Q.The reaction of amines with mineral acids to form ammonium salts shows that these are basic in nature. Aliphatic amines are stronger bases than ammonia whereas aromatic amines are weaker bases than ammonia. Aliphatic and aromatic primary and secondary amines react with acid chlorides, anhydrides and esters by nucleophilic substitution reaction. The main problem encountered during electrophilic substitution reactions of aromatic amines is that of their high reactivity. Substitution tends to occur at ortho-and para-positions. Hinsberg reagent is used for the identification and distinction between primary, secondary and tertiary amines. Aryldiazonium salts, usually obtained from arylamines, undergo replacement of the diazonium group with a variety of nucleophiles to provide advantageous methods for producing aryl halides, cyanides, phenols and arenes. Answer the following questions :
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🔒 Start your 14-day free trial to unlock the full solution →Part (a)Concept understanding — Basicity Order Amines
Basicity of Amines: From Intuition to Precision
Imagine you have a nitrogen atom with a lone pair of electrons — that pair is like a key that can grab a proton (H+). The more willing the nitrogen is to share that pair, the stronger the base. That's the core idea.
The Intuition: What Makes a Nitrogen "Want" a Proton?
Amines are organic derivatives of ammonia (NH3), where one or more hydrogen atoms are replaced by alkyl groups (R). Alkyl groups are electron-donating — they push electron density toward the nitrogen. More alkyl groups = more electron density on nitrogen = stronger base.
So you'd expect: tertiary > secondary > primary > ammonia. That's the inductive effect argument.
But reality is more interesting. In water (the usual solvent for basicity measurements), the order is:
Secondary > Primary > Tertiary > Ammonia
Why the reversal for tertiary amines? Because basicity isn't just about the free amine — it's about the stability of the conjugate acid (the ammonium ion RNH3+) once the proton is grabbed.
The Precise Explanation: Three Factors at Play
1. Inductive Effect (pushes electron density)
Alkyl groups donate electrons through sigma bonds. More alkyl groups = more electron density on N = stronger base. This favours: tertiary > secondary > primary > ammonia.
2. Solvation Effect (stabilises the conjugate acid)
Once the amine grabs a proton, the resulting ammonium ion is positively charged. Water molecules surround it, stabilising the charge through hydrogen bonding. The more hydrogens on the nitrogen, the more H-bonds can form.
Primary ammonium (RNH3+) has 3 H's → best solvation.
Secondary (R2NH2+) has 2 H's → good solvation.
Tertiary (R3NH+) has 1 H → poor solvation.
This favours: primary > secondary > tertiary.
3. Steric Hindrance (blocks solvation)
Bulkier alkyl groups physically block water molecules from approaching the charged nitrogen. This further reduces solvation in tertiary amines.
The Net Result: The Actual Order in Water
| Amine Type | Inductive Effect | Solvation | Steric Hindrance | Net Basicity (pKb) |
|---|---|---|---|---|
| Ammonia (NH3) | Weakest | Best (3 H's) | None | 4.75 |
| Primary (RNH2) | Moderate | Good (2 H's) | Minimal | ~3.4 |
| Secondary (R2NH) | Strong | Moderate (1 H) | Some | ~3.2 |
| Tertiary (R3N) | Strongest | Poor (0 H's) | Significant | ~4.2 |
pKb is the negative log of the base dissociation constant. Lower pKb = stronger base. So secondary (pKb ≈ 3.2) is the strongest, then primary (≈3.4), then tertiary (≈4.2), then ammonia (4.75).
The Final Answer
The basicity order of amines in aqueous solution is:
Secondary > Primary > Tertiary > Ammonia
This is the standard order for simple alkyl amines (methyl, ethyl, etc.). The inductive effect dominates from ammonia to secondary, but the loss of solvation and steric hindrance in tertiary amines drops them below primary.
A Quick Check: Why Not Tertiary? …
Why this formula?
Basicity Order of Amines: Why It Holds
Let's build this from first principles — understanding why amines have different basicities is essential for exams and for deeper chemistry.
