Chemistry : Carboxylic Acid & Derivatives

SECTION - I
SUBJECTIVE TYPE PROBLEMS

Problem 1 : Account for the following :

(a) Boiling points of carboxylic acids are higher than those of corresponding alcohols.
(b) The C—O bond in RCOOH is shorter than in R—OH.
(c) Acetic acid in the vapour state has a molecular mass of 120.
Solution : (a) The intermolecular hydrogen bonding and dipole-dipole attraction are greater in carboxylic
acids and exists as a dimer than in alcohols.
These forces are responsible for higher boiling points of carboxylic acids.
(b) Resonance exists in carboxylic acids. The main contributing resonance structures are

O O
R C 
 R C
O H O H:

(I) (II)

(II) resonance structure suggests that there is some double bond character in C—O
bond of the acid. This is responsible for the shorter bond length of C—O bond in
RCOOH.
(c) Acetic acid undergoes intermolecular hydrogen bonding and exists as a dimer.
O H O
C CH3
H3 C C
O H O
Thus, the molecular mass of acetic acid is 120 in vapour state.
Problem 2 : Explain :
(a) Acetic acid is a stronger acid than ethyl alcohol.
(b) Trichloro acetic acid is a stronger acid than acetic acid.
Solution : (a) Acetic acid is a stronger acid than ethyl alcohol because the acetate ion formed by
ionisation is stabilized by resonance while ethoxide ion has no resonance. The negative
charge in acetate ion is delocalized over two oxygen atoms while the negative charge
in ethoxide ion is localized on the single oxygen atom.
H
O O
H3C C 
 H3C C ; H3C C O
O O
Acetate ion
(Resonance structure H
Ethoxide ion
(No resonance is present)
Hence, CH3COO– ion is more stable and a weaker base than CH3CH2O– ion. As a
weaker base has a stronger conjugate acid, CH 3COOH is a stronger acid than
CH3 CH 2 OH.
Chemistry : Carboxylic Acid & Derivatives

(b) Electrons withdrawing substituents decrease the negative charge on the carboxylate
ion and stabilise it, i.e., loss of proton becomes relatively easy. Three chlorine atoms
are electron withdrawing substituents in trichloro acetic acid and thus, it is a stronger
acid than acetic acid.
Problem 3 : How will you obtain :
(a) Butanoic acid from 1-bromopropane?
(b) Propanoic acid from ethyne?
(c) 2-Methylbutanoic acid from 2-butanol?
(d) Butanoic acid from ethyl bromide?

KCN H 3O
Solution : (a) CH3 CH2CH2Br   CH3 CH2 CH2CN   CH3CH2CH2COOH
Mg CO2
or CH3CH2 CH2 Br 
Ether
 CH3 CH2CH2 MgBr   CH3 CH2 CH2COOMgBr

H
 CH3 CH2 CH2COOH
HCl Mg CO
(b) CHCH 
Hg 2
 CH2=CHCl 
Ether
 CH2=CHMgCl 
2
 CH2=CHCOOMgCl

H H 2 / Pd
 CH2 = CHCOOH  CH3CH2COOH
SOCl 2 Mg CO2
(c) CH3 CH 2 CH CH 3   CH3CH 2 CH CH 3 
Ether
 C2 H5 CH MgCl  
| | |
OH Cl CH3

H
C 2 H 5 CH COOMgCl  C 2 H5 CH COOH
| |
CH3 CH3

H2C CH2

O H 3O 
(d) CH3CH2Br + Mg CH3CH2MgBr  CH3CH2 CH2 CH2OMgBr  
[O]
CH3CH2CH2CH2OH 
KMnO 4 / H 2SO 4
 CH3 CH2CH2COOH

Problem 4 : (a) Write a note on Hell Volhard Zelinsky (HVZ) reaction.

