Sodium Carbonate → HCID 89463055, compound

HRID 1473278Notes

Reaction equation

HRID 1473278 reaction equation
O[C:2]1[C:3]2[CH:16]=[N:15][N:14]([CH2:17][C:18]3[CH:23]=[CH:22][C:21]([O:24][CH3:25])=[CH:20][CH:19]=3)[C:4]=2[C:5](=[O:13])[N:6]([CH3:12])[C:7]=1[C:8]([O:10][CH3:11])=[O:9].S(OS(C(F)(F)F)(=O)=O)(C(F)(F)F)(=O)=O.[O-]S(C(F)(F)F)(=O)=O.[CH3:49][C:50]1[CH:51]=[C:52](B(O)O)[CH:53]=[CH:54][C:55]=1[CH3:56].C(=O)([O-])[O-].[Na+].[Na+]>ClCCl.O1CCOCC1.O.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.CCOC(C)=O>[CH3:49][C:50]1[CH:51]=[C:52]([C:2]2[C:3]3[CH:16]=[N:15][N:14]([CH2:17][C:18]4[CH:23]=[CH:22][C:21]([O:24][CH3:25])=[CH:20][CH:19]=4)[C:4]=3[C:5](=[O:13])[N:6]([CH3:12])[C:7]=2[C:8]([O:10][CH3:11])=[O:9])[CH:53]=[CH:54][C:55]=1[CH3:56]

Participants

11

Reactant 5

HCID 10340Sodium CarbonateHCID 67749Trifluoromethanesulfonic anhydrideHCID 27343483,4-Dimethylphenylboronic acidHCID 2758875TrifluoromethanesulfonateHCID 89463179HCID 89463179, compound

Product 1

HCID 89463055HCID 89463055, compoundYield 87.9%

Reagents, catalysts & solvents 5

HCID 178418397HCID 178418397, compoundCatalystHCID 962WaterSolvent2×HCID 6344DichloromethaneSolventHCID 8857Ethyl AcetateSolventHCID 312751,4-DioxaneSolvent

Conditions

Temperature
0 °C

Procedure

To a solution of methyl 4-hydroxy-1-(4-methoxybenzyl)-6-methyl-7-oxo-6,7-dihydro-1H-pyrazolo[3,4-c]pyridine-5-carboxylate (585 mg, 1.7 mmol) in dichloromethane (15 mL) was added TEA (0.48 mL, 3.4 mmol) and the mixture was cooled to 0° C. and triflic anhydride (0.32 mL, 1.87 mmol) was added dropwise. After 1 h the mixture was washed with saturated sodium bicarbonate/water and brine. The organic phase was dried over sodium sulfate and concentrated. To a solution of crude triflate in 1,4-dioxane (14 mL) was added (3,4-dimethylphenyl)boronic acid (0.33 g, 2.2 mmol), Palladium tetrakis (0.19 g, 0.17 mmol) and a solution of sodium carbonate (0.54 g, 5.05 mmol) in water (3.5 mL) and the mixture was heated to 70° C. under nitrogen atmosphere for 1 h. EtOAc and water was added and the mixture was washed with saturated sodium bicarbonate/water. The organic phase was dried over sodium sulfate, concentrated and purified on silica using EtOAc/hexanes 0-30% to provide the title compound (645 mg, 84%). 1H NMR (400 MHz, DMSO-d6) δ ppm 7.65 (s, 1H), 7.4 (d, 2H), 7.2 (d, 1H), 7.14 (s, 1H), 7.08 (d, 1H), 6.85 (d, 2H), 5.92 (s, 2H), 3.8 (s, 3H), 3.64 (s, 3H), 3.6 (s, 3H), 2.28 (s, 3H), 2.26 (s, 3H); ES-LCMS: 432.24 (M+1).

Workup

  1. washAfter 1 h the mixture was washed with saturated sodium bicarbonate/water and brine
  2. dry with materialThe organic phase was dried over sodium sulfate
  3. concentrationconcentrated
  4. washthe mixture was washed with saturated sodium bicarbonate/water
  5. dry with materialThe organic phase was dried over sodium sulfate
  6. concentrationconcentrated
  7. custompurified on silica

Sources & evidence

ORD record
ord-e9773e1eb6f2428abbb871ad9a152afe
Source dataset
uspto-grants-2015_04
Patent number
US09012642B2

Reaction notes

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