aromatic amines
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Aromatic Amines
• Recall:
• The amino group is a powerful activating group that directs ortho and para
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Reduction of Nitro Compounds
• Catalytic hydrogenation:
• Reduction with finely divided metal powders:
223.11 Synthesis of Amines
Reduction of Nitro Compounds
• LiAlH4 and NaBH4 fail to provide the amine
323.11 Synthesis of Amines
Problems
• Draw the products for the following reactions:
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Reductive Amination
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• Sodium cyanoborohydride, NaBH3CN and sodium triacetoxyborohydride, NaBH(OAc)3, are common choices in the lab for the reduction step
• Formaldehyde can be used to introduce methyl groups
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1023.7 Alkylation and Acylation Reactions of Amines
Problem
• Draw the complete mechanism for the following problem:
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Hofmann and Curtius Rearrangements
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The Hofmann Rearrangement
• Sometimes called the Hofmann hypobromite reaction• Cl2 is sometimes used in place of Br2
• A primary amide is the required starting compound
1323.11 Synthesis of Amines
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The Curtius Rearrangement
• Acyl azides provide access to primary amines via an isocyanate• Concerted reaction
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The Curtius Rearrangement
• The resulting isocyanate can be hydrated in acid or base
• Carbamic acids spontaneously decarboxylate
1723.11 Synthesis of Amines
Hofmann vs. Curtius
• In the Hofmann rearrangement, the isocyanate cannot be isolated as the reaction is carried out in aqueous base
1823.11 Synthesis of Amines
Curtius and Hofmann Rearrangements
• In both of these reactions, the alkyl group migrates with complete retention of configuration
1923.11 Synthesis of Amines
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Problems• Draw the mechanisms for the following rxns
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Acylation of Amines
• Amines can be converted into amides by reaction with acid chlorides, anhydrides, or esters.
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• See section 21.8 for review of these rxns
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