Q.(a) Explain why :
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🔒 Start your 14-day free trial to unlock the full solution →Part (a)Concept understanding — Electrophilic Aromatic Substitution
Electrophilic Aromatic Substitution – The First Meeting
Imagine you have a benzene ring — that perfect, flat hexagon of six carbons with alternating double bonds. It's stable, almost stubbornly so. You want to attach something new to it, say a bromine atom or a nitro group. But benzene doesn't react like an alkene. It doesn't just add across a double bond. Instead, it does something more elegant: it kicks out a hydrogen and keeps its aromatic ring intact.
That's the heart of Electrophilic Aromatic Substitution (EAS).
The Intuition: Why "Substitution" and Not "Addition"?
Benzene's stability comes from its delocalised π electrons — a cloud above and below the ring. This cloud is electron-rich, so it attracts electrophiles (electron-loving species). But if an electrophile simply added to a double bond, the ring would break its aromaticity, losing that huge stabilisation. That would be energetically costly.
So benzene does something smarter: it lets the electrophile attack, temporarily breaks aromaticity to form a high-energy intermediate (the arenium ion), and then loses a proton to restore the aromatic ring. The net result? A hydrogen is replaced by the electrophile. The ring is back to its stable, aromatic self.
The key trade-off: temporary loss of aromaticity is acceptable because the final product regains it. Addition reactions would permanently destroy aromaticity — benzene avoids that.
The Precise Statement
Electrophilic Aromatic Substitution is a reaction in which an electrophile (E+) replaces a hydrogen atom on an aromatic ring, proceeding through a sigma complex (arenium ion) intermediate, and restoring aromaticity after deprotonation.
The general equation:
Ar−H+EX+Ar−E+HX+
where Ar represents an aromatic ring.
The Mechanism in Three Steps
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Generation of the electrophile – Many EAS reactions need a catalyst to create a strong enough E+. For example, bromination uses FeBrX3 to polarise BrX2 into BrX+.
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Attack by the aromatic ring – The π electrons of benzene attack the electrophile, forming a sigma complex (also called the arenium ion or Wheland intermediate). This intermediate is non-aromatic — it has four π electrons delocalised over five carbons, and one sp3 carbon bearing the electrophile and a hydrogen.
Benzene+E+⟶Sigma complex (non-aromatic)
- Deprotonation – A base (often the counterion of the catalyst, like FeBrX4X−) removes the proton from the sp3 carbon. The pair of electrons from the C–H bond flows back into the ring, restoring the aromatic sextet.
Sigma complex+Base⟶Product+HX+
The sigma complex is not aromatic. It's a high-energy intermediate. Students often mistakenly think it's still aromatic — it isn't. That's why the step is fast and the complex is short-lived.
Why This Matters for Exams
EAS is the gateway to understanding how to put groups onto benzene rings. The rate-determining step is usually the formation of the sigma complex (step 2). The regiochemistry (where the electrophile goes) depends on whether the ring already has a substituent — that's the topic of activating/deactivating groups and ortho/para vs. meta directors.
But for now, remember this: …
Why this formula?
Electrophilic Aromatic Substitution: Why the Mechanism Holds
The Core Puzzle: Why Benzene Doesn't Just Add
Benzene (C6H6) has three double bonds — so why doesn't it undergo addition reactions like alkenes?
The answer lies in aromatic stabilisation: benzene's delocalised π-electron cloud (the "aromatic sextet") is about 150 kJ/mol more stable than a hypothetical cyclohexatriene with localised double bonds.
If benzene simply added an electrophile (like Br2), it would lose this stabilisation — a huge energy penalty.
So, nature chooses a different path: substitution instead of addition, preserving the aromatic ring.
The Key Formula: The Reaction Profile
The rate-determining step in electrophilic aromatic substitution (EAS) is the formation of the arenium ion (σ-complex):
Ar-H+E+slowAr-E+H(σ-complex)
Then, fast deprotonation restores aromaticity:
Ar-E+H+B−fastAr-E+BH
Why This Holds: The Energy Barrier Logic
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First step (slow): The electrophile E+ attacks the electron-rich ring. The σ-complex is non-aromatic — it has only 4 π-electrons delocalised over 5 carbons (the sixth carbon is sp3 hybridised). This intermediate is higher in energy than the starting benzene.
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Second step (fast): A base removes the proton, restoring the aromatic sextet. This step is strongly exothermic — the system regains ~150 kJ/mol of stabilisation.
