Q.Match the reactions given in Column I with the names given in Column II.
Column I:
(i)
Column II:
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🔒 Start your 14-day free trial to unlock the full solution →Concept understanding — Markovnikov Addition
The Intuition First
Imagine you have an alkene — a carbon-carbon double bond. That double bond is like a crowded room with two doors. When a molecule like HBr comes along, it wants to break that double bond and add across it. The question is: which carbon gets the hydrogen, and which gets the bromine?
You might think it doesn't matter — after all, the two carbons look similar. But they aren't. One carbon usually has more alkyl groups (methyl, ethyl, etc.) attached to it than the other. That carbon is more "electron-rich" — it has more friends pushing electrons toward it.
The hydrogen, being small and positively charged, is picky. It goes to the carbon that already has more hydrogens. Why? Because that carbon is less crowded and can stabilise the positive charge that forms temporarily during the reaction. The bromine, being large and negatively charged, goes to the other carbon — the one with more alkyl groups.
That's the intuition: the rich get richer. The carbon with more hydrogens gets another hydrogen. The carbon with more alkyl groups gets the halogen.
The Precise Statement
Markovnikov's Rule: When an unsymmetrical reagent (like HX, H₂O, etc.) adds to an unsymmetrical alkene, the hydrogen atom attaches to the carbon of the double bond that already has the greater number of hydrogen atoms.
In other words, for an alkene like CH3CH=CH2 (propene) reacting with HBr:
- Carbon 1 (the CH₂ end) has 2 hydrogens.
- Carbon 2 (the CH end) has 1 hydrogen.
- The H goes to carbon 1 (more hydrogens).
- The Br goes to carbon 2 (fewer hydrogens).
So the product is CH3CHBrCH3 (2-bromopropane), not CH3CH2CH2Br (1-bromopropane).
Why Does This Happen? The Real Chemistry
The reaction proceeds through a carbocation intermediate. When the H⁺ attacks the double bond, it can form one of two possible carbocations:
- A primary carbocation (if H⁺ goes to the more substituted carbon) — unstable.
- A secondary carbocation (if H⁺ goes to the less substituted carbon) — more stable.
The reaction chooses the path that gives the more stable carbocation. Alkyl groups stabilise carbocations through hyperconjugation and inductive effect — they donate electron density to the positively charged carbon.
The stability order of carbocations is: tertiary > secondary > primary > methyl. Markovnikov addition always proceeds through the most stable carbocation possible.
A Common Misconception
Many students think Markovnikov's rule means "hydrogen goes to the carbon with more hydrogens" because that carbon already has more hydrogens. That's backwards. The hydrogen goes there because that path leads to a more stable carbocation — the number of hydrogens is just a convenient way to predict the outcome, not the cause.
The One Big Exception …
Why this formula?
Markovnikov Addition: Why the Rule Holds
Markovnikov's rule is not a formula in the algebraic sense — it's a predictive principle for electrophilic addition to unsymmetrical alkenes. The "why" comes from carbocation stability and reaction mechanism.
The Rule in Words
When H–X adds to an unsymmetrical alkene, the hydrogen attaches to the carbon with more hydrogen atoms already attached, and the halogen (or X group) attaches to the carbon with fewer hydrogen atoms.
Example:
Propene (CHX3−CH=CHX2) + HBr → 2-bromopropane (major product), not 1-bromopropane.
Why This Happens: The Step-by-Step Reasoning
1. The Mechanism (Electrophilic Addition)
The reaction proceeds in two steps:
- Slow step (rate-determining): The alkene's π bond attacks the electrophilic HX+ from H–X, forming a carbocation intermediate.
- Fast step: The carbocation is attacked by the nucleophilic XX−.
2. The Key: Carbocation Stability
The more stable carbocation intermediate forms faster and determines the major product.
| Carbocation Type | Stability Order | Reason |
|---|---|---|
| Tertiary (3∘) | Most stable | +3 alkyl groups donate electron density via hyperconjugation and inductive effect |
| Secondary (2∘) | Intermediate | +2 alkyl groups |
| Primary (1∘) | Least stable | +1 alkyl group |
| Methyl (CHX3X+) | Unstable | No alkyl stabilization |
3. Applying to Propene + HBr
Propene: CHX3−CH=CHX2
Two possible protonation sites:
- Path A (Markovnikov): HX+ adds to CHX2 (terminal carbon) → forms secondary carbocation:
CHX3−CHX+−CHX3(2∘)
- Path B (Anti-Markovnikov): HX+ adds to CH (middle carbon) → forms primary carbocation:
CHX3−CHX2−CHX2X+(1∘)
Result: The secondary carbocation is more stable (by ~25–30 kJ/mol), so Path A is faster. The BrX− then attacks the positively charged carbon, giving 2-bromopropane.
The "Formula" — A Stability-Based Prediction
There is no algebraic formula, but a decision rule:
Major product=Product from the more stable carbocation
For alkenes with alkyl substituents, the stability order is:
Tertiary>Secondary>Primary>Methyl …
Concept: These are name reactions from organic chemistry — each is a standard method for forming carbon–carbon bonds or substituting halogens.
