CARBOXYLIC ACID & IT'S DERIVATIVES

IIT-JEE Syllabus

1. Carboxylic acid & it's derivatives

2. Characteristic reaction of carboxylic acid (formation of ester, acidchloride,

anhydride & amides)

Total No. of questions in Carboxylic Acid & It’s Derivatives are :

Solved examples…....…………………………..…24
Exercise # 1 …….……………………………….…35
Exercise # 2 …….……………………………….…35
Exercise # 3 …….……………………………….…20
Exercise # 4 ……………………………………..…11
Exercise # 5 ……………………………………..…19
Total No. of questions………………..144

*** Students are advised to solve the questions of exercises in the same sequence or as
directed by the faculty members.

CARBOXYLIC ACID & IT'S DERIVATIVES 1

 Index : Preparing your own list of Important/Difficult Questions
Instruction to fill

(A) Write down the Question Number you are unable to solve in column A below, by Pen.
(B) After discussing the Questions written in column A with faculties, strike off them in the
manner so that you can see at the time of Revision also, to solve these questions again.
(C) Write down the Question Number you feel are important or good in the column B.

COLUMN :A COLUMN :B
EXERCISE
NO. Questions i am unable
Good/Important questions
to solve in first attempt

Advantages

1. It is advised to the students that they should prepare a question bank for the revision as it is
very difficult to solve all the questions at the time of revision.

2. Using above index you can prepare and maintain the questions for your revision.

CARBOXYLIC ACID & IT'S DERIVATIVES 2

 EXERCISE # 1
R– C –O–Na+
Questions Preparation of carboxylic acid and ||
based on
derivatives O
Sodium Salt of carboxylic acid.
Q.1 Give the order of decarboxylation of the
Q.3 The oxidation of toluene with hot KMnO4
following acid –
CH3COOH ; CH2 =CH–CH2 – COOH ; gives –
I II (A) Benzoic acid (B) Benzaldehyde
NO2 (C) Benzene (D) Benzyl alcohol
CH2(COOH)2 ; O2N COOH CH3 CH3
NO2 Hot KmNO
Sol.[A]   4  + H 2O
III IV [O]
(A) I > II > III > IV (B) III > IV > II > I
(C) IV > III > II > I (D) I > III > II > IV Benzoic acid

Sol.[C] CH3 – C – O CH3 + CO2
unstable (I) Q.4 Identity the product Z in the series :
O
Na / C H OH HNO

CH3CN   
2 5
 X  
2

CH2=CH–CH2 –C–O CH2=CH–CH2 +CO2
O Stable due to KMnO / OH 
conjugation (II) Y  4  Z

(A) CH3CHO
H–O–C–CH2 –C – O HO–C –CH2 (B) CH3CH2CONH2
O O O (C) CH3COOH
stabilised due to (D) CH3CH2NHOH
resonance Sol.[C] CH3COOH
NO2 NO2
O 2N C–O O 2N  +CO2 Questions Chemical properties of carboxylic acids
based on
O and derivatives
NO2 NO2
more stable IV Q.5 Which of the following acid does not form
Therefore stability of carbanion -decarboxy- anhydride –
lation IV > III > II > I.
(A) CH3COOH
Option (C) is correct.
(B) CH-COOH
Q.2 The end product Y in the sequence of
reaction: CH-COOH
 (C) CH2COOH
RX CN  X NaOH  Y is –
(A) An alkene CH2COOH
(B) A carboxylic acid (D) CH-COOH
(C) Sod. salt of carboxylic acid
(D) A ketone HOOC-CH
Sol.[C] RX  CN 
 R–CN   R– C –H+NH3 D 2 NaOH Sol.[D] CH-COOH
||
O HOOC-CH
does not form anhydride
NaOH
Q.6 Formic acid and formaldehyde can be

CARBOXYLIC ACID & IT'S DERIVATIVES 3

 distinguished by treating with –
(A) Benedict’s solution (B) Tollen’s reagent
Q.9 X and Y in the following reaction sequence
(C) Fehling’s solution (D) NaHCO3
are–
Sol.[D] Formic acid is strong acid than formaldehyde
O
formic acid react with NaHCO3 and liberated P2 O 5
||
X  
 R– C –NH2 Br
2  Y
CO2 but formaldehyde does not react with OH

NaHCO3. (A) R–CN, RCH2NH2

Therefore option (D) is correct. (B) RNH2, RCN
(C) RCN, RNH2
(D) RCN, RCH2NH2
Q.7 The product formed when adipic acid is O
P2 O 5 ||
heated– Sol.[C] H2O+R–CN 
Br2
R– C –NH2
 R–NH2
 OH
COOH
(A) [X] [Y]
(B) C=O Therefore option (C) is correct.

O Q.10 Benzoic acid gives benzene on being heated

with X and phenol gives benzene on being
O
(C) heated with Y. Therefore X and Y are
O respectively –
COOH (A) Soda lime and copper
(D) (B) Zinc dust and sodium hydroxide
COOH (C) Zinc dust and soda lime
O (D) Soda lime and zinc dust
O
COOH
CH2–CH2–C–OH 
Sol.[B] + CO2 + H2O NaOH / CaO
CH2–CH2–C–OH Sol.[D]    + CO2
(soda lime )

O
Adipic acid Cyclo pentanone OH

Adipic acid undergo dehydration as well as Zn

dust

 + ZnO
decarboxylation to give cyclopentanone when
its heated. Therefore X and Y are respectively sodalime
Zn-dust.
So option (B) is correct.
Option (D) is correct.
Q.8 Ethyl acetate react with hydrazine to form -
(A) Acetamide and urea
(B) Acetic acid hydrazide and ethanol Q.11 COOH is converted into CHO
(C) Hydroxamic acid and ethanol
by–
(D) Ethyl isocyanate
Sol.[B] CH3–C–OC2H5 + NH2–NH2 
(A) (i) LiAlH4 (ii) Cu/
(B) (i) Cu/ (ii) LiAlH4
O
CH3–C–NH–NH2 + C2H5OH (C) (i) Ag2O (ii) Cu/
(D) (i)SOCl2(ii)LiAlH4
O Ethanol
Acetic acid COOH LiAlH OH
Sol.[A]  
4 
hydrazide
Therefore option (B) is correct.  Cu / 

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 CHO
— COONa + CO2

Therefore option (A) is correct C* is with in the product –

(A) CO2
O
Q.12
CH OH
3
 Y, Y is – (B) COONa
O
(C) Both
.