The overall reaction is exothermic, but the activation energy is dominated by the destabilisation of the σ-complex.
The Rate Law: Why It's First Order in Both
From the mechanism:
Rate=k[Arene][E+]
Reasoning:
- The slow step involves one molecule of arene and one molecule of electrophile.
- No other species appear before the rate-determining step.
- Therefore, the rate law is bimolecular — first order in each reactant.
This is not derived from the overall stoichiometry — it comes directly from the molecularity of the slow step.
The Hammett Equation: Quantifying Substituent Effects
For substituted benzenes, the rate constant k relative to benzene (k0) follows:
logk0k=σρ
Why This Holds
- σ (sigma constant): Measures the electronic effect of a substituent (electron-donating or withdrawing) relative to hydrogen. It is derived from the ionisation constants of benzoic acids — a purely empirical scale.
- ρ (rho constant): Measures the sensitivity of the reaction to substituent effects. A positive ρ means the reaction is favoured by electron-withdrawing groups (rare in EAS); a negative ρ means electron-donating groups accelerate the reaction.
Why it works:
The σ-complex has a positive charge delocalised over the ring. Substituents that stabilise this positive charge (electron-donating groups like −OH, −NH2) lower the activation energy — hence σ is negative for such groups. Electron-withdrawing groups (−NO2, −CN) destabilise the σ-complex — σ is positive.
The linear free-energy relationship holds because the transition state resembles the σ-complex in charge distribution.
The Directing Effect: Why Ortho/Para vs Meta
The position of substitution is governed by the stability of the σ-complex for each possible attack site. …
Part (b)Concept understanding — Alcohol Oxidation
Alcohol Oxidation: The Intuition First
Imagine you have a molecule of ethanol — the alcohol in your hand sanitizer or a drink. It has a carbon atom bonded to an –OH group. Now picture that –OH group as a "handle" that can be transformed. Oxidation, in organic chemistry, doesn't always mean adding oxygen — it often means removing hydrogen from a carbon that already has a bond to oxygen. For alcohols, oxidation is like "stripping away" hydrogen atoms from the carbon that holds the –OH, turning the alcohol into a more oxidized functional group.
Think of it this way: a primary alcohol (R–CH₂–OH) has two hydrogens on the carbon with the –OH. If you remove one hydrogen and the hydrogen from the –OH, you get an aldehyde (R–CHO). Remove both hydrogens (and the –OH hydrogen), and you get a carboxylic acid (R–COOH). A secondary alcohol (R–CHOH–R') has only one hydrogen on that carbon — remove it, and you get a ketone (R–CO–R'). A tertiary alcohol has no hydrogen on that carbon — so it cannot be oxidized without breaking the carbon skeleton.
That's the core intuition: oxidation of an alcohol is about removing hydrogens from the carbon bearing the –OH group. The more hydrogens you can remove, the more oxidized the product.
The Precise Statement
Alcohol oxidation is the process in which an alcohol loses hydrogen atoms (dehydrogenation) from the carbon bonded to the –OH group, increasing the number of C–O bonds (or decreasing C–H bonds). The outcome depends on the class of the alcohol:
| Alcohol Class | Structure | Product after oxidation | Reagent example |
|---|---|---|---|
| Primary (1°) | R–CH₂–OH | Aldehyde (R–CHO) then Carboxylic acid (R–COOH) | PCC (stops at aldehyde); K₂Cr₂O₇/H⁺ (goes to acid) |
| Secondary (2°) | R–CHOH–R' | Ketone (R–CO–R') | K₂Cr₂O₇/H⁺, CrO₃, etc. |
| Tertiary (3°) | R₃C–OH | No reaction (under normal conditions) | — |
A common mistake: students think "oxidation" always adds oxygen. For alcohols, it's removal of hydrogen from the carbon with the –OH. The oxygen from the –OH stays — it's the hydrogens that leave.
Why Does Tertiary Alcohol Not Oxidize?
Look at the carbon with the –OH in a tertiary alcohol: it has three carbon groups attached and no hydrogen. To form a C=O bond, you'd need to remove a hydrogen from that carbon — but there is none. The only way to oxidize a tertiary alcohol is to break a C–C bond (strong and difficult), which is not typical oxidation. So in standard organic chemistry, tertiary alcohols are inert to mild oxidizing agents.
A Real-World Analogy
Think of the alcohol carbon as a "parking spot" with a certain number of hydrogen "cars." Primary alcohol has two cars parked. Oxidation is like towing away one car (→ aldehyde) or both cars (→ carboxylic acid). Secondary alcohol has one car — tow it away, and you get a ketone. Tertiary alcohol has zero cars — nothing to tow, so no reaction.
