Work Book (Phase  V)

Subjective:

Board Type Questions

1. Assign d,  and meso character to the following

(i) COOH (ii) COOH

H OH H OH

H OH HO H
COOH COOH
(iii) COOH (iv) COOH

HO H HO H

HO H H OH
COOH
COOH

2. Write structure of (2Z, 4E)  3  ethyl  2, 4  hexadiene.

3. Biological reduction of pyruvic acid gives (+) lactic acid, represented by Fischer projection
shown. Assign R/S configuration.
COOH

H3C C COOH Biological

HO H
reduction
O CH3
(pyruvic acid) ( ) lactic acid

4. Assign R and S configuration to the products when cyclopentene reacts with

(a) cold KMnO4 (b) Br2 water

5. Identify the product of the following reaction with proper configuration.

Br CH3
2
OH

SN

H H

6. In the following molecules indicate presence of a centre of chirality with an asterisk (*).
(a) CH3 (b) Br

Cl

CH3
7. Are the following compounds chiral – enatiomers or achiral- Identical mirror images?

H H
C C H and H C C
H CH3 H3C H

8. Give the aldol condensation product of CH3CH = CHCHO.

9. Arrange the following in increasing extent of hydration.

O O CHO CHO
Br
Br

10. Explain the reason for the stability of choral hydrate.

11. What is the product of the following reaction?

O

(C 6H5) 3P = C(CH 3)2 ?

12. In which of the following compounds would you except intramolecular H bonding to occur
(a) o – nitro phenol (b) o – hydroxybenzoic acid
(c) o – fluoro phenol (d) methyl salicylate (oil of winter green)

13. Outline steps of the following conversion

NH2
Br
Br

Br

14. Convert
(a) acetylene into n-butyl alcohol.
(b) propane into 1 – propanol, 2 – propanol and allyl alcohol.
15. An organic compound with molecular formula C10H18O contains no double or triple bonds.
It reacts with hydrochloric acid to give dichloride as shown
Cl

H3C CH3

Cl
CH3
Deduce the structure of the organic compound.
16. Would it be possible to form di-t-butyl ether from dehydration of t-butyl alcohol?

17. Suggest reaction conditions for the following conversion

OH

O
COOH
O
H3C

18. Predict the most acidic hydrogen in the following compounds.

(a) O (b) O

(c) H (d) O
N
O
O

19. Which of the following compounds would be expected to decarboxylate when heated?
(a) O O (b) O

OH
HO
OH
O
(c) O O (d) O O

HO

20. Saponification of esters of optically active alcohols proceeds with retention of

configuration. Explain.

21. O
NaOBr,  2 
H2N C NH2  N2  CO3  Br  H2O
Calculate volume of N2 gas obtained at NTP from 1mL of body fluid containing 6 g of
urea.

22. Barbituric acid is formed when diethyl malonate reacts with urea. What is the type of
isomerism shown by it?
23. Convert CH3COOH into (CH3)2NH.

24. Arrange the following in increasing basic nature.

N N

N N
H
Piperidine (I) Pyridine (II) Imidazole (III)
True and False

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25. Tertiary alcohols are more reactive towards halogen acids than secondary alcohols.

26. 2-Pentanol or 3- pentanol on treatment with HCl gives both 2-chloropentane and 3-
chloropentane.

27. Terminal Gem-dihalides on hydrolysis yield aldehydes.

28. m-Chlorobromobenzene is an isomer of m-bromochlorobenzene.

29. Aldehydes react with alcohols in presence of dry HCl gas to form acetals.

30. Aldehyde group is m-directing and deactivates the benzene ring towards further
electrophilic substitution reactions.

31. Bromination of propionic acid with bromine in presence of small amount of red
phosphorus gives   bromopropionic acid.

32. Acid chlorides react with aromatic hydrocarbons in presence of anhydrous AlCl 3 to form
aromatic ketones.

Fill in the Blanks

33. A mixture of phenol and phthalic anhydride when heated with conc. H 2SO4
forms…………..which is used as an ……in acid-base titrations.

34. Phenol on treatment with bromine water gives……..but with bromine in CS 2, it mainly
gives……….

35. Chloropicrin is formed by the action of ……on chloroform.

36. Alkyl halide with……….Ag2O gives alcohol and ………………Ag2O gives ether.

37. The reaction of acetyl chloride with diethylcadmium followed by hydrolysis gives………..

38. The structure of the intermediate product formed by the oxidation of toluene with CrO 3
and acetic anhydride, whose hydrolysis gives benzaldehyde, is…………
39. Oxidation of o-xylene with alkaline KMnO4 gives…………

40. Hell-Volhard-Zelinsky reaction involves the replacement of an ……….atom from the alkyl
group of a monocarboxylic acid by a ……atom.

