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Subject-CHEMISTRY Class-XII
AMINES
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.
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
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
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 N(CH3)2 CH3
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
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).
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?
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.
OH–
C6H5N N Cl– P
pH 9 – 10
CH3
CH3 OH
HO CH3
H3C
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
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 C6H5PO4 (D) C6H5N2 Cl– H2 O C6H5OH
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
O 2N CH 3 O 2N NH2
A)
C) H3 C H 3C 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.
–11 –16
39. Diacetamide, (CH3CO)2NH, is much more acidic (Ka = 10 ) than acetamide (Ka = 8.3 × 10 ), 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
H3 C CH2CH3 H3C CH2CH3
e) N f) N
H CH3
(aziridine N )
43. Predict the organic products formed when the following amides are treated with alkaline bromine water.
c) H
CONH 2
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)
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)
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
NHCH3
O
(c) O
(d) CH2=CH2 + N(C2H5)3
N CH3
O
(e) NH2
(NH4)2S reduces only one –NO2 group.
NO2
36.
+ N(CH 3)3
N N N N D
CH 3 H3C CH 3 H3C CH 3 H3C CH 3
CH 3
A B C
+ +
(C) (i) Br2 / Fe (ii) Mg/THF (iii) ;H (iv) PCC / CH2Cl 2 (v) NH3 / H (vi)
O
LiAlH4
39. O O
CH3 C N C CH3 is more resonance stabilised.
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
NO 2
+
N2
O2N 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.
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
SOLUTIONS (CPP-AMINES)
Hoffmann
1. C6H5CH2CONH2
degradation
C6H5CH2NH2
2. Options B and C give elimination products cyclohexene does not react with NH3
O NH NH2
NaBH CN
3
+ NH3
reduction
imine
NK
O
H 2 ; Ni/Pt
5. RX + KCN RCN RCH2NH2
So, KCN can be used to incorporate an addition –CH2 group to an alkyl halide & then to form an amine.
6. 2–H O H & Pt
2
R C O + H2 N R R C N R RCH2 N R
H H H
2° amine
7. O
NaBH CN in methanol
3
(CH3)2NH + C6H11N(CH3)2
8. H O H
LiAlH4 in ether
C6H5 C C NH2 C6H5 C CH2 NH2
(No change
in configuration)
CH3 CH3
(R)
10. Reducive amination of an aldehyde or ketone gives us a 1° amine containing 2° alkyl group.
13. In options A, B & C, Hoffmann elimination ceases in the middle because of lack of -hydrogen.
14. Only secondary amine fits the facts given in the question.
15. In this reaction Amine is attacking as a nucleophile & according to availability of lone pair C5H9NH2 is the
best nucleophile amongst all the given compounds.
FIITJEE 9
16. H3C C CH2 CH3 + H3C CH CH2 CH3
O NH2
NaBH CN
H3C C C2H5 3
Meso + Chiral
N
H3C CH CH2 CH3
N
H3C H
CH CH
C2H5 C2H5
H3C
This product may be meso as it may have plane of symmetry or chiral.
17. C6H5SO2Cl in aq. NaOH is Hinsberg’s reagent used to distinguish 1°, 2° & 3° amines.
19. In Hofmann elimination least substituted alkene is formed hence it gives 4-methyl-1-pentene.
21. + +
N N N N
(CH3)3N +
22. LiAlH
4 Hoffmann
C N CH2NH2 CH2
elimination
25. OH O– CH3
CH3 CH3 HO
26.
FIITJEE 10
27. OH Me OH Me
Me
HNO2 HNO2 Me 1, 2-Hydride shift
Me P –N2 Me
NH2
O Me OH Me
Me
Me Me
Me
28. O O
NH2 NH C CH3 NH C CH3 NH2
(CH3CO)2O HNO3
H2SO4
NO2 NO2
29. CH3 O O
NH2 Oxidation C OH C
O
–H2O
C OH C
O O
30.
31. OH OH
NaNO2 + HCl Ph C CH CH3
Ph C CH CH3
Ph NH2 Ph
O OH 1, 2-Ph migration
CH3
Ph C CH Ph C CH CH3
Ph
Ph
32.
33.
NH3HSO4 NH2 NH3
455 - 475 K
–H2O
SO3–
SO3H Sulphanilic acid
FIITJEE 11
Subjective
O
(c) O
(d) CH2=CH2 + N(C2H5)3
N CH3
O
(e) NH2
(NH4)2S reduces only one –NO2 group.
NO2
36.
+ N(CH 3)3
N N N N D
CH 3 H3C CH 3 H3C CH 3 H3C CH 3
CH 3
A B C
+ +
(C) (i) Br2 / Fe (ii) Mg/THF (iii) ;H (iv) PCC / CH2Cl 2 (v) NH3 / H (vi)
O
LiAlH4
39. O O
CH3 C N C CH3 is more resonance stabilised.
HNO
2
N-nitrosoamine
(yellow oil)
N(CH3)2 N(CH3)2
HNO
2
N O
FIITJEE 12
A) O 2N
41. (a) + +
N2 N2
CH O NO 2
B)
is more reactive than
NO 2
+
N2
O2N 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.
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 13