Page 1 of 9 CPP - SANKALP_CAD-3-PH-V

CPP
SHEET – 3 (PROPERITES OF CARBOXYLIC ACID)
SUBJECTIVE (LEVEL – 1)

1. How will you convert:-

i) CH3COOH into C2H6
ii) CH3COOH into C2H5OH
iii) CH3COOH into methylamine
iv) Propanoic acid into 1-propanol
v) Propanoic acid into lactic acid
vi) Benzoic acid to 3-bromobenzoic acid
vii) Benzoic acid to benzaldehyde
viii) Benzoic acid to benzene
ix) Benzoic acid to benzyl alcohol
x) Benzoic acid to benzyl ethanoate
xi) Benzoic acid to benzyl chloride
xii) Benzoic acid to benzonitrile
xiii) Benzoic acid to benzamide

2. Complete the following:-

Re d P
i) CH3COOH + Br2 
Re d P
ii) CH3COOH + Cl2 
H2SO 4
iii) CH3COOH + CH3OH  

iv) CH3COOH + SOCl2 
v) CH3COOH + LiAlH4 
vi) C6HCOOH + Na2CO3(aq.) 

vii) C6H5COOH + PCl5  
Electrolysis
viii) CH3COOK + H2O  
?
ix) C6H6 + 
Anhy AlCl3
 C6H5 COCH3

3. Write short notes on the following:-

i) Kolbe’s electrolytic reaction.
ii) Hell-Volhard-Zelinskyl reaction
iii) Esterification reaction
iv) Decarboxylation reaction
v) Hunsdiecker reaction

4. Write balanced chemical equations for the following reactions:-

i) Thionyl chloride reacts with benzoic acid
ii) Decarboxylation of malonic acid
iii) Acetic acid is heated with red phosphorus and HI

5. What happens when acetic acid is treated with

i) NaHCO3 ii) Zn metal
iii) LiAlH4 iv) Ethanol and a drop of conc. H2SO4
v) NH3 and then heat vi) PCl5
vii) Soda lime
18 18
6. What would you expect to happen to O label in a mixture of ethanoic acid, hydrochloric acid and H2O ,
explain?

7. Malonic acid (Propanedioic acid), on heating does not form cyclic anhydride, rather it gives ethanoic acid, why?

8. When butanoic acid is heated with soda lime, besides decarboxylation product propane, some 4-heptanone is
also formed. Explain the formation of 4-heptanone.

9. Complete the following equation by writing the missing A, B, C, D ….. etc.

O H
(a) LiAlH4
H3C C N  (A)

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Page 2 of 9 CPP - SANKALP_CAD-3-PH-V
O

LiAlH4
(b) O  (B)

SUBJECTIVE (LEVEL – 2)
1. Predict product in the following reactions:
18
H2SO4
(a) C6H5 — COOH C2H5 — OH 



18
O
(b)
H2SO4
C6H5 C OH  CH3 CH2 OH 



2. As discussed above in the mechanism of esterification, during acid catalysed esterification, oxygen of alcohol
18
is usually retained. However when ethanoic acid is refluxed with labelled tertiary butanol, (CH3 )3 C — OH , in
presence of H2SO4, the major product is CH3COOC(CH3)3, without O18 in ester, explain.

3. Complete the following reactions:

H2O2 K 2Cr2O7 P2O5
H2C CH2  B2H6 
OH
 H
 A 
Heat
B

4. 2-butenedioic acid exist in two configurational forms A and B, of which A on simple heating undergoes
intramoleclar dehydration to form a cyclic anhydride while B does not dehydrate on simple heating. Identify A
and B and explain the reactions.

5. Alkyl benzene, containing at least one -H in the side chain, on refluxing with alkaline KMnO4 followed by
acidification yields benzoic acid. Three isomeric, aromatic hydrocarbons A, B and C, have molecular formula
C8H10. All on refluxing with alkaline KMnO4 followed by acidification gives isomeric products with their
molecular formula C8H6O4. Oxidation product of A, on simple heating loses a molecule of water giving
D(C8H4O3) but oxidation products of B or C do not dehydrate on simple heating. Also, oxidation product of B is
non-polar while other two oxidation products are polar. Identify A, B, C and D.

6. Convert propanoic acid into

(i) 2-hydroxy butanoic acid (ii) 2-butenoic acid
(iii) 1-butene (iv) 2-butene

OBJECTIVE

1. In the reaction sequence:


H3C COOH   [Y]

OH
[Y] will be:
O
(a) (b) CH2 = CH —COOH
H3C HC O
O

OH O
(c) (d) H3C CH3
H2C CH2 COOH
O
O

2. In the given reaction:

(i) AgOH
CH3—CH2—COOH  (ii) Br2 / 
[X]

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Page 3 of 9 CPP - SANKALP_CAD-3-PH-V
[X] will be:
(a) Ethyl bromide (b) Propyl bormide
(c) Propyl propanoate (d) All of these

3. Benzoic acid on treatment with hydrazoic acid in the presence of concentrated sulphuric acid gives:
(a) Benzamide (b) Sodium benzoate
(c) Aniline (d) C6H5CON3