IIT Level Question

41. Comment on the chirality of the following molecules

(a) H H (b) H CH3

C C C C C C

Cl Cl Cl CH3
42. For each of the following additions, predict the regiochemistry of each adduct and
determine whether the product mixture is optically active. If not, determine whether the
inactivity results from the absence of chiral centres, the formation of equal amounts of
enantiomers or formation of a meso compound.
(a) (b)
DCl D 3O

43. Comment upon the nature of products in the following.

(a) H
OH

SOCl 2

H
CH3
(b) CH2CH3

CH3CH2OH
H3C Br
SN1

CH2CH2CH3

44. Identify A to E in the following

O
DIBAH LiAlH4 KMnO4
B C OCH3 A C
H 2O H2 O H

PCl 5

E
B D

45. Identify products in the following reaction

OH
(a)

SO2 Cl2  i KOH 

  A 
 ii HCl
 B 
C6H5NMe2

C

CO 2 Et
(b) NO2


NH4HS
 D 
NaNO , H SO , 00 C
 E 
H2 O
F
2 2 4

NO2
(c) OH

Bu Bu
i PbO , C H

 ii Br2 
2 6 6
G

Bu

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46. Identify A, B and C.
H H
TsCl NaBr
A B
Pyridine
CH3 OH

PBr3
C
Identify A, B and C.

47. What is wrong in these reactions?

(a) H C O
3
CH3OH OH
CH3O

H3C OCH 3
(b)

H2SO 4

OH

48. Identify the products

(a)
Conc. KMnO4

 , H O
A
3

(b) CH2

H3 O

Hbr
 B 
Mg Ether
 
CO2
  C



HBr, peroxide
 
Mg Ether
 
CO2 H3 O
  D

49. Explain the difference in the following observation

5 N NaOH
CHCH CHCH3

CHCH CHCH3 OH

O CR di. NaOH
CH CHCHCH3
O
OH
50. The pKa values for the amino acid cysteine are 1.8, 8.3 and 10.8. Assign these pKa
values to the functional groups in cysteine and draw the structure of the molecule in aq.
Solution at pH 1, 5, 9.
Objective:

Multiple choice questions with single correct options

1. COOH Configuration at C1 and C2 atoms are:

H OH
HO H
COOH
(A) d and d (B)  and 
(C) R and R (D) R and S

2. H CH3 CH3 H

CH3 H H CH3

(A) (B)
A and B are
(A) achiral identical mirror images (B) chiral enantiomers
(C) geometrical isomers (each separately) (D) racemic mixture

3. Which of the following compounds are enantiomers?

(A) CH3 CH3 (B) CH3 CH3

HO H H OH HO H
H OH and
and HO H
H OH HO H
HO H CH3
CH3
CH3 CH3
(C) CH3 CH3 (D) CH3 CH3

H OH H OH HO OH HO H
and and
HO H H OH H H HO H
CH3 CH3 CH3
CH3

4. Meso – tartaric acid is optically inactive due to the presence of

(A) two chiral carbon atoms (B) molecular unsymmetry
(C) molecular symmetry (D) external compensation

5. Which of the following compounds can occur in enantiomeric forms?

(A) H (B) H

COOH H 5 C2 COOH
(C) H (D) COOH

H COOH H COOH

6. Ethylene glycol reacts with excess of PCl5 to give

(A) 1, 1 – dichloroethane (B) 1, 2 – dichloroethane
(C) 1, 1, 1 – trichloroethane (D) 2, 2 – dichloroethane

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7.
  F 


H
H2 O
Br2 , CCl4
 C4H8Br2
H3C OH
How many structures of F are possible?
(A) 2 (B) 5
(C) 6 (D) 3
HOOC
8.

OH

O 2N

2 moles NaNH 2
A
C CH

OH
The product A will be
OOC OOC
(A) (B)

OH OH

O 2N O 2N

C CH
C C
O
OH
HOOC HOOC
(C) (D)

O
OH

O 2N
O 2N

C CH
C C
O
O

9. O
PBr3

(X) 
H2O
H3C CH CH3 Mg/ ether
 (Y)

OH
The final product is
(A) (B)

OH O
(C) O (D) None of the above

10. During dehydration of alcohols to alkanes by heating with conc. H 2SO4, the initial step is
(A) formation of an ester (B) protonation of alcohol molecule
(C) formation of carbocation (D) elimination of water
11. The correct acidic order of the following is
 OH OH

