoic acid (ii) Carbon and Hydrogen to Ethanoic acid
(iii) Ethanol to Propanone (iv) Ethanal to Lactic acid
(v) Ethanal to 2-hydroxybut-3-enoic acid (vi) Benzamide to Toluene
(vii) Benzoic acid to Benzophenone (viii) Acetone to 2-Methylpropan- 2-ol
(ix) Malonic acid to Acetic acid.
3. Compound A (C
6
H
12
O
2
) on reaction with LiAlH
4
yielded two compounds B and C. The compound B on oxidation
gave D, which on treatment with aqueous alkali and subsequent heating furnished E.E on catalytic
hydrogenation gave C.D was oxidised to form F which is monobasic carboxylic acid with molecular mass 60.
Deduce the structures of A, B, C, D.
4. 30 g of monobasic carboxylic acid A consumed 0.5 moles of NaOH for its neutralisation. A is subjected to
following treatments :
[A]
P / Cl
2
|
.
|
\
|
derivative
Monochloro

OH H C with
tion Esterifica
5 2
(Ester)

.) alc ( KCN
[B]
Acid
Hydrolysis

Dicarboxylic acid [C]
C 150
Heat

A
Give structures of A, B, C providing the sequence of reactions.
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5. Complete the following by supplying [A] to [F] :
CH
4

] A [
CH
3
Br
.) anhyd ( AlCl
H C
3
6 6

[B]
] C [

6. An organic compound A on treatment with ethyl alcohol gives carboxylic acid B and compound C. Hydrolysis
of C under acidic conditions give B and D. oxidation of D with KMnO
4
also gives B.B on heating with
Ca(OH)
2
gives E with molecular formula C
3
H
6
O. E does not give Tollens test or reduce Fehling solution but
forms 2, 4-Dinitrophenyl hydrazone. Identify A, B, C, D, E.
7. When a gas A is passed through dry KOH at low temperature, a deep red coloured compound B and a gas
C are obtained. The gas A on reaction with but-2-ene followed by treatement with Zn/H
2
O yields acetaldehyde.
Identify A, B, C.
8. Complete the following sequence of reactions with appropriate structures.
CH
3
CH
2
COOH
2
Br / P
(A)
+

H ) ii (
.) alc ( KOH ) i (
(B).
9. An acidic compound (A), C
4
H
6
O
3
looses its optical activity on strong heating yielding (B), C
4
H
6
O
2
which
reacts readily with KMnO
4
and decolourises it. (B) forms a derivative (C) with SOCl
2
which on reaction with
(CH
3
)
2
NH gives (D). The compound (A) also forms unstable compound (E) on treatment with dilute chromic
acid (E) decarboxylate readily to give (F) C
3
H
6
O which on treatment with amalgamated zinc and HCl gives
hydrocarbon (G). Give structures of (A) to (G).
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MISSCELLANEOUS QUESTION BANK
PART - I
1. (C) 2. (C) 3. (A) 4. (D) 5. (D)
6. (D) 7. (A) 8. (C) 9. (C) 10. (B)
11. (C) 12. (C) 13. (D) 14. (C) 15. (B)
16. (B) 17. (B) 18. (C) 19. (C) 20. (D)
21. (C) 22. (C) 23. (A) 24. (C) 25. (A)
26. (B) 27. (C) 28. (B) 29. (B) 30. (B)
31. (A) 32. (C) 33. (C) 34. (C) 35. (D)
36. (A) 37. (C) 38. (B, C) 39. (A, D)
PART - II
1. (A) =CH
3
CH
2
CH
2
OH ; (B) =CH
3
CH =CH
2
; (C) = Br CH CH CH
|
Br
2 3
;
(D) =CH
3
C CH ; (E) =
3 3
CH C CH
||
O
; (F) =
OH N
||
CH C CH
3 3
3. A is
5 2 2 2 3
H OC C CH CH CH
||
O
(Ethyl butanoate)
B is C
2
H
5
OH (Ethanol)
C is CH
3
CH
2
CH
2
CH
2
OH (1-Butanol)
D is CH
3
CHO (Ethanal)
4. (A) =CH
3
COOH; (B) = ; (C) =
5. [A] =Br
2
/hv [B] =
[C] =Cl
2
(g)/hv [D] =
[E] = [F] =NH
2
OH/H
+
6. (A) =
3 3
CH C O C CH
|| ||
O O
; (B) = OH C CH
||
O
3
(C) =
3 5 2
CH OC H C
||
O
; (D) = CH
3
COOH +C
2
H
5
OH ; (E) =
3 3
CH C CH
||
O
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7. (A) =
3 3
CHCH CH CH
(B) =2KO
3
+KOH.H
2
O
(C) =
2
O
2
1
9. (A) = ; (B) =
(C) = ; (D) =
(E) = ; (F) = ; (G) =

Carboxylic Acids and Acid Derivatives Carbonyl - Pdfcgvdufgdyufgduyfgsdyfgsdygbxcghvyufgxdzuyfgdf

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IDEAL 21ST CENTURY COMPETITIONS

) optical inactive optical active

(s) is involved in cyanohydrin formation.

nucleophile does not react with 2,2,6-trimethylcyclohexanone.

IDEAL 21ST CENTURY COMPETITIONS

The slowest step is :

, Zn-Hg/ Con. HCl (D) CrO

30. +KOH +Br

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