Synthesis of 2-(2-Methoxyethyl)- and 2-(2-Thiomethoxyethyl)-aniline and Related Compounds

Article abstract of DOI:10.1007/BF00807163

2-(2-Nitrophenyl)-ethanol (2) was methylated with dimethyl sulfate to give 2-(2-methoxyethyl)-1-nitrobenzene (3a) which then was reduced with hydrazine hydrate in the presence of Raney nickel to 2-(2-methoxyethyl)-aniline (1a).Compound 1a can be transformed into the N-monosilylated derivative 4 by lithiation with n-butyllithium and subsequent reaction with chlorotrimethylsilane.Reaction of 2 with p-toluenesulfonyl chloride yields 2-(2-nitrophenyl)-ethyl p-toluenesulfonate (5), which reacts with sodium thiomethoxide to give 2-(2-thiomethoxyethyl)-1-nitrobenzene (3b). 3b was reduced with hydrazine hydrate in the presence of Raney nickel to yield 2-(2-thiomethoxyethyl)-aniline (1b).Ethyl (2-nitrophenyl)-acetate (6) could be dimethylated with methyl iodide in the presence of potassium tert-butoxide and 18-crown-6 to give ethyl 2-methyl-2-(2-nitrophenyl)-propionate (7).Reduction of 7 with lithium borohydride yields 2,3-dihydro-3,3-dimethyl-1H-indole (9) and 2-<(1-hydroxy-2-methyl)-2-propyl>-aniline (10). - Keywords: 2-Functionalized anilines; Hemilabile ligands; Imido ligands