ORGANIC CHEMISTRY

IIT QUESTIONS ON
CARBONYL COMPOUNDS
&
CARBOXYLIC ACIDS & IT'S DERIVATIVE

CONTENTS
EXRECISE - I(A)
EXRECISE - I(B)
EXRECISE - II(A)
EXRECISE - II(B)
ANSWER KEY
 EXERCISE-I (A)

Q.1 The formation of cyanohydrin from a ketone is an example of:

(A) Electrophilic addition (B) Nucleophilic addition
(C) Nucleophilic substitution (D) Electrophilic substitution

Q.2 The enolic form of acetone contains:

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

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

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

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

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

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

Q.6 Under Wolff Kishner reduction conditions, the conversions which may be brought about is?
(A) Benzaldehyde into Benzyl alcohol (B) Cyclohexanol into Cyclohexane
(C) Cyclohexanone into Cyclohexanol (D) Benzophenone into Diphenylmethane

Q.7 In the reaction, P is

SeO
CO 2  P + Se + H2O

(A) CH3COCHO (B) CH3COOCH3 (C) CH3COCH2OH (D) None

 
Q.8 In the Cannizzaro reaction given below, 2Ph–CHO OH  Ph–CH2OH + PhCO 2 the slowest step is:
(A) the attack of OH– at the carbonyl group
(B) the transfer of hydride to the carbonyl group
(C) the abstraction of proton from the carboxylic acid
(D) the deprotonation of Ph–CH2OH
Q.9 Among the given compounds, the most susceptible to nucleophilic attack at the carbonyl group is
(A) MeCOCl (B) MeCHO (C) MeCOOMe (D) MeCOOCOMe
[IIT 1997]
Q.10 In a Cannizzaro reaction the intermediate which is the best hydride donor is: [IIT 1997]
H H
| |

(A) C 6 H 5  C  O (B) C 6 H 5  C  O  (C) (D)
| |
OH O
Q.11 CH3CHO + H2NOH  CH3 – CH = N – OH. The above reaction occurs at: [
 (A) pH = 1 (B) pH = 4.5 (C) Any value of pH (D) pH = 12

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

Q.13 The product obtained via oxymercuration (HgSO4–H2SO4) of 1-butyne would be

O
||
(A) CH 3CH 2  C  CH 3 (B) CH3CH2CH2CHO
(C) CH3CH2CHO + HCHO (D) CH3CH2COOH + HCOOH

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

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

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

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

Q.16 A new carbon-carbon bond formation is possible in

(A) Cannizzaro reaction (B) Friedel-Crafts alkylation
(C) Clemmensen reduction (D) Reimer-Tiemann reaction

Q.17 The enol form of acetone, after treatment with D2O gives:
OD O OH OD
| || | |
(A) CH 3  C  CH 2 (B) CD 3  C  CD 3 (C) CH 2  C  CH 2 D (D) CD 2  C  CD 3

Q.18 Which of the following has the most acidic hydrogen:

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

Q.19 The appropriate reagent for the following transformation:



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

Q.20 A mixture of benzaldehyde and formaldehyde on heating with aqueous NaOH solution gives:
(A) benzyl alcohol and sodium formate (B) sodium benzoate and methyl alcohol
(C) sodium benzoate and sodium formate (D) benzyl alcohol and methyl alcohol

Q.21 Compound A (molecular formula C3H8O) is treated with acidified potassium dichromate to form a
product B (molecular formula C3H6O). B forms a shining silver mirror on warming with ammonical silver
 nitrate. B when treated with an aqueous solution of H2NCONHNH2. HCl and sodium acetate gives a
product C. Identify the structure of C.
(A) CH3CH2CH = NNHCONH2 (B) CH 3  C  NNHCONH 2
|
CH 3

(C) CH 3  C  NCONHNH 2 (D) CH3CH2CH=NCONHNH2

|
CH 3

i ) NaOH ( excess )100C

Q.22 (     
( ii ) H  / H 2 O

any one of the products formed is :

(A) (B)

(C) (D)