OH

CH3 NO2
(I) (II) (III)
(A) I > II > III (B) III > I > II
(C) II > III > I (D) I > III > II
12. What is formed when glycerol reacts with HIO4?
(A) 2 formic acid molecules and one formaldehyde molecule
(B) 2 formaldehyde and one formic acid molecule
(C) 3 formic acid molecules
(D) 3 formaldehyde molecules
13. Phenol is heated with phthalic anhydride in presence of conc. H 2SO4. The product gives
pink colour with alkali. The product is
(A) phenolphthalein (B) bakelite
(C) salicylic acid (D) fluorescein
14. The reaction of with RMgX leads to the formation of
O
(A) RCHOHR (B) RCHOHCH3
(C) R2CHCH2OH (D) RCH2CH2OH
15. In the following compounds
NO2

OH H3C OH OH O 2N OH

(I) (II) (III) (IV)

The order of acidity is
(A) III > IV > I > II (B) I > IV > III > II
(C) II > I > III > IV (D) IV > III > I > II

16. An organic compound ‘X’ on treatment with acidified K 2Cr2O7 gives a compound ‘Y’ which
reacts with I2 and sodium carbonate to form triiodomethane. The compound ‘X’ is
(A) CH3OH (B) CH3COCH3
(C) CH3CHO (D) CH3CHOHCH3

17. In the reaction of phenol with CHCl 3 and aqueous NaOH at 70C (343K ), the electrophile
attacking the ring is
(A) CHCl3 (B) CHCl2
(C) :CCl2 (D) COCl2
18. The compound which gives most stable carbonium ion on dehydration is
(A) (B
)

OH OH
(C) (D) OH
OH

19. An ether is more volatile than alcohol having the same molecular formula. This is due to

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 (A) intermolecular hydrogen bonding in alcohols
(B) dipolar character of ether
(C) alcohols having resonance structure
(D) intermolecular hydrogen bonding in ethers

20. O
Me Me

C CH2 X CH CH2

Me Me OH
X could be
(A) LiAlH4 (B) NaBH4
(C) LiAlH4/BF3 (D) NaH
21. CH2OH
O
NaBH4
A A is

C
O CH3
O
(A) CH2OH (B) CH2OH
HO O

CH2OH CH2OH
(C) CH2OH (D) CH2OH
HO HO

C
O O CH2 CH2OH

22. CH3 CH3

H P is
H3C C C CH3 P

OH OH
(A) CH3 CH3 (B) CH3 CH3

H3C C C CH3 H3C C C CH3

O
(C) CH3 O (D) CH3 H

H3C C C CH3 H3C C C CH3

CH3 CH3 OH
23. A compound X of molecular formula C4H10O is soluble in conc. H2SO4. It does not react
with sodium metal but is cleaved by HI to give CH 3I and an alcohol Y which gives
iodoform. ‘X’ may be
(A) C2H5OC2H5 (B) CH3OCH2CH2CH3
(C) C2H5CHOHCH3 (D) H3C O CH CH3

CH3
24. CH3
18 H A is
H2 O A
H3C C CH2

O
(A) (B)
18
OH OH

HO18 HO
(C) (D)
18
OH OH

HO
HO 18

25. Which one is not cyclic ether?

(A) O (B)
O O

(C) (D) O

O O
O
26. O

H
A

A is
(A) OH (B) CH2OH

CH3
CH3
OH
OH
(C) CH2OH (D) CH3

CH3

CH3 OH

27. O
O
Oxalic acid A
O
O
Hence, A 
conc. H2 SO4
 B; B is
(A) O (B) O
O

O O
(C) O CH2 (D) None

OH OH

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28.

O CH3

CH3OH CH3OH
CH3O H2SO 4
[A]

[B]
A and B are
(A) (B)
H CH3 H OCH3 CH3 OCH3
and H and H
OH3C OH HO CH3
H3CO OH HO CH3
(C) (D)
OCH3 CH3
H3C H OH H H CH3
and and

H3CO CH3 H3CO H3CO OH

H OH OH

29. O

HgSO4 / H2SO 4
C CH A

(A) O (B) O

C CH3 CH2CHO

O
(C) O (D) OH

COOH CH2CHO

30. What are A, B and C in the following?

O
Raney Ni, H2 Pt, 1 mol H 2
B A

NaBH4, CH3OH

C
O
(A)
in all cases

OH
(b)
in all cases

(C) OH

in all cases

OH
(D) O OH

A: B: C:
31. O

1. KBrO, 
2. H
COCH3  A 3. 
CH3
A is
(A) O (B) O

COOH CH3

CH3
(C) (D) COOH
COOH

CH3
OH OH

32. m-chlorobenzaldehyde on reaction with conc. KOH at room temperature gives

(A) potassium m-chlorobenzoate and m-hydroxy benzaldehyde
(B) m-hydroxybenzaldehyde and m-chlorobenzyl alcohol
(C) m-chlorobenzyl alcohol and m-hydroxybenzyl alcohol
(D) potassium m-chlorobenzoate and m-chlorobenzyl alcohol