(A) CH2 – CH2 (B) CH2 – CH2

(D) None
OH COOCH3 OCH3 COOH
(C) Both are correct (D) None is correct O O
 
O Sol.(A) C–O–H + Na O–C–OH 
H  OCH *
Sol.[A]  3  OH . C – OCH3
O
.
Sod. Bicarbonate
O
O
[Y]   *
Therefore option (A) is correct. C–O–Na + H–O–C–O–H CO2 + H2O
O
Therefore option (A) is correct.
Q.13 End product of this conversion
O Q.15 Identify the product A in the following
|| reaction
1. NaBH
CH3– C –CH2CH2CH2CO2H  4  is –
2. H O / H COOH 
2
CH2  CH3COOH + A
COOH
(A) O
O (A) CO2 (B) CH3CHO
CH3 (C) CH3OH (D) None of these
CH3 COOH 
Sol.[A] CH2  CH3COOH + CO2
COOH
(B) O
O Therefore option (A) is correct.
(C) O
O
(D) CH3– CH –CH2 – CH2CO2H Q.16 A carboxylic acid (x) & (y) on heating with
P2O5 (x) give corresponding anhydride but
OH
(y) remain unaffected. Carboxylic acid (y)
O
|| is-
Sol.[A] CH3– C –CH2CH2CH2COOH NaBH
  (A) CH3COOH (B) HCOOH
4

OH H–O (C) both (A & B) (D) CH3CH2COOH

CH3–C–CH2–CH2–CH2–C=O Sol.[B] Carboxylic acid (y) is HCOOH
+ +
H /H3O Q.17 Malonic acid and succinic acid are
distinguished by -
O (A) Heating (B) NaHCO3
O
CH3 (C) Both A & B (D) None of these
Sol.[A] By Heating
Therefore option (A) is correct.
Q.18 Which of the following statement is correct -
(A) Nucleophilic additions to the carbon-
Q.14 COOH + NaHC*O3 oxygen double bond is a characteristic
reaction of aldehyde and ketones.

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 (B) Carboxylic acid and their derivative are (D) C6H5CH2COOC2H5
characterized by nucleophilic substitution Sol.[ B] C6H5COOC2H5 esters cannot undergo claisen
reaction. self condensation
(C) In both case initial step involves a O
nucleophilic attack on the carbonyl
Q.22 (
A)
 C
carbon but in second step aldehyde and O
O2 C
ketone accept a proton to yield additional
O
product whereas in the case of acyl COOH
compound leaving group is ejected to H O / soda lim e
2   
form substitutional product.
Oxidizing agent (A) used is
(D) All are correct
(A) K2Cr2O7 / H+ (B) AlK . KMnO4
Sol.[D] Factual
(C) Chromic Acid (D) V2O5
Sol.[D] Oxidizing agent (A) used is V2O5
Q.19 The relative order of reactivity of acyl
derivatives is - Q.23 In the reaction
O O O C6H5NH2 NaNO / HCl
 2  
|| || || 0  5º C
(A) R – C –Cl > R – C – O – C – R > H / H O
O O (A) CuCN
 (B)  
2
 (C)
KCN
|| ||
R – C – NH2 > R – C – OR' the product (C) is -
O O (A) C6H5CH2NH2 (B) C6H5COOH
|| || (C) C6H5OH (D) None of these
(B) R – C –Cl > R – C – OR' > Sol.[B] Product (C) is C6H5COOH
O O O
|| || || Q.24 Benzoic acid on treatment with hydrazoic
R– C – O – C – R > R – C – NH2RBT
acid (N3H) in the presence of concentrated
O O O
|| || || sulphuric acid gives
(C) R – C – Cl > R – C – O – C – R > (A) Benzamide
O O (B) Sodium benzoate
|| || (C) Aniline
R – C – OR' > R – C – NH2R
(D) C6H5CON3
(D) None of the above
Sol.[C] Factual
O O O
|| || || Q.25 Number of cross products in the given
Sol.[C] R – C – Cl > R – C – O – C – R >
O O reaction: (Without considering stereoisomers)
|| || CH3COOC2H5 + C6H5–CH2–COOC2H5
R – C – OR' > R – C – NH2R C H ONa
 
2 5

C 2 H 5 OH
Q.20 What is the correct order of alkaline
hydrolysis of different ester CH3COOCH3 (A) One (B) Three
(C) Two (D) Four
[rate = r1] , CH3COOC2H5
Sol.[C] Two
[rate = r2] CH3COOC3H7 [rate = r3] -
(A) r1 >r2 > r3 (B) r1 < r2 < r3 Q.26 Arrange following compounds in decreasing
(C) r1 < r2 > r3 (D) r1 > r2 < r3 order of reactivity for hydrolysis reactions -
(I) C6H5COCl
Sol.[A] r1 >r2 > r3
(II) NO2 COCl
Q.21 Which of the following esters cannot undergo
claisen self condensation -
(III) CH3 COCl
(A) CH3CH2CH2CH2COOC2H5
(B) C6H5COOC2H5
(C) C6H11CH2COOC2H5
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 O
 True / False type questions
(IV) OHC C–Cl
Q.30 Acetonitrile on hydrolysis with a dilute
(A) II > IV > I > III (B) II > IV > III > I
mineral acid gives acetone.
(C) I > II > III > IV (D) IV > III > II > I 
Sol.[A] II > IV > I > III Sol. CH 3  C  N HOOH  CH 3 COOH  NH 3
  /
H

Acetonitrile Acetic acid
Q.27 In the given reaction sequence :
 Acetonitrile on hydrolysis with a dilute mineral
( i ) KMnO / O H / 
CH3–CH2–OH   4 

 (A) acid give acetic acid, not an acetone.
(ii ) H
( i ) SOCl
 2  (B) 2   (C) will be -
Br / KOH Therefore statement is false.
( ii ) NH 3 / 

(A) Methylamine Q.31 Esterfication involves the heating of a

(B) Eltylamine carboxylic acid with an alcohol in presence of
(C) Propylamine a protonic acid (H2SO4 or HCl gas) as
(D) Acetamide catalyst.
Sol.[A] (C) will be Methylamine Sol. In esterfication reaction :

Q.28 Which optically active compound on H2SO4

CH3–C–OH + C2H5OH
reduction with LiAlH4 will give optically or HCl(gas)
inactive compound ? O alcohol
acid
(A) CH3–CH–COOH
CH3C–OC2H5 + H2O
OCH3
(B) CH3–CH2–CH–COOH O
ester
OH Therefore statement is true.
(C) CH3–CH2–CH–COOH
CH2OH
(D) CH3–CH–CH2–COOH  Fill in the blanks type questions
OH Q.32 Kolbe’s electrolysis of potassium succinate
Sol.[C] CH3–CH2–CH–COOH gives CO2 and ........
Sol. Ethylene
CH2OH

O Q.33 In Hoffmann-bromamide reaction, the

P2 O 5 CH 3 MgBr migration of an alkyl or aryl group occurs
Q.29 CNH2  W   X
 H 3O from ....... to ..... atom.
Sol. Carbon, nitrogen
( yellowppt .) 
  