Key Reagents to Remember (for exams)
- PCC (pyridinium chlorochromate): oxidizes 1° alcohols to aldehydes only — stops there.
- K₂Cr₂O₇ / H₂SO₄ (acidified potassium dichromate): oxidizes 1° alcohols all the way to carboxylic acids; 2° alcohols to ketones. (Not to be confused with Jones reagent, which is specifically CrO₃ dissolved in dilute aqueous H₂SO₄, often used in acetone — a related but distinct oxidant with the same general 1°→acid / 2°→ketone outcome.) …
Why this formula?
Alcohol Oxidation: Why the Reactions Work the Way They Do
Alcohol oxidation is a fundamental reaction in organic chemistry, and understanding why it proceeds as it does is crucial for Indian board exams (Class 12, JEE, NEET). Let's break it down step-by-step.
1. The Core Idea: Loss of Hydrogen
Oxidation in organic chemistry means loss of hydrogen (or gain of oxygen). For alcohols, this happens at the carbon bearing the –OH group.
- Primary alcohol (R−CH2OH): Has two hydrogens on the carbon attached to –OH.
- Secondary alcohol (R2CHOH): Has one hydrogen on that carbon.
- Tertiary alcohol (R3COH): Has zero hydrogens on that carbon.
Key insight: The number of hydrogens on the carbon with –OH determines if and how far oxidation can go.
2. Why Primary Alcohols Give Aldehydes (Then Carboxylic Acids)
Step 1: Aldehyde formation
When a primary alcohol (R−CH2OH) is oxidized, the first product is an aldehyde (R−CHO).
Why? The oxidizing agent (like K2Cr2O7 / H2SO4 or PCC) removes two hydrogens:
- One from the –OH group
- One from the carbon atom
The carbon–oxygen bond becomes a double bond (C=O), forming the aldehyde.
R−CH2OH[O]R−CHO+H2O
But why stop here? The aldehyde still has one hydrogen on the carbonyl carbon. If a strong oxidant is present, it can remove that hydrogen too.
Step 2: Carboxylic acid formation
With excess strong oxidant (e.g., K2Cr2O7 / H2SO4, heat), the aldehyde is further oxidized to a carboxylic acid (R−COOH).
R−CHO[O]R−COOH
Why does this happen? The aldehyde's carbonyl carbon is electrophilic (partially positive). Water (from the reaction medium) adds to it, forming a gem-diol intermediate. The oxidant then removes two more hydrogens, giving the acid.
Exam tip: To stop at the aldehyde, use a mild oxidant like PCC (pyridinium chlorochromate) in anhydrous conditions — no water means no gem-diol formation.
3. Why Secondary Alcohols Give Ketones (and Stop)
A secondary alcohol (R2CHOH) has only one hydrogen on the carbon with –OH. Oxidation removes:
- One hydrogen from –OH
- One hydrogen from the carbon
This forms a ketone (R2C=O).
R2CHOH[O]R2C=O+H2O
Why does it stop here? The ketone has no hydrogen on the carbonyl carbon. Without that hydrogen, further oxidation (under normal conditions) is impossible — you'd need to break a C−C bond, which requires much harsher conditions.
Key result: Secondary alcohols cannot be oxidized further than ketones under standard conditions.
4. Why Tertiary Alcohols Do NOT Oxidize
A tertiary alcohol (R3COH) has zero hydrogens on the carbon bearing –OH.
What happens if you try? The oxidant cannot remove any hydrogen from that carbon. The only possible reaction would be breaking a C−C bond, which doesn't happen under normal oxidation conditions.
Result: Tertiary alcohols are resistant to oxidation under mild to moderate conditions. They require strong heating with powerful oxidants (like K2Cr2O7 / H2SO4, heat) to break carbon–carbon bonds — this is destructive oxidation, not useful for synthesis.
5. The "Why" in One Table
| Alcohol Type | Hydrogens on C–OH | Product | Why? |
|---|---|---|---|
| Primary (1∘) | 2 | Aldehyde → Carboxylic acid | Two hydrogens available; aldehyde still has one more |
Part (a)
(i) Why is −COOH in benzoic acid meta-directing? It is a deactivating group that withdraws electrons by resonance and induction. Its resonance withdrawal specifically removes electron density from the ortho and para positions (positive charge appears there in the resonance structures), leaving the meta position least deactivated — so the electrophile enters meta.
