Part of JOC-06 — Amines & Diazonium Salts

Applications of Diazonium Salts in Synthesis

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Diazonium salts are the "Swiss Army knife" of aromatic synthesis. Starting from ArNH2 (easily made from ArNO2), you can access: ArCl SandmeyerCuCl\frac{Sandmeyer}{CuCl}, ArBr SandmeyerCuBr\frac{Sandmeyer}{CuBr}, ArI (KI), ArCN -> ArCOOH SandmeyerCuCNthenhydrolysis\frac{Sandmeyer}{CuCN then hydrolysis}, ArOH H2Owarm\frac{H2O}{warm}, ArF (Balz-Schiemann), ArH (H3PO2), ArNO2 NaNO2Cu\frac{NaNO2}{Cu}, Ar-N=N-Ar' (coupling). Synthetic strategies: (1) To put -F on benzene: aniline -> diazonium -> ArF (Balz-Schiemann). No direct electrophilic fluorination is practical. (2) To put -I on benzene: aniline -> diazonium -> ArI (KI). (3) Meta-directed synthesis: put -NO2 first (meta-director), reduce to -NH2 after substitution, then diazotise and replace as needed.

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