 Y 
 Z will be
Ca ( OH ) 2 , I 2 Q.34 Ethanenitrile on hydrolysis gives ...........
O Sol. Ethanoic acid
(A) C–CH3 (B) COOH Q.35 Hell-Volhard Zelinsky reaction involves the
replacement of an ....... atom from the alkyl
O group of a monocarboxylic acid by a .....
(C) C (D) atom.
Sol. -hydrogen, halogen

O
Sol.[C] Z will be C

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 EXERCISE # 2
H O
Part-A (Only single correct answer type (C) HCN 3 
H O
Questions) (D) CH3CONH2 
2

H O
red P LiAlH Sol.[C] HCN 3  H–COOH + NH 4
Q.1 X 
HI
 CH3COOH  
4  Y. What
Formic acid is strong acid, that its capable of
does not true for X and Y –
changing orange coloure of Cr2 O 72 to green
(A) X is hydrocarbon of general formula
colour Cr+3.
CnH2n+2 while Y belong to alkanol
(B) X can be obtained by reducing
Q.3 In the reaction sequence –
CH3CH2Cl while Y by its hydrolysis
CH3CO X
(C) X gives positive litmus test but Y does O CH3CONH2
not CH3CO
Y Z
(D) X and Y both belong to different  CH3C N  CH3COOC2H5
homologeous series (A) NaOH, PCl5, Na + alcohol
Sol.[C] CH3– (B) NH3, P2O5, aqueous ethanol/H+
CH3 

red P
CH3COOH
4  CH3CH2OH
LiAlH (C) NH3, NaOH, Zn + NaOH
HI
(D) NH3, Conc. H2SO4, aqueous methanol
[X] [Y] CH3CO NH3
Y give positive litmus test but 'X' does not. Sol.[B] O X
CH3–C–NH2 + CH3COOH
CH3CO
Therefore option (C) is correct. O
 P2O5 (Y)

Q.2 The product of which of the following CH3C  N + H2O

reaction is capable of changing orange colour  Aqueous ethanol
of Cr2 O 72 to green colour of Cr – +3
CH3COOH + C2H5OH

(A) CH3(COOH)2  
H 3O 
(B) CH3CN 

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 CH3–C–OC2H5 O
O (A) CH3–C–O–CH2–CH2–CH2–CH3
Therefore option (B) is correct. (B) CH3CH2–O–COC3H7
(C) CH3–O–COC4H9
O
Q.4 OHC–CH2–CH2 –CH2–CH2–OH (D) CH3–CH2–C–O–CH2–CH2–CH3
O Sol.[B]
H O
is converted into O by – C3H7 C–OCH2CH3 3  C3H7 C–OH + CH3CH2OH
O O
(A) (i) KMnO4 (ii) H+, H Alcohol give positive
(B) (i) Na2Cr2O7 (ii) H+,  Iodoform reaction
(C) (i) Ag2O (ii) H+,  Therefore option (B) is correct.
(D) All of these
Sol.[C] OHC–CH2–CH2 –CH2–CH2–OH
O
 Ag2O
NaBH O LiAlH
HOOC–CH2–CH2–CH2–CH2–OH Q.7 Y  4 
CH OH
 
4  X
3

O
H+/ O
O X and Y are –
O

Therefore option (C) is correct. O

(A) in both case

. O O OH
Q.5 , on saponification of the given OH
(B) in both case
. O O OH
ester is formed – O
(A) OH OH and OHC–CHO
OH O
(C) ,
CH2 – CH2 OH
(B) OH–CH2–CH2–OH and OHC–COOH
OH OH
(C) CH2 – CH2 and HOOC–COOH
(D) Formation of A and B is not possible
OH OH Sol.[C] LiAlH4 is powerful, non selective reducing
(D) HO–CH2–CH2–COOH and HCOOH agent. It reduces a wide range of functional
O H H–O group –COOH, COOR, –CN, – C –NH2
O ||
CH2 C O O
.
O
Sol.[C] + —
But NaBH4 is more specific and selective for
CH2 C . O O the reduction of aldehydes and ketones. It has
O
O H H–O no effect on ester nitro group, C = C etc.
Therefore option (C) is correct. O O

O NaBH 4 O OH
  LiAlH
 4 
Q.6 A sweet smelling ester, with molar mass 116, CH OH
3 OH
on hydrolysis produces a carboxylic acid and
an alcohol. Alcohol give positive iodoform OH O OH
reaction which of the following formula could [Y] [X]
correspond to above statements – Therefore option (C) is correct.

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 NaN  Conc.H SO OH
Q.8 CH3–CH2–COOH  
3

2

4
X

COCl
by reaction R1 Sol.[B]
Br2 / P
CH3–CH2–COOH   Y

O
by reaction R2 COOH
Which is correct alternate – 
Q.10 CH2COOH  X, X is –
(A) X Y
CH3CH2NH2 CH3 – CHCOOH O
O O
Br C COOH
R1 R2 O
(A) CH2C (B) CH3
Schmidt HVZ
O
(B) X Y O
CH3CH2CONH2 CH3CH2COBr CH2COOH
R1 R2 (C) (D) None
HVZ Schmidt
(C) X Y O
CH3CH2NH2 CH3CH2COBr CH2COOH
R1 R2 Sol.[C] X is
HVZ Schmidt
(D) None of these
NaN  Conc .H SO
Sol.[A] CH3CH2COO  
3

2
4  Br

(i ) Mg ether
CH3CH2NH2 + N2 + CO2
Q.11 O (ii ) CO
is reacted with  2 Z.
[x]
C O

(iii ) H 3 O
This reaction is known as Schmidt reaction H
CH3
[R1]
The final product Z is –
Br / P
CH3CH2COOH 2 CH3 CHCOOH + HBr COOH

|
Br O
(A)
[Y]
C O
This reaction is known as Hell-Volhard- H
CH3
zelinsky (HVZ) reaction.
COOMgBr
Therefore option (A) is correct.

(B) O
Q.9 In the given reaction : C O
OH H
COOH CH3
PCl
3  [X] COOH

[X] will be - (C) O

Cl OH C H
COOH
COCl CH3
(A) (B)
COOH
Cl
O COCl (D)
(C) O (D)
COOH
C
CH3
O

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 Br O
 •• 
O D + CO2  ND2  ND – C – O
Sol.[C] O (i ) Mg ether
  
 D–OD
C O [Y]
CH3 H
ND / 
MgBr COOH C–OH 3
 C–ND3
O O
O 

CO 2 O
H 3O C–ND3 + 4KOH + Br2 
C OMgr C H
CH3 H CH3 O

Therefore option (C) is correct. NH2 + 2Br + K2CO3 + 2D2O

Therefore option (A) is correct.

( i ) NH 3 ,  ( i ) ND 3 , 
Q.12 Y   COOH   ,
( ii ) KOD , Br2  ( ii ) KOH , Br2 

X, what are X and Y – Q.13 An ester (I) with molecular formula C9H10O2
was treated with excess of CH3MgBr and the
(A) X is NH2 ; Y is ND2
complex so formed was treated with H2SO4 to
give an olefin (II). Ozonolysis of (II) gave a
(B) X is ND2 ; Y is NH2
ketone with molecular formula C8H8O which
show positive iodoform test. The structure of (I)
(C) both ND2
is –
(A) C6H5COOC2H5 (B) C6H5COOC6H5
(D) both NH2
(C) H3COCH2COC6H5
(i ) ND (D) p– CH3O – C6H4– COCH3
Sol.[A] COOH  
3 
 CH3
Sol.[A] C6H5COC2H5 + CH3MgBr C6H5–C–OC2H5
C–NH2 + H2O
O O OMgBr

•• H OD CH3MgBr H3O+
C–N +
H
O CH3 CH3
O3 Con. H2SO4
 Br–Br C6H5–C–CH2 C6H5–C–CH3
C–N–H [II]
••
OH
O CH3

•• Br OD C6H5–C–CH2O
C–N +
H
O O
O Rotophenon
•• Re arrangemen t
   
C – N – Br 

Therefore option (A) is correct.
••
N–C–O + Br
Q.14 CH2 – CH2 on reaction with diethyl oxalate
OD
 ••
••
N = C = O + OD  N–C=O NH2 NH2
 form –
O
||
(A) NH2CH2NH– C COOC2H5

