Hydrazine hydrate (1:1) → HCID 73504797, compound

HRID 590814Notes

Reaction equation

HRID 590814 reaction equation
O=C1C2C(=CC=CC=2)C(=O)[N:3]1[C:12]1[C:16]2[CH:17]=[N:18][C:19]([NH:21][C:22]([NH:24][C@@H:25]([C:27]3[CH:32]=[CH:31][CH:30]=[CH:29][CH:28]=3)[CH3:26])=[O:23])=[CH:20][C:15]=2[NH:14][N:13]=1.[B-](F)(F)(F)[F:34].[B-](F)(F)(F)F.C1[N+]2(CCl)CC[N+](F)(CC2)C1.O.NN>CC(N(C)C)=O.CO.CCO>[NH2:3][C:12]1[C:16]2[CH:17]=[N:18][C:19]([NH:21][C:22]([NH:24][C@@H:25]([C:27]3[CH:32]=[CH:31][CH:30]=[CH:29][CH:28]=3)[CH3:26])=[O:23])=[C:20]([F:34])[C:15]=2[NH:14][N:13]=1

Participants

7

Reactant 3

HCID 24654Hydrazine hydrate (1:1)HCID 2724933SelectfluorHCID 118271929HCID 118271929, compound

Product 1

HCID 73504797HCID 73504797, compound

Reagents, catalysts & solvents 3

HCID 702EthanolSolventHCID 887MethanolSolventHCID 31374DimethylacetamideSolvent

Procedure

(R)-1-(3-(1,3-Dioxoisoindolin-2-yl)-1H-pyrazolo[4,3-c]pyridin-6-yl)-3-(1-phenylethyl)urea (114 mg, 0.267 mmol) was dissolved in DMA (1 mL) and methanol (1 mL), charged with powdered Selectfluor® (108 mg, 0.305 mmol), and stirred at room temperature for 20 h. The solvents were concentrated in vacuo and the residue was purified by flash chromatography (3-15% MeOH/DCM). The crude mixture obtained was then dissolved in EtOH (3 mL), charged with hydrazine hydrate (0.130 mL, 2.67 mmol), and heated to 85° C. for 30 min. The solvents were concentrated in vacuo and the residue was purified by mass-triggered reverse phase HPLC followed by purification via flash chromatography (2-10% MeOH/DCM) to give (R)-1-(3-amino-7-fluoro-1H-pyrazolo[4,3-c]pyridin-6-yl)-3-(1-phenylethyl)urea. MS ESI calc'd. for C15H15FN6O [M+1]+ 315. found 315. 1H NMR (500 MHz, DMSO-d6) δ 8.55 (s, 1H), 7.42-7.34 (m, 4H), 7.27 (m, 1H) 5.07 (q, J=6.7 Hz, 1H), 1.58 (d, J=7.0 Hz, 4H).

Workup

  1. concentrationThe solvents were concentrated in vacuo
  2. customthe residue was purified by flash chromatography (3-15% MeOH/DCM)
  3. customThe crude mixture obtained
  4. temperatureheated to 85° C. for 30 min
  5. concentrationThe solvents were concentrated in vacuo
  6. customthe residue was purified by mass-triggered reverse phase HPLC
  7. customfollowed by purification via flash chromatography (2-10% MeOH/DCM)

Sources & evidence

ORD record
ord-f9ca9e9de26042e88befde3516296334
Source dataset
uspto-grants-2016_01
Patent number
US09233979B2

Reaction notes

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