1. What Does "Basicity" Mean Here?
Basicity of an amine is its ability to accept a proton (H+).
The stronger the base, the more readily it grabs H+.
The equilibrium is:
R3N+H2O⇌R3NH++OH−
The base dissociation constant Kb measures this:
Kb=[R3N][R3NH+][OH−]
A larger Kb means a stronger base.
2. The Key Factor: Electron Density on Nitrogen
The lone pair on nitrogen is what accepts H+.
More electron density on nitrogen → stronger base.
Why? Because a proton (H+) is attracted to negative charge. If the nitrogen's lone pair is more "available" (less tightly held), it binds H+ more easily.
3. The Two Competing Effects
✓ Inductive Effect (Electron-Donating)
Alkyl groups (−CH3, −C2H5, etc.) are electron-donating via the inductive effect.
They push electron density toward nitrogen.
- More alkyl groups → more electron density on N → stronger base.
This suggests:
3∘>2∘>1∘>NH3
✗ Solvation Effect (Hydration of the Conjugate Acid)
When the amine accepts H+, it forms R3NH+ (a positively charged ion).
This ion is stabilized by water molecules (hydration).
- More H atoms on the NH+ group → more hydrogen bonding with water → better stabilization of the conjugate acid.
- Better stabilization of R3NH+ → stronger base (because the equilibrium shifts toward protonation).
This suggests:
1∘>2∘>3∘ (since 1∘ has 3 H's, 2∘ has 2, 3∘ has 1)
4. The Actual Order (Aqueous Solution)
In water, the observed order for aliphatic amines is:
2° > 1° > 3° > NH3
Wait — that's not simply "more alkyl = stronger". Why?
The Reasoning (Step by Step)
-
From NH3 to 1∘: Adding one alkyl group increases electron density (inductive effect) → stronger base.
So 1∘>NH3.
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From 1∘ to 2∘: Adding a second alkyl group further increases electron density → even stronger base.
So 2∘>1∘.
-
From 2∘ to 3∘: Here, the solvation effect becomes dominant.
The 3∘ amine has only one H on the NH+ group → poor hydration of the conjugate acid.
The inductive effect is still present, but the loss of solvation outweighs the gain in electron density.
So 3∘ is weaker than 2∘.
Thus, the net order is:
2° > 1° > 3° > NH3
5. The Key Formula(e) to Remember
For gas phase (no solvent):
Only inductive effect matters:
3° > 2° > 1° > NH3
For aqueous solution (common in exams): …
Part (b)Concept understanding — Sandmeyer Reaction
The Core Intuition
Imagine you have a benzene ring with an amino group (−NH2) attached. You want to replace that amino group with a chlorine, bromine, or cyano group. Direct substitution is nearly impossible — the amino group is stubbornly attached. But there's a clever detour.
The trick is to first convert the amino group into a diazonium salt (Ar−N2+). This diazonium group is a fantastic leaving group — it's practically begging to leave. The problem is that if you just heat it, it leaves as nitrogen gas and you get a mess. You need to control what replaces it.
Sandmeyer found that if you use a cuprous halide (CuCl, CuBr) or cuprous cyanide (CuCN), the copper helps transfer the halogen or cyano group onto the ring in a clean, high-yielding reaction. The copper acts like a molecular taxi — it picks up the halogen and drops it off exactly where the diazonium group left.
The Precise Statement
Ar−N2+X−CuX or CuCNAr−X+N2
where X=Cl,Br,CN
The Sandmeyer Reaction is the replacement of the diazonium group (−N2+) on an aromatic ring by chlorine, bromine, or a cyano group, using the corresponding cuprous halide or cuprous cyanide as the reagent.
The Mechanism (What Actually Happens)
The reaction proceeds through a radical mechanism, not a simple substitution. Here's the sequence:
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The cuprous ion (Cu+) transfers one electron to the diazonium ion. This breaks the N≡N bond, releasing nitrogen gas and generating an aryl radical (Ar∙).
-
The cupric ion (Cu2+) that forms now has a halogen attached. The aryl radical abstracts this halogen from copper, giving you the final product Ar−X and regenerating Cu+ to continue the cycle.