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 H CH3
N CH3–NH–C–CH2–CH2–CH–OH
O
(B) O
O
N
Therefore option (C) is correct.
H
(C) H2N–CH2–CH2–N–COOH Q.16 Which carboxylic acid (X) of equivalent mass
H of 52g / eq loses CO2 when heated to give an
(D) H2N – CH2 – CH2 – N = C–COOC2H5 acid (Y) of equivalent mass of 60g/eq.
(A) CH3COOH
OC2H5 (B) CH2(COOH)2
H
NH–H C2H5–O (C) HOOCCH2CH2COOH
O N
CH2 C O (D) HOOC(CH2)3COOH
Sol.[B] + — Sol.[B] The carboxylic acid (X) is CH2(COOH)2
O
CH2 C N
O
H Q.17 59 g of amide obtained from the carboxylic
NH–H C2H5–O
acid RCOOH, on heating with alkali gave 17g
+ 2C2H5OH of ammonia. The acid is –
(A) HCOOH (B) CH3COOH
Therefore option (B) is correct.
(C) CH3CH2COOH (D)C6H5COOH
Sol.[B] The acid is CH3COOH
Q.15 Give the structure of the expected product of COOH
the following reaction
CH3 Na / NH / ROH
Q.18   
3
 ? Product is –
O + CH3NH2 — (X)
COOH
O COOH
CH3 (A) (B)
(A) O COOH
COOH
NCH3 (C) (D)
CH3
COOH COOH
(B) O
Na / NH / ROH
HO NCH3 Sol.[B]   
3

O
||
(C) CH3–NH– C – CH2CH2– CH –CH3 Part-B (One or more than one correct
answer type Questions)
OH
(D) None Q.19 Which one of the following compounds will
give HVZ reaction ?
CH3 COOH

Sol.[C] O + CH3–NH–H  (A)

COOH
(B)
O COOH
CH3
CH3–NH–C–CH2–CH2–CH–O
– (C) COOH (D)
+
H

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 COOH Q.23 The best methods to reduce cyclohex-2-en-1-
one to cyclohex-2-en-1-ol is are –
Sol.[B,C] COOH , of the compounds (A) PCC, CH2Cl2
(B) MPV reduction
will give HVZ reaction (C) NaBH4
(D) Ni/H2
Q.20 Phenol and benzoic acid may be distinguished
O OH
by their reaction with – NaBH4
Sol.[B] 

(A) Aqueous NaOH
(B) Aqueous NaHCO3
Cyclohex-2- ene-1-one Cyclohex-2-ene-1-ol
(C) Neutral FeCl3
(D) Aqueous NH3 NaBH4 is more specific and selective for the
Sol.(B), (C) Phenols are weaker acids than carboxylic reduction of aldehydes and ketones. It has no
acid. It is because of this reason that phenols do effect on C = C, C = C nitro group ester.
not decompose carbonates and bicarbonates
Therefore option (C) is correct.
evolving CO2. This test distinguishes phenols
and carboxylic acid. Q.24 Which of the following on oxidation with
Neutral FeCl 3 alkaline KMnO4 followed by acidification
C6H5OH    Blue or violet colour
Benzoic acid does not react with Neutral FeCl3. with HCl would give benzoic acid ?
Therefore option (B) and (C) are correct. (A) Toluene (B) Ethylbenzene
(C) o-Xylene (D) p-Xylene
CH3 COOH
Q.21 In the given reaction :
O O KMnO / H 
Sol.[A, B]  4
[X]
R– C – OH  R – C – O – CH3
[X] will be - Tolune Benzoic acid
(A) CH2N2 (B) CH3OH/H CH2–CH3 COOH
(C) MeCOOH (D) Me2SO4
Sol.[A,B,D] X will be CH2N2, CH3OH/H, Me2SO4 KMnO / H 
 4

Q.22 Which of the following statements are true Ethyl benzene Benzoic acid
about HCOOH ? Therefore option (A) and (B) are correct.
(A) It is a stronger acid than CH3COOH
(B) It forms formyl chloride with PCl5
(C) It gives CO and H2O on heating with Q.25 Nitrogen gas is evolved when HNO2 reacts
conc. H2SO4 with –
(D) It reduces Tollen’s reagent (A) C6H5COCH3 (B) C6H5CONH2
Sol.[A,C,D]
(C) CH3CH2NH2 (D) NH2CONH2
(A) HCOOH is a strong acid than CH3COOH
Sol.[B,C,D]
(B) HCOOH + PCl5  HCOCl + PoCl3 + HCl
HNO
Unstable C6H5 C –NH
2  C6H5COOH + N2 + H2O
2

|| Benzoic acid
So the formyl chloride does not form. O
Conc .H SO
(C) HCOOH   
2
4  CO + H2O CH3CH2NH2 
+ 
2 HNO
CH3CH2OH + N2 H2O


(D) Formic acid reduces to tollen's reagent NH2CONH2 + HNO2  2N2 3H2O + CO2
Therefore option (A), (C) and (D) are correct. Therefore option (B), (C) and (D) are correct.

Q.26 Which of the following on reduction with

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 LiAIH4 will give ethyl alcohol ? (D) (CH3CO)2O+C2H5OHCH3 C –OC2H5+CH3COOH
(A) (CH3CO)2O ||
O
(B) CH3COCl Ethyl acetate
(C) CH3CONH2 Therefore option (A),(B),(C) and (D) are correct.
(D) CH3COOC2H5
Sol.[A,B, D] Q.28 The formula C4H4O4 can represent –
O
(A) A cyclic ester of dibasic acid
CH3C LiAlH (B) A cis-dibasic acid
O 
 2CH3CH2OH
4
(A)
CH3C (C) A trans-dibasic acid
Ethyl alcohol
O (D) An , -unsaturated dibasic acid which
LiAlH on heating forms a monobasic acid
 
(B) CH3– C –Cl 4
C2H5OH+LiCl+AlCl3
|| Sol.[A,B,C,D]
O Formula C4H4O4 represent.
LiAlH 4
(C) CH3CH2– C –NH
2 
 CH3CH2CH2 NH2+H2O (A) A cyclic ester of dibasic acid
|| O
O
LiAlH CH2–O–C
(D) CH3COOC2H 5   4
CH3CH2OH + CH3OH
So option (A), (B) and (D) are give the ethyl CH3–O–C
alcohol by reduction with LiAlH4. O
(B) A cis-dibasic acid
Q.27 Ethyl acetate can be prepared by – H–C–COOH
(A) Reaction of ethyl alcohol with acetic acid
in presence of dry HCl gas H–C–COOH
(B) Treatment of acetaldehyde with Maleic acid
Al(OC2H5)3 (C) A trans-dibasic acid
(C) Reaction of acetyl chloride with ethyl H–C–COOH
alcohol in presence of acidic medium
(D) Reaction of acetic anhydride with ethyl COOH–C–H
alcohol in presence of acidic medium Pumaric acid
Sol.[A,B,C,D] 

H (D) HC CH  CH2=CH–COOH+CO2
(A) C2H5OH+CH3– C –OH
2  CH3 C –OC2H5
|| || COOH COOH Monobasic acid
O O
Therefore option (A),(B),(C) and (D) are correct.
O H
Al (OC H )
(B) CH3C + O = C – CH
3    C
2 5 3

H Part-C (Assertion & Reasoning type

Acetaldehyde O Questions)
CH3C–O–CH2–CH3 The following questions 29 to 30 consists of
Ethyl acetate two statements each, printed as Assertion
This reaction is know as and Reason. While answering these
Tischenko reaction. questions you are to choose any one of the
(C) CH3 C –Cl + C2H5OH  CH3 C –OC2H5 + HCl following five responses.
|| || (A) If both Assertion and Reason are true and
O O
the Reason is correct explanation of the
Ethyl acetate
Assertion.