33. The end product ‘C’ in the following sequence of chemical reactions is
CaCO3 
CH3 COOH   A   B 
NH2 OH
C
(A) acetaldehyde oxime (B) formaldehyde oxime
(C) methyl nitrate (D) acetoxime

34. In cannizzaro reaction given below:


2PhCHO 
OH
 PhCH2OH  PhCO2 
the slowest step is
(A) the attack of OH at the carbonyl group
(B) transfer of hydride ion to carbonyl group
(C) abstraction of proton form carboxylic acid
(D) deprotonation of Ph  CH2OH

35. Reduction with aluminium isopropoxide in excess of isopropyl alcohol is called MPV
reduction. What will be the final product when cyclohex-2-enone is selectively reduced by
MPV reduction?
(A) cyclohexanol (B) cyclohex-2-enol
(C) cyclohexanone (D) benzene

36. Which of the following reagents convert C6H5COCHO to C6H5CHOHCOOH?

(A) aq. NaOH (B) Acidic Na2SO3
(C) Na2CrO4/H2SO4 (D) NaNO2/HCl

37. The enol form of acetone, after treatment with D 2O, gives
(A) H3C C CH2 (B) O

OD D 3C C CD3
(C) H2C C CH2D (D) OD

OH D 2C C CD3

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38. Reduction of can be carried out with
C O to CH2

(A) catalytic reduction (B) Na/C2H5OH

(C) Wolff-Kishner reduction (D) LiAlH4
39. Identify the compounds A and B in the following reaction sequence
 CH3  2 C  O 

H O
NaCN
HCl
 A 
Heat
B 3

(A) A  CH3 COOH B   CH3 CO  2 O

(B) A   CH3  2 C  OH CN B   CH3  2 C  OH COOH
(C) A  CH3 CHO B  CH3 COOH
(D)  CH3  2 C  OH CN B   CH3  2 C  O
40. Which of the following has the most acidic hydrogen?
(A) 3-hexanone (B) 2, 4 – hexanedione
(C) 2, 5 – hexanedione (D) 2, 3 – hexanedione
41. A mixture of benzaldehyde and formaldehyde on heating with aq. 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
OHC
42. CHO

 i NaOH /1000 C

 ii H / H O

2

CHO
OHC
Major product is
HOOC OH
(A) COOH (B)
HOOC

COOH COOH
HOOC
HO
O OH
(C) (D)
O HO

O OH
HO
O

43. Compound ‘A’ (molecular formula C3H8O is treated with acidified potassium dichromate
to form a product ‘B’ (molecular formula C 3H6O). ‘B’ forms a shining silver mirror on
warming with ammonical silver nitrate. ‘B’ when treated with an aq. solution of
NH2CONHNH2.HCl and sodium acetate gives a product ‘C’. Identify the structure of ‘C’.
(A) H3CH2CHC NNHCONH2 (B) H3C C NNHCONH2

CH3
(C) H 3C C NCONHNH2 (D) H2CH3CHC HCONHNH2

CH3
44. Which of the following compounds would have the smallest value for pKa?
 (A) CHF2CH2CH2COOH (B) CH3CH2CF2COOH
(C) CH2FCHFCH2COOH (D) CH3CF2CH2COOH

45. When CH2 = CH  COOH is reduced with LiAlH4, the compound obtained will be
(A) O (B) O

H OH
(C) OH (D) O

OH

46. Identify the correct order of boiling points of the following compounds:-
O O

OH H OH
(I) (II) (III)
(A) I > II > III (B) III > I > II
(C) I > III > II (D) III > II > I
47. The major product obtained when Br2 / Fe is treated with
O
HN
H3 C CH3

is

(A) O (B) O
HN
HN
H3 C CH3
H3C CH3

Br

Br
(C) O (D) O
HN
HN
H3 C CH3
H3C CH3

Br

Br
48. An ester (A) with molecular formula C9H10O2 was treated with excess of CH3MgBr and the
complex so formed was treated with H2SO4 to give an olefin (B). Ozonolysis of (B) gave a
ketone with molecular formula C8H8O which shows positive iodoform test. The structure
of (A) is:
(A) C6H5COOC2H5 (B) CH3COCH2COC6H5
(C) p – CH3O – C6H4 – COCH3 (D) C6H5COOC6H5