(ii) Why is NaHSO3 used to purify aldehydes/ketones? They add NaHSO3 to give crystalline, water-soluble bisulphite adducts (R-CH(OH)SO3Na). Impurities are separated, then the pure carbonyl compound is regenerated with dilute acid or base. The reaction is reversible, which makes purification possible. …
Part (a): −COOH is meta-directing because resonance withdrawal deactivates o/p most; NaHSO3 forms reversible crystalline adducts used to purify carbonyl compounds; carboxylic acids fail carbonyl tests because −OH resonance lowers the carbonyl's electrophilicity. Part (b): A = propan-2-ol, B = propanone, C = iodoform.
Part (a)
(i) −COOH is meta-directing
The carboxyl group is a strong deactivator (both −R and −I). Drawing the resonance structures of the substituted benzene shows the developing positive charge (electron depletion) sits at the ortho and para carbons; the meta carbon is spared. So although the whole ring is deactivated, meta is the least deactivated, and the incoming electrophile chooses it. "Meta-directing" means meta is preferred, not that meta is activated.
(ii) NaHSO3 for purification
Aldehydes and most methyl ketones undergo nucleophilic addition of bisulphite to give crystalline, water-soluble adducts:
R-CHO+NaHSO3→R-CH(OH)-SO3Na
Non-carbonyl impurities stay behind; the adduct is filtered, and treatment with dilute acid or base regenerates the pure carbonyl compound. Because the addition is reversible, the pure aldehyde/ketone is recovered — the basis of the purification.
(iii) Carboxylic acids don't give carbonyl reactions
In −COOH the hydroxyl oxygen lone pair conjugates with the C=O:
R-C(=O)-OH↔R-C(-O−)=O+H …
Showing the 12 most recent of 52 on this concept.
- CBSE 2026Set A1 markMCQQ.When vapours of an alcohol are passed over hot reduced copper, it gives an alkene. The alcohol is(a) Primary(b) Secondary(c) Tertiary(d) None of these
›Reveal solutionSolution
Over hot reduced copper (573 K), a primary alcohol gives an aldehyde, a secondary gives a ketone, and a tertiary gives an alkene.
When alcohol vapours are passed over hot reduced copper the behaviour depends on the class of alcohol:
- Primary alcohol -> dehydrogenation -> aldehyde
- Secondary alcohol -> dehydrogenation -> ketone …
- CBSE 2026Set ANNUAL1 markQ.Write the name of product obtained when vapour of ethyl alcohol are passed over heated Copper at 573 K.
›Reveal solutionSolution
Passing alcohol vapours over heated copper catalyses either dehydrogenation (for 1° and 2° alcohols) or dehydration (for 3° alcohols), depending on alcohol type.
…
- CBSE 2026Set ANNUAL1 markMCQQ.Dehydration of tertiary alcohols with copper at 573 K gives:(a) Aldehyde(b) Ketone(c) Alkene(d) None of these
›Reveal solutionSolution
Passing alcohol vapours over heated copper at 573 K is a classification test: 1° alcohols → aldehydes, 2° alcohols → ketones, but 3° alcohols (no α-H on the carbinol carbon available for dehydrogenation) undergo dehydration to give an alkene.
When vapours of an alcohol are passed over copper catalyst at 573 K:
- Primary alcohols are dehydrogenated (lose H2) to aldehydes: RCH2OHCu,573KRCHO+H2
- Secondary alcohols are dehydrogenated to ketones: R2CHOHCu,573KR2C=O+H2 …
- CBSE 2026Set ANNUAL1 markMCQQ.When vapour's of a compound X are passed over heated copper, the major product obtained is the acetone. The compound X is:(a) n-Propyl alcohol(b) Iso-propyl alcohol(c) Acetaldehyde(d) Propane
›Reveal solutionSolution
Vapours passed over heated copper dehydrogenate 2° alcohols to ketones; since the product is acetone (a ketone), X must be a secondary alcohol — isopropyl alcohol.
Over heated copper (573 K), alcohols are catalytically dehydrogenated based on their class:
- 1° alcohol → aldehyde
- 2° alcohol → ketone
- 3° alcohol → alkene (dehydration) …
- CBSE 2026Set ANNUAL1 markMCQQ.The most suitable reagent for the conversion of RCH2OH→RCHO is(a) KMnO4(b) K2Cr2O7(c) LiAlH4(d) PCC (Pyridinium Chlorochromate)
›Reveal solutionSolution
Selective oxidation of a 1° alcohol to an aldehyde (without over-oxidation to the acid) requires an anhydrous, mild oxidant — PCC — rather than a strong aqueous oxidant.
