Chapter 9: Amines

(i) 1 – Methylethanamine ( 1⁰ amine )

(ii) Propan – 1 – amine ( 1⁰ amine )

(iii) N – Methyl – 2 – methyl ethanamine ( 2⁰ amine )

(iv) 2 – Methylpropan – 2 – amine ( 1⁰ amine )

(v) N – Methyl benzamine or N – methylaniline ( 2⁰ amine )

(vi) N – Ethyl – N – methyl ethanamine ( 3⁰ amine )

(vii) 3 – Bromobenzenamine or 3 – bromoaniline ( 1⁰ amine )

(i) Dimethylamine and Methylamine can be made notable by the carbylamine test.

Carbylamine test: Foul-smelling isocyanides or carbylamines are formed when Aliphatic and aromatic primary amines are heated with chloroform and ethanol potassium hydroxide.

Methylamine (being an aliphatic primary amine)  gives a positive carbylamine test, but dimethylamine does not.

(ii) Tertiary amines and Secondary can be made notable by allowing them to react with Hinsberg’s reagent (benzene sulphonyl chloride, C₆ H₅ SO₂ Cl ).

A product which is insoluble alkali is formed when Secondary amines react with Hinsberg’s reagent to form a product that is insoluble in an alkali. For example, N, N – diethyl amine reacts with Hinsberg’s reagent to form N, N – diethyl benzene sulphonamide, which is insoluble in an alkali. Tertiary amines, however, do not react with Hinsberg’s reagent.

(iii) Azo-dye test can distinguish aniline & Ethylamine.

When aromatic amines are made to react with HNO ₂ ( NaNO ₂ + dil. HCl ) at 0 – 5 ° C, A dye is obtained, which is followed by making it react with the alkaline solution of 2 – naphthol. The dye is observed to be in the following colours: yellow, red, or orange in colour. A brisk effervescence is given out by Aliphatic amines due to the evolution of N₂ gas under analogous conditions.

(iv) Benzylamine and Aniline can be made notable by reacting them with nitrous acid, which is made ready in situ from sodium nitrite and mineral acid. Unstable diazonium salt is formed when nitrous acid reacts with Benzylamine, which gives a by-product as alcohol, along with the evolution of N₂ gas.

In another case, HNO ₂ reacts with aniline at a very low temperature which in turn forms stable diazonium salt. Hence, the evolution of nitrogen gas does not happen.

(v) N-methylaniline and Aniline can be made notable by using the Carbylamine test.

On heating Primary amines with ethanolic, chloroform and potassium hydroxide, foul-smelling isocyanides or carbylamines are formed. As Aniline is a primary aromatic primary, it gives a positive carbylamines test. On the other h&, as N-methyl aniline is a secondary amine, it does not give a positive carbylamines test.

(i) p K_b of methylamine is lesser than that of aniline.

When in the above process, Aniline is under resonance, the electrons available on the N – atom is delocalised over the benzene ring. Hence, the electrons on the N – atom is available in less quantity to donate.

While considering the case of methylamine ( due to the + I effect of methyl group ), the electron density on the N – atom is improved. As an outcome, we see that methylamine is more basic than aniline.

Hence, p K_b of methylamine is lesser than that of aniline.

(ii) Aniline is not soluble in water, while Ethylamine is.

When Ethylamine is reacted with water, it tends to form intermolecular H – bonds with water.

Thus, it becomes soluble in water.

However, aniline does form H – bonding with water to a very great extent reason being the presence of a large hydrophobic – C₆ H₅ group. Therefore, aniline is not soluble in water.

(iii) Methylamine in the water, when made to react with ferric chloride, precipitates hydrated ferric oxide.

Due to the presence of – CH₃ group & + I effect, water is less basic than methylamine.

In water, thus, methylamine gives out OH ^– ions by gaining H ⁺ ions from water.

In the above process, Ferric chloride ( FeCl ₃ ) splits, forming Fe^{3 +} & Cl ^– ions in water.

OH ^– ion then combines with Fe³⁺ ion and forms an impulse of hydrated ferric oxide.