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49. O

CH3COOOH
  P. P is

(A) O (B) O

O
(C) O (D) O

O HO OH

50. X and Y in the following reaction sequence are:-

O
P2O5
X 
 R C NH2 

Br2
Y
OH
(A) R – CN, RCH2NH2 (B) RNH2, RCN
(C) RCN, RNH2 (D) RCN, RCH2NH2
Multiple choice questions with more than one option correct
51. 1 – propanol and 2 – propanol can be best distinguished by
(A) oxidation with KMnO4 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 KMnO4 followed by reaction with Tollen’s solution

52. Which of the following statements are correct?

(A) CrO3.H2SO4 in acetone oxidizes 2° alcohols to ketones
(B) Jones reagent which is chromic acid in aqueous acetone solution oxidizes 1° alcohol
to aldehyde and 2° alcohol to ketone but does not effect double bond.
(C) chromic acid oxidizes 1° alcohols to carboxylic acid.
(D) the formation of cyanohydrin from a ketone is an example of electrophilic addition

53. O CH
CH
2 CH
2

 ?

Product is
(A) OH
(B) OR

*
CH2CH CH2 CH2 CH CH2

(C) OH
(D) OH

CH2 CH CH2

*
H2 C CH CH2
54. How much bromine is needed to produce tribromophenol from one mole of phenol?
 (A) 3.0 mole (B) 1.5 mol
(C) 240 g (D) 480 g

55. Which of the product expected in the following reaction?

CH3
Cl
NaNH2

NH

3

CH3 CH3
(A) (B)
NH2

NH2
(C) CH3 (D) None of these

NH2

56. Which of the following reactions depict the nuclophilic substitution of C 2H5Br?
(A) C2H5Br  C2H5 SNa   C2H5 SC2H5  NaBr
(B) C2H5Br  2H 
 C2H6  HBr
(C) C2H5Br  AgCN  C2H5NC  AgBr
(D) C2H5Br  KOH 
 C2H5OH  KBr

57. Which of the following are electrophilic substitution reactions?

(A) (B)
FeCl3
 Cl2   fumin g H2SO 4 

(C) (D) None of these

UV light
 Cl2 


58. On treatment with a clear solution of CrO 3 in dilute H2SO4, an aliphatic alcohol gives a
greenish opaque solution within 2-3 seconds. The alcohol can be
(A) CH3CH2OH (B) CH3

H3C CH CH CH3

OH
(C) H3CHC CH3 (D) CH3

OH H3C C OH

CH3
59. Treatment of n-propylamine with nitrous acid gives
(A) CH3CH=CH2 (B) CH3¾CH2¾CH2OH
(C) H3C CH CH3 (D) none of these

OH
60. Which of the following statements are correct?

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 (A) The two carbon-oxygen bond length in formic acid are different.
(B) The two carbon-oxygen bond lengths in sodium formate are equal
(C) The carbon-oxygen bond length in formic acid is less than that in sodium formate.
(D) The carbon-oxygen bond length in formic acid is greater than that in sodium formate

61. Nitration of phenol with dilute nitric acid at 293 K gives

(A) o-nitrophenol (B) p-nitrophenol
(C) m-nitrophenol (D) 2, 4, 6-nitrophenol

62. The product obtained in the equation:

CH3  NO2  Cl2  NaOH 
is
(A) ClCH2NO2 (B) Cl2CHNO2
(C) Cl3CNO2 (D) CH3NH2

63. Phenyl cyanide can be obtained by

PO , Ac O, 
(A) C6H5CONH2 
2 5
 (B) C6H5  CH  NOH 
2

1. NaNO / HCl
(D) C6H5NH2  
Alc. KOH
(C) C6H5Cl  2
2. CuCN

64. Isopropylamine can be obtained by

(A)  CH3  2 CHO  NH 2OH  ?  LiAlH


4

(B)  CH3  2 CO  NH 3  ? 

H / Ni 2

(C) H3C
CHOH NH3 
H3C
(D) none of these

65. Which of the following will yield p-tert. Butylphenol?

(A) CH3

H
Phenol H3C C CH2  

(B) Phenol   CH3  3 COH 

H


(C) Phenol   CH3  3 CCl 
AlCl
3

(D) None of these

66. Which of the following statements are correct?

(A) Benzaldehyde reduces Fehling’s solution
NaOH
(B) C6H5CHO  C6H5CHO  C6H5CH  CHC6H5  O2 is a Claisen-Schmidt
reaction.
(C) pKa (formic acid) is less than pKa (acetic acid)
(D) o-Toluidine is more basic than aniline
67. Which of the following statements are correct?
(A) When phenol vapour is passed over Zn dust, bezene is produced.
(B) The phenolic OH group is ortho and para directing
(C) o-nitrophenol has a lower boiling point than p-nitrophenol
(D) Phenol is more acidic than o-cresol
68. Which of the following will give vinyl chloride?
 2
Hg
(A) CH  CH  HCl  
(B) H2C CH2 Cl 2  H 2C NaOH
CH2  


