LR DAV By: Dipak Kumar Parida

ORGANIC COMPOUNDS CONTAINING

NITROGEN(AMINES AND BDC)

Name:___________________________________
School:__________________________________________________________________________________________

Prepared by:
Dipak Kumar Parida
PGT, Chemistry, DAV

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LR DAV By: Dipak Kumar Parida

AMINES
i) The organic compounds obtained by replacing one, two or all three H-atoms of
ammonia by respective no of alkyl groups are called amines.
−H −H −H
NH3 ⎯⎯
+R
⎯→ R − NH2 ⎯⎯
+R
⎯→ R2NH ⎯⎯+R
⎯→ R3N
0
(1 amine) (2 amine) (30amine)
0

ii) Amines are classified into three types like

a. Primary or 10 amine
b. Secondary or 20 amine
c. Tertiary or 30 amine
iii) When one H-atom of ammonia is replaced by one alkyl group, it is called as
primary or 10 amine which has functional group –NH2.
Eg. CH3–NH2 CH3–CH2–CH2–NH2, C6H5NH2
Methyl amine n-propyl amine Aniline
iv) When two H-atoms of ammonia are replaced by two alkyl or aryl groups then it
is called as secondary or 20 amine which has functional group –NH-
Eg. CH3–NH–CH3 CH3–NH–C2H5 C6H5-NH-CH3
Dimethyl amine Ethyl methyl amine N-methyl aniline
v) When all the three H-atoms of ammonia are replace by three alkyl or aryl
groups then it is called as tertiary or 30 amine.
Eg. CH3 − N − CH3 CH3 − N − C2H3
| |
CH3 C3H7

Trimethyl amine Ethyl methyl n-propyl amine

Nomenclature:
Aliphatic amines have general formula of CnH2n+3N.
The IUPAC name for 10 amine is alkanamine.
The IUPAC name for 20 amine is N-Alkylalkanamine.
The IUPAC name for 30 amine is N,N–Dialkyl alkanamine
Eg. CH3 − CH |
− NH2 CH3–CH2–NH2
CH3

Propan-2-amine Ethanamine

CH3–NH–CH3
N–Methyl methanamine CH3–NH–C2H5 (N-Methylethanamine)
CH3– N| –CH3 N, N– Dimethylmethanamine
CH3

CH3– N| –CH3 N-Ethyl–N–Methylpropanamine

C 2H7

(Benzanilide)

C6H5-NH-COCH3 - N-Phenylthanamide(Acetanilide)

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LR DAV By: Dipak Kumar Parida

Isomerism :
Amines show four types of isomerism like 1. Chain Isomerism
2. Position Isomerism
3. Metamerism
4. Functional Isomerism
1. Chain Isomerism : The chain isomers are differ in the nature of carbon chain.
C4H11N
CH3–CH2–CH2–CH2–NH2 CH3 – CH|
–CH2–NH2
CH3

Butan –1–amine 2-Methylpropan-1–amine

2. Position isomerism
The isomers differ in the position of the same functional group.
C3H9N
CH3–CH3–CH2–NH2 CH3– N| –CH3
NH2

Propan–1–amine Propan-2-amine

3. Metamerism :
The isomers differ in the nature of alkyl groups around same functional group.
C4H11N :
C2H5–NH–C2H5, (diethyl amine) and CH3–NH–C3H7 (Methyl n –propyl amine)
4. Functional isomerism:
The isomers differ in the nature of functional group.
C3H9N :
CH3–CH2–CH2–NH2 CH3–NH–C2H5 CH3– N |
– CH3
CH3

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LR DAV By: Dipak Kumar Parida

Preparation of amines:
1. By Reduction of nitrocompounds:
Nitrocompounds on reduction with acidic medium like Sn & HCl or Fe
and HCl or Zn and HCl or by catalytic reduction(H2 in Pt/Pd/Ni)give
primary amines.
R–NO2 ⎯⎯⎯⎯
[H]
Sn&HCl
→ R–NH2+2H2O

Eg. i) C2H5–NO2 ⎯⎯⎯⎯

[H]
Sn&HCl
→ C2H5–NH2+2H2O

ii)
NOTE: Fe and HCl is more preferred as FeCl2 formed gets hydrolysed to form
HCl by which only small amount of HCl is required for the reduction process.
2. By reduction of alkyl cyanides(Mendius reaction)
Alkyl cyanides on reduction with LiAlH4 or H2 & Ni or Na and C2H5OH give
primary amines.
R–C  N+4[H] ⎯⎯⎯
LiAlH4
→ R–CH2–NH2
Eg. i) CH3–C  N+4[H] ⎯⎯⎯
LiAlH4
→ CH3–CH2–NH2
ii) CH3–CH2–C  N+4[H] ⎯⎯⎯
LiAlH4
→ CH3–CH2–CH2–NH2
Ethyl cyanide n-propyl amine
iii)

3. By reduction of acid amides: Acid amides on reduction with LiAlH4 give

primary amines.
O
||
R − C− NH2 + 4[H] ⎯⎯⎯
LiAlH4
→ R − CH2 − NH2 + H2O
O
||
Eg. i) CH3 − C− NH2 + 4[H] ⎯⎯⎯
LiAlH4
→ CH3 − CH2 − NH2 + H2O
O
||
ii) C6H5 − C− NH2 + 4[H] ⎯⎯⎯
LiAlH4
→ C6H5 − CH2 − NH2 + H2O
(Benzamide) (Benzyl amine)
4. By Hoffman Ammonolysis of alkyl halides:

Alkyl halides when heated with alcoholic solution of ammonia at 100 0C then a mixture of

amines along with quaternary ammonium salt are formed. This is a nucleophilic substitution

reaction.
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+
 R

→ R − N− R 

Alcohol, 1000 C R− X
R − X + H − NH2 ⎯⎯⎯⎯⎯→ R − NH2 ⎯⎯⎯
→ R2NH ⎯⎯⎯
|
R− X R− X −
−HX
− HX
→ R3N ⎯⎯⎯−HX
 x
|

 R 


+
 CH3


→ CH3 − N − CH3 ⎯⎯⎯→ CH3 − N − CH3  I−
|
CH3 −I
Ex: CH3 − I + H − NH2 ⎯⎯⎯→ CH3 − NH2 ⎯⎯⎯→ CH3 − NH − CH3 ⎯⎯⎯
1000 C
−HI −HI
CH3 −I CH3 −I
−HI | |
CH3  CH3 

NOTE: This is not a suitable method for preparation of primary amines as a mixture of 10, 20,

30 amines along with quaternary ammonium salt is formed which need separation.