(b) Write a short note on Koch reaction.
Solution : (a) When a carboxylic acid that contains -hydrogen atoms is treated with chlorine or
bromine in presence of phosphorus, the -hydrogen atoms are replaced by halogen
atoms. This reaction is called Hell Volhard Zelinsky (HVZ) reaction. This reaction is
used for the synthesis of -substituted carboxylic acids.
Cl 2
CH3COOH 
(P) ClCH2COOH + HCl


hv
R CH 2 COOH + Cl2 
[P] RCH(Cl)COOH  RC(Cl2)COOH
(b) This reaction is used for the conversion of alkenes into monocarboxylic acids. When a
mixture of alkene, carbon monoxide and steam is heated under pressure at 350°C in
presence of ortho phosphoric acid (H3PO4), monocarboxylic acid is formed.
H 3PO 4
CH 2  CH 2  CO  H 2 O 
Pr essure, 350o C
 CH3CH 2COOH
Ethene Pr opionic acid
 Chemistry : Carboxylic Acid & Derivatives

Problem 5 : Arrange the following in order of increasing acidity :

(i) HCOOH, ClCH 2 COOH,CH 3 COOH
(ii) CH3COOH, (CH 3)2CHCOOH, (CH 3)3CCOOH
(iii) ClCH2COOH, Cl2CHCOOH, Cl3CCOOH
(iv) ClCH2COOH, CH3CH2COOH, ClCH2CH2COOH, (CH3)2CHCOOH, CH3COOH
(v) CH3COOH, Cl2CHCOOH, CH 3CH2COOH, Cl3 CCOOH, ClCH2COOH
Solution : (i) CH3COOH < HCOOH < ClCH2COOH
(ii) (CH3)3CCOOH < (CH3)2CHCOOH < CH3COOH
(iii) ClCH2COOH < Cl2CHCOOH < Cl3CCOOH
(iv) (CH3)2CHCOOH < CH3CH2COOH < CH3COOH < ClCH2CH2COOH <
ClCH2COOH
(v) CH3CH2COOH < CH3COOH < ClCH2COOH < Cl2CHCOOH < Cl3CCOOH
Problem 6 : How will you distinguish between :
(a) Formic acid and acetic acid?
(b) Oxalic acid and acetic acid?
(c) Succinic acid and oxalic acid?
Solution : (a) (i) Formic acid produces silver mirror with ammonical silver nitrate solution. Acetic
acid does not give this test.

HCOOH  2Ag(NH 3 ) 2 NO3 

 2Ag  CO 2  2NH 4 NO3  2NH 3
Formic acid Tollen 's reagent Silver mirror

(ii) Formic acid forms a white precipitate with HgCl2 solution. Acetic acid does not
respond to this test.
(b) (i) Oxalic acid when heated decomposes and evolves CO2. The gas when passed
through lime water forms a white precipitate.
COOH
| 
 HCOOH  CO 2
COOH Formic acid
Oxalic acid

CO2 + Ca(OH)2  CaCO3 + H2O

Acetic acid does not give this test.
(ii) Oxalic acid acts as a reducing agent. The decolourisation of acidified KMnO4
solution occurs when oxalic acid is added to it and the solution is warmed. This test
is also not given by acetic acid.
2KMnO4 + 3H2SO4  K2SO4 + 2MnSO4 + 3H2O + 5O
COOH
|  [O] 
 2CO2  H 2 O
COOH
(iii) Oxalic acid is a solid while acetic acid is a liquid with characteristic odour.
(c) Both the chemical tests used in part (b) of this question can also be employed to make
distinction between oxalic acid and succinic acid.
Chemistry : Carboxylic Acid & Derivatives

Problem 7 : Compare the products formed on heating the following dicarboxylic acids :
(a) Oxalic acids (b) Malonic acid
(c) Succinic acid (d) Adipic acid
Solution : (a) Oxalic acid on heating loses a molecule of CO2 and converted into formic acid.
COOH 200o C
|   HCOOH  CO 2
COOH Formic acid

(b) Malonic acid, on heating undergoes decarboxylation

COOH
H2 C 
 CH 3COOH  CO2
Acetic acid
COOH

Malonic acid
(c) Succinic acid forms anhydride by eliminating a water molecule.
CH2COOH CH2CO
Heat