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 (B) If both Assertion and Reason are true but (b) Cannizaro’s reaction (ii) red brown
Reason is not correct explanation of the precipitate
Assertion. (c) Aldol condensation (iii) aldehyde
+ Zn–Hg/HCl
(C) If Assertion is true but the Reason is false.
(d) Fehling solution (iv) aldehydes
(D) If Assertion is false but Reason is true. containing no
(E) If Assertion & Reason are false. -hydrogen
(e) Claisen-Schmidt (v) carbonyl
Q.29 Assertion : Nitration of benzoic acid gives
reaction compounds having
m-nitrobenzoic acid.
Reason : carboxylic group increases the -hydrogen
relative electron-density at meta-position. Sol. (A) iii, (B)iv, (C)v, (D)ii, (E)  i
O Factual
|| Q.33 Column-A Column-B
Sol.[C] – C –OH, is an electron attracting group thus (Reagents reacting with (Product formed)
cause deactivation of benzene ring particularly PhCH2COOH)
at o, p that m-position, thus electrophilic reagent (a) CH3MgBr (i) PhCH2COCl
can attack at m-position. (b) PCl5 (ii) PhCH2COOCH3
Therefore assertion is true but the reason is (c) NH3, followed by (iii) CH4
false. heating
So option (C) is correct. (d) CH3OH in the presence(iv) PhCH2CONH2
of conc. H2SO4
Sol. (A)  iii, (B)i, (C)iv, (D)ii
Q.30 Assertion : CH3COCH2COOC2H5 will give Factual
iodoform test.
Q.34 Column-A Column-B
Reason : It contains CH3CO–group linked to
(a) PhCONH2  (i) B2H6/AcOH/H2O
a carbon atom.
PhCH2OH
Sol.[D] Ethyl acetoacetate (CH3 C –CH2COOC2H5) does
|| O
O
not give iodogorm test, although it contains
(b) O  (ii) LiAlH4
CH3– C group attached to carbon (methylene
|| C6H5
O
CH2OH–(CH2)2–CHOH–C6H5
group). This is due to active nature of
(c) C6H5CH=CH–COOH (iii) H2/Pd + BaSO4
methylene group at which iodination occurs and
not on methyl group of CH3CO unit. C6H5–CH=CH2OH
Therefore assertion is false but reason is true so (d) CH3COClCH3–CHO (iv) None
option (D) is correct. Sol. (A)  iv, (B)ii, (C)iv, (D)iii,
Factual
Q.35 Column-A Column-B
Part-D Column Matching reduction
(a) RCN   (i) 1° Amine
Q.31 Column-A Column-B (i ) CH MgBr
(b) RCN  3  (ii) Alcohol
(a) H.V.Z. reaction (i) potassium salt of ( ii ) H 2 O
Monocarboxylic acid hydrolysis
(c) RNC   (iii) Ketone
(b) Oxidation of Formic (ii) replacement of
acid -hydrogen by HNO
(d) RNH2  
2
 (iv) Acid
halogen
(c) –COOH group (iii) H2O + CO2 Sol. (A)  i, (B)iii, (C)i, iv, (D)ii
(d) Salt in Kolbe’s (iv) deactivating Factual
electrolytic reaction
Sol. (A)ii, (B)iii, (C)iv, (D)i ,
Factual
Q.32 Column-A Column-B
(a) Clemmenson (i) ,-unsaturated
reduction compound

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 EXERCISE # 3
Therefore fluoro acetic acid is stronger than
Part-A Subjective Type Questions chloroacetic acid.

Q.1 Fluoro acetic acid is stronger than chloro

acetic acid.
Q.2 C – O bond length in formic acid are 1.23 Aº

Sol. F–CH2–C–OH F–CH2 –C–O and 1.36 Aº but in sodium formate both
 –I carbon and oxygen bonds have same value
O O
(strong –I power) i.e. 1.27 Aº.
 Sol. In sodium formate both carbon and oxygen
Cl–CH2–C–O–H Cl–CH2 –C–O bonds have same value because in formate ion
O O equal resonating structure is formed.
Anion stabilised by
–I group.

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 –
– CH2Cl
O O O
(B) ;
H–C  H–C  H–C CH2Cl
–
O O O (C) CN /H3O+;
–
–

But resonance does not present in formic acid. (D) C=O

Therefore C–O bond length in formic acid are
different.
Moist Ag O [O] D
Q.3 The C – G bond in acid derivative is expected Q.7 A   
2
 B  C 
 Na / C H OH I
to be shorter and stronger than alkyl (HCOO)2Ca  G  2 5  H 

2, SOCl 2
derivative.
H O
Sol. In acid derivative CH3CN 3  X
Resonance present KCN HO
R–C–G  A  J 
3
X
xÅ R – C – G  R–C=G Sol. (A) CH3Cl ; (B) CH3OH ;
O
R–CH2–G O O (C) HCOOH ; (D) Ca(OH)2 ;
yÅ no Resonance Double bond (G) HCHO ; (H) CH3Cl ;
O
characters are (I) KCN ; (J) CH3CN ;
present
(X) CH3COOH
Therefore C–G bond in acid derivative is
CH COOH
expected to be shorter and stronger than alkyl Q.8 HC CH excess

3
 (A)  B+C
derivative.
HOH
 CH3COOH
Q.4 Ester (A) PCl
5  B + C aq
. KOH

Sol. (A) CH3CH(OOCCH3)2 ;
(CH3)2CHCH2OH
H / Pd (B) CH3CHO ;
B + C 2  (D) LiAlH
 4 
BaSO 4 (C) (CH3CO)2O
(CH3)2CHCH2OH
Sol. (A) (CH3)2CHCOOCH2CH(CH3)2 ;
(B) (CH3)2CHCOCl ; Q.9 On standing in dilute aqueous acid,
(C) (CH3)2CHCH2Cl compound A is smoothly converted to
COOH mevaionolactone.

