Triphenylphosphine → HCID 57458240, compound

Participants

Reaction Steps

Into a sealable tube was weighed 1.24 g of 3-bromophenylsulfonamide, 112 mg of triphenylphosphine, 40 mg of palladium acetate, 32 mg of copper (I) iodide, and 5 mL of triethylamine. To this suspension was added 2.0 mL of trimethylsilylacetylene and the vessel was sealed, was set in an oil bath, and was rapidly stirred at 90-950C. After 1 h the reaction was cooled, unsealed, and was filtered with added ethyl acetate to remove solids. The filtrate was concentrated in vacuo and the residue was purified by silica gel flash chromatography (Jones Flashmaster, 50 g silica gel, gradient elution from 100% hexanes to 20% ethyl acetate over 30 minutes). Appropriate fractions were combined and concentrated in vacuo affording 3-trimethylsilanylethynyl-benzenesulfonamide as a faintly yellow semi-crystalline solid, yield: 908.3 mg (68%). 1H NMR (CDCl3): δ 8.02 (s, 1H), 7.85 (d, J=8 Hz, 1H), 7.64 (d, J=8 Hz, 1H), 7.48 (t, J=8 Hz, 1H), 5.02 (br s, 2H), 0.26 (s, 9H). Into a 50 mL flask was weighed 423.7 mg of trifluoromethanesulfonic acid 2-(2-chlorophenyl)-5-trifluoromethyl-2H-pyrazol-3-yl ester (1.07 mmol), 325.6 mg (1.28 mmol) of alkyne, 26.5 mg of copper (I) chloride, and 69.3 mg (600 μmol) of triphenylphosphine, followed by 5 mL of DMF. The reaction was heated at 80-850C for 5 h then was quenched by addition of 3 M HCl. The reaction mixture was washed into a separatory funnel with ethyl acetate and 3.0 M HCl. The ethyl acetate was separated, washed with brine, was dried (Na2SO4), and concentrated in vacuo. The residue was purified by silica gel flash chromatography (Jones Flashmaster, 50 g silica gel, gradient elution from 100% hexanes to 40% ethyl acetate over 30 minutes). Appropriate fractions were combined and concentrated in vacuo affording the product as a grayish powder, yield: 78.4 mg (17%); 1H NMR (CDCl3): δ 7.89 (m, 1H), 7.84 (s, 1H), 7.60 (d, J=8 Hz, 1H), 7.35-7.6 (m, 5H), 6.94 (s, 1H), 4.82 (s, 2H); MS (ES): 426 [M+H]+.

Provenance & Evidence