Reasoning:
- (i) Aryl halide + alkyl halide + Na gives an alkylarene. This is the Wurtz–Fittig reaction (cross-coupling of two different halides). → matches (b).
- (ii) Two aryl halides + Na in ether gives a biaryl. This is the Fittig reaction (homocoupling of aryl halides). → matches (a). …
This is a matching problem linking four organic reactions to their standard name. The correct mapping is (i)→ (b), (ii)→ (a), (iii)→ (d), (iv)→ (c).
The key to solving this is recognising the reagent pattern and the product structure — each reaction has a classic signature that tells you which name it belongs to. Let’s walk through them one by one.
-
Reaction (i): C6H5X+RXNaC6H5R
An aryl halide and an alkyl halide react with sodium metal to give an alkylbenzene. This is a cross-coupling between an aromatic and an aliphatic halide.
That’s the hallmark of the Wurtz–Fittig reaction — it’s a variant of the Wurtz reaction where one partner is aromatic.
→ Matches with (b).
-
Reaction (ii): 2C6H5X+2NaEtherC6H5−C6H5+2NaX
Two aryl halides couple in the presence of sodium to form a biaryl (diphenyl). No alkyl halide is involved.
This is the Fittig reaction (sometimes called the Wurtz–Fittig reaction when alkyl halides are also present, but here it’s purely aromatic).
→ Matches with (a).
-
Reaction (iii): C6H5N2+X−Cu2X2C6H5X+N2
A diazonium salt is decomposed by cuprous halide (Cu2X2) to replace the diazonium group with a halogen. Nitrogen gas is evolved.
This is the classic Sandmeyer reaction — the copper(I) halide catalyses the substitution.
→ Matches with (d).
-
Reaction (iv): C2H5Cl+NaIdry acetoneC2H5I+NaCl …
Concept: Named Reactions in Organic Chemistry (Aryl and Alkyl Halides)
This is a matching question based on recognising the reagent, conditions, and product pattern of standard named reactions.
Method: Pattern Recognition by Reagent & Product Type
Steps:
- Identify the substrate — is it an alkyl halide, aryl halide, or diazonium salt?
- Identify the reagent and conditions — Na/ether, Cu₂X₂, NaI/acetone, etc.
- Match the transformation to the standard reaction definition.
Step-by-step matching:
(i) C6H5X+RXNaC6H5R
- Substrate: Aryl halide + Alkyl halide
- Reagent: Sodium metal
- Product: Alkyl benzene
- Pattern: Combination of Wurtz reaction (alkyl-alkyl) and Fittig reaction (aryl-aryl) → Wurtz-Fittig reaction
- Match: (b)
(ii) 2C6H5X+2NaEtherC6H5−C6H5+2NaX
- Substrate: Two aryl halides
- Reagent: Sodium in dry ether
- Product: Biphenyl (diaryl)
- Pattern: Coupling of two aryl halides → Fittig reaction
- Match: (a)
(iii) C6H5N2+X−Cu2X2C6H5X+N2
- Substrate: Diazonium salt
- Reagent: Cuprous halide (Cu₂X₂)
- Product: Aryl halide + N₂ gas
- Pattern: Replacement of diazonium group by halogen using copper catalyst → Sandmeyer reaction
- Match: (d)
(iv) C2H5Cl+NaIdry acetoneC2H5I+NaCl
- Substrate: Alkyl chloride
- Reagent: NaI in dry acetone …
Here are the common mistakes students make when matching these reactions, along with how to avoid each.
Mistake 1: Confusing the Wurtz-Fittig and Fittig Reactions
- The Mistake: Students often mix up reaction (i) and (ii). They see sodium (Na) and an aryl halide in both and assume they are the same type of reaction. Specifically, they might label (i) as the Fittig reaction or (ii) as the Wurtz-Fittig reaction.
- Why it happens: Both reactions use sodium metal and involve aryl halides. The key difference is the number of different halides used.
- How to Avoid:
- Focus on the reactants.
- Wurtz-Fittig (i): Involves two different halides: one aryl (C6H5X) and one alkyl (RX). The product is an alkylbenzene (C6H5R).
- Fittig (ii): Involves only one type of halide: an aryl halide (C6H5X). The product is a biphenyl (C6H5−C6H5).
- Memory Trick: "Wurtz-Fittig" has W and F — think "With Friends" (two different partners: alkyl + aryl). "Fittig" is just F — think "Family" (same type: aryl + aryl).
- Focus on the reactants.
Mistake 2: Forgetting the Catalyst in the Sandmeyer Reaction
- The Mistake: Students match reaction (iii) with the Sandmeyer reaction but forget the crucial role of the copper(I) halide (Cu2X2). They might think any diazonium salt decomposition is a Sandmeyer reaction.
- Why it happens: The reaction looks simple: a diazonium salt (C6H5N2+X−) is converted to an aryl halide (C6H5X). Students memorize the "diazonium to halide" part but miss the specific reagent.
