Ethylamine hydrochloride → 6-chloro-N-ethyl-1-trityl-1H-pyrazolo[4,3-c]pyridin-3-amine

HRID 590796Notes

Reaction equation

HRID 590796 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]1[C:33](O)=O.C(=O)([O-])[O-].[K+].[K+].Cl.C(N)C.[OH-].[NH4+]>CS(C)=O.[Cu]I>[Cl:1][C:2]1[N:7]=[CH:6][C:5]2[C:8]([NH:31][CH2:32][CH3:33])=[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 11198Ethylamine hydrochlorideHCID 11430Potassium CarbonateHCID 14923Ammonium HydroxideHCID 145742L-ProlineHCID 895258586-Chloro-3-iodo-1-trityl-1H-pyrazolo[4,3-c]pyridine2×

Product 1

HCID 1182720066-chloro-N-ethyl-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; 5.53 g, 10.60 mmol), proline (0.42 g, 3.65 mmol), copper (I) iodide (0.21 g, 1.103 mmol), potassium carbonate (7.40 g, 53.5 mmol), and ethylamine hydrochloride (2.78 g, 34.1 mmol) were stirred in DMSO (30 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-ethyl-1-trityl-1H-pyrazolo[4,3-c]pyridin-3-amine. MS ESI calc'd. For C27H23ClN4 [M+1]+ 439. found 439.

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-b340ca210ebb4a15b375539f5f879250
Source dataset
uspto-grants-2016_01
Patent number
US09233979B2

Reaction notes

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