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. …
- GSEB Higher Secondary Certificate (HSC) Examination 2026Set ANNUAL1 markMCQQ.Which is the major product Z in the following reaction? [benzene ring]-CH2-CH=CH2 + HBr --Peroxide--> Z(a) [benzene ring]-CH2-CH2-CH2-Br(b) benzene ring with -CH2-CH2-CH3 and ring -Br (ortho, as drawn)(c) [benzene ring]-CH2-CH(Br)-CH3(d) benzene ring with -CH2-CH=CH2 and ring -Br (non-adjacent position, as drawn)
›Reveal solutionSolution
HBr + peroxide adds via a free-radical mechanism, giving the anti-Markovnikov product — Br ends up on the terminal (less substituted) carbon.
Starting material: an allylbenzene, Ar–CH2–CH=CH2, reacting with HBr in the presence of peroxide.
Normally (no peroxide), HBr would add via ionic Markovnikov addition (H to the carbon with more H's, Br to the more substituted carbon, via the more stable carbocation). But peroxides trigger a radical chain mechanism (the peroxide effect / Kharasch effect), which is exclusive to HBr among the hydrogen halides:
- Peroxide generates a Br• radical. …
- GUJCET 2024Set 131 markMCQQ.What is the major product in the following reaction? CH3−HCCH3−CH=CH2HX? (3-methylbut-1-ene reacting with HX) (A) X−CH2−HCCH3−CH2−CH3 (X on the terminal carbon, methyl and H on the second carbon) (B) CH3−XCCH3−CH2−CH3 (X on the second, methyl-bearing carbon) (C) CH3−HCCH3−CH2−CH2−X (X on the terminal carbon of the far end) (D) CH3−HCCH3−XCH−CH3 (X on the carbon adjacent to the methyl-bearing carbon)
›Reveal solutionSolution
HX adds Markovnikov; the intermediate 2° carbocation undergoes a 1,2-hydride shift to a more stable 3° cation before X attaches.
Concept. In electrophilic addition of HX, the proton adds to give the more stable carbocation, which can rearrange to an even more stable one. …
- GUJCET 2021Set 151 markMCQQ.What is A in following reaction? Phenyl group with −CH2−CH=CH2 side chain (allylbenzene) +HCl→A. [FIGURE: structures of the four product options are drawn] (A) 2-chloro-substituted benzene ring bearing a −CH2−CH=CH2 (allyl) side chain (Cl on the ring, ortho) (B) benzene ring with a −CH2−CH2−CH2−Cl side chain (C) benzene ring with a −CH(Cl)−CH2−CH3 side chain (Cl on the carbon attached to ring) (D) benzene ring with a −CH2−CH(Cl)−CH3 side chain (Markovnikov product, Cl on middle carbon)
›Reveal solutionSolution
Allylbenzene + HCl → Markovnikov addition; Cl goes to the more substituted (middle) carbon.
Concept: For addition of HX to an unsymmetrical alkene, H adds to the carbon with more hydrogens and X to the carbon that forms the more stable (more substituted) carbocation. …
- GSEB Higher Secondary Certificate (HSC) Examination 2020Set ANNUAL1 markMCQQ.The IUPAC name of major organic product of the reaction CH3CH2CH=CH2 + HBr --(peroxide)--> is ______.(a) 1-Bromobutane(b) 2,2-Dibromobutane(c) 1,2-Dibromobutane(d) 2-Bromobutane
›Reveal solutionSolution
Peroxides reverse the usual (Markovnikov) regiochemistry of HBr addition to an alkene, because the reaction now proceeds by a free-radical chain mechanism that places Br on the terminal carbon.
CH3CH2CH=CH2 (but-1-ene) + HBr, normally (no peroxide, ionic mechanism) follows Markovnikov's rule, putting Br on the more substituted internal carbon (giving 2-bromobutane). But in the PRESENCE of peroxide, the reaction switches to a free-radical chain mechanism (the Kharasch/peroxide effect): a Br. radical adds first to the terminal (less hindered) carbon of the double bond, generating the more stable secondary …
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