Water → HCID 69935281, compound

HRID 341076Notes

Reaction equation

HRID 341076 reaction equation
OCCC[C:5]1[CH:10]=[CH:9][CH:8]=[CH:7][C:6]=1[N:11]1[C:35](=[O:36])[C:14]2=[CH:15][N:16]([CH2:23][C:24]3[CH:29]=[CH:28][C:27]([N:30]4[CH:34]=[CH:33][CH:32]=[N:31]4)=[CH:26][CH:25]=3)[C:17]3[CH:18]=[CH:19][CH:20]=[CH:21][C:22]=3[C:13]2=[N:12]1.CC(OI1(OC(C)=O)(OC(C)=O)O[C:48](=[O:49])[C:47]2C1=CC=C[CH:46]=2)=O.C(=O)(O)[O-].[Na+].O.S([O-])([O-])(=O)=S.[Na+].[Na+]>ClCCl>[C:48]([C:5]1[CH:10]=[CH:9][CH:8]=[CH:7][C:6]=1[N:11]1[C:35](=[O:36])[C:14]2=[CH:15][N:16]([CH2:23][C:24]3[CH:29]=[CH:28][C:27]([N:30]4[CH:34]=[CH:33][CH:32]=[N:31]4)=[CH:26][CH:25]=3)[C:17]3[CH:18]=[CH:19][CH:20]=[CH:21][C:22]=3[C:13]2=[N:12]1)(=[O:49])[CH2:47][CH3:46]

Participants

7

Reactant 5

HCID 962WaterHCID 24477Sodium ThiosulfateHCID 159087Triacetoxyperiodinane2×HCID 516892Sodium Bicarbonate3×HCID 68154200HCID 68154200, compound

Product 1

HCID 69935281HCID 69935281, compound

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

(±)-2-[2-(Hydroxypropyl)phenyl]-5-{[4-(1H-pyrazol-1-yl)phenyl]methyl}-2,5-dihydro-3H-pyrazolo[4,3-c]quinolin-3-one (Example 657, 81 mg, 0.17 mmol), 1,1,1-tris(acetyloxy)-1,1-dihydro-1,2-benziodoxol-3-(1H)-one (Dess-Martin periodinane, 0.11 g, 0.25 mmol, 1.5 equiv), sodium bicarbonate (71 mg, 0.85 mmol, 5 equiv) and water (8.0 μL, 0.44 mmol, 2.6 equiv) were combined in dichloromethane (8 mL) and stirred vigorously for 30 minutes. Additional Dess-Martin periodinane (0.11 g, 0.25 mmol, 1.5 equiv) was added and the mixture was stirred for an additional 45 minutes. The mixture was treated with sodium bicarbonate (3 mL, aqueous saturated) and sodium thiosulfate (3 mL, aqueous saturated) and stirred vigorously for 30 minutes. The mixture was poured into sodium bicarbonate (15 mL, aqueous saturated) and extracted with dichloromethane (2×50 mL) and the combined organic extracts were dried with sodium sulfate, filtered and concentrated in vacuo. The residue was purified by silica gel gradient chromatography (100:0 to 0:100; hexanes:ethyl acetate containing 5% methanol), providing the titled compound: 1H-NMR (400 MHz, CDCl3) δ 8.45 (1H, s), 8.37 (1H, dd, J=7.2, 2.2 Hz), 7.94-7.91 (2H, m), 7.74-7.72 (3H, m), 7.57-7.43 (5H, m), 7.35 (1H, d, J=7.6 Hz), 7.31 (2H, d, J=8.4 Hz), 6.47 (1H, m), 5.49 (2H, s), 2.73 (2H, q, J=7.6 Hz), 1.13 (3H, t, J=7.2 Hz) ppm; high resolution mass spectrometry (ES+) m/z 474.1919 [(M+H)+; calculated for C29H24N5O2: 474.1925].

Workup

  1. stirringthe mixture was stirred for an additional 45 minutes
  2. stirringstirred vigorously for 30 minutes
  3. extractionextracted with dichloromethane (2×50 mL)
  4. dry with materialthe combined organic extracts were dried with sodium sulfate
  5. filtrationfiltered
  6. concentrationconcentrated in vacuo
  7. customThe residue was purified by silica gel gradient chromatography (100:0 to 0:100; hexanes:ethyl acetate containing 5% methanol)

Sources & evidence

ORD record
ord-2dd14b40a7e24d14b1d7e2f86fc5816b
Source dataset
uspto-grants-2014_11
Patent number
US08895580B2

Reaction notes

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