H O
 O
2

CH2COOH CH2CO
Succinic acid Succinic anhydride

(d) Adipic acid on heating at 300°C, it is converted into cyclic compound i.e., cyclopentanone.
CH2
CH2
HOOC(CH 2 ) 4 COOH  
Adipic acid
CO + CO2 + H2O
CH2
CH2
Cyclopentanone

Problem 8 : Two organic compounds (A) and (B) have the molecular formula, C 4H6. Both the
compounds decolourise bromine in CCl4. Compound (A) on oxidation gives propionic
acid and carbon dioxide. Compound (A) also gives a precipitate with ammonical silver
nitrate. Compound (B) does not give precipitate with ammonical silver nitrate but
oxidises to oxalic acid and carbon dioxide. Deduce the structural formulae of (A) and
(B).
Solution : Both the compounds are unsaturated hydrocarbons as they decolourise bromine in CCl4.
The following compounds, alkynes or alkadienes can be expected :
(i) CH3 CH2 CCH 1-Butyne
(ii) CH3 CC—CH3 2-Butyne
(iii) CH2=CH—CH=CH2 1, 3-Butadiene
Since one of the compounds gives precipitate with ammonical silver nitrate, it must be (i). (i)
on oxidation gives propionic acid. Hence, (i) is (A).
CH3 CH 2 C  CH  4[O] 
 CH 3 CH 2 COOH  CO 2
1 Butyne (A) Pr opionic acid

Since (B) does not give precipitate with ammonical silver nitrate, it can be (ii) and (iii). The
compound (B) is (iii) as on oxidation it gives oxalic acid.
CH 2  CH  CH  CH 2  10 [O] 
 COOH  COOH  2CO 2  2H 2O
1, 3 Butadiene (B)
 Chemistry : Carboxylic Acid & Derivatives

Problem 9 : An organic compound, C4H6O4 (A), when heated with acetic anhydride gives another
compound, C4H4O3 (B), which in turn reacts with ammonia to give a third compound,
C4H5O2 N (C). Both (B) and (C) may be hydrolysed to (A). WIth chlorine (A) gives
monochloro-compound (D) which reacts with caustic potash to give either C4H4O5K2(E)
or C4H2O4K2(F) depending upon the conditions of the reaction. Identify the compounds
(A) to (E).
Succinic acid Succinic anhydride Succinimide
CH2COOH CH2CO CH2CO
Heated NH3
Solution : 
(CH CO) O
 O   NH
3 2

CH2COOH CH2CO CH2CO

(C 4 H 6 O 4 ) (C 4 H 4 O3 ) (C 4 H5 O 2 N)
[A] [B] [C]

H2 O

H 2O

CHClCOOH CH(OH)COOK CHCOOK

Cl2
 KOH

 or
CH2COOH CH2COOK CHCOOK
[D] (C 4 H 4 O5 K 2 ) (C 2 H 2 K 2 )O 4
Monochlorosuccinic [E] [F]
acid Pot. malate Pot.funmarate

Problem 10 : Two compounds possess the same empirical formula CH2O. The vapour density of
compound (A) is 15 while that of (B) is 30. (A) reduce Fehling’s solution but did not
react with NaHCO 3 while (B) did not reduce Fehling’s solution but produced
effervescences with NaHCO3. Deduce the structural formulae of (A) and (B).
Solution : Empirical mass = 30
Molecular mass of (A) = 2 × 15 = 30; Molecular mass of (B) = 30 × 2 = 60;
Molecular formula of (A) = CH2O; Molecular formula of (B) = C2H4O2
From reaction, it is evident that (A) is an aldehyde and (B) is an acid. (A) is, therefore,
HCHO (formaldehyde) and (B) is CH3COOH (acetic acid).
Chemistry : Carboxylic Acid & Derivatives

SECTION - II
SINGLE CHOICE PROBLEMS
Problem 1. How will you distinguish the products obtained by the acidic hydrolysis of

H2C C CH3 & H3 C CH2 CH2 O C CH3

O COCH3 O
(I) (II)

