bromomethanesulfonamide

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A mixture of fluorene-9-carboxylic acid ethyl ester (1) (11 g, 46.2 mmoL), potassium carbonate (6.4 g, 46.2 mmoL, 1 eq) and a mixture of bromomethanesulfonamide and iodomethanesulfonamide [prepared from bromomethanesulfonyl chloride see, Trice et al., J. Org. Chem., 32, 990(1967) by reaction with ammonia gas in cold ether followed by reaction with excess sodium iodide in refluxing acetonitrile] (9.1 g, 1 eq) in dry dimethylformamide (100 mL, from sieves) was stirred under nitrogen for 18 h. Water (200 mL) was then added and the solution was acidified with 1N aqueous hydrochloric acid (100 mL) and extracted with ethyl acetate (3×100 mL). The combined organic phases were then washed with brine (3×200 mL), dried (MgSO4), and concentrated. The residue was purified by column chromatography on silica gel using 40% ethyl acetate in hexane to provide 4.8g (31%) of product (2): mp 150°-156° C.; IR (KBr) 3360, 1710, 740, 725 cm-1 ; 1H NMR (CDCl3, 200 MHz) 7.78-7.69 (m, 4 H), 7.50-7.32 (m, 4 H), 4.38 (bs, 2 H, exchangeable), 4.12 (q. 2 H), 4.11 (s, 2 H), 1.12 (t, 3 H), MS m/z 331 (M+), 178 (base peak). extracted with ethyl acetate (3×100 mL) The combined organic phases were then washed with brine (3×200 mL) dried (MgSO4) concentrated The residue was purified by column chromatography on silica gel using 40% ethyl acetate in hexane

反応条件: temp:80.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A suspension of 1.4 g of a 60% sodium hydride/oil dispersion was prepared in 10 ml of dry DMSO, under an atmosphere of nitrogen. 4-Bromothiophenol (6.5 g) was dissolved in 11 ml of dry DMSO and added slowly to the above suspension. When frothing had subsided 6.0 g of bromomethanesulfonamide was added and the reaction mixture was heated to 80° C. for 2 hours. The reaction mixture was cooled to room temperature and poured into 150 ml of ethyl acetate, filtered from a solid and extracted with brine. The organic phase was dried over anhydrous sodium sulfate and concentrated under vacuum. The resultant residue was recrystallized from toluene to yield 7.9 g (81.4%) of product. added slowly to the above suspension was added The reaction mixture was cooled to room temperature filtered from a solid extracted with brine The organic phase was dried over anhydrous sodium sulfate concentrated under vacuum The resultant residue was recrystallized from toluene

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A mixture of fluorene-9-carboxylic acid ethyl ester (1) (11 g, 46.2 mmoL), potassium carbonate (6.4 g, 46.2 mmoL, 1 eq) and a mixture of bromomethanesulfonamide and iodomethanesulfonamide [prepared from bromomethanesulfonyl chloride see, Trice et al., J. Org. Chem., 32, 990(1967) by reaction with ammonia gas in cold ether followed by reaction with excess sodium iodide in refluxing acetonitrile] (9.1 g, 1 eq) in dry dimethylformamide (100 mL, from sieves) was stirred under nitrogen for 18 h. Water (200 mL) was then added and the solution was acidified with 1N aqueous hydrochloric acid (100 mL) and extracted with ethyl acetate (3×100 mL). The combined organic phases were then washed with brine (3×200 mL), dried (MgSO4), and concentrated. The residue was purified by column chromatography on silica gel using 40% ethyl acetate in hexane to provide 4.8g (31%) of product (2): mp 150°-156° C.; IR (KBr) 3360, 1710, 740, 725 cm-1 ; 1H NMR (CDCl3, 200 MHz) 7.78-7.69 (m, 4 H), 7.50-7.32 (m, 4 H), 4.38 (bs, 2 H, exchangeable), 4.12 (q. 2 H), 4.11 (s, 2 H), 1.12 (t, 3 H), MS m/z 331 (M+), 178 (base peak). extracted with ethyl acetate (3×100 mL) The combined organic phases were then washed with brine (3×200 mL) dried (MgSO4) concentrated The residue was purified by column chromatography on silica gel using 40% ethyl acetate in hexane