Why KMnO4 and K2Cr2O7 (a, b) fail: these are strong oxidising agents used in aqueous, typically acidified medium. The initially formed aldehyde reacts with water to form a geminal diol (aldehyde hydrate), RCH(OH)2, which is itself readily oxidised further by these strong oxidants to the carboxylic acid, RCOOH. So the reaction cannot be stopped cleanly at the aldehyde stage.
Why LiAlH4 (c) fails: this is a powerful reducing agent (it reduces esters, acids and other carbonyls down to alcohols) — the wrong direction entirely for an oxidation.
…
- CBSE 2026Set ANNUAL1 markQ.Complete the following reaction: aniline (benzene ring with an −NH2 substituent) +Br2(aq)→ ?
›Reveal solutionSolution
The −NH2 group is a powerful activating, ortho/para-directing group, so aniline reacts instantly with bromine water at all three activated ring positions to give 2,4,6-tribromoaniline as a white precipitate.
The lone pair on the amino nitrogen delocalises into the aromatic ring by resonance, strongly raising electron density especially at the ortho (2,6) and para (4) positions. This makes those three positions so reactive toward electrophiles that no Lewis-acid catalyst is required (unlike ordinary benzene bromination, which needs FeBr3), and substitution does not stop after one bromination — it proceeds at all three activated sites simultaneously: …
- CBSE 2026Set ANNUAL1 markQ.Fill in the blank: In addition of bromine in CCl4 to an alkene resulting in disappearance of reddish brown colour of bromine constitutes, an important method for the detection of ______ in a molecule.
›Reveal solutionSolution
Decolourisation of bromine in CCl4 detects unsaturation (C=C double bond).
An alkene readily adds bromine across its carbon-carbon double bond to form a colourless dibromide:
C=C + Br2 -> Br-C-C-Br
…
- CBSE 2026Set ANNUAL1 markQ.Write True or False: Bromo, iodo and polychloro derivatives of hydrocarbons are heavier than water.
›Reveal solutionSolution
True - these halogen derivatives are denser than water.
The heavy halogen atoms (Br, I) and multiple chlorine atoms greatly increase the molar mass and density of the molecule. As a result, bromo, iodo and polychloro derivatives of hydrocarbons (e.g. bromoform, iodoform, chloroform, …
- CBSE 2026Set SEM31 markMCQQ.The reagent which can be used for the following transformation is: phenol (C6H5OH) -> salicylaldehyde (2-hydroxybenzaldehyde, OH and CHO on adjacent ring carbons)(a) i) CHCl3, NaOH, 60-80 C ii) dil. HCl(b) i) CO2, NaOH, 120-140 C ii) dil. HCl(c) i) CCl4, NaOH, 60-80 C ii) dil. HCl(d) i) HCHO, NaOH ii) dil. HCl
›Reveal solutionSolution
Phenol + CHCl3 + NaOH (60-80 C) then acidification gives 2-hydroxybenzaldehyde (salicylaldehyde) by the Reimer-Tiemann reaction. Correct option (a).
In the Reimer-Tiemann reaction, chloroform (CHCl3) with aqueous NaOH generates dichlorocarbene (:CCl2), the electrophile. It attacks the phenoxide ring, chiefly at the ortho position; subsequent hydrolysis on acidification (dil. HCl) converts the -CHCl2 group into -CHO, introducing an aldehyde group ortho to -OH.
Product: salicylaldehyde (2-hydroxybenzaldehyde).
- CO2/NaOH (option b) is the Kolbe reaction, giving salicylic acid (-COOH), not the aldehyde. …
- CBSE 2025Set 56/5/11 markMCQQ.CH3CH2OH can be converted to CH3CHO by : (A) catalytic hydrogenation (B) treatment with LiAlH4 (C) treatment with PCC (D) treatment with KMnO4
›Reveal solutionSolution
The key idea is that converting ethanol (CH3CH2OH) to ethanal (CH3CHO) is a controlled oxidation of a primary alcohol to an aldehyde. The correct reagent is PCC (pyridinium chlorochromate), which stops at the aldehyde stage without over-oxidizing to a carboxylic acid.
This question tests your understanding of alcohol oxidation — a core reaction in organic chemistry. Ethanol is a primary alcohol. To get an aldehyde, you need to oxidize it partially. The challenge is that many strong oxidizers will push the reaction all the way to the carboxylic acid (acetic acid, CH3COOH). So the trick is choosing a reagent that is mild enough to stop at the aldehyde.
