SYNTHESIS OF 2-(2-METHOXYETHYL)-ANILINE AND 2-(2-THIOMETHOXYETHYL)-ANILINE AND RELATED-COMPOUNDS

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).