5. By reduction of alkyl isocyanide:

Reagent: H2/Ni or LiAlH4 or Na/C2H5OH
R − NC ⎯⎯⎯
[H ]
LiAlH 4
→ R − NH − CH 3

Ex: CH 3 − CH 2 − NC ⎯⎯⎯
[H ]
LiAlH 4
→ CH 3 − CH 2 − NH − CH3

6. By Hoffman Bromamide(degradation) reaction: Acid amides when heated

with bromine and caustic soda (NaOH) or caustic potash (KOH) solution
form primary amines containing one carbon atom less.
So this reaction is used for reducing carbon atoms from a compound i.e.
in step down conversion.
O
||
R - C- NH2 + Br2 + 4NaOH ¾ D¾® R - NH2 + Na2CO3 + 2NaBr + 2H2O

Acid amide 10 amine

O
||
Eg. i) CH3 - C- NH2 + Br2 + 4NaOH ¾ D¾® CH3 - NH2 + Na2CO3 + 2NaBr + 2H2O
O
||
ii) C2H5 - C- NH2 + Br2 + 4NaOH ¾ D¾® C2H5 - NH2 + Na2CO3 + 2NaBr + 2H2O

iii)

Mechanism: The intermediate compounds are bromamide, Nitrene, alkyl isocyanate

and carbamic acid.

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LR DAV By: Dipak Kumar Parida

In this reaction, migration of alkyl or aryl group takes place from carbonyl carbon to
the nitrogen atom.

6. By Gabriel phthalimide reaction:

Phthalimide when treated with alcoholic KOH then potassium phthalimide is formed
which on heating with alkyl halide gives N-alkyl phthalimide. The N-alkyl phthalimide on
acidic or alkaline hydrolysis gives primary amines.

Note:
a. Aromatic primary amine like Aniline can’t be prepared by Gabriel phthalimide
synthesis because aryl halide prevent nucleophilic substitution reaction i.e. the
nucleophile phthalimide ion can’t attack the haloarene.
b. This method is preferred for synthesis of primary amine as secondary and tertiary
amines are not prepared by this method by which there is no need of separation.
c. The phthalic acid so formed can again be used to convert into phthalimide.
PQ:
1. Write all the structural isomers of amines corresponding to molecular formula C 4H11N.
2. Convert:
a)Ethyl chloride to Propanamine
b)Benzyl chloride to 2-phenylethanamine
c)Benzene to aniline
d)Benzene to N,N-dimethylaniline
e) Acetic acid to methyl amine
e)1,4-Dichlorobutane to hexane-1,6-diamine
f)Benzoic acid to aniline

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LR DAV By: Dipak Kumar Parida

g)Ethanol to ethylmethyl amine

h) Methanol to ethanoic acid
3. What happens when:
a) Benzamide heated with Br2 and KOH
b) Phthalic acid heated with NH3 followed by strong heating
c) Ethyl Cyanide treated with H2 in Ni
d) Phenyl cyanide is reduced with LiAlH4
4. Write IUPAC name of
a) (CH3 )3 C − CH 2 − NH 2 b) (C2 H 5 )2 NH c) C6 H 5 N (CH 3 )2 d) CH3 − NHCH (CH 3 )2
5. An organic compound A upon reacting with NH3 gives B. On heating, B gives C. C in
the presence of KOH with Br2 to give CH3CH2NH2. Write the structure of A.
6. Which of the following reagent would not be a good choice for reducing an aryl nitro compound to an
amine?
a)H2(excess)/Pt b) LiAlH4 in ether c)Fe and HCl d)Sn and HCl
7. 10
In order to pepare amine from an alkyl halide with simultaneous ddition of one CH2 group in the
carbon chain, the reagent used as a source of nitrogen is:
a)NaNH2 b)NaNO2 c)KCN d)C6H4(CO)2N-K+
8. The source of nitrogen in Gabriel synthesis of amines is:
a)NaNH2 b)NaNO2 c)KCN d)C6H4(CO)2N-K+
9. The correct IUPAC name for CH2=CHCH2-N-CH3 is:
a)Allylmethyl amine b)2-Amino-4-pentene c)4-Aminopent-1-ene d)N-Methylprop-2-en-1-amine
10. Which of the following reactions will not give primary amine as the product?

a) CH 3CONH 2 ⎯⎯⎯
LIAlH 4
H O+
→ b) CH 3CONH 2 ⎯⎯⎯⎯
Br2 / KOH
→
3

c) CH 3CN ⎯⎯⎯
LIAlH 4
H O+
→ d) CH 3 NC ⎯⎯⎯
LIAlH 4
H O+
→
3 3

Physical properties:
1. Solubility:
i) Lower members are soluble in water as they form intermolecular hydrogen
bonding with water molecules.
ii) The solubility decreases with increase in size of alkyl group which make
hindrance in formation of H-bonding.
iii) Aromatic amines are very less soluble or insoluble in water due to bulkier
phenyl group which tends to retard the formation of H-bonding.
CH3NH2 > C2H5CH2 > C3H7NH2 > C6H5NH2
iv) Among different isomeric amines the solubility decreases in the order
10 amine > 20 amine > 30 amine, due to decrease in tendency of formation of H-
bonding.
Ex: (C2H5)2NH < C2H5NH2
2. Physical state: Lower members like methyl amine, dimethyl amine, ethyl amine
are gases at room temperature. Higher members are liquids.

