SECTION 23 ² AMINES 23-1 -- Primary (1°), Secondary (2 ...ochemnotes.com/section23-amines.pdf · x Complicated Amines (i.e. Aniline) Can ´Flatten Outµ 23-4 ... x Use of Pthalimide

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SECTION 23 AMINES

23-1 -- Primary (1°), Secondary (2°), and Tertiary (3°) Amines

23-1 -- Nomenclature of Amines Common Names Alkyl Amines IUPAC Names Alkanamines

Naming Amines With NH2 as a Substituent (Branch) Use of N- as a Locator Ammonium and Iminium Ions

23-3 -- Structures of Amines Simple Amines are Pyramidal

Complicated Amines (i.e. Aniline) Can Flatten Out 23-4 -- Spectroscopy of Amines IR Spectroscopy of Amines

1H NMR Spectroscopy of Amines 23-5 -- Basicity of Amines Amine Basicity Relative to H2O and OH-

Alkylamines and Their Conjugate Acids (pKa ~ 10-11) Resonance Effects and Electron-Withdrawing Substituents 23-7 -- Acidity of Amines

Alkyl Amines (pKa ~ 35-38) Have Very Strong Conj. Bases - Amide Ions, R2N-

23-8 -- Reactions of Amines pp.23-8 through pp.23-19 BIG TOPIC

23-8 -- Alkylation of Amines

Direct Alkylation of Amines (SN2 with Amines as Nucleophiles) Exhaustive Alkylation of Amines

Reductive Alkylation of Amines (Use of NaBH4 or H2/catalyst) 23-10 -- Gabriel Synthesis of 1° Amines Use of Pthalimide in an SN2 Reaction

Gabriel Synthesis Adds NH2 to the R-group of R-Br 23-12 -- Preparation of Amines via Reduction Reactions Reduction of Azides (R-N3)

Reduction of Nitriles (R-C N:) Reduction of Amides Using Lithium Aluminum Hydride (LiAlH4, or LAH ) 23-13 -- The Hofmann Elimination

Step 1 - Overalkylation of the Amino Group Step 2 Switching I- with OH- Step 3 - E2 Elimination (via Heat, ) to Form Less-Substituted Alkene

Hofmann Regiochemistry is Observed 23-14 -- The Hofmann Rearrangement

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Involves Transformation of 1° Amide in Basic Solution to an Amine 23-15 -- The Curtius Rearrangement

Converts an Acyl Azide to an Amine Mechanism Involves an Isocyanate Intermediate (O=C=N-R) Curtius Rearrangements Performed in H2O vs. in Alcohol (R OH)

23-16 -- Diazonium Ion Chemistry

[ R-N N R-N=N ]+1 , an Alkyl Diazonium Ion (Add lone pairs on N s!!)

N2 is an Excellent Leaving Group (l.g.) Diazonium Ions are Very Unstable Aryl Diazonium Ions (Ar-N N:)+1 are More Stable

Aryl Diazonium Ions in Electrophilic Aromatic Substitution (E.A.S) Reactions Azobenzenes and UV-VIS Spectroscopy 23-18 -- Rearrangement of Alkyl Azides

Analogous to Curtius Rearrangement Rearrangement Occurs Thermally (via Heat), or Photochemically (via UV light)

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SECTION 23 – AMINES

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