CPP

IIT-JEE
Subject-CHEMISTRY Class-XII

AMINES

PREPARATION AND PROPERTIES

1. Which of the following reagents would be best for converting phenylacetamide (C6H5CH2CONH2) to
benzylamine (C6H5CH2NH2)?
(A) LiAlH4 in ether. (B) i) P2O5 & heat; ii) LiAlH4 in ether.
(C) H2 & Pt catalyst. (D) aqueous NaOBr.

2. Which of the following reagents and conditions would be best for the preparation of cyclohexylamine?
(A) cyclohexanone + NH3 + NaBH3CN. (B) cyclohexylbromide + 2 NH3.
(C) cyclohexylbromide + NaNH2. (D) cyclohexene + NH3.

3. Which of the following statements concerning amine oxides is not true?

(A) chiral amine oxides may be resolved.
(B) the nitrogen has a positive formal charge.
(C) the nitrogen hybridization is sp3.
(D) all types of amines can form amine oxide derivatives.

4. What reagent is the source of nitrogen in the Gabriel synthesis of amines?

(A) sodium azide, NaN3 (B) sodium nitrite, NaNO2
(C) potassium cyanide, KCN (D) potassium phthalimide, C6H4(CO)2NK

5. In order to prepare a 1º-amine incorporating an additional CH2 group from an alkyl halide, what reagent is
often used as the nitrogen source?
(A) sodium amide, NaNH2 (B) sodium azide, NaN3
(C) potassium cyanide, KCN (D) potassium phthalimide, C6H4(CO)2NK

6. What set of conditions would be useful for preparing a 2º-amine?

(A) 2º-RBr + NaNH2
(B) (i) 2º-RBr + NaN3 (ii) H2 & Pt
(C) (i) 1º-RNH2 + 1º-RCHO (ii) H2 & Pt
+
(D) (i) 2 1º-RBr + potassium phthalimide (ii) H3O & heat

7. Which of the following procedures would be best for preparing dimethylcyclohexylamine, C6H11N(CH3)2?
(A) (i) dimethylamine + cyclohexanone (ii) NaBH3CN in methanol
(B) dimethylamine + cyclohexylbromide in ether
(C) cyclohexylamine + 2 CH3I in ether
(D) (i) cyclohexylbromide + NaCN in methanol (ii) 2 CH3Li in THF

8. What reagent would be best for converting the amide of (R)-2-phenylpropanoic acid, C6H5CH(CH3)CONH2,
into (R)-1-amino-2-phenylpropane?
(A) excess H2 & Pt. (B) NaOBr in aqueous base.
(C) NaBlH4 in methanol (D) LiAlH4 in ether.

9. What reagent would be best for converting the amide of (R)-2-phenylpropanamide, C6H5CH(CH3)CONH2,
into (R)-1-phenylethylamine?
(A) excess H2 & Pt. (B) NaOBr in aqueous base.
(C) NaBH4 in methanol (D) LiAlH4 in ether.

FIITJEE 1
10. Which of the following procedures would be best for preparing isobutylisopropylamine,
(CH3)2CHNHCH2CH(CH3)2?
(A) (CH3)2CHBr + (CH3)2CHCH2NH2
(B) (i) (CH3)2CHBr + (CH3)2CHCONHNa (ii) LiAlH4 in ether
(C) (i) (CH3)2CHNH2 + (CH3)2CHCH=O (ii) H2 & Pt
(D) (CH3)2CHCN + (CH3)2CHNH2

11. Which of the following compounds is the strongest base?

(A) (CH3)2NCH2CO2CH3. (B) (CH3)2NCOCH3. (C) (CH3)2NC≡N. (D) (CH3)2N-N=O.