Acidic
Q.23  Products formed by P & Q can be differentiated by:
Hydrolysis

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

(C) NaHSO3 (D) Fehlings solution

Q.24 The order of reactivity of phenyl Magnesium Bromide with the following compounds is

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

CH COONa
Q.25 + X 3 

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

NaOC H in absolute
Q.1 C6H5–CHO + CH3 – COOC2H5  25   (D).
C 2H 5OH and heat

( i ) KCN / H SO
Q.2 C = O    
2
4  D.
(ii ) LiAlH 4

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

Q.4 An aldehyde (A) (C11H8O), which does not undergo self aldol condensation, gives benzaldehyde and
two mole of (B) on ozonolysis. Compound (B), on oxidation with silver ion, gives oxalic acid. Identify
the compounds (A) and (B).

Q.5 (a) Write the intermediate steps for each of the following reaction.
(i) C6H5CH(OH)CCH  C6H5CH=CHCHO

(ii) H


(b) Show the steps to carry out the following transformations.

(i) Ethylbenzene  benzene
(ii) Ethylbenzene  2-phenylpropionic acid

Q.6 (CH3)2CHOCH3 HI

( excess
 ), heat
 (A) + (B)

( i ) LiAlH
Q.7 (
C)
   4  (D)
( ii ) H  , heat

Q.8 What would be the major product in each of the following reaction?

Base


Q.9 Identify (A), (B) and (C), and give their structures.

Br
2  A + B
NaOH

C (C7H12O)

Q.10 Five isomeric para-disubstituted aromatic compounds A to E with molecular formula C8H8O2 were
given for identification. Based on the following observations, give structure of the compounds.
(i) Both A and B form a silver mirror with Tollen's reagent; also, B gives a positive test with FeCl3 solution
(ii) C gives positive iodoform test.
(iii) D is readily extracted in aqueous NaHCO3 solution.
(iv) E on acid hydrolysis gives 1,4-dihydroxybenzene.
Q.11 Write structures of the products A, B, C, D and E in the following scheme.

Na  Hg HNO / H SO
CH2CH2CH3 Cl / FeCl 3
2    A  
3
 B   2 
4  C
HCl

CH CHCH O  Na  H / Pd / C
 D 2  E
2  2  

Q.12 C6H12 HCl

 C6H13Cl + (C)
(A) (B)
ozonolysis
(D)   (E)
(A) ozonolysis
  (F) + (G) NaOH  HCOONa + 1° alcohol
(D) is isomer A. E gives negative test with Fehling solution but gives iodoform test. F and G gives Tollen's
test but do not give iodoform test. Identify A to G.

Q.13 An organic compound (P), C5H10O reacts with dil. H2SO4 to give (Q) and (R). Both (Q) and (R) give
positive iodoform test. The reactivity of organic compound (P) is 1015 times more than ethylene with
respect to dil. H2SO4.
(i) Identify the compounds (P), (Q) and (R).
(ii) Give reason for the extraordinary reactivity of compound (P).

 (i ) O
/
Q.14 H  X   3
 Y NaOH

( ii ) Zn / CH COOH 3

Identify X and Y.

Q.15 Which of the following disaccharide will not reduce Tollen's reagent?

(a) (b)

(Q) (P)
 EXERCISE - II (A)
O
||
Q.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 O
|| ||
(A) R  C  NHBr (B) R–N=C=O (C) R–NHBr (D) R  C  N

Q.2 Which of the following carboxylic acids undergo decarboxylation easily:

(A) C6H5CO–CH2COOH (B) C6H5COCOOH
(C) C 6 H 5CH 2  COOH (D) C 6 H 5CH 2  COOH
| |
OH NH 2

Q.3 The molecular weight of benzoic acid in benzene as determined by depression in freezing point method
corresponds to :
(A) Ionization of benzoic acid (B) Dimerisation of benzoic acid
(C) Trimerisation of benzoic acid (D) Solvation of benzoic acid

Q.4 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

Q.5 Benzoyl chloride is prepared from benzoic acid by:

(A) Cl2, hv (B) SO2Cl2 (C) SOCl2 (D) Cl2, H2O

Q.6 Which of the following acids has the smallest dissociation constant?
(A) CH3CHFCOOH (B) FCH2CH2COOH (C) BrCH2CH2COOH (D) CH3CHBrCOOH

Acidic

Q.7 Hydrolysis Products formed by P & Q can be differentiated by [IIT 2003]

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

(C) NaHSO3 (D) Fehlings solution

Q.8 When benzamid is treated with POCl3, the product is: [IIT 2004]
(A) Benzonitrile (B) Aniline (C) Chlorobenzene (D) Benzylamine

Q.9 Which of the following is obtained when 4-Methylbenzenesulphonic acid is hydrolysed with excess of
sodium acetate? [IIT 2005]
—
(A) CH3 CO O N a (B) CH3 + SO3


(C) CH3 SO 3 N a + CH3COOH (D) CH3 SO2O. COCH3 + NaOH
 EXERCISE - II (B)
Q.1 Compound (A) (C6H12O2) on reduction with LiAlH4 yielded two compounds (B) and (C). The compound
(B) on oxidation gave (D) which on treatment with aqueous alkali and subsequent heating furnished (E).
The latter on catalytic hydrogenation gave (C). The compound (D) was oxidised further to give (F)
which was found to be monobasic acid (molecular mass = 60.0). Deduce the structure of (A), (B), (C),
(D) and (E).
Q.2 In the following reactions, identify the compounds (A), (B), (C) and (D)
PCl5 + SO2  (A) + (B)
(A) + CH3COOH  (C) + SO2 + HCl
2(C) +b (CH3)2Cd  2(D) + CdCl2
Q.3 Complete the following equations by writing the missing A and B
(i) CH3CH2COOH P
/ Br2
 (A) (
i ) Alc.KOH ( excess)
    (B)
( ii ) H 

O
CrO3
||
(ii) C4H8O3(A)  (B) Warm
 CH 3  C  CH 3  CO 2

Q.4 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 trifluoromethyl
group and has an equivalent weight of 128. Give structures of (A) to (D) with proper reasoning. (Atomic
weight of fluorine = 19).
Q.5 Identify A and B in the following equations:

O
||
( i ) OH  H C  CH  C  OH
CH2 NaOEt
  (A) (B)    3

( ii ) H  |
CH 2  C  OH
||
O
Q.6 Write the structure of product A & B: ]
O
|| H3O 
CH 3  C  O18C 2 H 5   A + B

Q.7 Identify X, Y and Z in the following synthetic scheme and write their structure. Explain the formation of
labelled formaldehyde (H2C*O) as one of the products when compound Z is treated with HBr and
BaC*O3 + H2SO4 C (gas) [C* denotes C14]
(i ) Mg / ether LiAlH
CH 2  CH  Br   Y   4  Z
(ii ) X
(iii ) H3O

Q.8 Mention two esters produced when a racemic mixture of 2-phenyl propanoic acid is treated with (+)
2-butanol. What is the stereochemical relationship between these esters?
Q.9 Give major products A, B, C and D in following reaction sequence.

KCN
 A (
i ) NaOEt / EtOH H O
   B 3  C
DMF ( ii ) PhCHO / 
D
 CARBONYL COMPOUND
ANSWER KEY
EXERCISE-I (A)

Q.1 B Q.2 A Q.3 D Q.4 B

Q.5 D Q.6 D Q.7 A Q.8 B
Q.9 A Q.10 D Q.11 B Q.12 A,D
Q.13 A Q.14 A,B,D Q.15 B Q.16 B,D
Q.17 B Q.18 B Q.19 B Q.20 A
Q.21 A Q.22 C Q.23 D Q.24 C
Q.25 C
EXERCISE-I (B)

Q.1 C6H5CH = CHCOOC2H5 Q.2 C

(D) (a racemic mixture)

Q.3 C 6 H 5  C  CH 3 and C 6 H 5  C  CH 3
|| ||
N  OH HO  N
syn anti(isomers )

