Ch 24 Amines Flashcards
Synthesis of Amines: Reduction of Nitriles
RCH2X – NaCN – > RCH2CN – 1) LiAlH4, ether / 2) H2O – > R-CH2NH2
Synthesis of Amines: Reduction of Amides
Amide – 1) LiAlH4, ether / 2) H2O – > RCH2NH2
Synthesis of Amines: Reduction of Nitrobenzenes
NO2 – H2, Pt – > NH2
Can also use : Fe, H2SO4
SnCl2, H2SO4
Synthesis of Amines: Sn2 Alkylation of alkyl halides
Ammonia + R-X – > RNH3 X- –NaOH– >RNH2 Primary
Primary + R-X – > RNH2 X- –NaOH– > R2NH Secondary
Secondary + R-X – > R3NH X- –NaOH– > R3N Tertiary
Tertiary + R-X – > R4N X- Quaternary
Synthesis of Amines: Gabriel Amine Synthesis
Ring Bonded N-H – 1) KOH / 2) R-X – > Ring bonded N-R – NaOH, H2O – > RNH2
Synthesis of Amines: Reduction of Azides
RCH2-X – Na+ N3- – > RCH2-N=N=N – 1) LiAlH4,ether / 2) H2O – > R-NH2
Synthesis of Amines: Reductive Animation of Aldehydes / Ketones
Ketone – NH3, NaBH4 – >R-CH-NH2 w/ CH bonded R’
Synthesis of Amines: Hofmann rearrangement of amides
Amide – NaOH, Br2, H2O– > R-NH2 + CO2
Synthesis of Amines: Curtius rearrangement of acyl azides
Acid Chloride – Na+ N3-, ethanol – > O=C-N=N=N –H2O,Heat – > RNH2 + CO2 + N2
Reactions of Amines: Hofmann elimination
H3C-CH2-NR2 – 1) CH3I / 2) Ag2O, heat – > Alkene
Reactions of Amines: Diazotinzation
R-NH2 + HNO2 + H2SO4 – > R-N-trip bnd-N + HSO4-
Reactions of arenediazonium salts: Nucleophilic Substitutions
R-N-trip bnd-N + HSO4- – HCl, CuCl – > R-Cl
Reactions of arenediazonium salts: Nucleophilic Substitutions
R-N-trip bnd-N + HSO4- – HBr, CuBr – > R-Br
Reactions of arenediazonium salts: Nucleophilic Substitutions
R-N-trip bnd-N + HSO4- – NaI – > R-I
Reactions of arenediazonium salts: Nucleophilic Substitutions
R-N-trip bnd-N + HSO4- – KCN, CuCN – > R-CN
