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Chemistry · Ch 7 — Alcohols, Phenols and Ethers

Summary

Summary

  • Classification: Alcohols (R-OH\text{R-OH}), phenols (Ar-OH\text{Ar-OH}), and ethers (R-O-R’\text{R-O-R'}) are classified by the number of alkyl/aryl groups attached to the oxygen.
  • Nomenclature: IUPAC names use suffix -ol for alcohols, -phenol for phenols, and -oxy (or alkoxy) for ethers; common names use alcohol, phenol, and ether.
  • Preparation of alcohols: Hydration of alkenes (Markovnikov addition), reduction of carbonyl compounds (RCHO→NaBH4RCH2OH\text{RCHO} \xrightarrow{\text{NaBH}_4} \text{RCH}_2\text{OH}), and Grignard reaction (RMgX+HCHO→RCH2OH\text{RMgX} + \text{HCHO} \rightarrow \text{RCH}_2\text{OH}).
  • Preparation of phenols: From diazonium salts (ArN2+→H2OArOH\text{ArN}_2^+ \xrightarrow{\text{H}_2\text{O}} \text{ArOH}), or from cumene (isopropylbenzene) via hydroperoxide rearrangement.
  • Preparation of ethers: Williamson synthesis (R-O−+R’X→R-O-R’\text{R-O}^- + \text{R'X} \rightarrow \text{R-O-R'}) and dehydration of alcohols (2ROH→H2SO4,140∘CR-O-R+H2O2\text{ROH} \xrightarrow{\text{H}_2\text{SO}_4, 140^\circ\text{C}} \text{R-O-R} + \text{H}_2\text{O}).
  • Physical properties: Alcohols and phenols have higher boiling points than ethers due to intermolecular O-H⋯O\text{O-H}\cdots\text{O} hydrogen bonding; ethers have lower boiling points and are less polar.
  • Acidity: Phenols (pKa≈10\text{p}K_a \approx 10) are more acidic than alcohols (pKa≈16\text{p}K_a \approx 16) due to resonance stabilization of phenoxide ion; electron-withdrawing groups increase acidity, electron-donating groups decrease it.
  • Reactions of alcohols: Dehydration to alkenes (E1/E2), oxidation to aldehydes/ketones (using PCC\text{PCC} or K2Cr2O7\text{K}_2\text{Cr}_2\text{O}_7), and esterification with carboxylic acids.
  • Reactions of phenols: Electrophilic substitution (bromination, nitration, Friedel-Crafts) occurs at ortho and para positions due to -OH\text{-OH} activation; also form coloured complexes with FeCl3\text{FeCl}_3. …