Ethanol → HCID 67088931, compound

HRID 1943935Notes

Reaction equation

HRID 1943935 reaction equation
[CH3:1][CH:2](OC(/N=N/C(OC(C)C)=O)=O)C.[OH:15][C:16]1[C:24]2[C:19](=[N:20][CH:21]=[C:22]([N+:25]([O-:27])=[O:26])[CH:23]=2)[N:18]([C:28]([O:30][C:31]([CH3:34])([CH3:33])[CH3:32])=[O:29])[N:17]=1.CCO.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>C1COCC1.CO>[CH2:1]([O:15][C:16]1[C:24]2[C:19](=[N:20][CH:21]=[C:22]([N+:25]([O-:27])=[O:26])[CH:23]=2)[N:18]([C:28]([O:30][C:31]([CH3:34])([CH3:33])[CH3:32])=[O:29])[N:17]=1)[CH3:2]

Participants

7

Reactant 4

HCID 702EthanolHCID 11776TriphenylphosphineHCID 5363146Diisopropyl azodicarboxylateHCID 178452559HCID 178452559, compound

Product 1

HCID 67088931HCID 67088931, compound

Reagents, catalysts & solvents 2

HCID 887MethanolSolventHCID 8028TetrahydrofuranSolvent

Procedure

A solution of DIAD in THF (10 mL) was added slowly via a syringe pump under N2 at room temperature for 1 hour to a solution of tert-butyl 3-hydroxy-5-nitro-1H-pyrazolo[3,4-b]pyridine-1-carboxylate (0.35 g, 1.2 mmol), EtOH (0.069 g, 1.5 mmol), and PPh3 (0.49 g, 1.9 mmol). The reaction mixture was poured onto water (20 mL) and extracted with EtOAc. The combined organic layers were washed with brine, dried over MgSO4, and concentrated under reduced pressure to give the crude material. The crude material was treated with MeOH to give tert-butyl 3-ethoxy-5-nitro-1H-pyrazolo[3,4-b]pyridine-1-carboxylate as a precipitate. The filtrate was concentrated and treated with a solution (10:1 hexane:EtOAc) to precipitate triphenylphosphineoxide. Then, the filtrate was concentrated and flash chromatographed (SiO2, 10:1=hexane:EtOAc) to afford tert-butyl 3-ethoxy-5-nitro-1H-pyrazolo[3,4-b]pyridine-1-carboxylate (total 0.237 g, 62% yield). LRMS (ACPI pos) m/e 209.0 ((M-Boc)+1).

Workup

  1. additionThe reaction mixture was poured onto water (20 mL)
  2. extractionextracted with EtOAc
  3. washThe combined organic layers were washed with brine
  4. dry with materialdried over MgSO4
  5. concentrationconcentrated under reduced pressure
  6. customto give the crude material

Sources & evidence

ORD record
ord-45d0fab8b36e44ee88a5fc5d448eb090
Source dataset
uspto-grants-2013_03
Patent number
US08394795B2

Reaction notes

Loading…