Haloalkanes & Haloarenes
Class XII • Organic Chemistry • Unit 6
1. Introduction & Classification
Definition: Haloalkanes (Alkyl halides) and Haloarenes (Aryl halides) are obtained by the
replacement of hydrogen atom(s) in hydrocarbons by halogen atoms (X = F, Cl, Br, I).
Importance in Daily Life:
Chloramphenicol: Antibiotic for Typhoid.
Chloroquine: Treatment for Malaria.
Halothane: Anaesthetic in surgery.
Thyroxine: Iodine-containing hormone (prevents Goiter).
A. Classification based on Hybridisation
1. Compounds containing sp³ C—X Bond:
Alkyl Halides (R-X): Halogen attached to alkyl chain. (1°, 2°, 3°)
Allylic Halides: Halogen attached to sp³ carbon next to a C=C double bond.
CH₂=CH—CH₂—X
Benzylic Halides: Halogen attached to sp³ carbon next to an aromatic ring.
Ph—CH₂—X
2. Compounds containing sp² C—X Bond:
Vinylic Halides: Halogen attached directly to C=C double bond.
CH₂=CH—X
(Very stable due to partial double bond character!)
Aryl Halides: Halogen attached directly to Benzene ring.
Ph—X
2. Nature of C-X Bond
Since halogen atoms are more electronegative than carbon, the carbon-halogen bond is polarized.
—Cδ+ — Xδ-
Periodic Trends (Group 17)
Property Trend Reason
Bond Length C-F < C-Cl < C-Br < C-I Size of halogen atom increases.
Bond Enthalpy C-F > C-Cl > C-Br > C-I Longer bonds are weaker and easier to break.
Reaction
Important Board Question:
Why is the dipole moment of Chloromethane (CH₃Cl) higher than Fluoromethane (CH₃F)?
Dipole Moment (μ) = Charge (q) × Distance (d)
• Fluorine is more electronegative (high q), but the C-F bond is very short (low d).
• Chlorine has less charge but a significantly longer bond length.
• The product (q × d) is maximum for C-Cl.
Order: CH₃Cl > CH₃F > CH₃Br > CH₃I
3. Methods of Preparation
A. From Alcohols (R-OH)
This is the most widely used method because alcohols are easily accessible.
Reaction
1. Groove's Process (Lucas Reagent)
R—OH + HCl (ZnCl₂) ⟶ R—Cl + H₂O
Reagent: Conc. HCl + Anhydrous ZnCl₂.
Reactivity: 3° > 2° > 1°
3° Alcohols react instantly (Turbidity). 1° require heating.
Reaction
2. Darzen's Process (Thionyl Chloride)
R—OH + SOCl₂ ⟶ R—Cl + SO₂↑ + HCl↑
★ Why is this preferred?
Because the by-products (SO₂ and HCl) are gases and escape, leaving behind pure alkyl halide
without needing distillation.
Reaction
3. Phosphorous Halides
R—OH + PCl₅ ⟶ R—Cl + POCl₃ + HCl
3R—OH + PCl₃ ⟶ 3R—Cl + H₃PO₃
B. From Hydrocarbons
Reaction
1. Free Radical Halogenation
CH₃CH₂CH₂CH₃ + Cl₂ (UV Light) ⟶ Mixture
• Produces a mixture of isomeric mono- and polyhaloalkanes.
• Difficult to separate pure components (Low yield).
Reaction
2. Electrophilic Addition (From Alkenes)
Addition of Hydrogen Halides (HX).
CH₃-CH=CH₂ + H-I ⟶ CH₃-CH(I)-CH₃
Markovnikov's Rule:
"The negative part of the addendum (Halide ion) attaches to the carbo
n atom
possessing fewer hydrogen atoms."
Peroxide Effect (Anti-Markovnikov):
• Only applies to HBr.
• Only in presence of Peroxide.
CH₃-CH=CH₂ + HBr (Peroxide) ⟶ CH₃-CH₂-CH₂-Br
C. Halogen Exchange Reactions
Crucial Name Reactions for synthesizing Iodides and Fluorides.
Reaction
1. Finkelstein Reaction
Used to prepare Alkyl Iodides.
R—X + NaI (Dry Acetone) ⟶ R—I + NaX↓
(X = Cl, Br)
Mechanism Note: NaCl or NaBr is less soluble in acetone and precipitates out. By Le Chatelier's
principle, removing the product drives the reaction forward.
