SECTION 23 ² AMINES
23-1 -- Primary (1°), Secondary (2°), and Tertiary (3°) Amines
23-1 -- Nomenclature of Amines
x Common Names ² ´Alkyl Aminesµ
x IUPAC Names ² ´Alkanaminesµ
x Naming Amines With ²NH2 as a Substituent (Branch)
x Use of ´N-´ as a Locator
x Ammonium and Iminium Ions
23-3 -- Structures of Amines
x Simple Amines are Pyramidal
x Complicated Amines (i.e. Aniline) Can ´Flatten Outµ
23-4 -- Spectroscopy of Amines
x IR Spectroscopy of Amines
x 1H NMR Spectroscopy of Amines
23-5 -- Basicity of Amines
x Amine Basicity Relative to H2O and OHx Alkylamines and Their Conjugate Acids (pKa ~ 10-11)
x Resonance Effects and Electron-Withdrawing Substituents
23-7 -- Acidity of Amines
x Alkyl Amines (pKa ~ 35-38) Have Very Strong Conj. Bases - Amide Ions, R2N23-8 -- Reactions of Amines ² pp.23-8 through pp.23-19 ² BIG TOPIC
23-8 -- Alkylation of Amines
x Direct Alkylation of Amines (SN2 with Amines as Nucleophiles)
x Exhaustive Alkylation of Amines
x Reductive Alkylation of Amines (Use of NaBH4 or H2/catalyst)
23-10 -- Gabriel Synthesis of 1° Amines
x Use of Pthalimide in an SN2 Reaction
x Gabriel Synthesis Adds ²NH2 to the R-group of R-Br
23-12 -- Preparation of Amines via Reduction Reactions
x Reduction of Azides (R-N3)
x Reduction of Nitriles (R-CƱN:)
x Reduction of Amides Using Lithium Aluminum Hydride (LiAlH4, or ´LAHµ)
23-13 -- The Hofmann Elimination
x Step 1 - Overalkylation of the Amino Group
x Step 2 ² ´Switchingµ I- with OHx Step 3 - E2 Elimination (via Heat, ¨) to Form Less-Substituted Alkene
x ´Hofmann Regiochemistryµ is Observed
23-14 -- The Hofmann Rearrangement
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x Involves Transformation of 1° Amide in Basic Solution to an Amine
23-15 -- The Curtius Rearrangement
x Converts an Acyl Azide to an Amine
x Mechanism Involves an Isocyanate Intermediate (O=C=N-R)
x Curtius Rearrangements Performed in H2O vs. in Alcohol (R·OH)
23-16 -- Diazonium Ion Chemistry
x [ R-NƱN ÅÆ R-N=N ]+1 , an Alkyl Diazonium Ion (Add lone pairs on N·s!!)
x N2 is an Excellent Leaving Group (l.g.)
x Diazonium Ions are Very Unstable
x Aryl Diazonium Ions (Ar-NƱN:)+1 are More Stable
x Aryl Diazonium Ions in Electrophilic Aromatic Substitution (E.A.S) Reactions
x Azobenzenes and UV-VIS Spectroscopy
23-18 -- Rearrangement of Alkyl Azides
x Analogous to Curtius Rearrangement
x Rearrangement Occurs Thermally (via Heat), or Photochemically (via UV light)
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SECTION 23 – AMINES
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