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3. Boiling point:
i) Amines have higher boiling point than non polar molecular like alkanes but
lower boiling point than alcohols or carboxylic acids of comparable
molecular masses. In amines there exists intermolecular H-bonding which is
stronger than van der waals force of attraction exist in alkanes. So amines
have higher boiling point than alkanes.
ii) But the O-H bond exists in alcohols and carboxylic acids are more polar than
N-H bond of amines due to higher electronegativity of oxygen. So the H-
bond of alcohols and monocarboxylic acids are stronger than amines. So
alcohols and acids have higher boiling point than amine.
Hence, C2H6 < C2H5NH2 < C2H5OH < CH3COOH.
iii) Among isomeric amines, the B.P. follows the order
30 amine < 20 amine< 10 amine
This is because in 10 amine the extent of hydrogen bonding is highest as 3 H-
atoms are attached to nitrogen.
Ex: Trimethylamine < Ethylmethylamine < propan-1-amine
B.P. = 2.90C 360C 47.80C
Chemical properties:
1. Basic nature of amines:
i) Like ammonia, amines are also basic in nature which is due to presence of lone
pair of electron at nitrogen atom.
R–NH2+H2O → RNH3+ + OH−
The dissociation constant of the base is given as
[RNH3+ ] OH− 
Kb = , pKb = –log Kb
R − NH2 
Stronger bases have higher value of Kb but lower value of Pkb.
ii) All the aliphatic amines are stronger base than ammonia. This is due to the + I
effect of alkyl groups. The alkyl groups donate electrons towards the -N atom
and increase the availability of lone pair of electrons at N-atom. This increases
the basic strength of amines.
iii) Again the basic strength increases with the increase in number of alkyl groups.
So the expected basic strength of different amines is
30 amine > 20 amine > 10 amine
But the above order is only true in gaseous phase or in non-aqueous solvent.
iv) In the aqueous solution 20 amines are more basic than 10 and 30 amine. This is
due to a steric effect and solvation effect. In the aqueous solution, amines
accept proton to convert into ammonium cation. The ammonium cations are
stable due to formation of intermolecular hydrogen bonding with water
molecules. The ammonium cation of 10 amine is most stable because it has 3
H-atoms to form hydrogen bonds, while 30 ammonium cation is least stable as
it has only 1 H-atom to form H-bond. Again in 30 amine due to three bulky alkyl
groups, the steric hindrance is maximum. So it is least basic. So according to

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LR DAV By: Dipak Kumar Parida

the combined effect of inductive effect, H-bonding and steric factors, 20 amine
is most basic .

v) In methyl amines, the stability due to H-bonding predominates over the stability
due to inductive effect. So for -CH3 group 10 amine is a stronger base than 30
amines.
i.e. (CH3)2NH>CH3NH2>(CH3)3N i.e. 20 amine > 10 amine > 30 amine
vi) But if the alkyl groups are bigger than CH3 gr, due to steric hindrance the
stability due to +I effect predominates over the stability due to H-bonding. So
for higher alkyl groups, 30 amine is a stronger base than 10 amine.
i.e. (C2H5)2NH>(C2H5)3N>C2H5–NH2, 20 amine > 30 amine > 10 amine for C2H5
and higher alkyl group.
vii) Aniline is a weaker base than aliphatic amines as well as ammonia due to
resonance and less stability of anilinium ion.

Due to resonance the electron density at nitrogen atom of aniline decreases by which the
basic strength decrease.
So, C6H5NH2 < NH3 < C2H5NH2
viii) When the hydrogen atom of the amino group in aniline is replaced by electron
donating alkyl group then the basic strength increases. This is due to +I effect
of the alkyl group.
Ex : NH3 > C6H5N(CH3)2 > C6H5NH-CH3 > C6H5NH2
ix) When the hydrogen atom of the amino group in aniline is replaced by electron
withdrawing phenyl group then the basic strength decreases. This is due to -R
effect of the aryl group.
Ex : (C6H5)3N < (C6H5)2NH < C6H5NH2 < NH3
x) The aralkyl amines are stronger base than aniline due to absence of resonance
the lone pair of electron of N atom is more available for protonation than
aniline. So, C6H5NH2 < C6H5CH2NH2
xi) The aralkyl amines are stronger base than ammonia but weaker base than
aliphatic amine due to weaker +I effect of benzyl group.
So, C6H5NH2 < NH3 < C6H5CH2NH2 < CH3 NH2
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xii) The EWG like –NO2, -CN, -X etc decreases the basic strength of aniline as
thety decrease the electron density at N atom while EDG like –R, -OR/ etc
increases the basic strength of aniline as they increase the electron density at
N atom.
xiii) The ortho substituted aniline is always a weaker base than aniline and other
substituted aniline due to electronic effect and streic effect which is called ortho
effect.

xiv) The basic strength decreases with increase in EN of the carbon atom attached to
nitrogen atom.

