tert-Butyl Nitrite

Used Chemicals

• p-Anisidine [A0487]
• p-Toluenesulfonic Acid Monohydrate (= p-TsOH-H₂O) [T0267]
• Potassium Iodide [P1721]
• tert-Butyl Nitrite (= tBuONO) [N0357]
• Acetonitrile

Procedure

To a solution of p-anisidine (123 mg, 1.0 mmol), p-TsOH-H₂O (190 mg, 1.0 mmol, 1.0 eq.), KI (415 mg, 2.5 mmol, 2.5 eq.) in acetonitrile (5 mL) was added dropwise tBuONO (0.30 mL, 2.5 mmol, 2.5 eq.) at 0 °C and the mixture was stirred at same temperature for 30 min. Then the reaction mixture was heated 60 °C and stirred for 4 h. After quenching with water (15 mL), it was extracted with ethyl acetate (15 mL x 3) and the organic layer was washed with 2 mol/L HCl aq. (15 mL), sat. NaHCO₃ aq. (15 mL), brine (15 mL), dried over sodium sulfate and filtered. The solvent was removed under reduced pressure and the residue was purified by column chromatography (on silica gel, ethyl acetate:hexane = 1:4) to give 4-iodeanisole as a red solid (202 mg, 86% yield).

Experimenter’s Comments

The reaction mixture was monitored by UPLC.

Analytical Data

4-iodeanisole

¹H NMR (400 MHz, CDCl₃); δ 7.56 (d, J = 8.0 Hz, 2H), 6.68 (d, J = 8.0 Hz, 2H), 3.78 (s, 3H).

Lead Reference

• A New, One-Step, Effective Protocol for the Iodination of Aromatic and Heterocyclic Compounds via Aprotic Diazotization of Amines
• E. A. Krasnokutskaya, N. I. Semenischeva, V. D. Filimonova, P. Knochel, Synthesis 2007, 81.

Reference

• Benzyne Click Chemistry with in Situ Generated Aromatic Azides
  • F. Zhang, J. E. Moses, Org. Lett. 2009, 11, 1587.

References

• 1)Synthesis of Dioxin-like Monofluorinated PCBs: for the Use as Internal Standards for PCB Analysis.
  • R. Sott, C. Hawner, J. E. Johansen, Tetrahedron 2008, 64, 4135.
• 2)Arylethynyl Substituted 9,10-Anthraquinones: Tunable Stokes Shifts by Substitution and Solvent Polarity.
  • J. Yang, A. Dass, A.-M. M. Rawashdeh, C. Sotiriou-Leventis, M. J. Panzner, D. S. Tyson, J. D. Kinder, N. Leventis, Chem. Mater. 2004, 16, 3457.