Triphenylphosphine → HCID 57458240, compound

HRID 1673011Notes

Reaction equation

HRID 1673011 reaction equation
Br[C:2]1[CH:3]=[C:4]([S:8]([NH2:11])(=[O:10])=[O:9])[CH:5]=[CH:6][CH:7]=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[CH3:31][Si:32]([C:35]#[CH:36])([CH3:34])[CH3:33]>C([O-])(=O)C.[Pd+2].C([O-])(=O)C.[Cu]I.C(N(CC)CC)C>[CH3:31][Si:32]([C:35]#[C:36][C:2]1[CH:3]=[C:4]([S:8]([NH2:11])(=[O:10])=[O:9])[CH:5]=[CH:6][CH:7]=1)([CH3:34])[CH3:33]

Participants

7

Reactant 3

HCID 11776TriphenylphosphineHCID 66111TrimethylsilylacetyleneHCID 27347653-Bromobenzene-1-sulfonamide

Product 1

HCID 57458240HCID 57458240, compound

Reagents, catalysts & solvents 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 167845palladium(II) acetateCatalystHCID 8471TriethylamineSolvent

Procedure

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]+.

Workup

  1. customInto a sealable tube was weighed
  2. customthe vessel was sealed
  3. customwas set in an oil bath
  4. temperatureAfter 1 h the reaction was cooled
  5. filtrationunsealed, and was filtered with added ethyl acetate
  6. customto remove solids
  7. concentrationThe filtrate was concentrated in vacuo
  8. customthe 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)
  9. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-29c3206882994ca3b5457b449268dfbb
Source dataset
uspto-grants-2011_08
Patent number
US07998995B2

Reaction notes

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