PQ:
11. Arrange the following in the increasing order of basic strength:
i) C6H5NH2, C2H5NH2, (C2H5)2NH, NH3.
ii) C2H5NH2, C6H5NH2, NH3, C6H5CH2NH2, (C2H5)2NH
iii) CH3NH2, (CH3)2NH, (CH3)3N, C6H5NH2, C6H5CH2NH2
iv) C2H5NH2, (C2H5)2NH, (C2H5)3N, C6H5NH2

v)

vi)

vii)
12. Arrange the following in the increasing order of B.P.:
i) n-C4H9NH2, (C2H5)2NH, C2H5N(CH3)2
ii) n- C4H9OH, C2H5CH(CH3)2, n-C4H9NH2
iii) CH3NH2, C2H5NH2, C6H5NH2
13. Which is most basic? a) C6H5NH2 b) (C6H5)2NH c) CH3NH2 d) (CH3)2NH

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2. Reaction with HCl:

As amines are basic in nature so they react with HCl to form salts.
CH3–NH2+HCl → [CH3NH3]+Cl–
C6H5–NH2+HCl → [C6H5NH3]+Cl–
(Aniline) (Anilinium chloride)
3.Reaction with alkyl halide (alkylation):
Primary amines react with alkyl halide to form first secondary amine, then
tertiary amine and finally quaternary ammonium salt.
R− X R− X
R–NH2+X–R ⎯⎯⎯
−HX
→ R2NH ⎯⎯⎯
−HX
→ R3N ⎯⎯⎯ →[R 4N]+ X −
10 amine 20 amine 30 amine Quaternary salt
CH3 −I
Eg. i) CH3–NH2+CH3–I ⎯⎯⎯
−HI
→(CH3 )2 NH ⎯⎯⎯
−HI
→(CH3 )3 N ⎯⎯⎯
CH3I
→[(CH3 )4 N]+ I−
ii)

4.Reaction with acid chloride: (Acylation)

The introduction of acyl group (RCO-) in reactant is called acylation reaction.
a. Primary amines react with acid chloride or acid anhydride to form N-alkyl acid amides.
O O
|| ||
Ex: C2H5 − NH H + Cl − C− CH3 ⎯⎯
→ C2H5 − NH − C− CH3 + HCl
Ethyl amine Acetyl chloride N-Ethyl acetamide

b. Secondary amines react with acid chloride to form N, N-Dialkyl acid amides.
O O
|| ||
CH3 − N − H + Cl − C− CH3 ⎯⎯
→ CH3 − N − C− CH3 + HCl
| |
CH3 CH3

Tertiary amines don’t react with acid chloride as they don’t have replaceable hydrogen
atom attached to N-atom.
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5.Carbylamine reaction:
Primary amines when heated with chloroform and alcoholic KOH solution then alkyl
isocyanides or alkyl carbylamines are formed which have very unpleasant smell. This is
called carbylamine reaction.

R–NH2+CHCl3+3KOH(alc) ⎯⎯ → R–NC+3KCl–BH2O

Eg. i) CH3–NH2+CHCl3+3KOH(alc) ⎯⎯ → CH3–NC+3KCl+3H2O

ii). C2H5–NH2+CHCl3+3KOH(alc) ⎯⎯ → C2H2–NC+3KCl+3H2O

iii)
But secondary and tertiary amines don’t respond to carbylamine reaction. So this
reaction is used to distinguish primary amine from secondary and tertiary amine.
14. Reaction with nitrous acid :
a) Aliphatic primary amines react with nitrous acid to form alcohols and evolve
N2 gas. As nitrous acid is unstable so it is prepared from NaNO2 and HCl.
R–NH2+HNO2 ⎯⎯
→ R–OH+N2+H2O
Eg. i) CH3–NH2+HNO2 ⎯⎯
→ CH3–OH+N2+H2O
ii) C2H5–NH2+HNO2 ⎯⎯
→ C2H5–OH+N2+H2O
Aromatic primary amines like aniline react with HNO2 at ice cold temp. to form benzene
diazonium chloride.

So nitrous acid can be used to distinguish between aliphatic and aromatic primary amine.
b) Both aliphatic and aromatic secondary amines react with nitrous acid to
form nitrosoamine which is an yellow oily liquid.
Eg. CH3– N –H+H–O–N=0 ⎯⎯
→ CH3– N –N=O+H2O
| |
CH3 CH3

Dimethyl amine N, N–Dimethyl nitrosoamine

The nitrosoamines on warming with phenol and few drops of conc. H2SO4 form a green
solution which turns blue on adding NaOH and then red on dilution. This test is called
Liberman’s nitroso reaction and is used to distinguish secondary amines from primary and
tertiary amines.

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c) Aliphatic tertiary amines react with nitrous acid to form nitrite salt soluble in
water.
R3N+HNO2 ⎯⎯
→ [R3NH]+NO2-
Eg. i) (CH3)3N+HNO2 ⎯⎯
→ [(CH3)3NH]+NO2–
Aromatic 30 amines like substituted aniline reacts with tertiary amine to form p-
nitroso aniline

N,N dimethyl aniline reacts with HNO2 to form p-nitroso-N,N-dimethyl aniline.

So HNO2 can be used to distinguish between primary, secondary and tertiary
amine.
7.Reaction with Hinsberg’s reagents:
Benzene sulphonyl chloride is known as Hinsberg reagent.
i) Primary amines react with Benzene sulphonyl chloride to form N-alkyl benzene
sulphonamide which is soluble in KOH.

ii) Secondary amines react with benzene sulphonyl chloride to form N, N–Dialkyl
benzene sulphonamide which is insoluble in KOH.

iii) Tertiary amines don’t react with benzene sulphonyl chloride.

Note
i) Hinsberg reagent is used to distinguish between 10, 20 and 30 amine.
ii) Hinsberg method is also used for the separation of three different types of
amines.
8. Reaction with aldehydes:
Primary amines react with aldehydes to form Schiff’s base.
R–CH=O+H2N–R ⎯⎯
→ R–CH=N–R+H2O
Aldehyde Schiff’s base
Eg. CH3–CH=O + H2N–C2H5 ⎯⎯
→ CH3–CH=N–C2H5+H2O

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10. Electrophilic substitution reaction:

As –NH2 is a strongly activating group due to its +R effect so anline is highly reactive towards
electrophiles than benzene. –NH2 is o- and p-directing substituent.
a. Halogenation: aniline reacts with Br2 water to form 2,4,6 tribromoaniline.

In order to get monobromo aniline it is 1st protected by acylation reaction and then
undergoes bromination. The acetanilide again on hydrolysis gives the aniline.

b.Nitration: Aniline on nitration gives a mixture of o-, p- and m-nitro aniline. The m-nitro
aniline is because some aniline molecule undergo protonation to form anilinium ion where
the –NH3+ gr is meta directing substituent.