Cl Cl
6000 C
(C) CH2  CH2  Cl2 

KOH
(D) ClCH2  CH2Cl 
ethanol

69. Vinyl chloride undergoes
(A) addition reactions (B) elimination reactions
(C) substitution reactions (D) none of these

70. Which of the following methods can be used for the preparation of acetylene?
(A) CH 3CHCl2  alc. KOH 
(B) ClCH2CH2Cl  alc. KOH 
liq. NH
(C) ClCH 2CH2Cl  NaNH2 

3

(D) None of these

71. Aryl halides undergo

(A) the Fittig reaction (B) the Ullmann reaction
(C) the Grignard reaction (D) none of these

72. Which of the following reagents can be used to distinguish CH 2=CHCH2Cl from
CH3CH2CH2Cl?
(A) Na fusion; HNO3, AgNO3 (B) Ag(NH3)2OH
(C) AgNO3/C2H5OH (D) Br2/CCl4

73. Alkyl iodides can be prepared by

CCl
(A) RCH2COOAg  I2 

4
 RCH2I
acetone
(B) RCH2Cl  NaI 

 RCH2I  NaCl
(C) R  OH  HI  RI  H2O
(D) CH4  I2  CH3I

74. The reaction of glycerol with HIO4 gives

(A) formaldehyde (B) formic acid
(C) iodic acid (D) oxalic acid

75. On being treated with HCl, acetone gives

(A) mesityl oxide (B) phorone
(C) mesitylene (D) aldol

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Match the Following

76. Match the following:

X Y Z
1. Decarboxylation 1. LiAlH4 1. a-bromoacids
2. Hell-Volhard Zelinsky 2. Aq. sodium 2. Carboxylic acids
reaction ethanoate
3. Grignard reagents 3. Sodalime 3. Ethane
4. Electrolysis 4. Br2 in presence of 4. Alcohols
red P
5. Reduction of aldehydes 5. Dry ice (solid CO2) 5. Removal of CO2
and ketones with

77. Match the statements given in Column A with Column B.

Column A Column B
1. Methanal disproportionates in the presence (a) Benzoin condensation
of conc. Alkali
2. C6H5 CHO  KCN
 C6H5 CH(OH)COC6H5 (b) Acetaldehyde
3. Aldehyde which gives iodoform test (c) Wolf-Kishner reduction
4. N2H4 /(CH3 )3 COK 
(CH3 )2 CO (CH3 )2 CH2 (d) Cannizzaro’s reaction

78. Match the following Column A and Column B

Column A Column B
1. Williamson’s synthesis (a) Estimation of alkoxy groups
2. Zeisel method (b) Reaction of phenol with
diethyl sulphate in presence of
NaOH
3. Oxonium salts (c) Involves heating of an alkyl
halide with sodium alkoxide
4. Phenetole (d) Combination of ethers with
inorganic acid

79. Match the following Column A and Column B

Column A Column B
1. Tollen’s reagent (a) 50% NaOH solution
2. CH3COCH3 (b) Hexamethylenetetramine
3. HCHO (c) Oxidising agent
4. HCHO + NH3 (d) Ba(OH)2

Comprehension 1

In a polyhydric alcohol, the total numbers of hydroxyl groups are estimated by the following
methods:
(i) A known mass of the acetyl derivative of polyhydric alcohol is taken. It is mixed with an
excess volume of a standard alkali solution. Both are refluxed. Alkali is used in the
hydrolysis of acetyl derivative. The unused alkali is measured by doing titration with a
standard acid solution and total number of hydroxyl groups (n) can thus be calculated
stoichiometrically.
CH COCl nKOH
A(OH)n 
3

 A(OCOCH3 )  A(OH)n  nCH3COOK
polyhydric acetyl derivative
alcohol
(ii) Total number of –OH groups in vicinal position can be calculated by periodic acid or lead
tetra acetate oxidation.

C OH C O
HIO4

or Pb(OCOCH3 )4


C OH C O

Read the above paragraph carefully and give the answer of following questions:

80. 0.436 g of acetyl derivative of a polyhydric alcohol (molecular mass = 92) require 0.336 g
KOH for hydrolysis. The total numbers of hydroxyl group(s) in the alcohol are:
(A) 1 (B) 2
(C) 3 (D) 4

81. The product formed by reaction of ethylene glycol and periodic acid (HIO 4) is:
(A) Acetic acid (B) Formic acid
(C) Formaldehyde (D) Glyoxal

82. A compound with molecular formula C4H10O3 is converted by the action of acetyl chloride
to a compound with molecular weight 190. The original compound has:
(A) One –OH group (B) Two –OH groups
(C) Three –OH groups (D) No –OH group

83. The ratio of the number of moles of lead tetra acetate required for the oxidation of 1 mole
of glucose to that of 1 mole of fructose is:
(A) 1 : 1 (B) 2 :1
(C) 5 : 4 (D) 4 : 5
Comprehension  2
Aldehyde & Ketone are polar molecule. Nucleophiles attacks >C = O at carbon (positively
charged) and electrophiles are attacked by oxygen. The characteristic reaction of Aldehyde &
Ketone is nucleophilic addition to the carbon of carbonyl group.