The key insight: copper changes oxidation state (Cu+→Cu2+→Cu+), shuttling electrons to break the diazonium bond and then delivering the halogen. This is why the reaction works — the copper mediates a radical pathway that simple heating cannot achieve.
Why This Matters for Exams
Scope: The reaction works only for Cl, Br, and CN. You cannot get F or I this way — fluorine is too reactive, and iodine requires different conditions (the Gattermann reaction using copper powder instead of cuprous salts).
Yields: Sandmeyer gives excellent yields (70-90%), much better than the older Gattermann method. This is why it's the preferred industrial route for these substituted aromatics. …
Part (a)
(i) CH3NH2 more basic than (CH3)3N in water. Basicity in water depends on solvation of the conjugate acid. CH3N+H3 has three N–H bonds for H-bonding to water (well solvated); (CH3)3N+H has only one, and its bulky methyls hinder solvation. The better solvation outweighs the extra +I, so CH3NH2 is the stronger base.
(ii) CH3CONH2NaOBrA=CH3NH2 (methylamine, Hofmann bromamide) C6H5COClbaseB=C6H5CONHCH3 (N-methylbenzamide). …
Part (a): CH3NH2>(CH3)3N in water (better solvation of the conjugate acid); CH3CONH2NaOBrCH3NH2C6H5COClC6H5CONHCH3; the C3H9N amine giving an alkali-insoluble Hinsberg product is CH3NHCH2CH3. Part (b): aniline → benzonitrile by diazotisation + Sandmeyer (CuCN); −NH2 is acetylated before nitration to moderate reactivity and prevent oxidation.
Part (a)
(i) Why CH3NH2 is a stronger base than (CH3)3N in water
In water the base's strength depends on how well its conjugate acid is stabilised by hydrogen bonding to solvent. CH3N+H3 has three N–H bonds and is heavily solvated; (CH3)3N+H has only one N–H, and the three bulky methyl groups block water molecules. This poor solvation outweighs the greater inductive donation of three methyls, so CH3NH2 is the stronger base (aqueous order: (CH3)2NH>CH3NH2>(CH3)3N>NH3).
(ii) Structures of A and B
CH3CONH2NaOBrACH3NH2 (Hofmann bromamide; one C lost)
CH3NH2C6H5COClbaseBC6H5CONHCH3 (N-methylbenzamide, Schotten–Baumann benzoylation).
(b) Identifying X (C3H9N)
A Hinsberg product insoluble in alkali means a secondary amine (its sulphonamide has no acidic N–H). Among the isomers of C3H9N — propan-1-amine, propan-2-amine (both 1°), N-methylethanamine (2°) and trimethylamine (3°) — only the secondary amine fits: …
Showing the 12 most recent of 36 on this concept.
- CBSE 2026Set 56/3/11 markMCQQ.Among the following, which is the strongest base ? (A) 4-nitroaniline [O2N−C6H4−NH2] (B) Benzylamine [C6H5CH2NH2] (C) 4-methylaniline [CH3−C6H4−NH2] (D) Aniline [C6H5NH2]
›Reveal solutionSolution
Basicity of amines depends on electron density on nitrogen. Benzylamine has an alkyl group (electron-donating) attached to the amino group, making it the strongest base among the given aromatic amines. The correct option is (B).
Why Basicity Order Matters Here
The question asks you to compare the basic strength of four amines. In organic chemistry, basicity is directly linked to how readily the nitrogen atom can donate its lone pair. The more electron-rich the nitrogen, the stronger the base. For aromatic amines, the key factor is resonance and substituent effects — electron-donating groups increase basicity, while electron-withdrawing groups decrease it.
Let’s break down each compound.
-
Aniline (D) — C6H5NH2
The lone pair on nitrogen is delocalised into the benzene ring through resonance. This makes the nitrogen less available to accept a proton, so aniline is a weaker base than aliphatic amines.
-
4-nitroaniline (A) — O2N−C6H4−NH2
The nitro group (−NO2) is a strong electron-withdrawing group. It pulls electron density away from the nitrogen via both inductive and resonance effects. This drastically reduces the electron density on nitrogen, making it the weakest base among the four.