To get p-nitro aniline, it is 1st protected by acylation reaction and then undergo nitration.

c.Sulphonation: Aniline reacts with conc. H2SO4 to form p-amino benzene sulphonic acid.

d.Friedel-Craft reaction: Aniline doesn’t undergo Friedel-Craft reaction because as it is

basic in nature it reacts with AlCl3 which is an Lewis acid and is the catalyst of the reaction to
form a salt where the substituent acts as a strong deactivating substituent.

Examples: Do the Conversion:

1) Methyl amine ⎯⎯
→ Ethyl amine
CH3–NH2 ⎯⎯⎯
HNO2
→ CH3 -OH ⎯⎯⎯
PCl3
→ CH3-Cl ⎯⎯⎯⎯
alc.KCN
→ CH3-CN ⎯⎯⎯[H]
LiAlH4
→ CH3-CH2-NH2

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2) Ethyl amine ⎯⎯
→ Methyl amine
CH3-CH2-NH2 ⎯⎯⎯
HNO2
→ CH3 –CH2-OH ⎯⎯⎯⎯⎯⎯ [O]
K 2Cr2O7 /H2SO4
→ CH3COOH ⎯⎯⎯
NH3

→
Br2 +NaOH
CH3CONH2 ⎯⎯⎯⎯→ CH3-NH2
3) 4-Nitrotoluene to 2- bromo benzoic acid

4) 3- Methyl aniline to 3-nitrotoluene

5) Aniline to 1,3,5-tribromobenzene

6) Benzene to m-bromophenol

7) Nitrobenzene to benzoic acid

8) p-Nitroaniline to 3,4,5-Tribromobenzene

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9) Benzamide to toluene

10) Aniline to benzyl alcohol

PQ:
15. Assertion(A): Acylation of amines gives a monosubstituted product whereas alkylation
of amines gives polysubstituted product.
Reason(R ): Acyl group sterically hinders the approach of further acyl groups.
16. Assertion(A): Hoffmann’s bromamide reaction is given by primary amines.
Reason(R ): Secondary amine is stronger base than primary amine.
17. Assertion(A): N,N-diethylbenzene sulphonamide is insoluble in alkali.
Reason(R ): Sulphonyl group attached to nitrogen atom is strong electron
withdrawing group.
18. What happens when?
a) Aniline reacts with benzoyl chloride.
b) Aniline reacts with excess of methyl iodide.
c) Aniline reacts with CHCl3in alc. KOH
d) Aniline reacts with Benzene sulphonyl chloride
e) Aniline reacts with Br2 in CCl4
f) Aniline reacts with conc. H2SO4 followed by heating.
Benzene Diazonium Chloride(BDC)
Aromatic diazonium salt is stable due to resonance the C-N bond acquirs partial double bond
character and again the phenyl carbocation is unstable.

But aliphatic diazonium salt is unstable and it is converted into alcohol by hydrolysis.
R-N2+ ⎯⎯
→ R+ + N2, R+ + H-OH ⎯⎯
→ R-OH + H+
Preparation of BDC by Diazo reaction(Diazotisation):
Aniline reacts with HNO2 and HCl at ice cold temperature to give BDC.
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Mechanism:

Synthetic application of BDC:

1. Synthesis of benzene: BDC reacts with hypophosphorous acid solution or ethanol to
form benzene.
Or, C6H5N2Cl + H3PO2 + H2O ⎯⎯
→ C6H6 + H3PO3 + N2 + HCl
C6H5N2Cl + CH3CH2OH ⎯⎯
→ C6H6 + CH3CHO + N2 + HCl
2. Synthesis of phenol: BDC warm with dil. acid to form phenol.
+
C6H5N2Cl + H2O ⎯⎯⎯
H
Warm
→ C6H5-OH + N2 + HCl

3. Sandmeyer reaction: This reaction is used to synthesize chloro benzene, bromo

benzene and cyano benzene from BDC.
BDC when treated with CuCl in HCl or CuBr ib HBr or CUCN in KCN the chloro
benzene or bromo benzene and cyano benzene are formed respectively.

Mechanism:

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Gatterman Reaction: BDC when treated with Cu in HCl or Cu in HBr then chloro benzene or
bromo benzene are formed respectively.

4. Synthesis of Iodobenzene: BDC when heated with KI then iodobenzene is formed.

KI , 
C6H5N2Cl ⎯⎯⎯ → C6 H 5 − I + N2 +KCl
5. Synthesis of Fluorobenzene: BDC when treated with Fluoroboric acid followed
byheating then fluorobenzene is formed.

6. Synthesis of Nitrobenzene: BDC when treated with Fluoroboric acid followed by

heating with NaNO2 and Cu then nitrobenzene is formed.

7. Coupling reaction(Azo dye test): BDC react with phenol in alkaline medium to form
orange colour p-hydroxy azo benzene. BDC reacts with aniline in acidic medium to
form p-amino azobenzene which has yellow colour.

Mechanism: It is electrophilic substitution reaction.

