Potassium Carbonate → 6-chloro-N-methyl-1-trityl-1H-pyrazolo[4,3-c]pyridin-3-amine

HRID 590793Notes

Reaction equation

HRID 590793 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.[NH:31]1CCC[C@H:32]1C(O)=O.C(=O)([O-])[O-].[K+].[K+].Cl.CN.[OH-].[NH4+]>CS(C)=O.[Cu]I>[Cl:1][C:2]1[N:7]=[CH:6][C:5]2[C:8]([NH:31][CH3:32])=[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

8

Reactant 5

HCID 11430Potassium CarbonateHCID 14923Ammonium HydroxideHCID 145742L-ProlineHCID 6364545Methylamine hydrochlorideHCID 895258586-Chloro-3-iodo-1-trityl-1H-pyrazolo[4,3-c]pyridine2×

Product 1

HCID 1182724066-chloro-N-methyl-1-trityl-1H-pyrazolo[4,3-c]pyridin-3-amine

Reagents, catalysts & solvents 2

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 679Dimethyl SulfoxideSolvent

Procedure

6-Chloro-3-iodo-1-trityl-1H-pyrazolo[4,3-c]pyridine (Intermediate 1C; 6.08 g, 11.65 mmol), proline (0.42 g, 3.65 mmol), copper(I) iodide (0.24 g, 1.260 mmol), potassium carbonate (9.83 g, 71.1 mmol), and methylamine hydrochloride (3.26 g, 48.3 mmol) were stirred in DMSO (45 mL) at 70° C. for 24 h. Room temperature was attained, ammonium hydroxide was added, and the products extracted into DCM (×2). The combined organic extracts were washed with brine, dried over MgSO4, filtered, and concentrated in vacuo. Purification of the residue by flash chromatography (6-50% EtOAc-hexanes) gave 6-chloro-N-methyl-1-trityl-1H-pyrazolo[4,3-c]pyridin-3-amine MS ESI calc'd. For C26H21ClN4 [M+1]+ 425. found 425.

Workup

  1. customRoom temperature
  2. extractionthe products extracted into DCM (×2)
  3. washThe combined organic extracts were washed with brine
  4. dry with materialdried over MgSO4
  5. filtrationfiltered
  6. concentrationconcentrated in vacuo
  7. customPurification of the residue by flash chromatography (6-50% EtOAc-hexanes)

Sources & evidence

ORD record
ord-48ce9db52e794b63a99f20805e6b577c
Source dataset
uspto-grants-2016_01
Patent number
US09233979B2

Reaction notes

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