G12 NCERT Unit-13 Amines
G12 NCERT Unit-13 Amines
(i)
(ii)
(iii) (C2 H5 )2 CHNH2
(iv) (C2 H5 )2 NH
Solution:
Primary: (i) and (iii)
−N atom is attached with one carbon or one alkyl group.
Secondary: (iv)
−N atom is attached with two carbons or two alkyl groups.
Tertiary: (ii)
−N group attached with three carbons or three alkyl group.
13.2. (i) Write structures of different isomeric amines corresponding to the
molecular formula, C4 H11 N.
(ii) Write IUPAC names of all the isomers.
(iii) What type of isomerism is exhibited by different pairs of amines?
Solution:
(i), (ii): The structures and their IUPAC names of different isomeric amines
corresponding to the molecular formula, C4 H11 N is given below:
4 3 2 1
(a) CH3 − CH2 − CH2 − CH2 − NH2
Parent carbon chain = 5 membered (pent)
Solution:
(i) Considering +I effect of alkyl groups, NH3 , C2 H5 NH2 , and (C2 H5 )2 NH
can be arranged in the increasing order of their basic strengths as:
NH3 < C2 H5 NH2 < (C2 H5 )2 NH
Again, in C6 H5 NH2 acceptability of proton is less than NH3 . Thus, we
have:
Aromatic amine < Aliphatic Amine (Basic character)
Also due to the −I effective of C6 H5 group, the electron density on the
N −atom in C6 H5 CH2 NH2 is lower than that on the N −atom in C2 H5 NH2 ,
but more than that in NH3 . Therefore, the given compounds can be arranged
in the order of their basic strengths as:
C6 H5 NH2 < NH3 < C6 H5 CH2 NH2 < C2 H5 NH2 < (C2 H5 )2 NH (overall
basic strength)
(ii) Basic character ∝ +I effect
Due to +I effect −C2 H5 the basic character should be (C2 H5 )3 N >
(C2 H5 )2 NH > C2 H5 NH2 in the gaseous phase. But in aqueous state
hydrogen bonding is also taking place and extent of hydrogen bonding is
1° > 2° > 3° amine
13.5. Complete the following acid-base reactions and name the products:
(i) CH3 CH2 CH2 NH2 + HCl ⟶
(ii) (C2 H5 )3 N + HCl
Solution:
n-propylamine is basic and HCl is acidic. So, acid-base reaction is taking place
and salt is formed.
(i) CH3 CH2 CH2 NH2 + HCl → CH3 CH2 CH2 NH3+ Cl−
n−Propylamine n−Propylammoniumchloride
With excess methyl iodide, in the presence of Na2 CO3 the solution, N, N-
dimethylaniline (quaternary ammonium salt) produces N, N, N-
trimethylanilinium carbonate.
13.7. Write chemical reaction of aniline with benzoyl chloride and write the name of
the product obtained.
Solution:
Propan-2-amine
(c) CH3 − NH − C2 H5
N −Methylethanamine
(d)
N, N −Dimethylmethanamine
In (a) and (b), −NH2 group is attached to one – C atom. So, it is primary
amine.
Concept Insight: Primary aliphatic amines react with nitrous acid to form
diazonium salt which being unstable liberate nitrogen gas.
13.9. Convert
(i) 3 −Methylaniline into 3 −nitrotoluene.
(ii) Aniline into 1,3,5 − tribromobenzene.
Solution:
(i)
(ii)
13.11. Give one chemical test to distinguish between the following pairs of compounds.
(i) Methylamine and dimethylamine
(ii) Secondary and tertiary amines
(iii) Ethylamine and aniline
(iv) Aniline and benzylamine
Δ
(CH3 )2 NH + CHCl3 + 3KOH → No reaction
(ii) Hinsberg’s reagent (benzenesulphonyl chloride, C6 H5 SO2 Cl) is used to
distinguish between secondary and tertiary amines.
Secondary amines on reaction with Hinsberg’s reagent give a product
which is insoluble in an alkali.
For example, N, N −diethylamine on reaction with Hinsberg’s reagent
forms N, N −diethylbenzenesulphonamide, which is insoluble in an alkali.