BDC

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PQ:
19. Do the following conversions:
a) Nitrobenzene to acetanilide
b) Acetanilide to p-nitroaniline
c) Aniline to nitrobenzene
d) Propane nitrile to ethanol
e) Benzene-p-nitroaniline
f) Aniline to m-bromonitrobenzene
g) Aniline to 3,5-dibromonitrobenzene
h) Aniline to 3,5-dibromo-4-iodonitrobenzene
i) Toluene to p-toluidine
j) p-Toluidine diazonium chloride to p-toluic acid
20. Complete the following reactions:
i) C6H5NH2 + C6H5COCl ⎯⎯
→
ii) C2H5NH2 + C6H5SO2Cl ⎯⎯
→
iii) (C2H5)NH+ HNO2 ⎯⎯
→
iv) C6H5NH2+ HCl(aq) ⎯⎯
→
O
||
v) C6 H5 − C − NH 2 ⎯⎯⎯
LiAlH 4
H 2O
→

vi) C6H5 NH2 + Br2(aq) ⎯⎯

→

vii)
21. The gas evolved when methyl amine reacts with nitrous acid is:
a)NH3 b)N2 c)H2 d)C2H6
22. Which of the following compound will not undergo azo coupling reaction with benzene
diazonium chloride.
a)Aniline b)Phenol c)Anisole d)Nitrobenzene
23. Which of the following reagent is used to convert benzene diazonium chloride into
benzene?
a) CH3OH b) H3PO2 c) Br2-H2O d) LiAlH4

***********************************xxxxx*****************************

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ASSIGNMENT, Amines and BDC(Chapt.No-9)

1. Write chemical equations for the following conversions
i) Aniline to benzyl alcohol
ii) Phenol to aniline
iii) Aniline to benzonitrile
iv) Nitro benzene to phenol
v) Aniline to chloro benzene
vi) Ethanamine to ethanoic acid
vii) Methanamine to iodomethane
viii) Nitromethane to dimethylamine
ix) Chlorobenzene to para chloroaniline.
x) Aniline to N-phenyl ethanamide
xi) n-Hexane nitrile to 1-aminopentane
xii) Aniline to benzoic acid
xiii) P-chloroaniline to para chlorobenzyl amine
xiv) Aniline to 2,4,6-trobromofluorobenzene
xv) Aniline to p-bromoaniline
2. Illustrate the following reactions giving a chemical equation in each case:
i) Gabriel phthalimide synthesis
ii) Coupling reaction(Azo dye test)
iii) Hoffmann’s bromamide reaction.
iv) Carbylamine reaction
v) Acetylation
vi) Diazo reaction
vii) Gattermann reaction
viii) Sandmayer reaction
ix) Hoffmann ammonolysis
3. Complete the following chemical equations:
OH −
i) C6H5N2Cl + C6H5NH2 ⎯⎯⎯
→
ii) C6H5N2Cl + CH3CH2OH ⎯⎯
→
iii) RNH2 + CHCl3 +KOH ⎯⎯
→
iv) C6H5N2Cl + H3PO2 + H2O ⎯⎯
→
v) C6H5NH2 + Conc. H2SO4 ⎯⎯
→
vi) C6H5NH2 + (CH3CO)2O ⎯⎯
→
C6H5N2Cl ⎯⎯→
KI
vii)

viii) C6H5N2Cl ⎯⎯⎯⎯⎯ i ) HBF4

ii ) NaNO2 ,Cu , 
→
4. Give one chemical test each to distinguish between the compounds in the following pairs:
i) Methyl amine and dimethyl amine
ii) Aniline and benzyl amine

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iii) Ethylamine and aniline

iv) Aniline and N-Methylaniline
5. Write structures and IUPAC names of
i) The amide which gives propanamine by Hoffmann bromamide reaction
ii) The amine produced by the Hoffmann degradation of benzamide
6. Account for the following:
i) Diazonium salts of aromatic amines are more stable than those of the aliphatic amines
ii) Ethyl amine is soluble in water but aniline is almost insoluble.
iii) Tertiary amines doesn’t undergo acylation reaction.
iv) Aniline readily reacts with bromine water to give 2,4,6 tri bromo aniline
Or Electrophillic substitution in case of aromatic amines takes place more rapidly than in benzene.
v) Aniline doesn’t undergo Friedel Crafts reaction
vi) Aromatic primary amines(Aniline) can’t be prepared by Gabriel Phthalimide synthesis.
vii) Gabriel phthalimide synthesis is preferred for synthesis of primary amines.
viii) Hoffman Ammonolysis is not a suitable method for preparation of primary
amines.
ix) Fe and HCl is more preferable for reduction of nitro compounds to form primary
amines.
x) Although amino group is o- and p- directing in aromatic electrophilic substitution
reactions, aniline on nitration gives a substantial amount of m-nitroaniline.
xi) Pkb of aniline is more than that of methyl amine. Or Methyl amine is more basic than aniline
Aliphatic amines are stronger bases than aromatic amines.
xii) Aqueous solution of methyl amine reacts with iron(III) chloride to precipitate iron(III) hydroxide.
xiii) The boiling point of amines are lower than those of corresponding alcohols.
xiv) Before reacting aniline with HNO3 for nitration it is converted to acetanilide
xv) CH3CONH2 is a weaker base than CH3CH2NH2.
amines are more basic than comparable alcohols.
xvi) Amines are less acidic than alcohols of comparable molecular mass.
xvii) Amines are more basic than alcohols of comparable molecular masses.
xviii) Reactivity of –NH2 group gets reduced in acetanilide
Or acetylation of aniline reduces its activation effect.
Or Acetanilide is less reactive than aniline towards electrophiles
xix) Primary amines have higher boiling point than tertiary amines.
xx) Aniline soluble in aq. HCl
xxi) Benzene diazonium chloride is not stored and is used immediately after its preparation.
xxii) (CH3)2NH is more basic than (CH3)3N in aq. Solution.
xxiii) Acylation of aniline is carried out in the presence of pyridine.
xxiv) Aniline cannot be prepared by ammonolysis of chlorobenzene under normal condition.
xxv) N-alkylbenzene sulphonamide is soluble in alkali but N,N-dialkylbenzenesulphonamide is
insoluble in alkali.
7. Arrange the following substances
C6H5NH2, (C2H5)2NH, (C2H5)3N, C2H5NH2