COOH   Me
Q.5 A  B (1) H O 
 
3

COOH ( 2) 
O O
O CH2COOH
COOH C Me
Sol. (A) ; (B) O O
COOH C O
CH3
O
OH
COOH Suggest a reasonable mechanism for this
LiAlH HCl
Q.6  
4  (A) 
 (B) reaction. What other organic product is also
COOH
formed ?
CH2COOH HO

(C)

BaO
 Me
 OH O
CH2COOH O
H2C CH3
Sol. O H2O +
(D) + CO2 + H2O CH2COOH CH2 CH3
CH2OH Me
Sol. (A) ;
CH2OH
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 Intermol D (C3H6O). Which can also synthesised from
ester
methyl
CH3
OH Sol. (A) (CH3)2CHCONH2; (B) (CH3)2CHNH2;
O
(C) (CH3)2CHOH; (D) CH3COCH3
O
Q.12 An organic compound A (C8H8O) an
Q.10 Outline reasonable mechanisms for each of treatment with NH2OH. HCl give B and C.
the following reactions. Compound B and C can be converted into D
and E respectively by treatment of H2SO4.
(a) + BrMgCH2CH2CH2CH2MgBr
O O Compound B, C, D and E are all isomer of
molecular formula C8H9NO. When D is
1. THF
 boiled with KOH, an oil F (C6H7N) separate
2. H 2 O
HO CH2CH2CH2OH out. F react rapidly with CH3COCl to give
back (D). On other hand. E on boiling with
(b) alkali followed by acidification give a white
H2NCH2CH2 S O solid G (C7H6O2). Identify A to G.
HS O CH3
spon tan eous –C–CH3 –C=N–OH
   N O Sol. (A) ; (B) ;
H
CH3 OH O
Sol. (a) –C = N –NH–C–CH3
O O (C) ;(D) ;
+
    O
Br–Mg–CH2 CH2–Mg–Br
–C–NH–CH3 –NH2
CH2 – CH2 (E) ; (F) ;
O

O OH –C–OH
(G)
OH . OH
CH2 CH2
CH2 CH2
CH2 – CH2
Q.13 An organic compound (A) of formula C3H6O
from a monoxime with hydroxylamine and
•• ••
(b) HNCH2–CH2 S O form iodoform on heating with I2 and NaOH
••
and sodium acetate. Compound A on reaction
H
with NaCN and dil H2SO4 gave product B.
Which on hydrolysis produced (C).
–
O O Compound (C) on heating gave (D), which on
decarboxylation gave (E) of formula C3H6.
N–H N–H
HS HS Compound (E) on ozonolysis gave one
molecule of acetaldehyde and one of
methanal. What are A to E ?
Q.11 An organic compound A (C4H9NO) on
Sol. (A) CH3–CO–CH3;
treatment with bromine and alkali form (B)(CH3)2C(OH)CN ;
another compound B (C3H9N) on treatment (C) (CH3)2C(OH)COOH ;
with sodium nitrite and dilute hydrochloric (D) CH2=C–(CH3)–COOH ;
acid. B yield C (C3H8O). C can be oxidized to (E) CH3–CH=CH2
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 O O
Q.14 Compound (A) with an empirical formula, (B) CH3–CH2–C–CH2–C–OH
C7H9N on diazotization give a product which O O
undergoes reaction with Cu2Cl2 & HCl to
(C) CH3–C–CH–C–OH
give a compound (B). B on oxidation give a
compound (C). Compound (A) on treatment CH
with Br2/H2O form C7H6NBr3 (D). Give the (D) All
structural formula of A, B, C & D. O O O
 ••
NH2 Cl Sol.(A) CH3–C–CH2–C–OH  CH3–C–CH2+CO2

Sol.
–
CH3 CH3 OH O
NH2 H2O/H+
Br Br CH3–C=CH2 CH3–C=CH2
Cl
CH3–C–CH3
CH3
COOH Br OH
Therefore option (A) is correct.

Part-B Passage based Question Q.16 Arrange the following in the increasing order
of ease of decarboxylation.
Passage - I (Q. 15 to 17)
O O
-keto acids are highly unstable acids and
undergo decarboxylation on heating at 90º– I. CH3–C–CH2–C–OH
100ºC Via formation of cyclic transition state. O O
Decarboxylation of -keto acids involves II. CH3–C–CH2–CH2–C–OH
both free acids and the carboxylate ion. Loss COOH
of CO2 from carboxylate ion yields the O2N NO2
III.
carbanion which is stabilised by resonance.
O O O
•• •• NO2
R–C–CH2–C–O R – C – CH2 + CO2 O

•• CH2–C–OH
O IV.
R–C=CH2
(A) I < II < III < IV (B) II < I < IV < III
This carbonion is formed faster than the
(C) II < IV < I < III (D) IV < III < II < I
simple carbanion i.e. alkyl carbanion that
would be form a simple carboxylate ion Q.17 What will be the final product in the
(RCOC–) because it is more stable. It is more following reaction :
stable of course due to accommodation of the O
negative charge by the keto group. PCl
KCN
CH3–C–H 5  A  B
H O
Q.15 Which of the following on heating gives NaOH
 
2
 C HCl
 
 D  E
acetone –
O O O
(A) CH3–C–NH2
(A) CH3–C–CH2–C–OH

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 O ••
O
(B) CH3–CH2–C–OC2H5
CH3–C–OC2H5 O O
(C) CH3–CH2–CH3
O CH2–C–OC2H5 CH3–C–CH2–C–OC2H5

(D) CH3–CH2–C–OH O
O This reaction also takes place between ester
PCl Cl and ketone having atleast one -hydrogen.
Sol.(D) CH3–C–H 5  CH3CH
Ketone behaves as nucleophile. In diesters
Cl
[A] KCN intramolecular claissen condensation gives a
CN cyclic -ketoester.
CH3CH
CN Q.18 What is X in the following reaction.
[B]
O O
H2O/NaCl
COOH NaCl COONa C–OC2H5 (i ) C H ONa / C H OH
CH3CH CH3CH +    2 
2 5 5
 X
COOH COONa C–OC2H5 ( ii ) H
 [C] [C]
O
O O
CH3–CH2–COOH+CO2
Therefore option (D) is correct. CH2–C–OC2H5
(A)
Passage - II (Q. 18 to 20) O O
Claisen condensation takes place between
two molecules of ester in presence of strong C–OC2H5
base like R–ONa in alcohol or NaH in ether. (B)
Two ester molecules may be same or O O O
different. The basic need of this reaction is
the presence at least one -Hydrogen, the C–C–OC2H5
reaction is termed as crossed claissen (C)
condensation.
O
This reaction is an example of nucleophilic
substitution reaction. In this reaction one O O
molecules of ester behaves as substrate and (D)
C–C–OC2H5
other molecule having -Hydrogen atom
O O
behaves as nucleophile.
The product of the reaction is -Ketoester. H 
  

Sol.(C) + C2H5O +C2H5OH

Step (i)

H O O O O O O–
•—•
C2H5O –
CH2–C–OC2H5 CH2–C–OC2H5 
 C–OC2H5 C–OC2H5
Step (ii) +
C–OC2H5 C–OC2H5
O O
•• O O
CH2–C–OC2H5 + CH2–C–OC2H5

••
O O O O

CH3–C–OC2H5 C–C–OC2H5 + C2H5O

CH2–C–OC2H5
Therefore option (C) is correct.
O

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 (B) CH3–CH2–N O
O
COOC2H5
CH2–CH2–C–OC2H5 C 2 H 5 ONa
Q.19   A.
C H OH
(C) CH3–CH2–N
CH2–CH2–C–OC2H5 2 5

COOC2H5
O O
What is A– O
O C–OC2H5
O
(D) CH3–CH2–N
(A) CH2–C–OC2H5

O O H O
–
C–OC2H5 CH2–CH–C–OC2H5 C2H5O
(B) Sol.(B) CH3–CH2–N
CH2–CH2–C–OC2H5
O O
O
O
(C) C–OC2H5 
CH2–CH–C–OC2H5
O C2H5–N
O CH2–CH2–C–OC2H5
C–CH3 O
(D)

Sol.(C)
O

H O O CH2–CH–C–OC2H5

 –
CH2–CH–C–OC2H5 C2H5O CH2–CH–C–OC2H5 C2H5–N C–O
CH2–CH2 OC2H5
CH2–CH2–C–OC2H5 CH2–CH2–C–OC2H5
O O

C2H5–N O
–
O OC2H5
O C–OC2H5
O O
C
C–OC2H5 CH–C–OC2H5 O
CH2
 Therefore option (B) is correct.
–C2H5O CH2 CH2
Therefore option (C) is correct.

