Assignment

Amines
1. What is the correct name for a molecule that has two amino groups in opposing
(para) locations around a benzene ring?
a) Benzenediamine
b) Benzene-1,4-diamine
c) p-Aminoaniline
d) 4-Aminobenzenamine
2. When acetamide is converted to methylamine, what is the name of the reaction?
a) Friedel-Craft’s reaction
b) Hofmann reaction
c) Hoffmann bromamide degradation reaction
d) Hinsberg reaction
3. For which of the following is the Hinsberg approach used?
a) Preparation of primary amines
b) Separation of amine mixtures
c) Preparation of tertiary amines
d) Preparation of secondary amines
4. Which of the following is the IUPAC name of the chemical in which an ethyl group
replaces one hydrogen of ammonia?
a) Ethanamine
b) Aminoethane
c) Ethylamine
d) Ethane amine
5. Which of the following statements concerning methylamine is correct?
a) Methylamine is stronger base than NH3
b) Methylamine is less basic than NH3
c) Methylamine is slightly acidic
d) Methylamine forms salts with alkali
6. Which of these substances has a lower melting point than amine?
a) Alcohol
b) Ether
c) Carboxylic acid
d) Phosphine

Directions: These questions consist of two statements, each printed as Assertion and Reason.
While answering these questions, you are required to choose any one of the following four
responses.
(a) If both Assertion and Reason are correct and the Reason is a correct explanation of the
Assertion.
(b) If both Assertion and Reason are correct but Reason is not a correct explanation of the
Assertion.
(c) If the Assertion is correct but Reason is incorrect.
(d) If both the Assertion and Reason are incorrect.

Q.1. Assertion : Aromatic 1°amines can be prepared by Gabriel phthalimide synthesis.

Reason : Aryl halides undergo nucleophilic substitution with anion formed by phthalimide
Q.2. Assertion : Only a small amount of HCl is required in the reduction of nitro compounds
with iron scrap and HCl in the presence of steam.
Reason : FeCl2 formed gets hydrolysed to release HCl during the reaction.
Q.3. Assertion : Amines are basic in nature.
Reason : Amines have lone pair of electrons on nitrogen atom.
Q.4. Assertion : Acetanilide is less basic than aniline.
Reason : Acetylation of aniline results in decrease of electron density on nitrogen.
Q.5. Assertion : Nitration of aniline can be conveniently done by protecting the amino group
by acetylation.
Reason : Acetylation increases the electron-density in the benzene ring.
Q.6. Assertion : Aniline does not undergo Friedel-Crafts reaction.
Reason : –NH2 group of aniline reacts with AlCl3 (Lewis acid) to give acid-base reaction
Q.7. Assertion : Acylation of amines gives a monosubstituted product whereas alkylation of
amines gives
poly-substituted product.
Reason : Acyl group sterically hinders the approach of further acyl groups.
Q.8. Assertion : Nitrating mixture used for carrying out nitration of benzene consists of
conc. HNO3+ conc. H2SO4
Reason : In presence of H2SO4, HNO3 acts as a base and produces NO2+ ions.
CASE-STUDY

Read the passage given below and answer the following questions:
Amines are alkyl or aryl derivatives of ammonia formed by replacement of one or more hydrogen atoms.
Alkyl derivatives are called aliphatic amines and aryl derivatives are known as aromatic amines. The
presence of aromatic amines can be identified by performing dye test. Aniline is the simplest example of
aromatic amine. It undergoes electrophilic substitution reactions in which - NH2 group strongly activates
the aromatic ring through delocalisation oflone pair of electrons of N-atom. Aniline undergoes
electrophilic substitution reactions. Ortho and para positions to the -NH2 group become centres of high
electrons density. Thus, -NH2 group is ortho and para-directing and powerful activating group. The
following questions are multiple choice questions.
Choose the most appropriate answer:
(i) Cyclohexylamine and aniline can be distinguished by

(a) Hinsberg test (b) carbylamine test (c) Lassaigne test (d) azo dye test
(ii) Which of the following compounds gives-dye test?
(a) Aniline (b) Methyl amine (c) Diphenyl amine (d) Ethyl amine
(iii) Oxidation of aniline with manganese dioxide and sulphuric acid produces
(a) phenylhydroxylamine (b) nitrobenzene (c) p-benzoquinone (d) phenol.
(iv) Aniline when treated with conc, HNO3 and H2SO4 gives
(a) phenylhydroxylamine (b) m-nitroaniline (c) p-benzoquinone (d) nitrobenzene.

