Potassium Fluoride → HCID 25014404, compound

HRID 421741Notes

Reaction equation

HRID 421741 reaction equation
Cl[C:2]1[CH:3]=[C:4]2[C:12](=[O:13])[C:11]3[CH:14]=[C:15]([CH2:18][S:19]([N:22]([CH3:29])[C:23]4[CH:28]=[CH:27][CH:26]=[CH:25][CH:24]=4)(=[O:21])=[O:20])[CH:16]=[CH:17][C:10]=3[CH:9]=[CH:8][C:5]2=[N:6][CH:7]=1.[CH3:30][N:31]1[CH:35]=[C:34](B2OC(C)(C)C(C)(C)O2)[CH:33]=[N:32]1.[F-].[K+].F[B-](F)(F)F.C([PH+](C(C)(C)C)C(C)(C)C)(C)(C)C>C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd].CN(C=O)C>[CH3:29][N:22]([C:23]1[CH:28]=[CH:27][CH:26]=[CH:25][CH:24]=1)[S:19]([CH2:18][C:15]1[CH:16]=[CH:17][C:10]2[CH:9]=[CH:8][C:5]3=[N:6][CH:7]=[C:2]([C:34]4[CH:33]=[N:32][N:31]([CH3:30])[CH:35]=4)[CH:3]=[C:4]3[C:12](=[O:13])[C:11]=2[CH:14]=1)(=[O:21])=[O:20]

Participants

7

Reactant 4

HCID 522689Potassium FluorideHCID 2734635Tri-tert-butylphosphine tetrafluoroborateHCID 27739871-Methyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-pyrazoleHCID 57541245HCID 57541245, compound

Product 1

HCID 25014404HCID 25014404, compound

Reagents, catalysts & solvents 2

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 6228DimethylformamideSolvent

Conditions

Temperature
130 °C

Procedure

1-(3-Chloro-5-oxo-5H-benzo[4,5]cyclohepta[1,2-b]pyridin-7-yl)-N-methyl-N-phenylmethanesulfonamide (4.4 g, 10.36 mmol), 1-methyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H pyrazole (2.59 g, 12.43 mmol), potassium fluoride (1.985 g, 34.2 mmol), tri-t-butylphosphonium tetrafluoroborate (0.270 g, 0.932 mmol), and Pd2(dba)3 (0.379 g, 0.414 mmol) were combined as solids and placed under a nitrogen atmosphere. DMF (104 ml) was added, the mixture was degassed, and then the reaction was heated to 130° C. with stirring for 2 h. After cooling to room temperature, the mixture was poured into aqueous sodium hydrogen carbonate (saturated, 250 mL) and extracted with dichloromethane (4×250 mL). The organic extracts were combined, dried over Na2 SO4, and concentrated under reduced pressure. The residue was then dissolved in hot dioxane (500 mL). Hexanes were added until a precipitate formed. After standing at room temperature overnight, the precipitate was collected to afford the title compound as a gray solid. 1H NMR (600 MHz, DMSO-D6) δ 9.22 (d, 1H); 8.53 (d, 1H); 8.47 (s, 1H); 8.15 (s, 1H); 8.14 (d, 1H); 7.78 (m, 2H); 7.39 (d, 1H); 7.32 (m, 5H); 7.20 (m, 1H); 4.75 (s, 2H); 3.88 (s, 3H); 3.23 (s, 3H). LRMS (APCI) calculated for C21H21N4O3S [M+H]+, 409.1; found 409.1.

Workup

  1. customthe mixture was degassed
  2. temperatureAfter cooling to room temperature
  3. additionthe mixture was poured into aqueous sodium hydrogen carbonate (saturated, 250 mL)
  4. extractionextracted with dichloromethane (4×250 mL)
  5. customdried over Na2 SO4
  6. concentrationconcentrated under reduced pressure
  7. dissolutionThe residue was then dissolved in hot dioxane (500 mL)
  8. additionHexanes were added until a precipitate
  9. customformed
  10. waitAfter standing at room temperature overnight
  11. customthe precipitate was collected

Sources & evidence

ORD record
ord-a9dd17cf6a374ceaacefbc079a80feb3
Source dataset
uspto-grants-2012_01
Patent number
US08101603B2

Reaction notes

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