Q.20 What will be the product in the following

reactions –
O
CH2–CH2–C–OC2H5
CH3–CH2–N
CH2–CH2–C–OC2H5
O
C 2 H 5 ONa
   Product
C H OH2 5

(A) CH3–CH2–N O

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 EXERCISE # 4
O O
*
 IIT JEE objective questions (C) CHI 3
* –+
Ph CH3 Ph O Na
Q.1 When benzamide is treated with POCl3, the O O
product is – [IIT-2004] (D)
*
CH 3 I
(A) Benzonitrile (B) Aniline * –+
Ph CH3 Ph O Na
(C) Chlorobenzene (D) Benzylamine
Q.4 Give major products A, B, C and D in
Sol.(A) C6H5–C–N H2 + pOCH3 C6H5–CN–H2O following reaction sequence. [IIT–2004]
O Benzonitrile CH2–Cl
Benzamid
KCN 1) NaOEt / EtOH
Therefore (A) is correct.  A    
DNF 2 ) PhCHO / 

H3O
B C
CH 3 COONa (1) SOCl2
Q.2 MeO CHO + X   
 D
 (2) CH3NH2
CH2–CN
MeO CH=CH–COOH

[IIT-2005] Sol. (A)

CH 2COOH
| CN
(A) (B) BrCH2–COOH
CHO
(C) COOH(CH3CO)2O (D) (CH3CO)2O CH=C–
Sol.(D) This reaction is an example of Perkins reaction
(B)
MeO CHO + (CH3CO)2O
CH3COONa
Acetic anhydride COOH
CH=C–
MeO CH=CH–COOH
(C)
Therefore option (D) is correct.
CONHCH3
Q.3 In the following reaction sequence, the CH = C
correct structures of E, F and G are-
O O
I
(D)
Heat
 [E] 
2
NaOH
[F] + [G]
Ph * OH
(* implies 13C labelled carbon) Passage (Q.5 to Q.7)
[IIT- 2008] In the following reaction sequence, products
E F G I, J and L are formed. K represents a reagent.
O O 1. Mg / ether
1. NaBH 2. CO
(A) CHI3 Hex-3-ynal  4  I  2 
 J

* * –+ 2. PBr3 3. H 3 O
Ph CH3 Ph O Na
Me Cl
O O K H
 
2
L
(B) CHI3 O Pd / BaSO 4
* –+ quinoline
Ph CH3 Ph O Na
[IIT-2008]

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Q.5 The structure of the product I is -

Me H2 Pd-BaSO4
(A) Me Br (B) Br
(C) Me Br (D) Me Br
Sol. [D] Me Br CH3–CH2 CH2–CH2–CHO

Q.6 The structures of compounds J and K, C=C

respectively, are - H H
(A) Me COOH and SOCl2 (L)
OH
(B) Me and SO2Cl2
O
Me Q.8 The carboxyl functional group (–COOH) is
(C) COOH and SOCl2 present in - [IIT-2012]
(D) Me COOH and CH3SO2Cl (A) picric acid (B) barbituric acid
(C) ascorbic acid (D) aspirin
Sol. [A] Me COOH and SOCl2 Sol.[D] Factual

Q.9 The compound that undergoes decarboxylation

Q.7 The structure of product L is - most readily under mild condition is –
(A) Me CHO [IIT-2012]
COOH COOH
(B) Me CHO CH2COOH O
CHO
(C) Me (A) (B)
(D) Me CHO COOH CH2COOH
1. NaBH 4
Sol. [C] CH3–CH2–CC–CH2–CHO   COOH O
2. PBr3
(C) (D)
CH3–CH2–CC–CH2–CH2–Br
COOH
[I] O O

Sol. [B] 
 + CO2
1. Mg/ether
2. CO2
3. H3O+ Q.10 With reference to the scheme given, which of
the given statement(s) about T, U, V and W is
CH3–
(are) correct ? [IIT-2012]
CH2–CC–CH2–CH2–COOH O

[J] O

H 3C T
[K] = SOCl2
LiAlH4

CH3–CH2– CrO3 / H 
v   U (
CH 3CO ) 2 O excess
  w
CC–CH2–CH2–COCl (A) T is soluble in hot aqueous NaOH
(B) U is optically active
(C) Molecular formula of W is C10H18O4
(D) V gives of effervescence on treatment with
aqueous NaHCO3
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Sol. [A,C,D]
O
O CH2OH ||
CH2–O–C–CH3
O O
LiAlH
 4  excess
 ||
OH ( CH 3 .CO ) 2 O O–C–CH3
CH3 U CH3
CH3 T W
Cr O3/H+
COOH

COOH
V

Q.11 Identify the binary mixture(s) that can be separated into individual compounds, by differential extraction, as shown
in the given scheme. [IIT-2012]

NaOH(aq)
Compound 1 + Compound 2
Binary mixture containing
Compound 1 and Compound 2 NaHCO3(aq)
Compound 1 + Compound 2
(A) C6H5OH and C6H5COOH (B) C6H5COOH and C6H5CH2OH
(C) C6H5CH2OH and C6H5OH (D) C6H5CH2OH and C6H5CH2COOH
Sol. [B,D]
Factual

EXERCISE # 5
 IIT JEE objective questions O
||
Q.1 Acetamide is treated separately with the (A) R– C –NHBr (B) R–N=C=O
following reagents. Which one of the these O
|| Br
would give methyl amine ? [IIT-1983] (C) R–NHBr (D) R– C –N
Br
(A) PCl5
Sol.(A,B) The intermediates involved are RCONH–Br
(B) NaOH + Br2
and R–N=C=O (isocyanate). This is clear from
(C) Sodalime the mechanism involved.
(D) Hot conc.H2SO4 Br2 + 2NaOH  NaBr + NaOBr + H2O
Sol. [B] Factual Sodium
hypobromite
O
||
Q.2 The reaction of R– C –NH2 with a mixture of
Br2 and KOH gives R–NH2 as a product. The
intermediates involved in this reaction are–
[IIT-1992]

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 O O Therefore option (B) is correct.
•• 
– –
R–C–NH2–OBr R–C–N – Br + OH

H Q.5 Benzoyl chloride is prepared from benzoic

(N-Bromoamide) acid by– [IIT-2000]
OH–, –H2O (A) Cl2, h  
 (B) SO2Cl2
O O
••  (C) SOCl2
••
R–C–N R–C–N – Br (D) Cl2, H2O
••
Sol.[C] C6H5COOH + SOCl2  C6H5COCl + SO2+HCl
Nitrene
– ••
Therefore option (C) is correct.
R–N=C=O 2OH R–NH2+CO3–2
Isocyanate Amine
Therefore option (A) and (B) are correct.
 IIT JEE subjective questions

