Bromide ion → HCID 59278313, compound

HRID 1361125Notes

Reaction equation

HRID 1361125 reaction equation
Br[C:2]1[N:7]=[CH:6][C:5]([CH2:8][NH:9][C:10]([C:12]2[C:13]3[CH:20]=[N:19][N:18]([C:21]4[CH:26]=[CH:25][C:24]([F:27])=[CH:23][CH:22]=4)[C:14]=3[CH:15]=[N:16][CH:17]=2)=[O:11])=[CH:4][CH:3]=1.[CH3:28][O:29][C:30](=[O:36])[CH2:31][CH2:32][S:33]([O-:35])=[O:34].[Na+].CCOC(C)=O.[Br-]>CS(C)=O.[Cl-].[Na+].O.[Cu]I>[CH3:28][O:29][C:30](=[O:36])[CH2:31][CH2:32][S:33]([C:2]1[CH:3]=[CH:4][C:5]([CH2:8][NH:9][C:10]([C:12]2[C:13]3[CH:20]=[N:19][N:18]([C:21]4[CH:26]=[CH:25][C:24]([F:27])=[CH:23][CH:22]=4)[C:14]=3[CH:15]=[N:16][CH:17]=2)=[O:11])=[CH:6][N:7]=1)(=[O:35])=[O:34]

Participants

8

Reactant 4

HCID 259Bromide ionHCID 8857Ethyl AcetateHCID 23665669Sodium 1-Methyl 3-SulfinopropionateHCID 45138009HCID 45138009, compound

Product 1

HCID 59278313HCID 59278313, compound

Reagents, catalysts & solvents 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 679Dimethyl SulfoxideSolventHCID 57417360Sodium chloride; waterSolvent

Conditions

Temperature
110 °C

Procedure

To a solution of 1-(4-fluorophenyl)-1H-pyrazolo[3,4-c]pyridine-4-carboxylic acid (6-bromopyridin-3-ylmethyl)-amide (150 mg, 0.35 mmol) in DMSO (2 mL) was added sodium 3-methoxy-3-oxopropane-1-sulfinate (125 mg, 0.717 mmol) followed by copper (I) iodide (135 mg, 0.708 mmol). The mixture was then warmed in a microwave at 110° C. for 35 minutes. The reaction was monitored by TLC (EtOAc) indicating a new slightly more polar product than starting bromide. The reaction was then diluted with brine (10 mL) and extracted with EtOAc (4×10 mL). The combined organic layers were washed with brine (5×10 mL), dried over magnesium sulfate, filtered and concentrated. The solid was dissolved in dichloromethane and purified by silica gel chromatography eluting with EtOAc-dichloromethane (25:75, then 1:1, then 75:25). The material from the column was triturated with ether to afford the title compound.

Workup

  1. extractionextracted with EtOAc (4×10 mL)
  2. washThe combined organic layers were washed with brine (5×10 mL)
  3. dry with materialdried over magnesium sulfate
  4. filtrationfiltered
  5. concentrationconcentrated
  6. dissolutionThe solid was dissolved in dichloromethane
  7. custompurified by silica gel chromatography
  8. washeluting with EtOAc-dichloromethane (25:75
  9. customThe material from the column was triturated with ether

Sources & evidence

ORD record
ord-fa992d67ed2249b68e80b220b2338175
Source dataset
uspto-grants-2011_02
Patent number
US07879873B2

Reaction notes

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