-
4-methylaniline (C) — CH3−C6H4−NH2
The methyl group is electron-donating (hyperconjugation + inductive effect). It pushes electron density toward the ring, which slightly increases electron density on nitrogen compared to aniline. So 4-methylaniline is a stronger base than aniline, but still weaker than benzylamine.
-
Benzylamine (B) — C6H5CH2NH2 …
-
- CBSE 2026Set ANNUAL1 markQ.Why is methanamine a stronger base than ammonia?
›Reveal solutionSolution
Basicity of an amine depends on how available its nitrogen lone pair is to accept a proton; an alkyl group's electron-donating (+I) inductive effect increases that availability compared with plain ammonia.
In ammonia, NH3, the nitrogen is bonded only to three hydrogens, which contribute no electron-donating effect of their own. In methanamine, CH3−NH2, the methyl group is electron-releasing (+I effect): it pushes electron density through the C−N sigma bond onto the nitrogen atom, increasing the electron density available in its lone pair.
A more electron-rich lone pair is a better proton acceptor (Lewis base), so protonation is favoured more strongly for methanamine than for ammonia:
CH3NH2+H+⇌CH3NH3+(favoured more than)NH3+H+⇌NH4+ …
- CBSE 2026Set ANNUAL1 markQ.Arrange the following in decreasing order of their basic strength: C2H5NH2, (C2H5)2NH, (C2H5)3N, C6H5NH2
›Reveal solutionSolution
Aqueous basicity of amines balances +I electron release (favours more alkyl groups), steric hindrance to solvation of the protonated ion (disfavours bulky/3° amines), and resonance delocalisation of the lone pair (drastically weakens aniline).
Factors at play
- +I effect: each ethyl group pushes electron density onto N, making the lone pair more available and increasing basicity — this alone would predict 3∘>2∘>1∘.
- Steric hindrance to solvation: basicity in water is effectively measured by how well the protonated (R3NH+) ion is stabilised by H-bonding with water. A bulky, highly alkyl-substituted ammonium ion like (C2H5)3NH+ is harder to solvate, which lowers its effective basicity in water — this pulls 3∘ amines down.
- Aromatic ring delocalisation: in aniline, C6H5NH2, the lone pair on N is delocalised into the benzene ring by resonance, making it far less available for protonation — anilines are always much weaker bases than aliphatic amines. …
- CBSE 2025Set ANNUAL1 markMCQQ.Which one of the following is not Sandmeyer's reaction?(a) C6H5N2Cl + Cu2Br2 --HCl-->(b) C6H5N2Cl + Cu (powder) --HCl, heat-->(c) C6H5N2Cl + Cu2Cl2 --HCl-->(d) C6H5N2Cl + CuCN --KCN-->
›Reveal solutionSolution
Sandmeyer's reaction specifically uses cuprous salts (Cu2Cl2, Cu2Br2, CuCN) to convert a diazonium salt into the corresponding aryl halide/nitrile; using copper powder itself instead of a cuprous salt is the Gattermann reaction, a related but distinct method.
Benzenediazonium chloride (C6H5N2Cl), formed by diazotisation of aniline, can be converted to various aryl derivatives:
- C6H5N2Cl + Cu2Cl2/HCl → C6H5Cl (chlorobenzene) — Sandmeyer's reaction
- C6H5N2Cl + Cu2Br2/HCl → C6H5Br (bromobenzene) — Sandmeyer's reaction
- C6H5N2Cl + CuCN/KCN → C6H5CN (benzonitrile) — Sandmeyer's reaction …
- CBSE 2025Set ANNUAL1 markMCQQ.Which of the following is most basic?(a) C6H5NH2(b) NH3(c) C2H5NH2(d) (C2H5)2NH
›Reveal solutionSolution
In aqueous solution, basicity of these amines follows secondary > primary > NH3 > aniline — aniline is weakest because its nitrogen lone pair is delocalised into the benzene ring, while a secondary alkylamine's two electron-donating ethyl groups make it the strongest base here.