(iv) Aniline, when nitrated, gives a substantial amount of m-nitroaniline, while the amino group is o, p – directing in aromatic electrophilic substitution reactions.

Nitration is carried out in an acidic medium. In an acidic medium, aniline is protonated to give anilinium ion (which is meta-directing ).

Due to the above reason, nitration aniline gives a considerable amount of m-nitroaniline.

(v) Aniline does not take Friedel-Crafts reaction.

Friedel-Crafts reaction is performed in the presence of AlCl ₃. But, as we know, AlCl ₃ has an acidic nature, whereas aniline does not. Aniline is basic in nature. Therefore, aniline is then reacted with AlCl _3, forming a salt (this has been shown in the equation given below).

The electrophilic substitution in the benzene ring is deactivated because of the positive charge on the

N – atom. Hence, aniline does not undergo the Friedel-Crafts reaction.

(vi) On comparing the stabilities, we observe that the stability of Diazonium salts of aromatic amines is more than that of aliphatic amines.

Resonance is undergone by the diazonium ion, which is depicted in the figure given below.

The stability of the diazonium ion is accounted for by this resonance. Thus, the stability of diazonium salts of aromatic amines is higher than that of aliphatic amines.

(vii) Gabriel phthalimide synthesis is usually preferred for synthesizing primary amines.

Gabriel phthalimide synthesis is chosen because only 1 ° amine is formed.

This synthesis does not form 2° or 3° amines. Therefore, a pure 1° amine could be formed. Hence, Gabriel phthalimide synthesis is chosen for the synthesis of primary amines.

(i) C₂ H₅ NH₂ à presence of one – C₂ H₅ group

( C₂ H₅ )₂ NH à presence of two – C₂ H₅ groups.

Therefore, the + I effect is additional in (C ₂ H ₅) ₂ NH than in C ₂ H ₅ NH ₂. Therefore, the electron density over the N-atom is more in (C₂ H₅) ₂ NH than in C₂ H₅ NH ₂. Hence, (C₂ H₅)₂ NH is more basic than C₂ H₅ NH₂.

Also, both C₆ H₅ NH CH₃ & C₆ H₅ NH₂ are less basic than ( C₂ H₅ )₂ NH & C₂ H₅ NH₂ due to the delocalisation of the lone pair in the former two. Further, among C₆ H₅ NH CH₃ & C₆ H₅ NH₂, the former will be more basic due to the + T effect of – CH₃ group. Hence, the order of increasing basicity of the given compounds is as follows:

C₆ H₅ NH₂ < C₆ H₅ NHCH₃ < C₂ H₅ NH₂ < ( C₂ H₅ )₂ NH

We know that the higher the basic strength, the lower the p K _b values.

C₆ H₅ NH₂ > C₆ H₅ NH CH ₃ > C₂ H₅ NH ₂ > ( C₂ H₅ ) ₂ NH

(ii) C₆ H₅ N(CH₃) ₂ is more basic than C₆ H₅ NH ₂ due to the presence of the + I effect of two

– CH₃ groups in C₆ H₅ N(CH₃)₂. Further, CH ₃NH ₂ contains one – CH₃ group while

( C₂ H₅ )₂NH contains two – C₂ H₅ groups. Thus, (C₂ H₅ )₂ NH is more basic than C₂ H₅ NH₂.

Now, C₆ H₅ N( CH₃ )₂ is less basic than CH₃ NH ₂ because of the – R effect of – C₆ H₅ group.

Hence, the increasing order of the basic strengths of the given compounds is as follows:

C₆ H₅ NH₂ < C₆ H₅ N(CH₃)₂ < CH₃ NH₂ < (C₂ H₅)₂ NH

(iii) (a)

In p – toluidine, the presence of the electron-donating – CH₃ group increases the electron density on the N-atom. Thus, p – toluidine is more basic than aniline. In the other case, the presence of the electron-withdrawing – NO₂ group decreases the electron density over the N – atom in p – nitroaniline. Thus, p-nitroaniline is less basic than aniline. Hence, the increasing order of the basic strengths of the given compounds is as follows: p – Nitroaniline < Aniline < p – Toluidine

