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 wit h hydrazine hydrate in the presence of Raney nickel to 2-(2-methoxyeth yl)-aniline (1a). Compound 1a can be transformed into the N-monosilyla ted derivative 4 by lithiation with n-butyllithium and subsequent reac tion 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-nitr obenzene (3b). 3b was reduced with hydrazine hydrate in the presence o f Raney nickel to yield 2-(2-thiomethoxyethyl)-aniline (1b). Ethyl (2- nitrophenyl)-acetate (6) could be dimethylated with methyl iodide in t he presence of potassium tert-butoxide and 18-crown-6 to give ethyl 2- methyl-2-(2-nitrophenyl)-propionate (7). Reduction of 7 with lithium b orohydride yields 2,3-dihydro-3,3-dimethyl-1H-indole (9) and 2-[(1-hyd roxy-2-methyl)-2-propyl]-aniline (10).