- How to Avoid:
- Memorize the specific reagent. The Sandmeyer reaction is defined by the use of a cuprous halide (Cu2X2 or CuX) as a catalyst.
- Compare with similar reactions:
- Sandmeyer: C6H5N2+Cl−Cu2Cl2/HClC6H5Cl
- Gattermann reaction: C6H5N2+Cl−Cu/HClC6H5Cl (uses copper metal, not its salt).
- Simple substitution (without catalyst): C6H5N2+Cl−H2OC6H5OH (gives phenol, not halide).
- Exam Tip: If you see Cu2X2 or CuX with a diazonium salt, the answer is Sandmeyer.
Mistake 3: Misidentifying the Finkelstein Reaction
- The Mistake: Students fail to recognize reaction (iv) as the Finkelstein reaction because they don't immediately see the "iodide for chloride" swap. …
- CBSE 2025Set ANNUAL1 markQ.Draw the structure of the major monohalo product: 1-methylcyclohexene (a cyclohexene ring with a CH3 substituent on one of the double-bond carbons) +HI→?
›Reveal solutionSolution
Markovnikov addition of HI to 1-methylcyclohexene puts I on the more substituted carbon (C-1, which already bears –CH3), via the more stable tertiary carbocation, giving 1-iodo-1-methylcyclohexane.
In 1-methylcyclohexene the double bond is between ring carbons C-1 and C-2, with a –CH3 group on C-1. Electrophilic addition of HI proceeds in two steps:
Step 1 (protonation): H+ adds to the alkene carbon that gives the more stable carbocation. Adding H+ to C-2 places the positive charge on C-1, which is a tertiary carbocation (bonded to the ring's C-2 and C-6, plus the –CH3 group). Adding H+ instead to C-1 would place the charge on C-2, only a secondary carbocation. Since 3° carbocations are more stable (greater hyperconjugation/inductive stabilisation from three alkyl groups) than 2°, the reaction proceeds through the C-1 cation — this is Markovnikov's rule (the H goes to the carbon already bearing more hydrogens, i.e. C-2).
1-methylcyclohexene+H+→1-methylcyclohexan-1-yl cation (3°, at C-1)
…
- CBSE 2024Set ANNUAL1 markQ.Complete the following reaction: 1-methylcyclohexene (a cyclohexene ring with a CH3 substituent on one of the double-bond carbons) +HI→?
›Reveal solutionSolution
Markovnikov's rule: with unsymmetrical alkenes, H+ from HX adds to the carbon that generates the more stable (here, tertiary) carbocation, and the halide ion then bonds to that carbon.
1-Methylcyclohexene has its ring double bond between C1 (bearing the CH3 substituent) and C2 (bearing only H). Protonation of the alkene can occur in two ways:
- H+ adds to C1 ⇒ carbocation forms at C2, a secondary carbocation (flanked by C1 and C3, both ring carbons).
- H+ adds to C2 ⇒ carbocation forms at C1, a tertiary carbocation (bonded to CH3, C2 and C6 — three carbon substituents). …
- CBSE 2020Set NC1 markQ.Write the reaction with conditions for conversion of 2-methylpropene into 1-bromo-2-methylpropane.
›Reveal solutionSolution
Ordinary Markovnikov addition of HBr to 2-methylpropene would put Br on the more-substituted carbon; getting the anti-Markovnikov product (Br on the terminal carbon) needs the peroxide-initiated free-radical mechanism (Kharasch/peroxide effect).
Target: 2-methylpropene, (CH3)2C=CH2 (isobutylene), converted into 1-bromo-2-methylpropane, (CH3)2CH–CH2Br — i.e. Br ends up on the terminal (less substituted) carbon, which is the opposite regiochemistry to normal Markovnikov addition (which would instead place Br on the more substituted carbon, giving 2-bromo-2-methylpropane).
…
- CBSE 2019Set ANNUAL1 markQ.Identify the products A and B formed in the following reaction: CH3–CH2–CH=CH–CH3+HCl→A+B
›Reveal solutionSolution
CH3–CH2–CH=CH–CH3 is pent-2-ene; electrophilic addition of HCl proceeds via protonation to give whichever secondary carbocation is more stabilised, so the products are a mixture of 2-chloropentane (major) and 3-chloropentane (minor).
The alkene CH3–CH2–CH=CH–CH3 is pent-2-ene, numbered C1H3–C2H2–C3H=C4H–C5H3, with the double bond between C3 and C4 (equivalently C2–C3 counting from the other end). Since this alkene is unsymmetrically substituted but both carbons of the double bond are internal, protonation of either carbon gives a secondary carbocation, so a mixture of two constitutional isomers is obtained:
- H+ adds to C3: leaves the cation at C4, giving CH3–CH2–CH2–CH+–CH3 — this secondary cation is flanked by a −CH2CH2CH3 (propyl) group on one side and a −CH3 on the other, i.e. more hyperconjugating α-hydrogens overall, making it the somewhat more stabilised carbocation. Cl− then attacks here, giving CH3–CH2–CH2–CHCl–CH3, i.e. 2-chloropentane (major). …
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