(b) C₆ H₅ NHCH₃ is more basic than C₆ H₅ NH₂ due to the presence of electron-donating – CH₃ group in

C₆ H₅ NHCH₃. Again, in C₆ H₅ NHCH₃, the – C₆ H₅ group is directly attached to the N – atom. However, it is not so in C₆ H₅ CH₂ NH₂. Thus, in C₆ H₅ NHCH₃, the – R effect of the – C₆ H₅ group decreases the electron density over the N-atom. Therefore, C₆ H₅ CH₂ NH₂ is more basic than C₆ H₅ NHCH₃. Hence, the increasing order of the basic strengths of the given compounds is as follows: C₆ H₅ NH₂ < C₆ H₅ NHCH₃ < C₆ H₅ CH₂ NH₂.

(iv) In the gas phase, there is no solvation effect. As a result, the basic strength mainly depends upon the + I effect. The higher the +I effect, the stronger the base. Also, the greater the number of alkyl groups, the higher 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 extent of H-bonding existing in any compound decides the boiling point of compounds. The higher extensive the H – bonding in the compound, the higher will be the boiling point. ( CH₃ )₂ NH has only one H – atom, while C₂ H₅NH₂ has two H – atoms. Subsequently, C₂ H₅ NH₂ undergoes more extensive H-bonding than (CH₃)₂NH. Therefore, the boiling point of C₂ H₅ NH₂ is more than that of (CH₃)₂ NH.

Also, O is more electronegative than N. Thus, C₂ H₅ OH forms stronger H – bonds than C₂ H₅ NH₂. As a result, the boiling point of C₂ H₅ OH is higher than that of C₂ H₅NH₂ & (CH₃)₂ NH.

Based on the above explanation, the compounds given in the question can be arranged in the ascending order of their boiling points, which is given below:

( CH₃ )₂ NH < C₂ H₅ NH₂ < C₂ H₅ OH

(vi) The more extensive the H – bonding, the higher the solubility. C₂ H₅ NH₂ contains two H – atoms, whereas (C₂ H₅) ₂ NH contains only one H-atom. Thus, C₂ H₅ NH₂ undergoes more extensive H – bonding than (C₂ H₅)₂ NH. Hence, the solubility in water of C₂ H₅ NH₂ is more than that of (C₂ H₅)₂ NH.

Further, the solubility of amines decreases with an increase in the molecular mass. This is because the molecular mass of amines increases with an increase in the size of the hydrophobic part. The molecular mass of C₆H₅NH₂ is greater than that of C₂ H₅NH₂ & (C₂ H₅) ₂ NH.

Hence, the increasing order of their solubility in water is as follows:

C₆ H₅ NH ₂ < ( C₂ H₅ )₂ NH < C₂ H₅ NH₂

Question 13.6 :

Describe a method for the identification of primary, secondary and tertiary amines. Also, write chemical equations of the reactions involved.

Primary, secondary and tertiary amines can be identified and distinguished by Hinsberg’s test. In this test, the amines are allowed to react with Hinsberg’s reagent, benzene sulphonyl chloride (C₆ H₅ SO₂ Cl). The three types of amines react differently to Hinsberg’s reagent. Therefore, they can be easily identified using Hinsberg’s reagent. Primary amines react with benzene sulphonyl chloride to form N-alkyl benzene sulphonyl amide, which is soluble in alkali.

Due to the presence of a strong electron-withdrawing sulphonyl group in the sulphonamide, the H – atom attached to nitrogen can be easily released as a proton. So, it is acidic and dissolves in alkali.

Secondary amines react with Hinsberg’s reagent to give a sulphonamide which is insoluble in alkali.

There is no H – atom attached to the N-atom in the sulphonamide. Therefore, it is not acidic and insoluble in alkali. On the other tertiary amines do not react with Hinsberg’s reagent at all.

Question 13.7:

Write short notes on the following.

(i) Carbylamine reaction

(ii) Diazotisation

(iii) Hofmann’s bromamide reaction

(iv) Coupling reaction

(v) Ammonolysis

(vi) Acetylation

(vii) Gabriel phthalimide synthesis.

