Short Notes: Unit 11 - Alcohols, Phenols and Ethers (NCERT Chemistry Class 12)
1. Classification
A. Alcohols
• Organic compounds containing -OH group attached to an sp3 hybridised carbon.
• Types by Carbon Type:
• Primary (1°): -OH on 1° carbon (e.g., ethanol).
• Secondary (2°): -OH on 2° carbon (e.g., isopropanol).
• Tertiary (3°): -OH on 3° carbon (e.g., tert-butanol).
• Special Types:
• Allylic alcohol: -OH adjacent to a C=C bond.
• Benzylic alcohol: -OH next to an aromatic ring.
• Vinylic alcohol: -OH directly on a sp2 carbon (unstable).
• Monohydric, Dihydric, Trihydric, Polyhydric: Based on number of -OH groups.
B. Phenols
• -OH group directly attached to an aromatic ring.
• Types: Monohydric (phenol), Dihydric (catechol, resorcinol), Trihydric (pyrogallol).
C. Ethers
• Compounds with R-O-R or Ar-O-R.
• Symmetrical: Both R groups same.
• Unsymmetrical: R groups different.
2. Nomenclature
Alcohols:
• IUPAC: Replace -e of alkane with -ol. Number chain from -OH.
• Common: Alkyl name + "alcohol" (e.g., methyl alcohol).
Phenols:
• Base name: Phenol. Substituents use ortho/meta/para or locants.
Ethers:
• IUPAC: Larger alkyl = parent; smaller = alkoxy (e.g., methoxyethane).
• Common: Alkyl groups + "ether" (e.g., ethyl methyl ether).
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3. Preparation
Alcohols:
1. From Alkenes:
2. Acidic Hydration: H2O/H+ (Markovnikov).
3. Hydroboration-Oxidation: BH3/THF, then H2O2/NaOH (Anti-Markovnikov).
4. From Carbonyl Compounds:
5. Reduction of Aldehydes/Ketones: NaBH4/LiAlH4 → 1° or 2° alcohols.
6. Reduction of Carboxylic Acids/Esters: LiAlH4.
7. Grignard Reaction: R-MgX + carbonyl → Alcohol (depends on carbonyl type).
8. From Haloalkanes: R-X + OH⁻ (substitution).
Phenols:
1. From Chlorobenzene: NaOH (fused), high T/P.
2. From Benzene Sulphonic Acid: NaOH fusion, then acidification.
3. From Diazonium Salts: Hydrolysis of benzene diazonium chloride.
4. From Cumene: Oxidation to cumene hydroperoxide, then acid cleavage.
Ethers:
1. Dehydration of Alcohols: Symmetrical ethers via conc. H2SO4.
2. Williamson Synthesis: Alkoxide + 1° alkyl halide → ether (SN2).
4. Physical Properties
• Boiling Point: Alcohols > Ethers > Alkanes (due to H-bonding).
• Solubility: Alcohols and phenols are soluble in water (low mol. mass).
• Acidity:
• Alcohols < Water < Phenols < Nitro-Phenols.
• Phenoxide ion is resonance stabilized.
• Electron-withdrawing groups increase acidity (e.g., -NO2).
5. Chemical Reactions
Alcohols:
• With Metals: R-OH + Na → R-O⁻ Na⁺ + H2.
• Lucas Test: Alcohol + HCl/ZnCl2 → Alkyl halide (tertiary fastest).
• Dehydration: Alcohol → Alkene + H2O (acidic conditions).
• Oxidation:
• 1° → Aldehyde → Carboxylic Acid.
• 2° → Ketone.
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Phenols:
• Electrophilic Substitution: o-/p- directing.
• Bromination: Br2 (aq) → 2,4,6-tribromophenol.
• Nitration: HNO3 → o-/p-nitrophenols.
• Kolbe's Reaction: CO2 + phenoxide (125°C, 5 atm) → o-hydroxybenzoic acid.
• Reimer-Tiemann: CHCl3 + NaOH → o-hydroxybenzaldehyde.
• With Zn (heat): Phenol → Benzene.
Ethers:
• Inert: No reaction with dilute acids or bases.
• Cleavage by HX: R-O-R' + HX → R-X + R'-OH.
• Peroxide Formation: On standing in air.
6. Named Reactions (Very Important)
• Hydroboration-Oxidation: Anti-Markovnikov alcohol.
• Williamson Synthesis: Ether formation via SN2.
• Kolbe's Reaction: Salicylic acid from phenol.
• Reimer-Tiemann: Salicylaldehyde from phenol.
7. Important MCQ/Objective Points
• IUPAC/Common naming rules.
• Reagents & conditions in each reaction.
• Order of acid strength: Alcohol < Water < Phenol < o-nitrophenol.
• Lucas Test reactivity: 3° > 2° > 1° alcohol.
• Mechanism type: SN1/SN2 (Williamson = SN2).
• Electrophilic substitution in phenol = o/p products.
• Grignard product: Formaldehyde → 1°, Aldehyde → 2°, Ketone → 3° alcohol.
End of Notes