CHEMICAL REACTION AND HINSBERG TEST

12. The nitrogen atom in each of the following tertiary amines may be removed as trimethyl amine by repeated
Hofmann eliminations (exhaustive methylation followed by heating with AgOH).
Which of the amines requires the greater number of Hofmann sequences to accomplish this?
CH3 CH3
N(CH3)2
N N

N
A B C D

13. Only one of the following amines will lose its nitrogen atom as trimethyl amine by repeated Hofmann
elimination reactions (exhaustive methylation followed by heating with AgOH). Identify that amine.
CH3
N
N N
N

A CH3 B C D

14. A nitrogen containing compound dissolves in 10% aq. sulphuric acid..

The Hinsberg test (C6H5SO2Cl in base) gives a solid product that is not soluble in 10% aq. NaOH..
Which of the following would best fit these facts?
(A) N,N-dimethylaniline, C6H5N(CH3)2. (B) N-methylbenzamide, C6H5CONHCH3.
(C) N-methylaniline, C6H5NHCH3. (D) benzylamine, C6H5CH2NH2.

15. Which of the following amines reacts most rapidly with para-nitrophenylacetate, p-NO2C6H4OCOCH3?
(A) para-methoxyaniline,.p-CH3OC6H4NH2 (B) para-nitroaniline, p-NO2C6H4NH2.
(C) aniline, C6H5NH2. (D) cyclopentylamine, C5H9NH2.

16. What product mixture is expected from reaction of (S)-2-aminobutane with 2-butanone in the presence of
NaBH3CN?
(A) a pair of enantiomers.
(B) a pair of diastereomers, both meso.
(C) a pair of diastereomers, one meso one chiral.
(D) a pair of diastereomers, both chiral (not enantiomers).

17. What reagent is used in the Hinsberg test of amines?

(A) (CH3CO)2O & pyridine (B) C6H5SO2Cl in aq. NaOH
(C) NaNO2 in aq. H2SO4 (D) CH3I (excess) followed by AgOH

18. Which of the following will be the favored product from the reaction shown below?

19. What is the chief product from the Hofmann elimination of 4-methyl-2-aminopentane?
(A) 4-methyl-1-pentene (B) 4-methyl-2-pentene (C) 2-methyl-1-pentene (D) 2-methyl-2-pentene

FIITJEE 2
20. The Hinsberg test of a C5H14N2 compound produces a solid that is insoluble in 10% aq. NaOH.
This solid derivative dissolves in 10% aq. sufuric acid. Which of the following would best fit these facts?
(A) NH2CH2CH2CH2N(CH3)2 (B) (CH3)2NCH2CH2NHCH3
(C) NH2CH2C(CH3)2CH2NH2 (D) (CH3)2NCH2N(CH3)2.

21. Repeated Hofmann elimination reactions (exhaustive methylation followed by heating with AgOH) will often
remove a nitrogen atom from an amine molecule.
Which of the following compounds is the likely product in this case?

Hofmann
N 
Eliminations

A B C D

22. What sequence of reactions would best accomplish the following reaction?

(A) i) LiAlH4 in ether; ii) 3 CH3I followed by heating with AgOH

(B) i) LiAlH4 in ether; ; ii) P2O5 & heat
(C) i) 20% H2SO4 & heat; ii) P2O5 & heat
(D) H2 & Lindlar catalyst

23. What is the likely product from the following reaction?

N 1. H2O2
 OH O
2. heat
(> 110°C)
A B C D

24. Amines are well known to be stronger bases and nucleophiles than alkenes.
Why do enamines, preferentially react with electrophiles at a double bond carbon rather than at nitrogen?
(A) the nitrogen is sterically hindered by alkyl substituents.
(B) nitrogen is more electronegative than carbon.
(C) the carbocation formed by electrophilic attack at C-2 is stabilized by pi-bonding with the lone pair of
electrons on nitrogen.
(D) ammonium cations are less stable than carbocations.

