2-碘茴香硫醚

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: 3-Chloroperoxybenzoic acid (77%, 2.7 g, 11.99 mmol) was added to a solution of 2-iodothioanisole (3 g, 11.99 mmol) in dichloromethane (50 mL). The reaction was stirred for 1 hour. Calcium hydroxide (1.33 g, 18 mmol) was added and the mixture stirred for 15 minutes. The solid was removed by filtration through Hyflo®, washing well with dichloromethane. The filtrate was concentrated in vacuo. The residue was purified by flash column chromatography on silica, eluting with 20% then 40% ethyl acetate/isohexane, to give 1-iodo-2-(methylsulfinyl)benzene as a colourless oil (2.8 g, 88%). 1H NMR (500 MHz, CDCl3) δ 7.92 (1H, d, J=7.8 Hz), 7.82 (1H, d, J=7.8 Hz), 7.62 (1H, t, J=7.6 Hz), 7.23-7.21 (1H, m), 2.79 (3H, s). the mixture stirred for 15 minutes The solid was removed by filtration through Hyflo® washing well with dichloromethane The filtrate was concentrated in vacuo The residue was purified by flash column chromatography on silica eluting with 20%

反应条件: temp:-10.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: 0.811 g (3.24 mmole) of 2-methylmercaptoiodobenzene were dissolved in 2 ml of ether, cooled to −10° C., and 1.62 ml (3.24 mmole) of isopropylmagnesium chloride (2 M solution in tetrahydrofuran) were added dropwise. After stirring for one hour at ° C., 0.50 g (2.16 mmole) of the 2-(dimethylaminophenylmethyl)cyclohexanone prepared according to Example 1 and dissolved in 2 ml of ether was added dropwise, and the whole was stirred for 15 hours at RT. The reaction mixture was worked up by adding 2 ml of saturated ammonium chloride solution while cooling in an ice bath and was extracted three times at RT with 5 ml of ether each time. The combined organic extracts were dried over sodium sulfate, filtered, and concentrated by evaporation on a rotary evaporator (500 to 10 mbar). 0.84 g of crude base (109% of theory) was obtained, from which 0.483 g of 2-(dimethylaminophenyl-methyl)-1-(2-methylsulfanylphenyl)cyclohexanol, hydrochloride (38.0% of theory) was obtained according to the procedure described in Example 1 (3rd Stage) with chlorotrimethylsilane/water in 2-butanone. The hydrochloride decomposes on heating above 230° C. was added dropwise the whole was stirred for 15 hours at RT while cooling in an ice bath was extracted three times at RT with 5 ml of ether each time The combined organic extracts were dried over sodium sulfate filtered concentrated by evaporation on a rotary evaporator (500 to 10 mbar)

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: The title compound was prepared in analogy to Example 5 starting from 1-iodo-2-methylsulfanyl-benzene (commercially available) and 3-{[phenyl-(3-phenyl propynoyl)-amino]-methyl}-benzoic acid methyl ester. 1H NMR (300 Hz, CDCl3): δppm 2.31 (s, 3H), 3.90 (s, 3H), 5.00 (dd, 2H), 6.03 (d, 1H), 6.60-6.64 (m, 2H), 7.04 (t, 1H), 7.26-7.30 (m, 2H), 7.33-7.56 (m, 9H), 7.95 (d, 1H), 8.01 (s, 1H).

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: 3-Chloroperoxybenzoic acid (77%, 2.7 g, 11.99 mmol) was added to a solution of 2-iodothioanisole (3 g, 11.99 mmol) in dichloromethane (50 mL). The reaction was stirred for 1 hour. Calcium hydroxide (1.33 g, 18 mmol) was added and the mixture stirred for 15 minutes. The solid was removed by filtration through Hyflo®, washing well with dichloromethane. The filtrate was concentrated in vacuo. The residue was purified by flash column chromatography on silica, eluting with 20% then 40% ethyl acetate/isohexane, to give 1-iodo-2-(methylsulfinyl)benzene as a colourless oil (2.8 g, 88%). 1H NMR (500 MHz, CDCl3) δ 7.92 (1H, d, J=7.8 Hz), 7.82 (1H, d, J=7.8 Hz), 7.62 (1H, t, J=7.6 Hz), 7.23-7.21 (1H, m), 2.79 (3H, s). the mixture stirred for 15 minutes The solid was removed by filtration through Hyflo® washing well with dichloromethane The filtrate was concentrated in vacuo The residue was purified by flash column chromatography on silica eluting with 20%