Electron-donating alkyl (+I) groups on nitrogen increase electron density on N, making the lone pair more available to accept a proton, so alkyl-substituted amines are more basic than NH3. Between primary and secondary alkylamines in water, the extra +I contribution from the second ethyl group in (C2H5)2NH outweighs its slightly greater steric hindrance/solvation penalty, making it the strongest base of this set: (C2H5)2NH > …
- CBSE 2025Set ANNUAL1 markQ.The reaction (benzenediazonium chloride, C6H5-N2+Cl-, treated with Cu/HCl) giving (chlorobenzene, C6H5-Cl, + N2 + CuCl) is named as ........... .
›Reveal solutionSolution
Replacing a benzenediazonium salt's -N2+Cl- group with -Cl using elemental COPPER POWDER and the corresponding halogen acid (HCl) is the Gattermann reaction — a variant of the better-known Sandmeyer reaction, which instead uses a cuprous salt (Cu2Cl2) rather than copper metal.
C6H5-N2+Cl- --Cu/HCl--> C6H5-Cl (chlorobenzene) + N2 + CuCl
…
- CBSE 2025Set ANNUAL1 markMCQQ.Benzenediazonium chloride (structure shown, a benzene ring with a –N2+Cl– substituent) + Cu2Cl2 --HCl--> ? The product of this reaction is (structures shown as options):(a) Benzene ring with an –OH substituent (phenol)(b) Benzene ring with an –NCl substituent(c) Benzene ring with a –Cu substituent(d) Benzene ring with a –Cl substituent (chlorobenzene)
›Reveal solutionSolution
Treating benzenediazonium chloride with Cu2Cl2 (cuprous chloride) and HCl replaces the −N2+Cl− group with −Cl, giving chlorobenzene — a classic Sandmeyer reaction.
The diagram shows benzenediazonium chloride reacting with Cu2Cl2/HCl. This is the Sandmeyer reaction, in which the diazonium group of an aryldiazonium salt is replaced by a halogen (Cl or Br) using the corresponding cuprous halide as catalyst:
C6H5N2+Cl−Cu2Cl2HClC6H5Cl+N2↑
…
- CBSE 2025Set ANNUAL1 markQ.Arrange the following in decreasing order of their basic strength: C6H5NH2, C2H5NH2, (C2H5)2NH, NH3
›Reveal solutionSolution
Diethylamine is the strongest base (two electron-donating ethyl groups, still well solvated), followed by ethylamine, then unsubstituted ammonia, with aniline the weakest because the ring delocalises the nitrogen lone pair by resonance.
Basicity of an amine depends on how available the nitrogen lone pair is to accept a proton, which in aqueous solution is governed by three competing effects: (i) the +I (electron-donating) effect of alkyl groups, which pushes electron density onto N and increases basicity; (ii) steric hindrance and the extent of solvation (H-bonding) of the resulting ammonium cation, which is reduced by bulky/more numerous alkyl groups and lowers basicity; and (iii) resonance delocalisation of the lone pair, which sharply lowers basicity when N is attached to an aromatic ring.
- (C2H5)2NH (diethylamine, 2°): two ethyl groups give a strong +I effect, and being only disubstituted it is still reasonably well solvated in water — the strongest base of the set.
- C2H5NH2 (ethylamine, 1°): one +I-donating ethyl group, well solvated — a stronger base than plain ammonia but weaker than the disubstituted amine above. …
- CBSE 2024Set 56/3/11 markMCQQ.The order of increasing basicities of CH3NH2 (I), (CH3)2NH (II), (CH3)3N (III) and C6H5NH2 (IV) in aqueous media is : (A) IV < III < I < II (B) II < I < IV < III (C) I < II < III < IV (D) II < III < I < IV
›Reveal solutionSolution
In aqueous solution, basicity of amines depends on a balance between the inductive effect (which increases electron density on nitrogen) and solvation of the conjugate acid (which stabilises it). For methyl-substituted amines, the order is (CH3)2NH>CH3NH2>(CH3)3N>C6H5NH2, so the correct option is (A).
