Chapter 21 I Naming 21 1 1 Substituted Amines of groups on N 2 Named as alkanamines N alkyl amines 3 As amino substituents 4 As alkyl amines II Structure and Physical Properties 21 2 tetrahedral pyramidal sp3 racemization of N centers III Acidity and Basicity 21 4 1 Amines are weak acids requires very strong base 2 Amines are moderate bases stronger than alcohols weaker than alkoxides A More steric hinderance leads to greater basicity except tertiary solvent disruption 8 3 3 Ammonium ions named as alkylammonium anions 4 Resonance stabilized amines IV Synthesis of amines 1 Indirect alkylation 21 5 A Direct alkylation leads to polyalkylations B Cyanide displacement reduction C Azide displacement reduction D Gabriel synthesis 2 Reductive amination 21 6 A Imine Imminium formation R B Can form polycyclic compounds 3 From Carboxylic amides 21 7 reduction with LAH 20 2 or Ho man rearrangement 20 7 V Reactions of Amines 1 Ho man elimination 21 8 A Elimination of tetraalkylammonium hydroxides B Gives least stable alkene anti zaitsev 2 Mannich reaction 21 9 enol iminium A Mechanism nitrogen aldol analog 3 Nitrosation 21 10 amines react with nitrosyl cations NO A Nitrosyl cation formation NaNO2 HCl B Attack by tertiary amines C Secondary amines lead to N nitrosamines D Primary amines carbocations Chapter 22 Benzene Substituents I Reaction at the Benzyl Position 22 1 1 Radical Halogenation 2 Solvolysis SN1 3 SN2 100x faster more reactive than primary sp3 4 Acidity of benzylic Hs 5 Oxidation 22 2 A Oxidative cleavage of alkyl groups must have at least one benzylic Hs B Selective benzylic oxidation of OHs Recitation review
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