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i) In an increasing order of basic strength in water

ii) In a decreasing order of basic strength in gas phase.
8. Write the structure of
i) N-methylethanamine
ii) 2-Aminotoluene
iii) Prop-2-en-1amine
9. Write the IUPAC name of:
i) C6H5N+(CH3)3Br-

ii) CH3 − NH − CH 2 − CH ( NO2 ) − CH 3

iii) C6H5-NH-CO-CH3
10. Why How is the basic strength of aromatic amines affected by the presence of electron releasing group
and electron donating group on the benzene ring?
11. Describe a method for the identification of primary, secondary and tertiary amines. Also write chemical
equations of the reaction involved.
12. Arrange the following in increasing order of basic strength:
i) C6H5NH2, C6H5N(CH3)2, (C2H5)NH, CH3NH2
ii) Aniline, p-nitroaniline and p-toluidine
13. Explain the observed Kb order
Et2NH, Et3N,EtNH2 in aqueous solution
14. Give the structure of A, B, C in the following reactions:
−
NaOH + Br2
i) CH3CH2I ⎯⎯⎯
NaCN
→ A ⎯⎯⎯⎯⎯⎯
OH , Partial hydro.
→ B ⎯⎯⎯⎯ →C
H O/ H + NH ,
C6H5N2Cl ⎯⎯⎯
→ A ⎯⎯⎯⎯
→ B ⎯⎯⎯ →C
CuCN
ii) 2 3

Fe+ HCl NaNO + HCl H O/ H +

iii) C6H5NO2 ⎯⎯⎯→ A ⎯⎯⎯⎯
2
⎯
→ B ⎯⎯⎯⎯
2
→C
Br + KOH
C6H5COOH ⎯⎯⎯ → A ⎯⎯⎯
→ B ⎯⎯⎯⎯
→C
3 NH 2 Heat
iv)
15. What is Hinsberg reagent?
16. Arrange the following compounds in increasing order of dipole moment:
CH3CH2CH3, CH3CH2NH2, CH3CH2OH
17. A compound Z with molecular formula C3H9N reacts with C6H5SO2Cl to give a solid, insoluble in alkali.
Identify Z.
18. Arrange the following:
i) C2H5NH2, C6H5NHCH3, (C2H5)2NH, C6H5NH2( In decr. Order of PKb value)
ii) C6H5NH2, (C2H5)2NH, C2H5NH2 ( Increasing order of solubility)
iii) C2H5OH, (CH3)2NH, C2H5NH2 ( In. order of B.P.)
19. An amide A with molecular formula C7H7ON undergoes Hoffmann Bromamide degradation reaction to
give amine B. B on treatment with nitrous acid at 273-278Kform C and on treatment with Chloroform
and ethanolic KOH forms D. C on treatment with ethanol gives E. Identify A, B, C, D and E and write
the sequence of chemical equations.
20. A hydrocarbon A(C4H8) on reaction with HCl gives a compound B(C4H(Cl), which on reaction with 1
mol of NH3 gives compound C(C4H11N). on reacting with NaNO2 and HCl followed by treatment with
water, compound C yields an optically active alcohol D. Ozonolysis of A gives 2 moles of acetaldehyde.
Identify compound A to D. Explain the reactions involved.
21. A colourless substance A(C6H7N) is sparingly soluble in water and gives a water soluble compound B
on reacting with mineral acid. On reacting with CHCl3 and alc. Potash A produces an obnoxious smell
due to the formation of compound C. Reaction of A with benzenesulphonyl chloride gives compound D
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which is soluble in alkali. With NaNO2 and HCl A forms compound E which reacts with phenol in
alkaline medium to give an orange dye F. Identify compounds A to F.
22. A compound X with molecular formula C3H9N reacts with C6H5SO2Cl to give a solid, insoluble in
alkali. Identify X and give the IUPAC name of the product. Write the reaction involved.

MCQ

1. Ethylamine reacts with nitrous acid to form :

a) methyl alcohol b) ethyl alcohol c) ethane d) ethyl nitrite
2. The reaction between primary amine, chloroform and few drops of alcoholic KOH is known as:
a) Hofmann’s reaction b) Kolbe’s reaction
c) Carbylamine reaction d) Reimer-Tiemann’s reaction
3. Gabriel phthalimide synthesis is used in the preparation of:
a) 10 amine b) 20 amine c) 30 amine d) 40 amine
4. The strongest base among the following is:
a) C6H5NH2 b) CH3NH2 c) (CH3)2 NH d) (CH3)3 N
5. The correct order of basic nature of CH3NH2, (CH3)2 NH, (CH3)3 N and NH3 is:
a) CH3NH2 > (CH3)2 NH > (CH3)3 N> NH3 b) (CH3)3 N > (CH3)2 NH > CH3NH2 > NH3
c) (CH3)2 NH > CH3NH2 > (CH3)2 N > NH3 d) NH3 > (CH3)3 N > CH3NH2 > (CH3)2 NH
6. When acetamide reacts with Br2 and caustic soda, then we get:
a) acetic acid b) bromoacetic acid c) ethylamine d) CH3NH2
7. Which one of the following on reduction with LiAIH4 yields a secondary amine ?
a) Methyl cyanide b) Nitroethane c) Methyl isocyanide d) Acetamide
8. How many primary amines are possible for the formula C4H11N ?
a) 5 b) 6 c) 3 d) 4
9. During acetylation of amines, what is replacd by acetyl group ?
a) Hydrogen atom attached to nitrogen atom
b) One or more hydrogen atoms attached to nitrogen atom
c) One or more hydrogen atoms attached to carbon atom
d) Hydrogen atoms attached to either carbon atom or nitrogen atom
10. Which one of the following is called a carbylamines ?
a) RNC b) RCONH2 c) RCN d) RCH = NH
11. The correct order basicities of the following compounds is:

a) 2 > 1 > 3 > 4 b) 1 > 3 > 2 > 4 c) 3 > 1 > 2 > 4 d) 1 > 2 > 3 > 4
12. Ethyl isocyanide on hydrolysis in acidic medium gives:
a) ethanoic acid and ammonium salt b) propanoic acid and ammonium salt
c) Ethylamine salt and methanoic acid d) methylamine salt and ethanoic acid
13. C6H5C  N + 4 H ⎯⎯⎯⎯→
SnCl2 /HCl
C6H5CH2NH2
The above reaction is:
a) Mendius reaction b) Schmidt reaction c) Rosenmund reaction d) Stephen’s reaction
14. Which of the following is obtained in carbylamines reaction ?
a) C2H5NH2 b) COCl2 c) C6H5CN d) C6H5NC
15. Which one of the following methods is neither meant for the synthesis not for separation of
amines ?