Whereas, tertiary amines do not react with Hinsberg’s reagent because
they do not have hydrogen.
(iii) Azo-dye test can be used to distinguish between ethylamine and aniline.
When aromatic amines react with HNO2 (NaNO2 + dil. HCl) at 0 − 5o C,
followed by a reaction with an alkaline solution of 2-naphthol, a dye is
formed. The dye formed is usually yellow, red or orange coloured.
On the other hand, aniline reacts with nitrous acid at a low temperature to
form a stable diazonium salt. Nitrogen gas is not evolved in this case.
Aniline undergoes resonance. So, the electrons on the nitrogen atom are
delocalised over the benzene ring. Therefore, the electrons on the nitrogen
atom are less available to donate. So, the basic character is less.
K b value
pK b value
But aniline does not form H −bonds with water to a very large extent due
to the presence of a large hydrophobic −C6 H5 group. Hence, aniline is
insoluble in water.
(iii)
Amines are more basic than water because the lone pair donor atom in
amine is nitrogen and in water is oxygen. And nitrogen is less
electronegative atom than oxygen.N can easily donate lone pair and +I
effect of −CH3 group, methylamine is more basic than water. Therefore, in
water, methylamine produces OH − ions by accepting H + ions from water.
+
CH3 − NH2 + H − OH → CH3 − NH3 + OH−
(Base) (Acid) (Salt)
Ferric chloride (FeCl3 ) dissociates in water to form Fe3+ and Cl− ions.
FeCl3 ⟶ Fe3+ + 3Cl−
Then, OH − ion reacts with Fe3+ ion and forms a precipitate of hydrated
ferric oxide.
2Fe3+ + 6OH − ⟶ Fe2 O3 . 3H2 O
Hydrated ferric oxide (ppt)
Due to the positive charge on the nitrogen atom (shows −I effect and it is
meta directing), electrophilic substitution in the benzene ring is deactivated.
Hence, the Friedel-Crafts reaction will not take place in aniline.
(vi) The aromatic diazonium ion undergoes resonance.
This resonance is the reason for the stability of the diazonium ion. While in
aliphatic amine no delocalisation takes place. Hence, the diazonium salts of
aromatic amines are more stable than those of aliphatic amines.
(vii) Only 1o amine is formed by Gabriel phthalimide synthesis. 2° and 3°
amines are not formed in this synthesis. So, a pure 1° amine can be obtained.
Therefore Gabriel phthalimide synthesis is preferred for synthesizing
primary amines.
(iv) The basic strength mainly depends upon the electron-donating group (+I
effect) because there is no solvation effect in the gas phase. More is the +I
effect, stronger is the base. Also, the more the number of alkyl groups, the
higher is the +I effect. Therefore, the given compounds can be arranged in
the decreasing order of their basic strengths in the gas phase as follows:
(C2 H5 )3 N > (C2 H5 )2 NH > C2 H5 NH2 > NH3
(v) The boiling points of compounds depend on the hydrogen bonding present
in the compound. The more extensive the H −bonding in the compound, the
higher is the boiling point. (CH3 )2 NH contains only one H −atom whereas
C2 H5 NH2 contains two H −bonding than (CH3 )2 NH. Hence, the boiling
point of C2 H5 NH2 is higher than that of (CH3 )2 NH.
Boiling point ∝ force of attraction ∝ H- bond
Force of attraction between C2 H5 OH is also H-bond. C2 H5 OH forms
stronger H −bonds than C2 H5 NH2 and (CH3 )2 NH.
(ii)
(iii)
(iv)
(v)
(vi)
(vii)
(viii)
13.15. Describe a method for the identification of primary, secondary and tertiary amines.
Also, write chemical equations of the reactions involved.
Solution:
Hinsberg’s test is used to identify and distinguish primary, secondary and tertiary
amines. In the Hinsberg’s test, the amines are allowed to react with Hinsberg’s
reagent, benzenesulphonyl chloride (C6 H5 SO2 Cl). Different types of amines react
differently with the Hinsberg’s reagent.
Primary amines react with benzenesulphonyl chloride to form
N −alkylbenzenesulphonyl amide which is soluble in alkali.
