Diisopropylamine → HCID 58382050, compound

HRID 2205860Notes

Reaction equation

HRID 2205860 reaction equation
[CH3:1][N:2]1[CH:6]=[C:5](I)[CH:4]=[N:3]1.[C:8]([Si:10]([CH3:13])([CH3:12])[CH3:11])#[CH:9].C(NC(C)C)(C)C.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>CN(C=O)C.[Cu]I.C([O-])(=O)C.[Pd+2].C([O-])(=O)C>[CH3:1][N:2]1[CH:6]=[C:5]([C:9]#[C:8][Si:10]([CH3:13])([CH3:12])[CH3:11])[CH:4]=[N:3]1

Participants

8

Reactant 4

HCID 7912DiisopropylamineHCID 11776TriphenylphosphineHCID 66111TrimethylsilylacetyleneHCID 27347731-Methyl-4-iodo-1H-pyrazole

Product 1

HCID 58382050HCID 58382050, compoundYield 67%

Reagents, catalysts & solvents 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 167845palladium(II) acetateCatalystHCID 6228DimethylformamideSolvent

Conditions

Temperature
60 °C

Procedure

1-Methyl-4-iodo-pyrazole (18) (5.0 g 24.04 mmole) was dissolved in DMF (32 mL) and ethynyltrimethylsilane (4.76 mL, 3.31 g, 33.7 mmole) was added followed by diisopropylamine (4.46 mL, 3.21 g 31.78 mmole), copper(I) iodide (304 mg 1.59 mmole) and triphenylphosphine (1.26 g 4.81 mmole). The reaction was flushed with argon. Palladium acetate (351 mg 1.56 mmole) was added and the reaction was again flushed with argon. It was heated at 60° C. for 60 mins. The reaction was cooled, added to water (350 ml) and extracted with ether (3×100 mL). The organic solution was filtered from a brown solid which was washed with a little more ether. The organic solution was washed with water (3×80 mL), brine, dried and evaporated. The crude product was flash chromatographed (silica) using 1:4 ethyl acetate:cyclohexane and then 1:3 ethyl acetate:cyclohexane to give the title compound as a solid (2.85 g 67%). 1H-NMR (CDCl3, 500 MHz): δ 0.24 (s, 9H), 3.87 (s, 3H), 7.50 (s, 1H), 7.58 (s, 1H).

Workup

  1. customThe reaction was flushed with argon
  2. customthe reaction was again flushed with argon
  3. temperatureThe reaction was cooled
  4. additionadded to water (350 ml)
  5. extractionextracted with ether (3×100 mL)
  6. filtrationThe organic solution was filtered from a brown solid which
  7. washwas washed with a little more ether
  8. washThe organic solution was washed with water (3×80 mL), brine
  9. customdried
  10. customevaporated
  11. customchromatographed (silica)

Sources & evidence

ORD record
ord-a109f2d2c1f94a5c89968654b63bdab9
Source dataset
uspto-grants-2016_06
Patent number
US09371319B2

Reaction notes

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