The question asks for the increasing order of basicity in aqueous media — that’s the key. In water, basicity is not just about how much the nitrogen “wants” to donate its lone pair; it’s also about how stable the resulting ammonium ion is once it forms. Two effects compete here: the inductive effect of alkyl groups (which push electrons toward nitrogen, making it more basic) and the solvation effect (water molecules stabilise the charged ammonium ion by hydrogen bonding — more hydrogens on the nitrogen mean better solvation).
For aniline (C6H5NH2), the lone pair on nitrogen is delocalised into the aromatic ring, making it far less available for protonation. That’s why it’s always the weakest base among these four — no contest.
Now, among the methylamines, the trend in the gas phase (no solvent) is clear: more methyl groups → more electron donation → stronger base. So gas-phase order would be (CH3)3N>(CH3)2NH>CH3NH2>NH3. But in water, the story changes because the conjugate acid of trimethylamine, (CH3)3NH+, has only one N–H bond — it can form only one strong hydrogen bond with water. The conjugate acid of dimethylamine, (CH3)2NH2+, has two N–H bonds, so it’s better solvated and more stabilised. This extra stabilisation outweighs the extra inductive effect of the third methyl group, making dimethylamine the strongest base in water.
Let’s walk through the reasoning step by step.
-
Identify the weakest base first.
Aniline (IV) has its lone pair conjugated with the benzene ring — resonance delocalisation reduces electron density on nitrogen drastically. It is by far the least basic. So IV must come first in the increasing order. That eliminates options (B) and (C), which place aniline later.
-
Compare the three methylamines in water.
The inductive effect of methyl groups increases electron density on nitrogen, favouring basicity: more methyl groups → stronger base, all else equal. But “all else” is not equal in water. The conjugate acid’s ability to be stabilised by solvation depends on the number of N–H bonds: each N–H can hydrogen-bond with water.
- (CH3)3NH+ has one N–H.
- (CH3)2NH2+ has two N–Hs.
- CH3NH3+ has three N–Hs.
More N–H bonds mean better solvation, which lowers the energy of the conjugate acid and thus makes the base stronger. So solvation favours the opposite order: more hydrogens → stronger base.
-
The net effect in water is a compromise. …
-
- CBSE 2024Set D1 markMCQQ.Which of the following is the most basic?(a) C6H5NH2(b) (C6H5)2NH(c) C2H5NH2(d) (C2H5)2NH
›Reveal solutionSolution
Aliphatic amines > aromatic; secondary diethylamine is most basic here.
Basicity depends on availability of the nitrogen lone pair:
- Aromatic amines C6H5NH2 (aniline) and (C6H5)2NH (diphenylamine) are weak bases because the lone pair is delocalised into the benzene ring(s); diphenylamine is the weakest.
- Aliphatic amines are stronger bases due to the electron-releasing (+I) alkyl groups. …
- CBSE 2024Set B1 markQ.Fill in the blank: Methyl amine is ______ acidic than ethyl amine.
›Reveal solutionSolution
Ethyl amine is a stronger base than methyl amine because the larger ethyl group has a greater +I (electron-releasing) effect than methyl, so relative to ethylamine, methylamine is more acidic/less basic.
Basicity of simple aliphatic amines increases as the alkyl group attached to nitrogen becomes a better electron donor (+I effect), because this raises electron density on nitrogen and better stabilises the positive charge on the protonated ammonium ion formed.
…
- CBSE 2024Set ANNUAL1 markMCQQ.One of the reagents for Sandmeyer reaction is(a) Cu/HBr(b) CuBr/HBr(c) Cu at 573K(d) None of these
›Reveal solutionSolution
The Sandmeyer reaction converts an aryl diazonium salt to an aryl halide using a cuprous halide (Cu(I) salt) together with the corresponding hydrohalic acid.
ArN2+ Cl- --(CuBr / HBr)--> ArBr + N2 + ...
CuBr/HBr installs -Br (Sandmeyer); analogously CuCl/HCl installs -Cl, and CuCN/KCN installs -CN.
…
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