63069-48-7

106-47-8

63069-48-7

88149-53-5

General method: 4-Chloroaniline (20.0 mmol) was dissolved in a solvent mixture of H2O (100 mL) and MeOH (300 mL) and the pH was adjusted to 1-2 by adding concentrated HCl (tested using pH paper). Subsequently, NaICl2 aqueous solution (50% w/w, 1.1-4.8 molar equivalents, see table for exact dosage) was slowly added dropwise and the reaction mixture was stirred for 3-4 hours at room temperature. Upon completion of the reaction, the reaction was quenched by adding saturated NaHSO3 aqueous solution until the starch test was negative. If no significant precipitate was generated in the reaction mixture, the pH was adjusted to alkaline by dropwise addition of 1 M NaOH aqueous solution (tested using pH paper), followed by extraction with Et2O. The organic phases were combined, dried with MgSO4, filtered and concentrated under reduced pressure to give the solid product. If a precipitate was generated in the reaction mixture, the solid was first separated by gravity filtration, then the filtrate was adjusted to slightly basic (using 1 M NaOH aqueous solution) and extracted with Et2O. The organic extracts were combined, dried with MgSO4, filtered and concentrated under reduced pressure to give the solid product. All solid products were analyzed by TLC (silica gel plates, different ratios of hexane/ethyl acetate as unfolding agent). If the products were mixtures, they were separated and purified by fast column chromatography (silica gel, hexane/ethyl acetate = 9:1, unless otherwise stated). The final products were characterized by melting point (compared to literature values), IR, MS, 1H-NMR, 13C-NMR spectra and elemental analysis (for new compounds). It should be noted that the reaction products of anilines 1a-1j are mostly known compounds, while theanisidines failed to yield characterizable products.