Phenols - Riemer-Tiemann reaction

  • Introduction to phenols
    • Definition: Organic compounds that contain a hydroxyl group (-OH) attached to an aromatic ring
    • Examples:
      1. Phenol (C6H6O) - simplest aromatic alcohol
      2. 2,4-dinitrophenol (C6H4N2O5) - used as a pesticide
  • Riemer-Tiemann reaction
    • Definition: A method used to convert phenols into ortho-substituted phenols
    • Reactants:
      1. Phenol
      2. Chloroform (CHCl3)
      3. Sodium hydroxide (NaOH)
    • Equation: Phenol + CHCl3 + NaOH → Ortho-substituted phenol + NaCl + H2O
  • Mechanism of the Riemer-Tiemann reaction
    • Step 1: Deprotonation of phenol by NaOH
    • Step 2: Formation of dichlorocarbene (CHCl3 + NaOH → CHCl2Na + NaCl + H2O)
    • Step 3: Attack of dichlorocarbene on the ortho position of the deprotonated phenol
    • Step 4: Acidification to obtain the ortho-substituted phenol
    • Example:
      • Reaction: Phenol + CHCl3 + NaOH → 2-Hydroxy-5-chlorobenzaldehyde + NaCl + H2O
  • Importance of the Riemer-Tiemann reaction
    • Synthetic applications:
      1. Synthesis of ortho-substituted phenols for pharmaceutical purposes
      2. Preparation of intermediates for various organic reactions
    • Discovery of new compounds with potential biological activities
  • Limitations of the Riemer-Tiemann reaction
    • Only works with electron-rich phenols
    • Reactivity decreases with increasing steric hindrance on the phenolic ring
    • Chloroform is toxic and environmentally hazardous

Aromatic Amines - Sandmeyer reaction

  • Introduction to aromatic amines
    • Definition: Organic compounds that contain a nitrogen atom attached to an aromatic ring
    • Examples:
      1. Aniline (C6H5NH2) - simplest aromatic amine
      2. N,N-dimethylaniline (C8H11N) - used as a dye intermediate
  • Sandmeyer reaction
    • Definition: A method used to convert aromatic amines into different functional groups
    • Reactants:
      1. Aromatic amine
      2. Sodium nitrite (NaNO2)
      3. Mineral acid (e.g., HCl, H2SO4)
      4. Cu(I) salt (e.g., CuCl, CuBr)
    • Products: Can include aryl halides, aryl nitriles, and aryl thiols
    • Example:
      • Reaction: Aniline + NaNO2 + HCl → Chlorobenzene + NaCl + N2 + H2O
  • Mechanism of the Sandmeyer reaction
    • Step 1: Formation of diazonium salt
    • Step 2: Decomposition of diazonium salt to generate the desired product
    • Example:
      • Reaction: Aniline + NaNO2 + HCl → Chlorobenzene + NaCl + N2 + H2O
  • Importance of the Sandmeyer reaction
    • Versatile method for the synthesis of various functional groups
    • Widely used in the pharmaceutical and dye industries
  • Limitations of the Sandmeyer reaction
    • Limited to primary aromatic amines
    • Requires careful control of reaction conditions due to the reactivity of diazonium salts
    • Side reactions and by-products can occur in complex reaction systems

Phenols - Riemer-Tiemann reaction

  • Introduction to phenols
    • Definition: Organic compounds that contain a hydroxyl group (-OH) attached to an aromatic ring
    • Examples:
      • Phenol (C6H6O) - simplest aromatic alcohol
      • 2,4-dinitrophenol (C6H4N2O5) - used as a pesticide
  • Riemer-Tiemann reaction
    • Definition: A method used to convert phenols into ortho-substituted phenols
    • Reactants:
      • Phenol
      • Chloroform (CHCl3)
      • Sodium hydroxide (NaOH)
    • Equation: Phenol + CHCl3 + NaOH → Ortho-substituted phenol + NaCl + H2O
  • Mechanism of the Riemer-Tiemann reaction
    • Step 1: Deprotonation of phenol by NaOH
    • Step 2: Formation of dichlorocarbene (CHCl3 + NaOH → CHCl2Na + NaCl + H2O)
    • Step 3: Attack of dichlorocarbene on the ortho position of the deprotonated phenol
    • Step 4: Acidification to obtain the ortho-substituted phenol
    • Example:
      • Reaction: Phenol + CHCl3 + NaOH → 2-Hydroxy-5-chlorobenzaldehyde + NaCl + H2O
  • Importance of the Riemer-Tiemann reaction
    • Synthetic applications:
      • Synthesis of ortho-substituted phenols for pharmaceutical purposes
      • Preparation of intermediates for various organic reactions
    • Discovery of new compounds with potential biological activities
  • Limitations of the Riemer-Tiemann reaction
    • Only works with electron-rich phenols
    • Reactivity decreases with increasing steric hindrance on the phenolic ring
    • Chloroform is toxic and environmentally hazardous

