User:Benjah-bmm27/degree/2/TJS

Introduction
"Aromatic Compounds and Amines", Professor Tom Simpson FRS

Amines

 * CLW for amines
 * amine alkylation
 * Gabriel synthesis
 * sodium azide amine synthesis
 * reductive amination (with NaBH3CN)
 * Hofmann rearrangement
 * nitrosation

Electrophilic aromatic substitution

 * Benzene does not easily undergo electrophilic addition, unlike alkenes...
 * ...so it undergoes electrophilic aromatic substitution instead

Adding particular substituents

 * Halo groups, -X: electrophilic halogenation
 * Nitro groups, -NO2: aromatic nitration
 * Sulfo groups, -SO2OH: aromatic sulfonation
 * Organyl groups, -R:
 * Alkyl groups: Friedel-Crafts alkylation
 * Acyl groups: Friedel-Crafts acylation
 * Formyl group: Gattermann-Koch reaction
 * HCO+ is an intermediate

Substitution patterns

 * Activating and deactivating groups, and the arene substitution patterns they cause
 * Inductive and mesomeric effects

Ipso substitution

 * Ipso substitution
 * Grignard reaction with aryl halides
 * PhBr + Mg → PhMgBr
 * PhMgBr + E+ → PhE + [MgBr]+
 * if E = RCHO then PhE = PhCH(OH)R
 * if E = CO2 then PhE = PhCO2H
 * via aryldiazonium ions, [ArN2]+
 * nitrosation of aryl amines at 0 °C with HNO2:
 * HNO2 formed in situ from NaNO2 and HCl): NaNO2 + HCl → HNO2 + NaCl
 * ArNH2 + HNO2 → [ArN2+][Cl−]
 * Sandmeyer reactions: PhN2+ + CuX (and sometimes KX, too) → PhX + N2
 * apparently go via a radical-nucleophilic mechanism involving an aryl radical
 * an easy route to PhI: PhN2+ + CuI + KI → PhI + N2
 * chemically feasible unlike the prohibitively expensive PhH + I2 + AgNO3 → PhI + AgI + HNO3)
 * Balz–Schiemann reaction: an easy route to PhF
 * PhN2+ + HBF4 → PhF + N2 + BF3 + H+
 * mild conditions unlike the explosively exothermic PhH + F2 + cat. AlF3 → PhF + HF
 * Gomberg-Bachmann reaction: aryl-aryl coupling via ArH + Ar′N2+ + base → Ar-Ar′

Nucleophilic aromatic substitution

 * Nucleophilic aromatic substitution

Functional group interconversions in aromatics

 * Wolff-Kishner reduction (KOH, N2H4)
 * Clemmensen reduction (Zn, HCl)
 * Reduction of nitro compounds
 * e.g. with SnCl2 in HCl
 * Baeyer-Villiger oxidation

Later topics

 * Electrophilic aromatic substitution of naphthalene
 * Birch reduction
 * Claisen rearrangement
 * Fries rearrangement