Δ
C2 H5 − NH2 + CHCl3 + 3KOH(alc. ) → C2 H5 − NC + 3KCl + 3H2 O
Ethanamine Ethyl carbylamine
( )
or ethyl isocyanide
(ii) Diazotisation
Aliphatic or Aromatic primary amines react with nitrous acid (prepared in
situ from NaNO2 and a mineral acid such as HCl) at low temperatures
(273 − 278 K) to form diazonium salts. The above conversion of primary
aromatic amines into diazonium salts is known as diazotisation.
For example, on treatment with NaNO2 and HCl at 273 − 278 K, aniline
produces the compound benzene diazonium chloride, with NaCl and H2 O
as by-products.
⊕
R − NH2 → R − N2 Cl
NaNO2⁄HCl Diazonium chloride
Reaction Mechanism:
For example,
𝐷𝑖𝑙 𝑁𝑎𝑂𝐻 at 𝑝𝐻 = 8.5 to 9.5 reacts with −𝐻 of phenol group. Due to this
phenoxide ion is formed. It activates the ring. When the phenoxide ion
reacts with a diazonium salt, it results in the formation of azo dye. This
reaction is called coupling reaction.
This substituted ammonium salt when treated with a strong base such as
sodium hydroxide, amine is obtained.
(vi) Acetylation
Acetylation (or ethanoylation) is the process of introducing an acetyl
group into a molecule.
When amines react with benzoyl chloride, the reaction is also known as
benzoylation. And this is followed by an electrophile substitution reaction
For example,
(ii)
(iii)
(iv)
(v)
(vi)
(vii)
(viii)
(ix)
(i)
(ii)
(iii)
(iv)
(v)
(vi)
Solution:
(i)
(ii)
(iii)
(iv)
(v)
(vi)
13.19. An aromatic compound ‘A’ on treatment with aqueous ammonia and heating forms
compound ‘B’ which on heating with Br2 and KOH forms a compound ‘C’ of
molecular formula C6 H7 N. Write the structures and IUPAC names of compounds
A, B and C.
Solution:
It is given in the question the compound ‘C’ having the molecular formula, C6 H7 N
is formed by heating compound ‘B’ with Br2 and KOH. Reaction with Br2 or KOH
is a Hoffman bromamide degradation reaction and is given by an amide. The
formed product is an amine (one carbon down amide). Therefore, compound ‘B’ is
an amide and compound ‘C’ is an amine. The only amine having the molecular
formula, C6 H7 N is aniline, (C6 H5 NH2 ).
Therefore, compound ‘B’ must be benzamide, (C6 H5 CONH2 )
Further, benzamide is formed by heating compound ‘A’ with aqueous ammonia.
Therefore, compound ‘A’ must be benzoic acid.
The given reaction occurs in the following sequence:
(ii)
C6 H5 N2 Cl + H3 PO2 + H2 O → C6 H6 + N2 + H3 PO3 + HCl
Benzenediazonium Benzene
chloride
−NH2 group is basic and H2 SO4 is acid. Hence salt is formed by an acid-
base reaction.
(iv)
C6 H5 N2 Cl + C2 H5 OH → C6 H6 + CH2 CHO + N2 ↑ +HCl
Benzene diazonium Ethanol Benzene Ethanol
chloride
(vi)
(vii)
But aryl halides do not undergo nucleophilic substitution with the anion formed
by the phthalimide because positive charge on the benzene ring is highly unstable
due to the double bond character.
(ii) Aliphatic primary amines react with nitrous acid (prepared in situ from
NaNO2 and a mineral acid such as HCl) to form unstable aliphatic
diazonium salts, which further produce alcohol and HCl with the evolution
of N2 gas.
R − NH2 → R + NH-2 + H+
(Acid) Amide ion
(Conjugate base)
(Tertiary amine)
Very less hydrogen bonding in tertiary amine due to steric hindrance of
alkyl group (-R).
To break the hydrogen bond, extra energy is required to separate the
molecules of primary amines. Hence, primary amines have higher boiling
points than tertiary amines.
(iii) Due to the -R effect of the benzene ring, the electrons on the N-atom are
less available in case of aromatic amines. Therefore, the electrons on the