Let’s examine each option.
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Option (A): Catalytic hydrogenation
Hydrogenation (H2 with a metal catalyst like Pd, Pt, or Ni) is a reduction process. It adds hydrogen across double or triple bonds. Ethanol has no multiple bonds to reduce — it’s already saturated. This would do nothing. So this is wrong.
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Option (B): Treatment with LiAlH4
Lithium aluminium hydride is a powerful reducing agent. It reduces carbonyl compounds (aldehydes, ketones, acids, esters) to alcohols. Using it on ethanol would be pointless — ethanol is already an alcohol. It cannot oxidize anything. So this is also wrong.
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Option (C): Treatment with PCC
PCC (pyridinium chlorochromate, C5H5NH+CrO3Cl−) is a mild oxidizing agent specifically designed for the conversion of primary alcohols to aldehydes. It works in anhydrous conditions (typically in dichloromethane) and stops cleanly at the aldehyde stage.
The reaction:
CH3CH2OHPCCCH3CHO
This is the textbook method. So this is correct.
- Option (D): Treatment with KMnO4 …
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- CBSE 2025Set 56/6/11 markMCQQ.Which one of the following amines gives an alcohol on reaction with HNO2 ? (A) C6H5NH2 (aniline) (B) C2H5NH2 (C) (C2H5)2NH (D) (C2H5)3N
›Reveal solutionSolution
The key idea is that primary aliphatic amines react with nitrous acid (HNO2) to give alcohols via a diazonium intermediate that decomposes. Among the options, only C2H5NH2 (ethylamine) is a primary aliphatic amine, so it yields ethanol. The correct option is (B).
The reaction of an amine with nitrous acid (HNO2) is a classic test to distinguish between primary, secondary, and tertiary amines. Nitrous acid is unstable and is prepared in situ by reacting sodium nitrite (NaNO2) with a mineral acid like HCl or H2SO4. The outcome depends entirely on the class of the amine.
For primary aliphatic amines (like ethylamine), the reaction proceeds through an unstable alkyldiazonium salt. This salt spontaneously decomposes to give a carbocation, which then reacts with water to form an alcohol. This is the only case where an alcohol is the major product.
For primary aromatic amines (like aniline), the diazonium salt formed is stable at low temperatures (0–5°C) and does not give an alcohol with water — it gives phenol only upon heating or under specific conditions. At room temperature, aniline reacts with HNO2 to give a diazonium salt that can couple or decompose to other products, but not ethanol.
For secondary amines (like diethylamine), the reaction yields a yellow, oily N-nitrosamine — no alcohol is formed.
For tertiary amines (like triethylamine), the reaction gives a nitrosamine salt or simply dissolves, again no alcohol.
So the only amine that reliably gives an alcohol under standard conditions is a primary aliphatic amine.
Let’s check each option:
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Option (A): C6H5NH2 (aniline) — This is a primary aromatic amine. With HNO2 at 0–5°C, it forms a stable benzenediazonium salt. This salt does not decompose to give an alcohol at low temperature; it requires heating with water to yield phenol. Under the usual conditions of the reaction (room temperature or slightly above), aniline gives a diazonium salt that may undergo coupling or other reactions, but not an alcohol. So this is not the answer.
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Option (B): C2H5NH2 (ethylamine) — This is a primary aliphatic amine. The reaction with HNO2 proceeds as:
C2H5NH2+HNO2→[C2H5N2+]H2OC2H5OH+N2+H+
The intermediate ethyldiazonium ion is unstable and immediately loses N2 to form an ethyl carbocation, which then reacts with water to give ethanol. This is the classic case where an alcohol is produced. So this is the correct option.
- Option (C): (C2H5)2NH (diethylamine) — This is a secondary amine. With HNO2, it forms a yellow, oily N-nitrosamine: …
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- CBSE 2025Set ANNUAL1 markQ.Aniline does not undergo Friedel-Crafts reaction. Give reason.
›Reveal solutionSolution
The catalyst itself reacts with aniline's basic amino group, deactivating the ring before any substitution can occur.
Friedel–Crafts reactions (alkylation/acylation) require the Lewis acid catalyst AlCl3. Aniline's −NH2 group is strongly basic (it has a lone pair on nitrogen), so it readily reacts with AlCl3 to form a salt/complex (C6H5N+H2−AlCl3−).
…
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