Ammonium Chloride → HCID 86689035, compound

HRID 388431Notes

Reaction equation

HRID 388431 reaction equation
[I:1][C:2]1[C:10]2[C:5](=[N:6][CH:7]=[N:8][C:9]=2[NH:11][C:12](=[O:18])[O:13][C:14]([CH3:17])([CH3:16])[CH3:15])[N:4]([C:19]2[CH:24]=[CH:23][C:22]([N+:25]([O-])=O)=[CH:21][CH:20]=2)[N:3]=1.[NH4+].[Cl-]>C1COCC1.CCO.O.[Fe]>[NH2:25][C:22]1[CH:23]=[CH:24][C:19]([N:4]2[C:5]3=[N:6][CH:7]=[N:8][C:9]([NH:11][C:12](=[O:18])[O:13][C:14]([CH3:15])([CH3:16])[CH3:17])=[C:10]3[C:2]([I:1])=[N:3]2)=[CH:20][CH:21]=1

Participants

5

Reactant 2

HCID 25517Ammonium ChlorideHCID 71256098HCID 71256098, compound

Product 1

HCID 86689035HCID 86689035, compoundYield 86.4%

Reagents, catalysts & solvents 2

HCID 23925IronCatalystHCID 18504229Ethanol tetrahydrofuran waterSolvent

Conditions

Temperature
50 °C

Procedure

To a solution of tert-butyl 3-iodo-1-(4-nitrophenyl)-1H-pyrazolo[3,4-d]pyrimidin-4-ylcarbamate (28) (4.29 g, 8.7 mmol) in THF/EtOH/H2O (40 mL/20 mL/10 mL) was added Fe powder (2.43 g, 43.45 mmol) and NH4Cl (4.65 g, 86.9 mmol). The resulting mixture was purged with N2 before heated to 50° C. for 2 h. The mixture was cooled and filtered through a Celite pad. The solvents were evaporated and the residue was separated in DCM and water. The aqueous layer was extracted with DCM (X4). The combined organic layers were dried over Na2SO4. Solvent was removed under vacuum and purified by flash chromatography (0-60% EA in PE with 0.5% TEA) to provide tert-butyl 1-(4-aminophenyl)-3-iodo-1H-pyrazolo[3,4-d]pyrimidin-4-ylcarbamate (29) (3.4 g, 86%) as a yellow solid. LC-MS (ESI): m/z (M+1) 453.0.

Workup

  1. customThe resulting mixture was purged with N2
  2. temperatureThe mixture was cooled
  3. filtrationfiltered through a Celite pad
  4. customThe solvents were evaporated
  5. customthe residue was separated in DCM
  6. extractionThe aqueous layer was extracted with DCM (X4)
  7. dry with materialThe combined organic layers were dried over Na2SO4
  8. customSolvent was removed under vacuum
  9. custompurified by flash chromatography (0-60% EA in PE with 0.5% TEA)

Sources & evidence

ORD record
ord-0494bbaa08504dd38c3d8fe1b44f7ed6
Source dataset
uspto-grants-2013_02
Patent number
US08377946B1

Reaction notes

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