CHO 
Q.4 Ozonolysis
   + 2| Ag
 COOH
COOH |
COOH
(B) (Oxalic acid)

Q.5 (a) (i) C6H5CH(OH)CCH H
3O
 C6H5CH  C  CH
|
OH2
 
C6H5CH=CHCHO OH
C6H5CH=C= CH  C6H5CH=C= C H
|
OH

H 


Q.6 CHOCH3 HI

(excess
 )  CHL + CH3I


Q.7 6 5

C H CHO
  Q.8 Base

 Base

(C) (D)
Q.9 Br  NaOH + CHBr3
2  


(A) (B) (C)

Q.10 (A) or (B) (C) (D) (E)

Q.11 (A) (B) (C) (D)

(E)

Q.12 Me3C – CH=CH2 HCl

 Me2 C –CHMe2 + Me3C– CH –Me
| |
Cl Cl
(A) (B) (C)

alc. KOH

(A) Ozonolysis
   HCHO + Me3C–CHO NaOH 
(F) (G)
HCOONa + Me3C–CH2OH (1°alcohol)

Q.13 C5H10O is

H + C2H5OH
 2

H O

Highly stable carboctaion
P is stabilized by resonance
 
ring
/ expansion
Q.14 H     

O
NaOH 3 
  Zn / CH 3COOH

(X)

Q.15 In structure (P) both the rings are present in acetyl form therefore it will not hydrolyse in solution that why
Fehling solution cannot react with this.
In structure (Q) one ring present in the form of hemiacetal. This will hydrolysed in solution it can reduce
Fehling solution.

EXERCISE - II (A)

Q.1 A,B Q.2 A Q.3 B Q.4 D Q.5 C Q.6 C Q.7 D

Q.8 A Q.9 C
EXERCISE - II (B)

Q.1 (A) CH3CH2CH2COOCH2CH3; (B) CH3CH2OH ; (C) CH3CH2CH2CH2OH; (D) CH3CHO;

(E) CH3CH= CHCHO

Q.2 (A) SOCl2; (B) POCl3; (C) CH3COCl; (D) CH3COCH3

Q.3 (i) (A) CH3CHBrCOOH; (B) CH2 = CHCOOH;

(ii) (A) CH3CH(OH)CH2COOH; (B) CH3COCH2COOH

Q.4 (A) (CH3CH3CO)2O; (B) CF3CH2COOH; (C) CH3CH2COOH; (D) (CF3CH2CO)2O

HC  (COOC 2 H 5 ) 2
|
Q.5 (A) NaCH(COC2H5)2; (B) CH 3  HC  COOC 2 H 5

Q.6 (A) CH3COOH; (B) C2H5O18H

Q.7 BaC*O3 + H2SO4  C*O2(X) + BaSO4

(i ) Mg ,(ii ) C*O
CH2=CH–Br   2 
(iii ) H3O 

CH2=CH–C*OOH(Y) LiAlH
 4 

CH2=CHC*H2OH(Z) H
 CH2=H–C* H 2 C* H 2 CH=C*H2
 Br–  Br–
CH2=CH–C*H2 Br BrCH2 – CH=C*H2
O3ZnH2O  O3ZnH2O Br–C*H2CHO + HCHO Br–CH2CHO + HC*HO

H
|
Ph H (  ) CH3CH 2 C OH
| | |
CH3
Q.8 CH 3  C  COOH + CH 3  C  COOH     
| | conc.H 2SO 4 , 
H Ph
(racemic mixture)
Ph H H H
| | | |
CH 3  C  C  O  C  CH 2CH 3 + CH 3  C  C  O  C  CH 2CH 3
| || | | || |
H O CH 3 Ph O CH 3
during esterification reaction only –COOH and –OH partcipates. There is no effect on structure or
configuration of carbon adjacent to these groups. So when(±) acid reacts with pure (+) alcohol two
esters are produced which are diastereoisomers of each other.

Q.9 (A) (B) (C) (D)