Chloroacetylation of Substituted Methoxyphenols: Synthesis and Subsequent Transformations

The synthesis and rearrangement reactions of 2-methoxyphenyl chloroacetate in the presence of low amounts of catalysts to form o- and p-hydroxy-3-methoxyphenacyl chlorides are described in this study. A method for obtaining m-methoxyphenyl chloroacetate is developed, based on the chloroacetylation of m‑methoxyphenol in benzene solution.. The reactions of m-methoxyphenyl chloroacetate are rearranged for the first time in the presence of low amounts of FeCl3, MoCl5, WCl6, ZnCl2, SnCl4, VCl3, FeCl3⋅6H2O, Fe2(SO4)3, iron acetylacetonate (IAA), and iron salicylate (ISA). The reaction leads to the formation of 2‑hydroxy-4-methoxyphenacyl chlorides and 4-hydroxy-2-methoxyphenacyl chlorides. The percentage ratio of isomers depends on the reaction conditions. The synthesis of 4-methoxyphenyl chloroacetate via reaction with diphenylthiocarbazone in the presence of dimethylformamide is studied. The structure of the substances is elucidated with UV, IR, and NMR spectroscopies.