BENZENE DIAZONIUM CHLORIDE AND ANILINE

25. Given reaction, P will be :
OH

OH–
C6H5N  N Cl– P
pH 9 – 10

CH3
CH3 OH

(A) C6H5 – N = N (B) C6H5 – N = N

HO CH3
H3 C
CH3
(C) C6H5 – N = N (D) C6H5 – N = N

OH OH
26. Which of the following aryl amines will not form a diazonium salt on reaction with sodium nitrite in
hydrochloric acid.
(A) m-Ethylaniline (B) p-Aminoacetophenone
(C) 4-Chloro-2-nitroaniline (D) N-Ethyl-2-methylaniline

FIITJEE 3
27. Predict the major product in the following reaction.
OH Me
Me
HNO2
Me P
NH2
OH Me OH Me OH Me
O Me Me
(A) Me (B) CH2 (C) (D) Me
Me
Me Me Me OH
NH2

28. (CH3CO)2O HNO3 H+

A B C
H2SO4 H2O
C is :
NH2 NH2 NO2 NO2

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

NO2 NO2
NO2 NO2

29. An organic compound (A) C9H13N dissolves in dil. HCl and releases N2 with HNO2 giving an optically active
alcohol. Alcohol on oxidation gives dicarboxylic acid, which on heating forms anhydride. The organic
compound A is :
NH2 CH3 CH3
NH2
(A) (B) (C) NH2 (D)
CH3

NH2
30. Which of the following is not the correct reaction of aryldiazonium ion.
CuCl / HCl 
(A) C6H5N2 Cl–    C6H5 Cl (B) C6H5N2 Cl–  HBF4   C6H5F

(C) C6H5N2 Cl–  H3PO2  C6H5PO 4 (D) C6H5N2 Cl–  H2 O  C6H5 OH

31. The final major product of the reaction is :

OH
NaNO2 + HCl
Ph C CH CH3
Ph NH2
OH O O O OH OH
Ph CH3
(A) Ph C C CH3 (B) C CH CH3 (C) Ph C CH (D) Ph C C CH3
Ph Ph Ph Ph CH3
32. Consider the following diazonium ion :

Me2N N2 O2N N2

(P) (Q)

MeO N2 CH3 N2

(R) (S)
The order of reactivity towards diazo coupling with phenol in presence of dil NaOH is :
(A) P > Q > R > S (B) Q > S > R > P (C) P > R > S > Q (D) S > R > Q > P

FIITJEE 4
33. Anilinium hydrogen sulphae on heating with sulphuric acid at 453-473 produces.
(A) benzenesulphonic acid (B) m-Aminobenzene sulphonic acid
(C) Sulphanilic acid (D) Aniline

SUBJECTIVE

34. Write the products for the following reactions.

(a) Ethylamine + benzoyl chloride 
 (b) Methyl amine + succinic anhydride 

(c) product of (b) + heat 
 (d) tetraethylammonium hydroxide + heat 

(e) m-Dinitrobenzene + H2S/NH3 

35. Write simple chemical tests that would distinguish between
(a) benzylamine and benzamide (b) allylamine and propylamine

(c) aniline and N-methylamine (d) cyclohexylamine and piperidine

ex.CH3I Ag2O,H 2O /Δ ex.CH3I

36. N-methylpiperidine   A   B   C (piperdine )
Ag2O,H 2O /Δ N
C  D

Write the structures of A-D.

37. Show how the following transformations can be accomplished.

O 2N CH3 O 2N NH2
A)

B) CH3O CH3O CH(NH2)CH3

C) H3C H3C CH2CH2NH2

38. Predict the major products when the following compounds are heated:
(a) diethyldi-n-propylammonium hydroxide;
(b) dimethylethyl(2-chloroethyl)ammonium hydroxide;
(c) dimethylethyl-n-propyl ammonium hydroxide.
(d) dimethylethyl tert-butylammonium hydroxide.

39. Diacetamide, (CH3CO)2NH, is much more acidic (Ka = 10–11) than acetamide (Ka = 8.3 × 10–16), and
-10
roughly comparable to benzenesulfonamide ( K a =10 ). How can you account for this ?

40. Write the products obtained when N-methylaniline and N,N-dimethyl aniline react with nitrous acid ?

41. Benzenediazonium chloride couples with phenol, but not with the less reactive anisole. 2,4-
Dinitrobenzenediazonium chloride, however, couples with anisole; 2,4,6-trinitrobenzenediazonium chloride
even couples with mesitylene.
(a) How can you account for this ?
(b) would you expect p-toluenebenzenediazonium chloride to be more or less reactive as a coupling
reagent than benzenediazonium chloride.

