Cesium carbonate → HCID 118272274, compound

HRID 590801Notes

Reaction equation

HRID 590801 reaction equation
[Cl:1][C:2]1[N:7]=[CH:6][C:5]2[C:8](I)=[N:9][N:10]([C:11]([C:24]3[CH:29]=[CH:28][CH:27]=[CH:26][CH:25]=3)([C:18]3[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=3)[C:12]3[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=3)[C:4]=2[CH:3]=1.C(CC(=O)C)(=O)C.C(=O)([O-])[O-].[Cs+].[Cs+].[OH-].[NH4+:45]>CN(C=O)C.[Cl-].[Na+].O.CC(CC(C)=O)=O.CC(CC(C)=O)=O.[Cu].CCOC(C)=O>[Cl:1][C:2]1[N:7]=[CH:6][C:5]2[C:8]([NH2:45])=[N:9][N:10]([C:11]([C:24]3[CH:29]=[CH:28][CH:27]=[CH:26][CH:25]=3)([C:18]3[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=3)[C:12]3[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=3)[C:4]=2[CH:3]=1

Participants

9

Reactant 4

HCID 10796Cesium carbonateHCID 14923Ammonium Hydroxide2×HCID 31261AcetylacetoneHCID 895258586-Chloro-3-iodo-1-trityl-1H-pyrazolo[4,3-c]pyridine2×

Product 1

HCID 118272274HCID 118272274, compound

Reagents, catalysts & solvents 4

HCID 45052134Bis(pentane-2,4-dione-kappa~2~O~2~,O~4~)copperCatalystHCID 6228DimethylformamideSolventHCID 8857Ethyl AcetateSolventHCID 57417360Sodium chloride; waterSolvent

Conditions

Temperature
60 °C

Procedure

A mixture of 6-chloro-3-iodo-1-trityl-1H-pyrazolo[4,3-c]pyridine (Intermediate 1C; 5.0 g, 9.58 mmol), acetylacetone (0.979 mL, 9.58 mmol), cupric acetylacetonate (0.251 g, 0.958 mmol), and cesium carbonate (6.24 g, 19.17 mmol) in DMF (25.2 mL) were charged in a sealed vessel. The system was degassed and ammonium hydroxide (13.33 mL, 96 mmol) was added. The reaction was heated at 60° C. for 16 h. The reaction was then poured into a solution of 10% NH4OH aq. (150 mL), brine (50 mL), and EtOAc (75 mL). The layers were separated and the aqueous phase was extracted with EtOAc (75 mL). The combined organic layers were washed with brine, dried over Na2SO4, and evaporated in vacuo. The residue was purified by flash chromatography (0-45% EtOAc/Hexanes) to afford 6-chloro-1-trityl-1H-pyrazolo[4,3-c]pyridin-3-amine. MS ESI calc'd. for C25H19ClN4 [M+1]+ 411. found 411.

Workup

  1. additionwere charged in a sealed vessel
  2. customThe system was degassed
  3. customThe layers were separated
  4. extractionthe aqueous phase was extracted with EtOAc (75 mL)
  5. washThe combined organic layers were washed with brine
  6. dry with materialdried over Na2SO4
  7. customevaporated in vacuo
  8. customThe residue was purified by flash chromatography (0-45% EtOAc/Hexanes)

Sources & evidence

ORD record
ord-13d8f1d64adc4f1fa7bb1b2912cec89f
Source dataset
uspto-grants-2016_01
Patent number
US09233979B2

Reaction notes

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