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Mistake Bank: Haloalkanes & Haloarenes | Chemca

Mistake Bank: Haloalkanes & Haloarenes | Chemca

The Mistake Bank

Class 12 - Chapter 10: Haloalkanes & Haloarenes

Substitution or Elimination? The conditions decide, not you.

Aqueous vs Alcoholic KOH

Reagent Conditions

Scenario: $CH_3CH_2Cl$ reacted with Alcoholic KOH ($KOH_{alc}$).

What Students Do

Student sees OH group and assumes substitution.

Product: Ethanol ($CH_3CH_2OH$).

(Wrong! This happens with Aqueous KOH.)

The Correct Way

Alcoholic = Elimination!

In alcohol, the ethoxide ion ($C_2H_5O^-$) acts as a strong base, not just a nucleophile.

It abstracts a $\beta$-hydrogen, causing Dehydrohalogenation.

Product: Ethene ($CH_2=CH_2$).

Grignard + Moisture

Grignard Reagent

Scenario: Prepare Phenyl Magnesium Bromide ($PhMgBr$) in a flask containing moist air.

What Students Do

Student writes the formation reaction: $PhBr + Mg \rightarrow PhMgBr$.

Assumes product is stable.

The Correct Way

Grignard hates Protons!

Grignard reagents are extremely strong bases. If there is any moisture ($H_2O$), they abstract the proton immediately.

$$ PhMgBr + H_2O \rightarrow Ph-H + Mg(OH)Br $$

Product: Benzene (The reagent is destroyed).

KCN vs AgCN

Ambident Nucleophiles

Scenario: Reaction of Ethyl Chloride ($C_2H_5Cl$) with $AgCN$ (Silver Cyanide).

What Students Do

Student sees "CN" and attaches Carbon.

Product: Ethyl Cyanide ($C_2H_5CN$).

(This happens with ionic KCN!)

The Correct Way

AgCN is Covalent!

In AgCN, the Carbon is bonded to Silver covalently, so only the Nitrogen lone pair is available for attack.

Result: Attack occurs via Nitrogen.

Product: Ethyl Isocyanide ($C_2H_5NC$).

Reactivity of Chlorobenzene

Nucleophilic Substitution

Scenario: React Chlorobenzene with aqueous NaOH at room temperature.

What Students Do

Student applies SN mechanism.

Product: Phenol.

(Haloarenes are stubborn!)

The Correct Way

Partial Double Bond Character!

Due to resonance, the C-Cl bond acquires partial double bond character. It is very strong.

No Reaction occurs at room temperature.

Requires drastic conditions (623K, 300atm) to force the reaction (Dow's Process).

Stereochemistry of SN2

Mechanism

Scenario: Draw the product of SN2 reaction on (R)-2-Bromobutane.

What Students Do

Student replaces Br with OH while keeping the same orientation.

Product: (R)-2-Butanol.

(Retention of configuration?)

The Correct Way

Walden Inversion (Umbrella Flip)!

In SN2, the nucleophile attacks from the backside.

This flips the configuration of the molecule.

Product: (S)-2-Butanol (Inversion of configuration).

SN1 Stability Check

Mechanism

Scenario: Which undergoes SN1 faster? Benzyl Chloride ($C_6H_5CH_2Cl$) or Chlorobenzene?

What Students Do

Student thinks: "Both have benzene rings, so they are similar."

Or thinks Chlorobenzene is $2^\circ$ (it's not) and Benzyl is $1^\circ$.

The Correct Way

Look at the Carbocation!

Benzyl Cation: Stabilized by Resonance ($Ph-CH_2^+$). Very fast SN1.

Phenyl Cation: Positive charge on $sp^2$ carbon. Highly unstable. No SN1.

Answer: Benzyl Chloride is much faster.

Confess Your Sins!

"Organic reactions have conditions. If you ignore them, they will ignore you."

Did one of these catch you? Or do you have a different horror story from your last exam?

Scroll down to the comments section below and tell us:

"Which mistake were you making?"

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