4. In the given reaction:

OH
COOH
PCl3
 [X]

[X] will be:

Cl OH
COOH COCl
(a) (b)

Cl
O
O COCl
(c) (d)

5. Sodium bicarbocate reacts with salicylic acid to form;

OH
COONa
(a) C6H5ONa (b)

ONa ONa
COOH COONa
(c) (d)

6. Which one of the following will go decarboxylation on heating?

(a) Succinic acid (b) Phthalic acid
(c) Malonic acid (d) Adipic acid
7. In the given reaction:
(i) Br2 / P
CH3 — COOH  (ii) NaCN
[X]
(iii) H2O / H / 

[X] will be:

(a) CH3COOH (b) COOH—CH2—CH2—COOH
H2C CO CO
(c) O (d) H2C O
H2C CO CO

8. Which optically active compound on reduction with LiAlH will give optically inactive comound?
H3C CH COOH H3C CH CH COOH
(a) (b)
OCH3 OH
H3C CH2 CH COOH H3C CH CH2 COOH
(c) (d)
CH2OH OH
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Page 4 of 9 CPP - SANKALP_CAD-3-PH-V
9. In the given reaction:
COOH

HBr
 [X]

[X] will be:

COBr COOH
Br
(a) (b)

COOH COOH
Br
(c) (d)

10. Reducing property of formic acid is due to the presence of:

O
(a) —OH (b)
C H
O
(c) (d) All of these
C OH

11. In which reaction product is hydrocarbon?

Electrolysis I2 / 
(a) RCOOK   (b) RCOOAg  
CH3

Cl2 / h
(c) CH3 — CH3   (d) H3C C Cl C 2H5OH
 

CH3

12. An optically active compound ‘X’ has molecular formula C4H8O3. It evolves CO2 with sq. NaHCO3. ‘X’ reacts
with LiAlH4 to give an achiral compound. ‘X’ is:
COOH Me
(a) H 3C (b) H3C
OH COOH
H C CH COOH OH
3
(c) (d) COOH
CH2OH H3C

13. In the given reaction:

O
CH3
LiAlH4
C6H5 C N  [X]
CH3
[X] will be:
(a) C6H5—CH2OH (b) C6H5COOH
CH3
(c) C6H5CONH2 (d) C6H5 CH2 N
CH3

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Page 5 of 9 CPP - SANKALP_CAD-3-PH-V
14. Which of the following carboxylic acids undergo decarboxylation easily:
(a) C6H5CO—CH2COOH (b) C6H5COCOOH
H5C6 CH2 COOH C6H5 CH2 COOH
(c) (d)
OH NH2

15. When propionic acid is treated with aqueous NaHCO3, CO2 is liberated. The ‘C’ of CO2 comes from
(a) Methyl group (b) Carboxylic acid group
(c) Methylene group (d) Bicarbonate

16. Benzoyl chloride is prepared from benzoic acid by:

(a) Cl2, h (b) SO2Cl2
(c) SOCl2 (d) Cl2, H2O
——
ANSWER KEY SHEET - 3
SUBJECTIVE – Level – 1
1. i) CH3 COOH  Ag
 Br2 / hv
 CH3 COOAg  Na
 CH3Br   CH3  CH3
CCl4 D.E

or
NaOH Br2 / hv Na / D.E
CH3 COOH 
CaO
 CH4   CH3Br   C2H6
or
O
SOCl2 H2 , Pd
CH3 COOH  H3C C Cl 
BaSO4
 CH3 CHO HI
 C2H6
Re d P
or Wolff Re duction
or
Clemmensen Re duction

or
KOH / aq.
CH3 COOH 
Electrolysis
 C2H6  CO2  H2
ii) (i) LiAlH4
CH3 COOH   CH3 CH2OH
(ii) H2O

iii) NH3
CH3 COOH  Br2
 CH3 CONH2   CH3NH2
 KOH

iv) (1) LiAlH4

CH3  CH2  COOH  CH3CH2CH2OH
(2) H2O

v) Br OH
Br2 / Re d P (1) aq. NaOH
CH3  CH2  COOH   H3C C COOH 
(2) HCl dil
 H3C C COOH

H H
vi) COOH COOH

Br2 / FeBr3
 


Br
vii) COOH CHO

CH2OH
LiAlH4 PCC
H2O
 

viii) COOH

NaOH / CaO
 

ix) COOH
CH2OH
LiAlH4

H2O

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Page 6 of 9 CPP - SANKALP_CAD-3-PH-V
x) O

COOH CH2OH H2C O C CH3

LiAlH4 CH3COOH

H2O
 

xi) COOH COCl

SOCl2


xii) COOH CONH2 C N

NH3 P2O5


 


xiii) COOH CONH2

NH3




2. i) CH2BrCOOH ii) CH2ClCOOH

iii) CH3COOCH3 iv) CH3COCl
v) CH3CH2OH vi) C6H5COONa + CO2 + H2O
vii) C6H5COCl + POCl3 + HCl viii) C2H6 + CO2 + KOH + H2
ix) CH3COCl or (CH3CO)2O
4 i)
COOH  SOCl2  COCl  SO 2  HCl

ii) O

OH 200 Co

H2C   CH3 COOH  CO 2

OH

O
iii) HI / Re d P
CH3 COOH   C2H6

5. i) NaHCO3
CH3COOH   CH3COONa + CO2 + H2O
ii) Zn
CH3COOH  (CH3COO)2Zn + H2
iii) LiAlH4
CH3COOH  CH3CH2OH
iv) C2H5OH / H
CH3COOH 