(a) Fehling’s solution (b) NaHSO3

(b) D.N.P. (d) Luca’s test
H O
Solution : H2 C C CH3 
3
 H2 C C CH 3 CH 3 COCH
O COCH 3 OH
Tautomerizes
H2 C C CH3 H3 C C CH3
OH O
H O
H3 C CH CH O C CH3 
3
 H3 C CH CH OH + CH 3 COOH
O
Tautomerizes
CH3 — CH  CH — OH CH 3 — CH 2 — CHO
In the first case after hydrolysis a ketone has been formed. But in the second case aldehyde
has been formed. Therefore, these can be distinguished by Fehling’s solution.
... (a)

CHO CHO

(i) excess NaOH

Problem 2.   
(ii) H / H 2 O


CHO CHO
O
COOH COOH

(a) (b)

COOH COOH
O
COOH CH2 OH CH2 OH COOH

(c) (d)
COOH CH2 OH COOH CH2 OH
 Chemistry : Carboxylic Acid & Derivatives

- -
O O O
CHO CHO HO C H CH O HO C CH 2


Solution : OH
  


CHO CHO CHO CHO CHO CHO

OH
O O OH
O C CH 2

H O

2


OHC CHO CHO CHO

On repeating, the same process once again

OH OH OH OH
O
CH2 C O CH2 C O

H / H O

 
2


C CH2 C CH2
O O
OH OH O OH OH

Problem 3. CH(OH)CH3 on dehydration mainly gives

H3C CH3

(a) (b)

(c) (d)
Chemistry : Carboxylic Acid & Derivatives

CH3
CH3
H  H
Solution : CH(OH)CH 3
 H 2O
 Ring
CH   

Exp.

CH3 shift (A)

H
more stable
CH3
H 



(B)
less stable
Exocyclic double bonds are relatively unstable with respect to endocyclic double bonds, so
(A) is predominant than (B).
O

Problem 4. undergoes a reaction in presence of H + to give (A). The most probable

structure of (A) would be

OH OH
CH3

(a) (b)

CH3
CH3 CH3
O O

(c) (d)
CH3 H3C CH3
CH3

+
O O H O H O H


H  CH
Solution :     3
 CH3
shift
H
H3C CH3 H3C CH3 H3C CH3 H3C

OH


H
 
CH3
CH3
 (b)
 Chemistry : Carboxylic Acid & Derivatives

Problem 5. In the following reactions,


OR
Ph Cl 
ROH
 (A)
O
Cl

OR
Ph 
ROH
 (B)
O
The compounds (A) and (B) respectively are
(a) Both are PhCH2CH2COOR
(b) Both are PhCH(COOR)CH3
(c) PhCH2COCH2OH, PhCH(OH)COCH3
(d) PhCH(OH)COCH3, PhCH2COCH3
Solution : Both the isomeric reactants give the same cyclic intermediate.

RO  Cl
PhCH 2COCH 2 Cl 
 ROH
Ph CH CH2 Cl 
 Ph CH CH2
C C
O O
Cl

OR
Ph — CH— CO — CH3 
 Ph CH CH2 
 Ph HC CH2
|
Cl C C
O O
The more stablized carbanion is formed by ring opening of intermediate whichleads to the
final product.

 OR ROH
Ph HC CH2 
 Ph — C H — CH3 — COOR 
Proton
 PhCH 2 CH 2COOR
C transfer

O
(a)

Problem 6. Ph3CO — OCPh3   (A) The compound (A) would be
O
||
(a) Ph3COPh (b) Ph — C— O — C— Ph
||
O
Ph 2 C— OPh
(c) | (d) Ph3C—CPh3
Ph 2 C — OPh
Ph
|
Solution : PH 3CO — OCPh 3 
 
 2Ph 2 C — O
radical (I)
Now aryl migration proceeds via a bridged transition state.
Ph
Ph2C  Ph 2 C — O — Ph
O 
radical (I)
Chemistry : Carboxylic Acid & Derivatives

The driving force of this rearrangement is the greater stability of radical (II). Finally,
Ph2C OPh
2Ph 2COPh 