   
O  H Y    Y O

H
In condensation of Aldehyde & Ketone takes place only when it consist  carbon atom consisting
  hydrogen , the reaction will takes place in presence of dilute alkali in this one Aldehyde is
partially converted to its enolate anion by base. The enolate undergoes nucleophilic addition to
the carbonyl group. The alkoxide formed in nucleophilic addition step then abstracts a proton
from the solven to yield aldol consisting aldehydes & hydroxyl group.
O

H O
 HO     R  H2O
R Base Enolate

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 O O O OH O

H O H H 2O
H
R
R R R R R
Aldol
The reactivity of carbonyl compound for nucleophilic addition depends on inversely of +I effect.
Read the above paragraph carefully and answer the questions given below it:

84. Which of the following undergoes aldol condensation?

(A) H H (B) Cl H

H3C Cl

CH3 O Cl O
(C) H (D) Cl

O CHO

85. O CH3
 A 
CH3 N
H3C
CH3
H3C
(A) (CH3)2 – NH (B) (CH3)3 – N
(C) (CH3)3C – NH2 (D) None

86. Which one is most reactive for addition of alcohol on carbonyl group?
(A) C6H5CHO (B) HCHO
(C) H3C CH3 (D) CH3.CHO

87. How many aldol products can form when 2 butanone & propanal reacts in presence of
dilute base:
(A) 4 (B) 5
(C) 6 (D) 7

Comprehension  3

To convert 1-bromopropane into 1-bromobutane, chemists A and B designed two paths.

Chemist A:
CH3Br Na h
CH3CH2CH2Br 
Wurtz
 CH3CH2CH2CH3 
Br
 CH3CH2CH2CH2Br
2
Step I Step II
Chemist B:
  i HCHO
Mg / Ether  ii H3O
CH3CH2CH2Br 
Step I
 CH3CH2CH2MgBr 
Step II
 CH3CH2CH2CH2OH
HBr

Step III
 CH3CH2CH2CH2Br
Based on these methods, answer the following questions:

88. Better yield of CH3CH2CH2CH2Br is obtained by

(A) chemist A (B) chemist B
(C) equally in both (D) no prediction can be made
89. While attempting synthesis, assistant of B read the instruction as
 3 i H O
CH3CH2CH3MgBr 
 ii HCHO

Then product formed would have been
(A) CH3CH2CH2CH2OH (B) CH3CH2CH2OH
(C) CH3CH2CH3 (D) all of these
90. Chemist A had the problem of getting so many side products in step I beside getting n-
butane. These side products are
(A) CH3CH2CH3 , CH3CH  CH2
(B) CH3CH2CH3 , CH3CH  CH2 , CH3CH3 ,CH4
(C) CH3CH2CH3 , CH3CH  CH2 , CH3CH3 , CH3  CH2  4 CH3
(D) CH3CH3 , CH3 CH  CH2

91. Chemist A obtained a resolvable optically inactive mixture in step II, as major product.
This mixture contains:
(A) 1-bromobutane and 2-bromobutane (B) d-and  -2-bromopropane
(C) d-and  -3-bromopentane (D) d-and  -2-bromobutane
Comprehension  4

Alkyl halides undergo SN reactions as well as E1, E2 and ECB reactions, depending on the
nature of substrate and nucleophile. Carboxylic acids can be converted into -bromo carboxylic
acids and thus it can be used as intermediate in the synthesis of so many other compounds.
O O

A?
RCH2 COH 
 RCHCOH

Br
Based on the above intermediate, answer the following questions:
92. A used to carry out this conversion is
(A) PBr3 (B) PBr5
(C) P; Br2/H2O (D) Br2, 

93. One sub-intermediate is also formed in the above reaction:

(A) Br O (B) O

RC COH RCH COBr

Br Br
(C) O (D) No sub intermediate is formed

RCH2 COBr

94. Conversion of a carboxylic acid into -halo carboxylic acid is called

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 (A) Cannizzaro reaction (B) Refromatsky reaction
(C) Perkin reaction (D) Hell-Volhard-Zelinsky reaction
95. O O

RCH2CHCOH RCH2 CHCOH

Br OH
For the above conversion reagent used is
(A) alcoholic NaOH (B) NaOH, H+
(C) both of these (D) none of these
 ANSWERS TO GRAND ASSIGNMENT

Subjective:

Board Type Questions

1. (i) and (iii) meso

(ii) d – isomer (iv)   isomer

2.