FIITJEE 5
42. Which of the following compounds are capable of being resolved into enantiomers ?
a) N-ethyl-N-methylaniline

b) 1, 2, 2-trimethylaziridine c)
 d)
N

N
H3C CH 2CH3 H 3C CH2 CH3

e) N f) N
H CH3
(aziridine N )

43. Predict the organic products formed when the following amides are treated with alkaline bromine water.

a) Ph-CH2CH2-CO-NH2 b) H2N-CO-(CH2)4-CO-NH2

c) H

CONH2
H

44. Complete the following acid-base reactions, and predict whether the reactants or products are
favoured.

b) + CH3COOH
a) + CH3COOH
N N
H
+
NH3
c) + d) +
N+ N N
H H H

* * * * *
ANSWER KEY (CPP AMINES)
PREPARATION AND PROPERTIES

1. (D) 2. (A) 3. (D) 4. (D) 5. (C) 6. (C) 7. (A) 8. (D) 9. (B) 10. (C) 11. (A)

Chemical Reaction and Hinsberg Test

12. (A) 13. (D) 14. (C) 15. (D) 16. (C) 17. (B) 18. (A) 19. (A) 20. (B) 21. (B) 22. (A)
23. (B) 24. (C)

Benzene Diazonium chloride and Aniline

25. (A) 26. (D) 27. (C) 28. (B) 29. (C) 30. (C) 31. (C) 32. (B) 33. (C)

FIITJEE 6
 Subjective Answers

34 (a) O (b) O
C
NHC2H5 OH
NHCH 3

O
(c) O
(d) CH2=CH2 + N(C2H5)3
N CH3

O
(e) NH2
(NH4)2S reduces only one –NO2 group.

NO2

35. (a) Benzylamine is soluble in aq. HCl, while benzamide is not.

(b) Br2 / H2O or Baeyer’s reaagent
(c) (i) NaNO2 / HCl (ii) -naphthol. Aniline froms a coloured compound (dye).
(d) Hinsberg’s test and NaNO2 / HCl

36.
    + N(CH 3)3
 
N N N N D
CH 3 H3C CH 3 H3C CH 3 H3C CH CH 3
3
A B C

37. (A) (i) KMnO4/ (ii) NH3/ (iii) Br2 / KOH

(B) (i) CH3COCl / AlCl3 (ii) NH3 / H+ (iii) LiAlH4

(C) (i) Br2 / Fe (ii) Mg/THF (iii) ; H+ (iv) PCC / CH2Cl2 (v) NH3 / H+ (vi)
O
LiAlH4

38. (a) CH2=CH2 + C2H5N(C3H7)2 (b) CH2=CHCl + (CH3)2NC2H5

(c) CH2=CH2 + (CH3)2NC3H7 (d) Isobutene (This is an exception in Hoffman
elimination)

39. O O
CH3 C N C CH3 is more resonance stabilised.

40. NHCH3 H3C N N O

HNO
2


N-nitrosoamine
(yellow oil)

N(CH3)2 N(CH3)2

HNO
2


N O

FIITJEE 7
41. (a) + +
N2 N2
NO 2
is more reactive than

NO2
+
N2
O 2N NO2
is still more reactive

NO2
(b) p-toluenebenzenediazonium chloride is less reactive than benzenediazonium chloride.

42. Pyramidal inversion is possible when the following two conditions are satisfied :
1. Nitrogen has lone pair.
2
2. Nitrogen should be able to become sp hybridised.

43. (a) Ph–CH2–CH2–NH2 (b) H2N–(CH2)4–NH2

(c) H

H NH2

All are examples of Hoffmann bromamide rearrangement Migrating group migrates with retention of
configuration.

44.
(a) reactants are weak acid & weak base
(b) reactants are weak acid & weak base
(c)
is less basic than
N N
(d) NH2
is less basic than
N
H

FIITJEE 8