Aromatic Amines - Sandmeyer reaction

  • Introduction to aromatic amines
    • Definition: Organic compounds that contain a nitrogen atom attached to an aromatic ring
    • Examples:
      • Aniline (C6H5NH2) - simplest aromatic amine
      • N,N-dimethylaniline (C8H11N) - used as a dye intermediate
  • Sandmeyer reaction
    • Definition: A method used to convert aromatic amines into different functional groups
    • Reactants:
      • Aromatic amine
      • Sodium nitrite (NaNO2)
      • Mineral acid (e.g., HCl, H2SO4)
      • Cu(I) salt (e.g., CuCl, CuBr)
    • Products: Can include aryl halides, aryl nitriles, and aryl thiols
    • Example:
      • Reaction: Aniline + NaNO2 + HCl → Chlorobenzene + NaCl + N2 + H2O
  • Mechanism of the Sandmeyer reaction
    • Step 1: Formation of diazonium salt
    • Step 2: Decomposition of diazonium salt to generate the desired product
    • Example:
      • Reaction: Aniline + NaNO2 + HCl → Chlorobenzene + NaCl + N2 + H2O
  • Importance of the Sandmeyer reaction
    • Versatile method for the synthesis of various functional groups
    • Widely used in the pharmaceutical and dye industries
  • Limitations of the Sandmeyer reaction
    • Limited to primary aromatic amines
    • Requires careful control of reaction conditions due to the reactivity of diazonium salts
    • Side reactions and by-products can occur in complex reaction systems

Slide 21 Phenols - Riemer-Tiemann reaction

  • Introduction to phenols
    • Definition: Organic compounds that contain a hydroxyl group (-OH) attached to an aromatic ring
    • Examples:
      • Phenol (C6H6O) - simplest aromatic alcohol
      • 2,4-dinitrophenol (C6H4N2O5) - used as a pesticide Slide 22 Riemer-Tiemann reaction
  • Definition: A method used to convert phenols into ortho-substituted phenols
  • Reactants:
    • Phenol
    • Chloroform (CHCl3)
    • Sodium hydroxide (NaOH)
  • Equation: Phenol + CHCl3 + NaOH → Ortho-substituted phenol + NaCl + H2O Slide 23 Mechanism of the Riemer-Tiemann reaction
  • Step 1: Deprotonation of phenol by NaOH
  • Step 2: Formation of dichlorocarbene (CHCl3 + NaOH → CHCl2Na + NaCl + H2O)
  • Step 3: Attack of dichlorocarbene on the ortho position of the deprotonated phenol
  • Step 4: Acidification to obtain the ortho-substituted phenol Slide 24 Mechanism of the Riemer-Tiemann reaction (continued)
  • Example:
    • Reaction: Phenol + CHCl3 + NaOH → 2-Hydroxy-5-chlorobenzaldehyde + NaCl + H2O Slide 25 Importance of the Riemer-Tiemann reaction
  • Synthetic applications:
    • Synthesis of ortho-substituted phenols for pharmaceutical purposes
    • Preparation of intermediates for various organic reactions
  • Discovery of new compounds with potential biological activities Slide 26 Limitations of the Riemer-Tiemann reaction
  • Only works with electron-rich phenols
  • Reactivity decreases with increasing steric hindrance on the phenolic ring
  • Chloroform is toxic and environmentally hazardous Slide 27 Aromatic Amines - Sandmeyer reaction
  • Introduction to aromatic amines
    • Definition: Organic compounds that contain a nitrogen atom attached to an aromatic ring
    • Examples:
      • Aniline (C6H5NH2) - simplest aromatic amine
      • N,N-dimethylaniline (C8H11N) - used as a dye intermediate Slide 28 Sandmeyer reaction
  • Definition: A method used to convert aromatic amines into different functional groups
  • Reactants:
    • Aromatic amine
    • Sodium nitrite (NaNO2)
    • Mineral acid (e.g., HCl, H2SO4)
    • Cu(I) salt (e.g., CuCl, CuBr) Slide 29 Sandmeyer reaction (continued)
  • Products: Can include aryl halides, aryl nitriles, and aryl thiols
  • Example:
    • Reaction: Aniline + NaNO2 + HCl → Chlorobenzene + NaCl + N2 + H2O Slide 30 Importance and limitations of the Sandmeyer reaction
  • Importance:
    • Versatile method for the synthesis of various functional groups
    • Widely used in the pharmaceutical and dye industries
  • Limitations:
    • Limited to primary aromatic amines
    • Requires careful control of reaction conditions due to the reactivity of diazonium salts
    • Side reactions and by-products can occur in complex reaction systems