HCID 67420753, compound → HCID 136053070, compound

HRID 1875713Notes

Reaction equation

HRID 1875713 reaction equation
[C:1]([O:5][C:6]([N:8]1[CH2:13][CH2:12][CH2:11][C:10]2[NH:14][N:15]=[C:16]([C:17]3[CH:22]=[C:21]([Cl:23])[C:20]([O:24]CC4C=CC=CC=4)=[CH:19][C:18]=3[O:32]CC3C=CC=CC=3)[C:9]1=2)=[O:7])([CH3:4])([CH3:3])[CH3:2].C(OC(N1CCC2C(C3C=C(Cl)C(OCC4C=CC=CC=4)=CC=3OCC3C=CC=CC=3)=NNC=2C1)=O)(C)(C)C>C(O)C.C(O)(=O)C.[Pd]>[C:1]([O:5][C:6]([N:8]1[CH2:13][CH2:12][CH2:11][C:10]2[NH:14][N:15]=[C:16]([C:17]3[CH:22]=[C:21]([Cl:23])[C:20]([OH:24])=[CH:19][C:18]=3[OH:32])[C:9]1=2)=[O:7])([CH3:4])([CH3:2])[CH3:3]

Participants

6

Reactant 2

HCID 67420753HCID 67420753, compoundHCID 67421505HCID 67421505, compound

Product 1

HCID 136053070HCID 136053070, compoundYield 48%

Reagents, catalysts & solvents 3

HCID 23938PalladiumCatalystHCID 176Acetic AcidSolventHCID 702EthanolSolvent

Procedure

A mixture of 3-(2,4-bis-benzyloxy-5-chloro-phenyl)-1,5,6,7-tetrahydro-pyrazolo[4,3-b]pyridine-4-carboxylic acid tert-butyl ester (e) and 3-(2,4-bis-benzyloxy-5-chloro-phenyl)-1,4,5,7-tetrahydro-pyrazolo[3,4-c]pyridine-6-carboxylic acid tert-butyl ester (f) (7 g, 13 mmol) was dissolved in a mixture of ethanol (50 mL) and glacial acetic acid (10 mL) at room temperature before the addition of 10% Pd/C (1 g). The reaction mixture was stirred under hydrogen atmosphere (20 psi) for 10 h. The suspension was filtered through celite and the filtrate was concentrate to small volume and ethylacetate (200 mL) was added. The solution was washed with 1 M NaHCO3 solution, then with brine and dried. The solvent was removed and the crude reaction mixture was carefully chromatographed on silica gel eluting with ethylacetate/methanol 6/1 to provide 3-(5-chloro-2,4-dihydroxy-phenyl)-1,5,6,7-tetrahydro-pyrazolo[4,3-b]pyridine-4-carboxylic acid tert-butyl ester (g) (2.3 g, 48% yield).

Workup

  1. filtrationThe suspension was filtered through celite
  2. concentrationthe filtrate was concentrate to small volume and ethylacetate (200 mL)
  3. additionwas added
  4. washThe solution was washed with 1 M NaHCO3 solution
  5. dry with materialwith brine and dried
  6. customThe solvent was removed
  7. customthe crude reaction mixture
  8. customwas carefully chromatographed on silica gel eluting with ethylacetate/methanol 6/1

Sources & evidence

ORD record
ord-3e0fa83f53294bbabc2c1d218dd8b575
Source dataset
uspto-grants-2012_11
Patent number
US08309578B2

Reaction notes

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