10.
1 Introduction
• Halogen derivatives are organic compounds in which one or more hydrogen
atoms of hydrocarbons are replaced by halogens (F, Cl, Br, I).
• General formula: R–X (where R = alkyl/aryl group and X = halogen).
• Parent family = Hydrocarbons.
10.2 Classification
(A) Based on Hydrocarbon Skeleton
1. Haloalkanes (Alkyl halides):
Halogen attached to sp³ carbon of saturated chain.
e.g., CH₃CH₂Cl (ethyl chloride)
o Primary (1°): R–CH₂–X
o Secondary (2°): R₂CH–X
o Tertiary (3°): R₃C–X
2. Haloalkenes (Vinylic halides):
Halogen attached to sp² carbon of double bond.
e.g., CH₂=CH–Cl (vinyl chloride)
3. Haloalkynes:
Halogen attached to sp carbon of triple bond.
e.g., CH≡C–Cl (chloroacetylene)
4. Haloarenes (Aryl halides):
Halogen directly attached to aromatic ring.
e.g., C₆H₅Cl (chlorobenzene)
5. Benzylic halides:
Halogen attached to carbon adjacent to benzene ring.
e.g., C₆H₅CH₂Cl (benzyl chloride)
(B) Based on Number of Halogen Atoms
• Monohalogen compounds: 1 halogen (CH₃Cl)
• Dihalogen compounds: 2 halogens (CH₂Cl₂)
• Trihalogen compounds: 3 halogens (CHCl₃)
• Polyhalogen compounds: more than 3 halogens (CCl₄)
Type Common Name IUPAC Name
CH₂Cl₂ Methylene chloride Dichloromethane
CH₃CH₂Br Ethyl bromide Bromoethane
Type Common Name IUPAC Name
(CH₃)₃CBr Tert-butyl bromide 2-Bromo-2-methylpropane
CH₂=CHCl Vinyl chloride Chloroethene
C₆H₅CH₂Br Benzyl bromide Bromomethylbenzene
10.4 Methods of Preparation
1. From Alcohols
R–OH + HX → R–X + H₂O
o Catalyst: ZnCl₂ / conc. HCl (Lucas reagent)
o Order of reactivity: 3° > 2° > 1°
Examples:
o With SOCl₂: R–OH + SOCl₂ → R–Cl + SO₂ + HCl
o With PCl₅: R–OH + PCl₅ → R–Cl + POCl₃ + HCl
2. Halogenation of Hydrocarbons
o Alkane + Cl₂ (hv) → Alkyl chloride + HCl
o Controlled conditions for monohalogenation.
3. From Alkenes and Alkynes
o Addition of HX: CH₂=CH₂ + HBr → CH₃CH₂Br
o Markovnikov’s Rule applies.
4. From Silver Salts of Acids (Hunsdiecker Reaction)
RCOOAg + Br₂ → R–Br + CO₂ + AgBr
5. Finkelstein Reaction:
R–Cl + NaI (in acetone) → R–I + NaCl↓
6. Swarts Reaction:
R–Cl + AgF → R–F + AgCl↓
7. Sandmeyer Reaction:
Ar–N₂Cl + CuCl → Ar–Cl + N₂ (prepares aryl halides)
10.5 Physical Properties
• Polarity: C–X bond polar; carbon positive (δ⁺), halogen negative (δ⁻).
• Bond strength order: C–F > C–Cl > C–Br > C–I
• Boiling Point: Increases with molar mass (RI > RBr > RCl > RF).
• Solubility: Insoluble in water (non-polar), soluble in organic solvents.
• Density: Alkyl iodides > bromides > chlorides.
10.6 Chemical Properties
(A) Nucleophilic Substitution Reactions (SN)
General Reaction:
R–X + Nu⁻ → R–Nu + X⁻
Examples:
1. R–X + NaOH → R–OH + NaX (alcohol formation)
2. R–X + NaOR′ → R–O–R′ + NaX (ether formation)
3. R–X + R′COOAg → R′COOR + AgX (ester)
4. R–X + NH₃ → R–NH₂ + HX (amine)
5. R–X + KCN → R–CN + KX (nitrile)
6. R–X + AgCN → R–NC + AgX (isocyanide)
7. R–X + KNO₂ → R–ONO (alkyl nitrite)
8. R–X + AgNO₂ → R–NO₂ (nitroalkane)
(B) Mechanisms
1. SN2 (Bimolecular Nucleophilic Substitution):
o One-step reaction.
o Rate = k[R–X][Nu⁻]
o Inversion of configuration.
o Favored by 1° alkyl halides.
2. SN1 (Unimolecular Nucleophilic Substitution):
o Two-step reaction via carbocation.
o Rate = k[R–X]
o Racemization of product.
o Favored by 3° alkyl halides.
(C) Elimination Reactions (β-elimination)
• Formation of alkenes:
R–CH₂–CH₂–X + KOH (alc.) → R–CH=CH₂ + KX + H₂O
o Zaitsev’s rule: Major product = most substituted alkene.
10.7 Reactions of Aryl Halides (Haloarenes)
1. Electrophilic Substitution:
e.g., C₆H₅Cl + Br₂ (Fe catalyst) → o- and p-bromochlorobenzene
2. Nucleophilic Substitution:
o Difficult due to resonance and sp² carbon.
o Activated when –NO₂ or other –I groups present at ortho/para.
Example:
p-nitrochlorobenzene + NaOH (aq) → p-nitrophenol
• Sandmeyer & Gattermann Reactions:
Used for introducing halogens into aromatic rings from diazonium salts.
• Test • Observation • Inference
• AgNO₃ in • Chloride present
• White ppt
ethanol
• Fast turbidity (3°), slow (2°), • Type of alcohol (via
• Lucas Test halide)
none (1°)
• NaI in acetone • Precipitate of NaCl/NaBr • Finkelstein reaction
• Beilstein test • Green flame • Halogen present
10.9 Uses
• Chloroform (CHCl₃): Solvent, anesthetic.
• Carbon tetrachloride (CCl₄): Cleaning agent.
• DDT, Freons: Insecticides and refrigerants (environmentally controlled).
• Vinyl chloride: PVC manufacture.
• Alkyl halides: Starting materials for alcohols, ethers, nitriles, amines.
10.10 Environmental Impact
• Freons (CCl₂F₂) destroy ozone layer.
• DDT causes bioaccumulation.
• Green Chemistry promotes use of eco-friendly halogen-free compounds.