Trityl chloride → 5-chloro-3-iodo-1-trityl-1H-pyrazolo[3,4-b]pyridine

HRID 539921Notes

Reaction equation

HRID 539921 reaction equation
[Cl:1][C:2]1[CH:3]=[C:4]2[C:10]([I:11])=[N:9][NH:8][C:5]2=[N:6][CH:7]=1.C([O-])([O-])=O.[Na+].[Na+].[C:18](Cl)([C:31]1[CH:36]=[CH:35][CH:34]=[CH:33][CH:32]=1)([C:25]1[CH:30]=[CH:29][CH:28]=[CH:27][CH:26]=1)[C:19]1[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=1>CN(C)C=O.CCOCC>[Cl:1][C:2]1[CH:3]=[C:4]2[C:10]([I:11])=[N:9][N:8]([C:18]([C:19]3[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=3)([C:31]3[CH:32]=[CH:33][CH:34]=[CH:35][CH:36]=3)[C:25]3[CH:26]=[CH:27][CH:28]=[CH:29][CH:30]=3)[C:5]2=[N:6][CH:7]=1

Participants

6

Reactant 3

HCID 6456Trityl chloride2×HCID 10340Sodium CarbonateHCID 178478277HCID 178478277, compound

Product 1

HCID 679756695-chloro-3-iodo-1-trityl-1H-pyrazolo[3,4-b]pyridine

Reagents, catalysts & solvents 2

HCID 3283Diethyl EtherSolventHCID 6228DimethylformamideSolvent

Procedure

To a stirred mixture of 5-chloro-3-iodo-1H-pyrazolo[3,4-b]pyridine, 31, (11.6 g, 38.5 mmol), and Na2CO3 (12.2 g, 115 mmol) in N,N-dimethylformamide (200 mL) was added trityl chloride (11.8 g, 42.4 mmol). The mixture was stirred at room temperature overnight. After 16 hr, additional trityl chloride (1.61 g, 5.78 mmol) was added. And the mixture was heated to 60° C. for 45 min. The mixture was cooled, diluted with Et2O, washed with water (2×), brine (2×), dried over Na2SO4, filtered and concentrated in vacuo. Flash chromatography (SiO2, 0-40% EtOAc-Hexanes, gradient elution) provided the desired product as a colorless material which was further purified by flash chromatography (SiO2, 100% DCM, isocratic elution): 1H NMR (300 MHz, CDCl3) δ 8.15 (d, J=2.3 Hz, 1H), 7.70 (d, J=2.3 Hz, 1H) and 7.23-7.18 (m, 15H) ppm.

Workup

  1. waitAfter 16 hr
  2. temperatureAnd the mixture was heated to 60° C. for 45 min
  3. temperatureThe mixture was cooled
  4. washwashed with water (2×), brine (2×)
  5. dry with materialdried over Na2SO4
  6. filtrationfiltered
  7. concentrationconcentrated in vacuo
  8. washFlash chromatography (SiO2, 0-40% EtOAc-Hexanes, gradient elution)

Sources & evidence

ORD record
ord-648085c9ff9b4e24b9df870bd8ef9711
Source dataset
uspto-grants-2014_10
Patent number
US08871774B2

Reaction notes

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