 CH3COOC2H5
v) NH3
CH3COOH   CH3CONH2


vi) PCl5
CH3COOH   CH3COCl
vii) NaOH
CH3COOH   CH4
CaO

6. O18 will be incorporated into acid as

O O 18

H3C C OH  H2O18 

HCl
 H3C C O18 H  H2O

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Page 7 of 9 CPP - SANKALP_CAD-3-PH-V
Mechanism
H
+
O O OH

H3C C OH  H  H3C C 
H
OH  
 H3C C O18 H

H O H OH
18 (I)
In the subsequent step, I will lose a molecule of water to form back the carboxylic acid. However, because
heavier isotope forms stronger covalent bond, during dehydration of (I), it is the O16 that will be lost, not O18 as
7. O

COOH
O  
H2C 
  CH3 — COOH  CO 2
COOH
(Malonic acid)
O
Cyclic anhydride

As shown above, decarboxylation proceeds through a resonance stabilized carbanion

O O

HOOC CH2 C O  CO 2  H2C C OH

H2C C OH
Therefore, decarboxylation is preferred over the formation of a less-stable, four membered,cyclic anhydrie.
8. Calcium oxide, a very strong base, from soda lime forms some calciuim butanoate (CH3CH2CH2COO)2Ca,
which decomposes to give 4-heptanone as
O
O
H3C H2C H2C C O
Ca  Heat
 H C 3 CH  CaCO3 3
4-heptanone
H3C H2C H2C C O

O
Calcium butanoate

The above reaction has been used earlier for preparation of ketones.

9. (a) (A) H3C CH 2 NH

CH2OH

(b)
CH2OH

SUBJECTIVE – Level – 2
O
1. (a) 18
C6H5 C O C2H5

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Page 8 of 9 CPP - SANKALP_CAD-3-PH-V

O O18
(b)
C6H5 C OC2H5  C6H5 C OC2H5
(Major)

2. In presence of acid catalyst, 3° alcohols undergo rapid protonation followed by loss of H2O forming a 3°
carbocation.
CH3 CH3
18 +
H3C C OH H 
 H3C C  H2O18
 H2O

CH3 CH3
I
H
OH CH3 O CH3 O CH3
+ H 
H3C C O  C CH3 H3C C O C CH3   H3C C O C CH3

CH3 CH3 CH3

I
COOH

3. (a) (B)
O

O
COOH
4. The two configurational isomers are cis and trans 2-butenediocic acid of which A is the cis isomer
O O

H C
C OH
Heat
  O  H2 O
C OH
H C
O O
Cis-2-butenedioic acid (A)

Due to proximity of the two carboxyl groups in space in cis isomer, intramolecular condensation takes place
giving cyclic anhydride. The trans isomer (B) cannot give cyclic anhydride due to geometry reason.
HOOC H
C
Heat
  No cyclic anhydride
C
H COOH
(B) Rotation about double
bond is restricted

5. Obviously, A, B and C are isomeric dimethyl benzenes because their oxidation products have two carboxyl
groups each. Also, A is 1, 2-dimethyl benzene because its oxidation product is forming cyclic anhydride onj
heating. B is 1, 4-dimethyl benzene because its oxidastion product is non-polar. Hence,

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Page 9 of 9 CPP - SANKALP_CAD-3-PH-V
O
CH3 COOH
[O[
  Heat
  O
CH3 COOH
A
Phthalic acid O
Phthalic anhydride

[O[
H3C CH3   HOOC COOH

B Terephthalic acid
(  0)

CH3 COOH
[O[
 

CH3 COOH
Isophthalic acid

6. (i) OH
SOCl2
CH3CH2COOH  CH3CH2COCl   H3C
 CH3CH2CHO  H2 / Pd
BaSO4
HCN
H2O
CH 2 C H
CN

H3 O

OH

H3C
COOH
H
conc. H2SO4
H3C CH2 CH COOH 
Heat
 CH3 — CH  CH — COOH

(ii) OH
(From i)

LiAlH4 PCl5 NaCN H LiAlH4
CH3CH2COOH  CH3CH2CH2OH     
H2O
 CH3CH2CH2COOH 
(iii) PCl5 C2H5ONa
  CH3CH2CH2CH2Cl 
C2H5OH
 CH3 — CH2 — CH  CH2
(  e lim ination)
LiAlH4H2SO 4
(iv) CH3 CH2 CH2 COOH  CH3CH2CH2CH2OH 
Heat
 CH3—CH = CH —CH3

(From iii)

OBJECTIVE
1. D 2. A
3. C 4. B
5. B 6. C
7. A 8. C
9. B 10. B
11. A 12. C
13. D 14. A
15. D 16. C

——

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