3. (S)

4. (a)
cold KMnO4

syn addtion
 R S

HO OH
H H
(b)

 Br2
anti addtion
 Br H
R R

H H H Br

5. Br

Br CH3 CH3 H CH3
 2
(cis)    OH , SN
s lo w
H

H H H HO H
 (trans)
OH (T.S)

7. Chiral – enantiomers

8. H3CHC CHCHO H CH2 CH CHCHO

  H2 O 

CH3(CH=CH) 3CHO
In this case condensation of allylic hydrogen and not that of vinylic hydrogen takes place.

11. CH3

C (C6H5)3P = O

CH3

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13. NH2 NH2
Br Br
Br Br
Br 2  i NaNO  HCl; 00 C

 ii H3PO 2 H2 O 
2

Br Br

15. OH

H3C CH3

21. 22.4  10 7 LN2 at NTP

22. Tautomerism

24. III < I < II

True and False

25. T 26. T

27. T 28. F

29. T 30. T

31. F 32. T

Fill In the Blanks

33. phenolphthalein, indicator

34. 2, 4, 6-tribromophenol, 4-bromophenol

35. nitric acid

36. moist, dry

37. butanone

38. C6H5CH(OCOCH3)2
39. phthalic acid

40. alpha hydrogen, halogen

IIT level Questions

41. (a) There is no chiral carbon, but the molecule is chiral (an allene)
(b) There is no chiral carbon and there is a plane of symmetry between two ¾CH3 groups.
Hence it is not a chiral molecule.
42. (a) Cl (b) OD
* *
* *
D D

43. (a) H
Cl

H
CH3
There is no change in configuration (stereospecific retention)
(b) C2 H5 C2 H5

H3C OC2H5 H5 C2 O CH3

CH2CH2CH3 CH2CH2CH3
(retention) (inversion)
A mixture is formed due to SN1 reaction (racemisation)

44. O

A: CH2OH B: C H

O O

C: C OH D: C Cl

E : H2/Pd/BaSO4 or sulphur in quinoline.

45. OH OH OH

Cl Cl Cl Cl Cl Cl

A: B: C:

CO2Et CO2H
NH2 N2 HSO 4 OH O

But But

D: E: F: G:

NO 2 NO 2 NO 2
But But
 one e transfer oxidation 


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46. H H H Br H H

A: B: C:

CH3 OTs CH3 H CH3 Br

47. (a) In basic medium Nu- attacks oxiranes at the less substituted carbon.
O
CH 3OH
CH 3O

OH OCH 3
(actual product)
Nu attacks here
(b) Carbocation undergoes rearrangement

H2SO 4 1, 2 methyl shift

-H2O
OH
-H

48. CH3

COOH Br
A: B:
COOH

CH3 CH2COOH

COOH
C: D:

50. COOH
HS

NH2

COOH
At pH = 1 HS

NH3
O
At pH = 5
C O
  pKa of  COOH
HS

NH3 O

C O
At pH = 9   pKa value of  NH3  S

NH3
Objective:

1. C 2. A 3. A 4. C
5. B 6. B 7. D 8. A
9. A 10. B 11. B 12. B
13. A 14. D 15. D 16. D
17. C 18. B 19. A 20. C
21. C 22. C 23. D 24. A
25. D 26. B 27. A 28. B
29. B 30. D 31. B 32. D
33. D 34. B 35. B 36. A
37. B 38. C 39. B 40. B
41. A 42. B 43. A 44. B
45. C 46. B 47. A 48. A
49. B 50. C 51. C, D 52. A, B, C
53. A, D 54. A, D 55. A,B 56. A, C, D
57. A, B 58. A, B, C 59. A, B, C 60. A, B, C
61. A, B 62. A, B, C 63. A, B, D 64. A, B, C
65. A, B, C 66. C, D 67. A, B, C, D 68. A,B,C, D
69. A, B 70. A, B, C 71. A, B, C 72. C, D
73. B, C 74. A, B, C 75. A, B
76. 1–3–5, 2–4–1, 3–5–2, 4–2–3, 5–1–4
77. 1–d, 2–a, 3–b, 4–c
78. 1–c, 2–a, 3–d, 4 –b
79. 1–c, 2–d, 3–a, 4–b
80. C 81. C 82. B 83. A
84. A 85. C 86. A 87. C
88. B 89. C 90. C 91. D
92. C 93. B 94. D 95. B

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