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a) Hinsher’s method b) Hofmann’s method c) Wurtz reaction d) Curtius

reaction
16. Which of the following chemicals are used to manufacture methyl isocyanate that caused
“Bhopal Tragedy”?
(i) Methylamine (ii) Phospgene (iii) Phosphine (iv)
Dimethylamine
a) (i) and (ii) b) (iii) and (iv) c) (i) and (iii) d) (ii) and (iv)
17. Which one of the following statements about CH3CN is not true?
a) Its IUPAC name is ethane nitrile
b) The bond between C and N is a triple bond
c) The C – C – N bond angle is 1800
d) The carbon-carbon bond is longer than the carbonnitrogen bond
c) It has a relatively high boiling point due to hydrogen bonding
18. Which of the following reacts with Hinsberg’s reagent to form the product soluble in KOH ?
a) Primary amine b) Secondary amine c) Tertiary amine d) Quaternary amine
19. Potassium phthalimide reacts with ‘A’ which on hydrolysis gives isopentylamine, what is ‘A’ ?

20. Which has the highest pKb value ?

a) R3C – NH2 b) R2NH c) RNH2 d) NH3
21. CH3NH2 + CHCl3 + KOH ⎯⎯ → nitrogen containing compound + KCl + H2O. Nitrogen containing
compound is:
+ −
a) CH3 − C  N b) CH3 − NH − CH3 c) CH3 − N  C d) CH3 − N  C
22. The molecular formula C3H9N cannot represent :
a) 10 amine b) 20 amine c) 30 amine d) quaternary salt
23. The correct order of basic nature in aqueous solution is:
a) C6H5NH2 > NH3 > CH3NH2 > (CH3)2 NH b) NH3 > C6H5NH2 > CH3NH2 > (CH3)2NH
c) (CH3)2 NH > CH3NH2 > NH3 > C6H5NH2 d) CH3NH2 > (CH3)2 NH > NH3 > C6H5NH2
24. Which one of the following is most basic ?
a) FCH2NH2 b) FCH2CH2CH2NH2 c) C6H5NH2 d) C6H5CH2NH2
25. An alphatic amine on treatment with alcoholic carbon disulphide and mercuric chloride forms
ethyl isothiocyanate, the reactionis known as:
a) Hofmann’s reaction b) Hofmann’s rearrangement
c) Hofmann’s mustard oil reaction d) Hofmann’s bromamide degradation reaction
26. Consider the following reaction
C6H5NO2 ⎯⎯⎯→ X ⎯⎯⎯⎯ → Y + HCl
Sn / HCl 6 5C H COCl

What is Y?
a) Acetanilide b) Benzanilide c) azobenzene d) hydrazobenzene
27. Which is more basic?
a) benzyl amine b) aniline c) acetamide d) none of these
28. Nitrobenzene gives azoxybenzene and hydrazobenzene when reduced
a) in acidic medium b) in neutral medium
c) electrolytically d) in alkaline medium

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H O+
29. C6H5CN + CH3MgBr ⎯⎯ → Q ⎯⎯⎯ 3
→P
The product P in the above reaction is:
a) C6H5COCH3 b) C6H5CH(OH)CH3 c) C6H5CHO d) C6H5COOH
30. CH 3CH 2Cl ⎯⎯⎯
→ X ⎯⎯⎯→ Y ⎯⎯⎯⎯⎯→ Z
NaCN Ni / H 2 Aceticanhydride

Z in the reaction sequence is

a) CH3CH2CH2NHCOCH3
b) CH3CH2CH2NH2
c) CH3CH2CH2CONHCH3
d) CH3CH2CH2CONHCOCH3
ASSERTION-REASON TYPE QUESTIONS:
1. A:Ammonolysis of alkyl halides is not a suitable method for preparation of pure primary amines.
R:Ammonolysis of alkyl halides yields mainly secondary amines.
2. A:Benzonitrile is prepared by the reaction of chlorobenzene with potassium cyanide.
R:Cyanide ion is a strong nucleophile.
3. A:Aniline does not undergo Friedel -Crafts reaction.
R:Friedel -Crafts is an electrophilic substitution reaction.
4. A:Gabriel phthalimide cannot be used for the preparation of primary aromatic amines.
R:Aryl halides undergo nucleophilic substitution with the anion formed by phthalimide.
5. A:Aniline reacts with bromine water at room temperature to form 2,4,6-tribromoaniline,
R: -NH2 group is ortho and para directing and a powerful activating group.
6. A:Ethylamine is soluble in water whereas aniline is not.
R:Ethylamine dissolves in water due to intermolecular H-bonding.
7. A:pKbof aniline is more than that of methylamine.
R:In aniline ,the lone pair ofelectrons on nitrogen atom is delocalised over the benzene ring.
8. A:Boiling point of tert-butylamine is much higher than that of n-butylamine .
R:Tertiary amines do not undergo H-bonding due to absence of H-atoms on N-atom.
9. A:N-Ethylbenzene sulphonamide is soluble in alkali.
R:Hydrogen attached to nitrogen in sulphonamide is strongly acidic.
10. A:Acetanilide is less basic than aniline.
R:Acetylation of aniline results in decrease of electron density on nitrogen.
11. A:Only a small amount of HCl is required in the reduction of nitro compounds with iron scrap.
R:FeCl2 formed gets hydrolysed to release HCl during the reaction.

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