Ethyl Acetate → HCID 71680611, compound

HRID 1406573Notes

Reaction equation

HRID 1406573 reaction equation
Br[C:2]1[CH:3]=[CH:4][C:5]([N:12]2[C:16]([NH:17][S:18]([C:21]3[CH:26]=[CH:25][C:24]([C:27]([CH3:30])([CH3:29])[CH3:28])=[C:23]([F:31])[CH:22]=3)(=[O:20])=[O:19])=[CH:15][C:14]([CH3:32])=[N:13]2)=[C:6]2[C:11]=1[N:10]=[CH:9][CH:8]=[CH:7]2.CC(=O)CC(=O)C.C(=O)([O-])[O-].[Cs+].[Cs+].C(OCC)(=O)C.[OH-].[NH4+:53]>CN(C=O)C.[Cu]I>[NH2:53][C:2]1[CH:3]=[CH:4][C:5]([N:12]2[C:16]([NH:17][S:18]([C:21]3[CH:26]=[CH:25][C:24]([C:27]([CH3:30])([CH3:29])[CH3:28])=[C:23]([F:31])[CH:22]=3)(=[O:20])=[O:19])=[CH:15][C:14]([CH3:32])=[N:13]2)=[C:6]2[C:11]=1[N:10]=[CH:9][CH:8]=[CH:7]2

Participants

8

Reactant 5

HCID 8857Ethyl AcetateHCID 10796Cesium carbonateHCID 14923Ammonium HydroxideHCID 31261AcetylacetoneHCID 86694543HCID 86694543, compound

Product 1

HCID 71680611HCID 71680611, compoundYield 70%

Reagents, catalysts & solvents 2

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 6228DimethylformamideSolvent

Conditions

Temperature
120 °C

Procedure

To a stirring solution of N-(1-(8-bromoquinolin-5-yl)-3-methyl-1H-pyrazol-5-yl)-4-t-butyl-3-fluorobenzenesulfonamide (0.052 g, 0.10 mmol) in ammonium hydroxide (1 mL) and DMF (1 mL) was added 2,4-pentanedione (0.006 g, 0.06 mmol), cesium carbonate (Cs2CO3, 0.064 g, 0.20 mmol), and copper(I) iodide (CuI, 0.0095 g, 0.050 mmol). The reaction mixture was heated at 120° C. in microwave for 2 h. After cooling to room temperature, ethyl acetate (100 mL) was added to the reaction mixture and washed with deionized water (20 mL) and brine (2×20 mL). The organic layer was dried (Na2SO4), filtered, and concentrated in vacuo. The resulting crude purified by reverse phase HPLC (C18 column, acetonitrile-H2O with 0.1% TFA as eluent) to give the title compound as a brown solid (0.032 g, 0.070 mmol, 70%). 1H NMR (400 MHz, CD3OD) δ 8.80 (d, J=3.2 Hz, 1H), 7.53 (dd, J=1.2, 8.4 Hz, 1H), 7.45 (dd, J=4.0, 8.4 Hz, 1H), 7.40 (t, J=8.0 Hz, 1H), 7.32 (dd, J=2.0, 8.4 Hz, 1H), 7.22 (dd, J=2.0, 12.0 Hz, 1H), 7.08 (s, 2H), 6.12 (s, 1H), 2.28 (s, 3H), 1.41 (s, 9H); MS: (ES) m/z calculated for C23H25FN5O2S [M+H]+ 454.2. found 454.2.

Workup

  1. temperatureAfter cooling to room temperature
  2. washwashed with deionized water (20 mL) and brine (2×20 mL)
  3. dry with materialThe organic layer was dried (Na2SO4)
  4. filtrationfiltered
  5. concentrationconcentrated in vacuo
  6. customThe resulting crude purified by reverse phase HPLC (C18 column, acetonitrile-H2O with 0.1% TFA as eluent)

Sources & evidence

ORD record
ord-8d1dfa60120c4e49802fa23d127d4174
Source dataset
uspto-grants-2014_12
Patent number
US08916601B2

Reaction notes

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