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  • Amines Short Notes

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    Advik Gupta
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    The document discusses amines, including their classification, preparation methods, chemical reactions, physical properties, and tests. Amines are classified as primary (1o), secondary (2o), or tertiary (3o) depending on the number of alkyl or aryl groups bonded to the nitrogen atom. They can be prepared through various substitution and reduction reactions such as ammonolysis, alkylation of azides, and reduction of nitro compounds. Amines undergo reactions characteristic of both bases and organic compounds, such as forming salts with acids and undergoing electrophilic aromatic substitution. Primary and secondary amines have higher boiling points and solubility than tertiary amines due to hydrogen bonding.

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    Amines Short notes

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    The document discusses amines, including their classification, preparation methods, chemical reactions, physical properties, and tests. Amines are classified as primary (1o), secondary (2o), or tertiary (3o) depending on the number of alkyl or aryl groups bonded to the nitrogen atom. They can be prepared through various substitution and reduction reactions such as ammonolysis, alkylation of azides, and reduction of nitro compounds. Amines undergo reactions characteristic of both bases and organic compounds, such as forming salts with acids and undergoing electrophilic aromatic substitution. Primary and secondary amines have higher boiling points and solubility than tertiary amines due to hydrogen bonding.

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    © All Rights Reserved
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    4 views2 pages

    Amines Short Notes

    Uploaded by

    Advik Gupta
    The document discusses amines, including their classification, preparation methods, chemical reactions, physical properties, and tests. Amines are classified as primary (1o), secondary (2o), or tertiary (3o) depending on the number of alkyl or aryl groups bonded to the nitrogen atom. They can be prepared through various substitution and reduction reactions such as ammonolysis, alkylation of azides, and reduction of nitro compounds. Amines undergo reactions characteristic of both bases and organic compounds, such as forming salts with acids and undergoing electrophilic aromatic substitution. Primary and secondary amines have higher boiling points and solubility than tertiary amines due to hydrogen bonding.

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    Amines

    ▪ Basic Nomenclature and Classification of Amines ▪ Chemical reactions of Amine


    a. 1o amine 1. Reactions showing with basic nature
    b. 2o amine i. Reaction with acids to form salts
    c. 3o amine ii. Reaction with Chloro Platinic/Auric acid
    iii. Reaction with H2O
    ▪ Preparation of Amines 2. Benzoylation reaction
    1. Ammonolysis of alkyl halide 3. Reaction with Tilden reagent(NOCl)
    → NH3/ /-HX 4. Reaction with Phosgene(COCl2)
    → SN2 mechanism 5. Electrophilic Substitution reaction
    → Order of reactivity : RI > RBr > RCl > RF i. Sulphonation
    → 1o,2o,3o and Quarternary ammonium salt are formed ii. Friedel Crafts Alkylation/ Acylation❌
    2. Ammonolysis of alcohols iii. Ipso substitution(-COOH, -SO3H)
    → NH3/Al2O3/ 6. Reaction with HNO2
    → Quarternary ammonium salt is not formed due to steric hindrance i. 1o amine
    → In excess ammonia is used, then main product will be 1 o amine ii. 2o amine
    3. Alkylation of Azide ion and Reduction iii. 3o amine
    → Much better method to prepare 1o amine iv. 3o aryl amine
    → R-X, LAH 7. Diazonium salt, Diazotisation reaction
    → SN2 attack by Azide ion ▫ Coupling reaction of BDC
    4. Hoffmann exhaustive alkylation ▫ Preparation of Benzene Diazonium salt
    → 1o, 2o , 3o amine to 4o ammonium salt 8. Libermann's nitro reaction
    → Reagent = CH3I → Phenol reacts with (HONO)
    → Quarternary ammonium halide salt react with moist Ag 2O to give → Forms p-nitrosophenol
    silver halide as precipitate → Tautomerism occurs
    → Quarternary ammonium hydroxide on at 400K, undergoes → In presence of conc. H2SO4 = GRB
    elimination and produces alkene
    5. Hoffmann Bromamide degradation
    → Amides => Amines ▪ Test involving Amines
    → For 1o aliphatic or aromatic Amide 1. Carbylamine reaction(Iso-Cyanide Test)
    → Reagent = KOH/Br2 → CHCl3/ alc. KOH/
    6. Reduction of Nitro compounds → Only for 1o aliphatic or aromatic amine
    → H2/Pd or Metal+Acid or LAH → Alkyl Isocyanide => Very bad smell(Product)
    7. Reduction of Nitriles and Isonitriles → Nu- = RNH2 , E+ = CCl2
    8. Reduction of Oxime 2. Hinsberg's Test
    9. Reduction of Amides → Ph-SO2Cl
    10. Reductive of Amination → SN2 mechanism
    11. Gabriel-phthalimide synthesis → 1o amine✔, 2o amine✔, 3o amine❌
    → For 1o aliphatic amines 3. Hoffmann's mustard oil test
    → Alc. KOH/ R-X/ H2O(-OH) i. CS2/ HgCl2/
    → Phthalimide => 1o aliphatic amine ii. Alkyl Isothiocyanate(Smell like mustard oil)
    → Follows SN2 mechanism
    12. By Hydrosysis R-NC and RNCO
    13. From Grignard Reagent(R-MgX)
    14. Schmidt reaction
    → Reagent = N3H-H2SO4/
    → Acyl chloride => 1o amine