Reaction
2. Swarts Reaction
Used to prepare Alkyl Fluorides.
R—Br + AgF ⟶ R—F + AgBr
Reagents: Heavy metal fluorides like AgF, Hg₂F₂, CoF₂, SbF₃.
This is one of the few methods to directly introduce Fluorine.
4. Physical Properties
1. Boiling Points
Molecules are polar and have strong dipole-dipole interactions and Van der Waals forces.
Trend with Mass: R-I > R-Br > R-Cl > R-F
Trend with Branching:
For isomeric haloalkanes, Boiling Point decreases as branching increases.
Why?
Branching makes the molecule more spherical ⟶ Surface Area decreases ⟶ Van der Waals
forces decrease ⟶ Boiling Point drops.
n-Butyl bromide (375K) > tert-Butyl bromide (346K)
2. Solubility
Haloalkanes are Insoluble in Water.
Reasoning:
To dissolve, energy is needed to break the H-bonds between water molecules. The new
attractions formed between Haloalkane and Water are weaker and don't release enough energy
to compensate.
However, they are soluble in organic solvents.
5. Nucleophilic Substitution Reactions
The most important characteristic reaction of Alkyl Halides.
Nu:⁻ + R—X ⟶ R—Nu + X:⁻
Nucleophiles Table
Reagent Nucleophile Product
NaOH (aq) OH⁻ Alcohol
NaOR' R'O⁻ Ether (Williamson)
NH₃ (alc) NH₃ Amine
KCN CN⁻ Nitrile (Cyanide)
AgCN Ag-CN Isocyanide
Ambident Nucleophiles:
Groups like Cyanide (CN) and Nitrite (NO₂) have two attacking centers.
• KCN is ionic ⟶ CN⁻ attacks via Carbon ⟶ Cyanide.
• AgCN is covalent ⟶ N lone pair attacks ⟶ Isocyanide.
6. Mechanism: SN2
Substitution Nucleophilic Bimolecular
Reaction
Rate ∝ [Alkyl Halide] [Nucleophile]
Order: Second Order Kinetics.
Steps: Single Step (Concerted).
Mechanism: Bond breaking (C-X) and bond making (C-Nu) happen simultaneously.
Stereochemistry: Inversion
The nucleophile attacks from the Back Side (opposite to the halogen).
The product configuration is inverted (like an umbrella turning inside out in the wind).
Walden Inversion.
Reactivity Order
1° > 2° > 3°
Reason: Steric Hindrance. Bulky groups in 3° halides block the approach of the nucleophile.
7. Mechanism: SN1
Substitution Nucleophilic Unimolecular
Reaction
Rate ∝ [Alkyl Halide]
Order: First Order Kinetics.
Steps: Two Steps.
Step 1: Formation of Carbocation (Slow/RDS)
The C-X bond breaks to form a planar carbocation intermediate.
Step 2: Attack of Nucleophile (Fast)
The nucleophile attacks the planar carbocation from either side.
Stereochemistry: Racemisation
Since the carbocation is planar (sp²), attack can happen from front or back with equal probability.
This results in a 50:50 mixture of Retention and Inversion products (Racemic Mixture).
Reactivity Order
3° > 2° > 1°
Reason: Stability of Carbocation. 3° carbocations are most stable due to inductive effect (+I) and
hyperconjugation.
8. Stereochemistry Basics
Essential definitions for board exams.
Chirality: An object that is non-superimposable on its mirror image (like hands) is chiral.
Condition: Presence of an Asymmetric Carbon (Carbon bonded to 4 different groups).
Enantiomers: Stereoisomers that are non-superimposable mirror images.
• Same Boiling/Melting points.
• Rotate Plane Polarised Light in opposite directions (Dextro/Laevo).
Racemic Mixture: An equimolar mixture of two enantiomers.
• Optically Inactive due to external compensation (rotation of one cancels the other).
Reaction
Enantiomers (Mirror Images)
9. Elimination Reactions
Dehydrohalogenation (β-Elimination)
R—CH₂—CH(X)—R + Alc. KOH ⟶ Alkene
Reagent Distinction:
• Aq. KOH: Substitution (forms Alcohol).
act proton.