Ph2C OPh
 (c)
Problem 7. When allyl chloride reacted with sodamide in tetrahydrofuran solution, a hydrocarbon
C3H4 was obtained. The structure of hydrocarbon would be
(a) CH 2  C  CH 2 (b) Cyclopropene
(c) CH3C  CH (d) none of these

Solution : Ph 2C — COOH  HI 
 Ph 2 — C H — COOH  HI 
 Ph 2 — CHCOOH  I 2
| |
OH I

(Hydrogen iodine is a very powerful reducing agent)

(b)
EtONa acid
Problem 8. (CH 3 )2 CO + 2(CO2 Et)2  
-H O
 Product
2

The product of the above reaction is

O OH

(a) HOOC O COOH (b) HOOC COOH

O
O

(c) (d) O C C O
C
COOH O
O
C
O
H2 C CH2
EtONa acid
Solution : (CH 3 ) 2 CO  2(CO2 Et)2   COOEt C C COOtE 
 H 2O

O
O O HOOC OH
 (a)
Problem 9. An organic (A) on the treatment with benzaldehyde in presence of NaOH folowed by
LiAlH 4 gives compound (B) which on heating gives compound (X). If (X) is

CH
, then the compound (A) would be
 Chemistry : Carboxylic Acid & Derivatives

O
O
OH
(a) (b)

O O

CHCOOH
(c) (d)

OH
O O OH
O CH3
LiAIH 4 CH
 
Solution : C H+ 

– 2H2O

CH

(c)
Problem 10. The final product (D) of the reaction. is
Ph 3P CH 3COCH 2CH3 
t  BuOK H / H2O
PhOCH 2 Cl   (A)   (B)   (C)   (D)

H
(a) OPh CH C CH3 (b) Ph O C CH CH3
H2 C CH3 OH Et

O
(c) H C CH CH3 (d) none of these
Et

t  BuOK
Solution :  PhOCH 2 P Ph 3 Cl 
PhOCH 2 Cl  PPh 3  [t  BuOH]
 PhO — CH  PPh 3
(A)  HCl (B)
H3C C CH3
H 2C CH3
H
 
H 2O H
Ph O C CHCH3   PHO  CH — CHCH 3  Ph O— CH  CCH 3
 H
|
H O CH2 CH3 (C)
CH2CH3
Hemiacetal

–PhOH
O
H C CH CH3
Et (D)

 (c)
Chemistry : Carboxylic Acid & Derivatives

SECTION - III
MULTIPLE CHOICE PROBLEMS
O
||
Problem 1: The reaction of R —C — NH 2 with a mixture of Br2 and KOH gives R—NH2 as a product.
The intermediates involved in this reaction are :
O
||
(a) R —C — NHBr (b) R—N==C==O

O
Br
(c) R—NHBr (d) R C N
Br
Solution : (a, b)
Problem 2: Urea is prepared in the laboratory by the action of NH3 on :
(a) carbonyl chloride (b) ethyl carbonate
(c) cyanamide (d) carbon dioxide
Solution : (a, b)
Problem 3: Acetoacetic ester in used for the synthesis of :
(a) , -unsaturated acids (b) -keto acids
(c) mono carboxylic acids (d) dicarboxylic acids
Solution : (a, b, c, d)
Problem 4: Starting from diethyl malonate, what type of acids can be prepared from it :
(a) succinic acid (b) barbituric acid
(c) adipic acid (d) monoalkyl acetic acid
Solution : (a, b, c, d)
Problem 5: Acetic anhydride may be prepared by the reaction of acetic acid with :
(a) CH2==C==O (b) LiAlH4
(c) P 2 O 5 (d) C2H5OH/HgSO4 on heating
Solution : (a, c, d)
 Chemistry : Carboxylic Acid & Derivatives

MISCELLANEOUS PROBLEMS
SECTION - IV
COMPREHENSION TYPE PROBLEMS

Write up – I
Ester gives nucleophilic addition reaction followed by elimination reaction with carbon nucleophile.
When carbon nucleophile is of an ester then the reaction is known as Claisen condensation reaction.
This reaction is also carried out between ester and a ketone. A successful Claisen condensation requires
an ester with two -hydrogens and an equivalent amount of base rather than a catalytic amount of
base.

