Ethyl 2-chloro-1,3-oxazole-5-carboxylate → HCID 59564714, compound

HRID 1027608Notes

Reaction equation

HRID 1027608 reaction equation
Cl[C:2]1[O:3][C:4]([C:7]([O:9][CH2:10][CH3:11])=[O:8])=[CH:5][N:6]=1.[Cl:12][C:13]1[CH:21]=[C:20]2[C:16]([CH:17]=[N:18][N:19]2[S:22]([C:25]2[CH:30]=[CH:29][CH:28]=[CH:27][CH:26]=2)(=[O:24])=[O:23])=[C:15]([Sn](C)(C)C)[CH:14]=1>CN(C)C=O.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.[Cu]I>[Cl:12][C:13]1[CH:21]=[C:20]2[C:16]([CH:17]=[N:18][N:19]2[S:22]([C:25]2[CH:30]=[CH:29][CH:28]=[CH:27][CH:26]=2)(=[O:23])=[O:24])=[C:15]([C:2]2[O:3][C:4]([C:7]([O:9][CH2:10][CH3:11])=[O:8])=[CH:5][N:6]=2)[CH:14]=1

Participants

6

Reactant 2

HCID 26369855Ethyl 2-chloro-1,3-oxazole-5-carboxylate3×HCID 595647036-Chloro-1-(phenylsulfonyl)-4-(trimethylstannyl)-1H-indazole3×

Product 1

HCID 59564714HCID 59564714, compoundYield 39.3%

Reagents, catalysts & solvents 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)Catalyst3×HCID 178418397HCID 178418397, compoundCatalyst3×HCID 6228DimethylformamideSolvent3×

Conditions

Temperature
100 °C

Procedure

In 4 batches, tetrakis(triphenylphosphine)palladium(0) (3.37 g, 2.92 mmol), ethyl 2-chloro-1,3-oxazole-5-carboxylate (6.65 g, 37.9 mmol, available from Apollo Scientific) and copper(I) iodide (1.11 g, 5.83 mmol) were added to a solution of 6-chloro-1-(phenylsulfonyl)-4-(trimethylstannanyl)-1H-indazole (13.28 g, 29.2 mmol) in N,N-dimethylformamide (52 ml). In 3 of the batches, tetrakis(triphenylphosphine)palladium(0) (1.03 g, 0.89 mmol), ethyl 2-chloro-1,3-oxazole-5-carboxylate (2.03 g, 11.59 mmol) and copper(I) iodide (0.34 g, 1.78 mmol) were added to a solution of 6-chloro-1-(phenylsulfonyl)-4-(trimethylstannanyl)-1H-indazole (4.06 g, 8.91 mmol) in N,N-dimethylformamide (16 ml). In the fourth batch, tetrakis(triphenylphosphine)palladium(0) (0.28 g, 0.24 mmol), ethyl 2-chloro-1,3-oxazole-5-carboxylate (0.55 g, 3.14 mmol) and copper(I) iodide (0.09 g, 0.48 mmol) were added to a solution of 6-chloro-1-(phenylsulfonyl)-4-(trimethylstannanyl)-1H-indazole (1.10 g, 2.42 mmol) in N,N-dimethylformamide (4 ml). Each batch was heated and stirred at 100° C. under microwave irradiation for 30 min. The mixtures were allowed to cool to RT and the combined precipitated product suspended in diethyl ether and collected by filtration, washing with further diethyl ether then drying in a vacuum oven for 72 h. Approximately 5.2 g of the resultant solid was dissolved in dichloromethane and passed through Celite, eluting with further dichloromethane. The solvent was evaporated in vacuo to give the title compound as a pale orange solid (4.95 g).

Workup

  1. temperatureEach batch was heated
  2. temperatureto cool to RT
  3. customthe combined precipitated product
  4. filtrationcollected by filtration
  5. washwashing with further diethyl ether
  6. customthen drying in a vacuum oven for 72 h
  7. dissolutionApproximately 5.2 g of the resultant solid was dissolved in dichloromethane
  8. washeluting with further dichloromethane
  9. customThe solvent was evaporated in vacuo

Sources & evidence

ORD record
ord-4f6f09c0cb8d40cda50cfccdf82dd9a7
Source dataset
uspto-grants-2014_05
Patent number
US08735390B2

Reaction notes

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