• Alc. KOH: Elimination (forms Alkene). Acts as a strong base to abstr
Zaitsev Rule (Saytzeff Rule)
"In dehydrohalogenation reactions, the preferred product is that alkene which has the greater
number of alkyl groups attached to the doubly bonded carbon atoms." (More substituted alkene is
more stable).
Reaction
Example: 2-Bromopentane
⟶ Pent-2-ene (Major - 81%)
⟶ Pent-1-ene (Minor - 19%)
10. Reaction with Metals
Reaction
1. Grignard Reagent
R—X + Mg (Dry Ether) ⟶ R—Mg—X
Structure: The C-Mg bond is covalent but highly polar (C is δ-). The Mg-X bond is ionic.
Caution: Grignard reagents are highly reactive to protons (water, alcohol).
R-Mg-X + H₂O ⟶ R-H + Mg(OH)X
(This converts Alkyl Halide to Alkane)
Reaction
2. Wurtz Reaction
2RX + 2Na (Dry Ether) ⟶ R—R + 2NaX
• Used to prepare symmetrical alkanes with even carbon atoms.
• Not suitable for tertiary halides (Elimination occurs).
11. Reactions of Haloarenes
Why are they unreactive towards Nucleophilic Substitution?
This is a standard reasoning question.
Resonance Effect: The lone pair on Halogen conjugates with the benzene ring. The C-X bond acquires
Partial Double Bond Character. Breaking a double bond is much harder than a single bond.
Cl: Cl+
Hybridisation: The C in C-X bond is sp² hybridised. It has more s-character (33%) and is more
electronegative, holding the bond pair tightly. Bond length is shorter (169 pm) vs Alkyl Halide (177
pm).
Instability of Phenyl Cation: SN1 is ruled out because self-ionisation would produce a phenyl cation,
which is very unstable.
A. Nucleophilic Substitution (Drastic Conditions)
Reaction
Dow's Process
Chlorobenzene + NaOH (623K, 300atm) ⟶ Phenol
Requires extreme temperature and pressure.
Effect of Nitro Group (-NO₂)
Presence of Electron Withdrawing Groups (EWG) like NO₂ at Ortho and Para positions increases
reactivity significantly.
Compound Condition Needed
Chlorobenzene 623 K
p-Nitrochlorobenzene 443 K
2,4-Dinitrochlorobenzene 368 K
2,4,6-Trinitrochlorobenzene Warm Water!
Complex) through
Reason: NO₂ group stabilizes the carbanion intermediate (Meisenheimer
resonance.
Note: NO₂ at Meta position has NO effect on reactivity.
B. Electrophilic Substitution Reactions
Halogen atom is an exception in organic chemistry:
Deactivating: Due to -I effect (withdraws electrons).
Ortho-Para Directing: Due to +R resonance effect (increases electron density at o/p positions).
Reaction
1. Halogenation
Ph-Cl + Cl₂ (Anhyd FeCl₃) ⟶ 1,4-Dichlorobenzene (Major)
Reaction
2. Nitration
Ph-Cl + HNO₃/H₂SO₄ ⟶ 1-Chloro-4-nitrobenzene (Major)
Reaction
3. Friedel-Crafts Alkylation
Ph-Cl + CH₃Cl (Anhyd AlCl₃) ⟶ 1-Chloro-4-methylbenzene
Reaction
4. Wurtz-Fittig & Fittig
• Fittig: 2 Ph-X + 2Na ⟶ Diphenyl
• Wurtz-Fittig: Ph-X + R-X + 2Na ⟶ Alkylbenzene (Toluene)
12. Polyhalogen Compounds
Reaction
1. Dichloromethane (CH₂Cl₂)
Solvent, Paint remover. Harmful to CNS.
Reaction
2. Chloroform (CHCl₃)
Solvent, Anaesthetic (obsolete).
Danger: Oxidises in air/light to PHOSGENE (COCl₂), a deadly gas.
2CHCl₃ + O₂ ⟶ 2COCl₂ + 2HCl
Stored in dark bottles filled to brim to exclude air.
Reaction
3. Iodoform (CHI₃)
Yellow solid. Antiseptic. Properties due to liberation of free Iodine.
Reaction
4. Freons (CFCs)
Stable, unreactive gases. Refrigerants (Freon-12). Cause Ozone Depletion.
Reaction
5. DDT
Insecticide. Non-biodegradable. Causes Biomagnification (accumulates in fatty tissues). Banned.
~ End of Chapter ~