Q.3 Which of the following carboxylic acids Q.6 Give reasons for the following in one or two
undergo decarboxylation easily– [IIT-1995] sentences.
(A) C6H5CO–CH2COOH “Acetic acid can be halogenated in the
(B) C6H5COCOOH presence of P and Cl2, but formic acid cannot
(C) C6H5 CH 2 –COOH be halogenated in the same way.”
|
OH [IIT-1983]
(D) C6H5 CH 2 –COOH Sol. Because acetic acid has -hydrogen atoms
| which can replace by halogen but formic acid
NH 2 does not have -hydrogen.
Sol.[A]
O O Q.7 Write down the reactions involved in the

C6H5–C–CH2 –C – O
–
C6H5–C –CH2+CO2 preparation of the following using the

reagents indicated against in parenthesis.
This carbanion
“Propionic anhydride from propionaldehyde”
is stabilized
[AgNO3, NH4OH, P2O5]
due to resonance
O [IIT-1984]
|| AgNO 3
Sol. CH3CH2CHO + Ag2O  

Therefore C6H5– C –CH2COOH undergo NH 4 OH
decarboxylation easily. So option (A) is correct. propionaldehyde (Tollen’s reagent)
CH3CH2COOH + 2Ag
Q.4 The molecular weight of benzoic acid; in propionic acid
benzene as determined by depression in CH3CH2COOH
freezing point method corresponds to– P2O5 CH2CH2CO
+ O
[IIT-1996] –H2O CH2CH2CO
CH3CH2COOH
(A) Ionization of benzoic acid
Propionic anhydride
(B) Dimerisation of benzoic acid
(C) Trimerisation of benzoic acid
(D) Solvation of benzoic acid Q.8 Give reason in one or two sentences for the
Sol.[B] Benzoic acid exists dimmer in benzene following :
O H O “Formic acid is a stronger acid than acetic
C C acid.” [IIT-1985]
O H O
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 O O B = CH3—CH2—CO— CH — COOC2H5
+ – |
Sol. CH3 C O H, H C O H CH 3
Acetic acid ethyl (2-methyl, 1,3-ketopentanoate)
+I effect C = CH3—CH2—CO— CH —COOH
Acetic acid weaker acid than formic acid due |
to + I effect, Hence, formic acid is stronger CH 3
acid than acetic acid. 2-methyl, 3-keto, pentanoic acid

Q.9 Arrange the following in the order of their Q.12 Write balanced equations for the following
increasing case of hydrolysis : reaction :
CH3COOC2H5, CH3COCl, (CH3CO)2O, “Acetamide is reacted with bromine in the
CH3CONH2 [IIT-1986] presence of potassium hydroxide.”
Sol. CH3CONH2 < CH3COOC2H5 < (CH3CO)2O [IIT-1987]
< CH3COCl Sol. CH3CONH2 + Br2 + 4KOH  CH3NH2
+ K2CO3 + 2KBr + 2H2O
acetamide methyl amine
Q.10 Complete the following with appropriate (It is Hofmann’s bromide reaction.)
structures : [IIT-1986]
C H OH
(CH3CO)2O   CH3COOH + ?
2 5
Q.13 Give reasons for :
C 2 H 5 OH “Carbon oxygen bond lengths in formic acid
Sol. (CH3CO)2O CH3COOH +
CH3COOC2H5 are 1.23 Å and 1.36 Å and both the carbon
oxygen bonds in sodium formate have the
same value, i.e., 1.27 Å.” [IIT-1988]
Q.11 A liquid X, having a molecular formula
Sol. Both the carbon-oxygen bonds in sodium
C6H12O2 is hydrolysed with water in the formate have the same value because of
presence of an acid to give a carboxylic acid resonance hybrid of two equivalent structures.
Y and an alcohol Z. Oxidation of Z with
chromic acid gives Y. What are the Q.14 Compound (A) (C6H12O2) on reduction with
structures of X, Y and Z. [IIT-1986] LiAlH4 yielded two compounds (B) and (C).
Sol. Since X is hydrolysed to give an acid Y and The compound (B) on oxidation gave (D)
an alcohol Z and thus, X is an ester R— which on treatment with aqueous alkali and
COOR’.
HOH subsequent heating furnished (E). The latter
RCOOR’   RCOOH + R’OH

H on catalytic hydrogenation gave (C). The
X Y Z compound (D) was oxidised further to give
(ii) Oxidation of alcohol Z gives an acid Y, it (F) which was found to be monobasic acid
shows that Z is a primary alcohol, i.e.,
R—CH2OH (molecular mass = 60.0). Deduce the structure
[O] of (A), (B), (C), (D) and (E). [IIT-1990]
R’OH  R—CH2OH
Sol. (A) CH3CH2CH2COOCH2CH3;
X Y
R—CH2OH
[O ]
 RCOOH (R’=R—CH2) (B) CH3CH2OH;
So, X = R—COOCH2R (C) CH3CH2CH2CH2OH;
 X is (D) CH3CHO;
CH3 CH2 C CH2 CH2 CH3
(E) CH3CH = CHCHO
O
propyl propanoate
Hence,
A = CH3—CH2—COOC2H5 Q.15 In the following reactions, identify the
ethyl propanoate compounds (A), (B), (C) and (D).
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 PCl5 + SO2 (A) + (B) H 3C COOC2H5
(A) + CH3COOH  (C) + SO2 + HCl
CH
2(C) + (CH3)2 Cd  2(D) + CdCl2
[IIT-1994] Br ( i ) OH 
(B)  



Sol. (A) SOCl2 ; (B) POCl3 ; (ii ) H 

(C) CH3COCl; (D) CH3COCH3 O

H3C–CH–C–OH

Q.16 Complete the following equations by writing CH2–C–OH [IIT-1999]

the missing A and B O
P / Br2
(i) CH3CH2COOH  (A) Sol. (A) NaCH(COC2H5)2;
( i ) Alc. KOH ( excess )
     (B) [IIT-1995] HC – (COOC2H5)2

( ii ) H (B)
CH3–HC–COOC2H5
CrO
(ii) C4H8O3(A) 3  (B) Warm

O
|| Q.19 Write the structure of product A & B –
CH3 – C – CH3 + CO2 [IIT-1997] [IIT – 2000]
Sol. (i) (A) CH3CHBrCOOH; O
(B) CH2 = CHCOOH; || H O
CH3– C –O18C2H5 3  A + B
(ii) (A) CH3CH(OH)CH2COOH; Sol. (A) CH3COOH;
(B) CH3COCH2COOH (B) C2H5O18H

Q.17 A mixture of an acid anhydride (A) and a

monobasic acid (B) on heating produces
another monobasic acid (C) of equivalent
weight 74 and an anhydride (D). The acids
and anhydrides remain in equilibrium. The
anhydride (D) contains two identical fluoro-
alkyl groups. The acid (B) contains a
trifluoro-methyl group and has an equivalent
weight of 128. Give structures of (A) to (D)
with proper reasoning. (Atomic weight of
fluorine = 19). [IIT-1998]
Sol. (A) (CH3CH3CO)2O; (B) CF3CH2COOH;
(C) CH3CH2COOH; (D) (CF3CH2CO)2O

Q.18 Identify A and B in the following equations.

O

COC2H5 NaOEt
CH2   (A)
COC2H5

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