(i) Carbylamine reaction

Carbylamine reaction is used as a test for the identification of primary amines. When aliphatic and aromatic primary amines are heated with chloroform and ethanolic potassium hydroxide, carbylamines (or isocyanides) are formed. These carbylamines have very unpleasant odours. Secondary and tertiary amines do not respond to this test.

(ii) Diazotization

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. This conversion of aromatic primary amines into diazonium salts is known as diazotization.

For example, on treatment with NaNO ₂ & HCl at 273 – 278 K, aniline produces benzene diazonium chloride, with NaCl & H₂ O as by-products.

(iii) Hoffmann bromamide reaction

When an amide is treated with bromine in an aqueous or ethanolic solution of sodium hydroxide, a primary amine with one carbon atom less than the original amide is produced. This degradation reaction is known as the Hoffmann bromamide reaction. This reaction involves the migration of an alkyl or aryl group from the carbonyl carbon atom of the amide to the nitrogen atom.

(iv) Coupling reaction

The reaction of joining two aromatic rings through the − N = N – bond is known as the coupling reaction. Arene diazonium salts, such as benzene diazonium salts, react with phenol or aromatic amines to form coloured azo compounds.

It can be observed that the para-positions of phenol and aniline are coupled with the diazonium salt. This reaction proceeds through electrophilic substitution.

(v) Ammonolysis

When an alkyl or benzyl halide is allowed to react with an ethanolic solution of ammonia, it undergoes a nucleophilic substitution reaction in which the halogen atom is replaced by an amino (– NH₂) group. This process of cleavage of the carbon-halogen bond is known as ammonolysis.

When this substituted ammonium salt is treated with a strong base, such as sodium hydroxide, the amine is obtained.

Though primary amine is produced as the major product, this process produces a mixture of primary, secondary and tertiary amines, and also a quaternary ammonium salt, as shown.

(vi) Acetylation

Acetylation (or ethanoylation) is the process of introducing an acetyl group into a molecule.

Aliphatic and aromatic primary & secondary amines undergo acetylation reaction by nucleophilic substitution when treated with acid chlorides, anhydrides or esters. This reaction involves the replacement of the hydrogen atom of – NH₂ or > NH group by the acetyl group, which results in the formation of amides. In order to transfer the equilibrium to the right-hand side, the HCl that is produced while the reaction is on is removed almost immediately as it is produced. This reaction is performed in the existence of a base (such as pyridine) which is comparatively stronger than the amine.

The reaction, also known as benzoylation, is the reaction that occurs when amines react with benzoyl chloride. One of the examples is illustrated below.

(vii) Gabriel phthalimide synthesis

Gabriel phthalimide synthesis is a convenient and important method for the synthesis of aliphatic primary amines. It includes the reaction between phthalimide with ethanolic potassium hydroxide forming the potassium salt of phthalimide. This salt is then heated with an alkyl halide, which is succeeded by alkaline hydrolysis to give in the resultant primary amine.

Question 13.8:

Accomplish the following conversions.

(i) Nitrobenzene to benzoic acid

(ii) Benzene to m-bromophenol

(iii) Benzoic acid to aniline

(iv) Aniline to 2, 4 ,6-tribromofluorobenzene

(v) Benzyl chloride to 2-phenylethanamine

(vi) Chlorobenzene to p-chloroaniline

Question 13.9 :

Give the structures of A, B and C in the following reactions.

Question 13.10:

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 C₆H₇N. Write the structures and IUPAC names of compounds A, B and C.

It is given that compound ‘C’ has the molecular formula, and C₆ H₇ N is formed by heating compound ‘B’ with Br₂ and KOH. This is a Hoffmann bromamide degradation reaction. 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’ (from which ‘C’ is formed) must be benzamide (C₆ H₅ CO NH₂).

Further, benzamide is formed by heating compound ‘A’ with aqueous ammonia.

Therefore, compound ‘A’ must be benzoic acid.

The given reactions can be explained with the help of the following equations:

Question 13.11:

Complete the following reactions.