1. Why is an alkylamine more basic than ammonia?

2. Arrange the following compounds in an increasing order of basic strengths in their
aqueous solutions : NH3, CH3NH2, (CH3)2NH, (CH3)3N
3. Give the IUPAC name of H2N — CH2—CH2—CH = CH2.
4. Arrange the following compounds in an increasing order of their solubility in water :
C6H5NH2, (C2H5)2NH, C2HSNH2
5. Give a chemical test to distinguish between ethylamine and aniline.
6. How may methyl bromide be preferentially converted to methyl isocyanide?
7. Arrange the following compounds in increasing order of solubility in water :
C6H5NH2, (C2H5)2NH, C2H5NH2
8. Arrange the following in increasing order of basic strength :
C6H5NH2, C6H5NHCH3, C6H5CH2NH2
9. The conversion of primary aromatic amines into diazonium salts is known as
10. Out of CH3—NH2 and (CH3)3N, which one has higher boiling point?
11. Give the chemical tests to distinguish between the following pairs of compounds :
(i) Ethyl amine and Aniline
(ii) Aniline and Benzylamine
12. Describe the following giving the relevant chemical equation in each case :
(i) Carbylamine reaction
(ii) Hofmann’s bromamide reaction
13. Complete the following reaction equations :
(i) C6H5N2Cl + H3PO2 + H2O →
(ii) C6H5NH2 + Br2 (aq) →
14. Give IUPAC names of the following compounds :

15. How are the following conversions carried out :

(a) Aniline to p-hydroxyazobenzene
(b) Ethanoyl chloride to Ethanenitrile.
16. How are the following conversions carried out?
(i) CH3CH2Cl to CH3CH2CH2NH2
(ii) Benzene to aniline
17. How would you account for the following :
(a) Aniline is a weaker base than cyclohexyl amine.
(b) Methylamine in aqueous medium gives reddish-brown precipitate with FeCl3.
18. How would you account for the following :
(a) Electrophilic susbstitution in case of aromatic amines takes place more readily
than benzene.
(b) Ethanamide is a weaker base than ethanamine.
19. Giving an example for each describe the following reactions :
(i) Hofmann’s bromamide reaction
(ii) Gatterman reaction
(iii) A coupling reaction
20. Complete the following reaction equations:

21. Complete the following reaction equations :

(i) C6H5Cl + CH3COCl →
(ii) C2H5NH2 + C6H5SO2Cl →
(iii) C2H5NH2 + HNO2 →
22. In the following cases rearrange the compounds as directed :
(i) In an increasing order of basic strength :
C6H5NH2, C6H5 N(CH3)2, (C2H5)2NH and CH3NH2
(ii) In a decreasing order of basic strength :
Aniline, p-nitroaniline and p-toluidine
(iii) In an increasing order of pKb values :
C2H5NH2, C6H5 NHCH3, (C2H5)2NH and C6H5NH2
23. Complete the following chemical equations :

24. State reasons for the following :

(i) pKb value for aniline is more than that for methylamine.
(ii) Ethylamine is soluble in water whereas aniline is not soluble in water.
(iii) Primary amines have higher boiling points than tertiary amines.
25. Write chemical equations for the following conversions :
(i) Nitrobenzene to benzoic acid.
(ii) Benzyl chloride to 2-phenylethanamine
(iii) Aniline to benzyl alcohol.
26. Give the structure of A, B and C in the following reactions:
27. Give the structure of A, B and C in the following reactions :

28. Give the structures of A, B and C in the following reactions : How will you convert the
following :
(i) Nitrobenzene into aniline
(ii) Ethanoic acid into methanamine
(iii) Aniline into N-phenylethanamide
29. Give the structures of A, B and C in the following reactions :

30. Account for the following :

(i) Primary amines (R-NH2) have higher boiling point than tertiary amines (R 3N).
(ii) Aniline does not undergo Friedel – Crafts reaction.
(iii) (CH3)2NH is more basic than (CH3)3N in an aqueous solution.
31. An aromatic compound ‘A’ on treatment with aqueous ammonia and heating forms
compound ‘B’ which on heating with Br 2 and KOH forms a compound ‘C’ of molecular
formula C6H7N. Write the structures and IUPAC names of compounds A, B and C.
32. Describe a method for the identification of primary, secondary and tertiary amines.
Also write chemical equations of the reaction involved.
33. Give reasons:
(i) Acetylation of aniline reduces its activation effect,
(ii) CH3NH2 is more basic than C6H5NH2.
(iii) Although —NH2 is o/p directing group, yet aniline on nitration gives a significant
amount of m-nitroaniline.
34. An aromatic compound ‘A’ of molecular formula C 7H7ON undergoes a series of
reactions as shown below. Write the structures of A, B, C, D and E in the following
reactions :

35. (a) Write the structures of main products when aniline reacts with the following
reagents :
(i) Br2 water (ii) HCI (iii) (CH3CO)2O/pyridine
(b) Arrange the following in the increasing order of their boiling point :
C2H5NH2, C2H5OH, (CH3)3N
(c) Give a simple chemical test to distinguish between the following pair of
compounds : (CH3)2NH and (CH3)3N
36. An aromatic compound ‘A’ of molecular formula C 7H6O2 undergoes a series of
reactions as shown below. Write the structures of A, B, C, D and E in the following
reactions :

37. (a) Write the structures of main products when benzene diazonium chloride reacts
with the following reagents :
(i) H3PO2 + H2O (ii) CuCN/KCN (iii) H2O
(b) Arrange the following in the increasing order of their basic character in an
aqueous solution :
C2H5NH2, (C2H5)2NH, (C3H5)3N
(c) Give a simple chemical test to distinguish between the following pair of
compounds :
C6H5—NH2 and C6H5—NH—CH3

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