    ▪ Physical Properties of Amine


    1. Boiling point
    → 1o amine > 2o amine > 3o amine
    → Intermolecular forces in 1o amine and 2o amine
    → H bonding
    2. Solubility
    → 1o amine > 2o amine > 3o amine
    → 1o amine and 2o amine can form H-bond with water
    → Decreases with increase in size of alkyl group
    3. Basic nature
    → Inductive effect(3o > 2o > 1o)
    → Steric hindrance
    → Inversely prop. to No. of resonating structure
    → Aromatic amines are less basic than Aliphatic
    → %s ∝ Electronegativity ∝ 1/Basicity
    → Aniline are more basic than substituted Aniline
    → Ortho substituted Aniline are less basic due to ortho effect

    Organic Chemistry⌬ Page 1


    Amines
    ▪ Basic Nomenclature and Classification of Amines ▪ Chemical reactions of Amine
    a. 1o amine 1. Reactions showing with basic nature
    b. 2o amine i. Reaction with acids to form salts
    c. 3o amine ii. Reaction with Chloro Platinic/Auric acid
    iii. Reaction with H2O
    ▪ Preparation of Amines 2. Benzoylation reaction
    1. Ammonolysis of alkyl halide 3. Reaction with Tilden reagent(NOCl)
    → NH3/ /-HX 4. Reaction with Phosgene(COCl2)
    → SN2 mechanism 5. Electrophilic Substitution reaction
    → Order of reactivity : RI > RBr > RCl > RF i. Sulphonation
    → 1o,2o,3o and Quarternary ammonium salt are formed ii. Friedel Crafts Alkylation/ Acylation❌
    2. Ammonolysis of alcohols iii. Ipso substitution(-COOH, -SO3H)
    → NH3/Al2O3/ 6. Reaction with HNO2
    → Quarternary ammonium salt is not formed due to steric hindrance i. 1o amine
    → In excess ammonia is used, then main product will be 1 o amine ii. 2o amine
    3. Alkylation of Azide ion and Reduction iii. 3o amine
    → Much better method to prepare 1o amine iv. 3o aryl amine
    → R-X, LAH 7. Diazonium salt, Diazotisation reaction
    → SN2 attack by Azide ion ▫ Coupling reaction of BDC
    4. Hoffmann exhaustive alkylation ▫ Preparation of Benzene Diazonium salt
    → 1o, 2o , 3o amine to 4o ammonium salt 8. Libermann's nitro reaction
    → Reagent = CH3I → Phenol reacts with (HONO)
    → Quarternary ammonium halide salt react with moist Ag 2O to give → Forms p-nitrosophenol
    silver halide as precipitate → Tautomerism occurs
    → Quarternary ammonium hydroxide on at 400K, undergoes → In presence of conc. H2SO4 = GRB
    elimination and produces alkene
    5. Hoffmann Bromamide degradation
    → Amides => Amines ▪ Test involving Amines
    → For 1o aliphatic or aromatic Amide 1. Carbylamine reaction(Iso-Cyanide Test)
    → Reagent = KOH/Br2 → CHCl3/ alc. KOH/
    6. Reduction of Nitro compounds → Only for 1o aliphatic or aromatic amine
    → H2/Pd or Metal+Acid or LAH → Alkyl Isocyanide => Very bad smell(Product)
    7. Reduction of Nitriles and Isonitriles → Nu- = RNH2 , E+ = CCl2
    8. Reduction of Oxime 2. Hinsberg's Test
    9. Reduction of Amides → Ph-SO2Cl
    10. Reductive of Amination → SN2 mechanism
    11. Gabriel-phthalimide synthesis → 1o amine✔, 2o amine✔, 3o amine❌
    → For 1o aliphatic amines 3. Hoffmann's mustard oil test
    → Alc. KOH/ R-X/ H2O(-OH) i. CS2/ HgCl2/
    → Phthalimide => 1o aliphatic amine ii. Alkyl Isothiocyanate(Smell like mustard oil)
    → Follows SN2 mechanism
    12. By Hydrosysis R-NC and RNCO
    13. From Grignard Reagent(R-MgX)
    14. Schmidt reaction
    → Reagent = N3H-H2SO4/
    → Acyl chloride => 1o amine

    ▪ Physical Properties of Amine


    1. Boiling point
    → 1o amine > 2o amine > 3o amine
    → Intermolecular forces in 1o amine and 2o amine
    → H bonding
    2. Solubility
    → 1o amine > 2o amine > 3o amine
    → 1o amine and 2o amine can form H-bond with water
    → Decreases with increase in size of alkyl group
    3. Basic nature
    → Inductive effect(3o > 2o > 1o)
    → Steric hindrance
    → Inversely prop. to No. of resonating structure
    → Aromatic amines are less basic than Aliphatic
    → %s ∝ Electronegativity ∝ 1/Basicity
    → Aniline are more basic than substituted Aniline
    → Ortho substituted Aniline are less basic due to ortho effect

    Organic Chemistry⌬ Page 1

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