Problem 1: Consider the given reaction

C 2 H5 ONa ester (X)
CH 3 — COOC2 H 5 
C H OH
 enolate ion 
claisen condensation
 Product
2 5

For the above reaction the most reactive ester is :

O O
|| ||
(a) C6 H5 COOC 2 H 5 (b) C 2 H5O —C — C— OC2 H5

O
||
(c) HCOOC 2H 5 (d) C2 H 5O —C — OC 2 H 5

Solution : (b)

O
||
(i) C2 H 5ONa / C2 H 5OH
Problem 2: In the given reaction C 2 H 5 O —C —(CH 2 )3 — CH 2 — COOC 2 H 5 
(ii) H O / HCl
[X]
2

[X] is :

O O
O

COOC2 H5 C CH3
(a) (b)

O O

O
CHO
(c) (d)

Solution : (a)
Chemistry : Carboxylic Acid & Derivatives

Problem 3: In the given reaction

O O

CHO
 X 


[X] is :
O
||
(a) H —C — Cl (b) HCl + CO

COOC2 H5
(c) HCOOC2H 5 (d)
COOC2 H5

Solution : (c)

Write up – II
Dicarboxylic acids contain two carboxylic acid groups. Acidity of carboxylic depends upon stability of
intermediate formed. The -hydrogen present in carboxylic acid is labile. Dicarboxylic acids on
decarboxylation from monocarboxylic acids, alkanes and cyclic ketones depending upon conditions.
Greater the symmetry, higher will be the melting point.

Problem 4: Which of the following is most acidic?

(a) Oxalic acid (b) Malonic acid
(c) Succinic acid (d) Adipic acid
Solution : (a)
Problem 5: Sodium adipate on electrolysis gives.
(a) But-2-ene (b) But-1-ene
(c) Cyclobutane (d) Cyclobutene
Solution : (c)
Problem 6: Maleic acid on reaction with alkaline KMnO4 gives
(a) d (+) tartaric acid
(b) l (–) tartaric acid
(c) Racemic mixture of tartaric acid
(d) Meso tartaric acid
Solution : (d)
 Chemistry : Carboxylic Acid & Derivatives

MATCHING TYPE PROBLEM

7. Match List I with List II and select the correct answer from the codes given below the lists :
List I List II
O
||
(A) CH3 —C — N 3 1. Lossen rearrangement

O
||
(B) CH3 —C — NH 2 2. Schmidt rearrangement
(C) CH3 COOH/N3 H 3. Hofmann rearrangement
O O
|| ||
(D) C6 H5 —C — NH — O —C — CH 3 4. Curtius rearrangement

(A) (B) (C) (D)

(a) 3 4 1 2
(b) 3 4 2 1
(c) 4 3 2 1
(d) 4 3 1 2
Sol. (c)

ASSERTION-REASON TYPE PROBLEMS

The question given below consist of an ASSERTION and the REASON. Use the following key for the
appropriate answers
(a) If both Assertion and Reason are correct and Reason is the correct explanation for Assertion
(b) If both Assertion and Reason are correct and Reason is not the correct explanation for
Assertion
(c) If Assertion is correct but Reason is not correct.
(d) If Assertion is incorrect but Reason is correct.
8. Assertion : When CH3COCl reacts with chiral alcohol, stereochemistry of the alcohol is inverted.
Reason : Carbon-oxygen bond in the alcohol is never broken, so the configuration of the stereocentre
is retained.
Solution : (d)
9. Assertion : CH3COCl is converted to CH3CONH2 on reaction with NH3.
Reason : Cl is a weak nucleophile and better leaving group.
Solution : (a)
10.Assertion : Ethyl cyanide on reaction with LiAlH4 does not form ethyl amine.
Reason : Acidic hydrolysis of RCN forms RCOOH .
Solution : (b)