Question 13.12:

Why cannot aromatic primary amines be prepared by Gabriel phthalimide synthesis?

Gabriel phthalimide synthesis is usually used for the formation of aliphatic primary amines. This includes nucleophilic substitution ( SN₂ ) of alkyl halides by the anion produced by the phthalimide.

However, nucleophilic substitution with the anion formed by the phthalimide is not undergone by aryl halides.

Therefore, Gabriel phthalimide synthesis is not preferred for preparing aromatic primary amines.

Question 13.13:

Write the reactions of

(i) Aromatic with nitrous acid.

(ii) Aliphatic primary amines with nitrous acid.

(i) Aromatic amine when reacts with nitrous acid (which is made in situ from NaNO₂ and a mineral acid, such as

(HCl) at 273 – 278 K forming stable aromatic diazonium salts, i.e., NaCl and H₂ O.

(ii) Aliphatic primary amines, when reacted with nitrous acid. (made in situ from NaNO₂ and a mineral acid, such as HCl, forming unstable aliphatic diazonium salts, which later produce alcohol and HCl, along with the evolution of N₂ gas.)

Question 13.14:

Give a plausible explanation for each of the following.

(i) Why are alcohols more acidic than amines of comparable molecular masses?

(ii) Why do tertiary amines have lower boiling points than primary amines?

(iii) Why are aromatic amines weaker bases than aliphatic amines?

(i) Protonation of amines gives amide ions.

In the same way, alcohol gives away a proton which results in an alkoxide ion.

In an amide ion, N-atom has a negative charge on it, while in the alkoxide ion, the O- atom has a negative charge is on it. In view of the fact that O is more electronegative than N, O has the ability to hold the negative charge more effortlessly than N. consequently, the alkoxide ion is more stable than the amide ion. Therefore, alcohols more acidic than amines of comparable molecular masses

(ii) There are no H-atoms present in a molecule of a tertiary amine, while two hydrogen atoms are present in primary amines. Primary amines undergo extensive intermolecular H-bonding because of the presence of H-atoms.

Consequently, additional energy would be required to detach the molecules of primary amines. Therefore, tertiary amines have lower boiling points than primary amines.

(iii) The availability of N-atom is fewer in aromatic amines; this is because of the R effect of the benzene ring. Thus, the electrons on the N-atom in aromatic amines cannot be donated easily. This explains why aliphatic amines are stronger bases than aromatic amines.

Chapter 13 Amines of Class 12 Chemistry is prepared as per the CBSE Syllabus for 2023-24. Amines are derivatives of ammonia obtained by the replacement of hydrogen. In the Class 12 NCERT Solutions for this chapter, students will be able to understand the nomenclature, properties and structure of amines. Amines are the most important nitrogen-containing organic compounds. Solved examples based on the basicity of amines, synthesis and reactions undergone by amines are well explained by our subject experts.

1. Structure of Amines
2. Classification
3. Nomenclature
4. Preparation of Amines
5. Physical Properties
6. Chemical Reactions
7. Methods of preparation of Diazonium Salts
8. Physical Properties
9. Chemical reactions
10. Importance of Diazonium salts in Synthesis of aromatic Compounds

Amines are derivatives of ammonia. They are obtained by replacing hydrogen atoms with an alkyl or aryl group. Either one or two or all three hydrogen atoms are replaced. Based on the number of hydrogen atoms replaced, amines are classified into three: Primary, Secondary and Tertiary amines.

Primary amines are formed when one hydrogen atom of ammonia is replaced by R or Ar. Secondary amines are formed when two hydrogen atoms of ammonia or one hydrogen atom of R-NH₂ are replaced by an alkyl or aryl group. When all three hydrogen atoms of NH₃ are replaced by an alkyl or aryl group, it is called a tertiary amine. This was a brief about the chapter according to the latest CBSE Syllabus.

To know more about the classification of amines like primary, secondary and tertiary and common names and IUPAC names of amines, properties of amines, methods of preparation, the difference between primary, secondary and tertiary amines, the importance of Diazonium salts, etc., sign up for free to BYJU’S – The Learning App to access the NCERT Solutions.

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